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Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl.

2010
UHV-based techniques for
surface science and research in
heterogeneous catalysis
Prof. Dr. Karl-Heinz Ernst
Nanoscale Materials Science
Empa, Swiss Laboratories for Materials Science and Technology
08. 11. 2009 9:45-10:30 (HCI H8.1)
10. 11. 2009 8:45-10:30 (HCI H2.1)
ftp://ftp.empa.ch/pub/empa/outgoing/KHErnst/
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Contents
1. Introduction & Nomenclature
1.1. Why ultra-high vacuum? Gas kinetics & vacuum pumps
1.2. The concept of model systems (examples from surface science)
1.2.1. Single crystal surfaces: Miller indices, adsorption sites, coverage,
adsorbate superstructures
1.2.2. Closing the materials and pressure gap: more complex model systems
Examples for application of UHV techniques
2. Probes for surfaces: photons, electrons, ions, etc.
3. Surface structure: Low energy electron diffraction (LEED)
4. Electronic structure and chemical composition
4.1. X-ray photoelectron spectroscopy (XPS)
4.2. Auger electron spectroscopy (AES)
4.3. High-resolution electron energy loss spectroscopy (HREELS)
5. electronic and geometric surface structure: Scanning tunneling microscopy
(STM).
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Short introduction of your docent
Lehre/Berufsfachschule (Professional Training),
Degree: Chemisch-Technischer Assisitent (CTA)
Chemical Engineering at the University of Applied Sciences
(Technische Fachhochschule, TFH) Berlin,
Degree: Chemie-Ingenieur (grad)
Chemistry at Freie Universitt Berlin (FUB),
Degree: Diplom-Chemiker

Graduate Study at the Inst. f. Physical Chemistry, FU Berlin and at the


Berlin Electron Storage Ring for Synchrotron Radiation (BESSY),
(subject: Solid state physics related)
Supervisor: K. Christmann, 2nd thesis expert reader: G. Ertl
Degree: Dr. rer. nat. (PhD)
Habilitation at University Zurich,
Degree: Private Docent

Professor title (University Zurich 2010)


