2008 Advanced Materials

Characterization Workshop

X-ray analysis methods

Mauro Sardela, Ph.D.
The Frederick Seitz Materials Research Laboratory
University of Illinois at Urbana-Champaign
Sponsors:

Sponsors:

Supported by the U.S.

Supported
Department
by the
of Energy
U.S. Department
under grants
of Energy
DEFG02-07-ER46453
under grant DEFG02-91-ER45439
and DEFG02-07-ER46471
2008University
2007 University
of Illinois
of Illinois
Board of
Board
Trustees.
of Trustees.
All rights
Allreserved.
rights reserved.

Outline
X-rays interactions with the matter
Fundaments of diffraction
Powder diffraction methods
Size / strain analysis
Search / Match, structure determination
Quantitative analysis, whole pattern fitting
X-ray parallel beam methods
Thin film crystallographic orientation
Glancing / Grazing angle XRD methods
Texture - preferred orientation methods

Residual stress analysis methods

High resolution XRD methods
Rocking curve analysis
Reciprocal lattice mapping
X-ray reflectivity methods

X-ray fluorescence methods

X-ray analysis summary
Comparison with other techniques
Quick guide to the FS-MRL x-ray analysis facilities
Recommended literature.

X-ray interactions with matter

Coherent
scattering

Incident x-ray photons

h0

h0
125

25
0. 1

rays rays
1
0. 0

UV

V)
(ke

Incoherent
scattering
Fluorescence

h1

h2

Photoelectron

e-

e-

Visible

2 nm ~30 m

0
10 m) 20
(n

h: photon
e-: electron

50 m 5 cm

Coherent
Coherentscattering
scattering
(Thompson
(Thompsonscattering
scattering/ /
diffraction):
diffraction):
o
incident
hh
incidentphoton
photon
o
interacts
- withno
interactswith
witheewith
no
energy
energyloss
lossand
andno
nophase
phase
change
change

Auger electron

Interaction
volume
Sample

Fluorescence:
Fluorescence:
- absorb incident
(a)
(a)K/L
K/Lshell
shellee- absorb incident
energy
o; ;
energyhh
o
(b)
(b)outer
outershell
shelle-e-cascade
cascadedown
down
filling
fillingthe
theholes
holescausing
causing
secondary
secondaryphotons
photons
emission
2).).
emission(h(h
2

Incoherent
Incoherentscattering
scattering
(Compton
(Comptonscattering):
scattering):
(a)
o
- absorbsincident
(a)eeabsorbs
incidentenergy
energyhh
o
(excited
(excitedphotoelectron);
photoelectron);
(b)
part
of
the
energy
is
emitted
(b) part of the energy is emittedatat
different
1 and
different
differentenergy
energyhh
1 and different
phase.
phase.

Auger
Augerelectron
electronemission:
emission:
(a)
hh
0 used
to eject e- from
atom;
(a)incident
incident
0 used to eject e from atom;
nd
(b)
2
e
drops
to
lower
nd
(b) 2 e drops to lowerlevels
levelstotofill
fillthe
the
hole
holeand
andaaphoton
photonisisemitted;
emitted;
(c)
photon
isisabsorbed
by
valance
(c)the
theemitted
emitted
photon
absorbed
by
valance
ee-,-,which
whichionizes
ionizesand
andleaves
leavesthe
theatom.
atom.

Photoelectron
Photoelectronemission:
emission:
hh
0 energy
is used to eject electron e- with
0 energy is used to eject electron e with
kinetic
energy
=
h

B.E.(binding
kinetic energy = ho B.E.(bindingenergy).
energy).
o

X-ray interactions with matter

Coherent scattering
(3)

(Diffraction, Thompson or
Rayleigh scattering)

E0

(1)

(2)

E0

Incoherent scattering
(Compton scattering)

E0

Electron

Photon

(1)

E1<E0

(3)
(2)

Photon

Electron

Nucleus
(1)
(2)
(3)

Nucleus

Incoming photon
Oscillating electron
Scattered photon
No loss of energy.

E1=EL-EK

Fluorescence
E0

(1)
(2)
(3)

(1)

(3)

Auger electron

(4)

E0

Photon

(2)
(1)
(2)
(3)
(4)
(5)

Incoming photon
Energy is partially transferred to electron
Scattered photon (energy loss).

(3)

(1)

(2)

Nucleus

Electron
Incoming photon
L
Expelled electron (photoelectron)
shell
Hole is created in the shell
Outer shell electron moves to the inner shell hole
Energy excess emitted as characteristic photon.

K
L
shell
(1)
(2)
(3)

Nucleus
Electron

Incoming photon excites inner shell electron

Excitation energy is transferred to outer electron
Electron ejected from atom (Auger electron)
4

Fundaments of diffraction

Real space
Set of planes

Reciprocal space
Point

(h k l)

hkl
2/d
origin

M. von Laue 1879-1960

X-rays from crystals, 1912.

Fundaments of diffraction

Real space

Reciprocal space

d
2/d

origin

Fundaments of diffraction

Real space

Reciprocal space

origin

Fundaments of diffraction

Real space

Reciprocal space

Braggs law
Det
ect
or

Diff
rac
ted

Ewalds sphere

eam
nt b
e
d
i
bea
m Inc

y
X-ra ce
r
sou

k1
k0 (= radius)

2 d sin = n

Elastic (Thompsons)
scattering

q = k1 k0
q: scattering vector
q = (4 /) sin

18621942

1890-1971

Paul P. Ewald
81888-1985

Fundaments of diffraction
Real space

Reciprocal space

Detector
scan

2/ scan

(2)

(2/)

Diffracted
beam

Rocking curve
(sample) scan

()

Rocking
curve scan:
to scattering
vector

()
Scattering
vector

c
In

(2/)

Detector Scan:
around
Ewalds sphere

am
be
nt
e
d
i

hkl

(2)
q

hk

2/ scan:
radial, // to
scattering
vector

k1

k0
9

Fundaments of diffraction
Real space
Detector
scan

2/ scan

(2)

(2/)

Diffracted
beam

Reciprocal space

Rocking
curve scan

()
Scattering
vector

Glancing angle
Constant sampled
volume

am
be
nt
e

cid
In

Defects, material quality

Rocking
curve scan:
Mosaicity
()
to scattering vector
Texture
Texture strength
(2/)

Detector Scan:
around Ewalds
analysis sphere

Phase
Grain size analysis
(2)
Unit cell determination
Stress analysis
q
Lattice distortion, strain
h k Composition, alloying
l

2/ scan:
radial,
// to scattering
vector

hkl

k1

k0
10

Typical contents from XRD pattern (diffractogram)

Si powder sample

PDF
PDF(ICDD/JCPDS)
(ICDD/JCPDS)

Peak
Peakposition:
position:

identification,
identification,structure,
structure,lattice
latticeparameter
parameter

Peak
Peakwidth:
width:

crystallite
crystallitesize,
size,strain,
strain,defects
defects

Peak
Peakarea
areaor
orheight
heightratio:
ratio:
preferred
preferredorientation
orientation

Peak
Peaktails:
tails:

Diffuse
Diffusescattering,
scattering,point
pointdefects
defects

Background:
Background:

amorphous
amorphouscontents
contents

11

Powder diffraction methods

Crystalline? Amorphous?
What elements, compounds, phases
are present?
Structure? Lattice constants?
Strain?
Grain sizes? Grain orientations?
Is there a mixture? What % ?
Powders, bulk materials, thin films,
nanoparticles, soft materials.

12

Bragg-Brentano focusing configuration

Receiving
slit

Focus
X-ray
source

Single crystal
monochromator
()

Detector

Divergence
slit
Secondary
Optics:
Scatter and soller slits

Focusing
circle

Detector
rotation
(2)

specimen

(variable during
measurement)

Angle of
incidence
()

Diffractometer circle
13
(fixed during measurement)

Bragg-Brentano focusing configuration

Receiving
slit

Focus
X-ray
source

Single crystal
monochromator
()

Detector

Divergence
slit
Secondary
Optics:
Scatter and soller slits

Focusing
Divergent
Divergent
circle

beam
beam
not
not good
good for
for
grazing
grazing
incidence
incidence
analysis
analysis

specimen

(variable during
measurement)

Angle of
incidence
()

Sample
Sample height
height
positioning
positioning isis critical
critical

Detector
rotation
(2)

Diffractometer circle
14
(fixed during measurement)

Instrumentation: powder diffraction

Soller
slits
Cu
x-ray
source

Divergence
slit
s am

ple

Scatter slit
Soller slits
Receiving
slit

Rigaku D/Max-b
x-ray diffractometer
Bragg-Brentano
configuration

Detector

(top view)

CMM XRD facilities

Curved graphite
monochromator

2 ~ 0.2O

CMM instrument: Rigaku D/Max-b XRD system

15

Instrumentation: stress, phase analysis

Optional
filter or
attenuator

Bragg-Brentano configuration
with programmable slits

Top view

ple
sam

Vertical mask
X-ray source:
Cu, line focus

2
Programmable
anti-scatter slits

Programmable
divergence slit
[> (1/32) deg]

Detector

Programmable
receiving slits
Curved graphite
monochromator

Programmable
attenuator

Programmable slits can be

used for applications
requiring limited or
constant illuminated area
in the sample.

