The 15th International Conference on

Secondary Ion Mass Spectrometry

1216 September 2005
Manchester, UK
Abstract book and programme
i
Tabl e of Cont ent s

PAGE
Wel come t o SIMS XV Manchest er 2005 i i

Acknowl edgement s i i i

Commi t t ees
UK Or gani si ng Commi t t ee i i i
Di scussi on Day Wor ki ng Par t y i v
SIMSXV Pr oceedi ngs Edi t or i al Team i v
Int er nat i onal Commi t t ee i v
Int er nat i onal Sci ent i f i c Commi t t ee i v

Invi t ed Speaker s
Pl enar y Lect ur er s v
Cor e Conf er ence v
Symposi um on Ar chaeomet r y, Cosmochemi st r y and Geol ogy v
Di scussi on on Chal l enge of Mol ecul e Speci f i c Anal ysi s and Imagi ng i n Or gani c
and Bi osyst ems v

Exhi bi t i on
Locat i on vi
Par t i ci pant s vi
Hour s vi

Soci al Pr ogr amme vi i

Gener al Inf or mat i on
Or al Pr esent at i ons vi i i
Di scussi on Day Pr ocedur es vi i i
Of f i ce Locat i ons vi i i

Pr ogr amme i x- xxvi i

Abst r act s 1- 339

Aut hor Index 340- 347

Manuf act ur er s Adver t s 348

ii
Wel come t o SIMS XV Manchest er 2005

On behal f of t he SIMSXV Or gani si ng Commi t t ee i t i s a gr eat pl easur e t o wel come you t o t he Uni ver si t y
of Manchest er t o par t i ci pat e i n t he 15
t h
Int er nat i onal Conf er ence on Secondar y Ion Mass Spect r omet r y.
As wel l as bei ng t he f i r st t i me t hat a SIMS Int er nat i onal Conf er ence has come t o t he UK, our conf er ence
i s one of t he f i r st i nt er nat i onal conf er ences t o be hel d i n t he Uni ver si t y of Manchest er t hat was cr eat ed
i n 2004 by br i ngi ng t oget her UMIST and The Vi ct or i a Uni ver si t y of Manchest er . It i s t he l ar gest si ngl e
si t e uni ver si t y i n t he UK. As a conf er ence t hat expl or es t he cut t i ng edge of our sci ence we shoul d f eel
at home because r esear ch i s at t he hear t of t hi s Uni ver si t y. It has a di st i ngui shed hi st or y i n r esear ch,
i nnovat i on and ent er pr i se st r et chi ng back over 75 year s. No f ewer t han 23 f or mer st af f and st udent s
have gone on t o become Nobel pr i zewi nner s. Maj or sci ent i f i c advances at Manchest er i ncl ude
Rut her f or d's wor k l eadi ng t o t he spl i t t i ng of t he at om and t he devel opment of t he wor l d's f i r st moder n
comput er .

It i s a ver y exci t i ng t i me f or SIMS and we have sought t o hi ghl i ght t hi s i n our choi ce of t he i nvi t ed
speaker s and i n some novel aspect s of t he pr ogr amme. Ther e ar e new chal l enges i n semi conduct or
mat er i al s anal ysi s as new mat er i al s ar e bei ng expl or ed. Thi s i s r ef l ect ed i n t he f ocused sessi on on
advanced di el ect r i c mat er i al s or gani sed by Joe Bennet t . The devel opment of cl ust er i on beams of f er s
ver y si gni f i cant new oppor t uni t i es i n compl ex mat er i al s anal ysi s. The sessi on or gani sed by Ni ck
Wi nogr ad and sponsor ed by IONTOF wi l l expl or e t he sput t er i ng phenomena and t he new anal yt i cal r ul es
t hat may emer ge. The one- day Symposi um or gani sed by Mar k Dowset t on t he expl oi t at i on of SIMS i n
t he f i el ds of Ar chomet r y, Cosmochemi st r y and Geol ogy br i ngs some hi st or i cal l y i mpor t ant
appl i cat i ons of SIMS t oget her wi t h ver y new devel opment s i n t he cont r ast i ng ar eas of space sci ence and
t he pr eser vat i on of anci ent ar t ef act s. The expl oi t at i on of SIMS abi l i t y t o pr obe compl ex chemi st r y at
hi gh spat i al r esol ut i on i n i t s appl i cat i on t o t he st udy of bi ol ogi cal t i ssue and cel l ul ar mat er i al s wi l l be
expl or ed i n dept h dur i ng t he Di scussi on Day sponsor ed by ULVAC-Phi . We ar e par t i cul ar l y pl eased t hat
we ar e abl e t o wel come a number of bi ol ogi st s and user s of ot her mass spect r al t echni ques t o
par t i ci pat e i n t hi s Di scussi on. However , per usal of t he r est of t he pr ogr amme, post er s and or al s, shows
t hat exci t i ng devel opment s ar e not l i mi t ed t o t hese ar eas. We have a r eal f east t hat I hope al l wi l l
enj oy.

We ar e ver y honour ed t o wel come t he Nobel Laur eat e, Pr of essor Si r Har r y Kr ot o FRS t o gi ve our pl enar y
l ect ur e on Monday. The gr eat pot ent i al of f er ed by cl ust er i on beams as exempl i f i ed by C
60
+
makes hi s
l ect ur e on t he f ur t her i nsi ght s i nt o f ul l er ene and nanot ube f or mat i on par t i cul ar l y i nt er est i ng. We ar e
al so ver y pl eased t o wel come Pr of essor Si mon Gaskel l who i s t he Associ at e Vi ce- Pr esi dent f or Resear ch
her e i n Manchest er . He has an enor mous r eput at i on i n t he appl i cat i on of mass spect r omet r y t o t he
bi osci ences. As SIMS seeks t o cont r i but e t o bi ol ogi cal st udi es hi s pl enar y l ect ur e on Wednesday wi l l , I
am sur e, be l i st ened t o wi t h gr eat i nt er est .

Thi s ser i es of Int er nat i onal Conf er ences was f ounded by Pr of essor Al f r ed Benni nghoven i n Mnst er i n
1975. The Int er nat i onal Commi t t ee t hat has gui ded t he ver y successf ul ser i es of meet i ngs si nce t hen
has deci ded i t i s t i me t o st and down. It i s t her ef or e wi t h some ant i ci pat i on t hat we l ook f or war d t o
t he i naugur at i on of a new Int er nat i onal Commi t t ee dur i ng t hi s Conf er ence.

Manchest er has a gr eat i ndust r i al hi st or y. It i s now ver y successf ul l y r ei nvent i ng i t sel f as a post -
i ndust r i al cent r e of sci ence, t echnol ogy, spor t , cul t ur e and commer ce. We hope t he soci al pr ogr amme
wi l l hel p you t o get a f eel f or t he past and sampl e some of t he new t hi ngs on of f er . The conf er ence
di nner on Wednesday wi l l be i n t he Town Hal l bui l t at t he hei ght of Manchest er s i ndust r i al power .

We hope t he meet i ng and your st ay i n Manchest er wi l l be up t o your hopes and expect at i ons. If you
have any quest i ons or pr obl ems do not hesi t at e t o ask f or hel p at t he Regi st r at i on Desk, f r om one of
t he st udent hel per s i n t hei r bl ue pol o shi r t s or f r om a member of t he Or gani si ng Commi t t ee.

John Vi cker man, Chai r
Ian Gi l mor e, Co-Chai r
iii
Acknowl edgement s

The SIMS XV or gani si ng commi t t ee gr at ef ul l y acknowl edge t he gener ous suppor t of t he f ol l owi ng
compani es and or gani sat i ons:
Exhi bi t or s:
CAMECA Gr oup
Evans Anal yt i cal Gr oup
Ful l Waf er Anal ysi s Inc
Hi den Anal yt i cal Lt d
Ionopt i ka Lt d
ION- TOF GmbH
John Wi l ey & Sons Lt d
KLA Tencor Cor por at i on
Kor e Technol ogy Lt d
Kr at os Anal yt i cal Lt d
Lei ca Mi cr osyst ems ( UK) Lt d
Mi l l br ook Sci ent i f i c Inst r ument s PLC
SPECS GmbH
Sur f aceSpect r a Lt d
ULVAC PHI Inc

Wi t h speci al t hanks t o t he Maj or Sponsor s of SIMS XV:
CAMECA GmbH
Cascade Sci ent i f i c Lt d
Ionopt i ka Lt d
ION- TOF GmbH
ULVAC PHI Inc

Ot her Val ued Cont r i but or s t o SIMS XV:
Kr at os Anal yt i cal Lt d
Nat i onal Physi cal Labor or at or y
Sur f aceSpect r a Lt d
The Br i t i sh Vacuum Counci l
The UK Sur f ace Anal ysi s For um





Commi t t ees

UK Organi sing Commi t t ee
Chai r : Pr of essor John Vi cker man
The Uni ver si t y of Manchest er
Co- Chai r : Dr Ian Gi l mor e
Nat i onal Physi cal Labor at or y
Secr et ar y: Dr Ian Fl et cher
ICI, Wi l t on
Tr easur er / f und- r ai si ng: Pr of essor Roger Webb
Uni ver si t y of Sur r ey
Exhi bi t i on Coor di nat or : Mr Rowl and Hi l l
Ionopt i ka Lt d
Pr ogr amme Coor di nat or : Pr of essor John Wat t s
Uni ver si t y of Sur r ey
Communi cat i ons Coor di nat or : Dr Al ex Hender son
The Uni ver si t y of Manchest er
iv
Local Pr ogr amme Co- Chai r s: Dr Ni ck Lockyer and Dr Ian Lyon
The Uni ver si t y of Manchest er
Publ i ci t y Coor di nat or : Dr Davi d Sykes
Loughbor ough Sur f ace Anal ysi s
Member s: Pr of essor Mar k Dowset t
Uni ver si t y of War wi ck
Dr Mar t i n Seah
Nat i onal Physi cal Labor at or y

Di scussi on Day Worki ng Part y

Pr of essor John Vi cker man The Uni ver si t y of Manchest er , UK
Pr of essor Ni chol as Wi nogr ad Penn St at e Uni ver si t y, USA
Pr of essor Davi d Cast ner Uni ver si t y of Washi ngt on, Seat t l e, USA
Pr of essor Hei hr i ch Al r l i nghaus Uni ver si t t Mnst er , Ger many
Pr of essor Cl aude Lechene Har var d Medi cal School , USA
Dr Ian Gi l mor e Nat i onal Physi cal Labor at or y, UK

SIMS XV Proceedi ngs Edi t ori al Team
Pr of essor John Vi cker man The Uni ver si t y of Manchest er
Dr Ian Gi l mor e Nat i onal Physi cal Labor at or y
Pr of essor Mar k Dowset t Uni ver si t y of War wi ck
Dr Al ex Hender son The Uni ver si t y of Manchest er
Pr of essor Hel mut Wer ner The Net her l ands

Int ernat i onal Commi t t ee
Pr of essor A Benni nghoven, Chai r man ION- TOF, Ger many
Pr of essor V T Cher epi n Ukr ai ni an Academy of Sci ences, Ukr ai ne
Char l es A. Evans, Jr . Ful l Waf er Anal ysi s, USA
Pr of essor Yoshi masa Ni hei Uni ver si t y of Tokyo, Japan
Pr of essor Geor ges Sl odzi an Uni ver si t y of Par i s- Sud, Fr ance
Pr of essor H W Wer ner The Net her l ands
Pr of essor Pet er Wi l l i ams Ar i zona St at e Uni ver si t y, USA

Int ernat i onal Scient i fi c Commi t t ee
Dr Joe Bennet t SEMATECH, USA
Pr of essor Dr Al f r ed Benni nghoven ION- TOF, Ger many
Dr Ar naud Del cor t e Uni ver si t Cat hol i que de Louvai n, Bel gi um
Pr of essor Mar k Dowset t Uni ver si t y of War wi ck, UK
Pr of essor Bar bar a Gar r i son Pennsyl vani a St at e Uni ver si t y, USA
Dr Ian Gi l mor e Nat i onal Physi cal Labor at or y, UK
Pr of essor Yoshi kazu Homma Tokyo Uni ver si t y of Sci ence, Japan
Pr of essor Masahi r o Kudo Sei kei Uni ver si t y, Japan
Dr Char l es Magee Evans East , USA
Pr of essor John Vi cker man, Chai r man The Uni ver si t y of Manchest er , UK
Pr of essor Amy Wal ker Washi ngt on Uni ver si t y, USA
Pr of essor Andr ew Wee Nat i onal Uni ver si t y of Si ngapor e, Si ngapor e
Pr of essor Kl aus Wi t t maack GSF, Ger many
v
Invi t ed Speakers

Pl enary Lect urers
Pr of essor Si r Har r y Kr ot o FRS, Nobel Laur eat e, Fl or i da St at e Uni ver si t y, USA; For mer l y of Uni ver si t y of
Sussex, UK
Some New Insi ght s i n t o t he Mechani sms of Ful l er ene and Nanot ube For mat i on

Pr of essor Si mon Gaskel l , The Uni ver si t y of Manchest er , UK
The cont ri but i on of mass spect r omet ry t o t he bi o-sci ences
Core Conference
Sat oka Aoyagi , Shi mane Uni ver si t y, Japan
Joe Bennet t , Int er nat i onal SEMATECH, USA
Pat r i ck Ber t r and, Uni ver si t Cat hol i que de Louvai n, Bel gi um
Ar naud Del cor t e, Uni ver si t Cat hol i que de Louvai n, Bel gi um

Bar bar a Gar r i son, Penn St at e Uni ver si t y, USA

Mi chael Kar as, Johann Wol f gang Goet he Uni ver si t y of Fr ankf ur t , Ger many
Yuj i Kat aoka, Fuj i t su Labor at or i es Lt d, Japan
Paul Ronshei m, IBM, USA

Wi l f r i ed Vander vor st , IMEC, Bel gi um

Mat t Wagner , Pr oct or and Gambl e Inc. , USA
Lu-Tao Weng, The Hong Kong Uni ver si t y of Sci ence and Technol ogy
Kl aus Wi t t maack, GSF, Ger many
Andr eas Wucher , Uni ver si t y of Essen, Ger many
Symposi um on Archaeomet ry, Cosmochemist ry and Geol ogy
Bi l l Compst on, Aust r al i an Nat i onal Uni ver si t y, Canber r a
Annemi e Adr i aens, Uni ver si t y of Ghent , Bel gi um
Davi d McPhai l , Imper i al Col l ege, UK
Chr i s Car r , The Uni ver si t y of Manchest er , UK
Pet er Hoppe, Max-Pl anck Inst i t ut e, Mai nz, Ger many
Di scussi on on The Chal lenge of Mol ecule Speci fi c Analysis and Imagi ng in
Organi c and Bi o-syst ems
Andr ew Ewi ng, Pennsyl vani a St at e Uni ver si t y, USA
vi
Exhi bi t i on


Exhi bi t i on Locat i on
Renol d Bui l di ng, Concour se ( C15)


Exhi bi t i on Par t i ci pant s
CAMECA Gr oup
Evans Anal yt i cal Gr oup
Ful l Waf er Anal ysi s Inc
Hi den Anal yt i cal Lt d
Ionopt i ka Lt d
ION- TOF GmbH
John Wi l ey & Sons Lt d
KLA Tencor Cor por at i on
Kor e Technol ogy Lt d
Kr at os Anal yt i cal Lt d
Lei ca Mi cr osyst ems ( UK) Lt d
Mi l l br ook Sci ent i f i c Inst r ument s Lt d
SPECS GmbH
Sur f aceSpect r a Lt d
ULVAC PHI Inc

Exhi bi t i on Hour s
Monday 8. 30 19. 00
Tuesday 8. 30 17. 00
Wednesday 8. 30 14. 00
Thur sday 8. 30 20. 00
Fr i day 8. 30 13. 00


vii
Soci al Programme


At a gl ance Sunday Monday Tuesday Wednesday Thur sday Fr i day
Af t er noon

Excur si on
Eveni ng

Wel come
Recept i on
Post er
Sessi on
1
Museum
of
Sci ence
and
Indust r y
Conf er ence
Banquet -
Manchest er
Town Hal l
Post er
Sessi on 2
Gui ded
Pub
Tour

Wel come Recept i on
Thi s wi l l t ake pl ace on Sunday i n West on Room I, Manchest er Conf er ence Cent r e, 18. 00 21. 00.

Museum of Sci ence and Indust r y
Tuesday 13t h Sept ember 20. 00 22. 30

Si t uat ed i n t he ol dest passenger r ai l way bui l di ngs i n t he wor l d t hi s museum shows of f Manchest er s
pr oud i ndust r i al her i t age. Exhi bi t i ons i ncl ude t he l ar gest col l ect i on of wor ki ng st eam mi l l engi nes i n
t he wor l d, t he wor ki ngs of a 1830s War ehouse and a Fi br es, Fabr i cs and Fashi on Gal l er y.

Conf er ence Excur si on
Wednesday 14t h Sept ember

Opt i on A Quar r y Bank Mi l l Indust r i al Her i t age Cent r e
Founded i n 1784 Quar r y Bank Mi l l i s an unr i val l ed exampl e of a wat er - power ed cot t on mi l l . Awar d-
wi nni ng gal l er i es ar e devot ed t o wor ki ng exampl es of t ext i l e machi nes t hat made t he r egi on t he
bi r t hpl ace of t he Indust r i al Revol ut i on. Si t uat ed i n 384 acr es of beaut i f ul count r ysi de t hi s r emar kabl e
Geor gi an museum i s uni que and hi ghl y r ecommended.

Opt i on B The Quays Exper i ence
Over l ooki ng t he r edevel oped Manchest er Shi p Canal ar e some of Manchest er s pr emi er t our i st
at t r act i ons. You may l i ke t o vi si t t he Lowr y Ar t Gal l er y, t he desi gner shoppi ng out l et or si mpl y spend
t i me r el axi ng i n t hi s pl easant wat er f r ont l ocat i on. A shor t wal k acr oss t he canal wi l l t ake you t o t he
ar chi t ect ur al l y st r i ki ng Imper i al War Museum.

Opt i on C Manchest er Uni t ed Museum & St adi um Tour
Thi s t our wi l l enabl e you t o r el i ve t he t r i umphs, t r agedi es and t r ophi es of one of t he most f amous
f oot bal l t eams i n t he wor l d. The t our wi l l al l ow you t o expl or e t he Hal l of Fame and dazzl i ng Tr ophy
Room and si t i n t he hei ght s of t he Nor t h St and, t he manager s dug out and t he Home changi ng r oom.
Then emer ge f r om t he pl ayer s t unnel t o t he r oar of t he cr owd.

Manchest er Town Hal l
Wednesday 14t h Sept ember Conf er ence Banquet 19. 30 23. 00

Af t er Di nner speaker : Dr Andr ew Coat es, Mul l ar d Space Sci ence Labor at or y, Uni ver si t y Col l ege London,
"Deep Impact : The Ul t i mat e Cl ust er SIMS Exper i ment "

The Town Hal l i s Manchest er 's gr eat est monument and f or many i s t he qui nt essent i al Vi ct or i an
Ar chi t ect ur e. The Town Hal l uni f i es ar chi t ect ur e, f i ne ar t s, scul pt ur e and symbol i sm of t he Vi ct or i an
age.

Gui ded Pub Tour ("Pub Cr awl ")
Fri day 16t h Sept ember - Addi t i onal Soci al Pr ogramme
Af t er t he mai n conf er ence t he l ocal commi t t ee, wi t h consi der abl e hel p f r om t he st udent s of
Manchest er Uni ver si t y, ar e pl eased t o of f er a gui ded t our of Manchest er s f i nest Pubs, t o sui t al l
t ast es! In t he UK t hi s i s known as a "Pub Cr awl ".
viii
General Inf ormat i on

Pr esent er s

Or al pr esent at i ons must be t i med t o l ast no l onger t han 17 mi nut es, l eavi ng at l east 3 mi ns f or
quest i ons. The t i me l i mi t s wi l l be st r i ct l y enf or ced. Or al pr esent er s usi ng power poi nt shoul d
pr ef er abl y have t hei r pr esent at i on on a memor y st i ck, so t hat i t can be l oaded on t o t he conf er ence
comput er pr i or t o begi nni ng of t he sessi on. If pr esent er s must use t hei r own l ap- t ops t hey must ensur e
t hat t hei r comput er s ar e l i nked up and wor ki ng pr i or t o t he begi nni ng of t he sessi on. An over head
pr oj ect or wi l l be avai l abl e f or pr esent er s who wi sh t o use i t .

Di scussi on Day Pr ocedur es

The paper s t o be Di scussed ar e avai l abl e f or down-l oad on t he web-si t e. It wi l l be assumed t hat t he
paper s have been r ead BEFORE t he meet i ng.

The paper s have been gr ouped i nt o 3 t opi c ar eas see t he pr ogr amme. Ther e wi l l be 4 Di scussi on
sessi ons. The t hi r d t opi c ar ea wi l l be spl i t i nt o t wo Di scussi on sessi ons.

Paper pr esent er s ar e gi ven a MAXIMUM of 5 mi nut es t o pr esent t he mai n poi nt s of t hei r paper s usi ng
t he i n house PC or over head pr oj ect or . They wi l l be al l owed j ust 3 power poi nt or over head sl i des.

Af t er t he paper pr esent er s have gi ven t hei r t al ks t he Chai r of t he sessi on wi l l open t he sessi on t o
di scussi on. Al l conf er ence at t endees ar e wel come t o cont r i but e ( her eaf t er r ef er r ed t o as a
cont r i but or ) vi a quest i ons, comment s or l onger cont r i but i ons r el evant t o t he ar ea cover ed by t he
paper s under di scussi on. No cont r i but or wi l l be al l owed t o speak f or l onger t han 5 mi nut es or pr esent
mor e t han 2 sl i des of dat a. The Chai r wi l l gui de t he f l ow of t he di scussi on and has t he absol ut e r i ght t o
det er mi ne who wi l l cont r i but e. At t he end of t he desi gnat ed t i me, t he Chai r wi l l br i ef l y summar i se t he
out come of t he Di scussi on.

If a cont r i but or wi shes t o pr esent dat a, an over head pr oj ect or wi l l be avai l abl e f or i mmedi at e use. If
cont r i but or s wi sh t o use power poi nt , t hey must use t he conf er ence comput er and pr ovi de t he sl i des ( no
mor e t han 2) t o t he oper at or on a memor y st i ck or CD bef or e t he st ar t of t he sessi on.

Audi o or vi deo r ecor di ng of t he Di scussi on i s not al l owed. In or der t o obt ai n a r ecor d of t he Di scussi on
f or publ i cat i on i n t he Pr oceedi ngs, par t i ci pant s ar e asked t o submi t t hei r cont r i but i ons i n wr i t i ng.
When a cont r i but or asks a quest i on, makes a comment or gi ves a cont r i but i on, t hey ar e asked t o
cl ear l y st at e t hei r name and af f i l i at i on. Number ed pr of or ma wi l l be handed out i n t he Lect ur e Theat r e
each t i me a cont r i but i on i s made and r emar ks may be hand wr i t t en by t he cont r i but or and handed i n t o
t he Edi t or i al Desk at t he end of t he sessi on, or t hey may be sent i n t o t he Edi t or s af t er war ds. The
Edi t or s wi l l ci r cul at e t he r emar ks by emai l t o t he r el evant aut hor s and cont r i but or s af t er t he meet i ng.
Cont r i but or s and aut hor s wi l l be abl e t o check t he accur acy of t he r ecor d, edi t and r evi se t hem as
r equi r ed. The deadl i ne f or t he submi ssi on of quest i ons and comment s wi l l be 1 week af t er r ecei pt and
3 weeks f or paper aut hor s t o submi t t hei r f i nal r epl i es. The Edi t or s r eser ve t he r i ght t o deci de whet her
a cont r i but i on i s appr opr i at e.

Conf er ence Of f i ce

Renol d Bui l di ng
Uni ver si t y of Manchest er
Sackvi l l e St , Manchest er M60 1QD

Phone: +44 (0)161 306 4099
Fax: +44 (0)161 306 4070
Emai l : mcc. r eg@manchest er . ac. uk

Of f i ce Locat i ons

Pr esent er s Room Renol d Bui l di ng F1
Pr oceedi ngs Edi t or i al Of f i ce Renol d Bui l di ng F2
SIMS XV Of f i ce Renol d Bui l di ng F6

ix
Programme


Monday 12
t h
Sept ember
Session 1 C16
08:40 Opening Address:
Professor Dame Nancy Rothwell DBE, FRS, Vice President for
Research, The University of Manchester
Professor Alfred Benninghoven, Chair of the International Committee
Professor John Vickerman, Chair of the SIMSXV Committee
09:00 FUN2-I-Mo-A01 Atoms, Clusters, and Photons: Energetic
Probes for Mass Spectrometry
B Garrison
09:40 FUN2-O-Mo-A02 Secondary Ion Yield Enhancement due to
Cluster Ion Bombardment: A Surprise?
K Wittmaack
10:00 FUN2-O-Mo-A03 Energy and angular distributions of secondary
ions in the sputtering of gold by swift Aun
clusters. Emission mechanisms
S Bouneau,
S Della-Negra,
Y Le Beyec, M Pautrat,
M H Shapiro,
T A Tombrello
10:20 FUN2-O-Mo-A04 Effect of Molecular Binding Energy on
Sputtering of Thin Organic Overlayers by keV
Ga And C60 Bombardment
B Czerwiski,
B J Garrison, R Samson,
N Winograd, Z Postawa
10:40 Coffee
11:00 FUN2-I-Mo-A05 A fundamental review of organic ion
emission using cluster ion beams
A Wucher
11:40 FUN2-O-Mo-A06 Applications of a Bismuth-Cluster Ion Gun in
Inorganic Surface Analysis and Depth Profiling
F Kollmer, R Moellers,
T Grehl, D Rading,
E Niehuis
12:00 FUN2-O-Mo-A07 Sputtering of Amorphous Ice Induced by C60
and Au3 Clusters
M F Russo Jr,
I A Wojciechowski,
B J Garrison
12:20 FUN2-O-Mo-A08 Molecular Ion Emission from Single Large
Cluster Impacts
S V Verkhoturov,
G J Hager, J E Locklear,
R D Rickman,
C Guillermier,
E A Schweikert
12:40 FUN2-O-Mo-A09 Stretching the limits of static SIMS with C60+ A Delcorte, C Poleunis,
P Bertrand
13:00 Lunch
14:00 Plenary-Mo-A10 Some New Insights in to the Mechanisms of
Fullerene and Nanotube Formation
Professor Sir Harry
Kroto FRS
15:00 CLU-O-Mo-A11 Molecular depth profiling with cluster ion
source
J Cheng, N Winograd
15:20 CLU-O-Mo-A12 Temperature-Controlled Depth Profiling in
Polymeric Biomaterials using Cluster
Secondary Ion Mass Spectrometry (SIMS)
C Mahoney, G Gillen,
A Fahey, C Zu, J Batteas,
D Hook
15:40 Coffee
16:00 CLU-O-Mo-A13 Using Polyatomic Primary Ions to Probe Amino
Acids in Water Ice
G X Biddulph,
X A Conlan, N P Lockyer,
JC Vickerman
16:20 CLU-O-Mo-A14 Chemical effects in C60 irradiation of polymers R Mllers, N Tuccitto,
E Niehuis, A Licciardello
16:40 CLU-O-Mo-A15 Molecular Depth Profiling of Organic and
Biological Materials
J S Fletcher, X A Conlan,
E A Jones, N P Lockyer,
J C Vickerman
17:00 CLU-O-Mo-A16 Probing Thin Overlayers With Variable Energy
/ Cluster Ion Beams
A Spool, R White
x

Session 2 C2
09:00 FUN1-I-Mo-B01 The limitations of SIMS in nanoscale
technologies : quantitative near-surface
and interfacial analysis of complex systems
W Vandervorst,
T Janssens, L Geenen,
C Huyghebaert, T Conard,
B Brijs
09:40 FUN1-O-Mo-B02 Ionization probability of sputtered particles as a
function of their energy
Yu Kudriavtsev,
A Villegas, A Godines,
S Gallardo, R Asomoza
10:00 FUN1-O-Mo-B03 Detection of Molecular Hydrogen Anions H2-,
D2-, H3- and D3-
H Gnaser, R Golser,
W Kutschera, A Priller,
P Steier, A Wallner
10:20 FUN1-O-Mo-B04 Sputtering and Desorption Processes at Low-
Energy Ion Bombardment of Single Crystal
Surfaces
A A Dzhurakhalov,
S E Rahmatov
10:40 Coffee
11:00 FUN1-O-Mo-B05 Sputtering of Mixed Clusters from a NiAl
Surface
B V King, J F Moore,
W F Calaway,
I V Veryovkin, M J Pellin
11:20 FUN1-O-Mo-B06 Quantitative fundamental studies in SIMS
using O18 implant standards
P Williams, K Franzreb,
J Lorincik, R C Sobers, Jr
11:40 FUN1-O-Mo-B07 Atomic Scale Modifications to a Silicon Sample
during SIMS Analysis
M Wiedenbeck, R Wirth
12:00 FUN1-O-Mo-B08 Correlating the angular variation of the sputter
yield with surface oxygen concentration during
O2+ bombardment of Ge.
T Janssens,
C Huyghebaert,
W Vandervorst
12:20 FUN1-O-Mo-B09 Processes active in group IB secondary ion
formation/survival: Measurements of work
function and electronic structure
P van der Heide

12:40 FUN1-O-Mo-B10 Statistical model for evaluating the relative
contribution of different Sik+ bond states to the
ionisation probability of Si+ sputtered from
SiOx
K Wittmaack, F Friedrich,
V Betz
13:00 Lunch
14:00 Plenary-Mo-A10 Some New Insights in to the Mechanisms of
Fullerene and Nanotube Formation
Professor Sir Harry
Kroto FRS
15:00 QUA-O-Mo-B11 SIMS Quantification of Binary Alloys and
Composition Depth Profiling of Multilayers
Using a Buckminsterfullerene (C60) Ion
K J Kim, D W Moon,
C J Park, P Chi,
D Simons, G Gillen
15:20 QUA-O-Mo-B12 Quantitative interpretation of the TOFSIMS
decay data for the analysis of layer closure by
ALD
W Vandervorst, T Conard,
J Wolstenholme
15:40 Coffee
16:00 QUA-O-Mo-B13 Activities of SIMS Standardization in ISO/TC
201/SC6
Y Homma
16:20 QUA-O-Mo-B14 Important increase of negative secondary ion
sensitivity during SIMS analysis by neutral
cesium deposition
P Philipp, T Wirtz,
H-N Migeon, H Scherrer
16:40 QUA-O-Mo-B15 Study of the Pd-Rh interdiffusion by ToF-SIMS,
RBS and PIXE: nature of the sputtered atom
and ionization probability
L Houssiau, J Brison,
R Hubert, S Lucas
17:00 QUA-O-Mo-B16 The peculiarities of secondary negative ions
emission under Cs bombardment in a
presence of oxygen
A Merkulov


Poster Session 1, 17:20 19:00 C15/B1
FUN-P-Mo-P01 Static SIMS - Results of a VAMAS
Interlaboratory and the Protocol for a New
Study
I S Gilmore, F M Green,
M P Seah

FUN-P-Mo-P02 Strong composition-dependent variation of H Gnaser, Y Le, W Su
xi
MCs+ sensitivity factors in TiOx and GeOx (x <
2) films
FUN-P-Mo-P03 Surface roughness effects in quantitative
analysis of ToF-SIMS data
J Armitage, D A Armitage,
D Briggs, M C Davies
FUN-P-Mo-P04 Accurate SIMS depth profiling for high
concentration samples
S Saito, J Yamagata,
T Nakamoto, Y Miyakoshi,
Y Nakamura, Y Fujiyama
FUN-P-Mo-P05 Chemical derivatization technique in ToF-SIMS
for quantification analysis of surface amine
groups
T G Lee, J Kim, D Jung,
D W Moon
FUN-P-Mo-P06 SIMS Quantification of Matrix and Impurity
Species in AlxGa1-xN
C J Gu, F A Stevie,
Y N Saripalli, M Johnson,
D Griffis
FUN-P-Mo-P07 Round-Robin Study of Arsenic Implant Dose
Measurement in Silicon by SIMS
D Simons, K Kim,
R Benbalagh, J Bennett,
A Chew, D Gehre,
T Hasegawa, C Hitzman,
J Ko, R Lindstrom,
B MacDonald, C Magee,
N Montgomery, P Peres,
P Ronsheim,
S Yoshikawa,
M Schuhmacher,
W Stockwell, D Sykes,
M Tomita, F Toujou,
J Won
FUN-P-Mo-P08 PLA-PMMA blends : a study by XPS and ToF
SIMS
D Cossement,
R Gouttebaron, M Hecq,
V Cornet, R Lazzaroni
QUA-P-Mo-P09 Sputter Yields in Diamond Bombarded by Ultra
Low Energy Ions
B Guzman de la Mata,
M G Dowsett, D Twitchen
QUA-P-Mo-P10 Comparative study of negative cluster
emission in sputtering of Si, Ge, and their
oxides
M Perego, S Ferrari,
M Fanciulli
QUA-P-Mo-P11 Non-Linearity and Non-Additivity of Secondary
Ion Emission of Metals and Semiconductors
under Cluster Ion Bombardment
U Rasulev, S N Morozov
QUA P-Mo-P12 Comparison of detection efficiencies of
negatively charged gold-alkanethiolate-, gold-
sulfur- and gold-clusters in ToF-SIMS
T Rietmann, S Sohn,
M Schrder, D Lipinsky,
H F Arlinghaus
QUA-P-Mo-P13 Direct cluster emission and electron capture at
sputtering of silicon under cesium ion
bombardment
B Atabaev

QUA-P-Mo-P14 Energy distributions of atomic and molecular
ions sputtered by C60+ projectiles
A Delcorte, C Poleunis,
P Bertrand
QUA-P-Mo-P15 Decay reactions of (SiO2)nO- clusters:
dissociation energies and structures
N Dzhemilev,
S E Maksimov,
L F Lifanova,
Sh T Khojiev,
O F Tukfatullin
QUA-P-Mo-P16 Formation of atomic ions in fragmentation of
sputtered clusters
N Dzhemilev
QUA-P-Mo-P17 Steady-state Cs surface concentration on Si
and Ge after low energy Cs+ bombardment by
SIMS
P Chen, T.Conard,
T. Janssens,
W Vandervorst
QUA-P-Mo-P18 AFM Study of the Sims Beam Induced
Roughness in Monocrystalline Silicon in
Presence of Initial Surface or Bulk Nanometric
Sized Defects
B Fares, C Dubois,
B Gautier, J C Dupuy,
F Cayrel
QUA-P-Mo-P19 Properties and Use of the Depth Resolution
Function in Sims Analysis
J C Dupuy, N Baboux,
B Gautier, G Prudon
QUA-P-Mo-P20 Determination of energy dependent ionization P Mazarov, A Samartsev
xii
probabilities for sputtered particles A Wucher
QUA-P-Mo-P21 Transient affects active during secondary ion
emission from Si and SiO2 surfaces under Cs+
primary ion impact
P van der Heide
QUA-P-Mo-P22 Studies into the removal of SIMS transient
affects in the analysis of Si wafers with Cs+
primary ions
P van der Heide
QUA-P-Mo-P23 Modelling the negative ionisation of sputtered
carbon atoms
J Silva
QUA-P-Mo-P24 Modeling the dissociation and ionization of a
sputtered organic molecule
V Solomko, M Verstraete,
A Delcorte, B J Garrison,
X Gonze, P Bertrand
QUA-P-Mo-P25 Analysis of SIMS for LB Film due to the
Thermal Decomposition using QMD Method
N Kato, M Kudo, T Ida,
K Endo
QUA-P-Mo-P26 XY+ bombardement / Csdeposition: evolution
of Cs surface concentration with respect to
bombardment conditions by TRIDYN
simulations
P Philipp, T Wirtz,
H-N Migeon, H Scherrer
ACG-P-Mo-P27 uleSIMS characterization of silver reference
surfaces
V Palitsin, M G Dowsett,
I W Oloff, R Gibbons
ACG-P-Mo-P28 Ion-Tof Analysis of Corroding Museum Glass S Fearn, D McPhail,
C Helliwell
ACG-P-Mo-P29 ToF-SIMS applied to historical archaeology in
the Alps
R N S Sodhi,
W C Mahaney,
M W Milner
ACG-P-Mo-P30 Obsidian Hydration Dating from Sims H+
Profiling Based on Saturated Surface (Ss)
Layer
I Liritzis, Th Ganetsos

ACG-P-Mo-P31 SIMS Depth Profiling for Obsidian Hydration
Dating
S Novak, C Stevenson
ACG-P-Mo-P32 Automated Ion Imaging with the NanoSIMS Ion
Microprobe
E Groener, P Hoppe
ACG-P-Mo-P33 Measurement of 26Al Diffusion in Single
Crystalline 2/1-Mullite by SIMS Depth Profiling
P Fielitz, S Weber,
G Borchardt,
M Schmcker,
H Schneider
ACG-P-Mo-P34 SIMS Quantification of Very Low H2O
Contents
D Rhede, M Wiedenbeck
ACG-P-Mo-P35 Preferential Oxidation of Chalcopyrite Surface
Facets Characterized by ToF-SIMS and SEM
M Al-Harasheha,
F Rutten, D Briggs,
S Kingman
ISO-P-Mo-P36 High Throughput Screening of Novel Oxide
Conductors using SIMS
S Fearn, J C H Rossiny, J
A Kilner
ISO-P-Mo-P37 Resonant Laser-SNMS of Boron for Analysis of
Paleoceanographic Samples
G Vering, C Crone,
P Kathers, J Bijma,
H F Arlinghaus
CLU-P-Mo-P38 Secondary Ion Emission from Indium
Sputtered by Gold-Cluster Projectiles
S Morozov, U Kh Rasulev
CLU-P-Mo-P39 Secondary Ion Emission from Silicon under
Sim- and Aum- Cluster Ions Bombardment
S Morozov, U Kh Rasulev
CLU-P-Mo-P40 Cluster sputtering of silicon and silicon carbide
under subkeV polyatomic SF5 ion
bombardment
B Atabaev

CLU-P-Mo-P41 Secondary Ion Emission from Phthalocyanine
Films with Gold-Cluster Projectiles
S Morozov,
G L Pakhomov,
U Kh Rasulev
CLU-P-Mo-P42 Molecular Dynamics Simulations to Explore
Chemical Reactions and Topography
Formation in the Bombardment of Si(100) with
C60
K Krantzman,
D B Kingsbury,
B J Garrison
CLU-P-Mo-P43 Evaluation of secondary ion yield K Aimoto, S Aoyagi,
xiii
enhancement from polymer material by using
TOF-SIMS equipped with a gold cluster ion
source
N Kato, N Iida,
A Yamamoto,M Kudo
CLU-P-Mo-P44 Molecular Dynamics Study of Particle Emission
by Reactive Cluster Ion Impact
T Aoki, S Ninomiya,
J Matsuo
CLU-P-Mo-P45 High-intensity Si cluster ion emission from a
silicon target bombarded with large Ar cluster
ions
S Ninomiya, T Seki,
T Aoki, J Matsuo
CLU-P-Mo-P46 Characterization of Drug-Eluting Stent (DES)
Materials with Cluster Secondary Ion Mass
Spectrometry (SIMS)
C Mahoney, A Fahey,
G Gillen, D Patwardhan,
M K McDermott
CLU-P-Mo-P47 Performance of a C60+ Ion Source on a
Dynamic SIMS Instrument
A Fahey, G Gillen, P Chi
CLU-P-Mo-P48 TOF-SIMS Imaging of OLED using a Au
Cluster Ion Beam
S Bryan, J H Hammond,
N Sekiya, A Yamamoto
CLU-P-Mo-P49 Au-Analyte Adducts Resulting from Single
Massive Gold Cluster Impacts
G Hager, C Guillermier,
S V Verkhoturov,
E A Schweikert
CLU-P-Mo-P50 Organic SIMS with single massive gold
projectile: Ion yield enhancement by silver
metallization
C Guillermier, V Pinnick,
J Locklear,
S V Verkhoturov,
E A Schweikert
CLU-P-Mo-P51 Kinetic energy distributions of neutral In and
In2 sputtered by polyatomic ion bombardment
A Samartsev, A Wucher
CLU-P-Mo-P52 Mass spectra and ionization probabilities of
Indium species sputtered by atomic and
polyatomic ion bombardment.
A Samartsev, A Wucher
CLU-P-Mo-P53 Study of Polymer Fragmentation using
Polyatomic Primary Ions
X Conlan, I S Gilmore,
A Henderson,
N P Lockyer,
J C Vickerman
CLU-P-Mo-P54 Influence of Primary Ion Species on the
Secondary Cluster Ion Emission Process from
SAMs of Hexadecanethiol on Gold
M Schrder, D Lipinsky,
H F Arlinghaus
BIO1-P-Mo-P55 Enhanced Peptide Molecular Imaging by
Aqueous Droplet
Y Murayama, M Komatsu,
H Hashimoto
BIO1-P-Mo-P56 TOF-SIMS analysis of fresh frozen, freeze-
dried rat cerebellum
H Nygren, K Brner,
P Malmberg,
B Hagenhoff,
J-E Mnsson
BIO1-P-Mo-P57 Cardiac cell and tissue analysis by gold cluster
ion bombardment
M Aranyosiova,
A Chorvatova,
D Chorvat jr, D Velic
BIO1-P-Mo-P58 Hair Dye distribution in human hair by ToF
SIMS
B-J Chen, W-Y Chen,
Y-C Ling
BIO1-P-Mo-P59 Model Multilayer Structures for Three-
Dimensional Cell Imaging
J Kozole, C Szakal,
N Winograd
BIO1-P-Mo-P60 Is it possible to differentiate between intact and
denatured adsorbed proteins without using
recognising reactions?
P Rossbach, R Crockett,
H Troxler, S Equey
BIO1-P-Mo-P61 Competitive adsorption of proteins on polymers
membranes studied by ToF-SIMS and PCA
M Henry, P Bertrand
BIO1-P-Mo-P62 Dynamic SIMS Analysis of Cryo-Prepared
Biological and Geological Specimens
M Dickinson, P J Heard,
J H A Barker, A C Lewis,
D Mallard
BIO1-P-Mo-P63 Lipid Profiling of Prostate Cancer Cells Using
ToF-SIMS
M Baker, M D Brown,
N W Clarke, E Gazi,
P Gardner, C A Hart,
N P Lockyer,
J C Vickerman
BIO1-P-Mo-P64 Lipid and Sterol analysis of Candida albicans
using TOF-SIMS
B Tyler, S Attavar
xiv
BTC-P-Mo-P65 G-SIMS of Biodegradable Homo-Polyesters R Ogaki, M C Davies,
I S Gilmore, M Alexander
BTC-P-Mo-P66 Quantitative ToF-SIMS study of adsorbed
proteins
T G Lee, Y P Kim,
H S Kim, D W Moon
NAN-P-Mo-P67 Imaging, Spectra, and Chemometrics of ToF-
SIMS of Alkyl Monolayers on Silicon,
Germanium and Silicon Nitride made by Laser
Activation, Chemomechanical
G Jiang, Y-Y Lua,
A Arafat, H Zuilhof,
M R Linford
NAN-P-Mo-P68 RuO2/SiO2/Si and SiO2/porous Si/Si
interfaces analysed by SIMS
M wil, P Konarski,
M Pajk, T Bieniek,
A Kosiski
NAN-P-Mo-P69 The SIMS investigation of structural effect of
oxygen segregation on superplastic deformed
nanobulk titanium surfaces
B Atabaev,
R Dzabbarganov,
F Yuzikaeva, R Valiev,
D Gundarev, Y Kolobov,
M Ivanov, G Korb, L
Zeipper, T Weisgarber
NAN-P-Mo-P70 Supramolecular host-guest complexes base on L Rabara, M Aranyosiova,
P Chandoga,, I Bugar,
D Velic, D Chorvat
ORG1-P-Mo-P71 End group effect on surface and interfacial
segregation in PS-PMMA blend thin films
L Kailas, P. Bertrand
ORG1-P-Mo-P72 Empirical evaluation of metal deposition for the
S-SIMS analysis of organic compounds in thick
samples
R De Mondt,
L Adriaensen,
F Vangaever, J Lenaerts,
L Van Vaeck, R Gijbels
ORG1-P-Mo-P73 S-SIMS in advanced textile research: study of
additives to tune the hydrophilic/hydrophobic
properties of polypropylene films
B Boschmans,
M Vanneste, L Ruys,
L Van Vaeck
ORG1-P-Mo-P74 S-SIMS analysis of plasma treated 'real life'
polypropylene films
B Boschmans,
M Vanneste, L Ruys,
E Temmerman, C Leys,
L Van Vaeck
ORG1-P-Mo-P75 Surfactant Cationisation In ToF-SIMS Analysis M Perkins, C J Roberts,
F J M Rutten, D Briggs,
M C Davies, A Friedmann
ORG1-P-Mo-P76 TOF-SIMS investigation of the distribution of a
cosmetic ingredient in the epidermis of the skin
M Okamoto, N Tanji,
Y Katayama, J Okada
ORG1-P-Mo-P77 Development of a highly sensitive analysis
technique for surfactants by time-of-flight
secondary ion mass spectrometry
N Tanji, M. Okamoto
ORG1-P-Mo-P78 Surface Characterization of Self Assembled
Monolayers of Alkane Dithiols
S Rangarajan, B J Tyler
DAT-P-Mo-P79 Application of Advanced Data Analysis
Techniques in ToF-SIMS: Toward Faster
Relevant Observations for Industrial Problem-
Solving
M Seasholtz, G E Mitchell,
C Weikart, J W McCoy,
G E Potter
DAT-P-Mo-P80 ToF SIMS identification of diterpenes after
chromatographic separation.
A Orik, H F Arlinghaus,
G Vering, R Orikov,
V Cechinel-Filho
MAT-P-Mo-P81 Examination of the Influence of Boron on the
Microstructure and Properties of Low C Ferritic
Steels using NanoSIMS and TEM
S Ahmed,
J M Titchmarsh,
M R Kilburn,
C R M Grovenor
MAT-P-Mo-P82 Carbon analysis in steel microstructure D Loison,
V Champmartin-Philippe
MAT-P-Mo-P83 SIMS Analysis of Nitrogen in Various Metals
and ZnO
Y Li, X Wang, S P Smith

19:00
Manufacturers Session C16

Millbrook The Millbrook Desktop MiniSIMS - New TOF
Version Now Available
J Eccles
xv
ULVAC-PHI New SIMS Developments from ULVAC-PHI J Hammond
Kratos Surface analysis with high energy and spatial
resolution XPS
C Blomfield
ION-TOF TOF.SIMS 5, Recent Developments and
Applications
M Terhorst
CAMECA Recent developments in CAMECA SIMS. Part
1: magnetic sector instruments
M Schuhmacher
CAMECA Recent development in CAMECA SIMS. Part
2: quadrupole instruments
H Maul
Cascade Characterisation of Advanced Semiconductor
Materials at Cascade Scientific
C Mulcahy


Evans East T
2
SIMS Replot Software: Everything You Ever
Wanted From Replot Software But Were Too
Afraid To Ask
C W Magee


Tuesday 13
t h
Sept ember
Session 3 C16
09:00 ACG-I-Tu-A01 The geological ion microprobe: the first 25
years of dating zircons
W Compston,
S W J Clement
09:40 ACG-I-Tu-A02 Applications of SIMS to archaeometry and
cultural heritage
A Adriaens
10:20 ACG-O-Tu-A03 The use of nanoSIMS to critically test claims of
early (3.5 billion year old) life
M Kilburn, D Wacey,
N Mcloughlin,
C R M Grovenor,
M D Brasier
10:40 Coffee
11:00 ACG-I-Tu-A04 NanoSIMS: A new tool in cosmochemistry P Hoppe
11:40 ACG-O-Tu-A05 IDLE: (Interstellar Dust Laser Explorer), A New
Instrument for Submicron Analyses of Stardust
- Quantification in SIMS and Laser SNMS
T Henkel, J Tizard, I Lyon
12:00 ACG-O-Tu-A06 Analyses of Micrometeorite Impact Features
on the Salyut 7 Russian Space Station
Titanium Tank
V Jantou, D McPhail,
R Chater, A Kearsley
12:20 ACG-O-Tu-A07 Application of the 182Hf-182W chronometer to
eucrite zircon and initial solar 182Hf
abundance a multicollector SIMS approach
M Whitehouse,
G.Srinivasan
12:40 ACG-O-Tu-A08 Surface analysis of ancient glass artefacts with
ToF-SIMS: a novel tool for provenancing?
F Rutten, M J Roe,
J Henderson, D Briggs
13:00 Lunch
14:00 ACG-I-Tu-A09 SIMS Analysis of Ancient Materials D S McPhail
14:40 ACG-O-Tu-A10 SIMS analysis of particles in Aerogel S Sinniah, K Kotian,
R J Chater, D S McPhail,
A Kearsley, A Butterworth,
B Hagenhoff, M J Burchell
15:00 ACG-I-Tu-A11 Investigation into the Nature of Historical
Tapestries Using Time of Flight Secondary
Ion Mass Spectrometry
C Carr, M Hacke
15:40 Coffee
16:00 ACG-O-Tu-A12 Measurement of Sulfur Isotope Ratios in
Micrometer-Sized Samples by NanoSIMS
B Winterholler, P Hoppe,
S Mostefaoui,
M O Andreae, S Foley
16:20 ACG-O-Tu-A13 Basic Experiment of Remote SIMS Method for
Lunar Surface Observation
K Tanaka, S Sasaki
16:40 ACG-O-Tu-A14 Secondary Ionization Mass Spectrometric
Analysis of Impurity Element Isotope Ratios in
Nuclear Reactor Materials
D Gerlach, J B Cliff,
D E Hurley, B D Reid,
W W Little,
G H Meriwether,
T A Simmons
xvi
17:00 ACG-O-Tu-A15 Combined SIMS / SEM technique for
environmental monitoring of nuclear facilities:
detection, analysis, and characterization of
radionuclides in microm
L Sangly, S Diallo,
O Marie, S Baude
17:20 ACG-O-Tu-A16 Application of SIMS analyses on oxygen and
hydrogen transport in SOFC materials
N Sakai, K Yamaji,
T Horita, H Kishimoto,
M E Brito, H Yokokawa
17:40 ACG-O-Tu-A17 Characterisation of irradiated nuclear fuel with
SIMS
Ch Valot, L Desgranges,
B Pasquet

Session 4 C2
08:40 ORG1-I-Tu-B01 SSIMS analysis of organics, polymer
blends and interfaces
L-T Weng, C-M Chan
09:20 ORG1-O-Tu-B02 ToF-SSIMS analysis of plasma chemically
deposited co-polymer films
U Oran, S Swaraj,
J F Friedrich,
W E S Unger
09:40 ORG1-O-Tu-B03 ToF-SIMS: Accurate Mass Scale Calibration F Green, I S Gilmore,
M P Seah
10:00 ORG1-O-Tu-B04 Diffusion study of multi-organic layers in
OLEDs by ToF SIMS
W-Y Chen, B-J Chen,
Y-C Ling, H-H Shih,
C-H Cheng
10:20 ORG1-O-Tu-B05 3-D TOFSIMS Characterization of Black spots
in Polymer Light Emitting diodes
C Bulle-Lieuwma,
P van de Weijer
10:40 Coffee
11:00 ORG1-I-Tu-B06 Interpretation of SIMS Spectra and Images
using Careful Application of Multivariate
Analysis
M Wagner, D J Graham,
D G Castner
11:40 ORG1-O-Tu-B07 PCA of TOF-SIMS Spectra from Self-
Assembled Monolayers: The affects of data
normalization
D Graham, M S Wagner,
D G Castner
12:00 ORG1-O-Tu-B08 Simulation of SIMS for Polymers under the
Assumption of Thermal Decomposition using
QMD Method
K Endo, T Ida, N Kato,
H Sugimoto, D Matsumoto
12:20 ORG1-O-Tu-B09 G-SIMS-FPM: The Full Picture - Combined
Positive and Negative Ion Fragmentation Study
I Gilmore, F M Green,
M P Seah
12:40 ORG1-O-Tu-B10 SIMS Studies of Polymeric Tertiary Structure in
Monolayers
R Rey-Santos,
A M Piwowar,
R M Nowak, J A Gardella
Jr
13:00 Lunch
14:00 BIO1-O-Tu-B11 ToF-SIMS imaging as a tool to study the
spatial behaviour of bioorganic surface
components in brain tissue and single
neuroblastoma cells
M Altelaar, K Jalink,
R P J de Lange,
R A H Adan,
R M A Heeren,
S R Piersma
14:20 BIO1-O-Tu-B12 Direct NanoSIMS imaging of diffusible
elements in surfaced block of cryo-processed
biological samples
P Hallgot, J-N Audinot,
H-N Migeon
14:40 BIO1-O-Tu-B13 Imaging and differentiation of cellular
responses to ionizing radiation by time-of-flight
secondary ion mass spectrometry
L Wu, E J Nelson,
M G Knize, K S Kulp,
D L Shattuck,
C B Thomas, J S Felton,
K J Wu
15:00 BIO1-O-Tu-B14 Introduction of a Cryosectioning-ToF-SIMS
Instrument for Analyzes of Non-Dehydrated
Biological Samples
J Moeller, A Beumer,
D Lipinsky,
H F Arlinghaus
15:20 BIO1-O-Tu-B15 TOF-SIMS imaging of Chlorhexidine-
digluconate transport in frozen hydrated
biofilms of the fungus Candida Albicans
B Tyler, S Rangaranjan,
J Mller, A Beumer,
H Arlinghaus
15:40 Coffee
16:00 BIO1-O-Tu-B16 Investigating Lipid Interactions and the
Process of Raft Formation in Cellular
C McQuaw,
A G Sostarecz, L Zheng,
xvii
Membranes Using Model Membranes A G Ewing, N Winograd
16:20 BIO1-O-Tu-B17 ToF-SIMS Studies of Bacillus Using Principal
Component Analysis with Possible
Identification and Taxonomic Applications
C Thompson, J Fletcher,
A Henderson,
N P Lockyer, R Goodacre,
J C Vickerman
16:40 BIO1-O-Tu-B18 Bioforensics characterization of Bacillus spores
using ToF-SIMS
J Cliff, K H Jarman,
N B Valentine,
S L Golledge, D J Gaspar,
D S Wunschel, K L Wahl
17:00 BIO1-O-Tu-B19 Acquisition of Chemical Information from Cell
Samples using TOF-SIMS Imaging
D Breitenstein,
C Rommel, P Goering,
R Wehrspohn,
J Wegener, E Tallarek,
B Hagenhoff
17:20 BIO1-O-Tu-B20 Development of SIMS as a Novel Investigative
Tool for the Analysis of Cell Sheets and their
Extracellular Matrix Proteins
D Castner, H E Canavan,
M Greenfeld, X Cheng,
D J Graham, B D Ratner
17:40 BIO1-O-Tu-B21 7.9 eV Single Photon Ionisation of Derivatized
Peptides
P D Edirisinghe,
J F Moore, M J Pellin,
L Hanley

Session 5 C9
08:40 CLU3-O-Tu-C01 The massive cluster probe in SIMS. Influence
of the projectile size and of the energy on
sputtering and desorption-ionisation from
various solids
S Della-Negra
09:00 CLU3-O-Tu-C02 Coarse-Grained Molecular Dynamics Studies
of Cluster-Bombarded Benzene Crystals
E Smiley,
I A Wojciechowski,
Z Postawa, N Winograd,
B J Garrison
09:20 CLU3-O-Tu-C03 Topography Formation During C60+
Bombardment of Silicon
G Gillen, J Batteas,
C Michaels, P Chi,
A Fahey, J Small,
J Verkouteren, K J Kim
09:40 CLU3-O-Tu-C04 Fundamental Studies of Water Ice by Cluster
Ion Bombardment
C Szakal, J Kozole,
M F Russo Jr,
B J Garrison, N Winograd

10:00 CLU3-O-Tu-C05 Secondary ion emission from organic targets
impacted with Gold projectiles of 1-500 atoms
C Guillermier,
S Della Negra, V Pinnick,
R D Rickman,
E A Schweikert
10:20 CLU3-O-Tu-C06 Prospects and Challenges of Cluster SIMS J Matsuo
10:40 Coffee
11:00 CLU3-O-Tu-C07 Comparison of TOF-SIMS and XPS Analysis
Using a C60 Ion Beam
N Sanada, T Miyayama, J
S Hammond,
A Yamamoto, S R Bryan
11:20 CLU3-O-Tu-C08 XPS and UPS Analysis of PMMA Films
Bombarded by keV C60+ Ions
I Bolotin, S H Tetzler,
L Hanley
11:40 CLU3-O-Tu-C09 3D Molecular Imaging Using Cluster SIMS G Gillen, C Mahoney
12:00 CLU3-O-Tu-C10 SIMS Depth Profiling of Polymer Blends with
Protein Based Drugs
C M Mahoney, J (P) Yu,
J A Gardella Jr
12:20 CLU3-O-Tu-C11 Depth Profiling of a Medical Device-copolymer
using a C60+ Cluster Ion Source
R Braun, J Cheng,
E E Parsonage, J Moeller,
N Winograd
12:40 CLU3-O-Tu-C12 ToF/SIMS analysis of fluorocarbon-grafted
PET with a gold cluster ion source
Z Zhua, M Kelley
13:00 Lunch

xviii
Wednesday 14
t h
Sept ember
Session 6 C16
08:40 Plenary-We-A01 The contribution of mass spectrometry to
the bio-sciences
Professor S Gaskell
09:40 ORG2-O-We-A02 Suppression and enhancement of non-native
molecules within biological systems
E Jones, N P Lockyer,
J C Vickerman
10:00 ORG2-I-We-A03 Why MALDI works From Hypotheses to
Experimental Evidence
M Karas
10:40 Coffee
11:00 ORG2-O-We-A04 A Comparative Study of Secondary Ion Yield
from Biological Membranes Using Au, Au3 and
C60 Ion Beams
M Baker, J S Fletcher,
H Jungnickel,
N P Lockyer,
J C Vickerman
11:20 ORG2-I-We-A05 Matrix-Enhanced Secondary Ion Mass
Spectrometry
A Delcorte
12:00 ORG2-O-We-A06 Matrix-Assisted Cluster SIMS J Locklear, C Guillermier,
S V Verkhoturov,
E A Schweikert
12:20 ORG2-O-We-A07 S-SIMS and MetA-SIMS study of organic
additives in thin polymer coatings
L Adriaensen,
F Vangaever, J Lenaerts,
R Gijbels
12:40 ORG2-O-We-A08 A new analysis of the depolymerised
fragments of lignin polymer in the plant cell
walls using ToF-SIMS
K Saito, T Kato,
H Takamori, T Kishimoto,
A Yamamoto,
K Fukushima
13:00 Lunch

Session 7 C2
08:40 Plenary-We-A01 The contribution of mass spectrometry to
the bio-sciences
Professor S Gaskell
09:40 DEP1-I-We-B01 Depth Profiling for Emerging
Semiconductor Materials
P Ronsheim
10:20 DEP1-O-We-B02 Room Temperature Diffusion of Boron in
Crystalline Si During SIMS Depth Profiling
E Napolitani,
D De Salvador,
A Carnera, S Mirabella,
F Priolo
10:40 Coffee
11:00 DEP1-O-We-B03 An unexpected solution to the Na and Li depth
profiling problem in oxides
T Byklimanli
11:20 DEP1-O-We-B04 SIMS quantitative depth profiling of matrix
elements in semiconductor layers
G Guryanov, T P St.Clair,
R Bhat, C Caneau,
S Nikishin, B Borisov,
A Budrevich
11:40 DEP1-O-We-B05 Depth Profiling of Ultrathin Films and Their
Multilayers by DSIMS
P Babor, M Potocek,
M Urbanek, J Mach,
J Spousta, L Dittrichova,
J Sobota, Z Bochnicek,
T Sikola
12:00 DEP1-O-We-B06 Shallow B depth profiling in Si without
complete oxidation of the analytical area
T Byklimanli,
J W Marino
12:20 DEP1-O-We-B07 SIMS depth profiling of Boron ultra shallow
junctions using oblique O2+ beams down to
150eV
M Juhel, F Laugier,
D Delille, C Wyon,
L F Tz Kwakman,
M Hopstaken
12:40 DEP1-O-We-B08 Cesium/Xenon dual beam depth profiling:
nature of the sputtered atom and ionization
probability
J Brison, R Hubert,
T Conard, W Vandervorst,
L Houssiau
13:00 Lunch

xix
Session 8 C9
08:40 Plenary-We-A01 The contribution of mass spectrometry to
the bio-sciences
Professor S Gaskell
09:40 BTC-O-We-C01 The use of a desktop TOF-SIMS instrument in
the field of biomedical surface modification
B Cliff, A J Eccles,
N Long, P Vohralik
10:00 BTC-O-We-C02 ToF-SIMS imaging of micropatterned proteins
and cells
T G Lee, H K Shon,
K-B Lee, I S Choi,
D W Moon
10:20 BTC-O-We-C03 Bioactive Molecules for Biomimetic Materials:
Quantification of RGD Peptide Sequences by
ToF-S-SIMS Analysis
M C Durrieu, S Poulin,
S Polizu, LH Yahia
10:40 Coffee
11:00 BTC-O-We-C04 Characterization of PNA Microarrays as a
Function of Primary Ion Species
S Hellweg, A Jakob,
J D Hoheisel, T Grehl,
H F Arlinghaus
11:20 BTC-O-We-C05 Direct ToF-SIMS Analysis of Thin Layer
Chromatography Plates
D Michaelis, G Jiang,
A Parent, T Anderson,
P B Savage, M R Linford
11:40 BTC-O-We-C06 Quantitative analysis of bio-surfaces using
ToF-SIMS
T G Lee, J Kim, Y P Kim,
D Jung, H S Kim,
D W Moon
12:00 BTC-O-We-C07 Nanoscale Surface of Carbon Nanotube Fibers
for Medical Applications:
S Polizu, M Maugey,
S Poulin, P Poulin,
LH Yahia
12:20 BTC-O-We-C08 ToF-SIMS imaging of gradient polyethylene
surface with biofunctional groups
T G Lee, H K Shon,
M S Kim, H B Lee,
D W Moon
12:40 BTC-O-We-C09 Studies by imaging TOF-SIMS of bone
mineralization on porous titanium implants
after one week in bone
C Eriksson, U Bexell,
K Brner, H Nygren
13:00 Lunch

Thur sday 15
t h
Sept ember
Session 9 C16
08:40 DIS-I-Th-A01 Molecule Specific Imaging and Analysis in
Biology: What are the Challenges and The
Important Applications
A Ewing

DIS-O-Th-A02 Why dont biologists use SIMS R M A Heeren,
L A McDonnell,
S Luxembourg,
A F M. Altelaar,
S R Piersma
DIS-O-Th-A03 Improvements in SIMS continue. Is the end in
sight?
N Winograd, Z Postawa,
J Cheng, C Szakal,
J Kozole, B Garrison
09:40
DIS-O-Th-A04 ToF-SIMS analysis of bio-systems Are
polyatomic primary ions the solution?
E A Jones, J S Fletcher,
C E Thompson,
D A Jackson,
N P Lockyer,
J C Vickerman
11:00 Coffee
DIS-O-Th-A05 Information from Complexity: Challenges of
ToF-SIMS Data Interpretation
D Castner,
D J Graham, M Wagner
DIS-O-Th-A06 Rapid discrimination of the casual agents of
urinary tract infection using ToF-SIMS with
chemometric cluster analysis
J S Fletcher,
A Henderson, R M Jarvis,
N P Lockyer,
J C Vickerman,
R Goodacre
11:20
DIS-O-Th-A07 Multivariate Statistical Image Processing for
Molecular Specific Imaging in Organic and Bio-
B Tyler
xx
systems
DIS-O-Th-A08 Spatial Statistics and Interpolation Methods for
TOF SIMS Imaging
J Gardella, T M Milillo
13:00 Lunch
DIS-O-Th-A09 Quantitative imaging of cells with SIMS-
Nanoautography with stable isopte tracers
C Lechene, H Francois-
Saint-Cyr, G McMahon
DIS-O-Th-A10 High resolution SIMS imaging of cations in
mammalian cell mitosis, and in Drosophila
polytene chromosomes
R Levi-Setti, K L Gavrilov,
M B Neilly, R Strick,
P L Strissel
DIS-O-Th-A11 Specimen preparation and calibration for
NanoSIMS analysis of biological materials
C Grovenor, K Smart,
M Kilburn, B Shore,
J Dilworth, B Martin,
C Hawes, R Rickaby
14:00
DIS-O-Th-A12 Cellular Localization of a 15n Labelled Peptidic
Vector using Nanosims Imaging
J-L Guerquin-Kern,
W Roemer, L Johannes,
P Duchambon, D Carrez,
T-D Wu
15:40 Coffee
DIS-O-Th-A13 Label- and amplification-free genotyping of
genomic DNA
O Brandt, J Fldner,
S Hellweg, M Schrder,
A Stephan,
H F Arlinghaus,
J D Hoheisel, A Jacob
DIS-O-Th-A14 Mass Spectrometric Characterization of
Elements and Molecules in Cell Culture and
Tissue
H Arlinghaus,
C Kriegeskotte,
M Fartmann, J Mller,
D Lipinsky
DIS-O-Th-A15 Quantitative analysis of biological membrane
composition with high lateral resolution
S Boxer, C G Marxer,
M L Kraft, S Fishel,
P K Weber , I D Hutcheon
DIS-O-Th-A16 Imaging lipid distributions in model membranes
with selectively deuterated components using
Time of Flight Secondary Ion Mass
Spectrometry (ToF-SIMS)
M Biesinger, D Miller,
R R Harbottle,
F Possmayer,
N S McIntyre
DIS-O-Th-A17 Localisation of lipids in freeze-dried mouse
brain sections by imaging ToF-SIMS
P Sjvall, B Johansson,
J Lausmaa
16:00
DIS-O-Th-A18 Localization of Cholesterol in Rat Cerebellum
with Imaging TOF-SIMS. Effect of tissue
preparation
H Nygren, K Brner,
P Malmberg, B Hagenhoff

Session 10 C2
08:40 SEM-I-TH-B01 Characterizing High-K and Low-K Dielectric
Materials for Semiconductors: Progress
and Challenges
J Bennett

09:20 SEM-O-Th-B02 Characterization of HfO2 dielectric films with
low energy SIMS
Z (J) Jiang, K Kim,
J Lerma, D Sieloff,
H Tseng, R I Hegde,
T Y Luo, J Y Yang,
D H Triyoso, P Tobin
09:40 SEM-O-Th-B03 SIMS Analysis for HfSiO(N) thin films S Miwa, S Kusanagi,
H Kobayashi
10:00 SEM-O-Th-B04 Nitrogen profiling in high-k layers has much to
gain from a combined TOFSIMS-Angle
resolved XPS combined study
T Conard, W Vandervorst,
B Brijs, P Mack
10:20 SEM-O-Th-B05 Back Side SIMS Analysis of Hafnium Silicate F Stevie, C Gu, J Bennett,
R Garcia, D P Griffis
10:40 Coffee
11:00 SEM-O-Th-B06 HfSiO(N) composition depth profiling: can we
get a quantitative answer using SIMS?
T Conard, P Chen,
T Janssens, B Brijs,
W Vandervorst, P Mack
11:20 SEM-O-Th-B07 Quantitative Si Depth Profiling of HfxSiyO2 H Maul, H-U Ehrke,
xxi
Using Normal Incidence Cs and ERD N Loibl
11:40 SEM-O-Th-B08 Dynamic SIMS Analysis of Low-k Dielectric
Materials
I Mowat, X-F Lin,
M H Yang
12:00 SEM-O-Th-B09 ToF-SIMS and AFM studies of low-k dielectric
etching in fluorocarbon plasmas
P Lazzeri, X Hua,
G Oehrlein, E Iacob,
M Barozzi, M Bersani,
M Anderle
12:20 SEM-I-Th-B10 Ultrashallow depth profiling by using SIMS
and Ion Scattering Spectroscopy
Y Kataoka
13:00 Lunch
14:00 NAN-I-Th-B11 Static SIMS for analysis of molecular
conformation and orientation
P Bertrand
14:40 NAN-O-Th-B12 Characterisation of electrospun nanowebs with
Static SIMS
P Van Royen,
A M dos Santos,
L Van Vaeck, E Schacht,
L Ruys
15:00 NAN-O-Th-B13 Towards Molecular Electronic Circuitry:
Selective Deposition of Metals on Patterned
Self-Assembled Monolayer Surfaces
C Zhou, G Nagy,
A Walker
15:20 NAN-O-Th-B14 Particle-induced desorption from self-
assembled monolayers: signatures of an
intricate balance between inter- and
intramolecular interactions
E Vandeweert,
F Vervaecke,
S Wyczawska, P Lievens,
R E Silverans
15:40 Coffee
16:00 PAR-I-Th-B15 SIMS of Nanoparticles K Wittmaack
16:40 PAR-O-Th-B16 Examining Ion Sputtering of Nanoparticles and
Nanoporous Materials
D Gaspar, A S Lea,
D R Baer, M H Engelhard
17:00 PAR-O-Th-B17 Characterization of Individual Atmospheric
Aerosol Particles with TOF-SIMS
R Peterson, A Nair, H Shi,
S Dambach,
H Arlinghaus, B J Tyler
17:20 PAR-O-Th-B18 TOF-SIMS analysis of ultrafine carbon
particles with a pulsed beam sputter mode
W Szymczak, E Karg
17:40 PAR-O-Th-B19 Urban and rural aerosol particle
characterisation by SIMS and SSMS compared
with environmentally related children diseases
P Konarski, J Hauszka,
M wil, K Pisiewicz,
H Srugaa-Stawik

Poster Session 2, 18:00 20:00 C15/B1
DEP-P-Th-P01 Sodium and hydrogen analysis of room
temperature glass corrosion using low energy
Cs sims
S Fearn, R J H Morris
DEP-P-Th-P02 Application of B-doped Si Multiple Delta-Layers
for Calibration of SIMS Depth Scale
K J Kim, D W Moon,
P Chi, D Simons
DEP-P-Th-P03 An Alternative Method of Using an Electron
Beam for Charge Compensation During
uleSIMS Experiments
B Guzman de la Mata,
M G Dowsett,
R J H Morris
DEP-P-Th-P04 Ultra Shallow SIMS Depth Profiling A Wee, R Liu, S K Tan,
A R Chanbasha, K L Yeo,
C M Ng
DEP-P-Th-P05 Narrow surface transient and high depth
resolution SIMS using 250eV O2+
A R Chanbasha,
A T S Wee
DEP-P-Th-P06 SIMS Depth Profiling of Rubber Tyre Cord
Bonding Layers prepared using 64Zn depleted
ZnO
W S Fulton, D E Sykes,
G C Smith, K J Titchener
DEP-P-Th-P07 High Sensitive Analysis of Atmospheric Gas
Elements
S Miwa, I Nomachi,
H Kitajima
DEP-P-Th-P08 MEM-deconvolution analysis of ultra-shallow
junction depth profiles
M Tomita, H Tanaka,
M Koike, M Yoshiki,
S Takeno, N Sugita,
M Obuchi
DEP-P-Th-P09 Calibrations of ToF-SIMS sputter rates in
alumina scales formed on FeCrAl alloys
J Engkvist, R Berger,
U Bexell, T M Grehk,
xxii
M Olsson
DEP-P-Th-P10 Boron Ultra Low Energy SIMS Depth Profiling
improved by Rotating Stage
D Giubertoni, E Iacob,
M Barozzi, S Pederzoli,
L Vanzetti, M Anderle,
M Bersani
DEP-P-Th-P11 Characterization of layers and interfaces
during the silicide formation of CoSix and NiSiy
U Breuer, A Scholl,
A Besmehn, Q Zhao,
M Zhang, E Rije
DEP-P-Th-P12 Deconvolution of SIMS Depth Profiles in the
Presence of Beam Induced Roughness
B Fares, B Gautier,
J C Dupuy, G Prudon,
P Holliger
DEP-P-Th-P13 SIMS characterisation of superconductive
MgB2 layers prepared by ion implantation and
pulsed plasma treatment
P Konarski, M wil,
J Piekoszewski,
W Kempinski,
J Stanislawski
DEP-P-Th-P14 Useful Yields and Depth Resolution in TOF-
SIMS Depth Profiling
T Hoshi, S R Bryan,
J S Hammond, N Iida,
S Iida, A Yamamoto
DEP-P-Th-P15 Ultra-low energy O2+ sputtering for improved
accuracy in SIMS depth profiles
Z Li, T Hoshi, S R Bryan,
J S Hammond, H Iwai
DEP-P-Th-P16 ToF-SIMS Depth Profiling of (Ga,Mn)As
Capped With Amorphous Arsenic: Effects of
Annealing Time
U Bexell, V Stanciu,
P Warnicke, M sth,
P Svedlindh
DEP-P-Th-P17 Emission of impurity-matrix type dimers from
GaX semiconductors (X = N, P, As, Sb).
D Y. Kazantsev,
A P Kovarsky
SEM-P-Th-P18 Quantitative analysis of surface contaminants
on silicon wafers by means of TOF-SIMS
P Rostam-Khani,
J Philipsen, E Jansen,
H Eberhard, P Vullings
SEM-P-Th-P19 Determination of the organic contaminations
on Si wafer surfaces by static ToF-SIMS:
improvement of the detection limit with C60+
C Poleunis, A Delcorte,
P Bertrand
SEM-P-Th-P20 Quantitative SIMS analysis of SiGe
composition with low energy O2+ beams
Z X Jiang, K Kim,
J Lerma, A Corbett,
D Sieloff, M Kottke,
R Gregory, S Schauer
SEM-P-Th-P21 SIMS analysis of impurities and nitrogen
isotopes in gallium nitride thin films
H Haneda, T Ohgaki,
I Sakaguchi, H Ryoken,
N Ohashi, A Yasumori
SEM-P-Th-P22 SIMS profiling of doped NiSi gates T Janssens, M A Pawlak,
J A Kittl, M Fouchier,
W Vandervorst
SEM-P-Th-P23 Study of SIMS ionization probabilities of
different composition of In(AlxGa1-x)P
J Sameshima, A Karen
SEM-P-Th-P24 Profiles of boron and matrix elements through
thin SiON layer
J Sameshima,
T Hasegawa, T Nishina,
T Nishitani, K Yoshikawa,
A Karen
SEM-P-Th-P25 Non-destructive B, P and As Dosimetry Using
Normal Incidence Oxygen
H Maul, H-U Ehrke,
N Loibl,
C Schnrer-Patschan
SEM-P-Th-P26 Determination of impurities and main elements
in thin film structures InN/GaN on sapphire.
V Y Davydov,
D Y Kazantsev,
A P Kovarsky,
M A Yagovkina, H Lu,
W J Schaff
SEM-P-Th-P27 Characterization of Laser-Fired Contacts in
PERC Solar Cells: SIMS and TEM Analysis
Applying Advanced Preparation Techniques
U Zastrow, L Houben,
D Meertens, A Grohe,
T Brammer,
E Schneiderlchner
SEM-P-Th-P28 C60+ Cluster Beam Depth Profiling of
Semiconductor Materials
P Chi, G Gillen, A Fahey,
E Windsor, K J Kim
SEM-P-Th-P29 Correlation of SIMS sputtering rate variations M Juhel, F Laugier,
xxiii
with primary beam current drifts: an effective
application to high precision full wafer mapping
C Wyon, L F T Kwakman,
M Hopstaken
SEM-P-Th-P30 Improving the growth of HfO2 ALD layers by
modifying growth parameters and reducing
precursors contaminants
T Conard, A Delabie,
W Vandervorst
SEM-P-Th-P31 Measurements of Ti-Containing Barrier
Materials and Low-K dielectric Films Using
Backside Polishing SIMS
M H Yang, J Lan,
I Mowat, R Humayun,
J Sun
SEM-P-Th-P32 Phosphorous degassing from Poly Silicon
under thermal exposure: A ToF-SIMS depth
profile investigation
S G Alberici, A Elbaz,
R Piagge
SEM-P-Th-P33 SIMS Analysis of Multiple Quantum Wells in a
Vertical Cavity Surface Emitting Laser
Structure Using the Mixing-Roughness-
Information depth Model
S Ootomo, H Maruya,
S Seo, F Iwase
SEM-P-Th-P34 Thermal effects on 1H and 2H distributions in
atomic layer deposition of HfO2 and Al2O3
using heavy water (D2O)
P Holliger, F Martin,
F Pierre, G Reimbold,
P Rivallin, D Jalabert,
C Hobbs
SEM-P-Th-P35 Investigations of LED Structure with Graded
InxGa1-xP Buffer by SIMS Method
A Vincze, J Kov,
L Peternai, S Hasenhrl,
Mvesel
SEM-P-Th-P36 The influence of impurity profile on ultrashallow
GaAs sidewall tunnel junction characteristics
T Ohno, Y Oyama,
J-I Nishizawa
SEM-P-Th-P37 Ultra low energy SIMS depth profiling of sub-
2nm Silicon oxynitride films
C Mulcahy, B Bck,
P A Ebblewhite, S Biswas
SEM-P-Th-P38 TOF-SIMS studies on Rose Bengal devices:
Search for the mechanism responsible for
resistive switching
A Besmehn, A Scholl,
B Lssem, M Alba,
S Karthuser, U Breuer
BIO2-P-Th-P39 Imaging of Human Liver Cell Intoxicated by
Heavy Metal using Time-of-flight Secondary
Ion Mass Spectrometry (TOF-SIMS)
F-D Mai, B-J Chen,
W Chen
BIO2-P-Th-P40 Study of the mechanism of diatoms
multiplication by means of 29Si isotope tracing
J-N Audinot, C Guignard,
H-N Migeon, L Hoffmann
BIO2-P-Th-P41 Quantitating MIMS Ratios Using Hue,
Saturation, and Intensity Displays
D Benson, C Lechene
BIO2-P-Th-P42 High order of DNA replication identified in
fibroblasts nuclei with Multi-Isotope Imaging
Mass Spectrometry
A Cohen, C Lechene
BIO2-P-Th-P43 Multi-isotope imaging mass spectrometry
(MIMS) quantitative mapping of protein
turnover in the bullfrog saccula
D-S Zhang, D P Corey,
C Lechene
BIO2-P-Th-P44 Tectorial Membrane Protein Turnover
Revealed by Multi-isotope Imaging Mass
Spectrometry
D A Cotanche, C Lechene
BIO2-P-Th-P45 Multi-Isotope Imaging Mass Spectrometry of
Larval Zebrafish for Studying Acute Renal
Failure
D Hentschel, J Bonventre,

C Lechene

BIO2-P-Th-P46 Determination of Steady State Cs+
Implantation in Biological Samples
G McMahon, C Lechene
BIO2-P-Th-P47 Stable isotopes for individual cell retrieval after
transplantation
G Benichou, C Lechene
BIO2-P-Th-P48 The analysis of boron in the human glyoma
graft by dyanamic secondary ion mass
spectrometry(SIMS)
T Yoshida, K Yokoyama,
M Okabe, S Kawabata,
Y Kajimoto, S Miyatake
BIO2-P-Th-P49 Bioaccumulation of chromium in aquatic
macrophyte Borreria scabiosoides Cham. &
Schltdl.
K Gavrilov,
P A Mangabeira
NAN-P-Th-P50 Atomic distribution in quantum dots- a ToF
SIMS study
W-Y Chen, B-J Chen,
Y-C Ling
NAN-P-Th-P51 The lateral resolution of ToF-SIMS analysed by
means of an advanced nanoscale strip-pattern
M Senoner, T Wirth,
W Unger
xxiv
PAR-P-Th-P52 Analysis of Volatile Nanoparticles Emitted from
Diesel Engine using Tof-Sims and Silver
Deposition / Tof-Sims
M Inoue, A Murase,
M Yamamoto, S Kubo
PAR-P-Th-P53 Quantitative characterizations of styrene-
butadiene core-shell latexes by TOF-SIMS and
Pyrolysis GC/MS
T Maekawa

PAR-P-Th-P54 Characterization of individual complex particles
in urban atmospheric environment
K Suzuki, K Yamada,
M Nojima, B Tomiyasu,
Y Nihei
PAR-P-Th-P55 TOF-SIMS measurements of the exhaust
particles emitted from gasoline and diesel
engine vehicles
B Tomiyasu, M Owari,
Y Nihei
PAR-P-Th-P56 Depth profile of coated hollow spheres R Orikov, A Orik,
H F Arlinghaus,
S Hellweg, M Kupkov,
M Kabtov
ORG2-P-Th-P57 Surface Chemical Analysis of Thermally
Degraded Cotton
R Mitchell, C M Carr
ORG2-P-Th-P58 Secondary Ion Statistics and Determination of
Nanocluster (m > 10^7 amu) Ion Registration
Efficiency.
S Kirillov, I Baranov,
A V Novikov, V Obnorskii,
S Yarmiychuk
ORG2-P-Th-P59 Towards a Fully Optimised Organic LED
Device: Analysis of Surface Synthesis Using
Coupling Reactions by ToF-SIMS
R Pinna, F Jamme,
F J M Rutten, E F Smith,
M R Willis, D Briggs,
M R S McCoustra
ORG2-P-Th-P60 G-SIMS of Thermosetting Polymers P N Hawtin, J F Watts,
M-L Abel
ORG2-P-Th-P61 Quantitative and High Mass ToF-SIMS Studies
of Siloxane Segregation in Hydrogel Polymers
Using Cryogenic Sample Handling Techniques
D J Hook, P L Valint Jr,
L Chen, J A Gardella Jr
ORG2-P-Th-P62 Identification of Hydrocarbon Contamination in
Mass Spectra
N L Yakovlev, J J Gray
ORG2-P-Th-P63 Effect of dilute acrylic acid vapour on lubricated
recording hard-disk media surfaces
R Ji, T Liew, T C Chong
ORG2-P-Th-P64 ToF-SIMS analysis of model nuclear waste
glasses
S Ristori, A Tognazzi,
A Magnani, P Frugier,
O Spalla, C Rossi
ORG2-P-Th-P65 ToF-SIMS as a reliable tool for carotenoids
and chlorophyll detection in natural samples:
fruits, flowers and microalgae
L Houssiau, C Bittencourt,
H Sarmento, J-P Descy,
J-J Pireaux
ORG2-P-Th-P66 Using Time-of-Flight Secondary Ion Mass
Spectrometry to Investigate Reaction,
Destruction, Penetration and Aggregation of
Vapor-Deposited Metal Atoms
Z Zhu, D L Allara,
N Winograd
ORG2-P-Th-P67 Depth Profile Analysis of OLED Devices Using
TOF-SIMS with Gradient Shaving Preparation
T Shibamori, H Seki,
T Matsunobe, N Man,
Y Nakagawa
ORG2-P-Th-P68 ToF-SIMS: Going Beyond Surface Chemical
Composition
K Lloyd, G S Blackman,
D J Walls,
D G Swartzfager
ORG2-P-Th-P69 Selective Detection of Organic Compounds on
Modified Polymer Surfaces Using TOF-SIMS in
Combination with Derivatization
M Kwon, Y Lee,
J H Hong, S Han, H Kim
ORG2-P-Th-P70 Surface Spectroscopic Imaging of PEG-PLA
Tissue Engineering Constructs With ToF-SIMS
G Tsourapas,
F J M Rutten, D Briggs,
M C Davies,
M Shakesheff
MAT-P-Th-P71 Characterization of the 3D-distribution of
impurities in InP semiconductor using SIMS
S H Haji Hosseini
Gazestani,
M R Hantehzadeh,
M Ghoranneviss,
M Shariati, A H Sari,
xxv
A Shokouhy
MAT-P-Th-P72 TOFSIMS Analysis of SiC-Cu Composites for
Thermal Management Applications
R Treichler, G Lefranc,
T Weissgaerber, T Kiendl
MAT-P-Th-P73 NanoSIMS analysis of Ca doping at a grain
boundary in a superconducting YBCO Ca-
123/123 bicrystal
C Dark, M R Kilburn,
C Schneider, J Mannhart,
C R M Grovenor
MAT-P-Th-P74 Selective oxidation of Fe-1.5Mn alloys:
quantitative description of annealed surfaces
D Loison, N Robert,
V Champmartin-Philippe
D Bouleau
INS-P-Th-P75 SIMS Analysis using a new Noble Sample
Stage
S Miwa, I Nomachi,
H Kitajima
INS-P-Th-P76 The "second life" of Cameca cesium ionizer Y Kudriavtsev,
V Mishurnuy, A Villegas,
A Godines, R Asomoza
INS-P-Th-P77 Caesium Sputter Ion Source Compatible S Belykh, V V Palitsin,
R J H Chang,
I V Veryovkin,
A P Kovarsky, A Adriaens,
M Dowsett, F Adams
INS-P-Th-P78 Recent Developments and Applications of
CAMECA Quadrupole SIMS Tools
H-U Ehrke, H Maul,
N Loibl, A Sears,
C Schnrer-Patschan
INS-P-Th-P79 Improved automation system for the CAMECA
IMS 7f.
P Peres, E de Chambost,
A Merkulov,
M Schuhmacher
INS-P-Th-P80 Development and characterisation of the new
NanoSIMS 50L
F Hillion, A Merkulov,
F Horrard
20:00 Manufacturers Users Meetings

Fri day 16
t h
Sept ember
Session 11 C16
09:00 DEP2-O-Fr-A01 Comparison between the SIMS and MEIS
Techniques for the characterisation of ultra
shallow Arsenic implants
M Bersani, D Giubertoni,
M Barozzi, S Pederzoli,
E Iacob, J A van den
Berg, M Werner
09:20 DEP2-O-Fr-A02 Collaborative SIMS Study and Simulations of
Implanted Dopants in Si
N L Yakovlev, C C Lee,
H Y Chan, R Liu,
A T S Wee,
M P Srinivasan,
C M Ng, D Gui, L Chan,
A R Chanbasha,
N J Montgomery,
C P A Mulcahy, S Biswas,
H-J L Gossmann,
M Harris
09:40 DEP2-O-Fr-A03 On the limitations of closely spaced delta
layers for the assessment of various
parameters in sputter profiling
M Dowsett, M P Seah
10:00 DEP2-O-Fr-A04 Secondary ion measurements for oxygen
cluster ion SIMS
S Ninomiya, T Seki,
T Aoki, J Matsuo
10:20 DEP2-O-Fr-A05 Surface oxidation during O2+ bombardment of
Si:
T Janssens,
C Huyghebaert,
W Vandervorst
10:40 Coffee
11:00 DEP2-O-Fr-A06 Correlation between the ionization probability
of Si and Ge and the Cs surface concentration
P Chen, T Conard,
T Janssens, L Geenen,
W Vandervorst
11:20 DEP2-O-Fr-A07 SIMS evaluation of the compositional
properties and layer integrity of GaNAs
superlattices
C Mulcahy, S J Barker,
R S Williams,
M Hopkinson,
xxvi
M J Ashwin,
P N Stavrinou, G Parry,
S Biswas, T S Jones
11:40 DEP2-O-Fr-A08 Shave-Off Depth Profiling by the Nano Beam
Sims
M Nojima, A Maekawa,
T Yamamoto,
B Tomiyasu, T Sakamoto,
M Owari, Y Nihei
12:00 DEP2-O-Fr-A09 Different optical conductivity enhancement
(OCE) protocols to eliminate charging during
ultra low energy SIMS profiling of
semiconductor and semi insulating materials
R J H Morris,
M G Dowsett,
R J H Chang
12:20 DEP2-O-Fr-A10 Diffusion in Lithium Niobate Wafers K K Soni, K P Gadkaree,
G M Guryanov
12:40 DEP2-O-Fr-A11 SIMS Depth Profiling of Deuterium Labeled
Polymers in Polymer Multilayers
S E Harton, H Ade,
F A Stevie, D P Griffis
13:00 Closing Address
13:15 Lunch

Session 12 C2
09:00 ORG3-I-Fr-B01 Mutual Information Theory for Biomedical
Applications
S Aoyagi
09:40 ORG3-O-Fr-B02 Characterisation of human hair by means of
static ToF-SIMS: a comparison between Ga+
and C60+ primary ion
C Poleunis, E P Everaert,
A Delcorte, P Bertrand
10:00 ORG3-O-Fr-B03 SIMS Analysis of Biological Materials Using
Cluster Ion Sources
R Kersting,
D Breitenstein, E Tallarek,
M Fartmann,
B Hagenhoff, R Mllers,
D Rading, F Kollmer,
T Greh, E Niehuis
10:20 ORG3-O-Fr-B04 A complete cryo-chain for the combined SIMS
and SEM-EDXA analysis of physiologically
relevant elements in biomedical samples
W H Schroeder, U Breuer,
R Metzner, H P Bochem
10:40 Coffee
11:00 BIO2-O-Fr-B05 Submicron-scale coccolith chemistry revealed
by nanoSIMS
R E M Rickaby,
N Belshaw, M R Kilburn,
A Taylor,
C R M Grovenor,
C Brownlee
11:20 BIO2-O-Fr-B06 Molecular Specificity of CN- Secondary Ion
Formation using Multi-Isotope Imaging Mass
Spectrometry
H Franois-Saint-Cyr,
G McMahon,
B J Glassner, C Unkefer,
C Lechene
11:40 BIO2-O-Fr-B07 Cations in mammalian cells and
chromosomes: Elemental abundances by
SIMS affected by sample preparation protocols
R Levi-Setti, K L Gavrilov,
R Strick, P L Strissel
12:00 BIO2-O-Fr-B08 Multi-Isotope Imaging Mass Spectrometry
(MIMS) of a Nitrogen-Fixing Bacterium
D L Distel, Y Luyten,
C Lechene
12:20 BIO2-O-Fr-B09 Specific Mg2+ and Ca2+ binding at
Heterochromatic DNA Giemsa bands and their
Evolutionary Role in Chromosomal Structure
P L Strissel, K L Gavrilov,
R Levi-Setti, R Strick
12:40 BIO2-O-Fr-B10 Zinc ion image and measurements for
concentration of the islet of Langerhans
M Okabe, T Yoahida,
K Takaya, H J Mathieu
13:15 Lunch

Session 13 C9
09:40 INS-O-Fr-C01 Implementing a SIMS ion source on the NRL
Trace Element Accelerator Mass Spectrometer
K S Grabowski,
D L Knies, C Cetina
10:00 INS-O-Fr-C02 Isotope Ratio Measurement with an
Electrometer Array on the Cameca IMS nf
P Williams, J Lorincik,
R Hervig, M B Denton,
xxvii
R Sperline, G Slodzian
10:20 INS-O-Fr-C03 The Development of a Range of C60 Ion Beam
Systems
R Hill, P Blenkinsopp,
A Barber, C Everest
10:40 Coffee
11:00 INS-O-Fr-C04 Development of a TOF version of the desktop
MiniSIMS utilising a continuous primary ion
beam
B Cliff, A J Eccles,
C Jones, N Long,
P Vohralik
11:20 INS-O-Fr-C05 Application of the Hadamard Transform to
ToF-SIMS
A Fahey, C M Mahoney,
J W Hudgens
11:40 MAT-O-Fr-C06 Imaging of oxide structures and reaction
pathways
C A Mims,
P M Brodersen, L Reimus,
A J Jacobson, C Chen
12:00 MAT-O-Fr-C07 Study of the carbon distribution in multi-phase
steels using the NanoSIMS 50.
N Valle, J Drillet,
O Bouaziz, H-N Migeon
12:20 MAT-O-Fr-C08 TOF-SIMS study of photocatalytic
decomposition reactions on nanocrystalline
TiO2 films
H Gnaser, A Orendorz,
C Ziegler, E Rowlett,
W Bock
12:40 MAT-O-Fr-C09 TOF-SIMS study of paper surface coated with
ZnO nanoparticles
A V Ghule, K Ghule,
W-Y Chen, B-J Chen,
Y C Ling
13:15 Lunch



Abst ract s


FUN2-I-Mo-A01
1
Atoms, Clusters and Photons: Energetic Probes for Mass
Spectrometry

Barbara J. Garrison

Department of Chemistry
104 Chemistry Building
Penn State University
University Park, PA 16802
bjg@psu.edu


The use of energetic atomic ions and cluster ions in addition to pulsed lasers over the years has
expanded the size and diversity of molecules amenable for study by mass spectrometry. Although
all the processes involve a fast energy deposition at the surface of a solid, an induced motion of the
molecules into the gas phase with relatively low thermal energy and characteristic mass peaks that
can be similar, the physics of ejection in each case is quite different. A discussion of various
processes illustrated by animations will be presented.


References:
[1] Molecule Liftoff from Surfaces, B. J. Garrison, A. Delcorte and K. D. Krantzman, Accts. Chem. Res., 33, 69-
77 (2000)
[2] High Yield events of molecule emission induced by keV particle bombardment, A. Delcorte and B. J.
Garrison, J. Phys. Chem. B, 104, 6785-6800 (2000)
[3] Enhancement of Sputtering Yields due to C
60
vs. Ga Bombardment of Ag{111} as Explored by Molecular
Dynamics Simulations, Z. Postawa, B. Czerwinski, M. Szewczyk, E. J. Smiley, N. Winograd and B. J.
Garrison, Analytical Chemistry, 75, 4402-4407 (2003)
[4] Microscopic Insights into the Sputtering of Ag{111} Induced by C
60
and Ga Bombardment of Ag{111}, Z.
Postawa, B. Czerwinski, M. Szewczyk, E. J. Smiley, N. Winograd and B. J. Garrison, J. Phys. Chem. B, 108,
7831-7838 (2004)
[5] MD simulations of water ice sputtering induced by C
60
bombardment: Evidence for plume formation, I. A.
Woiciechowski and B. J. Garrison, in preparation.
[6] Microscopic Mechanisms of Laser Ablation of Organic Solids in the Thermal and Stress Confinement
Irradiation Regimes, L. V. Zhigilei and Barbara J. Garrison, Journal of Applied Physics, 88, 1281-1298 (2000)
[7] MD Simulations of MALDesorption - Connections to Experiment, L. V. Zhigilei, Y. G. Yingling, T. E. Itina,
T. A. Schoolcraft and B. J. Garrison, Int. J. Mass Spectrom. Ion Processes, 226, 85-106 (2003)

FUN2-O-Mo-A02
2
Secondary Ion Yield Enhancement due to Cluster Ion Bombardment:
A Surprise?

K. Wittmaack


GSF-National Research Centre for Environment and Health
Institute of Radiation Protection, 85758 Neuherberg, Germany
wittmaack@gsf.de


SIMS studies using primary ions of large molecules (clusters) are a topic of current interest (see,
for example; the Proceedings of SIMS XIII and SIMS XIV). Measured secondary ion yields I

were
often compared with results obtained under bombardment with heavy atomic ions like Ga
+
. The
results were quantified in terms of the ratio

a , c
r = I

(cluster)

/

I

(atom). In cases where

a , c
r was
found to be significantly larger than unity, the observed ratios were considered as being due to a
yield enhancement effect, indicating that the results were somehow unexpected. It should be
noted, however, that secondary ion yields are not easy to predict. If sputter ejection and ion
formation are assumed to be independent processes, ion yields may be described as the product of
the sputtering yield Y and the ionisation probability

, i.e.


Y I . (1)
If, apart from the use of atomic (subscript a) or cluster ion (c) beams, secondary ion yields are
measured under identical experimental condition, including the same primary ion energy, and ion
yields are normalised to the same beam current, the yield ratios derived from Eq. (1) read
( )( )

=
a c a c a c,
Y Y r . (2)
Equation (2) implies that large values of

a c,
r can be due to large values of the ratio
a c
Y Y or the
ratio

a c
or both. The purpose of this study was to calculate the ratio
a c
Y Y for a variety of
relevant projectile-target combinations.

The calculations are based on the simplifying assumption that the sputtering yield due to cluster
ion bombardment is the sum of the yields due to each constituent of the cluster. Use is made of the
recent demonstration [1] that sputtering yields can be calculated rather accurately, at least for
amorphous targets, by combining the well-known analytical yield formula due to Sigmund with the
threshold function according to Bohdansky. Calculations were performed for cluster ions of SF
6
and
C
n
, with n up to 60 (Buckminster fullerene). Heavy atomic ions are represented by Ga and Xe. The
ratios
a c
Y Y were found to be characterised by a comparatively sharp threshold at energies which
are higher the larger the number of atoms in the cluster. For C
60
vs Ga or Xe, the threshold energy is
between 1 and 2 keV, for targets of Ag and C. Slightly above the threshold the ratios are initially
very small,
a c
Y Y 1 (a strong yield degradation!), but exceed unity at about twice the threshold
energy. At the frequently used energy of 15 keV,
Ga C60
Y Y was found to be 3.0, 5.9, and 6.6, for
targets of Ag, Si, and C, respectively, increasing monotonically towards higher beam energies.

The calculated yield ratios are compared with a variety of experimental secondary ion yield
enhancement data taken from the literature. The comparison suggests that a significant if not large
fraction of the observed secondary ion yield enhancement due to cluster ion bombardment can be
attributed to differences in the sputtering yields.

References:
[1] K. Wittmaack, Phys. Rev. B 68 (2003) 235211
FUN2-O-Mo-A03
3
Energy and angular distributions of secondary ions in the sputtering
of gold by swift Au
n
clusters. Emission mechanisms

S. Bouneau
a*
, S. Della-Negra
a
, Y. Le Beyec
a
, M. Pautrat
a
, M.H. Shapiro
b
and T.A. Tombrello
c

a
Institut de Physique Nuclaire dOrsay, IN2P3-CNRS and Universt Paris Sud, F-91406 Orsay Cedex
b
Division of Physics, California State University, P.O. Box 6866, Fullerton, C.A. 92834-6866, USA
c
Division of Physics, Mathematics and Astronomy, California Institute of Technology, Pasadena, C.A, 91125 USA
* Email : bouneau@ipno.in2p3.fr


Energy and angular distribution of negative ions ( Au
n
-
, 1<n<5) emitted from gold target
bombarded by Au, Au
4
, Au
9
projectiles at 200 keV/atom were measured with a multi-pixel position
sensitive detector [1]. This multi-parameter detection system and the coincidence data analysis
event by event allow to identify the emitted ions and to correlate emission angle and energy. It is
shown that the angular distributions are symmetrical with respect to the normal to the target and the
most energetic particles are the most forward peaked which correspond to fast emission processes
[2]. Two models have been used to fit the distributions :
A sum of linear collision cascades and of thermal spike emission
A thermal spike emission with two regimes of average temperatures.
Experimental data have been also obtain at 40 keV/atom. The comparison of the experimental
angular and energy distributions with these two models will be presented and discussed.


References:
[1] S. BOUNEAU, P. COHEN, S. DELLA-NEGRA, D. JACQUET, Y. LE BEYEC, J.LE BRIS, M. PAUTRAT, R.
SELLEM,
Review of Scientific Instruments 74 (2003) 57
[2] S. Bouneau, S. Della-Negra, D. Jacquet, Y. Le Beyec, M. Pautrat, M.H. Shapiro and T.A. Tombrello,
Phys. Rev. B, vol. 71,13 (2005) ----

FUN2-O-Mo-A04
4
Effect of Molecular Binding Energy on Sputtering of Thin
Organic Overlayers by keV Ga And C
60
Bombardment

B. Czerwiski
a
, B.J. Garrison
b
, R. Samson
a
, N. Winograd
b
, and Z. Postawa
a,*


a
Smoluchowski Institute of Physics, Jagiellonian University, ul. Reymonta 4, Krakw 30-059, Poland
b
104 Chemistry Building, Department of Chemistry, Penn State University, University Park, PA 16802,USA
e-mail: zp@castor.if.uj.edu.pl


The mechanism of ion-stimulated desorption of organic overlayers on metal substrates is
examined using molecular dynamics (MD) computer simulations. The investigated systems are
represented by thin layers of benzene, polystyrene on Ag{111} and alkanethiol molecules adsorbed
on Au{111}. The molecular binding energy of these overlayers varies from ~0.5 eV for benzene to
~1.9 eV for alkanethiol. The organic overlayers are bombarded with 15keV single Ga and
polyatomic C
60
projectiles which are recognized as valuable sources for desorption of high mass
ions in secondary ion and secondary neutral mass spectrometry (SIMS/SNMS) experiments. The
sputtering yields of molecular species and their mass, internal, angular and kinetic energy
distributions were analyzed depending upon the type of the projectile and the type of a formed
overlayer.
Our calculations indicate that chemical analysis of thin organic films performed by detection of
sputtered neutrals will not benefit from the use of C
60
projectiles. Essentially, both the Ga and C
60

particles remove most of the organic material in the region of impact although the mechanisms
responsible for material removal are different. For monoatomic projectiles most of the energy is
deposited at a significant depth below the surface. This energy is subsequently redistributed inside
the crystal, leading to a formation of a highly excited volume. In this case, intact organic molecules
are ejected by collisions with departing substrate particles and by a correlated upward motion of Ag
atoms in the surface region. This latter process is associated with the formation of a subsurface void
taking place a few ps after the projectile impact. In contrast, strongly nonlinear processes occur
during C
60
bombardment. These nonlinear processes lead to the enhanced removal of material and
the formation of a macroscopic crater. In this case intact organic molecules are ejected via a
concerted action of unfolding of the crater which acts as a sling or catapult that hurls the organic
molecules into the vacuum.

FUN2-I-Mo-A05
5
Fundamentals of Cluster Ion Beams in SIMS

Andreas Wucher *

Department of Physics, University of Duisburg-Essen, D-45117 Essen, Germany
wucher@uni-essen.de


The application of cluster ion beams as desorption probes appears to be a major breakthrough in
molecular SIMS. The general observation is that secondary ion yields, particularly those of complex
molecular species, are significantly enhanced and mass spectra are greatly simplified if polyatomic
projectiles are employed instead of atomic species. Apart from the sensitivity increase, the high
sputter yield associated with the cluster/solid interaction also appears to allow for molecular depth
profiling studies without the accompanying damage accumulation normally associated with atomic
bombardment. It is particularly this property which opens new roads towards high resolution three
dimensional chemical characterization of complex structures like organic thin films, arrays or even
single biological cells.
During the recent years, the emergence of commercially available cluster ion guns with good
beam quality and sub-micron imaging capability has dramatically propelled applications of this
technique. In fact, the rapidly growing body of published work leads one to expect that cluster
beams will be routinely used in SIMS experiments in the very near future. The fundamentals
behind the observed improvements, on the other hand, are not yet clear, although details are
emerging quickly. For instance, a basic question that must be resolved is to determine whether the
observed secondary ion yield enhancement occurs as a consequence of increased ionization
efficiency, or is due to a more effective desorption process. In that respect, the presently available
data appear to be mixed, indicating that both effects may contribute in different proportions
depending on the specific projectile/target combination. Moreover, the mechanisms leading to the
apparent reduction of bombardment induced chemical damage accumulation must be elucidated. In
a simplified picture, one might assume that due to the high sputter yield or total desorption rate
induced by cluster projectiles, damaged material may be removed from the surface with comparable
rate as how it is is created. A systematic proof of this concept, however, appears to be still lacking.
Other observed cluster beam effects, including improved depth resolution in depth profile analysis,
surface smoothing by cluster bombardment etc., still remain largely unexplained.
The talk will attempt to briefly draw together the extensive work addressing these questions that
has been gathered by many groups during the past decade. Particular emphasis will be given to a
few recent developments that may serve to illustrate some of the basic concepts behind the magic of
cluster SIMS.

FUN2-O-Mo-A06
6
Applications of a Bismuth-Cluster Ion Gun in Inorganic Surface
Analysis and Depth Profiling

F. Kollmer*, R. Moellers, T. Grehl, D. Rading, E. Niehuis

ION-TOF GmbH, Gievenbecker Weg 15, 48149 Muenster, Germany

e-mail: felix.kollmer@iontof.com


TOF-SIMS is a very sensitive surface analytical technique, covering a wide range of organic and
inorganic applications. It provides detailed elemental and molecular information about surfaces,
thin layers, interfaces, and full three-dimensional analysis of the sample.

In recent years cluster primary ions emitted from a LMIS (liquid metal ion source) have been
successfully applied for the analysis of organic surfaces by TOF-SIMS. Compared to monoatomic
primary ion bombardment the use of clusters leads to a considerable enhancement of the secondary
ion efficiency up to several orders of magnitude. In particular the newly developed Bi cluster source
combines the fundamental benefits of cluster ion bombardment with a high brightness source to
give high lateral resolution in organic imaging down to 100 nm.

In this contribution we will investigate the performance of Bi liquid metal cluster ion source in
inorganic TOF-SIMS applications. Tasks like trace metal detection and dual beam depth profiling
appeared to be those application where a Ga liquid metal ion gun has clear advantages. We will
compare Bi and its clusters with the Ga performance regarding detection limits, data rates, mixing
and depth resolution.

FUN2-O-Mo-A07
7
Sputtering of Amorphous Ice Induced by C
60
and Au
3
Clusters

Michael F. Russo Jr.
a
, Igor A. Wojciechowski
a
, Barbara J. Garrison
a,
*

a
Department of Chemistry, 104 Chemistry Building, Penn State University, University Park, Pa 16802
mfr129@psu.edu


Previous studies of collision induced sputtering have shown the numerous advantages to using
C
60
over atomic ions such as Ga [1-4]. Among the advantages are vastly increased yields, shallower
damage area, and less mixing of the substrate layers. While these findings are enough to warrant
the use of C
60
, there remains a lack of fundamental understanding as to the physical nature of these
phenomena. Due to the similar total mass of Au
3
and C
60
, examining differences in their sputtering
outcome give way to an understanding of C
60
s unique properties irrespective of mass, and makes
Au
3
a logical choice for comparison. Using the strategy for modeling bombardments of an
amorphous water ice crystal from previous works [5-7], molecular dynamics simulations are
performed in which the water ice substrate was bombarded with either Au
3
or C
60
. Through this
comparative study, several aspects of the sputtering event were considered in order to yield clues as
to the dynamic behavior of this event. These include plume dynamics, penetration depth of incident
particle, damage shape and depth, and the extent of mixing occurring within the substrate layers.


References:
[1] Z. Postawa, B. Czerwinski, M. Szewczyk, E. J. Smiley, N. Winograd and B. J. Garrison, Anal. Chem. 75(17), 4402
(2003).
[2] Z. Postawa, B. Czerwinski, M. Szewczyk, E. J. Smiley, N. Winograd and B. J. Garrison, J. Phys. Chem. B 108,
7831-7838 (2004).
[3] Z. Postawa, B. Czerwindki, N. Winograd and B. Garrison, J. Phys. Chem. B, submitted, 2005.
[4] S. Sun, C. Szakal, A. Wucher and N. Winograd, Phys Rev. B., submitted, 2005.
[5] I. A. Wojciechowski, S. Sun, C. Szakal, N. Winograd, and B. J. Garrison, J. Phys. Chem. A 108, 2993-2998 (2004).
[6] I. A. Wojciechowski, U. Kutliev, S. Sun, C. Szakal, N. Winograd, and B. J. Garrison, SIMS XIV Proceedings, Appl.
Surf. Sci., 231-232, 72-77 (2004).
[7] I. A. Wojciechowski and B. J. Garrison, J. Phys. Chem. B, 109 2894-2898 (2005).
FUN2-O-Mo-A08
8
Molecular Ion Emission from Single Large Cluster Impacts

S. V. Verkhoturov
*
, G. J. Hager, J. E. Locklear, R. D. Rickman, C. Guillermier
and E. A. Schweikert

Department of Chemistry, Texas A&M University,
College Station, Texas 77842-3012 USA
verkhoturov@mail.chem.tamu.edu


A distinctive feature of large projectile bombardment is the SI multiplicity [1]. The emission of
multiple ions from one projectile impact is of great interest for surface analysis if there are multiple
co-emitted molecular SIs which give an accurate representation of the surface spot tested. We
present here the first experimental observation of the distribution of molecular ions per projectile
impact. The study was carried out on targets of phenylalanine and C
60
bombarded with 134 keV
Au
400
4+
and 18 keV C
60
+
. The same targets were also examined with 28 keV Au
9
+
. The experiments
were performed in the event-by-event bombardment-detection mode. The secondary ions were
identified with linear time-of-flight mass spectrometers equipped with either a single anode or an 8-
anode detector. The data were collected and stored such that we can, for example, extract the mass
spectrum corresponding to all impacts from which a set number of Sis, n

, is detected [2]. The total

spectra of the secondary ions are the sum of the spectra corresponding to different n

. The
phenylalanine ion Ph
-
(m/e = 172) yield measured by this summation is ~ 93% in the case of 134
keV Au
400
4+
bombardment. The bombardment of a C
60
target by large projectiles results in the
efficient emission of multiple intact C
60
-
(total yield for Au
400
4+
bombardment is 16%). The co-
emission of multiple ions can be described with a multiplicity report, i.e. the distribution of the
number of ions detected per event, ( ) P n

. The Au
400
4+
projectile induces abundant multi-ion
emission; the average number of detected ions (atomic, fragment, molecular and cluster ions) per
event is 10. In case of the Au
9
+
, one ion is detected on average per projectile impact. The single
impact method allows to derive the distribution ( ) P k

which is a distribution of the number of the

identical intact molecular ions detected per event. The distribution ( ) P k

measured for
phenylalanine ions is broad in case of Au
400
4+
bombardment. The number of events, where one,
two, or three Ph
-
ions are emitted, is of the same order of magnitude. The Au
9
+
projectile is much
less effective for multi-ion emission of the intact molecules (number of events versus number of Ph
-

ions is follows an exponential decay function). We discuss the possible mechanisms of multi-
emission of intact molecular ions, and describe how the experimentally measured molecular ion
distributions are related to the initial distributions of ionized and neutral molecules.