www.empa.mss
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
1988 - 1990 Lecturer in Physical Chemistry, TFH Berlin
1990 - 1991 Post-Doctorate at the University of Washington, Seattle,
USA, Group of Prof. C. T. Campbell
1992 - 1992 Research Associate with the Special Research Fond No. 6
(SFB 6) of the German National Science Foundation (DFG)
at the Free University, Berlin.
1992-present Senior scientist at Empa Dbendorf, since 1998 head of
Surface Technology Group, www.empa.ch/mss
(now Molecular Surface Science Group, MSSG)
8/99-5/2000 On sabbatical leave to UC Berkeley, Department of Physics
and Lawrence Berkeley National Laboratory, California,
USA, Group of Prof. Y.-R. Shen
9/2003-8/2004 On sabbatical leave to Univ. of Washington, Seattle, USA,
Department of Bioengineering, Group of Prof. Viola Vogel
Scientific Publications (Oct. 2010): 109 (68 peer reviewed)
Hobbies: Sailing, Diving, Mountaineering (down-graded now to: hiking)
Professional Experience
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
K. Christmann
Introduction to Surface Physical Chemistry
Steinkopf Verlag Darmstadt 1991
G. Ertl / J. Kppers
Low energy electrons and surface chemistry
VCH, Weinheim 1985
P. D. Woodruff / T. A. Delchar
Modern techniques in surface science
Cambridge University Press, Cambridge 1989
M. Henzler / W. Gpel,
Oberchenphysik des Festkrpers,
Teubner, Stuttgart 1991
A. Zangwill
Physics at Surfaces
Cambridge University Press, Cambridge 1989
R. I. Masel, Principles of Adsorption and Reaction on
Solid Surfaces, Wiley & Sons, New York, 1996
Books on surface science
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Why UHV? Collision frequency of gas particles with a surface
At 300 K and 1 atm for N
2
, Z
A
is
about 3 x 10
23
s
-1
cm
-2
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
At 300 K, if every N
2
molecule that strikes this surface remains adsorbed,
a complete monolayer is formed in about 3 ns.
If p=10
-3
torr (1.3 x 10
-6
atm), t=3x10
-3
s
If p=10
-6
torr (1.3 x 10
-9
atm), t=3 s
If p=10
-9
torr (1.3 x 10
-12
atm), t=3000 s or 50 minutes
Requirement for Experiment in Vacuum: Clean surface quickly becomes
contaminated through molecular collision - p must be less than about
1.3 x 10
-12
atm (10
-9
torr).
10
-10
to 10
-11
torr (UHV - ultrahigh vacuum) is lowest pressure routinely
available in vacuum chamber.
A single crystal surface has about 1 x 10
19
m
-2
atoms (1 x 10
15
cm
-2
)
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
With the assumption of an atom surface density of 310
14
cm
-2
, M = 28 (N
2
for
Air), T = 300 K and a given pressure p, there are ~10
6
[p[mbar] monolayers] of
gas atoms per second adsorbed on the surface. This is with the assumption that
each molecule hitting the surface will be adsorbed (sticking coefficient S = 1).
As a typical surface analytical measurement will take some minutes up to several
hours, a pressure in the range of 10
-10
10
-11
mbar is required. Such low pressures
can be achieved and maintained using Turbo- molecular-, Ion-Getter-, Cryo- and
Oil-Diffusion-Pumps. The following table gives the pressure ranges for different
vacuum regimes.
Pressure Range Vacuum Regime
1-10
-3
mbar Rough Vacuum
10
-3
-10
-5
mbar Medium Vacuum
10
-5
-10
-8
mbar High Vacuum (HV)
Better 10
-9
mbar Ultra High Vacuum (UHV)
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Vacuum pumps
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
real catalyst / real conditions
model catalyst / UHV
real catalyst / UHV
model catalyst / real conditions
A real catalyst is too complex to understand:
The concept of model systems
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
The Noble Prize in Chemistry 2007: Gerhard Ertl
Employing well-defined surfaces as model systems
for heterogeneous catalysis
Heidelberg,
29.06.2007
N
2
+ 3H
2
2NH
3
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Kinetic Oscillations in CO oxidation
work function
measurements
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Ernst et al, J. Catal. 1992
r-WGS reaction over Cu(110)
CO
2
+ H
2
H
2
O + CO
Single crystals allow
normalization to surface sites
and a better comparison with
other catalysts (if the
number of sites is know as
well).
Turn-over rates can be
related to surface structure
and change of such
(reconstruction).
Change in stady-state H-
coverage lifts reconstruction and
induces lower catalyst activity
673 K,
PH2 = 760 torr
573 K,
PH2 = 760 torr
673 K,
PH2 = 110 torr
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Topography of
catalysts via
scanning tunneling
microscopy (STM)
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
z
x
y
y
x
z
y
x
z
c) b) a)
e) f) d)
Close-packed FCC surfaces are common model systems
Single crystal surfaces are ordered systems that allow the use
of diffraction methods
1.2.1. Single crystal surfaces: Miller indices, adsorption sites, coverage,
adsorbate superstructures
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Miller indices
z
x
y y
x
z
y
x
z
c) b) a)
e) f) d)
(100) (110) (111)
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
C
0
C
0
2
= 6.696
C
0
1.4215
Surface science at the (0001) graphite surface
(mainly for self-assembly phenomena at the liquid-solid interface, but
many studies of metal clusters - vacuum and liquid - are known)
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Stepped surfaces as model systems
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
The structure of surfaces
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
422 S.J. Jenkins, S.J. Pratt / Surface Science Reports 62 (2007) 373429
Table 11
Corresponding gure numbers in which top-down views of fcc, bcc and hcp
surfaces from the master hierarchy are presented in the Gazetteer
fcc Fig. bcc Fig. hcp Fig.
{111} 30 {110} 34 {0001} 38
{100} 30 {3032} 39
{211} 35 {3034} 39
{110} 31 {100} 36 {1120} 40
{311} 31 {111} 36 {1122} 40
{210} 32
{531} 33 {321} 35 {1010} 41
{310} 36 {1011} 41
{331} 31 {332} 36 {3038} 41
{211} 31 {411} 36 {3 0 3 10} 41
{511} 31 {433} 36 {4154} 42
{310} 32 {611} 36 {5272} 42
{320} 32 {521} 37 {4156} 42
{321} 33 {543} 37 {1121} 44
{731} 33 {631} 37 {1124} 43
{751} 33 {653} 37 {1126} 43
{421} 33 {4150} 43
{753} 33 {7188} 43
:
:
{4152} 46
{2131} 45
{2130} 43
Fig. 30. The only at fcc surfaces. The {111} and {100} surfaces are triply-
reexive (X
3
) and quadruply-reexive (X
4
) respectively.
Fig. 31. Selected stepped fcc surfaces. All are reexive (X) apart from {110}, which is doubly-reexive (X
2
).
422 S.J. Jenkins, S.J. Pratt / Surface Science Reports 62 (2007) 373429
Table 11
Corresponding gure numbers in which top-down views of fcc, bcc and hcp
surfaces from the master hierarchy are presented in the Gazetteer
fcc Fig. bcc Fig. hcp Fig.
{111} 30 {110} 34 {0001} 38
{100} 30 {3032} 39
{211} 35 {3034} 39
{110} 31 {100} 36 {1120} 40
{311} 31 {111} 36 {1122} 40
{210} 32
{531} 33 {321} 35 {1010} 41
{310} 36 {1011} 41
{331} 31 {332} 36 {3038} 41
{211} 31 {411} 36 {3 0 3 10} 41
{511} 31 {433} 36 {4154} 42
{310} 32 {611} 36 {5272} 42
{320} 32 {521} 37 {4156} 42
{321} 33 {543} 37 {1121} 44
{731} 33 {631} 37 {1124} 43
{751} 33 {653} 37 {1126} 43
{421} 33 {4150} 43
{753} 33 {7188} 43
:
:
{4152} 46
{2131} 45
{2130} 43
Fig. 30. The only at fcc surfaces. The {111} and {100} surfaces are triply-
reexive (X
3
) and quadruply-reexive (X
4
) respectively.
Fig. 31. Selected stepped fcc surfaces. All are reexive (X) apart from {110}, which is doubly-reexive (X
2
).
422 S.J. Jenkins, S.J. Pratt / Surface Science Reports 62 (2007) 373429
Table 11
Corresponding gure numbers in which top-down views of fcc, bcc and hcp
surfaces from the master hierarchy are presented in the Gazetteer
fcc Fig. bcc Fig. hcp Fig.
{111} 30 {110} 34 {0001} 38
{100} 30 {3032} 39
{211} 35 {3034} 39
{110} 31 {100} 36 {1120} 40
{311} 31 {111} 36 {1122} 40
{210} 32
{531} 33 {321} 35 {1010} 41
{310} 36 {1011} 41
{331} 31 {332} 36 {3038} 41
{211} 31 {411} 36 {3 0 3 10} 41
{511} 31 {433} 36 {4154} 42
{310} 32 {611} 36 {5272} 42
{320} 32 {521} 37 {4156} 42
{321} 33 {543} 37 {1121} 44
{731} 33 {631} 37 {1124} 43
{751} 33 {653} 37 {1126} 43
{421} 33 {4150} 43
{753} 33 {7188} 43
:
:
{4152} 46
{2131} 45
{2130} 43
Fig. 30. The only at fcc surfaces. The {111} and {100} surfaces are triply-
reexive (X
3
) and quadruply-reexive (X
4
) respectively.
Fig. 31. Selected stepped fcc surfaces. All are reexive (X) apart from {110}, which is doubly-reexive (X
2
).
422 S.J. Jenkins, S.J. Pratt / Surface Science Reports 62 (2007) 373429
Table 11
Corresponding gure numbers in which top-down views of fcc, bcc and hcp
surfaces from the master hierarchy are presented in the Gazetteer
fcc Fig. bcc Fig. hcp Fig.
{111} 30 {110} 34 {0001} 38
{100} 30 {3032} 39
{211} 35 {3034} 39
{110} 31 {100} 36 {1120} 40
{311} 31 {111} 36 {1122} 40
{210} 32
{531} 33 {321} 35 {1010} 41
{310} 36 {1011} 41
{331} 31 {332} 36 {3038} 41
{211} 31 {411} 36 {3 0 3 10} 41
{511} 31 {433} 36 {4154} 42
{310} 32 {611} 36 {5272} 42
{320} 32 {521} 37 {4156} 42
{321} 33 {543} 37 {1121} 44
{731} 33 {631} 37 {1124} 43
{751} 33 {653} 37 {1126} 43
{421} 33 {4150} 43
{753} 33 {7188} 43
:
:
{4152} 46
{2131} 45
{2130} 43
Fig. 30. The only at fcc surfaces. The {111} and {100} surfaces are triply-
reexive (X
3
) and quadruply-reexive (X
4
) respectively.
Fig. 31. Selected stepped fcc surfaces. All are reexive (X) apart from {110}, which is doubly-reexive (X
2
).
422 S.J. Jenkins, S.J. Pratt / Surface Science Reports 62 (2007) 373429
Table 11
Corresponding gure numbers in which top-down views of fcc, bcc and hcp
surfaces from the master hierarchy are presented in the Gazetteer
fcc Fig. bcc Fig. hcp Fig.
{111} 30 {110} 34 {0001} 38
{100} 30 {3032} 39
{211} 35 {3034} 39
{110} 31 {100} 36 {1120} 40
{311} 31 {111} 36 {1122} 40
{210} 32
{531} 33 {321} 35 {1010} 41
{310} 36 {1011} 41
{331} 31 {332} 36 {3038} 41
{211} 31 {411} 36 {3 0 3 10} 41
{511} 31 {433} 36 {4154} 42
{310} 32 {611} 36 {5272} 42
{320} 32 {521} 37 {4156} 42
{321} 33 {543} 37 {1121} 44
{731} 33 {631} 37 {1124} 43
{751} 33 {653} 37 {1126} 43
{421} 33 {4150} 43
{753} 33 {7188} 43
:
:
{4152} 46
{2131} 45
{2130} 43
Fig. 30. The only at fcc surfaces. The {111} and {100} surfaces are triply-
reexive (X
3
) and quadruply-reexive (X
4
) respectively.
Fig. 31. Selected stepped fcc surfaces. All are reexive (X) apart from {110}, which is doubly-reexive (X
2
).
422 S.J. Jenkins, S.J. Pratt / Surface Science Reports 62 (2007) 373429
Table 11
Corresponding gure numbers in which top-down views of fcc, bcc and hcp
surfaces from the master hierarchy are presented in the Gazetteer
fcc Fig. bcc Fig. hcp Fig.
{111} 30 {110} 34 {0001} 38
{100} 30 {3032} 39
{211} 35 {3034} 39
{110} 31 {100} 36 {1120} 40
{311} 31 {111} 36 {1122} 40
{210} 32
{531} 33 {321} 35 {1010} 41
{310} 36 {1011} 41
{331} 31 {332} 36 {3038} 41
{211} 31 {411} 36 {3 0 3 10} 41
{511} 31 {433} 36 {4154} 42
{310} 32 {611} 36 {5272} 42
{320} 32 {521} 37 {4156} 42
{321} 33 {543} 37 {1121} 44
{731} 33 {631} 37 {1124} 43
{751} 33 {653} 37 {1126} 43
{421} 33 {4150} 43
{753} 33 {7188} 43
:
:
{4152} 46
{2131} 45
{2130} 43
Fig. 30. The only at fcc surfaces. The {111} and {100} surfaces are triply-
reexive (X
3
) and quadruply-reexive (X
4
) respectively.
Fig. 31. Selected stepped fcc surfaces. All are reexive (X) apart from {110}, which is doubly-reexive (X
2
).
422 S.J. Jenkins, S.J. Pratt / Surface Science Reports 62 (2007) 373429
Table 11
Corresponding gure numbers in which top-down views of fcc, bcc and hcp
surfaces from the master hierarchy are presented in the Gazetteer
fcc Fig. bcc Fig. hcp Fig.
{111} 30 {110} 34 {0001} 38
{100} 30 {3032} 39
{211} 35 {3034} 39
{110} 31 {100} 36 {1120} 40
{311} 31 {111} 36 {1122} 40
{210} 32
{531} 33 {321} 35 {1010} 41
{310} 36 {1011} 41
{331} 31 {332} 36 {3038} 41
{211} 31 {411} 36 {3 0 3 10} 41
{511} 31 {433} 36 {4154} 42
{310} 32 {611} 36 {5272} 42
{320} 32 {521} 37 {4156} 42
{321} 33 {543} 37 {1121} 44
{731} 33 {631} 37 {1124} 43
{751} 33 {653} 37 {1126} 43
{421} 33 {4150} 43
{753} 33 {7188} 43
:
:
{4152} 46
{2131} 45
{2130} 43
Fig. 30. The only at fcc surfaces. The {111} and {100} surfaces are triply-
reexive (X
3
) and quadruply-reexive (X
4
) respectively.
Fig. 31. Selected stepped fcc surfaces. All are reexive (X) apart from {110}, which is doubly-reexive (X
2
).
Selected fcc surfaces
S.J. Jenkins, S.J. Pratt / Surface Science Reports 62 (2007) 373429 423
Fig. 32. Selected achiral kinked fcc surfaces. All are reexive (X).
Fig. 34. The only at bcc surface. It is doubly-reexive (X
2
).
Fig. 35. Selected stepped bcc surfaces; note that the {211} surface is reexive
(X) and therefore achiral, whereas all other stepped bcc surfaces including
{321} are chiral (D, L).
Fig. 33. Selected chiral (D, L) kinked fcc surfaces.
S.J. Jenkins, S.J. Pratt / Surface Science Reports 62 (2007) 373429 423
Fig. 32. Selected achiral kinked fcc surfaces. All are reexive (X).
Fig. 34. The only at bcc surface. It is doubly-reexive (X
2
).
Fig. 35. Selected stepped bcc surfaces; note that the {211} surface is reexive
(X) and therefore achiral, whereas all other stepped bcc surfaces including
{321} are chiral (D, L).
Fig. 33. Selected chiral (D, L) kinked fcc surfaces.
S.J. Jenkins, S.J. Pratt / Surface Science Reports 62 (2007) 373429 423
Fig. 32. Selected achiral kinked fcc surfaces. All are reexive (X).
Fig. 34. The only at bcc surface. It is doubly-reexive (X
2
).
Fig. 35. Selected stepped bcc surfaces; note that the {211} surface is reexive
(X) and therefore achiral, whereas all other stepped bcc surfaces including
{321} are chiral (D, L).
Fig. 33. Selected chiral (D, L) kinked fcc surfaces.
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
S.J. Jenkins, S.J. Pratt / Surface Science Reports 62 (2007) 373429 423
Fig. 32. Selected achiral kinked fcc surfaces. All are reexive (X).
Fig. 34. The only at bcc surface. It is doubly-reexive (X
2
).
Fig. 35. Selected stepped bcc surfaces; note that the {211} surface is reexive
(X) and therefore achiral, whereas all other stepped bcc surfaces including
{321} are chiral (D, L).
Fig. 33. Selected chiral (D, L) kinked fcc surfaces.
fcc surfaces without mirror planes
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
S.J. Jenkins, S.J. Pratt / Surface Science Reports 62 (2007) 373429 423
Fig. 32. Selected achiral kinked fcc surfaces. All are reexive (X).
Fig. 34. The only at bcc surface. It is doubly-reexive (X
2
).
Fig. 35. Selected stepped bcc surfaces; note that the {211} surface is reexive
(X) and therefore achiral, whereas all other stepped bcc surfaces including
{321} are chiral (D, L).
Fig. 33. Selected chiral (D, L) kinked fcc surfaces.
Selected bcc surfaces
S.J. Jenkins, S.J. Pratt / Surface Science Reports 62 (2007) 373429 423
Fig. 32. Selected achiral kinked fcc surfaces. All are reexive (X).
Fig. 34. The only at bcc surface. It is doubly-reexive (X
2
).
Fig. 35. Selected stepped bcc surfaces; note that the {211} surface is reexive
(X) and therefore achiral, whereas all other stepped bcc surfaces including
{321} are chiral (D, L).
Fig. 33. Selected chiral (D, L) kinked fcc surfaces.
424 S.J. Jenkins, S.J. Pratt / Surface Science Reports 62 (2007) 373429
Fig. 36. Selected achiral kinked bcc surfaces. All are reexive (X) except for {111} and {100}, which are triply-reexive (X
3
) and quadruply-reexive (X
4
)
respectively.
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
S.J. Jenkins, S.J. Pratt / Surface Science Reports 62 (2007) 373429 425
Fig. 37. Selected chiral (D, L) kinked bcc surfaces.
Fig. 38. The only at hcp surface. It is a bayonet surface and designated XX
6
o
.
Selected hcp surfaces
426 S.J. Jenkins, S.J. Pratt / Surface Science Reports 62 (2007) 373429
Fig. 39. The only interrupted-at hcp surfaces. These surfaces are uniterminated-reexive and designated XXu.
Fig. 40. The only meandering row hcp surfaces. The {11

