Topic #8: Spectroscopy Techniques

Photon in, Electron out Photoemission Spectroscopy (PES) X-ray Photoemission Spectroscopy (XPS - 200 to 2,000 eV source) Ultraviolet Photoemission Spectroscopy (UPS - 10 to 50 eV source) Auger Electron Spectroscopy (AES) - also possible! Electron in, Electron out (inelastic) Auger Electron Spectroscopy (AES) Electron Energy Loss Spectroscopy (EELS) Photon in, Photon out X-ray Absorption Spectroscopy (XAS) Extended X-ray Absorption Fine Structure (EXAFS)

Phys 661 - Baski

Spectroscopy Techniques

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Electron Spectroscopy: Survey Scan (PES+AES)

PES Lines

Auger Lines

Electron energy spectrum of Ni due to 1.25 keV photon (Mg Ka). X-axis = binding energy = hv - E(kinetic) Y-axis = N(E)/E because admittance of spectrometer decreases as 1/E.
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Electron Spectroscopy: Mean Free Path

Schematic of energetic photons incident on a surface and creating characteristic electrons relatively deep in the solid. Only electrons created near the surface escape with no loss of energy.

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Spectroscopy Techniques

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Electron Spectroscopy: Mean Free Path

Universal curve for electron mean free path with a minimum near 50 eV.
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Electron Spectroscopy: Energy Detectors

Single-pass CMA

Double-pass CMA

Cylindrical Mirror Analyzers (CMA) use an electrostatic field to guide electrons with a specific energy to the detector.

Phys 661 - Baski

Spectroscopy Techniques

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Electron Spectroscopy: Energy Detectors

CHA Channel Plate

Concentric Hemispherical Analyser (CHA) operates on principle similar to CMA, but with a different geometry. Channel Plate Analyzer spatially images electron intensity from the sample at each given energy.
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PES/XPS: Apparatus

X-ray Photoelectron Spectroscopy (XPS) consists of an x-ray source (Mg-1254 eV, Al-1487 eV) that bombards a sample and a detector for measuring the energies of the emitted electrons.
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PES/XPS: Survey Scan

Survey scan of Pd over large energy range shows relative intensities of 3d, 3p, and 3s energy levels.
Taken from www.chem.qmw.ac.uk/surfaces/scc/scat5.htm
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Synchrotron PES: High Resolution Data

Ge 3d Core Level Valence Band

Data from John Phys 661 - Baski

Carlisle (VCU 2000).Spectroscopy Techniques

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PES/XPS: Energy Level Basics

Energy Diagram PES/XPS Spectra

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Spectroscopy Techniques

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Background: Orbital Angular Momentum l

n 1 2

l = 0 (s) l = 1 (p)

l = 2 (d)

3 4 5
6 7

l = 3 (f)

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Spectroscopy Techniques

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Background: Spin-Orbit Energy Levels

Spin-Orbit Zeeman mj = 3/2 mj = 1/2 mj = 1/2 mj = 3/2 mj = 1/2 mj = 1/2 j = 1/2

j = 3/2 l = 1 (p) s = 1/2

j l s, l s m j j, j 1,... j 1, j

l = 0 (s) s = 1/2 j = 1/2

Phys 661 - Baski Spectroscopy Techniques

mj = 1/2
mj = 1/2
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PES/XPS: Energy Level Basics

j
1S1/2 1/2 2S1/2 1/2,3/2 2P1/2, 2P3/2

n=1 n=2 Spin-Orbit Splitting

n=3

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Spectroscopy Techniques

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PES/XPS: Binding Energy Values

Binding energies of K (n = 1), L (n = 2), M (n = 3), and N shells

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PES/XPS: Binding Energy Cross Sections

2p 1s 3d 4f

Calculated cross sections (1.5 keV photon energy) give probabilities for observing electrons from various energy levels.
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PES/UPS: Chemical Shifts of Si oxide

Si 2p3/2 Core Level

Observe shift to higher binding energies with increasing oxidation state (electronegative oxygen binds electron more strongly).
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AES: Auger Electron Spectroscopy

3 L2,3 L1 2
3) Auger e- leaves using excess energy Ek = E1- E2 - E3 Use three letters corresponding to the three involved energy levels, e.g. KLL. 2) Higher energy e- fills core hole

K 1
1) Incoming e- (or photon) knocks out core e-

AES is a three-electron process, where the Auger electron has a kinetic energy determined by the energy levels . AES is usually more surface sensitive than PES.
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AES: Survey Scan and Differentiated Scan

Raw spectrum of Pd

Differentiated spectrum

Typically use differentiated spectrum (dN / dE) in order to increase signal to noise.
Taken from www.chem.qmw.ac.uk/surfaces/scc/scat5.htm
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EELS: Electron Energy Loss Spectrum

EELS for Al (primary 2 keV) shows loss peaks that are combinations of surface and bulk plasmon losses.
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Blank slide

Phys 661 - Baski

Spectroscopy Techniques

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XAS: X-ray Absorption Spectroscopy

Energy Diagram Apparatus
photon in, photon out

XAS is a photon in / photon out process. Cross sections for XAS vs. Auger (photon in / electron out) depend on nuclear charge Z (Auger dominates for lower Z).
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Spectroscopy Techniques

XAS: Survey & High Resolution Scans

XAS Spectrum (survey scan)

XAS + EXAFS Spectrum (high-resolution scan)

K-level

L-levels

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Spectroscopy Techniques

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EXAFS: Extended X-ray Absorption Fine Structure

EXAFS is periodic structure near XAS edge due to electron scattering. Fourier analysis of periodicities yields information about atomic spacings.
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EXAFS: Spectrum and Fourier Transform

XAS of Ge shows sharp rise at 11 keV (K-edge), where modulation above edge is EXAFS data. Fourier transform shows nearest neighbor and the second nearest neighbor distances.
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