[1] R. D. Rickman, S. V. Verkhoturov, E. A.Schweikert, Appl. Surf. Sci. 231-232 (2004) 54-58.
[2] R. D. Rickman, S. V. Verkhoturov, G. J. Hager, E. A. Schweikert, J. A. Bennet Int. J. Mass Spectrom. 241, (2005)
57-61.
Work supported by NSF (CHE-0449312) and R.A. Welch Foundation (A-1482).
FUN2-O-Mo-A09
9
Stretching the limits of static SIMS with C
60
+


A. Delcorte*, C. Poleunis and P. Bertrand

PCPM, Universit catholique de Louvain, Croix du Sud 1, B-1348 Louvain-la-Neuve, Belgium, e-mail:
delcorte@pcpm.ucl.ac.be


It has been shown by Vickerman and co-workers that buckminsterfullerene projectiles induce a
drastic enhancement of the parent and fragment ion yields in static SIMS of organic materials [1].
These results have been confirmed with our TRIFT instrument, recently equipped with a similar
C
60
+
source. Under 15 keV bombardment, yield increases of 2-3 orders of magnitude in comparison
with Ga
+
primary ions have been measured for various organic samples, including PS oligomer,
Irganox 1010 spin-coated films and adsorbed protein layers. In the case of PS films, fullerene
projectiles induce the direct desorption of positively charged oligomers, without the need of a
cationizing metal atom.
Our experiments with metal cluster/nanoparticle samples show that, even for such analytes, the
use of a low-atomic mass substrate (organic material, carbon particles) causes a large yield
enhancement under C
60
+
bombardment. It also allows us to extend significantly the traditional mass
range of static SIMS. In particular, when an overlayer of gold clusters sitting on top of an organic
film is bombarded with 15 keV C
60
+
ions, a series of clusters up to a mass of about 20,000 Da
(Au
100
-
: 19,700 Da) is detected. At such high mass, the detection efficiency of our spectrometer
becomes the limiting factor.
Beyond the analytical achievement, this contribution addresses the basics of the fullerene-surface
interaction, using the measured yields and kinetic energy distributions of fragments and molecular
ions, together with the insights provided by recent molecular dynamics simulations [2].


[1] D. Weibel, S. Wong, N. Lockyer, P. Blenkinsopp, R. Hill, J. C. Vickerman, Anal. Chem. 75 (2003) 1754.
[2] Z. Postawa, Appl. Surf. Sci. 231-232 (2004) 22.
Plenary-Mo-A10
10
Some New Insights in to the Mechanisms of Fullerene and Nanotube
Formation

Harry Kroto

Department of Chemistry and Biochemistry
The Florida State University Tallahassee, Florida 32306-4390, USA
kroto@chem.fsu.edu


Fullerene molecules and their elongated nanotube cousins have now been the subject of intense
study for nearly 15 years. They still promise to play major roles in almost every possible area of
21
st
Century science and technology from medicine and molecular electronics to materials science
and civil engineering. This promise will only be realized when accurate control of nanoscale
structure assembly and growth is achieved. However the mechanisms whereby various types of
nanostructures assemble are still very poorly understood. Over the last decade or so, we have
examined a wide range of approaches to nanotube formation and from these studies some
interesting new insights have been gained especially with regard to metal catalysed nanostructure
formation. We have however also learned that we have still a long way to go!





Selected Publications
'C60: Buckminsterfullerene', H W Kroto, J R Heath, S C O'Brien, R F Curl and R E Smalley. Nature, 318(No.6042),
162-163,(1985).

Transition Metal Surface Decorated Fullerenes as Possible Catalytic Agents for the Creation of Single-walled
Nanotubes of Uniform Diameter, Birkett, P.R., Cheetham, A.J., Eggen, B.R., Hare, J.P., Kroto, H.W. and Walton,
D.R.M., Chem. Phys. Lett. 281, 111-114 (1997).

Field Emission from Non-aligned Carbon Nanotubes Embedded in a Polystyrene Matrix, Poa, C.H., Silva, S.R.P.,
Watts, P.C.P., Hsu, W.K., Kroto, H.W. and Walton, D.R.M., Appl. Phys. Lett., 80, 3189 (2002).

Tungsten Disulphide Sheathed Carbon Nanotubes, Whitby, R.L.D., Hsu, W.K., Boothroyd, C.B., Fearon, P.K., Kroto,
H.W. and Walton, D.R.M. ChemPhysChem 2, 620-623 (2001).

Shock-wave Resistance of WS2 Nanotubes, Zhu, Y.Q., Sekine, T., Brigatti, K.S., Firth, S., Tenne, R., Rosentsveig,
R., Kroto, H.W. and Walton, D.R.M., J. Am. Chem. Soc. 125, 1329-1333 (2003).
CLU-O-Mo-A11
11
Molecular Depth Profiling with Cluster ion sources

Juan Cheng and Nicholas Winograd*

Department of Chemistry, the Penn State University, University Park, PA 16802
nxw@psu.edu


Cluster bombardment of molecular films with SIMS has been successful in many recent studies.
There are in fact five properties of cluster bombardment: enhanced sputtering yields, particularly of
biomaterials; enhanced molecular ion yields, particularly at high mass; reduced topography and
interface mixing; reduced damage cross-sections and molecular depth profiling capability in some
cases. We have found a reproducible platform of well-defined sugar films (trehalose) with doped
peptides, the depth profiling of which has been able to help us elucidate all five of these properties.
Stable molecular ions of several hundred Daltons, both from trehalose and from the doped peptides
are observed during erosion by C
60
. The total sputter yield is found to be in a range from 300 to 500
trehalose molecules per C
60
projectile. Moreover, we will present a simple model that explains the
important features of the depth profile. One observation of special interest is the molecular ion
transients observed during the initiation of the depth profile. For example, the trehalose signal
exhibits an initial rise with C
60
dose before decreasing to a steady state value. This initial rise is a
critical observation that also correlates with the m/z 18 and 19 signals. These results suggest that
C
60
is an effective means of producing protons that may ultimately lead to protonation of the
molecule and a resulting enhanced signal. Finally, AFM investigations of topography and
interfacial structure suggest that interface widths of only few nm may possible to achieve using this
approach. In general, these observations suggest that cluster beams will be successfully applied to
molecular depth profiling of a number of complex organic materials.
CLU-O-Mo-A12
12
Temperature-Controlled Depth Profiling in Polymeric Biomaterials
using Cluster Secondary Ion Mass Spectrometry (SIMS)

Christine Mahoney
a
, Greg Gillen
a
, and Albert Fahey
a
,
Chang Zu
a
, James Batteas
a
and Daniel Hook
b


a
National Institute of Standards and Technology, 100 Bureau Drive, Mail Stop 8371,
Gaithersburg, MD, 20899-8113, USA
b
Bausch & Lomb / R&D, 1400 North Goodman Street, Rochester, NY 14609, USA
cmahoney@nist.gov


Cluster primary ion sources, such as C
60
+
, C
8
-
, Au
3
+
, SF
5
+
and more recently Bi
3
+
, have
generated considerable interest for organic SIMS analysis, where they have resulted in significant
improvements (up to 1000 fold) in characteristic molecular secondary ion yields and in some cases
have resulted in decreased beam-induced damage [i]. This in turn has resulted in enhanced
sensitivity for molecular imaging applications. More importantly depth profiling through organic
and polymeric materials has been achieved. The growing list of polymers amenable to depth
profiling with cluster primary ion beams include poly(lactic acid) (PLA), poly(glycolic acid)
(PGA), poly(lactic-co-glycolic acid) (PLGA), poly(ethylene oxide) (PEO), poly(propylene oxide)
(PPO), Poly(caprolactone) (PCl), poly(methyl methacrylate) (PMMA), poly(hydroxyethyl
methacrylate) (PHEMA), poly(n-butyl methacrylate) (PBMA), various polypeptides, and gelatin
[ii].
In the current work, Secondary Ion Mass Spectrometry (SIMS) employing an SF
5
+
polyatomic
primary ion source was used to depth profile through various polymeric biomaterials at a series of
temperatures from 163 K to 398 K. The depth profile characteristics (e.g. interface widths, sputter
rates, damage cross sections, and overall secondary ion stability) were monitored as a function of
temperature. It was found that at low temperatures, the secondary ion stability increased
considerably for most materials. In addition, the interfacial widths were significantly lower.
Corresponding AFM images indicated that there was also decreased sputter induced topography
formation at these lower temperatures in PMMA samples. Higher temperatures were typically
correlated with increased sputter rates. However the improvements in interfacial widths and overall
secondary ion stability were not as prevalent as was observed at low temperatures. The importance
of glass transition temperature (T
g
) on the depth profile characteristics was also apparent. Resulting
PMMA depth profile characteristics were compared with that of poly(lactic acid) (PLA), considered
to be one of the more successful cases of polymer depth profiling (very low damage cross-sections,
high sputter rates, small interface widths). The resulting interface widths and damage cross sections
of PMMA at cryogenic temperatures were comparable to PLA at room temperature.


[i] Gillen, G.; Roberson, S. Rapid Commun. Mass Spectrom. 1998, 12, 1303-1312.; Kollmer, F. Appl. Surf. Sci.
2004, 231-232, 153-158.; Weibel, D.; Wong, S.; Lockyer, N.; Blenkinsopp, P.; Hill, R.; Vickerman, J.C. Anal. Chem.
2003, 75, 1754-1764.
[ii] Mahoney, C.M.; Roberson, S.V.; Gillen, G. Anal. Chem. 2004, 76, 3199-3207.; Wagner, M.S. Anal. Chem.
2005, 77(3), 911-922.; Mahoney, C.M.; Yu, J.X.; Gardella, J.A. Jr. Depth profiling of poly(L-lactic acid)/Pluronic

polymer blends with Time-of-Flight Secondary Ion Mass Spectrometry (TOF-SIMS) Accepted for publication in
Analytical Chemistry (March 2005).; Wagner, M.S. Surf. Int. Anal. 2005, 37(1), 42-70.; Sostarecz, A.G.; McQuaw,
C.M.; Wucher, A.; Winograd, N.; Anal. Chem. 2004, 76, 6651-6658.

CLU-O-Mo-A13
13
Using Polyatomic Primary Ions to Probe Amino Acids in Water Ice

G.X Biddulph
a*
, X.A. Conlan
a
, N.P. Lockyer
a
, J.C. Vickerman
a

a
Surface Analysis Research Centre, School of Chemical Engineering and Analytical Science University of Manchester .
PO Box 88 Manchester M60 1QD, UK


Since the development of polyatomic primary ions, increases in secondary ion yield from organic
materials using Au
3
+
polyatomic primary ion have been shown [1]. Through ToF-SIMS studies of
several molecular solids, significant enhancement of high mass molecular ion yields have been
observed using C
60
+
.
These include yield enhancements of biologically significant molecular species
[2]. SIMS analysis of biological samples is an ever-growing area of importance from analysis of
cellular events [3] to bio-imaging of tissue [4]. Freezing the samples of biologically significant
materials to maintain chemical integrity is a common technique [5]. The role of the ice matrix
during the SIMS analysis of these samples is therefore of great interest.

The emission of cluster ions from pure water ice have been observed in the past [6]. In this study
on pure water ice we show that protonated water species [H
2
O]
n
H
+
are more prevalent than (H
2
O)
n
+

ions after bombardment by Au
+
monoatomic and Au
3
+
and C
60
+
polyatomic projectiles. This data
reveals also significant differences in water cluster yields under bombardment by these three
projectiles. The amino acids alanine and histidine in solution have been studied and have shown a
profound effect on the water cluster ion yields observed using a C
60
+

ion beam. The mechanism of
ion formation during sputtering from water ice surfaces will be discussed in the light of this data.


[1] N. Davies, D.E. Weibel, P. Blenkinsopp, N. Lockyer, R. Hill, J.C. Vickerman, Applied Surface
Science 203-204 (2003) 223-227
[2] D.E. Weibel, S. Wong, N.P. Lockyer, P. Blenkinsopp, R. Hill, J.C. Vickerman, Anal. Chem, 75
(2003) 1754-1764.
[3] S.G. Ostrowski, C.T. Van Bell, N. Winograd and A.G. Ewing. Science 305 (2004) 71-73.
[4] P. Sjoevall, J Lausmaa, B. Johansson. Anal. Chem. 76 (2004) 42714278.
[5] B. Cliff, N. Lockyer, H. Jungnickel, G. Stephens, J.C. Vickerman, Rapid Commun. Mass Spectrom. 17, 2163-2167
(2003).
[6] H.A. Donsig and J.C. Vickerman, J. Chem. Soc. Faraday Trans., 93, 2755-2761, 1997.

CLU-O-Mo-A14
14
Chemical effects in C
60
irradiation of polymers

R. Mllers
a
, N. Tuccitto
b
, E. Niehuis
a
, A. Licciardello
b,
*

a
ION-TOF GmbH, Gievenbecker Weg 15, 48149 Mnster, Germany
b
Dipartimento di Scienze Chimiche, Universit di Catania, V. A.Doria 6, 95125 Catania, Italy
alicciardello@unict.it


During the last few years, in connection with the development of polyatomic primary ion sources,
new perspectives appeared in SIMS of organic materials and of polymers in particular, due to the
spectacular enhancement of the secondary ion emission efficiency compared with monoatomic
primary ions, that allows to obtain significant improvements both in static SIMS spectra and in
SIMS imaging. Moreover, some authors have shown very interesting results on organics [1] by
using C
60
primary ions beyond the static limit. In particular on the basis of the results obtained on
polymethylmethacrylate (PMMA) assumed as model polymer, it has been suggested that depth
profiling of polymers is feasible [2]. Such an attractive possibility could be connected with the high
sputter yield and the very low penetration depth of the C
60
ions, that in some way sputter away
the damaged region leaving a more or less undamaged surface behind. On the other hand it is well
known that PMMA can undergo chain scission phenomena under ion irradiation, although in
different experimental conditions [3]. The latter phenomena, if active under keV C
60
bombardment,
could explain as well the high erosion rates observed and could be compatible with the low level of
damage left at the surface. In such hypothesis the possibility of depth profiling of polymers would
be greatly limited, since it would be strongly connected with the radiation chemistry of the
particular polymer under consideration.
Aim of the present work is to study the effect of the chemical nature of the polymer on its
behaviour under C
60
irradiation beyond the static limit. For this purpose we have chosen PMMA
and polystyrene (PS), two polymers that are a well known example of contrasting behaviour under
ion beam irradiation. Indeed PMMA is the prototype of positive tone resist (i.e. a polymer where
chain scission is the prevailing irradiation induced chemical event) while PS acts as a negative
resist, where crosslinking is the dominant mechanism of ion beam damage. In addition we have
considered a few other polymers in order to extent our test. Our results, obtained with both C
60

beams and more conventional monoatomic projectiles, show that a) there is an appreciable
influence of the chemical structure on the behaviour of the polymer under dynamic SIMS
conditions and that b) the high erosion rates observed in some polymers are at least partly due to ion
beam-initiated depolymerization phenomena. This suggests that C
60
depth profiling of polymers,
although probably feasible in some particular instances, cannot be considered a general tool.


[1] (a) D.E.Weibel, N.Lockyer, J.C. Vickerman, Appl.Surf.Sci 231-232 (2004) 146; (b) A.G.Sostarecz, S.Sun,
C.Szakal, A.Wucher, N.Winograd, Appl.Surf.Sci 231-232 (2004) 179; (c) R. Mllers, R. Kersting, F. Kollmer, D.
Rading, T.Grehl, E. Niehuis, proc. SIMS Europe 2004, Muenster, 2004, p.106.
[2] C.Szakal, S.Sun, A.Wucher, N.Winograd, Appl.Surf.Sci 231-232 (2004) 183
[3] (a) A.Licciardello, M.E.Fragal, G.Foti, G.Compagnini, O.Puglisi; Nucl. Instr. Methods in Phys. Res B116 (1996)
168; (b) M.E. Fragal, G. Compagnini, L. Torrisi, O. Puglisi, Nucl. Instr. Methods in Phys. Res. B141 (1998) 169

CLU-O-Mo-A15
15
Molecular Depth Profiling of Organic and Biological Materials

J. S. Fletcher*, X. A. Conlan, E. A. Jones, N. P. Lockyer, J. C. Vickerman

Surface Analysis Research Centre, SCEAS, University of Manchester. Manchester M60 1QD. UK

E-mail: John.Fletcher@manchester.ac.uk


The desire for increased secondary ion yield, particularly from organic samples, has provided the
impetus for the development of a number of polyatomic ion sources. Early experiments using SF
5
+

demonstrated a coincidental reduction in subsurface damage accumulation in polymer samples [1].

The development of a practical C
60
+
ion beam system has yielded results that show even less
damage accumulation than with other polyatomic sources [2] leading to the suggestion that pseudo
damage free analysis may be possible including molecular depth profiling. Molecular dynamics
simulations suggest that along with dissipating the majority of its energy in the uppermost surface
layers of the sample each impacting C
60
+
particle can remove both damage products and pristine
analyte molecules. [3] In this scenario it is clear that matrix effects may play a significant role and
indeed the reports showing the least damage during depth profiling have described the analysis of
molecular species in high yield matrices such as ice. [4]

In this paper we report several molecular depth profiling studies on samples including thin
organic layers, bulk polymers along with both real and model biological systems. We present data
from C
60
+
experiments compared to similar analysis performed using a monatomic ion (Au
+
) and
polyatomic metal cluster ion (Au
3
+
). On specific samples Au
3
+
can show comparable yield
enhancement to C
60
+
and currently allows higher spatial resolution, but does not give the
corresponding damage reduction.


[1] F. Kotter, a. Benninghoven, Applied Surface Science, 133 (1998) 47-57
[2] D.E Weibel, S.Wong, N.P. Lockyer, P. Blenkinsopp, R. Hill, J.C. Vickerman, Anal. Chem. 75 (2003)
1754-1764
[3] S. Sun, C. Szakal, E. J. Smiley, Z. Postawa, A. Wucher, B. J. Garrison, N. Winograd, Applied Surface
Science, 231-232 (2004) 64-67
[4] A. Wucher, S. Sun, C. Szakal, N. Winograd Applied Surface Science. 231-232 (2004) 68-71

CLU-O-Mo-A16
16
Probing Thin Overlayers With Variable Energy / Cluster Ion Beams

A. Spool*, R. White

Hitachi Global Storage Technologies Inc., 5600 Cottle Road, San Jose, CA 95193, USA
Email: Alan.Spool@Hitachigst.com


A series of thin carbon overcoated samples of magnetic recording disks proved an ideal set of
samples to explore sampling depth and ion formation trends under a variety of analytical conditions.
Tested were variations in energy of the primary ion beam, variations in cluster size (Au
1
, Au
2
, Au
3
),
variations in overcoat thickness and variations in their type. The results show the somewhat
expected reduction in the intensity of atomic ions from the underlying metal layer with reduction in
primary ion energy and increase in primary ion cluster size. Perhaps more interesting is the nearly
linear variation in the intensity of these atomic species as a function of over layer thickness., and
how this variation changes when the nature of the overcoat is changed. Comparisons with SIMS
M
x
Cs
y
depth profiles provides evidence that the metal signals being seen through the carbon over
layers is not the result of varying amounts of bare spots, but is due to atomic ions emerging from
beneath the overcoat during the sputter event. Profiles taken using the same sputter source
conditions (700 eV Cs+) but using different analytical primary ion energies show that despite the
difference in the analytical depth for the different conditions, the M
x
Cs
y
depth profiles are
unaffected. The results indicate either that the sputtered neutrals must be pre-associated with the Cs
at the surface, or else the neutrals eventually captured in Cs clusters must have low kinetic energy in
order to be captured, and thus are much more likely to have come from the surface than from any
significant depth. Thus the M
x
Cs
y
depth profiles have a better depth resolution than than atomic ion
based profile would under the same conditions.
The series of samples were fortuitously dosed at the back end of the sputter system with a
relatively unique Dinonyl Phthalate species, which allows us with the same sample set to probe the
effects of different primary ion beam energy and cluster size on the spectrum of a discrete adsorbed
molecular species, similar to work that has been performed in the development of the GSIMS
method {1}. In this series, lower energy and higher cluster size did not necessarily lead to a
relatively more intense molecular ion. Instead, ions prominent in the EI mass spectrum, including
even electron ions, were more consistently enhanced at lower energies and higher cluster sizes.
Another interesting observation is that the total of the secondary ion counts (dominated by the
adsorbed organic species) varied with film thickness at any given analytical condition, with higher
intensity spectra found for thinner overcoated films. This would be consistant with secondary
electrons, which would be largely originating in the buried metal layer, having a substantial
influence on the formation of these organic ions, as has been suggested previously [2].


[1] I.S. Gilmore, M. P. Seah, J. E. Johnstone, Proceedings of the 12th SIMS Conference, Brussels (2000) 801
[2] A.M. Spool, Surf. Interface Anal., 36 (2004) 264
FUN1-I-Mo-B01
17
The limitations of SIMS in nanoscale technologies : quantitative near-
surface and interfacial analysis of complex systems

W. Vandervorst, T.Janssens, L.Geenen, C.Huyghebaert, T.Conard, B.Brijs

IMEC, Kapeldreef 75, B-3001 Leuven, Belgium
email: vdvorst@imec.be


The use of Secondary Ion Mass Spectrometry (SIMS) has grown consistently over many years
primarily for its extreme sensitivity combined with high depth resolution and quantification
properties. In particular in the semiconductor area, this have become eminent and SIMS is one of
the main characterization methods to study dopant and impurity incorporation and diffusion
enabling the development of devices with ever decreasing dimensions. With the advent of sub-45
nm technologies, the semiconductor industry is moving towards the use of extremely shallow (< 10-
20 nm) dopant profiles. Dopant diffusion and activation is no longer pursued by long, high
temperature anneal processes causing excessive diffusion but rather by ultra short anneal cycles
(RTA, laser anneal, solid phase epitaxial regrowth,.) such that metastable concentrations can be
achieved (exceeding solid solubility limits) and (the very limited) outdiffusion becomes entirely
dominated by transient (enhanced) diffusion. Subtle changes in profile shapes need to be monitored
as these contain all the relevant physics and thus dopant profiling with a depth resolution better than
1 nm becomes a prerequisite. At the same time many new materials are being introduced such as
high k and low k dielectrica, (workfunction engineered) metal gates, strained Si-layers and even
new substrate materials such as Ge instead of Si. Their introduction puts serious challenges on
SIMS as the problem of depth resolution now becomes coupled with additional matrix effects and
ionization yield variations at the various interfaces.
In this paper we discuss some of the fundamental aspects of SIMS depth profiling (sputter yield
variations, ionization yield variations, differential shift, escape depths) in relation to a series of
challenging examples highlighting the increasing difficulty of SIMS to meet those targets as well as
potential alternatives (H-RBS, H-ERDA, LEAP) which may aid SIMS to solve the se problems.
Examples discussed are :
1. quantitative near-surface and interfacial profiling : the role of outdiffusing oxygen on
profile distortions and optimized (?) profiling conditions, transients with Cs,
2. limitations of the dilute limit in high dose implants
3. complex high k layers : composition, underlayer interdiffusion, impact on dopant
profiles,
4. dopant distribution in workfunction engineered silicides used as gate material
5. dopant profiles in Ge : roughness, dilute limit,..
6. Ge-migration in monolayers of Si
7. localized impurities in metallization systems such as Cu
FUN1-O-Mo-B02
18
Ionization probability of sputtered particles as a function of their
energy

Yu.Kudriavtsev*, A.Villegas, A.Godines, S.Gallardo, R.Asomoza

Dep. Ingenieria Electrica - SEES, Cinvestav-IPN, Av.IPN # 2508, Mexico, D.F.
E-mail: yuriyk@cinvestav.mx


In this study we investigated the energy distribution of positive Si ions, sputtered from crystalline
silicon by O
2
+
ion beam.
Any energy distribution, measured by SIMS, represents a convolution of the initial energy
distribution with an apparatus function, which is defined by the bandwidth of used energy analyzer
and by a dependence of the transmitting coefficient of used optical system on the energy of
analyzed ions. In this study we searched the apparatus function by a comparison of the energy
distribution of secondary Na
+
ions, measured under the same conditions, with theoretical energy
distribution of sputtered Na atoms (the Sigmund-Thompson model). Ionization probability of Na
was estimated equal to unity for used SIMS regime.
As the next step of the study, we made a de-convolution of the experimental energy distribution
of silicon ions with the apparatus function and found the true Si
+
energy distribution. Finally, we
compared the energy distribution of Si
+
ions and Si atoms (the Sigmund-Thompson model) and
found the energy dependence of the ionization probability P
Si
+
(E) of sputtered Si particles.
The found ionization probability can be separated in two parts: the low energy part (<20eV),
where the ionization probability is a power function of the energy (P
Si
+
(E)E
0.6
), and the high
energy part (>30eV), where the ionization probability keeps constant (P
Si
+
(E)const).
In order to explain the found P
Si
+
(E), we compared the energy distribution of secondary Si atoms
and their escape depth. We found that only atoms, sputtered from the top monoatomic layer can
form the low energy part of the ions energy distribution. The high energy part of the spectrum is
formed by atoms sputtered from the top monolayer and to a smaller extent from deeper layers. After
that we estimated that there are two different ionization mechanisms for sputtered atoms depending
on their energy and their escape depths, and, as a consequence, on the time of a passage of the
surface layer by sputtered particles.
FUN1-O-Mo-B03
19
Detection of Molecular Hydrogen Anions H
2

, D
2

, H
3

and D
3

by SIMS and AMS

H. Gnaser
1,*
, R. Golser
2
, W. Kutschera
2
, A. Priller
2
, P. Steier
2
, A. Wallner
2


1
Department of Physics, University of Kaiserslautern, D67663 Kaiserslautern, Germany
2
VERA Laboratory, Institut fr Isotopenforschung und Kernphysik, Universitt Wien, A1090 Wien, Austria
*
gnaser@rhrk.uni-kl.de


In view of the ubiquitousness of hydrogen, the negative H
2

species is probably one of the

most fundamental and important molecular anions. Commonly considered [iii,iv] too short-lived
(lifetime ~ 10
15
s) to be detected directly, it is nonetheless believed to be rather crucial in various
collision processes like dissociative attachment, associative detachment, or collision detachment.
Despite of several experimental efforts during the past three decades [v,vi,vii,viii], the possible
existence and the lifetime of the molecular hydrogen anions (H
2

and D
2

) remained uncertain.
The existence of long-lived (metastable) molecular hydrogen anions H
2

, D
2

, H
3

and D
3

is
demonstrated in the present study. These anion species were produced by sputtering of TiH
2
, TiD
2

and HfH
2
targets with Cs
+
ions and were identified by secondary-ion mass spectrometry (SIMS) and
accelerator mass spectrometry (AMS). From their respective flight times through the spectrometer,
the lifetimes of these molecular hydrogen anions can be inferred to be at least several s. From the
SIMS data, the following apparent abundance ratios (relative to the atomic ions) are derived:
H
2

/H

= 3.510
6
, H
3

/H

= 1.710
8
, D
2

/D

= 310
5
, D
3

/D

= 710
9
.
It is proposed that molecular hydrogen species with high rotational and vibrational excitation
are formed in sputtering that are stable on the time scale of the experiment, in agreement with
theoretical calculations [ix] which predict the existence of highly rotationally excited anions with
lifetimes in the s range.


[iii] D.R. Bates, in Advances in Atomic Molecular, and Optical Physics, Vol. 27, eds., D. Bates and B. Bederson
(Academic, San Diego, 1991), p. 1
[iv] W. Domcke, Phys. Rep. 208, 97 (1991).
[v] R.E. Hurley, Nucl. Instrum. Methods 118, 307 (1974).
[vi] W. Aberth, R. Schnitzer, M. Anbar, Phys. Rev. Lett. 34, 1600 (1975).
[vii] Y.K. Bae, M.J. Coggiola, J.R. Peterson, Phys. Rev. A 29, 2888 (1984).
[viii] W. Wang, A.K. Belyaev, Y. Xu, A. Zhu, C. Xiao, X.-F. Yang, Chem. Phys. Lett. 377, 512 (2003).
[ix] R. Golser, H. Gnaser, W. Kutschera, A. Priller, P. Steier, A. Wallner, M. ek, J. Horek, W. Domcke,
submitted to Phys. Rev. Lett.
FUN1-O-Mo-B04
20
SPUTTERING AND DESORPTION PROCESSES AT LOW-
ENERGY ION BOMBARDMENT OF SINGLE CRYSTAL
SURFACES

A.A. Dzhurakhalov*, S.E. Rahmatov

Arifov Institute of Electronics, F.Khodjaev Str. 33, 700125 Tashkent, Uzbekistan
e-mail: dzhurakhalov@mail.ru


The sputtering at grazing angles touches only surface layers and submonolayer coverings of
crystal. Therefore such sputtering is the unique tool of research of surface (determination its
element composition and structure at atom level). Such researches are necessary for creation of new
methodical bases of diagnostics and modification of surface.
In the present work the peculiarities of the formation of the primary knock-on recoil atoms of
matrix and desorption of adsorbed oxygen molecules at low-energy grazing ion bombardment of
single crystal surfaces have been investigated by computer simulation.


In the figure the dependences of sputtering yield versus on the crystal orientation at 10 keV N
+

bombardment of clean and oxygen covered Ag(110) surface are presented (here angle of incidence
counted from the surface is 15
0
). There are some characteristic maximums in these curves. By
analyzing of trajectories of incident ions it was found that the channeling of bombarding particles in
determined directions entails the formation of these peaks. It is seen there are some differences in
the case of clean (solid curve) and adsorbed (dashed curve) surfaces. In some directions the
presence of adsorption layer results to the increase of sputtering yield of matrix atoms. The strong
correlation between sputtering yield and crystal orientation was found.
FUN1-O-Mo-B05
21
Sputtering of Mixed Clusters from a NiAl Surface

*B.V. King
a
, J.F. Moore
b
, W.F. Calaway
b
, I.V. Veryovkin
b
, and M.J. Pellin
b


a
University of Newcastle, Newcastle, NSW, Australia.
b
Argonne National Laboratory, Argonne, IL, USA.
Bruce.King@newcastle.edu.au


Clusters sputtered from NiAl(111) using 15keV Ar
+
at 60 incidence from the surface normal
have been measured by laser postionization using 7.87eV photons from an F
2
laser. The signals due
to Ni
x
Al
y
(where x = 0-6, y = 0-7) clusters were observed to rise linearly with laser intensity,
indicating that ionization occurred in a one-photon process. Furthermore, the cluster ion yields fell
with nuclearity, n, according to the relation I n
-
, where was found to be related to the values
found for pure Ni and for pure Al.
This work was supported by the U.S. Department of Energy, BES - Materials Science, under
Contract W-31-109-ENG-38.
FUN1-O-Mo-B06
22
Quantitative fundamental studies in SIMS using
18
O implant
standards

Peter Williams*, Klaus Franzreb, Jan Lorincik, Richard C. Sobers, Jr.

Dept. of Chemistry and Biochemistry, Arizona State University, University Drive,
Tempe, AZ 85287, USA
* Corresponding author
pw@asu.edu


Recently we introduced a new and powerful method for quantifying surface oxygen levels during
sputtering using
18
O implant standards. Because
18
O remains at trace levels even in stoichiometric
oxides, such implants can be detected superimposed on the intrinsic
18
O level and, after background
subtraction, can be used to quantify the level of surface oxygen during depth profiling. This method
allows quantitative investigation of variation of sputtering yields and sputtered ion yields with
surface oxygen content and similarly allows investigation of profile distortions arising from ion
beam mixing and oxygen-induced segregation, again with accurately known surface oxygen levels.
A number of new results, and confirmation of some old results, have been obtained in this work.
In particular:
(a) We find that in general surface oxygen levels can significantly exceed the nominal saturation
stoichiometry of the oxides. For example, O/Si ratios approaching 6:1 are measured in the
sputtered flux from O-saturated Si. This is consistent with the formation of fully O-
terminated surfaces and a shallow sputtered atom escape depth that significantly oversamples
the outermost atomic layer.
(b) Positive and negative sputtered ion yields have been accurately measured in a number of
materials as a function of surface oxygen content. The responses of different elements to
changing O levels vary widely. For example Al in Si has a high positive ion yield even at
very low O levels and is little enhanced by added O, whereas B
+
is enhanced by a larger
factor than Si
+
. In contrast, B in Cu has a higher positive ion yield than Cu at low O levels
but is not detectably enhanced as O levels rise, so that at high O levels the Cu
+
yield exceeds
the B
+
yield. The B
+
useful ion yield in fully oxidized Cu is a factor of 100 lower than in
fully oxidized Si. These results suggest that in addition to oxygen-induced matrix effects,
there exist strong matrix effects both in the absence of O, and also in fully oxidized surfaces.
(c) Oxygen-induced segregation that alters ion beam mixing decay lengths is shown for a variety
of elements to be a much stronger effect when oxygen is delivered from the gas phase than
when oxygen ion beams are used to produce the same surface O level, indicating that the
near-surface oxygen gradient is a key parameter in segregation. In addition, no discontinuities
in segregation are seen when the O level is that of a saturated oxide, indicating that exclusion
of dopant elements from a surface oxide layer is not a major cause of the observed
phenomena.
The general utility of
18
O implant standards for fundamental SIMS studies will be discussed in
this paper.
FUN1-O-Mo-B07
23
Atomic Scale Modifications to a Silicon Sample during SIMS Analysis

Michael Wiedenbeck, Richard Wirth

GeoForschungsZentrum Potsdam, Telegrafenberg, D14473 Potsdam, Germany
michawi@gfz-potsdam.de

A complete understanding of SIMS analytical results must include knowledge of the chemical
and structural modifications of the sample which are induced by primary ion bombardment. In
order to define better this aspect of the SIMS analytical process we have used a high resolution
transmission electron microscope to investigate material removed from the bottom of a SIMS crater.

High purity silicon metal from a polished Si-wafer was loaded into our Cameca ims 6f SIMS
instrument. A 4nA, 16O- primary beam was accelerated to a net energy of 22.5 keV per nucleon
and this beam was rastered over a 50 x 50 micron area. Bombardment progressed for 10 min,
which was well after equilibrium sputtering conditions had been achieved. The sample was next
transferred to our FEI FIB200 instrument for Ga ion milling. An area in the middle of the flat-
bottom SIMS crater was selected, from which a 10 micron long and ~80 nm thick foil was cut. This
foil, the long axis of which had been parallel to the floor of the SIMS crater, was transferred to a
standard carbon coated grid for high resolution TEM analysis using our Philips CM200 instrument.

This study observed a number of features produced during the SIMS sputtering process. At the
samples top, formally the center of the SIMS crater floor, we detected a 110 micron wide zone of
amorphous material in which no evidence for any crystal structure was found. The boundary
between this amorphous layer and the underlying crystalline Si-metal showed a near-atomic layer
sharpness. This contact was highly parallel to the original sample surface, showing a variation of
only a few atomic layers over the width of a high resolution image. Finally, a linescan using O-K,
Si-K and Pt-M lines clearly showed the presence of implanted oxygen within the amorphous zone,
reaching levels up to a factor of 5 above instrument background levels. The profile of the oxygen
distribution was found to be slightly asymmetric, with an apparently constant maximum
concentration of oxygen giving way to a linear falloff in oxygen content towards the bottom of the
amorphous zone. There is some hint that the oxygen concentration in this ~50 nm wide tail drops to
background levels ~10 nm beyond the boundary between the amorphous and crystalline materials,
though this observation requires further confirmation.
FUN1-O-Mo-B08
24
Correlating the angular variation of the sputter yield with surface
oxygen concentration during O
2
+
bombardment of Ge.

T. Janssens
a,*
, C. Huyghebaert
a
, and W. Vandervorst
a,b

a
IMECvzw, kapeldreef 75,B-3001 Leuven, Belgium
b
also: INSYS, KULeuven, Belgium


The accurate determination of dopant profiles in Ge with SIMS is indispensable to support the
recent developments in IC manufacturing. In this study we focus on the oxygen incorporation
during oxygen bombardment of Ge, a practice commonly used to enhance the secondary ion
emission.
Recently an in-situ way to determine the O/Si flux from a bombarded Si surface by measuring a
known O
18
implant in Si was reported [1] and applied [2]. We have also performed a similar study
in Ge, whereby in particular the drastic changes in Ge-sputter yield under oxygen bombardment
will be correlated with a change in O/Ge composition in the near surface region.






















At 3keV the angular variation of the Ge sputter yield, shown in Fig. 1, is smooth and not influenced
by sudden changes in surface oxidation. For lower energies (<1keV O
2
+
) a distinct step is visible in
a narrow angular region which is very different from the much smoother sputter yield transition in
Si (open symbols). This steep increase above a critical angle (e.g. 20 degrees at 0.5keV O
2
+

bombardment) is related to the formation of an unstable, volatile Ge-oxide, which upon evaporation
drastically reduces the near-surface oxygen concentration causing a fast increase in the Ge sputter
yield. These changes in surface concentrations are quantified through the analysis of an
18
O-
implant using the methodology described in [1].


[1] K. Franzeb, J.Lorincik and P. Williams, Surface Science vol.573, no.2-10 (2004) 291-309,
[2] T. Janssens, C. Huyghebaert, W. Vandervorst, this conference

0 10 20 30 40 50 60
0.1
1


Y
Ge
3keV Y
Ge
0.5keV
Y
Ge
0.27keV Y
Si
0.27keV
S
p
u
t
t
e
r

Y
i
e
l
d

(
a
t
o
m
s
/
O

a
t
o
m
)
Impact angle

Fig. 1: Angular dependence of Si (open symbols)
ad Ge (closed symbols) sputter yields under O
2
+

bombardment.
FUN1-O-Mo-B09
25
Processes active in group IB secondary ion formation/survival:
Measurements of work function and electronic structure

P.A.W. van der Heide *.

Centre for Materials Chemistry (CMS), Chemistry Department, 136 Fleming, University of Houston, Houston, Texas
77204-5003, U.S.A.
pvanderheide@uh.edu


Secondary ion production from Cu, Ag and Au substrates under 1keV Cs
+
primary ion impact are
examined by comparing both positive and negative secondary ion yield variations with work
function variations, and intensities of the plasmon loss features noted in x-ray photo-electron
spectroscopy. With the exception of the low energy secondary ions of Ag
-
, all exhibited trends
consistent with the electron tunnelling model, i.e. correlations with work function were noted. The
plasmon loss structure from Ag reveals excitation in the form of 4d core hole production. When
present in the departing population, this would face a high probability of being filled via charge
transfer from the 4s-5p band, i.e. Ag
-
formation. A scaling between the intensities of plasmon loss
peaks from Cu, Ag and Au and the work function dependence, or lack of, is also noted. This confers
with the above arguments and suggests that some fraction, of the Cu
-
and Au
-
secondary ions also
arise from collective oscillation induced core hole formation.
FUN1-O-Mo-B10
26
Statistical model for evaluating the relative contribution of different
Si
k+
bond states to the ionisation probability of Si
+
sputtered from SiO
x


K. Wittmaack
a,
* F. Friedrich
b
and V. Betz
b

GSF-National Research Centre for Environment and Health
a
Institute of Radiation Protection
b
Institute of Biomathematics and Biometry
85758 Neuherberg, Germany
wittmaack@gsf.de


The ionisation probability, , of sputtered atoms is the key parameter characterising the yield of
secondary ions emitted from an ion bombarded solid. It has been known for a long time that is
strongly dependent on the chemical composition of the sample. Of particular interest from an
analytical point of view is the strong enhancement of
+
, the ionisation probability of positively
charged secondary ions, produced by the presence of oxygen in the topmost layer(s) of the eroded
sample. Experimental data suggest that individual oxygen atoms produce only a small enhancement
compared to the case of full oxidation. However, quantitative data for
+
(k), i.e. for different bond
states k, are not known in any detail.
The purpose of this study was to determine relative ionisation probabilities,
r
+
(k) =

+
(k)/
+
(k=0), for the emission of Si
+
from inert-gas bombarded silicon containing oxygen at
different concentration levels. The ionisation probability for pure silicon is denoted
+
(k=0),
equivalent to a sample with all atoms in bond state Si
0
. The oxygen concentration, c, is counted
in normalised units, c = 1 denoting full oxidation (SiO
2
). The occupation of states k was
calculated under the assumption of a purely statistical distribution. This assumption should be
justified at least at low oxygen concentrations. The frequency distributions P(k,c) were found to
vary monotonically, with maxima at c = k/4. P(0,c), for example, has a maximum at c = 0 (pure
silicon) and decreases steadily with increasing c; P(2,c) exhibits a maximum at c = , as one
might expect intuitively, and vanishes for c = 0 and c = 1. The contribution of each bond state to
the total ionisation probabilities
+
(c) is P(k,c)
+
(k). Hence
( ) ( ) ( ) k c , k P c
k
+
=
+

=
4
0
. (1)
Experimental data were taken from measurements of the secondary ion yield of Si
+
emitted from
argon bombarded silicon, doped with oxygen by implantation [1]. The effect of oxygen
incorporation on the Si
+
yield becomes particularly clear from data in the form
( ) ( ) ( ) { }1 0 = =
+ + +
k c c
r
, (2)
i.e., by subtracting the relative ionisation probability due to pure silicon. The experimental data for

r
+
(c) could be described very well by the statistical model using the following state dependent
parameters:
r
+
(k=1) = 6,
r
+
(2) = 25,
r
+
(3) = 3000, and
r
+
(4) = 5000, with typical uncertainties
of about 20% for 1 k 3. The uncertainty for k = 4 is larger due to the lack of data in the range
c 0.4. Conceivable deviations from the pure statistical model are discussed.


[1] K. Wittmaack, Surf. Sci. 112 (1981) 168

QUA-O-Mo-B11
27
SIMS Quantification of Binary Alloys and Composition Depth
Profiling of Multilayers Using a Buckminsterfullerene (C
60
) Ion

K. J. Kim
a
*, D. W. Moon
a
, C. J. Park
a
, P. Chi
b
, D. Simons
b
and G. Gillen
b


a
Division of Chemical Metrology and Materials Evaluation, Korea Research Institute of Standards and Science,
P.O.Box 102, Yuseong, Daejeon 305-600, Korea
b
Surface and Microanalysis Science Division, National Institute of Standards and Technology, Gaithersburg, MD
20899-8371, USA
kjkim@kriss.re.kr


Quantitative depth profiling is one of the most important research subjects in surface analysis.
Generally, x-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES) are
used for the quantitative surface analysis of major elements in multi-component systems. Secondary
ion mass spectrometry (SIMS) is a powerful technique for the in-depth analysis of solid materials.
However, SIMS is difficult to apply for the quantitative analysis of major components due to severe
matrix effects. Therefore SIMS is more commonly used for the quantitative analysis of minor
impurities.
Fe-Ni and Pt-Co alloy thin films were developed as certified reference materials (CRMs) for
quantitative surface analysis of major components. Three alloy films with different compositions
for each binary system were grown on Si (100) wafers by ion beam sputter deposition. The
compositions of Fe-Ni alloy thin films were certified by an isotope dilution method using
inductively coupled plasma-mass spectrometry (ICP-MS) and those of Pt-Co alloys were certified
by ICP-optical emission spectroscopy (OES). Ni/Fe and Pt/Co multilayers were also grown by the
same method.
An ion beam of buckminsterfullerene (C
60
+
) has been reported to be useful for depth profiling of
a metallic multilayer by lowering the effective sputtering energy and prohibiting surface
topographic development. In this study, a C
60
+
ion beam was studied as a sputtering source for the
quantitative analysis of binary alloy films and the quantitative depth profiling of multilayer films.
Calibration curves were derived from linear fits between the nominal compositions and the SIMS
compositions calculated using relative sensitivity factors from reference alloy films (Fe
51
Ni49,
Pt
40
Co
60
). SIMS depth profiling was performed with a magnetic sector SIMS system using 14.5
keV impact energy C
60
+
ions and negative ion detection. The calibrated SIMS compositions of Fe-
Ni alloy films showed a slope of 1.034 and an offset value of -1.89 %. No interface artefacts were
found in a depth profile of an Fe/Ni multilayer. However, for Pt-Co alloy films, the calibration line
slope was 0.898 and the offset value was 3.04 % due to matrix effect.
The severe interface artefact was also observed in a depth profile of a Pt/Co multilayer and it was
quantitatively correlated with a gradual variation of matrix composition through the Pt/Co and
Co/Pt interfaces. The interface artefact could be removed by conversion of the profile to a
composition depth profile using the calibration curve. The depth resolutions of a Pt/Co multilayer
derived from the composition depth profile using an 84 %-16 % definition were much larger than
those measured from the original depth profile.
QUA-O-Mo-B12
28
Quantitative interpretation of the TOFSIMS decay data for the
analysis of layer closure by ALD

W. Vandervorst, T. Conard, J. Wolstenholme

a
IMEC, SPDT/MCA, Kapeldreef 75, 3001 Leuven, Belgium
b
ThermoElectron, East Grinstead, United Kingdom
Email: vdvorst@imec.be


Future generations of semiconductor devices will require the use of ultra-thin layers of high-k
materials (e.g. hafnium oxide or hafnium silicate) as gate dielectric materials in their CMOS
transistors. These materials will be deposited using methods such as atomic layer deposition (ALD).
In growing these layers, the aim is to achieve uniformity of thickness over the whole of the
semiconductor wafer.
However, ALD growth suffers from island formation depending on the starting surface. The
growth quality can be usually investigated by looking at the decay of the substrate intensity as a
function of surface coverage [1,2] and/or Low Energy Ion Spectrometry. Whereas the TOFSIMS
methodology is much faster than LEIS, it only has led to qualitative results as the quantitative
interpretation of the decay lengths has been hampered by uncertainties related to the escape depth of
a secondary ion and ionization probabilities, among others caused by possible reactions at the high-
k/Si interface. An additional question which has been raised is whether one could deduce from the
decay length, eventual differences in surface coverage versus a varying thickness of the grown
islands.
We have developed now a model which allows to calculate the TOFSIMS intensity for a bilayer
system including the ionisation effect from the substrate, the difference in growth mode (random,
preferential) and ion escape depth. In this way it is possible to conclude from a growth curve
whether the TOFSIMS decay reflects the (progressive) closure of the film or the increased thickness
of the high k islands. The model is complemented/validated with a similar approach using Angular
Resolved XPS [3] and will be demonstrated for HfO2-high k layers grown on different substrates
which are known to cause a very different ALD-growth [2].


[1] Conard, T.; Vandervorst, W.; Petry, J.; Zhao, C.; Besling, W.; Nohira, H.; Richard, O, Applied Surface Science
vol.203-204 : 400-3 , 15 Jan. 2003
[2] Puurunen, R.L.; Vandervorst, W.; Besling, W.F.A.; Richard, O.; Bender, H.; Conard, T.; Chao Zhao; Delabie, A.;
Caymax, M.; De Gendt, S.; Heyns, M.; Viitanen, M.M.; de Ridder, M.; Brongersma, H.H.; Tamminga, Y.; Thuy Dao;
Toon de Win; Verheijen, M.; Kaiser, M.; Tuominen, M., Journal of Applied Physics vol.96, no.9 : 4878-89 , 1 Nov.
2004
[3] J.Wolstenholme,ICMI, 2005
QUA-O-Mo-B13
29
Activities of SIMS Standardization in ISO/TC 201/SC6

Yoshikazu Homma

Department of Physics, Tokyo University of Science
Shinjuku, Tokyo 162-8601, Japan
homma@rs.kagu.tus.ac.jp


The standardization of surface chemical analysis is proceeding in Technical Committee 201 (TC
201) of the International Organization for Standardization (ISO). Sucommitee 6 (SC 6) is
responsible for the standardization of SIMS and related techniques. So far, the SC 6 activity has
been focused on creating standards of quantification and depth profiling using dynamic SIMS. Four
International Standards have been developed. Two of them are related to the analysis of boron in
silicon, which is one of the most important dopant-matrix systems in the semiconductor industry.
Others are on the determination of relative sensitivity factors from ion-implanted reference
materials, and on the estimation of depth resolution parameters using multiple delta-layer reference
materials. Current activities in standardization of dynamic SIMS expand to shallow depth profiling
(the development of a method for depth calibration in shallow region), and another dopant-matrix
system (the development of a method for depth profiling of arsenic in silicon). Also, SC 6 has
started discussion about standardization of static SIMS. As a first step, a method for confirming
repeatability and constancy of the relative intensity scale in static SIMS is being developed.
QUA-O-Mo-B14
30
Important increase of negative secondary ion sensitivity during SIMS
analysis by neutral cesium deposition

P. Philipp
a
*, T. Wirtz
a
, H.-N. Migeon
a
, H. Scherrer
b


a
Laboratoire dAnalyse des Matriaux, Centre de Recherche Gabriel Lippmann,
41 rue du Brill, L-4422 Belvaux, Luxembourg
b
Laboratoire de Physique des Matriaux, Ecole des Mines, Parc de Saurupt, F-54042 Nancy Cedex, France
philipp@crpgl.lu


The Cation Mass Spectrometer (CMS) is a SIMS prototype developed in our laboratory [1,2] in
order to perform quantitative analysis with optimal sensitivity and high depth and lateral resolution
in the MCs
x
+
and M
-
modes [3]. For this aim, a patented neutral Cs evaporator for varying the Cs
surface concentration over the whole range has been developed and installed on the CMS [4]. The
sputtering and the Cs introduction have been decoupled successfully by applying simultaneously
X
y+
bombardment and neutral Cs deposition. X stands for any element or cluster except Cs.
Currently the CMS is equipped with a Cs
+
and a Ga
+
gun. These guns have been used for
studying the useful yield variations of negative secondary ions (Si
-
, Al
-
, Ni
-
, In
-
, P
-
, Ga
-
, As
-
) with
respect to the Cs surface concentration. The Cs surface concentration was calculated from
simulations realized with the TRIDYN code [5]. Furthermore the observed variations of the useful
yield were linked to work function shifts measured by recording energy spectra of secondary ions.
Finally the influence of the electron affinity of the analyzed elements on secondary ion ionization
probability became visible. Qualitative agreement with the predictions of the electron tunnelling
model was obtained.
Several applications will give further evidence of successful optimization of the useful yield for
elements with high electron affinity.


[1] T. Mootz, B. Rasser, P. Sudraud, E. Niehuis, T. Wirtz, H.-N. Migeon in: A Benninghoven, P. Bertrand, H.-N.
Migeon, H. W. Werner (Eds.), Secondary Ion Mass Spectrometry, SIMS XII, Elsevier, Amsterdam (2000) p. 233
[2] P. Philipp, T. Wirtz, H.-N. Migeon, H. Scherrer, Appl. Surf. Sci. 231-232 (2004) 754-757
[3] T. Wirtz, H.-N. Migeon, H. Scherrer, Int. J. Mass Spectrom. 225 (2003) 754-757; T. Wirtz, H.-N. Migeon, Surf.
Science, 557 (2004) 57-72; T. Wirtz, H.-N. Migeon, Surf. Science 561 (2004) 200-207
[4] T. Wirtz, H.-N. Migeon, Appl. Surf. Sci. 231-232 (2004) 940-944
[5] W. Mller, W. Eckstein, Nucl. Instr. and Meth. in Phys. Res. B 2 (1984) 814; W. Mller, W. Eckstein, J. P.
Biersack, Comput. Phys. Commun. 51 (1988) 355

QUA-O-Mo-B15
31
Study of the Pd-Rh interdiffusion by ToF-SIMS, RBS and PIXE:
Semi-quantitative depth profiles with MCs
+
clusters

L. Houssiau
a,*
, J. Brison
a
R. Hubert
b
and S.Lucas
b

a
University of Namur (FuNDP), LISE laboratory; 61, rue de Bruxelles, B-5000 Namur, Belgium
b
University of Namur (FuNDP), LARN laboratory; 61, rue de Bruxelles, B-5000 Namur, Belgium


The
103
Pd radio-isotope is used in brachytherapy, a cancer treatment using radioactive
implants. It is produced by nuclear reactions on Rh targets, from which it is extracted. One
extraction method consists in annealing the Rh irradiated target under vacuum. By diffusion and
evaporation
103
Pd is extracted keeping the Rh in a solid form.
The Pd-Rh interdiffusion has then been studied by ToF-SIMS, RBS and PIXE. Sandwich
Pd(60nm)/Rh(200nm) layers were deposited by DC-magnetron on glassy carbon substrates and
were subsequently annealed up to 1000C in order to measure Pd diffusion into Rh. Those layers
were then profiled by ToF-SIMS using Cs
+
. Large PdCs
+
and RhCs
+
yields were measured and used
for profiling since the clusters are less sensitive to matrix effects.
Nevertheless, several calibration steps were necessary to convert the ToF-SIMS profiles into
real diffusion depth profiles. Homogeneous Rh
x
Pd
1-x
coatings were processed with various
concentrations, they were analyzed by PIXE, RBS and ToF-SIMS. The ToF-SIMS [PdCs
+
]/[RhCs
+
]
ratios were plotted vs. the Pd/Rh ratios obtained by PIXE and an excellent linear correlation was
found, allowing the conversion of PdCs
+
ion yields into Pd concentration. Secondly, the sputtering
yields were measured and were found to vary linearly from 5.2 in pure Rh to 7.5 in pure Pd. That
allowed us to calibrate the yield-axis of the TOF-SIMS profiles in terms of Pd concentration and the
sputtering time-axis in terms of depth.
All ToF-SIMS diffusion depth profiles were then converted. A clear relation between the
annealing temperature and the Pd diffusion in the Rh layer was found. In summary, this work shows
that ToF-SIMS can successfully be used to probe and quantify diffusion, following preliminary
calibrations.
QUA-O-Mo-B16
32
The peculiarities of secondary negative ions emission under Cs
bombardment in a presence of oxygen

A. Merkulov
a,
*

a
CAMECA, 103 bld. Saint-Denis, 92400 Courbevoie Cedex
Email address: merkulov@cameca.fr


Ion yields of elements in 3
d
, 4
th
, 5
th
periodic table group emitted under Cs bombardment in a
presence of oxygen are recorded. Different semiconductor crystalline targets as monatomic as
well as binary compounds such as Si, Ge, SiGe, and SiC are employed. The ion yield variation
on oxygen partial pressure in the analytical chamber obtained for different ions allows to take
step forward to development of secondary ion emission model from solids. Electron tunneling
ionization model utilization is straitened as obtained results can not be satisfactory explained
within the model. Computer simulation of the oxygen surface concentration is performed.
Influence of the variable ion density of Cs bombardment on recorded ion yield is investigated.
Possible ways of practical utilization the ion yield enhancement effect for quantitative analysis of
ultra-shallow semiconductor structure and interfaces will be discussed.
FUN-P-Mo-P01
33
STATIC SIMS RESULTS OF A VAMAS INTERLABORATORY
AND THE PROTOCOL FOR A NEW STUDY

I.S.Gilmore
*
, F.M.Green & M.P Seah

National Physical Laboratory, Teddington, Middlesex, UK
Tel: +44 (0)20 8943 6922; Fax:+44 (0)208 8943 6453;
e-mail: Ian.Gilmore@npl.co.uk


For many years Static SIMS has been considered as an unreliable technique. All of this is now
beginning to change with excellent instrumentation and the development of reference methods and
procedures. Here we shall present a summary of the results of the second VAMAS static TOF-
SIMS inter-laboratory study [1]. This major study involved data from 32 laboratories from 16
countries with more than 1000 spectra!
The principal objectives are (i) to determine the repeatability of instruments, (ii) to determine the
reproducibility between laboratories and (iii) to evaluate variations in spectral response between
different types of SIMS instruments. Three reference materials were used in this study, a thin spin
cast polycarbonate (PC) film on a silicon wafer, a thin layer of polystyrene oligomers on
polycrystalline silver (PS) and PTFE. Excellent repeatabilities are found with 85% of instruments
achieving an average repeatability of 1.9%. A Relative Instrument Spectral Response (RISR) is
used to evaluate variations in the spectral response between different generic types of instrument.
The high quality of the data here allows the effects of primary ion type, detector aperture and
detection efficiency of high mass ions to be studied in detail. For instance spectra for Ga primary
ions and Cs primary ions can be related at a 4.5% level. Using the RISR the equivalence of spectra
between instruments can be as good as 4%. However, without the RISR spectra vary in relative
intensities by more than 250%. Part of this work is now incorporated in a draft ISO standard for
repeatability and constancy of the relative intensity scale.
In this work there have been two interlaboratory studies (1) Static SIMS Interlaboratory study - a
survey of the issues [2] and (2) TOF-SIMS Interlaboratory study - evaluating repeatability and
reproducibility and testing G-SIMS [1]. The above results develop the platform and show the need
for a third study (3) Static SIMS Interlaboratory study - repeatability and constancy of the relative
intensity scale, mass scale calibration and quantification. The protocol and participation details for
the third study to provide data to validate the draft standard, study a procedure to calibration the
mass scale [3] and to evaluate basic aspects of quantification using SIMS will be discussed.


[1] I S Gilmore, M P Seah and F M Green, submitted to Surf. Interface Anal.
[2] I S Gilmore and M P Seah, Surf. Interface Anal., 29 (2000) 624.
[3] F M Green, I S Gilmore and M P Seah, these proceedings.

FUN-P-Mo-P02
34
Strong composition-dependent variation of MCs
+
sensitivity factors
in TiO
x
and GeO
x
(x 2) films

Hubert Gnaser
1,2,*
, Yongkang Le
3
, Weifeng Su
3


1
Department of Physics, University of Kaiserslautern, D-67663 Kaiserslautern, Germany
2
Institute for Surface and Thin Film Analysis, University of Kaiserslautern, D-67663 Kaiserslautern, Germany
3
Department of Physics, Fudan University, Shanghai 200433, PR China
*
gnaser@rhrk.uni-kl.de


Quantification still constitutes a major limitation of SIMS analyses, in particular for major
components. This problem can often be alleviated by employing MCs
+
ions (where M designates
the analyte of interest), yielding relative sensitivity factors that exhibit little (or no) dependence on
the composition [x,xi]. Unfortunately, for several important materials like oxides this favorable
condition appears not to hold. In the present work, we examine the use of MCs
+
ions for the
quantitative evaluation of TiO
x
(0.2 x 2) and GeO
x
(0.001 x 2) films. To obtain reference
data, Auger-electron spectroscopy (AES), secondary-neutral mass spectrometry (SNMS) and
energy-dispersive X-ray spectroscopy (EDX) were used.
A detailed comparison of the depth profiles recorded on these oxide films by MCs
+
mass
spectrometry with those obtained by AES or SNMS revealed that the relative sensitivity factors
derived to calibrate the O/Ti and O/Ge concentration ratios depend pronouncedly on the oxygen
concentration. Specifically, with increasing oxygen content OCs
+
ions form much more efficiently
(as compared to TiCs
+
or GeCs
+
ions), an enhancement amounting to more than a factor of ten.
Concurrently, the formation of TiOCs
+
or GeOCs
+
ions increases drastically. From these
comparative data, the oxygen-concentration dependence of the relative sensitivity factors for
OCs
+
/TiCs
+
and OCs
+
/GeCs
+
ions could be established. These relations provide the possibility of an
accurate quantification of TiO
x
and GeO
x
films with a wide range of values of x by means of MCs
+

mass spectrometry.


[x] H. Gnaser, J. Vac. Sci. Technol. A 12, 452 (1994).
[xi] H. Gnaser, in Recent Research Developments in Vacuum Science & Technology, Vol. 4, S.G. Pandalai, Ed.,
(Transworld Research Network, Trivandrum, 2003), p. 111.
FUN-P-Mo-P03
35
Surface roughness effects in quantitative analysis of ToF-SIMS data

J.C. Armitage
a
, D.A. Armitage
b
, D. Briggs
a
, M.C. Davies
a
*

a
Centre for Surface Chemical Analysis and School of Pharmacy, The University of Nottingham,
Nottingham, NG7 2RD, UK.
b
Biomaterials and Tissue Engineering, Eastman Dental Institute, University College London,
256 Grays Inn Road, London, WC1X 8LD, UK.
martyn.davies@nottingham.ac.uk


ToF-SIMS provides highly specific chemical information on surfaces. However, there are many
questions about its use as a quantitative tool. This study focuses on the effect of roughness on
obtaining reproducible quantitative information. As a model system we have investigated a series of
gold coated abrasive papers with a maximum particle size ranging from 15 to 58 microns. As these
systems exhibit random roughness, precision measurement samples with defined roughness have
also been investigated and a gold coated microscope slide with nm level roughness has been
employed as a control. Each sample was analysed in imaging mode and the variance in ion yield
calculated across the image. Surface roughness was measured by atomic force microscopy and laser
profilometry. We have found a positive correlation between increasing roughness and increasing
variance in ion yield. These findings suggest that the topography of a surface may be fundamental
in ascertaining whether the sample can be considered as a candidate for utilising meaningful
quantitative data.
FUN-P-Mo-P04
36
Accurate SIMS depth profiling for high concentration samples

S.Saito*, J.Yamagata, T.Nakamoto,
Y.Miyakoshi, Y.Nakamura, Y.Fujiyama

Tsukuba Laboratory, Sumika Chemical Analysis Service, Ltd.,
6 Kitahara, Tsukuba, Ibaraki, 300-3266, Japan
Email: s.saito@scas.co.jp


Measurements conducted in SIMS are highly accurate when dealing with samples of ppb-ppm
dopant order in monocrystal silicon. In these cases, relative standard derivation (RSD) is reduced to
1-2%. Concentration and depth varies in semiconductor samples. Recently, there is an increase in
the ion implantation process when the peak concentration is the percent order. The assay accuracy
of highly concentrated samples of B, BF
2
and P, etc, increases notably. However, assay accuracy
suffers if the measurement is repeatedly carried out in highly concentrated samples of As, In. [1]
Detection of the stabilized matrix ion is important when carrying out quantitative analysis in
SIMS. After such quantitative analysis of the compound semiconductor is done, ions such as Ga,
As, and In etc. are detected in the GaAs samples while ions such as Ga, GaN etc. are detected in the
GaN samples as a matrix ion. In the GaN sample, a stabilized matrix ion can be detected. This is
not the case, however, in the GaAs sample, where a stabilized matrix ion cannot be detected. In
both cases where the detection of the stabilized Ga ion has not been detected, it was announced that
the problem was with the electronegativity. We, however, regard that As, In do not stabilize due to
different factors.
The above outcomes are a result of measuring the high concentration and compositions that
exceeded the range of SIMS. However, there are a phenomena which differ in each element in
regards to its instability. Also, it is a result of O
2
+
and Cs
+
beams. We believe that stabilization did
not occur because As, In is a low-melting-point element. Therefore, in the SIMS measurement, we
observed the physical damage which the primary beam inflicted on the sample. It was observed how
the sample temperature of the measured area changed when the primary ion beam energy and
current density were changed. As a result, we attempted to realize satisfactory measurement
stability of low-melting-point elements.


[1] M.Tomita, et al., Proceedings of Secondary Ion Mass Spectrometry SIMS XIII, Elsevier (2003) 465.
FUN-P-Mo-P05
37
Chemical derivatization technique in ToF-SIMS for quantification
analysis of surface amine groups

Tae Geol Lee
a,
*, Jinmo Kim
b
, Donggeun Jung
b
, Dae Won Moon
a


a
Nano-Surface Group, Korea Research Institute of Standards and Science (KRISS), P.O.Box 102, Daejeon 305-600,
Korea
b
Department of Physics, Brain Korea 21 Physics Research Division and Institute of Basic Science, Sungkyunkwan
University, Suwon 440-746, Korea
tglee@kriss.re.kr


Controlling the surface density and selectivity of specific functional groups that exist on the
surface is crucial in biomaterial applications since functional groups control the immobilization of
proteins or cells. The surface amine density of plasma-polymerized ethylenediamine (PPEDA) thin
film deposited on a glass surface was controlled as a function of deposition plasma power and
quantified using UV-visible absorption spectrometry [1]. To compare with the UV-visible
absorption spectrometry, a chemical derivatization technique in time-of-flight secondary ion mass
spectrometry (ToF-SIMS) was developed to quantify the surface density of amine groups of
PPEDA thin film. Chemical tags were hybridized with the surface amine groups and were detected
in ToF-SIMS spectra as characteristic molecular secondary ions. We found good linear correlations
between the surface densities of the amine groups and the normalized intensities of several
secondary ions.


[1] J.H. Moon, J.W. Shin, S.Y. Kim, J.W. Park, Langmuir 12 (1996) 4621-4624.
FUN-P-Mo-P06
38
SIMS Quantification of Matrix and Impurity Species in Al
x
Ga
1-x
N

C. J. Gu
a
, F. A. Stevie
a*
, Y. N. Saripalli
b
, M. Johnson
b
, D. Griffis
a
,

a
Analytical Instrumentation Facility, North Carolina State University,
Box 7531, 2410 Campus Shore Drive, Raleigh, NC 27695, USA
b
Photonics Research Center, North Carolina State University,
Box 8617, 2410 Campus Shore Drive, Raleigh, NC 27695, USA
*Email: fred_stevie@ncsu.edu


New applications in optoelectronic devices and high power electronic devices continue to be
developed using Al
x
Ga
1-x
N. The quantification of matrix and impurity species in Al
x
Ga
1-x
N is
essential for matrix composition analysis, dopant control, and impurity control. Dynamic SIMS
quantification in Al
x
Ga
1-x
N

is challenging because of matrix and charging effects. The secondary
ion yield of matrix and impurity species varies in Al
x
Ga
1-x
N with different AlN mole fraction (x).
Al
x
Ga
1-x
N also shows charging effects when the material becomes more insulating with increasing
AlN mole fraction.
In this work, a SIMS quantification method is developed for the Al
x
Ga
1-x
N system over the range
of x = 0 to 1. A set of Al
x
Ga
1-x
N films prepared on SiC or sapphire substrates with AlN mole
fraction ranging from 0 to 0.58 were implanted with
16
O,
24
Mg and
29
Si. Very high Al concentration
Al
x
Ga
1-x
N samples were created using high dose ion implantation of Ga into AlN. With these
samples, calibration curves of matrix ion intensity ratio for quantification of Ga and Al matrix
constituents, Relative Sensitivity Factors (RSF) for impurity species, and sputter rate as a function
of Al mole fraction were obtained. Using these calibration curves, the matrix and impurity
concentrations of an unknown Al
x
Ga
1-x
N sample can be determined, and the elemental composition
of multi-layer Al
x
Ga
1-x
N samples can be measured. Electron beam charge neutralization methods
for high Al content Al
x
Ga
1-x
N are shown. The calibration curves using O
2
+
bombardment and
positive secondary ion extraction, using Cs
+
bombardment and negative secondary ion extraction,
and using the MCs
+
[1] technique are presented.


[1] Y.Gao, J. Appl. Phys. 64 (7) (1988) 3760
FUN-P-Mo-P07
39
Round-Robin Study of Arsenic Implant Dose Measurement in Silicon
by SIMS

D. Simons
a,
*, K. Kim
b
, R. Benbalagh
c
, J. Bennett
d
, A. Chew
e
, D. Gehre
f
, T. Hasegawa
g
, C.
Hitzman
h
, J. Ko
i
, R. Lindstrom
a
, B. MacDonald
j
, C. Magee
k
, N. Montgomery
l
, P. Peres
c
, P.
Ronsheim
m
, S. Yoshikawa
n
, M. Schuhmacher
c
, W. Stockwell
j
, D. Sykes
e
, M. Tomita
o
, F. Toujou
n
,
and J. Won
p

a
National Institute of Standards and Technology, Gaithersburg, MD, USA;
b
Korea Research Institute of Standards and
Science, Taejon, Korea;
c
Cameca, Courbevoie, France ;
d
ATDF, Austin, TX, USA ;
e
Loughborough Surface Analysis
Ltd, Loughborough, UK;
f
AMD, Dresden, Germany;
g
Toray Research Center Inc., Shiga, Japan;
h
Full Wafer
Analysis, Santa Clara, CA, USA;
i
Hynix Semiconductor Inc., Ichon, Korea;
j
Spansion, Sunnyvale, CA, USA;
k
Evans
East, East Windsor, NJ, USA;
l
Cascade Scientific, Uxbridge, UK;
m
IBM Microelectronics, Hopewell Junction, NY,
USA;
n
Matsushita Electric Industrial Co., Osaka, Japan;
o
Toshiba Corp., Yokohama, Japan;
p
Samsung Advanced
Institute of Technology, Yongin, Korea
Email: david.simons@nist.gov

An international round-robin study was undertaken under the auspices of SIMS subcommittee SC
6 of International Organization for Standardization Technical Committee TC 201 on Surface
Chemical Analysis. The purpose of the study was to determine the best analytical conditions and
the level of interlaboratory agreement for the determination of the implantation dose of arsenic in
silicon by SIMS. Motivations for this study were (a) the relatively poor interlaboratory agreement
that was observed in a previous round-robin study before a certified reference material had become
available; (b) the observation that the use of Si
3
-
as a matrix species combined with AsSi
-
detection
may result in improved measurement repeatability compared with Si
2
-
[1]; and (c) the observation
that point-by-point normalization can extend the linearity of SIMS response for arsenic in silicon
beyond 1x10
16
/cm
2
[2].
Fifteen SIMS laboratories participated in this study, as well as two laboratories that performed
Low energy Electron-induced X-ray Emission Spectrometry (LEXES) and one that made
measurements by Instrumental Neutron Activation Analysis (INAA). The labs were asked to
determine the implanted arsenic doses in three unknown samples using as a comparator Standard
Reference Material 2134, with a certified dose of 7.33x10
14
atoms/cm
2
. The unknown samples had
nominal arsenic doses of 2x10
13
atoms/cm
2
, 8x10
14
atoms/cm
2
, and 1.5x10
16
atoms/cm
2
, all
implanted at 100 keV. The SIMS labs were requested to perform their analyses at low mass
resolving power using Cs
+
ion bombardment and AsSi
-
detection. Matrix signals to be monitored
were Si
2
-
and Si
3
-
, and matrix normalization was to be done both point-by-point and to the average
matrix signal. A few labs also made measurements at high mass resolving power or with O
2
+
ion
bombardment and detection of As
+
and Si
+
.
As expected, the use of a common reference material by all laboratories resulted in much better
interlaboratory agreement than was seen in the previous round-robin that lacked a common
comparator. The relative standard deviation among laboratories was less than 4 % for the medium-
dose sample, and somewhat larger for the low- and high-dose samples. There was no clear effect of
the use of Si
2
-
vs. Si
3
-
matrix signals on within- or between-laboratory repeatability. The high-dose
sample showed a significant difference between point-by-point and average matrix normalization
because the matrix signal decreased in the vicinity of the implant peak, as previously observed [2].
The dose from point-by-point normalization was in closer agreement with that determined by
INAA.
[1] P.H. Chi, D.S. Simons, J. M. McKinley, F.A. Stevie, and C.N. Granger, J. Vac. Sci. Technol. A 20 (2002) 688-692
[2] M. Tomita et al., Appl. Surf. Sci. 203-204 (2003) 465-469
FUN-P-Mo-P08
40
PLA-PMMA blends : a study by XPS and ToF SIMS

D. Cossement
1*
, R. Gouttebaron
1
, M. Hecq
1
, V. Cornet
2
, R. Lazzaroni
2


1
Laboratoire de Chimie Inorganique et Analytique
2
Laboratoire de Chimie des Matriaux Nouveaux
Materia Nova, Site Initialis, 1 Avenue Nicolas Copernic, B-7000 Mons, Belgique
damien.cossement@umh.ac.be


Polymethylmethacrylate (PMMA) and polylactic acid (PLA) are known for a long time for being
biocompatible. In addition to this, PLA is biodegradable. The combination of PLA with PMMA
would allow to make implants, prostheses, plastic packaging interesting from an environmental
point of view.
The aim of this paper is to determine what could be the possibilities of quantification by ToF-
SIMS for some polymer blends. XPS being quantitative, we first used this technique to determine
the compositions of different PLA/PMMA blends, over 60-100 depth. By XPS deconvolution of
the C1s signal, we found a very good agreement with the initial compositions. For ToF-SIMS
treatment data, we used PCA analysis on negative spectra allowing to discriminate one polymer
from the other one. By Partial Least Square Regression, we found also a good agreement between
the ToF-SIMS predicted and initial compositions. This shows that, as previously shown in the
literature
1
, if the secondary fragments are correctly selected, ToF-SIMS can lead to quantitative
results. In addition, such a stated agreement between XPS (60 analyzed) and ToF-SIMS (10
analyzed) measurements show that there is no segregation of one of the two polymers onto the
surface.


[1] Weng, L.-T. ; Chan, C.-M. Appl. Surf. Sci. 2003, 203-204, 532
QUA-P-Mo-P09
41
Sputter Yields in Diamond Bombarded by Ultra Low Energy Ions

B. Guzmn de la Mata
a,
*, M. G. Dowsett
a
, D. Twitchen
b



a
Advanced SIMS Projects. Department of Physics. University of Warwick. CV4 7AL. UK.
b
Element Six Ltd. King's Ride Park, Ascot. SL5 8BP UK
Email: B.Guzman-de-la-Mata@warwick.ac.uk


Artificial diamond has a huge range of potential applications in micro-electronics, engineering,
and chemistry. When undoped, single crystal CVD diamond combines high thermal conductivity
with very high electrical resistivity and breakdown strength, and when doped it has a high carrier
mobility over a wide temperature range. It is therefore an ideal material for high power, high
voltage electronic devices, and for use in extreme environments. Diamond process development
requires parallel development in characterization techniques such as ultra low energy SIMS
(uleSIMS), especially in the ability to depth profile for impurities and dopants at high depth
resolution.
As a contribution to the background knowledge required we have measured the sputter yields of
single crystal CVD diamond using O
2
+
, Cs
+
and Ar
+
primary ions in the energy range 300 eV to
2 keV. We compare these with yields for silicon and GaAs. We show that the erosion rates with
oxygen are 10 times what would be expected from ballistic processes and essentially energy
independent in the measured range. This result agrees with the anomalously high sputter yield
observed in the ion etching context [1]. Conversely, positive ion yields for elements such as boron
are very low in comparison with silicon. This points to a reactive ion etching process liberating CO
or CO
2
rather than sputtering as the principal erosion process.
This is both problematic and beneficial for SIMS analysis. Oxygen can be used to reach buried
structures in diamond efficiently, and the effects of the near-normal incidence beam are planarizing
as they are in silicon. Conversely, since positive ion yields are low, alternative probes or strategies
must be found for high sensitivity profiling of electropositive elements.


[1] S. Kiyohara, I. Miyamoto, Nanotechnology, 7, (1996) 270.
QUA-P-Mo-P10
42
Comparative study of negative cluster emission in sputtering of Si, Ge,
and their oxides

M. Perego
a,*
, S. Ferrari
a
and M. Fanciulli
a


a
Laboratorio MDM-INFM, Via Olivetti 2, 20041 Agrate Brianza (Mi) Italy

*E-mail addres: michele.perego@mdm.infm.it


The process of ion formation under primary ion bombardment is a very complex phenomenon
leading to the emission of charged [1] and neutral [2] clusters. In a recent work [3] we investigated
the emission of negative cluster ions from Si
x
Ge
1-x
alloys with Ge content ranging from 0 to 1. We
found that, under Cs
+
bombardment, different clusters signals show a different dependence on Ge
concentration. Surprisingly Si
n
-
clusters with n3 are less sensitive to Ge concentration than Si
-
and
Si
2
-
. Also Ge
n
-
clusters show a peculiar behaviour. Very strong matrix effects were observed for Ge
-
. At high germanium concentration the Ge
-
intensity decreases while an opposite behaviour is
followed by the other clusters. Moreover we observed that, in steady state condition, the fractions of
silicon and germanium atoms in the sputtered ion flux are equivalent to their elemental fractions in
the alloy. This result is not totally unespected if we consider the observations we made in a
previous work [4] on negative cluster emission from silicon oxide. Despite the large difference
between the silicon and oxygen monoatomic ions, we found that the fraction of oxygen is
approximately only 2 times higher than expected according to the stoichiometry. The aim of the
present work is to complete this study extending the analysis to a GeO
2
matrix and comparing its
mass spectrum with that obtained from SiO
2
. The emission of negative secondary ions from silicon
germanium and their oxides is studied by dual beam time of flight secondary ion mass spectrometry
using low energy Cs
+
ions for sputtering and Ga
+
ions at 25 keV for analysis. A systematic analysis
of the homonuclear (Ge
n
-
, O
n
-
) and heteronuclear (Ge
n
O
m
-
) clusters is presented. Affinities and
discrepancies with the SiO
2
mass spectrum are pointed out. A clear picture of the fragmentation and
ionization processes in silicon and germanium, as well as in their oxides, has been obtained.


[1] A. Benninghoven, W. Sichtermann, S. Storp, Comparative study of Si(111), silicon oxide, SiC and Si
3
N
4
surfaces
by secondaryion mass spectroscopy (SIMS), Thin Solid Films 28, 59-64 (1975)
[2] H. Gnaser, Negative cluster ions in sputtering of Si,SiC and graphite: Abundance distributions, energy spectra snd
fragmentation processes Nucl. Instr. and Meth. B, 164-165, 705-714 (2000)
[3] M. Perego, S. Ferrari, M. Fanciulli, Negative cluster emission in sputtering of Si
1-x
Ge
x
alloys: a full spectrum
approach, Surf. Sci. Submitted
[4] S. Ferrari, M. Perego, M. Fanciulli, Quantitative depth profiling at silicon/silicon oxide interfaces by means of Cs
+

sputtering in negative mode by ToF-SIMS: a full spectrum approach, Appl. Surf. Sci. 203-204, 52-55 (2003)

QUA-P-Mo-P11
43
Non-Linearity and Non-Additivity of Secondary Ion Emission of
Metals and Semiconductors under Cluster Ion Bombardment

U.Kh. Rasulev
*
and S.N. Morozov

Arifov Institute of Electronics, Akademgorodok, 700125 Tashkent, Uzbekistan
E-mail: Rasulev@ariel.uzsci.net


One of the more perspective directions in SIMS improvements, as shown by the recent
studies, is an application of molecular ions as projectiles. However, there is no clear
understanding of the physical nature of the observed significant non-additive enhancement of the
secondary ion emission yield under molecular bombardment and further fundamental studies in
this field are required.
Collision of a molecular ion with a solid creates a unique situation when the atoms of the
molecular projectiles, practically coherently in time and space, interact with the target atoms, each
atom of the bombarding ion interacts with an area of the solid excited or to be excited by another
atom of the same ion. Therefore, it can be expected that great densities of energy transferred to the
solid will lead to experimental manifestation of long discussed so-called non-linear cascades
and/or thermal spikes, and interaction coherence will lead to the molecular effect non-additivity of
the secondary processes, i.e. when the effect created by the molecular ion M
m
is not equal to the
sum of the yields created by the m separate atoms with the same velocity [1].
Cluster ion emission (mass and energy spectra) from a variety of the metal and semiconductor
surfaces upon impact of cluster ions (Au
m
-
(m=1-9); Si
m
-
(m=1-6)) with "SIMS energy" 1<E
o
<10
keV/atom is investigated by tandem magnetic mass spectrometry [2].
The high non-additivity of sputtering of Ta, Nb, V, Au, In, Si as cluster ions M
n
+
has been found
and studied [2-6]. The non-additivity factor K
m,m
depends on projectile energy and velocity,
projectile-target mass ratio, target features and increases with the raise in n and m reaching, for
example for m=3, m=1, E
o
=6 keV/atom, K
3,1
=60 for Ta
10
+
, 75 for Nb
10
+
, 80 for V
10
+
, 85 for Au
9
+

and 25 for In
12
+
.
The direct experimental proofs of developing the high-density cascades or thermal spikes making
a considerable contribution to atomic ion emission of metals under molecular bombardment have
been obtained [3,5].
Under semiconductor bombardment by molecular ions, the effect of the significant raise in the
yield of valence-saturated impurity-containing cluster ions has been found and studied. For
example, the yield of the Si
3
B
+
, Si
3
C
+
, Si
2
N
+
ions exceeded ~100, ~200 and >1000 times than the
yield of the corresponding B
+
, C
+
, N
+
ions [2,6]. The results have become a basis for a new method
of SIMS analysis using the cluster ions as primary and secondary ones - cluster-SIMS-cluster.


1. Y.LeBeyec, Int.J.Mass Spectrom. Ion Processes 174, (1998) 101
2. Sh.Akhunov, S.N.Morozov, U.Kh. Rasulev, Nucl.Instr. Meth.B 203 (2003) 146.
3. S.N.Morozov, U.Kh. Rasulev, Nucl.Instr.Meth.B 203 (2003) 192.
4. U.Kh.Rasulev. Proceedings XVI Int.Conf.Ion Surface Interaction 2003, Moscow 2003, v.1, p.31-36
5. S.N.Morozov, U.Kh. Rasulev, Technical Phys.Letters 29 (2003) 75.
6. U.Kh. Rasulev, S.N.Morozov, Izv.Akad.Nauk.Ser.Fiz., 66 (2002) 522;68(2004)393.
QUA-P-Mo-P12
44
Comparison of detection efficiencies of negatively charged gold-
alkanethiolate-, gold-sulfur- and gold-clusters in ToF-SIMS

T. Rietmann*, S. Sohn, M. Schrder, D. Lipinsky and H.F. Arlinghaus

Physikalisches Institut, Westflische Wilhelms-Universitt, Wilhelm-Klemm-Str. 10, D-48149 Mnster, Germany
*email address: thomas.rietmann@uni-muenster.de


In order to improve quantification of high mass ions the influence of cluster composition on
detection efficiencies has been studied using a TOF-SIMS IV type time-of-flight secondary ion
mass spectrometer with the extended capability of postaccelerating ions up to 20 keV. In this
experimental study we focus on the comparison of detection efficiencies for three types of
negatively charged secondary cluster ions: gold-alkanethiolate-clusters (Au
x
M
y
-
), gold-sulfur-
clusters (Au
x
S
y
-
) and gold-clusters (Au
x
-
) sputtered from self-assembled monolayers of
hexadecanethiols on gold substrates using 10 keV Ar
+
primary ions. The detection efficiencies were
derived on the basis of a function for the secondary electron yield proposed by Gilmore [1] and a
second order approximated Poisson probability distribution for electron propagation and
amplification within the microchannel plate.
In addition to the well known dependance of detection efficiencies on ion mass and energy,
which has already been studied for positively charged ions [1,2], we were able to show a similar
behaviour for the investigated negatively charged secondary ions. We have observed major
variations among the three types of clusters at similar mass and energy as predicted in a theoretical
approach by Gilmore [1]. The observed differences are due to the different composition of the
investigated clusters which has a major influence on the kinetic ion induced electron emission
within the microchannel plate. For the first time it was possible to experimentally verify these
predictions for detection efficiencies.


[1] I.S. Gilmore, M.P. Seah, Int. J. Mass Spectrom. 202 (2000) 217-229
[2] E. Niehuis, Doctoral thesis, Mnster (1988)
QUA-P-Mo-P13
45
Direct cluster emission and electron capture at sputtering of silicon
under cesium ion bombardment

B. Atabaev

Arifov Institute of Electronics, 33 F. Khodjaeva Street, Tashkent, 700125, UZBEKISTAN

Email: atabaev@ariel.uzsci.net


The yields of neutral and negatively-charged silicon Si
n
(n=1-4) clusters sputtered by 3 keV
cesium ions from silicon crystal were monitored during the evaporated potassium adsorption on
sample surface [1]. The yields of neutral silicon clusters and ionisation probability IP of negatively-
charged ions were determinated by conversion sputtered cluster to negatively ions under scattering
on surface with extremely low work function. The associated work function WF variations were
determinated in situ from the energy shifts of the sputtered ions emission-energy spectra. The total
change in work fuction amounted up to 2,5 eV. The lowering of WF induces an exponential
increase of the negatively-charged cluster emission and ionisation probability IP of the sputtered
silicon cluster ions. The ionisation probability IP negatively-charged carbon cluster ions were
monitored for velocity effect investigation [2]. For monomer and dimer an influence of the velocity
on the ionisation probability was odserved,whereas for larger clusters no distinct dependence was
found. There are two main mechanisms of cluster sputtering- recombination of spatially correlated
recoils and direct cluster emission. The our presented experiments shown that the model of direct
emission and electron capture by sputtered clusters are confirmed. The high ionisation probability
of silicon clusters can be explained by formation of adsorbed on surface small clusters with
molecular electron affinity, direct electron capture from surface and intact emission by precursor
cluster-recoil non-binary collision. On the basis of the above obtained data relating to a strict
correlation between the negatively-charged silicon cluster yield and the change of sputtered surface
work function WF, we can assume that the ionisation probability of clusters can be explained by
direct electron capture in process of electron transition between adsorbed cluster and surface. The
electron capture process increase stability of sputtered silicon clusters.


[1] M. Abdullaeva, B. Atabaev, R Dzabbarganov, NIMB 62, (1991) 43-46.
[2] H. Gnaser , proceedings of the ICACS-19 Conference, Paris, 2001,212.
QUA-P-Mo-P14
46
Energy distributions of atomic and molecular ions sputtered by C
60
+

projectiles

A. Delcorte*, C. Poleunis and P. Bertrand

PCPM, Universit catholique de Louvain, Croix du Sud 1, B-1348 Louvain-la-Neuve, Belgium, e-mail:
delcorte@pcpm.ucl.ac.be


In the process of investigating the interaction of fullerene projectiles with adsorbed organic
layers, we measured the kinetic energy distributions (KEDs) of fragment and parent ions sputtered
from an overlayer of polystyrene (PS) oligomers cast on silver under 15 keV C
60
+
bombardment.
These measurements have been conducted using our TRIFT spectrometer, recently equipped with
the C
60
+
source developed by Ionoptika [1]. For atomic ions, the intensity corresponding to the high
energy tail decreases in the following order: C
+
(E
-0.4
) > H
+
(E
-1.5
) > Ag
+
(E
-3
). In particular, the
distribution of Ag
+
is not broader than those of Ag
2
+
and Ag
3
+
clusters, in sharp contrast with 15 keV
Ga
+
bombardment. A similar observation was made by Sun et al. for Ag atoms and dimers
sputtered from an HNO
3
-etched silver sample and it was explained by the specific energy
dissipation mechanism of C
60
+
projectiles (superheated nanovolume) [2]. Even though the ion
structures and masses are very different, the KED of Ag-cationized PS oligomers resembles that of
Ag
+
and Ag
n
+
clusters. A specific feature of fullerene projectiles is that they induce the direct
desorption of positively charged oligomers, without the need of a cationizing metal atom. The
energy spectrum of these PS
+
ions is significantly narrower then that of Ag-cationized oligomers.
For characteristic fragments of PS, such as C
7
H
7
+
and C
15
H
13
+
, the high energy decay is very steep
(E
-4
- E
-8
), similar to the case of monoatomic ion bombardment. In comparison, reorganized
aromatic ions (C
10
H
8
+
) exhibit a broader distribution, consistent with the higher excitation energy
needed for their formation.
Recent MD simulations modeling a similar sample help us suggest interpretations for some of
the observed behaviors [3], while others remain to be explained. This first report on the energy of
molecular ions constitutes starting material for future fundamental studies of the interaction
between fullerenes and thin organic layers.


[1] D. Weibel, S. Wong, N. Lockyer, P. Blenkinsopp, R. Hill, J. C. Vickerman, Anal. Chem. 75 (2003) 1754.
[2] S. Sun, C. Szakal, E. J. Smiley, Z. Postawa, A. Wucher, B. J. Garrison, N. Winograd Appl. Surf. Sci. 231-232
(2004) 64.
[3] B. Czerwiski, A. Delcorte, B. J. Garrison, N. Winograd, Z. Postawa, Abstract submitted to the 17
th
International
Conference on Ion Beam Analysis, Spain, June 2005.



QUA-P-Mo-P15
47
DECAY REACTIONS OF (SiO
2
)
n
O
-
CLUSTERS: DISSOCIATION
ENERGIES AND STRUCTURES

N.Kh.Dzhemilev*, S.E.Maksimov, L.F.Lifanova, Sh.T.Khojiev, O.F. Tukfatullin

Arifov Institute of Electronics, Uzbek Academy of Sciences, 700125, Tashkent, Uzbekistan
e-mail dzhemil@ariel.uzsci.net


An investigation of cluster decay processes allows obtain new information both about the cluster
emission and about chemical and physical properties of these clusters. In the work we have
measured the kinetic energy release distributions (KERD) of (SiO
2
)
n
O
-
(SiO
2
)
n-1
O

+SiO
2
clusters
(n=2-7) using SIMS with double focusing of Nier-Jonson type [1] within the 10
-6
-10
-4
s time scale
after emission. Clusters were sputtered from silicon by Xe
+
ions with surface blowing by O
2
. In the
technique of the studies of cluster KERD measurements modified by us [2] for ion sputtering was
used. This distribution determines a fraction of the cluster vibrational energy released as a result of
decay and converted into translational energy of the fragments. These translational energies carry
information about the dissociation energies cluster decays.
Using the results of measurements and applying the theory of Klots [3], we have obtained the
dissociation energy for (SiO
2
)
n
O
-
(n=2-7). The comparison between experimental results on the
measurements of dissociation energy of sputtered (SiO
2
)
n
O
-
and theoretically calculated values of
the binding energy of (SiO
2
)
n
structures in their ground states [4,5] have shown their almost
complete identity. This allows suggest, that vibrational energy, which is deposited on concrete bond
and results in the break of SiO
2
, does not depend on O
-
. Therefore, a nucleus of complex ion
consists of SiO
2
monomers, and O
-
anion as charge carrier is located on the outside of a nucleus. In
the frameworks of this suggestion, basing on the calculated theoretically stable structures of neutral
clusters, we have obtained first information about the possible structures of charged dynamically
stable gas-phase (SiO
2
)
n

-
(n=2-7) clusters.


[1] A.D.Bekkerman, N.Kh.Dzhemilev, V.M.Rotstein. Surf. and Interf. Anal. 15 (1990) 587.
[2] I.V.Veryovkin, S.V.Verkhoturov, A.M.Goldenberg, N.Kh.Dzhemilev, Izv. RAN. Ser. Fiz. 58, 3 (1994) 57. (in
Russian)
[3] C.E.Klots, Z. Phys. D21 (1991) 335.
[4] J.A.Harkless, D.K.Stillinger, J.Stillinger. Phys. Chem. 100 (1966) 1098.
[5] W.C.Lu, C.Z.Wang, V.Nguyen, M.W.Schmidt, M.S.Gordon, K.M.Ho. J. Phys. Chem. A 2003, 107, 6936.
QUA-P-Mo-P16
48
FORMATION OF ATOMIC IONS IN FRAGMENTATION OF
SPUTTERED CLUSTERS

N.Kh.Dzhemilev

Arifov Institute of Electronics, Uzbek Academy of Sciences, 700125, Tashkent, Uzbekistan
e-mail dzhemil@ariel.uzsci.net


MD simulations of Ag sputtering by keV-Ar have shown, that the majority of sputtered clusters is
spontaneously fragmented in picosecond range after emission [1]. A mass spectrum is enriched with
small clusters and atoms, and the energy distributions of particles of initial origin - with fragment
particles having narrower distributions.
To assess information, we measured energy distributions of Al
n
+
, Cu
n
+
, Au
n
+
(n=15) in
sputtering by Xe
+
(8,5 keV) using double focusing SIMS with reverse geometry. Studying the most
probable energy (E
m
) and the energy spectra at half-height (
0,5
), characterizing energy
distributions, we have established: a)
m
(Al
+
)<
m
(Al
2
+
)
m
(Al
3
+
), and
E
m
(Cu
3
+
)<E
m
(Cu
+
)<E
m
(Cu
2
+
), that well correlates with [2]; b)
m
and
0,5
for Au
2
+
are abnormally
higher in comparison with Au
+
. c) Negative branches of Cu
+
, Au
+
, Al
+
spectra contain extended
"prepeaks", which are weakly developed for Cu
2
+
, Au
2
+
and are absent for Al
2
+
-Al
4
+
. Energy
distributions transformations can be explained only basing on unimolecular transitions occuring
within time window of ~10
-12
10
-10
s after emission [1].
Theoretical analysis, based on energy balance calculations of dissociating clusters with ionization
potential (IP) included into cluster structure, points to the following. For u
+
,Au
+
fragment ion
formation
3
+

+
+
2
reaction is more probable, than the reaction with neutral atom formation
because IP(M)<IP(M
2
) [3]. For Al
+
formation Al
n
+
Al
+
+Al
n-1
(n=2-7) reaction is more probable,
than Al
n
+
Al
n-1
+
+Al decay [4], because for n=2-14 IP(Al)<IP(Al
n
) [5]. M
+
fragment ion energy
distributions become narrower by the factor of n/(n-k) (k=1,2), than the spectrum of M
n
+
, as
initial kinetic energy of M
n
+
is divided proportionally to the masses of formed fragments. Appeared
part of
+
in nascent M
+
spectra causes
0,5
narrowing and

shift to the range of low energies

of
+
integral distribution.


[1] A. Wucher, B.T.Garrison, Phys. Rev. 846, 8 (1992) 4855.
[2] G. Slodzian, Revue de Phys. 8, (1973) 105.
[3] K. Balasubramanian, Yi.Fend Ring, Chem. Phys. Lett. 159, 5-6 (1989) 452.
[4] N.Kh. Dzhemilev, A.D. Bekkerman, S.E. Maksimov, V.I. Tugushev, Appl. Surf. Sci. 203-204 (2003) 118.
[5] W.A. Saunder, P. Fayet, L. Woeste, Phys. Rev. A39 (1989) 4400.


QUA-P-Mo-P17
49
Steady-state Cs surface concentration on Si and Ge after low energy
Cs
+
bombardment by SIMS

P.Chen
a,b,
*,T.Conard
a
, T. Janssens
a
, and W. Vandervorst
a,b

a
IMEC, SPDT-MCA, Kapeldreef 75, B-3001 Leuven, Belgium
b
KULeuven, INSYS, Kasteelpark Arenberg, B-3100 Leuven, Belgium
email: Ping.Chen@imec.be


In order to understand negative ion formation under Cs-bombardment, it is essential to provide
first the basic data i.e. the energy and angular dependence of the steady-state Cs concentration. In
this work we have studied the Cs-concentration during Cs-bombardment of Si and Ge with a focus
on conditions relevant to high resolution analysis i.e. energies between 500ev and 5kev and at
impact angles from 0
o
to 60
o
.
The in-situ internal Cs depth profiles have been measured with a low energy O
2
+
beam similar to
the work of S.Yoshikawa
[1]
. However a determination of the optimum oxygen condition is
necessary as this impacts on the results as well. For instance when comparing oxidizing versus non-
oxidizing conditions (cfr Fig.1) it is clear that distortions like Cs-segregation are apparent and the
long decay length (arrow 1) is possibly due to segregation
[2]
. The high Cs surface peak (arrow 2) is
not real
[3]
, but an artefact due to the enhanced sputtering rate in transient region or/and Cs anti-
segregation towards the surface. So a low energy (0.5-1 keV) and high angle (60
o
) O
2
+
beam was
chosen to minimize the distortions on the Cs profile due to the oxygen incorporation. Moreover, in
order to understand the influence of Cs on the matrix signal
30
Si
-
(arrow 3) in the (oxidized) near-
surface region a thin (10nm) SiO
2
/Si was also studied.
0 10 20 30 40 50 60 70 80
10
2
10
3
10
4
10
5
10
6 2

30
Si
+
by 500ev0
o
O
2
+

133
Cs
+
by 500ev0
o
O
2
+

133
Cs
+
by1kev60
o
O
2
+
I
n
t
e
n
s
i
t
y

o
f

s
e
c
o
n
d
a
r
y

i
o
n
s

(
c
o
u
n
t
s
/
s
)
Depth (nm)
3
1
Fig.1 Cs internal profiling of Si implanted with
5kev 0
o
Cs
+
using 500ev 0
o
& 1kev 60
o
O2
+

0 5 10 15 20 25 30 35 40 45 50
10
1
10
2
10
3
10
4
10
5
10
6
5kev 0
o
5kev 30
o
5kev 45
o
5kev 60
o
I
n
t
e
n
s
i
t
y

o
f

S
e
c
o
n
d
a
r
y

i
o
n
s

1
3
3
C
s +

(
c
o
u
n
t
s
/
s
)
Depth (nm)
Fig. 2 Cs internal profiling of Si implanted
with 5kev Cs
+
using 1kev 60
o
O
2
+

0 5 10 15 20 25 30 35 40 45 50
10
1
10
2
10
3
10
4
10
5
10
6
5kev 0
o
5kev 30
o
5kev 45
o
5kev 60
o
n
t
e
n
s
i
t
y

o
f

s
e
c
o
n
d
a
r
y

i
o
n
s

1
3
3
C
s +

(
c
o
u
n
t
s
/
s
)
Depth (nm)
Fig. 3 Cs internal profiling of Ge implanted
with 5kev Cs
+
using 500ev 60
o
O
2
+

Comparing the internal Cs profiles as obtained for a 5kev Cs
+
implantation in Si and Ge, (cfr Fig.
2&3) one can observe a very clear difference. Whereas in the Si-case the Cs-profile depth scales
with the angle of incidence, in the Ge-case a very similar profile is always obtained solely reduced
in Cs-content with increasing angle. In addition the stationary profiles shows a strong dip at the
surface implying an important preferential sputtering component.
The internal SIMS profiles have been further compared with XPS results in order to further
quantify the Cs steady-state concentration for the different experimental conditions and to relate
them to observable parameters such as the sputter yield and ionisation degree
[4]
.


[1] S.Yoshikawa, H.Morita, etc, Applied surface science Vol. 203-204, (2003) 252-255
[2] M.K.Bhan and J.A.Killer, Nuclear Instruments Methods in Physics Research B, Vol. 64, (1992) 641-645
[3] R.Valizadeh, J.A. van den Berg, etc, Nuclear Instruments and Methods in Physics Research B, Vol.64, (1992) 609-
613
[4] P.Chen, T.Janssens, L.Geenen and W.Vandervorst, Poster contribution at SIMS EUROPE 2004 (Munster -
Germany) Angular and energy dependence of the sputtering yield of Ge and Si under Cs
+
bombardment
QUA-P-Mo-P18
50
AFM STUDY OF THE SIMS BEAM INDUCED ROUGHNESS IN
MONOCRYSTALLINE SILICON IN PRESENCE OF INITIAL
SURFACE OR BULK NANOMETRIC SIZED DEFECTS

B. Fares
(1)
, C. Dubois
(1)
, B. Gautier
(1)
, J.C. Dupuy
(1)
, F. Cayrel
(2)


(1) Laboratoire de Physique de la Matire (UMR CNRS 5511), INSA de lyon, 7 Avenue Capelle, F-69621
VILLEURBANNE cedex, France
(2) Laboratoire de Micro-lectronique de Puissance, Universit de Tours, 16 rue Pierre et Marie Curie,F-37071 TOURS
cedex 2, France

christiane.dubois@insa-lyon.fr


Beam Induced Roughness (BIR) is a well known phenomenon which appears when sputtering
monocrystalline silicon [1-2]. It results in a degradation of the depth resolution at low energy
sputtering. A great amount of experimental works exist and experimental conditions to avoid BIR
are relatively well-controlled [3-4-5] but the physical phenomena which lead to the apparition of the
BIR are still not clearly understood, especially the very first steps of development.
We show that in presence of nanometric sized defects on the surface or in the bulk, the BIR
develops far more rapidly than usual. It appears as soon as the crater reaches the defects and rapidly
has the same morphology as than reported on Si free from any treatment, with waves perpendicular
to the sputtering beam.
We follow the development of the BIR by monitoring the increase of Si
++
and SiO
2
+
signals
during SIMS sputtering. The topography of the crater bottoms is measured using an Atomic Force
Microscope (AFM).
Surface modification by Reactive Ion Etching (RIE) is responsible for premature development of
BIR, while samples with initial roughness of other types do not accelerate it.
The presence of cavities in the bulk leads or not to a sudden and irreversible roughness,
depending on their characteristics.
These two examples confirm that roughness is a phenomenon which appears at a very local scale
and develops afterwards until it reaches a steady state which corresponds to the well described BIR.
We will present, for each type of sample the AFM measurements at different steps of the
evolution of the roughness. This study of the behaviour of the BIR in presence of voluntarily
introduced defects allows us to better understand the basic physical phenomena involved in its
apparition.


[1] Stevie F.A. et Kahora P.M., J. Vac. Sci. Technol. A, 6 (1): 1988, 76-79,
[2] Elst K., Vandervorst W. et Alay J., J. Vac. Sci. Technol. B, 11(6): 1993, 1968-1981
[3] Alkemade P.F.A. and Jiang Z.X., J. Vac. Sci. Tech B; 19 (5): 2001, 1699-1705
[4]

Fares B, Gautier B, Baboux N, Prudon G, Holliger P and Dupuy J C, App Surf Sci, 231-232: 2004: 678-683
[5] Liu R and Wee A.T.S., Appl Surf Sci, 231-232, 2004, 653-657
QUA-P-Mo-P19
51
PROPERTIES AND USE OF THE DEPTH RESOLUTION
FUNCTION IN SIMS ANALYSIS

J.C. Dupuy, N. Baboux, B. Gautier, G. Prudon

a
Laboratoire de Physique de la Matire (UMR CNRS 5511), INSA de lyon, 7 Avenue Capelle, F-69621
VILLEURBANNE cedex, France

jean-claude.dupuy@insa-lyon.fr


The depth resolution during the SIMS analysis is perfectly well described by the Depth
Resolution Function (DRF), which is the response to the analysis of a perfect (ideal) delta-marker.
The physical phenomena involved in the analysis impose that the DRF possess precise properties
[1], and lead to an analytical expression of the DRF [2], sometimes called Analytic Resolution
Function (ARF) [3]. The analytical description of the DRF has shown its relevance in the case of
the analysis of boron in silicon with an oxygen primary beam, with or without oxygen flooding. The
parameters of the DRF, which can be described by the convolution of a gaussian with a decreasing
exponential (or with a double exponential: rising and then decreasing), reflects perfectly the
characteristics of the depth resolution and must be analysed in experimental conditions exempt from
any disturbing phenomenon: intrinsic width of the delta-layer used to measure the DRF, non-planar
layers, intrinsic roughness of the surface or beam induced roughness...
In this paper, we present some examples of experimental measurements of the DRF using
different primary energies and we discuss the validity of the fitting of the parameters and their
interdependance, and we relate them to the physical phenomena which take place during the SIMS
analysis. We will verify the linearity of the process, which validates the convolution and the use of
the deconvolution to recover the profiles in the steady state.
We also discuss the properties of the DRF and its consequences on the analysis of some profiles.
Beyond the capabilities of the deconvolution, which are well described elsewhere [4], it is possible
to take advantage of the analytical properties of the DRF. For example, a partial analytical
deconvolution is possible. The precise fitting of the gaussian parameter of the DRF allows us to
measure the broadening of the profiles due to e.g. the diffusion, with a nanometric precision, and
using only a medium primary energy SIMS analysis.


[1] S.Hofmann, Surf. Interf.Anal., 21: 673-678, 1994
[2] M. Dowsett, G. Rowlands, P. Allen, R. Barlow, Surf. Interf.Anal., 21 : 310-315, 1994
[3] K. Wittmaack, Applied. Surf. Sci., 203-204: 268-272, 2003
[4] B. Gautier, R. Prost, G. Prudon, and J.C. Dupuy, Surf Interf. Anal, 26 :974-983. 1998

QUA-P-Mo-P20
52
Determination of energy dependent ionization probabilities for
sputtered particles

P.Mazarov, A.Samartsev and A. Wucher

Department of Physics, University of Duisburg-Essen, D-45117 Essen, Germany
wucher@uni-essen.de


We present a novel method to determine the spectral ionization probability of sputtered species as
a function of their emission velocity or energy. The technique is based on simultaneous detection of
neutral and ionic species in a reflectron time-of-flight mass spectrometer. Neutral species are
postionized by means of single photon ionization using an intense UV laser beam, the spatial
dimension of which being matched with the sensitive volume of the mass spectrometer. The
generated photoions are extracted by means of a pulsed HV potential which is applied to the sample
simultaneously with the ionizing laser pulse. Secondary ions are detected by switching the
ionization laser off and leaving the remainder of the experiment unchanged. This way, those ions
are detected which have evolved in the field-free space above the surface and are present in the
ionization volume at the firing time of the extraction pulse. As a consequence, secondary neutrals
and ions are detected under otherwise identical experimental conditions regarding, for instance, the
probed emission solid angle and velocity interval as well as instrument transmission effects.
Provided the single photon postionization process is saturated, the ionization probability can
therefore be directly calculated from the respective signal ratio. The detected emission velocity is
selected by the temporal delay between primary ion and laser/extraction pulses, with the velocity
resolution being primarily determined by the applied primary ion pulse width. Using sufficiently
short pulses in connection with a controlled delay variation, the spectral ionization probability
) (v
+
can be determined without any prior knowledge of possible energy discrimination effects in
instrument transmission etc.

We have applied the above technique to investigate the spectral ionization probability of In

atoms
released from a polycrystalline indium surface under bombardment with 25-keV Ga
+
ions. The
results show a relatively strong variation of
+
by several orders of magnitude in the velocity range
between 1 and 10 km/s. In contrast, much weaker dependencies are observed at velocities above
and below that range. Comparing the measured ionization probability with theoretical predictions,
we find that none of the prevailing ionization models is capable of describing the experimental data
over the whole velocity range studied.
QUA-P-Mo-P21
53
Transient affects active during secondary ion emission from Si and
SiO
2
surfaces under Cs
+
primary ion impact

P.A.W. van der Heide *

Centre for Materials Chemistry (CMS), Chemistry Department, 136 Fleming, University of Houston, Houston, Texas
77204-5003, U.S.A.
pvanderheide@uh.edu


Mechanisms active in positive and negative secondary ion formation/survival from Si and SiO
2

substrates under 1keV Cs
+
primary ion impact are examined. Of particular interest is the
enhancement of negative secondary ions/quenching of positive secondary ions noted over the
transient region from SiO
2
(this substrate exhibits a significant band gap which should quench any
variations resulting from work function shifts). Analysis of photo-electron spectra collected over the
valence region revealed the production of sub-band states, whose area increased with sputtering
time. This introduces an alternative ionization/neutralization channel under which a resonance
charge transfer process Could explain the results observed. Secondary ion yield variations with
work function variations noted from the Si substrate concur with this possibility. Furthermore,
minimal ion induced Auger electron production was also noted from SiO
2
(expected since
symmetric collision probabilities are quenched in SiO
2
). These are noted in spectra from Si.
QUA-P-Mo-P22
54
Studies into the removal of SIMS transient affects in the analysis of Si
wafers with Cs
+
primary ions

P.A.W. van der Heide *

Centre for Materials Chemistry (CMS), Chemistry Department, 136 Fleming, University of Houston, Houston, Texas
77204-5003, U.S.A.
pvanderheide@uh.edu


In a recent publication [1] it was noted that the buildup of Cs introduced through Cs
+
primary ion
irradiation of a H terminated Si wafer scaled with the difference between the Si
-
and Si
2
-
secondary
ion intensities. Subsequent studies have shown (a) that the difference in various molecular
secondary ion intensities provides similar correlations with Cs uptake, and (b) that this can be used
to account for Cs induced transient affects in a manner consistent with the electron tunneling model.
Transient affects resulting from O within native oxide terminated Si wafers are known to decrease
with increasing molecular size, i.e. are weaker in both the Si
2
-
and Si
3
-
populations. Thus, by using
appropriate secondary ion signals, the possibility of reducing transient affects apparent in ultra-
shallow depth profile analysis is introduced. This possibility is demonstrated using several as
received Si wafers containing shallow As and Sb implants.


P.A.W. van der Heide. Surface Science, Vol 555, (2004), pp 193-208.
QUA-P-Mo-P23
55
Modelling the negative ionisation of sputtered carbon atoms

J. A. M. C. Silva

Physics Department, Faculty of Science and Technology, New University of Lisbon
2829-516 Caparica, Portugal
jcs@fct.unl.pt


In a previous paper [1], the energy distribution of sputtered carbon negative ions was determined
experimentally and the energy and angular distributions of carbon atoms sputtered from a graphite
surface was determined from a computer simulation. From the ratio of the two distributions, the
probability of formation and subsequent survival of negative ions was obtained. The results showed
that the charge transfer between a sputtered C atom and the surface it abandons can be understood
within the usual resonant charge transfer (RCT) model: for Z (coordinate measured perpendicular
and relative to the image plan) less than Zc (where the affinity and Fermi levels cross), electron
capture leads to the formation of C- ions which can be destroyed by electron loss for Z>Zc. At low
energy, below around 25 eV, the C- ions are formed with an almost unit probability in the small Z
region and the final C- ion population is simply given by the survival of the negative ions as they
travel from Zc to infinity. In the high energy region (above around 25 eV), the C atoms leave the
surface too fast for an efficient electron capture to take place and the final C- ion population is
limited by the electron capture step at small distances.
In the present work, a theoretical analysis of the problem of formation and survival of the carbon
ions was attempted. The procedure employed used the Coupled Angular Modes (CAM) method [2]
to calculate the position and width of the carbon affinity level in front of a free-electron metal
surface with a work function and a conduction band width equal to those of graphite. Then, a semi-
classical rate equation approach including a phenomenological function DoS (Density of States) was
used to describe the time evolution of the negative ion and the two neutral sub states populations
with the charge transfer rates obtained in the CAM calculation.
The calculated charge transfer rates are very high, leading to a fast formation of the negative ion
state, with the population of this state in excess of 90\% up to an energy of 25 eV at Zc. The general
trend of the negative ion population dependence on the inverse perpendicular velocity obtained
experimentally was reproduced in the calculation: a high degree of ionisation at low velocity and a
decreasing fraction of negative ions at higher energy. However, the experimental results showed a
decrease of the negative ion population with energy which starts suddenly around 25 eV and
evolves much faster than the smoother variation obtained with the rate equations.
The population of negative ions is propagated from Zc to infinity to obtain the final population.
The deceleration of the negative ions due to the interaction with their image charges and the relative
abundance of each sputtered atom energy (expressed by the Sigmund-Thompson factor) were taken
in consideration to obtain the energy distribution of sputtered negative carbon ions. Agreement with
the experimental result is good at low energy but poor at high energy when a graphite work function
of 4.0 eV is used.
The calculations presented in this work involved a number of assumptions relating to the graphite
electronic properties, the way these were treated in the CAM calculation and also on the use of the
rate equation to treat the charge transfer dynamics, which we thoroughly discuss.

