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Surface

Analysis Methods
X-ray Photoelectron Spectroscopy

Outline
Photoelectric Eect Instrumenta8on
X-ray source Electron energy analyzer Ar ion gun Neutralizer Vacuum system

XPS Examples

Photoelectric Effect
Light striking a surface causes electron excita8on Einstein, Nobel Prize 1921

Photoelectric eect as an analy8cal tool Kai Siegbahn, Nobel Prize 1981

X-ray Photoelectron Spectroscopy


X-ray hv 1253.6 eV Ek = kinetic energy e- e- of electrons Ev hv

e- Ek = hv-B.E.- valence electrons

B.E. = hv-Ek-
15000

Eb
C1S 6000 5000

core electrons

Survey Scan
O1S

High Res Scan

Counts

10000 F1S 5000 N1S

Counts

4000 3000

-NO2

-NH2

1000

800

600

400

200

410 408 406 404 402 400 398

Binding Energy, eV

Binding Energy, eV

Photoemission
Photoemission can be thought of as three steps (a) Photon absorp8on and ioniza8on (ini8al state eects) (b) Response of atom and crea8on of photoelectron (nal state eects) (c) Transport of electron to the surface (extrinsic eects)

Photoelectron Escape Depth


e- X-ray hv 1253.6 eV e- e-

e- inelastic scattering

10 nm

15000

Counts Core level electrons that have lost KE due to collisions within sample

10000 5000 0

600

400

200

Binding Energy, eV

Photoelectrons Auger electrons X-rays

Auger process and x-ray photon emission Low atomic number elements, the most probable transi8ons occur when a K-level electron is ejected by the primary beam, an L-level electron drops into the vacancy, and another L-level electron is ejected (KLL) Higher atomic number elements have LMM and MNN transi8ons that are more probable than KLL.

Chemical Effects in XPS


Chemical ShiV: The change in binding energy of a core electron of an element due to a change in the chemical bonding environment of that element

Withdrawal of electron charge Addi8on of electron charge

Increased B.E. Decreased B.E.

XPS Schematic

X-ray source Electron energy analyzer Ar ion gun Neutralizer Vacuum system

XPS - source
X-ray anode like SAXS Al, Mg or Ag radia8on

Can also use synchrotron radia8on

Spatial Resolution
Two ways to create spa8ally resolved photoelectron map of a surface Focus your X-rays (dicult) Focus your photoelectrons (easier)

Focusing Electrons
Much like electron microscopy, apertures and lenses are used to focus electrons

Imaging XPS
By focusing the photoelectrons you can scan across a sample much like SEM Can generate XPS images Alterna8vely, can use a 2D detector to image all photoelectrons simultaneously, like SAXS

In prac8ce both methods can be used

Charge Neutralization
Photoelectric process is a net oxida8on, thus a build up of posi8ve charge occurs For a conduc8ve sample this is negated by grounding Insula8ng samples however cannot dissipate the charge Sample charging results in aberra8ons in the spectra Electron gun can be used to alleviate charging problem

XPS Detectors

Delay-line detector similar to SAXS or use a photomul8plier tube (limited lateral resolu8on)

Example: PET

1 2 3 3 2 2

-(-O-C- -C-O-CH2-CH2-)- = O
1

Poly-ethylene-terephthalate

= O
1

Spin Orbital Splitting


For p, d, f orbitals two peaks are observed The separa8on between peaks is similar for all compounds of a given element Peak area ra8os are the same for a given orbital

Spin-orbital spli`ng

Quanti\ication
Must account for inelas8cally scabered electrons when considering baseline Transmission Factor a func8on of detec8on eciency of an electron in the analyzer which is a func8on of the electron energy Orbital Cross-Sec8on another correc8on based on the ioniza8on probabili8es calculated from scabering theory In prac8ce the transmission factor and orbital cross sec8on are automa8cally computed by the analysis soVware

Depth Effects
Sample with dierent depths of oxide layers Note large chemical shiV dierence between SiO2 and elemental Si

Si oxide Si elemental

Sampling Depth

Electrons in a solid have a nite mean free path For typical X-ray energies (Al, Mg) the depth sampled is < 10 nm Thus XPS is a surface sensi8ve technique However, we may want to look deeper or shallower, how do we achieve this?

Angle Resolved XPS (ARXPS)


To look at shallower slices we can rotate the sample at an angle to the detector

Example: Al lm

Depth Pro\iling
To go deeper into the sample we can use an ion gun to etch away the top layers Typically performed with Ar+ ions, energies of 0.5-5 kV

Example of a depth prole of a glass with a metal alloy in the centre

XPS Imaging

Photoresist Si oxide Si metal

Image by scanning at a given B.E. for each element

XPS Imaging
Can record spectra at selected posi8ons

XPS Imaging
Line prole generated showing the loca8on of C, Siox and Simet

Energy Losses in XPS


Plasmon Loss In some materials there is a probability of loss of a specic amount of energy due to interac8on between the photoelectron and other electrons b bulk plasmon s surface plasmon

Some electrons loose energy more than once

Energy Losses in XPS


Shake up peaks For some materials the photoelectric process leads to forma8on of an ion in an excited state instead of the ground state.

Example: Iden8ca8on of Cu (II) by shake up peaks

X-ray induced Auger Spectroscopy (XAES)


Talked briey about the Auger process earlier Since it is simply an electron our detector records the events

XAES
Some8mes photoelectron peak is insucient for oxida8on state iden8ca8on XPS Spectra of Cu2O and Cu metal

Spectra of Cu LMM peak demonstrates dierence

Wagner Plot
Wagner introduced a new parameter to XPS analysis , the Auger parameter = K.E.Auger + B.E.Photoelectron