CMM instrument: Panalytical Xpert #2 XRD system

16

Crystallite size analysis

Scherrers equation:
Size =

Not accounting for peak

broadening from strain and
defects

k*
cos () * (FWHM)

k : shape factor (0.8-1.2)

Measured along the

specific direction normal to
the (hkl) lattice plane
given by the 2 peak position

: x-ray wavelength
FWHM: full width at

half maximum (in radians)

Peak
Peakwidth
width(FWHM)
(FWHM)

___ Measurement
___ Fit

Peak
Peakposition
position2
2
17

FWHM vs. integral breadth

Imax
It does not take into
account the lower part ()I
max
of the profile

FWHM (deg)

The square-topped profile has the same area

and peak height as the measured curve.
Integral breadth = (total area) / (peak height)
Integral breadth (deg)

18

Peak shape analysis

Peak fit:
Gaussian
Lorentzian
Pearson-VII (sharp peaks)
Pseudo-Voigt
(round peaks)

Measurement

Information from fit:

Position
Width (FWHM)
Area
Deconvolution
Skewness

Fit

___ Measurement
___ Fit

19

Correction for instrument resolution

Use FWHM curve as a function of 2 from
standard sample (NIST LaB6)
- specific for each diffractometer

FWHM:
= (meas)D (instr)D

D: deconvolution parameter
Measurement
Instrument function

D : 1 (~ Lorentzian)
= (meas) (instr)
D : 2 (~ Gaussian)
2 = (meas)2 (instr)2
D : 1.5
1.5 = (meas)1.5 (instr)1.5

Software: MDIs Jade + 8.0

20

10

Potential artifacts in size determination

D

FWHM:
= (meas)D (instr)D

Size, nm
Measured
peak
D=1
width (o) (Lorentzian)

Size, nm
D = 1.5

Size, nm
D=2
(Gaussian)

0.3

56.4

38.0

32.6

0.5

24.2

19.2

17.7

0.75

14.1

12.0

11.5

10.1

8.8

8.6

1.5

6.3

5.8

5.7

4.6

4.3

4.2

Assume:
Instrument resolution ~ 0.15o
2 = 40o
Cu radiation

Large difference
(up to 48%!) for
narrow peaks (large sizes)

Smaller difference
(~ 10%) for
broad peaks (small sizes)
21

Strain effects in diffraction lines

d

No strain
(2)
Macrostrain
uniform strain
(lattice distortion)

Peak position
shift
(lattice constant
change)

Uniform strain

Microstrain
nonuniform strain
(lattice distortion)

FWHM

Peak width
change

Nonuniform strain
22

11

Size and strain in peak shape analysis

(FWHM)*cos()
(FWHM)*cos()==k/(size)
k/(size)++(strain)*sin()
(strain)*sin()

(FWHM)*cos()

Williamson-Hall
Method
Acta Metall. 1 (1953) 22.

sin()
Intercept
Intercept~~1/(size)
1/(size)
Slope
Slope~~micro
microstrain
strain

FWHMstrain = 4*(strain)*tan

23

Other methods of grain size analysis

Rietveld
Rietveldrefinement
refinementmethod:
method:
Refines
Refinesthe
thewhole
wholediffraction
diffractionpattern
pattern(including
(includingbackground)
background)
Needs
Needsdetailed
detaileddata
dataover
overaawide
wideangular
angularrange
range
Gives
one
average
size
value
Gives one average size value
Works
Worksbetter
betterfor
forpowder
powdersamples
samples(not
(notwell
wellwith
withfilms
filmswith
withstrong
strongpreferred
preferredorientation)
orientation)
Data
Dataprocessing
processing(refinement
(refinementand
andplay
playwith
withparameters)
parameters)isistime
timeconsuming.
consuming.

H. Rietveld
(1932-)

Warren-Averback
Warren-Averbackmethod:
method:
Standard
Standardsample
sample->->Instrumental
InstrumentalBroadening
Broadening->->Correct
Correctmeasured
measuredpeaks
peaksassuming
assuming
2
error-type
exp(-p)2->->Use
UseScherrers
Scherrersequation
equation
error-typeofoffunction
function(main
(mainassumption)
assumption)I I~~exp(-p)

Jones
Jonesmethod:
method:
Measured
Measuredprofile
profile==convolution
convolution(pure,
(pure,instrument)
instrument)
Use
UseFourier
Fourierintegrals
integralsfor
forall
allthe
theprofiles
profiles(measured,
(measured,pure,
pure,instrument)
instrument)
Use
ratio
of
the
integrals
to
determine
Use ratio of the integrals to determinesizes.
sizes.

24

12

Pattern treatment, S/M and structure refinement

Intensity

1.
2.
3.
4.
5.
6.

Background treatment
Peak fit
Search/Match (PDF)
Composition (w%)
Grain sizes, lattice parameters
Structure determination refinement

Weight % of
parts in the
mixture

2(o)

Software:
MDIs Jade + 8.0

25

Whole pattern fitting and structure refinement

Pattern from a Li-Nibased battery cathode
(003)

Powders, polycrystalline films or nanostructures, mineralogy, cements,

ceramics, pharmaceutics, polymers, biomaterials.
Identification, quantification (w%) and structure determination of mixtures,
impurities, multiple phases and amorphous fractions.

(104)

Intensity (a.u.)

Bragg-Brentano or parallel beam x-ray analysis.

Quantification of crystallinity, texture, twinning, grain size and strain.

(101)

(110)
C(002)

(012)
(006) (015)

Pattern simulation and structure refinement (Rietveld analysis).

(018)
(107)

(113)

2-theta ( )

Pattern treatment:
* Peak profile fit
* Search / Match
* Pattern Indexing
* Cell Refinement
* Pattern Simulation
* RIR w% quantification
* Rietveld structure refinement
Data: Sardela, UIUC
Sample: Abraham et al, ANL

Pattern indexing, lattice parameters determination, unit cell refinement,

atomic positions, bonds distances and angles.

Results obtained from the measured pattern:

Search / Match:

LiNi0.7Co0.3O2, major (minor: C graphite)

Structure:

Hexagonal R-3m (166) <1/3,2/3,2/3>,

Z=1, hR4

Cell
(Rietveld
refinement):

a= 2.86285 ; b= 2.86285 ; c= 14.17281

= 90o = 90o = 120o
Unit cell volume: 100.6 ()3
Density: 4.8383 g cm-3
Linear Absorption Coefficient: 385.5 cm-1

Average bond
distances
(Rietveld):

Ni-O: 1.9570 , Ni-Li: 2.8729 ,

Ni-Ni: 2.8629 , Co-O: 1.9570 ,
Co-Ni: 2.8629 , Co-Li: 2.8729
Li-O: 2.1117 , Li-Li: 2.8629 ,
O-O: 2.7983

Quantitative
analysis:

82.9 w% LiNi0.7Co0.3O2, 17.1 w% C

Crystallite size:

> 1000

Strain:

0.05%

Ni
O
Li

Co
26

13

New: S/M assisted by whole pattern fitting

Multi-phase mixture
powder data

Software: MDIs Jade + 8.0

27

New: S/M assisted by whole pattern fitting

Whole pattern fitting using possible pdf hits in search for best phase ids

R is being minimized
(whole pattern fitting)

Possible
Possiblepdf
pdfhits
hitsafter
afterS/M
S/M
28

14

New: S/M assisted by whole pattern fitting

Unmatched peaks
are now fitted

New
Newpdf
pdfhits
hitsare
arenow
now
automatically
automaticallyadded
added
29

New: S/M assisted by whole pattern fitting

R: 45.5 w%, XS: 463 nm

H: 31.0 w%, XS: 273 nm
A: 23.5 w%, XS: 28 nm

Whole pattern
fitted

R
H

3 phases matched: Rutile, Hematite, Anatase

30

15

X-ray parallel beam methods

Rough, irregular surfaces

Film / Substrate systems

Near surface
region

Glancing / grazing angle applications.