[1] J.A.M.C. Silva, C.M.R. Henriques, O.M.N.D. Teodoro and A.M.C. Moutinho, App. Surf. Sci., 144 (1999) 208
[2] D. Teillet-Billy and J.~P. Gauyacq, Surf. Sci. 239 (1990) 343.
QUA-P-Mo-P24
56
Modeling the dissociation and ionization of a sputtered organic
molecule

V. Solomko
a,*
, M. Verstraete
a
, A. Delcorte
a
, B.J. Garrison
b
, X. Gonze
a
and P. Bertrand
a

a
Unit de Physico-Chimie et de Physique des Matriaux, Universit Catholique de Louvain, Croix du Sud 1, Louvain-
la-Neuve B-1348, Belgium
b
Department of Chemistry, Penn State University, 512 Davey Laboratory, University Park, PA 16802, USA


The evolution of an organic molecule [1,2,3,4-tetraphenylnaphthalene (TPN)] during and after
sputtering from a gold surface has been analysed by classical molecular dynamics (MD; SPUT2000
code, [1]) and ab initio calculations (ABINIT code, [2]) to gain insight into ionization and
fragmentation processes occurring in SIMS. The calculated ionization energy of the TPN molecule
is 6.2 eV (5.4 eV for benzene) and the unimolecular dissociation energy for the reaction channel
involving the loss of a phenyl ring is 5.4 eV. This reaction is experimentally observed as the major
decomposition channel for excited TPN molecules in the gas phase. On the other hand, our
previous MD calculations have shown that the internal energy of sputtered TPN molecules can be
significantly larger than 5-6 eV [3]. Therefore, it appears energetically possible to relax such
excited molecules via both fragmentation and ionization.
Sputtered organic molecules are typically not very rigid. Their bonds rotate and bend, thus
changing the overlap between different orbitals, possibly favoring dissociation and ionization
processes. Our analysis of the molecular motion after emission shows that the oscillations along the
phenyl-naphthalene bond direction, expected to induce the molecule fragmentation, are relatively
small (they store only about 0.2 eV of energy). On the other hand, the relative energy stored in the
phenyl-phenyl interactions, modulated by their rotation and bending, oscillates over a range of 8
eV.
To study this complicated system ab initio, we propose to virtually decompose the TPN
molecule into its basic fractions. The rationale is that, if the molecule is very excited (which is the
case of sputtering in SIMS), then separated parts (e.g. pendant phenyl rings) can interact with each
other almost independently. To test this idea, a system containing two benzene rings has been
investigated by first principles calculations. The possible ionization scenarios are critically
discussed on the grounds of these calculation results.


[1] B. J. Garrison, A. Delcorte, K. Krantzman, Acc. Chem. Res. 33 (2000) 69.
[2] X. Gonze, J.-M. Beuken, R. Caracas, F. Detraux, M. Fuchs, G.-M. Rignanese, L. Sindic, M. Verstraete, G. Zerah, F.
Jollet, M. Torrent, A. Roy, M. Mikami, Ph. Ghosez, J.-Y. Raty and D.C. Allan. Comp. Mat. Sci. 25 (2002) 478.
[3] V.Solomko, A.Delcorte, B.J.Garrison and P.Bertrand, Applied Surface Science. 231-232 (2004) 48.

QUA-P-Mo-P25
57
Analysis of SIMS for LB Film due to the Thermal
Decomposition using QMD Method

Nobuhiko Kato, Masahiro Kudo, Tomonori Ida,
1
Kazunaka Endo
1


Applied Physics, Seikei University, Musashino-city, Tokyo 180-8633, Japan,

1
Laboratory of Theoretical Chemistry, Graduate School of Natural Science
and Technology, Kanazawa University, Kanazawa 920-1192, Japan
(*corresponding: kato-nobuhiko@st.seikei.ac.jp)


In our previous work [1], the cleavage sites of polymers in static and time-of-flight secondary ion
mass spectra (SIMS) can be estimated from the two-center bond energies for the electric neutral
model oligomers using semiempirical AM1 MO method [2] under the main assumption of the
thermal decomposition process for the cleavage of polymer bonds on the utmost surface of solid
polymer sample. The thermal decomposition of CH
3
(CH
2
)
19
COOH model molecule for the LB film
has been simulated by quantum molecular dynamics (QMD). In the calculations, we controlled the
Nse-Hoover thermostats [3-5] in the thermal energy range of 14 20 kcal/mol, and the sampling
position data with a time step of 0.5 fs were carried out up to 5000 steps. We obtained the
distribution of thermal decomposed fragment products to the main chain carbon number from the
output data at the 5000 step in 20 runs. Fig. 1 shows the thermal decomposed products of
CH
3
(CH
2
)
19
COOH model molecule at the 5000 step with 20 kcal/mol thermal energy. The
calculated distribution of the decomposition products enables us to be compared with the
experimental results of gas mass spectra and SIMS under the assumption of thermal decomposition
process for the cleavage of polymer bonds. In the total fragments of the LB model molecule at 5000
MD step in the 20 runs, we confirmed that there are 90 % neutral charged fragments, 5 % positive
and 5% negative charged ion-fragments, respectively. Thus, we can obtain the calculated
distribution of the positive ion charged fragments to the experimental result of the positive ions [7]
in TOF-SIMS in Fig.2.



Fig. 1. Thermal decomposed products to the main chain Fig. 2. CH
3
(CH
2
)
n
intensities from LB films on
carbon numbers of LB model molecule different substrates as a function of the
number of CH
2
group


References
[1] K. Endo, T. Hoshi, N. Kobayashi, H. Miura, M. Kudo, Polym. J., 29,457(1997).
[2] M. J. S. Dewar, E. G. Zoebisch, Theochem 180, 1 (1988): M. J. S. Dewar, E. G. Zoebisch, E. F. Healy, J. J. P.
Stewart, J. Am. Chem. Soc. 107, 3902 (1985).
[3] S. Nos, Mol. Phys.,52,255(1984): J. Mol. Phys., 81,511(1984).
[4] W. G. Hoover, Phys. Rev. A31,1695(1985).
[5] C. W. Gear, The numerical integration of ordinary differential equations of various orders, Report ANL 7126,
Argonne National Laboratory(1985).
[6] M. Kudo, N. Ogura, S. Yamada, Y. Ichinohe, S. Yoshida, T. Watanabe, T. Hoshi, K. Endo, Secondary Ion Mass
Spectrometry, SIMS-XI (John Wiley&Sons, Chichester, 1998)471-474.
O
2
4
6
8
1O
12
14
16
18
1 J 6 7 9 11 1J 16 17
QUA-P-Mo-P26
58
X
y+
bombardment / Cs deposition: evolution of Cs surface
concentration with respect to bombardment conditions by TRIDYN
simulations

P. Philipp
a
*, T. Wirtz
a
, H.-N. Migeon
a
, H. Scherrer
b


a
Laboratoire dAnalyse des Matriaux, Centre de Recherche Gabriel Lippmann,
41 rue du Brill, L-4422 Belvaux, Luxembourg
b
Laboratoire de Physique des Matriaux, Ecole des Mines, Parc de Saurupt, F-54042 Nancy Cedex, France
philipp@lippmann.lu


The Cation Mass Spectrometer (CMS) is a SIMS prototype developed in our laboratory [1,2] in
order to perform quantitative analysis with optimal sensitivity and high depth and lateral resolution
in the MCs
x
+
and M
-
modes [3]. For this purpose, a patented neutral Cs evaporator for varying the
Cs surface concentration over the whole range has been developed and installed on the CMS [4].
The sputtering and the Cs introduction have been decoupled successfully by applying
simultaneously X
y+
bombardment and neutral Cs deposition. X stands for any element or cluster
except Cs.
Experiments on the CMS gave the useful yield variations of negative secondary ions (Si
-
, Al
-
, Ni
-
,
In
-
, P
-
, Ga
-
, As
-
) with respect to the Cs surface concentration. While another paper submitted to this
conference by the same authors investigates the increase of negative secondary ion sensitivity by
means of neutral cesium deposition, the present paper explains how the Cs surface concentrations
have been calculated from simulations realized with the TRIDYN code [5] and how they have been
related to the useful yields obtained under specific experimental conditions. Furthermore we study
the influence of substrate and primary ion type on the cesium surface concentration.


[1] T. Mootz, B. Rasser, P. Sudraud, E. Niehuis, T. Wirtz, H.-N. Migeon in: A Benninghoven, P. Bertrand, H.-N.
Migeon, H. W. Werner (Eds.), Secondary Ion Mass Spectrometry, SIMS XII, Elsevier, Amsterdam (2000) p. 233
[2] P. Philipp, T. Wirtz, H.-N. Migeon, H. Scherrer, Appl. Surf. Sci. 231-232 (2004) 754-757
[3] T. Wirtz, H.-N. Migeon, H. Scherrer, Int. J. Mass Spectrom. 225 (2003) 754-757; T. Wirtz, H.-N. Migeon, Surf.
Science, 557 (2004) 57-72; T. Wirtz, H.-N. Migeon, Surf. Science 561 (2004) 200-207
[4] T. Wirtz, H.-N. Migeon, Appl. Surf. Sci. 231-232 (2004) 940-944
[5] W. Mller, W. Eckstein, Nucl. Instr. and Meth. in Phys. Res. B 2 (1984) 814; W. Mller, W. Eckstein, J. P.
Biersack, Comput. Phys. Commun. 51 (1988) 355

ACG-P-Mo-P27
59
uleSIMS characterization of silver reference surfaces

V.V. Palitsin* , M.G. Dowsett, I.W. Oloff, R. Gibbons

Advanced SIMS Projects, Physics Department, University of Warwick, CV4 7AL Coventry UK
Email: v.v.n.palitsin@warwick.ac.uk


Corrosion processes are the result of interactions between a material and the surrounding
environment. They usually involve a number of chemical, physical and electrochemical processes in
the interface region. These are of particular concern in the conservation of museum objects made of
metal. In this case, the corrosion process results in the formation of altered layers of different
thicknesses on their surfaces. With time, various environmental factors leave their signature on the
surface and threaten the continued existence of the object. In order to determine which methods to
use to suppress or prevent the decay it is necessary to understand how an artefact interacts with the
environment and have an accurate knowledge of the chemistry of the alteration process.
Since the products formed at the early stages of corrosion are in the form of very thin layers
(a few nanometres thick), only surface sensitive techniques can be exploited to provide information
about the composition at this stage. The ability of one of these techniques, SIMS, in application to
archaeometry and cultural heritage has been recently reviewed by Adriaens [1] and Dowsett [2].
Ultra low energy SIMS (uleSIMS), developed in recent years, is high sensitive analytical
technique allows profiles from the top nms of a sample to be detected, at a depth resolution of
1 nm. In the present work, the ability of uleSIMS in characterization of the early stages of
corrosion formed on reference surfaces of silver samples has been investigated. We show that due
to high sensitivity and surface specificity uleSIMS can be effectively used to study surface
chemistry and in the development of reference surfaces themselves. In particular, handling
contaminants, surface dust, and residues from polishing are relatively easy to identify so that the
parts of the mass spectrum specific to the early stage corrosion can be identified.


[1] A. Adriaens, in: D.C. Creagh, D.A. Bradley (Eds.), Radiation in Art and Archaeology, Elsevier, Amsterdam, The
Netherlands, 2000, p. 180.
[2] M. Dowsett, A. Adriaens, Nucl. Instrum. Meth. B, 226 (2004) 38-52.
ACG-P-Mo-P28
60
Ion-Tof Analysis of Corroding Museum Glass

Sarah Fearn
1*
, David McPhail
1
, Colin Helliwell
2

1
Department of Materials, Imperial College, Exhibition Road, London, SW7 2AZ,UK
2
Ion-Tof, Tascon, Gmbh, Meunster, Germany
E-mail: s.fearn@imperial.ac.uk


Glass deterioration remains a serious issue for many museum collections around the world. Many
of the glass artifacts within the collections have been made from compositions that are very
hygroscopic. The glass readily absorbs moisture from the atmosphere and forms corrosion salts on
the glass surface. If the salts are left to develop, not only do they cause a loss in clarity of the object
but more seriously will permanently damage and stain the glass surface
[1]
. The objects must
therefore be cleaned to remove these corrosion products.
In cleaning the object it is important that any further intervention with the museum piece does not
cause more or speed up the deterioration process, however, the effect of cleaning procedures on
glass objects has not been monitored. In this work, a replica museum glass has been cleaned using a
known surfactant (synperonic) and de-ionised water. The glass was then aged at room temperature
at 40%RH for one week. A sample which had not been cleaned at all was also aged under the same
conditions. The glass was then imaged and analysed using a Bi beam in an Ion-Tof SIMS
instrument.
The imaging results showed that the corrosion salts were forming heterogeneously across the
surface and analysis of these salts indicated the presence of formates, and carbonates. The mass
spectra also showed that the surfactant had remained on the glass, even after ageing. It is hoped that
further work will be able to determine whether or not the presence of the surfactant on the surface
reduces or increases the rate of glass corrosion.


[1] Walters, H. V and Adams, P. B, J. Non Cryst. Solids, 19: 183, 1975.
ACG-P-Mo-P29
61
ToF-SIMS applied to historical archaeology in the Alps

R.N.S. Sodhi
a,
*, W.C. Mahaney
b
, M.W. Milner
b

a
Surface Interface Ontario, Department of Chemical Engineering and Applied Chemistry, University of Toronto,
Toronto, Ontario, Canada M5S 3E5
b
Geomorphology and Pedology Lab, York University, 4700 Keele St., N. York, Ontario, Canada, M3J 1P3
Email: sodhi@chem-eng.utoronto.ca

The actual route Hannibal followed during the invasion of Italia in the Second Punic War is one
of the major questions of antiquity, one that historians/archaeologists have long studied. There are
six possible cols Hannibal could have used and one of the many bits of evidence in the ancient
literature that might help answer this question is the location of fired rock, the result of a
conflagration Hannibal is reputed to have employed to reduce the size of boulders in a two-tier
blocking rockslide on the lee side (e.g. Italian) some distance down from the high col. The only
route with fired rock along the roadway leading to the Po River Valley is below the Col du Clapier,
one of the possible northern routes. TOF-SIMS investigation of the 100-micrometer-thick burned
crust in hornblende schist interlaced with veins of quartz-feldspathic minerals yields various
elements C, Mg, Na, Ca, Si, Ti, P, Al, Fe and associated fragments. Hydrocarbon fragments are
thought to be products of combustion whereas Ca and Na along with Mg-Fe silicates are derived
from the country rock. Aeolian components along with clay minerals settled onto rock surfaces
following firing. While the SIMS data clearly would not provide an age for the burnt rock,
compositional evidence of the conflagration may relate to Hannibals actual route.

ACG-P-Mo-P30
62
OBSIDIAN HYDRATION DATING FROM SIMS H
+
PROFILING
BASED ON SATURATED SURFACE (SS) LAYER

I. Liritzis
a,*
and Th.Ganetsos
b

a,*
Laboratory of Archaeometry, Dept. of Mediterranean Studies, University of the Aegean, 1 Demokratias Ave., Rhodes
85100, Greece
b
T.E.I. of Lamia, Dept. of Electronics, 3
rd
Km O.N.R. Lamia-Athens, Lamia 35100, Greece
E-mail: liritzis@rhodes.aegean.gr


Recent advances in water diffusion dating of archaeological obsidian tools involved: i) SIMS H
+

profiling, ii) numerical solution of diffusion assuming exponential dependence of concentration, C,
as a function of diffusion coefficient D, iii) determination of Cs and Xs, concentration and depth,
respectively, at surface saturation layer encountered near the surface rim, iv) certain boundary and
initial conditions, v) the rate of change of C versus x, was attributed to Ds in a inverse manner of
gradient dC/dx (=flux/gradient), for a 3
rd
order polynomial fit of H
+
profile, and vi) based on Ficks
law of diffusion, an age equation (diffusion age) was devised, the new method named SIMS-SS [1,
2]. SIMS profiles were taken by a PHI Model 6300 and 6600 quadrupole-based SIMS. So far, over
30 dates have been produced for archaeological obsidian tools over the World and the SIMS-SS
ages versus archaeological and mean radiocarbon ages were in excellent concordance.
Here, a) the sensitivity in the determination of SS layer is reassessed, and b) an elaboration of
accuracy and precision of older and new data sets of different obsidians provides a detailed error
evaluation, both via a novel in-house made MATLAB software.


[1] Liritzis. et. al., J.Radioanal. Nucl. Chem, 261 (1) (2004) 51-60.
[2] Brodkey.R.S & Liritzis.I, Mediterranean Archeology & Archaeometry 4(2) (2004) 67-82.

ACG-P-Mo-P31
63
SIMS Depth Profiling for Obsidian Hydration Dating

S. W. Novak
a
*, C. Stevenson
b


a
Evans East, 104 Windsor Center Drive, East Windsor, NJ 08520
b
Virginia Department of Historic Resources, 2801 Kensington Ave., Richmond, VA 23221
snovak@evanseast.com


The obsidian hydration dating (OHD) technique has been used for many years to obtain dates for
archaeological artefacts. This technique uses the fact that a freshly exposed obsidian surface
adsorbs water with time. If suitably calibrated the thickness of the hydrated layer can be used to
calculate the age that the obsidian was worked. The traditional method was to cross section the
artefact and measure the hydration layer thickness optically. Recent work has demonstrated that
this traditional method can have significant non-systematic errors when compared to infrared
spectroscopy and SIMS. We have collected numerous SIMS profiles in the last few years in an
attempt to better calibrate the OHD technique. SIMS measurements are carried out using a Physical
Electronics quadrupole-based instrument. Standard profiling conditions use a 5keV Cs beam at 60
degrees (500nA) with negative secondary ion detection. Quadrupole SIMS offers several
advantages for this type of measurement, including easy charge compensation, low extraction field
and ability to tilt the sample for alignment. Calibration is via a deuterium ion implanted obsidian,
which serves to calibrate both the H concentration and depth scale. For the hydration layer
thickness measurement, the important parameter is the thickness of the hydration layer, as measured
at the fall of the H profile. Repeat measurements indicate this thickness can be measured to
within 1% on some samples. Roughness of the fractured obsidian surface may distort the shape of
the hydration profile, but does not appear to alter the measurement of the hydration layer thickness.
Recent laboratory experiments exposing fresh obsidian to 100% humidity conditions for times up to
250 days have calibrated the diffusion of water in obsidian at low temperatures. Additional
experiments by Ambrose [1] clearly show the temperature dependency of water diffused into
obsidian at low temperatures for times up to 25 years. These data have been used to calculate ages
for obsidian artefacts that agree well with
14
C dates of co-existing material [2] (Figure 1).


[1] Ambrose, W., Novak S.W., Abdelrehim, I., Medit. Archeol. Archaeom. 4, 17-31 (2004).
[2] Liritzis, I., Diakostamatiou, M., Stevenson C. M., Novak, S.W., Abdelrehim, I, J. Radioanalytical. Nucl. Chem. 261,
51-60 (2004),
0 1000 2000 3000 4000 5000 6000 7000 8000
0
1000
2000
3000
4000
5000
6000
7000
8000


1
4
C

D
a
t
e

(
Y
r
)
SIMS Date (Yr)

Figure 1. Comparison of SIMS OHD dates with
14
C dates from coexisting contexts.
ACG-P-Mo-P32
64
Automated Ion Imaging with the NanoSIMS Ion Microprobe

Elmar Grner
*
and Peter Hoppe

Max-Planck-Institute for Chemistry, Cosmochemistry Department, P. O. Box 3060, 55020 Mainz, Germany
groener@mpch-mainz.mpg.de


Automated ion imaging systems had been developped for Cameca IMS3f and IMS6f ion
microprobes [1-3]. These systems were shown to be very useful for the analysis of large number of
presolar dust grains, in particular with respect to the identification of rare types of presolar grains,
such as SiC X grains and oxides. The application of these systems is restricted to the study of
micrometer-sized grains, thereby by-passing the major fraction of presolar grains which are sub-
micrometer in size. The new generation Cameca NanoSIMS 50 ion microprobe combines high
spatial resolution, high transmission for secondary ions, and simultaneous detection of up to 6
isotopes which makes the NanoSIMS an unprecedented tool for the analysis of presolar materials
[e.g., 4, 5]. Here, we report on the first steps towards the development of a fully automated ion
imaging system for the NanoSIMS at MPI for Chemsitry in order to extend its analytical
capabilities further.
The ion imaging consists of 4 steps: (i) Secondary ion image acquisition of up to 5 isotopes in
multi-detection in an aera with size defined by the user. (ii) Automated particle recognition in 1-5
pre-selected images. (iii) Automated measurement of all recognised particles with appropriate raster
sizes and measurement times to achieve the required precision for isotopic ratios (e.g.,
17
O/
16
O) as
defined by the user. (iv) Stage movement to new area and repetition of steps (i) to (iii). We will
apply this technique to the study of presolar grains and aerosol particles dispersed on Au foils and
of meteoritic thin sections.


[1] Nittler L. R. et al., Astrophys. J. 483 (1997) 475-495.
[2] Hoppe P. et al., Meteoritics Planet. Sci. 35 (2000) 1157-1176.
[3] Nittler L. R. and Alexander C. M. OD., Geochim. Cosmochim. Acta 67 (2003) 4961-4980.
[4] Messenger S. et al., Science 300 (2003) 105-108.
[5] Mostefaoui S. and Hoppe P., Astrophys. J. 613 (2004) L149-L152.
ACG-P-Mo-P33
65
Measurement of
26
Al Diffusion in Single Crystalline 2/1-Mullite
by SIMS Depth Profiling

P. Fielitz
a,
*, S. Weber
b
, G. Borchardt
a
, M. Schmcker
c
, H. Schneider
c


a
Technische Universitt Clausthal, D-38678 Clausthal-Zellerfeld, Germany
b
Ecole des Mines, F-54052 Nancy, France
c
Deutsches Zentrum fr Luft- und Raumfahrt, D-51147 Kln, Germany
Email: peter.fielitz@tu-clausthal.de


Mullite (Al
4+2x
Si
2-2x
O
10-x
, 0.2 < x < 0.5) is an important candidate for advanced structural and
functional ceramics with some outstanding properties: low thermal expansion, low thermal
conductivity, and excellent creep resistance. The measurement of the aluminium diffusion by
classical radio tracer experiments is generally difficult because aluminium has only one stable
isotope (
27
Al) and some radioactive isotopes with very short half-life times (less than about 7
minutes) besides the radioactive isotope
26
Al, which has a very long half-life time of 7.410
5
years
and thus a very low specific activity.
Secondary Ion Mass Spectrometry was applied to measure the depth distribution of the quasi-
stable tracer isotope
26
Al in single crystalline 2/1-mullite after a diffusion experiment. We found
that it is very crucial for a successful application of the SIMS-technique to develop an enhanced
preparation technique for the
26
Al
2
O
3
containing layers onto the specimen surface. The application
of the ink jet technology allows the deposition of
26
Al
2
O
3
micro particles onto a small surface area
of oxide specimens which drastically reduces the necessary amount of
26
Al (and thus the cost) per
experiment.
ACG-P-Mo-P34
66
SIMS Quantification of Very Low H
2
O Contents

D. Rhede and M. Wiedenbeck

GeoForschungsZentrum Potsdam,
Telegrafenberg, D-14473 Potsdam, Germany
rhede@gfz-potsdam.de


The accurate quantification of hydrogen in nominally anhydrous silicate minerals is a key
analytical challenge facing research into the geochemical evolution of the Earths mantle. The
focus of our investigation is to establish which conditions employing a
16
O
-
primary beam provide
the lowest detection limit for H
2
O, with the goal of providing precise and routine SIMS analyses at
the < 50 ppm H
2
O level. This work has been extended to asses the relative merits of using
16
O
-
vs.
133
Cs
+
primary ions and to compare our optimized strategies with methods reported earlier in the
literature [1,2].

Enhancements to the vacuum system of our Cameca ims 6f instrument (concurrent storage of up
to 12 samples and reference materials at pressure < 2.0E-07 Pa [3]) and an improved liquid nitrogen
Dewar assured that, despite the use of sample embedding resin, the total pressure in our secondary
ion source was better than 5.0E-08 Pa for all analyses. This is of crucial relevance, as the detection
limit ultimately achieved for hydrogen is largely dependent on the vacuum quality in the sample
chamber. Likewise, we have devoted much attention towards optimizing our sample preparation
strategy, as large amounts of adsorbed hydrogen adversely impact both the duration of a single
analysis and the reproducibility of the instrument calibration at low hydrogen concentrations.

Our work has been based mostly on the analysis of seven well characterized, gem quality garnet
reference samples with H
2
O contents of between 17 and 870 ppm which were established
independently using other techniques [4]. Additionally, an in-house produced dry, synthetic olivine
crystal which was additionally degassed at 1100C for 12 hours in air was employed as a nominal
blank. Our data illustrate the complex nature of the interaction between the residual vacuum
contaminants and the activated sputter surface. Similar detection limits of < 5 ppm H
2
O have been
achieved using both
16
O
-
and
133
Cs
+
primary ions, however an advantage of using Cs
+
primary ions
to analyze H
2
O-poor samples is that a steady state
1
H count rate is achieved more rapidly. It is
apparent that a major challenge facing our work is obtaining independently characterised reference
materials which are extremely H
2
O depleted (< 5ppm H
2
O) and which are know to be homogeneous
as the 10m scale achieved by SIMS and for which accurate concentration data are available.


[1] H, Yamazaki (1997) J, Vac. Sci. Technol. A, 15/5, 2542-2547.
[2] K. Koga, E. Hauri, M. Hirschmann and D. Bell (2003) Geochem. Geophy. Geosys., 4/2, 20p.
[3] M. Wiedenbeck, D. Rhede, R. Lieckefett and H. Witzki (2004) App. Sur f. Sci., 231-232, 888-892.
[4] J. Maldener, A. Hsch, K. Langer and F. Rauch (2003) Phys. Chem. Minerals, 30, 337-344.

ACG-P-Mo-P35
67
Preferential Oxidation of Chalcopyrite Surface Facets Characterized
by ToF-SIMS and SEM

Mohammad Al-Harasheh
a
, Frank Rutten
b,
*, David Briggs
b
and Sam Kingman
a


a
School of Chemical, Environmental and Mining Engineering
b
Centre for Surface Chemical Analysis and School of Pharmacy
The University of Nottingham, Nottingham NG7 2RD UK
frank.rutten@nottingham.ac.uk


Chalcopyrite (CuFeS
2
) is the source of a significant amount of the worlds copper. Recently
the use of hydrometallurgical (solution based) methods for the production of copper from
chalcopyrite have become more attractive due to environmental reasons such as lower energy
demand, and less gaseous emissions such as SO
2
. Unfortunately, Chalcopyrite is known to be
highly resistant to oxidation due to the formation of a passivating polysulphide layer on its surface
during dissolution. Furthermore, it has been reported that elemental sulphur is formed on selective
sites and fissures of chalcopyrite fracture surfaces [1]. In order to investigate this process,
investigations of freshly cleaved surfaces prior to and after dissolution were carried out.
This work reports that the freshly cleaved chalcopyrite surface exhibits highly selective
reactivity depending on the exposed facets. ToF-SIMS was used to qualitatively characterize
various planes of freshly cleaved chalcopyrite particles. It was found that certain sites exhibit
pronounced contamination from atmospheric hydrocarbons upon fracture, whereas other sites were
highly unreactive and remarkably free from adventitious hydrocarbon contamination. The positive
ion spectra recorded from these facets are indeed dominated by peaks from Fe- and Cu-elements
and related compounds. The negative ion spectra for the reactive sites show high a high content of
oxidised (sulphur) species.
After recording the ToF-SIMS images, the particles were carefully removed from the
sample holder and subjected to leaching in acidified ferric sulphate solution, a common oxidising
agent used in hydrometallurgical processes. The same particles were repositioned in the SIMS
instrument to allow recording of images and spectra from exactly the same areas as characterized
prior to the treatment. The differences between the sites of low and high reactivity, as detected
before leaching, were more subtle than prior to leaching, whereas SEM analysis showed clear
evidence for selective attack of ferric sulphate to specific planes.
Attempts were made to explain the selective dissolution based on the distribution of S, Fe
and Cu at different planes of chalcopyrite at various cleavage planes of chalcopyrite crystal.


[1] D.L. Jones, D.L. and E. Peters, The leaching of chalcopyrite in ferric sulphate and ferric chloride, in Extractive
Metallurgy of Copper, J.C. Yannopoulos and J.C. Agarwal, Eds., New York (1976) 632-653
ISO-P-Mo-P36
68
High Throughput Screening of Novel Oxide Conductors Using SIMS

Sarah Fearn
1*
, Jeremy C. H. Rossiny
1
and John A. Kilner
1

1
Centre for Ion Conducting Membranes, Department of Materials, Imperial College, Exhibition Road, London, SW7
2AZ,UK
E-mail: s.fearn@imperial.ac.uk


There is a constant requirement for novel high performance mixed conducting oxides for a
variety of applications including cathodes for solid oxide fuel cells and as oxygen separation
membranes. The conventional method of approaching this problem is by synthesising oxide
compositions obtained from considerations of crystal structure and chemistry. However, due to the
time consuming nature of the synthesis only a few chosen compositions can be explored. A way
round this is the use of combinatorial methods to explore much wider ranges of compositions based
upon rational choices of starting compositions.
Arrays of ceramic dot samples (~2mm dia. 500m high) have been synthesised using an ink jet
based robot system, LUSI (London University Search Instrument)
[1]
. These arrays will then undergo
isotopic exchange with oxygen 18 and then be analysed with high resolution SIMS to identify
materials with a high degree of exchange with oxygen gas at a given temperature. As this is the first
time that SIMS has been combined with oxides produced via the ink jet process, the starting
material for the arrays will be the perovskite with the general formula La
1-x
Sr
x
Co
1-y
Mn
y
O
3
. This
has been selected as its transport properties are well known and there is enough previous
information on this material system to verify that the experimental protocols on the arrays are
correct
[2]
.
In this paper we will present the results of the simulation of the of these arrays for the system La
1-
x
Sr
x
Co
1-y
Mn
y
O
3
for arrays with a varying content of the transition metal (y) when annealed at
temperatures close to 1000C, together with the first SIMS analyses of the combinatorial dots. This
will also be combined with the simulation of the oxygen exchange with a ceramic dot sample to
predict the distribution of oxygen within the dot and the high resolution SIMS analysis of
exchanged ceramic dots.


[1] http://www.materials.qmul.a.c.uk/research/facilities/lusi/robot.php
[2] R. A. De Souza and J. A. Kilner Solid State Ionics, 106, 1998, 175-187
ISO-P-Mo-P37
69
Resonant Laser-SNMS of Boron for Analysis
of Paleoceanographic Samples

G. Vering
a
, C. Crone
a
, P. Kathers
a
, J. Bijma
b
, and H.F. Arlinghaus
a,*


a
Physikalisches Institut, Universitt Mnster, Wilhelm-Klemm-Str 10,
D-48149 Mnster, Germany
b
Carbon Group, Alfred Wegener Institute for Polar and Marine Research,
D-27570 Bremerhaven, Germany
*
e-mail address: arlinghaus@uni-muenster.de


Various oceanic sediment properties yield useful information for reconstructing environmental
parameters of the past. Calcite shells of foraminifera, which are accumulated in the sediment, are an
important object for such paleoceanographic studies. Foraminifera are unicellular organisms
encased by a calcite shell. They lived in almost all parts of the ocean along the entire
paleoceanographic time scale. The isotope ratio of boron incorporated in the calcite shell delivers
information about the pH-value of the ocean at the time the shell was formed. Since the boron
fraction of such a shell is about 5 ppm [1], an extremely sensitive technique is necessary for an
exact boron isotope ratio determination [2]. Resonant laser secondary neutral mass spectrometry
(r-laser-SNMS) was used to measure boron isotope ratios in calcite shells dissolved in hydrochloric
acid and in single untreated calcite shells.
Analysis was carried out with a time-of-flight mass spectrometer equipped with an electron
impact gun for sputtering and a Ga
+
LMIG. For ionizing the sputtered neutrals, laser beams of two
tunable dye-lasers pumped by an Nd:YAG laser and the fundamental wavelength of the Nd:YAG
laser were applied. The resonant ionization of boron was accomplished via a three-step ionization
scheme.
After optimizing the boron ionization and the detection process, boron isotope ratio analyses
were performed on dissolved shells and directly on single foraminiferal shells. The analysis of
dissolved foraminiferal shells has to deal with contaminants such as dirt and/or solvent residues.
These must be thoroughly removed from the shell surface. The advantage of measuring the isotope
ratios directly in the calcite shell is that various cleaning procedures and dissolving processes can be
avoided. Surface contaminants may be removed by Ar
+
ion beam sputtering. Especially for
untreated foraminiferal shells, the obtained data showed it to be possible to use r-laser-SNMS for
measuring isotope ratios of ultra-trace elements with high accuracy.


[1] D.W. Lea, in: Modern Foraminifera, ed. B.K. Sen Gupta, Kluwer Academic Publishers (1999), p. 259-277.
[2] G. Vering, C. Crone, J. Bijma, and H.F. Arlinghaus, Appl. Surf. Sci. 203-204, 785-788 (2003).
CLU-P-Mo-P38
70
Secondary Ion Emission from Indium Sputtered by Gold-Cluster
Projectiles

S.N.Morozov
*
and U.Kh.Rasulev

Arifov Institute of Electronics, Akademgorodok, Tashkent 700125, Uzbekistan
E-mail: serg.moroz@sarkor.uz


Considerable enhancement of the secondary ion yields observed for molecular projectiles is of
great interest in applying this phenomenon for SIMS [1-5]. A significant non-additivity of the
secondary ion yield, particularly molecular ones, has been observed under bombardment by cluster
ions in the energy range of 1-10 keV per atom in the projectile [5-8]. The additional intensive yield
of secondary atomic ions with quasi-thermal energies connected with appearing of the thermal
spikes has been found under bombardment of Ta, Nb, V and Au by gold-cluster projectiles [6-8].
Performed in this work, the experimental studies of emission of the atomic and cluster In
n
+
(n=1-
15) ions in sputtering of indium by the cluster Au
m
-
(m=1-9) ions within the energy range E
o
= 621
keV have demonstrated a significant non-additive increase in the yield of the secondary ions with
the raise in the number of atoms in the cluster projectiles. However, the non-additivity factors, in
the case of indium, are several times less than those for the metals V, Nb, Ta and Au we studied
earlier [6-8]. The other features of the indium mass spectra is the presence of the slightly sloping
areas in the dependence of the yield of secondary cluster ions In
n
+
on the number of constituent
atoms n. For instance the yield of In
n
+
is practically unchanged (or even increases) with the raise in
n within the range of n from 8 to 13 when Au
2
-
- Au
5
-
projectiles are used.
A significant non-linear increase in the yield of In
1
+
, In
2
+
, In
3
+
ions having quasi-thermal energies
has been found with the raise in the number of atoms in the bombarding ions. Earlier we observed
the emission of V
+
, Nb
+
, Ta
+
, Au
+
, Au
2
+
ions containing quasi-thermal component when cluster
projectiles were used [6-8]. This is the first experimental observation of cluster ion emission with
number of constituent atoms up to 3 containing quasi-thermal component under molecular
bombardment. The non-additivity factors of increasing the yield of the atomic ions with quasi-
thermal energies reach great values. For example, the factor of non-additive increasing of the yield
of quasi-thermal component of In
+
ion emission in transition from Au
2
-
to Au
5
-
projectiles - K
2,5

reach values of 60 for energy 3 keV/atom in Au
m
-
.
A comparative analysis of the features of the mass and energy spectra of secondary ion emission
of In has been performed in this work and a link of the phenomena under observation with
formation of thermal spikes under molecular bombardment has been discussed.


[1] F. Kotter and A. Beninghoven, Appl. Surf. Sci. 133 (1998) 47.
[2] M.J. Van Stipdonk, TOF-SIMS: Surface Analysis by Mass Spectrometry, Edited by John C. Vickerman and
David Brigs, IM Publication and Surface Spectra, Huddersfield (2001) 309.
[3] Y.Le Beyec, Int. J. Mass Spectrom. 174 (1998) 101.
[4] A. Brunelle, S. Della-Negra, J. Depauw, D. Jacquet, Y. Le Beyec, M. Pautrat, K. Baudin, H.H. Andersen, Phys.
Rev. A 63 (2001) 022902.
[5] U.Kh. Rasulev, S.N.Morozov, Izv.Akad.Nauk.Ser.Fiz., 66 (2002) 522.
[6] S.N.Morozov, U.Kh.Rasulev, Nucl. Instr. and Meth. B, 203 (2003) 192.
[7] S.N. Morozov, U.Kh. Rasulev, Izv. Akad. Nauk. Ser. Fiz., 68 (2004) 393.
[8] S.N. Morozov, U.Kh. Rasulev, Appl. Surf. Science 231-232 (2004) 78.
CLU-P-Mo-P39
71
Secondary Ion Emission from Silicon under Si
m
-
and Au
m
-
Cluster
Ions Bombardment

S.N.Morozov* and U.Kh.Rasulev

Arifov Institute of Electronics, Akademgorodok, 700125 Tashkent, Uzbekistan
E-mail: serg.moroz@sarkor.uz


It has been shown by the results of recent studies [1-7] that cluster ion bombardment gives strong
non-additive enhancement of secondary ion yields especially of large molecular ones. Wide
perspectives of molecular projectile application in SIMS stimulate the search for optimal types of
cluster projectiles. The most considerable enhancement of secondary ion emission of molecular ions
has been obtained by using Au
m
and C
60
cluster ions. The most important area of SIMS application
remains the ultra-shallow depth profiling of silicon. Evidently in this case the silicon cluster ions
could be most preferable as projectiles because the profiling process will not accompanied by
contamination of inhomogeneous atoms from the ion beam that could distort the result of SIMS
analysis. Moreover, the self-sputtering mode is considered as very effective. Besides the theoretical
interpretation and computer simulation of the process become more clear and transparently.
In the present work the comparative studies of the emission of cluster Si
n
+
ions (n = 1 11) and
polyatomic Si
n
X
+
ions (X is B, C, N) under bombardment of single crystalline silicon by cluster
Si
m
-
(m = 1 6) and Au
m
-
(m = 1 9) ions with energy E
o
= 4 18 keV have been carried out. A
modernized experimental set-up [5] was used.
Significant non-additive enhancement of the yield of Si
n
+
cluster ions and most polyatomic ones
has been observed with an increase in the number of atoms in the cluster projectiles. The relative
abundance of Si
n
+
secondary cluster ions more rapidly decreased with increasing n for Si
m
-

projectiles as compared to Au
m
-
ones [5,7]. In spite of the fact that the yields of secondary cluster
ions under Si
m
-
bombardment was less than those under Au
m
-
bombardment, the non-additivity
factors were about the same values for both Si
m
-
and Au
m
-
projectiles with the same number of
atoms - m. For example, in changing the primary atomic Au
1
-
, Si
1
-
ions to cluster Au
3
-
, Si
3
-
ones, the
factors of non-additive enhancement of the yields of secondary Si
n
+
ions are about 30 - 35 for n = 8
- 10. This unexpected behavior of the non-additivity factors in transition from heavy cluster
projectiles to light ones will be interesting for theoretical interpretation. Sharp increase in the yield
of Si
3
B
+
, Si
3
C
+
, Si
2
N
+
ions by 100 1000 times has been observed when both Si
m
-
and Au
m
-

projectiles with m = 5 9 instead of atomic ones were used. These results confirm the advantages
of analysis by the cluster-SIMS-cluster mode [7].

[1] Y.LeBeyec, Int.J.Mass Spectrom. Ion Processes 174, (1998) 101
[2] A. Brunelle, S. Della-Negra, J. Depauw, D. Jacquet, Y. Le Beyec, M. Pautrat, K. Baudin, H.H. Andersen, Phys.
Rev. A 63 (2001) 022902.
[3] M.J. van Stipdonk, in: J.C.Vickerman, D.Brigs (Eds.), TOF-SIMS: Surface Analysis by Mass Spectrometry, IM
Publication and Surface Spectra, Huddersfield, 2001, p 309.
[4] S.N.Morozov, U.Kh. Rasulev, Nucl.Instr.Meth.B 203 (2003) 192.
[5] Sh.Akhunov, S.N.Morozov, U.Kh. Rasulev, Nucl.Instr. Meth.B 203 (2003) 146.
[6] S.N.Morozov, U.Kh.Rasulev, Appl. Surf. Sci. 231-232 (2004) 78.
[7] U.Kh. Rasulev, S.N. Morozov, Izv. Akad. Nauk. Ser. Fiz. 2002, 66, N4, P. 522 (in Russian).
CLU-P-Mo-P40
72
Cluster sputtering of silicon and silicon carbide under subkeV
polyatomic SF
5
ion bombardment

B. Atabaev


Arifov Institute of Electronics,
33 F. Khodjaeva street, Tashkent, 700125,
Email: atabaev@ariel.uzsci.net


The application of polyatomic primary ions in SIMS is becoming increasingly important for basic
reseach and analitcal applications [1,2]. The emission of silicon and silicon-carbon cluster ions has
been observed for Si crystal irradiated by SF
5
, C
2
F
6
and Au
5
ions [3,4]. We present here an
enhahcement that compares a primary Ar and SF
5
ions effectiveness on specific analyte by
examining the secondary atomic and cluster ion yields. Polyatomic primary slow subkeV SF
5
ion
bombardment of Si and SiC crystals have been shown to greatly increase the yield (10-50) of
silicon and mixed silicon-carbon cluster ion emission as well as the small enhancement (1.5-2) of
atomic ion emission observed. The exponentional distributions of silicon and silicon-carbon cluster
ions can be explained using model of the cluster formation through nascent cluster emission and
subsequent decomposition [5]. So while the high density collision cascade theory is well understood
and is know to be responsible for sputtering under high energy ions, there is a need to understand
the different origin of sputtering of semiconductor mareials on the concept of direct sputtering of
adsorbed silicon and silicon-carbon clusters by spatially correlated recoils under polyatomic
bombardment. The energy dependencies of cluster emission shown sharply threshold at subkeV
polyatomic SF
5
bombardment. This effect can be explained by decay of SF
5
molecule projectiles
and disappearing of spatially correlated recoils at molecular-lattice atom non-binary collision.


[1] A. Benninghoven, D. Stapel, Proceedings of the SIMS-12 Conference, Brussels, 1999,p.222.
[2] M. Van Stipdonk, V. Santiago, E. Schweikert, Proceedings of the SIMS-12 Conference,Brussels,p.287.
[3] H. Yamamoto, Y Baba, Surf. Sci.,433-435, 1999, p.890.
[4] U. Rasulev, S. Morozov, Proceedings of the ISI-2001 Conference, 2001, Moscow,p. 522.
[5] A. Wucher, B. Garrison, J. Chem. Phys.,105,14, 1996, p.5299.
CLU-P-Mo-P41
73
Secondary Ion Emission from Phthalocyanine Films with Gold-
Cluster Projectiles

S.N.Morozov
a,*
, G.L.Pakhomov
b
, U.Kh.Rasulev
a


a
Arifov Institute of Electronics, Akademgorodok, Tashkent 700125, Uzbekistan.
b
Institute for Physics of Microstructures, GSP105, Nizhny Novgorod 603950, Russia.
*
E-mail: serg.moroz@sarkor.uz


SIMS analysis of thick organic films has some difficulties connected with material destruction
and decrease in the yield of molecular ions in changing the static SIMS to the dynamic one. Use of
molecular projectiles in this case can be very perspective because of sharp enhancement of the yield
of large molecular ions [1-5].
In the present study we report some results of SIMS analysis of phthalocyanine (Pc) and metal
phthalocyanine (AlFPc, CuPc) films with cluster and atomic projectiles. We have used mass
selected gold-cluster ions Au
m
-
(m=1-9) and atomic ions O
-
, Cl
-
at energies of E
o
= 6 18 keV.
Phthalocyanine micron films were thermally evaporated onto Si(411) plates. An experimental setup
containing a sputtering ion source, magnetic separator of primary ions and magnetic mass-
spectrometer of secondary ions MI 1201 was used. Use of the low density of primary ion current ~
0.1 - 1 n/cm
2
allowed observation of the dependence of the secondary ion yield on a dose that
corresponds to changing the static SIMS to the dynamic one 10
12
- 10
14
cm
-2
.
The yield of the quasi-molecular ions Pc
+
, AlFPc
+
, CuPc
+
and the ions of large characteristic
fragments increases immediately with the raise in bombarding ion mass, particularly in changing
the atomic primary ions to the cluster ones. So, the yield of the molecular ions Pc
+
increases by 15
times in changing O
-
to Au
-
and further by 25 times in changing Au
-
to Au
9
-
for bombarding ion
energy 12 keV. The yield of the large characteristic fragments also enhanced. Spectrum degradation
has been found with the raise in a dose of the primary ions; this degradation manifests itself in
decreasing the yield of both molecular ions and large fragments for a dose exceeding 3*10
12
cm
-2
.
The special features of non-additive enhancement of the molecular ion yield in transition to the
cluster ion bombardment, as well as the reasons for the critical dose dependence of the yield of
different groups of secondary ions for a limit exceeding that of the static SIMS have been discussed.


[1] D. Stapel, O. Brox and A. Beninghoven, Appl. Surf. Sci V.140 (1998) 156.
[2] D. Stapel, and A. Beninghoven, Appl. Surf. Sci V.174 (2001) 261.
[3] Y.Le Beyec, Int. J. Mass Spectrom. 174 (1998) 101.
[4] A. Brunelle, S. Della-Negra, J. Depauw, D. Jacquet, Y. Le Beyec, M. Pautrat, K. Baudin, H.H. Andersen, Phys.
Rev. A 63 (2001) 022902.
[5] D.E.Weibel, N.Lockyer and J.C. Vickerman, 14
th
Intern. Conf. SIMS XIV, San Diego, Sept. 14 - 19, 2003, abstract
book, p 61.
CLU-P-Mo-P42
74
Molecular Dynamics Simulations to Explore Chemical Reactions and
Topography Formation in the Bombardment of Si(100) with C
60

a
Kristin D. Krantzman*,
a
David B. Kingsbury,
b
Barbara J. Garrison

a
Department of Chemistry and Biochemistry,
College of Charleston, 66 George Street, Charleston, SC 29412, United States
b
Department of Chemistry, 104 Chemistry Building,
Penn State University, University Park, PA 16802, United States


The dramatic success in the use of C
60
+
as a primary ion beam source for static Secondary Ion
Mass Spectrometry (SIMS) has inspired exploratory research in the use of C
60
+
for depth profiling.
The low energy per atom in the primary projectile is directly related to the depth resolution, and
therefore, C
60
+
has the potential to produce ultra-high resolution SIMS depth profiles. Gillen and
co-workers have recently reported interesting results from SIMS depth profiling experiments of
3000 electron volt C
60
+
bombardment of a silicon substrate. The experiments show degradation in
depth resolution that is thought to be the result of unusual topography formation. Molecular
dynamics simulations of the bombardment of a silicon substrate with C
60
+
are performed, which
examine chemical reactions between carbon and silicon and the composition and topography of
deposits that form in the substrate. A Tersoff multi-body interatomic potential developed for multi-
component systems is used, which has been successful in predicting the properties and defects of
SiC. In addition, simulations that examine the effect of successive multiple hits by the primary
projectile will be discussed.
CLU-P-Mo-P43
75
Evaluation of secondary ion yield enhancement from polymer
material by using TOF-SIMS equipped with a gold cluster ion source

K. Aimoto
a,
*, S. Aoyagi
b
, N. Kato
a
, N. Iida
c
, A. Yamamoto
c
and M. Kudo
a


a
Department of Applied Physics, Faculty of Engineering, Seikei University
3-3-1, Kitamachi, Kichijioji, Musashino, Tokyo, 180-8633, Japan
b
Department of Regional Development, Faculty of Life and Environmental Science, Shimane University
1060 Nishikawatsu-cho, Matsue-shi, Shimane, 690-8504, Japan
c
ULVAC-PHI Inc., 370 Enzo, Chigasaki, Kanagawa, 253-8522, Japan


It has been recognized that cluster ion beam as an primary ion source for TOF-SIMS is
significantly useful for material characterization since it provides less surface damages resulting in
higher secondary ion yields compared with conventional monoatomic or diatomic ion sources. A
great number of research results have already been reported using such cluster ions as Au
3
+
, Bi
3
+
and C
60
+
and distinct improvement in the secondary ion intensities from organic materials is
demonstrated compared with Ga
+
or Cs
+
. The detailed quantitative evaluation of the enhancement,
e.g. the energy dependence of the primary ion and the detected mass dependence on the
enhancement of the secondary ion intensity, however, has not been fully studied yet.
In this study, we investigated the intensity enhancement obtained by Au
+
and Au
3
+
compared
with Ga
+
bombardment using a polymer sample with different molecular weight distribution.
As polymer samples, we used polyethylene glycol, PEG, with different average molecular weight
(400 and 1000) prepared on a Si substrate cast by spin coating method. TOF-SIMS measurements
were carried out with a Au cluster primary ion source and a Ga ion source over the mass range
appropriate for each sample. The evaluation of the secondary ion intensities consisting of some
number (n) of the repeating unit and sodium ( [ HO-(CH
2
-CH
2
-O)
n
-H-Na]
+
) were carried out and
the intensity enhancement of each peak were calculated for the measurements of the Au
+
and Au
3
+

compared with Ga
+
bombardment.
It was found out that the enhancement of the secondary ion intensity was about 20 to 80 for Au
+

and about 300 to 2600 for Au
3
+
compared with Ga
+
bombardment. It was also found out that the
degree of the secondary ion intensity enhancement for both Au
+
and Au
3
+
increased as the mass of
the secondary ion increases.
The dependence of the mass of the detected secondary ions on the yield enhancement will be
discussed in detail as well as the effect of the energy and the mass of the primary cluster ions.
CLU-P-Mo-P44
76
Molecular Dynamics Study of Particle Emission
by Reactive Cluster Ion Impact

Takaaki Aoki
*
, Satoshi Ninomiya and Jiro Matsuo

Quantum Science and Engineering Center, Kyoto University, Gokasho, Uji, 611-0011, JAPAN
aoki@sakura.nucleng.kyoto-u.ac.jp


The impact process of large cluster ion is of interest because it causes high-density particle
collision and energy deposition at very narrow area at target surface. This characteristic collisional
process implies large motion of surface atoms and enhancement of chemical reaction. From the
view point of SIMS measurement, these effects are expected for high sputtering yield with shallow
penetration range of probe ions, which results in the improvement of depth resolution. However, the
mechanism of particle emission during cluster ion irradiation is still unknown.
In this study, the molecular dynamics (MD) simulations of fluorine clusters impacting on silicon
surface were performed. By iterating collisional simulations on a same target, accumulation of
incident atoms and evolution of surface morphology were examined as well as emission process of
precursors. When (F
2
)
300
clusters were sequentially irradiated on Si(100) target at 6keV of total
incident energy, column-like surface structure covered with F atoms was formed. As the number of
incident clusters increased, sputtering yield of Si atoms also increased because the target surface
was well fluoridised to provide SiF
x
precursors. Size distribution of emitted particles showed that
SiF
2
was the major sputtered particle, but various types of silicon-fluoride compounds such like
Si
2
F
x
, Si
3
F
x
and very large molecules consists of hundred atoms were also observed. This size
distribution was similar to that under thermal equilibrium condition at high-temperature.
Mechanism of sputtering with reactive cluster ion and comparison with experimental data will be
discussed.
CLU-P-Mo-P45
77
High-intensity Si cluster ion emission from a silicon target bombarded
with large Ar cluster ions

Satoshi Ninomiya*, Toshio Seki, Takaaki Aoki, and Jiro Matsuo

Quantum Science and Engineering Center, Kyoto University, Uji, Kyoto 611-0011, Japan
ninomiya@nucleng.kyoto-u.ac.jp


Si cluster ions emitted from silicon targets have been measured with a quadrupole mass
spectrometer under large Ar cluster ion bombardment. High-intensity cluster ion beams with the
current density of a few A/cm
2
were used. Average size of Ar cluster ions is 3000 atoms/cluster.
Energy of incident cluster ions were varied from 10 to 25 keV. Emission of Si cluster ions from
silicon targets bombarded with keV-energy atomic Ar ions has been reported [1]. The yield of Si
4
+

was 3 orders of magnitude lower than that of Si
+
under atomic Ar ion bombardment. We have found
that Si
4
+
yields under Ar cluster ion bombardment were about 100 times higher than that yields
under atomic Ar ion bombardment. Si cluster ions larger than Si
4
+
were also detected. Emission
mechanism of Si cluster ions under large Ar cluster bombardment was quite different from that
under atomic Ar ions, due to high-density energy deposition at extremely narrow region at Si
surfaces.


[1] D. Lipinsky, R. Jede, O. Ganschow, and A. Benninghoven, J. Vac. Sci. Technol. A 3(5) (1985) 2007-2017.
CLU-P-Mo-P46
78
Characterization of Drug-Eluting Stent (DES) Materials with Cluster
Secondary Ion Mass Spectrometry (SIMS)

a
Christine Mahoney
a
Albert Fahey,
a
Greg Gillen,
b
Dinesh Patwardhan, and
b
M. Ken McDermott
cmahoney@nist.gov

a
National Institute of Standards and Technology, 100 Bureau Drive,
Mail Stop 8371, Gaithersburg, MD, 20899-8113, USA
b
Center for Devices and Radiological Health, Food and Drug Administration, 12725 Twinbrook Parkway,
HFZ-150, Rockville, MD 20852, USA

With cardiovascular disease continuing to escalate worldwide, there is much excitement in the
cardiology community about drug eluting stents (DES) which are a promising new treatment for
coronary artery disease. The concept behind DES is the controlled release of a drug (paclitaxel,
sirolimus) from a polymer film or multiple polymeric layers. The release of these drugs helps to
prevent the process of restinosis, or the build up of smooth muscle cells, at the site of the stent.
Since the fabrication of these devices can often be quite difficult, it is important that extensive
analysis of the final product as well as all formulation steps is done in order to determine the
integrity of the device for product development and quality control purposes. Dissolution studies
will be able to monitor the rate of drug release. However these studies need to be correlated with
actual structural information, compositions and defects within the device. Cluster SIMS will be
able to do this, with a high sensitivity (ppm) and high spatial resolution, both laterally (~0.1 um)
and as a function of depth (1 10 nm), as compared to other analytical methods. It is particularly
important in these materials to characterize the molecular composition of the surface and near
surface region of the device (1-100 nm) because this region controls the biocompatibility and
influences the magnitude and temporal variation of drug release.
This talk will focus on the results from an ongoing collaboration with the Food and Drug
Administration (FDA) involving the analysis of real DES and DES materials using cluster SIMS.
We further explore the utility of cluster SIMS in depth profiling of materials commonly utilized in
DES, including poly(ethylene-co-vinyl acetate (PEVA), Poly(lactic-co-glycolic acid) (PLGA),
poly(n-butyl methacrylate) (PBMA) and various poly(urethanes), in addition to the commercial
drugs Paclitaxel and Sirolimus (used in Taxus

and Cypher

stents respectively). The resultant

molecular depth profiles obtained from the various polymeric films utilized for DES applications
show very little degradation in molecular signal as a function of SF
5
+
primary ion dose when
experiments were performed at cryogenic temperatures. Polymeric films (e.g. polyurethanes and
PLGA) containing varying concentrations of drug will also be analyzed as a function of depth. This
capability will allow us to correlate the compositional information with the FDAs dissolution
studies. Finally, depth profiling in actual DES will be performed with cluster SIMS in order to
establish feasibility for real world sample analysis.
CLU-P-Mo-P47
79
Performance of a C60
+
Ion Source on a Dynamic SIMS Instrument

Albert J. Fahey
a
*, Greg Gillen, Peter Chi

a
National Institute of Standards and Technology
100 Bureau Dr. Stop 8371
Gaithersburg, MD 20899-8371, U.S.A
Albert.fahey@nist.gov


An IonOptika
1
C
60
+
ion source has been fitted onto a CAMECA
1
ims-4f. Stable ion beams of
C
60
+
and C
60
2+
have been obtained with typical currents approaching 20 nA under conditions that
allow for several hundred hours of source operation. The beam has been able to be focussed into a
spot size of ~1 m and scanning ion images acquired.
Previous efforts with cluster ion sources used for analyzing both organic and inorganic materials
have been very successful. Minimization of beam-induced damage with organic materials has
allowed depth profiling of polymers and enhanced ion yields for high-molecular weight fragments.
Inorganic material analysis has benefited in the area of ultra-shallow depth-profiling as well as for
analysis of some particularly difficult systems such as Ni-Cr multi-layers. We have performed
analyses to characterize the performance of C
60
+
and C
60
2+
. Depth profiles of Cr-Ni with C
60
+
have
produced excellent results. We have discovered that under bombardment energies of <12 kV on Si
that C
60
+
will sputter material from the sample but will also produce deposition at a rate that
exceeds the sputter rate. The performance of the source and our experiences with its operation will
be reviewed. In addition some characteristic analysis data will be shown and discussed.


[1] Certain commercial equipment, instruments, or materials are identified in this document. Such identification does
not imply recommendation or endorsement by the National Institute of Standards and Technology, nor does it imply
that the products identified are necessarily the best available for the purpose.
[2] J. Doe, A.N. Other, Journal of SIMS 12 (1999) 1024-1026.
CLU-P-Mo-P48
80
TOF-SIMS Imaging of OLED Devices using a Au Cluster Ion Beam

S.R. Bryan
a,
*, J.H. Hammond
b
, N. Sekiya
b
, A. Yamamoto
b
.

a
Physical Electronics, 18725 Lake Drive East, Chanhassen, MN 55317 USA
b
ULVAC-PHI, Inc. 370 Enzo, Chigasaki, 253-0084 Japan
sbryan@phi.com


Organic light emitting diode (OLED) technology is a growing research area which may lead to
next generation display and lighting commercial products [1]. OLED is based on the use of multi-
layers of thin molecular or polymer materials which emit light directly when a voltage is applied.
The total thickness of the multi-layer film structure is usually less than 500nm. No backlighting is
needed, as is the case of LCD displays, which means that OLED displays are less expensive, lighter
and require less power. In fact, OLED displays can be made on a flexible substrate such as a clear
plastic film or a reflective metal foil rather than the traditional glass substrate. The organic layers
can be doped with specific enhancing molecules to get the desired brightness and color.
This new cutting edge technology based on patterned organics requires analytical techniques that
can characterize the organic structure of the devices with submicron spatial resolution and good
depth resolution. TOF-SIMS offers one of the only techniques that can provide the needed spatial
resolution with molecular specificity.
One of the most important commercial developments in TOF-SIMS instrumentation in recent
years has been the introduction of cluster ion beams for enhancement of organic molecular
secondary ion yields. Although Ga
+
LMIG sources, which have been used in TOF-SIMS since
1990, has sufficient spatial resolution for most applications, the secondary ion yield of organic
molecules from Ga
+
sputtering is insufficient for many applications. Development of the Au LMIG
emitter, which allows TOF-SIMS analysis with Au
+
, Au
2
+
or Au
3
+
, extends the capabilities of TOF-
SIMS to image patterned organic materials. The capabilities of imaging with the Au LMIG emitter
will be compared to the Ga emitter for characterization of OLED devices. Spatial resolution,
damage cross-sections, and ultimate detection limits will be compared between Ga, Au, Au
2
, and
Au
3
for typical molecules used in OLED devices.

CLU-P-Mo-P49
81
Au-Analyte Adducts Resulting from Single Massive Gold Cluster
Impacts

G. J. Hager
*
, C. Guillermier, S. V. Verkhoturov, and E. A. Schweikert

Center for Chemical Characterization and Analysis
Texas A&M University, College Station, Texas 77843
hager@mail.chem.tamu.edu


Recent experiments have shown that surface bombardment using 40 - 136 keV Au
400
4+

primary ions produces large molecular ion yields, some in excess of unity, with minimal surface
damage [1]. A surprising observation is the occurrence of Au analyte adducts as part of the ejecta
desorbed by single Au-cluster impact. A first study of in-situ Au-adducts obtained from Au
400
4+

bombardment of phenylalanine, glycine, histidine and CsI is presented here.
The experiments were run on a custom-designed setup comprising a Liquid Metal Ion
Source, LIMS, a Wien filter for mass analysis of the primary ion beam, a beam pulser for single
projectile bombardment, and linear ToF-MS. The LMIS, which uses a Au-Si eutectic, has been
described elsewhere [2]. This source can produce gold clusters from Au
2
+
to Au
1000
z+
. For 10 < n/z
< 1000 (where n = number of Au atoms), a maximum beam intensity is obtained at n/z = 100. With
the Wien filter set for n/z = 100, the mean charge of the clusters was found to be z = 4, thus n = 400.
The experiments were run in the event-by-event bombardment-detection mode with primary ion
energy of 136 keV at the limit of single projectile impacts on various organic and inorganic targets
in the negative mode. Secondary ions were detected with a dual microchannel plate eight-anode
assembly coupled to pulse counting electronics. Data processing was performed with Total Matrix
of Events software which is designed for experiments in the event-by-event detection mode [3].
For the bombardment conditions noted, we are able to detect in-situ Au-analyte adduct ions
from surfaces including phenylalanine, histidine, glycine and CsI. The gold adducts are formed
with various secondary ions which include fragment ions (AuCN
-
, Y = 0.02 - 0.04; AuI
-
, Y =
0.115), molecular ions (Au(M)
-
, Y = 0.03 0.10; AuCsI
-
, Y = 0.16), and cluster ions (Au(M
2
-H)
-
, Y
= 0.01 0.10; AuMCN
-
, Y = 0.01 0.09; Au(CsI)
2
-
, Y = 0.039). Further, close to one percent of
the primary projectile impacts result in the emission of more than one adduct of similar m/z. The
mechanism of adduct formation remains to be elucidated. A key observation is that the adducts are
formed in the bombardment-desorption event from the constituents of the incident massive cluster,
i.e. the Au-adducts observed here are not the result of Au implanted from previous projectiles.
Indeed, we obtained the same yield for AuI
-
when bombarding a CsI target over an area of 2 mm
2

with 10
3
primary ions as with 10
5
primary ions.


[1] A. Tempez et al., Rapid Comm. Mass Spec., 8, 371, (2004).
[2] P. Attal et al., Nucl. Instr. Meth. Phys. Res. A, 328, 293, (1993).
[3] R. D. Rickman et al., Appl. Surf. Sci., 231-232, 54-58 (2004).

Work supported by NSF Grant CHE-0135888 and R. A. Welch Foundation Grant A-1482.
CLU-P-Mo-P50
82
Organic SIMS with single massive gold projectile: Ion yield enhancement
by silver metallization

C. Guillermier
*
, V. Pinnick, J. Locklear, S. V. Verkhoturov and E. A. Schweikert

Center for Chemical Characterization and Analysis
Texas A&M University, College Station, Texas 77843
cguillermier@mail.chem.tamu.edu


Bombardment of various organic targets has shown that an average of 20 SIs are generated from
the impact of a single massive gold projectile Au
n
q+
with n/q=100 at 340eV/atom. We are referring
here to negative ion emission. Among the SIs of highest yields are the deprotonated molecular ion
and CN
-
. They vary from 50% to 150% depending on the target. The experiments were run in an
instrument consisting of a Liquid Metal Ion Source and a TOF-MS with an 8 anode detector for SI
identification.
The purpose of this study was to test if silver metallization could still further enhance the SI
yields. Metallization has been shown to be an efficient method for increasing molecular ion yields
from organic targets in SIMS [1]. The target examined were vapor deposited glycine on silicon
wafers coated with 1, 3 and 5nm thick silver layers and uncoated glycine as a reference. With a 1nm
silver layer, the CN
-
yield is 200% vs 100% for uncoated glycine. For 3 and 5nm the CN yield was
180%. The enhanced response of CN is of practical interest since a molecule can be labeled with
13
C and/or
15
N and hence be detected with high accuracy via the labeled CN.
The average total number of SIs per projectile impact increased to 25 with a 1nm silver coating
vs 20 SIs for glycine alone. 18SIs were detected in the case of a 5nm silver coating. A large
amounts of Ag(CN)
n
-
, AgO(CN)
n
-
and Au(CN)
n
-
were also observed in the case of a 1nm coated
glycine. For example a yield of 36% was recorded for Ag(CN)
2
-
which is 3 times the yield for the
same SI from uncoated glycine.
Similar experiments with C
60
projectiles are in progress.


[1] A. Delcorte, P. Bertrand, Appl Surf. Science, 231-132 (2004) 250-255

Work supported by NSF Grants CHE-0135888, CHE-0449312 and R. A. Welch Foundation Grant A-1482
CLU-P-Mo-P51
83
Kinetic energy distributions of neutral In and In
2
sputtered by
polyatomic ion bombardment

Andrey Samartsev, Andreas Wucher *

Department of Physics, University of Duisburg-Essen, D-45117 Essen, Germany
wucher@uni-essen.de


Energy distributions of In monomers and In2 dimers released from a polycrystalline indium
surface under bombardment with 5 and 10 keV,

1
Au ,

2
Au ,

3
Au projectiles have been
investigated by means of laser postionization time-of-flight mass spectrometry. The results show a
clear transition from distributions typical for linear cascade sputtering at 5-keV

1
Au impact to a
collisional spike dominated emission process at 10-keV

3
Au impact. More specifically, the
measured emission energy spectrum can be decomposed into a linear cascade contribution well
described by the Thompson formula and an additional spike contribution. The latter manifests as a
low-energy peak, which is found to strongly increase with increasing projectile nuclearity or energy
and dominate the spectrum for 10-keV cluster projectiles. The kinetic energy distributions of
Indium dimers also depend on the projectile nuclearity. In the case of spike dominated emission, the
most probable kinetic energy of Indium dimers is shifted to lower energies, but higher than that
observed for the emitted monomers. This finding is remarkable since the opposite order is observed
under bombardment conditions leading to cascade sputtering.
Converting the data to emission velocity instead of energy spectra, we find an even more
interesting transition. In cases where the spike contribution to the sputtering yield is insignificant
(>15%) the velocity distributions of monomers and dimers significantly differ from each other in a
way that the since the most probable velocity of dimers is lower and the asymptotic high-velocity
slope is larger than for monomers. Under spike-dominated conditions, on the other hand, the
velocity distributions of monomers and dimers both shift to lower velocities and, more interestingly,
become apparently identical. This finding suggests the particle emission process from a spike must
be considered as a collective process, very much resembling the quasi-free expansion of a
superheated gas into the vacuum. In fact, our data can be favourably described by the so-called gas
flow thermodynamic model based on this concept, which has originally been proposed to explain
the emission characteristics during sputtering of condensed rare gases [2]. In contrast, we find that
our measured spectra cannot be consistently interpreted in terms of a thermal spike emission
mechanism.


[1] M.W. Thompson, Phil. Mag. 18, 377, (1968)
[2] H.M. Urbassek and J. Michl, Nucl. Instr. and Meth. B22, 480-490, (1987)

CLU-P-Mo-P52
84
Mass spectra and ionization probabilities of Indium species sputtered
by atomic and polyatomic ion bombardment.

Andrey Samartsev, Andreas Wucher *

Department of Physics, University of Duisburg-Essen, D-45117 Essen, Germany
wucher@uni-essen.de


The sputtering of a polycrystalline Indium surface under bombardment with Au
1
-
, Au
2
-
, Au
3
-
, Au
5
-
ions with kinetic energies of 5 and 10 keV ions was investigated by means of TOF-SIMS and -
SNMS. The projectiles are produced by a sputter ion source based on Cesium bombardment of a
gold target. Postionization of neutral species leaving the surface was performed by means of single
photon ionization from an intense UV laser beam operated at a wavelength of 193 nm. It is shown
that the primary ion current obtained from the cluster ion source suffices to detect sputtered neutral
In
n
clusters up to n = 30. Secondary ions were detected without the laser, but under otherwise
exactly the same experimental conditions as postionized neutrals. From the comparison of both
signals, the ionization probabilities of sputtered indium atoms and clusters are determined and
compared for different bombarding conditions and projectiles. Using these data, the partial sputter
yields of different emitted species regardless of the charge state are determined. Results show
that all partial yields produced by polyatomic projectiles are enhanced with increasing projectile
nuclearity and energy. Comparing the results for conditions of constant impact velocity, a 1.9 fold
enhancement is observed for total yield upon transition between mono- and diatomic projectiles.
For the partial yields of In
n
clusters, this factor is found to increase with increasing cluster size and
reaches >100 for In
12
. The ionization probability of all emitted species is found to exhibit practically
no dependence on the projectile impact energy. For sputtered In
n
clusters, this quantity strongly
increases with increasing cluster size n. As a function of projectile nuclearity, we find a decreasing
ionization probability for sputtered monomers with increasing number of constituent gold atoms,
amounting to about a factor of 4 upon transition from Au
1
-
to Au
5
-
at equal impact energy. For
sputtered dimers and larger clusters, on the other hand, practically no influence of projectile
nuclearity is observed outside our experimental error.

CLU-P-Mo-P53
85
Study of Polymer Fragmentation using Polyatomic
Primary Ions

X.A. Conlan
a
*, I.S. Gilmore
b
, A. Henderson
a
, N.P. Lockyer
a
, J.C. Vickerman
a

a
Surface Analysis Research Centre, School of Chemical Engineering and Analytical Science University of Manchester
Po Box 88 Manchester M60 1QD, UK
b
National Physics Laboratory, Centre for Optical and Analytical Measurement,
Teddington TW11 0LW, Middlesex, UK
email: x.conlan@postgrad.umist.ac.uk


The benefits of polyatomic primary ion sources have been shown since the use of SF
6
0
[1] and the
further development of SF
5
+
,

resulting in a higher secondary ion yield for a large range of organic
materials [2]. Since this early development increases in secondary ion yield from organic materials
using Au
3
+
polyatomic primary ion compared to Au
+
monoatomic primary ion have been reported
[3]. Also through ToF-SIMS studies of several molecular solids significant enhancement of
secondary ion yields have been observed using C
60
+
[4].

Polymer systems have been studied using monoatomic ion beams for some time here we look at a
standard polymer Polyethylene terephthalate (PET). Distinct fragmentation pathways resulting from
high energy primary ion bombardment of PET have been observed. [5] One via a positively charged
ion pathway and the other via the formation of radical species. Here we follow the progression of
the PET fragmentation pathways under bombardment of Au
+
, Au
3
+

and C
60
+
ion beams.

Interest in bio-polymers and their environmentally friendly applications has increased in recent
years as practical bio-polymers have developed [6]. Here we look towards employing polyatomic
primary ions to gain a further understanding of the more complex bio-polymers systems using
polyatomic primary ions.


[1] A.D. Appelhaus, J.E. Delmore, Anal. Chem. 61 (1989) 1087-1093
[2] F.Kotter, A. Benninghoven, Applied Surface science. 133 (1998) 47-57
[3] N. Davies, D.E. Weibel, P. Blenkinsopp, N. Lockyer, R. Hill, J.C. Vickerman, Applied Surface
Science 203-204 (2003) 223-227
[4] D. E. Weibel, S. Wong, N. P. Lockyer, P. Blenkinsopp, R. Hill, J. C. Vickerman, Anal. Chem, 75
(2003) 1754-1764.
[5] G. J. Leggett, J. C. Vickerman. International Journal of Mass Spectrometry, 122, (1992), 281-319.
[6] L. Averous. Journal of Macromolecular science, C44 3 (2004) 231-274
CLU-P-Mo-P54
86
Influence of Primary Ion Species on the Secondary Cluster Ion
Emission Process from SAMs of Hexadecanethiol on Gold

M. Schrder, D. Lipinsky and H.F. Arlinghaus
*


Physikalisches Institut, Westflische Wilhelms-Universitt, Wilhelm-Klemm-Str. 10, D-48149 Mnster, Germany
*
email adress: hearlin@uni-muenster.de


In order to investigate the secondary cluster ion emission process of organo-metallic compounds
under keV ion bombardment, self-assembled monolayers (SAMs) of alkanethiols on gold are ideal
model systems. In this experimental study, we focus on the influence of the primary ion species on
the emission processes of gold-alkanethiolate cluster ions from a hexadecanethiol SAM on gold.
For this purpose we carried out time-of-flight secondary ion mass spectrometry (TOF-SIMS)
measurements using the following primary ion species: Ar
+
, Xe
+
, SF
5
+
, C
60
+
(10 keV), Au
+
, Au
3
+
,
Bi
+
, Bi
3
+
, Bi
3
++
, Bi
5
++
, Bi
7
++
(25 keV).
It is well known that gold-alkanethiolate cluster ions Au
x
M
y
-
with M = S-(CH
2
)
15
-CH
3
, x-3 y
x+1 show intense peaks in negative mass spectra. We derived yields Y, disappearence cross sections
and the resulting formation efficiencies E exemplarily for the gold-hexadecanethiolate cluster
ions Au
x+1
M
x
-
up to x=7. Assuming a surface coverage of 1 and correcting the signal intensities for
the detection probability D, we were able to determine the transformation probability P and found
an exponentielly decreasing behaviour for increasing x-values.
In contrast to the well-known increase in formation efficiency for molecular secondary ions when
moving from lighter to heavier (e.g. Ar
+
to Xe
+
) and from monoatomic to polyatomic (e.g. Xe
+
to
SF
5
+
) primary ions, we find a distinctly different bahviour. For heavier and polyatomic primary
ions, there is a drecrease in formation efficiency for the gold-hexadecanethiolate clusters, which is
more pronounced for higher values of x.
BIO1-P-Mo-P55
87
Enhanced Peptide Molecular Imaging
by Aqueous Droplet

Y. Murayama, M. Komatsu, H. Hashimoto

Advanced Analysis Div., Leading-edge Technology Development, Canon Inc.
3-30-2 Shimomaruko, Ohta-ku, Tokyo 146-8501, Japan
E-mail address: murayama.yohei@canon.co.jp


TOF-SIMS has possibility of becoming a very powerful tool for measurement of mass-images in
many kinds of biomaterials. For more accurate discrimination of biomolecules in the images, a
technique for detecting larger peptide molecules is acquired. A new methodology, droplet-enhanced
secondary ion mass spectrometry, is reported for the molecular analysis of biomaterials. In order to
promote the ionization of molecular ions, a few micro liter of aqueous solution containing sodium
salt or acid was dropped onto peptide samples before TOF-SIMS measurement. Using this
technique, we have successfully obtained strong molecular secondary ion signals from thin film
samples of peptide molecules 521< m/z < 7649. The sodium salt agent was selected as an effective
ionization promoter for small peptides about < m/z 2000. Addition of sodium ion to the peptide
molecules likely induces proton adsorption onto them. On the other hand, the acid agent was
effective for larger peptide ionization, and particularly enhanced multivalence peptide ion signals
(e.g. [M+2H]
2+
, [M+3H]
3+
). Moreover, this technique simultaneously activated ionization of each
kind of peptide molecules in a multicomponent sample with keeping the original distribution. Thus,
this technique can be used for the analysis and imaging detection of trace quantities of high mass
species in biological/tissue samples. We have also succeeded in detection and quantification of
nanogram levels of chemical reaction products with the Bubble Jet Printing droplets. These
techniques suggest the future TOF-SIMS usefulness for getting peptide/protein maps from
biomaterial samples in assessing disease and drug efficacy.

BIO1-P-Mo-P56
88
TOF-SIMS analysis of fresh frozen, freeze-dried rat cerebellum

a
Hkan Nygren,
a
Katrin Brner,
a
Per Malmberg,
b
Birgit Hagenhoff and
c
Jan-Eric Mnsson


a
Department of Anatomy and Cell Biology, University of Gteborg, P.O. Box 420, SE-40350 Gteborg.
b
Tascon GmbH, Mnster, Germany (www.tascon-gmbh.de)
c
Department of Neurochemistry, University of Gteborg, Sahlgrenska Mlndal Hospital,


High pressure-frozen, freeze-fractured and freeze-dried rat cerebellum was analyzed with a TOF-
SIMS IV instrument equipped with a Bi cluster ion source. Data were collected separately as
spectra of high mass resolution m/m > 5000 and images at high lateral resolution < 300 nm.
Images were made showing the localization of the peaks m/z = 22.99, sodium, and m/z = 39.1,
potassium. Images were also made showing the distribution of the peak at m/z = 86 representing a
known fragment of the phosphorylcholine head group of sphingomyelin and phosphatidylcholine
(Al-Saad, Siems et al. 2003), and was used for the localization of phospholipids in the present
study. Significant peaks were also seen at m/z = 369 and 385, which have been characterized with
electrospray Q-TOFMS. These peaks were used for imaging the distribution of cholesterol. Larger
specific fragments were found at m/z=851, m/z=835 and m/z=823. These fragments represent the
24:0 galactosylceramide [M+Na]+ (m/z=851), [M-O+Na]+ (m/z=835) and [M-c2h2+Na]+
(m/z=823) and have been found previously with other mass spectroscopic methods such as
MALDI-TOF MS. These peaks were assembled into images showing the localization of
galactosylceramide.
The 24:1 sulfatide galactosylceramide-3-O-sulfate can be located in the TOF-SIMS spectra
recorded in the negative mode at m/z=888, and the hydroxylated counterpart h24:1 can be seen at
m/z=904. The dominating species in the spectra are m/z=890 and m/z=906, representing 24:0 and
hydroxylated h24:0 sulfatide galactosylceramide-3-O-sulfate. These peaks have been characterized
by electrospray Q-TOF MS of purified sulfatide galactosylceramide-3-O-sulfate.
Figure 1 shows an overlay image of the distribution of sodium (red), potassium (green) and
cholesterol (blue) in the inner part of the granular layer of rat cerebellum.
Figure 2 shows an overlay of sodium (red), colesterol (blue) and galactosylceramid (green) in the
same area.


Figure 1 Figure 2
BIO1-P-Mo-P57
89
Cardiac cells and tissue analysis by gold cluster ion bombardment

Monika Aranyosiova
a,b
*, Alzbeta Chorvatova
c
, Dusan Chorvat jr.
a
, Dusan Velic
a,b

a
International Laser Center, SK-81219 Bratislava, Slovakia
b
Faculty of Natural Sciences, Comenius University, SK-84215 Bratislava, Slovakia
c
Research Center of Sainte Justine Hospital , Montreal, Canada
aranyosiova@ilc.sk


Cardiac cells and tissue of rat with spontanneous hypertense diagnosis were studied.
Motivation is to find the chemical signature between hypertense and healthy rat cardiomyocytes and
to proove capabilities of SIMS technique as a diagnostic tool in medicine. The use of gold cluster
ion beams in secondary ion mass spectrometry to analyze cardiac cells and tissue was investigated.
SIMS technique can be exploited in the chemical characterization and distribution of specific
molecular ions in biological samples. The samples of cardiac tissue were prepared by cutting thin
slices and deposited on Si substrate. The samples of single cardiac cells in physiological solution
were dropped and dried on Si substrate. The experiments were performed by using TOF-SIMS IV
instrument (ION-TOF, Muenster, Germany). The primary ion source was gold LMIG and 25 keV
Au
+
and Au
3
+
primary ion bombardment was used for the analysis. The investigation was focused
on the determination and distribution of the phospholipides, cholesterol and other characteristic
molecular ions in the single cell membrane and tissue slices [1].
Polyatomic primary ions Au
3
+
provide approximately 10 times higher yield of molecular
ions with higher masses from cells and tissue samples compared to Au
+
. Therefore a choice of a use
is the Au
3
+
cluster beam with a clear advantage. In positive polarity, membrane related ions as
cholesterol (m/z 369.4, 385.4) and phosphatydilcholine (m/z 147.1, 184.1) were clearly identified in
both samples. In the mass range m/z 720 900 fragments were observed and most probably
correspond to phospholipides. Peaks over mass m/z 1200 might correspond to cardiolipin, a unique
phopholipid typical for cardiomyocytes membrane containing 65 and 81 carbons. In animal tissues,
cardiolipin contains almost exclusively 18 carbon fatty acids and 80% of them is typically linoleic
acid [2]. Peaks in the range of mass m/z 428.4 432.4 are characteristic for cardiomyocytes and
were determined in both polarities in both samples. In negative polarity, PO
2
and PO
3
most
probably represent the phosphate group of phospholipides. Linoleic acid peak (m/z 279.5), other
fatty acids peaks, and phosphatidylglycerol, as a precursor of cardiolipin synthesis, were identified.
ToF SIMS images of the cells and tissue were obtained from 500 x 500 m
2
areas in both
polarities. Distributions of phospholipides, cholesterol and mulecular ions in the mass range m/z
428.4 432.4 are complementary.
SIMS technique along with Au
3
+
cluster primary ion beam is a promissing tool for detection
of high mass biomolecules. Chemical differentiation between healthy and diseased cells and tissues
would be superior and crucial for clinical purposes in medicine.

The financial supports of VEGA 1/0216/03 and APVT 298 are acknowledged.


[1] D. Touboul, F. Halgland, A. Brunelle, R. Kersting, E. Tallarek, B. Hagenhoff, O. Laprevote, Anal. Chem. 76 (2004)
1550 - 1559
[2] Schlame M. and Rustow B., Biochem. J. 272 (1990) 589-595
BIO1-P-Mo-P58
90
Hair Dye distribution in human hair by ToF SIMS

Bo-Jung Chen, Wen-Yin Chen,

Yong-Chien

Ling*

Department of Chemistry, National Tsing Hua University,
Hsinchu, Taiwan-30013, Republic of China
ycling@mx.nthu.edu.tw


Commercial hair coloring products contain a mixture of p-phenylenediamine, benzenediols,
aminophenols and other activated aromatic substrates which are dye precursors involved in the
process of hair dying. [1, 2]. A major difficulty in the application of hair for biomonitoring is the
contamination problem and the poorly understood mechanisms of uptake, incorporation and binding
of elements in the hair matrix.[3]
Time of flight-secondary ion mass spectrometry (TOF-SIMS) has become one of the most
sensitive analytical techniques in surface science. In this work, the extent of hair explored to hair
dye was detected by imaging TOF-SIMS. The hair sample was cut in cross and longitudinally
sections first. The distribution of hair dye in the internal hair section was detected afterwards. The
internal hair section of different parts (front, meddle and root), before and after the application of
hair dye, was compared based on their secondary ions images. The preliminary results indicated that
hair was a good candidate for biomonitoring with ToF SIMS.


[1] M. Gago-Dominguez, J.E. Castelao, J.M. Yuan, M.C. Yu, R.K. Ross, Int. J. Cancer 91 (2001) 575.
[2] L.S. Cook, K.E. Malone, J.R. Daling, L.F. Voigt, N.S. Weiss, Cancer Causes Control 10 (1999) 551.
[3] I.M. Kempson, W.M. Skinner, P.K. Kirkbride, Biochimica et Biophysica Acta 1624 (2003) 1 5.

BIO1-P-Mo-P59
91
Model Multilayer Structures for Three-Dimensional Cell Imaging

Joseph Kozole
a*
, Christopher Szakal
a
, and Nicholas Winograd
a



a
Department of Chemistry, 104 Chemistry Building Penn State University, University Park, Pennsylvania 16802
*
jjk302@psu.edu


The recent employment of cluster primary ion sources, particularly C
60
+
and Au
3
+
, has led to the
potential for three-dimensional ToF-SIMS imaging of biological species because of large sputter
yields and minimal damage accumulation after cluster bombardment [1]. The ability to obtain
chemical-specific information as a function of depth in biological cells is expected to offer valuable
insight into biological activity at the sub-cellular level. The plausibility of this prospective
application can be better established through the detailed understanding of cluster primary ion
bombardment of biologically relevant molecules in cryogenically frozen water, the preserved native
environment of cellular material. The investigation at hand attempts to characterize the primary
cluster impact of biomaterials through molecular depth-profile studies involving multilayered,
frozen-hydrated films consisting of biologically relevant material. Model multilayer structures
include a frozen sucrose solution enclosed in a phospholipid film and a frozen histamine solution
buried by a pure water ice film. Preliminary data indicates that biomolecule information can be
uncovered after the sputter removal of an overlying layer with no appreciable loss of signal up to
micrometer scale distances. The results suggest that biomaterials such as membrane lipids do not
experience damage after C
60
+
primary ion bombardment and support the potential for three-
dimensional SIMS imaging of biological species. In addition, preliminary results involving image
depth profiles of model cell systems and biological cells will be presented to further establish three-
dimensional imaging as a plausible biological application of SIMS.


[1] A Wucher, S. Sun, C. Szakal, and N. Winograd. Anal. Chem. 2004, 76, 7234-7242

BIO1-P-Mo-P60
92
Is it possible to differentiate between intact and denatured adsorbed
proteins without using recognising reactions?

P. Rossbach
a
, R. Crockett
a
, H. Troxler
b
, S. Equey
a


a
Swiss Federal Laboratories for Material Science and Technology, Ueberlandstr. 129, 8600 Duebendorf, Switzerland
b
University Zuerich Childrens Hospital, Steinweisstr. 75, 8032 Zuerich, Switzerland
e-mail: peggy.rossbach@empa.ch


The interactions of proteins with surfaces play in important role in the field of medical
applications and bioengineering. For example, the adhesion of cells onto implant surfaces is driven
by adsorbed proteins. In other applications, e.g. stents, the opposite, i.e. an antibiofouling
behaviour, is necessary. Biosensors lose their function by the denaturation of the attached
biomolecules [1].
Today the differentiation between fully effective and denatured adsorbed proteins is made by
very specific correlations like antibodies or enzymatic attacks. This implies that the protein had to
be well known.
Our goal is developing a method that is capable of differentiating between fully intact and
denatured proteins in an adsorbed layer, without the need to know the proteins. Additionally, the
specific adsorption of native and denatured proteins is investigated.
Therefore, we investigate the adsorption of a mixture of lower mass proteins onto different
surfaces (Si, Ti, Al, DLC, Au) under identical conditions. Specific correlations between the proteins
and the surfaces should cause different compositions of the adsorbed layers on the different
surfaces. However, the absence of specific correlations should produce an identical adsorbat on
each surface. A comparision of the adsorbat layers derived from a solution of native proteins and a
solution of intentionally denatured proteins is made. The adsorbates are characterised by the
complementary methods MALDI-ToF, ToF-SIMS and XPS.


[1] J. J. Gray, Current Opinion in Structural Biology 2004, 14: 110-115

BIO1-P-Mo-P61
93
Competitive adsorption of proteins on polymers membranes studied
by ToF-SIMS and PCA

Marie Henry
*
, Patrick Bertrand

Universit catholique de Louvain
a
PCPM, Croix du Sud, 1 B1348 Louvain-la-Neuve, Belgium
marie.henry@pcpm.ucl.ac.be


In the development of an encapsulation membrane for bioartificial pancreas, we have studied by
ToF-SIMS the adsorption of human insulin and human serum albumin (HSA) on polycarbonate
(PC) membranes. Some membranes were made hydrophilic by an argon plasma surface treatment
followed by a dipping in a polyvinylpyrrolidone solution. This treatment was found to improve
insulin and glucose diffusion[1]. Previous works have demonstrated the possibility to detect and to
identify proteins[2] and to obtain information about the amount[3], the composition, the structure
and the conformation[4] of an adsorbed protein film. The first aim of this study was to determine
the possibility of insulin detection on the two kinds of polycarbonate membrane surfaces in
presence of HSA, the most abundant blood protein. The second aim was to compare the protein
layer composition on the two membrane surfaces: the native one and the hydrophilic treated one.
Adsorption isotherms in physiological conditions (pH=7, T=37) were followed for the two
proteins by looking at the intensity variation of characteristic protein and polymer substrate
fragments when increasing the protein concentration in the solution.
For single protein adsorption, the amount of adsorbed insulin decreases with the surface treatment
whereas it is not the case for HSA adsorption where we observed only a decrease in the affinity
between the protein and the surface. Principal Component Analysis (PCA) on protein fragments
from single adsorption permitted to determine, on each surface, specific protein fragments, which
are only characteristic of HSA or only characteristic of insulin.
For competitive adsorption, we followed the intensity variation of the insulin fingerprint
fragments. On the hydrophilic treated surface, insulin was detected on the surface from 5g/ml in a
solution containing 1000g/ml of HSA, whereas insulin was hardly identifiable on the native one.
Finally PCA allowed to differentiate the protein layer composition on the two surfaces for
competitive adsorption.


[1]L. Kessler et al, J. Biomater. Sci. Polymer Edn. 14(10) (2003) 1135.
[2]M. S. Wagner, D.G. Castner, Appl. Surf. Sci. 231 (2004) 366.
[3]M. Henry, P. Bertrand, Surf. Interface Anal.36 (2004).
[4]M. Henry, C. Dupont-Gillain, P. Bertrand, Langmuir 19 (2003) 6271.
BIO1-P-Mo-P62
94
Dynamic SIMS Analysis of Cryo-Prepared Biological and Geological
Specimens

M. Dickinson
a,*
, Dr. P.J. Heard
a
, Dr. J.H.A. Barker
b
, Dr. A.C. Lewis
a
, D. Mallard
c
.

a
Interface Analysis Centre, University of Bristol, 121 St. Michaels Hill, Bristol, BS2 8BS.
b
Rothamsted Research, Harpenden, Hertfordshire, AL5 2JQ.
c.
Department of Earth Sciences, University of Bristol, Wills Memorial Building, Bristol, BS8 1RJ.
M.Dickinson@bristol.ac.uk


Secondary Ion Mass Spectrometry has several characteristics that are advantageous for the
analysis of biological specimens. However, the greatest factor limiting research in these areas is the
sample preparation necessary to chemically and structurally stabilise the cells [1-2]. Although
analysis of frozen, hydrated samples using SEM/EDX is popular in the biological sciences the cryo-
preparation method is not a very well established technique within the SIMS community. The
literature documents only a few system modifications, usually of static TOF-SIMS instruments, to
permit cryo-analysis [3-6].

This work describes the modification of a dynamic magnetic sector SIMS instrument to permit
the analysis of frozen biological and geological samples. The SIMS instrument used for this study
combines SIMS analysis with the generation of ion-induced secondary electron images, allowing
direct superposition of the SIMS image onto the image of cellular structures. Secondary ion maps
have been acquired with sub-micron resolution, permitting the characterisation of sub-cellular
elemental distributions in plant cells and human fibroblast cells, as well as the distribution of
chemical impurities at grain boundaries in polar ice samples. This cryo-preparation technique
clearly extends the applicability of SIMS analysis to a wide range of samples.

Overlaid secondary ion maps of a cross section from a leaf of P. vittata showing C
2
-
(red), CN
-
(green) and O
-
(blue).


[1] Chandra S., Morrison G.H. (1992). Sample Preparation of Animal Tissues and Cell Cultures for Secondary Ion
Mass Spectrometry (SIMS) Microscopy. Biol. Cell 74, pp.31-42.
[2] Harvey D.M.R., Hall J.L., Flowers T.J. (1976). The Use of Freeze-Substitution in the Preparation of Plant Tissue for
Ion Localization Studies. J. Microsc. 107, pp.189-198.
[3] Bernius M.T., Chandra S., Morrison G.H. (1985). Cryogenic Sample Stage for the Cameca IMS-3f Ion Microscope.
Rev. Sci.Instrum. 56, pp.1347-1351.
[4] Cliff B., Lockyer N.P., Corlett C., Vickerman J.C. (2003). Development of Instrumentation for Routine ToF-SIMS
Imaging Analysis of Biological Material. Appl. Surf. Sci. 203-204, pp.730-733.
[5] Colliver T.L., Brummel C.L., Pacholski M.L., Swanek F.D., Ewing A.G., Winograd N. (1997). Atomic and
Molecular Imaging at the Single-Cell Level with TOF-SIMS. Anal. Chem. 69, pp.2225-2231
[6] Braun R.M., Blenkinsopp P., Mullock S.J., Corlett C., Willey K.F., Vickerman J.C., Winograd N. (1998).
Performance Characteristics of a Chemical Imaging Time-of-Flight Mass Spectrometer. Rapid Commun. Mass Sp. 12,
pp.1246-1252.
BIO1-P-Mo-P63
95
Lipid Profiling of Prostate Cancer Cells Using ToF-SIMS

M.J.Baker
1*
, M.D.Brown
2
, N.W.Clarke
2
, E.Gazi
2
, P.Gardner
1
, C.A.Hart
2
, N.P.Lockyer
1
,
J.C.Vickerman
1


1
Surface Analysis Research Centre, University of Manchester, P.O Box 88, M60 1QD
2
ProMPT Genito Urinary Cancer Research Group, Cancer Research UK, Paterson Institute, Christie Hospital NHS
Trust, Manchester, M20 4BX
*M.Baker-2@student.manchester.ac.uk


Recently we have initiated a systematic study to create a database of ToF-SIMS spectra
corresponding to key lipids which are important in cell functions. This database has been created
with a view of characterising cellular events which are co-ordinated by changes in the
phospholipids composition in cell membranes. One such example is the process of cytokinesis
whereby phosphatidylethanolamine is a key lipid that is required for completion of cell division [1].
Lipids have been associated with the progression of prostate cancer. Certain lipids have been
reported to play a role in proliferation of disease [2].
ToF-SIMS has been used to examine phospholipids in a variety of environments.
Phosphatidylcholine head groups have been imaged in PC-3 cells [3] also phospholipids have been
used to discriminate between spores and vegetative cells of bacteria [4]. Imaging ToF-SIMS has
been used to view the highly curved membranes during Tetrahymena mating. This has shown that
the phospholipids structure varies considerably in the mating junction because of the abundance of
highly curved membrane structures in that region [5].
In this study we use ToF-SIMS to monitor the phospholipid composition of stationary and motile
prostate cancer cells. The motile cells shall also be observed invading through matrigel. This will
lead to an understanding of cellular processes incurred in the plasma membrane at a molecular
level.


1
K.Emoto et al, Redistribution of phosphatidylethanolamine at the cleavage furrow of dividing cells during cytokinesis
Proc.Natl.Acad.Sci.USA ( Nov 1996 ) 93; 12867-12872
2
Editorial Comments, Arichadonic Acid Metabolism and Cancer of the Prostate ( 1998 ) 14:48-49
3
E.Gazi et al, The combined application of FTIR microspectroscopy and ToF-SIMS imaging in the study of prostate
cancer Faraday Discussion ( 2004 ) 126; 41-59
4
C.E.Thomposn et al, ToF-SIMS Studies as a tool to discriminate between spores and vegetative cells of bacteria
Applied Surface Science ( 2004 ) 231-232; 420-423
5
S.G.Ostrowski et al Mass Spectrometric Imaging of Highly Curved Membranes During Tetrahymena Mating Science (
July 2004 ) 305;71-73

BIO1-P-Mo-P64
96
Lipid and Sterol analysis of Candida albicans using TOF-SIMS

Bonnie Tyler
a
, Sachin Attavar
b


Department of Chemical Engineering, University of Utah, Salt Lake City, UT-84111.
bonniet@eng.utah.edu
a
, attavar@eng.utah.edu
b
.


Candida albicans is a major fungal pathogen of humans. There have been studies done that have
shown that Candida albicans are growing increasingly resistant to polyene and azole classes of
antifungal agents [1]. These classes of antifungal agents mainly target the ergosterol or ergosterol
biosynthesis pathways [2]. These cells are most infectious in biofilm growth form. Cells in the
interiors of the biofilms are shown to be at lesser metabolic activity. These cells have shown to be
quite comparable to late stationary phase cells. During our preliminary studies, we have observed
ergosterol levels in Candida albicans cells are various stages along growth curve.
To extract the lipids and sterols from Candida albicans, cells are broken down with glass beads.
After centrifuging, the supernatant is transferred onto a centrifuge tube. Sterols and lipids are
extracted from the supernatant using methylene chloride. Extracted lipids and sterols are coated
onto a silicon substrate and analyzed using TOF-SIMS. Signature peaks of ergosterol molecular
ions and head group of phosphoatidycholine were observed. Yeast cells from exponential phase and
stationary phase are used for analysis. There is a relative decrease in the ion counts for ergosterol
with age. This result could lead to a better explanation of Candida albicans resistant towards
antifungal agents.


1) Chandra J., Duncan M.K, Mukherjee K.P., Hoyer L.L., McCormick T., and Ghannoum M.A. Biofilm Formation by
the Fungal Pathogen Candida albicans: Development, Architecture, and Drug Resistance. Journal of Bacteriology. 183-
18 (sep 2001). 5385-5394
2). Bille J., Sanglard D. 2002 Current understanding of the modes of action of and resistance mechanisms to
conventional and emerging antifungal agents for treatment of Candida albicans. Candida and Candidiasis (2002). 349-
383
BTC-P-Mo-P65
97
G-SIMS of Biodegradable Homo-Polyesters

R. Ogaki
a,*
, M. C. Davies
a
, I. S. Gilmore
b
, M. Alexander
a

a
Laboratory of Biophysics and Surface Analysis, School of Pharmacy, University of Nottingham, University Park NG7
2RD, UK
b
Quality of Life Division, National Physical Laboratory, Teddington, Middlesex TW11 0LW, UK
paxro@nottingham.ac.uk


Static SIMS (SSIMS) is a powerful surface analytical technique which can provide detailed
information on complex surfaces. However, often much of the acquired information is too rich in
detail and the data analysis relies on analysts expertise and/or a limited number of materials in
SSIMS libraries. Gilmore & Seah [1] recently developed a library independent technique, G-SIMS
and successfully tested it on various types of materials including polymers, crystallisable organics
[2] and most recently on folic acid [3]. In G-SIMS, fragmentation is quantified in terms of the
partition functions of the fragments emitted from a surface plasma with effective temperature, T
p

and extrapolation of the data to low surface plasma temperature reveals the un-degraded parent
fragments from the SSIMS spectra. In this study, G-SIMS has been tested on biodegradable
polyesters including: poly (glycolic acid) (PGA), poly (lactic acid) (PLA), poly (hydroxybutyrate)
(PHB) and poly (caprolactone) (PCL). These materials are chosen to test G-SIMS capabilities on
the homologous series. Caesium and argon primary ion beams have been used for this study, since
as found by Gilmore & Seah [1] using two different primary ions at the same energy gives optimum
fragmentation ratio, F
x,
than using one primary ion source with different energies . The acquired G-
SIMS spectra from these polyesters yielded vital clues to fragmentation mechanisms as a function
of molecular structure and highlights a powerful application of G-SIMS.


[1] I S Gilmore and M P Seah, Appl. Surf. Sci., 161 (2000) 465.
[2] I S Gilmore and M P Seah, Appl. Surf. Sci. 187 (2002) 89.
[3] I S Gilmore and M P Seah, Appl. Surf. Sci. 203-204 (2003) 551.

BTC-P-Mo-P66
98
Quantitative ToF-SIMS study of adsorbed proteins

Tae Geol Lee
a,
*, Young Pil Kim
b
, Hak Sung Kim
b
, Dae Won Moon
a


a
Nano-Surface Group, Korea Research Institute of Standards and Science (KRISS), P.O.Box 102, Daejeon 305-600,
Korea
b
Department of Biological Sciences, Korea Advanced Institute of Science and Technology (KAIST), Daejeon 305-701,
Korea
tglee@kriss.re.kr


Quantitative analysis of biomolecules on surfaces is essential to various applications of biosensor
and biomaterial engineering. In particular, a quantitative study of protein interactions in various
environmental conditions is needed. Recently, static time-of-flight secondary ion mass spectrometry
(ToF-SIMS) has been an increasingly popular way of investigating adsorbed proteins due to its
chemical specificity and surface sensitivity [1]. However, there are few systematic quantification
studies of protein-ligand interactions due to the complex matrix effect, improper orientation and
deformation of the protein, and low molecular secondary ion efficiency from biomaterials. In the
present work, we show that it is possible to produce a quantitative SIMS study for surface coverage
in the protein-ligand interaction. As a model system, the interaction of the streptavidin and biotin-
functionalized surface is studied as a function of streptavidin concentration. Instead of the self-
assembled monolayer (SAM) surface, a G3 PAMAM dendrimer surface is used due to its properties
of providing surface orientation and elevating the surface density of the protein. Our data show that
a particular characteristic peak intensity of streptavidin can be used to quantify the surface
concentration regardless of the matrix effect. In terms of surface coverage, the results of the ToF-
SIMS measurements are well correlated to those of surface plasmon resonance (SPR)
measurements.


[1] M.S. Wagner, D.G. Castner, Langmuir, 17 (2001) 4649-4660.
NAN-P-Mo-P67
99
Imaging, Spectra, and Chemometrics of ToF-SIMS of Alkyl
Monolayers on Silicon, Germanium and Silicon Nitride made by Laser
Activation, Chemomechanical Modification, and Thermal Reactions

Guilin Jiang,
a
Yit-Yian Lua,
a
Ahmed Arafat,
b
Han Zuilhof,
b
Matthew R. Linford
a,*


a
Department of Chemistry and Biochemistry, Brigham Young University, Provo, UT 84602 USA
b
Laboratory of Organic Chemistry, University of Wageningen, Wageningen, The Netherlands
mrlinford@chem.byu.edu


Ultrathin organic films possess many properties that make them ideal for applications at the
micron and nanometer scales. ToF-SIMS continues to play a central role in characterizing these
new materials. Within the last few months, the Linford group has developed a new method for
simultaneously functionalizing and patterning silicon and germanium by laser activation of these
materials with nanosecond laser pulses. ToF-SIMS imaging of spots produced by this method
(LAMS Laser Activation-Modification of Surfaces) has been critical in demonstrating the
viability of this new chemical modification/surface patterning method. ToF-SIMS has also played
an important role in characterizing two other types of materials that will be discussed in this talk.
First, it has recently been shown that acid chlorides react chemomechanically with silicon (see C&E
News, March 21, 2005 issue, p.10). Second, ToF-SIMS characterization of a new class of alkyl
monolayers on silicon nitride developed by Zuilhof and coworkers will be discussed. For all of
these studies, principal components analysis (PCA) has proven to be very useful in understanding
the chemical variation between spectra.
NAN-P-Mo-P68
100
RuO
2
/SiO
2
/Si and SiO
2
/porous Si/Si interfaces analysed by SIMS

Micha wil
a, b,
*, Piotr Konarski
a
, Micha Pajk
c
, Tomasz Bieniek
c
, Andrzej Kosiski
d

a
Industrial Institute of Electronics, ul. Dluga 44/50, 00-241 Warszawa, Poland
b
Faculty of Physics, Warsaw University of Technology, Koszykowa 75, 00-662 Warszawa, Poland
c
Faculty of Electronics and Information Technologies, Warsaw University of Technology, Koszykowa 75,
00-662 Warszawa, Poland
d
Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warszawa, Poland

E-mail address: cwil@if.pw.edu.pl


Porous silicon opens new perspectives in areas until recently closed for silicon. Properties of
porous silicon depend strongly on porosity grade, pore dimensions, etc. In this work we try to
compare the interfaces between thin silicon oxide layers and two substrates bulk silicon and porous
silicon. SIMS depth profiles of these interfaces were performed using ultra-low energy (880 eV)
and low energy (5 keV) argon ion beams.
2 m thick porous silicon was prepared by an electrochemical etching of Si in HF solution.
Oxide layers were formed separately on bulk and porous silicon in the same furnace. The oxidation
conditions however were different. Bulk silicon samples were thermally oxidised in 1000 1100 C
and porous silicon samples in 750 C. Part of SiO
2
/Si samples were covered with 50 nm RuO
2

oxide.
Ultra-low energy Ar
+
ion beam (880 eV) was used for analysis of the SiO
2
layers (5, 15, 22, 50,
65, 83 nm thick). 06-350E Physical Electronics ion gun was used. Positive and negative secondary
ions were analysed by quadrupole mass spectrometer QMA 410 Balzers. Charge build-up effects
during positive secondary ion detection were observed dependent of the thickness of silicon oxide
layer. Sputtering rate was calibrated basing on ellipsometry measurements.
The SiO
2
/Si interface regions characterised by SIMS show differences related to the kind of a
substrate used. In case of 50 nm SiO
2
/porous Si interface, characteristic oxygen depletion region (20
nm thick) is present on the porous silicon side. The observed depletion was confirmed also by
Auger depth profiling. Possible segregation mechanisms were considered.

This work is partially financed by the State Committee for Scientific Research of Poland (project no. 4T11B02325).
NAN-P-Mo-P69
101
The SIMS investigation of structural effect of oxygen segregation on
superplastic deformed nanobulk titanium surfaces

B. Atabaev
a,
* , R. Dzabbarganov
a
, F. Yuzikaeva
a
, R. Valiev
b
, D. Gundarev
b
,
Y. Kolobov
c
, M. Ivanov
c
, G. Korb
d
, L. Zeipper
d
, T. Weisgarber
e


a,
* Arifov Institute of Electronics, F. Khodjaev st 33, 700125, Tashkent, Uzbekistan
b
Ufa State Aviation Technical University, St. K.Marx, 12, 45000, Ufa, Russia
c
Tomsk State University, Lenina st. 36, 634050, Tomsk, Russia
d
Austrian Research Centers Seibersdorf, 2444, Seibersdorf, Austria
e
Fraunhofer Institut fur Fertigungstechnik und Angewandte Materialforschung,
Winterbergstr. 28, 01277, Dresden, Germany
atabaev@ariel.uzsci.net


The mechanical properties of nano-crystalline Ti are controlled by very small concentrations of
interstitial dilute O and gas impurities, which have proved extremely hard to detect since they are
very non uniformly distributed in a nano structure. The goal of investigation is the influence of
nanostructure on surface segregation and formation titanium oxide clusters and cavities after heat
treatment with microhardness control. Using of programmed high temperature of secondary
negative ion mass spectrometry with Cs primary ion we measured of surface chemical composition
of samples VT-1-0: N1-poly-Ti; N2-nano1-Ti and N3-nano2-Ti. Poly Ti surface has high oxidation
reactivity and covered by oxygen in ultra high vacuum at room temperature. To measure of surface
chemical composition we used electron bombardment sample holder for short time heating of Ti
until 800C. This allowed to oxygen surface segregation or oxygen dissolution in bulk. The main
result is low temperature 300-400C oxygen surface segregation or oxygen dissolution in nano-
crystalline Ti. For poly Ti surface oxygen dissolution temperature is 600C. It is shown the SIMS
of negative ions has high sensitivity for impurities H, C, N, F, Cl, S, I and AlO, TiO. We
investigated also in first time for nanocrystalline Ti formation of AlO, TiO, TiO
2
, TiO
3
and TiO
4

negative ions from corrosion passivated Al
2
TiO
5
layer. Using optical microscopy we show that
concentration of titanium oxide cavities for nanostructured titanium N2 nano1-Ti sample is
drastically decreased than for N1-poly-Ti sample. Conclusively, it is suggested that contamination
of titanium oxide clusters and cavities at grain boundaries and in grain promotes cavity nucleation
and has a negative influence on the superplasticity and mechanical properties of nanostructured
titanium.
The work was supported by grant INTAS-nano-01-0320.
NAN-P-Mo-P70
102
Supramolecular host-guest complexes base on
cyclodextrin-diphenylhexatriene

L. Rabara
a,
, M. Aranyosiova
a,b,
, P. Chandoga
a,
, I. Bugar
b,
, D. Velic
a,b,
*, D. Chorvat
b,


a
Komensky University, 842 15 Bratislava, Slovakia
b
International Laser Center, 812 19 Bratislava, Slovakia
velic@ilc.sk

Self-assembling phenomena is considered in this contribution in a form of host-guest inclusion
complex with an attempt to form a supramolecular self-assembled layer on the surface [1]. Such
surface nanostructures are attracting considerable attention in fields like molecular biochemistry or
nanofabrication. The initial step in this direction is to characterize these host-guest complexes. The
studied host-guest complex is based on cyclodextrin molecule as the host and on diphenylhexatriene
molecule as the guest which inclusively binds into the host cavity. Cyclodextrin is in a form of -
cyclodextrin (C
42
H
70
O
35
) and diphenylhexatriene is a form of 1,6-diphenyl-1,3,5-hexatriene
(C
18
H
16
). Such a supramolecular cyclodextrin-diphenylhexatriene structure forms not only 1:1
complex, but also a higher order complexes in a form of nanowire [2].
Various solutions of diphenylhexatriene and cyclodextrin were characterized by using steady-
state fluorescence spectroscopy. The wavelength maxima of diphenylhexatriene triple vibrational
structure are 400, 423 and 451 nm, 402, 424 and 450 nm, 404, 426 and 452 nm, and 402, 425 and
450 nm in ethanol, methanol, acetone, and n-hexane, respectively. The evidence of the
supramolecular host-guest formation was based on different relative intensities of the vibrational
structure peaks. Interestingly, wavelength maxima in water were observed at 438, 468 and 494 nm
with double features.
Time-of-flight secondary ion mass spectrometry (TOF-SIMS IV, ION-TOF) was applied as an
attempt to proof the supramolecular formation in a form of the mass spectra. The complex forms in
aqueous solution of cyclodextrin (saturation at 10
-2
M concentration) while diphenylhexatriene has
extremely low solubility in water (10
-7
M). It is clearly a challenge to test a detection of a weakly
bond complex at very low concentration by using mechanism of collisions. A molecular ion of
cyclodextrin with m/Z 1133 was observed in negative polarity presumably after loosing one
hydrogen atom. Cationized molecules of cyclodextrin with Na and K were observed in positive
polarity at m/Z 1157 and 1173, respectively. The presence of diphenylhexatriene in the sample was
detected by measuring m/Z 232 in positive polarity as ionized molecular ion. The whole intact
supramolecular host-guest complex between cyclodextrin and diphenylhexatriene was observed in
cationized form with K at m/Z 1405. The focus is on the higher order complexes where the
complex cyclodextrin-diphenylhexatriene 2:1 was observed at m/Z 2500 in negative polarity. Peaks
corresponding to the higher order complexes are observed and the influences of substrate
background, additional complexation with solvent and impurities, and nanowire formation are
discussed.
The reported study represents a base how to characterize the supramolecular surface
nanostructured layer.

The financial supports of VEGA 1/0216/03 and APVT 298 are acknowledged.


[1] D. Velic, G. Koehler, Chem. Phys. Lett. 371 (2003) 483
[2] G. Li, L. B. McGown, Science 264 (1994) 249
ORG1-P-Mo-P71
103
End group effect on surface and interfacial segregation in PS-PMMA
blend thin films

L. Kailas*, P. Bertrand


Unit PCPM, Universit catholique de Louvain, 1 Croix du Sud, B-1348 Louvain-la-Neuve, Belgium
kailas@pcpm.ucl.ac.be


Thin films of Polystyrene (PS)/Poly (methyl methacrylate) (PMMA) blends of different
molecular weights and with different end groups were investigated using ToF-SIMS and AFM. PS
with -OH and -NH
2
end groups were blended in toluene solvent with pure PMMA homopolymer,
PMMA labelled with anthracene and PMMA having anhydride end group. The solution was spin-
casted on to silicon wafers and annealed at 160C in vacuum for 2 hours. The ToF-SIMS spectra of
PS-OH/PMMA with and without anthracene labelling resembled that of pure PS-PMMA blends
before and after annealing[1,2]. There was an increase of PMMA intensity after annealing. The
AFM images showed featureless surface before annealing and droplet shaped structures on the
surface with distinct phase shift from the surrounding matrix after annealing. Annealing is seen to
aid the complete phase separation leading to the formation of PS droplets on a PMMA matrix. On
the contrary, the PS-NH
2
blended with PMMA and anthracene labelled PMMA showed an increase
in PS intensity on the surface after annealing. The ToF-SIMS spectra were similar to that of a pure
PS-PMMA copolymer[1]. The PS-NH
2
with PMMA-Anhydride blend also behaved similar to that
of PS-NH
2
with PMMA. These results indicate a reactive blending leading to copolymer formation
at the surface. The PS-NH
2
/PMMA and PS-NH
2
/PMMA-Anhydride showed spinodal bi-
continuous structures on the surface before and after annealing as those found in pure PS-PMMA
copolymers after annealing. In that case, the copolymer formation is found to occur in the solution
itself and not after thermal treatment.


