2008 Advanced Materials

Characterization Workshop

X-ray analysis methods

Mauro Sardela, Ph.D.
The Frederick Seitz Materials Research Laboratory
University of Illinois at Urbana-Champaign
Sponsors:

Sponsors:

Supported by the U.S.

Supported
Department
by the
of Energy
U.S. Department
under grants of Energy
DEFG02-07-ER46453
under grant DEFG02-91-ER45439
and DEFG02-07-ER46471 1
© 2008©University
2007 University
of Illinois
of Illinois
Board of Board
Trustees.
of Trustees.
All rights
Allreserved.
rights reserved.

Outline
• X-rays interactions with the matter
• Fundaments of diffraction
• Powder diffraction methods
Size / strain analysis
Search / Match, structure determination
Quantitative analysis, whole pattern fitting
• X-ray parallel beam methods
Thin film crystallographic orientation
Glancing / Grazing angle XRD methods
• Texture - preferred orientation methods
• Residual stress analysis methods
• High resolution XRD methods
Rocking curve analysis
Reciprocal lattice mapping
• X-ray reflectivity methods
• X-ray fluorescence methods
• X-ray analysis summary
• Comparison with other techniques
• Quick guide to the FS-MRL x-ray analysis facilities
• Recommended literature. 2

1
 X-ray interactions with matter
Coherent Incoherent
Incident x-ray photons scattering scattering
hν0

hν0
Fluorescence
hν1
V) hν2 Photoelectron
25 (ke e-
125 0. 1
E
e-
γ X Auger electron
UV Visible
rays rays Interaction
2 nm ~30 μm volume hν: photon
1 0
0. 0 10 m) 20 e-: electron
λ (n 50 μm – 5 cm Sample

Coherent
Coherentscattering
scattering Fluorescence:
(Thompson Incoherent
Incoherentscattering Fluorescence:
(Thompsonscattering
scattering/ / scattering (a) - absorb incident
diffraction): (Compton
(Comptonscattering):
scattering): (a)K/L
K/Lshell
shellee- absorb incident
diffraction):
(a) - ννo energy
energyhh ννo; ;
incident
incidentphoton
ννo
hh (a)eeabsorbs
- absorbsincident
incidentenergy
energyhh (b) o
photon (excited o
(b)outer
outershell
shelle-e-“cascade”
“cascade”down
(excitedphotoelectron);
interacts - o down
interactswith
witheewith
- withnono photoelectron); filling
(b) fillingthe
the“holes”
“holes”causing
(b) part of the energy is emittedatat
energy part of the energy is emitted causing
energyloss
lossand
andnonophase
phase secondary
different νν1 and secondaryphotons
photons
change
change differentenergy
energyhh different
1 and different emission νν2).).
phase.
phase. emission(h(h 2

Auger
Augerelectron
electronemission:
emission:
Photoelectron (a)
(a)incident νν0 used
hh to eject e- from atom;
Photoelectronemission: incident -
emission: nd - 0 used to eject e from atom;
(b)
(b) 2 e “drops” to lowerlevels
2 e “drops” to lower
hhνν0 energy is used to eject electron e- with
- nd - levelstotofill
fillthe
the
0 energy is used to eject electron e with “hole”
kinetic energy = hν
kinetic energy = hνo – B.E.(bindingenergy).
– B.E.(binding energy). “hole”and
andaaphoton
photonisisemitted;
emitted;
(c)
(c)the
theemitted
o photon isisabsorbed by valance
emitted photon absorbed by valance
ee-,-,which
whichionizes
ionizesandandleaves
leavesthetheatom.
atom.
3

X-ray interactions with matter

Coherent scattering E0
(Diffraction, Thompson or (3) Incoherent scattering E1<E0
Rayleigh scattering) (Compton scattering) (3)
E0 (1) (2) E0
Electron (1)
Photon (2) Electron
Photon
Nucleus
Nucleus

(1) Incoming photon

(2) Oscillating electron
(3) Scattered photon (1) Incoming photon
No loss of energy. (2) Energy is partially transferred to electron
(3) Scattered photon (energy loss).

Fluorescence E1=EL-EK
Auger electron
(3) (3)
E0 (1) (4) E0 (1) (2)
Photon
Nucleus Nucleus
(2) K K
Electron L Electron
(1) Incoming photon L shell
(2) Expelled electron (photoelectron) shell
(3) Hole is created in the shell (1) Incoming photon excites inner shell electron
(4) Outer shell electron moves to the inner shell hole (2) Excitation energy is transferred to outer electron
(5) Energy excess emitted as characteristic photon. (3) Electron ejected from atom (Auger electron)
4

2
 Fundaments of diffraction

“Real” space
Set of planes
F Reciprocal space
Point

(h k l)

d hkl

2π/d

origin

M. von Laue 1879-1960

X-rays from crystals, 1912.
5

Fundaments of diffraction

“Real” space
F Reciprocal space

2π/d

origin

3
 Fundaments of diffraction

“Real” space
F Reciprocal space

origin

Fundaments of diffraction
“Real” space F Reciprocal space

Bragg’s law Ewald’s sphere

y
Det
ect X-ra ce
Diff
eam
or r
rac sou
ted
i dent b
bea
m Inc ω
2θ

k1
q
2θ
k0 (= radius)

2 d sin θ = n λ q = k1 – k0
Elastic (Thompson’s)
scattering q: scattering vector
q = (4 π/λ) sinθ
Paul P. Ewald
81888-1985
1862–1942 1890-1971

4
 Fundaments of diffraction
“Real” space Reciprocal space

Detector
scan 2θ/ω scan Rocking
curve scan:
Δ(2θ) Δ(2θ/ω) Rocking curve Δ(ω) ┴ to scattering
(sample) scan vector