Phase, stress gradients (depth profiles)

31

Parallel beam configuration

Negligible
Negligiblesample
sample
displacement
displacementissues
issues
(rough
(roughand
andcurved
curved
samples
samplesOK)
OK)

X-ray
source

Specific
Specificoptics
opticstotomaximize
maximize
intensities
intensities

Primary
Optics:

Parallel plates
collimation

mirror, slits, lens

Single crystal
monochromator
()
Detector
rotation
(2)

Parallel
beam

Angle of
incidence
()

Detector

specimen
Excellent
Excellentfor
forglancing
glancingangle
angle
(fixed
(fixed)
)applications
applications

32

16

Instrumentation: thin film, texture, stress analysis

Primary optics
option 1:
Crossed-slit
collimator

Parallel plate collimator

configurations

Top view

ple
sam

Optional
filter or
attenuator

X-ray source:
Cu, line or point focus

2
0.27o-

Crossed slits

parallel
plates
collimator

Primary optics option 2:

x-ray lenses

(slit+mask)

Vertical mask

Primary optics option 3:

programmable
divergence slit +
programmable
attenuator

Optional
0.1mm slit

~ 0.03-0.2o

Flat graphite
monochromator

Detector

Programmable
divergence slit

Programmable attenuator
CMM instrument: Panalytical Xpert #2 XRD system
33

Thin film orientation analysis

40 eV, = 0.95

8.5 eV, = 0.68

42.0

42.5

2 (deg)

MgO

Data:
Shin,
Petrov et al,
UIUC

20 eV, = 0.60

41.5

<110>

MgO
(002)

30 eV, = 0.75

41.0

TaN

MgO(001)
substrate

43.0

Cube
Cubeon
oncube
cube
epitaxy:
epitaxy:
//(001)
(001)
(001)TaN
TaN//(001)MgO
MgO
(100)
//(100)
TaN
//(100)MgO
43.5(100)
TaN

MgO

(220)
scans

-TaN1.17/MgO(001)
t = 500 nm
Ts = 600 C

Intensity (a.u.)

-TaN 002

-TaN
(002)

<110>

TaN film

<001>
MgO

MgO 002

Intensity (a.u.)

Example:

TaN

-TaNx/MgO(001)
t = 500 nm
Ts = 600 C
Ji/JTa = 11
fN = 0.125

scan (in-plane
surface direction)

<001>

2/
scan
(surface
normal
direction)

-TaN
-TaN

MgO

MgO

50

100

150

200

(deg)

250

300

350

34

17

Glancing angle x-ray analysis

Inc
surface
normal

ide
nt
x

(fixed)

-ra
y

be
am

-ray
dx
e
t
rac
Diff

m
bea

grains
: conventional Bragg-Brentano configuration
2- scans probe only grains aligned parallel to the surface

: parallel-beam grazing incidence configuration

2 scans probe grains in all directions
35

X-ray penetration depth vs. angle of incidence

Low angle region

-Type of radiation
- Angle of incidence
- Material (Z, A, , )

36

18

X-ray penetration and information depths

I0 exp(-l)
I0

d1

l = d1 + d2 =

Absorption factor =

1/e = (sin) /

(1) Penetration depth 1/e:

depth for Intensity = Io/e ~ 37% Io
(2) Penetration depth 63:
depth for AGIXRD = 1-1/e (~ 63%, tk=1)

d2

z
z +
sin sin (2 )

Absorption (sample w/ finite thickness)

Absorption (sample w/ infinite thickness)

For /2 configuration: A2 = 1 exp(-2/sin)

For GIXRD configuration:AGIXRD = 1 exp(-tk)
k = 1/sin + 1/sin(2 )
t: thickness
z: depth from surface
= m = linear absorption coefficient
m = mass absorption coefficient (tables)
: mass density
c: critical angle
: / 4 (imaginary part of refractive index)
= (c2)

63 = 1 / k =

sin sin(2)
[sin + sin(2)]

Bragg peak (2) dependent penetration depth!

(3) Information depth :

weighted average of sampling depth

1
1
= k +

1 exp(tk)

It will not exceed the thickness value!

(4) Penetration depth 1/e for ~ c:

Includes correction with refractive index n = 1- - i

1/e =

2
4

[(2 c2)2 + 2] -1/2 (2 - c2)

Excel spreadsheet calculator available at:

http://www-ssrl.slac.stanford.edu/materialscatter/gixs-calculator.xls
37

X-ray penetration and information depths

I0 exp(-l)
I0

1/e = (sin) /

(1) Penetration depth 1/e:

depth for Intensity = Io/e ~ 37% Io

d1

(2) Penetration depth 63:

depth for AGIXRD = 1-1/e (~ 63%, tk=1)

d2

500 nm thick TiO2 rutile film

( = 0.0528 m-1, Cu K radiation)
2 range: 22 60o

Angle of Penetration
incidence
depth
(o)
1/ (nm)

Information
depth
(nm)

0.9

298

180 - 182

1.8

595 (>t!!)

212 214

2.7

892 (>t!!)

224 226

63 = 1 / k =

Bragg peak (2) dependent penetration depth!

(3) Information depth :

weighted average of sampling depth

1
1
= k +

1 exp(tk)

It will not exceed the thickness value!

(4) Penetration depth 1/e for ~ c:

Includes correction with refractive index n = 1- - i

1/e =
From: M. Birkholz, Thin Film Analysis by X-ray
Scattering Wiley-VCH 2006

sin sin(2)
[sin + sin(2)]

2
4

[(2 c2)2 + 2] -1/2 (2 - c2)

Excel spreadsheet calculator available at:

http://www-ssrl.slac.stanford.edu/materialscatter/gixs-calculator.xls
38

19

Grazing angle vs. Bragg-Brentano configurations

Grazingincidence
incidenceanalysis
analysiswith
with
Grazing
parallel
beam
optics
parallel beam optics
Detectgrains
grainsininvarious
variousorientations
orientations
Detect
(includingtilted
tiltedtotothe
thesample
samplesurface).
surface).
(including
Fixedincident
incidentangle:
angle:constant
constantprobed
probed
Fixed
depthininthe
thesample
sampleduring
duringanalysis.
analysis.
depth
Lowangle
angleofofincidence:
incidence:
Low
highsensitivity
sensitivitytoto(ultra)
(ultra)thin
thinfilms;
films;
high
avoidartifacts
artifactsfrom
fromsubstrates;
substrates;
avoid
canbe
beused
usedfor
fordepth
depthprofiling
profilingatat
can
differentincidences.
incidences.
different
Slightlylower
lower2
2resolution:
resolution:ok
okfor
forbroad
broad
Slightly
peaks.
peaks.
Thinfilm
filmcollimation
collimationoptics:
optics:enhanced
enhanced
Thin
sensitivitytotothin
thinfilms.
films.
sensitivity
Parallelbeam:
beam:insensitive
insensitivetotosample
sample
Parallel
displacement
errors.
displacement errors.

Conventional
Conventional analysis
analysiswith
with
focusing
configuration
focusing configuration
Detect
Detectonly
onlygrains
grainswith
withorientation
orientation
parallel
paralleltotothe
thesample
samplesurface.
surface.
Sample
Sampleprobed
probeddepth
depthmay
mayvary
varyduring
during
the
theanalysis.
analysis.
Lower
Lowersensitivity
sensitivitytoto(ultra)
(ultra)thin
thinfilms;
films;
substrate
artifacts
are
problem.
substrate artifacts are problem.
Very
Verygood
good2
2resolution
resolutionand
andwellwellknown
knownmathematical
mathematicalformalism.
formalism.
Typical
Typicaloptics
opticsare
areideal
idealfor
forpowder
powder
samples
samplesand
andthick
thickfilms
filmswith
withno
no
preferred
preferredorientation.
orientation.
Focusing
Focusingconfiguration:
configuration:very
verysensitive
sensitive
totosample
sampledisplacement
displacementerrors
errors
39

Glancing angle x-ray analysis

Example:
Poly-Si
(~ 100 nm)

Si(001)

Substrate

Substrate

substrate

Glancing
angle
Conventional
2/ XRD

2-theta (degrees)
40

20

Grazing incidence x-ray analysis

Grazing incidence X-ray scattering (GIXS) analysis uses
low angle of x-ray beam incidence relative to the surface in
order to enhance diffraction from very thin layers.

(hkl)

Analysis of ultra-thin films (<10 nm), nanostructures or

topmost surface regions of the material.

sample
detector

Depth from surface ()

XRD
penetration
depth

(Incidence angle) / (critical angle)

x-ray s

Allows structure determination and quantification of lattice

parameters, rocking curve widths and crystallite size along
the surface direction (different from conventional XRD,
which probes surface normal directions).

ource

GIXS from a
ScN thin film on
MgO (001):
The results allow the
determination of in-plane
lattice parameter and
crystallite size;
Notice the differences in
the relative intensities of
the film and substrate peaks
at different in-plane angles
of incidence .

