1

Lecture Date: March 17

th
, 2008
Microscopy and Surface Anal ysi s 2
Reading Assignments for Microscopy and
Surface Anal ysi s
Skoog, Holler and Nieman, Chapter 21, Surface
Characterization by Spectroscopy and Microscopy
Hand-out Review Article: C. R. Brundle, J . F. Watts, and
J . Wolstenholme, X-ray Photoelectron and Auger
Electron Spectroscopy, in Ewings Analytical
Instrumentation Handbook, 3
rd
Ed. (J . Cazes, Ed.),
Marcel-Dekker 2005.
2
Introduction to the Solid State
In solids, atomic and molecular energy levels broaden into
bands that in principle contain as many states as there
are atoms/molecules in the solid.
P.A. Cox, "The ElectronicStructureandChemistryof Solids" OxfordUniversityPress, 1987.
C. Kittel, Solid-statePhysics, 7
th
Ed, Wiley, 1999.
W. A. Harrison, ElectronicStructureandthePropertiesof Solids, Dover, 1989.
Bands may be separated by a band gap with energy E
g
Energy Bands in the Solid State
Bands are continuous and delocalized over the material
Band widths are determined by size of orbital overlap
P.A. Cox, "The ElectronicStructureandChemistryof Solids" OxfordUniversityPress, 1987.
C. Kittel, Solid-statePhysics, 7
th
Ed, Wiley, 1999.
W. A. Harrison, ElectronicStructureandthePropertiesof Solids, Dover, 1989.
The highest-energy filled band (which may be only
partially filled) is called the valence band
The lowest-energy empty band is called the conduction
band
3
The Workfuncti on: A Barrier to Electron Emission
How does the electronic arrangement in solids affect
surfaces? In particular, how can an electron be removed?
P.A. Cox, "The ElectronicStructureandChemistryof Solids" OxfordUniversityPress, 1987.
C. Kittel, Solid-statePhysics, 7
th
Ed, Wiley, 1999.
W. A. Harrison, ElectronicStructureandthePropertiesof Solids, Dover, 1989.
For some electron being removed, its energy just as it
gets free is E
V
The energy required to remove the electron is the
workfunction (typically several eV)
Free electron!
The Workfuncti on: A Barrier to Electron Emission
Workfunctions vary from <2 eV for alkali metals to >5 eV
for transition metals.
DatafromCEM 924 Lectures presentedat MSU (2001).
The workfunction is the barrier to electron emission
like the wall in the particle-in-a-box concept.
Material Crystal State Workfunction (eV)
Na polycrystalline 2.4
Cu polycrystalline 4.4
Ag polycrystalline 4.3
Au polycrystalline 4.3
Pt polycrystalline 5.3
W polycrystalline 4.5
W(111) single crystal 4.39
W(100) single crystal 4.56
W(110) single crystal 4.68
W(112) single crystal 4.69
4
Basic Considerati ons for Surface Spectroscopy
Common sampling modes
Spot sampling
Raster scanning
Depth profiling
Surface contamination:
The obvious contamination/alteration of surfaces that can be the
result of less-than careful sample preparation
Solid surfaces can adsorb gases:
At 10
-6
torr, a complete monolayer of a gas (e.g. CO) takes just 3
seconds to form.
At 10
-8
torr, monolayer formation takes 1 hour.
Most studies are conducted under vaccuum although there are
newer methods that dont require this.
D. M. HerculesandS. H. Hercules, J. Chem. Educ., 1984, 61, 403.