[1]
Kailas, L.; Nysten, B.; Bertrand, P.; Surf. Interface Anal. 2004, 36, 1227
[2]
Kailas, L.; Nysten, B.; Audinot, J.-N.; Migeon, H.-N.; Bertrand. P.; Surf. Interface Anal. 2005, 37 in press
ORG1-P-Mo-P72
104
Empirical evaluation of metal deposition for the S-SIMS analysis of
organic compounds in thick samples

R. De Mondt
a*
, L. Adriaensen
a
, F. Vangaever
b
, J. Lenaerts
b
, L. Van Vaeck
a
, R. Gijbels
a


a
University of Antwerp, department of Chemistry (MiTAC), B-2610 Wilrijk, Belgium;
b
Agfa-Gevaert N.V., B-2640 Mortsel, Belgium
*roel.demondt@ua.ac.be


During the last three decades S-SIMS is developed into an analytical technique frequently used
for the analysis of organic compounds e.g. polymers, biomolecules, etc. However, the tendency
of organic compounds to give rather low secondary ion yields remains one of the major difficulties
in S-SIMS experiments. As a consequence, improvement of the secondary ion intensities is an
important goal in the further development of organic SIMS.
Several methods to enhance the secondary ion yields exist, like the use of polyatomic (SF
5
+
) or
cluster (Au
n
+
) primary ions instead of mono-atomic primary ions. More recently, the deposition of
a thin Au or Ag layer on the sample surface prior to analysis (Metal-Assisted SIMS) showed
promising results in this regard [1, 2]. However, the mechanism(s) responsible for the observed
yield enhancement is not yet fully understood.
In the present study the influence of temperature on MetA-SIMS measurements is tested.
Experiments were done on three different sample types, namely, a cationic dye spincoated on Si, a
cationic dye in polyvinylbutyral and a reductor in polyvinylbutyral deposited on a Si substrate.
From each of these a Au covered, a Ag covered and a blank sample were stored in an oven (80C),
at room temperature (20C) and in a freezer (-8C). These samples were measured over a period of
one month with TOF-S-SIMS. The obtained results are consistent with the concept of metal
diffusion in the organic layer before the occurrence of a signal enhancement effect. The diffusion
process appears to be highly dependent on the temperature of the environment. At elevated
temperatures enhanced ion signals were detected more rapidly than at room temperature. When
samples were kept below freezing level, no significant change in the ion yields could be detected as
a function of time.
Additional SEM measurements were performed on the metal-covered samples in order to get
more information on the distribution of the evaporated metals on the organic material.


[1] A. Delcorte, N. Mdard, P. Bertrand, Anal. Chem. 74 (2002) 4955-4968.
[2] L. Adriaensen, F. Vangaever, R. Gijbels, Anal. Chem. 76 (2004) 6777-6785.

ORG1-P-Mo-P73
105
S-SIMS in advanced textile research : study of additives to tune the
hydrophilic/hydrophobic properties of polypropylene films

B. Boschmans
a
*, M. Vanneste
b
, L. Ruys
b
, L. Van Vaeck
a


a
University of Antwerp (CDE), Department of Chemistry, Universiteitsplein 1, 2610 Wilrijk, Belgium
b
Centexbel, Technologiepark 7, 9052 Zwijnaarde, Belgium
E-mail address : Bart.Boschmans@ua.ac.be


Many industrial materials are still empirically optimised. Focus on sustained development leads
to increasing use of chemical surface engineering, which in turn requires methods capable of
determining the molecular composition of the outer material-environment interface. Within the
framework of a research project aiming at the development of new textiles, the feasibility of S-
SIMS analysis to trace back the additives and surface modifications of thick polypropylene films
has been explored.

All samples were measured by TOF-SIMS with Ga
+
(25keV) as primary ion, both in the positive
and negative ion mode. Unlike thin film analysis, the measurement of non-conducting materials as
thick as 20-200 m required an adequate charge compensation method to be developed. It was
found that sputters coating the samples with gold allowed the analysis of such real life samples
and detection of the additives introduced to give the surface hydrophilic properties. Specifically,
two types of additives were used to create hydrophilic PP: Argutec HYL 1480 PP

(Argus) and
Irgasurf HL 560

(Ciba). Concentrations of additives were situated between 1 and 3%. In spite of

the gold deposition, molecular information could be obtained on the original surface components,
although there were some difficulties in avoiding contamination.

The gold metallization technique appears to allow an increase of the applicability of S-SIMS to
real world samples from industrial applications and exploit the methods potential to collect precise
information on the molecular composition of surface components in polymeric matrices.
ORG1-P-Mo-P74
106
S-SIMS analysis of plasma treated real life polypropylene films

B. Boschmans
a
*, M. Vanneste
b
, L. Ruys
b
, E. Temmerman
c
, C. Leys
c
and L.Van Vaeck
a


a
University of Antwerp (CDE), Department of Chemistry, Universiteitsplein 1, 2610 Wilrijk, Belgium
b
Centexbel, Technologiepark 7, 9052 Zwijnaarde, Belgium
c
University of Ghent, Department of Applied Physics, Rozier 44, 9000 Gent, Belgium
E-mail address : Bart.Boschmans@ua.ac.be


Plasma treatment of polymers is a technique that has been expanding fast over the last years.
Numerous applications in the fields of new textiles, biomedical materials, fine chemicals,
composites, etc. need surface modification to improve their effectiveness with respect to properties
such as wettability, bio-compatibility, adhesion etc. Surface modification is achieved by
implantation of new functional groups, like hydroxyl-, carboxyl-, nitrogen-, groups, into the
polymer surface. Although plasmas are widely used, the involved chemistry is not well understood.
Few detailed S-SIMS studies have been done on plasma modified surfaces and revealed the extreme
complexity of the surface chemistry on the molecular level.

Samples consisted of polypropylene (PP) films with a thickness between 20 and 200 m, treated
with remote air plasma in order to introduce hydrophilic functional groups into the surface. Several
treatment times were applied to monitor the effect on the surface composition. Samples were sputter
coated with gold to compensate charge build-up and improve the ion yields. Bombardment with 25
keV Ga
+
primary ions was used in TOF-S-SIMS. Both positive and negative ion mass spectra were
recorded.

Results show that the application of the gold metallization allows intense signals up to the high
m/z-range (m/z 1000) to be detected for such real life samples. Compared to the data from non-
treated PP films, the mass spectra of plasma modified PP contain a number of additional signals.
Even for the shortest treatment times, modifications can be detected. The characteristic signals of
implanted functional groups show that mainly oxygen- and nitrogen-containing groups are
introduced. The implantation process also induces sputtering and chemical transformation of certain
compounds from the surface. All these mechanisms are reflected in the mass spectra.
ORG1-P-Mo-P75
107
Surfactant Cationisation In ToF-SIMS Analysis

M.C. Perkins
a
, C.J. Roberts
a
, F.J.M. Rutten
a,
*, D. Briggs
a
, M.C. Davies
a
and A. Friedmann
b


a
Laboratory of Biophysics and Surface Analysis, School of Pharmacy, University of Nottingham, University Park,
Nottingham NG7 2RD, UK
b
Syngenta, Jealotts Hill International Research Centre, Bracknell RG42 6EY, UK
E-mail: frank.rutten@nottingham.ac.uk


In the course of our investigation of the interaction of agro-chemical ingredients with plant leaf
surfaces we observed that the spectral appearance for the same material on different substrates can
vary considerably. Agrochemicals commonly tend to consist of a number of components including
a surfactant as well as active ingredients. Reference spectra recorded after deposition of the
surfactant Synperonic A7 deposited on a clean silicon substrate were compared to spectra recorded
after deposition of that same surfactant on a plant leaf, using the temperature controlled stage on our
ToF-SIMS instrument. Whereas on the reference sample peaks assigned to K-cationised C
13
and C
15

oligomers were prominently present, those for the former were only barely detectable upon
interaction with the plant leaf. Careful consideration of the potential ions that may be formed in the
process of secondary ion formation, allowed us to conclude that these spectral changes were most
likely not due to changes in the abundance of particular oligomers, but rather to changes in
cationisation. The particular repeat units of the oligomers under investigation further complicate
matters by leading to coincidence of peaks caused by different cationisation species. Whereas both
Na and K were present on the leaf as well as the silicon surface, on the first the spectrum is
dominated by Na-cationisation, whilst also showing some protonation, whereas the latter yields
spectra showing virtually only K-cationisation peaks. Addition of the active ingredient for a
particular agro-chemical formulation led to virtually total suppression of all but protonation.
This phenomenon was further investigated under more controlled conditions by adding a number
of salts to the surfactant solution at different concentrations prior to deposition on clean silicon
substrates. This allowed us to fully characterise the effect of changes in nature and concentration of
available cations on a substrate on the formation of surfactant-based cations in the SIMS process.
ORG1-P-Mo-P76
108
TOF-SIMS investigation of the distribution of a cosmetic ingredient in
the epidermis of the skin

M. Okamoto
a,
*, N. Tanji
a
, Y. Katayama
b
, J. Okada
b


a
Kao Corporation, 1334 Minato, Wakayama-shi, Wakayama, 640-8580, Japan
b
Kao Corporation, 2-1-3 Bunka, Sumida-ku, Tokyo, 131-8501, Japan
Email: okamoto.masayuki@kao.co.jp


In order to understand the mechanisms of the functions of a cosmetic ingredient, it is important to
know the distribution of the agents in the epidermis of the skin. Imaging analysis of these agents by
microscopic methods are quite difficult, therefore only a few studies have been reported so far. We
have investigated the analysis of cosmetic ingredient penetration into the skin using Time-of-Flight
Secondary Ion Mass Spectrometry (TOF-SIMS).
Pig skin, treated with a cosmetic preparation, was used as a model for human epidermis. The
sample was embedded in resin and cross-sections were carefully cut using an ultramicrotome (Nova
Ultratome ) with diamond knife. TOF-SIMS measurements were carried out with a TOF-SIMS IV
spectrometer (ION-TOF, Germany). A
197
Au
+
ion beam, with an ion energy of 25keV and at a
pulsed current of 1.0pA, was used as the primary ion source.
After investigation of the sample preparation methods, the ceramide derivatives contained in the
cosmetic preparation were detected as individual molecular ion peaks and it was revealed that these
agents can penetrate into the stratum corneum tissue. In TOF-SIMS analysis these agents are
detected as separated masses and it is thus considered to be one of the most versatile methods for
high resolution imaging analysis of such species.

ORG1-P-Mo-P77
109
Development of a highly sensitive analysis technique for surfactants
by time-of-flight secondary ion mass spectrometry

N. Tanji, M. Okamoto

Kao Corporation, 1334 Minato, Wakayama-shi, Wakayama, Japan
Email: tanji.noriyuki@kao.co.jp


A highly sensitive analytical technique for the determination of surfactants existing on a polymer
surface was developed. In order to achieve improvements to the signal intensity, the strategy of
chemically modifying surfactants including hydroxyl groups, by using amine-containing
compounds, was studied. As a result, it was found that 4-(Dimethylamino)phenyl isocyanate was
capable of reacting with the hydroxyl group.
The product obtained after chemical modification with stearyl alcohol was measured by time-of-
flight secondary ion mass spectrometry (TOF-SIMS). The signal of the compound appeared in
TOF-SIMS spectra as a positive ion peak (m/z = 432). This result indicates that the stearyl alcohol
was detected as a derivative, reacting with the hydroxyl and isocyanate groups of the modification
agent. Moreover, this modification could be performed under reaction conditions in the gas phase /
23 with 1,8-Diazabicyclo[5,4,0]undec-7-ene (DBU) as a catalytic agent.
We have demonstrated signal enhancement by using model samples, which were polypropylene
sheets with 0.25% of stearyl alcohol mixed in. The stearyl alcohol signal wasn't detected under
normal TOF-SIMS measurement conditions. After the modification reaction was carried out,
however, the stearyl alcohol derivative was observed with up to a 100-fold improvement in the
characteristic molecular secondary ion yield.
From the above-mentioned results, target compounds were detected both sensitively and
selectively by using this technique, even if several types of surfactants with hydroxyl group existed
on the sample surface.
ORG1-P-Mo-P78
110
Surface Characterization of Self Assembled Monolayers of Alkane Dithiols

Srinath Rangarajan and B. J. Tyler

Department of Chemical Engineering, University of Utah, Salt Lake City, UT 84112, USA.

This work is focused on the surface characterization of self-assembled monolayers (SAMs) of
dithioalkane-PEG-COOH. These molecules have been shown to attach firmly to gold surfaces
previously [1]. This novel dithiol consists of two C6 thiol change bound in the meta position on an
aromatic ring. The third meta position is occupied by a carboxyl terminated PEG chain.
Preliminary studies show superior coverage and stability of these SAMs when compared to
monothiols due to the two thiol chains and the aromatic ring. The PEG groups in the molecules will
help in minimizing protein fouling of bioactive surfaces [2]. Preliminary studies have been aimed
at characterization of such surfaces using ToF-SIMS for studying their chemical composition, the
uniformity and distribution of these molecules. ToF-SIMS has been shown to be especially sensitive
for studying self assembly of organic thin films and for studying the orientation of peptides in self
assembled monolayers [2, 3]. Mixed monolayers of these molecules with dithioalkane-PEG-OH
were also prepared and experiments were performed at varying solution concentrations and
incubation times. A comparison of primary ion sources will also be presented. These functionalized
surfaces can then used to attach to sugar molecules such as trehalose or the saccharide side chain of
the Fc regions of antibodies. Possible applications include the development of portable biosensors
for biological pathogens and their toxins.


References:
[1] Charles W. Spangler, Brenda D. Spangler et al, Polymer Preprints, 2004, 45(1), 524
[2] Sadhana Sharma, Robert W. Johnson et al, Langmuir, 2004, 20, 348-356
[3] M.S. Wagner, D.J. Graham et al., Surface Science, 2004, 570, 78-79
[4] Kirsten Luefgen, Horst Vogel et al., J. Am. Chem. Soc. 2003,125, 8911-8915
DAT-P-Mo-P79
111
Application of Advanced Data Analysis Techniques in ToF-SIMS:
Toward Faster Relevant Observations for Industrial Problem-Solving

Gregg E. Potter
a,*
, C. Weikart
b
, Gary E. Mitchell
a
, J. W. McCoy
c
, Mary Beth Seasholtz
a


a
1897 Bldg, Analytical Sciences, The Dow Chemical Co., Midland, MI 48667, USA
b
Chemical Scineces, The Dow Chemical Company, 1776 Bldg., Midland, MI 48674, USA
c
1454 E. Weldona Way, Superior, CO 80027, USA
gpotter@dow.com


The transition of an analytical technology such as ToF-SIMS to wide use in industrial problem-
solving is a function of both its analytical capabilities and its ability to be rapidly applied to often
ambiguous problems posed in the industrial setting. Questions such as how are these materials
different? or how is the surface of the bad material different from the good material? can be
more difficult to answer than they appear. Fortunately, advanced data analysis techniques can help
screen the large amounts of data more quickly, not only yielding component, but also system
information. This allows larger, designed experiments to be performed which can alleviate the
variability inherent to industrial samples and lessen sampling error. Example applications which
illustrate this will be presented.
DAT-P-Mo-P80
112
ToF SIMS identification of diterpenes after chromatographic
separation.

Andrej Orik
a
*, Heinrich F. Arlinghaus
b
,
Guido Vering
b
, Renta Orikov
a
, Valdir Cechinel-Filho
c


a
P.J. afrik University, Institute of Chemistry, Faculty of Science, Koice, Slovakia
b
Physical Institute, Wilhelm Westphalen University, Muenster, Germany
c
Ncleo de Investigation Quimico-Farmaceuticas, Universidade de Vale do Itaja (UNIVALI), 88302-202,
Itaja,SC,Brazil
orinak@kosice.upjs.sk


ToF-SIMS analysis was applied to identification of the model group of three diterpenoic
acids: Gibberellic, Kaurenoic and Abietic acids , that can be only poor detected with classical
liquid-chromatographic detectors. The mixture of them has been separated in capillary column high
performance liquid chromatography system. The analytes separated were then deposited on linearly
moving substrate that can be represented with :
chromatographic thin layer
silver vapour treated surface or silver vapour treated chromatographic thin layer
aluminium backed thin layer modified surface
monolithic silica thin layer
Raman spectroscopy suitable and commercially available chromatographic thin layer
Analytes depositing trace was analysed with ToF SIMS and surface images showed the character of
depositing trace.
The analytes separated ToF SIMS fragmentation schemes, necessary for identification
purposes, were constructed. These were compared with those obtained from different depositing
substrates and for both: negative and positive ions. It enables to establish final identification scheme
for all diterpenoic acids analysed. Discussed was application of principal component analysis to the
data interpretation and fragmentation ways construction.


Acknowledgements. This work was partially supported by the Slovak Grant Agency VEGA; Grant No.
1/0445/03. The authors wish to thank ION-TOF GmbH, Germany for temporary licence of ToF SIMS software
providing.

MAT-P-Mo-P81
113
Examination of the Influence of Boron on the Microstructure and
Properties of Low C Ferritic Steels using NanoSIMS and TEM

S. Ahmed
a,*
, J. M. Titchmarsh
a
, M. R. Kilburn
a
, C. R. M. Grovenor
a


a
Department of Materials, University of Oxford, Parks Road, Oxford, OX1 3PH, UK
*
E-mail address: shafiq.ahmed@materials.ox.ac.uk


The mass production of ferritic steel wire requires the intermediate fabrication of rod which is
uniformly ductile to undergo considerable deformation during the final cold wire-drawing process
without fracture. The ductility of the rods is directly influenced by ferrite grain size, a large grain
size giving greater ductility. However, in practice it has been observed that the grain size can vary
by large factors (~x3) between different batches of rod produced by the same fabrication route and
even over the cross-section of individual rods, with very small grains forming at the edge of rods
containing high concentrations of boron ~100ppm.
Interstitial elements such as B and N are known to affect grain size even when present in low
concentrations, probably during re-crystallisation: grain size increases with B concentration.
However, excessive B leads to brittleness. The presence of other elements such as C, Al, S and O,
plus alloying elements, can influence the segregation and precipitation of B and the observed
variations in grain size are likely to be caused by such interactions.
Transmission Electron Microscope (TEM) analysis has identified a large population of quenched-
in vacancy dislocation loops present in the steel rods which vary in size and density. This effect
could be due to deformation during the rolling process [1] and varies with the concentration of B.
Very small precipitates may also be associated with these dislocation loops. However, clarification
of the competing influences of low atomic number elements is difficult because of their low
concentrations.
NanoSIMS imaging with high spatial and mass resolution [2] provides a powerful means for
further investigation of the problem. A small scanning ion probe diameter (~50nm) allows the
identification of small precipitates and segregation of important low atomic number elements that
are traditionally difficult to reveal by other microanalytical techniques.
In this paper we report results of ferritic steel rod characterisation using NanoSIMS and the
comparison with TEM analysis of samples from the same rods. In addition, the sequential
characterisation of exactly the same area of a sample using both methods will be described. This
permits direct comparison of sensitivity and spatial resolution on the same individual particles
which helps optimisation of the most efficient characterisation strategy for a series of alloys in
which the concentrations of B, N and Al have been varied and correlated with grain size
distributions.


[1] S. Kojima, A. Yokoyama, M. Komatsu, M. Kiritani, Mat. Sci. & Eng. A350 (2003) 81
[2] G. Slodzian, F. Hillion, F.J. Stadermann, F. Horreard, SIMS XIII Proc., Nara (Japan) (2001) 798

MAT-P-Mo-P82
114
Carbon analysis in steel microstructure

LOISON Didier * - CHAMPMARTIN-PHILIPPE Valrie

Arcelor Research, Voie Romaine, BP 30320, MAIZIERES-LES-METZ CEDEX (France)
didier.loison@arcelor.com


To fulfil costumer requirements, particularly in the field of automotive market applications, High
Strengthened Steels developed by steel makers all over the world exhibit more and more complex
microstructure. Mechanical properties of such materials are directly bonded to the relative
proportion of each phases (generally bainite, retained austenite and martensite), as well as the
carbon amount located inside them.
When considering classic characterization techniques, local analysis of carbon at the micrometer
scale, in the range of few tenth percents is generally difficult due to either:
A low sensitivity for light elements
Strong matrix effects and / or corrupted analytical information (peak overlaps)
Poor volume resolution
For this kind of application, Secondary Ion Mass Spectrometry offers a good compromise
between reliability of quantitative measurements, lateral resolution and sensitivity.
To illustrate that point, we present a set of results combining Cs-SIMS analyses and optical
observations applied to the characterization of TRIP steels allowing determining the partition of
carbon, silicon, manganese and aluminium between residual austenite and bainite. Limits of such an
approach will be emphasized in terms of critical phase size and carbon content.



MAT-P-Mo-P83
115
SIMS Analysis of Nitrogen in Various Metals and ZnO

Yupu Li, Xiaohua Wang, and Stephen P. Smith

Charles Evans and Associates
810 Kifer Road, Sunnyvale, CA 94086, USA
yli@cea.com


It is well know that nitrogen has a very high ionization potential and zero electron affinity.
As a result, both secondary positive and negative ion yields of nitrogen atomic ions are poor or
absent. In common semiconductor material such as Si, N is normally profiled with a Cs
+
primary
beam and monitored using negative molecular ions of (Si+N)
-
. For ZnO, we have found that
nitrogen can be measured using a Cs
+
primary beam while monitoring (O+N)
-
. However, because
of ion yield variations and mass interferences, monitoring molecular ions of the type (matrix+N)
-
may not be useful for metal films. For example, in Ni, (
58
Ni+N) will be interfered by (
60
Ni+C). In
addition, such an analytical protocol cannot be used conveniently to analyze layered structures such
as Si/Ni/Cu. In this work, based on various ion-implanted standards, we report N profile
measurements in various metal films using a Cs
+
primary ion beam and monitoring (CsN)
+
or
(Cs
2
N)
+
cluster ions. The (Cs
2
N)
+
protocol will also work on common materials such as Si and so it
can potentially also work on multi-layers with different matrix elements. Comparisons between the
profiles measured by SIMS and the profiles simulated by SRIM will be discussed. Using an O
2

primary beam while monitoring N
+
atomic ions is an alternative protocol that can work for layered
samples; however, the detection limits may be poorer than for the (Cs
2
N)
+
mode.

Reference:
[1]. J.F. Ziegler, J.P. Biersack, and U. Littmark, The Stopping and Ranges of Ions in Solids (Pergamon,
ACG-I-Tu-A01
116
The geological ion microprobe: the first 25 years of dating
zircons

W. Compston & S. W. J. Clement,

Research School of Earth Science, The Australian National University,
Canberra, ACT, 0200, Australia


Andersen & Hinthorne reported in situ Pb isotope ages for lunar minerals in the early 1970s,
using the small Liebl ion microprobe and peak stripping to subtract isobaric interferences. This
worked for old, U-rich targets but not for younger minerals. Jim Long entered the race for in situ
mineral dating and used high resolution to separate isobars. Despite low sensitivity, he achieved
both
207
Pb/
206
Pb and
206
Pb/
238
U dating of zircons in the later 1970s. Earlier, beam transport theory
indicated to us that any small mass analyser set to the necessary resolution (5000R) would be too
insensitive for efficient measurement of ppm amounts of Pb. In 1980 we finished the 100 cm
instrument, SHRIMP I based on a magnetic analyser design of Matsuda (1974), which after the
usual agonies delivered both high resolution and high sensitivity. Using it, we had the luck a year
later to discover zircon grains 4200 million years old, far older than any previous terrestrial age.
Over the next ten years, we enjoyed a variety of dating and other isotopic projects, and SHRIMP
became enormously popular with geologists. A commercial version was completed in 1992.
Certain in situ isotope studies were not practical using SHRIMP II, such as Sr isotopes in
Ca-rich minerals in which Ca isotope dimers interfere with
87
Sr. Other examples are
147
Sm-
143
Nd
dating and Hf isotopes. All need high sensitivity at 20,000R to accumulate enough counts for
worthwhile precision, and little/no peak stripping. Matsuda (1990) published reverse-geometry
designs that meet these needs, one of which we built over 1994 to 1997. We achieved 20,000R but
only for limited beam divergence and consequent reduced sensitivity. We have since learned a
great deal about fringing fields, 3D ray-tracing and computer control, and the struggle to achieve
the design potential continues. Meanwhile the new SHRIMP is much in demand for zircon dating
and trace element studies at 6000R.
ACG-I-Tu-A02
117
Applications of SIMS to archaeometry and cultural heritage

Annemie Adriaens

Ghent University, Department of Analytical Chemistry, Krijgslaan 281-S12, B-9000 Ghent, Belgium
Annemie.Adriaens@UGent.be


Europe has a particularly rich and diversified cultural heritage, including buildings, monuments
and objects of all sizes. It forms the basis of present and future cultures, and through the skills,
beauty, and engineering genius it manifests, it is a vital source of inspiration and pleasure. Its
exploitation, in the form of displayed objects, is a direct and indirect source of revenue through
tourism and at the same time the basis for a rich diversity of learning. Nevertheless the physical
part of the European cultural heritage is deteriorating faster than it can be conserved, restored or
studied. Assets are being lost, or are at risk, through natural processes of decay, environmental
disasters, the direct effects of enhanced public access, conservation and preservation procedures
whose long-term effects were and are not understood, simple negligence, and war.
The use of advanced analytical methods is an essential prerequisite in this field as it provides the
means to understand the objects under investigation [1-4]. Through the identification of materials
and processes, we can reach back through time and develop a deeper understanding of the
craftsmanship and technology that was used. Such methods also allow us to perform authenticity
studies or contribute to the development of simple diagnostic techniques necessary for practical
conservation.
In the area of cultural heritage, SIMS has been applied to a diverse range of problems including
technology and authenticity, origin and provenance, degradation processes, such as corrosion and
weathering, and conservation [4]. At first sight the requirements of SIMS and of chemical analysis
in the area of cultural heritage appear to be diametrically opposed. SIMS is a destructive analytical
technique in the sense that sample material is consumed during the analysis (as with all forms of
mass spectrometry). In addition, like many forms of ion beam analysis, electron microscopy and
electron spectroscopies, the SIMS instrument can usually accommodate only a small sample with
maximum linear dimensions of some mm. A larger artefact will need to be sampled in some way
before SIMS analysis is possible. Finally, SIMS is a high or even ultra high vacuum technique, and
depends on good vacuum over the sample for many aspects of its data quality. Therefore, the
sample must be vacuum compatible. In fact, the latter requirement still allows samples as diverse as
oil paint and obsidian to be analyzed so this limitation is not so great. On the other hand, SIMS
offers unique combinations of attributes which warrant its use under appropriate circumstances,
including high depth and lateral resolution (nm and 10 s nm, respectively), molecular specificity
and fingerprinting and trace analysis in the ppmppb range. It is worth noting that although these
specifications can undoubtedly be achieved individually, they are often mutually incompatible and
even require different instruments for their attainment. Nevertheless, it is in combinations of
properties that SIMS has its strengths, and also in complementary use with other techniques.
In this presentation, an outline is given of applications to glasses, metals, pigments and human
remains, focusing on conservation problems such as the assessment and suppression of corrosion,
other degrading processes, identification of materials using speciation. The topic of ultra low
energy SIMS, newly applied to cultural heritage materials, is briefly described.


[1] A. Adriaens, Trend. Anal. Chem. 23(8) (2004) 583-586.
[2] A. Adriaens and G. Demortier, Nucl. Instrum. and Meth. B 226 (2004) 3-9.
[3] A. Adriaens, M. Dowsett, in: Non-destructive Microanalysis of Cultural Heritage Materials, K. Janssens, R. Van
Grieken (Eds.), Elsevier Science B.V.: Amsterdam, 2004, p. 73-128.
[4] M. Dowsett, A. Adriaens, Nucl. Instrum. Meth. B 226 (2004) 38-52.
ACG-O-Tu-A03
118
The use of nanoSIMS to critically test claims of early (3.5 billion year
old) life

M. R. Kilburn
a,
*, D. Wacey
b
, N. Mcloughlin
b
, C. R. M. Grovenor
a
, M. D. Brasier
b

a
Department of Materials, University of Oxford, Parks Road, Oxford, OX1 3PH
b
Department of Earth Sciences, University of Oxford, Parks Road, OX1 3PR
Email: matt.kilburn@materials.oxford.ac.uk
Questions concerning the origin of life and our place in the universe are fundamental to modern
science and society. Investigations of the earliest purported microfossils and their geochemical
traces require high resolution technology on account of their small size and typically poor
preservation and despite many claims, compelling evidence for life on earth before ~3 billion years
is not yet available. The resolution of this fundamental question depends upon acquiring multiple
lines of evidence for biogenicity including a plausible geological context, biological morphology
and biogeochemical evidence for metabolic pathways.
A recent discovery of micron scale mineralized tubes in 3.48 billion year old pillow lavas from
the Barberton Greenstone Belt, South Africa [1], together with suggested modern analogues in
ocean crust basalts [2] has once again highlighted the need for greater spatial resolution in the field
of biogeochemistry. Whilst the quality of data presented by Furnes et al [1] using conventional
electron microprobe x-ray element mapping and bulk rock carbon isotope analysis is not disputed it
lacks the spatial resolution to be compelling evidence for biogenicity.
We have recently discovered a potentially important assemblage of partially mineralized
microtubes (5-10 microns in diameter) in ~3.5 billion year old siliceous sediments from Western
Australia. In this study we are using the high spatial resolution of the Cameca nanoSIMS 50 to
geochemically map the minerals within the tubes, possible linings on the walls of the tubes and
zonations within their mineral host, analyzing for biologically important elements (e.g. C, N, P, S,
K, Fe) as well as isotopic variations (C, O, S) between the phases.

Figure 1. NanoSIMS elemental maps of C
2
, Si, S, and PO
2
in a mineralized microtube image size 60 m.

[1] H. Furnes, N.R. Banerjee, K. Muehlenbachs, H. Staudigel, M. de Wit, Science 304, 578-581 (2004).
[2] H. Furnes, H. Staudigel, I. Thorseth, T. Torsvik, K. Muehlenbachs, O. Tumyr, G
3
, Vol 2, No 8 (2001).
ACG-I-Tu-A04
119
NanoSIMS: A new tool in cosmochemistry

Peter Hoppe

Max-Planck-Institute for Chemistry, P.O. Box 3060, 55020 Mainz, Germany
hoppe@mpch-mainz.mpg.de


The Cameca NanoSIMS 50 is a new generation ion microprobe, characterized by high spatial
resolution (down to 50 nm), high transmission, and simultaneous detection of up to six isotopes [1].
After four years of operation the NanoSIMS has now become a well established tool in
cosmochemistry which has significantly contributed to a better understanding of the presence of
presolar matter in primitive solar system materials and on the early solar system history [e.g., 2, 3].
Examples for important breakthroughs are: (i) Discovery of silicate stardust in interplanetary dust
particles and primitive meteorites. These grains formed around evolved stars, are submicrometer in
size and were identified by O-isotopic mapping on the basis of large O-isotopic anomalies
(enhanced abundance of
17
O) compared to average solar system matter. (ii) Co-ordinated
NanoSIMS/TEM studies made it possible to obtain simultaneous information on the mineralogy,
structure, and isotopic composition of submicrometer-sized presolar materials. (iii) Extension of
isotopic studies to submicrometer-sized presolar SiC and spinel grains separated from primitive
meteorites by chemical and physical treatments. Most of the presolar grains are in this size range
and the study of those grains made it possible to obtain new astrophysical information. (iv)
Discovery of radiogenic
60
Ni from the decay of radioactive
60
Fe (half life 1.5 Ma) in troilites of the
Semarkona meteorite. The inferred initial
60
Fe/
56
Fe ratio of >10
-6
at the birth of our solar system
implies a supernova source for
60
Fe, which might have triggered solar system formation, and that
60
Fe was an important heat source for planetary melting.


[1] F. Hillion et al., In: Secondary Ion Mass Spectrometry SIMS IX (1993), p. 254.
[2] S. Messenger et al., Science 300 (2003), 105-108.
[3] S. Mostefaoui et al., Astrophys. J. (2005), in press.

ACG-O-Tu-A05
120
IDLE: (INTERSTELLAR DUST LASER EXPLORER), A NEW
INSTRUMENT FOR SUBMICRON ANALYSES OF STARDUST -
QUANTIFICATION IN SIMS AND LASER SNMS.

T. Henkel
a
, J. Tizard
a
, and I. Lyon
a*


a
School of Earth, Atmospheric, and Environmental Sciences, The University of Manchester, Manchester, M13 9PL,
United Kingdom
*
E-mail: ian.lyon@manchester.ac.uk


We have constructed a TOF-SIMS instrument based upon the BIO-TOF design [1]. SIMS
mapping of mass resolved secondary ions and molecules with an intrinsic mass resolving power of
3700 has been achieved with an estimated spatial resolution of 250nm. We are currently conducting
studies of non-resonant laser post-ionization of sputtered neutrals in order to improve the ionization
efficiency over SIMS and avoid matrix effects for more precise quantification of element
abundances. The laser used is a GAM F
2
excimer laser producing up to several mJ per pulse at
750Hz at a wavelength of 157nm. With a photon energy of 7.96eV, over 60% of the elements of the
periodic table may be non-resonantly photo ionized by single photon ionization. SNMS laser post
ionization improves detection sensitivity especially for elements with mid-range first ionization
potentials up to the single photon energy of 7.96eV like most transition metal, actinide, and
lanthanide elements. An unexpected observation is the photo ionization of Si (ionization potential
8.15eV) and we are studying the mechanisms that make this possible. SNMS ion yields are up to an
order of magnitude higher than SIMS for metals such as Mo and Ta and we are currently
quantifying the highest sensitivities obtainable using this technique for a range of elements.


[1] R.M. Braun et al., Rapid Communications in Mass Spectrometry (1998) 12, 1246-1252.
ACG-O-Tu-A06
121
Analyses of Micrometeorite Impact Features on the Salyut 7 Russian
Space Station Titanium Tank

Virginie Jantou
1
, David McPhail
1
, Richard Chater
1
, Anton Kearsley
2

1. Department of Materials, Imperial College London, SW7 2BP
2. Natural History Museum, London
(v.jantou@imperial.ac.uk)


Salyut 7 was the last of the Russian Salyut space stations, and the precursor to the Mir modular
space station. It was created to further perfect space station operations, and to study the docking of
large modules to the Salyut. Salyut 7 was launched on April 19th 1982 and it de-orbited on
February 7th 1991; it was destroyed during re-entry. The titanium tank studied in this paper was
recovered in South-America after re-entry, and it is riddled with several hundred craters of
micrometeoroids.

The aim of the present project is to investigate features of various micrometeoroid impacts on the
titanium tank. Even if the particles considered are in the order of the m, they travel at such high
velocity (from 5km.s
-1
up to 70km.
-1
) that their kinetic energies pose a significant threat to
spacecraft, therefore making it important to understand the effects of these impacts.

Hypervelocity impact tests were carried out at the University of Kent, Canterbury, in order to
study possible microstructural changes within the target materials following a hypervelocity impact
event. The target materials were two sections from the titanium tank and one section from a Ti-6Al-
4V alloy. The projectiles were different known minerals as well as one titanium alloy; the impact
velocity was also known. Microstructural changes and surface disruption around the crater were
investigated using a secondary ion mass spectrometer (SIMS). Focused Ion Beam (FIB) milling was
used in order to make TEM sections that would provide crystallographic information from the
impactor, the target material and above all the impacted region. This could permit us to establish
relationships between impact variables or material properties and crater morphology.







Fig 1: A SIMS image of a crater on the Ti-6Al-4V
alloy, on which a 2m layer of Pt was deposited,
tilted to 45.
Fig 2: A focused ion beam image of a milled
section in the centre of the crater, tilted to
45.
ACG-O-Tu-A07
122
Application of the
182
Hf-
182
W chronometer to eucrite zircon and initial
solar
182
Hf abundance a multicollector SIMS approach

M.J Whitehouse
a
,* G.Srinivasan
b
.

a
Swedish Museum of Natural History, Box 50007, SE-104 05 Stockholm, Sweden.
b
Department of Geology, University of Toronto, Toronto, ON M5S 3B1 Canada.
martin.whitehouse@nrm.se

The decay of
182
Hf to
182
W is a very useful relative chronometer for time scales of core formation
and silicate differentiation on planetary bodies. Refractory lithophile Hf and siderophile W, initially
almost chondritic in abundance, undergo significant fractionation during metal-silicate fractionation
prior to core formation. Formation time scales estimated from W isotope data for different
meteorites are based on translating relative differences in
182
Hf abundance into age using its ca. 9
Ma half-life together with an estimate of the initial
182
Hf abundance ([
182
Hf/
180
Hf]
SSI
)

in the solar
system. The relative time scale of metal-silicate differentiation in eucrites based on
182
Hf abundance
varies from ~ 4 Ma [1] to ~ 6-9 Ma [2] depending on which [
182
Hf/
180
Hf]
SSI
is used for calculation,
highlighting the importance of directly calibrating the abundance of a short-lived radionuclide
against an absolute chronometer. The U-Pb system in zircon (ZrSiO
4
), a mineral commonly found
in eucrites, is a widely used chronometer that can resist isotopic resetting at < 1000C. With high Hf
(1-2%) and exceedingly low W (< 1ppm), zircon is ideally suited to determination of the
182
Hf
abundance at the time of its formation.
Previous attempts to investigate the Hf-W systematics of eucrite zircon using both small (Cameca
IMS 4f [3]) and large (SHRIMP, SHRIMP-RG [4]) format ion microprobes have suffered from
limitations imposed respectively by the use of energy filtering with its attendant loss of signal, or
high mass resolution combined with inefficient peak-hopping monocollection. Here we report an
analytical routine developed on the Cameca IMS 1270 using four ion counting electron multipliers
(EMs) positioned along the focal plane in order to measure simultaneously the species
178
Hf
+
,
182
W
+
,
183
W
+
and
186
W
+
. The highest available nominal mass resolution of ca. 8000 was set by
entrance and exit slit widths of 60 m and 150 m respectively. Peak coincidence on the EMs was
optimised using NIST SRM 610 glass which yields large signals of both Hf and W. The quality and
width of the peak flats allowed an increase in effective mass resolution to be achieved by moving
the lowest mass EM slightly towards the low mass end of the array so that when used to centre
178
Hf
+
, the W signals were measured on the higher mass side of the W peak flats, further reducing
possible contribution from REE oxides (e.g.
166
Er
16
O
+
on
182
W
+
). Relative EM gains were adjusted
using a pulse height analysis routine and calibrated by a peak hopping experiment. These gains
were similar within a few percent, and noise levels were lower than 1 cpm. Calibration of Hf/W
ratios is problematic in zircon because of the low abundance of W. We therefore followed a
previously described method [4] that uses Yb as a proxy trace element for W in relative sensitivity
factor calibration, with NIST SRM 610 and Geostandards 91500 zircon as reference materials.
Applying our method to zircon in the eucrite A881467, we estimate a solar system initial
182
Hf/
180
Hf of (2.21.2) 10
-4
. This value agrees at the lower limit of experimental errors with those
values inferred from primitive meteorites and encompasses the higher values abundance inferred
from iron meteorites. The
182
Hf abundance determined from primitive meteorites appears to be a
lower limit and it remains possible that reservoirs with higher values were present.
[1] T. Kleine, C. Munker, K. Mezger, H. Palme Nature 418 (2002) 952-955.
[2] G.Quitte , J.L. Birck, Earth and Planetary Science Letters 219 (2004) 201-207.
[3] Srinivasan G. et al., Meteoritics and Planet Science (2000) #5127.
[4] T.R. Ireland T.R., M. Bukovanska, Geochimica Cosmochimica Acta 67 (2003)4849-4856.
ACG-O-Tu-A08
123
Surface Analysis of Ancient Glass Artefacts With ToF-SIMS: A Novel
Tool For Provenancing?

F.J.M. Rutten
a,
*, M.J. Roe
b
, J. Henderson
c
and D. Briggs
a
.

a
Centre for Surface Chemical Analysis and Laboratory of Biophysics and Surface Analysis, School of Pharmacy
b
School of Mechanical, Materials and Manufacturing Engineering
c
Department of Archaeology, School of Humanities
The University of Nottingham, Nottingham NG7 2RD, UK
E-mail: frank.rutten@nottingham.ac.uk

To understand the structure of ancient civilisations and their interactions archaeological
information is often crucial in establishing the existence of ancient trading routes and also
production centres for which any direct physical or written evidence no longer exists. Ancient glass,
which first appeared ca. 2500BC, has enormous potential to aid these investigations, but at present
it is only seldomly possible to provenance glass scientifically to the location of its production.
Ancient glass was extensively used decoratively, e.g. in the form of mosaic tesserae and beads, as
well as functionally in the form of glass vessels and windows. Glass manufacture often involved
mineral-rich colourants, sometimes in combination with crystalline opacifiers, to produce coloured,
opaque glass used not for its transparency but rather for its colourful appearance. As a great number
of ancient glass objects has been found over the years, investigation of glass objects has the
potential to yield a great deal of information not only on the glass manufacturing itself but also its
trading in ancient civilisations. The precise nature of colourants, opacifiers as well as other (trace)
elements in glass has, in a number of cases, been found to be highly specific for both the particular
production process employed, including raw materials, and sometimes its provenance [1].
Determining the co-location of different elements in small particulate inclusions in glass can give
crucial further information on provenance and employed fabrication technology when solely
detecting the presence of opacifiers and other (trace) elements is not sufficiently specific.
ToF-SIMS is uniquely capable to detect elements across the periodic table with often very high
detectivity and specificity, coupled with high lateral and depth-resolution. In a carefully designed
experiment, also employing scanning electron microscopy, this allowed us to detect and
characterise inclusions in a number of ancient glass samples as well as the surrounding matrix in
great detail. The use of a glass standard moreover allowed for the (semi-) quantification of the
elements detected [2].

[1] The Science and Archaeology of Materials: An investigation of Inorganic Materials
J. Henderson, Routledge, London (2000) Chapter 3
[2] A chemical-analytical round-robin of 4 synthetic ancient glasses, R.H. Brill, 9th International conference on glass,
Artistic and Historical Communications, Versailles, 1971, Paris 1972
ACG-I-Tu-A09
124
SIMS Analysis of Ancient Materials

DS McPhail*.

*
The Department of Materials, Imperial College, Prince Consort Road, London SW7 2BP.
d.mcphail@ic.ac.uk


The surface analysis centre in the Materials department at Imperial College is involved in a very
wide range of materials analysis programmes spanning many disciplines. Our aim is to exploit the
powerful attributes of SIMS in as many areas of materials science as possible and in this paper
examples are drawn from diverse areas including museum conservation, archaeology and
cosmology. The overall aim is to show how the analytical and ion beam processing capabilities of
SIMS can be applied in a variety of ways to yield useful information.
A significant fraction of the vessel glass collection at the Victoria and Albert Museum is showing
serious signs of decay [1], with the surfaces showing a cloudy appearance and /or a fine network of
cracks (crizzling). Typically this glass is relatively low in lime and magnesia and undergoes
atmospheric attack due to moisture in the air. Both active and passive conservation is essential if
these objects are to be saved. Following compositional analysis analogue glasses have been made
and then aged, in order to determine the corrosion mechanisms and kinetics. The addition of a FLIG
gun to our Atomika 6500 has facilitated ultra-low energy SIMS depth-profiling so that corrosion
rates can be determined without the need for accelerated ageing. It is important to note that very
low corrosion rates can lead to significant effects over long timescales, a comment that is pertinent
to the debate about using glass to store radioactive waste (one nanometre of corrosion per day leads
to 0.365mm of decay per millennium).
SIMS has also been used to evaluate the effects of cleaning procedures used on museum objects,
with special emphasis on laser cleaning. The surface analysis centre has formed a partnership The
London Laser Cleaning Consortium with the Victoria and Albert Museum, the Tate Gallery, the
Natural History Museum and the City and Guilds College. Our aim is to use SIMS to measure the
effects of laser cleaning on a museum object, exploiting the sensitivity of SIMS to determine
changes to the surface chemistry long before they become visible to the eye, and to monitor the rate
of recontamination of surfaces one they have been cleaned [2].
SIMS has been used to characterise the corrosion processes in archaeological glass samples from
Raqqa, Syria, and here the milling capabilities of the FEI FIB 200 instrument have been very useful
in opening-up a corrosion product prior to examination of the multilayer corrosion structure [3].
The final example involves the application of SIMS to the study of micrometeorites. A number
of materials have experienced micrometeorite impacts in low earth orbit, and there is an obvious
interest in studying these impact sites, as the impactors can date back to the origins of the universe.
We have studied micrometeorite impacts in a number of targets including solar cells from the
Hubble space telescope and the Titanium tank from the first Russian space station. In these studies
both the areas to be studied and the volume of residual impactor material available for mass
spectrometry is very limited, presenting SIMS with a significant challenge [4].


[1] S.E.T. Hogg, D.S. McPhail, V.L. Oakley and P.S. Rogers,
Conservation of Glass And Ceramics, Editor N. Tennent, Publ. James and James, ISBN 1 873936 18 4,(1999), 42-56.
[2] M. Sokhan, P.Gaspar, D.S. McPhail, A. Cummings, L Cornish, F. Hartog, C. Hubbard, V. Oakley and J.F. Merkel,
Journal of Cultural Heritage, 2003, vol. 4, no. 1001, 230-236.
[3] J. Henderson, S. D. McLoughlin and D.S. McPhail, Archaeometry, 46, 2004, 439-468.
[4] G.A. Graham, P.G. Grant, R.J. Chater, A.J. Westphal, A.T. Kearsley, C. Snead, G. Dominguez, A.L. Butterworth,
D.S. McPhail, G. Bench and J.P. Bradley, Meteoritics and Planetary Science, 2004, 39(9), 1461-1473.
ACG-O-Tu-A10
125
SIMS analysis of particles in Aerogel

S Sinniah
a
, K Kotian
b
, RJ Chater
a,
*, DS McPhail
a
, A Kearsley
c
, A Butterworth
d
, B Hagenhoff
e
and
MJ Burchell
f


a
Department of Materials, Imperial College, London SW7 2AZ, UK
b
Department of Physics, Imperial College, London SW7 2AZ, UK
c
Department of Mineralogy, The Natural History Museum, London SW7 5BD, UK
d
Space Sciences Laboratory, Univ of California at Berkeley, California 94035, USA
e
TASCON Gmbh, 48149 Muenster, Germany
f
School of Physical Science, University of Kent Canterbury, Kent CT2 7NR, UK


Aerogel is a silica foam with the lowest density known for a man-made material of between 5
and 150kg/m
3
. The material has been used mainly in insulation applications. Aerogel has also be
exposed in Earth orbit for the capture of dust particles from space on the MIR space station and
most recently on the NASA Stardust spacecraft flyby of the Comet Wild 2 in January 2004.
Analysis of collected particles returned to earth from both sources is expected to shed light on the
problems posed by space debris in Low Earth Orbit as well as the origins of the universe
Dust particles in space collide with the aerogel material at hypervelocity speeds in the range of 5
to 70km/sec and as a consequence may be buried far below the surface of the aerogel, fragment or
break up causing a void thinly coated with traces of impactor residue. The analysis by a suite of
different techniques on the impacted grains has been the topic of a number of recent papers[1-3]. In
this paper we discuss the results of SIMS analyses using static and dynamic SIMS instrumentation
on aerogel of various densities, an analogue sample prepared in terrestrial laboratories with mineral
particles of known composition and a sample from the an aerogel collector exposed on the MIR
space station.
The results shown here as figures are low-dose static SIMS images from a section perpendicular
to the exposed surface of an aerogel collector that was mounted on the MIR space station.

Optical Photograph
23
Na
+
image
24
Mg
+
image









The field of view of each of the images is 500microns x 500microns. The arrow pairs with each
image indicate the originally exposed surface to the space environment. From these figures it can
be seen that particles of differing composition can be visualized by SIMS analysis.


[1] Kettle, S., R.J. Chater, G.A. Graham, D.S. McPhail, and A.T. Kearsley, Applied Surface Science, 2004. 231-2: p.
893-898.
[2] Graham, G.A., R.J. Chater, D.S. McPhail, A.T. Kearsley, M.R. Lee, S. Kettle, and I.P. Wright, Meteoritics &
Planetary Science, 2002. 37(7): p. A56-A56.
[3] Westphal, A.J., C. Snead, A. Butterworth, G.A. Graham, J.P. Bradley, S. Bajt, P.G. Grant, G. Bench, S. Brennan,
and P. Pianetta, Meteoritics & Planetary Science, 2004. 39(8): p. 1375-1386.

ACG-I-Tu-A11
126
Investigation into the Nature of Historical Tapestries Using Time of
Flight Secondary Ion Mass Spectrometry

*Chris Carr & Marei Hacke

Textiles & Paper, School of Materials, The University of Manchester
chris.carr@manchester.ac.uk


Tapestries are inextricably woven into the fabric of European history and culture. In the 15-17
th

centuries tapestry manufacture was at its peak and was the definitive iconographic symbol of
power, wealth and cultural style. However in the subsequent centuries the condition of the tapestries
has generally deteriorated due to poor handling and exhibition conditions. Exposure to extended
periods of sunlight, has led to strength loss and more obviously to the loss of the intense vibrancy
and brilliance of the original coloured design.

The tapestries are composed of wool, silk and precious metal threads. While the silver and silver
gilt threads may tarnish and exhibit obvious discolouration, it is the predominant wool and silk
components, which on exposure to sunlight may also display discolouration and colour fade, but
more importantly strength loss leading to potential catastrophic fabric failure.

In this study the wool, silk and metal threads tapestry components are investigated using ToF-
SIMS and the nature of their fibre surfaces and the degradation processes established. In addition
the influence of the historical dyeing methods and scouring processes on the protein fibres are
investigated and their effect on the initial fibre properties determined. Periodically these historical
materials maybe cleaned and the potential impact of this interventive treatment on the
photodegraded materials discussed.
ACG-O-Tu-A12
127
Measurement of Sulfur Isotope Ratios in Micrometer-Sized Samples
by NanoSIMS

Brbel Winterholler
a,
*, Peter Hoppe
b
, Smail Mostefaoui
b
, Meinrat O. Andreae
a
, Stephen Foley
c

a
MPI for Chemistry, Dep. Biogeochemistry, Joh.-Joachim-Becher-Weg 27, D-55128 Mainz
b
MPI for Chemistry, Dep. Cosmochemistry, Joh.-Joachim-Becher-Weg 27, D-55128 Mainz
c
Johannes Gutenberg - University, Dep. Mineralogy, Joh.-J.-Becher-Weg 21, D-55099 Mainz
winterho@mpch-mainz.mpg.de


Analysis of sulfur isotope ratios of individual aerosol particles can provide detailed information
with regard to the origin and the transport of sulfur in the environment, which is difficult to obtain
by conventional bulk analysis techniques. The Cameca NanoSIMS 50 ion microprobe has a very
high useful yield of sulfur under Cs
+
bombardment, an excellent transmission/collection efficiency,
and the capability to measure all four S isotopes simultaneously in multi-collection. These features
permit to measure sulfur isotope ratios in sulfate grains down to 1 m or less in diameter with a
precision suitable for application in atmospheric science.
Two factors influence the precision of the analysis: 1. counting statistics, i.e., availability of
sample material, and 2. the spot to spot reproducibility of the analytical result. Both parameters can
be optimised by instrument tuning procedures and sample preparation. Spot to spot reproducibility
depends on the grain topography, sample charging, and sample matrix. Considering both the
counting statistical error and the spot to spot reproducibility a precision of 3 (2) for the
34
S
has been achieved on sample sizes down to 1 m of sulfate.
Aerosol particles are natural materials that have undergone several transformations and therefore
differ in sample matrix and water content. Accurate measurements require a good understanding of
the fractionation of sulphur during sputtering [1] and the dependence of instrumental mass
fractionation (IMF) on the instrument tuning [2]. Changes in IMF due to the charging of non-
conductive samples and the methods used for charge compensation as well as effects related to the
use of electron multipliers such as quasi simultaneous arrival (QSA) [3] and electron multiplier
aging during analysis have to be taken into account.
This study compares different analytical approaches to achieve maximum precision and
accuracy in ultra small sample volumes.


[1] R.L. Hervig, Rapid Communications in Mass Spectrometry 16 (2002) 1774-1778.
[2] G. Slodzian, Applied Surface Science 231232 (2004) 312.
[3] G. Slodzian, F. Hillion, F.J. Stadermann, E. Zinner, Applied Surface Science 231232 (2004) 874877.
ACG-O-Tu-A13
128
BASIC EXPERIMENT OF REMOTE SIMS METHOD FOR LUNAR
SURFACE OBSERVATION

Koji Tanaka and Susumu Sasaki

Japan Aerospace Exploration Agency
Institute of Space and Astronautical Science
3-1-1 Yoshinodai, Sagamihara-SHI 229-8510, JAPAN
(E-mail:ktanaka@isas.jaxa.jp)


This paper describes the results of a conceptual study and preliminary experiments for the lunar
surface observation using Remote SIMS (Secondary Ion Mass Spectrometry) method. Evidence of
the water ice in permanently shadowed craters at the lunar poles was detected by Lunar Prospector's
neutron spectrometer experiment [1]. Because of the low spatial resolution and the uncertainty in
indirect observations of the water ice, the direct exploration mission is expected. Remote SIMS is
considered to be a candidate for the in-situ observation method on the moon in order to obtain a
credible evidence of the ice occurrence. Irradiation of the lunar surface by the ion beams from the
Lander will induce secondary and back scattered radiation. Generated secondary ions can be
detected by a mass spectrometer installed on the Lander. The secondary radiation is characteristic of
the makeup of the lunar surface. We estimated a range of the observation and the size of the spot
irradiated by the ion beams. Also, we carried out the preliminary experiments of the secondary ion
generation using a cooling target with a water ice that simulates the permanently shaded region of
the lunar surface by the fast ion bombardment. It was confirmed that secondary ion yield of the
water ice under the various conditions of the primary beam.


[1]W.C.Feldman, S.Maurice, A.B.Binder, L.Barraclough, R.C.Elphic, D.J.Lawrence, Science 281 (1998) 1496-1500.

ACG-O-Tu-A14
129
Secondary Ionization Mass Spectrometric Analysis of Impurity
Element Isotope Ratios in Nuclear Reactor Materials

D. C. Gerlach*, J. B. Cliff, D. E. Hurley, B. D. Reid, W. W. Little, G. H. Meriwether, T. A.
Simmons

Pacific Northwest National Laboratory, P. O. Box 999, Richland, WA 99352, U.S.A.
*david.gerlach@pnl.gov


Secondary ionization mass spectrometry has been used for several years to measure isotope ratios
of selected impurity elements in irradiated reactor materials. Samples of reactor materials may be
obtained from fuel channels or supporting materials such as graphite or aluminum alloys. During
reactor operations and fuel burn up, some isotopes may decrease or increase due to nuclear
reactions and provide sensitive indicators of neutron fluence. The rate of change is related to cross
section for a particular isotope, and this allows different isotopes to be used as indicators of burn up
during different stages in the reactor operating history. Isotope ratios of B, Cl, and Li are useful for
low burnup stages early in reactor operations and Ti and Be isotope ratios are useful indicators at
later burn up stages. In a sequence of samples from one reactor, 10B/11B ratios decreased from
near natural values of 0.25 to < 0.03. Knowledge of the sample position within the reactor also
yields information on the fluence shape or profile. Direct SIMS measurements of isotope ratios
have been possible in materials, following shaping and surface cleaning trials which have included
dry ice micropellet blasting, plasma etching, and vacuum furnace treatment. Depending on the
sample matrix, some elements require separations and purification prior to SIMS analysis to
minimize or avoid interferences.
ACG-O-Tu-A15
130
Combined SIMS / SEM technique for environmental monitoring of
nuclear facilities: detection, analysis, and characterization of
radionuclides in micrometer-sized particles

Laure Sangly*, Sidy Diallo, Olivier Marie, and Stphane Baude

C.E.A. Bruyres-le-Chtel, BP 12, 91680 Bruyres-le-Chtel, France
Email: laure.sangely@cea.fr

Radionuclides from natural and anthropogenic sources are present at trace level in all the
compartments of the environment. A significant part of them is found as constituents of
micrometer-sized solid particles deposited in soils, sediments as well as onto biological indicators.
We will demonstrate a method combining SEM and SIMS techniques applied to the detection, the
analysis and the characterization of radionuclides in particles recovered from samples of special
interest in monitoring the environmental impact of nuclear activities. The particle samples have
been deposited on 0.5 inches sample mountings equipped with an internal 2D reference system.
Scanning electron microscopy The detection of uranium-containing particles has been
performed using a FEI XL 30 environmental SEM fitted with an EDAX system. The use of Gun
Shot Residue software allowed the automatic search for uranium-containing particles through back-
scattered electron image analysis and qualitative micro-analysis of major elemental composition by
energy dispersed X-ray spectrometry. Eventually, secondary electron images of uranium-containing
particles have been acquired in order to characterize their morphology.
Secondary ion mass spectrometry Isotopic analysis and ion microscopy have been performed
on the same sample mountings using the Cameca new generation instrument IMS 7f. The uranium
isotopic ratios have been determined in the individual particles previously detected in SEM with a
~0.7% 1 precision (relative standard deviation of the mean over measurement cycles). The
mapping of particles of interest has been obtained in ion microscope mode using a Resistive Anode
Encoder imagery detector.
The advantages of this new analytical approach are i) the limited sample preparation which
reduces cross-contamination risks, ii) the optimization of analytical response time, and the extensive
characterization of individual particles which is helpful in the identification of the radionuclide
sources.
ACG-O-Tu-A16
131
Application of SIMS analyses on oxygen and hydrogen transport in
SOFC materials

N. Sakai
*
, K. Yamaji, T. Horita, H. Kishimoto, M. E. Brito and H. Yokokawa

National Institute of Advanced Industrial Science and Technology
n-sakai@aist.go.jp


The transport properties of hydrogen (proton) or oxygen (oxide ion) in solids are very important
in the electrochemical reaction which proceeds at the electrode/electrolyte interface in solid oxide
fuel cells (SOFC). By using the labelled gases and SIMS analyses, it is possible to determine the
parameters of gas-solid interactions, i. e., the solubility [1], surface exchange rate and diffusivity [2]
which are important factors to control the electrochemical reaction. The visualization of oxygen
flow in the vicinity of electrode/electrolyte interface is possible by the combination of depth
profiling and imaging [3].
The oxygen transport in the vicinity of electrode/electrolyte interface was investigated by using
the model interface consists of gold (Au) or platinum (Pt) stripes as electrodes on the yttria
stabilized zirconia (YSZ), oxide ion conductor as electrolyte. The sample was treated in
18
O
2
(7
kPa) + H
2
18
O (2 kPa or 190 Pa) at T = 773 K for 300 s and quenched. The distribution of
18
O,
16
O
,

and metal components are analyzed by SIMS (ims5f CAMECA instruments Co.).
The
18
O distribution near Pt/YSZ treated at T =
773 K in
18
O
2
(7 kPa) + H
2
18
O (2 kPa) for 300 s is
shown in the figure. Most of
18
O diffuses from
triple phase interface of gas/Pt/YSZ, and there is no
18
O penetration through Pt as schematically shown
in the figure. It indicates that the platinum acts as a
blocking electrode at that condition. The
18
O
concentration in YSZ was increased with water
vapour pressure (p(H
2
18
O)) indicating that the
18
O
exchange reaction at YSZ surface is governed by
water molecule adsorbed on YSZ surface, which
agrees with our previous investigation [2]. These
transport properties can be correlated with the
cathode reaction mechanism in SOFC.
The application of the model interface and SIMS
analyses are is possible to the anode reaction
mechanism by using the nickel stripe
electrode/YSZ or rare earth doped ceria electrolyte
and gasses such as D
2
O, H
2
18
O, or CH
4
etc. Horita et al have found that the oxygen content in
nickel electrode changes with the type of electrolytes, and it also affect on the carbon deposition
behaviour [4]. In this presentation, the importance of SIMS data are demonstrated for both on
cathode and anode reactions of SOFC.

[1] N. Sakai, K. Yamaji, T. Horita, H. Yokokawa, Y. Hirata, S. Sameshima, Y. Nigara and J. Mizusaki, Solid State
Ionics 125 (1999) 325-331.
[2] N. Sakai, K. Yamaji, T. Horita, Y. P. Xiong, H. Kishimoto, H. Yokokawa, J. Electrochem. Soc., 150(6) (2003)
A689-A694.
[3] T. Horita, K. Yamaji, N. Sakai, M. Ishikawa, H. Yokokawa, T. Kawada, and T. Kato, J. Electrochem. Soc., 145 (9)
(1998) 3196-3202.
[4] T. Horita, H. Yokokawa, N. Sakai, K. Yamaji, T. Kato, Solid State Ionics 172 (2004) 93-99.
YSZ
X X X
18
O
Pt
~ 2m
~ 150m
18
O distribution at the platinum/YSZ
treated in
18
O
2
+ H
2
18
O at T73 K for 300 s,
and schematic view of
18
O flow.
ACG-O-Tu-A17
132
Characterisation of irradiated nuclear fuel with SIMS

Ch.Valot, Lionel DESGRANGES*, B.Pasquet

CEA/Cadarache Bat 316 13108 Saint-Paul lez Durance (FRANCE)

Lionel.desgranges@cea.fr


The optimisation of the nuclear fuel requires an in-depth characterisation of its behaviour after
irradiation in nuclear power plants. In addition to optical microscopy, SEM, EPMA and XRD, a
shielded SIMS was designed and installed [1] in our laboratory with the aim of providing
information both on the behaviour of nuclear fuel in reactor and on also on its potential behaviour in
(interim) storage conditions.
For that purpose, the studies performed with SIMS on irradiated nuclear fuel were focused on
three main axis :
1- The nuclear reactions occurring during the irradiation lead to the creation of many isotopes
giving crucial information on burn-up and more generally on nuclear reaction rates. It is
shown that SIMS measurements of isotopic ratios can be compared to theoretical neutronic
calculations, and hence can improve the evaluation of the production of radioactive
elements.
2- The safety of irradiated materials depends on the physical and chemical state of the radio
nuclides. Up to now little was known about low abundant but safety relevant radio-nuclides,
such as iodine for example. It is shown that the behaviour of iodine and other radio-nuclides
that can hardly be detected with EPMA is well characterised with SIMS.
3- The thermo-mechanical behaviour of the nuclear fuel is closely related to the fission gases
state, either dissolved in the ceramic, retained in bubbles or released in the fuel rod. We
have developed an original method which allows the gas measurement with SIMS [2] and
also the characterisation of the bubbles filled with gas, when they exist.


[1] B.Rasser, L.Desgranges, B.Pasquet, Applied Surface Science 203-204 (2003) 673-678
[2] L.Desgranges, B.Pasquet Nuclear Instruments and methods in Physics Research B 215 (2004) 545-551

ORG1-I-Tu-B01
133
SSIMS analysis of organics, polymer blends and interfaces

Lu-Tao Weng
a,*
and Chi-Ming Chan
b

a
Materials Characterization and Preparation Facility
b
Chemical Engineering Department
The Hong Kong University of Science and Technology
Clear Water Bay, Kowloon, Hong Kong
mcltweng@ust.hk
Static secondary ion mass spectrometry (SSIMS) and ToF SIMS in particular has become a key
surface analysis technique for organic and polymeric materials. The main advantage of SSIMS over
other surface techniques is its capability of providing high molecular specificity, high spatial
resolution and high sensitivity, which is ideal for elucidating complex chemistry of polymer
surfaces and interfaces. In particular, molecular structure information such as branching,
saturation/unsaturation, chain conformation, functional groups, molecular weight distribution, end
groups, segmental length etc. can be deduced from SSIMS spectra.
In this talk, the applications of SSIMS to organics and polymer surfaces and interfaces will be
illustrated by some recent examples, including:
1. Migration of polymer additive or processing aid during polymer processing;
2. Migration of end group during polymer crystallization [1];
3. Compatibilization of polymer blends [2,3];
4. Surface segregation driven by polymer crystallization [4, 5];
5. Polymer surface modifications [6].
The advantages and drawbacks of SSIMS in polymer analysis will be discussed.

[1] L Li., K.M. Ng., C.-M Chan., J.Y. Feng, X.M. Zeng and L.T. Weng, Macromolecules, 33 (2000) 5588.
[2] J.Y. Feng, L. Li, C.-M. Chan and L.T. Weng, Surf. Interface Anal., 33 (2002) 455.
[3] J.Y. Feng, L.T. Weng, L. Li and C.-M. Chan, Surf. Interface Anal., 33 (2000) 168.
[4] Y.G. Lei., Z.L. Cheung, K.M. Ng., L Li., L.T. Weng and C.-M. Chan, Polymer, 44 (2003) 3883-3890.
[5] Z.L Cheung., L.T. Weng, C.-M. Chan, W.M. Hou and L. Li, submitted for publication.
[6] L.T. Weng, P.C. L. Wong, K. Ho, S. Wang, Z. Zeng and S. Yang, Anal. Chem.,72 (2000) 4908.

ORG1-O-Tu-B02
134
ToF-SSIMS analysis of plasma chemically deposited co-polymer
films

U. Oran, S. Swaraj, J. F. Friedrich and W. E. S. Unger*

Working Group VIII.23 Thin Film and Surface Analysis Bundesanstalt fr Materialforschung - und prfung
(BAM) Unter den Eichen 44-46, D-12203 Berlin, Germany
umut.oran@bam.de, sufal.swaraj@bam.de, joerg.friedrich@bam.de, wolfgang.unger@bam.de


A plasma co-polymerization of functional group bearing monomer with a chain extending
hydrocarbon monomer can be used to exert a control on the concentration of surface
functionality in plasma deposited films. In a dedicated study ethylene or styrene as chain
extending monomers were plasma co-polymerized with allyl alcohol or allylamine as carrier
monomers for hydroxyl and amine groups, respectively. The composition of the feed gas was
systematically varied and the plasma co-polymers were preferentially analyzed in terms of their
density of functional groups by ToF-SSIMS (Time of Flight Static Secondary Ion Mass
Spectrometry). ToF-SSIMS analysis of the plasma deposited co-polymer films was performed
immediately after their preparation without any air contact, i.e., under so called in-situ
conditions.
The relative primary amino group concentration related to the CH
2
-NH
2
side chain groups at
the surface of respective plasma deposited co-polymer films could be derived from the
normalized yields of the CH
4
N
+
secondary ion. Similarly, yield of the CH
3
O
+
secondary ion
could be used to investigate the relative surface concentration of the OH groups involved in the
of CH
2
-OH side chain group.
It was found that through a careful selection of the feed gas composition the concentration of
surface functional groups in plasma deposited co-polymer films can be controlled. However, the
density of functional groups in the plasma co-polymers was varying non-linearly with respect to
the mol percentage of the monomers in the feed gas. It seems that under the deposition
conditions employed in this study the co-polymerization phenomenon is initiated by the plasma
and the different chemical reactivities of the monomers are responsible for the observed non-
linear variations.
ORG1-O-Tu-B03
135
TOF-SIMS: ACCURATE MASS SCALE CALIBRATION

F.M.Green
*
, I.S.Gilmore & M.P Seah

National Physical Laboratory, Teddington, Middlesex, UK
Tel: +44 (0)20 8943 6153; Fax:+44 (0)208 8943 6453;
e-mail: Felicia.Green@npl.co.uk


A study is presented of the factors affecting the calibration of the mass scale for Time-of-Flight
(TOF) Secondary Ion Mass Spectrometers (TOF-SIMS). At the present time, TOF-SIMS analysts
achieve a mass accuracy of only 150 ppm for large molecules (647 amu) and for smaller fragments
of < 200 amu may typically be 60 ppm [1]. The instrumental stability is 1 ppm and better than 10
ppm is necessary for unique identification of species. In the recent interlaboratory study [1] only 3
instruments out of 32 were within 10 ppm for smaller fragments. The experimental uncertainty can
lead to unnecessary confusion where peaks are wrongly identified or are ambiguous.

Here we study in detail the instrumental parameters of a popular single stage reflection
TOF-SIMS with ion trajectory calculations using SIMION [2]. The effect of the ion kinetic energy,
emission angle and other physical and instrumental operating parameters on the measured peak
position are determined. This clearly shows why molecular and atomic ions have different mass
accuracy and peak shapes. These data provide the basis for a coherent procedure for optimising the
instrumental settings for accurate mass calibration and rules by which inorganics and organics may
be incorporated. This leads to generic sets of ions for mass calibration, which, used for re-
calibration, improves the mass accuracy of the interlaboratory study data [3] by up to a factor of 4.
Now, 12 instruments out of 32 are within the 10 ppm range. A calibration protocol is developed that
gives a fractional mass accuracy of better than 11.5 ppm, an improvement of a factor of 5. The
effects of extrapolation beyond the calibration range are discussed and a recommended procedure
given to ensure that accurate mass of large molecules is achieved within a selected uncertainty.

One bonus of this study is that the instrument can now be operated as well in a regime with good
energy discrimination to study the fragmented energies of molecules. We shall discuss how this
compares with data from G-SIMS [4] and supports the G-SIMS concept.


[1] F M Green, I S Gilmore and M P Seah, in preparation.
[2] SIMION 3D version 7.0, D.A.Dahl, Idaho National Engineering and Environmental Laboratory.
[3] I S Gilmore, M P Seah and F M Green, submitted Surf Interface Anal.
[4] I S Gilmore and M P Seah, Appl. Surf. Sci., 161 (2000), p. 465.
ORG1-O-Tu-B04
136
Diffusion study of multi-organic layers in OLEDs by ToF SIMS

Wen-Yin Chen, Bo-Jung Chen,

Yong-Chien

Ling*, Hung-Hsin Shih, Chien-Hong Cheng

Department of Chemistry, National Tsing Hua University,
Hsinchu, Taiwan-30013, Republic of China
ycling@mx.nthu.edu.tw


Organic light emitting diodes (OLEDs) commonly consisted of transition layer, emitting layer
and metal electrode are promising display devices, owing to their fast response, high brightness,
wide viewing angle and low driving voltage [1]. Study on chemical structure and diffusion at
OLEDs interface was critical to understand their influence on the electroluminescence efficiency,
the long-term stability, and device lifetime [2, 3]. In a previous study, metal atoms in the electrode
were found to diffuse easily into organic layer after long-life operation and the growth of metal
oxide at the interface [4]. The similar phenomenon was expected to occur at organic interface. In
this work, tris(8-hydroxyquinoline) (Alq
3
) and N-bis[1-naphthy-(1,1-diphenyl)]-4,4-diamine
(NPB) was applied as emitting and transition layer, respectively. Using Tof SIMS, the characteristic
peak of pristine material was used to probe the extent of organic diffusion after different operation
time of OLED devices. Moreover, the distribution of Alq
3
film at different vaporization rate was
also studied in order to establish the relationship between preparation parameter and operational
characteristics.


[1] A. Nakamura, T. Tada, M. Mizukami, S. Yagyu, Appl. Phys. Lett. 84 (2004) 130.
[2] W. Song, Z. Li, S. K. So, Y. Qiu, Y. Zhu, L. Cao, Surf. Interface. Anal. 32 (2001) 105.
[3] N. Isomura, T. Mitsuoka, T. Ohwaki, Y. Taga, Jpn. J. Appl. Phys. 39 (2000) L312.
[4] A. Murase, M. Ishii, S. Tokito, Y. Taga, Anal. Chem. 73 (2001) 2245.
ORG1-O-Tu-B05
137
3-D TOFSIMS Characterization of Black Spots in Polymer Light
Emitting Diodes

C.W.T. Bulle-Lieuwma
a
, P. van de Weijer
a

a
High Tech Campus 37, 5656 AE Eindhoven, the Netherlands
C.W.T. Bulle-Lieuwma@philips .com

Research efforts into conjugated polymers have demonstrated the versatility of organic
semiconductors for a range of applications such as light-emitting diodes (LEDs). For organic LEDs
much progress has been made in improving their performance and reliability. Nevertheless, research
remains to be done in order to further improve device characteristics. In particular, both intrinsic
and extrinsic degradation mechanisms limiting the long-term stability of these devices are essential.
An example of extrinsic degradation is the formation of inhomogeneous non-emissive areas, the so-
called black spots. A number of mechanisms for the formation of dark spots have been proposed
[1]. Water penetration through pinholes in the cathode is widely accepted as the origin of black-spot
formation. Here, we will present a 3-D TOFSIMS study on the formation of black spots formed in
PolyLED devices based on an electroluminescent (EL) system with poly (3,4-
ethylenedioxythiophene) PEDOT on indium tin oxide (ITO) as anode and Al/Ba as cathode.
TOFSIMS has proven to be a valuable analysis method to monitor dark spot growth at the buried
metal/polymer interface. By alternating elemental mapping and sputtering of the device structure
using an IONTOF IV instrument, three-dimensional information on the chemical composition is
achieved. In 3-D TOFSIMS analysis the composition, shape and position of the black spots is
visualised. We have found that the EL dark spots in PolyLEDs originate as aluminiumoxide clusters
at the metal/polymer interface, which have never been reported sofar.








Fig. 1a shows the presence of black spots in electroluminescence after storage of the device after
operation at 6 mA/cm2 at 80 C and 50% RH for 500 hrs. The size and distribution of the bright
areas as observed in the O-distribution map of fig. 1b correspond to the black spots. The Al-
distribution map reveal an enhancement of the Al yield in the black spots as compared to the
surrounding areas. The ion yield of Al is strongly enhanced in an oxygen rich environment by
raising the workfunction (matrix effect), which will be discussed.
[1 ] D. Kolosov, D. S. Engkish,P.F. Barbara, S. R. Forrest, M. E. Thompson, Journal of Appl. Phys. 90(7) (2001) 3242-
3247

Fig 1a EL of a device after operation at 6 mA/cm
2
at 80 C and 50% RH for 500 hours.
Fig. 1b Mass resolved 3-D view of the Al/Ba/polymer structure obtained by TOFSIMS are shown at the right-hand
side of the figure. The corresponding projected image in 2-D view is shown at the left-hand. Lighter



a b
ORG1-I-Tu-B06
138
Interpretation of SIMS Spectra and Images using Careful Application
of Multivariate Analysis

M. S. Wagner
a,
*, D. J. Graham
b
, D. G. Castner
b


a
Procter & Gamble Company, 11810 E. Miami River Rd., Cincinnati, OH 45252
b
University of Washington, Department of Bioengineering, Seattle, WA 98195
* wagner.ms@pg.com


As analytical problems addressed using SIMS increase in chemical complexity, multivariate
analysis (MVA) methods are becoming increasingly important in the interpretation of SIMS spectra
and images [1]. However, successful and widespread application of MVA methods to SIMS data
analysis is limited by a lack of understanding and optimization of these methods for SIMS data
analysis. This presentation will provide an overview of the state-of-the-art of MVA methods for
SIMS spectra and images, with an emphasis on robust protocols to ensure that the MVA output is
reliable. Selection of appropriate MVA methods, data pre-treatment, and the capabilities and
limitations of MVA for SIMS data analysis will be discussed. Ongoing efforts in standardization
and optimization of MVA for SIMS data analysis, including a new web-based resource hosted by
the University of Washington, will be described.


[1] M.S. Wagner, D.J. Graham, B.D. Ratner, D.G. Castner, Surface Science (2004) 570: 78-97.
ORG1-O-Tu-B07
139
PCA of TOF-SIMS Spectra from Self-Assembled Monolayers: The
affects of data normalization

Daniel J. Graham*
a
, Matthew S. Wagner
b
, and David G. Castner
a


a
National ESCA and Surface Analysis Center for Biomedical Problems
Departments of Bioengineering and Chemical Engineering
University of Washington, Seattle WA 98195-1750 USA

b
Procter & Gamble Company, 11810 E. Miami River Rd., Cincinnati, OH 45252, USA
.
*graham@sarc.engr.washington.edu


The use of principal component analysis (PCA) and other multivariate analysis (MVA) routines
is increasing in the TOF-SIMS community. All MVA methods require preprocessing steps before
the analysis is carried out, yet no standards have been established on how data preprocessing should
be done. To address this issue, NESAC/BIO is establishing a web-based resource of SIMS spectra
and images that can be used by the SIMS community to learn MVA and optimize its performance
with TOF-SIMS data. This resource will contain data from well defined model systems such as self-
assembled monolayers (SAMs) to complex biological systems such as proteins and DNA
oligomers. It is hoped that this resource will stimulate efforts to standardize MVA analysis of TOF-
SIMS data and assure the continued high standard of work done by our community. Here we
present the affects of various data pretreatments (normalization to the total counts, normalization to
the sum of selected peaks, and log10 transformation) on the PCA results from a series of spectra
from mixed SAMs of decanethiol and octadecanethiol. Regardless of the data pretreatment PC1
captured between 80 to 90% of the variance in the data, but the separation between samples was
significantly enhanced by the use of log transformation of the input data set. This is likely due to the
fact that SAM samples produce many characteristic high mass, but low intensity, ions under TOF-
SIMS analysis. Log10 transformation of the data reduces the dynamic range of the data and
accentuates the influence of these lower intensity peaks. In the case of this mixed monolayer data,
this allowed better separation of the samples due to these high mass characteristic peaks. Systematic
studies such as these will enable education, optimization and standardization of MVA of TOF-
SIMS data throughout the community.

ORG1-O-Tu-B08
140
Simulation of SIMS for Polymers under the Assumption of
Thermal Decomposition using QMD Method

Kazunaka Endo, Tomonori Ida, Nobuhiko Kato, Hiroaki Sugimoto, Daisuke Matsumoto,

Laboratory of Theoretical Chemistry, Graduate School of Natural Science
and Technology, Kanazawa University, Kanazawa 920-1192, Japan
(*corresponding: endo@wriron1.s.kanazawa-u.ac.jp)

We described in previous works [1, 2] that the cleavage sites of representative polymers in static and time-
of-flight secondary ion mass spectra (SIMS) can be estimated from the two-center bond energies for the
electric neutral model oligomers using semiempirical AM1 MO method [3] under the main assumption of the
thermal decomposition process for the cleavage of polymer bonds on the utmost surface of solid polymer
sample. The thermal decomposition of hexamer model molecules for typical polymer (PE, PA, PAM,
PMMA, PET, PVC, PTFE) has been simulated by quantum molecular dynamics (QMD). In the calculations,
we controlled the Nse-Hoover thermostats [4-6] in the thermal energy range of 14 20 kcal/mol, and the
sampling position data with a time step of 0.5 fs were carried out up to 5000 steps. We obtained the
distribution of thermal decomposed fragment products with positive, neutral and negative charges to the
main chain carbon number, or the atomic mass unit from the output data at the 5000 step in 20 runs. As an
example, Fig. 1 shows the thermal decomposed data of PE model molecule at 800, 2300, 4000, and 5000
steps with 20 kcal/mol thermal energy. It can be seen from the figure that the smaller fragments exist with
the increasing sampling data steps. The calculated distribution of the decomposition products enables us to
be compared with the experimental results of gas mass spectra and SIMS under the main assumption of
thermal decomposition process for the cleavage of polymer bonds. In the total fragments of the PE polymer
at 5000 MD step in the 20 runs, we confirmed that there are 90 % neutral charged fragments, 5 % positive
and 5% negative charged ion-fragments, respectively. Thus, we showed the calculated distribution of the
positive ion charged fragments with the experimental result [7] in static SIMS in Fig.2.

800MD 2300MD

4000 MD 5000 MD
Fig. 1. Thermal decomposed data of PE model molecule Fig. 2 Calculated secondary positive-ion fragment
at 800, 2300, 4000, and 5000 MD steps spectra of the PE polymer model molecules
with the experimental results
References
[1] K. Endo, T. Hoshi, N. Kobayashi, H. Miura, M. Kudo, Polym. J., 29,457(1997).
[2] K.Endo, J. Mass. Spectro. Soc. Jpn., 49,135 (2001).
[3] M. J. S. Dewar, E. G. Zoebisch, Theochem 180, 1 (1988): M. J. S. Dewar, E. G. Zoebisch, E. F. Healy, J. J. P.
Stewart, J. Am. Chem. Soc. 107, 3902 (1985).
[4] S. Nos, Mol. Phys.,52,255(1984): J. Mol. Phys., 81,511(1984).
[5] W. G. Hoover, Phys. Rev. A31,1695(1985).
[6] C. W. Gear, The numerical integration of ordinary differential equations of various orders, Report ANL 7126,
Argonne National Laboratory(1985).
[7] J. G. Newman, B. A. Carlson, R. S. Michael, J. F. Mounlder, T.A. Hohlt, Static SIMS Handbook of Polymer
Analysis, Perkin-Elmer Corp., Physical Electronics Division; Elden Prairie, Minnesota, 1991.
ORG1-O-Tu-B09
141
G-SIMS-FPM: THE FULL PICTURE COMBINED POSITIVE
AND NEGATIVE ION FRAGMENTATION STUDY

I.S.Gilmore
*
, F.M.Green & M.P Seah

National Physical Laboratory, Teddington, Middlesex, UK
Tel: +44 (0)20 8943 6922; Fax:+44 (0)208 8943 6453;
e-mail: Ian.Gilmore@npl.co.uk


Static SIMS (SSIMS) is a powerful technique for the analysis of complex surfaces. However,
many view SSIMS as an excellent research tool but unreliable as an analytical method. This is
changing. Modern instruments have superb repeatability and reliability. In the VAMAS SSIMS
inter-laboratory study, the average repeatability of 85% of instruments has the excellent value of
1.9%. Accessibility to SSIMS measurements is increasing rapidly. However, the complexity of
mass spectra makes identification and quantification far from straightforward, even for the experts!
This is a major barrier to the wider take-up of SSIMS, especially in new fields. One way around
this problem is G-SIMS.
G-SIMS is a library-independent method providing a straightforward way to simplify SSIMS
spectra [1-3]. SSIMS spectra are composed of parent fragment ions amongst a large number of
high intensity degradation products. In G-SIMS, this fragmentation may be quantified in terms of
the partition functions of the fragments emitted from a surface plasma with effective temperature,
T
p
. By extrapolation of the data to low T
p
, the intensity of the degradation products rapidly reduces,
revealing the parent fragments. The latter peaks are directly characteristic of the material without
rearrangement and can enable direct interpretation and identification. This is fine for smaller
molecules but, within the plethora of possible larger molecules for which a total mass is insufficient
to provide adequate characterisation, an extension of G-SIMS using Fragment Pathway Mapping,
G-SIMS-FPM, provides a method to elucidate the required structure.
Previous work has focused on the fragmentation in the positive ion spectrum. Here we shall
discuss the use of negative ion G-SIMS and how the negative ion fragmentation augments the
positive ion data to provide a fuller picture of the fragmentation pathways that are mapped out as T
p

is varied.


[1] I S Gilmore and M P Seah, Appl. Surf. Sci., 161 (2000), p. 465.
[2] I S Gilmore and M P Seah, Appl. Surf. Sci. 187 (2002) 89-100.
[3] I S Gilmore and M P Seah, Appl. Surf. Sci. 203-204 (2003) 551-555.


ORG1-O-Tu-B10
142
SIMS Studies of Polymeric Tertiary Structure in Monolayers:
Polysiloxane Helical Coil Structures

Rosamil Rey-Santos, Alan M. Piwowar, Richard M. Nowak and Joseph A. Gardella Jr.*

Department of Chemistry, University at Buffalo, State University of New York
Buffalo, NY 14260-3000 USA
*gardella@acsu.buffalo.edu


The use of SIMS to probe molecular and polymer conformation at surfaces is a major challenge.
Recent SIMS studies of ordered polymers in monolayers formed at the air water interface have
shown that ion formation mechanisms are affected by tertiary structures in polymers [1-3]. A
particularly important result (1) for isotactic poly (methyl methacrylate) (PMMA) showed that a
double helical structure formed in monolayers resulted in a specific interchain ion formation
mechanism that dominated the spectrum, yielding a completely new set of fragmentations. Neither
syndiotactic PMMA or randomly coiled isotactic PMMA yielded this ion formation mechanism.
Poly (dimethyl siloxane) PDMS, produced from anionic polymerization with a narrow
polydispersity, can form well ordered helically coiled monolayers using Langmuir-Blodgett
methods at the air water interface, either in a hairpin configuration, if the endgroups are functional
or as flat helically coiled chains. Reflection absorption Fourier transform infrared (RA-FTIR)
spectroscopic analysis shows the changes in bonding between flat helically coiled PDMS and cast
films from dilute solvents, which produces a random coil configuration. Band shifts in the infrared
spectrum show evidence of changes in bonding, producing weaker bonds along the siloxane
backbone. These changes result in difference in the relative intensities of fragments formed in the
repeating pattern of clusters in the high mass ToF-SIMS spectra of the monolayers versus the
solution cast films. Both statistical chain break analysis and molecular mechanics simulations of
structure are used to support the analysis.
Both poly (diphenyl siloxane) (PDPS) and poly (methyl phenyl siloxane) (PMPS) produce
interesting ToF-SIMS spectra, and studies of RA-FTIR analysis of monolayers show interesting
band shifts between solvent cast films and ordered monolayers. Statistical chain break analysis of
ion formation and molecular mechanics simulations of both systems provide for a systematic series
of siloxane studies useful for potential surface analysis of siloxane polymers.

[1] R. W. Nowak, J. A. Gardella, Jr., T. D. Wood, P. A. Zimmerman and D. M. Hercules,
"Interchain Ion Formation in Secondary Ion Mass Spectrometry Resulting from the Double
Helical Structure of Isotactic Poly (methyl methacrylate) in Adsorbed Monolayers",
Analytical Chemistry, 2000, 72(19), 4585-90.
[2] W.-Y. Yan and J. A. Gardella, Jr. Time of Flight Secondary Ion Mass Spectrometry Study
of Ion Formation Mechanisms: Effects of End Group Chemistry", in Secondary Ion Mass
Spectrometry XI, G. Gillen, R. Lareau, J. Bennett and F. Stevie, Eds., John Wiley and Sons,
1998, 451-4.
[3] R. W. Nowak, Ph.D. Dissertation, Department of Chemistry, University at Buffalo, SUNY,
1994.
BIO1-O-Tu-B11
143
ToF-SIMS imaging as a tool to study the spatial behaviour of
bioorganic surface components in brain tissue and single
neuroblastoma cells

A.F.M. Altelaar
a,
*, K. Jalink
b
, R.P.J. de Lange
c
, R.A.H. Adan
c
, R.M.A. Heeren
a
and S.R.
Piersma
a


a
FOM-Institute for Atomic and Molecular Physics, Kruislaan 407, 1098 SJ Amsterdam, The Netherlands.
b
The Netherlands Cancer Institute, Division of Cell Biology, Plesmanlaan 121, 1066 CX Amsterdam, The Netherlands.
c
Department of Medical Pharmacology and Anatomy, Rudolf Magnus Institute for Neurosciences, Utrecht University,
Universiteitsweg 100, 3584 CG Utrecht, The Netherlands.
Email address: Altelaar@amolf.nl


Unravelling the spatial distribution of molecules present at a biological surface is an important
research topic in current molecular cell biology. Traditional ToF SIMS imaging of biological
surfaces has been limited to elemental and hydrocarbon fragment ions like the characteristic
phosphocholine headgroup ion at m/z 184. The introduction of polyatomic primary ion sources such
as Au
3
+
and C
60
has provided the means to image intact molecular ions. Alternatively, we have
introduced matrix enhanced (ME) SIMS and, more recently, silver and gold plasma deposition for
molecular imaging of tissue sections and cellular surfaces using a conventional Indium primary ion
source.
In ME-SIMS the MALDI matrix 2,5 DHB shows molecular weight signals > 2500 Da in brain
extract samples but its use in direct imaging of biological surfaces is difficult. For high resolution
imaging the deposition of micron-sized matrix crystals in a wet environment is needed, while high
mass sensitivity is obtained with large matrix molecules. Using electrospray deposition we show the
spatial distribution of intact molecular ions form single neuroblastoma cells at high-resolution using
ME-SIMS.
Metal-assisted (MetA) SIMS is another way to enhance the ionization yield of intact molecular
ions. Here the surface of a tissue section or single neuroblastoma cells is plasma coated by gold or
silver. The subsequent SIMS analyses show abundant signals up to 2000 Da, strictly localizing
within the tissue/cellular contours. The identity of the observed signals is unknown and further MS
and MS/MS experiments are underway to reveal the identity of these masses.
The quality of the resulting images in MetA-SIMS is high since the use of the metal prevents
surface charging during the SIMS analysis. We previously calculated the resolving power of the
ME-SIMS technique to be 2.9-m and using the same method find the resolving power for the
MetA-SIMS technique to be 1.55-m, with 600-nm pixel size. ME-SIMS and MetA-SIMS can be
used for imaging of (sub)cellular localizations of intact molecular ions.

BIO1-O-Tu-B12
144
Direct NanoSIMS imaging of diffusible elements in surfaced block of
cryo-processed biological samples.

P. Hallgot
a,
*, J.-N. Audinot
b
, H.-N. Migeon
b


a
LOral Recherche, Aulnay Sous Bois, France
b
Laboratoire dAnalyse des Matriaux, Centre de Recherche Public Gabriel Lippmann, 41, rue du Brill, L-4422
Belvaux, Luxembourg
(phallegot@rd.loreal.com)


SIMS analysis requires exposing a flat surface of the sample to the primary ion beam. Preparing
thin sections, which can be a discouraging step for a non-specialist, is therefore not mandatory.
Moreover, if a diffusible molecule or element has to be detected, dried or cryo-sections should be
cut which would require specific skills and apparatus, usually dedicated to transmission electron
microscopy. In order to overcome these limitations, we developped a new sample preparation
protocol that opens NanoSIMS analysis to laboratories which do not master electron microscopic
techniques.
In this protocol, the biological sample is fast frozen by rapid immersion in a liquid cryogen and
subsequently lyophilised. After complete removal of ice, the dried sample is embedded with Spurr
resin under vacuum, then cured as previously described [1] [2]. Next, a flat surface is created with a
diamond knife that cross-cut the area of interest in the sample. Afterward, the surfaced block is
inserted in Woods alloy using a NanoSIMS stub cast. A thin layer of a conductive metal is
deposited onto the free diamond-polished surface prior to analysis.
A study of the penetration of an iodine-containing hydrosoluble molecule in human hair
illustrates the preparation technique. A clear diffusion ring can be seen at mass 127
-
that cannot be
revealed when wet sectioning is used. The histology of the tissue is uncovered by the acquisition of
CN
-
maps which demonstrates that the optimal spatial resolution of the instrument can be achieved.


[1] P. Hallgot, C. Girod, R. Levi-Setti, Scanning Microscopy 4 (1990) 605-612.
[2] L. Edelmann, Journal of Microscopy 207 (2002) 5-26.

BIO1-O-Tu-B13
145
Imaging and differentiation of cellular responses to ionizing radiation
by time-of-flight secondary ion mass spectrometry (ToF-SIMS)

L. Wu
3
, E. J. Nelson
1
, M. G. Knize
2
, K. S. Kulp
2
, D. L. Shattuck
3
,
C. B. Thomas
2
, J. S. Felton
2
, K. J. Wu
1,*


1
Chemistry and Materials Science Directorate,
2
Bioscience Directorate
Lawrence Livermore National Laboratory, Livermore, CA 94550, USA
3
Department of Applied of Science,
4
Department of Chemistry
University of California Davis, Davis, CA 95616, USA

Email: wu17@llnl.gov


Radiation therapy is an important component of most therapeutic strategies for the treatment
of cancer. Although many studies have focused on the effects of radiation on cellular proteins and
signaling pathways, few studies have investigated small molecular changes immediately after
exposure to ionizing radiation and no studies have looked at these changes in individual cells.
Understanding these early events in the response to radiation will facilitate identification of
biomarkers of radiation damage or cells that are resistant to the effects of radiation.
In this model system study, time-of-flight secondary ion mass spectrometry (ToF-SIMS)
was used to investigate cellular response in Cs-137 irradiated cultured mammalian cells on a single
cell basis. Two human breast cancer cell lines MCF7 and T47D were selected and prepared for this
study. Cell samples were exposed with 2 Gy to 10 Gy level of ionization radiation, and
homogenized or freeze-fractured to expose the internal cell contents. Cell homogenates were
analyzed by ToF-SIMS spectral measurements, while imaging analysis was conducted on individual
cells. The mass spectra obtained from cellular compartments and individual cells were extracted
from the measurements and analyzed by principal component analysis (PCA). Our results
demonstrated a dose-response-related separation of cells from different treatment groups. By
analyzing the correlations between exposure and mass spectral response, specific cellular chemical
response to ionization radiation was determined. For example, we found mass peaks related to
phosphocholine increased with radiation dose. This result suggests that membrane lipid fragments
are detectable in the cell cytoplasm at the single cell level as a result of radiation damage.
Interestingly, some of the molecular fragments that were measurably changed immediately after
radiation began to return to control levels within 20 minutes. Together these results show that ToF-
SIMS can detect radiation damage in the range of 2 to 10 Gy and that the masses responsible for
cell damage and cell recovery can be determined from the complex mass spectra at the single cell
level.


This work was performed under the auspices of the U.S. Department of Energy by the University of California, LLNL
under contract No. W-7405-Eng-48. Additional support from National Cancer Institute grant CA55861 is gratefully
acknowledged.
BIO1-O-Tu-B14
146
Introduction of a Cryosectioning-ToF-SIMS Instrument for Analyzes
of Non-Dehydrated Biological Samples

J. Mller
1
, A. Beumer
1
, D. Lipinsky
1
, and H.F. Arlinghaus
1


1
Physikalisches Institut, Universitt Mnster, Wilhelm-Klemm-Str. 10,
D-48149 Mnster, Germany


ToF-SIMS and Laser-SNMS are increasingly important tools for analyzing the elemental and
molecular distribution in biological samples. However, in-vivo analyses of tissues or cell cultures
are impossible because of the necessity for the sample to accommodate the UHV conditions of the
instrument. Thus, fixing the sample in its vital state is essential.

A common preparation technique for preserving the chemical and structural integrity of the
biological sample is cryofixation, where elemental and molecular mobility is interrupted by rapid
cooling. Although in some cases the process of freeze-drying after cryofixation was used
successfully, this technique does have some limitations. On the one hand, the extraction of water
from the sample has a major influence on the composition of the sample, especially on the
concentration of soluted substances. On the other hand, the analysis of more than one layer of cells
is not possible because freeze-dried samples cannot be sectioned by cutting. In order to overcome
these limitations, a combined cryosectioning ToF-SIMS instrument was developed for directly
analyzing frozen, non-dehydrated biological samples

At the core of the new instrument is a uniquely designed vacuum cryo-sectioning chamber with a
rapid-entry airlock for introducing frozen samples. It is directly attached to the analysis chamber of
a ToF-SIMS instrument. Within the sectioning area, the temperature of the sample can be actively
controlled between -150 C and +20 C to optimize the cutting process. The upside-down
orientation of the sample surface ensures that the material which is cut off falls onto a cold shield.
Multiple cuttings are possible with cutting depths ranging currently from 5 to 40 m. The manually
controlled cutting process, which leaves clean block faces for ToF-SIMS analysis, can be observed
with a light microscope. The cooled biological sample with its freshly cut surface is directly
transferred to a temperature-controlled cryo-manipulator in the analysis chamber without exposure
to air or loss of temperature control. After the ToF-SIMS analysis is finished, the sample may be
returned to the cryo-sectioning chamber, where it may be re-cut in order to determine the elemental
and molecular distribution within the sample as a function of depth.

ToF-SIMS analyses can be optimized by choosing the right sample temperature. On the one
hand, it is necessary to keep the sample cold enough to avoid freeze-drying, on the other hand it is
advantageous to increase the sample temperature sufficiently that adsorbed molecules, especially
water molecules from the residual gas of the cutting chamber, can be removed and that further
adsorption processes during analysis are minimized.

Our measurements demonstrate that there is only a small temperature interval between the point
where adsorbed water is removed from the sample surface and the onset of freeze-drying. It was
found that under optimized sample temperature conditions the new cryo-sectioning ToF-SIMS
instrument is a powerful tool for analyzing frozen non-dehydrated biological samples.

BIO1-O-Tu-B15
147
TOF-SIMS imaging of Chlorhexidine-digluconate transport in frozen
hydrated biofilms of the fungus Candida Albicans.

Bonnie J. Tyler
1*
, Srinath Rangaranjan
1
, Jrg Mller
2
, Andre Beumer
2
, and Heinrich Arlinghaus
2

1
Dept. of Chemical Engineering, University of Utah, USA
2
Dept. of Physics, University of Mnster, Germany
e- mail: bonniet@eng.utah.edu


The formation of biofilms, communities of micro-organisms that colonizing a surface, leads to a
variety of difficult to treat diseases including infections of the oral cavity and infections associated
with medical implants. The dimorphic yeast, Candida albicans, is one of the primary organisms
associated with biofilm based infections and has been shown to become resistant to common anti-
microbial agents when growing as a biofilm. In this study, we have used TOF-SIMS to observe
penetration and efficacy of Chlorhexidine-digluconate (CHG), biocide, into the biofilms. CHG has
a broad spectrum of activity that includes C. albicans and susceptibility of C. albicans biofilms to
chlorhexidine has been shown to be significantly reduced compared to its action against suspended
organisms.

Mass transport resistance within biofilms has commonly been suggested as a resistance
mechanism but the measurement of transport of most anti-microbial agents in biofilms has proven
extremely difficult because of the heterogeneity of the biofilms and the difficulty in detecting these
agents within an intact biofilm. In this study, TOF-SIMS has been used to study the transport of
CHG in a frozen hydrated biofilm.

All measurements were made with a cryo-TOF-SIMS instrument under-development at the
University of Mnster. The instrument is outfitted with a uniquely designed in vacuum cryo-
sectioning chamber which is directly attached to the analysis chamber so that freshly cut surfaces
can be analyzed without exposure to air or loss of temperature. Biofilms were grown in two
different geometries and treated with CHG for times ranging up to 5 minutes. Samples were then
frozen in liquid propane and stored in liquid nitrogen until the time of analysis. The biofilms were
them cryo-sectioned either parallel or perpendicular to the direction of diffusion and imaged in the
TOF-SIMS instrument using a 2 Lens 25 kV Ga-Gun.

The spectra and images have been analyzed using a variety of statistical techniques including
principal components analysis (PCA), multi-component curve resolution (MCR), partial least
squares regression (PLS), and maximum autocorrelation factors (MAF). The results have been fit
to a Fickian diffusion model to determine an effective diffusivity for the biofilm of 80 30 m
2
/s
which is comparable to values measured earlier with FTIR and Raman spectroscopy.

Analysis of the images confirms heterogeneous distribution of the CHG within the biofilms.
Additionally, both living and dead cells can be identified by the sequestration of K+ and the
presence of cell markers. These measurements givew us the unique ability to simultaneously
observe the presence of an antimicrobial agent within the biofilm and viability of the cell
population. Additionally, cell components believed to be critical for the efficacy of CHG can also
be observed in the TOF-SIMS spectra. Current efforts in the project are directed at increasing the
sensitivity to both the CHG and the cellular components.
BIO1-O-Tu-B16
148
Investigating Lipid Interactions and the Process of Raft Formation in
Cellular Membranes Using Model Membranes

Carolyn M. McQuaw
a
, Audra G. Sostarecz
b
, Leiliang Zheng
a
, Andrew G. Ewing
a
, Nicholas
Winograd
a
*

a
Department of Chemistry, The Pennsylvania State University, 104 Chemistry Bldg., University Park, PA 16802
b
Institute for Medicine and Engineering, University of Pennsylvania, 1080 Vagelos Labs, Philadelphia, PA 19104
nxw@psu.edu


Recently, there is an increased interest in how lipids interact with each other, especially in the
lateral separation of lipids into coexisting liquid phases, as this is believed to be an attribute of raft
formation in cell membranes. ToF-SIMS has shown itself to be an excellent tool for investigating
cellular and model membrane systems. Our lab has recently shown the power of ToF-SIMS in
identifying unequivocally the contents of coexisting liquid lipid phases. We found using supported
lipid monolayers that the inclusion of dipalmitoylphosphatidylethanolamine (DPPE) to a
homogeneous dipalmitoylphosphatidylcholine/cholesterol (DPPC/CH) phase results in the
formation of cholesterol-rich domains.[1] Also, for coexisting DPPE, DPPE/CH phases the
DPPE/CH phase is actually lower in height than the DPPE phase.[2] This may help explain a
uniform bilayer thickness, as phosphatidylethanolamine (PE)-lipids are the most abundant lipids in
the inner membrane while phosphatidylcholine (PC)-lipids are more abundant in the outer and it is
known that a DPPC/CH phase is thicker than the DPPC phase. Currently we are exploring the
incorporation of sphinogmyelin into phospholipid-cholesterol mixtures in an effort to gain a better
understanding of its role in raft formation. To delve deeper into our lipid systems laser
postionization experiments of our model membranes are underway.


[1] A.G. Sostarecz, C.M. McQuaw, A.G. Ewing, N. Winograd. J. Amer. Chem. Soc. 126 (2004) 13882-13883.
[2] C.M. McQuaw, A.G. Sostarecz, L. Zheng, A.G. Ewing, N. Winograd. Langmuir 21 (2005) 807-813.
BIO1-O-Tu-B17
149
ToF-SIMS studies of Bacillus using Principal Component Analysis
with possible identification and taxonomic applications

C.E.Thompson,* J.Fletcher, A.Henderson, N.P.Lockyer, R.Goodacre, J.C.Vickerman

Surface Analysis Research centre, School of Chemical Engineering and Analytical Science. University of Manchester.
Manchester M60 1QD. UK
*c.thompson-3@postgrad.manchester.ac.uk


Multivariate data analysis can aid the interpretation of ToF-SIMS spectra from complex
systems including biological cell surfaces [1, 2]. For example, bacterial spores and vegetative cells
of Bacillus megaterium have been discriminated on the basis of their characteristic surface
chemistry using ToF-SIMS [1].
In this paper we discuss the application of ToF-SIMS with an Au
3
+
primary ion beam,
combined with Principal Component Analysis and Discriminant Factor Analysis for identification
of individual strains of Bacillus. Strains of Bacillus are known to vary in membrane lipid
composition [3]. The influence of the surface biochemistry on the success of the method will be
highlighted. The taxonomical applications include the rapid identification of pathogenic microbes
such as Bacillus cereus on food stuffs and clinical samples etc.


[1] C.E.Thompson, H.Jungnickel, N.P.Lockyer, G.M. Stephens, J.C. Vickerman, App. Surf. Sci. 231-232:420-3, 2003.
[2] S.J.Pachuta, App. Surf. Sci. 231-232:217-223 2004.
[3] Md Anwarul Haque and Nicholas J. Russel, Microbiogy, 150, 1397-1404, 2004.

BIO1-O-Tu-B18
150
Bioforensics characterization of Bacillus spores using ToF-SIMS

John B. Cliff
a,
*, Kristin H. Jarman
a
, Nancy B. Valentine
a
, Stephen L. Golledge
b
,
Daniel J. Gaspar
a
, David S. Wunschel
a
, Karen L. Wahl
a

a
Pacific Northwest National Laboratory, PO Box 999 Battelle Blvd., Richland, WA 99352, USA.
b
University of Oregon, 1252 University of Oregon, Eugene, OR 97403, USA
john.cliff@pnl.gov


Since the anthrax attacks in 2001, there has been an increased need for forensics characterization
of biological materials. Mass spectrometric techniques have been used in this regard for stable C, N
O, and H isotope analyses [1-3], and to detect heme groups present on spore surfaces from growth
on blood agar [4]. Because Bacillus species incorporate metals during spore formation, elemental
analysis is an attractive method to characterize spores. Elemental analyses using inductively-
coupled plasma mass spectrometry has been used to differentiate spore types and growth stages but
no direct inferences could be made about the growth media in which the spores were grown [5].
We demonstrate the use of time-of-flight secondary ion mass spectrometry (ToF-SIMS) in a
forensics application to distinguish Bacillus subtilis spores grown in various media based on the
elemental signatures of the spores. Triplicate culture replicates grown in each of four different
media were analyzed to obtain ToF-SIMS signatures comprised of 16 elemental intensities.
Analysis of variance was unable to distinguish growth media types based on
40
Ca-normalized
signatures of any single normalized element. Principal component analysis (PCA) proved successful
in separating the spores into groups consistent with the media in which they were prepared.
Confusion matrices constructed using nearest neighbor classification of the PCA scores confirmed
the predictive utility of ToF-SIMS elemental signatures in identifying sporulation medium. Perfect
classification was achieved when data were autoscaled prior to performing PCA. Theoretical
calculations based on the number and density of spores in an analysis area indicate an analytical
sample size of about 1 ng making this technique an attractive method for bioforensics applications.
Acknowledgements. This research was conducted under the Laboratory Directed Research and
Development Program of the U.S. Department of Energy. A portion of the research described in
this manuscript was performed at the W. R. Wiley Environmental Molecular Sciences Laboratory, a
national scientific user facility sponsored by the U.S. Department of Energy's Office of Biological
and Environmental Research and located at Pacific Northwest National Laboratory. The Pacific
Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy under
contract DE-AC05-76RLO1830. Support from the NSF (DMR-0216639) for the ToF-SIMS
instrumentation at the University of Oregon is gratefully acknowledged. Special thanks go to
Shannon Goodwin and Brian Pultz for SEM analyses.


[1] J. Horita, A.A. Vaas. J Forens. Sci. 48 (2003) 1-5.
[2] H.W. Kreuzer-Martin, M.J. Lott, J.V. Dorigan, J.R. Ehleringer. Proc. Nat. Acad. Sci. USA. 100 (2003) 815-819.
[3] H.W. Kreuzer-Martin, L.A. Chesson, M.J. Lott, J.V. Dorigan, J.R. Ehleringer. J. Forens. Sci. 49 (2004) 1-7.
[4] J.R. Whiteaker, C.C. Fenselau, D. Fetterolf, D. Steele, D. Wilson. Anal. Chem. 76 (2004) 2836-2841.
[5] C.M. Gikunju, S.M. Lev, A. Birenzvige, D.M. Schaefer. Talanta. 62, (2004) 741-744.
BIO1-O-Tu-B19
151
Acquisition of Chemical Information from Cell Samples Using TOF-
SIMS Imaging

Daniel Breitenstein
a
, Christina Rommel
b
, Petra Goering
a
, Ralf Wehrspohn
c
, Joachim Wegener
b
,
Elke Tallarek
a
, Birgit Hagenhoff
a,*
.

a
Tascon GmbH, Gievenbecker Weg 15, D-48149 Mnster
b
Institut of Biochemistry, Wilhelm-Klemm-Str. 2, D-48149 Mnster
c
Max Planck Institute of Microstructure Physics, Weinberg 2, D-06120 Halle, Germany
birgit.hagenhoff@tascon-gmbh.de


Our ongoing studies focus on the mass spectrometric imaging for cells, an emerging area in TOF-
SIMS research. In a joint research effort we want to elucidate the transport mechanism for drugs
through the blood-liquor barrier.
Being a vacuum technique TOF-SIMS faces some challenges for the analysis of epithelial cells.
A standard approach to maintain the cellular integrity of cells during the experiments is freeze
fracturing or cryomicrotomy. However, these techniques increase the experimental effort
significantly. As we were not interested in the lateral distribution of elemental species like Na of K
but small and middle sized molecules we concentrated on different fixation techniques instead.
Mainly, paraformaldehyd and glutardialdehyd were used and TOF-SIMS images of cellular
compounds could be obtained with high sensitivity.
In order to compare the results with a standard analytical technique in biochemstry, additionally
cells were treated with fluorescent dyes. The intact fluorophores could be detected successfully in
the TOF-SIMS images. The obtained mass resolved images for the fluorescent dyes were compared
successfully with the widely accepted technique of confocal laser scanning microscopy (CLSM),
proving the validity of the chosen mass spectrometric approach.


This work was supported by the German Federal Ministery for Education and Research (Grand: 0312002B).
BIO1-O-Tu-B20
152
Development of SIMS as a Novel Investigative Tool for the Analysis of
Cell Sheets and their Extracellular Matrix Proteins

Castner, D.G.;*
a-d
Canavan, H.E.;
a-c
Greenfeld, M.;
a,b,d
Cheng, X.;
b,c
Graham, D.J.;
a,c
Ratner, B.D.
a-d


a
National ESCA and Surface Analysis Center for Biomedical Problems (NESAC/BIO),
b
University of Washington Engineered Biomaterials (UWEB),
Departments of Bioengineering
c
and Chemical Engineering,
d
Box 351750 University of Washington, Seattle, WA, USA
castner@nb.engr.washington.edu


The Extracellular Matrix (ECM) is a complex aggregate of proteins and biomacromolecules that
is formed between cells. The ECM can profoundly influence the biology of animal cells in areas of
cell growth, differentiation, morphology, and metabolic response. Despite the obvious interest in
studying the ECM, the challenge for UHV surface analysis techniques is that the ECM is a buried
interface located between the layer of cells and the substrate they are growing on. Thus, the cells
must be removed without damaging the ECM to examine the ECM. This has not been possible
using traditional cell removal methods such as enzymatic digestion. Using poly(N-isopropyl
acrylamide) (pNIPAM), cells are observed spontaneously detach as a confluent sheet. This gives
unprecedented access to the underlying ECM. Recently, we have begun the first in-depth analysis
of the proteins present in the ECM after low-temperature liftoff of bovine aortic endothelial cells
(BAECs) from pNIPAM.[1,2]

Principal Component Analysis (PCA) of time-of-flight secondary ion
mass spectrometry (ToF-SIMS) spectra was used to examine the ECM remaining on the pNIPAM
substrate as well as the apical and basal sides of the cell layer. In this work, we find that ToF-SIMS
analysis of the basal surface of the harvested cell sheet clearly identifies the presence of molecular
ion fragments previously identified as having originated from amino acids.[3] This finding may
explain why cell sheets detached from NIPAM surfaces appear to retain their function upon transfer
to another growth surface.[4] Furthermore, PCA also easily distinguishes between the apical and
basal surfaces of the cells. Finally, we compare spectra from the ECM to that obtained from
adsorbed single protein solutions to identify the proteins present in the ECM and their association
with the cell and substrate surfaces.


[1] Canavan, H.E., et al., Langmuir 21 (2005) 1949-1955.
[2] Canavan, H.E., et al., accepted for publication in JBMR.
[3] Wagner, M.S., et al., Langmuir 17 (2001), 4649-4660.
[4] Kikuchi, A., et al, J. Biomat. Sci.-Polym. E. 9 (1998) 1331-1348.