Diffracted Δ(ω) 2θ/ω scan:

beam
Scattering Δ(2θ/ω) radial, // to
vector Detector Scan:
am scattering
be around
ent vector
id Ewald’s sphere
2θ In
c
ω hkl
Δ(2θ)

q k1
hk
l

k0

Fundaments of diffraction
“Real” space Reciprocal space

Detector
scan 2θ/ω scan • Defects, material quality
Rocking
• Mosaicity curve scan:
Δ(2θ) Δ(2θ/ω) Rocking Δ(ω) ┴ to scattering vector
curve scan • Texture
• Texture strength
Diffracted Δ(ω) 2θ/ω scan:
beam
Scattering Δ(2θ/ω) radial,
vector Detector Scan:
am
// to scattering
be around Ewald’s
nt
vector
cid
e •
Phase analysis sphere
2θ In ω• Grain size analysis hkl
Δ(2θ)
• Unit cell determination
• Stress analysis
• Glancing angle q
• Lattice distortion, strain k1
• Constant sampled h k • Composition, alloying
l
volume

k0

10

5
Typical contents from XRD pattern (diffractogram)
Si powder sample

“PDF”
“PDF”(ICDD/JCPDS)
(ICDD/JCPDS)

Peak
Peakposition:
position:
identification,
identification,structure,
structure,lattice
latticeparameter
parameter
Peak
Peakwidth:
width:
crystallite
crystallitesize,
size,strain,
strain,defects
defects
Peak
Peakarea
areaor
orheight
heightratio:
ratio:
preferred
preferredorientation
orientation
Peak
Peaktails:
tails:
Diffuse
Diffusescattering,
scattering,point
pointdefects
defects
Background:
Background:
amorphous
amorphouscontents
contents

11

Powder diffraction methods

Crystalline? Amorphous?

What elements, compounds, phases

are present?

Structure? Lattice constants?

Strain?

Grain sizes? Grain orientations?

Is there a mixture? What % ?

Powders, bulk materials, thin films,

nanoparticles, soft materials.

12

6
 Bragg-Brentano focusing configuration
Single crystal
Receiving monochromator
Focus slit (λ)

X-ray
source
Divergence Detector
slit

Secondary
Optics:
Scatter and soller slits
Focusing
circle Detector
(variable during specimen
measurement) rotation
(2θ)
Angle of
incidence
(ω)
Diffractometer circle
13
(fixed during measurement)

Bragg-Brentano focusing configuration

Single crystal
Receiving monochromator
Focus slit (λ)

X-ray
source
Divergence Detector
slit

Secondary
Optics:
Scatter and soller slits
Focusing
Divergent
Divergent
circle
beam
beam
(variable during specimen
Detector
measurement) rotation
not
not good
good for
for (2θ)
grazing
grazing Angle of Sample
Sample height
height
incidence
incidence
incidence positioning
positioning isis critical
critical
(ω)
analysis
analysis Diffractometer circle
14
(fixed during measurement)

7
 Instrumentation: powder diffraction

Soller Divergence
slits slit
s am
Cu ple
x-ray θ
source 2θ 2θ
Scatter slit
Soller slits
Rigaku D/Max-b Receiving
x-ray diffractometer slit
Bragg-Brentano
configuration
(top view) Detector
Curved graphite
monochromator
CMM XRD facilities Δ2θ ~ 0.2O

CMM instrument: Rigaku D/Max-b XRD system

15

Instrumentation: stress, phase analysis

Optional
Bragg-Brentano configuration filter or
with programmable slits attenuator
ψ Vertical mask
φ X-ray source:
ple Cu, line focus
Top view sam ω
2θ
Programmable Programmable Programmable
anti-scatter slits divergence slit attenuator
[> (1/32) deg]

Detector Programmable Programmable slits can be

receiving slits used for applications
requiring limited or
constant illuminated area
in the sample.
Curved graphite
monochromator CMM instrument: Panalytical X’pert #2 XRD system
16

8
 Crystallite size analysis
Scherrer’s equation:
Not accounting for peak
k*λ broadening from strain and
Size = defects
cos (θ) * (FWHM)

k : shape factor (0.8-1.2) Measured along the

λ: x-ray wavelength specific direction normal to
FWHM: full width at the (hkl) lattice plane
half maximum (in radians) given by the 2θ peak position

Peak
Peakwidth
width(FWHM)
(FWHM)

___ Measurement
___ Fit
Peak
Peakposition
position2θ
2θ
17

FWHM vs. integral breadth

Imax
It does not take into
account the lower part (½)I FWHM (deg)
max
of the profile

The square-topped profile has the same area

and peak height as the measured curve.

Integral breadth = (total area) / (peak height)

Integral breadth (deg)

18

9
 Peak shape analysis
Peak fit:
Gaussian
Lorentzian
Pearson-VII (sharp peaks)
Pseudo-Voigt
(round peaks) Measurement

Information from fit: Fit

•Position
•Width (FWHM)
•Area
•Deconvolution
•Skewness

___ Measurement
___ Fit

19

Correction for instrument resolution

Use FWHM curve as a function of 2θ from
standard sample (NIST LaB6) FWHM: β
- specific for each diffractometer
βD = (βmeas)D – (βinstr)D

D: deconvolution parameter
Measurement
D : 1 (~ Lorentzian)
Instrument function β = (βmeas) – (βinstr)

D : 2 (~ Gaussian)
β2 = (βmeas)2 – (βinstr)2

D : 1.5
β1.5 = (βmeas)1.5 – (βinstr)1.5

Software: MDI’s Jade + 8.0 20

10
 Potential artifacts in size determination
FWHM: β Assume:
βD = (βmeas)D – (βinstr)D • Instrument resolution ~ 0.15o
• 2θ = 40o
Measured Size, nm Size, nm Size, nm • Cu radiation
peak D=1 D = 1.5 D=2
width (o) (Lorentzian) (Gaussian)

0.3 56.4 38.0 32.6 Large difference

(up to 48%!) for
0.5 24.2 19.2 17.7 narrow peaks (large sizes)

0.75 14.1 12.0 11.5

1 10.1 8.8 8.6

Smaller difference
1.5 6.3 5.8 5.7 (~ 10%) for
broad peaks (small sizes)
2 4.6 4.3 4.2

21

Strain effects in diffraction lines

No strain

Δ(2θ)
Macrostrain
Peak position
uniform strain
shift
(lattice distortion)
Uniform strain (lattice constant
change)

Microstrain
nonuniform strain Peak width
FWHM change
(lattice distortion)

