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Electron Spectroscopies XPS: X-ray Photoelectron Spectroscopy AES: Auger Electron Spectroscopy
Ion Spectroscopies SIMS: Secondary Ion Mass Spectrometry SNMS: Sputtered Neutral Mass Spectrometry ISS: Ion Scattering Spectroscopy
What is XPS?
X-ray Photoelectron Spectroscopy (XPS), also known as Electron Spectroscopy for Chemical Analysis (ESCA) is a widely used technique to investigate the chemical composition of surfaces.
What is XPS?
X-ray Photoelectron spectroscopy, based on the photoelectric effect,1,2 was developed in the mid-1960s by Kai Siegbahn and his research group at the University of Uppsala, Sweden.3
1. H. Hertz, Ann. Physik 31,983 (1887). 2. A. Einstein, Ann. Physik 17,132 (1905). 1921 Nobel Prize in Physics. 3. K. Siegbahn, Et. Al.,Nova Acta Regiae Soc.Sci., Ser. IV, Vol. 20 (1967). 1981 Nobel Prize in Physics.
X-ray penetration depth ~1m. Electrons can be excited in this entire volume.
10 nm 1 mm2
X-ray excitation area ~1x1 cm2. Electrons are emitted from this entire area
1. At T=0 K:
Ef
N(E)/E
1.0
0.8
0.6
0.4
0.2
0.0
-0.2
-0.4
-0.6
-0.8
-1.0
KE(1s)
Vacuum Level, Ev
hv
Fermi Level, Ef
sample BE(1s)
E1s
Because the Fermi levels of the sample and spectrometer are aligned, we only need to know the spectrometer work function, spec, to calculate BE(1s).
Spectrometer KE(1s)
spec hv Ech
E1s
BE(1s)
A relative build-up of electrons at the spectrometer raises the Fermi level of the spectrometer relative to the sample. A potential Ech will develop.
Fermi Level
Binding Energy
Look for changes here by observing electron binding energies
Electron
Electron-nucleus attraction
ElectronNucleus Separation
Nucleus
Elemental Shifts
Binding Energy (eV) Element Fe Co Ni Cu Zn 2p3/2 707 778 853 933 1022 3p 53 60 67 75 89
Elemental Shifts
Final State
Conduction Band
Valence Band 2p 2s 1s
Valence Band
-B,K
Actual binding energy will represent the readjustment of the N-1 charges to minimize energy (relaxation): EB = Ef N-1 - Ei N
kqi
qi/rij
Potential at i due to surrounding charges
Weighted charge of i
Oxygen Atom
Electron-oxygen atom attraction (Oxygen Electronegativity)
C 1s Binding Energy
Shift to higher binding energy
Carbon Nucleus
2p1/2
Peak Area 91
3.65 3 : 4 79
Monopole transition: Only the principle quantum number changes. Spin and angular momentum cannot change. Shake-up: Relaxation energy used to excite electrons in valence levels to bound states (monopole excitation). Shake-off: Relaxation energy used to excite electrons in valence levels to unbound states (monopole ionization).
Photoelectrons travelling through the solid can interact with other electrons in the material. These interactions can result in the photoelectron exciting an electronic transition, thus losing some of its energy (inelastic scattering).
Metal
A=15.3 eV
O 1s
Insulating Material
21 eV x4
3d 4f 2p 4d 1s
Li B N F Na Al P Cl K Sc V M Co Cu G As Br Rb Y Nb Tc Rh Ag In Sb I Cs La Pr P Eu Tb Ho T Lu Ta Re Ir Au Tl Bi Be C O Ne M Si S Ar Ca Ti Cr Fe Ni Zn G Se Kr Sr Zr M Ru Pd Cd Sn Te Xe Ba Ce Nd S G Dy Er Yb Hf W Os Pt Hg Pb
Relative Sensitivity
Elemental Symbol
Cu 2p
100
Mct-eV/sec
Atomic Conc
%
80
Thousands
Ni Cu
49 51
N(E)/E
60
Ni 2p
40
20
0 -1100
-900
-700
-500
-300
-100
Comparison of Sensitivities
H Ne Co Zn Zr Sn Nd Yb Hg Th
1ppm
5E16
SIMS
1ppb
20
40 60 ATOMIC NUMBER
80
5E13 100
Pressure Torr
102 10-1 10-4 10-8 10-11
Remove adsorbed gases from the sample. Eliminate adsorption of contaminants on the sample. Prevent arcing and high voltage breakdown. Increase the mean free path for electrons, ions and photons.
Computer System
Inner Sphere
Analyzer Control
Multi-Channel Plate MultiElectron Multiplier Resistive Anode Encoder Position Computer Position Address Converter
Sample
5 4 .7
X-ray Generation
Incident electron
Conduction Band
Secondary electron
Conduction Band
X-ray Photon
Free Electron Level Fermi Level
Valence Band 2p 2s 1s 2p 2s 1s
Note: The light elements have a low cross section for X-ray emission.
Fence Anode 2
Cooling Water
Filament 1
Filament 2
Energy Analyzer
Sample
N Ca Na Cl
Pb
500
400
300
200
100
XPS analysis showed that the pigment used on the mummy wrapping was Pb3O4 rather than Fe2O3
N(E)/E
-C-O -C=O
-300 -295 -290 Binding energy (eV) -285 -280
Analysis of Materials for Solar Energy Collection by XPS Depth ProfilingThe amorphous-SiC/SnO2 Interface
Photo-voltaic Collector The profile indicates a reduction of the SnO2 occurred at the interface during deposition. Such a reduction would effect the collectors efficiency.
SnO2
Sn
Solar Energy
Conductive Oxide- SnO2 p-type a-SiC a-Si 500 496 492 488 484 480
Depth
Angle-resolved XPS
=15
More Surface Sensitive
= 90
Less Surface Sensitive
Information depth = dsin d = Escape depth ~ 3 = Emission angle relative to surface = Inelastic Mean Free Path
C(W) C(Au)
0.3 0.2 0.1 0
20
40
60
80
100