BIO1-O-Tu-B21
153
7.9 eV Single Photon Ionisation of Derivatized Peptides

Praneeth D. Edirisinghe,
a
Jerry F. Moore,
b
Michael J. Pellin,
b
and Luke Hanley,
a
*

a
Department of Chemistry, University of Illinois at Chicago, Chicago, Illinois 60607-7061
b
Materials Science Division, Argonne National Laboratory, Argonne, IL 60439
lhanley@uic.edu


Single photon ionisation shows great promise for enhancing ionisation yields with a minimum of
fragmentation. The F
2
excimer laser is an intense laboratory source of vacuum ultraviolet radiation,
but the 7.9 eV (157 nm) photons it generates are lower in energy than the ionisation potential of
many target species. Chemical labelling of peptides [1] with polycyclic aromatic hydrocarbons
(PAH) is shown here to allow efficient F
2
laser single photon ionisation of the entire labelled
peptide. PAH-labelling produces parent ion formation in some cases and fragmentation in other
cases. Napthalene and anthracene carboxylic acids and aminobenzoic acid are used to derivatise
various synthetic peptides, which are then analyzed by secondary ion (SIMS), direct laser
desorption (LDMS), secondary neutral (SNMS) with 157 nm photoionisation, and laser desorption
photoionisation mass spectrometry (LDPI MS) using a N
2
laser for desorption and 157 nm
photoionisation. LDPI MS display representative high mass peaks for the labelled peptides and
amino acids, with anthracene labelled peptides displaying intact parent ions. The aminobenzoic acid
and napthalene tags show high mass fragments of the parent ion, but no intact parent ion. Unlabeled
peptides and amino acids display only low mass ions signal in SIMS, LDMS, SNMS, and LDPI
MS. Neither does LDMS of tagged peptides and amino acids show any higher mass peaks. High
resolution LDPI MS of the smaller anthracene labelled peptides indicate that the dominant parent
ion is a radical cation rather than protonated, supporting the mechanism of single photon ionisation
of the anthracene label. LDPI MS of much larger peptides is also observed, but the experimental
mass resolution is insufficient to distinguish single photon ionisation from proton transfer.


[1] P.D. Edirisinghe, S.S. Lateef, C.A. Crot, L. Hanley, M.J. Pellin, W.F. Calaway, and J.F. Moore, Anal. Chem. 76
(2004) 4267-4270.
CLU3-O-Tu-C01
154
The massive cluster probe in SIMS. Influence of the projectile size and
of the energy on sputtering and desorption-ionisation from various
solids

S. Della-Negra

Institut de Physique Nuclaire dOrsay, IN2P3-CNRS and Universt Paris Sud
F-91406 Orsay Cedex
Email : dellaneg@ipno.in2p3.fr


The highly non-linear nature of the sputtering and secondary ion emission induced by the
bombardment of polyatomic projectiles of various solids is now well established and recognised.
Cluster ions are thus more and more used in Secondary ion mass spectrometry (S.I.M.S.) although
the processes of energy deposition and transfer involved in the cluster-solid interactions are still
unclear. The influence of the cluster size and of the impact energy on total sputtering and molecular
ion emission yields in S.I.M.S. of bio-organic samples has been studied over a large range of size
and energy [1-7]. A summary of data will be presented. The recent possibility to produce large
Au
n
q+
cluster beams (100< n/q<1000) with a Liquid Metal Ion Source (L.I.M.S.) [8] has opened
new possibilities which will be described. The range of energy has also been extended for smaller
cluster Au
n
with n around 10 until a few tens keV per atom. The most recent data show that the
ability of varying the cluster size and their energy provide a great sensitivity and flexibility of
bioorganic S.I.M.S. The future project of the Orsay group is a beam line including a cluster
L.M.I.S., a Wien filter and focusing systems installed on a compact high voltage platform (up to
150 kV). The combination of the delivered micro-beam (1 to 10 m) with an O.T.o.F.M.S. and a
multi-pixel channel plate detector would be particularly powerful and appropriate for mass
spectrometry and cluster SIMS molecular imaging of biological samples.


[1] S. DELLA-NEGRA, H. JORET, Y. LE BEYEC, M. BLAIN and E.A. SCHWEIKERT, Phys. Rev. Letters 63, 15 (1989)
1625.
[2] M. BENGUERBA, A. BRUNELLE, S. DELLA-NEGRA, J. DEPAUW, H. JORET, Y. LE BEYEC, M.G. BLAIN, E.A.
SCHWEIKERT, G. BEN ASSAYAG, P. SUDRAUD, Nucl. Instr. and Meth. B62 (1991) 8
[3] K. BOUSSOFIANE-BAUDIN, G. BOLBACH, A. BRUNELLE, S. DELLA-NEGRA, J. DEPAUW, P.
HAKANSSON and Y. LE BEYEC, Nucl. Instr. and Meth. B88 (1994) 160.
[4] H.H. Andersen, A. Brunelle, S. Della-Negra, J. Depauw, D. Jacquet, Y. Le Beyec, J. Chaumont, H. Bernas, Phys. Rev.
Lett. 80 (1998) 5433.
[5] A. BRUNELLE, S. DELLA-NEGRA, J. DEPAUW, D. JACQUET, Y. LEBEYEC, M. PAUTRAT, K. BAUDIN, H.H.
ANDERSEN, Phys. Rev. A 63 (2001) 22902.
[6] S. BOUNEAU, A. BRUNELLE, S. DELLA-NEGRA, J. DEPAUW, D. JACQUET, Y. LEBEYEC, M. PAUTRAT, M.
FALLAVIER, J.C. POIZAT, H.H. ANDERSEN, Phys. Rev. B 65 (2002) 144106
[7] Agns Tempez, J.A. Schultz, S. Della-Negra, J. Depauw, D. Jacquet, A. Novikov, Y. Lebeyec, M. Pautrat, M. Caroff, M.
Ugarov, H. Bensaoula, M. Gonin, K. Fuhrer, and Amina Woods, Rapid Communications in Mass Spectrometry, 18, 371-
376 (2004)
[8] S. BOUNEAU, S. DELLA-NEGRA, J. DEPAUW, D. JACQUET, Y. LEBEYEC, J.P. MOUFFRON, A. NOVIKOV,
M. PAUTRAT, N.I.M. 225 (2004) 579-589
CLU3-O-Tu-C02
155
Coarse-Grained Molecular Dynamics Studies of Benzene

Edward J. Smiley
a,
*, Igor A. Wojciechowski
a
, Zbigniew Postawa
b
, Nicholas Winograd
a
,
Barbara J Garrison
a


a
Department of Chemistry, 104 Chemistry Building, Penn State University,
University Park, Pa 16802, USA
b
Smoluchowski Institute of Physics, Jagiellonian University, Krakow, Poland
Email: ejs236@psu.edu


As high-energy cluster projectile beams become standard analysis probes for SIMS, simulating
large crystals is now a requirement for the modeling community due to the high impact energy of
the projectile. As crystals get larger, computer resources become a premium. Even though
computer technology has evolved to include large memory systems and fast processors, there are
still problems of having sufficient resources to run a calculation. We report on a method of studying
a full crystal of benzene after impact with a 500 eV C
60
projectile using a coarse-grained model.
The potentials developed for this model incorporate the C-H bond of benzene into a single coarse-
grained bead. This coarse-grained method has several advantages over atomistic models - the
amount of time to perform calculations has been drastically reduced and the interaction potentials
for this sample are simple Lennard-Jones pair potentials. A discussion is made as to how these
results compare to those obtained with fully atomistic calculations using the AIREBO potential.
CLU3-O-Tu-C03
156
Topography Formation During C
60
+
Bombardment of Silicon

Greg Gillen*, James Batteas, Chris Michaels, Peter Chi,
Albert Fahey, John Small, Jennifer Verkouteren and K.J. Kim

Surface and Microanalysis Science Division
National Institute of Standards and Technology, Gaithersburg, MD 20899-8371, USA
greg.gillen@nist.gov
Division of Chemical Metrology and Materials Evaluation, Korea Research Institute of Standards and Science,
P.O. Box 102, Yuseong, Daejeon 305-600, Korea


There is continued interest in the development of novel cluster primary ion beams for
applications in Secondary Ion Mass Spectrometry (SIMS). A C
60
+
primary ion incident on a
silicon substrate with an impact energy of 3000 eV would dissociate into 60 carbon atoms, each
with an impact energy of only 50 eV. Since the depth resolution of a SIMS depth profile is directly
related to the primary projectile energy, the use of such a cluster ion provides a possible method
for obtaining ultra-high resolution SIMS depth profiles. Based on our previous experience with
depth profiling of semiconductor materials using SF
5
+
and C
8
-
ion beams, it was hoped that C
60
+

cluster SIMS would provide large improvements in depth resolution over conventional SIMS.
Unexpectedly, initial evaluation of C
60
+
SIMS depth profiling using delta-doped test samples on an
ion microscope SIMS instrument demonstrated substantial degradation in depth resolution
compared to conventional SIMS depth profiling. This degradation is thought to result from the
formation of an unusual platelet like grain structure on the SIMS crater bottoms with individual
grains having a lateral dimension of ~ 0.5 m and a height of ~ 4 nm. Under certain experimental
conditions, we also observe deposition of an amorphous carbon layer onto the silicon sample rather
than sputter erosion. Finally, individual carbon rich deposits (~6 m in diameter) are formed in
some craters at high primary ion doses. A discussion of these effects, the limitations of using C
60
+

for silicon depth profiling and possible experimental solutions to the topography problem will be
discussed.
CLU3-O-Tu-C04
157
Fundamental Studies of Water Ice by Cluster Ion Bombardment

Christopher Szakal
a*
, Joseph Kozole
a
, Michael F. Russo Jr.
a
, Barbara J. Garrison
a
,
and Nicholas Winograd
a

a
Department of Chemistry, 104 Chemistry Building, Penn State University, University Park, PA 16802
*cws157@psu.edu


The fundamental sputtering properties of water ice are of profound interest for molecular
depth profiling of biological samples in their native environment. We report on a unique method of
studying amorphous water ice films of precise thicknesses in which pure water vapor is condensed
onto a pre-cooled, silver-coated quartz crystal microbalance (QCM). This novel scheme allows for
the determination of water ice sputter yields for any primary projectile as well as the primary ion
penetration depths into frozen aqueous sample targets. Specifically, we find a removal of
approximately 2500 water molecule equivalents/C
60
+
projectile with a depth of penetration around 4
nm. A discussion is made as to how these numbers compare to those obtained with Au projectiles
on the same system and how this small inherent depth resolution is valuable for molecular depth
profiling of frozen hydrated biological materials. Results from molecular dynamics (MD)
simulations of cluster ion bombardment into a water ice solid are also provided for comparison
purposes.
CLU3-O-Tu-C05
158
Secondary ion emission from organic targets impacted with Gold
projectiles of 1-500 atoms

C. Guillermier
a,*
, S. Della Negra
b
, V. Pinnick
a
, R. D Rickman
a
and E.A Schweikert
a

a
Texas A&M University
b
Institut de Physique Nucleaire, Orsay, France
cguillermier@mail.chem.tamu.edu


Recent studies show that large SI yields can be obtained from bombardment with massive Au
clusters [1, 2]. A question yet to be addressed is that of the optimum projectile characteristics for
generating a specified SI. We present here the first comprehensive set of SI yield for Au
n
projectiles
with 1<n<500. The bombardment energy used were those accessible in a practical SIMS
instrument, i.e. acceleration voltage of 10-30kV. The experiments were run with Au projectiles with
mass to charge ratio, n/q=1, 5, 9, 25, 50, 75, 100 and 1<q<5 produced by a LMIS equipped with a
wien filter for n/q selection [3] and a TOF set up with an 8 anodes detector. We report data for CN-
and M-H yields from vapor deposited Gly targets obtained in the event by event bombardment
detection mode.

1-SI yields for CN and Glycine increase as the E per cluster atoms, E/at, increase. For a
given E/at, the yields increases with the number of cluster constituents. The highest SI yield
measured was 100% for Gly and 70% for CN for a gold projectile with n/q=100 at 34kV of
acceleration voltage.
2-A comparison of SI yields obtained with projectiles of n/q in a 5 to 100 range, all at the
same total acceleration voltage shows a saturation in CN Yield for n/q=25 and for the acceleration
voltage range mentioned above. For Glycine the most effective projectile is the one corresponding
to n/q=100 at E/at=340eV.
3-The comparison of the yields per atom as a function of the energy per atom shows clearly
the well know cluster effect [4-5] for the molecular ion emission from the value n/q 5 to 100. On the
other hand for the CN
-
emission the cluster effect decreases with the increase of the n/q value.
4- Co-emission of multiple SIs is a key feature in bombardment with large clusters [5]. For
n/q=100 at 340eV/at we observe an average of 18 SIs of all masses per impact. For an acceleration
voltage of 34kV, the average number of SIs ejected per projectile decreases linearly with the size of
the projectile. An examination of the multiplicity associated with the emission of Gly shows that
projectile of n/q=100 are again most productive. An average of 18 SIs is obtained in case when at
least one Gly molecular ion is emitted. The multiplicity decrease with the size of the projectile to
7.5 SIs for n/q=25 and 3.2 SIs for Au
9.


Data from amino acids (Guanine, Histidine, Arginine, Proline) and peptide (His-Lys-Gly) show
similar trends for SI yield and multiplicity as a function of Au projectile characteristics.


[1] R. D Rickman, S. V Verkhoturov, E. A Schweikert, Appl. Surf. Sc 231-232 (2004) 54-58
[2] A. Tempez et al, Rapid Commun. Mass Spectrom 18 (2004) 371-376
[3] S. Bouneau et al. NIMB 225 (2004) 579-589
[4] K. Boussofiane-Baudin et al, NIMB 88 (1994) 160-163
[5] R.D Rickman, S.V Verkhoturov, E. S Parilis and E. A Schweikert Phys Rev Lett 92 (2004) 1-4

Work supported by NSF Grants CHE-0135888, CHE-0449312 and R. A. Welch Foundation Grant A-1482
CLU3-O-Tu-C06
159
Prospects and Challenges of Cluster SIMS

Jiro Matsuo

Quantum Science and Engineering Center, Kyoto University, Kyoto, Japan
Email: matsuo@nucleng.kyoto-u.ac.jp


A lot of efforts have been made to utilize molecular or cluster ions as a primary ion, because of
its superior capability for ultra low energy SIMS and bio-SIMS. There are two major reasons for
this prospect. One is cluster ions are equivalent to low energy beam. O
3
+
or SF
5
+
ions were utilized
to ultra low energy SIMS, in order to improve depth resolution. The other reason is that new
phenomena caused by multiple particle collisions and high-density energy deposition at very narrow
area at target surfaces. High puttering yield, enhancement of secondary ion yield and smoothing
effect of surfaces have been reported. It is very much difficult to generate high intensity cluster ion
beams. We have been successfully developed high intensity cluster ion beam from gaseous
materials, such as Ar, O
2
or SF
6
, for novel surface modification technique[1]. The average size of
the cluster ion is about a few thousands. More than 1mA of cluster ion current was obtained. This
new cluster ion source gave us an opportunity to overcome many fundamental problems of SIMS.
However, emission mechanism of secondary ions under large cluster ion bombardment is still
unclear.
Experimental results by using a new cluster SIMS system equipped with high-intensity cluster
ion source and will be shown, and prospect of cluster SIMS will be discussed comparing with
molecular dynamics (MD) simulation results


[1] I. Yamada, J. Matsuo, N. Toyoda, and A. Kirkpatrick, Mater. Sci. Eng., R.34, 231 (2001).
CLU3-O-Tu-C07
160
Comparison of TOF-SIMS and XPS Analysis Using a C
60
Ion Beam

N. Sanada
a,
*, T. Miyayama
a
, J. S. Hammond
a,b
, A. Yamamoto
a,
, and S. R. Bryan
b


a
ULVAC-PHI, Inc., 370 Enzo, Chigasaki, Kanagawa, 253-0084, Japan
b
Physical Electronics, 18725 Lake Drive East, Chanhassen, MN 55317, USA
* nsanada@phi.com


The analysis in materials and devices of chemical layers buried in the near surface region from 1
to 100 nm is of great interest to polymer and biomaterials scientists. However, it has been a great
challenge to get chemical information from this region of some materials because of chemical
damage observed following ion beam sputtering.
Recently, we have applied a buckminsterfullerene (C
60
) ion beam for sputter cleaning and depth
profiling to minimize chemical damage for organic and inorganic materials [1]. Extremely low
sputtering degradation of many fluorinated polymers such as polytetrafluoroethylene [1],
polyesters, gelatines, and multilayer latex materials [2] were observed by XPS.
The effects of different C
60
ion beam accelerating voltages and impact angles on accumulation of
residual carbon and chemical damage were examined with XPS using standard samples of
polyethyleneterephthalate (PET) and SiO
2
. The quantities of carbon residue in the SiO
2
film
reduced as the increasing accelerating voltages. The impact angle of the ion beam also affected the
carbon residue in the film. Based on these experiments, an optimized protocol for using a C
60
ion
beam with XPS was developed.
We will discuss TOF-SIMS analysis of polymers after sputter depth profiling with a C
60
ion beam
under the protocol optimized with XPS. For many polymers, the high energy resolution XPS spectra
following C
60
ion beam exposure showed a constant elemental and functional group stochiometry.
The higher sensitivity of TOF-SIMS analysis of these materials allows an examination of more
subtle changes induced by the C
60
ion beam not observed in the XPS analysis.


[1] N. Sanada et al., Surf. Interface Anal., 36 (2004) 280.
[2] D. Sakai, et al., J. Surf. Anal. (Tokyo), submitted.
CLU3-O-Tu-C08
161
XPS and UPS Analysis of PMMA Films Bombarded by keV C
60
+
Ions

Igor Bolotin, Stephanie H. Tetzler, and Luke Hanley*

Department of Chemistry, University of Illinois at Chicago, m/c 111,
845 West Taylor Street, 4500 SES, Chicago, Illinois 60607-7061
lhanley@uic.edu

The lack of damage by keV C
60
+
bombardment indicates its suitability for depth profiling of
many organic films, yet most experimental evidence for this phenomenon has been derived solely
from secondary ion yields. Independent probes of the surface modification that results from
polyatomic ion-surface collisions [1] permit comparison of SIMS data with experiments on ion-
surface modification [2]. Chemical modification, depolymerization, primary ion deposition, and
other ion-induced damage events can be probed by photoemission of the target surface before and
after ion bombardment. The experiments described here investigate 9 keV C
60
+
and C
60
2+
ion
modification of spin-coated polymethylmethacrylate (PMMA) thin films analysed by x-ray and
ultraviolet photoelectron spectroscopy (XPS and UPS, respectively). XPS shows little change in the
C/O ratio of PMMA upon ion bombardment. Changes in the C 1s and O 1s spectra are observed by
XPS, but these can be explained predominantly by differential charging effects. Regions of the
PMMA film close to the crater formed by ion bombardment, where the film is thinner, undergo less
charging during XPS. The thicker regions of the PMMA film, relatively unaffected by ion
bombardment, undergo more charging during XPS. A brief period of electron neutralization after
ion bombardment returns the XP spectra to those similar to undamaged films. These results support
the argument that PMMA films have no static limit in C
60
+
cluster SIMS, as little or no damage of
the PMMA structure appears evident. Furthermore, the trends observed for all photoelectron
experiments indicate that charging of insulated films during keV C
60
+
bombardment is not a
significant problem. The UPS results for ion-modified PMMA are also discussed in terms of
charging vs. film damage.


[1] E. Fuoco, G. Gillen, M.B.J. Wijesundara, W.E. Wallace, L. Hanley, J. Phys. Chem. B 105 (2001) 3950-3956.
[2] L. Hanley, S.B. Sinnott, Surf. Sci. 500 (2002) 500-522.
CLU3-O-Tu-C9
162
3D Molecular Imaging Using Cluster SIMS

Greg Gillen* and Christine Mahoney

Surface and Microanalysis Science Division, National Institute of Standards and Technology,
Gaithersburg, MD 20899-8371, USA
greg.gillen@nist.gov


In recent years, the use of cluster primary ion projectiles for organic secondary ion mass
spectrometry (SIMS) has gained increased interest as a method to improve molecular secondary ion
yields, facilitate improved sensitivity for large molecule analysis and minimize the accumulation of
beam-induced damage in selected organic materials. In this work, we report on our first attempts to
combine SF
5
+
and C
60
+
primary ion bombardment with secondary ion imaging on an ion
microscope SIMS instrument to produce 2 and 3 dimensional molecular depth profiles. Two related
investigations are being pursued for this project. In the first, we have used bevel depth profiling
SIMS to prepare bevel cross sections of molecular thin films using cluster beams. The resulting
bevel (sub degree bevel angle) provides a laterally magnified cross section of the sample that does
not contain the beam-induced damage that would be observed by conventional ion beam cross
sectioning. The beveled surface can then be examined using cluster SIMS or other available
microanalysis techniques. The 2
nd
part of this project is to explore 3D molecular SIMS imaging.
In this technique, a series of secondary molecular ion images are captured using cluster
bombardment as a function of increasing depth during dynamic SIMS sputtering of thin molecular
films. Several examples will be shown to demonstrate the feasibility of both bevel depth profiling
and 3D molecular SIMS for the analysis of thin polymer films, multilayer polymer films and
polymer films doped with pharmaceuticals.

CLU3-O-Tu-C10
163
SIMS Depth Profiling of Polymer Blends with Protein Based Drugs

Christine M. Mahoney
a
, Jinxiang (Peter) Yu
b
and Joseph A. Gardella Jr.
b,
*

a
Analytical Microscopy Group, Surface and Microanalysis Science Division,
National Institute of Standards and Technology, Gaithersburg, MD 20899USA

b
Department of Chemistry, University at Buffalo, State University of New York
Buffalo, NY 14260-3000 USA
*gardella@acsu.buffalo.edu


The use of SF
5
+
cluster ions for depth profiling has been successful for polymer-drug mixtures
and polymer blends [1-2]. This study reports results of the surface and in-depth characterization of
two component blend films of poly(L-lactic acid) (PLLA) and Pluronic surfactant [poly(ethylene
oxide) (A) poly(propylene oxide) (B) ABA block copolymer]. Angle dependant X-ray
photoelectron spectroscopy (XPS) and Time-of-flight secondary ion mass spectrometer (ToF-
SIMS) depth profiling were used for monitoring the surfactant's surface concentration at different
sampling depths. We found a critical saturation concentration of the surfactant, a depletion region
beneath the topmost surfactant enriched zone, and the existence of the surfactant's segregation in the
whole film with different intensities. A key comparison between the results from different methods
includes the depth scales of the distribution of components. Results from angle dependent XPS and
ToF-SIMS depth profiling are compared. With respect to the polymer blend results, we conclude
that the surfactant's surface segregation increases and then stays stable when increasing its bulk
concentration. These results suggest that the selection of the surfactant bulk concentration of the
thin film matrices for drugs/proteins delivery should achieve a relatively homogeneous distribution
of stabilizer/protein in the PLLA matrix.
ToF-SIMS depth profile analysis of three and four component blends of biodegradable
polymers, surfactants and proteins are reported. PLLA based membranes with bovine serum
albumin (BSA) and keratinocyte growth factor (KGF) are stabilized with surfactants to retain
activity of the protein for drug delivery in wound healing applications. Depth profiles are needed
to determine whether homogeneous distribution of the proteins are accomplished in thin
membrane films used for drug delivery.
[1] C. M. Mahoney, J. G. Gillen, and S. V. Roberson, Analytical Chemistry 2004, 76, 3199-
3207.
[2] C. M. Mahoney, J.-X. Yu and J.A. Gardella, Jr., Analytical Chemistry, 2005, in press.

CLU3-O-Tu-C11
164
Depth Profiling of a Medical Device-copolymer using a C
60
+
Cluster
Ion Source

Robert M. Braun
a,*
, Juan Cheng
b
, Edward E. Parsonage
c
, Jeff Moeller
c
and Nicholas Winograd
b


a
Bausch and Lomb Incorporated, Rochester, NY, USA
b
Penn State University, University Park, PA, USA
C
Boston Scientific SciMed Incorporated, Maple Grove, MN, USA
rbraun@bausch.com


A C
60
+
cluster ion probe has been utilized to obtain secondary ion mass spectra from a medical-
device, copolymer. The spectral data show significant enhancements in secondary ion yields when
compared to results obtained using Ga
+
ion bombardment. In addition, the use of C
60
+
cluster ions
allowed depth distributions of the polymer components to be obtained using primary ion doses
exceeding 6e14 C
60
+
/cm
2
. These results, in conjunction with atomic force microscopy images of
surface topography and metrology indicate the sputtered regions possess minimal artifacts
associated with the ion bombardment process. Surface roughness and domain structure within the
images are in agreement with data obtained from control regions outside the sputter craters. These
findings differ from depth profiles obtained using monoatomic sources like Ga
+
where significant
degradation is typically found on organic matrices after the ion bombarding process.


CLU3-O-Tu-C12
165
ToF/SIMS analysis of fluorocarbon-grafted PET with a gold cluster
ion source

Zhengmao Zhu
a
, Michael J. Kelley
a,b,*

a
Department of Applied Science, College of William and Mary, Applied Researach Center - 601,
12050 Jefferson Aveneue, Newport News, VA 23606m, USA
b
Free Electron Laser Dept., Thomas Jefferson National Accelerator Facility, MS 6A
12000 Jefferson Avenue, Newport News VA 23606, USA
mkelley@jlab.org

Irradiation of PET with 172 nm UV light in the presence of a small amount of vapor of
appropriate chemicals can form a grafted monolayer to impart special surface properties.
Photochemistry studies of PET suggest that active phenylene and ethoxy polymer end radicals may
result from a Norrish type I based decarbonylation process and they may be responsible for
initiating the grafting processes [1,2]. Using ToF/SIMS to examine a fluorocarbon-grafted PET
enabled us to identify not only species from the graft layer or the substrate, but also specific
fragments attributed to the above two type molecular linkages containing the graft molecule and the
substrate fragments. Compared to the gallium LIMG, the gold cluster ion source provided
increasingly enhanced total ion yields as the primary ion mass increased. At the same time,
substrate fragment ions from beneath the ~ 1 nm grafted layer became more and more prominent
relative to the fluorocarbon species, indicating apparently lower surface sensitivity with increased
primary ion mass. Further experiments and calculations suggested that the causes of the lowered
surface sensitivity were possibly the larger information depth from the increased sputter rates and
the selective enhancement of substrate ions. Differential enhancement of the fragments containing
the molecular linkages were also observed. Together with the different information depths of the
primary beams, these findings suggest different origins of the parent structures: ones are loosely
adsorbed on the surface; others are anchored to substrate polymer via covalent bonds.
Correspondingly, the mass fragment patterns support different fragmentation mechanisms: the
former fragments under the same rules in electron impact mass spectrometry; the latter came
through more violent collision processes.


[1]. Z.Zhu, M.J.Kelley; Appl.Surf.Sci. 234 (2004) 416.
[2]. Z.Zhu, M.J.Kelley; Appl.Surf.Sci. 231-232 (2004) 302.
Plenary-We-A01
166
THE CONTRIBUTION OF MASS SPECTROMETRY TO THE
BIOSCIENCES

Simon J Gaskell

Michael Barber Centre for Mass Spectrometry
School of Chemistry
University of Manchester
Manchester, UK


It is at least arguable that the analysis of biologically important molecules has provided the major
driving force for the development of mass spectrometry (MS) since the 1960s. It is incontrovertible
that the introduction of ionization methods suitable for the analysis of biopolymers in the 1980s
propelled the technique to the forefront of biochemical methods. Yet MS has intrinsic limitations
for the study of biomolecules: the characterisation of analyte stereochemistry is difficult to achieve
directly, for example, and analysis is performed in the gas-phase, a medium of limited immediate
biological relevance. The strengths of MS, on the other hand, are clear. The method achieves very
high sensitivity (though there remains significant scope for improvement), can provide great detail
of primary structure (particularly when tandem MS is employed), effectively handles complex
mixtures (again aided by tandem MS), and, perhaps most importantly, is able to provide rigorous
quantitative information. These attributes are critical to the contribution of MS to the emerging
field of systems biology, which seeks to define cellular processes by modeling the enormously
complex interactions that take place between components at the levels of genome, transcriptome,
proteome and metabolome. Rigorous and effective modeling requires extensive qualitative and
quantitative analytical data and MS has a clear role to play.
This lecture develops and illustrates these ideas with particular reference to the study of the
proteome the full complement of proteins in a cell or organism. The analytical problem is defined
by the multi-dimensionality of the proteome. Thus, the definition of primary protein sequence
must be accompanied by complementary data on post-translational modification, protein/protein
interactions, sub-cellular location, etc. Qualitative data must be accompanied by relative and
absolute quantification, and by an understanding of the dynamic nature of the proteome: individual
proteins are continuously synthesized and degraded, and the rate of turnover represents an important
biochemical parameter. To an extent, familiar analytical approaches may be applied in addressing
these challenges; stable isotope dilution, for example, represents a suitable conceptual framework
for absolute quantification. Proteomics, however, provides challenges that place unique demands
on both instrumentation and analytical strategy. These will be explored in this lecture and novel
analytical approaches will be described.

ORG2-O-We-A02
167
Suppression and enhancement of non-native molecules within
biological systems

E. A. Jones,
a
*; N. P. Lockyer,
a
; J. C. Vickerman
a


a
Surface Analysis Research Centre, CEAS, University of Manchester, UK
e.jones@postgrad.manchester.ac.uk


Imaging with Secondary Ion Mass Spectrometry (SIMS) is beginning to offer insights into
biological systems, breakthroughs such as the imaging of lipid distribution in cells and tissue have
been achieved due to the higher mass range and improved detection limits allowed by techniques
such as matrix enhancement and the use of cluster primary ion beams [1, 2].
On a smaller molecule scale, applying Static SIMS to the imaging of pharmaceuticals and
neurotransmitters, for example, within cells or tissue would have far reaching applications; however
apart from early proof of concept work [3] little has been achieved in this field.
As these compounds are generally found at very low levels, the majority of the analysed area will
be made up of bio-molecules such as lipids and proteins. It has previously been shown that the
molecular environment of the molecule of interest is very important when it comes to the formation
of secondary ions, highlighted by the success of matrix enhancement for some systems [4]; here we
demonstrate the effect that a range of bio-molecules has on molecules located within them. In some
cases complete suppression of secondary ion formation is seen even in 1:1 mixtures, whereas other
compounds abundant in tissue sections can act to enhance secondary ion yields.
Using imaging SIMS it can be shown that within a tissue section environments that promote
[M+H]
+
ion formation can be found side by side with areas that suppress the same signal, making it
difficult to map the distribution of a molecule accurately across such a heterogeneous sample.


[1] A. F. Altelaar, J. van Minnen, C. R. Jimenez, R. M. A. Heeren, S. R. Piersma, Anal Chem, (2005) 77, 735-741
[2] D. Touboul, F. Halgand, A. Brunelle,. Hagenhoff, O. Larprevote et. al, Anal. Chem, (2004), 76, 155-1559
[3] T.P. Roddy, D.M. Cannon, S.G. Ostrowski, N Winograd, A.G. Ewing, Anal. Chem (2002), 74, 4020-4026
[4] K. J. Wu, R. W. Odom, Anal. Chem, (1996), 68, 873-882
ORG2-O-We-A03
168
Why MALDI works From Hypotheses to Experimental Evidence

Michael Karas

Inst. of Pharmaceutical Chemistry
Biocenter
Johann Wolfgang Goethe University of Frankfurt
Marie-Curie-Str. 9-11
D-60439 Frankfurt a. Main
Germany
email karas@iachem.de


The original conceptual ideas on the MALDI process, i.e. matrix isolation, desorption via
disintegration of the matrix-analyte-crystal after laser excitation and ionization via photochemical
reactions has recently been revisited and refined. By using molecular probes, such as organic dyes
and extremely strong acids, clear evidence is provided that the pH is maintained in the matrix
crystals and that typical peptide analytes are incorporated in an ionized, resp. salt state. The
desorption process induced by the laser irradiation is now understood as a cluster ablation step
substantiated both by numerical calculations as well as by measurements of the ion characteristics,
namely their initial ion velocity. Consequently ions do not have to be generated, but are the "lucky
survivors" within a random charging and desolvation process which is again evidenced by a
chemical approach. Within this frame, connections to the situation in sputtering by ion impact will
be drawn and outlooks will be given.
ORG2-O-We-A04
169
A COMPARATIVE STUDY OF SECONDARY ION YIELD FROM
BIOLOGICAL MEMBRANES USING Au, Au
3
AND C
60
ION
BEAMS

M.J.Baker*, J.S.Fletcher, H. Jungnickel, N.P.Lockyer, J.C.Vickerman

Surface Analysis Research Centre, School of Chemical Engineering and Analytical Science, University of Manchester,
P.O Box 88, M60 1QD.
*M.Baker-2@student.manchester.ac.uk


Experimentally it has been shown that polyatomic gold clusters produce a strong non-linear
increase in yield over monoatomic gold [1] also it has been shown that C
60
induces significant
enhancement of secondary ion yields particularly at high masses for samples such as phospholipids
[2]. Molecular Dynamic Simulations show that the large polyatomic primary ions give large non-
linear yield enhancements of characteristic high mass fragments by imparting energy in the
uppermost layers [3].
A systematic study of biologically relevant phospholipids has been undertaken. This will study
how the phospholipids behave in different chemical environments.
Liposomes are phospholipid bilayers and as such can be treated as model cell membranes. We
use symmetric and asymmetric liposomes in a comparative study of secondary ion yields using
mono- and polyatomic ion beams.
We discuss the relevance of these results in the context of cellular ToF-SIMS analysis.


[1] N.Davies, D.E. Weibel, P.Blenkinsopp, N.Lockyer, R.Hill, J.C.Vickerman, Development and experimental
application of a gold liquid metal ion source Applied Surface Science (2003) 203-204;223-227
[2] D.Wiebel, S.Wong, N.Lockyer, P.Blenkinsopp, R.Hill, J.C.Vickerman, A C
60
Primary Ion Beam System for Time of
Flight Secondary Ion Mass Spectrometry: Its Development and Secondary Ion Yield Characteristics Analytical
Chemistry ( 2003 ) 75; 1754-1764
[3] Z.Postawa, B.Czerwinski, M.Szewczyk, E.J.Smiley, N.Winograd, B.J.Garrison Enhancement of Sputtering Yield
Due to C
60
versus Ga Bombardment of Ag {111} As Explored by Molecular Dynamics Simulations Analytical
Chemistry ( 2003 ) 75; 4402-4407
ORG2-I-We-A05
170
Matrix-Enhanced Secondary Ion Mass Spectrometry

Arnaud Delcorte

PCPM, Universit catholique de Louvain, Croix du Sud 1, B-1348 Louvain-la-Neuve, Belgium, e-mail:
delcorte@pcpm.ucl.ac.be


Since the beginnings of SIMS, the term matrix effects has been used to describe the drastic
influence of the chemical environment over the desorption/ionization yields of sputtered particles.
Elements like oxygen and cesium have been found to enhance the yields of, respectively, positive
and negative ions of other elements by several orders of magnitude. In organic SIMS, matrix and
substrate effects are also very important, as was already demonstrated almost three decades ago by
the use of transition metal substrates and metal salts for molecule cationization [1]. Matrix effects
constitute a huge obstacle for quantification but also an opportunity for secondary ion yield
enhancement, at a time when the explosion of SIMS imaging, triggered by the excellent focusing of
recent liquid metal ion probes, requires much higher yields than those we naturally measure. For
this reason, the possibility of improving molecular ion yields through special sample preparation
procedures recently generated a renewed interest in the static SIMS community.
This contribution critically reviews the experimental developments achieved by our group and
others with respect to the three following approaches: (i) blending the analyte with a low-molecular
weight organic matrix (MALDI-type preparation procedure); (iii) evaporating a noble metal layer
on the analyte sample surface (organic molecules, polymers); (iii) mixing alkali/noble metal salts
with the analyte. From the theoretical viewpoint, some useful results concerning the interaction of
kiloelectronvolt projectiles with mixed materials (matrix:analyte blend, metal substrate with analyte
overlayer, organic sample supporting a metal cluster) will be presented.


[1] H. Grade, R.G. Cooks, J. Am. Chem. Soc. 100 (1978) 5615.

ORG2-O-We-A06
171
Matrix-Assisted Cluster-SIMS

J.E. Locklear, C. Guillermier, S.V. Verkhoturov, and E.A. Schweikert
*


Center for Chemical Characterization and Analysis, Department of Chemistry,
Texas A&M University, College Station, Texas 77842-3012
*
Schweikert@mail.chem.tamu.edu


Various avenues have been pursued to improve sensitivity in secondary ion mass spectrometry
(SIMS) including higher energy projectiles, sample preparation techniques, and the use of massive
polyatomic projectiles. In this study, we have examined sample preparation techniques in
conjunction with polyatomic ion bombardment as a means to enhance SIMS sensitivity.
We have used 23 keV C
60
+
projectiles in the event-by-event bombardment and detection mode to
investigate the emission of the gramicidin S [M-H]- ion embedded in a matrix of sinapic acid. We
have observed an increase in the gramicidin S [M-H]- ion of approximately 8 times by controlling
the ratio of gramicidin S to sinapic acid. The gramicidin S [M-H]- yield initially rises sharply with
increasing matrix to analyte ratios followed by a slow decrease after the maximum which in this
case occurs at a matrix-to-analyte ratio of 10-1. Sinapic acid was selected as the matrix because of
its prior use in matrix-assisted laser desorption / ionization and matrix assisted SIMS with atomic
ions [1, 2]. This initial work warrants further studies optimizing matrix(ces).


References:
[1] A. Delcorte, S. Hermans, M. Devillers, N. Lourette, F. Aubriet, J.F. Muller, P. Bertrand, Appl. Surf.
Sci. 231-232 (2003) 131-135.
[2] F. Hillenkamp, M. Karas, R.C. Beavis, B. T. Chait, Anal. Chem. 63 (1991) 1193A-1202A.

Work supported by NSF (CHE-0449312) and R.A. Welch Foundation (A-1482).
ORG2-O-We-A07
172
S-SIMS and MetA-SIMS study of organic additives in thin polymer
coatings

L. Adriaensen
a*
, F. Vangaever
b
, J. Lenaerts
b
, R. Gijbels
a


a
University of Antwerp, department of Chemistry (MiTAC), B-2610 Wilrijk, Belgium;
b
Agfa-Gevaert N.V., B-2640 Mortsel, Belgium
* lesley.adriaensen@ua.ac.be


In recent years S-SIMS has become a well-established tool for the analysis of a wide variety of
organic surfaces. However, the tendency of organic molecules to give rather low secondary ion
yields remains one of the major difficulties in S-SIMS experiments. Especially when information
of the molecule distribution across a sample surface or throughout the sample bulk has to be
obtained, this becomes a serious problem.
In the present study a methodology for TOF-S-SIMS measurements is developed to gain
information on the distribution of molecules on and in polymer coatings (thickness < 100 m).
Experiments were carried out on systems consisting of one or more additive containing Butvar and
gelatine coatings. Several organic additives were selected: carbocyanine dyes, the pharmaceutical
Risperidone, basonyl blue and tetrabutylammonium bromide. The pure additives have been
measured on a Si substrate to obtain good reference spectra. After optimisation of the sample
preparation method, the coatings were embedded in epoxy resin and stored in an oven (60C) for 24
hours. Cross sections were made by means of a microtome. S-SIMS spectra were taken on the
prepared cross sections before and after Au was deposited on the sample surface [1]. Compared to
the blank samples, the Au covered samples give rise to more intense secondary ion signals.
Generally, the intact cations were more intense than the fragment ions. Apart from mass spectra,
images of the additive distribution in the coatings could also be acquired by recording structural ion
signals. It was possible to make secondary ion images of the additive molecule ions with a very
good lateral resolution.


[1] L. Adriaensen, F. Vangaever, R. Gijbels, Anal. Chem. 76 (2004) 6777-6785.

ORG2-O-We-A08
173
A new analysis of the depolymerised fragments of lignin polymer
in the plant cell walls using ToF-SIMS

K. Saito
a
, T. Kato
b
, H. Takamori
c
, T. Kishimoto
c
, A. Yamamoto
d
, K. Fukushima
a,
*

a
Graduate School of Bioagricultural Sciences, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, 464-8601, Japan
b
Technical Center, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, 464-8601, Japan
c
Graduate School of Agriculture, Kita 9, Nishi 9, Kita-ku, Hokkaido University, Sapporo 060-8589, Japan
d
ULVAC-PHI, Inc., 370 Enzo, Chigasaki, 253-0084, Japan
Email: kazu@agr.nagoya-u.ac.jp


Lignin in the plant cell walls is a complex, irregular polymer built from phenylpropane C
6
C
3

units that are connected via various CC and CO linkages, and is the second most abundant
biopolymer in nature after cellulose. Although there are few techniques to characterize in solid state
lignin samples, time-of-flight secondary ion mass spectrometry (ToF-SIMS) can analyze the surface
of lignin in solid state directly without any chemical pretreatment, which might change the lignin
chemical structure.
ToF-SIMS with Ga primary ion bombardment showed that lignin isolated from wood can be
characterized by specific positive ions possessing a substituted aromatic ring, which are the basic
building units of lignin polymer. This shows that ToF-SIMS is a useful tool for lignin structural
analysis. Peaks at m/z 137 was identified as C
6
C
1
benzyl ions ([C
8
H
9
O
2
]
+
) and peaks at m/z 151
was considered to arise from double-components, the C
6
C
1
benzoyl ion ([C
8
H
7
O
3
]
+
= 151.0394)
and the C
6
C
2
ion ([C
9
H
11
O
2
]
+
= 151.0758). In order to study the relationship between the
characteristic ions of lignin and the common interunit linkages, various lignin dimer model
compounds were investigated using ToF-SIMS. The resulting dimer spectra showed that the
characteristic ions at m/z 137 and 151 result from rupture of most common interunit linkages, 8-O-
4, 8-1, 8-5, and 8-8 linkages. There was no evidence of rupture of 5-5 biphenyl linkages. These
results show that ToF-SIMS offers a new tool for the direct analysis of the depolymerized
fragments of lignin polymer.



Figure. Common interunit linkages in lignin and the structures of characteristic
secondary ions of lignin at m/z 137 and 151.
(3.5-4%) (2%) (6-8%)
8-O-4 5-5

8-5 8-1
4-O-5 8-8
7-O-4
Lignin interunit linkages
C
C
C
O C
O
8
4'
C
C
C
O
O
C
8 5'
C
C
C
O
C
C
C
O
4
5'
C
C
C
O
C
C
C
O
5 5'
C
C
C
O
C 8
1'
C
C
C
O
C
C
C
O
8 8'
C
C
C
O C
O
7
4'
m/z 137
m/z 151
Characteristic ions of lignin
C8H9O2
+
C8H7O3
+
C9H11O2
+

OH
OCH
3
CH
2
OH
OCH
3
C O
OH
OCH
3
CH
2
CH
2
ToF-SIMS
Ga primary
ion
Which interunit linkages
are disrupted to give rise to
the characteristic ions of
lignin?
DEP1-I-We-B01
174
Depth Profiling for Emerging Semiconductor Materials

P.A. Ronsheim


IBM Server and Technology Group
Hopewell Junction, NY 12533 USA
ronsheim@us.ibm.com


Scaling of classical CMOS silicon devices, used to improve device performance and density
by reducing dimensions, has neared the end of its usefulness due to unacceptable increases in device
standby current. This is forcing changes in device structure and materials to continue to provide
improvements in circuit speed and operation. Materials changes in the gate dielectric to reduce
leakage, and improving the charge carrier mobility in the device channel are two recent
developments. This paper addresses the effect these materials changes will have on depth profiling
for device development and characterization.
Emerging semiconductor materials developments for the CMOS gate include metal gates,
fully silicided gate electrodes or FUSI, and high permittivity constant gate dielectric materials. [1,2]
Depth profiling issues for these materials are illustrated with examples. Carrier mobility can be
improved with use of Ge substrates, or with strain produced either by epitaxial growth on an
underlying crystalline lattice with a different lattice parameter, or with overlying compressive or
tensile deposited films. Another method to improve mobility is to change the substrate
crystallographic orientation. Building the p-channel devices on <110> Si crystal improves the hole
mobility, and n-channel devices remain on <100> film orientations. Some of these developments
cannot be investigated with depth profiling as they dont relate to impurity distributions, but the
<110> epi growth process and the Ge substrates require substantial depth profiling characterization.
Building devices on SOI substrates limits the silicon volume, with ultra-thin SOI using 5-10
nm Si film thicknesses. This is a realm of vanishing semiconductor materials, where the number of
carriers in a channel region is less than 10. Depth profiling must use lowest sputter energies
available to define distributions in the thin layers. The large area structures used for SIMS
measurements no longer effectively represent the actual devices, which have progressed from
planar structures, essentially one dimensional with perimeter contacts, to two dimensional devices
where lateral diffusion at mask edges was significant, and now to 3D devices such as the FinFET or
body-contacted SOI designs. The device becomes a low carrier-density Si volume, with
characteristics strongly driven by interface charge states, and characterization with sputtering or a
2D method such as SSRM cannot provide the device characterization necessary for optimization. A
3-D profiling method is required for dopant distributions, which, when combined with test
structures to measure interface states and trapped charge, can again characterize essential device
features.


[1] J. Kedzierski et al, IEDM 2002. p 247-250.

DEP1-O-We-B02
175
Room Temperature Diffusion of Boron in Crystalline Si
During SIMS Depth Profiling

E. Napolitani
a,
*, D. De Salvador
a
, A. Carnera
a
, S. Mirabella
b
, F. Priolo
b


a
MATIS-INFM and Dipartimento di Fisica, Universit di Padova, Via Marzolo 8, I-35131 Padova, Italy
b
MATIS-INFM and Dipartimento di Fisica e Astronomia, Universit di Catania, Via S. Sofia 64, I-95123 Catania, Italy
Email: napolitani@padova.infm.it


Recently we have demonstrated that substitutional boron in silicon can migrate even at room
temperature (RT) and below stimulated by a high self-interstitial (I) flux [1]. The I injection and the
B migration occur for long distances during Secondary Ion Mass Spectrometry (SIMS) profiling of
B deltas in Si at RT with O
2
+
, producing strong artifacts in the B profiles. The phenomenon is
suppressed after amorphization or by cooling the sample. The above data force to reconsider the
observations obtained in the last decades by SIMS at RT in light of possible long-range migration
artifacts. On the other hand, by properly controlling the injection of Is, SIMS provides new
experimental methods to investigate RT diffusion phenomena. Here we present our recent results,
obtained through a non-conventional use of SIMS, on the properties of the diffusion of B at
temperatures around RT and on the B interaction with the impurities or the damage produced by the
sputtering beam. We have investigated the role of different conditions, such as the sample
temperature or the oxygen flooding, on the migration of point defects and impurities and their
interaction and on the related B profile broadening. It is also shown that by properly controlling the
B migration, it is possible to obtain measurements of B deltas of unprecedented level of accuracy
and sensitivity.


[1] E. Napolitani, D. De Salvador, R. Storti, A. Carnera, S. Mirabella, F. Priolo, Phys. Rev. Lett. 93, 055901 (2004).
DEP1-O-We-B03
176
An unexpected solution to the Na and Li depth profiling problem in
oxides


Temel H. Byklimanli

Evans East, 104 Windsor Center, Suite 101, East Windsor NJ, 08520-1407
Email: temel@evanseast.com


Beam induced migration of the alkalis, especially Na and Li, in oxide thin films and bulk glass
have made it difficult to acquire accurate concentration depth profiles by any surface analytical
technique. Previously, we have used oxygen-bombardment with a standardized ion implanted SiO
2

thin film on Si sample to set up instrument parameters to minimize the alkali element migration due
to sample charging. However, the depth profile shapes have never matched expected ion implant
shapes. Alkali depth profiling analyses of bulk glass or thin film/glass interfaces appeared to be
further erroneous. All Na and Li profiles had long tails, misleadingly suggesting these elements
have diffused in the oxides.
In the present study, bulk glass, SiO
2
, and SnO
2
thin films on glass substrates were
simultaneously ion implanted with alkali metals. Several instrumental analysis protocols were
tested to achieve true implant shapes in bulk glass, which was expected to be the most difficult to
charge compensate. We discovered that the electron donor property of Cs bombardment provides
the best charge compensation, leading to the most accurate Na and Li profile shape. The analyses
carried out with a Cs primary ion beam did not suffer from sensitivity loss during positive ion
analyses in oxides. The results show dramatic improvement in analyses of sharp Na contamination
features and perfect matching with TRIM simulations for ion implant profiles.
DEP1-O-We-B04
177
SIMS quantitative depth profiling of matrix elements in
semiconductor layers

G. Guryanov
a,*
, T.P. St.Clair
b
, R. Bhat
c
, C. Caneau
c
, S. Nikishin
d
, B. Borisov
d
,
A. Budrevich
e


a
Corning Incorporated, SP-FR-01, Corning, NY 14831, USA
b
Corning Incorporated, SP-FR-05, Corning, NY 14831, USA
c
Corning Incorporated, SP-PR-02, Corning, NY 14831, USA
d
Texas Tech University, Lubbock, TX 79409, USA
e
Intel Corporation, MS RA1-329, Hillsboro, OR 97124, USA
E-mail: Guryanovgm@corning.com


SIMS is a well known technique for quantitative depth profiling of dopants and contaminants
with concentrations less than 1 at % [1]. For higher concentrations non linear relationship between
concentration and atomic ion yield is observed, and calibration curves are required for quantitative
depth profiling of matrix elements. It has been shown that acquiring molecular MCs+ secondary
ions (M is the matrix element to be depth profiled) under Cs+ bombardment results in significantly
reduced matrix effects [2]. A linear relationship between AlCs+/GaCs+ ion intensity ratios and
compositional ratio x/(1-x) for Al
x
Ga
1-x
N samples has been demonstrated for x=0.1-0.23[3]. In
addition, a linear relationship between Al at % (in the range from 3 to 20%) and Al/Ga ratio was
also found for Al
x
Ga
1-x
N under oxygen bombardment [4]. The slope of the calibration curve is
dependent on the analysis conditions used and the type of matrix being analyzed.
In this work, an approach for compositional characterization of a variety of III-V semiconductor
alloys without using standard samples and without building calibration curves will be presented.
This approach is similar to that used in XPS and is based on the ratio of MCs+ ion intensities to the
sum of all element intensities present in the semiconductor compound. A sensitivity factor of an
element, once determined and tabulated, can further be used for different compounds without
correction. Results obtained using SIMS are in a good agreement with data acquired using XPS and
RBS techniques. The method was tested using a variety of semiconductor compounds, and found
to be very powerful for SIMS quantification of matrix elements.


[1] R. G. Wilson, F. A. Stevie, C. W. Magee, Secondary Ion Mass Spectrometry, John Wiley and Sons, New York,
1989
[2] Y. Gao, J. Appl. Phys. 64(7), 3762(1988)
[3] Y. Gao, S. Mitha, C. Huang, R. Clark-Phelps, Larry Wang, Secondary Ion Mass Spectrometry, SIMS XI, G. Gillen,
et al., eds., John Wiley&Sons, Chichester(1998) 193
[4] J. Gu, F. Steve, A. Pivovarov, D. Griffis, Proceedings of 15
th
Annual Workshop on SIMS, Florida, USA, 2002,
p.105
DEP1-O-We-B05
178
Depth Profiling of Ultrathin Films and Their Multilayers by DSIMS

P. Babor
1
, M. Potocek
1
, M. Urbanek
1
, J. Mach, J. Spousta
1
, L. Dittrichova
1
, J. Sobota
2
, Z.
Bochnicek
3
, and T. Sikola
1


1
Institute of Physical Engineering, Brno University of Technology,
616 69 Brno, Czech Republic,
babor@fme.vutbr.cz.
2
Institute of Scientific Instruments, Czech Academy of Sciences,
Kralovopolska 147, 612 64 Brno, Czech Republic
3
Department of General Physics, Faculty of Science, Masaryk Universit,
Kotlarska 2, 611 37Brno, Czech Republic


Dynamic secondary ion mass spectroscopy (DSIMS) is a technique frequently used for depth
profiling of elemental composition of thin films. It is generally accepted that due to atom mixing by
primary ions of typical energies (100 keV), only the depth profiles of thin films thicker than 10 nm
can be investigated. However, quite recently, DSIMS has been used for profiling ultrathin films of
thicknesses below this value. In this applications the energy of the primary ion beam is limited to a
few hundreds of eV only and thus the mixing of atoms reduced.
In the contribution the ability of DSIMS to reveal depth profiles of ultrathin films (< 5 nm) and
their multilayers will be demonstrated. As an example, the results on depth profiling the structures
as Ni/C or Mo/Si multilayers prepared by magnetron sputtering and used for x-ray mirrors will be
given. Additionally, the depth profiles of ultrathin films of Co and Al
2
O
3
and of their magnetic
multilayers will be demonstrated as well. All these films were prepared by ion beam assisted
deposition (IBAD). At these measurements the depth resolution below 3 nm has been achieved and
the results were checked by X-ray reflection (XRR). To obtain such a resolution, optimum
measurement conditions have to be provided. In the contribution a developed imaging system
helping to set these conditions (e.g reduction of the crater effect, enhancement of sensitivity) will be
described.
DEP1-O-We-B06
179
Shallow B depth profiling in Si without complete oxidation of the
analytical area


Temel H. Byklimanli and John W. Marino

Evans East, 104 Windsor Center, Suite 101, East Windsor NJ, 08520-1407
Email: temel@evanseast.com


Near surface Boron characterization is becoming important as implantation energies are reduced.
With the emergence of new implantation techniques like Plasma Doping, near surface
characterization becomes even more important, in order to be able to compare with beam line
implants. Unfortunately, the traditional SIMS depth profiling using normal incidence bombardment
or O
2
flooding, which fully oxidizes the analytical in order to avoid surface ion detection
irregularities, produces an incorrect B profile shape within the top 10nm.
We have been experimenting with SIMS profiling which does not fully oxidize the surface. In
this technique we use RSFs calculated from B implanted SiO
2
and Si reference materials and
interpolate the RSF change across the SiO
2
/Si interface using the quantified O signal. Co-
measurement of the O signal also allows proper sputter rate to be applied for most accurate junction
depth and dose determination. Comparisons with techniques like NRA, ERDA and HR-RBS have
shown that our new technique can produce matching results for profile shape, dose and peak
concentration.
DEP1-O-We-B07
180
SIMS depth profiling of Boron ultra shallow junctions
using oblique O
2

+
beams down to 150eV.

M. Juhel
1,*
, F. Laugier
2
, D. Delille
3
, C. Wyon
2
, L.F.Tz. Kwakman
3
, and M. Hopstaken
3

1
STMicroelectronics, 850 rue Jean Monnet, 38926 Crolles, France
2
CEA-DRT-LETI CEA/GRE 17, rue des martyrs 38054 Grenoble Cedex, France
3
Philips Semiconductors, 860 rue Jean Monnet, 38920 Crolles, France
marc.juhel@st.com


65nm and 45nm CMOS technology nodes require Source and Drain junction depths of less than
15 10 nm. To be able to measure such junctions depths accurately we have investigated the depth
scale accuracy and depth resolution of SIMS boron depth profiling using an oxygen beam with sub-
500eV impact energy.
The analyses have been performed on an epitaxial grown multi-layer stack consisting of ultra-thin
boron doped silicon films separated by 6.4 nm thick undoped silicon films. The 6.4nm boron delta
layers spacing was measured using HR-TEM.
The Cameca IMS-Wf magnetic sector SIMS system with its optimised design of the extraction
ion optics, allows sputtering with an oxygen beam at an impact incidence angle of 45 and with
impingement energies as low as 150 eV.
In previous studies it was demonstrated that depth scale accuracy is limited by the variation of
erosion rate between the surface region and bulk silicon. Hence, one has to account for the higher
erosion rate in the top first nanometres of the film stack when determining the exact boron profile
[1]. The selected and well characterized multi-layer delta boron sample used in this
communication permits to directly observe the depth scale distortion from the relative shifts of the
boron peak positions. This method has been used to investigate the influence of impact energies and
oxygen pressure in the analytical chamber on the sputtering kinetics. Moreover,
30
Si
+
, O
+
and Si
2
+

ion intensities in the first 6 nm were accurately monitored to detect any variation of sputtering rate
and ion yields close to the surface region.
By appropriate tuning of the sample and primary beam voltages, the boron depth resolution can be
improved from 1.66nm/decade at 500eV to 0.83nm/decade at 150eV (decay length measured on the
fifth boron delta peak at a 36nm depth). In a similar way, by decreasing the oxygen beam energy, a
better depth scale accuracy is obtained as is demonstrated by the reduction of the boron peak shifts.
In previous studies two conditions were found to give a smooth sputtering of silicon with a sub-
500eV oxygen beam: normal incidence under high vacuum and 45 incidence combined with
oxygen flooding. These results point out that for impact energies < 200eV sputtering with O
2
+

induces a high degree of oxidation of the silicon surface and that oxygen flooding is no longer
needed for accurate depth scale quantification. This result was also observed for Germanium delta
layers deposited on Silicon [2].
In conclusion, a Boron implant depth profile application will be presented with data on sputtering
rates for the different Oxygen beam energies.


1. B.W. Schueler et al., App. Surf. Sci., 203-204, (2003), p. 847-850
2. Z. X. Jiang, J. Lerma, D. Sieloff, J. J. Lee, S. Backer, S. Bagchi, and J. Conner, J. Vac. Sci. Technol. B, 12, 630
(2004).


DEP1-O-We-B08
181
Cesium/Xenon dual beam depth profiling:
nature of the sputtered atom and ionization probability

J. Brison
a,
*, R. Hubert
b
, T. Conard
c
, W. Vandervorst
c
and L. Houssiau
a

a
University of Namur (FuNDP), LISE laboratory; 61, rue de Bruxelles, B-5000 Namur, Belgium
b
University of Namur (FuNDP), LARN laboratory; 61, rue de Bruxelles, B-5000 Namur, Belgium
c
IMEC, Kapeldreef 75, B-3001 Leuven, Belgium
Jeremy.Brison@fundp.ac.be


The detection of MCs
n
+
clusters under cesium bombardment provides a semi-quantitative
solution for ToF-SIMS depth profiles. In a previous work [1], weve shown the real improvement
brought by the cesium/xenon co-sputtering to the technique. This approach consists on diluting the
cesium beam with xenon ions, which allows the control of the cesium surface concentration and
thus provides a way to control the surface work function and to optimize the elemental and cluster
yields [2].
At first, we bombarded different metals and semi-conductors (e.g. Si, Au, Rh) and we found
that all the M
+
signals decrease exponentially with the cesium beam concentration. We also
observed that the MCs
+
and the Cs
+
signals exhibit optimums for well defined Cs/Xe mixture.
Those maximums are a consequence of the competition between the increasing Cs surface
concentration and the decreasing positive ionization probability. We developed simple models
based on the tunneling model that successfully fitted our results [1].
We then studied the influence of the sputtering parameters on those optimums and we
measured a shift to higher cesium beam concentration for higher sputtering energies. This result can
be explained by a decrease of the cesium surface concentration with the increase of the sputtering
yield Y, according to the relationship [Cs]
Surface
=(1+Y)
-1
[3].
In the present paper, we profiled a mixed metallic matrix in order to study the influence of
the leaving atoms nature on its ionization probability. In those conditions, the cesium surface
concentration and ionization probability are the same for all the elements of the bombarded matrix.
To perform this analysis, weve deposited a RhSi layer on silicon. The strong difference
between the Rh and the Si masses induces spectacular disparities in the M
+
curves.
That effect is due to the different perpendicular velocities of the sputtered atoms. Indeed, the
leaving Rh ions are slower than the silicon ones, spending more time in the interaction zone.
Moreover, the optimal mixture for the CsRh
+
signal is lower than the CsSi
+
one.


[1] J. Brison, T. Conard, W. Vandervorst and L. Houssiau., Appl. Surf. Sci., Vol 231-232C, p. 749-753 (2004)
[2] E. Niehuis and T. Grehl, proc. SIMS XII, p. 49 (2000)
[3] F. Schultz and K. Wittmaack, Radiat. Eff., Vol 29, p. 31 (1976)


BTC-O-We-C01
182
The use of a desktop ToF-SIMS instrument in the field of biomedical
surface modification

B. Cliff*, A.J. Eccles, N. Long, P. Vohralik

Millbrook Instruments Limited, Blackburn Technology Centre, Challenge Way, Blackburn, BB1 5QB, UK
Email: b.cliff@millbrook-instruments.com


The quadrupole based Millbrook MiniSIMS has long been involved in projects concerned with
surface modification in the biomedical field [1], in particular for areas where a high throughput and
ease of use are required. However for some applications the mass spectroscopic properties of the
quadrupole are not adequate in terms of mass range or sensitivity. Additionally, due to the
sequential mass scanning method of the quadrupole, the primary ion dose often exceeds the static
limit when a small area analysis is performed. To increase the performance and range of
applications, a Time of Flight (TOF) version of the instrument has been developed. This novel
instrument is described in full detail elsewhere [2]. However the main features are that it offers
parallel detection, a greatly extended mass range (>1000 Da), together with higher mass resolution
in order to investigate organic species in more detail.
The instrument is designed such that a sample may be analysed in several minutes, including
introduction to the vacuum system, additionally there is the option of a carousel whereby up to 25
samples may be mounted for analysis in one session. This ensures that the instrument can offer a
very high sample throughput for a SIMS instrument. The relatively low capital and running costs of
the instrument makes the analytical power of a true TOF-SIMS analysis available to many more
applications and users.
We will present work performed using the instrument in the biomedical field, with particular
reference to the analysis of a blood filtration system. This work shows how SIMS may be used
specifically to characterise an adsorption process, in conjunction with other high-throughput
techniques such as HPLC & NMR. The results showed that a small blood borne molecule,
creatinine, is preferentially adsorbed to a particular formulation of carbon bead from a blood
solution. However the creatinine is shown to degrade catalytically upon adsorption and the resulting
species remaining on the surface is successfully identified using ToF-SIMS. This work is useful in
creating replacements for non-selective blood filtration systems where the post-filtration processes
are both costly for the health service and very inconvenient for patients with kidney disease.


[1] D.J. Wilson et al., Surface and Interface Analysis 30 (2000), 36-39
[2] B.Cliff et al. This Volume

BTC-O-We-C02
183
ToF-SIMS imaging of micropatterned proteins and cells

Tae Geol Lee
a
, Hyun Kyong Shon
a
, Kyung-Bok Lee
b
, Insung S. Choi
b
, Dae Won Moon
a,
*

a
Nano-Surface Group, Korea Research Institute of Standards and Science (KRISS),
P.O.Box 102, Daejeon 305-600, Korea
b
Department of Chemistry and School of Molecular Science (BK21),
Korea Advanced Institute of Science and Technology (KAIST), Daejeon 305-701, Korea
dwmoon@kriss.re.kr


Micropatterns of spores displaying heterologous proteins have been recently generated by using
microcontact printing (CP) of the biotin-streptavidin system [1]. To see micropatterns of proteins
and spores, bulky fluorophores of tetramethylrhodamine
isothiocyanate (TRITC) and enhanced green fluorescent protein (EGFP) were labeled to
streptavidins and spores, respectively. For the present work, we will show dye label-free chemical
images of micropatterns of proteins and human epidermoid carcinoma A431 cells by using the
cluster primary ion beam in the ToF-SIMS technique. Our discussion of the usefulness of cluster
analysis ion beam will be based on comparitive experiments using Ga
+
, Au
+
and Au
3
+
primary
beams.


[1] T.J. Park, K.-B. Lee, S.J. Lee, J.P. Park, Z.-W. Lee, S.Y. Lee, I.S. Choi, J. Am. Chem. Soc. 126 (2004) 10512-
10513.
BTC-O-We-C03
184
Bioactive Molecules for Biomimetic Materials: Quantification of RGD
Peptide Sequences by ToF-S-SIMS Analysis

M.C. Durrieu
1
, S. Poulin
2,*
, S.Polizu
3
, LH. Yahia
3

1
INSERM

U577 Biomaterials and Tissue Repair , University Victor Segalen Bordeaux 2, 146 rue Lo
Saignat, 33076 Bordeaux Cedex, France. marie-christine.durrieu@bordeaux.inserm.fr
2,*
LASM, cole Polytechnique, C.P. 6079, succ. Centre-ville, Montral, Qubec, H3T 1J4, Canada
3
LIAB, cole Polytechnique, C.P. 6079, succ. Centre-ville, Montral, Qubec, , H3T 1J4, Canada
2,*
suzie.poulin@polymtl.ca


Implantable biomaterials, such as Ti-6Al-4V alloy, are designed to replace a part of the human
body and/or its associated functions. This system, containing the alloy onto which the
osteoprogenitor cells are deposited, is formed through the grafting of linear RGD molecules. A
previous XPS study of these new hybrid materials [1-2] revealed the modified surface at various
steps of the modification process. A quantification of the new bioactive surface was obtained, in
terms of surface coverage and the availability of functional surface groups.
The specific data obtained at the molecular level completes the chemical profile of the newly
modified surface and has permitted us to draw conclusions on its bioactivity. In fact, our
preliminary work proved that the bonding of the fibronectin cell attachment peptide Arginine-
Glycine-Aspartic acid (RGD) to a metallic surface is very successful in promoting the adhesion and
the proliferation of osteoprogenitor cells [1]. However, a fuller understanding of the relationship
between surface coverage and the contribution of each layer is required, in order to optimize the
efficiency of the RGD-modified surface, through optimal RGD bonding. We have used TOF-S-
SIMS analysis of this new surface to study each modification level.
Functional groups for peptide immobilization are required on the metallic surface, and their
presence has been identified by mass spectrum. A relative quantification of immobilized RGD
peptides is obtained by TOF-S-SIMS analysis. Molecular ion imaging informs us of the surface
evolution throughout the modification process and offers a description of each group. A
comparative analysis of the spectra has permitted us to correlate the presence of these species on the
surface with their bioactivities.


References:
[1] M. C.Durrieu,, F. Guillemot, S. Pallu, C. Labrugre, B. Brouillaud, R.Bareille, J. Amde, N. Barthe, M. Dard, and
C. Baquey. 2004. Cyclo-(DfKRG) peptide grafting onto Ti-6Al-4V: physical characterization and interest towards
human osteoprogenitor cells adhesion. Biomaterials, 25 (2004), 4837-4846.
[2] F.Guillemot, M.C. Port, C.Labrugre, and Ch. Baquey, Ti
4+
to Ti
3+
Conversion of TiO
2
Uppermost Layer by Low-
Temperature Vacuum Annealing: Interest for Titanium Biomedical Applications, J. of Colloid and Interface Sciences
255, (2002) 75-78.
BTC-O-We-C04
185
Characterization of PNA Microarrays as a Function of Primary Ion
Species

S. Hellweg
1
,

A. Jakob
2
, J.D. Hoheisel
2
, T. Grehl
3
, and H.F. Arlinghaus
1

1
Physikalisches Institut, Westflische Wilhelms-Universitt Mnster,
Wilhelm-Klemm-Str. 10, D-48149 Mnster, Germany
2
Functional Genome Analysis, Deutsches Krebsforschungszentrum Heidelberg,
Im Neuenheimer Feld 580, D-69120 Heidelberg, Germany
3
ION-TOF GmbH,
Mendelstr. 11, D-48149 Mnster, Germany


TOF-SIMS was used for the detailed examination of the immobilization process of PNA and its
hybridization capability to unlabeled complementary DNA-fragments [1]. PNA sequences were
immobilized onto Si and Au surfaces using different linking mechanisms. Unlabeled single-
stranded DNA was hybridized to these biosensor chips containing both complementary and non-
complementary immobilized PNA sequences. The hybridization of complementary DNA could
readily be identified by detecting phosphate-containing molecules from the DNA backbone such as
PO
3
-
. The achieved discrimination between complementary and non-complementary sequences was
very good.

Using different primary ions, secondary ion yield behavior and fragmentation patterns were
studied. This included monoatomic ions (Ar
+
, Xe
+
, Cs
+
, Au
+
, Bi
+
) as well as polyatomic and cluster
ions (SF
5
+
, Au
x
+
, Bi
x
+
). It was found that using polyatomic and cluster primary ions resulted in a
significantly increased yield of DNA-correlated fragments, resulting in higher signal intensities and
better signal-to-noise ratios.

It can be concluded that TOF-SIMS is undoubtedly a highly useful technique for identifying
unlabeled hybridized DNA on PNA biosensor chips. It may provide a rapid method for DNA
diagnostics and is suitable for studying the complexity of the immobilization and hybridization
processes. With the absence of the labelling procedure and the simultaneous increase of the
phosphate signal as a result of the increased DNA sequence length; this technique comes to be
especially useful for the direct analysis of genomic DNA.


[1] H.F. Arlinghaus, M. Schrder, J.C. Feldner, O. Brandt, J.D. Hoheisel, D. Lipinsky, Appl. Surf. Sci. 231-232, 392-
396 (2004).
BTC-O-We-C05
186
Direct ToF-SIMS Analysis of Thin Layer Chromatography Plates

David Michaelis, Guilin Jiang, Alexander Parent, Thomas Anderson, Paul B. Savage, Matthew R.
Linford*

Department of Chemistry and Biochemistry, Brigham Young University, Provo, UT 84602
mrlinford@chem.byu.edu


It has recently been reported that Direct analysis of thin layer chromatography (TLC) plates with
secondary ion mass spectrometry (SIMS) yields no satisfactory results.[1] In this presentation we
describe a system that does allow direct analysis by ToF-SIMS. These results suggest that certain
classes of solvent developing systems (mobile phases) and analytes on TLC will allow for direct
detection by SIMS, and that there may exist a large number of compounds and conditions for which
direct detection is possible. Thus, these results are relevant to the large communities of organic and
analytical chemists. In particular, we studied the S
N
2 displacement reaction of a high molecular
weight bromide with picolylamine to give an -amino amide product. For this particular reaction
the R
f
value of the starting material and product were identical. In addition, the various developing
agents applied to pure samples of the starting material and product on a TLC plate also showed
them to be identical. Thus, an additional form of analysis that could sense the differences between
the compounds on the TLC plate was needed. Direct analysis by ToF-SIMS (25 keV Ga
+
) showed
the starting material, product, the picolylamine, and the bare substrate to be significantly different.
The reaction progress was also followed by GC-MS, which confirmed reactivity. Further insight
into this problem was provided by a chemometrics analysis of the ToF-SIMS data.


[1] Orinak, A.; Arlinghaus, H.F.; Vering, G.; Orinakova, R.; Hellweg, S. Journal of Chromatography A in press.
BTC-O-We-C06
187
Quantitative analysis of bio-surfaces using ToF-SIMS

Tae Geol Lee
a,
*, Jinmo Kim
b
, Young Pil Kim
c
, Donggeun Jung
b
,
Hak Sung Kim
c
, Dae Won Moon
a


a
Nano-Surface Group, Korea Research Institute of Standards and Science (KRISS),
P.O.Box 102, Daejeon 305-600, Korea
b
Department of Physics, Brain Korea 21 Physics Research Division and Institute of Basic Science,
Sungkyunkwan University, Suwon 440-746, Korea
c
Department of Biological Sciences, Korea Advanced Institute of Science and Technology (KAIST),
Daejeon 305-701, Korea
tglee@kriss.re.kr


To study bio-related surfaces it is essential to know the identification, concentration and spatial
distribution of unknown molecules from sample surfaces. In particular, quantitative analysis of
molecules existing on the surface is crucial for using bio-surfaces for future applications.
Previously, time-of-flight secondary ion mass spectrometry (ToF-SIMS) technique played only an
ancillary role in the quantification analysis of bio-surfaces, mainly due to the complex matrix effect
and low molecular secondary ion efficiency from bio-surfaces. In this talk, I will suggest that the
ToF-SIMS technique can play an important role in the quantitative analysis of bio-surfaces. In our
model systems, the amine density of plasma-polymerized ethylene diamine (PPEDA) surface and
the streptavidin concentration which interacted with the biotin on the dendrimer monolayer were
quantitatively studied by ToF-SIMS in conjunction with UV-visible spectrometry and surface
plasmon resonance (SPR) techniques, respectively.
BTC-O-We-C07
188
Nanoscale Surface of Carbon Nanotube Fibers for Medical
Applications:
Structure and Chemistry Revealed by TOF-SIMS Analysis

S. Polizu
1*
, M. Maugey
2
, S. Poulin
3
, P. Poulin
2
, LHocine Yahia
1

1
LIAB, 2900 douard-Montpetit, cole Polytechnique, Montral, Qubec, Canada, H3T 1J4
2
Centre de Recherche Paul Pascal, CNRS, Bordeaux, France, F-33600
3
LASM, 2900 douard-Montpetit, cole Polytechnique, Montral, Qubec, Canada, H3T 1J4
*
polizu@grbb.polymtl.ca


The aim of our work is to provide, for the first time, nanoscale information about the surface chemistry
and structure of carbon nanotubes (CNTs) fibers for medical applications. In this study we report on the use
of static TOF-SIMS for surface analysis of carbon nanotube biomaterials. New fibers have been synthesised
by using a particle spinning process (PCS) consisting in the injection of aqueous CNT suspension in a
flowing coagulating bath, constituted from polyvinyl alcohol polymer [1]. The PCS ensures the
interconnection of the polymer chains and CNTs into fibers with variable length and diameter ranging from
50 to 70 m. Moreover, the presence of a copolymer in CNTs dispersion strengthens this network effect. In
fact, polylactic-co-glycolic acid copolymers, with two different molecular weights, are added in order to
obtain a new biocompatible biomaterial, resulting in two different formulations [2]. The surface properties of
this hybrid system guarantee the biocompatible response. A detailed analysis of three components reflects
the range of different types of formulation and reveals the chemical homogeneity of the surface. We report
on the potential of TOF-SIMS spectroscopy for the molecular identification of each component and their
different proportions in new fibers, as well as the significant role for TOF-SIMS imaging in furnishing
chemical maps. The chemical composition of the surface is evaluated through spectroscopy. Once the
specific peaks in the spectrum are evaluated for chemical information, imaging is obtained through
diagnostic ions, by mapping their distributions. The TOF-SIMS data are obtained from only 0.5 nm from the
surface and provide information about fiber structure. The complementary information sustained by SIMS
imaging contributes to elucidate the role of copolymer in the hybrid structure of new fibers. Hence, we are
able to establish the relative contribution of each of the three components from a chemical and a structural
point of view and thus, to predict the biocompatibility response.


References:
[1] B. Vigolo, A. Pnicaud, C. Coulon, C. Sauder, R. Pailler, C. Journet, P. Bernier, P. Poulin, Macroscopic Fibers
and Ribbons of oriented Carbone nanotubes, Science, 2000, Nov. 17, 290, 1331-1334.
[2] S. Polizu, M. Maugey, P. Poulin, LHocine Yahia, Carbon Nanotubes based Biomaterials: Biocompatible
Hybrid Fibers, In preparation

BTC-O-We-C08
189
ToF-SIMS imaging of gradient polyethylene surface with
biofunctional groups

Tae Geol Lee
a
, Hyun Kyong Shon
a
, Moon Suk Kim
b
, Hai Bang Lee
b
, Dae Won Moon
a,
*

a
Nano-Surface Group, Korea Research Institute of Standards and Science (KRISS),
P.O.Box 102, Daejeon 305-600, Korea
b
Nanobiomaterials Laboratory, Korea Research Institute of Chemical Technology (KRICT),
P.O.Box 107, Daejeon 305-600, Korea
dwmoon@kriss.re.kr


Gradient streptavidin-adsorbed polyethylene (PE) surfaces have been recently generated from a
gradient PE surface by using successive reactions of polyethylenimine (PEI), biotin, and
streptavidin [1]. Bulky fluorophore of FITC was labelled to the streptavidin to obtain gradient
fluorescent images. For this work, the ToF-SIMS imaging technique was used to obtain dye label-
free chemical images of gradient PE and its biofunctionalized surfaces. PEI reagents with varying
molecular weights and folate molecules, which are able to react with tumor cells, are successively
reacted with a gradient PE surface and examined using ToF-SIMS.


[1] M.S. Kim, K.S. Seo, G. Khang, H.B. Lee, Bioconjugate Chem., 16 (2005) 245-249.

BTC-O-We-C09
190
Studies by imaging TOF-SIMS of bone mineralization on porous
titanium implants after one week in bone

Cecilia Eriksson
1
, Ulf Bexell
2
, Katrin Brner
1
, Hkan Nygren
1


1
Department of Anatomy and Cell Biology, University of Gteborg, Gteborg, Sweden
2
Department of Materials Science, University of Dalarna, Borlnge, Sweden
E-mail: cecilia.eriksson@anatcell.gu.se


A clinically successful treatment of bone defects is to implant titanium in bone. The mechanism behind
bone healing around implants is not fully understood. One question, which this abstract deals with, is
whether the implant surface is mineralized prior to the surrounding bone or the other way around. Another
question, also dealt with here, is how implant porosity influence mineralization and bone formation.
Bone mineralization was studied by imaging TOF-SIMS. Titanium discs (1.0 mm thick, 2.5 mm in
diameter) were made porous through anodic oxidation. 6 different surfaces were developed with different
porosity. Two of these are presented in more detail, since they represent two extremes; surface A had a high
porosity (ca 20%) with an even pore distribution, while on surface B pores were scarce and unevenly
distributed. The discs were implanted in rat tibia for 1 week. The animals were then sacrificed and the discs
were placed in absolute ethanol at 20
o
C. The samples were warmed to room temperature, dried and
analysed in a TOF-SIMS instrument (PHI 2100 TRIFT II CE), equipped with a gallium liquid metal ion gun.
The samples were sputtered at 3kV in order to remove organic material. Positive mass spectra were recorded
and the ion profiles of the surfaces were imaged. Bone from the implant site was histologically prepared and
was investigated microscopically. To evaluate bone formation around the implants the contact between bone
and implant was calculated.
The results showed that Ca
2+
and CaOH were detected on all surfaces after 1 implantation week. These
ions are characteristic for hydroxyapatite as seen in spectra from reference samples (tooth) of the mineral.
The normalization images informs about the proportion of CaOH signal distribution to the appropriate Ti
signal. A strong normalization signal points to a predominant part of the organic compound CaOH in relation
to Ti. As can be seen in figure 1 surface A was more mineralized than surface B. Of all 6 surfaces surface A
had the third thickest coating of minerals, while surface B was the least mineralized surface.
All surfaces had contact with bone after 1 week. Surface A was the only surface that differed significantly
from a smooth implant control and it also had a significantly higher contact with bone than surface B.
In conclusion the results show that implant porosity influences both mineralization and bone formation. A
clear correlation between the two processes was not found, since the best mineralized surface was not the
surface with the best bone contact. The results indicate that bone forms in the tissue around the implant
before the implant surface is mineralized. The methods used are suitable tools for investigation of initial
healing around implant materials.
Figure 1
Ca CaOH Ti Normalization
A

B


DIS-I-Th-A01
191
Molecule Specific Imaging and Analysis in Biology: What are the
Challenges and The Important Applications

Andrew G. Ewing*

101 Chemisty B uilding
Penn State University
University Park, PA 16802
U.S.A.
age@psu.edu


It is becoming clear that mass spectrometry is a powerful tool for the analysis and imaging of
complex organic and biological systems. The discussion session "Meeting the Challenge of
Molecule Specific Analysis and Imaging in Organic and Bio-Systems" will attempt to illustrate the
challenges to be met in mass spectral imaging and analysis of biological samples. Some of these
challenges will be discussed here including the issues of sensitivity needed to obtain high resolution
images at the cellular and subcellular level, information that can be obtained with alternative
techniques and where will they be better vs. when SIMS will be better suited to the need, and finally
the need for depth profiling and mechanisms to achieve this goal for cellular samples.

There are a myriad of biological applications that mass spectrometric imaging can be used for in
biology. Nowhere is this more important that in small samples of tissue, single cells, and sub-
cellular organelles. Cell membranes are among the most poorly understood structures of cells as the
phospholipids, steroids, glycans, glycolipids, and glycoproteins that make up much of the
membrane structure are difficult to detect by most techniques. In addition, the chemical diversity of
the lipids alone is enormous with hundreds of permutations of the aliphatic tail groups possible and,
when the high variability of glycosylation is added, this becomes a problem of extreme complexity.
Mass spectrometry provides potentially great mass resolution and high detectability, but this
technique has been limited traditionally in its spatial resolution. Advances in mass spectral imaging
techniques developed as well as techniques on the horizon show promise in this area - especially in
analysis of inorganic ions, phospholipids, and vitamin A. Inorganic ions have been imaged in cells
with high success, phospholipids have been imaged with success in specific applications and these
techniques are under constant development, but small molecules have not been explored heavily to
date, Biologists of many ilk would welcome methods to spatially resolve and determine
concentration of molecules like cyclic AMP, inositol, glucose, ATP, thioesters, and small drugs
molecules (i.e. cancer drugs) to name a few. It would also be extremely interesting to have the
ability to image small transmitters in vesicles and the molecular machinery inside the nucleus,
mitochondria, golgi and endoplasmic reticulum. These are lofty goals, but mass spectrometry
provides a promise of selectivity, sensitivity, and spatial resolution to obtain many of the answers to
key questions in cell biology. Increased sensitivity and the resulting increase in spatial resolution,
depth profiling, development of simultaneous complementary techniques, and depth profiling will
all make this a break-through area in the decade to come. A weakness of mass spectral schemes is
that samples must be examined in vacuum and, hence, a final challenge is to develop schemes to
capture temporal snapshots of events taking place in a cell.
DIS-O-Th-A02
192
Why dont biologists use SIMS

R.M.A. Heeren, L.A. McDonnell, S. Luxembourg, A.F.M. Altelaar and S.R. Piersma

FOM-Institute for Atomic and Molecular Physics,
Kruislaan 407 , 1098 SJ Amsterdam, The Netherlands.


Secondary ion Mass Spectrometry is commonly used to study many different types of complex
surfaces. Yet, unlike other types of mass spectrometry, such as MALDI and ESI-MS, SIMS has not
made a significant impact in biological or biomedical research. The key features of the technique,
high spatial resolution, down to 50 nm, ToF-ms offering the promise of high mass analysis, its
surface sensitivity and the high scan rates seem to match ideally with several questions posed at the
cellular level. To this date, SIMS has had only limited success in the biological arena. Why is this
and what is needed to change this? This discussion paper will critically review the advances and the
usefulness of SIMS in biomedical research and compare it to other approaches that offer spatially
resolved molecular information available to a researcher with a biological interest. We will
demonstrate that the type of information generated by the various incarnations of SIMS is strongly
dependent on sample preparation and surface condition and is only poorly understood. Modern
approaches such as the cluster gun developments, ME-SIMS and MALDI stigmatic imaging on a
SIMS instrument might change the perception of SIMS being a tool for semiconductor
manufacturers and physicists, and might persuade biologists to use these innovative mass
spectrometric imaging tools.

DIS-O-Th-A03
193
Improvements in SIMS continue. Is the end in sight?

Nicholas Winograd
a
, Zbigniew Postawa
b
, Juan Cheng
a
,
Christopher Szakal
a
, Joseph Kozole
a,
Barbara J. Garrison
a


a
Department of Chemistry, Penn State University, University Park, PA 16802
b
Smoluchowski Institute of Physics, Jagiellonian University, Krakow, Poland, Department of Chemistry


Cluster ion bombardment is at the forefront of current ToF-SIMS research, particularly
when examining the feasibility of molecular depth profiling and three-dimensional imaging
applications. It has become increasingly clear that secondary ion emission after cluster projectile
impact results from a radically different sputtering mechanism than the linear collision cascades that
dominate after atomic ion bombardment. The new physics involved with cluster ion impacts
dramatically change the traditional approaches toward sample analysis with the SIMS technique.
Several new ion bombardment properties have emerged from experimental and theoretical work
involving cluster ions such as Au
3
+
, Bi
3
+
, SF
5
+
, and C
60
+
- all of which are commercially available
ion sources. These new properties lead to new rules for traditional static SIMS experiments,
provoking new methodologies, and introducing new applications especially where high mass
sensitivity and high-resolution imaging of organic and biological materials are necessary.

This paper aims to elucidate recent experimental and theoretical work on these new cluster ion
properties and offers insights into how these special properties can be used for future experiments
and applications.

DIS-O-Th-A04
194
ToF-SIMS analysis of bio-systems - Are polyatomic primary ions the
solution?

Emrys A. Jones
a
, John S. Fletcher
a
, Charlotte E. Thompson
a
, Dean A. Jackson
b
,
Nicholas P. Lockyer
a
, John C. Vickerman
a
,

a
Surface Analysis Research Centre, School of Chemical Engineering and Analytical Science
University of Manchester. Manchester. M60 1QD. UK
b
Faculty of Life Sciences,University of Manchester. Manchester. M60 1QD. UK
John.Vickerman@Manchester.ac.uk


We discuss the potential of cluster ion beams for overcoming difficulties experienced within
molecular analysis in conventional Static SIMS. Consideration of secondary ion yield, surface
damage and molecular depth profiling is included. Examples of the greatly increased secondary ion
yields from real world samples such as bacterial membranes are illustrated, the increase in
information then benefiting multivariate analysis techniques such as principle component analysis
(PCA). The increased efficiency of secondary ion formation with cluster beams, in conjunction with
the reduced subsurface damage associated with C60 bombardment is exemplified using a depth
profile through a phospholipid layer, where molecular information is obtained even following doses
of 2 1015 ions/cm2. This is developed further to the identification of molecular ions from the
interior of etched cells. Challenges that cannot be solved solely by increased secondary ion yields
and low sample damage have been considered and complications due to the influence of matrix
effects along with the effect of salt concentration on the fate of molecular signals in depth profiles
of biomaterials have been investigated.
DIS-O-Th-A05
195
Information from Complexity: Challenges of TOF-SIMS Data
Interpretation

Prof David Castner*, Daniel J. Graham

University of Washington


TOF-SIMS data is complex. This is true even of the simplest systems. Yet it is within this
complexity that information about sample composition, molecular orientation, surface order,
chemical bonding, sample purity, etc. is contained. The challenge is how to easily extract this
information from the spectra. Fortunately multivariate analysis (MVA) has shown promise in
taming the complexity challenges presented by TOF-SIMS spectra. TOF-SIMS data is well suited
for this type of analytical methodology since the spectra generated are inherently multivariate.
Multiple peaks are generated from the same surface molecules, and their relative yields are often
interrelated. MVA methods allow utilization of the entire spectrum to determine which peaks
correlate with various surface treatments or chemistry changes. The success of MVA methods such
as principal components analysis (PCA) and partial least squares (PLS) has lead to a great increase
in the interest of MVA in TOF-SIMS data processing. Nevertheless, we have only begun exploring
the capabilities of what methods such as PCA and PLS can do, and possibly more importantly, no
standards have been established for data preprocessing before these methods are applied. To realize
the full power of these methods we will need to understand better what data to use to answer a
given question, how to optimally process the data before applying MVA and how to correctly
interpret the outcomes from the analysis. Even with these caveats to MVA, PCA and PLS have
shown great success in the analysis of self-assembled monolayers, proteins, polymers, and extra
cellular matrix materials. PCA has also enabled accelerated analysis and interpretation of TOF-
SIMS imaging data sets that present an even more complexity due to their large size and low signal
to noise ratios.
Though much has been done to improve the methodologies of TOF-SIMS data processing and
analysis, there are still many challenges that stand between the complexities of the TOF-SIMS
fragmentation pattern and the information contained therein. To meet these challenges MVA
methods have been explored. For example, our group has explored how using model systems in
conjunction with PCA can extract information about the TOF-SIMS fragmentation process. PCA
has been applied to the identification of proteins based solely on the fragmentation pattern of the
amino acids. PLS has been applied to the quantification of binary and ternary protein mixtures.
Image processing methods and PCA are being explored to improve spatial resolution and species
identification in TOF-SIMS imaging.
The challenges of TOF-SIMS data interpretation will only get more complex. This is already
being demonstrated with the analysis of cells, tissues and the increasingly complex engineered
surfaces used in research and development today. These developments will increase the need for
well-controlled MVA methodologies. Standards need to be established in the proper application of
MVA methods to TOF-SIMS data. Model systems need to be studied to generate databases of
peaks related to the various surface components of cells and tissues. The fragmentation process of
the various ion beams used today need to be more fully understood. Moving forward in these areas
will aide in unlocking the information encoded in the complexities of TOF-SIMS spectra.
DIS-O-Th-A06
196
Rapid discrimination of the causal agents of urinary tract infection
using ToF-SIMS with chemometric cluster analysis

John S. Fletcher
a
, Alexander Henderson
a
, Roger M. Jarvis
b
, Nicholas P. Lockyer
a
, John C.
Vickerman
a
, Royston Goodacre
b


a
Surface Analysis Research Centre, School of Chemical Engineering and Analytical Science, The University of
Manchester, Manchester M60 1QD, UK
b
School of Chemistry, The University of Manchester, Manchester M60 1QD, UK


Advances in time of flight secondary ion mass spectrometry (ToF-SIMS) have enabled this
technique to become a powerful tool for the analysis of biological samples. Such samples are often
very complex and as a result full interpretation of the acquired data can be extremely difficult. To
simplify the interpretation of these information rich data, the use of chemometric techniques is
becoming widespread in the ToF-SIMS community. Here we discuss the application of principal
components - discriminant function analysis (PC-DFA) to the separation and classification of a
number of bacterial samples that are known to be major causal agents of urinary tract infection. A
large data set has been generated using three biological replicates of each isolate and three machine
replicates were acquired from each biological replicate. Ordination plots generated using the PC-
DFA are presented demonstrating strain level discrimination of the bacteria. The results are
discussed in terms of biological differences between certain species and with reference to FT-IR,
Raman spectroscopy and pyrolysis mass spectrometric studies of similar samples.

DIS-O-Th-A07
197
Multivariate Statistical Image Processing for Molecular Specific
Imaging in Organic and Bio-systems

Dr Bonnie Tyler

University of Utah


Although TOF-SIMS images contain a huge array of data on identity and distribution of chemical
species on a surface, processing these TOF-SIMS images to obtain clear contrast between the
chemically distinct regions, distinguish between chemical and topographic effects and identify
chemical species can be a formidable challenge. These goals are further complicated by the
extremely low signal to noise ratio typical in images, difficulties in isolating pure component
spectra and interference from topographic and matrix effects. Identifying compounds and
distinguishing between chemical and topographical features, require simultaneous analysis of
multiple ion images. As a result multivariate statistical techniques, including principal components
analysis (PCA) , multivariate curve resolution (MCR), maximum auto-correlation factors (MAF),
neural networks (NN) and mixture models (MM) can be powerful tools for exploring the spectral
images. Because some of these methods are strongly impacted by scaling, we have also explored a
variety of scaling methods including mean centering, auto scaling, mean scaling, and statistical
scaling. We have compared the utility of these techniques on a variety of samples including
biofilms, protein films, surfactants, and atmospheric particulate matter. PCA, MCR and MAF all
show potential for separating chemical effects from topographical effects with differing degrees of
success. MAF, which includes information on the nearest neighbors to each pixel, shows clear
advantages over PCA and MCR for reducing noise and identifying sparse components in the matrix.
However, MCR is better suited to identification of unknown compounds. Depending on the
assumptions used, neural networks and mixture models can be formulated either for sensitive or
insensitive to topographic effects. Mixture models, which allow the user to input a prior knowledge
about the statistical nature of noise in the data, can be particular powerful for interpreting low signal
to noise ratio images. If contextual information is included in the mixture model, segmentation of
SIMS images, that is, identification of chemically distinct regions within an image, can be readily
performed with a high degree of accuracy. The currently employed mixture models, however, are
only appropriate for sample images that contain only pure chemical regions and can give misleading
results when mixtures are present on the surface. The methods have been tested on both synthetic
images and real images of organic and biological specimens. A quantitative comparison of these
methods will be presented including comparisons on enhancement of image contrast, enhancement
of image resolution, isolation of pure component spectra, and region identification. No single
method proves superior for all of these objectives so we have developed strategies for combining
these methods to obtain optimal results.
DIS-O-Th-A08
198
Spatial Statistics and Interpolation Methods for TOF SIMS Imaging

Dr Joseph Gardella
a
, Tammy M. Milillo
b



a
University at Buffalo, State University of New York (SUNY)
b
Chemistry Department, SUNY Buffalo


Geographic information is analyzed using two and three dimensional spatial statistical methods
focused on interpolating spatial distributions1. Methods such as Kriging and inverse squared
distance weighting are often used to develop spatial distributions of common surface features
distributed over geographic distances of meters, kilometers, miles, etc1. Geospatial statistics have
not been widely applied to spatial chemical distributions of microscopic dimensions. In this paper,
we compare ordinary Kriging and inverse squared distance weighting for the analysis of ToF-SIMS
images of surface treated polymers2. By selectively and randomly eliminating pixels from the
original image, we evaluate the accuracy of images reconstructed from 1%, 0.1% and 0.01% of the
original dataset. We also discuss the use of CoKriging methods for surface and subsurface (in-
depth) distributions. Accurate image reconstruction from small data sets can provide added speed
to ToF-SIMS image collection and analysis, a potential advantage for on-line ToF-SIMS analysis in
the semiconductor industry.
Kriging is an interpolation method that can be applied to estimate concentration values at points
where no sampling has taken place. The values produced are a weighted linear combination of the
available sample points1. Characteristics of an ordinary kriging model consist of having a mean
error equal to zero and minimal error variance. These two criteria make ordinary kriging an
unbiased model. Kriging requires a variogram analysis of the distances between points. A
semivariogram or variogram model is a graphic representation of the similarity or autocorrelation
present in a dataset as a function of distance.
Inverse Distance Weighted, or IDW, is an additional interpolation method used in geostatistics
This interpolation method assigns weights inversely proportional to the distance that a particular
sample is separated from the point of estimation. Typically, inverse squared distance is used,
meaning that the weight assigned to a particular point diminishes by the square of the distance.
This approach is the most effective for accurately modeling the spatial autocorrelation because only
the points that are closest to the point of estimation will exert influence in the prediction. Using the
squared distance also reduces the number of calculations making this approach effective for
reducing the amount of computation needed to produce an estimate. It is also an exact interpolator,
which means theoretically it should produce the exact value given at a sample point. The IDW
method does not rely on a variogram model. It uses only the values of the known sample points to
estimate unknown points of interest.
Images from patterned fluoropolymers were prepared using TEM grids as masks for plasma
treatment and then treated areas were refunctionalized with siloxane functionality via a chemical
coupling process, following procedures developed in our laboratory2. ToF-SIMS images were
collected and processed using typical fluoropolymer ions for untreated (masked) regions and
siloxane related ions for the treated regions.


1.Isaak, E. H.; Srivastava, R. M., An Introduction to Applied Geostatistics. Oxford University Press: New York, 1989
2.Vargo, T. G.; Patrick M, T.; Gerenser, L. J.; Valentini, R. F.; Aebischer, P.; Hook, D. J.; Gardella, J. A., Monolayer
Chemical Lithography and Characterization of Fluoropolymer Films. Langmuir 1992, 8, 130-134
DIS-O-Th-A09
199
Quantitative Imaging of Cells with SIMS Nanoautography with
Stable Isotope Tracers

Claude Lechene, Hugues Francois-Saint-Cyr, Greg McMahon

National Resource for Imaging Mass Spectrometry, Harvard Medical School and Brigham and Womens Hospital,
Cambridge MA USA


The fundamental discovery that proteins in biological tissues turn over was made using a custom-
made mass spectrometer to measure the incorporation into proteins of the stable nitrogen isotope
15N {Schoenheimer, 1942}. 15N was used as a marker of amino acids and was provided in the
mouse diet as 15N-leucine. These seminal studies could not be pursued at the intra-cellular level
because there was no methodology to simultaneously image and quantitate stable isotopes and
because there is no useful radioactive isotope of nitrogen. Microautoradiography, essentially limited
to using 14C or 3H, has a poor lateral resolution, requires long exposure and is not quantitative. We
developed multi-isotope imaging mass spectrometry (MIMS) taking advantage of the high lateral
resolution, the high mass resolution at high transmission and over all the parallel detection of the
NanoSims50 to localize the presence and measure the relative abundance of molecules labelled with
stable isotopes in subcellular compartments. We will demonstrate the use of MIMS for the
quantitative imaging of protein renewal in subcellular structures of the cochlea and of the kidney
using leucine labelled with the stable isotope 15N, and of fatty acids transport after culturing
adipocytes in the presence of 13C oleic acid. We will show the colocalization of DNA and RNA by
mapping together the 81Br signal of the thymidine analog BrdU and the 15N signal of the RNA
precursor 15N-uridine, the fixation of nitrogen in bacteria, and the relative abundance of C, N and P
at the edge of lamellipodia in mammalian cells. With MIMS we can perform a kind of generalized
autoradiography, a nanoautography, using one or several of the large number of stable isotopes as
molecular tags that may be located and quantitated in submicronic biological tissues compartments.


Schoenheimer R: The dynamic state of body constituents. Harvard University Press, Cambridge, MA; 1942.



DIS-O-Th-A10
200
High resolution SIMS imaging of cations in mammalian cell mitosis,
and in Drosophila polytene chromosomes

R. Levi-Setti
a
, K.L. Gavrilov
a
, Mary Beth Neilly
b
, R. Strick
c
and P.L. Strissel
c

a
Enrico Fermi Institute and Department of Physics, University of Chicago,
Chicago, Illinois 60637, USA.
email address: riccardo@uchicago.edu
b
Dept. of Medicine, Hematology/Oncology Section, University of Chicago,
Chicago, Illinois 60637, USA
c
Dept. of Medicine, University of Erlangen-Nuernberg, 91054 Erlangen, Germany


Recent investigations using the University of Chicago high resolution scanning ion microprobe
(UC-SIM), have focused on the cation composition of mammalian cells and chromosomes
throughout the cell cycle [1]. From cation-chromosome depletion studies [1], Ca and Mg appear to
be important for chromosome condensation. In this report, we will present detailed observations of
cations (Ca, Mg, Na, K) in the chromosomes of Indian muntjac deer (IM) fibroblasts from prophase
through anaphase. Using precise cell synchronization procedures, we have obtained high-density
distributions of mitotic IM fibroblasts at narrow time intervals in the mitotic cycle beyond the
G2M-border. This allows the SIMS observation of mitotic cells (prepared by standard cytogenetic
protocols), at different stages of mitosis within the same UC-SIM field of view. Consequently,
subtle differences in cation contents between successive stages can be reliably quantified. Steps in
the dynamics of mitosis from metaphase through anaphase, and evidence of the strong association
of Ca with chromosomes are shown in the SIMS Ca maps of Fig. 1 below. In addition, Ca and Mg
SIMS maps will be shown, demonstrating early evolutionary association of these cations with the
polytene chromosomes of Drosophila melanogaster, whose DNA distribution had been previously
studied by BrdU labeling [2]. In conclusion, our results support that, in the evolution from lower
eukaryotes like Drosophila to mammals, cations played a key role in the condensation of
chromosomes during mitosis.


[1], Strick, et al., J. Cell Biology 155 (2001) 899-910.
[2]. Levi-Setti et al., J. Microscopy 175 (1994) 44-53.


DIS-O-Th-A11
201
Specimen Preparation and Calibration for NanoSIMS analysis of
Biological Materials

Chris Grovenor, Kat Smart, Mat Kilburn, Ben Shore
a
, Jon Dilworth
a
, Barry Martin
b
, Chris Hawes
b

and Ros Rickaby
c

Department of Materials, Oxford University, Parks Road, Oxford OX1 3PH, UK
a
Chemistry Research Laboratory, 12 Mansfield Road, Oxford, OX1 3TA, UK
b
Research School of Biological & Molecular Sciences, Oxford Brookes University, Oxford, OX3 0BP, UK
c
Department of Earth Sciences, University of Oxford, Parks Road, OX1 3PR, UK


In order to achieve reliable and reproducible analysis of biological materials by SIMS it is critical
both that the chosen specimen preparation method does not modify substantially the in-vivo
chemistry that is the focus of the study and that any chemical information obtained can be calibrated
accurately by selection of appropriate standards. In Oxford we have been working with our new
Cameca NanoSIMS50 on two very distinct classes of biological materials; the first where the
sample preparation problems are relatively undemanding human hair but calibration for trace
metal analysis is a critical issue, and the second human ovarian cancer cells (IGROV) prepared to
investigate uptake and trafficking of radiopharmeceutical compounds where reliable specimen
preparation by rapid freezing, fracturing and controlled drying to preserve the distribution of
diffusible species is the first and most demanding requirement. We will discuss our recent progress
in both these areas, showing examples of successful (and less successful) specimen preparation and
analysis protocols.
DIS-O-Th-A12
202
CELLULAR LOCALIZATION OF A 15N LABELLED PEPTIDIC
VECTOR USING NANOSIMS IMAGING

Dr Jean-Luc Guerquin-Kern*
ab
, Winfried Roemer
c
, Ludger Johannes
c
, Patricia Duchambon
b
,
Danile Carrez
b
, Ting-Di Wu
b


a
Institut Curie-Recherche
b
Unit d'Imagerie Intgrative, Institut Curie
c
UMR 144 CNRS/ Institut Curie


Characterizing the molecular mechanisms that control entry pathways into cells (immune system,
cancer cells, etc.) using of this knowledge to optimize and develop innovative therapeutic anti-
cancer approaches represents challenging aim. Light imaging methods are conventionally used to
differentiate molecules of interest and intracellular compartments. However, this supposes the
introduction of bulky molecular tags (fluorophore ) that conjugate to specific components. These
tags may change the physical properties of the components they label. We propose to use dynamic
SIMS imaging to follow the internalization and the intracellular localization of a 15N labelled
peptidic vector (B sub-unit of Shiga toxin1,2). We are using a Nanosims 50 microprobe
(CAMECA) that is able to measure several ion masses simultaneously and to provide high spatial
resolution and high mass resolution at high transmission3.
To produce the 15N labelled B sub-unit (STxB ), the cDNA of the STxB was sub cloned into an
expression vector and transferred into E.Coli (BL21DE3). 15N-labelled peptide was obtained using
15NH4Cl2 (1 g/l) in the culture medium as the sole source of nitrogen. The induction step with
0,1mM IPTG was prolonged to 18 h and finally the protein was purified4. This labelled vector was
incubated with Hela cells. Cell cultures were fixed at various times after incubation to follow the
internalization process. After chemical fixation, the samples were post fixed with osmium,
dehydrated and embedded in Spurr resin. Sections 100nm thick were placed on carbon coated TEM
grids. They were first observed by TEM microscopy and then analyzed by SIMS imaging using a
caesium primary ion beam focused to about 100 nm and scanned over a field between 30 to10 m.
Just after incubation (t = 0), the 15N enrichment is mainly located on the cell membrane
corresponding to the binding of the vector of the Gb3 receptor. With time, we observed the
internalization of the vector, which is mainly concentrated within a cellular compartment after
40min. By correlative imaging with TEM, we can associate this compartment with the Golgi region.
These results highlight the effectiveness of SIMS in the study of the mechanisms of molecule
internalization particularly if 15N labelled STxB is used simultaneously with various molecules
bearing a specific isotope (receptor, "hypothetic transporter", etc ..).


References:
[1] O'Brien, A. D., Tesh, V. L., Donohue-Rolfe, A., Jackson, M. P., Olsnes, S., Sandvig, K., Lindberg, A. A., and
Keusch, G. T. (1992). Shiga toxin: biochemistry, genetics, mode of action, and role in pathogenesis. Curr Top
Microbiol Immunol 180, 65-94.
[2] Johannes, L., and Goud, B. (1998). Surfing on a retrograde wave: how does Shiga toxin reach the endoplasmic
reticulum? Trends Cell Biol 8, 158-162.
[3] Slodzian, G., Daigne, B., Girard, F., and Hillion, F., Scanning secondary ion analytical microscopy with prallel
detection. Biol. Cell 74 (1992), 43-50.
[4] Mallard, F., and Johannes, L. (2002). Shiga toxin B-subunit as a tool to study retrograde transport. in: Methods Mol
Med - Shiga Toxin Methods and Protocols (Edited by: D Philpott and F Ebel), Vol. 73, Chapter 17, 209-220.

DIS-O-Th-A13
203
Label- and amplification-free genotyping of genomic DNA

Dr Jrg Hoheisel

German Cancer Research Centre


In the Division of Functional Genome Analysis, we are developing technologies for the
identification, description and evaluation of cellular functions and their regulation by producing and
processing biological information on a genomic scale. One emphasis in our efforts is work on
DNA-, protein- and peptide-microarrays. Many chemical and biophysical issues are being
addressed as part of this work in an attempt to understand the underlying procedural aspects,
thereby eventually establishing superior analysis procedures. Based on the technical advances, the
resulting methods are immediately put to the test in actual applications.
With respect to analysing as many sequence variations in parallel as possible potentially
extending the range to the analysis of the entire human genome in a single experiment we work
with peptide nucleic acids (PNAs). The structural difference between PNA used as probe on the
array and a nucleic acid target permits a direct detection of the bound nucleic acid by a simple
process that is much more sensitive than current techniques. Upon hybridisation of a DNA or RNA
sample to a PNA-array, the phosphates of the DNA/RNA can be utilised as an intrinsic label for
detection by secondary ion mass spectrometry (SIMS); PNA molecules are lacking phosphate
groups entirely. In an ongoing collaboration with Heinrich Arlinghaus (University of Mnster), we
established the processes for studies of genomic DNA without the need for amplification or
labelling.
Eventually, this method could be well suited for routine applications in areas such as medical
diagnosis. For its simplicity and speed, it should be superior to other processes. Currently, we are
involved in the production of a demonstrator in a collaboration with three company partners.
More information and pdf-files of the publications listed below can be found at:
www.dkfz.de/funct_genome/.


Brandt, O., Feldner, J., Stephan, A., Schrder, M., Schnlzer, M. Arlinghaus, H.F., Hoheisel, J.D. & Jacob, A. (2003).
PNA-microarrays for hybridisation of unlabelled DNA-samples.
Nucleic Acids Res. 31, e119.
Jacob, A., Brandt, O., Wrtz, S., Stephan, A., Schnlzer, M. & Hoheisel, J.D. (2003). Production of PNA-arrays for
nucleic acid detection.
Peptide Nucleic Acids; Protocols and Applications (Nielsen, P.E., ed.), Horizon Bioscience, Wymondham,
261-279.
Jacob, A., Brandt, O., Stephan, A. & Hoheisel, J.D. (2004). PNA Microarrays.
Methods in Molecular Biology (Niemeyer, C., ed.), Humana Press, Totowa, 283-294.
Arlinghaus, H.F., Schrder, M., Feldner, J.C., Brandt, O., Hoheisel, J.D. & Lipinsky, D. (2004). Development of PNA
microarrays for gene diagnostics with TOF-SIMS.
Appl. Surface Sci. 231232, 392396.
Brandt, O. & Hoheisel, J.D. (2004). Peptide nucleic acids on microarrays and other biosensors.
Trends Biotechnol. 22, 617-622.
DIS-O-Th-A14
204
Mass Spectrometric Characterization of Elements and Molecules in
Cell Culture and Tissue

Prof Heinrich Arlinghaus*, Christian Kriegeskotte, Michael Fartmann, Jrg Mller, Dieter
Lipinsky,

Universitt Mnster

The success of anti-cancer therapies such as boron neutron capture therapy as well as other
therapeutic and diagnostic strategies relies on the ability to selectively deliver compounds to target
cells while sparing normal tissue. Thus, it is crucially important to determine the distribution and
up-take of the targeting compounds. For many applications, however, current analytical methods
lack the sensitivity and selectivity necessary to determine the distribution of pharmaceutical ultra-
trace compounds within tissues with subcellular resolution.
We have applied time-of-flight secondary ion mass spectrometry (TOF-SIMS) and laser-
postionization secondary neutral mass spectrometry (Laser-SNMS) to image and quantify targeted
compounds, intrinsic elements and molecules with subcellular resolution in single cells of cell
cultures and tissues. Cancer cells type MeWo were incubated with the boronated compounds BSH
and BPA. The cells were sandwiched between two substrates, cryofixed, freeze-fractured, and
freeze-dried. Furthermore, after injection of BSH and BPA, different types of mouse tissue such as
brain and kidney as well as human tumors were extracted, prepared on a special specimen carrier
and plunged with high velocity into LN2-cooled propane for cryofixation. After trimming, these
tissue blocks were freeze-dried.
In our presentation, we will compare and discuss the advantages and disadvantages of TOF-SIMS
and Laser-SNMS for the analysis of cell cultures and tissues. We will especially discuss various
sample preparation techniques, the influences of the preparation techniques on lateral and mass
resolution, various possibilities for evaluating the structural and chemical integrity of the prepared
samples and for identifying cell structures, problems in quantifying samples and the possibility of
obtaining 3D molecular images of frozen tissues.
Our data will show that both TOF-SIMS and Laser-SNMS are capable for imaging elements and
molecules in cell cultures and tissues. It was found that especially Laser-SNMS is particularly well
suited for identifying specific cell structures and imaging ultra-trace-element concentrations in
tissues.
DIS-O-Th-A15
205
Quantitative analysis of biological membrane composition with high
lateral resolution

Dr Steven Boxer *
a
, Carine Galli Marxer
a
, Mary L Kraft
a
, Simon Fishel
a
, Peter K Weber
b
, Ian D
Hutcheon
b


a
Stanford University
b
Lawrence Livermore National Laboratory


During the past few years, our lab has developed a wide range of methods for patterning lipid
bilayers on solid supports [Accts. Chem. Res. 35, 149 (2002)]. These 2D fluids are a model for
biological membranes and a physical system with unusual properties. Methods have been
developed for controlling the composition of patterned membrane corrals by variations on
microcontact printing and microfluidics. Molecules can be moved around within these fluid
surfaces by a form of 2D electrophoresis.
The planar geometry of supported bilayer systems is ideal for high resolution imaging methods.
We have begun to explore the use of secondary ion mass spectroscopy using the NanoSIMS at the
Lawrence Livermore National Laboratory [Biophys. J., Feb 2005]. Because the NanoSIMS
operates under ultrahigh vacuum, it is necessary to preserve the lateral organization of the
membrane by rapid freezing and freeze-drying. Techniques adopted from the freeze-fracture and
cryoEM literature have been combined to preserve patterned supported bilayer membranes
organized on thin (optimally ~40 ) SiO2 layers on Si wafers. Microcontact printed thin layers (a
few monolayers) of proteins, used for membrane patterning, are readily detected. We find that 4-
fluoro-Phe-substituted proteins can be very sensitively and selectively detected by the F- signal; 4-
F-Phe can often be incorporated into proteins without greatly affecting function. Single lipid
bilayers can be detected by using specific ions, e.g. P-, CD- for deuterated lipid side chains,
13C14N- or 12C15N- with 13C or 15N introduced into the lipid head group, 18O- for cholesterol
on 18O-depleted SiO2. Artificially created composition variations on patterned surfaces can be
quantified by use of different types of internal standards. This is a major challenge and methods are
evolving. Thus, the sensitivity, selectivity and lateral resolution are sufficient to image and quantify
the composition of small domains related to rafts.
DIS-O-Th-A16
206
Imaging lipid distributions in model membranes with selectively
deuterated components using Time of Flight Secondary Ion Mass
Spectrometry (ToF-SIMS)

David Miller*, R.R. Harbottle, F. Possmayer, N.S. McIntyre

The University of Western Ontario


Time of Flight Secondary Ion Mass Spectrometry (ToF-SIMS) provides the capability to image
the distribution of molecular ions and their associated fragments that are emitted from monolayer
films. ToF-SIMS can be applied to the analysis of monolayers of complex lipid mixtures that act as
a model to understand the organization of cell membranes into solid-like domains called lipid rafts.
The ability to determine the molecular distribution of lipids using ToF-SIMS in monolayer films is
also important in studies of the function of pulmonary surfactant. One of the limitations of the use
of ToF-SIMS to studies of complex lipid mixtures found in biological systems, arises from the
similarity of the mass fragments that are emitted from the components of the lipid mixture. The use
of selectively deuterated components in a mixture overcomes this limitation and results in an
unambiguous assignment of specific lipids to particular surface domains. The use of deuterium
labelling to identify specific lipids in a multi-component mixture can be done by the deuteration of
a single lipid or by the addition of more than one lipid with selectively deuterated components.
Lipid identification is successful when the deuterated component is present at low concentrations
within the mixture. The incorporation of deuterium into the lipid chains does not alter the
miscibility or phase behaviour of these systems. The use of deuterium labelling to unambigiously
identify lipids and determine their distribution in monolayer films will be demonstrated using two
important biological systems: lipid rafts and studies of pulmonary surfactant.

