XPS (X ray photoemission spectroscopy)

/ESCA (Electron Spectroscopy for Chemical Analysis)

XPS
Core-levels:
core-levels are more atomic-like:
chemical shifts from formal oxidation
state of the atom, the local chemical and
physical environment :
like Auger electron it has also short :
Angular dependence has
diffraction effects:
Magnetic dichroism

electronic
element
chemical
surface sensitive
structure
magnetic

Theoretical consideration
As photoemission is
much more simple
process than Auger
process,
conservation of
energy then requires
that :
KE = h - ( E(A+ )
- E(A) ) -
The final term in
brackets,
representing the difference in energy between the ionized and neutral atoms,
is generally called the binding energy (BE) of the electron . ( is the work
function of the solid when KE is counted near surface, however, KE detected
by analyzer then is the work function of analyzer.)

Z dependence
BE follows the energy levels: BE(1s)>BE(2s)>BE(2p)
BE with same orbital increase with Z: BE(Mg1s)>BE(Na1s)

Elemental specific!

XPS data base

Main features of XPS

Three Step Model

1. Absorption
of the
photon and
excitation of
electrons
2.Transport of
electrons to
the surface
3.The escape of
the electrons
from surface
to the
vacuum.

Inelastic scattering

In the step 2, inelastic scattering let XPS spectra consists of core-level photoemission peaks imposed by a step-like structure (background) due to the
various mechanism to lose kinetic energy. Besides, there are also AES processes
visible.

XPS peak fit

XPS peak identification

Photoelectron lines: core-level,
valence bands, spin-orbit splitting
Auger lines
Chemical shifts
X-ray satellites
X-ray Ghost
Shake-up satellite
Multiplet satellite
Energy loss lines

Spin-Orbit splitting:

Spin-orbit splitting is
an initial state effect.
For any electron in
orbital with orbital
angular momentum,
coupling between
magnetic fields of
spin (s) and angular
momentum (l) occurs
Lower binding energy

Higher binding energy

Total angular momentum j

= |l s|, therefore for s
electron there is no
degeneracy, and other
orbitals have two
degeneracy:
- s orbitals are not spinorbit split - singlet in XPS
- p, d, f orbitals are
spin-orbit split - doublets
in XPS
- BE of lower j value in doublet is higher (BE 2p1/2 > BE 2p3/2)
- Magnitude of spin-orbit splitting increases with Z
- Magnitude of spin-orbit splitting decreases with distance from nucleus
(increased nuclear shielding)

Intensity ratio?

Core Level Chemical Shifts

Position of orbitals in atom is sensitive to chemical environment of
atom. In solid all core levels for that atom shifted by approx. same
amount (<10 eV). Chemical shift correlated with overall charge on
atom (Reduced charge increased BE)
For k-shell of an atom in a compound:

EB(k) = EB(k,qA) +V
where EB(k,qA) is the binding energy of a free ion, A, qA is the net
charge of A, and V is the potential at A due to all other atoms. V can
be described as:

V = e2qAqi/riA
(i is any other atoms except A), riA is the distance between i and A,
therefore chemical shift is:

EB(k)=EB(k,qA1)-EB(k,qA2 )+V1 V2
qA1 and qA2 is the difference of charge in two states.

XPS spectra for Si and its

compounds with F in a) and
chemical shifts vs. the charge in b)

Both S and Si binding energies

increase with psitive charge (the
loss of negative charge of
electron), and the same for C.
Functional
Group
hydrocarbon

C-H, C-C

Binding Energy
(eV)
285.0

amine

C-N

286.0

alcohol, ether

C-O-H, C-O-C

286.5

Cl bound to C

C-Cl

286.5

F bound to C

C-F

287.8

carbonyl

C=O

288.0

The
chemical
shifts due to the
variation of the
distribution of
the charges at
the atom site is
the main reason
for the other
name of XPS:

ESCA
(Electron
Spectroscopy for
Chemical Analysis)

As the samples shown before, binding energies of Al 3+ is higher than the

metal atom, in the meanwhile, the binding energy of O atom (more
positive charge) is higher than the O2- ion.

