X-Ray Photoelectron Spectroscopy (XPS)

Louis Scudiero http://www.wsu.edu/~scudiero; 5-2669

Electron Spectroscopy for Chemical Analysis (ESCA)

 The basic principle of the photoelectric effect was enunciated by Einstein

[1] in 1905 E = h
There is a threshold in frequency below which light, regardless of intensity, fails to eject electrons from a metallic surface. hc > em Where h - Planck constant ( 6.62 x 10-34 J s ), frequency (Hz) of the radiation and m work function

In photoelectron spectroscopy such XPS, Auger and UPS, the photon

energies range from 20 -1500 eV (even higher in the case of Auger, up to 10,000eV) much greater than any typical work function values (2-5 eV).

In these techniques, the kinetic energy distribution of the emitted

photoelectrons (i.e. the number of emitted electrons as a function of their kinetic energy) can be measured using any appropriate electron energy analyzer and a photoelectron spectrum can thus be recorded.
[1] Eintein A. Ann. Physik 1905, 17, 132

 By using photo-ionization and energy-dispersive analysis of the emitted Traditionally, these techniques have been subdivided according to the

photoelectrons the composition and electronic state of the surface region of a sample can be studied.

source of exciting radiation into : X-ray Photoelectron Spectroscopy (XPS or ESCA) - using soft x-ray (200 - 1500 eV) radiation to examine core-levels. Ultraviolet Photoelectron Spectroscopy (UPS) - using vacuum UV (10 45 eV) radiation to examine valence levels. Auger Electron Spectroscopy (AES or SAM) using energetic electron (1000 10,000 eV) to examine core-levels. carried out with radiation spanning a much wider and more complete energy range ( 5 - 5000+ eV ) but such work will remain, a very small minority of all photoelectron studies due to the expense, complexity and limited availability of such sources (Berkeley, Stanford, New York (2), Baton Rouge,
Argonne in the US).

Synchrotron radiation sources have enabled high resolution studies to be

One way to look at the overall photoelectron process is as follows : A + hv = A+ + e1. Conservation of energy then requires that : E(A) + hv = E(A+ ) + E(e-)

(energy is conserved)

2. Since the energy of the electron is present solely as kinetic energy (KE) this can be rearranged to give the following expression for the KE of the photoelectron : E(e-) = KE(e-) = hv [E(A+ ) - E(A)] 3. The final term in brackets represents the difference in energy between the ionized and neutral atoms, and is generally called the binding energy (BE) of the electron - this then leads to the following commonly quoted equation : KE = hv - BE

Photoelectrons
Vacuum Fermi Surface Valence Levels or 2p 2s Core Levels E 1s Photoelectron: BE = h - KE -

0 eV

or

Energy Diagram
Contact Potential

Eb (binding energy) is below the conduction band edge. Fermi energies of metal and spectrometer coincide (electrons

EF

transfer between metal and spectrometer until the EF align).

Contact potential; e( - sp). Ek :measured kinetic energy.

Eb = h - Ek esp (no need to know the work function of the sample

X-ray Sources
Their choice is determined by the energy resolution. Typical materials

are Mg and Al. A heated filament (cathode) emits electrons which are accelerated toward a solid anode (water cooled) over a potential of the order of 5 -20 kV. Holes are formed in the inner levels of the anode atoms by the electron bombardment and are then radioactively filled by transitions from higherlying levels: 1s 2p 3/2 1s 2p 1/2 Resulting in the emission of X-rays Mg K1, 2 at 1253.6 eV Al K1, 2 at 1486.6 eV

Typical emission of X-rays Typical geometry of an X-ray gun

Incident beam E = h

Escaped Si K X-ray (~1.74 keV)

Aluminum windows of 10-30 m thick separate the excitation region from the specimen. Additional x-ray lines (K3 and K4 ) and a continuous spectrum (Bremsstrahlung) are produced. Peaks 10 eV above the K 1, 2 with intensities of 8 % and 4 % of K 1, 2 and a continuous spectrum contribute to the BG.

X-ray Sources Available

X-rays Energy (eV) Natural Width (eV) 2.5 1.4 0.9 0.8 0.7

Cu K Ti K Al K Mg K Na K

8048 4511 1487 1254 1041

Kratos and PHI commonly use AlK and MgK

 To remove the unwanted radiation and increase the energy resolution the AlK is often monochromatized (cut a slice from the x-ray energy spectrum, removing both satellites and Bremstrahlung (which increases the BG level). Crystal used = quartz because can be obtained in near perfect form and can be elastically bent (bending does not affect resolution or reflectivity).
(1)

(2)

Beam (2) travels an extra dsin before reaching the surface and beam (1) Parallel Atomic Planes

n = 2dsin()
dsin

For first order (n =1) diffraction and Al K X-rays, = 8.3 for a distance d between planes of about 4 and a Bragg angle, of 78.5

Rowland circle
For Cu K (~1.55)

The crystal must lie along the circumference of the Rowland circle (focusing circle), Johann focusing geometry.