DIS-O-Th-A17
207
Localization of lipids in freeze-dried mouse brain sections by imaging
TOF-SIMS

Peter Sjvall
1
, Bjrn Johansson
2
and Jukka Lausmaa
1

1
SP Swedish National Testing and Research Institute. P.O. Box 857, SE-50115 Bors, Sweden
2
Department of Clinical Neuroscience, Karolinska Institutet, SE-17176 Stockholm, Sweden.


The use of TOF-SIMS for organic chemical analysis of biological tissue provides a number of advantages
as compared to other techniques, such as parallel identification and localization of unlabelled substances at
high spatial resolution. Since the TOF-SIMS analysis is made in vacuum, sample preparation procedures that
prevent evaporation of water during analysis are required. Therefore, the integrity of the sample structures
and lateral distributions of the investigated substances throughout the sample preparation steps are important
considerations. In this work, we have studied the distributions of a variety of lipids in freeze-dried mouse
brain sections by TOF-SIMS, using Au3+ as primary ions.
The mouse brains were frozen down to 80 C immediately after dissection. Thin (14 m) tissue sections
were prepared using a cryosectioning device and placed on glass slides. The refrozen samples were
submerged in a 0.15 M NH3HCOO solution during approximately 30 s, for desalting purposes, and then
again refrozen. Immediately before analysis, freeze drying was done by thawing the sample under vacuum
for a period of approximately 1 hour. In order to facilitate the localization of individual cells and subcellular
structures in the tissue sections, some samples were stained with 1% eosin Y in phosphate-buffered saline
(PBS) and destained in PBS only, prior to submersion in NH3HCOO solution. Eosin Y is a Br-containing
substance that provides a pink stain to the cytoplasm.
Positive and negative ion spectra and images were collected using a TOF-SIMS IV instrument (ION-TOF
GmbH) equipped with a Au cluster primary ion source. The Au3+ primary ion current was approximately
0.02 and 0.06 pA in burst alignment mode and bunched mode, respectively, and the size of the analysis area
was varied between 11 x 11 mm2 and 35 x 35 m2. The accumulated ion dose was always kept below 1013
cm-2 and inspection of the signal intensity during the analysis showed a decay of no more than 20%.
The recorded spectra contain peaks that could be identified as molecular ions of a number of different
lipids; cholesterol, phosphatidylinositol (PI) and sulfatide in the negative spectra, and cholesterol and
phosphatidylcholine (PC) in the positive spectra. The identification of the molecular ion peaks was made
possible by comparison with published ESI-MS results and by recording TOF-SIMS reference spectra from
pure lipid samples.
The TOF-SIMS images show differing and characteristic lateral distributions of the investigated lipids in
the brain sections. The results indicate a complementary localization of cholesterol and PC, with a high
cholesterol concentration in white matter regions and a high PC concentration in grey matter regions. The
sulfatide images show inhomogeneous distributions with high signal intensities in the white matter regions
and surrounding areas, in agreement with previous ESI-MS investigations3. The PI images display a
homogeneously distributed signal intensity in the grey matter regions, and a lower signal in the white matter
regions.
Analysis of the eosin Y-stained samples indicate that individual cells can be localized from ion images of
Br and/or quasimolecular ions of eosin Y. Preliminary results show that the cholesterol and PI signal
intensities are somewhat lowered due to the eosin Y staining, while the other lipid distributions are
essentially unaltered.
The different lateral distributions observed for the different lipids in this study, and their agreement with
previous knowledge, clearly indicate that the lipids are not significantly redistributed during the sample
preparation procedure. However, different control experiments using independent analysis techniques are
needed to investigate to what extent the recorded TOF-SIMS images reflect the lipid distributions in the
living tissue. Such studies are in progress.
This research was supported by EC FP6 funding (Contract no. 005045). This publication does not necessarily reflect the
views of the EC. The Community is not liable for any use that may be made of the information contained herein.
3 Han X, et al., J Neurochem. 82, 809 (2002)
DIS-O-Th-A18
208
Localization of Cholesterol in Rat Cerebellum with Imaging TOF-
SIMS. Effect of tissue preparation

Hkan Nygren
1
, Katrin Brner
1
Per Malmberg
1
and Birgit Hagenhoff
2

1. Department of Anatomy and Cell Biology, Gteborg University, Gteborg, Sweden.
2. Tascon Gmbh, Mnster, Germany.


Time-of-flight secondary-ion-mass-spectrometry (TOF-SIMS) was utilized to address the issue
of cholesterol localization in rat cerebellum, a subject not previously investigated.
Rat cerebellum was prepared by three different procedures: 1. Fixation in formaldehyde, freeze-
protection by sucrose, freezing in liquid nitrogen and sectioning by cryoultramicrotomy and drying
at room temperature, or, 2. Freezing in liquid nitrogen, cryostat sectioning at -40
o
C and drying at
room temperature, or, 3. High-pressure freezing, freeze fracturing and freeze drying.
The samples were analyzed in an imaging TOF-SIMS instrument equipped with a Bi
1-7
+
-source.
The cholesterol signal (m/z 369 and 385), showed high intensity in the glial cells in white matter,
and lower intensity in Purkinje cells and in nuclei of granular layer cells. Specimen treated by
procedure 1 showed some signs of diffusion of cholesterol in the tissue. Specimen treated by
procedure 2 showed freeze-damage of the cells. Specimen treated by procedure 3 showed distinct
localization of cholesterol in well preserved tissue. Thus, high pressure freezing and freeze
fracturing was used for further characterization of the distribution of cholesterol in rat cerebellum.


SEM-I-Th-B01
209
Characterizing High- and Low- Dielectric Materials for
Semiconductors: Progress and Challenges

Joe Bennett

ATDF, 2706 Montopolis Drive, Austin, TX 78741, USA
Email: joe.bennett@ATDF.com


The semiconductor industry continues to move away from older, SiO
2
based oxides toward
newer high- and low- materials for use as gate dielectrics and interlayer insulators, respectively.
Many manufacturing facilities already use low- materials in backend, interconnect process steps,
while the introduction of high- materials is progressing slower. The successful integration of these
materials into manufacturing processes can be greatly aided by SIMS, either using static SIMS to
investigate surface chemistry or dynamic SIMS for depth profiling. However, these advanced
materials are often complex mixtures of elements and physical phases that can complicate the
analysis. This presentation will describe some of the current progress in the use of SIMS to
characterize both high- and low- materials, and the challenges that remain.
Examples from our lab will be used to demonstrate that new generation, porous low-k materials
are highly susceptible to charging and that charge compensation is problematic. At sufficient
energies the electron beam used for charge compensation can damage or densify the material. The
issue of quantification will also be discussed and examples of backside SIMS to assess barrier metal
diffusion will be shown. For high-k materials, particularly thin HfO
2
and HfSiO films, examples
from our lab and the literature will be used to show the presence of preferential sputtering that
results in sputter rate variations under both O
2
+
and Cs
+
bombardment. Quantification of major
elements and dopants in HfSiO films is complicated by several factors including the thickness of
the films, preferential sputtering, and ion yield variations. Also, the issue of dopant penetration
through the films will be addressed.
SEM-O-Th-B02
210
Characterization of HfO
2
dielectric films with low energy SIMS

Z. X. Jiang
a, *
, K. Kim
a
, J. Lerma
a
, D. Sieloff
a
, H. Tseng
a
, R. I. Hegde
a
, T. Y. Luo
a
,
J. Y. Yang
b
, D. H. Triyoso
a
, and P. Tobin
a


a
. Advanced Products Research and Development Laboratory, Freescale Semiconductor, Inc., 3501 Ed Bluestein Blvd,
MD K10, Austin, TX, 78721, USA
b
. SOI, Taiwan Semiconductor Manufacturing Company
*: Author correspondence should be made, email: rat853@freescale.com


The advanced process development of MOSFET gate dielectrics has been calling for
inspection techniques that can provide reliable characterization of material composition, thickness,
topography, impurity, and thermal diffusion, etc. SIMS is one of the surface analysis techniques that
have found broad applications in support of high-K dielectric process development. This work
presents some applications of low energy SIMS in examining inter diffusion between HfO
2
and Si
during thermal anneal as well as nitrogen distribution in HfO
2
films with plasma nitridation.

For the analysis of the HfO
2
/Si interface, the artificial tail of the Hf profile inside Si is a
major obstacle to the accuracy of the measured Hf diffusion behavior. Although the tailing can be
reduced by optimizing the angle of incidence of an O
2
+
primary beam, SIMS profiling from the
backside of the sample appeared as the ultimate choice for good accuracy. Meanwhile, for SIMS
analysis of Si up-diffusion into a thin HfO
2
film (e.g., of 3 nm thick), attention should be paid to the
change in morphology of the HfO
2
film during high temperature anneals.

Profiling of shallow nitrogen distribution inside HfO
2
bulk and across the HfO
2
/Si interface
has been a challenge to low-energy SIMS with traditional approaches that used a primary Cs
+
beam
and detected CsN
+
or MN
-
(with M a matrix element) cluster ions. The problems are long surface
transient, pronounced matrix effect across the HfO
2
/Si interface, or poor detection sensitivity due to
mass interference. By using an O
2
+
beam for sputtering, we have reduced the surface transient
substantially. Further improvement was achieved through proper selection of secondary ions.
SEM-O-Th-B03
211
SIMS Analysis for HfSiO(N) thin films

Shiro Miwa * , Susumu Kusanagi, and Hajime Kobayashi.

Materials Analysis Center, Sony EMCS Corp., 4-16-1 Okata, Atsugi, 243-0021, Japan
Email: Shiro.Miwa@jp.sony.com


SIMS is often used to measure the impurities in Hafnium-silicate (HfSiO) thin films and to
observe the Nitrogen profile in Nitrided Hafnium-silicate (HfSiON) thin films to develop high-k
gate dielectrics in advanced CMOS LSIs, however, the N profiles obtained by SIMS are
questionable because they are different from those obtained by techniques such as High-resolution
Rutherford Backscattering Spectrometry and X-ray Photo-electron Spectroscopy. We have
measured the N profile in HfSiON film using both Cs and O2 primary ions with various incidence
angles, and observed an enhancement of the N ion signal at the surface and interface of HfSiON/Si
Cs ions even at an energy of 350eV. We have also found that the enhancement is alleviated with
O2 primary ions. On the other hand, it is important to determine if Hf is diffused into the Si
substrate from HfSiON film during the thermal processes. As Hf is easily moved from the film to
the Si substrate by the probe ion beam, it is difficult to use conventional front-side SIMS to
determine whether there has been diffusion of Hf. To resolve this problem, we have employed
back-side SIMS to obtain the precise Hf distribution near the HfSiON/Si interface..
SEM-O-Th-B04
212
Nitrogen profiling in high-k layers has much to gain from a combined
TOFSIMS-Angle resolved XPS combined study

T. Conard
a
, W. Vandervorst
a
, B. Brijs
a
, P. Mack
b

a
IMEC, SPDT/MCA, Kapeldreef 75, 3001 Leuven, Belgium
b
ThermoElectron, East Grinstead, United Kingdom
Email: tconard@imec.be


With the downscaling of the gate insulator (SiO
2
) in ICs, one expects the thickness for advanced
metal-oxide-semiconductor (MOS) devices, to reach the fundamental limits both from the point of
view of gate leakage current as well as from their intrinsic reliability. A solution to this problem is
the use of dielectric layers with higher electrical permittivity than SiO
2
. Consequently, alternative
gate insulators with high electrical permittivity are currently widely investigated for the future
generations of MOS transistors. The mainstream research concentrates on Hf based oxide systems
but the understanding of the physical properties of these films remains a challenge. Many different
analysis techniques are usually considered for the determination of thickness and/or composition of
thin layers. Among those, one usually finds Ellipsometry, TEM, XPS, TOFSIMS, XRR, ERD, RBS

Recent development in the field of high-k dielectrics include the presence of nitrogen in or
around the stack (interfacial layers and/or nitride capping layer). In this study, both MOCVD and
ALCVD layers will be considered. For the performance of the devices, it is very important to be
able to acquire knowledge of the depth distribution of the nitrogen in the layers with enough
accuracy. This remains a real challenge for SIMS due to varying matrices in which the nitrogen is
distributed. Next to the usual operational mode (Xe, Ar and Cs profiling in positive and negative
detection mode), we investigated to possibility of nitrogen detection through the use of MCs+
clusters while reducing surface Cs concentration at low energy by a Xe-Cs co-sputtering set-up. We
also previously introduced the possibility to detect nitrogen through the detection of CN- clusters by
a carbon flooding scheme. Neither of these studeis was fully conclusive as it was not possible to
predict the real nitrogen profile in high-k layers and thus assess out final measurement accuracy.
In the present study we have combined the TOFSIMS results with advanced ARXPS as well as high
resolution ERDA for obtaining quantitative nitrogen distribution profile and to determine the best
possible measurement scheme for SIMS profiling
SEM-O-Th-B05
213
Back Side SIMS Analysis of Hafnium Silicate

F. A. Stevie
a,
*, C. Gu
a
, J. Bennett
b
, R. Garcia
a
, D. P. Griffis
a


a
Analytical Instrumentation Facility, North Carolina State University
2410 Campus Shore Drive, Raleigh, NC 27695, USA
b
ATDF, 2706 Montopolis Drive, Austin, TX 78741, USA
fred_stevie@ncsu.edu


High-k dielectrics are under study as part of the effort to continually reduce semiconductor
device dimensions and hafnium silicate (HfSi
x
O
y
) is one of the most promising high-k materials. A
requirement of the dielectric is that the constituent elements cannot diffuse into adjacent device
regions during thermal processing. Analysis for inter-diffusion using front side SIMS of high-k
dielectrics has been complicated by matrix and sputtering effects.

Back side analysis was considered as an approach to improve the results obtained from the front
side. Use of a back side procedure that was successful for a copper diffusion study [1] provided a
specimen with excellent flatness. Magnetic Sector (CAMECA IMS-6F) SIMS analysis with low
energy O
2
+
bombardment shows none of the matrix and sputtering effects noted in the front side
data. Sufficient depth resolution was obtained to define the interface between the silicon substrate
and the HfSiO layer. It appears that there is an interfacial layer that may consist of a silicon rich
hafnium silicate. There is no evidence of hafnium diffusion into the silicon substrate.


[1] C. Gu, A. Pivovarov, R. Garcia, F. Stevie, D. Griffis, J. Moran, L. Kulig, and J. F. Richards, J. Vac. Sci. Technol.
B22, 350 (2004)

SEM-O-Th-B06
214
HfSiO(N) composition depth profiling: can we get a quantitative
answer using SIMS?

T. Conard
a
, P. Chen
a
, T.Janssens
a
, B.Brijs
a
, W. Vandervorst
a
, P. Mack
b


a
IMEC, SPDT/MCA, Kapeldreef 75, 3001 Leuven, Belgium
b
ThermoElectron, East Grinstead, United Kingdom
Email: tconard@imec.be


While HfO
2
still attracts most of the attention in the run for the best high-k material for high
performances application, there exists a high interest for Hf silicate material for low power
application in view of its thermal stability and charge trapping behavior. Both ALCVD and
MOCVD can grow silicate layers with varying composition but the composition profiles are very
difficult to determine, mostly for layers a few nm thick and at the interface.
In this study, we investigate a whole range of measurement conditions in order to determine the
best measurement scheme. The experimental conditions investigated here are Xe, Cs and O
2

sputtering at various angles and in both positive and negative polarities.
For thick samples (~10 nm), the actual composition was determined by XPS and high resolution
ERD and calibration curves of SIMS intensities as a function of concentration are easily obtained.
Thus any bulk composition can easily be determined. These curves are however generally highly
non linear due to the composition dependent oxygen preferential sputtering causing a depth
dependent ionization probability change. For thinner samples however, calibration curves are only
partly useful. Again use of complementary method are required to establish the SIMS quantification
accuracy. For very thin layers (< 3-4 nm) this can be doen by combining SIMS with the
composition profile retrieved from Angular Resolved XPS measurement leading to the Best
Known Method for Hf silicate profiling.
In addition to the analysis of the Si-profilethe method will be used to determined the nitrogen
profile in Hf silicates as well.

SEM-O-Th-B07
215
Quantitative Si Depth Profiling of Hf
x
Si
y
O
2
Using
Near Normal Incidence Cs and ERD

Hans Maul, H.-Ulrich Ehrke*, Norbert Loibl

CAMECA GmbH
Bruckmannring 40
85764 Oberschleissheim/Munich, Germany
ulrich.ehrke@cameca.fr


At the SIMS XIV conference a dozen of papers about hafnium depth profiling have been
presented.
A large variety of primary ion beam measuring parameters had been evaluated: O2 from 0 to
glancing incidence, Cs from 45 to glancing incidence, O and CH flooding, Ar, Xe, Ga co-
sputtering. Ionization yield and sputter rate change problems have been found as well as extreme
profile tails.
In this work near normal incidence Cs is used in an attempt to quantitatively depth profile Si in
HfxSiyO2. Si depth profiles of 5nm HfO2/Si and 5nm HfxSiyO2/Si samples measured with 500eV
near normal incidence Cs primary ions show reasonable Si, Hf and O depth profile shapes and
decay length. The Si intensity in the bulk provides a stable reference for precise sample-to-sample
process monitoring.
Comparison of SIMS and high-energy elastic recoil detection (ERD) data shows that the matrix
effect of the Si intensity in the HfSiO2 versus Si bulk amounts to only a factor of 3 at a 1:1 Si/Hf
concentration ratio. The erosion rate for HfO2 and HfxSiyO2 is the same and differs from the Si
bulk erosion rate by only 10%. The ERD data also confirm the enrichment of Si towards the
HfSiO2 surface seen by SIMS.

HfSiO, ERD
0.1%
1.0%
10.0%
100.0%
-2E+16 4E+16 1E+17
depth [at / cm_]
O
Si
Hf
HfSiO, SIMS
1E+3
1E+4
1E+5
1E+6
-1 2 5 8 11 14
apparent depth [nm]
18O
30Si
212HfO2
SEM-O-Th-B08
216
Dynamic SIMS Analysis of Low-k Dielectric Materials

*Ian A Mowat, Xue-Feng Lin, Ming Hong Yang.

810 Kifer Road, Sunnyvale, California, CA 94086, USA
imowat@cea.com


Dynamic SIMS, using magnetic sector and quadrupole instrumentation is a well established tool
for the characterization of dielectric layers in semiconductors. As the silicon-based semiconductor
industry moves towards the use of copper rather than aluminium, there is also a need to use lower k-
dielectric materials to reduce RC delay and also to reduce cross-talk between closely spaced wires.
These new materials pose serious challenges for implementation into semiconductor processes and
also for the analytical scientist doing measurements on them.
The move from inorganic materials such as SiO
2
and silicate glasses to organic or carbon-rich
low-k materials (of both the CVD and spin-on type) is a large change for the SIMS analyst. Low-k
dielectric films from multiple sources can be completely different materials with different analytical
issues. A major SIMS challenge for these materials is coping with their insulating nature and their
fragility. They can be extremely sensitive to electron beam damage during charge neutralization,
leading to difficulties in assigning depth scales and introducing unknown errors to secondary ion
counts and their subsequent conversion to concentrations.
This paper presents details regarding an investigation of the effects of electron and ion beam
exposure on a number of low-k materials. These effects and their impact on SIMS data will be
investigated using XPS, FTIR, AFM and profilometry. Further work investigating other issues will
also be presented, including ion yield variations, quantification, Au-coating and differences between
quadrupole and magnetic sector data. A number of examples will also be shown demonstrating the
quantitation of impurities and composition measurements on low-k dielectric films using various
SIMS operating modes.
SEM-O-Th-B09
217
ToF-SIMS and AFM studies of low-k dielectric etching in
fluorocarbon plasmas

P. Lazzeri
a,*
, X. Hua
b
, G. Oehrlein
b
, E. Iacob
a
, M. Barozzi
a
, M. Bersani
a

and M. Anderle
a


a
ITC-irst, via Sommarive 18, 38050 Povo, Trento, Italy
b
University of Maryland, College Park, MD 20742, USA
* email: plazzeri@itc.it


The introduction of ultra-low k (ULK) materials as silica substitutes in interconnect dielectrics is
extremely challenging. Nanoporous materials are needed to lower the effective k value as much as
possible. Porosity, however, promotes mass transport of contaminants during manufacturing which
affects device reliability and other detrimental phenomena. ToF-SIMS is a valuable tool for the
investigation of such issues, and as an important example of the application of this technique we
examine in this work the etching of several ULK dielectrics (spin-on, PECVD organo-silicates) and
SiO
2
in fluorocarbon plasmas.
These treatments typically modify the dielectrics chemically. In addition, while the etching
regime is known to depend on the plasma composition, we also observed that ULK porosity can
influence the onset of specific reaction pathways.
ToF-SIMS shows clearly that the etching of any dielectric material with reduced porosity is
concomitant with the formation of a surface layer of fluorocarbon compounds. This layer interferes
with the flux of plasma species and reduces the dielectric etching rate. No surface roughness
develops for these conditions, keeping the fluorocarbon coverage constant and this regime
stationary. On the other hand, when porosity exceeds a given threshold the fluorocarbon coverage
can be reduced completely. Direct plasma/dielectric interactions including ion bombardment are
then possible, and cause severe modifications of the pristine ULK, in particular massive diffusion of
plasma-related species into the dielectric bulk and surface coarsening due to anisotropic sputtering.
The investigation of such complex phenomena benefits directly the advancement of state-of-the-
art interconnect technology and for integrating novel materials and processes into ULSI
manufacturing.
SEM-I-Th-B10
218
Ultrashallow depth profiling by using SIMS
and Ion Scattering Spectroscopy

Y. Kataoka

Fujitsu Laboratories Ltd., 10-1 Morinosato-Wakamiya, Atsugi 243-0197, Japan
y.kataoka@jp.fujitsu.com


In recent years there is a growing demand of high depth resolution profiles, for example to
characterize interfaces reactions, multilayer structures in magnetic recording heads, ultra-shallow
dopant distributions and ultra-thin gate dielectrics structures in complimentary metal-oxide
semiconductor (CMOS) devices.
SIMS is widely employed for dopant depth profiling in semiconductor layers and devices,
providing accurate measurements of dopant distributions over concentrations from 1 x 10
13
to 1 x
10
21
cm
-3
. On the other hand, quantitative analysis for thin layer structures is a challenging task
because of matrix effect. Attempts have been made to overcome the matrix effect using the
detection of MCs
+
secondary ions sputtered by bombardment with Cs
+
primary ions [1,2], but basic
studies showed that MCs
+
ion yield depend in a complex manner on the sample material and the
bombardment conditions [3,4]. Even though the severe problems of quantitative analysis by SIMS
with Cs
+
were documented in a recent review [5,6], work on the characterization of thin layers has
been continued using MCs
+
SIMS. In particular, MCs
+
SIMS has been used for nitrogen depth
profiling in gate oxide layers (oxynitride), assuming or claiming that the matrix effect is
sufficiently small. As an alternative approach, SiN
+
and Si
2
N
+
detection using oblique
bombardment of low-energy O
2
+
has been investigated [7,8]. However, accuracy of the depth
profiles is not clear. Recently, another ion bombardment technique, a high-resolution Rutherford
backscattering spectroscopy (HRBS) system using a magnetic spectrometer has been developed,
which enable us to measure depth profiles with monolayer resolution. HRBS is also used for the
characterization of gate dielectrics, oxynitride and high-K layers.
In this study, SIMS and HRBS were employed for depth profiling of nitrogen in ultra thin gate
oxide layers, where nitrogen was incorporated at Si-SiO
2
interfaces and at the SiO
2
top surface,
respectively. SIMS depth profiling was done using the MCs
+
mode and the oblique O
2
+
bombardment mode. The aim of this study was twofold, (i) to explore the depth resolution under the
different ion bombardment techniques, SIMS and HRBS and (ii) to improve the accuracy in ultra-
shallow depth profiling.
From the measured depth profiles, we observed a large difference in the nitrogen distributions at
the SiO
2
top surface. The SiN
+
and Si
2
N
+
signals by the oblique O
2
+
bombardment mode were
extremely sensitive to the nitrogen concentration at the SiO
2
top surface. The profiles measured by
the other techniques showed unreasonable distributions. It is conceivable that a large transient
distorted the surface profile in MCs
+
mode and the damages due to high energies of He
+

bombardment shifted the nitrogen distribution at the top surface.


[1] Y. Gao, J. Appl. Phys. 64 (1988) 3760.
[2] C. W. Magee, W. L. Harrington and E. M. Botnick, Int. J. Mass Spectrom. Ion Phys. 103 (1988) 45.
[3] K. Wittmaack, Nucl. Instrum. Methods Phys. Res. B 64 (1992) 621.
[4] K. Wittmaack, Nucl. Instrum. Methods Phys. Res. B 85 (1994) 374.
[5] Y. Kataoka, M. Shigeno and K. Wittmaack, J. Vac. Sci. Technol. B 20 (2002) 441.
[6] Y. Kataoka, K. Yamazaki, M. Shigeno, Y. Tada and K. Wittmaack, Appl. Surf. Sci. 203/204 (2003) 43.
[7] K. Wittmaack and N. Loibl, in: Proc. of SIMS XIII, p131.
[8] K. Wittmaack and N. Loibl, in: Proc. of SIMS XIIV, p 92.
NAN-I-Th-B11
219
Static SIMS for analysis of molecular conformation and orientation

Patrick Bertrand

PCPM, Universit catholique de Louvain, Croix du Sud 1, B-1348 Louvain-la-Neuve, Belgium
bertrand@pcpm.ucl.ac.be


Owing to the sensitivity of Static SIMS to molecular structures and its selectivity to the
outermost surface layers, this technique is very well suited to gain information about conformation
and orientation of molecules at the surface. The aim of this presentation is to discuss critically and
to illustrate these Static SIMS unique features by reviewing results from different groups including
ours.
First, the SIMS information depth and its dependence on the molecular fragment ion size are
presented in order to justify this surface selectivity. This has been experimentally determined by
looking at the substrate signal attenuation when depositing organic layers in a controlled way on
different materials as it was done with polyelectrolytes and self-assembled monolayers. As
illustrated for polymers, this surface selectivity allowed SIMS to be sensitive to isomer
conformation of end groups, tacticity of macrochains and orientation of mobile pendant groups.
Based on these performances, Static SIMS has been used to study protein adsorption and
highlighted modifications in protein conformation, depending on the substrate hydrophilicity.
Finally, the limitations of Static SIMS analyses are discussed. Indeed, for sample surfaces non-
uniform at a nanoscale, which is beyond the limits of SIMS imaging, the chemical molecular
information cannot be sufficient. It has to be complemented by surface morphology information in
order to get a correct view of the system. This is illustrated by our recent study of very thin layers
of block copolymers and polymer blends, forming nanostructures at the surface.
NAN-O-Th-B12
220
Characterisation of electrospun nanowebs with Static SIMS

P. Van Royen a,*, A.M. dos Santos a, L. Van Vaeck a, E. Schacht b, L. Ruys c

a
Dept. of Chemistry, University of Antwerp, B-2610 Wilrijk, Belgium
b
Dept. of Org. Chem. - Polymer Materials Research Group, B-9000 Gent, Belgium
c
Centexbel-Gent, B-9052 Zwijnaarde, Belgium
* e-mail address: pieter.vanroyen@ua.ac.be


Nanostructured materials with a large surface-to-volume ratio are of much interest to the
scientific and technological community. Electrospinning (ES) is a conceptually simple method to
generate polymer fibres with a diameter in the range of 10-500 nm, packed into a nanofibre web.
Nanofibres with a specifically functionalised surface open new perspectives for a wide range of
materials with novel, unique properties such as scaffolds for tissue engineering, nanosensors,
diagnostics, etc.
The objective is to produce scaffolds based on nanofibres with chemical functionalities optimised
for the interaction with bio-molecules or cells. In contrast to the subsequent surface
functionalisation of electrospun webs, our approach aims at ES of functionalised polymers. Tensio-
active additives are used to steer the ES process and to obtain the desired concentration of
functional groups at the surface. A detailed physical and chemical analysis of the nanofibre web is
mandatory to guide the experimental optimisation of the ES process.
Surface analysis of nanoscale objects is a major challenge. The purpose of this paper is to
demonstrate the feasibility of static SIMS to assist the development of functionalised nanofibre
webs by ES. Specifically, experiments have focused on the poly(-caprolactone), an important
biodegradable polymer. Cetyltrimethylammonium bromide has been used as tensio-active additive.
Additional information on the fibre morphology has been collected using atomic force microscopy
and scanning electron microscopy.
In spite of the small fibre diameter and loose packing, mass spectra have been obtained with high
reproducibility, mass resolution and mass accuracy. Both the polymer and additive has been
detected by intense signals from structural ions. Complementary use of ion images provides support
the interpretation of the mass spectra. The ratio of the additive/polymer signals has been proven to
be useful to follow the physics and chemistry of the ES process.
NAN-O-Th-B13
221
Towards Molecular Electronic Circuitry: Selective Deposition of
Metals on Patterned Self-Assembled Monolayer Surfaces

Chuanzhen Zhou, Gabriella Nagy, Amy V. Walker
*


Department of Chemistry, Washington University in St. Louis, Campus Box 1134,
One Brookings Drive, St. Louis, MO 63130
walker@wustl.edu


We have developed a robust method by which to construct complex two- and three- dimensional
structures based on controlling surface chemistry. This work has important applications in
molecular and organic electronics, sensing, biotechnology, photonics and other technologies. Our
method is extensible to many different types of materials, easily parallelized, affords precise
nanoscale placement and is fully compatible with photolithographic fabrication processes. The
method is based on the deposition of metals on UV-photopatterned self-assembled monolayers
(SAMs). To demonstrate the method we have selectively vapor-deposited Mg on a patterned -CH
3
/
COOH terminated alkanethiolate surface. The deposited metal penetrates through the CH
3
SAM to
the Au/S interface while reacting with the -COOH terminal group and accumulating on top of the
other SAM.
NAN-O-Th-B14
222
Particle-induced desorption from self-assembled monolayers:
signatures of an intricate balance between inter- and intramolecular
interactions resolved by laser-ionization mass spectrometry

E. Vandeweert
*
, F. Vervaecke, S. Wyczawska, P. Lievens, and R.E. Silverans

Laboratorium voor Vaste-Stoffysica en Magnetisme, Katholieke Universiteit Leuven,
Celestijnenlaan 200D, B-3001 Leuven, Belgium.
erno.vandeweert@fys.kuleuven.ac.be


Many emerging applications in nanotechnology rely on the development of well-defined surfaces
functionalized with (sub-)monolayer coverages of complex organic molecules, such as highly
ordered self-assembled monolayers (SAMs) [1]. A particular promising trend is the exploitation of
SAMs as ultrathin resists in combination with electron- or ion-beam lithography.
Within this context, beams of fast, charged particles play a key role at various levels. Such
beams can be focused well into the nanometer regime to induce irreversible changes in the organic
overlayers and can thus be used to change the functionality of the system at the local level. On the
other hand, many of the most sensitive surface characterization techniques (including SIMS) are
based on the detection of events that are triggered by energetic particles. Although valuable
information on systems involving ultrathin organic overlayers can be gained, irradiation inevitably
also leads to an accumulation of changes in the structure and composition of the initially pristine
films, and as a consequence lead to changes in the properties of the systems.
A non-negligible fraction of the damage induced by the impact of ions and electrons is due to the
desorption of slow, neutral molecular fragments or even complete molecules [2]. Laser probing in
combination with mass spectrometry of desorbed species proves thereby to be a unique to study the
processes that occur during the dynamic interaction of energetic particles with organic overlayers.
It allows for (i) the efficient postionization of the ejected neutrals that is needed prior to charge-
sensitive detection and (ii) the decoupling of the desorption and detection event.
Results of an extensive study of the ion and electron-induced desorption of phenethyl mercaptan
C
6
H
5
-(CH
2
)
2
-SH (PEM) and 4,4-biphenyl-substisituted alkanethiols CH
3
-C
6
H
4
-C
6
H
4
-(CH
2
)
n
-SH
(BPn) (n = 1..6) adsorbed on Au(111), will be presented [3]. From these experiments, clear
indications of the influence of the geometric and electronic properties on the desorption
mechanisms were observed. These result in an odd-even effect related to the number of methylene
units in the alkane spacer or in pronounced differences in the ion-induced desorption behavior from
polymorphous biphenyl-based SAMs. Such SAMs were recently found to form when prepared at
different temperatures [4]. As such, it can be concluded that a delicate energy balance between the
moleculesubstrate bond and the intermolecular interactions not only governs the structural
properties of the monolayer but also has important repercussions on the stability and degradation of
the SAM. These results are thus not only elucidating from a fundamental point-of-view, but also
provide more insight towards a dedicated design of SAMs tailored for particular applications.
This work is financially supported by the Belgian Fund for Scientific Research Flanders (FWO), the
Femish Concerted Action Research Program (GOA) and the Interuniversity Poles of Attraction Program
(IAP) Belgian State, Prime Ministers Office Federal Office for Scientific, Technical and Cultural
Affairs. E. Vandeweert is a Postdoctoral Fellow of the FWO.


[1] R.K. Smith et al., Prog. Surf. Science 75 (2004) 1.
[2] E. Vandeweert et al., Appl. Phys. Lett. 82 (2003) 1114.
[3] P. Cyganik et al., J. Phys. Chem. B. 109 (2005) 5085.
[4] P. Cyganik and M. Buck, J. Am. Chem. Soc. 126 (2004) 5961.
PAR-I-Th-B15
223
SIMS of Nanoparticles

K. Wittmaack


GSF-National Research Centre for Environment and Health
Institute of Radiation Protection, 85758 Neuherberg, Germany
wittmaack@gsf.de


Secondary ion mass spectrometry is a well established technique for many applications in
surface analysis, including depth profiling of dopant distributions in semiconductors and other
materials, two-dimensional and even three-dimensional imaging or characterisation of organic
layers. Comparatively little work has been done to explore and optimise the use of SIMS for the
analysis of nanoparticles. This review describes the status of the field. Particular attention will be
paid to studies aimed at a characterisation of ambient and laboratory generated aerosol particles.
The two major routes taken in the past are single particle analysis and large area depth
profiling. The major problems are the heterogeneity of the particles in terms of composition,
shape and size. Proper understanding of the composition requires a detailed knowledge of the
frequently complex spectra of molecular ions emitted from the large variety of conceivable
compounds. Quantification is further aggravated by the fact that the size of the smallest particles
may be equivalent to or even less than the range of the primary ions. In such cases sputtered
particles are emitted from the whole surface area of bombarded nanoparticle. Hence the effective
sputtering yield will be much larger than from a bulk sample. The need for combining SIMS
with high-resolution imaging techniques like scanning electron microscopy will be illustrated.

PAR-O-Th-B16
224
Examining Ion Sputtering of Nanoparticles and Nanoporous
Materials
*

D.J. Gaspar, A.S. Lea, D.R. Baer, and M.H. Engelhard

Pacific Northwest National Laboratory, Richland, WA, 99352, USA
daniel.gaspar@pnl.gov


The behavior of nanomaterials varies in many cases from that observed for bulk materials.
During the course of studies on several different types of particles and nanostructured materials, we
have observed evidence that the extent of damage and material removal rates due to ion sputtering
may be significantly different than for continuous films or bulk forms of similar materials.
1,2
This
presentation will review our efforts to quantify the sputter and damage rates for some particle and
nanomaterial systems, including salt particles, iron oxide and cerium oxide nanoparticles and
nanoporous silica films. For the data presented here, material removal rates are monitored by
profilometry, TOF-SIMS, XPS and AES. Changes in material structure are measured by a variety of
methods including TEM, XRD and Nuclear Reaction Analysis. We suggest the contributions of
geometric factors and energy transfer modified by nanoscale features contribute to observed
variations. We examine the relationship of our observations to an established theory by Bradley and
Harper of ion-induced instability which drives ripple formation.
3
In particular, we look at where the
formulation of Bradley and Harper breaks down at the nanoscale, and provide several possible
implications. Finally, we apply a recently published semi-empirical formula for low energy
sputtering using Ar ions in understanding sputtering of nanoporous solids and collections of
nanoparticles, and comment on the meaning of the theory in the context of nanostructured
materials.
4


A portion of the research described in this manuscript was performed at the W. R. Wiley
Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the
U.S. Department of Energy's Office of Biological and Environmental Research and located at
Pacific Northwest National Laboratory. PNNL is operated for the Department of Energy by
Battelle.


References
1
D.J. Gaspar, M.H. Engelhard, M.C. Henry and D.R. Baer, Surf. Interface Anal., 37 (2005) 417-423.
2
Baer, D.R., M.H. Engelhard, D.J. Gaspar, D.W. Matson, K.H. Pecher, J.R. Williams, and C.M. Wang, J. Surf. Anal.,
12 (2005) In press.
3
Bradley, R.M. and J.E. Harper, J. Vac. Sci. Technol. A 6 (1988) 2390.
4
Seah, M.P., C. A. Clifford, F. M. Green and I. S. Gilmore, Surf. Interface Anal., Published online in Wiley
InterScience (www.interscience.wiley.com). DOI: 10.1002/sia.2032.

PAR-O-Th-B17
225
Characterization of Individual Atmospheric Aerosol Particles with
TOF-SIMS

R. E. Peterson
1
, A. Nair
1
, H. Shi
1
, S. Dambach
2
, H. Arlinghaus
2
and B. J. Tyler
2
*

Dept. of Chemical Engineering, 50 S Central Campus Dr. Rm 3290, University of Utah,
Salt Lake City, UT 84112-9203, USA

e-mail: bonniet@eng.utah.edu

The atmospheric aerosol consists of a complex mixture of organic and inorganic
compounds. The aerosol has important effects on human health, visibility, climate, and
precipitation chemistry. Past effort has concentrated on the determination of number, size and bulk
chemical analysis of these particles. However, individual particles vary in properties such as
toxicity, light attenuation properties and hygroscopic behavior which are functions of their shape
and three dimensional chemical composition. The ability to identify different types of particles via
these parameters is important in understanding the sources impacting a given location. For this
work, size segregated samples (via Al substrates in a Graseby Anderson 8 stage cascade impactor)
and bulk aerosol filter samples (via 47 mm Millipore Fluoropore filters) Salt Lake City, Utah over
a period from 2001 to 2005. Additionally, samples were collected of aerosol from sole sources
including forest fires, two stroke engines, diesel emissions and coal furnace emissions.
Multivariate statistical analysis was used to extract information from the SIMS images.
Images of the particles were separated from the image background, which significantly improved
our ability to acquire the composition of individual aerosol particles. A combination of multivariate
statistical techniques was used to identify both compounds and sources in Salt Lake City ambient
aerosol samples. We have found the surface of most particles is dominated by surfactant like
molecules. Particles originating from biomass burning, automotive emissions, and dust storms have
been clearly identified in the ambient aerosol samples. Instrumental and statistical techniques have
been used to enhance sensitivity to priority pollutants, in particular Poly Aromatic Hydrocarbons
(PAHs). Cold stage analysis and post ionization with a low intensity 157 nm laser show significant
potential for enhancing sensitivity to these semi-volatile compounds.
PAR-O-Th-B18
226
TOF-SIMS analysis of ultrafine carbon particles with a pulsed beam
sputter mode

W. Szymczak
a,
* and E. Karg
b


GSF-National Research Centre for Environment and Health

a
Institute of Radiation Protection

b
Institute of Inhalation Biology
85758 Neuherberg, Germany
szymczak@gsf.de


Health effect due to the inhalation of combustion generated nanoparticles are often explored
using ultrafine particles (UfPs) produced in a spark source generator [1]. The relevance of such
studies rests on the assumption that the employed particles can be used as a surrogate for ambient
particles as they are agglomerates of similar structure and primary particle size [2]. To substantiate
this assumption, a detailed analysis of the surface and bulk composition of the artificial particles is
mandatory.
The aim of this study was to determine the surface and in-depth composition of a electric spark
source (EC 90) and commercially available furnace (Printex 90, Degussa, Germany) generated
carbon UfPs by time-of-flight secondary ion mass spectrometry. EC 90 aerosols of ultrafine carbon
particles were produced by spark generation in 5N Ar and collected on cleaned Ag-filters as
produced or aftertreatment at 300C. Printex 90 aerosols were produced by compressed air
dispersion and collected on a cleaned Ag-filter. The TOF-SIMS instrument was modified to allow
operation with either short ( 2 ns) or long (up to 1000 ns) primary ion pulses so that surface
analysis and depth profiling could be performed routinely with the same beam. Using a pulsed beam
with variable frequency and pulse length from nanoseconds to microseconds facilitates controlled
sputter fluences from low as 10
12
ions/cm
2
up to 10
16
ions/cm
2
.
The investigations revealed a different behaviour of monitored yields in the positive and negative
TOF mode. The positive spectrum of fresh carbon aerosols are dominated by mostly the same
adsorbed contaminants which cover the underlying carbon UfPs. The level of contamination is
highest with the EC 90 aerosols collected as produced, lower with the EC90 aerosols with
aftertreatment at 300 C and lowest with the Printex 90 sample. With increasing sputter fluence the
overall yield decreases and the numerous contaminants are fast removed at a sputter fluence below
10
14
Ar ions/cm
2
. Sputter cleaned Printex 90 UfPs show distinct elemental signals of K
+
and Al
+
,
the latter is not present in EC 90.
In the negative TOF-mode the spectra of fresh carbon aerosols already give a clear picture of
carbon cluster with a characteristic even-odd intensity modulation. The spectra of both the EC 90
UfPs are very similar but different in details to the Printex 90 sample. Especially the oxygen based
signals are higher in the EC 90 sample. With increasing sputter fluence the yield of carbon based
signals reach a maximum at roughly 10
14
Ar ions/cm
2
. The relative intensity of carbon hydrogen
signals decreases only slowly with sputter cleaning and the EC 90 UfPs show a higher carbon
hydrogen content than the Printex UfPs.
TOF-SIMS with a pulsed beam sputter mode gives a more detailed insight in the surface and
bulk composition of artificial carbon UfPs. Sources of contamination can be identified and the
quality of spark generated aerosols improved.


[1] C. Roth, G. A. Ferron, E. Karg, B. Lentner, G. Schuhmann, S. Takanaka and J. Heyder, Aerosol Science and
Technology 38 (2004) 228.
[2] H. Saathoff, O. Moehler, U. Schurath, S. Kamm, B. Dippel and D., Journal of Aerosol Science, 34 (2003), 1277.
PAR-O-Th-B19
227
Urban and rural aerosol particle characterisation by SIMS and SSMS
compared with environmentally related children diseases

P. Konarski
a,
*, J. Hauszka
b
, M. wil
a, c
, K. Pisiewicz
d
, H. Srugaa-Stawik
e

a
Industrial Institute of Electronics, Dluga 44/50, 00-241 Warszawa, Poland
2
Institute of Public Health, Collegium Medicum, Jagiellonian University, Krakow, Poland
c
Faculty of Physics, Warsaw University of Technology, Koszykowa 75, 00-662 Warszawa, Poland
d
Podhale State College, Nowy Targ, Poland
e
Foundation on Children of Copper Basin, Legnica, Poland

*) pkonarsk@pie.edu.pl

Aerosol particles were collected in different environments in Poland in two towns Legnica and
Starachowice and in rural site near Krakow. The collected material has been characterised with
mass spectrometry methods. Bulk analysis of particulate matter collected on quartz fibre filters was
performed using spark source mass spectrometry (SSMS) with magnetic sector analyzer JEOL-
02BM2. Analysis of 20 chosen elements revealed the differences in total concentrations in the
particles from urban and rural environments. In urban aerosol collected in Legnica we found: Pb,
Cr - 20 times more than in rural environment, As, Sr - 10 times, Co - 7 times, Cl - 5 times, V, Y - 3
times, Ti, Mn, Cu, Se - 2 times and Fe, Ni, Zn, Br, Zr, Mo less than two times more than in rural
environment.
Aerosol particles for SIMS depth profile analysis were collected at Al-foils with the use of nine-
stage rotating plates cascade impactor. 5 keV Argon ion sputtering was performed with the use of
Physical Electronics 06-350E ion gun and mass analysis with QMA-410 Balzers 16 mm
quadrupole. The obtained results show core shell structure of particles dependent of their grain
size in the range of 300 nm to 15 m. Ion sputtering effects in stationary and sample rotation SIMS
measurements have been observed by SEM microscopy.
The results of characterization are compared with the medical study of the prevalence of
environmentally related children diseases observed in the investigated environments. Questionnaire
study and allergic skin prick tests were performed according to the protocol of International Study
of Asthma and Allergies in Childhood (ISAAC).

This work was partially financed by the State Committee for Scientific Research of Poland (project no. 6 P05D 016 21).
DEP-P-Th-P01
228
Sodium and Hydrogen Analysis of Room Temperature Glass
Corrosion Using Low Energy Cs SIMS

Sarah Fearn
*1
, R.J.H. Morris
2

1
Dept. of Materials. Imperial College, London, SW7 2AZ, UK
2
Dept. of Physics, Warwick University, Gibbet Hill Rd, Coventry, CV4 7AL, UK.
E-mail: s.fearn@imperial.ac.uk


Glass is often regarded as both a stable and durable material and its wide range of contemporary
applications reinforce this belief. However, there is nothing inherent in the glassy state that confers
stability and the problem of glass corrosion has been well documented by many workers
[1,2]
.

Glass
corrosion still affects commercial float glass production and glasses used to contain high level
nuclear waste. In order to prevent the corrosion it is necessary to understand the composition of the
corroded glass and the corrosion mechanism taking place. Therefore, compositional information is
needed from glass that is corroding under realistic conditions.
It has been recently shown that the application of low energy SIMS can be usefully applied to
monitor the leaching of sodium from a glass corroding at room temperature
[3]
. However, this is only
half of the corrosion process; as well as the leaching of alkali ions there is also the ingress of water
into the glass. In this work a glass has been aged at room temperature and known atmospheric
humidity for increasing periods of time. The aged glass has then been depth profiled using a low
energy (1keV) Cs beam monitoring both the sodium and hydrogen signals concurrently.
The depth profiles show that in the region directly below the glass surface that is severly depleted
in sodium, there is an increased level of hydrogen compared to the bulk glass indicating an increase
in the water content within this region. In all cases, the peak of the elevated hydrogen level occurs
just before the interface between the depleted region and the bulk glass.


[1] Walters, H. V and Adams, P. B, J. Non Cryst. Solids, 19: 183, 1975.
[2] Wicks, G. G, Corrosion of Glass, Ceramics, and Superconductors. Eds Clark D. E and Zoitos, B. K Noyes
Publications, 1991.
[3] Fearn, S., McPhail, D. S., Oakley, V., Applied Surface Science Vol. 231-232C pp510-514, 2004.

DEP-P-Th-P02
229
Application of B-doped Si Multiple Delta-Layers for Calibration of
SIMS Depth Scale

K. J. Kim
a
*, D. W. Moon
a
, P. Chi
b
and D. Simons
b


a
Division of Chemical Metrology and Materials Evaluation, Korea Research Institute of Standards and Science,
P.O.Box 102, Yuseong, Daejeon 305-600, Korea
b
Surface and Microanalysis Science Division, National Institute of Standards and Technology, Gaithersburg, MD
20899-8371, USA
kjkim@kriss.re.kr


The rapid progress in semiconductor and new materials industries requires more precise
profiling analysis in narrower and shallower regions. Recently the ITRS (International Technology
Roadmap for Semiconductors) has defined the analysis range for the measurement of 1 nm gate
oxide thickness and the distribution of doping elements within 20 nm shallow junctions. Therefore,
the development of certified reference materials (CRMs) is necessary for the self confidence and
mutual recognition of the analysis results in this limited shallow region.
Secondary ion mass spectrometry (SIMS) is the most popular technique for determining the in-
depth distribution of doping elements within 20 nm shallow junctions. However, the original
distribution of constituent elements can be seriously distorted by ion mixing, surface segregation
and surface topography developed during sputtering. B-doped Si multiple delta-layers (MDLs) have
been developed as certified reference materials for SIMS depth profiling analysis. Two CRMs with
different delta-layer spacings were grown by ion beam sputter deposition. The nominal spacing of
the MDL for shallow junction analysis is 10 nm and that for high energy SIMS is 50 nm. The total
thicknesses of the films were certified by high resolution transmission electron microscopy. These
B-doped Si MDLs can be used to calibrate the SIMS depth scale. The feature depths determined
from the crater depths measured by a stylus profilometer showed a good linear relationship with the
same feature depths measured from SIMS profiling using the calibrated film thickness for depth
scale calibration. These results indicate that an MDL with a certified thickness can be used as a
reference to check the depth scale determined by a stylus profilometer for measurement of sputter
depth.
The sputtering rate of the amorphous Si thin film grown by sputter deposition was found to be the
same as that of the crystalline Si substrate, which means that the sputtering rate measured with these
CRMs can be applied directly to a real analysis of crystalline Si. These CRMs were also found to be
useful in conjunction with an ISO standard procedure for the evaluation of SIMS depth resolution.
In the symposium, we will present some general applications of multiple delta-layer CRMs for
international standards related to semiconductor analysis.

DEP-P-Th-P03
230
An Alternative Method of Using an Electron Beam for Charge
Compensation During uleSIMS Experiments.

B. Guzmn de la Mata
a,
*, M. G. Dowsett
a
,
R J H Morris
a

a
Advanced SIMS Projects. Department of Physics. University of Warwick. CV4 7AL. UK.
Email: B.Guzman-de-la-Mata@warwick.ac.uk


SIMS analysis of insulators usning positive primary beams is routinely done by compensating
the induced charge with a coincident electron beam. In the case of SIMS depth profiling, the
established method [1] consists of focusing an electron beam into the SIMS crater with a current
well in excess of that of the ion beam. We have found that in the case of nitrogen doped diamond (a
highly resistive, but not completely insulating material) defocusing a low energy (500 eV) electron
beam [2] over the whole sample holder window is effective in stabilizing the signals and providing
charge compensation, despite the low electron beam current density. A mechanism rather similar
to that of the recently reported optical conductivity enhancement (OCE) [3] seems to be operating,
in that the electrons are stimulating surface conductivity in the diamond and creating a charge
leakage path to the sample holder. In this paper, we report on the usefulness of this method for this
and other insulating materials such as intrinsic diamond, SiO
2
, sapphire and float glass.


[1] K. Wittmaack, J. Appl. Phys. 50 (1979) 493
[2] R.Gibbons, M.G.Dowsett, J.Kelly, P.Blenkinsopp, R.Hill and D.Richards, Appl. Surface Sci, 203-204 (2003) 343
[3] M.G.Dowsett, R.Morris, Pei-Fen Chou, S.F.Corcoran, H.Kheyrandish, G.A.Cooke, J.L.Maul and S.B.Patel,
Appl. Surface Sci, 203-204 (2003) 500

DEP-P-Th-P04
231
ULTRA SHALLOW SIMS DEPTH PROFILING

Andrew T. S. Wee*, R. Liu, S. K. Tan, A.R. Chanbasha, K. L. Yeo, C. M. Ng

Department of Physics, National University of Singapore
Email: phyweets@nus.edu.sg


Ultra-large scale integration in the semiconductor industry today exploits the variation of
interfacial properties on a nanometer scale and requires analytical methods that can provide
adequate resolution at this scale. Achieving high depth resolution of the order of 1 nanometer is
critical today, and various methods have been developed to optimize depth resolution. The use of
lower energy ion bombardment in secondary ion mass spectrometry (SIMS) depth profiling has
become increasingly important for the characterization of ultra shallow junctions. Sputtering with
sub-keV primary ions results in shallower penetration of ions thus minimizing the relocation of the
original distribution and chemical mixing effect. However, the advantages of low energy sputtering
in many cases are offset by the development of crater bottom roughness and the problem is more
severe at oblique incidence in the sub-keV range.

We have studied the effect of oxygen flooding on the sputtered crater bottom composition and
topography in relation to SIMS depth resolution [1]. Sample rotation as a means of improving depth
resolution using sub-keV SIMS is critically evaluated, and found to be less effective than at higher
primary energies where the ion penetration depth is much higher [2]. We have performed in situ
XPS and SIMS analysis of O2+ beam-induced silicon oxidation[3]. The evolution of the secondary
ion profile shows similar trends with variation of oxygen concentration in the crater surface
measured by XPS. Preliminary results on the surface transient effects in ultra low energy O2+
sputtering of silicon as a function of incidence angle and energy will also be presented.[4]

To overcome surface transient effects, we have proposed a silicon-on-insulator (SOI) backside
depth profiling method [5]. The SOI layer, after removal of the buried-oxide (BOX) layer, provides
a smooth and flat surface for high resolution SIMS depth profiling from the backside. The backside
depth profiles give a significant improvement in depth resolution as compared to conventional
frontside SIMS depth profiling. The SIMS backside depth profiling was demonstrated to be
effective in the accurate measurement of ultra shallow implants [6], and was effectively used in our
investigation of boron penetration through decoupled plasma nitrided gate oxide [7], and was
evaluated for boron diffusion in silicon and silicon-on-insulator substrates [8].


[1] Ng C. M., Wee A. T. S., Huan C. H. A., See A., J. Vac. Sci. Technol. B 19 (2001) 829.
[2] Ng C. M., Wee A. T. S., Huan C. H. A., See A., Nucl. Instrum. Meth. B 179 (2001) 557.
[3] Tan S. K., Yeo K. L., Wee A. T. S., Surf. Interface Anal. 36 (2004) 640.
[4] A. R. Chanbasha, Wee A. T. S., submitted.
[5] Yeo K. L., Wee A. T. S., Liu R., Ng C. M., Surf. Interface Anal. 33 (2002) 373.
[6] Yeo K. L., Wee A. T. S., See A., Liu R., Ng C. M., Appl. Surf. Sci. 203 (2003) 335.
[7] Yeo K. L., Wee A. T. S., Liu R., Zhou F. F., See A., J. Vac. Sci. Technol. B 21 (2003) 193.
[8] Yeo K. L., Wee A. T. S., Chong Y. F., J. Appl. Phys. 96 (2004) 3692.
DEP-P-Th-P05
232
Narrow surface transient and high depth resolution SIMS using
250eV O
2
+


Ab Razak Chanbasha, A. T. S. Wee*

Department of Physics, National University of Singapore, 2 Science Drive 3, Singapore 117542
Email: phyweets@nus.edu.sg


Ultra-shallow junctions in semiconductors and multi-quantum wells (MQW) in lasers demand
high depth resolution for accurate depth profiling. SIMS has been widely used in depth profiling
and the use of ultra-low energy SIMS has demonstrated a narrower surface transient and an
improvement in depth resolution. In this work, we use an ATOMIKA 4500 SIMS depth profiler
with O
2
+
primary ion at an ultra-low energy of E
p
~ 250eV and incidence angles () of 0
o
, 40
o
and
60
o
without oxygen flooding. A sample with 10 delta layers of Si
0.7
Ge
0.3
nominally grown at 11nm
apart is used.

We observe that for applications like characterizing of ultra-shallow junctions, 0
o
is ideal as it
provides the narrowest surface transient (z
tr
) of 0.7nm compared to 40
o
with z
tr
of 1.0nm [1].
The depth resolution denoted by the full-width at half maximum (FWHM) of the
70
Ge
+
peaks is
1.6nm and is comparable at both 0
o
and 40
o
. However, in the case of MQW profiling, whereby
the quantum wells are normally located deeper, 40
o
is preferable. At this angle, the average
sputter rate of 47nm/min/nAcm
2
is significantly higher, more than double that at 0
o
, while there
is no loss in depth resolution and a better decay length (
d
) of 0.64nm/decade compared to
0.92nm/decade at 0
o
. Moreover, the dynamic range possible is also better at 40
o
. 60
o
is
not ideal, even though there is no sign of the onset of roughening. Although the higher sputter rate
is an advantage, the depth resolution deteriorates as the profile gets deeper.


[1] A. R. Chanbasha, Wee A. T. S., submitted.
DEP-P-Th-P06
233
SIMS Depth Profiling of Rubber Tyre Cord Bonding Layers
prepared using
64
Zn depleted ZnO

W. Stephen Fulton
a
, David E. Sykes
b,
*, Graham C. Smith
c
and Keith J. Titchener
c


a
OMG UK Ltd, Ashton New Road, Clayton, Manchester M11 4AT, UK.
b
Loughborough Surface Analysis Ltd, Holywell Park, Ashby Road, Loughborough LE11 3WS, UK.
c
Shell Global Solutions UK, Cheshire Innovation Park, Chester CH1 3SH, UK
d.e.sykes@lsaltd.co.uk


Adhesion of rubber to brass coated steel tyre cords is mediated by the presence of the zinc oxide
and copper/zinc sulphide layers formed during vulcanisation and moulding. Previous studies have
described how zinc diffuses through the rubber brass interface to be sulphidized to form zinc
sulphide, and how zinc combines with oxygen to create zinc oxide during dezincification. The zinc
is usually assumed to originate primarily in the brass of the tyre cord, however, zinc oxide is also
present as part of the rubber formulation. Here, we reveal how zinc from these sources is
distributed within the interfacial bonding layers, before and after heat and humidity ageing.
To differentiate between the two possible sources of interfacial zinc, zinc oxide produced using
64
Zn-isotope depleted zinc was mixed in the rubber formulation in place of the natural ZnO and the
zinc isotope ratios within the interfacial layers were followed by Secondary Ion Mass Spectroscopy
(SIMS) depth profiling. The contribution of zinc from each source was determined from variations
in the relative ratios of the zinc isotopes during depth profiling. Profiles were obtained for unaged,
heat-aged and humidity-aged wire samples and in each case a relatively large proportion of the zinc
incorporated into the interfacial layer as zinc sulphide was shown to have originated from ZnO in
the rubber compound.
The thickened dendritic structure produced by heat ageing was visualized in Transmission
Electron Microscopy (TEM) using a sample prepared by focussed ion beam (FIB) milling. Energy
Dispersive X-Ray (EDX) linescans showed more fully the role of zinc during the thickening of the
bonding interface and allowed an approximate estimate of the depth scale during the SIMS depth
profiling.

DEP-P-Th-P07
234
SIMS Analysis for Atmospheric Gas Elements

Shiro Miwa, Ichiro Nomachi, and Hideo Kitajima

Materials Analysis Center, Sony EMCS Corp., 4-16-1 Okata, Atsugi, 243-0021, Japan
Nanotechnos Corp., 5-4-30 Nishihashimoto, Sagamihara, 229-1131, Japan
Shiro.Miwa@jp.sony.com


SIMS is often used to detect Hydrogen, Carbon and Oxygen, which can act as dopant or kill
carriers in epitaxial-growth semiconductor films. As residual atmospheric gases will remain after
pumping of the vacuum chambers even to UHV, the detection limit of these elements is degraded.
We have modified the vacuum system of our Cameca ims-4f instrument in order to reduce residual
gasses. We have replaced the three original turbo molecular pumps with magnetic levelling-type
turbo molecular pumps and replaced the original mechanical pumps with dry pumps. We have also
added 30K-cryopanel with charcoal to the main vacuum chamber of the instrument in order to
minimize water vapor. Moreover we investigated the change in the detection limit of H, O and C as
a function of time We found that the detection limit is improved as the time during primary ion
bombardment is long.

DEP-P-Th-P08
235
MEM-deconvolution analysis of ultra-shallow junction depth profiles

M. Tomita
a,
*, H. Tanaka
a
, M. Koike
a
, M. Yoshiki
a
, S. Takeno
a
, N. Sugita
b
and M. Obuchi
b


a
Corporate Research & Development Center, Toshiba Corporation, 8 Shinsugita-cho, Isogo-ku, Yokohama 235-8522,
Japan
b
Analysis and Evaluation Center, Toshiba Nanoanalysis Corporation, 1 Komukai Toshiba-cho, Saiwai-ku, Kawasaki
212-8583, Japan
Email: mitsuhiro.tomita@toshiba.co.jp


Characterization of ultra-shallow junction depth profiles with ultra-high depth resolution is
indispensable for the development of new LSIs with the extension Xj of less than 10 nm. The
efforts have been made to decrease the primary ion energy of SIMS ion guns in order to improve
depth resolution. However, the depth resolution cannot be improved any further because low
sputtering yield by low energy ion bombardment (less than ~200 eV) causes extremely long SIMS
measurement time (several hours or more). Therefore, we have developed the deconvolution
analysis method for shallow-junction depth profiles, which is based on the maximum entropy
method (MEM) [1].
200-eV boron implanted sample (boron depth profiles with Xj of ~9 nm) was measured by 350-
eV oxygen primary ion with FEI SIMS4550 instrument. We found that MEM-deconvolution
analysis of the raw depth profile failed (see Figure 1). This failure was caused by the surface
transient effect, which involved with the variation of sputtering yield [2,3] and the variation of
depth resolution function in the transient region. Therefore, we attempted the correction of the
surface transient effect. However, since there is no report about the quantitative variation of depth
resolution function, we assumed that the
parameters of depth resolution function varied
from 0 to the definite values in the bulk
region, similar to the variation of sputtering
yield. Because deconvolution analysis cannot
be performed while varying depth resolution
function, the depth axis of the depth profile
was modified according to the variation in the
depth resolution function. After the correction
of sputtering yield and depth resolution
variations, the corrected depth profile was
MEM-deconvoluted. The deconvoluted depth
profile (see Figure 1) agrees very well with the
depth profile by the backside SIMS
measurement [4] that gives accurate profiles.
This result reveals for the first time that this
deconvolution analysis obtains accurate ultra-
shallow junction depth profiles in short
measurement time (1 hour or less).


[1] M. G. Dowsett, D. P. Chu, J. Vac. Sci. Technol. B16 (1998) 377.
[2] L. Shao, J. Liu, C. Wang, K. B.Ma, J. Zhang, J. Chen, D. Tang, S. Patel, W. K. Chu, Appl. Phys. Lett. 83 (2003)
5467.
[3] C. F. McConville, S. H. Al-Harthi, M. G. Dowsett, F. S. Gard, T. J. Ormsby, B. Guzman, T. C. Q. Noakes, P.
Bailey, J. Vac. Sci. Technol. B20 (2002) 1690.
[4] M. Tomita, C. Hongo, M. Suzuki, M. Takenaka, A. Murakoshi, J. Vac. Sci. Technol. B22 (2004) 317.

0 5 10 15 20 25 30
Deconvoluted raw profile
Deconvoluted corrected profile
10
16
10
17
10
18
10
19
10
20
10
21
10
22
10
23
B
o
r
o
n

c
o
n
c
e
n
t
r
a
t
i
Depth (nm)

Figure 1. Comparison of deconvoluted raw and
corrected depth profiles for 200-eV boron
implanted sample.
DEP-P-Th-P09
236
CALIBRATIONS OF TOF-SIMS SPUTTER RATES IN ALUMINA
SCALES FORMED ON FeCrAl ALLOYS

J. Engkvist
*
, R. Berger, U. Bexell, T.M. Grehk and M. Olsson

Dalarna University, SE-781 88 Borlnge, Sweden
*
Corresponding author: Phone +46-23-778633, Fax +46-23-778601, E-mail jei@du.se


ToF-SIMS depth profiling has been used to investigate alumina scales, formed during high
temperature oxidation of ferritic FeCrAl alloys. It is shown that ToF-SIMS depth profiling is a very
useful tool for investigating the elemental depth distribution within the alumina scales, even on a
ppm level. Further, a careful depth calibration makes it possible to determine the oxide scale
thicknesses in SIMS depth profiles. Oxide scale thicknesses from some hundred nm to about 1m
are investigated, using a Ga
+
primary ion source with an accelerating energy of 15 keV.
In order to determine the sputter rate, AFM has been used to measure the depth of the SIMS
sputter craters. Also, AFM reveals the topography at the bottom of the sputter craters. The sputter
rate is determined both in the alumina scale and in the bulk of the metal substrate. The determined
sputter rates in the oxide and the metal is compared to the sputter rate, when sputtering through the
oxide/metal interface. The sputter rate in grown oxide is compared to the sputter rate in a pure
single crystal of aluminium oxide.
Comparison is made between results obtained from depth profiling of alumina scales using SIMS
and AES.
DEP-P-Th-P10
237
Boron Ultra Low Energy SMS Depth Profiling improved
by Rotating Stage

D. Giubertoni
a,
*, E. Iacob
a
, M. Barozzi
a
, S. Pederzoli
a
, L. Vanzetti
a
, M. Anderle
a

and M. Bersani
a
.

a
ITC-irst, Centro per la Ricerca Scientifica e Tecnologica, Via Sommarive 18, 38050 Povo - Trento, Italy
giuberto@itc.it


Secondary ion mass spectrometry has been following ion implantation and diffusion process
developments in the last 30 years because of its high sensitivity, depth resolution, good
reproducibility and accuracy. However, the present demands of Microelectronics industry for
dopant distribution characterization are stressing and forcing SIMS possibilities. Present source/
drain extension features demand SIMS analyses with ultimate depth resolution (as low as 2.8
nm/decade for 65 nm technological node [1]), reduced both initial transient width and matrix effects
in presence of either surface oxide or buried oxide in SOI samples.









0 50 100 150
10
17
10
18
10
19
10
20
10
21









boron
30
Si
+

UHV
UHV + Rot.
O
2
flood + Rot.
Nominal

1
1
B

C
O
N
C
E
N
T
R
A
T
I
O
N

(
a
t
.
/
c
m
3
)
APPARENT DEPTH (nm)
10
5
10
6
10
7
10
8
3
0
S
i
+

I
N
T
E
N
S
I
T
Y

(
a
.
u
.
)


In this work we will present an improvement of boron ultra shallow characterization when
analyses are performed by a 0.5 keV (~68 incidence) O
2
+
beam [2]: the use of the oxygen flooding
together with the rotation of the stage allows a final decay length of 2.0 nm/dec reducing the
formation of the roughness on the crater bottom that is usual obtained when oblique incidence is
applied [3]. Results obtained by several configurations on both delta doped sample and samples of
technological interest will be reported in order to show how the different approaches impact on the
roughness formation and on the accuracy of the depth calibration. Crater bottom roughness
measurements by AFM will complete the methodological study. Advantages and limits of the
developed methodology on bulk and SOI samples will be discussed.


[1] International Technology Roadmap for Semiconductors 2004 update, Metrology Section, Table 119A, pag. 12.
DEP-P-Th-P10
238

[2] D. Giubertoni, M. Barozzi, M. Anderle, and M. Bersani, J. Vac. Sci. Technol. B 22(1), 2004, 336.
[3] Z. X. Jiang and P. F. A. Alkemade, J. Vac. Sci. Technol. B 16(4), 1998, 1971.
DEP-P-Th-P11
239
Characterization of layers and interfaces during the silicide formation
of CoSi
x
and NiSi
y


U.Breuer
a
*, A. Scholl
a
, A. Besmehn
a
, Q. Zhao
b
, M. Zhang
b
and E. Rije
b


a
Central Division of Analytical Chemistry (ZCH), Research Centre Jlich
b
Institute of Thin Films and Interfaces (ISG-1), Research Centre Jlich
uwe.breuer@fz-juelich.de


Semiconductor devices consist of heterogeneous layer systems with alternating dopants and/or
dopant concentrations as well as changing the matrix itself. Changing the matrix is normally used
for electrically insulation, forming an electrical contact or taking advantage of changing optical
properties. The determination of element distributions in such layer systems and interfaces with
good detection limits and depth resolution was done by different techniques like SIMS, SNMS or
AES for many decades.

The reproducible deposition of material on a substrate strongly depends on the quality of the
cleaning process prior to deposition. In this step contamination from the environment and a natural
oxide has to be removed without affecting smoothness or crystal quality. The deposition process
can have several interrupts for changing dopants or matrix. During these interrupts the actual
surface is potentially open for contamination from the gas in the deposition chamber. This
contamination will be determined in the interface region when depth profiling techniques are
applied. During silicide formation from a metal layer on silicon a huge number of atoms are moved
over several nm and this transport also affects the distribution of dopants intentionally present as
well as contaminations.

The determination of contaminations in the interface regions is difficult because the interfaces are
buried and rather thin. Because of the appropriate detection limits and depth resolution SIMS is the
method of choice for this task. Due to the limited time for sputtering through these interfaces
dynamic SIMS measurements using mass filters (quadrupole or sectorfields) can only monitor the
prime candidates and the rest is missed. The parallel mass detection and the high mass resolution
makes ToF-SIMS therefore the ideal method for getting more insight into the inventory at such
interfaces.

We will demonstrate the capabilities of the method for different silicide containing layer systems
(NiSi
x
, CoSi
y
) with different dopants (B, As and S). Depending on the availability of Si (infinite or
limited reservoir) different silicide phases can be determined and the redistribution of minor
elements with respect to this phases will be discussed. For buried CoSi films we find several
contaminations even at inner interfaces never exposed to atmosphere. Some of these silicides are
formed to be used as the metallization on a high-k dielectric gate. The characterization of this
deposition process was also done by ToF-SIMS in combination with XPS[1].

The retrospective analysis capability in ToF-SIMS enables to focus on a set of elements or
molecules and expand this without repeating the experiment. In addition the comparison of actual
with former data can indicate changes in the specific deposition system. Therefore each
measurement is to some extend an actual fingerprint.


[1] Besmehn, A.; Scholl, A.; Rije, E.; Breuer, U., Appl. Surf. Science, in press;
online available doi:10.1016/j.apsusc.2005.02.028
DEP-P-Th-P12
240
DECONVOLUTION OF SIMS DEPTH PROFILES IN THE
PRESENCE OF BEAM INDUCED ROUGHNESS

B. Fares
a
, B. Gautier
a
, J.C. Dupuy
a
, G. Prudon
a
, P. Holliger
b

a
Laboratoire de Physique de la Matire (UMR CNRS 5511), INSA de lyon, 7 Avenue Capelle, F-69621
VILLEURBANNE cedex, France
b
CEA-DRT LETI/DST CEA/GRE, 17 rue des Martyrs 38054 Grenoble Cedex 9, France

boubker.fares@insa-lyon.fr


The achievement of ultimate depth resolution of the SIMS analysis is still hampered by the
apparition of a beam induced roughness (BIR) in the crater bottom. Even though adequate
experimental conditions can be found to minimize the BIR [1], it may be a very useful option to
deconvolve profiles which have been blurred by the roughness.
The ability of deconvolution algorithms to improve the experimental depth resolution in the case
of boron [2-3] and arsenic [4] in silicon has already been shown earlier. The deconvolution of SIMS
profiles using a Depth Resolution Function (DRF) different from the DRF which has convolved the
profile has also been studied [5-6] and it has been shown that it was possible to recover partially the
original profile. In the case of the BIR, experimental data exist which describe the effect of the
roughness on the depth resolution. In particular, it has been shown that the contribution of the
roughness to the width of the SIMS profiles was a gaussian broadening, which means that a delta-
layer analysed in presence of BIR will be fairly well described by the convolution of the DRF with
a gaussian.
This present paper explores the deconvolution of SIMS depth profiles of boron delta layers in
silicon. The optimal experimental conditions which lead to the absence of BIR are found. When the
BIR is present, the effect of the roughness on the depth resolution is studied and the deconvolution
of the profiles is implemented. The performances of the deconvolution when the BIR is not present
are established by measuring the ultimate width of the deconvolved -layers and their separation.
When it is present, the sharpness of the deconvolved profile is measured and related to the
measured value of the roughness in the crater bottom. The role of the deconvolution in the
enhancement of the resolution is discussed.


[1] Liu R and Wee A.T.S., Appl Surf Sci, 231-232, 2004, 653-657
[2] Gautier B, Prost R, Prudon G, and Dupuy J-C, Surf Interface Anal, 1996; 24:733-745.
[3] Dowsett M.G., Rowald G., Allen P.N and Barlow R.D., Surf Interface Anal, 1994, 21:310-315
[4] Lee J W., Kim K J., Kim H K and Moon D W., Surf Interface Anal, 2005, 37:176-180
[5] Gautier B, Prost R, Prudon G, and Dupuy J-C, Surf Interface Anal, 1998; 26:974-983.
[6] Yang M H and Odom R., Material Research Society Proceedings, tome 669, 2001

DEP-P-Th-P13
241
SIMS characterisation of superconductive MgB
2
layers prepared by
ion implantation and pulsed plasma treatment

P. Konarski
a,
*, M. wil
a, b
, J. Piekoszewski
c, d
, W. Kempinski
e
, J. Stanislawski
c

a
Industrial Institute of Electronics, Dluga 44/50, 00-241 Warszawa, Poland
b
Faculty of Physics, Warsaw University of Technology, Koszykowa 75, 00-662 Warszawa, Poland
c
The Andrzej Sotan Institute for Nuclear Studies, 05-400 Otwock/wierk, Poland
d
Institute of Nuclear Chemistry and Technology, Dorodna 16, 03-145 Warszawa, Poland
e
Institute of Molecular Physics Polish Academy of Sciences, Smoluchowskiego 17,
60-179 Poznan, Poland

*) pkonarsk@pie.edu.pl


Thin films of magnesium diboride (MgB
2
), an intermetallic compound, possessing superconduc-
tive properties, were analysed by secondary ion mass spectrometry (SIMS). The synthesis of MgB
2

was performed by ion implantation method followed by plasma treatment.
The samples were prepared using the new two-step technique of ion implantation and plasma
treatment. Two kinds of structures were obtained when boron and magnesium were used as targets.
80 keV magnesium ions were implanted into boron samples and 100 keV boron ions into
magnesium strips. Plasma treatment was performed using hydrogen and argon 1 s plasma pulses
of fluence 2 4 J/cm
2
. Magnetic moment and electrical conductivity measurements confirmed
superconducting properties of the obtained layers.
SIMS depth profiling was performed using 5 keV Ar
+
ion beam (06-350E Physical Electronics)
and quadrupole mass spectrometry (QMA 410 Balzers). Relative sensitivity factors (RSF) for boron
and magnesium were obtained basing on SIMS analyses of bulk reference samples of MgB
2
, B and
Mg.
Obtained results allow modifying technology parameters of the synthesis of thin film MgB
2
.

DEP-P-Th-P14
242
Useful Yields and Depth Resolution in TOF-SIMS Depth Profiling

T. Hoshi
a,*
, S. R. Bryan
b
, J. S. Hammond
a, b
, N. Iida
a
, S. Iida
a
and A. Yamamoto
a


a
ULVAC-PHI, Inc., 370 Enzo, Chigasaki, Kanagawa, 253-0084, Japan
b
Physical Electronics, 18725 Lake Drive East, Chanhassen, MN 55317, USA
thoshi@phi.com


TOF-SIMS depth profiles obtained using the dual beam mode have became popular for
measuring the in-depth distributions of dopants and impurities in the microelectronics field. Dual
beam depth profiles can also be useful for the analysis of small defects, due to the superior TOF-
SIMS capabilities such as the high efficiency from parallel secondary ion detection, high mass
accuracy with mass resolution exceeding 10,000 M/dM, high depth resolution associated with low
energy sputtering, and the high spatial resolution of the LMIG analysis gun.
However the optimization of the TOF-SIMS parameters is not as simple as in dynamic SIMS.
The trade-offs between the conditions of the high energy pulsed analysis beam and the pulsed low
energy sputtering beam have a significant affect on the useful yield, dynamic range and depth
resolution.
The TOF-SIMS instrumental parameters in dual beam depth profiling were investigated to
optimize useful yield and depth resolution for delta doped boron samples. The results obtained with
the optimized TOF-SIMS dual beam parameters will be compared with results obtained by using a
quadrupole based dynamic SIMS instrument. The relative advantages of the two different
instrumental techniques will be discussed for a wider range of microelectronics and small defect
samples.
DEP-P-Th-P15
243
Ultra-low energy O
2
+
sputtering for improved accuracy in SIMS depth
profiles

Z. Li
a
, T. Hoshi
a,*
, S. R. Bryan
b
, J. S. Hammond
a, b
and H. Iwai
a


a
ULVAC-PHI, Inc., 370 Enzo, Chigasaki, Kanagawa, 253-0084, Japan
b
Physical Electronics, 18725 Lake Drive East, Chanhassen, MN 55317, USA
thoshi@phi.com


SIMS has shown its versatility in the analysis of high and medium energy ion implants by
providing accurate implant dose information, as well as ion implants depth distributions for high
and medium thickness films. Shrinking device geometries and the associated use of ultra-low
energy implants and ultra-thin gate oxide films present new challenges to the technique since a
major portion of these implants and oxide films are located in the immediate vicinity of the sample
surface. The need for measuring depth profiles for ultra-low energy implants in silicon and ultra-
thin insulating films pushes the technique towards unprecedented requirements of high depth
resolution and depth accuracy. It is also important that SIMS analytical conditions should be chosen
so that surface transient effects and sputter rate change are, if not eliminated, at least minimized.

These basic aspects of ultra-low-energy O
2
+
ion beam bombardment were investigated using a
Quadrupole based SIMS instruments for the analysis of delta-doped boron samples. A newly
designed ion gun has been used for ultimate low energy O
2
+
beam conditions (~ 100 eV). The
improved accuracy of SIMS depth profiles in terms of depth resolution will be discussed based on
changes in sputter rate, topography, and dual beam conditions, in order to obtain instrument
parameters for the most realistic depth profiles of implants and ultra-thin films. The results from
the ultimate low energy O
2
+
beam condition (~ 100 eV) will be used to estimate the boron profile
which would be obtained by a 0 eV O
2
+
beam.


DEP-P-Th-P16
244
TOF-SIMS DEPTH PROFILING OF (Ga,Mn)As CAPPED WITH
AMORPHOUS ARSENIC: EFFECTS OF ANNEALING TIME

U. Bexell
a,*
, V. Stanciu
b
, P. Warnicke
b
, M. sth
b
and P. Svedlindh
b


a
Dalarna University, SE-781 88 Borlnge, Sweden
b
Department of Engineering Sciences, Uppsala University, Box 534, SE-751 21 Uppsala, Sweden
*Corresponding author: Phone +46-23-778623, Fax +46-23-778601, E-mail ube@du.se


The development of molecular beam epitaxial techniques (MBE) has created semiconductor
materials with ferromagnetic properties. One of these materials is (Ga,Mn)As which has a relatively
high ferromagnetic transition temperature. In this compound Mn impurities ideally substitute Ga in
the GaAs lattice at random positions. If a high concentration of Mn is required the MBE growth has
to be performed at low temperatures. Due to this special growth situation defects are incorporated in
the lattice during the growth process. One is Mn atoms located at interstitial positions, which do not
participate in the ferromagnetism, and can couple antiferromagnetically with substituted Mn. Thus
the net ferromagnetic effect can be reduced and to improve the magnetic properties the Mn
interstitials must be passivated at the (Ga,Mn)As surface. A new procedure to passivate
ferromagnetic semiconductor is to cap the surface with amorphous As. This study focuses on the
influence of annealing time, with constant temperature, on the cap layer thickness and the Mn depth
distribution. Also, some XPS and AES results will be discussed.
DEP-P-Th-P17
245
Emission of impurity-matrix type dimers from GaX semiconductors
(X = N, P, As, Sb).

D.Yu. Kazantsev, A.P. Kovarsky.*

A.F. Ioffe Physico-Technical Inst. Russian Academy of Science. 26 Politekhnicheskaya Str.,
St. Petersburg 194021 Russia.
*e-mail: alex.kovarsky@mail.ioffe.ru.


Such impurities as carbon and oxygen spoil electrophysical properties of A
3
B
5
semiconductors.
SIMS-analysis provides a way to determine the concentration and in-depth distribution of C and O.
Emission of secondary atomic ions (
-
and
-
) and complex ions of the impurity-matrix type
from GaX compounds (X = N, P, As, Sb) under cesium primary ion bombardment was studied.
For consistent detection of the bulk-generated ions, samples were used whereto carbon and
oxygen were implanted by ion implantation.
For GaSb, swelling was shown to occur at the implantation dose of 115 cm
-2
; therefore, such
samples were unsuitable for the C and O signal calibration [1].
In the table, values of the normalized useful yield are listed for certain secondary ions containing
-

and
-
.
Normalized useful yield Secondary ions
GaN GaP GaAs GaSb
O
-
1 1 1 1
GaO
-
1.83 0.93 0.4 0.54
XO
-
0.014 0.18 0.1 0.06
C
-
1 1 1 1
GaC
-
0.025 0.06 0.006 0.003
XC
-
46 83.3 5.7 0.05
It turned out that the useful yield of such ions, as GaO
-
is several times greater than that of
-

ions for each matrix. On the other hand, the useful yield of GaC
-
ions is several factors of ten less
than that of
-
ions. Correlation has been observed between the yields of secondary complex ions
and bond broken energies in molecules, which confirms that the short range ordering holds during
target stirring under ion beam.
An attempt to interpret the obtained data using the model of dimer direct knocking-out and the
recombination model was made.


[1]. Kazantsev D.Yu., A.P. Kovarsky, Appl. Surf. Sci. 231-232 (2004) 826
SEM-P-Th-P18
246
Quantitative analysis of surface contaminants on silicon wafers by
means of TOF-SIMS

P. Rostam-Khani

*, J. Philipsen, E. Jansen, H. Eberhard, P. Vullings

Philips Semiconductors, QAS Department, Gerstweg 2,
6534 AE Nijmegen, The Netherlands
patrick.rostam-khani@philips.com


Measurement of surface contaminants on silicon wafers is essential for yield enhancement in IC
manufacturing. Depending on the nature of the contaminants different analytical techniques
(independent and well-calibrated techniques) are used in this field. For different contaminants
according to the SEMI ABCDM [1] classification such as
metal contamination (dopants)
VPD-ICP MS, (vapour phase decomposition inductively coupled plasma mass spectrometry),
acid/base contamination
LPE-IC (liquid phase extraction ion chromatography), or
organic (condensables) contamination
WD GC-MS (wafer desorber gas chromatography mass spectrometry)
is used. More recently, TOF-SIMS is introduced for monitoring surface contamination (metals,
ionics and organics) on patterned and non-patterned wafers. Today only normalized intensities are
reported for the most critical contaminants.
In February 2005 the new MEDEA + project HYMNE has been approved for two years [2].
Within this new project a sub task is entitled: TOF-SIMS wafer surface analysis. The goal is to
develop analytical procedures to use TOF-SIMS as a tool in contamination control for identification
and quantitative analysis of (sub)-surface and local contamination. This subtask is coordinated by
Philips Semiconductors Nijmegen and in total six different companies participate and collaborate.
For reliable and accurate quantification so-called relative sensitivity factors (RSF) should be
determined for TOF-SIMS analysis. To resolve the RSF always a second analytical technique as
afore mentioned is necessary. Due to the benefit of TOF-SIMS technique non-destructive properties
the identical wafer can be measured at least with two independent analytical techniques.
The RSFs of a standard package of 25 metal-ions have already been evaluated [3]. RSF for more
elements especially the so-called new materials (e.g. Pd, Hf, Zr, La) are under investigation. For
cations such as NH
x
(amines) sixteen compounds were selected from literature such as morpholine
and trimethylamine to start with. Surface application method and TOF-SIMS recovery studies will
start soon. A selection of 12 organic of which the most prominent condensable compounds such as
BHT (butylmethylphenol)) has been made. Beside the TOF-SIMS measurements a reproducible and
accurate procedure has to be found for reproducible application of organic compounds. The
presentation will show in detail the measurement strategy per category, the different procedures,
progress and results as well as plans for the near future. Furthermore studies were done on stability
and reproducibility of the TOF-SIMS analysis using evaluated RSFs. Here e.g. reference standard
was measured several times over a time period of a whole year.


[1] SEMI F21-1102 - Classification of Airborne Molecular Contaminant Levels in Clean Environments
[2] www.medea.org (HYMNE project 2T102)
[3] P. Rostam-Khani, M.J.P. Hopstaken, P. Vullings, G. Noij, O. OHalloran and W. Claassen Quantification Issues
of Trace Metal Contaminants on Silicon Wafers by means of TOF-SIMS, ICP-MS and TXRF Applied Surface
Science 231-232, 720 (2004)
SEM-P-Th-P19
247
Determination of the organic contaminations on Si wafer surfaces by
static ToF-SIMS: improvement of the detection limit with C
60
+


C. Poleunis*, A. Delcorte, P. Bertrand

a
Universit catholique de Louvain (UCL), Physico-Chimie et Phyique des Matriaux (PCPM),
Croix du Sud 1, B-1348 Louvain-la-Neuve, Belgium
Email: poleunis@pcpm.ucl.ac.be


It is well known in the semi-conductor industry that the organic contamination of wafer surfaces
can lead to serious difficulties in their production. This contamination generally comes either from
the clean room environment itself or from the plastic storage boxes used between different parts of
the processes. Among all the available surface characterisation techniques, static ToF-SIMS is well
suited to determine the composition of the organic contaminations at the surface of Si wafers [1,2].
Recently, the use of new polyatomic primary particles was shown to highly enhance the
secondary ion yields. In the case of C
60
+
primary ions, this enhancement could reach 2-3 orders of
magnitude in comparison with Ga
+
primary ions, for various organic materials [3]. Our TRIFT
ToF-SIMS instrument has been equipped with a C
60
+
ion source. In this study, we investigate the
yield improvement induced by C
60
+
ions instead of Ga
+
ions in the case of Si wafer surfaces.
Isopropanol cleaned Si wafers were stored in single wafer boxes (Fluoroware) and have been
analysed with both ion sources.
For an equivalent primary ion number, the results show that : 1) a high yield improvement is
measured for hydrocarbon contaminants with C
60
+
ions in comparison with Ga
+
ions (a yield
enhancement > 7000 is observed for the peak C
4
H
9
+
). This behaviour is even more pronounced for
higher mass positive secondary ions. For instance, a yield enhancement > 27000 is observed for the
peak at 661 m/z. This peak is characteristic of an antioxidant additive (Irgafos 168) classically
used in the manufacturing of polypropylene boxes. 2) The
28
Si
+
peak, that is the most intense in the
mass spectrum obtained with Ga
+
ions, is almost unnoticed in the mass spectrum for C
60
+
ions,
because of the very intense organic ion peaks surrounding it. Even so, the yield enhancement for
the
28
Si
+
peak itself is about 40. 3) In the case of the negative secondary ion mass spectra, an
important yield improvement is also observed for all the organic peaks (most of the time, the yield
enhancement reaches 3 orders of magnitude). 4) A series of negative silicon oxide clusters,
Si
n
O
(2n+1)
H
-
, is observed up to n = 16 (977 m/z) in the case of C
60
+
ions. With Ga
+
ions, the largest
negative silicon oxide cluster corresponds to n = 4 (257 m/z). Furthermore, the yield enhancement
for the peak at 137 m/z (Si
2
O
5
H
-
) reaches 67000. In conclusion, for an equivalent primary ion
number, the yield enhancement reaches 4 orders of magnitude with some of the observed secondary
ions.


[1] W. Storm, W. Vandervorst, C. Poleunis, P. Bertrand, .CleanRooms International, February 1996, S10.
[2] A. Karen, N. Man, T. Shibamori, K. Takahashi, Applied Surface Science 203-204 (2003) 541.
[3] D. Weibel, S. Wong, N. Lockyer, P. Blenkinsopp, R. Hill, J.C. Vickerman, Anal. Chem. 75 (2003) 1754.
SEM-P-Th-P20
248
Quantitative SIMS analysis of SiGe composition with low energy O
2
+

beams

Z. X. Jiang
a, *
, K. Kim
a
, J. Lerma
a
, A. Corbett
a
, D. Sieloff
a
, M. Kottke
a
, R. Gregory
a
, and S.
Schauer
a


a: Advanced Products Research and Development Laboratory, Freescale Semiconductor, Inc., 3501 Ed Bluestein
Blvd, MD K10, Austin, TX, 78721, USA
*: Author correspondence should be made, email: rat853@freescale.com


Quantitative analysis of SiGe composition with SIMS has gained great attention in order to meet
the increasing demand for SiGe process control. In general, the use of a calibration curve based on
multiple reference materials is applicable for any test samples that fall within the range under
calibration; however, it is desirable to perform quantitative analysis based on a single standard. The
success of the latter relies on the linearity between the sensitivity factors for the test samples and the
standard, either inside the SiGe film or with respect to the Si reference level inside the Si bulk.

Literature work has revealed constant Ge+ RSF with the Ge content up to 20 at. % for a 1 keV or
500 eV O2+ beam at normal incidence [1]. For 3 keV O2+ beams at normal incidence, some data
suggested a constant ratio between Ge and Si RSFs inside SiGe films with the Ge content up to 78%
[2], whereas some others indicated tremendous variation in the ratio with Ge content increasing
from 30% through 65% [3]. It is unclear whether LESIMS with an O2+ beam at 1 keV or below can
quantify Ge content of higher than 20 at. %. Furthermore, bombardment of a SiGe/SOI stack with
an O2+ beam often suffered from strong surface charging, posing additional challenges to the
quantification of SiGe composition with SIMS.

This work elaborated a study on the quantitative analysis of the composition of SiGe films on
either Si bulk or SOI substrate with a 1 keV O2+ beam at normal incidence. SiGe samples with Ge
content ranging from 13% to 65% were analyzed with SIMS, RBS, and AES. The Ge content as
measured with SIMS, based on a single SiGe/Si or SiGe/SOI standard, exhibited excellent
agreement with the corresponding RBS and AES data. It was concluded that LESIMS was capable
of providing accurate information on both composition and thickness of SiGe films with the Ge
content within the full range of this study.


References:
[1] H. L. Maul, P. F. Chou, and Y. H. Lu, Appl. Surf. Sci. 231-232, 713 (2004).
[2] U. Zastrow, J. Folsch, A. Much, K. Schmidt, and L. Vescan, SIMS X, 541 (1997).
[3] C. Huyghebaert, T. Conard, B. Brijs, and W. Vandervorst, Appl. Surf. Sci. 231-232, 708 (2004).
SEM-P-Th-P21
249
SIMS analysis of impurities and nitrogen isotopes
in gallium nitride thin films

Hajime HANEDA
a,
*, Takeshi OHGAKI
b
, Isao SAKAGUCHI
a
,
Haruki RYOKEN
c,
Naoki OHASHI.
a
, Atsuo YASUMORI
b


a
National Institute for Materials Science, 1-1 Namiki Tsukuba, Ibaraki 305-0044 Japan.
b
Tokyo University of Science, 2641 Yamazaki, Noda, Chiba 278-8510, Japan.
c
Kyushu University, 6-1 Kasuga-kouen, Kasuga 816-8580, Japan
haneda.hajime@nims.go.jp


Gallium nitride thin films were deposited on sapphire or zinc oxide substrates with a molecular
beam epitaxial method. Some thin films with Ga
14
N/Ga
15
N/Ga
14
N isotopic heterostructure were
also grown. A CAMECA type SIMS was employed to analyze impurities, such as substrate
elements, elements from K-cell, etc. Nitrogen isotopes were also analyzed. Some samples were
annealed in nitrogen atmosphere, and diffusivities of these elements and isotopes were evaluated.
Although nitrogen ions hardly diffuse under 1273K, zinc ions diffused from the substrate to thin
films. The diffusion mechanism in gallium nitride will be discussed.


SEM-P-Th-P22
250
SIMS profiling of doped NiSi gates

T. Janssens
a,*
, M.A. Pawlak
a
, J.A. Kittl
b
, M. Fouchier
a
and W. Vandervorst
a,c

a
IMECvzw, kapeldreef 75,B-3001 Leuven, Belgium
b
Affiliate researcher at IMEC from Texas Instruments
c
also: INSYS, KULeuven, Belgium


Engineering of the workfunction of metal gates is a requirement to enalbe the use of high k
dielectrica in advanced technologies. One approach is to combine a fully silicided gates (FUSI) with
the incorporation dopants at the interface silicide-dielectricum (SiO
2
, high k). A common porcess is
then the use of an implant into the poly-Si prior to the silicidation step. During the silicadation
process these dopants are pushed forward (snowploughed?) and appear to pile up at the interface.
As the amount of dopants at this interface determines the work function of the gate, it is important
to understand the influence of process parameters on the dopant dynamics during silicidation and
thus one needs accurate SIMS profiles. In this work we concentrate on the NiSi-gates (doped with
as) whereby various stages of partial (complete) silicidation are used in order to elucidate the
dopant migration mechanisms.
Standard SIMS analysis indicate that the Ni and Si ion intensities, which are needed to correlate
the position of the dopants relative to the material composition, show severe (SIMS related)
distortions near the silicide/oxide interface. To evaluate/minimize these artefacts the Ni and Si
profiles are determined with different sputtering conditions (ion beam, impact angle and energy) as
well as with backside SIMS.

Dramatic differences for the Ni and Si ion intensity of a
partially silicided sample can be seen when measured using
500eV O
2
+
bombardment from the front and back side (cfr
Fig.1). Whereas a pronounced Ni peak shows up at the
Si/SiON interface, when the sample is approached from the
front side, the latter is completely absent in the backside
SIMS profile. This observation implies that the Ni atoms are
pushed deeper into the sample very effectively by the
oxygen beam (even under non-oxidizing conditions!). The
pile up can then be explained by the fact that the SiON
interface acts as an diffusion barrier for the Ni atoms,
leading to a build up of Ni, which is sputtered away once the
SiON is mixed with the underlying Si layer. Further
comparison between front and back side SIMS shows that
also non oxidizing conditions (Cs bombardment) leads to
excessive tailing of the Ni profile.




Fig.1: 500eV O
2
+
bombardment of a
partially silicided gate. Front and
back side SIMS.
SEM-P-Th-P23
251
Study of SIMS ionization probabilities of different composition of
In(Al
x
Ga
1-x
)P

J.Sameshima , A.Karen

a
Toray Research Center, Inc., 3-7, Sonoyama 3-chome, Otsu, Shiga 520-8567
Junichiro_sameshima@trc.toray.co.jp


The optical device composed of III and V group elements usually includes multi-layers with
different composition. In SIMS measurement of these materials, quantification is often complicated
because the secondary ion yield changes due to Matrix effect. This effect depends on the kind of
materials as well as measurement condition such as detected elements, primary ion species,
secondary ion species, etc [1,2]. For III-V group compound material, negative ion yield was
investigated by some groups [3,4]. In general, ionization probability of negative ions sputtered by
Cs
+
depends on the concentration of Cs at the sputtered surface, and the Cs concentration is
inversely proportional to sputtering yield [5]. We have investigated systematically the change in
secondary ion yields of various elements of both impurities and matricies of In(Al
x
Ga
1-x
)P with
different composition. In this study, dependence of ionization probability on sputtering yield (and
therefore concentration of primary species at the sputtered surface) of various Al and Ga
composition are examined not only for negative secondary ions, but also for positive ions when Cs
+

is used. Magnetic sector type SIMS is used to detect both electronically positive and negative
elements with high sensitivity. We have tried to estimate Cs concentration at the sputtered surface
during Cs
+
sputtering.


[1] Dr. Stephen P. Smith, Secondary Ion Mass Spectrometry SIMS IX (1993) 227-230
[2] K. Wittmaack, Secondary Ion Mass Spectrometry SIMS X(1995) 39-46
[3] Y.Gao, Secondary Ion Mass Spectrometry SIMS VII(1989) 155-158
[4] K. Tsukamoto, S. Yoshikawa, M.Suzuki, T. Matsunaga and Y. Yoshioka, Secondary Ion Mass Spectrometry SIMS
VIII 1992 (147-150)
[5] V. R. Deline, William Katz, and C. A. Evans, Jr., Appl. Phys. Lett. 33(1978) 832-835


SEM-P-Th-P24
252
Profiles of boron and matrix elements through thin SiON layer

J.Sameshima
a
, T.Hasegawa
a
, T.Nishina
a
, T.Nishitani
a
, K.Yoshikawa
a
, A.Karen
a


a
Toray Research Center, Inc., 3-7, Sonoyama 3-chome, Otsu, Shiga 520-8567
.
Junichiro_sameshima@trc.toray.co.jp


For the analyses of gate insulating materials of thin silicon oxy-nitride (SiON) and dielectric
films, SIMS is one of the available tool along with TEM and ESCA etc. Especially, to investigate
the distribution of dopant in the thin films, SIMS is appreciably effective in these techniques
because of its depth profiling capability and high sensitivity. One of the problem occurring in this
SIMS measurement is the change of secondary ion yield at the interface as well as in the layers with
different chemical composition. To solve this problem, some groups have researched the
phenomenon for SiO
2
/Si interface [1,2,3,4]. In the present study, profiles of boron and matrix
elements in the Si/SiON layers on Si substrate have been investigated. The SiON layers with
various N composition were capped with amorphous Si film, then
11
B was ion-implanted through
this Si film. The dependence of boron secondary ion yield on N composition in the SiON layer was
investigated, considering the variation of profiles of matrix elements through the thin SiON. Both
O
2
+
and Cs
+
primary ions with low energy were applied for these measurements and oxygen flood
was used in some measurements with O
2
+
primary beam.


[1] W. Vandervorst, T. Janssens, R. Loo, M. Caymax, I. Peytier, R. Lindsay, J. Fruhauf, A. Bergmaier, G. Dollinger,
Applied Surface Science 203-204 (2003) 371-376
[2] S. Hayashi, K.Yanagihara, Applied Surface Science 203-204 (2003) 339-342
[3] M. Barozzi, D. Giubertoni, M.Anderle, M. Bersani, Applied Surface Science 231-232 (2004) 632-635
[4] Temel H. Buyuklimanli, John W. Marino, Steven W. Novak, Applied Surface Science 231-232 (2004) 636-639

SEM-P-Th-P25
253
Non-destructive B, P and As Dosimetry Using
Normal Incidence Oxygen

Hans Maul *, H.-Ulrich Ehrke, Norbert Loibl, Christoph Schnrer-Patschan

CAMECA GmbH
Bruckmannring 40
85764 Oberschleissheim/Munich, Germany
hans.maul@cameca.fr


Full wafer SIMS provides SIMS metrology without breaking the wafer. SIMS, known as a
destructive method in the scientific sense, can be regarded as non-destructive in the practical sense
provided it does nothing which would prevent the wafer to be returned to production. This can be
assumed as long as only oxygen primary ions are used. Depth profiling with oxygen primary ions
changes the wafer much less than the oxidation and patterning wafer processing steps. All what the
oxygen beam bombardment leaves behind is a small size shallow crater with some nanometer SiO2
at the bottom.
This work shows that non-destructive implant dose monitoring using oxygen primary ions is
not limited to B in Si and SiGe. Also ultra shallow P and As dose monitoring is made available
using normal incidence oxygen primary ions. Results of high precision dose monitoring and
mapping obtained by CAMECA`s full wafer quadrupole SIMS 4600 will be presented.
SEM-P-Th-P26
254
Determination of impurities and main elements in thin film structures
InN/GaN on sapphire.

V.Yu. Davydov
1
, D.Yu. Kazantsev
1
, A.P. Kovarsky
1*
, M.A. Yagovkina
1
, Hai Lu
2
, and
W.J. Schaff
2
.

1
A.F. Ioffe Physico-Technical Institute of the Russian Academy of Sciences, Saint Petersburg 194021, Russia.
2
Department of Electrical and Computer Engineering, Cornell University, Ithaca, New York 4853
*e-mail: alex.kovarsky@mail.ioffe.ru.


We tried to reveal correlation between the carrier concentration and the content of impurities and
the degree of stoichiometry in various InN samples. InN films were grown on sapphire substrates by
molecular beam epitaxy (MBE). In all the samples, an AlN nucleation layer and a GaN buffer layer
were grown before growing the InN layer itself.
X-ray diffraction was used to determine the crystallographic quality of the samples. Narrow X-
ray rocking curve profiles indicated that the crystallographic structure of nitride layers was perfect.
Small widths of all the Raman lines and a good agreement of polarized Raman spectra with X-ray
data also demonstrated the high quality of the crystallographic structures with the selection rules for
the wurtzite structure.
In-depth distribution of intrinsic and impurity elements was measured by SIMS. The quantitative
analysis of the Mg, C and O distribution was carried out using RSF for GaN. Furthermore, C and O
were determined in the ion image mode. The correlation between the integral concentration C and
O and the carrier concentration was found.
On account of extremely high selectivity of sputtering and complex morphology of the etching
crater bottom, our measurements provided rather different thickness values for InN and GaN layers.
The samples with thin films were characterized by the InN to GaN thickness ratio 1:3 for cesium
bombardment and 1:1 for oxygen bombardment.
SEM-P-Th-P27
255
Characterization of Laser-Fired Contacts in PERC Solar Cells:
SIMS and TEM Analysis Applying Advanced Preparation Techniques

U. Zastrow a,*, L. Houben b, D. Meertens b, A. Grohe c, T. Brammer a,# and E. Schneiderlchner
c,

a
Institute of Photovoltaics, Research Center Jlich GmbH, 52425 Jlich, Germany
b
Institute for Solid State Research, Research Center Jlich GmbH, 52425 Jlich, Germany
c
Fraunhofer Institute for Solar Energy Systems, Heidenhofstrasse 2, 79110 Freiburg, Germany

present address: Deutsche Cell GmbH, 09599 Freiberg/Sachsen, Germany

#
present address: Q-Cells AG, 06766 Thalheim, Germany
* email: u.zastrow@fz-juelich.de


Silicon solar cells with passivated emitter and rear contacts (PERC) yield high efficiencies due to
reduced carrier recombination at the metal-semiconductor contact interfaces. Laser-firing of rear
contacts (LFC) [1] is well fitted to the industrial fabrication of PERC silicon solar cells by
combining usual process equipment, simple wafer handling and high throughput capacity.
In the LFC process the contact is formed in atmosphere by a Nd:YAG-laser pulse treatment of a
layer structure of 2 m Al / 100 nm SiO
2
/ Si-wafer. Within a diameter of 80-100 m laser
ablation removes most of the Al-metallization while the dielectric SiO
2
layer destruction is
restricted to the spot center within a radius < 25 m.
In order to investigate significant local p-type doping of the Si-substrate the characterization
method has to be able to detect Al-concentrations < 10
18
cm
-3
. However, the topography and mor-
phology of the laser-crater formed by the combined ablation/melt process in atmospheric ambient is
a challenge for SIMS depth profile analysis.
Furthermore, cross-sectional transmission electron microscopy (TEM) is used as a complemen-
tary technique to provide the required information on the in-depth variation of the microstructure in
the transformed layers.
In this study we apply ion-beam supported preparation techniques for both mesa-separation by
trench sputtering [2,3] and FIB lift-out lamella cutting [4,5] for dynamic SIMS and TEM analysis
of single LFC contacts, respectively. Detailed compositional and structural informations from the
active LFC area are obtained combining both characterization techniques. While TEM and
microdiffraction pattern give evidence for a mixture of Al- and Si-crystals within the up to 1 m
thick surface layer according to the Al-Si phase diagram, spatially resolved SIMS depth profiling
indicates ppm-range Al-diffusion a few hundred nm into the buried, substantially undisturbed Si-
lattice.
In this poster the analytical methodology is demonstrated. LFC characterization results are pre-
sented and discussed in terms of the electronic properties of the metallurgical contact formation.


[1] R. Preu, E. Schneiderlchner, R. Ldemann, S. W. Glunz, patent WO 02/25742 (2001)
[2] K. Wittmaak, SIMS VIII, ed. by A. Benninghoven et al., Wiley-Chichester (1992) p. 211
[3] R. von Criegern, L. Weitzel, H. Zeininger, R. Lange-Gieseler, Surf. Interf. Anal. 15 (1990 ) 415
[4] M.H.F. Overwijk, F.C. van den Heuvel, C.W.T. Bulle-Lieuwma, J. Vac. Sci. Technol.B 11 (1993) 2021
[5] L.A. Giannuzzi, J.L. Drown, S.R. Brown, R.B. Irwin, F.A. Stevie, Microsc. Res. Tech. 41 (1998) 285
SEM-P-Th-P28
256
C
60
+
Cluster Beam Depth Profiling of Semiconductor Materials

Peter H. Chi, Greg Gillen, Albert Fahey, Eric Windsor, and K. J. Kim
*


National Institute of Standards and Technology
Gaithersburg, MD 20899 USA

*
Nano Surface Group, Korea Research Institute of Standards and Science
P.O Box 102,Yusong, Daejon 305-600, Korea


As integrated circuit dimensions shrink to sub-micrometer, the need for accuracy in depth
profiling and quantifying impurity implanted in semiconductor materials using secondary ion mass
spectrometry (SIMS) has become more demanding and challenging. To probe the shallow dopant
implants in Si and other materials, SIMS instruments, both quadrupole and magnetic sector, utilize
very low primary ion beam energy (in sub keV) to bombard the sample surface. In this condition, it
is difficult to obtain a well-focused and high current density beam, especially in a magnetic sector
instrument. Recently, there are many interests in using molecular ion beam to profile various
materials.1-2 Using polyatomic beams significantly increase the sputtering rate and improve depth
resolution on multi-metal layers sample. In this work, we are utilizing C60+ cluster primary ion
beam to sputter depth profile of Si, GaAs, metal, and multiple delta-layers materials. Initial results
showing good depth resolution obtained in multi-layer samples, but depth profile of silicon sample
showed some unexpected outcomes. Experiment results will be presented at the conference.


G. Gillen, R. King, and F. Chmara, J. Vac. Sci. Technol. A17, 845 (1999)
S. Sun, C. Szakal, T. Roll, P. Mazarov, A. Wucher, and N. Winograd, Surf. Interface Anal. 2004; 36: 1367.
SEM-P-Th-P29
257
Correlation of SIMS sputtering rate variations with primary beam
current drifts: an effective application to high precision full wafer
mapping

M. Juhel
1,*
, F. Laugier
2
, C. Wyon
2
, L.F.Tz. Kwakman
3
and M. Hopstaken
3

1
STMicroelectronics, 850 rue Jean Monnet, 38926 Crolles, France
2
CEA-DRT-LETI CEA/GRE 17, rue des martyrs 38054 Grenoble Cedex, France
3
Philips Semiconductors, 860 rue Jean Monnet, 38920 Crolles, France
marc.juhel@st.com


Quantification of SIMS depth profiles involves a crater depth measurement performed either by
stylus profilometry, optical profilometry or, more recently, in-situ laser interferometry [1].
Today, in the Semiconductors Industry, each of these techniques face some limitations given
the evolution of SIMS applications towards low energy depth profiling and high volume analysis.
Mechanical stylus profilometry has been widely used for depth measurements but reaches its
limit in accuracy for craters with depths below 50 nm that are typical for current CMOS technology.
While optical profilometry and laser interferometry are more precise in this respect, they in turn are
transparent to surface and buried oxides or silicon nitride and as such give rise to wrong depth
measurements in the presence of such oxides: these techniques are not applicable to the analysis of
patterned wafers.
Therefore, alternative means of sputter depth calibration are needed, especially if one wants to
take full advantage of the recent new instrumental improvements that finally have made it possible
to do automated SIMS on several full 300 mm wafers. To be able to measure the within wafer non-
uniformity of specific species accurately and reproducibly, the sputter characteristics have to be
known and to remain constant during the SIMS sequence that -when including 10-50 measurement
locations- may take several hours of analysis time.
The alternative solution proposed in this study is to first establish the correlation between the
sputtering rate and the primary beam current and then to use this correlation to correct the depth
profile for the experimental beam current drifts as these occur.
This methodology has been applied to a Cameca Ims-Wf magnetic sector SIMS with 300mm
wafer analysis capabilities and continuous beam current measurement during depth profiling.
With this instrument Boron and Arsenic implants in silicon have been analyzed using Cesium
and Oxygen as primary ions and ion impact energies of 500eV and 4keV. Under these analytical
conditions a linear correlation between the primary ion current value and the sputtering rate is
found. This finding is supported by direct crater measurements by optical and mechanical stylus
profilometry.
In this presentation we will elaborate our developed procedure for depth quantification in more
detail and also illustrate its benefit for applications such as the high precision measurements of
shallow junctions across a 300 mm wafer. Representative results obtained on an Arsenic implanted
wafer show a junction depth precision of 23.00 +/- 0.07nm (min/max range) over a 24 hours period:
with such precision SIMS can be used effectively for spatial uniformity analysis on 300mm wafers
and by this virtue offers great added value when it comes to support process development or
(metrology) tool qualification in Semiconductors R&D and Manufacturing centres.


[1] E. De Chambost, P.Monsallut, B. Rasser, M. Schuhmacher, Appl. Surf. Sci. 203/204 (2003) 391-395.
SEM-P-Th-P30
258
Improving the growth of HfO
2
ALD layers by modifying growth
parameters and reducing precursors contaminants.

