Advanced

Materials
Characterization
Techniques
LECTURE - 5

Pavan Bosukonda
 Energy Analyzers
Measure K.E.XPS – resolve electrons based on KE Cylindrical Mirror Analyzers (CMA)
No detection – only separation
High energy resolution & transmission
Concentric Hemispherical Analyzer (CHA)

Cylindrical Mirror Analyzers (CMA)

• Double focusing
• Take-off angle (47.7 deg)
• Higher transmission

• Poorer energy/angle resolution

• Sensitive to distance between sample
and detector
1.0 to 0.1 eV resolution

Double-pass CMA
Energy Analyzers
Concentric Hemispherical Analyzer (CHA)
Hemispherical sector analyzer
Spherical deflection analyzer
Electrostatic hemispherical analyzer

Most common – due to high resolution (0.01eV)

Much better than X-ray source energy spread

Less sensitive to distance

Transfer lens – accessibility to sample and collect

Larger areas
Lower transmission than CMA due to smaller
collection angle
Mode of operation

Fixed retard ratio (FRR) the potentials are scanned to allow different E0

Energy resolution is a function of E0

High quality CMA’s – 0.1 % of KE – so for 1000 eV electrons – 1 eV

Constant Analyzer Energy (CAE) or Fixed Analyzer Transmission (FAT) differently accelerated – transfer lens

Energy resolution independent of KE

Pass energy

Lower Pass energy – higher resolution but lower sensitivity

Energy resolution
Monochromatic sources - 0.2 to 0.3 eV
FWHM of the source (X-ray)
Non-Monochromatic sources - intrinsic line width (0.85 (Al-Kα))

Irreducible line width – reflecting core hole lifetime

Line width of the Photoelectron emission Lorentzian component
Line broadening by phonons (or other final state effects)
Gaussian component

High quality CHA at low pass energy (0.001 eV)

Energy resolution of the analyzer
High quality single pass CMA ~ 0.1%

Measure FWHM of a core level peak with minimal ∆𝐸𝑎

Ag-3d peak

Good quality instrument with monochromatic source and CAE/FAT mode (5-10 eV) analyzer – 0.3 -0.5 eV
Detectors

Number of electrons

Best sensitivity – individual counting of electrons

1 electron : -1.6 x 10-19 C or A (when single electron per sec)

Sensitivity of pulse counting electronics – 10-15 A

Amplifier Collector

Electron mulitpliers (EM) – amplification of signal

Discrete dynode EMs

Channeltrons (channel electron multipliers)

Microchannel plate detectors (MCP)

EMs

Discrete dynode EMs

Electron emissive material coated electrode

Individual electrodes (dynodes)

1cm x 1 cm

Gain - 109

Saturation ~ 1x106 cps

Channeltron

Gains - 108

1D arrays can be constructed

(binning of energy or increased sensitivity)

The amplification factor for EMs is function of KE

EMs
MCP

2 D array of parallel glass capillaries (10-25 micrometers)

Gain - 104
Axis ~ 7 deg

Chevron MCPs
Detector/collector

Anode collector – metal electrode – connected to pulse counting electronics

Phosphor screens Electrons Photons CCD camera

Delay line detector Used with MCPs

Imaging
Mapping particular energy spatially
Spatial mapping
Map the whole spectrum for every pixel

Scanning sample stage – millimeters of scan area

Scanning X-ray spot – Probe defined mode

Serial Imaging
Hundreds micrometers – raster the electron beam (monochromatic)

Collection area modulation – Lens defined mode

Hundreds micrometers - Transfer lens/aperture

Parallel Imaging Imaging area – few hundred micrometers

2 D detector

Energy filtering at focal points

Parallel imaging
Parallel imaging
Analysis procedures

Sample handling Size, Surface, UHV compatiblity

Data collection

Energy referencing

Charge compensation

X-ray damage
Data Collection
Low resolution spectra (survey scan)
0-1000 eV – poor energy resolution (>40 eV pass energy,
0.5 eV steps)
Selected regions – High resolution spectra-
longer recording times

Auger peaks identification – use different sources

Referencing
Energy reference
Calibration
Charge compensation

Insulating Samples – Charge Buildup

Charge Buildup – moderate (skewing the peaks to
Higher BE)

Charge Buildup – Extreme(neutralization of peaks)

Co-irradiating with low energy electron flood gun

(10 eV or less)
Avoid self compensation
Effective charge compensation - symmetric peaks

In case of ion beams – below sputtering threshold

Low intensity X-ray source

Low rate of charge removal + increased electron flux

Placing earthed conductive grid or conducting tape close to area analyzed

Coat sample with conducting material (Carbon/Au)

Photoelectron Intensities
Photoelectron cross sections

The probability that a photoelectron will be ejected from an atom/ion

Vary from element to element (also across energy levels)
Don’t vary with chemical environment
Or even oxidation state
Scofield cross sections (1976) – Al-Kα and Mg-Kα

Inelastic mean free path

Distance a PE can travel within the solid before loosing energy

by inelastic collisions
Photoelectron Intensities
Instrument Geometry
Quantification
Accuracy of 5-10 % (no reference materials)

Error sources

Background subtraction effectiveness

Inaccurate electron IMFP
Variation of concentration within the area analyzed
Microscopic inclusions
Homogenous area assumption
Macroscopic regions of different compositions

Thin films (less than sampling depth) Sensitivity Factor (F)

Instrument specific, element and level

I – area under the PE peak

Hydrogen unaccounted for (error in case of
Ca – concentration of PE emitting atom/ion substantial H content)
αpc – Photoelectron cross section J – X-ray flux
Kf – instrument factors (transmission) λIMFP – IMFP of PE
Depth Profiling
Layers – spatially homogenous at least within the area analyzed

Angle resolved XPS (AR-XPS) & Energy resolved XPS <10 microns

Sputter Depth Profiling >10 microns

Angle resolved XPS (AR-XPS) & Energy resolved XPS

Depth of interest ≤ 3𝜆𝐼𝑀𝐹𝑃 Sampling depth

Tilting sample - sequential

Parallel imaging
Depth Profiling
Parallel imaging

Energy-resolved XPS

𝜆𝐼𝑀𝐹𝑃 varies with K.E.

Different X-rays sources

Different core levels

Depth Profiling
SiO2
Sputter Depth Profiling TiB
Si
removal of surface atomic layers – by
Impact of energetic ions

Analyze beyond max. sampling depth

Less than max. sampling depth AR-XPS is

better

Ar+ ions – 0.5 to 5.0 keV

Cluster Ions – less damage

Sputtering – elastic collisions

Sputtering damage/errors
Preferential sputtering
Recoil implantation
Cascade mixing