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Surface Spectroscopic Techniques XPS

X-ray photoelectron spectroscopy (XPS) is a surface-sensitive technique that uses soft X-rays to analyze the elemental composition and chemical/electronic states of the elements within the top 1-10 nm of a material's surface. During an XPS analysis, soft X-rays eject core-level electrons from the sample surface, which are then analyzed by their kinetic energy to determine the elemental identity and chemical environment. XPS can provide both qualitative and quantitative information on all elements (except H and He) with detection limits of 0.1-1% atomic concentration.

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46 views67 pages

Surface Spectroscopic Techniques XPS

X-ray photoelectron spectroscopy (XPS) is a surface-sensitive technique that uses soft X-rays to analyze the elemental composition and chemical/electronic states of the elements within the top 1-10 nm of a material's surface. During an XPS analysis, soft X-rays eject core-level electrons from the sample surface, which are then analyzed by their kinetic energy to determine the elemental identity and chemical environment. XPS can provide both qualitative and quantitative information on all elements (except H and He) with detection limits of 0.1-1% atomic concentration.

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1

Surface spectroscopic techniques


XPS
http://www.lasurface.com
http://www.chem.qmul.ac.uk/surfaces/
http://www.chem.qmul.ac.uk/surfaces/scc
2
Surfacespectroscopic techniques
E
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3
Surfacespectroscopic techniques
Depthresolution
Spatial resolution
4
Beamin
Beamout
Surface
Principle of electron and ion-beamspectroscopy
Analyzed by spectrometer
Beamin Beamout
XPS Soft X-rays (200-2000eV) Core-level Photoelectrons
UPS VacuumUVradiation(10-45eV) ValencePhotoelectrons
AES Electrons Auger electrons
SIMS Ions Secondary ions
5
X-ray photoelectron spectroscopy
(XPS)
usingsoft x-rays (withaphotonenergyof 200-2000eV) to examinecore-levels
6
Outline
Introduction(XPSbasicprinciples)
Quantification.
Widescandata(lowresolution)
Narrowscandata(highresolution)
Chemical stateanalysis.
Sputterdepthprofiles.
Imaging
Applications in material sciences
7
General Introduction
Photoemissionwas first detected
by Hertz in1887,andexplained
By Einsteinin1905.
Photoemission process
Photonenergy E =h
Einstein explained that experiment and showthat
light behaves like particles
photoelectrons
Light Photons
h
8
9
Photo-ionization the surface by
monoenergeticsoftX-rays(wavelength0.11nm)
Photoelectrons are ejected fromthe surface
A + h A
+
+ e
-
Qualitativeanalysis
Identificationoftheelementsinthesamplecanbemadedirectly
fromthekineticenergies(KE) oftheseejectedphotoelectrons.
Quantitativeanalysis
Therelativeconcentrationsofelementscanbedetermined
fromthephotoelectronintensities.
Basic principles
a photon energy of 200-2000 eV
10
(KE)
A + h A
+
+ e
-
Photo-ionization
(Photoelectronformation)
Conservationof energy
E(A) + h = E(A
+
) + E(e
-
)
E(e
-
) = h -[ E(A
+
) -E(A) ]
KE = h - BE
BE = h - KE
Binding energy(BE) allows
identification of elements
11
Linewidth Energy (h) Radiation Anode
0.85eV 1486.6eV K(alpha) Al
0.7eV 1253.6eV K(alpha) Mg
Widely usedX-ray sources
BE = h - KE
known
detected
12
Palladium(Metal)
1s
2
2s
2
2p
6
3s
2
3p
6
4s
2
3d
10
4p
6
5s
2
4d
8
13