T. Conard, A. Delabie, W. Vandervorst

IMEC, SPDT/MCA, Kapeldreef 75, 3001 Leuven, Belgium
Email: tconard@imec.be


For the implementation of HfO
2
layers in sub 1 nm EOT devices, it is important to improve the
quality of very thin HfO
2
layers, deposited by Atomic Layer Deposition (ALD). One of the key
aspects in improving the electrical performance could also be to decrease the residual precursor
contamination to its lowest possible level.
In this study, we investigated the growth of HfO
2
by ALCVD with the HfCl
4
/H
2
O chemical
system. Due to its high sensitivity, (TOF)-SIMS is a method of choice in order to investigate the
presence of Cl contamination in the HfO
2
layers. In this study, we investigated the influence of
process parameters (temperature, pulse length, surface preparation, .) on the Cl residue present in
the layers. At the same time TOFSIMS was used to investigate the layer growth by looking at the
detailed growth curves and layer closure. This led to a better understanding of the reaction
mechanisms of the HfCl
4
/H
2
O ALD together with the reduction of the Cl concentration by 2 orders
of magnitude in optimised growth process. The results will be compared with electrical results
obtained in similar growth conditions.
Other important precursor contaminants can involve H and C. We show here that meaningful
results concerning these contaminants can only be obtained if the layers considered are capped by
an other material in order to avoid adsorbtion of airborne contaminants (H
2
O and hydrocarbons).
SEM-P-Th-P31
259
Measurements of Ti-Containing Barrier Materials and Low-K
dielectric Films Using Backside Polishing SIMS

Ming Hong Yang
a,
*, Jimmy Lan
a
, Ian Mowat
a
, Raashina Humayun
b
and Jianing Sun
b
.


a
Charles Evans & Associates,810 Kifer Road, Sunnyvale, CA 94086, USA
b
Novellus Systems, Inc, 4000 North First Street, San Jose, CA 95134, USA.
myang@cea.com
a,*



During SIMS analysis, titanium is typically monitored as a positive secondary ion because its
positive ion yield with oxygen bombardment is significantly higher than its negative ion yield with
Cs bombardment. However, for low-K dielectric materials, the high-energy (9keV) electrons used
for the charge neutralization can damage low-K materials during SIMS measurements when the
positive secondary species are monitored using a Cameca IMS 4f instrument. In the present work,
the electron energy was lowered to ~10 eV by switching the secondary ion from the positive to
negative so that the damage to the low-K materials was eliminated. Ti distribution was analyzed
using a Cs primary ion beam and Ti-containing negative ions were monitored as secondary ions to
improve the ion yield. In addition, advanced backside sample polishing was employed to reduce the
ion mixing effect that occurs when samples are profiled from the front side. The results for various
samples under different analytical conditions and preparation methods will be presented.
SEM-P-Th-P32
260
Phosphorous degassing from Poly Silicon under thermal exposure:
A ToF-SIMS depth profile investigation

S.G. Alberici
a,
*, A. Elbaz
b
, R. Piagge
b


a
FTM Division, Physics and Material Characterization Laboratory
b
FTM Division, R2 Operation & Technology Development
STMicroelectronics S.r.l., Via C. Olivetti, 2 I-20041 Agrate Brianza, Milan, Italy
stefano.alberici@st.com


Among many fields of application, Phosphorous is even used for polycrystalline Silicon (Poly Si)
doping in gate electrodes for Complementary Metal Oxides Semiconductor (C-MOS) based
electronic devices.
Irrespectively from the doping methodology applied by the manufacturer (P implant from
vacuum implanter after film deposition by LPCVD furnace and induced P diffusion or in situ
doping from PH
3
precursor using single wafer equipments), one of key concerns related to the
methodology itself is P mobility under thermal exposure that, in turn, can lead to a P depletion of
the Poly Si which has been previously doped.
Thermal exposures are required due to a number of successive steps that have to be performed in
order to realize the device.
In order to save the P content provided by the doping procedure, a possible solution is capping
the Poly Si by a film characterized by a relative low P diffusivity with respect to the one in Poly Si.
As a matter of fact, P diffusion in Poly Si is enhanced by inter granular diffusion that normally is
much higher than the one due to the Si lattice (bulk diffusion).
With this in mind, by capping the film with an amorphous layer, as a Si oxide, it is in principle
possible to reduce the trend of P to leave the underlying layer, so that this phenomenon can be
attenuated.
Aim of this work is analyzing, by ToF-SIMS depth profiling, Poly Si sample that have been P
doped and than subsequently thermally exposed, with and without a Si oxide capping layer, in order
to study the effectiveness of this barrier to prevent this depletion.
In this respect, the work shows the attitude of the ToF-SIMS depth profile technique in being a
vehicle in order to reveal the efficiency of this approach for microelectronic applications.
SEM-P-Th-P33
261
SIMS Analysis of Multiple Quantum Wells in a Vertical Cavity
Surface Emitting Laser Structure Using the Mixing-Roughness-
Information depth Model

S. Ootomo
a,
*, H. Maruya
a
, S. Seo
a
and F. Iwase
a


a
Yokohama R&D Laboratories, The Furukawa Electric Co., Ltd., 2-4-3, Okano, Nishi-ku, Yokohama, Japan
Email: ootomo.shinya@furukawa.co.jp


A vertical cavity surface emitting laser (VCSEL) structure, which includes an active cavity
sandwiched by top and bottom distributed Bragg reflector (DBR) mirrors, is very thick and
complex. Due to the existence of a top DBR with a few micrometers in thickness on an active
cavity, it is difficult to analyze thin (typically <10 nm) multiple quantum wells (MQWs) in an
active cavity.
In this paper, we describe the specific method to measure high-resolution depth profile of an
MQW structure in a VCSEL. Also, the resulting profile is quantitatively evaluated using the
mixing-roughness-information depth (MRI) model developed by Hofmann [1].
The sample is the starting wafer from which the 850-nm VCSEL are fabricated. The top
DBR consists of 25 pairs of Al
0.9
Ga
0.1
As/Al
0.2
Ga
0.8
As and of total thickness of about 3 m. The
cavity contains four undoped 6-nm-thick GaAs wells and five C-doped 10-nm-thick AlGaAs
barriers. The SIMS measurements are performed with a quadrupole SIMS instrument
(ADEPT1010, ULVAC-PHI Inc.). Our novel method consists of the following two steps. First, the
top DBR is rapidly sputtered using Cs
+
beam ions of 10 keV, rastered across an area of 500 m
1000 m
2
. Then, the active layer is carefully sputtered with a 1.5 keV Cs
+
primary beam scanning
over an area of 300 600 m
2
. The measured profile has enough depth resolution and the sufficient
number of data points, indicating that we can clearly distinguish between well and barrier layers.
From the reconstruction of true in-depth concentration profile by the MRI calculation, furthermore,
we can extract the values of aluminium mole fraction of 0.2 and doping concentration of 5 10
18

cm
-3
in modulation C-doped AlGaAs barrier layers.
This means that our method assisted by the MRI model is extremely promising for
determining the matrix element composition and doping concentration in the active layer.


[1] S. Hafmann, Surf. Interface Anal., 21, (1994), 673.
SEM-P-Th-P34
262
Thermal effects on
1
H and
2
H distributions in atomic layer deposition
of HfO
2
and Al
2
O
3
using heavy water (D
2
O)

P. Holliger
a,
*, F. Martin
a
, F. Pierre
a
, G. Reimbold
a
, P. Rivallin
a
, D. Jalabert
b
and C. Hobbs
c

a
CEA-DRT/LETI-CEA Grenoble, 17 rue des Martyrs, 38054-Grenoble Cedex 9, France
b
CEA-DSM/DRFMC-CEA Grenoble, 17 rue des Martyrs, 38054-Grenoble Cedex 9, France
c
.Freescale Crolles 2, 850 rue Jean Monnet, 38926-Crolles Cedex, France
*
Corresponding author: holliger@cea.fr


Incorporation of deuterium using D
2
O as the oxidant during the atomic layer deposition of high-k
gate dielectric on silicon should lead after post-metal annealing to a better passivation of defects
and interface states than those obtained with hydrogen species [1,2]. However, an optimised high-
k/D
2
O anneal process is required for manufacturing high performance CMOS. This paper reports
new investigations by SIMS on the deuterium incorporation inside thin HfO
2
and Al
2
O
3
layers
deposited by ALD using HfCl
4
and trimethylaluminium respectively and heavy water on a wide
range of thermal treatments.
SIMS experiments were carried out on a CAMECA IMS5F using Cs
+
primary beam at an impact
energy of 2 keV and an angle of incidence of 50 to the normal with the detection of MCs
2
+
(where
M = H, D, O, Si) secondary ions. This technique is appropriate for obtaining good performance in
very thin layer depth profiling of electronegative elements [3]. The results highlight the
hydrogen/deuterium isotope effect at different annealing temperatures. Deuterium profile shows a
concentration peak at the high-k/substrate interface; however, the D dose is low and becomes
sharper at high temperature. This preferential incorporation of deuterium at high temperature could
improve the interface quality and enhance the high-k device stability and reliability.


[1] I.C. Kizilyalli et al., IEDM 98 (1998) 935-938.
[2] H.H. Tseng et al., IEDM 03 (2003) 83-86.
[3] P. Holliger, F. Laugier, J.C. Dupuy, Surf. Interface Anal. 34 (2002) 472-476.


This work has been carried out in the frame of CEA-Lti / Freescale collaboration
SEM-P-Th-P35
263
Investigations of LED Structure with Graded InxGa1-xP Buffer by
SIMS Method

A. Vincze
1
,*, J. Kov
1
, L. Peternai
2
, S. Hasenhrl
3
, M.Vesel
2


1
International Laser Centre &
2
Department of Microelectronics, Slovak University of Technology,
Ilkovicova 3, 812 19 Bratislava, Slovak Republic
3
Slovak Academy of Science, Dubravska cesta 9, 84 104, Bratislava, Slovak Republic
E-mail address: vincze@ilc.sk


In recent years there has been a renewed interest in GaP in context of epilayers and
heterostructures. The drive for new devices like more efficient LEDs have stimulated the
development of the growth of GaP and its alloys, using metal organic chemical vapor deposition
(MOCVD). One possible solution of the light emitting diode (LED) development is the direct
growth of LED structure on GaP substrate. The InxGa1-xP ternary alloy represents proper material
for LED applications up to the direct indirect crossover of InxGa1-xP, which takes place for x in
the range from 0.27 to 0.29 [1]. Large lattice mismatch between GaP substrate and InxGa1-xP
epitaxial layers exhibiting direct bandgap structure represents a demanding control of the growth
process [2] and extensive optimization of the growth parameters is imperative [3].
InxGa1-xP layers were grown by low-pressure IR-heated LP MOCVD (AIXTRON AIX 200) on
GaP substrate. A 300 nm GaP Si doped buffer layer (n=1.91018 cm-3) was deposited before the
growth of step-graded Si doped InxGa1-xP buffer. It consists of eight 300 nm thick InxGa1-xP
layers with compositional change xIn~0.04 between the steps. On the top of the graded buffer the
N-P LED structure consisting of 1000 nm Si doped In0.36Ga0.64P and of 1000 nm Zn doped
In0.36Ga064P was grown. The growth conditions were in details described in reference [3]. The
lattice mismatch represents 2.37% between GaP substrate and top In0.36Ga0.64P layer. The
compositional changes of InxGa1-xP graded buffer inserted between GaP substrate and
subsequently grown In0.36Ga0.64P homojunction LED structure were investigated along the cross-
section by Raman spectroscopy.
The time of flight based SIMS instrument (Ion-TOF, SIMS IV) with high energy Au+ primary
source was employed for LED structure analysis. For the depth profiling of the structure the high
energy pulsed primary gun is combined with a low energy sputter guns (Cs+, O2+) because of low
erosion rate. The sputtering ion beam is rastered over the area of 300x300 m while the primary
beam is rastered within the 70x70 m area in the center of sputtered area. By the depth profiling of
the structure all the eight different In content steps have been detected. The p-n junction position in
the structure was resolved from Si and Zn doping profiles. The SIMS profile measurements
confirmed the unique structure growth process.

This work was partially supported by VEGA grants No. 1/0152/03, 1/0130/03, project
No. APVT-20-013902 and IST GaP LED project.


[1] J. Novk, S. Hasenhrl, R. Kdela, M. Kuera: Growth and characterisation of InxGa1-xP layers with composition
close to crossover from direct to indirect band gap. Journal of Crystal Growth (in print)
[2] W. Korber, K. W. Benz, Journal of Crystal Growth 73 (1985) 179
[3] S. Hasenhrl, J. Novk, I. Vvra, A. atka, Journal of Crystal Growth 272 (2004) 633
SEM-P-Th-P36
264
The influence of impurity profile on ultrashallow GaAs sidewall
tunnel junction characteristics

Takeo Ohno
a,
*, Yutaka Oyama
a,b
, Jun-ichi Nishizawa
b


a
Department of Materials Science, Graduate School of Engineering, Tohoku University,
Aramaki Aza Aoba 6-6-11-1021, Sendai 980-8579, Japan
b
Semiconductor Research Institute of Semiconductor Research Foundation,
Aramaki Aza Aoba 519-1176, Sendai 980-0845, Japan
E-mail: electron@stu.material.tohoku.ac.jp


The ISIT (ideal static induction transistor) [xii] and TUNNETT (tunnel injection transit time
effect diode) [xiii,xiv] are promising semiconductor devices for THz operation. In these devices, the
most important device segment is the performance of p
+
n
+
tunnel junction. At present, ultrashallow
(50 nm) GaAs sidewall tunnel junctions with the record peak current density of up to 31,000 A/ cm
2

has been achieved by molecular layer epitaxy [xv]. In this paper, SIMS measurements were applied
to investigate the influence of impurity profiles on the ultrashallow sidewall tunnel junction
characteristics.

The impurity (Be, Te and S) concentration and its profile in epitaxial layers were measured
by dynamic SIMS. The primary ion beam used was 1 keV Cs
+
ion with a beam current of 10 nA at
the 500x500 m
2
crater region, and BeAs
-
, Te
-
and S
-
ions were measured as the secondary ions.

From the SIMS profiles on the test-element-group area of each device chips, it is observed
that the Te and S profiles were very flat and steep. On the other hand, Be profile has been shown
pile-up with a concentration up to 10
20
cm
-3
at the regrowth tunnel junction interface. This result
could possibly offer a reason for the very high peak current density in conjunction with the very
steep impurity profiles up to > 2x10
19
cm
-3
nm
-1
.

The influences of AsH
3
surface treatment on the Be profile before regrowth of Be-doped
GaAs layer were also investigated. It is shown that the long AsH
3
surface treatment enhances the
steepness of Be profile, while the Be concentration gradient is above 2.5x10
19
cm
-3
nm
-1
for t=60
and 120 min, whereas that for t=30 min is 1x10
19
cm
-3
nm
-1
. The Be interface pile-up increases as
the AsH
3
treatment time is longer, while Be concentration is 9x10
19
, 1.2x10
20
and 1.5x10
20
cm
-3
for
t=30, 60 and 120 min, respectively. These phenomena affect the improvement of sidewall tunnel
junction characteristics.



[xii] J. Nishizawa, Proceedings of 11th Conference on Solid State Devices, (1979); Jpn. J. Appl. Phys. (Suppl.) 19-1,
(1980), p. 3.
[xiii] J. Nishizawa and Y. Watanabe, Sci. Rep. Res. Inst. Tohoku. Univ. 10(2), (1958), p. 91.
[xiv] K. Motoya and J. Nishizawa, Topics in Millimeter Wave Technology, Vol. 2, Chapter 1, pp. 1-46 (Academic Press,
1988).
[xv] Y. Oyama, T. Ohno, K. Tezuka, K. Suto and J. Nishizawa, Appl. Phys. Lett. 81, (2002), pp. 2563-2565.
SEM-P-Th-P37
265
Ultra low energy SIMS depth profiling of sub-2nm Silicon oxynitride
films

C. P. A. Mulcahy *, B. Bck, P. A. Ebblewhite and S. Biswas.

Cascade Scientific Ltd, ETC Building, Brunel Science Park,
Uxbridge, Middlesex, UK. UB8 3PH
*Corresponding Author. Email: cpa.mulcahy@brunel.ac.uk


Silicon oxynitride is currently one of the most researched silicon-based dielectric currently used
in IC fabrication. The properties of the oxynitride can be modified to achieve desirable functions by
specific engineering of thickness and stoichiometry. In the case of gate stacks, considerable
progress has been made in optimising oxynitride dielectrics in order to reduce boron penetration and
dielectric leakage with respect to pure SiO
2
allowing sub-2-nm dielectrics.
In this study we have used ultra low energy (ULE) SIMS as the primary tool to assess a range of
ultra thin (<50) silicon oxynitride films. Critical parameters such as stoichiometry and thickness
have been assessed using the technique and the results have been compared with in-depth analysis
of the same wafers using shallow angle surface XPS, depth profiling XPS and RBS studies. We
have shown that the results of ULE SIMS, depth profiling XPS and RBS studies are comparable
when considering stoichiometry of the nitrogen component of the film (up to 15% N), the most
critical variant allowing specific property modification. We also show that one-hit surface XPS
studies give excellent nitrogen dose correlation with the SIMS analyses. However, to achieve the
depth resolution required to observe the true elemental distribution of sub-2-nm dielectrics we show
that ULE SIMS is the key tool for assessing these novel structures.
SEM-P-Th-P38
266
TOF-SIMS studies on Rose Bengal devices:
Search for the mechanism responsible for resistive switching

A. Besmehn
a
*

, A. Scholl
a
, B. Lssem
b
, M. Alba
c
, S. Karthuser
b
, and U. Breuer
a


a
Central Division of Analytical Chemistry, Research Center Juelich GmbH, 52425 Juelich, Germany
b
Institute of Solid State Research and CNI-Center for Nanoelectronic Systems for Information Technology,
Research Center Juelich GmbH, 52425 Juelich, Germany
c
Infineon Technologies, CPR ND, 81730 Munich, Germany
a.besmehn@fz-juelich.de


As conventional semiconductor memory technology (DRAM and FLASH) faces tough barriers
for scaling below 50nm feature size resistive memories have recently attracted considerable interest.
Organic systems are promising candidates because of their scaling potential down to the molecular
level. Recently, layers of Rose Bengal (4,5,6,7-Terachloro-2',4',5',7'-tetraiodofluorescein disodium
salt) have been shown to resistively switch with high R
OFF
/R
ON
values [1]. This switching
mechanism has been attributed to molecular-specific behavior of Rose Bengal [1-3] but the origin is
still under investigation. To examine the switching behavior in more detail electronic studies were
performed on metal-insulator-metal (MIM) structures with systematically varied compositions,
consisting of an top electrode (Al or Ti), organic insulator layer (Rose Bengal or Xanthene), and a
bottom electrode (ZnO or ITO) [4]. The conclusion from this study is that the formation of
interfacial Aluminum oxide seems to be the origin of the switching effect. In addition Rose Bengal
devices show a loss of device stability with time [5].
To gain more insight in the microscopic processes involved at the interface and the organic
material an analytical technique is required that is capable to provide suitable depth resolution
according to the expected thin Al oxide interfacial layer (few nm), high mass resolution to solve
possible isobaric interferences of the Al compounds and fractionated organic material from the
Rose Bengal or Xanthene, and in addition the possibility for spectroscopic studies to detect
variation in composition of the organic material. A combination of TOF-SIMS depth profiling and
static TOF-SIMS spectroscopy can fulfil the analytical demands. Depth profiling allows to analyze
the elemental distribution in depth through the whole layered system and, if stopped at the interface,
makes the interface accessible for spectroscopic analysis. Measurements were done using the TOF-
SIMS IV instrument (Ion-TOF GmbH, Mnster, Germany).
The depth profiling supports that the switching behavior is mostly affected by the formation of
the Al oxide rather than the choice of the organic material. A degradation of Rose Bengal is obvious
in the spectra and profiles. The reason could be reduction of the organic material. This can be the
limiting factor of device lifetime.
In addition we hope to present first measurement results from these samples using the new Bi
cluster primary ion source, which reduce fractionation. This provides additional information on the
degradation of Rose Bengal. A comparison of the Ga and the Bi results will then be given.


[1] A. Bandyopadhyay and A.J. Pal, Appl. Phys. Lett. 82 (2003) 1215- 1217.
[2] A. Bandyopadhyay and A.J. Pal, Appl. Phys. Lett. 84 (2004) 999- 1001.
[3] A. Bandyopadhyay and A.J. Pal, J. Phys. Chem. B 107 (2003) 2531- 2536.
[4] Alba et al., in preparation.
[5] B. Lssem and S. Karthuser, private communication.
BIO2-P-Th-P39
267
Imaging of Human Liver Cell Intoxicated by Heavy Metal using Time-
of-flight Secondary Ion Mass Spectrometry (TOF-SIMS)

Fu-Der Mai
a*
, Bo-Jung Chen
b
, Winne Chen
b

a
Department of Applied Chemistry, Chung-Shan Medical University, Taichung, Taiwan 402. R.O.C
b
Department of Chemistry, National Tsing-Hua University, Hsinchu, Taiwan 300, R.O.C
davismai@csmu.edu.tw


Human liver cells intoxicated by six different heavy metals were analyzed by spatially resolved
time-of-flight secondary ion mass spectrometry

(TOF-SIMS) to directly visualize the distribution

of metal ions on a single cell basis. In order to enhance the lateral resolution, a protocol was
developed by combining the freeze-fracture sample pretreatment with molecular imprinting
techniques to transfer the intoxicated cells to a silicon wafer. Liver cells were immersed in a
solution containing six different heavy metal ions of various concentrations and time durations to
simulate the intoxication process. Reliable imaging data library associated with the metal
intoxication of human liver cells was created as a reference for future studies. We have quantified
the metal concentrations as well as depth profile of the liver cells on a single cell basis. This study
can pave the way to study the time-evolving damage to the human liver cells by heavy metals.
BIO2-P-Th-P40
268
Study of the mechanism of diatoms multiplication by means of
29
Si
isotope tracing

J.- N. Audinot
a*
, C. Guignard
b
, H.- N Migeon
a
and L. Hoffmann
b
.

a
Laboratoire dAnalyse des Matriaux, Centre de Recherche Public
Gabriel Lippmann 41, rue du Brill, L-4422 Belvaux, Luxembourg
b
Cellule de Recherche en Environnement et Biotechnologies, Centre de Recherche Public
Gabriel Lippmann, 41, rue du Brill, L-4422 Belvaux, Luxembourg
audinot@lippmann.lu


Diatoms are delicate unicellular organisms that have a yellow-brown chloroplast that enables
them to photosynthesize. For the most part, they are photosynthetic micro-organisms, although
some may live heterotrophically. They may be simple or branched, filamentous, and even
embedded in a gelatinous envelope or tube. All diatoms are enclosed in a silica frustule, that is
made up of two valves fitted together by a connective zone called a girdle. Multiplication of the
diatoms occurs by ordinary mitotic cell division. As a consequence, one diatom gives rise to 2
separate valves. During this multiplication, the diatoms absorb the silicon present in the
environment for the construction of the missing valve.

The aim of our study is to understand, observe and compare the mechanism of the construction of
the missing valve. In this objective, different types of diatoms have been transferred in a culture
medium enriched with
29
Si (ratio
29
Si/
28
Si = 1 compared to a natural isotope ratio of 0.05). The
distribution of the isotopes of silicon (
28
Si,
29
Si and
30
Si) has been obtained by NanoSIMS50
imaging. The lateral resolution of this instrument, combined with a high transmission at high mass
resolution, allows to determine in the frustule of the diatoms the isotopic ratio of silicon. With this
study we intend to determine for the first time the site of fixation of silicon in the diatoms and the
mechanism of multiplication.

16
O,
28
Si,
29
Si and
30
Si images of diatoms after growth in media enriched with
29
Si.
BIO2-P-Th-P41
269
Quantitating MIMS Ratios Using Hue, Saturation, and Intensity
Displays

D. Benson
a
, C. Lechene
b,
*

a
NSee Inc., 106 Greenhaven Lane, Cary, NC 27511, USA
b
NRIMS

, Harvard Medical School, and Brigham and Womens Hospital,

65 Landsdowne Street, Cambridge, MA 02139, USA
Email: cpl@.harvard.edu


In order to use secondary ion mass spectrometry to locate and measure isotope tags in subcellular volumes, we need
to identify on the atomic mass images regions containing the tag. This is done by labelling with a stable isotope of low
natural occurrence, for example
15
N, acquiring simultaneously quantitative images of both isotopes, for example
14
N
and
15
N (
12
C
14
N and
12
C
15
N) and normalizing by dividing pixel by pixel the low abundance isotope by the high
abundance one, thus obtaining an isotope ratio image. The areas on the isotope ratio image map that contain the isotope
label have a higher isotope ratio than the natural ratio, which results in a higher brightness in the image field. Regions of
interest (ROI) can thus identified from the neighbouring pixels and the value of excess isotope can be calculated. Yet,
the contrast of ratio images may be weak and much information contained in the quantitative mass images may be lost
if one uses simple visual inspection. From the inception of MIMS methodology, we have searched for a method that
would take full advantage of the quantitative information contained in each mass image. Images acquired with the
MIMS have a dynamic range of 16 bits and resulting ratios generate far more information than can be easily displayed
using simple grey level methods. Moreover, we wanted to identify ROI by a means independent of simple visual
recognition. In other words, instead of drawing ROI guided by the histology of the cells as revealed by the mass
images, we wanted to identify the existence of regions that might not be visible when displayed as 8-bit ratio images,
but yet that represented clusters of significant label accumulation. To take full advantage of our increased color
perception, we developed a method (introduced by Martin Poenie and Roger Tsien [1] for calcium imaging) to enable
identification of areas where mass ratios vary significantly from neighbouring regions. In order to identify those pixels
with significantly different isotope ratios than their neighbours, we use a hue saturation intensity (HSI) transformation
of the ratio image [2]. The HSI transformed images enabled us to outline ROI that were unsuspected from the histology
From a pair of isotope images, each corresponding pixel in the HSI ratio has a color determined by the ratio of the
counts and the intensity or brightness proportional to the significance of the counts. Pixels with low counts appear
darker and pixels with high counts appear brighter.
Hues are expressed in polar coordinates with blue->green->yellow->red increasing with the angle. These can be
thought of as a series of waves with blue, green, and red maximum phase shifted. We calculate the ratio at each pixel (x,
y) and convert it to a hue, H
(x, y)
using a simple linear equation (1),
H
(x, y)
= gN
(x, y)
/D
(x, y)
+ b, (1)
where N
(x,y)
and D
(x,y)
are the numerator and denominator counts at pixel x,y and g and b are constants to scale the ratios
to a desired range of hues. The intensity at each pixel, I
(x,y)
, is determined using either the minimum (2), maximum (3),
average (4) or sum of squares (5) of the numerator and denominator;
I
(x,y)
= min(N
(x,y)
,D
(x,y)
) (2)
I
(x,y)
= max(N
(x,y)
,D
(x,y)
) (3)
I
(x,y)
= (N
(x,y)
)+ D
(x,y)
)/2 (4)
I
(x,y)
= (N
(x,y)
)
2
+ D
(x,y)
2
) (5)
The saturation, S
(x,y)
is set to a constant value. The resulting HSI image is converted to RGB color space [2]; then
displayed and an operator interactively determines the range of ratios by adjusting the scaling constants, g and b, in
equation (1). The average intensity of the two source pixels determines the intensity for the resulting ratio, visually
weighting the resulting color to the significance of the starting counts. The resulting hue-intensity transformed ratio
image appears, at a given hue, brightest at pixels with the most counts and darkest at pixels with fewer counts.
After the ROI have been registered on the HSI image, they are projected on the original, unaltered quantitative mass
images, the atomic mass intensity counts are extracted, and statistics are calculated.
The HSI-ratio display allows us to take full advantage of our increased perception of color and of the quantitative
information contained in each mass image. It enables us to identify ROI with significant excess of the
15
N label (or any
label) by means independent of visual recognition of expected histological structures


[1] Poenie, M., et al., Calcium rises abruptly and briefly throughout the cell at the onset of anaphase. Science, 1986.
233(4766): p. 886-9.
[2] Castleman, K.R., Digital Image Processing. 1996: Prentice Hall.

National Resource for Imaging Mass Spectrometry

BIO2-P-Th-P42
270
High order of DNA replication identified in fibroblasts nuclei with
Multi-Isotope Imaging Mass Spectrometry

A. Cohen, C. Lechene *

NRIMS

, Harvard Medical School, and Brigham and Womens Hospital, 65 Landsdowne Street,
Cambridge, MA 02139, USA
Email: cpl@.harvard.edu


The major pathways of biosynthesis of nucleic acids and their breakdown have been mapped largely by
studies with cell extracts and purified. Thus there are significant gaps in our knowledge about the metabolic
pathways in most cells and tissues [1]. Also, many studies are consistent with an underlying structural
organization in the cell nucleus that influences genetic processes. Here, we show that MIMS methodology is
a powerful tool to study the spatial organization of DNA replication directly within cultured cells nuclei.
Cultures of human foreskin fibroblast in exponential growth were serum-deprived for 24 hours, then
pulsed with serum and
15
N-thymine (10M) for 18 hours, rinsed, fixed, and epon-embedded. 0.5m-thick
sections were prepared for MIMS. MIMS analysis was performed in parallel for
12
C
-
,
13
C
-
,
12
C
14
N
-
and
12
C
15
N
-
.
The results show the incorporation of
15
N-thymine exclusively in the nucleus, as expected. The
incorporation of
15
N within a given nucleus is discrete, in microdomains (table).

12
C
15
N/
12
C
14
N Ratio Values for Regions of Interest (ROIs)
Area
N
(number of
areas)
n (number
of pixels)
Mean Ratio
(
12
C
15
N/
12
C
14
N
x 1,000)
S.E.M.
Increase above
natural ratio
Epon 4 486 3.48 0.24 0.0%
Cytoplasm 3 87 3.56 0.65 0.0%
Nucleus (blue) 4 85 5.30 0.28 52%
Nucleus (green) 7 146 12.50 0.54 260%
Nucleus (red) 5 71 21.60 0.81 520%

In another set of experiments, we examined radioactive thymidine incorporation. Rat embryo fibroblasts
(RF52) were cultured in DME/F12 media with 10% fetal calf serum. They were successively: serum
deprived for 24 hours after they reached 40% confluence; pulsed for 24 hours with 10% FCS and 1 Ci of
14
C-thymidine, [2-
14
C], at a concentration of 19.2 nanomole/ml; fixed in their culture dish; (formaldehyde,
glutaraldehyde); detached from plastic with propylene oxyde; embedded (Epon-Araldite), sectioned at 0.5
m thickness; mounted on silicon chips for analysis.
MIMS analysis was performed in parallel for
12
C
-
,
14
C
-
,
12
C
14
N
-
and
12
C
15
N
-
.
The results are similar to the study of human foreskin fibroblasts. In addition they show that the
14
C label
can be used with great advantage of detection sensitivity in secondary ion mass spectrometry, as had been
reported in the pioneering work of [2]. We can estimate that MIMS detection of
14
C is several orders of
magnitude more sensitive than autoradiography. Even if only 1% of the
14
C atoms were sputtered and only
1 of the sputtered atoms were ionized, the efficiency of MIMS would still be 10
4
higher than that of
autoradiography.


[1] Kornberg, A. and T.A. Baker, DNA replication. 2nd ed. 1992, New York: W.H. Freeman. xiv, 931 p.
[2] Hindie, E., G. Blaise, and P. Galle, Origin of the cyanide secondary ions emitted from biological tissue under
ten keV cesium (1+) bombardment., in Second. Ion Mass Spectrom.SIMS 7, Proc. Int. Conf., A. Benninghoven,
Editor. 1990, Wiley: Chichester, UK. p. 335-8.

National Resource for Imaging Mass Spectrometry

BIO2-P-Th-P43
271
Multi-isotope imaging mass spectrometry (MIMS) quantitative
mapping of protein turnover in the bullfrog saccula

D-S. Zhang
a
, D. P. Corey
a
, C. Lechene
b,
*

a
Harvard Medical School, Department of Neurobiology, 220 Longwood Avenue, Boston MA 02115, USA
b
NRIMS

, Harvard Medical School, and Brigham and Womens Hospital, 65 Landsdowne Street, Cambridge, MA
02139, USA
Email: cpl@harvard.edu


The main protein component of hair cell stereocilia is actin, organized into oriented filaments that are
cross-linked to each other. Changes in hair cell actin filaments are common both in noise-induced and in
drug-induced hearing loss. Studies of the embryonic development of hair cells suggest that stereocilia grow
by the preferential addition of new actin proteins to the tips of the stereocilia. Yet, incorporation of labelled
amino acid into developing stereocilia seemed to indicate that new proteins are added to the bottom of the
bundles. Recently, from experiments on 10-15-day-old cultures of newborn rat and mouse Organ of Corti, it
was concluded that actin-GFP and espin-GFP are incorporated at the paracrystal tip, flow from tip to base,
and label the entire length of the stereocilium within. Experiments with GFP-actin gene expression, however,
have to be interpreted carefully for several reasons: (1) Only a few percent of cells are detected by directly
observing the fluorescence of GFP and these cells may not be representative of the whole population
expressing the gene; (2) Because of protein overexpression, the effect observed may be pharmacological; (3)
This is particularly important in the case of actin: a change in concentration of the actin monomers greatly
changes the speed of growth of actin filaments; and finally (4) difficult questions remain regarding the
fidelity with which GFP-actin reliably reflects the behaviour of endogenous actin[1].
We are developing a novel methodology, Multi-Isotope Imaging Mass Spectrometry (MIMS) that allows,
for the first time, quantification of protein turnover in small subcellular compartments using precursor amino
acid labelled with the stable isotope
15
N. We used MIMS to map the protein turnover in subcellular
structures of the bullfrog saccula, a model extensively studied in auditory physiology.
Frogs were fed a control diet for 2-3 days and then these voracious animals were fed
15
N enriched pellets
by hand. Frogs were sacrificed at 1, 2, 4, 8, 16, and 32 days after the start of the
15
N diet. Two frogs on the
control diet were sacrificed at the beginning and the end of the experiment. Bullfrogs were sacrificed by
pithing, fixed by cardiac perfusion with a fixative consisting of 4% formaldehyde and 0.1% glutaraldehyde.
They were kept in fixative until saccules were dissected, embedded, and sliced. We attempted embedding the
samples with an orientation maximizing longitudinal sections of the stereocilia. Sections were analyzed with
MIMS. We recorded quantitative images of regions of interest (ROI), containing stereocilia bundles, at mass
12
C,
13
C,
12
C
14
N and
12
C
15
N. Some ROIs were examined at high lateral resolution, over the length of
stereocilia.
The results reveal that after 32 days on a
15
N diet, the hair cell protein turnover reached approximately
20%. After a few days on the
15
N diet, there was already a small but statistically significant incorporation of
15
N in the saccular tissue. At all time points, the excess accumulation of
15
N in the stereocilia was lower than
in the hair cells apex. There was not statistically significant change in the level of excess
15
N along the
longitudinal axis of the stereocilia. Yet we have found some very small domains of high
15
N turnover that
appeared to be located towards the end or between the stereocilia. Finally, we found that some part of the
acellular otholitic membrane close to the reticular lamina had a surprisingly high turnover.
In conclusion, we have for the first time measured protein turnover in subcellular domains of the saccula.
These results, obtained in adult vertebrates maintained in physiological conditions, may indicate that the
turnover of protein in stereocilia may be more complex than assumed.


[1] Halpain, S., Actin in a supporting role, Nat Neurosci, 6 (2), 101-2, 2003.

National Resource for Imaging Mass Spectrometry

BIO2-P-Th-P44
272
Tectorial Membrane Protein Turnover Revealed
by Multi-isotope Imaging Mass Spectrometry

D.A. Cotanche
a
, C. Lechene
b,
*

a
Harvard Medical School, Department of Otology and Laryngology and Childrens Hospital,
Department of Otolaryngology, Boston, MA 02115, USA
b
NRIMS

, Harvard Medical School, and Brigham and Womens Hospital,

65 Landsdowne Street, Cambridge, MA 02139, USA
Email: cpl@harvard.edu


A lingering controversy in deafness research has focused on the tectorial membrane: does this
acellular structure renew its proteins? If so, how? We have visualized and quantified the turnover of
proteins in the tectorial membrane of chick cochleae. Using multi-isotope imaging mass
spectrometry (MIMS), we have overcome previous limitations in subcellular labelling and imaging
technologies. This new, widely applicable technology allows us to label subcellular structures with
any isotope(s) and measure their incorporation in tissues. The results of this study indicate that the
proteins of the tectorial membrane are, in fact, renewed regularly and that they flow from the apices
of the supporting cells between the cochlear hair cells.
Conventional methods for measuring protein turnover in sensory cells, such as labelling with
radioactive amino acids, have proven difficult and not adequate for the level of subcellular
resolution required. Images of the distribution of
15
N and other isotopes have, however, been
provided by secondary ion mass spectrometry. Nitrogen alone does not produce a secondary ion;
the secondary cyanide ion, CN-, which is primarily released from protein-rich regions of biological
tissue, provides anatomically recognizable images. The quantitation of isotope ratios in biological
tissues using secondary ion mass spectrometry, however, has been problematic. A tissues
enrichment in
15
N is based upon the measure of the isotopes increase over terrestrial abundance.
This must be calculated from the
15
N/
14
N isotope ratio. Because it is necessary to measure nitrogen
from the secondary ion CN
-
, the mass resolution of the spectrometer must be sufficient to allow the
separation of the mass 27 isobars,
12
C
15
N
-
,
13
C
14
N
-
, and
12
C
14
N
1
H
-
. MIMS offers a new and
innovative methodology for examining protein turnover in cells utilizing nonradioactive isotopes at
resolutions that reach below 50 nanometers. This new type of secondary imaging mass spectrometer
images at high resolution and is capable of measuring several ion masses simultaneously. The high
mass resolution makes it easy to distinguish the
12
C
15
N
-
ion from its isobars, so it is feasible to use
15
N as a molecular marker for identifying and quantifying the turnover of nitrogen-rich molecules in
subcellular domains. Thus, we have MIMS to examine the rates of protein turnover in tectorial
membrane of chick cochleae.
Chicks were fed a diet supplemented with
15
N-leucine for seven days. Chick ears were dissected
out and fixed in 1% glutaraldehyde and 1% osmium tetroxide in 0.1M sodium phosphate buffer for
1 hour. Following fixation, the tissues were dehydrated and embedded in Epon/Araldite and
sectioned to produce 1 m thin sections for light microscopy and 0.5 m sections mounted on
silicon chips for MIMS analysis.
Quantitative image analysis was performed at mass
12
C,
13
C,
12
C
14
N, and
12
C
15
N. The values of
the
12
C
15
N/
12
C
14
N isotope ratios revealed significant new protein incorporation by the acellular
tectorial membrane. The images of the
12
C
15
N/
12
C
14
N isotope ratios showed that the mechanism of
incorporation is a transfer from the apices of supporting cells to the basal layer of the tectorial
membrane. The transfer is accomplished by the formation of attachment links between the
supporting cells and the membrane.
Finally, these results settle the lingering controversy: does the tectorial membrane, which is
acellular, renew its proteins? If so, how? Yes, the tectorial membrane does renew its proteins. New
proteins flow from the apices of supporting cells to the basal layer of the tectorial membrane.

National Resource for Imaging Mass Spectrometry

BIO2-P-Th-P45
273
Multi-Isotope Imaging Mass Spectrometry of Larval Zebrafish for
Studying Acute Renal Failure

D. Hentschel
a
, J. Bonventre
b
, C. Lechene
c,
*

a
Department of Medicine, Brigham and Womens and Massachusetts General Hospitals, Boston, MA USA
b
Department of Medicine, Renal Division, Brigham and Womens Hospital and Harvard-Massachusetts Institute of
Technology Division of Health Sciences and Technology, Boston, MA, USA
c
NRIMS

, Harvard Medical School, and Brigham and Womens Hospital,

65 Landsdowne Street, Cambridge, MA, USA
Email: cpl@harvard.edu


Acute renal failure is a condition associated with high mortality. Lack of progress in our
understanding of the pathophysiological processes underlying this disease is in part due to the
complexity of existing rodent animal models. Simpler models like tissue culture suffer from cell
dedifferentiation in culture medium and lack the important context of matrix, blood vessels, injured
tubule cells, and inflammatory cells interaction that exists in acute renal injury. In addition, despite
the central importance of proteins to the proper structure and function of renal cells, and the
disruption of protein-containing structures in renal ischemia, little is known about the dynamics of
protein turnover in renal cells because of the lack of adequate methodology. In order to remove
some of these pitfalls, we are developing the use of zebrafish embryos, a well-established vertebrate
model for developmental, genetic and toxicologic studies, together with isotope ratio quantitative
imaging mass spectrometry.

Larval zebrafish have a pronephric kidney that consists of a central glomerulus connected to one
nephron on each side. We have developed a model of acute renal failure and a fluorescence-based
method for determining renal function in zebrafish larvae, and we have demonstrated a reduction in
renal function after injection of gentamicin or cisplatin.

In this first set of experiments, Zebrafish (TbingenAB) were grown and mated at 28.5C, and
embryos were kept and handled in standard E3 solution. Zebrafish embryos were labelled either by
injection of 15N-Thymidine, 15N-Thymine, or 15N-Glycine into the venous sinus, or by addition of
15N-Thymine or 15N-Glycine to the surrounding fish water. After 32 or 48 hours, they were fixed
overnight at 4oC in a solution of 1.5% glutaraldehyde, 1% paraformaldehyde, 70 mM NaPO4, 3%
sucrose, pH 7.2. The larvae were then embedded following an electron microscopy protocol for
zebrafish. Sections 0.5 microns thick were deposited on silicon chip supports and analyzed with
Multi-isotope Imaging Mass Spectrometry.

The histology of entire zebra fish embryos, approximately 1 mm long, can be observed by
mounting a mosaic of adjacent tiles, (100 m)2, analyzed at mass 12C14N. One sees the posterior
extension of the central nervous system, granular cells above the medulla oblongata, the notochord,
the gastro-intestinal, the pronephric tubules lie on top and below this structure, arching away from
it. Intra-cellular morphology- brush border, nucleoli, and other organelles, is well visible. We will
discuss the specifics of label incorporation. Strikingly, we noticed an increased incorporation of
15N-Glycine into one segment of the cross-section of the gut. This section of the gut wall was also
thicker, suggesting an area of increased growth. This observation would agree with the requirement
of a tortuous tubular structure to increase the cell number at the outer side of curvatures. Current
and future studies address the differences in protein and nuclei acid turnover of zebrafish pronephric
tubules at baseline and after injury with gentamicin, cisplatin, or hypoxia.


National Resource for Imaging Mass Spectrometry
BIO2-P-Th-P46
274
Determination of Steady State Cs
+
Implantation in Biological Samples

G. McMahon, C. Lechene*

NRIMS

, Harvard Medical School and Brigham and Womens Hospital,

65 Lansdowne Street, Cambridge, MA 02139, USA
Email: cpl@harvard.edu


When materials are analyzed by SIMS using a Cs
+
primary ion beam to sputter the sample and
enhance secondary ion emission, a time delay is observed before a steady state secondary ion count
rate is achieved. This phenomenon is well documented for inorganic materials, in particular Si, but
not in biological samples. A systematic study of biological samples has been undertaken to
determine the minimum Cs
+
dose required to achieve steady state Cs
+
implantation and thus to
optimize secondary ion emission.

Epon embedded sections of bullfrog fed with a diet enriched in
15
N for 32 days
1
were analyzed
with the prototype of the Cameca NanoSIMS 50. The primary Cs
+
ion beam current measured by a
Faraday cup located behind the sample was 0.6 pA. The primary beam diameter was approximately
35 nm. The net impact energy of the Cs
+
ions was 16 keV. Negative secondary ion signals for
12
C
-
,
13
C
-
,
12
C
14
N
-
, and
12
C
15
N
-
were measured simultaneously using electron multiplier detectors and the
13
C
-
/
12
C
-
and
12
C
15
N
-
/
12
C
14
N
-
isotope ratios were derived. We recorded the counts by scanning over
areas of 4 m
2
, 9 m
2
, and 16 m
2
. The scanned areas had not been previously exposed to the
primary Cs
+
ion beam.

The results show that the Cs
+
dose required to achieve a steady state secondary ion count rate was
the same for both C
-
and CN
-
ions. It was slightly smaller for the bullfrog tissue sample (mean dose
value of 4.7x10
16
atoms/cm
2
) than for the Epon embedding resin (mean dose value of 6.1x10
16

atoms/cm
2
). The time required to reach steady state counting ranged from 500s for a 4 m
2
analysis
area, to 2200s for a 16 m
2
analysis area for the tissue samples and consistently gave a rate of 150s /
m
2
of analysis area.

These results are a first step of systematic data gathering of the modalities of secondary ion
emission from biological samples bombarded with a primary Cs
+
ion beam. They also provide a
guide for optimizing implantation time and counting duration.


1. We thank Dr. D.P. Corey for feeding the bullfrogs.

National Resource for Imaging Mass Spectrometry

BIO2-P-Th-P47
275
Stable isotopes for individual cell retrieval after transplantation

G. Benichou
a
, C. Lechene
b,
*

a
The Schepens Eye Research Institute, 20 Staniford Street Boston, MA 02114, USA
b
NRIMS

, Harvard Medical School, and Brigham and Womens Hospital,

65 Landsdowne Street, Cambridge, MA 02139, USA
Email: cpl@harvard.edu


Following transplantation of allogeneic tissues and organs, some donor-derived cells are known
to leave the graft and present alloantigens to the hosts immune system. However, the exact nature
and frequency of donor cells infiltrating the hosts lymphoid tissues are still unclear. On the other
hand, the trafficking patterns of recipient immunocompetent cells recognizing alloantigens either
directly (intact donor MHC) or in the form of peptides loaded on host MHC molecules (indirect
presentation) are also unknown. These questions have remained unanswered due to the absence of
sufficiently sensitive techniques to accurately track and visualize low numbers of lymphocytes in
tissues. Here, we used the multi-isotope mass spectrometry (MIMS) method to track donor cells
after transplantation.

To test this, C57Bl/6 (B6, H-2
b
) mice were fed for two weeks with a
15
N diet. The mice were then
sacrificed and their spleen cells collected. 2 10
7
B6 spleen cells were injected subcutaneously in the
footpad of a fully allogeneic BALB/c mouse (H-2
d
). Two days later, draining popliteal lymph nodes
of recipients were collected and examined by MIMS for the presence of donor cells.

We clearly detected donor cells in different fields from recipient lymph nodes. A fast mapping
[2min per (100)
2
micron fields] at mass
12
C
14
N and
12
C
15
N of a large area of a lymph node section
allowed us to distinguish a few needles in a haystack, i.e., a handful of donor cells that were
15
N
labelled within an immense population of unlabelled receiver cells. Fields where the presence of
donor cells was suspected were then imaged at higher resolution. Individual donor cells were then
strikingly identified in the isotope ratio image of
12
C
15
N/
12
C
14
N. The isotope ratio image of
13
C/
12
C
of the same field taken simultaneously served as an internal control; it did not show any contrast
and the ratio value over the entire field was equivalent to the natural value. The frequency of
transplanted cells infiltrating the recipient lymph node was found to be 690 cells per million.

We conclude that the MIMS technique allows the detection and frequency determination of rare
cells infiltrating recipient lymphoid tissues after transplantation. The methodology is being
extended to study solid organ transplant models and the nesting of stem cells.

National Resource for Imaging Mass Spectrometry

BIO2-P-Th-P48
276
The analysis of boron in the human glyoma graft by dynamic
secondary ion mass spectrometry(SIMS)

T. Yoshida
a
, K. Yokoyama
b
, M. Okabe
a
, S. Kawabata
b
, Y. Kajimoto
b
, S. Miyatake
b


a
Toyama Medical and Pharmaceutical University, 2630 Sugitani, Toyama, 930-0194, Japan
b
Osaka Medical College, 2-7 daigakumachi, Takatuki, Oosaka, 569-8686,Japan
yosidato@ms.toyama-mpu.ac.jp


Recently, boron neutron capture therapy (BNCT) is one of the effective therapy for brain tumor
[1]. BNCT is use the nuclear reaction. Neutron irradiation (of the appropriate energy ) occurs the
nuclear reaction in the tumor cell with boron. Alpha particles and Lithium-7 occurred from boron
have high energy and scattered around. The scattered distance of alpha particles about 9m and the
Lithium-7 is 4m. It is considered these scattered distance are enough to kill the tumor cells with
boron compounds only. However, it is not clearly boron accumulation is enough to kill the tumor
cell and locate in the tumor not normal cells. Now we have two types of boron compounds. One is
sodium broncapte (BSH) which is able to accumulate in the cells when the brain blood barrier is
broken. The other is p-boronophenyl alanine (BPA) is able to accumulate in the cells by active
pathway. This defect is that much boron will accumulate in the normal cells as same as tumor cells.
The objection of this investigation was to assess the differences in the concentration of boron
between neoplasia and normal brain tissues in regions of the tumor brain interfaces as well as in
other areas of the brain with associated microscopic tumor infiltration. We used the rat with
human C6 glioma as model of brain tumor. The 6m sections form frozen brain tissues were
mounted on the silicon wafer (N type), and dried in the room temperature. Using a mass filtered
O2+ primary ion beam is accelerating to 4.5kV with a nominal beam current of 12 nA. They were
analyzed by an approcimate beam diameter of 5.0 m. The primary ion beam was raster scanned
over 150m x 150 m or 50m x 50m square regions. For each region analysis, sequential ion
images from 10B and 11B were acquired with integration times of 100 seconds each. As compared
the optical image and ion images, the distribution and intensity of 10B and 11B have been
investigation. We were able to see the distribution of 10B in the regions of the accumulated
neoplasm and tumor infiltration area in the normal. The concentration of 10B in the glioma was
strong in the interface area around the cluster of glioma as same as accumulated glioma region.
This tumor model and SIMS analysis are very convenient for the research about the effect of
treatment.


[1]S.Kawabata, S.Miyatake, Y.Kjimoto, Other, J.Neurooncol. 2003, 159-65.

BIO2-P-Th-P49
277
Bioaccumulation and physiological effects of chromium in aquatic
macrophyte Borreria scabiosoides Cham. & Schltdl.

P.A. Mangabeira
1,2


1
. Service Central dAnalyse (SCA), Chemin du Canal Echangeur de Solaize BP -22- 69390 Vernaison France,
pedro@sca.cnrs.fr; paom@uesc.br
2
. Department of Biology Universidade Estadual de Santa Cruz UESC, Rodovia Ilhus Itabuna, Km 16, CEP
45650000, Brazil. Email: paom@uesc.br

The capacity of Borreria scabiosoides Cham. & Schltdl. growing in hydroponic solutions to
remove Cr (III) from water was evaluated and their behaviour at different Cr (III) concentrations. Cr
distribution in roots and aerial parts with the cellular accumulation of Cr were analyzed. This
macrophytes efficiently removed Cr from water at concentrations of 25, 50mg Cr L1. The aim of
this paper was to investigate concentrations of aquatic macrophytes have frequently been used to
monitor freshwater pollution by heavy metals and pesticides. In tropical and subtropical regions,
because of its abundance were taken at several sites along the river course in order to investigate a
possible contamination of the river ecosystem Plant samples were collected from the river
Cachoeira located at 1447'S, 3916' W in the southern part of the state of Bahia (NE Brazil). High
resolution imaging secondary ion mass-spectrometry (HRI-SIMS) measurements were performed
using Scanning Ion Microprobe at the University of Chicago (UC-SIM). The Inductively Coupled
Plasma sector type mass spectrometer (HR-ICP-MS) were used to analyse all samples. In general,
plant roots exhibited higher metal concentrations than the aerial plants parts. Comparison between
morphological tissues of the sampled plants found that roots consistently presented higher metal
concentrations than either the stems or leaves. For B. scabisoides, metal concentrations followed the
order of roots > stems > leaves.

NAN-P-Th-P50
278
Atomic distribution in quantum dots- a ToF SIMS study

Wen-Yin Chen, Bo-Jung Chen,

Yong-Chien

Ling*

Department of Chemistry, National Tsing Hua University,
Hsinchu, Taiwan-30013, Republic of China
ycling@mx.nthu.edu.tw


Quantum dots (QDs) have shown tremendous potential applications such as in biological
labelling, sensor and optical electronic devices. This was attributed to their advantages of narrow
emission wave width, photostability and sensitivity compared to conventional organic-base dyes.
To broaden the applications of QDs, surface modification, core-shell QDs and metal dopant
techniques were applied on existing QDs [1-3]. Analytical information about the atomic distribution
in QDs is crucial to understand the influence of chemical structure on QDs functional property. Tof
SIMS with its inherent advantages of molecular sensitivity at nm-scale depth resolution is an ideal
method. We have devised a sample preparation method to make this become true. In this work, a
monolayer consisted of CdS:Mn functioned with amine ground was coated on a silica base. 3D
image obtained by ToF SIMS depicted the atomic distribution, which facilitated the study the
formation mechanism of these model QDs.


[1] S. Santra, H. Yang, P. H. Holloway, J. T. Stanley, R. A. Mericle, J. Am. Chem. Soc. 127 (2005) 1656.
[2] Y. Chen, Z. Rosenzweig, Nano Lett 2 (2002) 1300.
[3] S. K. Haram, B. M. Quinn, A. J. Bard, J. Am. Chem. Soc. 123 (2001) 8860.

NAN-P-Th-P51
279
The lateral resolution of ToF-SIMS analysed by means of an advanced
nanoscale strip-pattern

M. Senoner, Th. Wirth, and W. Unger

Bundesanstalt fr Materialforschung und prfung (BAM),
12200 Berlin, Germany
e-mail: mathias.senoner@bam.de


The lateral resolution of Secondary Ion Mass Spectrometry (SIMS) was been improved rapidly
over the last years and there is a great interest in imaging of sub-micron structures in surface
analysis and nanotechnology.
Recently we presented the certified reference material BAM-L002, a new type of test sample for
the determination of lateral resolution. It is an embedded cross section of epitaxially grown layers of
Al
x
Ga
1-x
As and In
x
Ga
1-x
As on GaAs substrate [1].
Now we have developed an advanced test sample made of the same material. It enables a more
accurate determination of lateral resolution due to its finely graded strip pattern. The strip pattern
includes strip gratings with periods ranging from 2 nm up to 600 nm. These strip gratings enable a
direct estimation of lateral resolution during the imaging process and therefore it is particularly
suitable for the adjustment and parameter optimization of imaging instruments. Furthermore the
finely graded strip gratings allows the determination of the modulation transfer function which is
the most complete description of lateral resolution of an imaging system. Isolated narrow strips
ranging from 0.3 nm up to 40 nm and an step transition between two wide strips enables the
determination of the line spread function which also describes the lateral resolution of the imaging
system.
Here we present first results with the advanced test sample. We have determined the modulation
transfer function and the line spread function of an TOF-SIMS IV instrument.
Additionally we have recalibrated the TOF-SIMS IV instrument by imaging of a certified
calibration distance between isolated narrow strips.


[1] M. Senoner, Th. Wirth, W. Unger, W. sterle, I. Kaiander, R. L. Sellin and D. Bimberg; BAM-L002 - A new type
of certified reference material for length calibration and testing of lateral resolution in the nanometre range, Surf.
Interface Anal. 36 (2004), 1423-1426

PAR-P-Th-P52
280
ANALYSIS OF VOLATILE NANOPARTICLES EMITTED FROM
DIESEL ENGINE USING TOF-SIMS AND
SILVER DEPOSITION / TOF-SIMS

Masae Inoue
a,
*, Atsushi Murase
a
, Masami Yamamoto
a
, Syuichi Kubo
a


a
Toyota Central R&D Labs., Inc., Nagakute, Aichi, 480-1192, Japan
Email: masae@mosk.tytlabs.co.jp


Recently, there has been particular concern for nanoparticles smaller than 50nm in diesel
particulate emissions because of their possible adverse effects on environment and human health.
To clarify the effects, it is essential to analyze size segregated nanoparticles in detail and to identify
the key materials that are involved in the nucleation process.
Diesel nanoparticles mainly comprise volatile organic compounds (low volatile hydrocarbons and
oxygenated hydrocarbons) and/or sulfuric acid. Formation mechanism of sulfuric acid nanoparticles
has already clarified. On the other hand, nucleation process of volatile organic material
nanoparticles is not clarified, because the key materials of these have not been analyzed in detail.
GC-MS is a powerful tool for analysis of main organic compounds in nanoparticles that originate in
diesel fuel and lubricant oil, however, it is difficult to detect lower volatile organic compounds that
seem to be key materials in the nucleation process. Therefore, we have attempted to identify the key
materials that are involved in the nucleation process using TOF-SIMS.
Two types of nanoparticles emitted from light-duty diesel engine under two engine operating
conditions were diluted and collected on aluminum substrate using a Micro Orifice Uniform
Deposit Impactor (MOUDI) and a nano-MOUDI.
We applied silver deposition/TOF-SIMS [1] to detect the high-molecular-weight oil components
(>C
30
hydrocarbons) in nanoparticles. This method is a useful technique for direct detection of
silver-cationized quasi-molecular ions from the organic materials that molecular ions cannot be
detected by conventional TOF-SIMS, such as hydrocarbons of lubricant oil, and the analysis of
metal-deposited sample surface like this is proposed as metal assisted-SIMS or MetA-SIMS [2-
4].
As a result, it was found that the lubricating oil components with a molecular weight more than
500 were concentrated in nanoparticles in the diameter of 18 to 32nm under one engine operating
condition and the higher molecular weight (>m/z 500) lubricating oil components were the key
materials in the nucleation process.
Concerning nanoparticles under another engine operating condition, these higher molecular
weight (>m/z 500) lubricating oil components were not detected. By using conventional TOF-
SIMS, however, it was clarified that the percentage content of oxygenated hydrocarbons increased
as the diameter of nanoparticles decreased, and oxygenated hydrocarbons were the key materials.
Therefore it was found that the key materials in nucleation process depend on the engine operating
conditions.
It was confirmed that TOF-SIMS and silver deposition/TOF-SIMS are powerful tools for
analysis of the key materials that are involved in the nucleation process of nanoparticles.


[1] M. Inoue, M. Murase, Appl. Surf. Sci., 231-232 (2004) 296-301.
[2] A. Delcorte, N. Medard, P. Bertrand, Anal. Chem., 74 (2002) 4955-4968.
[3] L. Adriaensen, F. Vangaever, R. Gijbels, Appl. Surf. Sci., 231-232 (2004) 256-260.
[4] A. Delcorte, P. Bertrand, Appl. Surf. Sci., 231-232 (2004) 250-255.
PAR-P-Th-P53
281
Quantitative characterizations of styrene-butadiene core-shell latexes
by TOF-SIMS and Pyrolysis GC/MS

Toshihiko Maekawa
a


a
Analysis Technology Center, Advanced Core Technology Laboratories,
Fuji Photo Film CO.,LTD, Kanagawa, Japan
toshihiko_maekawa@fujifilm.co.jp


Characterizations of the 100 nm size core-shell latexes, both parts were composed of styrene-
butadiene co-polymer, were established. The core-shell structure was revealed by TEM observation
of the latex film after modification of butadiene part with OsO4 vapor. Pyrolysis Gas
Chromatography combined with mass spectrometry (Py-GC/MS) of the latexes showed the average
chemical composition of the core part and the shell part. TOF-SIMS of the latex film gave the
characteristic peak for styrene and butadiene, these peak intensities were changing accordance with
chemical composition of the latexes. Surface composition of the latex film, which was
corresponding to the composition of the shell part of the latexes, was estimated from this peak
intensity ratio.
From the volume ratio of core and shell parts of the latexes estimated by TEM, average styrene
composition by Py-GC/MS and styrene composition of shell part of the latexes by TOF-SIMS, it
has been possible to evaluate the chemical composition of both core part and shell part of latexes
individually.
PAR-P-Th-P54
282
Characterization of individual complex particles
in urban atmospheric environment

K. Suzuki
a,
*, K. Yamada
b
, M. Nojima
a
, B. Tomiyasu
c
, Y. Nihei
a


a
Faculty of science and Technology, Science University of Tokyo, 2641 Yamazaki, Noda-shi, Chiba 278-8510, Japan
b
Mitsubishi Gas Chemical Company, 6-1-1 Shinjuku, Katsushika-ku, Tokyo 125-0051, Japan
c
Environmental Science Center, the University of Tokyo, 5-1-5 Kashiwanoha, Kashiwa-shi, Tokyo 277-8581, Japan
j7205704@ed.noda.tus.ac.jp


The recent study showed that the particles consisting of transition metals such as Fe, Ni and V
were associated with the lung injury [1]. In the studies about diesel exhaust particles (DEPs), these
particles consisting of transition metals had shown adverse effects about lung cancer under the
condition of coexisting with DEPs [2,3]. In this study, we made a close analysis of individual
atmospheric particles collected in urban environment, and obtained the detailed information of the
particles consisting of transition metals.
We performed a source apportionment of suspended particulate matter (SPM) using field
emission type scanning electron microscope/energy-dispersive X-ray spectroscopy (FE-SEM/EDS).
The analyzed particles were sampled from urban atmospheric environment near to road traffic and a
railroad by a personal air sampler (PS-47) and an electrostatic collection method air sampler
(SSPM-100). From the results of an FE-SEM/EDS analysis, SPM were classified into five types
including DEP and iron particles [4]. There were four types of iron particles. FE-SEM observation
revealed that some iron particles had minute attachments, and typical diameter was about 50 nm.
These adsorbed-particles were similar to DEPs in the shape. We measured X-ray spectra of the
carrier particles and adsorbed-particles.
We also obtained the information about the complex particles using a time of flight-secondary
ion mass spectrometry (TOF-SIMS). We compared the secondary ion mass spectrum patterns of
absorbed particles with them of carrier particles [5]. The apparatus was TRIFT
TM
II (Ulvac-phi)
using a Ga+ primary ion beam with diameter of 0.3 m. From the results of TOF-SIMS analysis, it
became clear that there were two types of iron particles (carrier particles) emitted from vehicles and
trains. The intensities of secondary ions (
12
C
+
,
12
C
1
H
+
and
12
C
2
1
H
3
+
) from adsorbed particles were
higher than the carrier particles. Because the DEPs were consisting of atomic carbon, we concluded
that the adsorbed particles on the complex particles were DEPs.


[1] Timothy M. Rice, Joseph D. Paulauskis; Differential ability of transition metals to induce pulmonary inflammation:
toxicology and applied pharmacology, 177, 46-53(2001).
[2] T. Ichinose, Y. Yajima, M. Nagashima, S. Takenosita, Y. Nagamachi, M. Sagai: carcinogenesis, 18, 185(1997).
[3] Ya-Mei Zhou, E. Pinkerton; Oxidative stress and NF- B activation in the lungs of rats: a synergistic interaction
between soot and iron particles: toxicology and applied pharmacology,190, 157-169(2003).
[4] K. Suzuki, B. Tomiyasu, Y. Nihei; Identification of composite particles of diesel exhaust particles and iron
particles of railroad origin: BUNSEKI KAGAKU 53 1 7-12 2004
[5] B. Tomiyasu, K. Suzuki, T. Gotoh, M. Owari and Y. Nihei; TOF-SIMS measurement for the complex particulate
matter in urban air environment: Applied Surface Science, 231-232, 15, 515-519(2004)
PAR-P-Th-P55
283
TOF-SIMS measurements of the exhaust particles emitted from
gasoline and diesel engine vehicles

B. Tomiaysu
a,
*, M. Owari
a
and Y. Nihei
b


a
Environmental Science Center, the University of Tokyo, 7-3-1 Hongo,
Bunkyo-ku, Tokyo 113-0033, Japan
b
Faculty of Science and Technology, Science University of Tokyo, 2641 Yamazaki,
Noda-shi, Chiba 278-8510, Japan
bunbu@esc.u-tokyo.ac.jp


In the atmosphere near the traffic route, a lot of exhaust particles emitted from gasoline and
diesel engine vehicles are suspended. As an air pollutant diesel emission particles have collected
much attention and been studied intensively. On the other hand, there is limited research about the
gasoline exhaust particles. The development of a novel source apportionment is required to classify
these exhaust particles, and to discuss the influence on human health by the atmosphere near the
traffic route. Exhaust particles originated from both types of engines are similar in major
composition and typical shape. It is difficult to classify these exhaust particles by using the source
apportionment based on main components of particles. In this study, we obtained the detailed
elemental information of these exhaust particles, and classified them into each exhaust source.
The environmental particles suspended in the atmosphere near the traffic route were collected
using a cascade-impactor-type particle sampler. The particles with diameter of 0.3-0.05 m were
collected on a carbon plate. By using the same particle sampler, two kinds of source particulate
were also collected. These samples were diesel exhaust particles and gasoline exhaust particles
emitted from each exhaust nozzle directly. The conditions of TOF-SIMS measurements were as
follows: Ga
+
primary ion beam, 25 kV acceleration, 120 pA beam current (DC mode), 11 kHz pulse
rate, 50 ns pulse width, 0.2 m beam diameter, 42 degrees incident angle from surface normal and
800 mass resolution. Under these conditions, spectra were obtained from 200 m x 200 m area of
high particle density part on each sample. The measurement time for each spectrum was about 40
min. The secondary ions such as Ca
+
, C
4
H
7
+
and C
5
H
9
+
(hydrocarbons) were strongly detected from
the gasoline exhaust particles. The intensity of Si
+
, SiC
3
H
9
+
(silicone) and NH
4
+
were relatively
high in the spectrum from the diesel exhaust particles. All of these secondary ions were also
detected from the environmental particle sample. Relative intensity of these secondary ions from
environmental particles will bring information on contribution of each emission source.
PAR-P-Th-P56
284
Depth profile of coated hollow spheres.

Renta Orikov
a
, Andrej Orik
a
*, Heinrich F. Arlinghaus
b
,
Sebastian Hellweg
b
, Miriam Kupkov
c
, Margita Kabtov
c

a
P.J. afrik University, Institute of chemistry, Faculty of Science, Koice, Slovakia
b
Physical Institute, Wilhelm Westphalen University, Muenster, Germany
c
Institute of Material Research, Slovak Academy of Science, Koice, Slovakia
orinak@kosice.upjs.sk


Porous lightweight materials have found increasing interest for various applications. Regular
structured cellular materials might be accessible by sintering the hollow metallic particles. The
properties of final product depend to a large extent on the properties of original hollow metallic
particles. Therefore, the preparation of reliable hollow spheres of defined parameters represents an
important step towards the cellular solids production by means of powder metallurgy route.
Electrochemical deposition of metallic coatings on the surface of hollow spherical particles
facilitates the required modification of the surface corresponding to high mechanical quality.
The suitable matrix for the preparation of relatively light but mechanically strong porous
materials was obtained by combination of current-less deposition of Cu layer on iron hollow micro-
particles followed by electrochemical plating by Ni.
In this study ToF-SIMS depth profiling and optical microscopy analysis with elements
mapping and line analysis are used to investigate the distribution of the coating components and
across the surface and subsurface layer of coated hollow particles.
Acknowledgements. This work was financially supported by the Slovak Grant Agency
VEGA; Grant No. 1/2118/05. The authors wish to thank ION-TOF GmbH, Germany for temporary
licence of ToF SIMS software providing.
ORG2-P-Th-P57
285
Surface Chemical Analysis of Thermally Degraded Cotton

R. Mitchell & C. M. Carr


An important performance criterion for textile materials is their ease of flammability. Therefore
in order to provide improved protection and safety many textile fibres are treated with a flame
retardant. Previous studies have focused on the fibre bulk properties during thermal degradation
with little information available about the vital surface interface behaviour. In this study the thermal
degradation of cotton has been investigated using the complementary surface analytical techniques
X-ray Photoelectron Spectroscopy (XPS) and Time of Flight Secondary Ion Mass Spectrometry
(ToF-SIMS). XPS analyses of cotton heated at 225
0
C for up to 23 hours indicated a progressive
increase in surface oxidation and formation of carboxyl and carbonate species. In addition thermal
migration of magnesium ions to the fibre surface was observed. ToF-SIMS analysis of the cotton
fibre surface demonstrated the presence of levoglucosan, which has been identified as an
intermediate in the burning of cellulosic materials. On extended heating, the surface concentration
of the levoglucosan initially increased but then remained constant. Extended heating of the cotton
fibre surface resulted in the loss of the characteristic cellulosic ToF-SIMS ions due to the oxidative
degradation of the cellulose polymer.
In addition the surface topography of the heated cotton has been further characterised by 3D
imaging of the fibre surface.
ORG2-P-Th-P58
286
Secondary Ion Statistics and Determination of Nanocluster
(m > 10
7
amu) Ion Registration Efficiency.

S.Kirillov, I.Baranov, A.V.Novikov, V.Obnorskii, S.Yarmiychuk

V.G.Khlopin Radium Institute, 2
nd
Murinskii avenue 28, 194021 St.-Petersburg, Russia
kirillov@atom.nw.ru


To register heavy ions (m>10
7
amu) the secondary ion (SI) emission from ion-ion converter is
usually used. When determining the registration efficiency (RE) it is assumed that the distribution
of SI number obeys the Poisson statistics. However, commonly this assumption is not proved [1].
To determine RE, we propose to compare the registration rate and the statistics of SI emitted
from the same sample measured with different converters. A criterion of the validity of the RE
estimation is the equality of ratios of the measured registration rates and those evaluated using
chosen statistics.
Using a designed tandem mass-spectrometer operating in the PDMS mode the m/q spectra of
gold nanocluster ions (<D>=18.1 nm, <m>=4.6*10
7
amu) desorbed by
252
Cf fission fragments from
the islet target were measured. Simultaneously, the distribution of SI emitted from different
converters was measured. Since only the m/q ratio is registered in TOF spectroscopy, different ions
with the same m/q cannot be distinguished. Therefore, some corrections for the measured m/q
should be made.
It was shown that the geometric distribution is the most suitable for description of the SI
distribution. The validity criterion of the RE determination was held true in the m/q range from
3.1*10
6
to 8.2*10
6
amu/e. For all converters RE decreases with increasing m/q and decreasing
energy of nanocluster. The resulting RE values were found to be 1.5 2 times lower than those
expected from Poisson distribution.


[1] Van-tan Nuen, K.Wien, I.Baranov, A.Novikov, V.Obnorskii, Rapid Commun. Mass-Spectrom. 10 (1996) 1463.

Work supported by the ISTC project #2390.
ORG2-P-Th-P59
287
Towards a Fully Optimised Organic LED Device: Analysis of Surface
Synthesis Using Coupling Reactions by ToF-SIMS

R. Pinna
a
, F. Jamme
a
, F.J.M. Rutten
b,
*, E.F. Smith
a
, M.R. Willis
a
,
D. Briggs
b
and M.R.S. McCoustra
a


a
School of Chemistry
b
Centre for Surface Chemical Analysis and Laboratory of Biophysics and Surface Analysis, School of Pharmacy
University of Nottingham, Nottingham NG7 2RD, UK
E-mail: frank.rutten@nottingham.ac.uk


Organic semiconductors have over a number of years promised much, but have delivered little by
way of practical end product. The most obvious exception to this is the recent and rapidly
burgeoning commercialisation of organic light emitting devices (OLEDs) utilising both small
molecules and polymers. Limitations in the lifetime of such devices are, however, a major concern.
With this in mind, this research aims to develop methodologies for the total synthesis of bulk
organic electroluminescent devices based on the surface synthesis of molecular wires and physical
vapour deposition of electroluminescent materials. OLEDs are commonly manufactured using
physical vapour deposition (PVD) techniques, our novel approach is intended to eliminate some of
the problems associated with PVD of OLED devices that result in their failure.
As a first step the gold anode is functionalised by reaction with an aminothiophenol self-
assembled monolayer (SAM), after which the following reaction steps are carried out under mild
ethanolic conditions, where TPA denotes terephtaldialdehyde and PDA denotes phenylendiamine:
All reaction steps have been carefully monitored with ToF-SIMS, polarisation-modulation
reflection absorption infrared spectroscopy (PM-RAIRS) and X-ray photoelectron spectroscopy
(XPS), confirming at each step that the molecular wire is indeed formed as intended. We believe
that the in situ synthesis of this length of molecular wire on a surface has not been achieved
previously, and forms a crucial step in the further development and optimisation of organic LED
devices.
NH
2
NH
2
AuS N C
H
C
H
N NH
2
(PDA)
+
AuS NH
2
CHO
CHO
AuS N C
H
CHO
+
(TPA)
(SAM)
ORG2-P-Th-P60
288
G-SIMS of Thermosetting Polymers

P. N. Hawtin*, J.F. Watts, M-L Abel

The Surface Analysis Laboratory, University of Surrey, Guildford, Surrey, GU2 7XH, UK
p.hawtin@surrey.ac.uk


The limitations of static secondary ion mass spectrometry (sSIMS) spectra for the identification
of unknown components due to the complexity of the spectra are well known [1]. Gentle-SIMS (G-
SIMS) has been shown to aid in the identification of a range of products including thermoplastic
polymers such as polystyrene, polytetraflouroethylene [2] and crystallisable organic materials such
as caffeine, glucose and bovine serum albumin [3]. By enhancing the higher mass peaks, it is often
possible to see the molecular ion or less fragmented structure, which aids in the identification of the
unknown component.
A study has been undertaken into using G-SIMS on mixtures and complex thermosetting
polymers. Multi-part epoxy resins have been used as the test samples, subjected to different degrees
of cure, as well as the original components. The samples were analysed by means of a gold source
capable of producing Au
+
and Au
3
+
clusters. Both were used at the following energies, 15, 20 and
25 KeV and in positive and negative acquisition mode.
Preliminary results have suggested that the G-SIMS technique is capable of yielding good results
from thermosetting systems containing multiple components. Epoxy and amine components in the
form of M
+
, (M+H)
+
and (M-H)
-
, are clearly visible in the G-SIMS spectra of the two unmixed parts
of the adhesive, with an accuracy sometimes as good as 5 ppm. When examining the cross-linked
system, G-SIMS indicates the presence of characteristic ions, which are not directly related to the
two component peaks of the adhesive. The cured adhesive, however, has minor ions in the G-SIMS
spectra characteristic of those from both the adhesive and the hardener.
These results are encouraging and show that simple molecules may be discriminated from a
mixture using G-SIMS. Some further work is currently in progress on the cured systems to improve
the procedure


[1] I. S. Gilmore and M. P. Seah, App. Surf. Sci., 231-232, 2004, 224-229
[2] I. S. Gilmore and M. P. Seah, App. Surf. Sci., 161, 2000, 465-480
[3] I. S. Gilmore and M. P. Seah, App. Surf. Sci., 203-204, 2003, 551-555

ORG2-P-Th-P61
289
Quantitative and High Mass ToF-SIMS Studies of Siloxane
Segregation in Hydrogel Polymers Using Cryogenic Sample Handling
Techniques

Daniel J. Hook
a
, Paul L. Valint, Jr.
a
, Lu Chen
b
and Joseph A. Gardella Jr.
b,
*

a
Bausch and Lomb Healthcare International,
1400 North Goodman Street, Rochester, N.Y. 14603-0450 USA

b
Department of Chemistry, University at Buffalo, State University of New York
Buffalo, NY 14260-3000 USA
*gardella@acsu.buffalo.edu


XPS analysis of polymer reorganization during exposure to aqueous environments has revealed
the composition and kinetics of near surface reorganization for many low surface energy polymers
[1,2]. A recent development of a protocol for cryogenic sample handling of hydrogel polymers [3]

This protocol was applied to the analysis of commercial hydrogel contact lens materials using
ToF-SIMS and XPS. These methods detected changes in surface chemistry between the hydrated
(frozen) and dehydrated surfaces. Analysis of the hydrated surfaces detected polymer components
indicative of the commercial formulation as well as ice clusters. Analysis of the dehydrated
materials detected changes in surface chemistry relative to the hydrated surface in addition to loss
of water due to sample dehydration. A quantitative standard additions method for ToF-SIMS data
was used to determine submonolayer amounts of PDMS impurities at the surface of the hydrogels.

ToF-SIMS analysis of a series of seven poly (allyl methacrylate-g-dimethylsiloxane), AMA-g-
DMS, graft copolymers in the hydrated state revealed high mass oligomeric ion distributions for
systems with bulk PDMS content greater than 25 weight percent. This marks the first time that
detection of high mass oligomeric ion distributions from hydrated (frozen) surfaces has been
reported. Analysis of the dehydrated surface detected formation of high mass oligomeric ion
distributions for systems with PDMS bulk content greater than 15 weight percent.

[1] A. M. Hawkridge, M. Toselli and J. A. Gardella, Jr., Investigation of the Water-Induced
Reorganization of Poly(caprolactone)-poly(fluoroalkylene oxide)-poly(caprolactone) Triblock
Copolymer Films by Angle Dependent X-ray Photoelectron Spectroscopy, Macromolecules 2002,
35, 6533-6538.
[2] Yuanxue Hou, George M. Tulevski, Paul L. Valint, Jr. and Joseph A. Gardella, Jr.,
Synthesis and Surface Analysis of Siloxane-Containing Amphiphilic Graft Copolymers, Poly(2-
hydroxyethyl methacrylate-g-dimethylsiloxane) and Poly(2,3-dihydroxypropyl methacrylate-g-
dimethylsiloxane), Macromolecules 2002, 35, 5953-5962.
[3] Daniel J. Hook, Ph.D. Dissertation, Department of Chemistry, University at Buffalo, State
University of New York, 2005.
ORG2-P-Th-P62
290
Identification of Hydrocarbon Contamination in Mass Spectra

N.L.Yakovlev
a,
* , J.J.Gray
a
.

a
Institute of Materials Research and Engineering, 3 Research Link, 117602 Singapore
Email niko-y@imre.a-star.edu.sg


Organic compounds in mass spectra are identified in many cases using peaks of specific ionized
molecules [1,2] or typical fragments [3]. In the case of hydrocarbons consisting of only two
elements C and H, the identification requires other approaches. The approach described here has
been developed for analysis of sources of hydrocarbon contamination on substrates after dry and
wet treatment through production process.
Samples of the substrates were taken for analysis from 4 stages of the process: (B) before
treatment as they come from high temperature process, (C) covered for storage with paper in direct
contact with the substrates, (E) after pre-washing, (F) after final washing and corresponding
detergents. Samples B were supposed to be originally clean and having contamination only from
air. The task was to determine, which stage gives contribution to the contamination on samples F.
During 5 months of monitoring, 8 sets of samples were taken and analysed with time of flight (ToF)
secondary ion mass spectrometry (SIMS) in static mode. Primary ions were Ar
+
10 keV, and
positive secondary ions were detected. The main component of the surface was SiO
2
; hydrocarbons
on this surface gave mass spectrum with highest peaks in the mass range 27 to 43 and gradually
decreasing intensity at increasing masses without any typical peaks. Thus the present approach is to
decompose the spectrum as a whole into fingerprints of each treatment stage.
Decomposition of a spectrum f(i) on components a
1
(i), a
2
(i), a
3
(i) etc means finding the
coefficients C
1
, C
2
, C
3
etc so that the function C
1
a
1
(i)+C
2
a
2
(i)+C
3
a
3
(i)+ has minimum root
mean square deviation from f(i), where i is the index of a peak, i=1 to m, and m is the number of
peaks. This is standard calculation, when the functions a(i) are known. In our case, they are
unknown, and we build them from the whole set of data for all samples. Each spectrum is regarded
as a vector in m-dimensional space; we find a fast converging orthogonal basis and decompose the
spectra on it. To provide fast convergence, the first basis vector a
1
(i) is chosen as the mean value of
the spectra to be decomposed; then projections of the spectra on the plane perpendicular to a
1
(i) are
calculated and the second basis vector a
2
(i) is chosen to minimize the projections on the plane
perpendicular to a
2
(i). The same is repeated for the basis vector a
3
(i) and so on. When the spectra
are decomposed on this basis; however some of the coefficients C are negative. Then the basis is
rotated in such way that all C values become positive, that physically correspond to contributions.
The fast convergence is not lost and we see that only the first two or three first components have
significant contribution, these are regarded as the independent sources of contamination.
In the result, important information on the substrate treatment was obtained. Samples C have
main contamination from the air; the contribution from the paper is very small. Samples E have
contamination from the air, water and pre-washing detergent. Samples F have contamination from
the air and containers used to store washed substrates. It was successfully confirmed that they do
not have contamination from the detergent used for final washing.


[1] V. Solomko, A. Delcorte, B.J. Garrison, P. Bertrand, Applied Surface Science 231232 (2004) 48-53.
[2] A. Wucher, S. Sun, C. Szakal, N. Winograd, Applied Surface Science 231232 (2004) 6871.
[3] Shiyong Liu, Chi- Ming Chan, Lu-Tao Weng, Ming Jiang, Polymer 45 (2004) 49454951.

ORG2-P-Th-P63
291
Effect of dilute acrylic acid vapour on lubricated recording hard-disk
media surfaces

Rong Ji*, Thomas Liew and T.C. Chong

Data storage Institute, 5 Engineering Drive 1, Singapore 117608,
Republic of Singapore
Email address: Ji_Rong@dsi.a-star.edu.sg


Weak corrosive gases such as acrylic acid could affect the drive reliability and induce corrosion
of magnetic hard disk media and head in an environment with elevated temperature and humidity
[1, 2]. To explore the tribological changes and corrosion mechanism induced by acrylic acid
vapour, we investigated the surface adsorption of dilute acrylic acid of magnetic hard disk media.
Our study found that the lubricated carbon overcoat surfaces of recording hard-disk media are
absorptive to both water and acrylic acid. TOF SIMS is used to measure the surface absorption of
acrylic acid (Figure 1). The mobility of lubricant and acrylic acid adsorbent is also compared using
TOF SIMS. The surface energy changes of the lubricant surfaces with different amount of acrylic
acid adsorbate are studied, and the micro-corrosion mechanism of hard disk media in the
environment of weak acid gas (acrylic acid) is interpreted.

C
2
HNO
2
C
2
HNO
2
C
3
H
3
O
2
C
2
HNO
2
DLAA0
DLAA1
DLAA2
C
3
H
3
O
2
DLAA3
C
3
H
3
O
2
C
2
HNO
2
C
3
H
3
O
2
C3H3O2
0
50
100
150
200
250
0 20 40 60 80 100 120
Exposed time
I
o
n

c
o
u
n
t
s
C3H3O2/Total
0
0.00002
0.00004
0.00006
0.00008
0.0001
0 20 40 60 80 100 120
Exposed time (hrs)
I
o
n

r
a
t
i
o

Figure 1 TOF SIMS mass spectra of the sample exposed for (a) 0 hrs, (b) 3hrs, (c) 48hrs and (d) 96hrs.
The plot of (e) the ion counts of C
3
H
3
O
2
-
and (f) ion ratio of C
3
H
3
O
2
-
/ Total versus the exposing time


[1] T. Liew, R. Ji, C. H. Seek and T. C. Chong Corrosion of magnetic recording heads and media, Tribology
International, Vol. 36 (2003), pp 447.
[2] Rong Ji, Thomas Liew, C.H. Seek and T.C. Chong, Corrosive Effect of Acrylic Acid on Magnetic Head and Media
of an Operating Hard Disk Drive, Tribology International, to be published.
[3] Thomas E. Karis, Water Adsorption on Thin Film Media, Journal of Colloid and Interface Science, 225, 196203
(2000), pp 196.
[4] Masahiro Yanagisawa, Water adsorption on lubricated carbon surface, Jpn. J. Appl. Phys. Vol. 40 (2001) pp.761.
[5] H. Matsumoto, H. Tani and T. Nakakawaji, Adsorption Properties of Lubricant and Additive for High Durability of
Magnetic Disks, IEEE Trans. Mag. Vol. 37, No. 4 (2001), pp3059.
ORG2-P-Th-P64
292
ToF-SIMS analysis of model nuclear waste glasses

Sandra Ristori
a*
, Antonio Tognazzi
b
, Agnese Magnani
b
, Pierre Frugier
c
,
Olivier Spalla
d
and Claudio Rossi
b


a) Dipartimento di Chimica, Universit di Firenze, Firenze, Italy
b) Dipartimento di Scienze e Tecnologie Chimiche e dei Biosistemi & Polo Universitario di Colle di Val dElsa,
Universit di Siena, Siena, Italy
c) Laboratoire d'tude du Comportement Long Terme, CEA Valrh, Bagnols-sur-Cze, France
d) Laboratoire Interdisciplinaire sur l'Organisation Nanomtrique et Supramolculaire,
CEA Saclay, Gif sur Yvette, France


Glass corrosion by water is a commonly encountered phenomenon and it concerns many aspects
of everyday life, as well as technological or artistic issues, e.g. glassware hazing; deterioration of
containers for the storage of toxic and radioactive substances, and aging of glass artworks or
stained-glass windows.
In the case of nuclear slag vitrification, the main objective is to ensure that waste glasses retain,
as long as possible, the radioactive elements that they contain. The role of hardeners, such as
zirconium, is fundamental in this process.
Morphological analysis, performed with SEM, AFM, and SAXS, has shown that during the
initial stage of alteration a nanostructured porous layer is formed at the glass surface, due to the
leaching of soluble elements (Na, Li, B,. ). Subsequently, the alteration proceeds at the interface
between the corroded layer and the intact core with a complex mechanism of dissolution and
reprecipitation.
Classical chemical analysis has been used to quantify the leaching of various elements, but
comparatively few studies have been performed in situ, to characterise the chemical composition of
the altered surfaces.
In this work, the surface of pristine and corroded sodium borosilicate glasses was studied through
SIMS spectroscopy, imaging, and shallow depth profiling. The combined use of different methods
allowed a detailed characterisation.
Inactive nuclear reference glass samples, formed by 30 elements (SON68) as well model
samples containing SiO
2
, CaO, B
2
O
3
, Na
2
O and ZrO
2
were investigated.
The leaching of soluble elements was confirmed by comparing spectra of intact and differently
altered glasses. However, in highly confined alteration conditions, phenomena of reprecitation and
crystallisation (phyllosicate formation) could play a role in modifying the quantity of leached ions.
A strong and new observation was that, in altered glasses, a higher concentration of oxygen
containing species (e.g XO
+
and XOH
+
) was evidenced on the surface. This may be correlated with
a different chemical environment of the metal cation X
n+
and with a higher amount of inner surface
in the porous layer.
Large scale structural inhomogeneities were found in all altered samples. They showed textures
of micrometer size, in line with results obtained from previous morphological analysis. However,
chemical inhomogeneities were only found in SONS68 altered glasses and they were attributed to
the effects of water corrosion processes in materials with complex composition.

ORG2-P-Th-P65
293
ToF-SIMS as a reliable tool for carotenoids and chlorophyll detection
in natural samples: fruits, flowers and microalgae

L. Houssiau
a,*
, C. Bittencourt
a
, H. Sarmento
b
, J.-P. Descy
b
and J.-J. Pireaux
a

a
University of Namur (FuNDP), LISE laboratory; 61, rue de Bruxelles, B-5000 Namur, Belgium
a
University of Namur, Laboratoire dEcologie des Eaux Douces; 61, rue de Bruxelles, B-5000 Namur, Belgium
laurent.houssiau@fundp.ac.be


In a previous work [1] we have demonstrated that ToF-SIMS is a reliable tool to probe bixin, a
natural carotenoid used as food colorant, present in annatto seeds. In this work, we have applied the
technique to a more systematic detection of carotenoids in natural samples such as fruits, flowers
and algae. Standards were also studied in order to obtain reference spectra, in which the sensitivity
and the straightforwardness of the technique were addressed. As it was the case for bixin, we found
that most carotenoids are readily detected by means of (M), (M+1) and (M+2) molecular ions. The
spectra recorded on the pulp part of Yellow Passion Fruit (Passiflora edulis) exhibit high intensity
peaks above m/z 400, which can be related to the following carotenoids: phytoene at m/z 544,
phytofluene m/z at 542, -carotene m/z at 540, neurosperene m/z at 538, -carotene m/z at 536,
lycopene m/z at 536, prolycopene m/z at 536, mutatochrome m/z at 552, -cryptoxanthin m/z at
552, -citraurin m/z at 432, antheraxanthin m/z at 584, violaxanthin and neoxanthin both at m/z
600. The saffron components were determined by direct analysis of the stigmata. On microalgae
samples, other carotenoids were identified. The complex spectra were compared with reference
spectra taken on lutein, zeaxanthin and -carotene. Since chlorophyll is a major constituent of
vegetal samples, its reference spectrum was also recorded. The M molecular ion of chlorophyll-a is
easily detected at m/z 892, along with high mass fragments which can be understood from the
molecular structure. The potentiality of the ToF-SIMS in analyzing cyanotoxins is under
investigation.


[1] L. Houssiau, M. Felicissimo, C. Bittencourt and J.J. Pireaux, Appl. Surf. Sci. 231-232 (2004) 416-419
ORG2-P-Th-P66
294
Using Time-of-Flight Secondary Ion Mass Spectrometry to Investigate
Reaction, Destruction, Penetration and Aggregation of Vapor-
Deposited Metal Atoms on Alkanethiol Self-Assembled Monolayers

Z. Zhu*, D. L. Allara, N. Winograd

Department of Chemistry, The Penn State University, University Park, PA 16802 USA
Email: zzz100@psu.edu


Time-of-flight secondary ion mass spectrometry (ToF-SIMS) has been used to study the interface
of metal/self-assembled monolayers (SAM) for several years [1-3]. Chemical reaction, destruction,
penetration and aggregation behavior of metal atoms on organic thin films can be easily
distinguished by SIMS spectra. In this work, we applied ToF-SIMS to investigate the behaviors of
vapor-deposited K, Au and Ti atoms on several alkanethiol SAMs. Via these sample systems, we
demonstrate some general rules for determining chemical reaction, penetration, aggregation and
destruction. For example, the appearance of new peaks and disappearance of original characteristic
peaks indicates the occurrence of chemical reaction or destruction. The S(CH
2
)
15
CO
2
K
-
peak is
observed after K is deposited on S(CH
2
)
15
CO
2
CH
3
film; and at the same time, the OCH
3
-
peak
drops, indicating CO
2
CH
3
groups react with K atoms to form CO
2
K moieties. With Ti atoms
deposited on S(CH
2
)
15
CO
2
H film, the CO
2
H
+
signal decreases and the TiC
+
signal appears,
suggesting that Ti destroys the film molecules. When Au is deposited on different SAMs, the Au
+

signal is found to be an indicator of different penetration modes. For the S(CH
2
)
15
CH
3
film,
intensities of Au
+
peak remain constant even after 16 layers of Au deposition, showing that Au
atoms penetrate through the organic thin film quickly and evenly. As a comparison, the Au
+
signal
from the S(CH
2
)
15
CO
2
K system greatly decrease after the same dose of Au deposition, indicating
that Au stays on top of the CO
2
K layer instead of penetrating it. Additionally, we find the
disappearance rate of original characteristic peaks is an indicator of aggregation of metal atoms.
When 2 nm of Ti is deposited onto CO
2
CH
3
and CH
3
surfaces, all CO
2
CH
3
-related signals
disappear, but CH
3
-related signals are still clearly observed, suggesting that smooth layers of Ti
form on top of the CO
2
CH
3
surface, but islands form on the CH
3
surface.


[1] A. Hooper, G. L. Fisher, K. Konstadinidia, D. Jung, H. Nguyen, R. Opila, R. W. Collins, N. Winograd and D. L.
Allara, J. Am. Chem. Soc. 121 (1999) 8052.
[2] B. C. Haynie, A. V. Walker, T. B. Tighe, D. L. Allara and N. Winograd, Appl. Surf. Sci. 203-204 (2003) 433.
[3] Z. Zhu, B. C. Haynie and N. Winograd, Appl. Surf. Sci. 321-322 (2004) 318.
ORG2-P-Th-P67
295
Depth Profile Analysis of OLED Devices Using TOF-SIMS with
Gradient Shaving Preparation

*T.Shibamori, H.Seki, T.Matsunobe, N.Man, and Y.Nakagawa

Toray Research Center, Inc.
3-7, Sonoyoma 3-chome, Otsu, Shiga, 520-8567, Japan
Takahiro_Shibamori@trc.toray.co.jp


OLED devices consist of several thin layers of organic materials and metals. Because the
organics are considered to be reactive at the interfaces of the layers on emitting, the depth profiling
of the organics and the analysis of the interfaces are important. But, the organics are damaged
chemically on the depth profiling with ion etching method, which is conventionally used for
profiling of thin layers. In order to obtain the depth profiles of the organics with less damage, we
measured the line profile by surface analysis techniques on a slope prepared by the gradient shaving
preparation [1-2], which have been developed in Toray Research Center Inc.
In this work, TOF-SIMS and microphotoluminescence measurements with the gradient shaving
preparation were applied to the polymer OLED devices having the structure of Al cathode / TPB,
butyl-PBD, polyvinylcarbazole (EML: 60nm)/ PEDOT-PSS (HTL: 80nm) / ITO anode / glass. We
obtained the depth profile of an electrically deteriorated sample, which brightness was decreased to
the half of the initial (Fig.1). Sodium was detected from the EML (emitter layer) of the deteriorated
sample. It is thought to be an impurity of the HTL (hole transport layer) and diffused into the EML
after deterioration. The diffusion of Sodium may cause a decrease in the emittance.
We will discuss on the comparison of minor organic components between samples, and the
correspondence of TOF-SIMS and microphotoluminescence measurements.





















[1] N.Nagai Analytical Sci., 17 suppl., i671 (2000)
[2] N.Man et al. Applied Surface Sci., 231-232 (2004) 353-356
Fig.1 Depth profile of a deteriorated sample
1.E-04
1.E-03
1.E-02
1.E-01
1.E+00
-100 0 100 200 300 400
Na
In
TPB?
EML HTL ITO
N
o
r
m
a
l
i
z
e
d

i
n
t
e
n
s
i
t
y

Distance(m)
140nm
ORG2-P-Th-P68
296
ToF-SIMS: Going Beyond Surface Chemical Composition

K.G. Lloyd*, G.S. Blackman, D.J. Walls, D.G. Swartzfager

DuPont Corporate Center for Analytical Sciences, DuPont Experimental Station, Building 323, P.O. Box 80323
Wilmington, DE 19880-0323
Kathryn.G.Lloyd@usa.dupont.com


The ability of ToF-SIMS to provide chemical structural and compositional information
relative to surfaces is well recognized. Newer heavier and/or polyatomic primary ion sources have
enhanced this ability by increasing the apparent yields of higher-mass molecular secondary ions.
However, there exists the potential to extend the characterization power of ToF-SIMS
beyond surface chemical characterization -- to electrical, morphological, and even mechanical
properties. Surface electrical properties can be explored by taking advantage of the way the
reflectron mass analyser is tuned. Polymer structural changes throughout the thickness of a film can
be explored by attempting to correlate ToF-SIMS data with Raman spectroscopy. Adhesion of thin
films can be studied by teaming ToF-SIMS with scanning probe technology. In addition, the use of
multivariate analysis can facilitate the investigation of sub-surface interfacial chemistry in
multilayer structures using ToF-SIMS depth profiling.
Some results from delving into these areas with ToF-SIMS will be presented.


ORG2-P-Th-P69
297
Selective Detection of Organic Compounds on Modified Polymer
Surfaces Using TOF-SIMS in Combination with Derivatization

Moonhee Kwon
a
Yeonhee Lee
b,
*, Ju Hi Hong
b
, Seunghee Han
b
, Haidong Kim
a


a
Department of Chemistry, Kyunghee University, Seoul , Korea
b
Advanced Analysis Center, Korea Institute of Science and Technology, Seoul 136-791, Korea
Email: yhlee@kist.re.kr


Characterization of the complex composition of non-volatile and thermally labile compounds has
been vastly improved by Time-of-Flight Secondary Ion Mass Spectrometry (TOF-SIMS). TOF-
SIMS spectra of a variety of polymeric materials have shown that oligomer distribution and
fingerprint mass spectra can be obtained [1,2]. This investigation encompasses work in the
development of SIMS methodology for the characterization of compounds formed during polymer
surface modification. TOF-SIMS was used in this study in combination with selective
derivatization reactions with functional group specific reagents. Derivatization techniques with
group specific reagents provide a means of identifying functional groups in a complex matrix, along
with significant enhancement of detection limits. The study proceeded in three steps. First,
derivatives of organic compounds as a model compound were monitored to determine the suitability
for detecting oxygenated species. Second, useful derivatization reactions were tested on functional
groups in the synthetic polymer chains. Third, the methods thus developed were applied to polymer
surfaces treated by Plasma Source Ion Implantation (PSII). 2,4-Dinitrophenyl hydrasone
derivatives were shown to yield informative TOF-SIMS spectra for a wide range of carbonyl
groups. 2-Fluoro-1-methylpyridinium derivatives were useful for characterization of organic
alcohols and phenolic compounds. Analysis of organic compounds derivatized by these methods on
polymeric materials demonstrated clearly that analysis in the presence of a carbonaceous matrix is
possible. The results yielded evidence for the formation of phenolic and carbonyl species as the
polymer is modified by PSII technique.


[1] I.V.Bletsos, D.M. Hercules, D. Greifendorf, A. Benninghoven, Anal. Chem. (1987) 57, 2384
[2] M.P. Chiarelli, A. Proctor, I.V. Bletsos, D.M. Hercules, H. Feld, A. Leute, A. Benninghoven, Macromolecules
(1992), 25, 6970
MAT-P-Th-P70
298
Surface Spectroscopic Imaging of PEG-PLA Tissue Engineering
Constructs With ToF-SIMS

G. Tsourapas
a
, F.J.M. Rutten
b,*
, D. Briggs
b
, M.C. Davies
b
and K.M. Shakesheff
a


a
Tissue Engineering
b
Laboratory of Biophysics and Surface Analysis,
School of Pharmacy, University of Nottingham, Nottingham NG7 2RD, UK
E-mail: frank.rutten@nottingham.ac.uk


The field of tissue engineering has developed rapidly over recent years, with much effort being
concentrated on the controlled attachment of cells to tissue engineering constructs. To do this
successfully a number of basic requirements have to be met, such as biodegradability,
biocompatibility, and prevention of non-specific and promotion of desired cell attachment.
Poly(lactic acid) (PLA) has been studied extensively in tissue engineering research due to its
well-established biodegradability and compatibility. Unfortunately it does suffer strongly from
non-specific cell attachment and a non-fouling modification is thus required to attain a feasible
material. In the work presented here this has been achieved by physically entrapping a polymer with
known anti-fouling properties, poly(ethyl glycol) (PEG) , into the surface. The method involves
swelling of the surface of PLA by a solvent/non-solvent mixture, followed by exposure to PEG
and finally reversal of the swelling by applying a non-solvent [1].
The thus modified surface was then characterised by a combination of ToF-SIMS (spectroscopy
as well as imaging) and X-ray photoelectron spectroscopy (XPS). Cell attachment was subsequently
investigated as a function of the amount of entrapped PEG. XPS was instrumental in quantifying the
amount of PEG entrapped at higher concentrations. The significantly higher sensitivity and superior
imaging capabilities of ToF-SIMS enabled a full characterisation of the PEG distribution at the low
concentrations required for the desired non-fouling properties which were well below the XPS
detection limit (ca. 10%). It was found that pronounced segregation effects of the order of tens of
microns were present at all PEG concentrations investigated.


[1] R.A. Quirk, M.C. Davies, S.J.B. Tendler, K.M Shakesheff, Macromolecules 33 (2000) 258
MAT-P-Th-P71
299
Characterization of the 3D-distribution of impurities in InP
semiconductor using SIMS

S. H. Haji Hosseini Gazestani, M. R. Hantehzadeh, M.Ghoranneviss,
M.Shariati, A. H. Sari, A. Shokouhy

Plasma Physics Research Center, I.A.University,
P.O.Box: 14665-678, Tehran, Iran


The impurities in semiconductors commonly were traced by secondary ion mass spectrometry
SIMS technique[1,2]. The InP samples were prepared and depth profiles of impurities were
obtained by SIMS. By comparing of results in different area of samples, it has been seen that
distribution of some elements are not uniform. The ion images also were obtained that confirm
some elements distributed as clusters.



[1] F.D. McDaniel et al., Nucl. Instr. And Meth. in Phys. Res. B 190 (2002) 826
[2] K. Tsukamoto, S. Yoshikawa, F. Toujou, H. Morita, Appl. Surf. Sci. 203-204(2003)404
MAT-P-Th-P72
300
TOFSIMS Analysis of SiC-Cu Composites for Thermal Management
Applications

R.Treichler*
a
, G.Lefranc
b
, T.Weissgaerber
c
, T.Kiendl
d


a,b,d
SIEMENS AG, Corporate Technology, D-81739 Mnchen, Otto-Hahn-Ring 6, Germany
c
Fraunhofer Institute for Manufacturing and Advanced Materials, Dept. Powder Metallurgy and Composite Materials
Email: rolf.treichler@siemens.com


With the continuous increase of package density in semiconductor manufacturing,
thermomechanic and thermoelectric considerations of power dissipation play an increasing role.
Failures by thermal fatigue due to different expansion coefficients of semiconductor circuits and
packaging material have become an important long term stability limiting issue. Therefore there is
a quest for improved packaging materials to complement or substitute traditional materials like Al,
Cu, and various transition metal alloys in this area. SiC-Cu composites have attracted strong
interest as they combine high thermal and electric conductivity with mechanical strength,
mouldability and low production costs. To improve this compound, thermomechanical and
thermoelectrical analyses are necessary, but a deeper understanding of the physical properties
requires the application of further analysis methods. In this study we applied the imaging
capabilities of TOFSIMS combined with its excellent detection limits to monitor the distribution of
the main matrix components as well as additives like Ti used to selectively improve the physical
parameters of the SiC-Cu composite. TOFSIMS proved to be an excellent and rapid analysis tool to
better understand and improve this material system.


Microscope and TOFSIMS images of a SiC-Cu (Ti) cross-section (SiC grains in a Cu matrix):







Si
superposition
Cu Ti
MAT-P-Th-P73
301
NanoSIMS analysis of Ca doping at a grain boundary in a
superconducting YBCO Ca-123/123 bicrystal


C. Dark
a,
*, M. R. Kilburn
a
, C. Schneider
b
, J. Mannhart
b
, C. R. M. Grovenor
a

a
Department of Materials, University of Oxford, Parks Road, Oxford, OX1 3PH, UK
b
Experimental Physics VI, University of Augsburg, D-86135 Augsburg, Germany
Email address: chrisdark999@yahoo.com


Calcium doping is well known to increase the grain boundary Jc values in YBCO but to lower the
Tc of the bulk material. As a result, strategies have been developed to grow multilayer structures
where this enhancement of Jc is optimised by rapid Ca diffusion along the YBCO grain boundary
from a Ca-doped 123 layer. We have used high resolution SIMS analysis to map the distribution of
Ca ions in three dimensions in a YBCO grain boundary grown on a 24 degree STO bicrystal with a
thin Ca-YBCO source layer.

We have used our Cameca NanoSIMS to map Ca, Sr and Ti every 20nm in depth from the top of
the YBCO surface into the STO substrate. These maps allow the variation of Ca ion concentration
with depth to be calculated, showing (i) an approximately exponential decrease in Ca concentration
as one moves further from the Ca source and (ii) that the top 30 nm of the YBCO boundary contains
no detectable Ca at all. Moreover, localised high concentrations of Ca can be detected at the YBCO
grain boundary, perhaps at regions with a high dislocation density.

We have also detected some diffusion of Sr and Ti up the boundary from the substrate. This kind
of high resolution analysis should allow the design of specimen growth processes to give the correct
Ca distribution for optimising the grain boundary properties.


Figure 1.
40
Ca map of the grain boundary (the scale bar is 6 mm).
MAT-P-Th-P74
302
Selective oxidation of Fe-1.5Mn alloys: quantitative description of
annealed surfaces

LOISON Didier * - N. ROBERT - CHAMPMARTIN-PHILIPPE Valrie BOULEAU Daniel

Arcelor Research, Voie Romaine, BP 30320, MAIZIERES-LES-METZ CEDEX (France)
didier.loison@arcelor.com


Galvanisation quality of HSS (High Strengthened Steels) is very dependant of the steel surface
states developed after annealing. Due to the large amounts of elements exhibiting a strong affinity
for oxygen (silicon, aluminium and manganese among others) present in such grades, heat treated
surfaces are sometimes largely covered by oxide particles or films that inhibits partly the reactive
wettability of steels in molten zinc. Moreover, this phenomenon is more or less accentuated
depending on the annealing conditions chosen. Consequences for the automotive customers if
considering the resistance to corrosion of these grades cannot be tolerated.
Since few years, Arcelor Research decided optimising annealing process parameters by the
development of predictive models allowing determining the surface states of flat carbon steels after
heat treatments [1][2]. Validation of such models based on the diffusion of elements more
oxidizable than iron and their precipitation as oxide phases needs to quantitatively describe the top
surface and the sub-surface of the considered material.
Coupling SIMS analyses, FEG-SEM image processing, TEM observations and electron
diffraction, we show how it is possible to fully describe model alloy surfaces (Fe-1.5Mn). Nature of
oxides precipitated, mean size of particles, surface covering yield and density of precipitation where
determined for different annealing conditions (temperature; atmosphere dew point; holding time)
and interpreted in terms of nucleation and growth of oxide particles. The in-depth distributions of
manganese and oxygen obtained by SIMS were finally compared to the model prediction. The good
agreement between measurement and model underline the usefulness of the CsM+ quantification
approach for such matrixes. A continuation of the study on annealed Fe-Si and Fe-Mn- Si grades is
under development at Arcelor Research.


[1] D. Loison D. Huin J.P Servais; R. Cremer; Galvatech 2001 congress; Brussels
[2] D. Huin H. Saint-Raymond D. Loison M.J. Cornu F. Bertrand; Galvatech 2003 congress; Chicago


INS-P-Th-P75
303
SIMS Analysis using a new Noble Sample Stage

Shiro Miwa
a,
* , Ichiro Nomachi
a
, and Hideo Kitajima
b


a
Materials Analysis Center, Sony EMCS Corp., 4-16-1 Okata, Atsugi, 243-0021, Japan
b
Nanotechnos Corp., 5-4-30 Nishihashimoto, Sagamihara, 229-1131, Japan
Email: Shiro.Miwa@jp.sony.com


When using a SIMS instrument with an optical gate system, such as a Cameca ims-4f, it is
essential to position the sample holder parallel to the electric field generated by secondary ion
optics. We have developed a noble sample stage for Cameca ims-series instruments which allow us
to adjust the tilt of the sample holder from outside the vacuum chamber. Using this stage, we can
measure the line profile for more than 20mm without any variation of the secondary-ion yield. We
can also vary the distance between the sample surface and the input lens of the secondary optics.
By shortening the distance, we can easily reduce the energy of the primary ions. The primary ion
beam is well focused because the focal length of the final lens of primary ion optics is shortened.
Third function of the stage is sample cooling using liquid nitrogen. The sample can be cooled to
below -150C. This is useful for samples such as organic materials that are easily damaged by an
ion beam or electron beam from an electron flood gun.
INS-P-Th-P76
304
The second life of Cameca cesium ionizer.

Yu.Kudriavtsev
1
*, V. Mishurnuy
2
, A.Villegas
1
, A. Godines
1
, R.Asomoza
1


1
Dep. Ingenieria Electrica - SEES, Cinvestav-IPN, Av.IPN # 2508, Mexico, D.F.
2
Instituto de Investigacion en Comunicacin Optica, San Luis Potos, Mexico
E-mail: yuriyk@cinvestav.mx


In this report we demonstrate a simple technique of the alteration of a Cameca cesium ionizer for
its future using in the cesium source.
We re-made the used ionizer: the top of it was removed together with the W plate. The internal
hole of the Mo (or Ta) tube was increased till 2mm of the diameter for the depth till around 3-4mm.
A piece of Mo rode with the diameter of 2mm and the length of 4-5 mm was bored across with a 0.5
mm drill. We fixed the Mo detail inside of the prepared hole by a special liquid ceramic (its fixation
happens after a heat treatment under 400
o
C). Fig. 1(a,b) shows the modified ionizer. After load of
Cs
2
CrO
4
powder the ionizer was ready to work.
After degassing (made by a standard manner) we checked some characteristics of the modified
Cs source. The total ion current was found as high as 100-150 nA with a good stability, enough for
depth profiling analysis of typical semiconductor structures. A well focused Cs ion beam with
current of 15-20 nA we have applied for SIMS routine analysis of electronegative elements. A
higher lateral resolution was found for modified ionizer in the microprobe mode in comparison with
the standard Cameca ionizer.


a) b)
Fig. 1 (a,b) Modified ionizer: a) view from above after ceramic fixation; b) side view (the ceramic
spume was removed before using).
INS-P-Th-P77
305
CAESIUM SPUTTER ION SOURCE COMPATIBLE
WITH COMERCIAL SIMS INSTRUMENTS

S.F.Belykh
a
*, V.V.Palitsin
a
, R.J.H. Chang
a
, I.V. Veryovkin
b
, A.P.Kovarsky
c
,
A.Adriaens
d
, M.Dowsett
a
, F. Adams
e


a
University of Warwick, Department of Physics, Warwick Coventry CV4 7AL, UK
b
Argonne National Laboratory, Materials Science Division, Argonne, IL 60439 USA
c
Ioffe Physical-Technical Institute, 194021 St.Petersburg, Russia
d
Ghent University, Department of Analytical Chemistry, B-9000 Ghent,Belgium
e
University of Antwerp, Department of Chemistry, 2610 Antwerp, Belgium
Email: s.belikh@warwick.ac.uk


One potential way to improve the SIMS technique is to use cluster ions as projectiles instead of
atomic ions. The bombardment of solids by keV/atom cluster ions leads to a non-additive
enhancement of the sputtered ion yields, a reduced penetration depth of constituent cluster atoms,
and a reduction of primary ion beam-induced damage (provided the clusters are small and the energy
is below 10 keV). These features of cluster-solid interaction are attractive for SIMS applications
related to both top monolayer surface analysis and depth profiling because the cluster ion
bombardment can increase both the elemental and molecular detection sensitivities and the depth
resolution when profiling.
In the context of benefits for SIMS analysis, the development of cluster ion sources compatible
with standard SIMS instruments is an effective, and relatively inexpensive way to improve the
analytical possibilities of high capital cost SIMS instruments. A source based on ions extracted from
a target bombarded by caesium is a suitable candidate to be combined with commercially available
SIMS equipment. The main advantage of such a source is the possibility of producing negative
cluster ions during keV Cs
+
sputtering of various metals and materials. Moreover, the negative ions
have the useful property of minimizing charging effects when used for insulator analysis.
Here we describe a simple design for a caesium sputter ion source compatible with vacuum, ion-
optical and power supply systems of commercially available SIMS instrumentation. It has been
tested with the Cameca IMS 4f instrument using negative cluster Si
n
-
, Al
n
-
, and Cu
n
-
ions, and will
shortly be retrofitted to a floating low energy ion gun (FLIG
TM
) of the type used on the Atomika/FEI
4500/4550 instruments. The results related to surface characterization, depth profiling, and non-
additive sputtering in the form of multiple charged ions are discussed.
INS-P-Th-P78
306
Recent Developments and Applications of CAMECA Quadrupole
SIMS Tools

H.-Ulrich Ehrke*, Hans Maul, Norbert Loibl, Adam Sears, Christoph Schnrer Patschan

CAMECA GmbH
Bruckmannring 40
85764 Oberschleissheim/Munich, Germany
ulrich.ehrke@cameca.fr


Depth profiling SIMS has become a routine technique for semiconductor process development
since quite a while. Nowadays SIMS is more and more used for process monitoring, mostly by
breaking the wafers and using SIMS lab tools.
Process monitoring tasks typically cover only a handful of well-defined applications. This
allows designing and providing full wafer SIMS tools tailor made for the particular process
monitoring requirements. While such tools are based on a common platform, their operation is
automated and simplified to the extent that they can be used at/in fab by operators with no prior
SIMS experience.
Two such full wafer process-monitoring tools based on Atomika quadrupole SIMS technology
have been recently developed:
A two Cs beam tool for EPI process monitoring in LED production
A one Oxygen beam only tool for ultra shallow B and As implant dose monitoring and SiGe
EPI process monitoring.
Features and applications of both tools will be reported and discussed.