22} surface is glissadic (XX), whereas {11

20} is reexive-glissadic (XX


2

).
S.J. Jenkins, S.J. Pratt / Surface Science Reports 62 (2007) 373429 427
Fig. 41. Selected stepped hcp surfaces. Note that {10

10} is doubly-reexive (XX


2

, XX
2

) with (, ) (, ), whereas {10

11} is reexive (XX

, XX

) with
(, ) (, ). In contrast, {30

38} and {3 0 3 10} are both uniterminated-reexive surfaces (XX


u
).
Fig. 42. Selected geminal hcp surfaces. All such surfaces are pure one-chiral (DX
u
, LX
u
).
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
2.1 GaAs-Oberachen
f
s
1
(a)
s
2
v
s
(b)
Abbildung 2.2: (a) Facettierte Oberache. Die ideale Oberache f zerfallt in die benachbarten
Flachen s
1
und s
2
. (b) Vizinalache. Die Orientierung der idealen Oberache v weicht um
einen kleinen Winkel von der Orientierung der stabilen Oberache s ab.
Eine ubersichtliche Darstellung der verschiedenen Orientierungen lat sich durch
eine stereograsche Projektion in die Ebene erreichen (ausf uhrlich z. B. in Ref. [32]).
Die stereograsche Projektion ist winkeltreu, so da sich Winkel zwischen verschie-
denen Flachen direkt bestimmen lassen. Aufgrund der Kristallsymmetrie sind viele
Ebenen aquivalent, insbesondere solche, deren Indizes durch zyklisches Vertauschen
auseinander hervorgehen [(11n) entspricht (n11)]. Daher gen ugt es f ur viele Zwecke,
die Projektion auf das stereograsche Dreieck zwischen (001), (011) und (111) zu be-
schranken (Abb. 1.1 auf S. 11).
Die drei niederindizierten Flachen an den Ecken des Dreiecks bilden eine Basis der
Kristallstruktur. Alle hoherindizierten Oberachen lassen sich aus diesen drei Flachen
aufbauen. Orientierungen, die auf den Seiten des Dreiecks liegen, sind Kombinationen
der Flachen an den jeweiligen Ecken. So sind z. B. die Flachen mit den Miller-Indizes
(11n) aus (111) und (001) zusammengesetzt (vgl. Abb. 5.1(b) auf S. 56). Aufgrund
dieser

Uberlegungen sieht man auch leicht, da (1 1 25) = 1 (111) + 24 (001) vizinal
zu (001) liegt. Allgemeing ultig ist das in diesem Absatz Dargestellte jedoch nur f ur
die idealen Oberachen. Auf GaAs(113) etwa bildet sich eine stabile Struktur, die
unabhangig von niederindizierten Oberachen ist [2, 3].
Als Zone bezeichnet man die Menge aller Flachen, die durch Drehung um eine be-
stimmte Achse ineinander ubergehen. Die Richtung dieser Achse gibt der Zone ihren
Namen. Untersuchungen auf Oberachen der [