Surface Spectrometric Anal ysi s
Surface spectrometric techniques:
X-ray fluorescence (from electron microscopy)
Auger electron spectrometry
X-ray photoelectron spectrometry (XPS/UPS)
Secondary-ion mass spectrometry (SIMS)
Depth profiling if you are going to study surfaces with
high lateral resolution (e.g. using microscopy), then
wouldnt it be nice to obtain information from various
depths within the sample?
5
The Basic Idea Behind Surface Spectrometry
Surface
Primary
photon
electron
ion
Secondary
photon
electron
ion
Photons, electrons,
ions: they can go in
and/or out!!!
Leads to lots of
techniques, and lots
of acronyms!
Primary Secondary Name of Technique
photon (X-ray/UV) electron XPS (ESCA) and UPS
photon (X-ray) or electron electron Auger electron spec. (AES)
ion ion SIMS (secondary ion MS)
photon ion LMMS (laser microprobe MS)
electron Photon (X-ray) SEM electron microprobe
Electron Microprobes and X-ray Emission
Electron microscopy (usually SEM) can also be used to
perform X-ray emission analysis in a manner similar to
X-ray fluorescence analysis
see the X-ray spectrometry lecture for details on the spectra
The electron microprobe (EM) is the commonly used
name for this type of X-ray spectrometry
Both WDS and EDS
detectors are used (as in
XRF), elemental mapping
Not particularly surface
sensitive!
6
Electron Microprobes: X-ray Emission
Electron Spectroscopy
Electron spectroscopy measuring the energy of
electrons.
Major forms:
Auger electron spectroscopy
X-ray/UV photoelectron spectroscopy
Electron energy loss spectroscopy (EELS)
7
Electron Spectroscopy: Surface Sensitivi ty
Electrons can only escape from shallow depths in the
surface of a sample, because they will undergo
collisions and lose energy.
XPS/AES region,
electrons that have
not been inelastically
scattered from
shallow regions
(mostly excitation of
conduction-band
electrons)
Deep electrons that
undergo inelastic
collisions but lose
energy (exciting e.g.
phonons)
Auger Electron Spectrometry (AES)
The Auger process can also be a source of spectral
information. Auger electrons are expelled from
atomic/molecular orbitals and their kinetic energy is
characteristic of atoms/molecules
However, since it is an electronprocess, analysis of
electronenergy is necessary!
This is unlike the other techniques we have discussed, most of
which measure photon wavelengths or energy
Auger electron emission is a three-step (three electron)
process, that leaves an atom doubly-ionized
8
AES: Basic Mechanism
SeeFigure21-7 inSkoog, et al. for arelatedfigure.
AES: Basic Mechanism
Auger electrons are created from outer energy levels (i.e.
less-tightly bound electrons, possibly valence levels).
This example
would be called a
LMM Auger
electron. Other
Common types
are denoted KLL
and MNN.
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AES: Efficiency of Auger Electron Production
Two competing
processes:
X-ray fluorescence
Auger electron emission
Auger electrons
predominate at lower
atomic number (Z)
Photoelectron emission
does not compete!
created vacancies shell K of number
produced photons K of number