Nonuniform strain
22

11
 Size and strain in peak shape analysis
(FWHM)*cos(θ)
(FWHM)*cos(θ)==kλ/(size)
kλ/(size)++(strain)*sin(θ)
(strain)*sin(θ)

(FWHM)*cos(θ)
Williamson-Hall
Method
Acta Metall. 1 (1953) 22.

sin(θ)

Intercept
Intercept~~1/(size)
1/(size)
Slope
Slope~~micro
microstrain
strain

FWHMstrain = 4*(strain)*tanθ
23

Other methods of grain size analysis

Rietveld
Rietveldrefinement
refinementmethod:
method:
• • Refines
Refinesthe
thewhole
wholediffraction
diffractionpattern
pattern(including
(includingbackground)
background)
• • Needs
Needsdetailed
detaileddata
dataover
overaawide
wideangular
angularrange
range H. Rietveld
• • Gives one average size value
Gives one average size value (1932-)
• • Works
Worksbetter
betterfor
forpowder
powdersamples
samples(not (notwell
wellwith
withfilms
filmswith
withstrong
strongpreferred
preferredorientation)
orientation)
• • Data
Dataprocessing
processing(refinement
(refinementand and“play”
“play”with
withparameters)
parameters)isistime
timeconsuming.
consuming.

Warren-Averback
Warren-Averbackmethod:
method:
Standard
Standardsample
sample->->Instrumental
InstrumentalBroadening
Broadening->->Correct
Correctmeasured
measuredpeaks
peaksassuming
assuming
2
“error”-type
“error”-typeofoffunction
function(main assumption)I I~~exp(-pφ)
(mainassumption) exp(-pφ)2->->Use
UseScherrer’s
Scherrer’sequation
equation

Jones’
Jones’method:
method:
Measured
Measuredprofile
profile==convolution
convolution(“pure”,
(“pure”,instrument)
instrument)
Use
UseFourier
Fourierintegrals
integralsfor
forall
allthe
theprofiles
profiles(measured,
(measured,“pure”,
“pure”,instrument)
instrument)
Use
Use ratio of the integrals to determinesizes.
ratio of the integrals to determine sizes.

24

12
 Pattern treatment, S/M and structure refinement
1. Background treatment
2. Peak fit Weight % of
3. Search/Match (“PDF”) parts in the
4. Composition (w%) mixture
5. Grain sizes, lattice parameters
6. Structure determination refinement
Intensity

2θ(o)

Software:
MDI’s Jade + 8.0

25

Whole pattern fitting and structure refinement

Pattern from a Li-Ni- •Bragg-Brentano or parallel beam x-ray analysis.
based battery cathode •Powders, polycrystalline films or nanostructures, mineralogy, cements,
(003) ceramics, pharmaceutics, polymers, biomaterials.
•Identification, quantification (w%) and structure determination of mixtures,
(104) impurities, multiple phases and amorphous fractions.
Intensity (a.u.)

•Quantification of crystallinity, texture, twinning, grain size and strain.

(101) •Pattern indexing, lattice parameters determination, unit cell refinement,

(110) atomic positions, bonds distances and angles.

(012)
•Pattern simulation and structure refinement (Rietveld analysis).
C(002) (018)
(006) (015)
(107) (113)
Results obtained from the measured pattern:
o
Search / Match: LiNi0.7Co0.3O2, major (minor: C graphite) Ni
2-theta ( ) Structure: Hexagonal R-3m (166) <1/3,2/3,2/3>,
Z=1, hR4
O
Cell a= 2.86285 Å; b= 2.86285 Å; c= 14.17281 Å
(Rietveld α= 90o β= 90o γ= 120o
refinement): Unit cell volume: 100.6 (Å)3
Pattern treatment: Density: 4.8383 g cm-3
* Peak profile fit Linear Absorption Coefficient: 385.5 cm-1 Li
* Search / Match Average bond Ni-O: 1.9570 Å, Ni-Li: 2.8729 Å,
* Pattern Indexing distances Ni-Ni: 2.8629 Å, Co-O: 1.9570 Å,
(Rietveld): Co-Ni: 2.8629 Å, Co-Li: 2.8729 Å
* Cell Refinement Li-O: 2.1117 Å, Li-Li: 2.8629 Å,
* Pattern Simulation O-O: 2.7983 Å
* RIR w% quantification Quantitative 82.9 w% LiNi0.7Co0.3O2, 17.1 w% C
Co
* Rietveld structure refinement analysis:
Crystallite size: > 1000 Å
Data: Sardela, UIUC Strain: 0.05% 26
Sample: Abraham et al, ANL

13
 New: S/M assisted by whole pattern fitting

Multi-phase mixture
powder data

27
Software: MDI’s Jade + 8.0

New: S/M assisted by whole pattern fitting

Whole pattern fitting using possible pdf hits in search for best phase id’s

“R” is being minimized

(whole pattern fitting)

Possible
Possiblepdf
pdfhits
hitsafter
afterS/M
S/M

28

14
New: S/M assisted by whole pattern fitting

Unmatched peaks
are now fitted

New
Newpdf
pdfhits
hitsare
arenow
now
automatically
automaticallyadded
added
29

New: S/M assisted by whole pattern fitting

R: 45.5 w%, XS: 463 nm

H: 31.0 w%, XS: 273 nm
A: 23.5 w%, XS: 28 nm

Whole pattern R
fitted
H A

3 phases matched: Rutile, Hematite, Anatase

30

15
 X-ray parallel beam methods

Rough, irregular surfaces

Film / Substrate systems

α Near surface
Glancing / grazing angle applications.
region Phase, stress gradients (depth profiles)

31

Parallel beam configuration

Negligible
Negligiblesample
sample
displacement
displacementissues
issues Specific
Specificoptics
opticstotomaximize
maximize
(rough
(roughand
andcurved
curved intensities
intensities Detector
samples
samplesOK)OK)

X-ray Single crystal

source Primary
Optics: Parallel plates monochromator
mirror, slits, lens collimation (λ)

Detector
Parallel
rotation
beam
(2θ)

Angle of specimen
incidence
(ω)
Excellent
Excellentfor
forglancing
glancingangle
angle
(fixedω)
(fixed ω)applications
applications 32