Angle of
incidence:

ScN(220)

0.50

Intensity (a. u.)

surface
normal

1.00
1.40
1.80
2.25
2.75
MgO(220)
57

58

Data: Sardela, Shin, Petrov, Greene et al, UIUC

59

60

61

62

63

64

65

2 ( )

41

Texture and preferred orientation methods

ed
ferr
Pre ntation
orie

Texture / Preferred orientation:

anisotropy of grain orientation
distribution.
Are the grain orientations distributed
randomly? Or is there a preferred
orientation?
What is the preferred orientation?
What is the % of random grains?
How strong and sharp is the texture?
For film / substrate systems:
what is the crystallographic orientation
between the substrate and the layers?

42

21

Determination of preferred orientation

Crystalline grains in a material may be preferentially distributed along one orientation (preferred orientation).
This may complicate the analysis using conventional XRD methods derived from powder techniques.

Methods:
Methods:
1.1. Compare
Comparerelative
relativepeak
peakheight
heightor
orarea
areaobtained
obtainedfrom
fromaa2/
2/scan
scanwith
withthe
theexpected
expected
relative
intensity
from
a
standard
(same
material)
with
no
preferred
orientation
relative intensity from a standard (same material) with no preferred orientation
(~
(~powder):
powder):Lotgering
Lotgeringfactors.
factors.
2.2. Use
the
relative
intensity
Use the relative intensitymethod
methodabove
abovecombined
combinedwith
withMarch-Dollase
March-Dollasepreferred
preferred
orientation
orientationcorrections
correctionstotoobtain
obtain%
%grains
grainsthat
thatare
aremore
moreoriented
orientedininaaspecific
specific
direction.
direction.
3.3. Use
Usethe
therocking
rockingcurve
curveanalysis
analysisofofaastrong
strongfilm
filmdiffraction.
diffraction.The
Thewidth
widthofofthe
therocking
rocking
curve
curvepeak
peakisisused
usedas
astexture
textureparameter.
parameter.
4.4. Perform
Performpole
polefigures
figurestotodetermine
determinethe
thepresence
presenceofofgrains
grainsofofaacertain
certainorientation
orientationinin
all
allsample
sampledirections.
directions.
5.5. Use
Usemultiple
multiplepole
polefigures
figuresfrom
frommultiple
multipleorientations
orientationstotoobtain
obtainOrientation
Orientation
Distribution
Functions:
%
of
grain
orientation
distributions
in
all
Distribution Functions: % of grain orientation distributions in allwafer
waferdirections.
directions.
43

X-ray pole figure analysis of textured materials

Texture results from a rolled Cu foil

Pole figures

Texture orientation and quantification.

Volume fraction of textured grains,
twinning and random distributions.
Texture strength and sharpness.
Crystallographic orientation.
Crystallographic relationship between
layers and substrate.

sample

detector

urce
x-ray so

(111)

Inverse
pole
figures

Orientation
distribution
function (ODF)

Data: Sardela, UIUC

44

22

Pole plot projections

Pole

Equatorial
plane

Wulff projection
(stereographic or
equal-angle projection)

Schmidt projection
(equal-area projection)
S

Side view
(normal to
equatorial plane)

r
O

AB = AS

Side view
(normal to
equatorial plane)

W
Equatorial
plane

Top view
(parallel to
equatorial plane)

Top view
(parallel to
equatorial plane)

OW = r tan(/2)

OS = 2 r tan(/2)
45

Basics of pole figure analysis

Surface
normal

hkl

(100) Pole figure

-1 0 0

010

001

0 -1 0

Azimuth
= 0, 90o,
180o, 270o
Tilt
= 0, 90o

Example: (100) cubic crystal

(111) Pole figure

-1 -1 1

-1 1 1

Pole figure plot

: [100],[100]

100

111

Tilt = 54.7o

1 -1 1

: [100],[111]

hkl
(110) Pole figure

-1 -1 0

0 -1 1

(radial / tilt)
(azimuthal rotation)

Azimuth
= 45o, 135o,
225o, 315o

-1 1 0

-1 0 1

011

Azimuth
= 0, 90o, 180o,
270o,45o, 135o,
225o, 315o

101
1 -1 0

Tilt = 45o,90o
110

46
: [100],[110]

23

Basics of pole figure analysis

Surface
normal

hkl

(100) Pole figure

010

001

Azimuth
= 30o,
150o, 270o
Tilt = 54.7o

Example: (111) cubic crystal

(111) Pole figure

-1 1 1

Azimuth
= 90o,
210o, 330o

Pole figure plot

: [111],[100]

100

111

1 -1 1

1 1-1

Tilt = 0, 70.5o
: [111],[111]

hkl
(110) Pole figure

-1 0 1

-1 1 0
011

0 1 -1
110

0 -1 1

Azimuth
= 60o, 120o,
240o, 300o, 90o,
210o, 330o.

101

(radial / tilt)
(azimuthal rotation)

1 -1 0

-1 0 1

Tilt = 35.3o, 90o

47
: [111],[110]

Fiber texture analysis

Example: Cu thin film
on Si (001) substrate
Conventional 2/ scan:
Cu(111)

Si

Grains:
56 nm

Cu(222)

48

24

Fiber texture analysis

Example: Cu thin film
on Si (001) substrate

(111) Pole figure:

= 70.53o

Conventional 2/ scan:
Cu(111)

Si

=0

Grains:
56 nm

(200)

(200) Pole figure:

=
(220)

54.74o

(311)
Cu(222)

All grains are <111> oriented along

the film growth direction.
Grains are randomly oriented along the surface
49

Fiber texture analysis

Sam
ple

(111) Fiber plot

Cu film on Si (001) substrate

Data after background subtraction

HWHM: 1.09o
(texture sharpness)

Detector
sour
X-ray

<111>

ce

Fiber texture:

3.5%
<5 7 13>+<112>
+<225> twinning

<111>
4.6%
<511>
twinning

Texture
direction

Random

n
Ra

m
do

Random

9.0%
random grains

Ran
dom
50

25

Residual stress analysis methods

Residual stress?
How much? (MPa GPa)
Type?
Direction (s)?
Stress gradients?

51

X-ray analysis of residual stress

Film Normal

stressed

Reflected
X-rays

Tilt :
o
+60

a0

film surface

L,

Incident
X-rays

Interplanar spacing d (Angstroms)

Diffracting planes

+45
o
+30o
+15
0
o
-15
o
-30o
-45
o
-60

d/d = [(1+)/E] sin2

1.173

79

1.172

80

81

82

83

84

85

2-theta ( )

1.171

1.170

1.169

Intensity (a.u.)

unstressed

Stress = -199 MPa

1.168
0.0

0.2

0.4

0.6

0.8

sin ()
Stress results from a steel sample

Data: Sangid et al, UIUC

Quantification of residual stress.

Compressive (-) and tensile (+) stress.
Crystallographic orientation of stress.
Sin2 and RIM methods.
and scan methods.
New glancing angle method (texture).
Determination of stress tensor.
Requires crystallinity (no amorphous).
52

26

Residual stress analysis: the sin2 method

Film Normal

unstressed
stressed

L,

Incident
X-rays

Reflected
X-rays

a0

film surface

a ()

Diffracting planes

4.55

HfN1.05/SiO2

4.54

= -0.03074
= 4.54521

4.53

a =

2
sin 2 =
4.52
1+

4.51

a ao
ao
a o
E

1+
2
sin 2
E
E

[(1 + ) sin

2 + a o = sin 2 +

2
= 4.533
1+
E
=
= 1.47 GPa (Compressive)
2 + (1 + )
ao = +

0.0 0.2 0.4 0.6 0.8 1.0

sin2

53
Data: Petrov et al, UIUC

High resolution XRD methods

Single crystals:

Accurate measurements of a, b, c, , ,
Detailed peak shapes: defects, mosaicity.

a
Film / substrate epitaxial systems:

Measure small variations a, c, (~ 10-5).

c + c

Measure layer tilts , ...