110]-Zone waren der Ausgangspunkt der


vorliegenden Arbeit. In Abb. 2.3 ist diese Zone dargestellt. In ihr liegen die Ebenen
mit den Indizes (11n). Die Winkel zwischen diesen Flachen sind in Tab. 2.1 zusam-
mengefat.
Bei Galliumarsenid sind die beiden durch Aufschneiden eines Kristalls erzeugten
Oberachen, also Vorder- und R uckseite, in der Regel nicht aquivalent, da der Sto aus
17
A surface of arbitrary orientation usually has a high surface energy. It
is common that the real surface deviates substantially from its
orientation and forms facets of the next most stable face (a) or close to
the original orientation exists a stable vicinal surface.
Faceting and vicinal surfaces
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
More realistic surface model
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Rekonstruktion, Relaxation
Relaxation: Vernderung der
Gitterkonstante senkrecht zur
Oberflche
Rekonstruktion: Parallel zur
Oberflche werden Atome neu
Angeordnet (grssere Einheitszelle)
z.B. 2x1 oder 7x7
Reconstructions and relaxation:
In reality the surface deviates from the bulk plane periodicity.
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
missing row reconstruction of clean surfaces
Pt(110) 1x2 reconstruction
Pt(110) 1x1
[001]
[110]
(111) micro facet
(CO adsorption lifts
reconstruction and creates
(1x1) surface!)
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Relaxation directly under a single molecule
The Cu step atom of a (211) surface is lifted
under a propene molecule (DFT calculation)
Rekonstruktion, Relaxation
Relaxation: Vernderung der
Gitterkonstante senkrecht zur
Oberflche
Rekonstruktion: Parallel zur
Oberflche werden Atome neu
Angeordnet (grssere Einheitszelle)
z.B. 2x1 oder 7x7
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
46 W. Reimer et aL / LEED analysis of the (2 X 1)H-Ni(110) structure
0 = 1.5 [5]. At T>~ 200 K a local reconstruction into a one-dimensionally
disordered phase starts already at rather low coverages [6]; it equally exhibits a
(1 2) pattern.
The present work is concerned with a LEED structural analysis of the low
t emperat ure (2 X 1) phase at 0 = 1.0 (There is strong evidence that the derived
local geomet ry of the adsorption site equally holds for all of the lattice gas
pha s e s a t O H ~< 1.0, e.g. by the coverage independent magni t udes of the
adsorpt i on energy, the frequency of the Ni - H vibration and the change in
work function in this coverage range).
Before starting the analysis of the adsorbat e covered system, also the
structure of the clean Ni ( l l 0) surface was determined. A full account of the
LEED structure analysis itself will be given elsewhere [7], in addition a similar
analysis of the (1 2) reconstructed surface was reported recently [8].
The LEED pat t ern of the (2 x 1)H phase is characterized by a systematic
extinction of the (0, n/ 2) beams at normal incidence indicating the presence
of a glide symmet ry pl ane [9] and thus of two H at oms per unit cell [2]. Based
on He diffraction experiments Rieder and Engel [2] proposed a structural
model which is reproduced in fig. l a and whereafter the adsorbed at oms form
a)
[110]
YH
]( %( o,,
,,' [0011 , [0011
b)
[110]
yH
dl
Z H
d12
[110] d23
L,,,[l'lo]
, 1001] - ' I 001]
Fig. 1. Models of the (2 x 1)H-Ni(110) structure: (a) for H atoms on quasi-threefold sites, top
view; (b) for H atoms on long-bridge sites, top view; (c) side view illustrating the structural
parameters; (d) geometry of the local Ni3-H adsorption cluster.
d
12
= 1.18
d
23
= 1.32
d
34
= 1.25
d
bulk
= 1.25
Relaxation p2mg (2x1)2H / Ni(110)
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Superstructures: Wood notation
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010

b
1
b
2






=
m
11
m
12
m
21
m
22






a
1
a
2






c)
a
2
a
1
b
1
b
2
a)
a
2
a
1
b
1
b
2
b)
a
2
a
1
b
1
b
2

2 0
0 2






Superstructures: Matrix notation

1 1
1 1







2 1
1 1






Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Adsorption sites
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Coverage
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
E
(x,y)
(
ad
t
(x,y)
t
t
E
(x,y)
repulsive t
a) b) c)
attractive t
x,y x,y x,y
(
diff
Ordered layers can only form with sufficient surface diffusion (a)
Adsorption energy is modulated via substrate corrugation (a) plus by lateral
interaction between adsorbed species (b)
When repulsion matches adsorption energy, saturation coverage is reached.
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
1.2.2. Closing the materials and pressure gap: more complex model systems
Examples for application of UHV techniques
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Closing the pressure and the materials gap
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Stable configurations of small clusters
Side length of the cube 1 nm 1 m 1mm
Number of bulk atoms (N
B
) 1 2.710
10
2.710
19

Number of surface atoms (N
S
) 29 5.410
7
5.410
13

NS/(N
B
+N
S
) 0.96 210
-3
210
-6

Number of edge atoms 12 3.610
4
3.610
7

Number of corner atoms 8 8 8
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Normalization of turnover rate w/surface sites
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Electronic structure related to cluster size: XPS
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Melting Point of Gold (Au)
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Relevant interactions for surface analytical methods
2. Probes for surfaces: photons, electrons, ions, etc
Photons
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Surface sensitive methods for elemental, chemical and structural analysis can
be achieved by using particles for excitation or detection, which interact
strongly with matter. With other words using particles with a very short mean
free path in matter.
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Inelastic mean free path of electrons as a function of the electron
energy for different materials. As can be seen is very energy but not
very material dependent.
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
3. Surface structure: Low energy electron diffraction (LEED)
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
fluorescent
screen
d
i
f
f
r
a
c
t
e
d

b
e
a
m
g
u
n
in
c
id
e
n
t
b
e
a
m
two dimensional
crystal lattice
(magnified)
diffraction
spots
Surface structure: Low energy electron diffraction (LEED)
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Primary electron energy 20 - 1000 eV
Ni(111)
sin 1/E)
= h/(2 m
e
e

U)
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
150 eV 250 eV
650 eV
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
125
DEUTSCHE BUNSEN-GESELLSCHAFT
UNTERRICHT
respect to the exact positions of atoms at a surface is some-
what more complicated and requires fully dynamical quantum
mechanical scattering calculations.
The use of LEED as a standard technique for surface analysis
started in the early 1960s when large enough single crystals
and commercial instruments became available for surface
studies. At rst the technique was only used for qualitative
characterization of surface ordering and the identication of
two-dimensional superstructures. The quantitative information
about the positions of the atoms within the surface is hidden
in the energy-dependence of the diffraction spot intensities,
the so-called LEED I-V, or I(E), curves. Computer programs and
the computer power to analyze these data became available in
the 1970s. With the ever growing speed of modern computers
LEED-IV structure determination has been applied to increas-
ingly complex surface structures. To date LEED is the most pre-
cise and versatile technique for surface crystallography.
For further information about the history, experimental setup,
and theoretical approaches of LEED refer to the books by Pen-
dry, [Pend74], Van Hove and Tong [Vanh79], Van Hove, Wein-
berg and Chan [Vanh86], and Clarke [Clar85]. The present ar-
ticle makes extensive use of these works.
2 BASIC PRINCIPLES
The basic principle of a standard LEED experiment is very sim-
ple: a collimated mono-energetic beam of electrons is directed
towards a single crystal surface and the diffraction pattern of
the elastically back-scattered electrons is recorded using a
position-sensitive detector. For electrons, like for all wave-like
objects, the angular intensity distribution due to the interfer-
ence of partial waves back-scattered from a periodic array is
described by Braggs law or, more conveniently, by a set of
Laue equations, one for each dimension of periodicity, which
predict a regular pattern of diffraction spots.
2.1 SURFACE PERIODICITY AND RECIPROCAL LATTICE
Because of the short penetration depth of low-energy elec-
trons the diffraction process is determined by a small number
of atomic layers at the crystal surface. The electrons do not
probe the full crystal periodicity perpendicular to the surface.
Therefore, the array of relevant scatterers is only periodic in
two dimensions. The surface lattice can be described by a pair
of lattice vectors a
1
and a
2
, which are parallel to the surface
plane, and the surface unit cell, i.e. the contents of the paral-
lelogram spanned by a
1
and a
2
. The surface consists of identi-
cal copies of the unit cell at every point
R = m
1
a
1
+ m
2
a
2
(3)
with integer numbers m
1
and m
2
. The left hand side of Figure
1 illustrates common square, rectangular and hexagonal sur-
faces and the lattice vectors dening their unit cells.
The two-dimensional Laue equations are based on reciprocal
lattice vectors within the surface plane which are dened by
the real space lattice vectors through a set of four simultane-
ous equations:
a
1
a*
1
= 2p a
2
a*
2
= 2p (4a)
a
1
a*
2
= 0 a
2
a*
1
= 0 (4b)
Figure 1 (left from top to bottom) arrangement of atoms in the {100} (square)
{110} (rectangular) and {111} (hexagonal) surfaces of a simple face cen-
tered cubic crystal lattice and a p(2x1) superstructure on a square surface;
the diagrams include lattice vectors defining the surface unit cell and the
corresponding reciprocal lattices (right).
a
1
a
2
a
1
a
2
a
*
1
a
*
2
a
*
1
a
*
2


