Electron Spectroscopy

for Chemical Analysis

This material is strictly for the MM653 course and shall not be utilised for any other purpose.

MM653

Surface Analysis - Wish List What Can be done?

EXCITATION

photons

EMISSION

Properties and reactivity of the surface will depend on: bonding geometry of molecules to the surface physical topography chemical composition chemical structure atomic structure electronic state
electrons

ions

Interaction with material

TRANSMISSION

Surface Analysis constraints

A sample with a surface of size 1 cm2 - this will have ~ 1015 atoms in the surface layer. In order to detect the presence of impurity atoms present at the 1 % level, a technique must be sensitive to ~ 1013 atoms. Contrast this with a spectroscopic technique used to analyse a 1 cm3 bulk liquid sample i.e. a sample of ca. 1022 molecules. The detection of 1013 molecules in this sample would require 1 ppb (one

part-per-billion) sensitivity - very few techniques can provide

anything like this level of sensitivity.

Add to this the need of Selectivity to surface atoms only!!!

The Photoelectron Process

X-rays in photoelectrons out

KE

Sample Surface Layer

Ev f valence band photon core levels Ef BE

binding energy (eV) = photon energy - kinetic energy - work function BE (eV) = h - KE -

After Photoemission

Fluorescence or Auger electron emission

The Photoelectron Spectrum

Photoelectrons out (inelastically, scattered) X-rays in

Photoelectrons out (elastically scattered)

d = 3l
Bonding to anti-bonding orbital transitions lead to peaks at higher binding energy (lower kinetic energy).

Surface Sensitivity of XPS

Penetration depth of the X-ray radiation is 102-103 nm. Surface sensitivity arises from the short distance the photoelectrons can travel in the solid before suffering inelastic scattering.
X-rays in Photoelectrons out

d
d = 3l

Surface Sensitivity of XPS

The average distance from the surface a photoelectron can travel without energy loss is defined as the inelastic mean free pathlength (IMFP), l.
Sampling depth, d, defined as the average distance from the surface for which 95% of photoelectrons are detected, d = 3l.
universal curve

X-ray Photoelectron spectroscopy is...

Surface sensitive - photoelectron signal from first 1-10 layers of atoms and molecules. Quantitative (!!?). Provides insight into the chemical state of the element. Sensitive - detection limit ~0.1 atomic %. Able to detect all elements except H and He. Nondestructive analysis.

JJ Coupling, Temperature effect and Life time broadening

The Photoelectron Spectrum

O 1s

O KLL Auger

Both photoemission and Auger peaks observed in a spectrum. Peaks are superimposed on a rising background, due to inelastically scattered photoelectrons.
C 1s

Cu 2p

Cu LMM Auger N 1s Cl 2p Inelastically scattered photoelectrons Cu 3s Cu 3p

Inelastically scattered photoelectrons contribute to the spectral background

Cu 2p1/2

Cu 2p3/2

S = Shake-up satellites 970 960 950 940 930

Photoelectron energy reduced by associated * transition

Chemical State Information

The binding energy of an electron is dependent on the atomic orbital the electron occupies and the chemical environment of the atom.

Valence electron, low binding energy

Core level electron, high binding energy

The variation of binding energy of a specific photoemission peak provides information on the chemical state of the atom or ion.

Ti 2p

Chemical shift due to Oxidation state Hybridisation Ionic character ie. nature of electron distribution

TiO2

XPS Spectra Showing the Chemical State of Si

Si elemental Si oxide Si oxide

Two samples with different SiO2 film thicknesses on Si substrate. -note large chemical shift between elemental Si and silicon dioxide peaks.

Si elemental

Si oxide

Si elemental

Instrumentation for XPS

X-ray source Electron energy Analyser Electron Counter Vacuum to Save hot components Tube filament Save surface from Adsorption for some time Avoid scattering in gas phase

Monochromated vs non-monochromated X-ray source

X-rays generated by accelerating high energy electrons onto an anode. The core holes created decay by emission of X-rays.
Commonly used X-ray sources anode material energy (eV) Mg 1253.6 Al 1486.6

Width (eV) 0.7 0.85

X-ray Intensity as a Function of Energy

X-ray Intensity (arbitrary units)

Ka1,2

Ka3,4 Bremstrahlung radiation

Use of a monochromator prevents electrons, Bremsstrahlung, satellite X-ray lines and heat radiation striking the sample. The monochromator also decreases the energy spread of the X-rays.

X-ray Energy / kV

Depth Profile through a TiN/SiO2 thin film on Si.

Thin layer coatings increasingly used in industry to improve surface properties. Depth profiling combined with XPS allows valuable film thickness and chemical state information to be determined. TiN SiO2 Si substrate

Depth Profile through a TiN/SiO2 thin film on Si.

High resolution of the Ti region indicates that Ti is also present as TiOx in the TiN layer.

TiO TiN TiO 2

TiOx persists through the entire TiN layer, as shown in the Ti 3d region recorded from the subsurface.

Depth Profile through a TiN/SiO2 thin film on Si.

Full Chemical state concentration depth profile through TiN film allowing determination of film thickness.