wide cell/41
x 10
4
0
2
4
6
8
10
12
14
C
P
S
1400 1200 1000 800 600 400 200 0
Binding Energy (eV)
O1s
C 1s
OKLL
C KLL
O
O
HO
HOH
2
C
HO
OH
O
O
HOH
2
C
HO
OH
O
O
HOH
2
C
HO
OH
Cellulose
14
Thedeeper-ejectedelectrons
-recapturedor trappedinthesolid
-loss energy duringthetravel to thesurface, resultingin
spectrumbackground
Surfacesensitivity of XPS
to Detector
Onlyelectronescapedfromatoms at
first fewlayers (top1-10nm) show
specific photoelectronpeak. (No energy loss)
15
Qualitative
Detection ofall elements from
3
Li to
103
Lr (Except HandHe)
Electronspectroscopy for chemical analysisor ESCA
Detection limits that range form0.1to1.0atom%
Chemical stateanalysis (Include Bonding and oxidation state)
Analysis capabilities
Relative elemental composition of the surface (depth 1-10nm)
Semi-Quantitative
None destructive (some damage to X-ray beamsensitive materials)
Conducting and insulating materials.
Spatial resolution for surface mapping from>10 mm
Depth profiling capabilities (1 m)
16
EstimatedAnalysis Time
Requires 2-4hours vacuumto pump down before analysis
Typical operating pressure is 10
-9
to 10
-11
Torr.
Could require overnight to pump down
Qualitativecan be performed in 5to 10minutes
Quantitative analysisrequires 1hour to several hours depending
on the information desired
17
Identificationof elements
Electrons fromall orbitalsof an atom
with BE <X-ray energycan be excited
Spin-Orbit Splitting
Characteristic photoelectron for elements
18
Note:The far e-fromnucleus,
the less BE
19
Typical XPS spectra
XPS Spectroscopic modeWide scan (Survey scan)
CleanAg
(High pass energy Ex. 160eV)
Doublets are present in the non-s levels
as a result of spin-orbital coupling.
20
Secondary ElectronEmission(Auger Electron)
l LowEnergy holeproduced
l HighEnergy electronfills hole andenergy is emitted
l Secondary Electroncanabsorbexcess energy
andenter vacuum(CalledAuger Electron)
Photoemission process
Auger effect
21
XPS Spectroscopic modeRegion scan (High resolution)
(Lowpass energy Ex. 20eVor 40eV)
Ag 3d region spectrum
Area of 3d
3/ 2
= 3
Area of 3d
5/ 2
5
Spin-Orbit Splitting
22
XPSoftheAg3dregionof
Agbasedcatalyston-Al
2
O
3
23
F 1s
F KLL Auger
C 1s
F 2s
F 1s
C C
F
F F
F
n
XPS Spectroscopic modeWidescan(Survey scan)
PTFE
24
100
F
I
F
I
% atomic ] A [
A
A

1
1
1
1
]
1

,
_

,
_

C C
F
F F
F
n
PTFE
Semi-quantification
25
XPS Spectroscopic modeRegionscan(Highresolution)
PTFE
C C
F
F F
F
n
C 1s F 1s
No doublet peaks from1s photoelectrons
C-F
C-F
291.5 eV 689 eV
26
XPSofPoly(ethyleneterephthalate)
Three different C atoms
27
Chemical State Identification
Since BE of a photoelectron is sensitive to the chemical
surroundings of the atom there is a chemical shift in BE.
XPS provides a tool to identify individual chemical states
of an element of interest.
28
Relationship between oxidation state and BE
+
e
Less d more attraction more BE d
Li < Be < B < C < N < O <F
BE (eV) :
60 120 180 285 400 530 689
More positive charge more attraction more BE
Pt < Pt
2+
< Pt
4+
BE at 4f
7/2
(eV) : 71-72 72-73 76
In case of same atom
In case of different atom
29
For example,the C 1s BE is observed to increase as the number of
Oatoms bonded to C increases.
As Ois highENatom, theattachedC is chargedpositively
(C-C) < (C-O) < (O-C=O) < (O-(C=O)-O)
Potential inorganic substances
285 286-287 288-289 291-291.5 BE C 1s (eV)
In case of same atom
More positive charge more attraction more BE
(C-C) <(C-N) <(C-O) <(C-F)
285 285-6 286-7 291-3 BE C 1s (eV)
30
Fitting peaks
C1: C2: C3 = 3: 1: 1
Gaussian Curve
288eV
286eV
285eV
31
OxidationStates of
Titanium(Ti 3d)
Ti
0
Ti
4+
Note: two spin orbit components exhibit the same chemical shift
(~4.6eV)
~4.6 eV
32
Use Reference data to identify chemical state information
http://www.lasurface.com
www.NIST.gov
XPS handbook
Areas under Gaussian curve proportional to ratio of
chemical species present
HighResolutionXPS andFittingPeak
33
Examples of BE (C) inpolymers
34
Examples of BE (C) inpolymers
35
XPS compositional depthprofiling
1. Non-destructive depth profiling method
2. Depth profiling by erosion with inert gas ions (Destructive method)
Angle-resolved XPS (ARXPS)
Sputtering the surface within the spectrometer and use
normal mode of XPS
36
I
d
= I
0
exp(-d/ sin)
(nm)
Beer-Lambert relationship
d
where I
d
= intensity of emitted photoelectron as a function of depth (d)
I
0
= intensity of emitted photoelectron froman infinity thick substrate
=inelastic mean free pathof electron (2-5nm)
=electron take-off angle relative to the surface
Depth andsensitivity
Normal mode =90
o
I
d
= I
0
exp(-d/ )
more d less I
1
37
Depth andsensitivity
I
d
= I
0
exp(-d/ )
P = I
d
/ I
0
= exp(-d/ )
If =90
o
P =probability of emitted electron reaches the surface and being analyzed
Surface-sensitive
=2-5nm
38
d = [ln(I/I
o
)] sin
Angle-resolvedXPS
d sin
I
d
= I
0
exp(-d/ sin)

e
e
3
3 3
Analysis Depth(d) =3sin
39
3 0.8 2.1
0.26
If =5 nm
15nm 10.5nm 4nm 1.3 nm
Analysis depth
(>95%signal)
Sampling depth as a function
of electron take-off angle