16
 Instrumentation: thin film, texture, stress analysis
Parallel plate collimator Primary optics Optional
configurations option 1: filter or
Crossed-slit attenuator
ψ collimator
φ X-ray source:
Top view ple Cu, line or point focus
sam ω
2θ
0.27o- Crossed slits
parallel (slit+mask) Primary optics option 2:
plates x-ray lenses
collimator Vertical mask

Δθ ~ 0.03-0.2o Optional Primary optics option 3:

0.1mm slit programmable
divergence slit +
Flat graphite Programmable programmable
monochromator divergence slit attenuator
Detector
Programmable attenuator

CMM instrument: Panalytical X’pert #2 XRD system

33

Thin film orientation analysis

<001> φ scan (in-plane
2θ/θ surface direction)
scan TaN Example: <110>
(surface
TaN film
normal <001> TaN
direction) MgO MgO(001)
substrate <110>
δ-TaNx/MgO(001) MgO
MgO
t = 500 nm
(002)
Ts = 600 °C (220) δ-TaN1.17/MgO(001)
MgO 002

Ji/JTa = 11
δ-TaN
φ scans t = 500 nm
Intensity (a.u.)

fN = 0.125 Ts = 600 °C
2
Data:
(002) Shin,
Petrov et al,
Intensity (a.u.)

δ-TaN 002 UIUC

40 eV, Γω = 0.95°

30 eV, Γω = 0.75°
δ-TaN
20 eV, Γω = 0.60°
Cube
Cubeon oncube
cube δ-TaN
epitaxy:
epitaxy:
8.5 eV, Γω = 0.68°
(001)
(001)TaN//(001)
TaN//(001)MgO
MgO
MgO MgO
41.0 41.5 42.0 42.5 43.0
(100)
43.5(100)TaN//(100)
//(100)MgO
TaN MgO
2θ (deg) 0 50 100 150 200 250 300 350
φ (deg) 34

17
 Glancing angle x-ray analysis

Inc
ide m
nt
x bea
surface -ra -ray
normal ω y be t edx
am rac
(fixed) Diff

grains

: conventional Bragg-Brentano configuration

2θ-ω scans probe only grains aligned parallel to the surface

+ : parallel-beam grazing incidence configuration

2θ scans probe grains in all directions
35

X-ray penetration depth vs. angle of incidence

Low angle region

-Type of radiation
- Angle of incidence
- Material (Z, A, ρ, μ)

36

18
 X-ray penetration and information depths

I0 exp(-μl) (1) Penetration depth τ1/e:

depth for Intensity = Io/e ~ 37% Io
I0
2θ − α τ1/e = (sinα) / μ
α
t z d1 d2 (2) Penetration depth τ63:
depth for AGIXRD = 1-1/e (~ 63%, μtkα=1)
sinα sin(2θ−α)
l = d1 + d2 = z + z τ63 = 1 / μkα = μ [sinα + sin(2θ−α)]
sin α sin (2θ – α)
Bragg peak (2θ) dependent penetration depth!

Absorption (sample w/ finite thickness)

Absorption factor =
Absorption (sample w/ infinite thickness) (3) Information depth τ :
weighted average of sampling depth
For θ/2θ configuration: Aθ2θ = 1 – exp(-2μ/sinθ)
1 1
For GIXRD configuration:AGIXRD = 1 – exp(-μtkα) τ = μk +
α 1 – exp(μtkα)
kα = 1/sinα + 1/sin(2θ – α)
It will not exceed the thickness value!
t: thickness
z: depth from surface
(4) Penetration depth τ1/e for α ~ αc:
μ = μm ρ = linear absorption coefficient Includes correction with refractive index n = 1- δ - iβ
μm = mass absorption coefficient (tables) √2 λ
ρ: mass density τ1/e = 4π [(α2 – αc2)2 + β 2] -1/2 – (α2 - αc2)
αc: critical angle
Excel spreadsheet calculator available at:
β: λμ / 4π (imaginary part of refractive index) http://www-ssrl.slac.stanford.edu/materialscatter/gixs-calculator.xls
δ = ½(αc2)
37

X-ray penetration and information depths

I0 exp(-μl) (1) Penetration depth τ1/e:

depth for Intensity = Io/e ~ 37% Io
I0
2θ − α τ1/e = (sinα) / μ
α
t z d1 d2 (2) Penetration depth τ63:
depth for AGIXRD = 1-1/e (~ 63%, μtkα=1)
sinα sin(2θ−α)
τ63 = 1 / μkα = μ [sinα + sin(2θ−α)]
500 nm thick TiO2 rutile film
(μ = 0.0528 μm-1, Cu Kα radiation) Bragg peak (2θ) dependent penetration depth!
2θ range: 22 – 60o

Angle of Penetration Information (3) Information depth τ :

incidence depth depth weighted average of sampling depth
α (o) τ1/ε (nm) τ (nm) 1 1
τ = μk +
α 1 – exp(μtkα)
0.9 298 180 - 182 It will not exceed the thickness value!
1.8 595 (>t!!) 212 – 214
(4) Penetration depth τ1/e for α ~ αc:
2.7 892 (>t!!) 224 – 226 Includes correction with refractive index n = 1- δ - iβ
√2 λ
τ1/e = 4π [(α2 – αc2)2 + β 2] -1/2 – (α2 - αc2)
From: M. Birkholz, “Thin Film Analysis by X-ray
Scattering” Wiley-VCH 2006 Excel spreadsheet calculator available at:
http://www-ssrl.slac.stanford.edu/materialscatter/gixs-calculator.xls