Detailed peak shapes: defects, strain, mosaicity.

c
a

54

27

Instrument resolution in reciprocal space

Beam angular divergence,
detector acceptance and
diffractometer sampling volume

Dif
frac
te

db

nt b
i de
I nc

eam

eam

sample

Angular
acceptance
of the
secondary
optics

Primary beam
divergence

Diffractometer
sampling
volume

(from primary optics)

Ewald sphere
55

Instrumentation: high resolution configuration

ple
sam

3-bounce
analyzer
crystal

4-reflection
Ge(220)
monochromator

slit

=12 arc-sec
/ = 5x10-5

Crossed slits

(triple axis:
12 arc-sec acceptance)

x-ray
source

slit

(variable slit+mask)

Lower
detector

x-ray
mirror

Programmable
attenuator

Upper detector

High resolution
configuration with
mirror and 4-reflections
monochromator
Line focus;
Parabolic x-ray mirror;
4-reflection monochromator
(12 arc-sec resolution);
Open detector or analyzer crystal.

(open: < 1o acceptance)

CMM instrument: Panalytical Xpert #1 XRD system
56

28

Instrumentation: high-resolution configuration

ple
sam

3-bounce
analyzer
crystal

Hybrid
Mirror

x-ray
source

(2-bounce monochromator +
X-ray mirror)

slit

=30 arc-sec

High resolution
configuration with
hybrid mirror

Mask

Programmable
attenuator

Lower
detector
(triple axis:
12 arc-sec acceptance)

Line focus;
Hybrid mirror (30 arc-sec resolution);
Open detector or analyzer crystal.

Upper detector
(open: < 1o acceptance)
CMM instrument: Panalytical Xpert #2 XRD system
57

High resolution x-ray analysis

High resolution methods using multi-reflection monochromator and possibly
analyzer crystal ( = 0.003o).
Sensitive to lattice distortions within 10-5.
Rocking curve analysis.
Film thickness measurements.
Strain relaxation and lattice parameter measurements.
Determination of alloy composition and superlattice periods.

Single crystals
Epitaxial films
Heterostructures
Superlattices
Quantum dots

Dynamical scattering simulation to determine composition variations and interface

smearing in heterostructures.

SiGe / Ge superlattice

InAs / GaAs multilayer

60

62

64

2-theta / omega ( )

66

68

Data: Zhang et al

Log intensity (a.u.)

Log intensity (a.u.)

Log intensity (a.u.)

Data: Wu et al, UIUC

58

InAs quantum dots on GaAs

Data: Sardela, UIUC

62

64

66

2-theta / omega ( )

68

70

62.5

63.0

63.5

64.0

64.5

2-theta / omega ( )

58

29

High resolution x-ray analysis

Example: strained
InxGa1-xAs on GaAs
(001) substrate

High resolution 2/ scan near GaAs(004)

GaAs (004)
InxGa1-xAs (004)
Thickness
fringes

Lattice structure

a// film = asubstrate

0.07o
0.04o

a film
>

asubstrate

(004)
InxGa1-xAs
(004)

GaAs

a = sin (substrate) - 1
a
sin (film)

Thickness =

2 cos

Data: Sardela
59
Sample: Highland, Cahill, Coleman et at, UIUC

asubstrate

High resolution x-ray analysis

Example: strained
InxGa1-xAs on GaAs
(001) substrate

High resolution 2/ scan near GaAs(004)

and dynamical scattering simulation
GaAs (004)
InxGa1-xAs (004)

Lattice structure

a// film = asubstrate

a film
>

asubstrate

(004)

0.76
at% In

243 nm

InxGa1-xAs
(004)

GaAs

asubstrate

Takagi-Taupin dynamical scattering simulation

Data: Sardela
60
Sample: Highland, Cahill, Coleman et at, UIUC

30

High resolution reciprocal space mapping

No strain relaxation:

a// = as

Sensitive to lattice distortions within

film
substrate

as

High resolution reciprocal lattice mapping requires multireflection monochromator and analyzer crystal in order to
separate strain from mosaicity.

Strain relaxation:

a// as

10-5.

Accurate lattice parameter determination (in and out of

plane).

Determination of strain and composition variations, strain

relaxation, mosaic size and rotation, misfit dislocation
density, nanostructure dimensions, lattice disorder and
diffuse scattering.

(224)

film
substrate

as

(224)

substrate

substrate

film
thickness
fringes

q001
film
Si1-xGex
on Si(001)

0.1 nm-1

Mosaicity
(diffuse
scattering)

q110

Si1-xGex
on Si(001)

0.1 nm-1

Data: Sardela et al

61

High resolution reciprocal space mapping

Layer structure
Strained Si (top layer, very thin)
Relaxed Si1-xGex (thick, many microns)

Example: strained Si layer

on Si1-xGex / Si substrate

Si(001) substrate

Lattice structure

Strain?

Strained Si

(004)
Relaxed Si1-xGex
(virtual substrate)

(224)

Lattice distortion?

(004)

Defects?

(224)
Strained Si

% of relaxation?
at % of Ge?

Si(001) substrate

Reciprocal lattice

Si substrate

q
Si1-xGex

q// 62

31

High resolution reciprocal space mapping

High resolution 2/ scan near Si(004)
Si substrate

Si1-xGex

Layer structure

Example: strained Si layer

Strained Si
on Si1-xGex / Si substrate

Strained Si (top layer, very thin)

Relaxed Si1-xGex (thick, many microns)
Si(001) substrate

Lattice structure

Strain?

Strained Si

(004)
Relaxed Si1-xGex
(virtual substrate)

(224)

Reciprocal lattice

Lattice distortion?

(224)
Strained Si

% of relaxation?
at % of Ge?

Si(001) substrate

(004)

Si substrate

q
Si1-xGex

Defects?

q// 63

High resolution reciprocal lattice map

Strained Si (top layer)
Relaxed Si1-xGex
Si(001) substrate

Map near Si(224)

[001]
0.1 nm-1

[110]

Data: Sardela
Sample: Zuo, UIUC
64

32

High resolution reciprocal lattice map

Strained Si
= - 0.77%
// = 0.64 %

Strained Si (top layer)

Si substrate

Relaxed Si1-xGex
Si(001) substrate

Map near Si(224)

4.60 at% Ge
7.52 at% Ge
11.45 at% Ge

Relaxed Si1-xGex
18.70 at% Ge
100% strain relaxation

[001]
0.1 nm-1
Data: Sardela
Sample: Zuo, UIUC

[110]

65

High resolution reciprocal lattice map

Strained Si (top layer)

Finite size

Composition and
strain gradients

Relaxed Si1-xGex
Si(001) substrate

Map near Si(224)

Analyzer streaks

Coherent length
in any direction:
2 / qi
i = x, y, z, //,

Mosaicity and
dislocations

[001]
0.1 nm-1

[110]

Data: Sardela
Sample: Zuo, UIUC
66

33

High resolution reciprocal lattice map

Strained Si (top layer)

Finite size

Composition and
strain gradients

Vertical coherent
length: 14 nm

Relaxed Si1-xGex
Si(001) substrate

Map near Si(224)

Analyzer streaks

Coherent length
in any direction:
2 / qi
i = x, y, z, //,

Mosaicity and
dislocations

Misfit dislocations:
average separation : 21 nm
density: 5 x 105 cm-1

[001]
0.1 nm-1

[110]

Data: Sardela
Sample: Zuo, UIUC
67

Comparison with TEM

EDS line scan

Data: Zuos group, UIUC

68

34

The shape of the reciprocal lattice point

Changes in
lattice parameter
(radial direction)

sca
n

004

224
can
)s

/2
(

[001]

G2

000

[110]

24

CTR, finite
layer
thickness,
superlattice
(along q)

Lateral sub-grain
boundaries
(along q//)
Mosaicity,
curvature,
orientation
(circumferential
direction)

69

X-ray reflectivity methods

Bulk materials:
Near surface
region

Liquids:

Multilayered systems:

Near surface and interface information on:

Density
Porosity
Roughness
Thickness in films (ultra thin to thick)
Amorphous or crystalline materials

70

35

X-ray reflectivity
nt x-r
a

Angle of incidence
relative to the surface
(omega or theta)

Sample

Log Reflectivity R

Critical
angle c

One sharp interface

(density e variation:
function at interface)

R ~ -4

Angle , or 2

Film thickness measurements: 2 300 nm.

One rough interface

Thickness fringes
= /[2*(thickness)]
dec
ay

Applicable to ultra-thin films, amorphous

or crystalline materials, multilayers and
liquids.

(broade variation
at interface)

Simulation and fitting: determination of

interface roughness (rms) at each interface,
roughness correlation and film porosity.

Two interfaces
~r
oug
h

Detector rotation:
angle 2-theta

r
Detecto

m
ay bea
red x-r
Scatte

y bea
m

Intensity

Incide

I ~ e

nes
s

Very sensitive to density variations.

Determination of critical angle, refractive
index and density.

71

X-ray reflectivity analysis of thin films

Complex
multilayers
Ultra-thin

10

2-theta ( )
Data: Heitzman et al, UIUC

Log intensity (a.u.)