K Auger
1
Top FigurefromStrobel and Heineman, Chemical Instrumentation, A Systematic Approach, Wiley, 1989.
AES: Spectrometer Design
AES instruments are designed like
an SEM often they are
integrated with an SEM/EDXA
system
Unlike an SEM, AES instruments
are designed to reach higher
vacuum (10
-8
torr)
Helps keep surfaces clean and free
from adsorbed gases, etc
Basic components:
Electron source/gun
Electron energy analyzer
Electron detector
Control system/computer
Ion gun (for depth profiling)
Electron
Gun
Sample
Energy
analyzer
Auger
electrons
Electron
detector
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AES (and XPS): Electron Energy Anal yzers
Two types of electron energy analyzers (also used in XPS):
Cylindrical mirror analyzer
(higher efficiency)
More common for AES
(Right) Diagramfromhttp://www.cea.com/cai/auginst/caiainst.htm
(Left) DiagramfromStrobel andHeineman, Chemical Instrumentation, A Systematic Approach, Wiley, 1989.
Concentric hemispherical analyzer
(higher resolution) better resolution, mostly
for XPS/UPS
2
1
2
2
2 1

R R
R R
k
V ke KE
electron

Electrons only pass if
their KE is:
AES: Detectors
More sophisticated detectors are needed to detect low
numbers of Auger electrons. Two types of electron-
multiplier detectors:
Discrete dynode
Continuous dynode
Both types of detector are also used in XPS/UPS!!!
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AES: Surface Anal ysis
AES is very surface sensitive (10-50 ) and its reliance on
an electron beam results in excellent lateral resolution
Diagramfromhttp://www.cea.com/cai/auginst/caiainst.htm
Electron beam does not
have to be monochromatic
Note: an X-ray beam can
also be used for AES, but is
less desirable b/c it cannot
currently be focused as tightly
(as is the case in XPS)
Auger electrons typically
have energies of <1000
eV, so they are only
emitted from surface
layers.
AES: Spectral Interpretati on
AES Electron Kinetic Energies* versus Atomic Number
(Most intense peaks only. Valid for CMA-type analyzers.)
*DataisfromJ.C. Vickerman(Ed.), "SurfaceAnalysis: ThePrincipal Techniques, JohnWileyandSons, Chichester, UK, 1997 .
Imagefromhttp://www.cem.msu.edu/~cem924sg/KineticEnergyGraph.html (accessed 12-Nov-2004)
12
AES: Typical Spectra
AES: Elemental Surface
Analysis
Very common application of
AES - elemental surface
analysis
For true surface analysis,
AES is better than SEM/X-ray
emission (electron
microprobe) because it is
much more surface sensitive
AES can be easily made
quantitative using standards.
Imagefromhttp://www.cem.msu.edu/~cem924sg/ (accessed 12-Nov-2004)
13
AES: Chemical Shifts
Chemical information (i.e.
on bonding, oxidation
states) should be found
in Auger spectra because
the electron energy
levels are sensitive to the
chemical environment.
In practice, it is not
(usually) there because
too many electron energy
levels are involved it is
difficult to calculate and
simulate Auger spectra.
X-ray Photoelectron Spectrometry (XPS)
Photoelectron spectroscopy is used for solids, liquids and
gases, but has achieved prominence as an analytical
technique for solid surfaces
XPS: soft x-ray photon energies of 200-2000 eV for
analysis of core levels
UPS: vacuum UV energies of 10-45 eV for analysis of
valence and bonding electrons
Photoelectric effect: Proposed by A. Einstein (1905),
harnessed by K. Siegbahn (1950-1970) to develop XPS
14
XPS: Basic Concepts
Like in AES, photoelectrons can not escape from depths
greater than 10-50 A inside a material
Schematically, the photoelectron process is:

e A h A
*

cation
atom or molecule
Like in AES, the kinetic energy of the emitted electron is
measured in a spectrometer
XPS: Review of X-ray Processes
15
XPS: Photoelectron Emission and Binding Energy
The kinetic energy of the emitted electron can be related
to the binding energy, or the energy required to remove
an electron from its orbital.
Higher binding energies mean tighter binding e.g. as atomic
number goes up, binding energies get tighter because of
increasing number of protons.
IP h E
binding