Shake-up and shake-off

Photoemission
process can leave the
ions in the ground
state (main peak) and
also possibly in an
excited sate (shakeup/shake-off
satellites), the latter
makes the KE of
photoelectron
less:
higher BE.
- excitation of electron
to bound state shakeup satellite
- excitation of electron
to
unbound
(continuum)
state
shake-of satellite

The shown is XPS

spectra for Cu 2p
photoemission at
different chemical
states. The shake-up
Lines does not exist
in Cu metal, and
is unique for CuO
And CuSO4

Some general rules

Shake-up features especially common in
transition metal oxides associated with
paramagnetic species. Generally, the shakeup/shake-off satellites have intensities and energy
separations from the parent photoelectron line that are
unique to each chemical state, which can be used to
analyze the chemical state of the elements. Even Some
Auger lines also exhibit changes due to these processes.
With transition metal, the absence of these lines is the
fingerprint for elemental or diamagnetic states.
Prominent satellites occurs with paramagnetic states.

Multiplet splitting and shake-up/shake-off lines are generally expected in

the paramagnetic states:

MnO XPS spectra

Chemical shifts are too
small to distinguish the
chemical states of Mn in
MnO from a). In b) the
satellites are due to Mn2+,
while for Mn3+ and Mn4+,
although there should be
satellites, they are with
higher binding energies.

Shake-up/Shake-off
satellites are another
reason for the
chemical sensitivity
of XPS

Multiplet satellite

Following
photoelectron
emission,
the
remaining
unpaired electron may couple
with other unpaired electrons
in the atom, resulting in an ion
with several possible final
state configurations with as
many different energies. This
produces a line which is split
asymmetrically into several
components.
For s-type orbital with other
unpaired electrons in the atom
there are split lines like in the
shown Figure for Mn 3s.
For p or even higher orbital
levels, is more complex and
subtle

Energy loss lines

eph + esolid

e*ph + e**solid

Photoelectrons travelling through the solid can interact with other electrons
in the material. These interactions can result in the photoelectron exciting an
electronic transition, thus losing some of its energy (inelastic scattering).
Most common are due to interband or plasmons (bulk or surface).

(bulk plasmon)
Surface
plasmon

The plasmon loss satellites are rarely sharp in insulators but very
prominent in the metals. The main peak is normally observed at
higher binding energy with several lines with the same energy
intervals and reduced intensity, and the interval can be not only
single one due to different origins: bulk or surface plasmons, bulk
one is more prominent and interval larger (21/2 factor of the
surface one).

Energy of Light

1 MeV

Gamma Ray

1 KeV
UV

Visible

Short wave radio

Broad-cast

10 eV 1 eV
-3

Infrared

10 eV
-6

10-3m 10-6m

X-ray

Wavelength
3
6
10
m 1 m
10
m
()

Energy
(E)

X-ray tube

Standard lab Xray source is by

very high energy e
beam hitting the
anode.

Early x-ray source

A common Dual anode X-ray tube

X-ray spectrum from x-ray tube

Characteristic lines from the X ray

fluorescence process (XRF) and a
broad background (Bremsstrahlung),
which is strongly depends on the
energy of the electron

Typical X-ray anode material (Mg and Al)

2p3/2 1s and 2p1/2
1s transitions produce
soft x-rays
K1,2 radiation
(unresolved doublet)
h (eV)
Mg
0.7

1253.6

Al
0.85

1486.6

FWHM (eV)

Same transitions in
doubly ionized Mg or Al
produce K3,4 lines at
h~ 9-10 eV higher
3p 1s transitions

Energies and widths of characteristic

soft X-ray lines of different materials

Mg K-shell X-ray emission spectrum

The full line

shows the
characteristic
line emissions
after
subtraction of
a constant
background as
shown by the
dashed line.
Note the
logarithmic
intensity
scale.

X-ray satellites

Emission from non-monochromatic x-ray

sources produces satellite peaks in XPS
spectrum at lower BE.

ghost peaks
O Ka at 524.9 eV

Ghost peaks are due to contamination of the x-ray source, which

produces x-ray emission at different wavelength and it can also
due to contamination of the sample holder etc.