Log intensity (a.u.)

2

12

Metallic
multilayer

sin2
Intercept:
refractive
index

2-theta ( )

10

Amorphous
PZT film

Log intensity (a.u.)

n=1
2

2.3 nm thick
polymer on Si

Non
crystalline

Data: Sardela, UIUC

Sample: Auoadi et al, SIU

12

Slope:
periodicity d

0.5

1.0

1.5

2.0

2.5

3.0

3.5

Theta ( )
Data: Mikalsen et al, UIUC

n2
sin2 = (2/2d)2 n2 (2 -1)
(modified Braggs law to include refractive index)
72

36

X-ray reflectivity information content

critical = (2)1/2

Reflectivity intensity (counts per sec.)

Critical angle: density, porosity

Refractive index = 1-+i

Thickness (Kiessig) fringes: angular separation

between oscillations gives thickness

t = (/2) / (sin2 sin1) =

~ (/2) /

Two sets of oscillations:

gives thickness of two layer structure
Amplitude of fringes: interface
roughness, density variations
Slope / shape of the
decay of the curve:
used to quantify interface
roughness in all interfaces

Angle of incidence (degrees)

73

X-ray reflectivity from superlattices

Reflectivity intensity (counts per sec.)

Example: 20 periods [1 nm SiO2 / 1 nm Si ] superlattice on Si wafer

Critical angle: gives density of each layer in the
superlattice (model dependent)

Thickness fringes:
angular separation gives total superlattice thickness

Number of fringes gives the total number of layers

in the superlattice

Superlattice main peaks:

angular separation gives period thickness
Slope: gives interface
roughness for each layer
in the superlattice (model dependent)
Angle of incidence (degrees)

74

37

X-ray reflectivity data fitting in ultra-thin films

Polymer
(few nm)

1,3,5-tribromo-2-nanyloxybenze:
C15H21Br3SiO3

SiO2

(~ 100 nm)

Si substrate

SiO2
thickness

Polymer thickness

Data: Sardela
Sample: Zhang, Rogers et al, UIUC
75

X-ray reflectivity data fitting

Best fit
rms: 0.26 nm
rms: 0.45 nm
rms: 0.24 nm

Polymer
2.0 nm, 1.30 g/cm3
SiO2
98.9 nm, 2.19 g/cm3
Si substrate

Data

Best fit

76

38

X-ray reflectivity data fitting

Fitting sensitivity to the
polymer thickness
(best fit: 2.00 nm)
2.2 nm
(+ 10 %)

simulation

Data

1.8 nm
(- 10 %)

simulation

77

X-ray reflectivity data fitting

Fitting sensitivity to the
polymer top roughness
(best fit: 0.26 nm)

0.2 nm
(- 0.06 nm)

simulation
Data
0.4 nm
(+ 0.14 nm)

simulation

78

39

X-ray reflectivity data fitting

Fitting sensitivity to
the polymer density
(best fit: 1.3 g/cm3)
Data
1.4 g/cm3
(+ 8 %)

simulation

1.2 g/cm3
(- 8 %)

simulation

79

X-ray reflectivity: summary

**Non
Nondestructive
destructivemethod
method

**Applicable
Applicableto
towhole
wholewafers
wafers(wafer
(wafermapping
mappingoption)
option)
**Fast
Fastmethod
method(in
(inmost
mostcases)
cases)
**Do
Donot
notdepend
dependon
oncrystalline
crystallinequality
qualityof
ofthe
thefilms
films(can
(canalso
alsobe
beused
usedin
inamorphous
amorphous
layers).
layers).
Quantification
Quantificationof:
of:

**Layer
Layerthickness
thicknessin
inthin
thinfilms
filmsand
andsuperlattices:
superlattices:11nm
nm~~11m
m(
(0.5-1%).
0.5-1%).
**Layer
density
and
porosity
(
1-2%).
Layer density and porosity ( 1-2%).
**Interface
Interfaceroughness:
roughness:0.1
0.110
10nm
nm(model
(modeldependent;
dependent;reproducibility
reproducibility~~3%).
3%).
**Layer
Layerdensity
densitygradients
gradients(variations
(variations>>2%).
2%).
**Interface
roughness
correlation
Interface roughness correlationin
insuperlattices
superlatticesand
andmultilayers.
multilayers.
Alternative techniques:
* Thickness: optical methods (TEM, SEM) poor contrast issues.
* Density: RBS (issues for ultra thin layers).
* Interface roughness: AFM (surface only not buried interfaces).
80

40

X-ray fluorescence methods

Bulk materials:

Which elements are present down to ppm levels?

Liquids:
What is the elemental composition (%) ?
Fast, accurate.
Liquids, solids, amorphous, crystalline materials.
Multilayered systems:

81

X-ray fluorescence (XRF)

Data: Panalytical (www.panalytical.com)

K1

LI
LII
LIII

L1
L1

Intensity (a.u.)

K2

Ti-K1

K1

K-K1

Ba-L1

Mn-K1
Fe-K1
Fe-K1

K-K1

L2

MI
MII
MIII
MIV
MV

Transition notation:
IUPAC:
<element><hole shell><originating shell>
Ex.: Cr-KLIII
Siegbahn: <element><hole shell><,,, etc.>
Ex.: Cr-K1
(for LIII to K transition in Cr)

Energy (keV)
Typical
Typicalplot:
plot:Intensity
Intensityvs.
vs.Energy.
Energy.
Line
Lineposition
positionassociated
associatedtotoelement
elementand
andspecific
specifictransition
transition
Line
positions:
fingerprint
of
Line positions: fingerprint ofthe
theelement.
element.
Element
identification
Na-U
or
Be-U.
Element identification Na-U or Be-U.
Peak
Peakassignment
assignmentuses
usesdatabase
databaseand
andsearch/match.
search/match.
Peak
Peakarea/height:
area/height:composition
composition(sub
(subppm
ppmtoto100%).
100%).
Peak
Peakoverlap
overlaprequires
requiresdeconvolution.
deconvolution.
Composition
Compositiondetermination
determinationrequires
requiresstandards,
standards,calibration.
calibration.
Fast
Fastdata
dataacquisition
acquisition(seconds
(secondstotohr).
hr).
Solids,
liquids,
powders,
thin
films,
Solids, liquids, powders, thin films,
Minimum
Minimumor
orno
nosample
samplepreparation
preparationrequired.
required.
82

41

EDXRF and WDXRF

Energy Dispersive XRF (EDXRF)
Sample

X-ray
tube

Peak assignment:
search/match software
Concentration:
down to sub-ppm

r
c to
e
t
De

Secondary target

Wavelength Dispersive XRF (WDXRF)

Sample
Energy resolution:
5-20 eV (WDXRF)
150-300 eV (EDXRF)

Collimator
Detector
X-ray
tube

An
al y
zer
c

rys
tal

Data: Horiba Jobin Yvon

http://www.jyinc.com/Spain/esdivisions/XRay/tutorial.htm
83

EDXRF and WDXRF

EDXRF

WDXRF

Dispersive system

Energy

Wavelength

Raw data

Intensity vs. Energy (keV)

Intensity vs. Detector angle (2).

X-ray tube
(Secondary Target)
Sample
Detector

X-ray tube
Sample
Collimator ( for // beam)
Analyzer Crystal
Detector (+ goniometer)

Elemental Range

Na U

Be U

Detection limit

Good for heavier elements (less optimum for

light elements)

Good for all range

Sensitivity

Good for heavier elements (less optimum for

light elements)

Moderate for light elements. Good for heavy

elements.

Resolution

Good for heavy elements (less optimum for

light elements)

Good for light elements (less optimum for heavy

elements)

Cost

Moderate

Relatively expensive

Measurement

Simultaneous

Sequential (moving detector on goniometer)

Simultaneous (fixed detector)

Moving parts

No

Crystal, goniometer

Detector

Solid state detector

Gas-filled (for Be Cu)

Scintillation (for Cu U).

Qualitative analysis

Peak area

Peak height

Basic set up

84

42

Basic EDXRF system configuration

Automatic
16 samples
changer
Ta or Ag
collimator

Filter
Automatic
secondary
target
changer

Si (Li)
detector

* *X-ray
X-raytube:
tube:Rh
Rh(side
(sidewindow)
window)3.3mA,
3.3mA,60kV.
60kV.