w BE h E
binding

(gas)
(solid)
http://www.chem.qmw.ac.uk/surfaces/scc/scat5_3.htm
XPS: Binding Energy
The workfunction w is usually linked to the spectrometer
(if the sample is electrically connected)
In gases, the BE is directly related to IP
Ionization potential the energy required to take an electron out
of its orbital all the way to the vacuum (i.e. far away!)
PE spectroscopy on gases is used to check the accuracy of
modern quantum chemical calculations
In conducting solids the workfunction is involved
Koopmans Theorem: binding energy =-(orbital energy)
Orbital energies can be calculated from Hartree-Fock
Another definition for XPS binding energy: the minimum energy
required to move an inner electron from its orbital to a region away
from the nuclear charge. Absorption edges result from this same
effect
16
XPS: Sources
Monochromatic sources using electrons
fired at elemental targets that emit x-rays.
Can be coupled with separate post-source
monochromators containing crystals, for high
resolution (x-ray bandwidth of <0.3 )
XPS Sources (hit core electrons):
Mg Ka radiation: hn =1253.6 eV
Al Ka radiation: hn =1486 eV
AgLa radiation: hn =2984.3 eV
UPS Sources (hit valence electrons):
He(I) radiation: hn =21.2 eV (~58.4 nm)
hn =23 eV (~53.7 nm)
He(II) radiation: hn =41 eV (~30.4 nm)
Focusing the spot and lateral resolution-
10-m diameter spots are now possible
A Thermo-Electron
Dual-anode (Al/Mg)
XPS source
XPS: Spectral Interpretati on
Orbital binding energies can be interpreted based on
correlation tables, empirical trends and theoretical
analysis.
Peaks appear in XPS spectra for distinguishable atomic
and molecular orbitals.
Auger peaks also appear in XPS spectra they are easily
distinguished by comparing the XPS spectra from two
sources (e.g. Mg and Al K
a
lines). The Auger peaks
remain unchanged w.r.t. kinetic energy, while the XPS
peaks shift.
17
XPS: Binding Energy Ranges
XPS Photoelectron Binding Energies versus Atomic Number (Z)
*DatafromC.D. Wagner, W.M. Riggs, L.E. Davis, J.F. Moulder andG.E. Muilenberg, Eds., "Handbook of X-ray PhotoelectronSpectroscopy,"
Perkin-Elmer Corp., FlyingCloud, MN, 1979.
Imagefromhttp://www.cem.msu.edu/~cem924sg/BindingEnergyGraph.html (accessed 12-Nov-2004)
XPS: Typi cal Spectra
An XPS survey spectrum of stainless steel:
Spectrumimagefromhttp://www.mee-inc.com/esca.html
18
XPS: Typi cal Spectra
An expanded XPS spectrum of the C
1s
region of PET:
Spectrumimagefromhttp://www.mee-inc.com/esca.html
XPS: Chemical Shifts
Peaks appear in XPS
spectra for distinguishable
atomic and molecular
orbitals.
Effects that cause chemical
shifts in XPS spectra:
Oxidation states
Covalent structure
Neighboring electron
withdrawing groups
Anything else that can affect
ionization/orbital energies
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XPS: Depth Profiling
Option 1: Sputtering techniques
Disadvantage can damage the surface
Advantage wide range of depths can be
sampled (just keep sputtering), e.g. 100 A
Option 2: Angle-resolved XPS (AR-XPS)
Reducing the photoelectron take-off angle
(measured from the sample surface) reduces
the depth from which the XPS information is
obtained. XPS is more surface sensitive for
grazing take-off angles than for angles close to
the surface normal (longer PE paths).
The most important application of angle
resolved XPS (AR-XPS) is in the estimation of
the thickness of thin films e.g. contamination,
implantation, sputtering-altered and segregation
layers.
For moreonAR-XPS, seeBriggsandSeah, Practical Surface Analysis, 2
nd
Ed., Vol. 1. Auger andX-ray PhotoelectronSpectroscopy, Wiley, 1990, pp. 183-186, 244-250
normal
grazing
Sample
electron
Depth Profiling with Angle-Resol ved XPS
AR-XPS data is often acquired by tilting the specimen
Example: gallium arsenside with a thin oxide layer on its surface:
AR-XPS figurefromC. R. Brundle, J. F. WattsandJ. Wolstenholme, inEwingsAnalytical InstrumentationHandbook 3
rd
Ed., Dekker 2005.
bulk
surface
(grazing)
Sample
electron
Grazing angle
(X-ray takeoff angle)
20
XPS: Applications
A modern application of XPS study the nature of PEG as a surface
coating to prevent biofouling in biosensors
Biofouling: the tendency of proteins to adsorb to silicon-based surfaces
XPS can be used, with AFM, to observe the coating of PEG onto
silicon surfaces (PEG-silane coupling) - Increased C 1s C-O signal