38

19
 Grazing angle vs. Bragg-Brentano configurations
Grazingincidence
Grazing incidenceanalysis
analysiswith
with Conventional
Conventional analysis
analysiswith
with
parallel beam optics
parallel beam optics focusing configuration
focusing configuration
Detectgrains
Detect grainsininvarious
variousorientations
orientations
Detect
Detectonly
onlygrains
grainswith
withorientation
orientation
(includingtilted
(including tiltedtotothe
thesample
samplesurface).
surface).
parallel
paralleltotothe
thesample
samplesurface.
surface.
Fixedincident
Fixed incidentangle:
angle:constant
constantprobed
probed
Sample
Sampleprobed
probeddepth
depthmay
mayvary
varyduring
during
depthininthe
depth thesample
sampleduring
duringanalysis.
analysis.
the
theanalysis.
analysis.
Lowangle
Low angleofofincidence:
incidence:
Lower
Lowersensitivity
sensitivitytoto(ultra)
(ultra)thin
thinfilms;
films;
••high
highsensitivity
sensitivitytoto(ultra)
(ultra)thin
thinfilms;
films;
substrate artifacts are problem.
substrate artifacts are problem.
••avoid
avoidartifacts
artifactsfrom
fromsubstrates;
substrates;
••can
canbe
beused
usedfor for“depth
“depthprofiling”
profiling”atat
differentincidences.
different incidences.
Very
Verygood
good2θ
2θresolution
resolutionand
andwell-
well-
known
knownmathematical
mathematicalformalism.
formalism.
Slightlylower
Slightly lower2θ
2θresolution:
resolution:ok
okfor
forbroad
broad
peaks.
peaks. Typical
Typicaloptics
opticsare
areideal
idealfor
forpowder
powder
samples
samplesand
andthick
thickfilms
filmswith
withno
no
Thinfilm
Thin filmcollimation
collimationoptics:
optics:enhanced
enhanced preferred
sensitivitytotothin
thinfilms.
films. preferredorientation.
orientation.
sensitivity
Focusing
Focusingconfiguration:
configuration:very
verysensitive
sensitive
Parallelbeam:
Parallel beam:insensitive
insensitivetotosample
sample totosample
displacement errors. sampledisplacement
displacementerrors
errors
displacement errors. 39

Glancing angle x-ray analysis

Example:

Poly-Si
(~ 100 nm)
Substrate Substrate
Si(001)
substrate

Glancing
angle

Conventional
2θ/θ XRD

2-theta (degrees)
40

20
 Grazing incidence x-ray analysis
• Grazing incidence X-ray scattering (GIXS) analysis uses
surface low angle of x-ray beam incidence relative to the surface in
normal
2θ
order to enhance diffraction from very thin layers.
(hkl) • Analysis of ultra-thin films (<10 nm), nanostructures or
topmost surface regions of the material.
• Allows structure determination and quantification of lattice
sample parameters, rocking curve widths and crystallite size along

ω the surface direction (different from conventional XRD,

which probes surface normal directions).
detector

α x-ray s
ource Angle of
incidence:
ScN(220)
0.50°
Depth from surface (Å)

GIXS from a

Intensity (a. u.)

XRD
penetration ScN thin film on 1.00°
depth MgO (001): 1.40°
•The results allow the
determination of in-plane
1.80°
lattice parameter and
crystallite size;
•Notice the differences in 2.25°
the relative intensities of
the film and substrate peaks 2.75°
at different in-plane angles MgO(220)
of incidence α.
(Incidence angle) / (critical angle) 57 58 59 60 61 62 63 64 65
o
Data: Sardela, Shin, Petrov, Greene et al, UIUC 2θ ( ) 41

Texture and preferred orientation methods

ed Texture / Preferred orientation:

ferr
Pre ntation anisotropy of grain orientation
orie distribution.

Are the grain orientations distributed

randomly? Or is there a preferred
orientation?

What is the preferred orientation?

What is the % of random grains?

How strong and sharp is the texture?

For film / substrate systems:

what is the crystallographic orientation
between the substrate and the layers?

42

21
 Determination of preferred orientation
Crystalline grains in a material may be preferentially distributed along one orientation (preferred orientation).
This may complicate the analysis using conventional XRD methods derived from powder techniques.

Methods:
Methods:
1.1. Compare
Comparerelative
relativepeak
peakheight
heightor
orarea
areaobtained
obtainedfrom
fromaa2θ/θ
2θ/θscan
scanwith
withthe
theexpected
expected
relative intensity from a standard (same material) with no preferred orientation
relative intensity from a standard (same material) with no preferred orientation
(~
(~powder):
powder):Lotgering
Lotgeringfactors.
factors.
2.2. Use
Use the relative intensitymethod
the relative intensity methodabove
abovecombined
combinedwith
withMarch-Dollase
March-Dollasepreferred
preferred
orientation
orientationcorrections
correctionstotoobtain
obtain%
%grains
grainsthat
thatare
aremore
moreoriented
orientedininaaspecific
specific
direction.
direction.
3.3. Use
Usethe
therocking
rockingcurve
curveanalysis
analysisofofaastrong
strongfilm
filmdiffraction.
diffraction.The
Thewidth
widthofofthe
therocking
rocking
curve
curvepeak
peakisisused
usedas
astexture
textureparameter.
parameter.
4.4. Perform
Performpole
polefigures
figurestotodetermine
determinethe
thepresence
presenceofofgrains
grainsofofaacertain
certainorientation
orientationinin
all
allsample
sampledirections.
directions.
5.5. Use
Usemultiple
multiplepole
polefigures
figuresfrom
frommultiple
multipleorientations
orientationstotoobtain
obtainOrientation
Orientation
Distribution
Distribution Functions: % of grain orientation distributions in allwafer
Functions: % of grain orientation distributions in all waferdirections.
directions.
43

X-ray pole figure analysis of textured materials

Texture results from a rolled Cu foil
Pole figures
ψ • Crystallographic orientation.
Orientation
• Texture orientation and quantification.
• Volume fraction of textured grains, distribution
twinning and random distributions.
Φ2 function (ODF)
• Texture strength and sharpness.
• Crystallographic relationship between
layers and substrate.