Monochromatic X-ray
1.

Goal to achieve

2.
3.

Energy
Analyzer

Rowland Circle
e-

Narrow peak width

Reduced background
No satellite & Ghost
peaks

Quartz
Crystal Disperser
n=2dsin

Sample
X-ray Anode

For quartz (1010)

surface, d=0.42 nm
and 78.5 degree for
Al K0.93 nm

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!

Sample charging effects

The light for XPS always charges surface positively (shifting of
spectrum to higher binding energy) and leads to general instability
(spectral noise). For the metal sample, which can be grounded and the
charges can be quickly gone. However, for insulator, this effects are
serious and need to be treated.

For XPS
(even AES)
never forget
ground the
sample !!!
C 1s shifts due to the charging

Inhomogeneous Surface Charging

Charging can even change the line shape due to Inhomogeneous
Surface Charging, which have different positive voltage on the surface.

In a lot of cases,
there is only
spectral
shift
due to charging,
which can be
determined by
comparison with
known
elemental XPS
lines,
for
example C 1s.

When the spectra is distorted

Charge Compensation

Other methods
electron
including make
flood gun
the sample very
mounted line
thin that is does
of sight with
not insulate,
sample
earthed metal
electron flood
mesh and very
gun mounted in
focused X-ray
analyzer axis +
spot can also
electromagnet
help
sometimes.
Which way is B field?

Quantitative analysis

X-ray
penetrate
much deep
than the
escape depth
of electrons

Can be found in
handbook

How to measure the

intensity
Lorentzian or
Gaussian functions
plus a background
(or even more
complicated
functions) of E can
be used to fit the
peak to subtract the
background. (More
complicated Shirely
background.)

Instrumentation (analyzers)

resolution
Acceptance
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)

Hemispherical Analyzer
Outer Sphere

Inner Sphere

Analyzer Control

Electron
Optics
Multi-Channel
channeltron Electron
Multiplier

X-ray
Source
Sample

5 4 .7

Most widely used for XPS

Hemispherical Analyzer
Pass energy: E = e U (b/a - a/b)
Resolution: E/E = (x1+x2)/2r + 2
=(a+b)/2
U is the voltage difference between inner and outer sphere; a
and b are radii of inner and outer spheres; x1 and x2 are the
radii of the entrance and exits apertures, respectively; a is the
maximum deviation of the electron trajectories at the entrance
with respect to the center line.

Why?

Angular resolved XPS

Photoemission is a dipole interaction, its Hamilton can be write as:

The transition possibility is:

with
Obviously the experimental geometry (the directions of the
incident light and electron emission) is crucial to the
photoemission process. Moreover, the electronic structure will be
influenced by the presence of the surface, its possible influence
will be present by the sample normal.
The change of emission angle with respect to the sample normal
can also give different surface sensitivity.
The angular dependence of XPS is how the photoelectron
diffraction (XPD) is done, which gives the structural
information of the surface.

Angular resolved XPS

Various
angular
dependence

Surface sensitivity change due to angle and photon energy

More Surface
Sensitive
less Surface
Sensitive

Same path
length but the
depth different

Can be done aslo with AES!

Sample for surface

sensitivity change
due to angle

For photoemission,

Ekin = h - EB

Change of photon energy can change photoelectron energy that

also changes the free path length of the photoelectrons(surface
sensitivity).
Cannot be done with AES!

AES vs. XPS

1. Common points
Both elemental and chemical sensitive
Both can be used to do quantitative analysis of chemical
composition.
Both are electron spectroscopy which have surface
sensitivity.
2. difference
AES: involved two electrons and one hole, due to coulomb
interaction (no selection rule), complicated, peak broad, can
be excited by many energetic particles including photon, no
intrinsic angular dependence, commonly use CMA, AES
peak in XPS spectra is with fixed Ekin.
XPS: involved in one electron, due to dipole interaction
(selection rule), peak sharp, simple, only excited by photon,
sensitive to angular geometry, often use angular resolved
analyzer, XPS peak is with fixed binding energy.