Automatic
filter
changer

* *Secondary
Secondarytargets:
targets:Gd,
Gd,Sn,
Sn,Ag,
Ag,Ge,
Ge,Fe,
Fe,Ti.
Ti.
Automatic
x-ray tube
position
changer

Two configurations:
--- direct collimated
--- secondary target

* *Filter:
Filter:Gd
Gd(6(6mil),
mil),Sn
Sn(4(4mil),
mil),Ag
Ag(2(2mil).
mil).
* *Detector
Detectorcollimators:
collimators:Ag,
Ag,Ta.
Ta.
* *Samples:
Samples:
16
16samples
samplesup
upto
to2
2diameter,
diameter,or
or
2
2square
squaremounts,
mounts,or
or

CMM instrument: Kevex Analyst 770 XRF system

1.25
1.25diameter
diameter(inserts).
(inserts).
2 active area.
* *Detector:
Si
(Li)
30mm
2
Detector: Si (Li) 30mm active area.
* *Energy
Energyresolution
resolution~~165
165eV.
eV.

85

XRF application
Spectroscopy investigation of icons
painted on canvas
Lj. Damjanovic et al, Belgrade

The Virgin and the Child, Unknown author

Museum of the Serbian Orthodox Church, Belgrade

http://www.srs.ac.uk/scienceandheritage/prese
ntations/Olgica_Marjanovic.pdf

Surface sample:
Original made of Au.
Restoration with Au imitation
Schlagmetal (Cu and Zn).
Fe: natural Fe-Al-silicate red
bole used for gilding the icon.

XRF and IR results show

pigments and binders
widely used in the XIX
century confirming that the
work is from late XIX to XX
centuries

Frame sample: Cu
and Zn (no Au)
-> Schlagmetal

86

43

X-ray analysis summary

Information
contents

% of crystallinity and amorphous contents

Identification and quantification of phases and mixtures
Chemical information (if crystalline)
Texture (type and strength) and fraction of random grains
Grain / crystallite size (> 2 nm)
Strain (> 10-5)
Stress (type, direction and value)
Relative crystallographic orientation
Lattice constants and unit cell type
Structure determination
Thickness (1.5 nm 3 mm)
Roughness (including buried interfaces)
Density and porosity
Relative fraction of domains
Defects and dislocation densities
Mosaic tilts and sizes

Detection limits

> 0.1 0.5 w%

Depth information

Up to 20 50 mm (typical)
> 10 nm and variable with glancing angle XRD

Lateral resolution

~ a few cm (typical)
10 mm (microdiffraction) 5 cm

Angular resolution

0.1o 2q (typical powder diffraction)

0.003o 2q (high resolution methods)

Sample requirement

Mostly non destructive

Sample sizes from ~ 50 mm to many cm
No vacuum compatibility required
Solids, liquids, gels

* Semiconductors
* Coatings
* Pharmaceutical
Cements
* Metals
* Ceramics
* Geology
* Archeology
* Biosciences
* Forensics
* Medical applications
* Nanotechnology
* Polymers
* Food science
* Combustion
* Energy
*

87

Comparison with other techniques

X-ray analysis methods

Other techniques

Sample
preparation
and vacuum
compatibility

o No vacuum compatibility required (except

XRF on vacuum).
o Any sample size (depends on the
goniometer size/weight capability).
o Rough surfaces acceptable (parallel beam
configuration).
o No sample preparation required (prep
recommended for the detection of unknown
phases or elements in XRD/XRF).

o Surface analysis and electron microscopy

techniques will require vacuum compatibility
and in many cases sample preparation.
o Optical techniques will do analysis on air.

Composition
and impurity
determination
and
quantification

~ 0.1 w % (XRF > ppm); may require

standards.
XRD: also phase information and % of
crystallinity.
Data averaged over large lateral area.

XPS: > 0.01 0.1 at % (may require depth

profiling).
SIMS: > 1 ppm (requires sputtering depth
profiling).
EDS: > 0.1 1 w % over small volume 1m3.
Little with phase information; averages over
small lateral areas (< 100 m).

Lattice
constants

o Better than within 10-5

o TEM: estimates ~ 10-3

Thickness in
thin films

HR-XRD or XRR: direct measurement (no

modeling for single or bi-layers).
Requires flat interfaces.

RBS: > 10 nm (requires modeling).

Ellipsometry: requires modeling.
TEM: requires visual contrast between layers.

Grain size

o Measures Crystallite Size.

o Typically ~ 1-2 nm microns, requires
size/strain assumptions/ modeling.
o Volume average size.

o SEM: grain size distribution averaged over

small area.
o TEM/SEM: number average size.

88

44

Comparison with other techniques

X-ray analysis methods

Other techniques

Texture

o Type and distribution averaged over large

sample volume.

o EBSD: within grain sizes dimensions, better

sensitivity at the surface.

Residual Stress

10 MPa, averaged over large sample

volume (large number of grains).
Needs crystallinity.
Measures strain and obtains stress from
Hookes law.
Averages macro and micro stresses over
large area of a layer.

Wafer curvature: No need for crystallinity.

Direct measurement of stress, but only
interlayer stress between film and substrate
(macrostress).

Depth
dependent
information

Phase, grain sizes, texture and stress

depth profiling requires x-ray information
depth modeling

Surface analysis depth profiling:

compositional depth profiles.

Surface or
Interface
roughness

XRR: interface roughness 0.01 5 nm,

including buried interfaces

SPM: top surface only; rsm~ 0.01-100 nm.

Defects

Misfit dislocations (HR-XRD).

Point defects (diffuse scattering with
model).
Extended defects (powder XRD with
model).
Average over larger sample area (> mm).

TEM: accurate identification of defects and

their densities; average over small sample
area. Sample preparation may introduce
artifacts.

Instrument cost

Portable instruments ~ $ 60 K.
Average well-equipped: ~ $ 200 300 K.
Top of the line ~ $ 500 K (including
microdiffraction and 2D detectors).

Surface analysis instruments > $ 500 K.

Electron microscopes ~ $ 300 K 1 M.
RBS ~ $ 2 M.
Raman, ellipsometry > $ 100 K.
89

Amazing x-ray samples

Pieces from Egyptian mummy
Powder from Inca ruins
Corrosion in pipes from IL water supply
Rocks from Mississippi river
Mud from a cadavers shoes
Dove chocolate
Corn starch
Train tracks
Heavy machinery valves
100 m micro chips
10 m superconductor single crystal
Next generation CPU processors
Micro extraction from Dutch paintings
Virus, bacteria, DNA, proteins
Powder from Mars terrain
Gasoline, electrical car battery
Bone implants
Pork tissue
90

45

Amazing x-ray samples

W. C. Roetgen wifes hand (1895)
Science and Society Picture Library / Science Museum

A. Bertha Roetgen
(1833-1919)

Wedding ring

It frightened Bertha terribly

as a premonition of death
After Boston Globe 11/6/95

W.C. Roetgen
(1845-1923)
1st Physics Nobel
91

Quick guide to our x-ray analysis instruments (1)

X-ray analysis instrumentation available as user facility in the FS-MRL
Instrument

Set up

Applications

Panalytical
Xpert (#1)

Source: Cu K1, line or point focus.

High resolution configuration.
4 or 2 reflection Ge monochromator (12 or 30
arc-sec parallel beam).
3 reflection Ge analyzer crystal (12 arc-sec
parallel beam).
Eulerian cradle.
Proportional detectors.

High resolution XRD capabilities.

Rocking curve.
Single crystals, epitaxial systems.
Reciprocal space mapping.
Reflectivity.
Curvature, wafer mapping, miscut, diffuse scattering.
Topography.
Glancing angle.
Parallel beam applications.
Max sample size: 10 cm diameter x 2 cm thick.

Source: Cu K1+K2, line or point focus.

Crossed slit collimator (variable aperture).
X-ray lens.
Programmable divergence slit.
Eulerian Cradle.
Parallel plate collimator and flat graphite
monochromator
Programmable receive and scatter slits and
graphite monochromator.
Proportional detectors.

.Phase, size, strain, stress, texture, crystallinity

.Parallel beam applications
.Bragg-Brentano applications
.General thin film analysis
.Glancing/grazing angle
.Max sample size: 10 cm diameter x 2 cm thick

Panalytical
Xpert (#2)

92

46

Quick guide to our x-ray analysis instruments (2)

X-ray analysis instrumentation available as user facility in the FS-MRL
Instrument

Rigaku
D/Max b

Rigaku
Laue

Bruker /
Siemens
D5000
(Fall 2008)

Kevex
Analyst 700
XRF

Set up

Applications

Source: Cu K1+K2, line focus.

Bragg-Brentano focusing configuration.
Theta/2theta goniometer.
Divergence, soller, scatter and receiving slits.
Curved graphite monochromator.
Scintillation detector.

Phase, size, strain, crystallinity.