2θ sample
φ
detector

ω
ψ
φ
urce
(111) x-ray so

Φ
Φ1
Inverse
pole
figures

ψ Φ
φ
Data: Sardela, UIUC 44

22
 Pole plot projections

Equatorial Pole
plane

Wulff projection
Schmidt projection
(stereographic or
(equal-area projection)
equal-angle projection)
A S
AB = AS

Side view
ψ r ψ B
r Side view
(normal to (normal to
equatorial plane) O W O
equatorial plane)
Equatorial
plane

Top view
(parallel to Top view
equatorial plane) W φ φ (parallel to
O O equatorial plane)
S

OW = r tan(ψ/2) OS = √2 r tan(ψ/2)

45

Basics of pole figure analysis

Surface
φ hkl (100) Pole figure
φ -1 0 0 Azimuth
ψ φ= 0, 90o,
normal 180o, 270o
001 010
0 -1 0

Tilt
ψ= 0, 90o

ψ 100 ψ: [100],[100]
φ
Example: (100) cubic crystal (111) Pole figure
-1 -1 1 -1 1 1 Azimuth
ψ φ= 45o, 135o,
Pole figure plot 225o, 315o
111

φ 1 -1 1 Tilt ψ= 54.7o
ψ hkl ψ: [100],[111]

(110) Pole figure φ -1 -1 0 -1 1 0

Azimuth
ψ -1 0 1 φ= 0, 90o, 180o,
270o,45o, 135o,
0 -1 1 011 225o, 315o
101
ψ(radial / tilt)
Tilt ψ= 45o,90o
φ (azimuthal rotation) 1 -1 0
110
ψ: [100],[110]
46

23
 Basics of pole figure analysis
Surface
φ hkl (100) Pole figure
φ Azimuth
φ= 30o,
normal 001 010
150o, 270o
ψ
Tilt ψ= 54.7o

100 ψ: [111],[100]
ψ
φ
Example: (111) cubic crystal (111) Pole figure -1 1 1
Azimuth
ψ φ= 90o,
Pole figure plot 210o, 330o
111
1 -1 1 1 1-1

φ Tilt ψ= 0, 70.5o
ψ hkl ψ: [111],[111]

(110) Pole figure φ -1 0 1 -1 1 0

Azimuth
011 φ= 60o, 120o,
ψ 0 1 -1 240o, 300o, 90o,
0 -1 1 110 210o, 330o.
101
ψ(radial / tilt)
Tilt ψ= 35.3o, 90o
φ (azimuthal rotation) 1 -1 0 -1 0 1

ψ: [111],[110]
47

Fiber texture analysis

Example: Cu thin film
on Si (001) substrate

Conventional 2θ/θ scan:

Si
Cu(111)
Grains:
56 nm

Cu(222)

48

24
 Fiber texture analysis
(111) Pole figure:
Example: Cu thin film ψ = 70.53o
on Si (001) substrate

Conventional 2θ/θ scan:

Si
Cu(111)
ψ=0
Grains:
56 nm

(200) (200) Pole figure:

ψ= 54.74o
(220)
(311)
Cu(222)

All grains are <111> oriented along

the film growth direction.
Grains are randomly oriented along the surface
49

Fiber texture analysis

Sam
ple
(111) Fiber plot
2θ Cu film on Si (001) substrate

ψ <111> Data after background subtraction

ω HWHM: 1.09o
Detector (texture sharpness) <111>

sour ce 4.6%
X-ray 3.5% <511>
<5 7 13>+<112> twinning
+<225> twinning
Fiber texture:
Texture
direction

9.0%
Random Random random grains

m Ran
n do dom
Ra 50

25
 Residual stress analysis methods

Residual stress?

How much? (MPa – GPa)

Type?

Direction (s)?

Stress gradients?

51

X-ray analysis of residual stress

Film Normal
unstressed Lφ,ψ
Incident Reflected
X-rays X-rays
a⊥ stressed ψ
aψ
ψ Tilt ψ:
film surface a0 σφ θ o
+60
Intensity (a.u.)

o
+45
o
+30o
Diffracting planes +15
0
o
-15
o
-30o
-45
Interplanar spacing d (Angstroms)

o
-60
Δd/d = σ [(1+ν)/E] sin2ψ
1.173

79 80 81 82 83 84 85
1.172 o
2-theta ( )
1.171
• Quantification of residual stress.
1.170 • Compressive (-) and tensile (+) stress.
• Crystallographic orientation of stress.
1.169
Stress = -199 MPa • Sin2ψ and RIM methods.
• ψ and ω scan methods.
1.168
0.0 0.2 0.4 0.6 0.8 • New glancing angle method (texture).
2
sin (ψ) • Determination of stress tensor.
Stress results from a steel sample • Requires crystallinity (no amorphous).
Data: Sangid et al, UIUC 52

26
 Residual stress analysis: the sin2ψ method
Film Normal
unstressed Lφ,ψ
Incident Reflected
X-rays X-rays
a⊥ stressed ψ
aψ
ψ
film surface a0 σφ θ

Diffracting planes

4.55 HfN1.05/SiO2
aψ − ao 1+ ν 2ν
4.54 δ = -0.03074 εψ = = σφ sin 2 ψ − σφ
ao E E
ξ = 4.54521
aψ (Å)

aÏ
4.53 aψ =
a oσφ
E
[(1 + ν) sin 2
]
ψ − 2ν + a o = δ sin 2 ψ + ξ
2ν
sin 2 ψ = 2δν
4.52 1+ ν ao = ξ + = 4.533 Å
1+ ν
4.51 Eδ
0.0 0.2 0.4 0.6 0.8 1.0 σφ = = −1.47 GPa (Compressive)
2δν + (1 + ν )ξ
sin2ψ 53
Data: Petrov et al, UIUC

High resolution XRD methods

Single crystals:

α γ b Accurate measurements of a, b, c, α, β, γ
β Detailed peak shapes: defects, mosaicity.
a c

+
Δa
a Film / substrate epitaxial systems:

Measure small variations Δa, Δc,… (~ 10-5).

c + Δc Measure layer tilts Δφ, ...

