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Analysis
Methods
X-ray
Photoelectron
Spectroscopy
Outline
Photoelectric
Eect
Instrumenta8on
X-ray
source
Electron
energy
analyzer
Ar
ion
gun
Neutralizer
Vacuum
system
XPS Examples
Photoelectric
Effect
Light
striking
a
surface
causes
electron
excita8on
Einstein,
Nobel
Prize
1921
B.E.
=
hv-Ek-
15000
Eb
C1S
6000
5000
core electrons
Survey
Scan
O1S
Counts
Counts
4000 3000
-NO2
-NH2
1000
800
600
400
200
Binding Energy, eV
Binding Energy, eV
Photoemission
Photoemission
can
be
thought
of
as
three
steps
(a) Photon
absorp8on
and
ioniza8on
(ini8al
state
eects)
(b) Response
of
atom
and
crea8on
of
photoelectron
(nal
state
eects)
(c) Transport
of
electron
to
the
surface
(extrinsic
eects)
e- inelastic scattering
10 nm
15000
Counts Core level electrons that have lost KE due to collisions within sample
10000 5000 0
600
400
200
Binding Energy, eV
Auger process and x-ray photon emission Low atomic number elements, the most probable transi8ons occur when a K-level electron is ejected by the primary beam, an L-level electron drops into the vacancy, and another L-level electron is ejected (KLL) Higher atomic number elements have LMM and MNN transi8ons that are more probable than KLL.
XPS Schematic
X-ray source Electron energy analyzer Ar ion gun Neutralizer Vacuum system
XPS
-
source
X-ray
anode
like
SAXS
Al,
Mg
or
Ag
radia8on
Spatial
Resolution
Two
ways
to
create
spa8ally
resolved
photoelectron
map
of
a
surface
Focus
your
X-rays
(dicult)
Focus
your
photoelectrons
(easier)
Focusing
Electrons
Much
like
electron
microscopy,
apertures
and
lenses
are
used
to
focus
electrons
Imaging
XPS
By
focusing
the
photoelectrons
you
can
scan
across
a
sample
much
like
SEM
Can
generate
XPS
images
Alterna8vely,
can
use
a
2D
detector
to
image
all
photoelectrons
simultaneously,
like
SAXS
Charge
Neutralization
Photoelectric
process
is
a
net
oxida8on,
thus
a
build
up
of
posi8ve
charge
occurs
For
a
conduc8ve
sample
this
is
negated
by
grounding
Insula8ng
samples
however
cannot
dissipate
the
charge
Sample
charging
results
in
aberra8ons
in
the
spectra
Electron
gun
can
be
used
to
alleviate
charging
problem
XPS Detectors
Delay-line detector similar to SAXS or use a photomul8plier tube (limited lateral resolu8on)
Example: PET
1 2 3 3 2 2
-(-O-C-
-C-O-CH2-CH2-)-
=
O
1
Poly-ethylene-terephthalate
=
O
1
Spin-orbital spli`ng
Quanti\ication
Must
account
for
inelas8cally
scabered
electrons
when
considering
baseline
Transmission
Factor
a
func8on
of
detec8on
eciency
of
an
electron
in
the
analyzer
which
is
a
func8on
of
the
electron
energy
Orbital
Cross-Sec8on
another
correc8on
based
on
the
ioniza8on
probabili8es
calculated
from
scabering
theory
In
prac8ce
the
transmission
factor
and
orbital
cross
sec8on
are
automa8cally
computed
by
the
analysis
soVware
Depth
Effects
Sample
with
dierent
depths
of
oxide
layers
Note
large
chemical
shiV
dierence
between
SiO2
and
elemental
Si
Si oxide Si elemental
Sampling Depth
Electrons in a solid have a nite mean free path For typical X-ray energies (Al, Mg) the depth sampled is < 10 nm Thus XPS is a surface sensi8ve technique However, we may want to look deeper or shallower, how do we achieve this?
Example: Al lm
Depth
Pro\iling
To
go
deeper
into
the
sample
we
can
use
an
ion
gun
to
etch
away
the
top
layers
Typically
performed
with
Ar+
ions,
energies
of
0.5-5
kV
XPS Imaging
XPS
Imaging
Can
record
spectra
at
selected
posi8ons
XPS
Imaging
Line
prole
generated
showing
the
loca8on
of
C,
Siox
and
Simet
XAES
Some8mes
photoelectron
peak
is
insucient
for
oxida8on
state
iden8ca8on
XPS
Spectra
of
Cu2O
and
Cu
metal
Wagner
Plot
Wagner
introduced
a
new
parameter
to
XPS
analysis
,
the
Auger
parameter
=
K.E.Auger
+
B.E.Photoelectron