indicates greater grafting density
S. Sharma, et al., XPS andAFM analysis of antifoulingPEG interfacesfor microfabricatedsiliconbiosensors, Biosensors and Bioelectronics, 20 227239 (2004).
XPS: Quantitati ve Applications
Quantitative XPS is not as widely used as the qualitative
version of the technique.
Variations in instrument parameters and set-up have
traditionally caused problems with reproducibility
Using internal standards, XPS can achieve quantitative
accuracies of 3-10% in most cases (and getting better
every year, as more effort is put into this type of analysis)
21
AES and XPS: Combined Systems
Dual Auger/XPS systems are very common, also
combined with a basic SEM
Note - SAM =scanning Auger microprobe
Auger is seen as complementary to XPS with generally
better lateral resolution
Both are extreme surface sensitive techniques:
AES better elemental quantitative analysis
XPS contains more chemical information
Also, remember that Auger peaks are often seen in XPS
spectra (and are hence useful analytically) they can be
identified by changing source, so that the X-ray peaks
shift (the Auger peaks do not).
Comparison of XPS, AES and Other Techniques
* =yes, with compensation for theeffects of samplecharging
SIMS =secondary ion mass spectrometry, discussed in theIon and Particle Spectrometry Lectures.
Characteristic AES XPS SEM/X-ray EM SIMS
Elemental range Li and higher Z Li and higher Z Na and higher Z All Z
Specificity Good Good Good Good
Quantification With calibration With calibration With calibration Correction
necessary
Detection limits
(atomic fraction)
10
-2
to 10
-3
10
-2
to 10
-3
10
-3
to 10
-8
10
-3
to 10
-8
Lateral resolution
(um)
0.05 ~1000 0.05 1
Depth resolution
(nm)
0.3-2.5 1-3 1000-50000 0.3-2
Organic samples No Yes Yes
*
Yes
Insulator samples Yes
*
Yes Yes
*
Yes
*
Structural
information
Elemental Elemental and
Chemical
Elemental Elemental and
Chemical
Destructiveness Low Very Low Medium Medium
SeeStrobel and Heineman, Chemical Instrumentation, A Systematic Approach, Wiley, 1989, pg. 832.
22
XPS: New Applicati ons
A recent report in Chem. Commun. (2005) by Peter
Licence and co-workers describes the use of XPS to
study ionic liquids
Normal liquids evaporate under ultrahigh vacuum (UHV),
ionic liquids do not (they have a vapor pressure of nearly
zero!)
Why? Ionic liquids have become important for
electrochemistry, catalysis, etc
See C&E News Oct. 31, 2005, pg 10.
Optional Homework Problems (for Study!)
Skoog, Holler and Nieman, Chapter 21.
Problems: 21-1, 21-2, 21-4, and 21-8.
23
Further Reading
Electron Microscopy and Electron Microprobe/X-ray Emission Analysis
1. J . I. Goldstein et al., Scanning Electron Microscopy and X-ray Microanalysis, 3
rd
Ed., Kluwer Academic,
2003.
2. J . J . Bozzola et al., Electron Microscopy: Principles and Techniques for Biologists, 2
nd
Ed., J ones and
Bartlett, 1998.
3. J . W. Edington, N. V Philips, Practical Electron Microscopy in Materials Science, Eindhoven, 1976.
Electron Microscopy and Electron Diffraction/Electron Energy Loss Spectroscopy
4. A. Engel and C. Colliex, Application of scanning transmission electron microscopy to the study of
biological structure, Current Biology 4, 403-411 (1993). (STEM and EELS)
5. W. Chiu and M. F. Schmid, Electron crystallography of macromolecules, Current Biology 4, 397-402
(1993). (ED and LEED)
6. W. Chiu, What does electron cryomicroscopy provide that X-ray crystallography and NMR cannot?,
Annu. Rev. Biophys. Biomol. Struct., 22, 233-255 (1993). (Electron Cryomicroscopy/Imaging)
7. L. Tang and J . E. J ohnson, Structural biology of viruses by the combination of electron cryomicroscopy
and X-ray crystallography, 41, 11517-11524 (2002). (Electron Cryomicroscopy/Imaging)
Optical Microscopy
8. R. H. Webb, "Confocal optical microscopy, Rep. Prog. Phys. 59, 427-471 (1996).
Force Microscopy:
9. R. J . Hamers, Scanned probe microscopies in chemistry, J. Phys. Chem., 100, 13103-13120 (1996).
Further Reading
Surface Spectrometric Methods (XPS and AES)
10. T. L. Barr, Modern XPS, Boca Raton: CRC Press (1994).
11. M. Thompson, M. D. Baker, A. Christie, and J . F. Tyson, Auger Electron Spectroscopy, New York:
Wiley (1985).
12. N. H. Turner, X-ray Photoelectron and Auger Electron Spectroscopy, Applied Spectroscopy Reviews,
35 (3), 203-254 (2000).