b
*
1
b
*
2
a
1
a
2
a
*
1
a
*
2
b
2
b
1

In order for the scalar products in (4a) to be dimensionless, the
reciprocal lattice vectors must have units of inverse length, nm
-1
.
As a consequence of (4b) a*
2
and a*
1
must be perpendicular
to a
1
and a
2
, respectively, which means that a rectangular real-
space lattice will also have a rectangular reciprocal lattice. For
non-rectangular lattices the angles are different in real space
and reciprocal space. The right-hand column of Figure 1 shows
the corresponding reciprocal lattices for each of the surfaces on
the left. The reciprocal lattice vectors dene the positions of the
diffraction maxima through the Laue equation (5).
k
||,out
(n
1
,n
2
) = k
||,in
+ n
1
a*
1
+ n
2
a*
2
(5)
k
||,out
is the component of the wave vector of the diffracted
electrons, which is parallel to the surface plane (by conven-
62 3 Experimentelles
Ru
CO
Ru
CO
a
/

3
a
Abbildung 3.16:
Adsorptionsstruktur von CO
auf Ru(001). Oben: Strukturmo-
dell und LEED-Bild (k-Raum)
der (

3)R30

CO-Bedeckung
(0.33 ML). Weitere Adsorption
von CO f uhrt zur Komprimierung
dieser Struktur bis zur CO-Satti-
gungsbedeckung (0.68 ML), deren
LEED-Bild im unteren Teil darge-
stellt ist.
Ru
CO
CO
CO
CO
3.4.3 Das Koadsorbatsystem CO/O/Ru(001)
Sauersto adsorbiert dissoziativ, also atomar auf Ruthenium.[Ove98, Ove96] Die
Bindungsenergie ist abhangig von der Bedeckung und betragt f ur 0.5 ML pro
Sauerstoatom E
B
=4.9 eV.[Ove98, Sta96] Die Adsorption erfolgt an dreifach ko-
ordinierten (hcp-hollow-)Platzen. Im Folgenden soll nur die (21)O-Bedeckung
(0.5 ML) bzw. die entsprechende Mischbedeckung mit CO diskutiert werden, da
diese Ausgangspunkt der durchgef uhrten Experimente ist. Sie wird anhand von
Referenzspektren prapariert, siehe hierzu Abbildung 3.18. Das LEED-Bild der
(21)O-Bedeckung ist im rechten Teil von Abbildung 3.17 dargestellt, es zeigt
eine (22)-Symmetrie da es uber drei mogliche Ausrichtungen der (21)-Struktur
gemittelt ist.
Die maximale CO-Bedeckung auf dieser O-Bedeckung betragt ca. 0.2 ML, was
einer (22)-Struktur entspricht. F ur das Gesamtsystem werden zwei unterschied-
liche Strukturen diskutiert.[Hof91, Kos92] Die sogenannte Honigwabenstruktur
ist im linken Teil von Abbildung 3.17 dargestellt. Gegen uber einer (21)O-
Struktur hat jedes zweite O-Atom einen Platzwechsel vollzogen, der auf der nur
mit O-Bedeckten Oberache energetisch ung unstig ware. Die Gesamtenergie der
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
128
BUNSEN-MAGAZIN 12. JAHRGANG 4/2010
UNTERRICHT
the uorescent screen have become commercially available in
recent years for applications that require low incident beam
currents, either to avoid beam damage (e.g. organic molecules)
or charging of insulating samples (e.g. oxides). These systems
can be operated with electron currents as low as 1 nA. Typical
LEED systems have diameters of around 140 mm.
The LEED pattern is recorded using a video camera with suit-
able image processing software. As with all methods that use
electrons as probes, vacuum conditions are required because
electrons cannot penetrate a gas atmosphere at normal pres-
sures. In general, however, the vacuum conditions required to
avoid contamination of clean surfaces are more rigorous (typi-
cally < 10
-9
mbar) than those imposed by the use of electrons
(typically < 10
-6
mbar).
4 APPLICATIONS
In this section we will discuss a small selection of typical ap-
plications of LEED in order to illustrate the different levels
at which this technique yields information about surface ge-
ometries.
4.1 LEED PATTERN: CO ON NI{111}
The adsorption of carbon monoxide on the {111} surface of
nickel is a good example how LEED diffraction patterns can
be used for a simple characterization of adsorbate structures.
With increasing coverage of CO adsorbed on Ni{111} four dif-
ferent LEED patterns are observed between about 0.30 and
0.62ML (1 ML corresponds to 1 molecule per substrate sur-
face atom):
a diffuse [2 1; -1 1] or p(3 x 3) R30 pattern between 0.3
and 0.4 ML,
a sharp [2 0; 1 2] or c(2 x 4) pattern for coverage around
0.5 ML,
a sharp [3 1; -1 2] or p(7 x 7) R19 pattern between 0.56
and 0.60 ML,
a more complicated [3 2; -1 2] pattern at the maximum cov-
erage of 0.62 ML, which is described as c(23 x 4)rect in
non-standard Wood notation.
Images of the rst three patterns are depicted in Figure 5 to-
gether with the corresponding real-space unit cells (red arrows
and dashed lines). The middle part of the Figure also shows
the complete (2x4) unit cell (in black). Note that the c in the
Wood notation c(2 x 4) means that the center and the corners
of the (2x4) unit cell are lattice points. Therefore the primitive
unit cell is only half the size, as indicated by the red arrows.
The matrix notation always refers to the primitive unit cell. The
yellow arrows in the LEED patterns (left) indicate the reciprocal
lattice vectors corresponding to the unit cells marked in red.
For the c(2 x 4) and p(7 x 7) R19 structures it is not pos-
sible to reach all diffraction spots by adding integer multiples
of these two vectors. This is because the observed pattern is
a superposition of LEED patterns arising from different parts
of the surface, where the ordered arrangements of molecules
are the same in principle but may have different orientations.
Such rotation or mirror domains are usually observed if the
superstructure has lower symmetry than the underlying sub-
strate alone. Any symmetry operation of the substrate surface
(rotation or mirror) that is not shared with the superstructure
will therefore convert the superstructure unit cell into a unit
cell that is equivalent but has a different orientation. This new
unit cell has a different reciprocal lattice with a new set of dif-
fraction spots. All orientation domains are equivalent and will,
therefore, cover equal areas of the surface. In the case of the
c(2 x 4) superstructure, which has a rectangular unit cell, the
missing symmetry is the three-fold rotation of the hexagonal
substrate surface; therefore there are two additional rotational
Figure 5: Experimental LEED patterns formed by CO adsorbed on Ni{111}
(left) and corresponding real-space unit cells (right): p(3 x 3) R30 (top,
E
kin
= 98eV) c(2 x 4) (middle, E
kin
= 129eV) and p(7 x 7) R19 (bottom,
E
kin
= 117eV). Note that the real space diagrams are rotated by about 30
with respect to the crystal orientation of the experiment; the dark structure
extending from the top left to the middle of the LEED patterns is the shadow
of the electron gun [Held98].
=0.33ML:p(3x3)R30
a
1
a
2
21
11
M=