40
ARXPS of Thioltreated
GaAs(100)
R-SH
R
-
S
H
41
AR-XPS of aSiliconWafer withaNativeOxide
Si 2p
3/2
(metal) BE ~99.0eV
Si 2p
3/2
(SiO
2
) BE ~103.0eV
Si
SiO
2
TOA
More surface sensitive, more SiO
2
is detected.
Si
0
SiO
2
42
Depthprofilingby sputtering(Destructivemethod)
43
Depthprofilingby sputtering(Destructivemethod)
XPSdepthprofile
ofSiO
2
onSi
Widescanquantitativeanalysis
If sputter rate is known,
thickness of the surface
layers can be calculated.
44 Regionscanqualitativeanalysis
Depthprofilingby sputtering(Destructivemethod)
XPSdepthprofileofSiO
2
onSi
Si =99.3eV
SiO
2
=103.3eV
Sputter time
45
XPS-Instrumentation
http://en.wikipedia.org/wiki/Image:System2.gif
1. Vacuumsystem
2. Samplepreparation
3. X-ray source
4. Electronenergy analyzer
5. Detectionsystem
46
Sample preparation
Solid samples are preferable. (Films, powder (pressed))
Stable in the UHV chamber
Sample can be conducting or insulating.
Mountingthe sample
Clips
Double sided adhesive tape
Single bar
Special holder stubs/cups are available for powder samples.
47
X-ray sources for XPS
< 5000 eV
48
X-ray sources for XPS
Formation of X-ray
Theenergy of X-ray (Photon) must
behighenough(at least 900eV)
to excitetheelectroninK-shell
of all elements.
Most popular anodematerials areAl andMg
Bombard metal target by
high energy electrons
then photon with known
energyare emitted
49
Al K
MgK
Photons
with known energy
50
Monochromatic X-ray
X-ray with a specific energy
Monochromation
51
X-ray Sources
2.1eV 5417 K(alpha) Cr
2.0eV 4510.9 K(alpha) Ti
2.6eV 2984.3 L(alpha) Ag
1.6eV 2042.4 L(alpha) Zr
0.85eV 1486.6 K(alpha) Al
0.7eV 1253.6 K(alpha) Mg
Line Width Energy (eV) Radiation Material
http:/ / www.thermo.com/ eThermo/ CDA/ Products/ Product_Detail/ 0,1075,15955-158-X-1-13080,00.html
52
Electron energy analyzer
1. Double Cylindrical Mirror Analyzer (CMA)
Lowresolution dE/E ~1%
Outer -Negative potential
Inner Ground
Only e-of a fixed energy can be passed and detected
53
2. Hemispherical Mirror Analyzer
54
l A potential difference between the cylinders or hemispheres allow
only electrons with specific kinetic energies to make it to the
electron detector.
l Varying potentials measure different kinetic energies
l Computer calculates binding energy
High resolution dE/E <0.5 %
55
Kratos Ultra (UK)
www.latrobe.edu.au
SampleMounting
56
Applications of XPS inMaterial Science
Metallurgy andCorrosion science
1. Interaction of a metal surface with its environment and
the formation of passive layer(Oxide film)
2. The breakdown of the surface filmby a localized phenomenon
such as pitting.
3. Elemental distributions on mineral particle surfaces
4.Depth profiles of corroded materials
57
Metallurgy
Stainless steel
Surface Cr richCr-oxide
Bulk Cr 18%, Ni 8%, Fe72%
58
http://www.eaglabs.com/techniques/analytical_techniques/xps_esca.php
W
WOxide
Identificationof Pittingcorrosion
59
CorrosionProblems onSteel Wires
a significantly higher concentration of iron
in the corroded areas coupled with
lower levels of calciumand sodium
which are attributed to the drawing lubricants
(Ca and Na stearates).
XPS images of a corroded stainless steel wire
Fe
Cl
Ca
C
60
Applications of XPS in Material Science
Microelectronics andSemiconductor Materials
XPS depthprofilingis used
to confirmthelayer uniformity
Semiconductor distributedBraggReflector Stack
61
62
Location of ppm/ppb levels of elements in the microstructure
Characterisation of ceramic compositional change with depth
Analysis of nmthick surface layers
Ceramics
Applications of XPS in Material Science
63
Thin film coatings on glass
Architectural glass, lenses, mirrors, and many other products are
coated to provide specific optical properties. These coatings are
often a stack of thin layers that can be characterized using Depth-profiling
XPS to verify the composition of the layers,
detect contaminants, and estimate layer thickness.
Fig.1:XPS sputter depth profile of
an architectural glass coating
64
Example Vanadium Phosphous
Oxide Catalyst Sample
65
Polymer surface modification
66
67
C60sputter depthprofilingof polymer films andsurfaces
RecentlyC60sputteringhas beenshownto bevery effectivefor removingsurface
contaminants andsputteringthroughpolymer films whilecausingminimal
chemical damage.
Fig.2:AC60sputter depthprofilethroughawax layer onpolyurethaneshows
theabilityto sputter throughorganic andpolymer materials without
causingsignificant chemical damageto thematerials.

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