Depth Profile through a TiN/SiO2 thin film on Si.

Si 2p region as a function of depth from the surface

Si 2p region shows chemical environment of the Si atoms.

Si SiO2 TiN

X-ray monochromator

Al 1486.6 eV- 0.9 eV Mg 1253.6 eV-0.7 eV

Quartz (100) crystal diffraction Line width to 0.25 eV (Al), Cuts Bremsstrahlung, satellites Can focus to <15 m.

Monochromated vs non-monochromated X-ray source

FWHM 0.46 eV

Monochromated Al Ka excited Ag spectrum

FWHM 0.97 eV

Non-monochromated Mg Ka excited Ag spectrum

Quantitative Surface Analysis of Poly(ethylene tetraphthalate) - PET

1 2 3 3 2 2 2

-(-O-C=
1

-C-O-CH2-CH2-)=
n

O
C 1s region
C(1) 285.0eV 65 at% C(2) 286.5eV 23 at% C(3) 289.2eV 12 at%

O
1

C1

O 1s region
O(1) 530.8eV 51 at% O(2) 532.1eV 49 at%

O2

O1

C3 C2

Angular Dependence of XPS

X-rays photoelectrons X-rays

photoelectrons

d > d*

d*

d=3lsinq

Angular Dependence of Phototelectron yield

Variable take-off angle: sample rotated to increase surface sensitivity

X-rays

3l

d= 3lsinq

X-rays
q

3l

d= 3lsinq

Angular Dependence of XPS

0 deg (bulk sensitive) 45 degrees

60 degrees

75 degrees (surface sensitive)

Non-destructive depth profile

By rotating the sample about its axis, the sampling depth can be changed. collecting data at different angles, will provide a nondestructive depth profile. this is limited to film thicknesses less than the sampling depth (~100 ).

Depth Profile - destructive

Destructive depth profile can be achieved by Ar+ bombardment of the sample to remove surface atoms, followed by data acquisition.
When the etch / spectrum cycle is repeated a destructive depth profile of several 1000s through the sample may be acquired.

Depth Profile through a TiN/SiO2 thin film on Si.

Thin layer coatings increasingly used in industry to improve surface properties. Depth profiling combined with XPS allows valuable film thickness and chemical state information to be determined. TiN SiO2 Si substrate

Depth Profile through a TiN/SiO2 thin film on Si.

High resolution of the Ti region indicates that Ti is also present as TiOx in the TiN layer.

TiO TiN TiO 2

TiOx persists through the entire TiN layer, as shown in the Ti 3d region recorded from the subsurface.

Depth Profile through a TiN/SiO2 thin film on Si.

Full Chemical state concentration depth profile through TiN film allowing determination of film thickness.

Depth Profile through a TiN/SiO2 thin film on Si.

Si 2p region as a function of depth from the surface

Si 2p region shows chemical environment of the Si atoms.

Si SiO2 TiN

Elemental Distribution

Destructive and non-destructive depth profiling provides information on elemental distribution from the surface into the bulk. What about elemental distribution across the surface? What modes of acquisition can be used to probe lateral (2-dimentional) distribution at the surface?

Definitions - resolution and sensitivity

Sensitivity - counts per second (cps) at the peak maximum.

Full width at half maximum (FWHM)- the width of a peak in eV defined at the point half way from the baseline to the peak maximum

Techniques Available
Analytical Technique Signal Measured Elemental Range Depth Resolution Surface info. SIMS
(secondary ion mass spectrometry) Secondary Ions H-U 5-30 Chemical composition Chemical structure

TOF-SIMS
(time-of-flight SIMS)

Secondary Ions

H-U, Large Organic

Molecules / Cluster Ions

2000 (Scanning Mode)

Adsorbate bonding

TEM
(transmission electron microscopy)

Transmitted Electrons X-Rays

Na-U EDX

N/A

FE-SEM, EDX
(field emission SEM)

Backscattered or Secondary Electrons and X-Rays

Na-U

1 - 5 micrometres

ISS
(ion scattering spectroscopy)

Ions

H- U

monolayer

atomic structure
chemical composition

AES/SAM ESCA/XPS RAIRS STM

Auger Electrons

Li-U

2-30nm

chemical composition

(Auger electron spectroscopy, scanning Auger microscopy) Photoelectrons Li-U 5 - 30nm chemical composition chemical structure monolayer Adsorbate bonding

(electron spectroscopy for chemical analysis, X-ray photoelectron spectroscopy) IR photons organic, some inorganics

(reflection-absorption infra-red spectroscopy)

solid surfaces

upper most atoms

physical topography

(scanning tunnelling microscopy)

Analytical Technique

Signal Measured

Elemental Range

Depth Resolution

surface info,

X-ray Monochromator The Rowland circle geometry

Toroidal quartz backplane Rowland circle diameter

Energy dispersion E ~ Rowland circle diam. For 500 mm 250 mm ~ 0.625 eVmm-1 ~ 1.25 eVmm-1

Electron gun & x-ray anode

Energy dispersive direction, E

Fixed mono spot

Cylindrical Mirror Analyser