=0.50ML:c(2x4)
a
1
a
2
20
12
M=


=0.57ML:p(7x7)R19
a
1
a
2
31
12
M=

CO / Ni(111)
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
a) b)

[001]
[110]
_
Mirror domains
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Superstructures
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
The adsorption site is not available
via static LEED
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Complete surface structure via dynamical I-V LEED and multiple
scattering theory
S.J. Jenkins, S.J. Pratt / Surface Science Reports 62 (2007) 373429 427
Fig. 41. Selected stepped hcp surfaces. Note that {10

10} is doubly-reexive (XX


2

, XX
2

) with (, ) (, ), whereas {10

11} is reexive (XX

, XX

) with
(, ) (, ). In contrast, {30

38} and {3 0 3 10} are both uniterminated-reexive surfaces (XX


u
).
Fig. 42. Selected geminal hcp surfaces. All such surfaces are pure one-chiral (DX
u
, LX
u
).
S.J. Jenkins, S.J. Pratt / Surface Science Reports 62 (2007) 373429 427
Fig. 41. Selected stepped hcp surfaces. Note that {10

10} is doubly-reexive (XX


2

, XX
2

) with (, ) (, ), whereas {10

11} is reexive (XX

, XX

) with
(, ) (, ). In contrast, {30

38} and {3 0 3 10} are both uniterminated-reexive surfaces (XX


u
).
Fig. 42. Selected geminal hcp surfaces. All such surfaces are pure one-chiral (DX
u
, LX
u
).
A
Fig. 1. (a) Top- (b) side-view of the two possible terminations
(A&) of a hccp (10%) surface.
ature could be controlled by a NiCi-Ni thermo-
couple spot-welded to the edge of the sample.
Further crystal preparatian in vacuum con-
sisted of cycles of argon sputtering at 3~-500 eV
ion energy and beam currents of 3-6 PA/cm
whereby the sample temperature was successively
increased up to 500 K followed by cycles of an-
nealing at 680 K. Since a phase transition from
the hcp to the fee phase occurs at 700 K much
Fig. 2. I&ED-pattern of the clean co(lOiO) surface at an
electron energy E, = 66 eV.
care was taken not to reach sample temperatures
above 680 K. After numerous sputter.-annealing
cycles only small amounts of carbon remained at
the surface which could be reactively removed by
oxygen at 650 K. Traces of oxygen impurity could
be reacted off by hydrogen at 680 K. The cleanli-
ness of the surface could be controlled very sensi-
tively by HREELS. A LEED pattern of the clean
surface at an electron energy E, = 66 eV is shown
in fig. 2.
LEED I/ 1/ curves were measured and recorded
by means of a video (auto) LEED system devel-
e ne r gy ieV)
Fig. 3. Experimental I/Y curves of four s~mmet~-equivalent
LEED-beams: (1.2). (I.?). f%.2) and ii.?).
H. Over et al. / A LEED structural analysis of the Co(lOi0) surface
Comparison of multilayer relaxations Ad,, and Ad,, for some rectangular single crystal surfaces
Cu(ll0) [24] Al(110) [25] Re(lOi0) [l] Fe(211) [26] c0(1010)
- 8.5( * 0.7)% - 8.4( * O.S)% - 17% - 10% - 12.8( ?0.5)%
+ 2.3( k 0.9)% + 4.9( f 1 .O)% + l-2% 1-58 + 0.76( k 0.2)%
for both crystals Re(lOi0) and Co(lOi0) indicat-
ing a similar relaxation mechanism for these hcp
surfaces.
To summarize, our LEED analysis of the clean
Co(lOi0) surface reveals that only termination A
represents the stable atomic configuration in the
surface, exhibiting a contraction of the first sub-
plane spacing by 123 *OS)% and no further re-
laxation deeper in the bulk. We note that the same
termination (A) was found previously for the clean
Re(lOi0) surface [l].
We thank Dr. A. Preusser for technical assis-
tance.
Note added in proof
After acceptance of our Letter a recent LEED
analysis from Lindroos et al. [27] concerning The
termination and multilayer relaxation at the Co-
(1010) surface was brought to our knowledge.
The Z/V curves of Lindroos et al. are in good
agreement with our results, but a discrepancy oc-
curs with respect to the magnitude of the first
layer contraction. While Lindroos et al. ascer-
tained a contraction of -6.5( *2)% we de-
termined a larger contraction of - 12.8( f 0.5)s.
References
[l] H.L. Davis and D.M. Zehner, J. Vat. Sci. Technol. 17
(1980) 190.
[2] G.L.P. Bertring, Surf. Sci. 61 (1976) 673.
[3] G.L.P. Berning, G.P. Alldredge and P.E. Viljoen, Surf.
Sci. 104 (1981) L225.
[4] B.W. Lee, R. Alsenz, A. Ignatiev and M.A. Van Hove,
Phys. Rev. B 17 (1978) 1510.
[5] M. Welz, W. Moritz and D. Wolf, Surf. Sci. 125 (1983)
473.
[6] G. Kleinle, W. Moritz, D.L. Adams and G. Ertl. Surf. Sci.
219 (1989) L637.
[7] K.-H. Ernst, E. Schwarz and K. Christmann. in prepara-
tion.
[8] K. Mliller and K. Heinz, in: The Structure of Surfaces,
Eds. S.Y. Tong and M.A. Van Hove (Springer, Berlin.
1986) p.105.
[9] M.A. Van Hove and S.Y. Tong, Surface Crystallography
by LEED, Springer Series in Chemical Physics (Springer.
Berlin, 1979).
[lo] W. Moritz, J. Phys. C 17 (1984) 353.
[ll] M. Maglietta, E. Zanazzi, F. Jona, D.W. Wepsen and
P.M. Marcus, Appl. Phys. 15 (1978) 409.
[12] L. Hedin and B.I. Lundquist, J. Phys. G 4 (1971) 2064.
[13] D.W. Marquardt, J. Sol. Indust. Appl. Math. 11 (1963)
431.
[14] G. KIeinle. W. Moritr and G. Ertl, Surf. Sci. 238 (1990)
119.
[15] G. Kleinle, Thesis, Freie Universitlt Berlin (1989).
[16] (a) P.J. Rous, J.B. Pendry, D.K. Saldin. K. Heinz, K.
Mliller and N. Bickel, Phys Rev. Lett. 57 (1986) 2950;
(b) P.J. Rous and J.B. Pendry, Comput. Phys. Commun.
54 (1989) 137.
[17] W. Moritz, H. Over, G. Kleinle, G. Ertl, in: The Structure
of Surfaces III, Eds. M.A. Van Hove, S.Y. Tong and Xie
Xide (Springer, Berlin, 1990) in press.
[18] H. Over, U. Ketterl, W. Moritz and G. Ertl, m prepara-
tion.
[19] G. Kleinle, J. Wintterlin, G. Ertl, R.J. Behm, F. Jona and
W. Moritz, Surf. Sci. 225 (1990) 171.
[20] E. Zanazzi and F. Jona, Surf. Sci. 62 (1977) 61.
[21] J.B. Pendry, J. Phys. C 13 (1980) 937.
[22] A. Preusser, Comput. Aided Geom. Design 3 (1986) 267.
[23] D.L. Adams, W.T. Moore and K.A.R. Mitchell, Surf. Sci.
149 (1985) 407.
[24] D.L. Adams, H.B. Nielsen, J.N. Andersen, 1. Steensgaard,
R. Feidenhansl and J.E. Sorensen, Phys. Rev. Lett. 49
(1982) 669.
[25] H.B. Nielsen, J.N. Andersen. L. Petersen and D.L. Adams,
.I. Phys. C. 15 (1982) L1113.
[26] J. Sokolov, H.D. Shih, U. Bardi, S. Jona and P.M. Marcus,
Solid State Commun. 48 (1983) 739.
[27] M. Lindroos, C.J. Barnes, P. Hu and D.A. King, Chem.
Phys. Lett. 173 (1990) 92.
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Absorption very fast - ~10
-16
s
- no photoemission for
- KE of photoelectron increases as BE decreases
- intensity of photoemission goes with intensity of photons
- need monochromatic (x-ray) incident beam
- a range of KEs can be produced if valence band is broad
- since each element has unique set of core levels, KEs can
be used to fingerprint element
Binding energy (BE) represents strength of interaction
between electron (n, l, m, s) and nuclear charge.
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Binding energy for different electron core levels
as a function of the atomic number
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
E
Kin
= E
B
E
B
= E
f
tot
(N-1) - E
i
tot
(N)
E
Kin
E
B
but relaxation occurs!
N-1 electrons react
on the created hole
RELAXATION
! E
B
smaller as E
0
Koopmans Theorem:
(frozen orbital approximation)
N-1 electrons do not
react on the hole
creation
E
B
= Orbital
eigenenergy = E
0
E
Kin
E
B
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Koopman's Theorem
The BE of an electron is simply difference between initial state (atom with
n electrons) and final state (atom with n-1 electrons (ion) and free
photoelectron) BE = Efinal(n -1)- Einitial (n)
If no relaxation followed photoemission, BE = - orbital energy which can be
calculated from Hartree-Fock
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Spin-orbit coupling
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
l = 1 (p)
l = 0 (s)
l = 2 (d)
l = 3 (f)
1
2
3
4
5
6
7
n
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
As the energy depends on n, l and j it is convenient to label the electron
states according to this three quantum numbers in the following way:
The value of n followed by the Label of the shell and as subscript the value
of j.
Quantum number Quantum number Quantum number X-ray
level
Spectroscopic
level
n l j
X-ray
level
Spectroscopic
level
1 0 1/2 K 1s
1/2
2 0 1/2 L
1
2s
1/2
2 1 1/2 L
2
2p
1/2
2 1 3/2 L
3
2p
3/2
3 0 1/2 M
1
3s
1/2
3 1 1/2 M
2
3p
1/2
3 1 3/2 M
3
3p
3/2
3 2 3/2 M
4
3d
3/2
3 2 5/2 M
5
3d
5/2
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
XPS survey spectrum of a clean Silver surface
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Ag3d detail spectrum of a clean Silver surface
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
PES/XPS: Apparatus
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Electron Spectroscopy: Energy Detector
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Schematic representation of the
Interaction of an electron beam
impinging in normal
direction on a surface.
How to make characteristic X-rays
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
For XPS
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
For first order diffraction of the AlK line, with = 8.3 , it is found
that quartz crystal spacing of the [10-10] planes is 4.25 and the Bragg
angle is thus 78.5. Quartz has many advantages, since it can be
obtained in perfect crystals of very large size, which can easily be bent
elastically and can be backed to high temperatures without damage or
distortion.
A crystal to monochromate
the MgK line is not known!!
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Electron energy
analyzer
Mono-energetic
X-ray source
Turbomolecular
Pump
Turbomolecular
Pump
Analyzer
Chamber
Analyzer
Chamber
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
The Swiss Light Source (SLS) in Villigen
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
!"#$%&'(&'#
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Chemical shift of PES
lines
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Poly(vinyl fluoride) -(CHF-CH
2
)-
In this case we can see that all the
fluorine atoms are equivalent but that
there are two inequivalent carbon atoms in
this polymer, where we should expect a
strong charge transfer due to the C-F
bond and therefore a strong chemical
shift.
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Poly(vinyltrifluorocetate)
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Ultraviolet photoelctron spectroscopy (UPS)
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Auger electron spectroscopy (AES)
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Schematic illustration of the KLL Auger electron emission process
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Typical representation
of an Auger spectrum
Auger Spectrum
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Diagram showing the energy
of the main Auger lines
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Scanning Auger Microscopy (SAM)
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Molecular Structure:
Angle-scanned X-ray Photoelectron Diffraction
x
-
r
a
y
s
x-ray tube
synchrotron
1st order
interference
forward-
focusing
analyzer
polar angle
azimuthal
angle
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010

