This action might not be possible to undo. Are you sure you want to continue?
for Chemical Analysis
This material is strictly for the MM653 course and shall not be utilised for any other purpose.
Surface Analysis - Wish List What Can be done?
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
Interaction with material
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
Sample Surface Layer
Ev f valence band photon core levels Ef BE
binding energy (eV) = photon energy - kinetic energy - work function BE (eV) = hν - KE - Φ
Fluorescence or Auger electron emission
scattered) X-rays in Photoelectrons out (elastically scattered) d d = 3l Bonding to anti-bonding orbital transitions lead to peaks at higher binding energy (lower kinetic energy).The Photoelectron Spectrum Photoelectrons out (inelastically. .
Surface Sensitivity of XPS Penetration depth of the X-ray radiation is 102-103 nm. X-rays in Photoelectrons out d d = 3l . Surface sensitivity arises from the short distance the photoelectrons can travel in the solid before suffering inelastic scattering.
defined as the average distance from the surface for which 95% of photoelectrons are detected. Sampling depth. l. ‘universal curve’ . d = 3l. d.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).
Sensitive .X-ray Photoelectron spectroscopy is. Surface sensitive . . • Nondestructive analysis.detection limit ~0. Provides insight into the chemical state of the element. Able to detect all elements except H and He. Quantitative (!!?)...1 atomic %.photoelectron signal from first 1-10 layers of atoms and molecules.
Temperature effect and Life time broadening .JJ Coupling.
Peaks are superimposed on a rising background.The Photoelectron Spectrum O 1s O KLL Auger Both photoemission and Auger peaks observed in a spectrum. 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 .
S Cu 2p1/2 S Cu 2p3/2 S = Shake-up satellites 970 960 950 940 930 Photoelectron energy reduced by associated Π – Π* 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. 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. Valence electron. .
nature of electron distribution TiO2 .Ti – 2p Chemical shift due to Oxidation state Hybridisation Ionic character ie.
-note large chemical shift between elemental Si and silicon dioxide peaks.XPS Spectra Showing the Chemical State of Si Si elemental Si oxide Si oxide Two samples with different SiO2 film thicknesses on Si substrate. Si elemental d d 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 .
6 Al 1486. X-ray Energy / kV . Bremsstrahlung.6 Width (eV) 0.4 Bremstrahlung radiation • Use of a monochromator prevents electrons. Commonly used X-ray sources anode material energy (eV) Mg 1253.2 Ka3. • The monochromator also decreases the energy spread of the X-rays. satellite X-ray lines and heat radiation striking the sample.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.7 0.85 X-ray Intensity as a Function of Energy X-ray Intensity (arbitrary units) Ka1.
Thin layer coatings increasingly used in industry to improve surface properties.Depth Profile through a TiN/SiO2 thin film on Si. TiN SiO2 Si substrate . Depth profiling combined with XPS allows valuable film thickness and chemical state information to be determined.
High resolution of the Ti region indicates that Ti is also present as TiOx in the TiN layer. as shown in the Ti 3d region recorded from the subsurface.Depth Profile through a TiN/SiO2 thin film on Si. TiO TiN TiO 2 TiOx persists through the entire TiN layer. .
Full Chemical state concentration depth profile through TiN film allowing determination of film thickness. .Depth Profile through a TiN/SiO2 thin film on Si.
Depth Profile through a TiN/SiO2 thin film on Si. Si SiO2 TiN . Si 2p region as a function of depth from the surface Si 2p region shows chemical environment of the Si atoms.
6 eV-0.6 eV.7 eV Quartz (10ī0) crystal diffraction Line width to 0.0.25 eV (Al).X-ray monochromator Al 1486. Cuts Bremsstrahlung. satellites Can focus to <15 μm.9 eV Mg 1253. .
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 .
0eV 65 at% C(2) 286.2eV 12 at% O 1 C1 O 1s region O(1) 530.Quantitative Surface Analysis of Poly(ethylene tetraphthalate) .8eV 51 at% O(2) 532.1eV 49 at% O2 O1 C3 C2 .PET 1 2 3 3 2 2 2 -(-O-C= 1 -C-O-CH2-CH2-)= n O C 1s region C(1) 285.5eV 23 at% C(3) 289.
Angular Dependence of XPS X-rays photoelectrons X-rays photoelectrons d d > d* d* d=3lsinq .
Angular Dependence of Phototelectron yield .
Variable take-off angle: sample rotated to increase surface sensitivity q 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) .
will provide a nondestructive depth profile. . • this is limited to film thicknesses less than the sampling depth (~100 Å). the sampling depth can be changed.Non-destructive depth profile • By rotating the sample about it’s axis. • collecting data at different angles.
. followed by data acquisition. When the etch / spectrum cycle is repeated a destructive depth profile of several 1000’s Å through the sample may be acquired.destructive Destructive depth profile can be achieved by Ar+ bombardment of the sample to remove surface atoms.Depth Profile .
TiN SiO2 Si substrate . Depth profiling combined with XPS allows valuable film thickness and chemical state information to be determined.Depth Profile through a TiN/SiO2 thin film on Si. Thin layer coatings increasingly used in industry to improve surface properties.
TiO TiN TiO 2 TiOx persists through the entire TiN layer.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. as shown in the Ti 3d region recorded from the subsurface.
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.Depth Profile through a TiN/SiO2 thin film on Si. 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? .
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 .Definitions .resolution and sensitivity Sensitivity .counts per second (cps) at the peak maximum.
5 micrometres ISS (ion scattering spectroscopy) Ions H. 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. EDX (field emission SEM) Backscattered or Secondary Electrons and X-Rays Na-U 1 . .30nm chemical composition chemical structure monolayer Adsorbate bonding (electron spectroscopy for chemical analysis. SIMS (secondary ion mass spectrometry) Secondary Ions H-U 5-30 Å Chemical composition Chemical structure TOF-SIMS (time-of-flight SIMS) Secondary Ions H-U. Large Organic Molecules / Cluster Ions 2000 Å (Scanning Mode) Adsorbate bonding TEM (transmission electron microscopy) Transmitted Electrons X-Rays Na-U EDX N/A FE-SEM.Techniques Available Analytical Technique Signal Measured Elemental Range Depth Resolution Surface info.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 .
25 eVmm-1 Electron gun & x-ray anode Energy dispersive direction. For 500 mm 250 mm ~ 0.X-ray Monochromator The Rowland circle geometry Toroidal quartz backplane Rowland circle diameter Energy dispersion E ~ Rowland circle diam.625 eVmm-1 ~ 1. E Fixed mono spot .
Cylindrical Mirror Analyser .
This action might not be possible to undo. Are you sure you want to continue?
We've moved you to where you read on your other device.
Get the full title to continue reading from where you left off, or restart the preview.