Analyzers
Dispersive analysis of the kinetic energy spectrum n(KE)
A field is applied between 2 parallel plates, distance s apart. The lower plate has slits a distance r apart (entrance and exit slits). The photoelectrons with kinetic energy KE are transmitted to the detector. By varying Vd the spectrum of electron kinetic energies can thus be obtained. KE is proportional to Vd therefore the plot of electron flux at the detector against V is the photoemission spectrum.
The parallel plate electrostatic analyzer

Vd =

2 sKE er

Spherical mirror analyzer

www.Kratos.com

The alternative to dispersive analysis is to discriminate the electron KE by a retarding electric field applied between the target region and the detector. Electrons with KE > eVr will reach the detector (a kind of filtration process).

Spectrometer
Photo ionization process has a rather low absolute probability (104 electrons per second, or 10-15 A) therefore electron multiplier (gain of 10 6) are used to obtain an accurately measurable current. Newer instruments use channel plates.

Components:
2 4 5

1. Source of radiation 2. Ionization Chamber 3. Electron energy analyzer 4. Electron detector 5. High vacuum system software and computer

Typical Wide Energy Scan

x 10 90 3

O 1s

80

Name O 1s C 1s Si 2p

Pos. 533.50 285.50 104.50

FWHM Area At% 1.633 139182.9 64.047 2.019 3470.7 3.696 1.692 35335.2 32.257

70

Immediate identification of the chemical composition of the surface.

CPS

60

50

40

Si 2p

O (Auger)

30

20

C 1s

10

1000 Washington State University--Pullman, WA

800

600 Binding Energy (eV)

400

200

The core electron binding energies (BE) of the elements are distinctive

Typical High Resolution Spectra

High-resolution acquisition scans yield information such as Chemical shifts Multiplet structure Satellites Chemical bonding

Surface Sensitive Technique

XPS is very surface sensitive

because only electrons from the top few atomic layers (mean free path ~1.5 nm) can escape without loss of energy. The absorption length of the Xrays is about 100 nm to 1000 nm.

Universal Curve

AXIS-165 multi-electron spectrometer

From Kratos analytical Inc.

Summary
A sample placed in ultra-high vacuum is irradiated with photons of energy (h); soft x-rays. Atoms on the surface emit electrons (photoelectrons) after direct transfer of energy from the photons to the core-level electron. This process can be summarized as follows: 1. A bound electron adsorbs the photon, converting some of its energy into kinetic energy. 2. As the electron leaves the atom some of its energy is used to overcome the Coulomb attraction of the nucleus, reducing its KE by its initial state BE. 3. At the same time the outer orbitals readjust, lowering the energy of the final state that is being created and giving this additional energy to the outgoing electron.

Photoelectric effect
Einstein:

= h

h electron

The 3 step model: 1.Optical excitation 2.Transport of electron to the surface (diffusion energy loss) 3.Escape into the vacuum

Solid

Vacuum

2 Diffusion energy loss 3 Escape

1 Excitation

The optical excitation probability is given by the photoionization cross-section (E) In quantum mechanics (E) in a subshell nl (principal and orbital quantum numbers) is given by

4 2 2 1 n ,l ( E ) = a 0 [ N n ,l [ E E n ,l ] ][lR 2 E ,l 1 + (l + 1) R 2 E ,l +1 ] 2l + 1 3
: fine structure constant 1/137, a0 Bohr radius (0.05 nm), Nn,l: number of e in the subshell, En,l the energy of the nl electrons, E: KE of the ejected electrons.

For n =1 and l =0

1,0 (E) =

4 2 2 a 0 N1,0 [E E1,0 ]R 2 E ,0+1 3

The radial dipole matrix elements are

E ,l 1

= P ( r ) rP ( r )dr
n ,l E ,l 1 0

Pnl(r)1/r and PE,l1(r)1/r are the radial parts of the single-particle wave functions of the initial (discrete) and final (continuum) states, respectively. For H, P10(r)=(1/ a0)3/22exp(-r/ a0).

Cooper Minimum: RE,l-1 << RE, l+1, thus RE, l+1 will give the basic features and the energy dependence of the cross-sections. For a radial wavefunction with nodes, RE, l+1 will go through 0 at a particular energy, giving rise to a minimum in the cross-section . Near photoionization threshold: R E, l+1 goes through 0 because 1. Final state (emitted) electron wavefunction is largely excluded from the core region 2. Initial state electron wavefunction has most strength, after it goes through a node. As the photon energy increases the final state electron wavefunction begins to penetrate the core and the overlap goes to 0 due to the node in the initial state wavefunction.
Reference: Cooper Minima in the Photoemission Spectra of Solids, S.L. Molodtsov et al.

Example: Copper (Cu+) versus Silver (Ag+) Increase or decrease of the PE signal of certain states

Photoemission intensity I ( )

total
4

[1

(3 cos 1)] 4

(: asymmetry parameter, : take off angle and total the total cross-section)

References
Surface Analysis, The Principal Techniques Edited by John C. Vickerman, John Wiley &Sons (1997). Handbook X-ray and ultraviolet photoelectron spectroscopy, Briggs, Heyden &Son Ltd (1977). Solid State Chemistry: Techniques, A. K. Cheetham and Peter Day, Oxford Science Publication (1987). Practical Surface Analysis by D. Briggs and M. P. Seah.
Websites: http://srdata.nist.gov/xps, http://www.xpsdata.com, http://www.lasurface.com, http://www.eaglabs.com