Absolute configuration of molecules
Fasel, Ernst, et al., Angew. Chem. Int. Ed. 43
(2004) 2853
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
The adsorption site is not available
via static LEED
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Electron Energy Loss Spectroscopy (EELS)
also known as high resolution EELS (HREELS)
Based on inelastic scattering of monoenergetic
beam of low energy electrons (E
i
= 1-10 eV)
from surface.
E
s
= E
i
- E
vib

Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Sunday, November 7, 2010
106
Heinrich Rohrer
Gerd Binnig
Nobel Prize (1986)
Scanning tunneling
microscopy (STM)
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
In classical science if a particle impinges a barrier (such as small ball hitting a
solid wall) there is no chance of the particle being found beyond the barrier.
In quantum mechanics this is not correct and we speak of a probability that the
electron can be found beyond the barrier.
Classical barrier no transmission,
only reflection
quantum barrier part transmission,
Part reflection
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
In quantum mechanics one must think of the electron has having wave-like as well
as particle-like properties wave-particle duality.
We speak of the wavefunction of the electron and we are interested in
wavefunction penetration and overlap.
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
When two materials (one of which is often in the form of a metal tip) are
brought close to one another and a potential difference V applied a
tunnelling current I occurs.
This can be expressed as
z is the separation between the two materials and
V is the potential difference applied and
E is the energy of the electron
is read as h bar and is Plancks constant (actually h is Plancks
constant and h bar is h/2)
m
*
is the effective electron mass
To a first approximation, STM is like doing an I-V measurement but with
the electrodes very close together.
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
However things are a little (a lot) more complicated than
that.
Firstly, the tip is often a sharpened tip using a strong solution
of KOH and a voltage applied.
An ideal tip has one
atom at the end of the tip.
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
0.25 mm
0.00025 mm
The distance of the tip from the surface is
1 nm = 0,000.001 mm while the height
regulation is accurate down to 1 pm =
0,000.000.001 mm
Ag(111)
For an analogous height resolution
using the Eiffel tower one must
position it at 1 mm above the
Champs lyses and scan it with an
accuracy of at least 0,001 mm.
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
electrons
When the tip is biased positive relative to the sample electrons flow from the
sample to the tip note the tunnel current is in the opposite direction.
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
There are two common modes for STM operation:
Constant Current Mode
By using a feedback loop the tip is vertically adjusted
in such a way that the current always stays constant.
Constant Height Mode
In this mode the vertical position of the tip is not
changed. The current as a function of lateral position
represents the surface image.

Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Constant current
contour
Bias voltage
Distance z
e
Sample
e e
e
Tip
Tunneling current e
-2

z
V
DC
Conductive part
Less Conductive part
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
If the tip-surface interaction is so important how
do we maintain accurate separation?
The electronics uses a feedback system. The
sample is mounted on a stage which is attached to
a piezoelectric material.
A piezoelectric material is a material that expands
or contracts when a voltage is applied to it.
During constant current STM when the feedback sensor detects a change in
the tunnel current, the voltage to the piezoelectric is changed to adjust the
height to keep the tunnel current the same
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
So if we have a metal tip and a metallic sample,
what exactly are we measuring/probing?
Band alignment under Zero bias
In the sample, there may be bands present, which
may be occupied or empty.
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Band alignment under positive sample bias
Electrons flow from the tip to the empty sample
bands or unoccupied sample states.

Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Band alignment under negative sample bias
Electrons flow from the filled sample bands or
occupied sample states.
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
This also applies to
semiconductors with their
states in the band gap
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Annealing of Cu(111) under the STM
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Step fluctuation on Cu(111)
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
A tool beyond imaging:
Manipulation of atoms and molecules
Sunday, November 7, 2010
Manipulations with the STM @ 4K
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Experiment:
- Adsorption on Cu(211) @ 30 K
- LT-STM @ 6 K
Propene
H
3
C
H
C=C
H
H
Cu(211)
CO
CO
Sunday, November 7, 2010
The smallest Swiss Cross in the world (or PR comes rst)
propene on Cu(211)
Sunday, November 7, 2010
INELASTIC ELECTRON TUNNELING (IET) - INDUCED ACTION
e
-
Translation
e
-
Desorption
e
-
Chemical Reaction
+ X
e
- Flipping (?)
Rotation
e
-
Sunday, November 7, 2010
Cu(211) propene
6.1nm x 4.9 nm
STM contrast from DFT
Adsorption at 40 K;
STM at 7 K
Sunday, November 7, 2010
Daniele Passerone, Empa
DFT results for single propene: two congurations
D. Passerone, Empa
Sunday, November 7, 2010
Rotamers & Enantiomers
Sunday, November 7, 2010
2
2*
1
*
1
1
1
*
2 2
*
1
1
6.1nm x 4.9 nm
Sunday, November 7, 2010
IET action spectroscopy: Rotation


(C=C) = 204.2 meV
s
(CH
3
) = 361.5 meV

a
(CH
3
) = 364.3 meV

a
(CH
3
) = 367.0 meV
1 2*
2* 1
2*
1
Sample bias (mV)
R
e
a
c
t
i
o
n
y
i
e
l
d
p
e
r
e
l
e
c
t
r
o
n
a c
b
10
-12
200
200 mV
400 300
360 mV
10
-11
10
-10
10
-9
10
-8
500
Parschau et al., Angew. Chem. Int. Ed. 48 (2009) 4065
threshold correlates with vibration!
Sunday, November 7, 2010

s
(CH
2
) = 369 meV


(CH) = 373 meV

a
(CH
2
) = 381 meV
Lateral hopping
action spectroscopy

s
(CH
2
) = 369 meV


(CH) = 373 meV

a
(CH
2
) = 381 meV
375 mV
10
-12
10
-11
10
-10
300 400 500 600
*
*
a
b
R
e
a
c
t
i
o
n
y
i
e
l
d
p
e
r
e
l
e
c
t
r
o
n
Sample bias (mV)
c
Sunday, November 7, 2010
enantio-conversion: from right to left and vice versa
10
1
10
1
10 1
N = 1.0 0.1
N = 1.9 0.2
Tunneling current (nA)
H
o
p
p
i
n
g

r
a
t
e
(
s
-
1
)
F
l
i
p
p
i
n
g

r
a
t
e
(
s
-
1
)
c a
b
Sunday, November 7, 2010

EHP

R-CH2 + H
Parschau et al., Angew. Chem. Int. Ed. 48 (2009) 4065
Sunday, November 7, 2010
- 2 V pulse
Oxidation: IET-induced chemistry
400 mV / 100 nA
+ 2 V pulse
Sunday, November 7, 2010
allene
propyne

(C=C) = 266.0 meV
-
(C=C=C) = 242.5 meV
Identication of the reaction product:
IET hopping action spectroscopy
CH
3
and C=C can be excited propyne
-
270 mV
370 mV
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
A Modern Tool for Studying Surface Processes:
Scanning Force Microscopy
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Quantitative understanding of nc-AFM
*
Resonance frequency: !
"
Width of resonance curve (FWHM): *
Q-factor:
!
"
!
#
*

!
" f
Q
S
Conservative forces shift of resonance curve 'f
Dissipative forces broadening of curve '*
attractive interaction
'f
*+'*
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
Quarzuhren sind aufgrund der darin enthaltenen Quarzoszillatoren hochprzise. Das
zeitgebende Element ist eine Stimmgabel aus einkristallinem Quarz, die bei einer
Frequenz von f
0
= 32 768 = 2
15
Hz schwingt.
Scanning force microscopy using a quartz tuning fork
Figure 2: Experimental setup. a) The NC-AFM/STM tuning fork sensor is glued onto the carrier
made of macor. Contacts P1 and P2 are the contacts of the excitation piezo. The signal from the
tuning fork is detected via contact T1 and T2. The m wire attached to the tip conducts the tunnel-
ing current. b) The walker unit is a tripod situated on shear stack piezos for the coarse approach.
The x-, y- and z-piezos are used during the scan process. The tuning fork is located opposite the
sample (only half of the sample is drawn to keep the view free to the sensor carrier). Further ex-
planations are given in the text. Schematic of the microscope on its support stage: (A) walker unit,
(B) x-, y-piezo and (C) z-piezo of the tripod scanner unit, (D) z dither piezo, (E) sensor carrier, (F)
tuning fork assembly, (G) sample (not fully drawn), (H) sample holder (not fully drawn), (I) sam-
ple stage, (J) microscope stage, (K) walker support and (L) shear stack piezos. The base plate has a
diameter of 10 cm.
amplier has to be placed nearby to improve the signal-to-noise ratio. The change of the tuning 93
fork frequency f is used as a feedback signal for NC-AFM. 94
The tip is electrically connected to a Pt
09
Rh
01
wire, 50 m in diameter (see gure 2 a). Using this 95
electrical contact, a bias voltage can be applied between tip and sample and a tunneling current can 96
be measured. This tunneling current serves as a feedback signal when operating in the STM mode. 97
However, while operating in one of the modes, AFM or STM, the other channel can always be co- 98
recorded. Much care has been taken to ensure that both channels, AFM and STM, are electrically 99
separated from each other, preventing cross talk. 100
5
Sunday, November 7, 2010
Prof Dr. Karl-Heinz Ernst, ETH ZH Catal. Vorl. 2010
(NiAl)
2
substrate
(Al
19
O
28
Al
28
O
32
)
2
. An oxygen deciency with unoccupied electronic states in the 411
aluminum oxide band gap was proposed. 412
Figure 10: Atomic resolution NC-AFM image of a straight antiphase domain boundary (type I) in
the aluminum oxide on NiAl(110). The scan area is 6.4 nm 6.4 nm in a) and b). b) An adjusted
model [42] has been superimposed in. The unit cell is extended by 3 along the long edge of the
unit cell. Inserted sites are given in lighter colors. Dashed lines indicate the extension. The dotted
line highlights wave-like oxygen rows along the unit cell. c) shows an enlarged section of the im-
age for better visibility (3.5 nm 3.5 nm). Yellow arrows denote the direction and length (3 ) of
the Burgers vector. Yellow loops indicate spacious arrangements of oxygen sites that are different
from all domain sites. f = -2.75 Hz, A
osc
= 3.8 , U
bias
= -220 mV.
An atomically resolved NC-AFM image of a straight APDB (type B I) is shown in gure 10. 413
Clearly visible, the boundary is marked by a fairly wide linear depression. The adjusted model 414
for the lateral positions at the APDB [42] is superimposed in gure 10b) and found to be in per- 415
fect agreement. From this we see that NC-AFM images the surface oxygen sites of the lm with 416
high accuracy. The above model is based on a unit cell that has been split up in the middle accord- 417
ing to STM images. Important structural elements of the oxygen sub-lattice are highlighted as well 418
as the extended unit cell and two equivalent lines between which the inserted new sites are visible. 419
Inserted sites are marked in a slightly different color to distinguish them from the usual sites in the 420
oxide unit cell: orange and light blue as compared to red and blue. In gure 10c) an enlarged sec- 421
tion of the elongated unit cell at the APDB is given. In the middle of the APDB a broken block of 422
8 O atoms appears, which is of the kind that is almost aligned with the NiAl[001] direction. A par- 423
ticularly spacious arrangement of oxygen atoms in the shape of a quadrangle (yellow dotted loops) 424
is formed at this block at the boundary. This is in agreement with DFT calculations [42], which as- 425
22
Insulator surfaces: Al
2
O
3
/ NiAl(111) and NaCl
Die "Nano-Schweiz
9.3 x 7.1 nm
2
NaCl-Insel mit AFM abgebildet
Sunday, November 7, 2010