Bragg-Brentano applications.
Rietveld analysis.
Mostly for powder, bulks and thin film with small preferred
orientation.

Source: Mo point focus.

Four circle sample stage (manual).
Polaroid film camera detection system.

Single crystal orientation.

Miscut information.
Crystallographic alignment prior to crystal cutting.

Source: Cu K1+K2, line focus.

Bragg-Brentano focusing configuration.
Theta / theta goniometer.
Horizontal sample load.
No sample movement required during analysis.
Divergence, scatter and receiving slits.
Scintillation detector.

Ideal for powder and soft samples (horizontal load).

Phase, size, strain, crystallinity.
Bragg-Brentano applications.
Rietveld analysis.
Mostly for powder, bulks and thin film with small preferred
orientation.

.Source: Rh (side window) 3.3mA, 60kV

.6 secondary targets, 2 detector collimators, 3
filters.
.Si (Li) solid state detector.
.Energy resolution 165 meV.

.Elemental identification: Na U.
.Liquids, solids, powder samples.
.Composition: > ppm (some standards available).

93

Recommended literature
Basic applications of x-ray diffraction:
Basic applications of x-ray diffraction:
X-ray diffraction a practical approach, C. Suryanarayana and M.G. Norton.
X-ray diffraction a practical approach, C. Suryanarayana and M.G. Norton.
Introduction to X-Ray Powder Diffractometry, R. Jenkins and R. Snyder,
Introduction to X-Ray Powder Diffractometry, R. Jenkins and R. Snyder,
Wiley-Interscience; 1996.
Wiley-Interscience; 1996.
X-ray characterization of materials, E. Lifshin, Wiley-VCH, 1999.
X-ray characterization of materials, E. Lifshin, Wiley-VCH, 1999.

Residual stress and stress gradients:

Residual stress and stress gradients:
Residual Stress: Measurement by Diffraction and Interpretation, I. C. Noyan
Residual Stress: Measurement by Diffraction and Interpretation, I. C. Noyan
and J. B. Cohen, Springer-Verlag, 1987.
and J. B. Cohen, Springer-Verlag, 1987.
Residual stress/strain analysis in thin films by X-ray diffraction, I.C.
Residual stress/strain analysis in thin films by X-ray diffraction, I.C.
Noyan, T.C. Huang and B.R. York, Critical Reviews in Solid State and Materials
Noyan, T.C. Huang and B.R. York, Critical Reviews in Solid State and Materials
Sciences, 20 (1995) 125 177.
Sciences, 20 (1995) 125 177.

Sample Preparation Methods:

Sample Preparation Methods:
X-ray analysis of clay minerals:
A practical guide for the preparation of specimens for x-ray fluorescence and xX-ray analysis of clay minerals:
A practical guide for the preparation of specimens for x-ray fluorescence and x- X-Ray Diffraction and the Identification and Analysis of Clay Minerals, D.M.
ray diffraction analysis, V.E. Buhrke, R. Jenkins and D.K. Smith; Wiley-VCH,
X-Ray Diffraction and the Identification and Analysis of Clay Minerals, D.M.
ray diffraction analysis, V.E. Buhrke, R. Jenkins and D.K. Smith; Wiley-VCH, Moore and R.C. Reynolds, Oxford University Press, 1997.
1998.
Moore and R.C. Reynolds, Oxford University Press, 1997.
1998.
X-ray fluorescence:
Rietveld Analysis:
X-ray fluorescence:
Rietveld Analysis:
Quantitative x-ray spectrometry, R. Jenkins, R.W. Gould and D. Gedcke,
The Rietveld Method ed. By R.A. Young, Oxford Press, 2000.
Quantitative x-ray spectrometry, R. Jenkins, R.W. Gould and D. Gedcke,
The Rietveld Method ed. By R.A. Young, Oxford Press, 2000.
Marcel Dekker Inc, 1995
Marcel Dekker Inc, 1995
Quantitative x-ray fluorescence analysis theory and application, G.R. Lachance
Thin Analysis by X-ray:
Quantitative x-ray fluorescence analysis theory and application, G.R. Lachance
Thin Analysis by X-ray:
and F. Claisse, Willey, 1995.
Thin Films Analysis by X-ray Scattering, M.Birkholz, Wiley-VCH, 2006
and F. Claisse, Willey, 1995.
Thin Films Analysis by X-ray Scattering, M.Birkholz, Wiley-VCH, 2006
Laue methods:
High-resolution X-ray analysis:
Laue methods:
High-resolution X-ray analysis:
Laue Method, J.L. Amoros, Academic Press Inc., 1975.
X-ray scattering from semiconductors, P. Fewster, Imperial College, 2001.
Laue Method, J.L. Amoros, Academic Press Inc., 1975.
X-ray scattering from semiconductors, P. Fewster, Imperial College, 2001.
High Resolution X-Ray Diffractometry And Topography, D.K. Bowen and B.
High Resolution X-Ray Diffractometry And Topography, D.K. Bowen and B. Two-dimensional XRD (with areal detectors):
K. Tanner, CRC, 1998.
Two-dimensional XRD (with areal detectors):
K. Tanner, CRC, 1998.
Microdiffraction using two-dimensional detectors, B.B. He, Powder Diffraction
High-Resolution X-Ray Scattering: From Thin Films to Lateral Nanostructures
Microdiffraction using two-dimensional detectors, B.B. He, Powder Diffraction
High-Resolution X-Ray Scattering: From Thin Films to Lateral Nanostructures 19 (2004) 110 -118.
(Advanced Texts in Physics), U. Pietsch, V. Holy and T. Baumbach, Springer;
19 (2004) 110 -118.
(Advanced Texts in Physics), U. Pietsch, V. Holy and T. Baumbach, Springer;
2004.
2004.
Fundaments of x-ray scattering:
Fundaments of x-ray scattering:
X-ray diffraction, B.E. Warren, Addison-Wesley, 1962.
Industrial applications of x-ray analysis:
X-ray diffraction, B.E. Warren, Addison-Wesley, 1962.
Industrial applications of x-ray analysis:
X-ray diffraction procedures for polycrystallines and amorphous materials, H.P.
Industrial Applications of X-Ray Diffraction by F. Smith (Editor), CRC, 1999.
X-ray diffraction procedures for polycrystallines and amorphous materials, H.P.
Industrial Applications of X-Ray Diffraction by F. Smith (Editor), CRC, 1999. Klug and L.E. Alexander, Wisley-Interscience, 1974.
X-Ray Metrology in Semiconductor Manufacturing, D.K. Bowen and B.K.
Klug and L.E. Alexander, Wisley-Interscience, 1974.
X-Ray Metrology in Semiconductor Manufacturing, D.K. Bowen and B.K.
Elements of x-ray diffraction, B.D. Cullity, Addison-Wesley, 1978.
Tanner, CRC, 2006.
Elements of x-ray diffraction, B.D. Cullity, Addison-Wesley, 1978.
Tanner, CRC, 2006.
Elements of Modern X-ray Physics, J. Als-Nielsen (Author), D. McMorrow,
Elements of Modern X-ray Physics, J. Als-Nielsen (Author), D. McMorrow,
Wiley, 2001.
Glancing/grazing incidence methods and reflectometry:
Wiley, 2001.
Glancing/grazing incidence methods and reflectometry:
Coherent X-Ray Optics (Oxford Series on Synchrotron Radiation), D. Paganin,
Thin film and surface characterization by specular X-ray reflectivity, E.
Coherent X-Ray Optics (Oxford Series on Synchrotron Radiation), D. Paganin,
Thin film and surface characterization by specular X-ray reflectivity, E.
Oxford University Press, 2006.
Chason and T. M. Mayer, Critical Reviews in Solid State and Materials
Oxford University Press, 2006.
Chason and T. M. Mayer, Critical Reviews in Solid State and Materials
Sciences, 22 (1997) 1 67.
Sciences, 22 (1997) 1 67.
Web resource: www.ccp14.ac.co.uk (free x-ray data analysis programs and
Web resource: www.ccp14.ac.co.uk (free x-ray data analysis programs and
Review on grazing incidence X-ray spectrometry and reflectometry, K.N.
tutorials)
Review
on
grazing
incidence
X-ray
spectrometry
and
reflectometry,
K.N.
Stoev and K. Sakurai, Spectrochimica Acta B: At Spectros, 54 (1999) 41-82.
tutorials)
Stoev and K. Sakurai, Spectrochimica Acta B: At Spectros, 54 (1999) 41-82.
94

47

Acknowledgements
Sponsors:

Frederick Seitz Materials Research Laboratory is

supported by the U.S. Department of Energy
under grants DEFG02-07-ER46453 and DEFG02-07-ER46471
95

48