Quantification of XPS

Most analyses use empirical calibration constants (called atomic

sensitivity factors) derived from standards:

Note: ASF for H, He very small

- undetectable in conventional
XPS!
Note: XPS spectrum will show
all peaks for each element in
same ratio
Note: Not all XPS peaks for an
element same intensity (in area
ratio proportional to ASF's) choose peak with largest ASF to
maximize sensitivity
Note: Sensitivity for each
element in a complex mixture
will vary

How to measure peak area I

Must include or correct

for (i) x-ray satellites (ii)
chemically shifted species
(iii) shake-up peaks (iv)
plasmon or other losses

XPS depth profiling analysis

Non-destructive
Angle resolved analysis
Sampling depths 10 to 100
Can use different x-ray
sources

Xray

Destructive
Energetic ion beam
sputtering
Sputter rates 10 to 100 /min

Angle resolved XPS

How can we change the degree of the surface sensitivity?
(1) To reduce kinetic energy of photoelectrons to the energy
corresponding to the minimum in the universal curve for
the IMFP, through decreasing of X-ray photo energy.
(2) To collect photoelectrons at more grazing emission angle

X = dcos
The emission angle () is
increased, the surface
sensitivity is increased.

Angle-dependent of Si 2p spectra obtained from

a Si wafer with a native oxide

Non-destructive depth profile

ARXPS measurements

Maximum-entropy model
Prog. Surf. Sci. 69(2002)125
Generate
profile with
models

Calculate peak
intensity

Factor limiting depth resolution and accuracy of

profiles

Physical factors:
Ion energy

Angle of ion incidence

Ion species

Instrumental factors:
Adsorption from residual gas atmosphere
Redeposition of sputtered species
impurities in beam(including neutrals, multiple charge etc)
Non-uniform ion beam intensity and time-dependent ion beam intensity
Crater quality

information depth

Sample characteristics:
Original surface roughness
Crystalline strusture and defects
Alloys, compounds, second phases, insulators

Radiation-induced effects:
Primary ion implantation
Atom mixing
Sputtered-induced roughness
Preferential sputtering and decomposition of compounds
Enhanced diffusion and segregation
Charging of insulators

Optimized depth profiling conditions

Ion Beam:

Low beam energy

Large incidence angle for smooth sample
Small incidence angle for rough sample
High mass ion species
Sample rotation
Large sputtered area
Pure gas feed

Instrumental:

Low partial pressure of reactive gases

Small analysis area and centred in crater
Low kinetic energy signal (low information depth)

Sample characteristics:
Smooth, polished surface
Non-crystalline, no second phases
Components with similar sputtering yields
Good electrical and thermal conductivities
Low interdiffusivities
Low Gibbsean segregation tendencies

Issue
Energetic ion beam can change sample
chemistry
All organic information lost
Preferential sputtering may change
observed stoichiometry

Surface after sputtering

Before sputtering

With sample
rotation

2 keV

0o

10 keV

75o

Imaging XPS
Chemical state x-ray
Gold x-ray photoelectron image (Au4f)

photoelectron image

The spatial resolution is poorer than that of other

imaging techniques such as SEM, STM et al.

XPS instrumentation
An XPS instrument has two main
components:

An X-ray source

An electron energy analyzer

Other optional items:

A low energy electron flood

gun

An ion source

All measurements must be made in ultra-high vacuum (UHV)

Early x-ray source

X-ray tube

Standard lab Xray source is by

very high energy e
beam hitting the
anode.

X-ray Generation

Incident
electron

X-ray
Photon

Secondary
electron

Conduction Band

Conduction Band

Valence Band

Valence Band

Free
Electron
Level
Fermi
Level

2p

2p

L2,L3

2s

2s

L1

1s

1s

Why were Mg and Al k X-ray used in XPS?

Twin anode (Mg/Al) source

Simple, relatively
inexpensive
High flux (1010 1012 photonss-1)
Polychromatic
Beam size ~ 1cm

Why Use an X-Ray Monochromator?

Better energy resolution that allows to separate photoelectron

lines with close binding energies

Improved signal to background ratio by removing background

caused by satellites and bremstrahlung. This allows to obtain
useful signals from elements present at small concentrations,
or from small analysis areas

Minimizes sample damage from heat and unwanted radiation

by separating X-ray source from sample

Monochromators are expensive and decrease the X-ray flux,

which means longer measurement times and less throughput

Principle of monochromatization of x-ray

Bragg relation:
n = 2dsin

Schematic illustrating Bragg angle

n:

diffraction order

x-ray wavelength

d:

crystal spacing

Bragg angle

Synchrotron Radiation
The synchrotron storage ring is a tubular vacuum chamber made to:
Hold an electron beam travelling through it at nearly the speed of
light. Maintain the high energy of the electron beam. As the
accelerating electrons circle the ring at relativistic velocities, they
give off intense beams of light including x-rays. By using a
monochromator the light will be Monochromatic.
Key properties of synchrotron radiation:
high intensity
tunability in wide range
near-coherence
polarized.
pulsed
well collimated

NUS has such a source in Singapore!

Electron Energy Analyzers

resolution

Acceptanc
e angle

Analyzer:
most
essential part of any
electron
spectroscopy,
its
characteristic
are:
energy range, energy
resolution, sensitivity
and
acceptance
angle. Normally its
functions
involve:
retarding
of the
incoming
electron,
selection
of
the
electrons with right
kinetic energy (pass
energy), detecting of
the
electrons
(channeltron)

Most common type of electrostatic deflection-type analyzer

called the concentric hemispherical analyzer (CHA)

Negative potential on two hemispheres V2 > V1

Potential of mean path through analyzer is

An electron of kinetic energy eV = V0 will travel a circular orbit

through hemispheres at radius R0
Since R0, R1 and R2 are fixed, in principle changing V1 and V2 will
allow scanning of electron KE following mean path through
hemispheres

Energy of resolution of Electron Energy Analyzers

1/2

A schematic cross
section of the
ESCALAB
spectrometer

Simplified optical schematics

for the ESCALAB
input lens system Large area XL spectroscopy
mode

XPS at the Magic Angle

Orbital Angular Symmetry Factor
LA () = 1 + A (3sin2/2 - 1)/2
where: = source-detector angle
= constant for a given sub-shell and X-ray photon
At 54.7 the magic angle
LA = 1

XPS systems in IMRE

ESCALAB 220i-XL system

Theta Probe system

Small area XPS (20m)

Imaging XPS (~2 m)
Superior depth profiling
He+ ion scattering
UPS

Analysis area (15m to 400 m)

Parallel ARXPS without sample tilting
Superior depth profiling
SEM
AES

Synchrotron realisation

Laboratory realisation

Strengths and Weaknesses

Strengths
Elemental identification of all elements except H and He
Chemical state identification (oxidation state)
Quantitative analysis
Can analyze insulating samples
Non-destructive depth profile by changing take-off angle
Weaknesses
Complex, expensive instrumentation, UHV technique
Detection limits typically ~500 ppm
Not usually spatially sensitive (smallest analytical area ~20 m)
Limited organic information
Sampling depth varies with electron KE (and material, sampling
depth typically 20-100 )