INS-P-Th-P79
307
Improved automation system for the CAMECA IMS 7f

P Peres
a,*
, E. de Chambost
a
, A. Merkulov
a
, M. Schuhmacher
a


a
CAMECA, 103 bld. Saint-Denis, 92400 Courbevoie Cedex
Email address: peres@cameca.fr


The CAMECA SIMS instruments has significantly improved the analysis throughput of the SIMS
laboratories equipped with most recent instruments from CAMECA, as they offer an increased level
of automation and operation efficiency.
The CAMECA IMS 7f is based, as for previous IMS xf series, on a double focusing mass
spectrometer. This unique instrument design provides top performances in terms of sensitivity, depth
resolution and mass resolution which are mandatory for depth profiling and secondary ion
microscopy applications.
An important new feature of the IMS 7f is its fully digital control system. All apertures and slits
are motor driven and computer controlled in standard, which provides an easier use of the instrument
through memorized settings and recipes. Combined to improved software capabilities, this new
feature allows to chain analyses with different analyses recipes without any operator attendance.
Also, this high automation level provides a reliable load-save of instrumental settings, thus ensuring
an optimised long term reproducibility.
This paper will present results of SIMS measurements performed on a CAMECA IMS 7f,
equipped with the fully motorized slits/apertures commands set. The goal of these measurements
was to evaluate the reproducibility of the motorized apertures presets and its influence on the long
term instrument stability.
A Statistical Process Control (SPC) of Relative Sensitivity Factor (RSF) for different dopants in Si
has been performed over a long period (weeks) for analyses at low or high mass resolution and with
O2+ or Cs+ primary ions conditions. Over this period, periodically, samples were transferred from
the airlock to the chamber, and the corresponding instrumental status file which contains all tuning
and motor positions presets was loaded. The data collected demonstrate an excellent reproducibility
of the instrumental settings compatible with a long term measurement precision in the 1% range.
Other parameters having an influence on the long term instrumental reproducibility will also be
discussed.


INS-P-Th-P80
308
Development and characterisation of the new NanoSIMS 50L

F. Hillion
a,
* , A. Merkulov
a
, F. Horrard
a


a
CAMECA , 103 Bd Saint-Denis, 92403 Courbevoie Cedex
hillion@cameca.fr


A new version of the high resolution ion microprobe NanoSIMS 50 [1,2] has been developed in
order to improve its performance mainly for cosmochemistry and earth science application.
A larger Mattauch Herzog-like magnetic sector has been designed allowing the parallel detection
of seven masses. It incorporates a new multicollection design with seven trolleys (one fix and six
mobile), each trolley being able to be equipped simultaneously with one miniature Electron
Multiplier (EM) and one Faraday Cup (FC). The mass dispersion M
max
/M
min
is 21 (example:
parallel collection from 1H to 19F or from 12C to 238U) and the minimum mass interval between
two adjacent trolleys has been reduced to M/58 in order to allow isotopic analysis up to iron.
The reproducibility of isotopic measurements has been improved thanks to the development of
software routines for automated secondary ion beam alignment in the optics, addition of Bfield
compensating coils before the entrance slits and optimisation of the acquisition conditions required
by micrometer-scale primary ion beam and small area analysis.
The moveable slits and apertures of the optics as well as the hexapole and the Z-axis of the
sample stage have been automated in order to achieve good reproducibility and improve easiness of
operation.
The capability to operate the NanoSIMS in multi-FC mode allows to envision earth science
application requiring permil isotopic ratio reproducibility together with sub-micron to a few micron
lateral resolution.
The performance of the new instrument will be detailed concerning the sputtering and useful
yield on a few elements and samples, the transmission/mass resolution curve and the reproducibility
of isotopic measurements with EMs and FCs in different acquisition modes.


[1] G. Slodzian, B. Daigne, F. Girard and F. Hillion : A high resolution scanning ion microscope with parallel detection
of secondary ions. Proceedings of the VIIIth SIMS Conference, Amsterdam, 1991
[2] F.Hillion, B. Daigne, F. Girard and G. Slodzian : A new high performance instrument : The CAMECA NanoSIMS
50. Proceedings of the 9th SIMS Conference, Yokohama nov. 1993.
DEP2-O-Fr-A01
309
Comparison between the SIMS and MEIS Techniques for the
characterisation of ultra shallow Arsenic implants

M. Bersani
a,
*, D. Giubertoni
a
, M. Barozzi
a
, S. Pederzoli
a
, E. Iacob
a
,
J. A. van den Berg
b
and M. Werner
b
.

a
ITC-irst, Centro per la Ricerca Scientifica e Tecnologica,
Via Sommarive 18, 38050 Povo - Trento, Italy
b
Joule Physics Laboratory, Institute of Materials Research,
University of Salford, Salford, M5 4WT, UK.
bersani@itc.it


One of the main limitations of the application of SIMS to ultra shallow implants is the
unavoidable formation of an initial transient region: in such region a linear relationship between
secondary ions and dopant concentration does not exist and the erosion rate can vary drastically.
Moreover the presence of a native or intentionally grown oxide complicates the measurement
because of the oxygen effect on the secondary ion yield [1].
The use of complementary techniques is essential if an accurate characterization of the top few
nanometers is required. Medium Energy Ion Scattering (MEIS) offers the advantage of an accurate
quantification and of an ultimate depth resolution <1 nm [2]. Best results are obtained for heavy
elements in light matrices but the detection limit achievable is always poorer than the one obtained
by SIMS. Nevertheless the combined use of the two techniques in the characterization of a heavy
element as arsenic in silicon is helpful to verify the accuracy of the SIMS analysis as well as to
understand the evolution of the damage recovery.








0 5 10 15
1E19
1E20
1E21








MEIS
'p-b-p' of
28
Si
-
'p-b-p' of
28
Si
2
-
'AVG' of
28
Si
2
- S
E
C
.

I
O
N

I
N
T
E
N
S
I
T
Y

(
c
t
s
.
/
s
e
c
.
)

A
s

C
O
N
C
E
N
T
R
A
T
I
O
N

(
a
t
/
c
m
3
)
DEPTH (nm)
10
4
10
5
10
6
10
7
28
Si
-
28
Si
2
-


In this work SIMS analyses, performed by a Cameca Sc-Ultra using a 0.5 keV impact energy Cs
+

beam (incidence angle ~45) and by collecting negative secondary ions, will be compared with
MEIS results. The latter were obtained using a 100 keV He
+
ion beam and the double alignment
configuration, in which the [ 1 1 1 ] channelling direction was combined with the [111] and [332]
blocking directions. The complementarity of the two analytical techniques in the characterization of
shallow As implants in silicon (implantation energy 3 and 1 keV) before and after annealing will be
illustrated, with particular reference to the As quantification at the SiO
2
/Si interface and to the depth
accuracy of SIMS analysis.


[1] W. Vandervorst et al., Appl. Surf. Sci. 231-232, 2004, 618-631.
[2] M. Werner et al., Nucl Instrum Meth. B216 (2004) 67-74
DEP2-O-Fr-A02
310
Collaborative SIMS study and simulations of implanted dopants in Si

N.L.Yakovlev
a
,*, C.C.Lee
a
, H.Y.Chan
b
, R.Liu
c
, A.T.S.Wee
c
, M.P.Srinivasan
c
,
C.M.Ng
d
, D.Gui
d
, L.Chan
d
, A.R.Chanbasha
e
, N.J.Montgomery
f
, C.P.A.Mulcahy
f
,
S.Biswas
f
, H.-J.L.Gossmann
g
and M. Harris
g


a
Institute of Materials Research and Engineering, 3 Research Link, 117602 Singapore
b
Department of Chemical and Biomolecular Engineering, National University of Singapore, 117576 Singapore
c
Department of Physics, National University of Singapore, 2 Science Drive 3, 117542 Singapore
d
Chartered Semiconductor Manufacturing Ltd., 60 Woodlands Industrial Park D, Street 2, 738406 Singapore
e
Omega Scientific Pte Ltd, 1 Kaki Bukit View #05-15/16 Techview, 415941 Singapore
f
Cascade Scientific Ltd, ETC Building, Brunel Science Park, Uxbridge, UB8 3PH, U.K.
g
Axcelis Technologies, 108 Cherry Hill Drive, Beverly, MA 01915-1053, USA
Email: niko-y@imre.a-star.edu.sg


Implantation of doping elements has become the main technique to achieve ultra-shallow source
and drain regions in semiconductor devices. The distribution of dopants affects electric field in the
devices and, as device features shrink, it has macroscopic impact on device characteristics. Hence
the accurate determination of dopant depth profiles is important for improving the device
performance. The distribution of implanted elements can be calculated using molecular dynamics
(MD) theory. Physically, it is measured using secondary ion mass spectrometry (SIMS).
Five SIMS teams measured the depth profiles of F, P, As and Ge, which were implanted in
Si(100) wafers at energies 1 to 10 keV. The instruments used in this Round Robin are: magnetic
sector SIMS, quadrupole SIMS and time-of-flight (ToF) SIMS. Cs was used as the sputtering ion
and negative secondary ions were monitored. For a particular element and implantation energy, all
measurements show similar descending slope on the depth profile, except for the following cases.
Quadrupole SIMS is unable to mass resolve P from
30
SiH, hence the tails of the P profiles appears
to have higher intensity. ToF SIMS uses Ga as the analysis ion beam, which increases ion mixing
of Ge and As, resulting in a delayed slope of Ge and As profiles.
The profiles simulated using MD coincide with the SIMS profiles on the trailing slope of the
implanted peak. On the rising slope, there are differences depending on how the native silicon
oxide is taken into account in the calculation. We propose a method of using the ranges of
coincidence to recalibrate SIMS profiles for reducing the contribution of experimental artefacts.
Discrepancies between the simulation and SIMS data obtained with different instruments for F, P,
As and Ge will also be presented and discussed.

Figure 1. Example of depth profiles of phosphorus implanted at 2 keV, dose 510
13
cm
-3
and normal incidence in
Si(100). Lines - SIMS measurements, open circles - MD simulation.
DEP2-O-Fr-A03
311
On the limitations of closely spaced delta layers for the assessment of
various parameters in sputter profiling

*M. G. Dowsett
a
and M. P. Seah
b


a
Advanced SIMS Projects, Department of Physics, University of Warwick, Coventry CV4 7AL, UK
b
Quality of Life Division (bldg 15), National Physical Laboratory, Teddington,
Middlesex TW11 0LW, UK
M.G.Dowsett@warwick.ac.uk


Various structures containing delta-doped layers have been mooted for use as reference
materials in sputter profiling e.g. [1]. A carefully designed sample can provide markers for the
accurate calibration of sputter yields, and reveal the onset and evolution of surface nano-topography
[2,3]. It is a common simplifying practice to associate some part of the measured delta layer
response (peak, centroid...) with an apparent depth, and then see how this depth varies as a function
of analytical conditions in order to determine the true depth of the original feature. In this case the
part of the response which is used is a "feature depth indicator" (FDI) [3].
In this paper we show that if the delta layers are too close together, the coalescence of the
responses shifts the FDI's at either end of a set of delta's, in a manner which depends on the shape of
the response. This invalidates attempts to, for example, obtain a piecewise estimate of the sputter
yield (i.e. as a function of depth). To overcome this problem one must deconvolve the responses or
obtain the position of the FDI's by fitting superposed sets of responses to the data and using the
inter-delta spacing as a fitting parameter. However, no known procedure will work if the deltas are
within the SIMS transient region as the shape of the profile is dominated by the variation in
ionization probability.


[1] Y. Homma, H. Takenaka, F. Toujou, A. Takano, S. Hayashi and R. Shimizu, Surf. Interface Anal. 35 (2003) 544
[2] J. H. Kelly, M. G. Dowsett, P. Augustus and R. Beanland, Appl. Surface Sci. 203-204 (2003) 260
[3] M. G. Dowsett, J. H. Kelley, G. Rowlands, T. J. Ormsby, B. Guzmn, P. Augustus and R. Beanland, Appl. Surface
Sci. 203-204 (2003) 273
DEP2-O-Fr-A04
312
Secondary ion measurements for oxygen cluster ion SIMS

Satoshi Ninomiya*, Toshio Seki, Takaaki Aoki, and Jiro Matsuo

Quantum Science and Engineering Center, Kyoto University, Uji,
Kyoto 611-0011, Japan
ninomiya@nucleng.kyoto-u.ac.jp


Secondary ion mass spectrometry (SIMS) is widely used for analysis of semiconductors. Depth
resolution in nano meter range is indispensable for SIMS, because semiconductor devices are
getting smaller and smaller in size. Low energy atomic ions, such as oxygen and cesium, have been
commonly used as primary ions for SIMS in order to improve depth resolution. Low sputtering
yields and low secondary ion yields are problems in low energy (<keV) atomic ion SIMS. Small
oxygen cluster ions such as O
3
+
, which has been lately used, are possible to decrease primary ion
energy per atom. However, those problems still remain. We have proposed to use oxygen cluster
ions much larger than molecule ions as primary ions for SIMS to solve these fundamental problems.
Moreover, cluster ion beams give higher depth resolution, because cluster ions have a capability to
smooth surfaces. Generation of high-intensity cluster ion beams with the current density of a few
A/cm
2
has been developed at Kyoto University. In this study, secondary ions emitted from silicon
targets have been investigated with a quadrupole mass spectrometer under oxygen cluster ion
bombardment. Average size of oxygen cluster ions is 1000 atoms/cluster. Large enhancement of
secondary ion yields produced by oxygen cluster ions was found. Emission mechanism of
secondary ions under cluster ion bombardment will be discussed.
DEP2-O-Fr-A05
313
Surface oxidation during O
2
+
bombardment of Si:
does a critical angle exist?

T. Janssens
a,*
, C. Huyghebaert
a
, and W. Vandervorst
a,b

a
IMECvzw, kapeldreef 75,B-3001 Leuven, Belgium
b
also: INSYS, KULeuven, Belgium


Recently an in-situ way to determine the (near-surface) O/Si composition from a bombarded Si
surface has been proposed based on the O/Si flux quantified using an in-situ O
18
implant [1]. This
method takes into account the dynamic nature of sputtering and the information depth of this
method coincides with the depth of origin of sputtered ions. The O/Si ratio reflects the surface
oxidation if effects like oxygen desorption or preferential sputtering are not influencing the
measured O/Si flux significantly. Based on the same methodology Sobers et al [2] revisited Au-
segregation once more and conclude that the concept of a critical angle is non-existing.
Unfortunately instrumental limitations in [1-2] restrict this work to (very) high-energy (4-17 keV)
argon and oxygen beams at (large) fixed angles whereby the degree of oxidation can only be varied
through different levels of oxygen flooding. On the other hand previous work on for instance
segregation [3] and surface oxidation [4] , has shown a very pronounced angular dependence which
has been correlated with the formation of a full oxide (leading to the concept of the critical angle) .
In this work we have extended the methodology of ref [1] to the (normally used) energies
(250eV-5keV) whereby the steady state surface composition during O
2
+
bombardment is changed
by varying the impact angle between 0-60 degrees. The obtained surface composition is correlated
with sputter yields and ionization yields and the surface composition as determined with LEIS [5].
Moreover we have established the correlation between the (angular dependent) segregation
behavior of elements like Au, Cu, Ga with the changes in surface oxidation as derived from this
methodology.


[1] K. Franzeb, J.Lorincik and P. Williams, Surface Science vol.573, no.2-10 (2004) 291-309,
[2] R.C. Sobers, K.Franzeb and P. Williams, abstract at 17
th
Annual Workshop on SIMS Colorado (2004)
[3] Y. Homma, T Maruo, Surf. and Int. Anal. vol.14 (1989) 725
[4] K. Wittmaack, Surf. Sci. 419(1999)249
[5] T. Janssens, C. Huyghebaert, W. Vandervorst, A. Gildenpfennig and H.H. Brongersma, Appl. Surf. Sci. 203-204
(2003) 30


DEP2-O-Fr-A06
314
Correlation between the ionization probability of Si and Ge and the
Cs surface concentration

P.Chen
a,b,
*,T.Conard
a
, T. Janssens
a
, L. Geenen
a
and W. Vandervorst
a,b

a
IMEC, SPDT-MCA, Kapeldreef 75, B-3001 Leuven, Belgium
b
KULeuven, INSYS, Kasteelpark Arenberg, B-3100 Leuven, Belgium
email: Ping.Chen@imec.be


In this study we want to correlate the negative ionisation probability ( ) , E

of Si and Ge to the
corresponding Cs surface concentration ( ) , E C
s
Cs
[1]
. For Si and Ge bombarded with Cs
+
ions at
energies varying between 500ev and 5kev and impact angles from 0
o
to 60
o
. Due to the angular
dependence of the transmission efficiency , only ionisation probabilities measured at the same
impact angle can be compared directly.
In a first approximation the Cs surface concentration can be calculated as 1/(1+ ( ) , E Y )
[2]
. For Si
it is found that ( )

, E correlates to the sputter yield as

( )
( ) ( )
C
E Y
E |
!
\
|
\
(
+

~
0
0 o
, 1
1
,
, as shown in
Fig.1. The exponent C stays approximately constant (3) at all angles. For Ge on the other hand, the
exponent depends strongly on the impact angle, as shown in Fig.2. The decrease of C with
increasing angles indicates that the Cs surface concentration can no longer be described by the ratio
1/(1+Y) but that it is also influenced by other parameters, such as an increase in the scattering
coefficient of Cs
+
primaries. The reduced variation in ionisation yield with impact angle indicates
an overestimation of the Cs surface concentration by 1/(1+Y).
To further understand the relation between ( ) , E

and ( ) , E C
s
Cs
, we try to correlate ( ) , E

directly to ( ) , E C
s
Cs
, as obtained in-situ by measuring the Cs depth profiling on pre-sputtered
surfaces with low energy O
2
+
beam and ex-situ by X-ray photoelectron spectroscopy (XPS) analyses
[1]
.


[1] P.Chen, T. Conard, T. Janssens, L. Geenen and W. Vandervorst, abstract submission to SIMS XV 2005
(Manchester - UK) O
2
+
depth profiling of steady-state Cs concentration on Si and Ge under low energy Cs
+

bombardment by SIMS
[2] P.Chen, T.Janssens, L.Geenen and W.Vandervorst, Poster contribution at SIMS EUROPE 2004 (Munster -
Germany) Angular and energy dependence of the sputtering yield of Ge and Si under Cs
+
bombardment
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
10
-6
10
-5
10
-4
10
-3
YX
3
0g
30g
45g
60g

.

o
f

S
i

w
i
t
h

C
s
+
1/(1+Y
Si
)

Fig.1 the correlation of

of Si to 1/(1+Y
Si
)
For one angle each symbol reflects a different energy
0.1 0.2 0.3 0.4 0.5 0.60.7
10
-8
10
-7
10
-6
10
-5
10
-4
10
-3
YX
1
YX
7
YX
5/2
YX
4

.

o
f

G
e

w
i
t
h

C
s
+
1/(1+Y
Ge
)
0g
30g
45g
60g

Fig.2 the correlation of

of Ge to 1/(1+Y
Ge
)
For one angle each symbol reflects a different energy
DEP2-O-Fr-A07
315
SIMS evaluation of the compositional properties and layer integrity of
GaNAs superlattices

C. P. A. Mulcahy
a,
*, S. J. Barker
b
, R. S. Williams
b
, M. Hopkinson
c
, M. J. Ashwin
b
,
P. N. Stavrinou
b
, G. Parry
b
, S. Biswas
a
and T. S. Jones
b


a
Cascade Scientific Ltd., ETC Building, Brunel Science Park, Uxbridge, Middlesex, UK. UB8 3PH

b
Centre for Electronic Materials and Devices, Imperial College, London, UK. SW7 2BZ
c
EPSRC National Centre for III-V Technologies, University of Sheffield, UK. S1 3JD
*Corresponding Author. Email: cpa.mulcahy@brunel.ac.uk


GaAs-based dilute nitride alloys, such as GaNAs and GaInNAs, have recently emerged as
promising materials for long-wavelength telecommunications applications. The use of GaNAs in
diffusion-limiting/strain-compensating layers and in novel active-region structures means that its
material properties and behaviour upon annealing are important considerations for dilute-nitride-
based structures. In this paper, we present a study of dilute GaN
x
As
1-x
(0.005 < x < 0.03) multiple
quantum well (MQW) structures grown at 480-500C on semi-insulating GaAs(001) substrates in a
solid-source MBE system using a nitrogen rf-plasma source. The samples have been characterised
using ultra low energy (ULE) SIMS. Several of these samples were examined using ULE SIMS
before and after ex-situ annealing (600 < T < 900C, 15 s < t < 60 min) in order to study the
thermally-induced atomic re-arrangement. The study shows that ULE SIMS is essential in order to
clarify nitrogen diffusion and layer integrity in these novel GaNAs structures.
DEP2-O-Fr-A08
316
SHAVE-OFF DEPTH PROFILING BY THE NANO BEAM SIMS

M. Nojima
a, b,
*. A. Maekawa
a,b
, T. Yamamoto
a,b
, B. Tomiyasu
b, c
, T. Sakamoto
a, d
, M. Owari
b,c
,
and Y. Nihei
a


a
Tokyo University of Science, 2641 Yamazaki, Noda, JP-278-8510 Chiba, Japan
b
The University of Tokyo, IIS, 4-6-1 Komaba, Meguro-ku, JP-153-8505 Tokyo, Japan

The University of Tokyo, ESC, 7-3-1 Hongo, Bunkyo-ku, JP-113-0033 Tokyo, Japan

Kogakuin University, 2665-1 Nakano-cho, Hachioji-city, JP-192-0015 Tokyo, Japan
Email address : mnojima@rs.noda.tus.ac.jp


The nano beam SIMS with an FIB and a Mattauch-Herzog type mass analyzer is heavily
modified for the shave off depth profiling and elemental mapping in local area [1, 2]. In the shave-
off process, primary ion beam always keeps the edge of the sample and the sample is shaved
completely while obtaining depth profile. The features of shave-off depth profiling are
1. The signal intensity has no relationship with sputtered depth of analyzed area.
2. Depth is not defined by the function of the sputtering time, but defined as a function of
magnification projected on a display. The depth for shave-off depth profiling is not affected by
selective sputtering, sputtering yields and/or surface roughing.
3. Its dynamic range of depth direction is controlled by the property of an FIB micromachining
process. The dimension of dynamic range is some 10 nm to some 10 m.
The shave-off depth profiling is powerful .depth scaling method especially for samples with
rough surface or buried structures. In this presentation, we will demonstrate the shave-off depth
profiles of multi-layer, nano structure in DRAM and failure point on Cu wiring.


[1] M. Nojima, M. Toi, A. Maekawa, B. Tomiyasu, T. Sakamoto, M .Owari and Y .Nihei, Applied Surface Science,
(2004) 231-232 930-935
[2] M. Nojima, M. Toi, A. Maekawa, B. Tomiyasu, T. Sakamoto, M .Owari and Y .Nihei, e-Journal of Surface Science
and Nanotechnology, (2004) 2 131-135
DEP2-O-Fr-A09
317
Different optical conductivity enhancement (OCE) protocols to
eliminate charging during ultra low energy SIMS profiling of
semiconductor and semi-insulating materials

R.J.H. Morris
a,*
, M.G. Dowsett
a
and R.J.H. Chang
a

a
Dept of Physics, University of Warwick, Gibbet Hill Road, Coventry, CV4 7AL, UK.
*Email: R.Morris@warwick.ac.uk


A major problem associated with low energy SIMS analysis of both insulating and highly
resistive layers is the phenomenon of charging. It is also well known that electron beam charge
compensation typically applied to insulating samples is often ineffective in the case of resistive
materials. We recently reported on a novel, simple and effective method referred to as optical
conductivity enhancement (OCE) for the suppression of signal instability during profiling of
intrinsic SiGe. This uses intense illumination from a laser diode to generate electron-hole pairs in
the material, thereby increasing the local conductivity.
The current work builds on these initial findings by applying the technique to a wider variety of
semiconductor and semi-insulating materials and employing different wavelength lasers for the
illumination process. The materials on which we report here include intrinsic SiGe,
31
P
as-implanted into Si, and Cr doped semi-insulating GaAs. All these materials suffer from large
surface potential changes under normal low energy (<1 keV) oxygen profiling conditions unless
some form of charge compensation is applied.
From SIMS profiles of the various materials used we show that the potential instabilities
observed arise from material- and beam-dependent effects occurring during ion bombardment. The
mechanisms which lead to the potential instability play a significant role in the protocol required to
overcome the charging behaviour. One of the major findings is that the spatial illumination pattern
is important, and differs between sample types. In the case of the semi-insulating surface, for
example, an illuminated line between the crater and the sample ground is required so as to produce
a conducting path across the sample surface. For the semiconductor materials however, effective
charge compensation is achieved by focusing the laser into the crater during profiling.
In all the cases studied, where highly resistive layers or reversed bias semiconductor junctions
were involved, OCE is found to offer a simpler and superior method in its effectiveness to electron
beam charge compensation.


[1] K. Wittmaack, J. Appl Phys. 50(1), (1979).
[2] W. Reuter, M. L. Yu, M. A. Frisch, M. B. Small, J. App. Phys, 51(2), (1980).
[3] M.G. Dowsett, R. Morris, Pei-Fen Chou, S.F. Corcoran, H. Kheyrandish, G.A. Cooke, J.L. Maul, S.B. Patel, Appl.
Surface Sci, 203-204 (2003) 500-503.
DEP2-O-Fr-A10
318
Diffusion in Lithium Niobate Wafers

K. K. Soni, K. P. Gadkaree, and G. M. Guryanov

Corning Incorporated, Science & Technology Division
Corning, NY 14831, USA.
Email: sonikk@corning.com


Lithium niobate is an important crystalline material with excellent electro-optic properties
for use in photonic modulators. Lithium niobate single crystals of stoichiometric composition, i.e.,
with Li:Nb ratio close to 50:50 have significantly improved electro-optic properties. However, it is
not possible to grow defect-free stoichiometric single crystals of good quality from a melt via
standard techniques. Commercially available and commonly used crystals are made via a melt of
congruent composition with a Li:Nb ratio of about 48.6:51.4. For optical devices, only about top 10
m layer of the wafer is of consequence because the optical field penetrates only a few microns
deep in the case of Mach Zender modulator applications. Therefore, if the surface layer can be made
stoichiometric, all the benefits of a stoichiometric material will be derived, without having to make
the entire wafer of this composition. Our approach in this study consists of diffusion of Li ions,
from a Li source with large excess of lithium to allow rapid formation of a stoichiometric surface
layer, in a congruent wafer.

The measurement of Li/Nb ratio is critical to assess the stoichiometry of lithium niobate and
to monitor diffusion of Li in the lithiation process. However, the measurement of Li/Nb ratio is a
formidable task. Techniques such as electron microprobe, X-ray photoelectron spectroscopy and
auger electron spectroscopy do not have adequate sensitivity for Li. Indirect approaches such as
infra-red spectroscopy, X-ray diffraction, Curie temperature measurement have been attempted to
measure the Li/Nb ratio but these methods lack the chemical specificity and spatial resolution
required for the current process. Moreover, these indirect methods require calibration with standards
of known composition. In contrast, SIMS can detect Li isotopes at trace levels. In this study, we
chose ToF-SIMS because analyses can be performed without any charge build-up at the surface of
insulators such as lithium niobate. Moreover, all isotopes can be analyzed in parallel and detailed
retrospective interrogation of individual films and interfaces is possible. While SIMS depth
profiling is a common approach to analyze up to 10 m surface region, imaging methodologies can
analyze ~100 m or deeper regions. The imaging methodology is, however, less commonly
employed and requires careful cross-sectioning of lithium niobate crystal samples. We also obtained
composition depth profiles using dynamic SIMS instruments.

ToF-SIMS results demonstrate that our lithiation process results in an increase of the Li/Nb
ratio above the congruent value and that it approaches or exceeds the stoichiometric value. The
enrichment of Li extends to ~300 m below surface and is uniform in the near surface region
(~40 m) the depth of interest for waveguide fabrication. This enrichment occurs for both z-cut
and x-cut orientations. In addition, the lithiation process works well whether Ti is introduced
simultaneously with Li or subsequently. In addition, we confirmed our observation using a
6
Li-
enriched lithium source in our lithiation process and observed an increase of the
6
Li/
7
Li ratio in the
wafer surface region. Our SIMS results were further corroborated using a neutron depth profiling
technique.
DEP2-O-Fr-A11
319
SIMS Depth Profiling of Deuterium Labeled Polymers in Polymer
Multilayers

Shane E. Harton
a
, Harald Ade
b
, Fred A. Stevie
c,
*, Dieter P. Griffis
c


a
Dept. of Materials Science & Engineering, Box 7907, North Carolina State University
Raleigh, NC 27695, USA

b
Dept. of Physics, North Carolina State University, Box 8202, Raleigh, NC 27695, USA
c
Analytical Instrumentation Facility, North Carolina State University, 2410 Campus Shore Drive
Raleigh, NC 27695, USA
fred_stevie@ncsu.edu


Thin planar polymer films are model systems for probing physical phenomena related to
molecular confinement at polymer surfaces and polymer-polymer interfaces. Existing experimental
techniques such as forward recoil spectrometry (FRES) and neutron reflectometry (NR) have been
used extensively for analysis of these systems, although they suffer from relatively low depth
resolution (FRES) or difficulties associated with inversion to real space (NR). In contrast,
Secondary Ion Mass Spectrometry (SIMS) can provide real-space depth profiles of tracer labeled
polymers directly with sufficient depth resolution for optimal analyses of these systems. Deuterated
polystyrene (dPS) has been employed as the tracer polymer and has been imbedded in a matrix of
either unlabeled PS or poly(cyclohexyl methacrylate). These doped films have been placed on
either poly(methyl methacrylate) or poly(2-vinyl pyridine) and thermally annealed. Varied analysis
conditions for a magnetic sector instrument (CAMECA IMS-6f) were used to optimize the depth
resolution and sensitivity while minimizing matrix effects and sample charging. Both Cs
+
and O
2
+

have been used as the primary ion source with detection of negative and positive secondary ions
respectively. Impact energy and primary ion species have been shown to affect matrix ion count
rate for the various films studied.

















[1] Harton, S. E.; Stevie, F. A.; Ade, H. Macromolecules, in press (2005)

A SIMS deuterium depth profile of a system involving diffusion-controlled reactive
coupling between reactive dPS and reactive PMMA [1]. The dPS is in a layer of
unreactive PS. High depth resolution SIMS analysis allows identification of the
diffusion gradient and the excess of dPS that is pinned at the interface. Constant
matrix ion intensity was achieved through the PS/PMMA interface.
ORG3-I-Fr-B01
320
Mutual Information Theory for Biomedical Applications

Satoka Aoyagi*

Department of Regional Development, Faculty of Life and Environmental Science, Shimane University
1060 Nishikawatsu-cho, Matsue-shi, Shimane, 690-8504, Japan
aoyagi@life.shimane-u.ac.jp


Time-of-flight secondary ion mass spectrometry (TOF-SIMS) is capable of chemical imaging of
proteins on insulated samples in principal. However, selection of specific peaks related to a certain
protein, which are necessary for chemical imaging, out of numerous candidates had been difficult
without an appropriate spectrum analysis technique. Therefore some analysis methods have been
applied to interpret SIMS spectra of protein samples. In this study mutual information [1-3] was
applied to select specific peaks related to sample proteins in order to obtain chemical images. The
samples are protein-adsorbed dialysis membranes. Protein adsorption causing a lowering of
diffusive permeability and dialysis performance is one of big issues in the dialysis treatment of
renal failure. Bovine serum albumin adsorption onto three kinds of dialysis membranes has been
evaluated with TOF-SIMS [4]. In the present study three kinds of proteins were evaluated and
compared.
Three kinds of proteins, chymotripsinogen, bovine serum albumin, cytochrom C adsorbed onto
commercially available hollow-fiber dialysis membranes were measured by means of TOF-SIMS
(TFS-2000, Physical Electronics) with the gallium ion source and then TOF-SIMS spectra were
analyzed using the mutual information. In the sample preparation, the proteins were flowed into the
membranes under a filtration condition. TOF-SIMS spectra of each sample were estimated based on
the values of mutual information.
Specific peaks of fragment ions related to chymotripsinogen and bovine serum albumin were
selected. In this condition, however, specific peaks to cytochrom C were not able to find comparing
with other proteins because all of specific peaks to cytochrom C selected with the samples without
co-existing proteins were also related to other proteins. Finally, chemical images of
chymotripsinogen and bovine serum albumin, respectively, adsorbed onto the membranes with co-
existing proteins were obtained using specific peaks to each protein selected by the results of
mutual information.
The results of TOF-SIMS images of proteins on the membranes show different tendency of
adsorption depending on proteins and membrane materials. TOF-SIMS imaging obtained with the
mutual information is a powerful tool to estimate proteins on medical and biomaterials [5, 6].
Further study is needed to obtain every protein images on the membranes with co-existing proteins.


[1] C.E. Shannon, W. Weaver, "The mathematical theory of information", University of Illinois Press, Urbana, IL,
(1947).
[2] K.Eckschlager, V. Stepanek, K. Danzer, J. Chemometrics 4, (1990) 195-216.
[3] ] S. Aoyagi, M. Hayama. U. Hasegawa, K. Sakai, M. Tozu, T. Hoshi and M. Kudo, e-Journal of Surface Science and
Nanotechnology, 1 (2003) 67-71.
[4] S. Aoyagi, M. Hayama, U. Hasegawa, K. Sakai, M. Tozu, T. Hoshi and M. Kudo, Journal of Membrane Science,
236(1-2) (2004) 91-99.
[5] S. Aoyagi, S. Hiromoto, T. Hanawa and M. Kudo, Applied Surface Science, 231-232 (2004) 470-474.
[6] S. Aoyagi and M. Kudo, Biosensors & Bioelectronics, 20(8) (2005) 1626-1630.
ORG3-O-Fr-B02
321
Characterisation of human hair by means of static ToF-SIMS:
a comparison between Ga
+
and C
60
+
primary ions

C. Poleunis
a,
*, E. P. Everaert
b
, A. Delcorte
a
, P. Bertrand
a


a
Universit catholique de Louvain (UCL), Physico-Chimie et Phyique des Matriaux (PCPM),
Croix du Sud 1, B-1348 Louvain-la-Neuve, Belgium
b
Unilever R&D Port Sunlight, Bebington Wirral CH63 3JW, UK
Email: poleunis@pcpm.ucl.ac.be


It has been already established that the hair surface is chemically mainly composed by proteins
and lipids. Among all the available surface techniques, static ToF-SIMS is well suited to
characterise the human hair. Recently, the use of new polyatomic primary particles was shown to
highly enhance the secondary ion yields. In the case of C
60
+
primary ions, this enhancement could
reach 2-3 orders of magnitude in comparison with Ga
+
, for various organic materials [1].
We recently equipped our TRIFT ToF-SIMS instrument with a C
60
+
ion source. In this study,
we investigate the yield improvement induced by C
60
+
ions instead of Ga
+
ions in the case of
Caucasian dark brown hair. On a bunch of hair fibres, an area taken approximatively at 5cm from
the hair root has been analysed with both sources.
The results show that : 1) a high improvement is observed in the detection of amino acids with
C
60
+
primary ions in comparison with Ga
+
ions (yield enhancement factor > 2000 for the peak CNO
-
). A similar behaviour is observed for the positive secondary ions characteristic of the amino acids.
2) The majority of the atomic ions, such as Na
+
, Ca
+
, O
-
, S
-
, constitute minor peaks with C
60
+
ions
while they are often dominating in the case of Ga
+
ions. However, with the C
60
+
source, a series of
inorganic combination peaks with the elements Ca, S and O are observed in the positive spectra (i.e.
CaSO
4
+
), while they are marginal with the Ga
+
source. 3) For the mass range beyond 100 m/z and
in both polarities, the hair fingerprints are similar with both sources. In general, for a same primary
ion fluence, the C
60
+
ion source gives intensities between 2 and 3 orders of magnitude higher than
the Ga
+
one.


[1] D. Weibel, S. Wong, N. Lockyer, P. Blenkinsopp, R. Hill, J.C. Vickerman, Anal. Chem. 75 (2003) 1754.
ORG3-O-Fr-B03
322
SIMS Analysis of Biological Materials Using Cluster Ion Sources

Reinhard Kersting
a
, Daniel Breitenstein
a
, Elke Tallarek
a
, Michael Fartmann
a
, Birgit Hagenhoff
a*
,
Rudolf Mllers
b
, Derk Rading
b
, Felix Kollmer
b
, Thomas Greh
b
, Ewald Niehuis
b


a
Tascon GmbH, Gievenbecker Weg 15, 48149 Mnster, Germany
b
IONTOF GmbH, Gievenbecker Weg 15, 48149 Mnster, Germany


With the advent of polyatomic primary ions sub-m lateral resolution and femtomol sensitivities
have become possible for the characterisation of organic and biological materials. Although
polyatomic primary ions are meanwhile used in routine analysis, the understanding of the
underlying physical principles is still limited.

We therefore performed systematic investigations on the emission behaviour of secondary ions
from biological materials under different types of primary ion bombardment. Starting on model
samples such as Langmuir-Blodgett layers samples progressed to biological tissues and single
epithelial cells. Primary ions included Bi
1
+
, the cluster ions Bi
3
+
, Bi
3
++
, Bi
5
+
as well as C
60
+
and
C
60
++
. Both, experiments under static and dynamic SIMS conditions were performed.

The investigation focussed on the obtainable yield, the damage behaviour as well as the
respective information depth. It could be shown that under dynamic SIMS conditions the organic
nature of the respective sample has a decisive influence.
.
ORG3-O-Fr-B04
323
A complete cryo-chain for the combined SIMS and SEM-EDXA
analysis of physiologically relevant elements in biomedical samples

W. H. Schrder
a
*, U. Breuer
b
, R. Metzner
b
and H. P. Bochem
c


a
Phytosphere Institute,
b
Central Division of Analytical Chemistry

c
Institute of Bio- and Chemosensors; Forschungzentrum Jlich
w.schroeder@fz-juelich.de , uwe.breuer@fz-juelich.de


Among the best studied systems at the molecular scale in plant physiology are ion transport
mechanisms. These mechanisms are typically studied on isolated cells or membranes. Very little is
known, however, about the function of identified transporters at the tissue or whole plant level.
Plant samples are particularly difficult to prepare for microbeam analysis, and therefore serve as
good test samples for a variety of biomedical tissues. Since the analytes of interest are usually
highly diffusible, shock freezing typically is the method of choice as a first step in specimen
preparation. We established a complete cryo-transfer chain from sample shock freezing up to
microbeam analysis by SIMS and EDXA in conjunction with SEM to study structure function
relationships.
In the presented examples tissue samples were quickly taken from plants and immediately shock
frozen in a quenching liquid such as melting propane at ca. -150C. The frozen specimens were
then further cooled to liquid nitrogen temperature and transferred into a shuttle that was
subsequently evacuated. The shuttle was used to transfer the samples to a freeze fracture device to
produce fracture faces that could be coated with metal or carbon to avoid charging during later
analysis. Samples ready for analysis were transferred to the cryo-stage in a LEO Gemini VP 1550
instrument, equipped with an Oxford INCA for imaging and EDXA analysis. Alternatively the
samples were transferred to an IONTOF TOFSIMS IV for imaging element and isotope analysis.
First results of element distribution images at the tissue and cellular level obtained from shock
frozen tissue samples are presented.

BIO2-O-Fr-B05
324
Submicron-scale coccolith chemistry revealed by nanoSIMS

R. E. M. Rickaby
a
, N. Belshaw
a
, M. R. Kilburn
b
*, A. Taylor
c
, C. R. M. Grovenor
b
, C. Brownlee
c


a
Department Of Earth Sciences, University of Oxford, Parks Road, Oxford, OX1 3PR
b
Department Of Materials Science, Parks Road, University of Oxford, OX1 3PH
c
Marine Biological Association, The Laboratory, Citadel Hill, Plymouth, Devon
E-mail address: matt.kilburn@materials.ox.ac.uk


To probe the record and forcing mechanisms of past climate change, we rely on indirect
chemical proxies encapsulated within exquisitely crafted biominerals. In order to apply proxies
reliably, we need to understand how biomineralisation processes, including the transport of ions
from seawater across membranes, and the precipitation of calcite on an organic matrix, exert control
over the trace metal chemistry of the biomineral. ICPMS analyses of cultured cells suggest that the
chemistry of coccolith calcite is most influenced by biological discriminations compared to the
chemistry of e.g. foraminifera. We exploit the high spatial resolution analytical capability of the
Cameca nanoSIMS 50 to investigate the trace metal selectivity during biomineralisation of
coccolith calcite. First, we obtain sub-micron scale maps of the distribution of trace metals (e.g. Sr)
in coccolith calcite to investigate whether the organic mineral template controls the selection and
assembly of Ca and similarly sized trace ions into the calcite. Second, we map the intracellular
distribution of metals in cells grown in spiked media to resolve discriminatory steps associated with
ion transport during mineralisation.


Figure 1. (a)
12
C
14
N
-
and (b)
16
O
-
image of semi-thin (1m) section of resin embedded Coccolithus pelagicus obtained
with Cs
+
beam of Oxford NanoSIMS.
12
C
14
N
-
beam resolves intracellular organelles and intricate relationship between
organic template and calcite.
16
O
-
is produced from external calcite platelets encircling cell. (c)
16
O
-
image of an entire
C. pelagicus (d)
12
C
14
N
-
at higher magnification demonstrates sub-micron scale mapping potential of NanoSIMS.
BIO2-O-Fr-B06
325
Molecular Specificity of CN
-
Secondary Ion Formation using Multi-
Isotope Imaging Mass Spectrometry

H. Franois-Saint-Cyr
a
, G. McMahon
a
, B.J. Glassner
a
, C. Unkefer
b
, C. Lechene
a,
*

a
NRIMS

, Harvard Medical School and Brigham and Womens Hospital,

65 Lansdowne Street, Cambridge, MA 02139, USA
b
National Stable Isotopes Resource, Los Alamos National Laboratory,
B-3, MS G758, Los Alamos, NM 87545, USA
Email: cpl@harvard.edu


The fundamental discovery that proteins in biological tissues are continuously renewed was made
using a custom-made mass spectrometer to measure the incorporation into proteins of the amino
acid leucine labelled with the stable nitrogen isotope
15
N [1]. These seminal studies could not be
pursued at the intra-cellular level because there was no methodology to simultaneously image and
quantitate a stable isotope, and because there is no useful radioactive isotope of nitrogen. Imaging
of stable-isotope distribution has been possible, however, since the development of secondary ion
mass spectrometry (SIMS). Yet until now, SIMS technology has presented irreconcilable tradeoffs
[2] that have severely limited its use as a major discovery tool in biology. In order to use secondary
ion mass spectrometry to locate and measure isotope tags in subcellular volumes, we needed
solutions to three major problems. First, in order to obtain quantitative ultrastructural images, the
analysis must have sufficiently high lateral resolution, and the quantitation and imaging must be
associated. Second, because the quantitation of label is based upon the measurement of isotope
ratios, we ought to be able to simultaneously record data from several isotopes, which must be
exactly in register. Third, because in practice
15
N ions do not form, nitrogen is detected as a cyanide
ion. Thus, the mass resolution needs to be high enough to separate the isobars
12
C
15
N
-
and
13
C
14
N
-
.
A new generation of secondary ion mass spectrometer meets these requirements. It can measure
several ion masses in parallel, it has high mass resolution at high transmission, and it has a spatial
resolution of ~35 nm [3, 4]. These extraordinary capabilities opened the possibility of using stable
isotopes as molecular markers, in particular
15
N. We developed the methodology of multi-imaging
mass spectrometry (MIMS) for locating and measuring stable-isotope labelled molecules in intra-
cellular compartments.
An essential question related to CN
-
quantitative imaging is whether the secondary CN
-
ion signal
arises predominantly from: 1) the primary production of C-N molecular fragments, 2) the
recombination of C and N atoms produced separately, or 3) the combination of both mechanisms.
To answer this question we synthesized a series of
13
C- and
15
N- labelled polyglycines (Figure 1),

varying two parameters: the distance between the labels, and the labels neighbouring environment
(i.e.,
13
C present or not as part of a carbonyl group). Powdered polyglycines were solubilized in
deionised water to a concentration of 73mM to 130mM and were applied as microdroplets to
C
C
O
O
N
H
H
H H
H H
C
C
N C
C
O
O
N
H
H
H H
H H
C
C
N
C
C
O
*
N
*
C
O
N
H
H
H H
H H
C
C
C
O
*
N
*
C
O
N
H
H
H H
H H
C
C
C
O
*
N
*
C
O
N
H
H
H H
H H
C
C
C
O
*
N
*
C
O
N
H
H
H H
H H
C
C
O
*
N
C
O
N
H
H
H H
H H
*
C C
C
O
*
N
C
O
N
H
H
H H
H H
*
C C
C
C
O
*
N
*
C
O
N
H
H
H H
H H
C
C
C
O
*
N
*
C
O
N
H
H
H H
H H
C
C
C
O
*
N
*
C
*
C
O
N
H
H
H H
H H
C
C
O
*
N
*
C
*
C
O
N
H
H
H H
H H
C
C
O
O
N
H
H
H H
H H
C
C
N C
C
O
O
N
H
H
H H
H H
C
C
N
C
C
O
*
N
*
C
O
N
H
H
H H
H H
C
C
C
O
*
N
*
C
O
N
H
H
H H
H H
C
C
C
O
*
N
*
C
O
N
H
H
H H
H H
C
C
C
O
*
N
*
C
O
N
H
H
H H
H H
C
C
O
*
N
C
O
N
H
H
H H
H H
*
C C
C
O
*
N
C
O
N
H
H
H H
H H
*
C C
C
C
O
*
N
*
C
O
N
H
H
H H
H H
C
C
C
O
*
N
*
C
O
N
H
H
H H
H H
C
C
C
O
*
N
*
C
*
C
O
N
H
H
H H
H H
C
C
O
*
N
*
C
*
C
O
N
H
H
H H
H H
Figure 1. A portion of the unlabeled polyglycine (OH(COCH
2
NH)
5
H) is shown at the top left.
The relat ive positions of the
13
C- and
15
N- labels in the isotopically labeled derivative
polyglycines used in this study are indicated (*) in the adjacent figures.
C
C
O
O
N
H
H
H H
H H
C
C
N C
C
O
O
N
H
H
H H
H H
C
C
N
C
C
O
*
N
*
C
O
N
H
H
H H
H H
C
C
C
O
*
N
*
C
O
N
H
H
H H
H H
C
C
C
O
*
N
*
C
O
N
H
H
H H
H H
C
C
C
O
*
N
*
C
O
N
H
H
H H
H H
C
C
O
*
N
C
O
N
H
H
H H
H H
*
C C
C
O
*
N
C
O
N
H
H
H H
H H
*
C C
C
C
O
*
N
*
C
O
N
H
H
H H
H H
C
C
C
O
*
N
*
C
O
N
H
H
H H
H H
C
C
C
O
*
N
*
C
*
C
O
N
H
H
H H
H H
C
C
O
*
N
*
C
*
C
O
N
H
H
H H
H H
C
C
O
O
N
H
H
H H
H H
C
C
N C
C
O
O
N
H
H
H H
H H
C
C
N
C
C
O
*
N
*
C
O
N
H
H
H H
H H
C
C
C
O
*
N
*
C
O
N
H
H
H H
H H
C
C
C
O
*
N
*
C
O
N
H
H
H H
H H
C
C
C
O
*
N
*
C
O
N
H
H
H H
H H
C
C
O
*
N
C
O
N
H
H
H H
H H
*
C C
C
O
*
N
C
O
N
H
H
H H
H H
*
C C
C
C
O
*
N
*
C
O
N
H
H
H H
H H
C
C
C
O
*
N
*
C
O
N
H
H
H H
H H
C
C
C
O
*
N
*
C
*
C
O
N
H
H
H H
H H
C
C
O
*
N
*
C
*
C
O
N
H
H
H H
H H
F i g u r e 1 . A p o r t i o n o f t h e u n l a b e l e d p o l y g l y c i n e ( O H ( C O C H
2
NH)
5
H) is shown at the top left.
The relat ive positions of the
13
C- and
15
N- labels in the isotopically labeled derivative
polyglycines used in this study are indicated (*) in the adjacent figures.
BIO2-O-Fr-B06
326
cleaned Si chips. The polyglycines were analyzed by MIMS by applying a primary ion current of
0.64pA onto each sample. Five series of four masses were simultaneously measured, always
including
12
C and
13
C but varying the combination of recorded CN
-
ions paired as follows:
(
12
C
14
N
-
,
12
C
15
N
-
), (
12
C
14
N
-
,
13
C
14
N
-
), (
12
C
14
N
-
,
13
C
15
N
-
), (
12
C
15
N
-
,
13
C
15
N
-
), and (
13
C
14
N
-
,
13
C
15
N
-
).
Based upon the magnitude of the observed
13
C
15
N/
12
C
14
N ratios relative to the position of the
13
C- and
15
N- labels within the various polyglycines a number of conclusions can be drawn:
1. Recombination of the C and N atoms is a significant source of secondary CN
-
ions.
2. This recombination is higher the closer the two labels are to each other.
3. When the two labels are immediately adjacent there is an increase of 3-orders of magnitude
in the
13
C
15
N/
12
C
14
N ratio relative to the unlabeled polyglycine.
4. The amount of recombination is reduced 40-50% when the
13
C label is part of a carbonyl
group, irrespective if the
15
N label is immediately adjacent to
13
C or separated by a glycine
unit.
In addition to increasing our understanding of basic processes, this study should enable the
development of astute labelling schemes for biological experiments, paving the way for even more
sensitive measurements of isotope ratios in subcellular domains.

[1] Schoenheimer, R., The dynamic state of body constituents. The Edward K. Dunham Lectures for the Promotion of
the Medical Sciences. 1942, Cambridge, MA: Harvard UP. 78.
[2] Ireland, T., New Tools for Isotopic Analysis. Science, 1999. 286: p. 2289-2290.
[3] Slodzian, G., et al. A high resolution scanning ion microscope with parallel detection of secondary ions. in 8
th

International Conference on Secondary Ion Mass Spectrometry. 1991. Amsterdam, The Netherlands.
[4] Slodzian, G., et al., Scanning secondary ion analytical microscopy with parallel detection. Biol Cell, 1992. 74(1):
p. 43-50.

National Resource for Imaging Mass Spectrometry

BIO2-O-Fr-B07
327
Cations in mammalian cells and chromosomes: Elemental abundances
by SIMS affected by sample preparation protocols

R. Levi-Setti
a,*
, K.L. Gavrilov
a
, R. Strick
b
and P.L. Strissel
b

a
Enrico Fermi Institute and Department of Physics, University of Chicago, Chicago, Illinois 60637, USA
b
Dept. of Medicine, University of Erlangen-Nuernberg, Universitaetstr. 21-23, D-91054 Erlangen, Germany
email address: riccardo@uchicago.edu


We are continuing our systematic investigation of the presence of cations in mammalian cells and
chromosomes throughout the cell cycle, using the University of Chicago high resolution scanning
ion microprobe (UC-SIM). In the conduct of experiments directed toward such goal, of concern has
been the need to reconcile the relative cation abundances observed for cytogenetically prepared
chromosomes, with those resulting from the method of choice for cell preparation, i.e.
cryopreservation. In fact, it has been often suspected that the cytogenetic methodologies generally
adopted in the preparation of mitotic chromosomes, such as e.g. the use of methanol/acetic acid as
fixative, may alter substantially the native relative cation abundances in chromosomes, while this
may not be the case for cryopreserved cells.
In view of the above, we have engaged in a systematic evaluation of the effects on the residual
cation relative abundances, of various protocol steps needed for the preparation of mitotic
chromosomes. For cultured cells, we have also explored methods of fast drying of frozen and freeze-
fractured cells, alternative to lyophilization. We follow a protocol of cryo-preservation similar to that
described by Chandra et al. 1986 [1]. Cells plated on Si chips are sandwiched with another Si chips
with 10 m polystirene spheres as spacers. The sandwich is rapidly immersed in liquid N
2
slush,
then pried apart with a razor blade, still in the slush. We find comparable coverage of fractured cells
on both sides of the sandwich. One side of the sandwich is then lyophilized as control, while the
other is plunged, still frozen, into different fixative agents, such as methanol:acetic acid 3:1,
methanol and absolute ethanol. Freeze-fracture followed by lyophilization often disrupts the cell
integrity, while fast drying in methanol and ethanol preserve the cytology of the cells in detail, so
that optical microscopic images and SIMS maps of the corresponding regions of the fractured cells
can be identified and compared. Only cell nuclei and chromosomes are preserved by the
methanol/acetic acid fixative. SIMS depth profiles over narrow areas have been used to quantify
cation abundances in depth, since the feeble 45 keV Ga
+
probe current of the UC-SIM probe (~30
pA) yields high resolution cell-size images of only the surface layers of cell samples.
Our findings indicate that Na and K in cells are drastically removed by drying in methanol,
ethanol, and methanoll/acetic acid. The Ca and Mg contents (in the nuclear region of interphase
cells) are comparable for lyophilized, methanol-and ethanol-dried frozen cells. Exposure to the
methanol/acetic acid fixative (~ 10') depletes Ca by ~ 30% and Mg by a factor 3-4. The
chromosomal Ca content decreases with time of exposure to the fixative beyond 10'. In methanol-
dried frozen cells, the chromosomal region of mitotic cells shows a significant increase in Ca and
Mg contents relative to those of interphase cells, suggesting that this drying method may represent a
viable approach to our goal of cell cycle study.
Toward the detection of the dynamics of cation uptake and release throughout the cell cycle, we
have also focused on the use of
44
Ca as a possible tracer of, in particular, Ca metabolism [2].


[1] S. Chandra, G.H. Morrison, C.C. Wolcott. Imaging intracellular elemental distribution and ion fluxes in cultured cells
using ion microscopy: a freeze-fracture methodology, J. Microscopy 144, Pt 1 (1986) 15-37.
[2] R. Levi-Setti, K.L. Gavrilov, P.L. Strissel, R. Strick. Ion microprobe imaging of 44Ca-labeled mammalian
chromosomes, Appl. Surface Science 231-232 (2004) 479-484.


BIO2-O-Fr-B08
328
Multi-Isotope Imaging Mass Spectrometry (MIMS) of a Nitrogen-
Fixing Bacterium

D. L. Distel
a
, Y. Luyten
a
, C. Lechene
b,
*

a
Department of Biochemistry, Microbiology, and Molecular Biology, 5735 Hitchner Hall, University of Maine, Orono,
ME 04469
b
NRIMS

, Harvard Medical School, and Brigham and Womens Hospital, 65 Landsdowne Street, Cambridge, MA
02139, USA
Email: cpl@harvard.edu


Biological nitrogen fixation (diazotrophy) converts molecular nitrogen (N
2
), which cannot be assimilated by plants or
animals, into more biologically available form of ammonium. This metabolic pathway, which occurs only in a small
percentage of prokaryotic microorganisms and is absent from eukaryotes, provides a principal source of combined
nitrogen for the biosphere and helps to alleviate nitrogen limitation for growth in agriculture and in many natural
ecosystems. Diazotrophic prokaryotes may be found in marine and aquatic environments as well as soils. Moreover,
many plants and some animals may exploit the nitrogen fixing capabilities of bacteria through specific symbiotic
associations, e.g. Rhizobium species within root nodules of leguminous plants or diazotrophic bacteria proposed to
occur in digestive systems of termites and within the cells of marine shipworms and diatoms. Biological nitrogen
fixation provides a significant fraction of the total nitrogen required for food production by agriculture and fisheries
worldwide and thus it is difficult to underestimate its importance to human health and nutrition. Here we report the
heterogeneous distribution of nitrogen fixation among population of Teredinibacter turnerae bacteria imaged and
measured with MIMS.
Teredinibacter turnerae is diazotrophic marine bacterium that can be isolated from the tissues of wood burning
marine bivalves (family Teredinidae) and grown in pure culture. Cells of T. turnerae were grown in sealed 16 ml
Hungate tubes containing 15.5 mls of simple salt medium (SBM amended with 0.5% sucrose without combined
nitrogen) allowing a headspace of 0.5 ml of atmospheric gas. After three days the headspace gas was removed by
displacement with fresh medium and replaced with 0.5 ml of
15
N gas (99%). Cells were then incubated at 22C with
gentle shaking for 0, 0.25, 0.5 1, 2, 4, 8, 16, and 32 hr. After incubation, cells were sedimented by centrifugation
(12,000 x g, 10 min, 4C) and fixed by re-suspension in 500 l 3.7% formaldehyde in seawater for 30 min. Cells were
then washed by sedimentation (14,000 x g, 10 min, room temp) and re-suspension first in 50% EtOH and again in
distilled water. Cells were finally resuspended in 10l of distilled water and 2 l was applied to the silicon wafer and
air-dried at 37C. Cells of E. faecalis were prepared identically except that cells were grown in Tryptic Soy Broth
medium (Bacto) at 37 C for 2.5 hours (~ 8 doublings).
Mass images of Teredinibacter turnerae (nitrogen fixing bacteria) and Enterococcus faecalis (does not fix nitrogen)
cultured for 120 hours in
15
N atmosphere were recorded at mass
12
C
14
N,
12
C
15
N,
12
C and
13
C. Teredinibater turnerae, a
nitrogen-fixing bacterium, has a rod appearance. It is barely visible at mass
12
C
14
N but it is seen as intensely labelled at
mass
12
C
15
N because it has used gaseous
15
N to build its molecular constituents. On the contrary, Enterococcus
faecalis, a bacterium that does not fix nitrogen, is visible as grapes of cocci at mass
12
C
14
N and is barely visible at mass
12
C
15
N because it does not use gaseous nitrogen and did not incorporate
15
N above its natural ratio. Teredinibacter
turnerae incorporated an enormous quantity of
15
N with a
12
C
15
N/
12
C
14
N isotope ratio at least 100 times higher than the
natural ratio. The heterogeneity of nitrogen fixation among bacteria within a population of Teredinibacter turnerae
cultured 32 hours in
15
N gas is demonstrated with the Hue Saturation Intensity (HSI) images of the
12
C
15
N/
12
C
14
N ratios.
They reveal the location and the distribution of ratio values, i.e. of nitrogen fixation, among the bacteria within the
analyzed field, spanning a broad range, from a maximum 19 fold higher to a minimum 43% higher than the natural
ratio.
We also found large differences of
15
N incorporation in Teredinibacter turnerae (cultured 96 hours in
15
N
atmosphere) visible and measured among a few touching bacteria, or even within a single bacterium.
In conclusion MIMS methodology is a powerful tool to study the metabolism of individual bacteria within a
population and will be an invaluable tool in the investigation of diazotrophy in natural environments and in exploring
the activity of diazotrophic symbionts in the tissues of plants and animals.

National Resource for Imaging Mass Spectrometry

BIO2-O-Fr-B09
329
Specific Mg
2+
and Ca
2+
binding at Heterochromatic DNA Giemsa
bands and their Evolutionary Role in Chromosomal Structure

P. L. Strissel
a
, K. L. Gavrilov
b
, R. Levi-Setti
b
and R. Strick
a*

a
Dept. of Medicine, University of Erlangen-Nuernberg, Universitaetsstr. 21-23, D-91054 Erlangen, Germany
b
Enrico Fermi Institute and Department of Physics, University of Chicago, Chicago, Illinois 60637
email address pamela.strissel@gyn.imed.uni-erlangen.de


Our research interests have focused on cation-DNA and cation-protein interactions in
terms of their roles in higher order chromosomal structure. Our previous study [1] directly
analyzed the cation composition of cryo-preserved mammalian interphase and mitotic cells and
chromosomes at a resolution of 50 nm using the University of Chicago high resolution scanning
ion microprobe (UC-SIM). Quantitative UC-SIM compositional images of cryo-preserved cells
demonstrated that during interphase Ca
2+
and Mg
2+
were present throughout the cytoplasm but at
mitosis associated with chromatin. Our findings support an important divalent cation role in
mitotic chromatin compaction.
Recently SIMS analyses from both human and mammalian Indian muntjac metaphase
chromosomes detected specific binding of Mg
2+
to chromosomal p and q arm
heterochromatic regions correlating with conventional Giemsa (G-) bands [2]. In addition,
detailed Mg
2+
image density peaks along the chromosomes indicated that Mg
2+
peaks
correspond to the location of G-bands. We are presently investigating whether cations have an
evolutionary chromosomal distribution in other organisms, specifically in the salivary gland
endoreduplicated chromosomes from Diptera, Drosophila melanogaster as well as in primitive
Dinoflagellate species. Interestingly, Dinoflagellate chromosomes have no histones but were
shown, using indirect methodology, to remain fully compacted throughout the cell cycle by both
Ca
2+
and Mg
2+
[3]. For our analysis, salivary gland chromosome squashes were prepared on
silicon discs and then examined using the UC-SIM. Preliminary results showed that both Ca
2+

and Mg
2+
bind equally to the G-bands on Drosophila salivary gland chromosomes. Currently, we
are examining a direct localization of Ca
2+
and Mg
2+
on Dinoflagellate chromosomes. Our
results support a direct role for Mg
2+
in promoting and maintaining the higher order chromatin
structure of heterochromatic regions in mammals and in humans. Whereas in Diptera and
possibly in Dinoflagellates both Ca
2+
and Mg
2+
have co-evolved to function in chromosome
compaction at heterochromatic regions.


[1] Strick, R., Strissel, P.L., Gavrilov, K., and Levi-Setti, R. Cation-Chromatin Binding as Shown by Ion
Microscopy is Essential for the Structural Integrity of Chromosomes, Journal of Cell Biology 155 (2001) 899-
910.
[2] Strissel, P.L., Strick, R., Gavrilov, K., Levi-Setti, R. Specific Mg
2+
binding at human and Indian muntjac
chromosomal Giemsa bands, Applied Surface Science 231-232 (2004) 485-489.
[3] Herzog M, Soyer MO. The native structure of dinoflagellate chromosomes and their stabilization by Ca2+ and
Mg2+ cations. Eur J Cell Biol., 1 (1983) 33-41.

BIO2-O-Fr-B10
330
Zinc ion image and measurements for concentration of
the islet of Langerhans

M. Okabe
1
, T. Yoahida
1
, K. Takaya
1
, H.J.Mathieu
2


1
Department of Regenerative Medicine (old Anatomy2),
Toyama Medical and Pharmaceutical University, JAPAN
2
EPFL - Swiss Federal Institute of Technology Lausanne,
Materials Institute (IMX) - Surface Analysis (LMCH).
e-mail: okabe@toyama-mpu.ac.jp


The method of ashed specimens is a simple and high sensitive method for studying the
distribution of trace elements on SIMS measurements; especially elements that have low ionization
yield (like Zn) in biological sample[1]. On the pre-sputtering(pre-treatment) rat pancreas specimen
for about 2500 s under the condition that was low current O2+primary beam(10
-10
- 10
-9
A), there
was no charge up and Zn secondary ion signal could be detected. However, ashed rat pancreas
specimen also had no charge up and much more strong secondary ion signal was detected than that
of pre-treatment specimen.
The Zinc ion image of islet of Langerhans in rat pancreas was shown by TOF-SIMS using Au
3
+

ion source and O
2
+
pre sputtering technique. The Zn ion detection limit on biological sample with
TOF-SIMS(Bi1+ primary ion source) was about 50 ppm. On the other hand, Dynamic SIMS(O
2
+
, O
-
) cloud detect the Zn ion under 370 ppm.
In the field of semiconductor, the conditions for Zn measurements is normally done under Cs
+
primary beam condition and using the detection of CsM
+
technique. However, the sensitivity of
CsZn
+
was lower than that of Zn
+
induced by O
2
+
primary ion beam on the biological sample.
We will consider best conditions for Zn ion images and for measuring the concentration of Zn in
the islet of Langerhans semi-quantitive value(as relative value).


[1] M. Okabe, T. Yoshida, R. Yoshii, K. Takaya, Applied Surface Science203-204, (2003), 714-717
INS-O-Fr-C01
331
Implementing a SIMS ion source on the NRL
Trace Element Accelerator Mass Spectrometer

K.S. Grabowski*, D.L. Knies, and C. Cetina

Naval Research Laboratory, Washington, DC 20375
grabowski@nrl.navy.mil


The NRL Trace Element Accelerator Mass Spectrometer facility has recently received the front end
of a Cameca IMS 6f SIMS instrument to function as an ion source for demanding mass spectrometry
analysis. To enable uncompromised injection from both the Cameca SIMS at 10 keV and from the
existing NEC 40-Cathode MC-SNICS at 70 keV, a new injector has been designed. It allows
optimized injection at either 10 keV or 70 keV at a terminal voltage of 2.5 MV by adding a new
compound Einzel lens inside the pressure tank of the Pelletron and by inverting the tank direction.
The lens is placed in drift space alongside the chain motors at normally the high-energy end of NEC
9S-DH2 Pelletron. This end becomes the low-energy injection end by rotating the tank 180. In
addition to the new injection optics, the high-energy mass spectrometer will be completely
reconfigured by adding a 15-deflection charge-state selector, removing 10 meters of flight path, and
replacing the present S-bend with a U-bend in order to form an angle-focusing energy-insensitive
mass spectrometer. These modifications will provide improved mass spectrometry performance, both
for the existing ion source and the soon to be installed SIMS.
INS-O-Fr-C02
332
Isotope Ratio Measurement with an
Electrometer Array on the Cameca IMS nf
Peter Williams
a,
*, Jan Lorincik
a
, Rick Hervig
a
, M. Bonner Denton
b
, Roger Sperline
b
, and
Georges Slodzian
c

a
Arizona State University, University Drive, Tempe, AZ 85287, USA
b
University of Arizona, P.O. Box 210041, Tucson AZ 85721, USA
c
Universite Paris Sud, 91405 ORSAY Campus, Paris, France
* Corresponding author: pw@asu.edu


The objective of our work is to achieve accurate isotopic analysis of implanted solar wind
samples returned from space, by developing a sensitive high dynamic range electrometer array for
multiple ion detection in magnetic-sector SIMS spectrometers. Precision better than 0.1% is
required for isotopic analysis of implanted O where the doses for
17
O and
18
O are anticipated to be ~
1 x10
11
and ~ 5 x 10
11
atoms/cm
2
respectively, and thus signals for all three isotopes must be
integrated continuously over the entire depth profile.
Towards this goal we have converted the ASU IMS 3f to a multiple ion detection SIMS (3
neighbour-mass ions in our case) by modifying the ion optics between the magnet and the exit slit
to produce a flat (rather than inclined) focal plane in which off-axis ions are brought to a double
focus, allowing high mass resolution operation. An electrometer array detector is placed in the
modified focal plane. Feedback capacitances in the individual electrometers can be as small as 4
fF, allowing exceptional charge sensitivity approaching the single electron level. The array detector
is fixed on a vertically movable holder together with three fixed-gap (non-movable) slits, which
allows switching between multiple ion detection and a standard operation of the instrument without
the need for venting the system and re-installing the original (movable) slits.
In the first series of experiments on the upgraded IMS 3f we used a conducting magnetite (Fe
3
O
4
)
sample and a 14.5 kV Cs
+
primary ion beam in order to generate a high flux of O
-
ions. We have
successfully operated the instrument in the parallel-detection mode and confirmed that the current
set-up is capable of high mass resolution for all three oxygen isotopes, which is necessary for the
separation of OH and OD mass interferences, and that the sensitivity of the new ion detector is close
to that of the electron multiplier.
INS-O-Fr-C03
333
The Development of a Range of C
60
Ion Beam Systems

R. Hill
a*
, P. Blenkinsopp
a
, A. Barber
a
, C. Everest
a
.

a
Ionoptika Ltd., Epsilon House, Chilworth Science Park, Southampton, SO16 7NS, UK
r.hill@ionoptika.com
p.blenkinsopp@ionoptika.com
a.barber@ionoptika.com
c.everest@ionoptika.com


C
60
ion beams are being used in a widening variety of analytical applications. The interaction of
the C
60
molecule with most sample surfaces differs markedly from that of an atomic ion beam,
leading to elevated sputter yields and ion yields [1-2]. A further important consequence of C
60

bombardment is very low residual damage after sputtering of surface layers[3].
We have developed a range of C
60
ion beam systems for use in static SIMS, dynamic SIMS,
SIMS imaging, including intracellular imaging of biological compounds, and in surface cleaning
and depth profiling in electron spectroscopy.
We will describe the design criteria for the C
60
range and illustrate the performance of these
systems with recent applications data.


[1] N. Davies, D.E. Weibel, P. Blenkinsopp, N.P. Lockyer, R. Hill, and J.C. Vickerman, Applied Surface Science 203-
204 (2003) 223-227.
[2] A. Delcorte and B. J. Garrison, J. Phys. Chem. B. 104, 6785 (2000).
[3] D.E. Weibel, S.C.C. Wong, N.P. Lockyer, P. Blenkinsopp, R. Hill, and J.C. Vickerman,.Anal. Chem. 2003, 75 1754
1764.
INS-O-Fr-C04
334
Development of a TOF version of the desktop MiniSIMS
utilising a continuous primary ion beam

B. Cliff, A.J. Eccles*, C. Jones, N. Long, P. Vohralik

Millbrook Instruments Limited, Blackburn Technology Centre, Challenge Way, Blackburn, BB1 5QB, UK
Email: a.j.eccles@millbrook-instruments.com


The Millbrook MiniSIMS [1] remains a unique concept in SIMS instrumentation, incorporating
static, imaging and dynamic SIMS in a single compact desktop unit. The instrument is being used
in a wide range of applications where its low cost and high sample throughput are more important
than the higher specification or flexibility in configuration offered by conventional instrumentation.
An upgraded version of the MiniSIMS based on a time of flight (TOF) mass spectrometer has now
been developed. This is still a desktop instrument, and still has similarly low capital and running
costs.
Commercial SIMS instrumentation to date has used a pulsed primary ion beam. Ultimately this
approach provides the most efficient use of sample material, but the low duty cycle (< 0.1%) greatly
extends analysis times. TOF analysers in which the secondary ion beam is pulsed [2,3] have been
developed for other areas of mass spectrometry. These have all the usual TOF attributes of parallel
mass detection, high mass resolution and extended mass range, but also feature much higher duty
cycles of typically 25-50%. In a SIMS analysis, the result is much faster data acquisition, with
typical times of less than a second for a spectrum and less than a minute for a high quality image
with full retrospective analysis capability.
At this duty cycle it becomes feasible to perform a SIMS analysis with a continuous primary
beam if ultimate efficiency is not required. In imaging mode this gives a further advantage, because
the design avoids the potential degradation of the scanning primary beam which is inherent in
pulsing; the maximum image lateral resolution can therefore be maintained. Moreover, in depth
profiling, a continuous beam allows all sputtered material to contribute towards the analysis by
eliminating the requirement for cycling between etching and analysis modes.
The combination of a TOF spectrometer and a continuous primary beam is thus ideally suited to
the concept of a high-throughput instrument able to acquire spectra, images and depth profiles. The
instrumental design will be described and data will be presented to compare the quadrupole and
TOF versions. Case studies will be used to demonstrate the additional areas of application that have
become accessible using the new instrument.


[1] A.J. Eccles, T.A. Steele, Proceedings of SIMS XI, Eds. G. Gillen et al., John Wiley & Sons Chichester (1998) 775
[2] M. Guilhaus, Journal of Mass Spectrometry 30 (1995) 1519-1532
[3] Millbrook Instruments Limited, European Patent No. 0919067 (1996)


INS-O-Fr-C05
335
Application of the Hadamard Transform to ToF-SIMS

Albert J. Fahey
a
*, Christine M. Mahoney, Jeffery W. Hudgens

a
National Institute of Standards and Technology
100 Bureau Dr. Stop 8371
Gaithersburg, MD 20899-8371, U.S.A
Albert.fahey@nist.gov


The Hadamard transform has successfully been applied to Time-of-Flight (ToF) mass
spectrometry; achieving duty-cycles of up to 50%
1
. Typical duty cycles in ToF-SIMS are ~10
-5
. A
50% duty-cycle would represent an improvement of as much as ~10
4
in data rate, however dead-
time considerations may limit the practical duty cycle to ~1%. This would still represent an
increase in data rate of nearly 10
3
. We are investigating the application of the Hadamard transform
to Time-of-Flight (ToF) SIMS. This may be particularly useful for applications that require 2D or
3D imaging where a paucity of data can lead to statistical artefacts. It may also be useful for
imaging of molecular species.
Hadamard transform mass spectrometry employs a pseudorandom pulse sequence to achieve duty
cycles of up to 50%. Hadamard-type difference sets can be used to modulate (i.e. pulse) the
primary ion beam in a SIMS instrument. The most straightforward application of this method
would be to modulate the blanking plates of the three-lens Ga
+
gun on our IonTof ToF-SIMS IV
2

instrument with a pseudorandom pulse sequence. Once the data is acquired the inverse Hadamard
transform can be applied. Currently, circuitry is being constructed and programs written to
implement this method. The theory of operation and some initial data will be presented.
Limitations and future applications will be discussed.


[1] A. Brock, N. Rodriguez, and R. Zare, Review of Scientific Instruments 71, 3 (2000) 1306-1318
[2] Certain commercial equipment, instruments, or materials are identified in this document. Such identification does
not imply recommendation or endorsement by the National Institute of Standards and Technology, nor does it imply
that the products identified are necessarily the best available for the purpose.
MAT-O-Fr-C06
336
Imaging of oxygen reaction pathways in complex oxide structures

Charles A. Mims
a,
*, Peter M. Brodersen
a
, Leszek Reimus
a
, Allan J. Jacobson
b
, Chonglin Chen
b


a
aDept. Chem. Eng., University of Toronto, Toronto, Ontario M5S3E5 Canada
b
Dept. Chemistry, University of Houston, Houston Texas 77024, USA
*mims@chem-eng.utoronto.ca


We have used isotope exchange in
18
O containing gas atmospheres followed by ToF-SIMS
imaging (2-D and 3-D) to investigate the pathways of oxygen activation and transport in complex
oxide materials. The materials are various mixed (ionic-electronic) conducting oxides of interest in
solid-oxide fuel cell cathodes and in oxygen transport membranes, e.g. La
1-x
Sr
x
Co
3-y
, La
1-x
Sr
x
Fe
1-y
,
M
y
O
3-d
(M = Co, Cr, Cu, Ni), M
1-x
Ba
x
CoO
y
(Re = Nd, Pr) and La
2
NiO
4-d
. We have used patterned
composite samples prepared by (1) laser-ablation to produce highly oriented thin films 100-500 nm
thick on single crystal oxide substrates as well as (2) ink-jet printing on single crystal and ceramic
substrates. These techniques allow for the investigation of various important pathways involved in
oxygen activation, such as the significance of surface perfection to oxygen activation rates, the
importance of triple phase boundaries (TPB) in oxygen activation and transport barriers at well
defined buried interfaces between two oxide phases. We have also investigated the role of oxide
composition by combinatorial deposition / printing of a suite of oxide stoichiometries. In our studies
we have observed more than a 100-fold variation in surface activation rates with variation in the
structural perfection of the thin films. Interfacial barriers to oxygen transport and enhanced oxygen
activation at TPB have also been shown. These and other examples will be discussed.
MAT-O-Fr-C07
337
Study of the carbon distribution in multi-phase steels using the
NanoSIMS 50.

N. Valle
a
*, J. Drillet
b
, O. Bouaziz
b
,

H.-N. Migeon
a


a
Laboratoire dAnalyse des Matriaux, CRP-Gabriel Lippmann 41 rue du Brill, L-4422 Belvaux, Luxembourg.
b
Arcelor Research, Voie Romaine, BP 30320, 57283 Maizires Ls Metz, France.
valle@lippmann.lu


The study of the carbon distribution in multi-phase steels is fundamental to predict the
mechanical properties and to understand the phase transformations. However, carbon quantification
on a local scale is difficult due to the small size of the microstructural components and the low
carbon concentration included. The techniques used at present (Parallel Electron Energy Loss
Spectroscopy or atom probe) are very local and complex. Therefore alternative techniques are
mandatory to perform this type of analysis. In this work, using the NanoSIMS 50 which combines
high lateral resolution and high sensitivity, a new approach is proposed to study carbon levels in
steels. Moreover, in comparison with other techniques, it allows analysis of bulk materials
(simplified preparation), analysis of the same area as observed by SEM and an overall view of the
carbon distribution in the microstructure.
Analyses were performed on dual-phase steels (ferrite and martensite) with concentrations of
carbon ranging from 0.2 to 0.8 wt %. The aims of this study are:
to establish the relation between the secondary ion intensities and the carbon concentrations
in order to provide quantitative measurements,
to determine the limit of detection of carbon in steel.
Finally, these results will be used, for example, for the characterization of the bainite, a metastable
phase, usually in steel, which is formed by cooling of the austenite phase. The knowledge of the
carbon amount in bainite is essential to better understand the bainitic transformation and the
mechanical behaviour.






Carbon distribution in steel.
Field of view: (2020)m
2









MAT-O-Fr-C08
338
TOF-SIMS study of photocatalytic decomposition reactions
on nanocrystalline TiO
2
films

Hubert Gnaser
1,2,*
, Adam Orendorz
1
, Christiane Ziegler
1,2
, Elisabeth Rowlett
2
, Wolfgang Bock
2


1
Department of Physics, University of Kaiserslautern, D-67663 Kaiserslautern, Germany
2
Institute for

Surface and Thin Film Analysis (IFOS), University of Kaiserslautern,
D-67663 Kaiserslautern, Germany
*
gnaser@rhrk.uni-kl.de


Nanocrystalline TiO
2
has attracted great interest in recent years due to its many potential
applications. Among these, the photocatalytic properties of TiO
2
are of utmost relevance: to degrade
organic or biological pollutants in (waste) water or in the atmosphere indeed constitutes a very
promising prospect [xvi,xvii,xviii]. Numerous studies [xix,xx] have investigated such photocatalytic
degradation processes induced by UV irradiation, employing nanaocrystalline TiO
2
particles in
suspensions. Theoretically, the underlying mechanisms appear to be the following [xxi]: TiO
2
is a
semiconductor with a band gap of E
g
~ 3.2 eV. A UV-photon with an energy greater than E
g
may
create an electron-hole pair in a TiO
2
nanocrystallite. If these charge carriers do not recombine, but
rather diffuse to the crystallite surface, they may induce there the reduction/oxidation of adsorbed
molecules, leading, eventually, to the catalytic degradation of any pollutant species present.
In order to elucidate the details of such reaction pathways, nanocrystalline TiO
2
films (with 12
nm average crystallite size) were covered by methylene blue and studied, both in the pristine state
and upon UV exposure, by TOF-SIMS. Distinct mass signals from the methylene blue parent
molecule (m/z = 284 amu) and from fragment ions are observed for the as-prepared samples. Upon
irradiation with UV light under atmospheric conditions, the surface composition is pronouncedly
changed, an observation ascribed to photocatalytic reactions induced by UV photons: the parent
molecule is diminished whereas intermediate reaction products are identified to be present at the
TiO
2
surfaces. Eventually, the parent molecule and the characteristic fragment species disappear
completely upon further exposure to UV light.


[xvi] A. Mills, S. LeHunte, J. Photochem. Photobiol. A 108, 1 (1997).
[xvii] A. Fujishima, T.N. Rao, D.A. Tryk, J. Photochem. Photobiol. C 1, 1 (2000).
[xviii] H. Gnaser, B. Huber, C. Ziegler, in Encyclopedia of Nanoscience and Nanotechnology, Vol. 6, H.S. Nalwa,
Ed., (American Scientific Publishers, Stevenson Ranch, 2004), p. 505.
[xix] D.F. Ollis, H. Al-Ekabi, Eds., Photocatalytic Purification and Treatment of Water and Air, (Elsevier, Amsterdam,
1993).
[xx] M.R. Hoffmann, S.T. Martin, W. Choi, and D.W. Bahnemann, Chem. Rev. 95, 69 (1995).
[xxi] A.L. Linsebigler, G. Lu, and J.T. Yates Jr., Chem. Rev. 95, 735 (1995).
MAT-O-Fr-C09
339
TOF-SIMS study of paper surface coated with ZnO nanoparticles

Anil Vithal Ghule, Kalyani Ghule, Wen-Yin Chen, Bo-Jung Chen, Yong Chien Ling*

Department of Chemistry, National Tsing Hua University,
Hsinchu, Taiwan-30013, Republic of China
ycling@mx.nthu.edu.tw


ZnO is considered as workhorse of technological developments as it shows excellent electrical,
optical, and chemical properties with broad range of applications as semiconductors, in optical
devices, piezoelectric devices, surface acoustic wave devices, sensors, transparent electrodes, solar
cells etc. [1] Uniform and nanoscale coating of ZnO nanoparticles on suitable substrates is
important for desired applications. With this motivation we use a simple sonochemical approach for
coating ZnO nanoparticles (~20 nm) on the paper surface.[2] The surface morphology was
characterized by scanning electron microscope (SEM), and it showed that the ZnO nanoparticles
were selectively deposited on the cellulose fibers. Thus, to support our observation and investigate
the nature of coated ZnO nanoparticles, blank paper and ZnO nanoparticles coated paper was
analyzed by X-ray diffraction and TOF-SIMS. TOF-SIMS (static) in positive and negative detection
mode was used for analysis of the paper surface. Dynamic TOF-SIMS was also used to estimate the
thickness of the coated layer. With advancement of nanotechnolgy, nanoscale coating of ZnO on
paper surface have potential applications as substrates for functional coatings and printing, UV inks,
optical communications, protection, barriers, portable energy, photocatalytic wallpaper with
antibacterial activity etc.


[1] L. Vayssieres, Adv. Mater., 2003, 15, 464.
[2] K. Ghule, A. V. Ghule, Y. C. Ling, J. Am. Chem. Soc. (communicated)


340
Author Index


Abel, M.-L., 288
Adams, F., 305
Adan, R. A. H., 143
Ade, H., 319
Adriaens, A., 117, 305
Adriaensen, L., 104, 172
Ahmed, S., 113
Aimoto, K., 75
Alba, M., 266
Alberici, S. G., 260
Alexander, M., 97
Al-Harasheh, M., 67
Allara, D. L., 294
Altelaar, A. F. M., 143, 192
Anderle, M., 217, 237
Anderson, T., 186
Andreae, M. O., 127
Aoki, T., 76, 77, 312
Aoyagi, S., 75, 320
Arafat, A., 99
Aranyosiova, M., 89, 102
Arlinghaus, H., 44, 69, 86, 112, 146, 147, 185, 204,
225, 284
Armitage, D. A., 35
Armitage, J. C., 35
Ashwin, M. J., 315
Asomoza, R., 18, 304
Atabaev, B., 45, 72, 101
Attavar, S., 96
Audinot, J.-N., 144, 268
Babor, P., 178
Baboux, N., 51
Baer, D. R., 224
Baker, M. J., 95, 169
Baranov, I., 286
Barber, A., 333
Barker, J. H. A., 94
Barker, S. J., 315
Barozzi, M., 217, 237, 309
Batteas, J., 12, 156
Baude, S., 130
Belshaw, N., 324
Belykh, S. F., 305
Benbalagh, R., 39
Benichou, G., 275
Bennett, J., 39, 209, 213
Benson, D., 269
Berger, R., 236
Bersani, M., 217, 237, 309
Bertrand, P., 9, 46, 56, 93, 103, 219, 247, 321
Besmehn, A., 239, 266
Betz, V., 26
Beumer, A., 146, 147
Bexell, U., 190, 236, 244
Bhat, R., 177
Biddulph, G. X., 13
Bieniek, T., 100
Bijma, J., 69
Biswas, S., 265, 310, 315
Bittencourt, C., 293
Blackman, G. S., 296
Blenkinsopp, P., 333
Bochem, H. P., 323
Bochnicek, Z., 178
Bck, B., 265
Bock, W., 338
Bolotin, I., 161
Bonventre, J., 273
Borchardt, G., 65
Borisov, B., 177
Brner, K., 88, 190, 208
Boschmans, B., 105, 106
Bouaziz, O., 337
Bouleau, D., 302
Bouneau, S., 3
Boxer, S., 205
Brammer, T., 255
Brasier, M. D., 118
Braun, R. M., 164
Breitenstein, D., 151, 322
Breuer, U., 239, 266, 323
Briggs, D., 35, 67, 107, 123, 287, 298
Brijs, B., 17, 212, 214
Brison, J., 31, 181
Brito, M. E., 131
Brodersen, P. M., 336
Brown, M. D., 95
Brownlee, C., 324
Bryan, S. R., 80, 160, 242, 243
Budrevich, A., 177
Bugar, I., 102
Bulle-Lieuwma, C. W. T., 137
Burchell, M. J., 125
Butterworth, A., 125
Byklimanli, T. H., 176, 179
Calaway, W. F., 21
Canavan, H. E., 152
Caneau, C., 177
Carnera, A., 175
Carr, C., 126
Carr, C. M., 285
Carrez, D., 202
Castner, D. G., 138, 139, 152, 195
Cayrel, F., 50
Cechinel-Filho, V., 112
Cetina, C., 331
Champmartin-Philippe, V., 114, 302
Chan, C.-M., 133
Chan, H. Y., 310
Chan, L., 310
Chanbasha, A. R., 231, 232, 310
Chandoga, P., 102
Chang, R. J. H., 305, 317
Chater, R. J., 121, 125
Chen, B.-J., 90, 136, 267, 278, 339
Chen, C., 336
Chen, L., 289
Chen, P., 49, 214, 314

341
Chen, W.-Y., 90, 136, 267, 278, 339
Cheng, C.-H., 136
Cheng, J., 11, 164, 193
Cheng, X., 152
Chew, A., 39
Chi, P. H., 27, 79, 156, 229, 256
Choi, I. S., 183
Chong, T. C., 291
Chorvat Jr., D., 89, 102
Chorvatova, A., 89
Clarke, N. W., 95
Clement, S. W. J., 116
Cliff, B., 182, 334
Cliff, J. B., 129, 150
Cohen, A., 270
Compston, W., 116
Conard, T., 17, 28, 49, 181, 212, 214, 258, 314
Conlan, X. A., 13, 15, 85
Corbett, A., 248
Corey, D. P., 271
Cornet, V., 40
Cossement, D., 40
Cotanche, D. A., 272
Crockett, R., 92
Crone, C., 69
wil, M., 100, 227, 241
Czerwiski, B., 4
Dambach, S., 225
Dark, C., 301
Davies, M. C., 35, 97, 107, 298
Davydov, V. Yu., 254
de Chambost, E., 307
de Lange, R. P. J., 143
De Mondt, R., 104
De Salvador, D., 175
Delabie, A., 258
Delcorte, A., 9, 46, 56, 170, 247, 321
Delille, D., 180
Della-Negra, S., 3, 154, 158
Denton, M. B., 332
Descy, D.-P., 293
Desgranges, L., 132
Diallo, S., 130
Dickinson, M., 94
Dilworth, J., 201
Distel, D. L., 328
Dittrichova, L., 178
dos Santos, A. M., 220
Dowsett, M. G., 41, 59, 230, 305, 311, 317
Drillet, J., 337
Dubois, C., 50
Duchambon, P., 202
Dupuy, J. C., 50, 51, 240
Durrieu, M. C., 184
Dzabbarganov, R., 101
Dzhemilev, N. Kh., 47, 48
Dzhurakhalov, A. A., 20
Ebblewhite, P. A., 265
Eberhard, H., 246
Eccles, A. J., 182, 334
Edirisinghe, P. D., 153
Ehrke, H.-U., 215, 253, 306
Elbaz, A., 260
Endo, K., 57, 140
Engelhard, M. H., 224
Engkvist, J., 236
Equey, S., 92
Eriksson, C., 190
Everaert, E. P., 321
Everest, C., 333
Ewing, A. G., 148, 191
Fahey, A., 12, 78, 79, 156, 256, 335
Fanciulli, M., 42
Fares, B., 50, 240
Fartmann, M., 204, 322
Fearn, S., 60, 68, 228
Felton, J. S., 145
Ferrari, S., 42
Fielitz, P., 65
Fishel, S., 205
Fletcher, J. S., 15, 149, 169, 194, 196
Foley, S., 127
Fouchier, M., 250
Franois-Saint-Cyr, H., 199, 325
Franzreb, K., 22
Friedmann, A., 107
Friedrich, F., 26
Friedrich, J. F., 134
Frugier, P., 292
Fujiyama, Y, 36
Fukushima, K., 173
Gadkaree, K. P., 318
Gallardo, S., 18
Ganetsos, Th., 62
Garcia, R., 213
Gardella Jr., J. A., 142, 163, 198, 289
Gardner, P., 95
Garrison, B. J., 1, 4, 7, 56, 74, 155, 157, 193
Gaskell, S. J., 166
Gaspar, D. J., 150, 224
Gautier, B., 50, 51, 240
Gavrilov, K. L., 200, 327, 329
Gazi, E., 95
Geenen, L., 17, 314
Gehre, D., 39
Gerlach, D. C., 129
Ghoranneviss, M., 299
Ghule, A. V., 339
Ghule, K., 339
Gibbons, R., 59
Gijbels, R., 104, 172
Gillen, G., 12, 27, 78, 79, 156, 162, 256
Gilmore, I. S., 33, 85, 97, 135, 141
Giubertoni, D., 237, 309
Glassner, B. J., 325
Gnaser, H., 19, 34, 338
Godines, A., 18, 304
Goering, P., 151
Golledge, S. L., 150
Golser, R., 19
Gonze, X., 56
Goodacre, R., 149, 196
Gossmann, H.-J. L., 310
Gouttebaron, R., 40
Grabowski, K. S., 331
Graham, D. J., 138, 139, 152, 195

342
Gray, J. J., 290
Green, F. M., 33, 135, 141
Greenfeld, M., 152
Gregory, R., 248
Greh, T., 322
Grehk, T. M., 236
Grehl, T., 6, 185
Griffis, D. P., 38, 213, 319
Grohe, A., 255
Grner, E., 64
Grovenor, C. R. M., 113, 118, 201, 301, 324
Gu, C., 38, 213
Guerquin-Kern, J.-L., 202
Gui, D., 310
Guignard, C., 268
Guillermier, C., 8, 81, 82, 158, 171
Gundarev, D., 101
Guryanov, G., 177, 318
Guzmn de la Mata, B., 41, 230
Hacke, M., 126
Hagenhoff, B., 88, 125, 151, 208, 322
Hager, G. J., 8, 81
Haji Hosseini Gazestani, S. H., 299
Hallgot, P., 144
Hauszka, J., 227
Hammond, J. H., 80
Hammond, J. S., 160, 242, 243
Han, S., 297
Haneda, H., 249
Hanley, L., 153, 161
Hantehzadeh, M. R., 299
Harbottle, R. R., 206
Harris, M., 310
Hart, C. A., 95
Harton, S. E., 319
Hasegawa, T., 39, 252
Hasenhrl, S., 263
Hashimoto, H., 87
Hawes, C., 201
Hawtin, P. N., 288
Heard, P. J., 94
Hecq, M., 40
Heeren, R. M. A., 143, 192
Hegde, R. I., 210
Helliwell, C., 60
Hellweg, S., 185, 284
Henderson, A., 85, 149, 196
Henderson, J., 123
Henkel, T., 120
Henry, M., 93
Hentschel, D., 273
Hervig, R., 332
Hill, R., 333
Hillion, F., 308
Hitzman, C., 39
Hobbs, C., 262
Hoffmann, L., 268
Hoheisel, J., 203
Hoheisel, J. D., 185
Holliger, P., 240, 262
Homma, Y., 29
Hong, J. H., 297
Hook, D., 12
Hook, D. J., 289
Hopkinson, M., 315
Hoppe, P., 64, 119, 127
Hopstaken, M., 180, 257
Horita, T., 131
Horrard, F., 308
Hoshi, T., 242, 243
Houben, L., 255
Houssiau, L., 31, 181, 293
Hua, X., 217
Hubert, R., 31, 181
Hudgens, J. W., 335
Humayun, R., 259
Hurley, D. E., 129
Hutcheon, I. D., 205
Huyghebaert, C., 17, 24, 313
Iacob, E., 217, 237, 309
Ida, T., 57, 140
Iida, N., 75, 242
Iida, S., 242
Inoue, M., 280
Ivanov, M., 101
Iwai, H., 243
Iwase, F., 261
Jackson, D. A., 194
Jacobson, A. J., 336
Jakob, A., 185
Jalabert, D., 262
Jalink, K., 143
Jamme, F., 287
Jansen, E., 246
Janssens, T., 17, 24, 49, 214, 250, 313, 314
Jantou, V., 121
Jarman, K. H., 150
Jarvis, R. M., 196
Ji, R., 291
Jiang, G., 99, 186
Jiang, Z. X., 210, 248
Johannes, L., 202
Johansson, B., 207
Johnson, M., 38
Jones, C., 334
Jones, E. A., 15, 167, 194
Jones, T. S., 315
Juhel, M., 180, 257
Jung, D., 37, 187
Jungnickel, H., 169
Kabtov, M., 284
Kailas, L., 103
Kajimoto, Y., 276
Karas, M., 168
Karen, A., 251, 252
Karg, E., 226
Karthuser, S., 266
Kataoka, Y., 218
Katayama, Y., 108
Kathers, P., 69
Kato, N., 57, 75, 140
Kato, T., 173
Kawabata, S., 276
Kazantsev, D. Yu., 245, 254
Kearsley, A., 121, 125
Kelley, M. J., 165

343
Kempinski, W., 241
Kersting, R., 322
Khojiev, Sh. T., 47
Kiendl, T., 300
Kilburn, M. R., 113, 118, 201, 301, 324
Kilner, J. A., 68
Kim, H., 297
Kim, H. S., 98, 187
Kim, J., 37, 187
Kim, K., 210, 248
Kim, K. J., 27, 39, 156, 229, 256
Kim, M. S., 189
Kim, Y. P., 98, 187
King, B. V., 21
Kingman, S., 67
Kingsbury, D. B., 74
Kirillov, S., 286
Kishimoto, H., 131
Kishimoto, T., 173
Kitajima, H., 234, 303
Kittl, J. A., 250
Knies, D. L., 331
Knize, M. G., 145
Ko, J., 39
Kobayashi, H., 211
Koike, M., 235
Kollmer, F., 6, 322
Kolobov, Y., 101
Komatsu, M., 87
Konarski, P., 100, 227, 241
Korb, G., 101
Kosiski, A., 100
Kotian, K., 125
Kottke, M., 248
Kov, J., 263
Kovarsky, A. P., 245, 254, 305
Kozole, J., 91, 157, 193
Kraft, M. L., 205
Krantzman, K. D., 74
Kriegeskotte, C., 204
Kroto, H., 10
Kubo, S., 280
Kudo, M., 57, 75
Kudriavtsev, Y., 18, 304
Kulp, K. S., 145
Kupkov, M., 284
Kusanagi, S., 211
Kutschera, W., 19
Kwakman, L. F. Tz., 180, 257
Kwon, M., 297
Lan, J., 259
Laugier, F., 180, 257
Lausmaa, J., 207
Lazzaroni, R., 40
Lazzeri, P., 217
Le Beyec, Y., 3
Le, Y., 34
Lea, A. S., 224
Lechene, C., 199, 269, 270, 271, 272, 273, 274, 275,
325, 328
Lee, C. C., 310
Lee, H. B., 189
Lee, K.-B., 183
Lee, T. G., 37, 98, 183, 187, 189
Lee, Y., 297
Lefranc, G., 300
Lenaerts, J., 104, 172
Lerma, J., 210, 248
Levi-Setti, R., 200, 327, 329
Lewis, A. C., 94
Leys, C., 106
Li, Y., 115
Li, Z., 243
Licciardello, A., 14
Lievens, P., 222
Liew, T., 291
Lifanova, L. F., 47
Lin, X. -F., 216
Lindstrom, R., 39
Linford, M. R., 99, 186
Ling, Y.-C., 136, 278, 339
Ling, Y.-L., 90
Lipinsky, D., 44, 86, 146, 204
Liritzis, I., 62
Little, W. W., 129
Liu, R., 231, 310
Lloyd, K. G., 296
Locklear, J. E., 8, 171
Locklear, V. P. J., 82
Lockyer, N. P., 13, 15, 85, 95, 149, 167, 169, 194, 196
Loibl, N., 215, 253, 306
Loison, D., 114, 302
Long, N., 182, 334
Lorincik, J., 22, 332
Lu, H., 254
Lua, Y.-Y., 99
Lucas, S., 31
Luo, T. Y., 210
Lssem, B., 266
Luxembourg, S., 192
Luyten, Y., 328
Lyon, I., 120
MacDonald, B., 39
Mach, J., 178
Mack, P., 212, 214
Maekawa, A., 316
Maekawa, T., 281
Magee, C., 39
Magnani, A., 292
Mahaney, W. C., 61
Mahoney, C. M., 12, 78, 162, 163, 335
Mai, F.-D., 267
Maksimov, S. E., 47
Mallard, D., 94
Malmberg, P., 88, 208
Man, N., 295
Mangabeira, P. A., 277
Mannhart, J., 301
Mnsson, J. E., 88
Marie, O., 130
Marino, J. W., 179
Martin, B., 201
Martin, F., 262
Maruya, H., 261
Marxer, C. G., 205
Mathieu, H. J., 330

344
Matsumoto, D., 140
Matsunobe, T., 295
Matsuo, J., 76, 77, 159, 312
Maugey, M., 188
Maul, H., 215, 253, 306
Mazarov, P., 52
McCoustra, M. R. S., 287
McCoy, J. W., 111
McDermott, M. K., 78
McDonnell, L. A., 192
McIntyre, N. S., 206
Mcloughlin, N., 118
McMahon, G., 199, 274, 325
McPhail, D. S., 60, 121, 124, 125
McQuaw, C. M., 148
Meertens, D., 255
Meriwether, G. H., 129
Merkulov, A., 32, 307, 308
Metzner, R., 323
Michaelis, D., 186
Michaels, C., 156
Migeon, H.-N., 30, 58, 144, 268, 337
Milillo, T. M., 198
Miller, D., 206
Milner, M. W., 61
Mims, C. A., 336
Mirabella, S., 175
Mishurnuy, V., 304
Mitchell, G. E., 111
Mitchell, R., 285
Miwa, S., 211, 234, 303
Miyakoshi, Y., 36
Miyatake, S., 276
Miyayama, T., 160
Moeller, J., 164
Mller, J., 146, 147
Mllers, R., 6, 14, 322
Montgomery, N., 39, 310
Moon, D. W., 27, 37, 98, 183, 187, 189, 229
Moore, J. F., 21, 153
Morozov, S. N., 43, 70, 71, 73
Morris, R. J. H., 228, 230, 317
Mostefaoui, S., 127
Mowat, I., 216, 259
Mulcahy, C. P. A., 265, 310, 315
Murase, A., 280
Murayama, Y., 87
Nagy, G., 221
Nair, A., 225
Nakagawa, Y., 295
Nakamoto, T., 36
Nakamura, Y., 36
Napolitani, E., 175
Neilly, M. B., 200
Nelson, E. J., 145
Ng, C. M., 231, 310
Niehuis, E., 6, 14, 322
Nihei, Y., 282, 283, 316
Nikishin, S., 177
Ninomiya, S., 76, 77, 312
Nishina, T., 252
Nishitani, T., 252
Nishizawa, J.-i., 264
Nojima, M., 282, 316
Nomachi, I., 234, 303
Novak, S. W., 63
Novikov, A. V., 286
Nowak, R. M., 142
Nygren, H., 88, 190, 208
Obnorskii, V., 286
Obuchi, M., 235
Oehrlein, G., 217
Ogaki, R., 97
Ohashi, N., 249
Ohgaki, T., 249
Ohno, T., 264
Okabe, M., 276, 330
Okada, J., 108
Okamoto, M., 108, 109
Oloff, I. W., 59
Olsson, M., 236
Ootomo, S., 261
Oran, U., 134
Orendorz, A., 338
Orik, A., 112, 284
Orikov, R., 112, 284
sth, M., 244
Owari, M., 283, 316
Oyama, Y., 264
Pajk, M., 100
Pakhomov, G. L., 73
Palitsin, V. V., 59, 305
Parent, A., 186
Park, C. J., 27
Parry, G., 315
Parsonage, E. E., 164
Pasquet, B., 132
Patwardhan, D., 78
Pautrat, M., 3
Pawlak, M. A., 250
Pederzoli, S., 237, 309
Pellin, M. J., 21, 153
Perego, M., 42
Peres, P., 39, 307
Perkins, M. C., 107
Peternai, L., 263
Peterson, R. E., 225
Philipp, P., 30, 58
Philipsen, J., 246
Piagge, R., 260
Piekoszewski, J., 241
Pierre, F., 262
Piersma, S. R., 143, 192
Pinna, R., 287
Pinnick, V., 82, 158
Pireaux, J.-J., 293
Pisiewicz, K., 227
Piwowar, A. M., 142
Poleunis, C., 9, 46, 247, 321
Polizu, S., 184, 188
Possmayer, F., 206
Postawa, Z., 4, 155, 193
Potocek, M., 178
Potter, G. E., 111
Poulin, P., 188
Poulin, S., 184, 188

345
Priller, A., 19
Priolo, F., 175
Prudon, G., 51, 240
Rabara, L., 102
Rading, D., 322
Rading, T., 6
Rahmatov, S. E., 20
Rangarajan, S., 110, 147
Rasulev, U. Kh., 43, 70, 71, 73
Ratner, B. D., 152
Reid, B. D., 129
Reimbold, G., 262
Reimus, L., 336
Rey-Santos, R., 142
Rhede, D., 66
Rickaby, R., 201, 324
Rickman, R. D., 8, 158
Rietmann, T., 44
Rije, E., 239
Ristori, S., 292
Rivallin, P., 262
Robert, N., 302
Roberts, C. J., 107
Roe, M. J., 123
Roemer, W., 202
Rommel, C., 151
Ronsheim, P. A., 39, 174
Rossbach, P., 92
Rossi, C., 292
Rossiny, J. C. H., 68
Rostam-Khani, P., 246
Rowlett, E., 338
Russo Jr., M. F., 7, 157
Rutten, F. J. M., 67, 107, 123, 287, 298
Ruys, L., 105, 106, 220
Ryoken, H., 249
Saito, K., 173
Saito, S., 36
Sakaguchi, I., 249
Sakai, N., 131
Sakamoto, T., 316
Samartsev, A., 52, 83, 84
Sameshima, J., 251, 252
Samson, R., 4
Sanada, N., 160
Sangly, L., 130
Sari, A. H., 299
Saripalli, Y. N., 38
Sarmento, H., 293
Sasaki, S., 128
Savage, P. B., 186
Schacht, E., 220
Schaff, W. J., 254
Schauer, S., 248
Scherrer, H., 30, 58
Schmcker, M., 65
Schneider, C., 301
Schneider, H., 65
Schneiderlchner, E., 255
Schnrer-Patschan, C., 253, 306
Scholl, A., 239, 266
Schrder, M., 44, 86
Schrder, W. H., 323
Schuhmacher, M., 39, 307
Schweikert, E. A., 8, 81, 82, 158, 171
Seah, M. P., 33, 135, 141, 311
Sears, A., 306
Seasholtz, M. B., 111
Seki, H., 295
Seki, T., 77, 312
Sekiya, N., 80
Senoner, M., 279
Seo, S., 261
Shakesheff, K. M., 298
Shapiro, M. H., 3
Shariati, M., 299
Shattuck, D. L., 145
Shi, H., 225
Shibamori, T., 295
Shih, H.-H., 136
Shokouhy, A., 299
Shon, H. K., 183, 189
Shore, B., 201
Sieloff, D., 210, 248
Sikola, T., 178
Silva, J. A. M. C., 55
Silverans, R. E., 222
Simmons, T. A., 129
Simons, D., 27, 39, 229
Sinniah, S., 125
Sjvall, P., 207
Slodzian, G., 332
Small, J., 156
Smart, K., 201
Smiley, E. J., 155
Smith, E. F., 287
Smith, G. C., 233
Smith, S. P., 115
Sobers, Jr., R. C., 22
Sobota, J., 178
Sodhi, R. N. S., 61
Sohn, S., 44
Solomko, V., 56
Soni, K. K., 318
Sostarecz, A. G., 148
Spalla, O., 292
Sperline, R., 332
Spool, A., 16
Spousta, J., 178
Srinivasan, G., 122
Srinivasan, M. P., 310
Srugaa-Stawik, H., 227
St.Clair, T. P., 177
Stanciu, V., 244
Stanislawski, J., 241
Stavrinou, P. N., 315
Steier, P., 19
Stevenson, C., 63
Stevie, F. A., 38, 213, 319
Stockwell, W., 39
Strick, R., 200, 327, 329
Strissel, P. L., 200, 327, 329
Su, W., 34
Sugimoto, H., 140
Sugita, N., 235
Sun, J., 259

346
Suzuki, K., 282
Svedlindh, P., 244
Swaraj, S., 134
Swartzfager, D. G., 296
Sykes, D., 39, 233
Szakal, C., 91, 157, 193
Szymczak, W., 226
Takamori, H., 173
Takaya, K., 330
Takeno, S., 235
Tallarek, E., 151, 322
Tan, S. K., 231
Tanaka, H., 235
Tanaka, K., 128
Tanji, N., 108, 109
Taylor, A., 324
Temmerman, E., 106
Tetzler, S. H., 161
Thomas, C. B., 145
Thompson, C. E., 149, 194
Titchener, K. J., 233
Titchmarsh, J. M., 113
Tizard, J., 120
Tobin, P., 210
Tognazzi, A., 292
Tombrello, T. A., 3
Tomiaysu, B., 283
Tomita, M., 39, 235
Tomiyasu, B., 282, 316
Toujou, F., 39
Treichler, R., 300
Triyoso, D. H., 210
Troxler, H., 92
Tseng, H., 210
Tsourapas, G., 298
Tuccitto, N., 14
Tukfatullin, O. F., 47
Twitchen, D., 41
Tyler, B. J., 96, 110, 147, 197, 225
Unger, W., 134, 279
Unkefer, C., 325
Urbanek, M., 178
Valentine, N. B., 150
Valiev, R., 101
Valint, Jr., P. L., 289
Valle, N., 337
Valot, Ch., 132
van de Weijer, P., 137
van den Berg, J.A., 309
van der Heide, P. A. W., 25, 53, 54
Van Royen, P., 220
Van Vaeck, L., 104, 105, 106, 220
Vandervorst, W., 17, 24, 28, 49, 181, 212, 214, 250,
258, 313, 314
Vandeweert, E., 222
Vangaever, F., 104, 172
Vanneste, M., 105, 106
Vanzetti, L., 237
Velic, D., 89, 102
Vering, G., 69, 112
Verkhoturov, S. V., 8, 81, 82, 171
Verkouteren, J., 156
Verstraete, M., 56
Vervaecke, F., 222
Veryovkin, I. V., 21, 305
Vesel, M., 263
Vickerman, J. C., 13, 15, 85, 95, 149, 167, 169, 194,
196
Villegas, A., 18, 304
Vincze, A., 263
Vohralik, P., 182, 334
Vullings, P., 246
Wacey, D., 118
Wagner, M. S., 138, 139
Wahl, K. L., 150
Walker, A. V., 221
Wallner, A., 19
Walls, D. J., 296
Wang, X., 115
Warnicke, P., 244
Watts, J, F,, 288
Weber, P. K., 205
Weber, S., 65
Wee, A. T. S., 231, 232, 310
Wegener, J., 151
Wehrspohn, R., 151
Weikart, C., 111
Weissgaerber, T., 101, 300
Weng, L.-T., 133
Werner, M., 309
White, R., 16
Whitehouse, M. J., 122
Wiedenbeck, M., 23, 66
Williams, P., 22, 332
Williams, R. S., 315
Willis, M. R., 287
Windsor, E., 256
Winograd, N., 4, 11, 91, 148, 155, 157, 164, 193, 294
Winterholler, B., 127
Wirth, R., 23
Wirth, Th., 279
Wirtz, T., 30, 58
Wittmaack, K., 2, 26, 223
Wojciechowski, I. A., 7, 155
Wolstenholme, J., 28
Won, J., 39
Wu, D.-W., 202
Wu, K. J., 145
Wu, L., 145
Wucher, A., 5, 52, 83, 84
Wunschel, D. S., 150
Wyczawska, S., 222
Wyon, C., 180, 257
Yagovkina, M. A., 254
Yahia, L. H., 184
Yahia, L'H., 188
Yakovlev, N. L., 290, 310
Yamada, K., 282
Yamagata, J., 36
Yamaji, K., 131
Yamamoto, A., 75, 80, 160, 173, 242
Yamamoto, M., 280
Yamamoto, T., 316
Yang, J. Y., 210
Yang, M. H., 216, 259
Yarmiychuk, S., 286

347
Yasumori, A., 249
Yeo, K. L., 231
Yoahida, T., 330
Yokokawa, H., 131
Yokoyama, K., 276
Yoshida, T., 276
Yoshikawa, K., 252
Yoshikawa, S., 39
Yoshiki, M., 235
Yu, J., 163
Yuzikaeva, F., 101
Zastrow, U., 255
Zeipper, L., 101
Zhang, D.-S., 271
Zhang, M., 239
Zhao, Q., 239
Zheng, L., 148
Zhou, C., 221
Zhu, Z., 165, 294
Ziegler, C., 338
Zu, C., 12
Zuilhof, H., 99

348
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