Δφ Detailed peak shapes: defects, strain, mosaicity.

c

a 54

27
 Instrument resolution in reciprocal space

Dif
Beam angular divergence, frac
te eam
db nt b
i de
ω
detector acceptance and eam
I nc
diffractometer sampling volume sample

Angular
acceptance
of the
secondary
optics
Primary beam
2θ divergence
Diffractometer ω (from primary optics)

sampling
volume
Ewald sphere

55

Instrumentation: high resolution configuration

4-reflection x-ray
x-ray
φ Ge(220) source
ψ monochromator mirror
ple slit
sam ω
slit
3-bounce 2θ Δθ =12 arc-sec
analyzer Δλ/λ = 5x10-5
crystal High resolution
Crossed slits configuration with
(variable slit+mask)
mirror and 4-reflections
monochromator
Programmable • Line focus;
attenuator • Parabolic x-ray mirror;
“Lower” • 4-reflection monochromator
detector (12 arc-sec resolution);
(triple axis: “Upper” detector • Open detector or analyzer crystal.
12 arc-sec acceptance) (open: < 1o acceptance)
CMM instrument: Panalytical X’pert #1 XRD system
56

28
 Instrumentation: high-resolution configuration
Hybrid
Mirror x-ray
φ
ψ (2-bounce monochromator +
X-ray mirror)
source
ple
sam ω
slit
3-bounce 2θ Δθ =30 arc-sec
analyzer
crystal
Mask High resolution
configuration with
hybrid mirror
Programmable
attenuator •Line focus;
“Lower” •Hybrid mirror (30 arc-sec resolution);
•Open detector or analyzer crystal.
detector
(triple axis:
12 arc-sec acceptance) “Upper” detector
(open: < 1o acceptance)
CMM instrument: Panalytical X’pert #2 XRD system
57

High resolution x-ray analysis

• High resolution methods using multi-reflection monochromator and possibly
analyzer crystal (Δθ = 0.003o).
• Sensitive to lattice distortions within 10-5. Single crystals
• Rocking curve analysis.
Epitaxial films
Heterostructures
• Film thickness measurements.
Superlattices
• Strain relaxation and lattice parameter measurements.
Quantum dots
• Determination of alloy composition and superlattice periods.
• Dynamical scattering simulation to determine composition variations and interface
smearing in heterostructures.

InAs / GaAs multilayer SiGe / Ge superlattice InAs quantum dots on GaAs

Data: Sardela, UIUC Data: Zhang et al
Data: Wu et al, UIUC
Log intensity (a.u.)
Log intensity (a.u.)

Log intensity (a.u.)

62 64 66 68 70 62.5 63.0 63.5 64.0 64.5

58 60 62 64 66 68 o
o 2-theta / omega ( ) o
2-theta / omega ( ) 2-theta / omega ( )
58

29
 High resolution x-ray analysis
High resolution 2θ/θ scan near GaAs(004)
Example: strained
InxGa1-xAs on GaAs
(001) substrate
GaAs (004)
InxGa1-xAs (004)

Thickness
Lattice structure
fringes
a// film = asubstrate
0.07o
0.04o
(004)
a┴ film
InxGa1-xAs
>

asubstrate (004)

GaAs Δa = sin θ(substrate) - 1 Thickness = λ

a sin θ(film) 2 Δθ cosθ

Data: Sardela
asubstrate 59
Sample: Highland, Cahill, Coleman et at, UIUC

High resolution x-ray analysis

High resolution 2θ/θ scan near GaAs(004)
Example: strained and dynamical scattering simulation
InxGa1-xAs on GaAs
(001) substrate
GaAs (004)
InxGa1-xAs (004)

Lattice structure
a// film = asubstrate
243 nm
0.76
at% In
(004)
a┴ film
InxGa1-xAs
>

asubstrate (004)

GaAs
Takagi-Taupin dynamical scattering simulation
Data: Sardela
asubstrate 60
Sample: Highland, Cahill, Coleman et at, UIUC

30
 High resolution reciprocal space mapping
•High resolution reciprocal lattice mapping requires multi-
No strain relaxation: reflection monochromator and analyzer crystal in order to
separate strain from mosaicity. Strain relaxation:
a// = as
•Sensitive to lattice distortions within 10-5. a// ≠ as
•Accurate lattice parameter determination (in and out of
film a┴ plane). a┴ film
•Determination of strain and composition variations, strain
substrate relaxation, mosaic size and rotation, misfit dislocation substrate
density, nanostructure dimensions, lattice disorder and
as diffuse scattering. as
(224) (224) substrate
substrate
film

thickness
fringes Δq001 Mosaicity
(diffuse
scattering)
film
Δq110
0.1 nm-1
Si1-xGex 0.1 nm-1
Si1-xGex
on Si(001) on Si(001)
Data: Sardela et al
61

High resolution reciprocal space mapping

Layer structure
Strained Si (top layer, very thin) Example: strained Si layer
Relaxed Si1-xGex (thick, many microns) on Si1-xGex / Si substrate
Si(001) substrate

Lattice structure

Strained Si Strain?
Reciprocal lattice
(004) Lattice distortion? (004) (224)
Relaxed Si1-xGex Strained Si
(virtual substrate) (224) % of relaxation?
Si substrate
at % of Ge? Δq┴
Si(001) substrate Si1-xGex
Defects?
Δq// 62

31
 High resolution reciprocal space mapping
High resolution 2θ/θ scan near Si(004)
Si1-xGex Si substrate
Layer structure
Strained Si (top layer, very thin) Example: strained Si layer
Relaxed Si1-xGex (thick, many microns) on Si1-xGex / Si substrate
Strained Si

Si(001) substrate

Lattice structure

Strained Si Strain?
Reciprocal lattice
(004) Lattice distortion? (004) (224)
Relaxed Si1-xGex Strained Si
(virtual substrate) (224) % of relaxation?
Si substrate
at % of Ge? Δq┴
Si(001) substrate Si1-xGex
Defects?
Δq// 63

High resolution reciprocal lattice map

Strained Si (top layer)

Relaxed Si1-xGex
Si(001) substrate

Map near Si(224)

[001]
0.1 nm-1
Data: Sardela
Sample: Zuo, UIUC
[110]
64

32
 High resolution reciprocal lattice map
Strained Si
ε⊥ = - 0.77% Strained Si (top layer)
ε// = 0.64 % Si substrate Relaxed Si1-xGex
Si(001) substrate

4.60 at% Ge Map near Si(224)

7.52 at% Ge

11.45 at% Ge

Relaxed Si1-xGex
18.70 at% Ge
100% strain relaxation [001]
0.1 nm-1
Data: Sardela
Sample: Zuo, UIUC
[110]
65

High resolution reciprocal lattice map

Strained Si (top layer)

Finite size Relaxed Si1-xGex
Composition and
Si(001) substrate
strain gradients

Map near Si(224)

Analyzer streaks

Mosaicity and Coherent length

dislocations in any direction:
2π / Δqi
i = x, y, z, //, ┴

[001]
0.1 nm-1
Data: Sardela
Sample: Zuo, UIUC
[110]
66

33
 High resolution reciprocal lattice map

Strained Si (top layer)

Finite size Relaxed Si1-xGex
Composition and
Si(001) substrate
strain gradients
Vertical coherent
length: 14 nm Map near Si(224)

Analyzer streaks

Mosaicity and Coherent length

dislocations in any direction:
2π / Δqi
i = x, y, z, //, ┴

Misfit dislocations: [001]

average separation : 21 nm
0.1 nm-1
density: 5 x 105 cm-1 Data: Sardela
Sample: Zuo, UIUC
[110]
67

Comparison with TEM

EDS line scan

Data: Zuo’s group, UIUC

68

34
 The “shape” of the reciprocal lattice point

Changes in

ω
sca
lattice parameter

n
(radial direction)
Lateral sub-grain
004 boundaries
224
(along q//)

can Mosaicity,
θ)s
[001] /2 curvature,
(ω 24 orientation
G2
CTR, finite (circumferential
000 direction)
layer
thickness,
superlattice
(along q⊥)
[110]

69

X-ray reflectivity methods

Bulk materials:
Near surface
region

Liquids: Near surface and interface information on:

Density
Porosity
Roughness
Thickness in films (ultra thin to thick)
Amorphous or crystalline materials
Multilayered systems:

70

35
 X-ray reflectivity
Detector rotation:
Incide
nt x-r r angle 2-theta
a y bea ay bea
m Detecto
m red x-r
Scatte
Angle of incidence
relative to the surface Sample
(omega or theta)

Intensity
Critical
angle θc One sharp interface
(density ρe variation:
δ function at interface)
R ~ θ -4
Log Reflectivity R

θ Angle ω, θ or 2θ

• Film thickness measurements: 2 – 300 nm.

One rough interface
• Applicable to ultra-thin films, amorphous
Thickness fringes (“broad”ρe variation or crystalline materials, multilayers and
Δθ = λ/[2*(thickness)] at interface) liquids.
• Simulation and fitting: determination of
dec Two interfaces interface roughness (rms) at each interface,
ay
~r roughness correlation and film porosity.
oug ΔI ~Δ ρe
h nes • Very sensitive to density variations.
s
• Determination of critical angle, refractive
θ index and density.
71

X-ray reflectivity analysis of thin films

Complex
multilayers
Ultra-thin Data: Sardela, UIUC
Non
Sample: Auoadi et al, SIU crystalline
n=1
2
2.3 nm thick 3 Metallic Amorphous
polymer on Si 4 multilayer PZT film
Log intensity (a.u.)
Log intensity (a.u.)

Log intensity (a.u.)

0 2 4 6 8 10 12 0.5 1.0 1.5 2.0 2.5 3.0 3.5

2 4 6 8 10 12
o o o
2-theta ( ) 2-theta ( ) Theta ( )
sin2θ
Data: Heitzman et al, UIUC Slope: Data: Mikalsen et al, UIUC
Intercept: periodicity d
refractive
index η
n2

sin2θ = (λ2/2d)2 n2 – (η2 -1)

(modified Bragg’s law to include refractive index)

72

36
 X-ray reflectivity information content
θcritical = (2δ)1/2
Critical angle: density, porosity Refractive index = 1-δ+iβ

Thickness (Kiessig) fringes: angular separation

Reflectivity intensity (counts per sec.)

t = (λ/2) / (sinθ2 – sinθ1) =

between oscillations gives thickness ~ (λ/2) / Δθ

Two sets of oscillations:

gives thickness of two layer structure

Amplitude of fringes: interface

roughness, density variations

Slope / shape of the

decay of the curve:
used to quantify interface
roughness in all interfaces

Angle of incidence (degrees)

73

X-ray reflectivity from superlattices

Example: 20 periods [1 nm SiO2 / 1 nm Si ] superlattice on Si wafer

Critical angle: gives density of each layer in the

superlattice (model dependent)
Reflectivity intensity (counts per sec.)

Thickness fringes:
angular separation gives total superlattice thickness

Number of fringes gives the total number of layers

in the superlattice

Superlattice main peaks:

angular separation gives period thickness

Slope: gives interface

roughness for each layer
in the superlattice (model dependent)

Angle of incidence (degrees)

74

37
 X-ray reflectivity data fitting in ultra-thin films

Polymer 1,3,5-tribromo-2-nanyloxybenze:
(few nm) C15H21Br3SiO3

SiO2
(~ 100 nm)

Si substrate

SiO2
thickness

Polymer thickness

Data: Sardela
Sample: Zhang, Rogers et al, UIUC
75

X-ray reflectivity data fitting

Best fit
rms: 0.26 nm
Polymer
2.0 nm, 1.30 g/cm3
rms: 0.45 nm
SiO2
98.9 nm, 2.19 g/cm3
rms: 0.24 nm
Si substrate

Data

Best fit

76

38
X-ray reflectivity data fitting

Fitting sensitivity to the

polymer thickness
(best fit: 2.00 nm)

2.2 nm
(+ 10 %)
simulation
Data

1.8 nm
(- 10 %)
simulation

77

X-ray reflectivity data fitting

Fitting sensitivity to the

polymer top roughness
(best fit: 0.26 nm)

0.2 nm
(- 0.06 nm)
simulation

Data

0.4 nm
(+ 0.14 nm)
simulation

78

39
 X-ray reflectivity data fitting

Fitting sensitivity to
the polymer density
(best fit: 1.3 g/cm3)

Data
1.4 g/cm3
(+ 8 %)
simulation

1.2 g/cm3
(- 8 %)
simulation

79

X-ray reflectivity: summary

**Non
Nondestructive
destructivemethod
method
**Applicable
Applicableto
towhole
wholewafers
wafers(wafer
(wafermapping
mappingoption)
option)
**Fast
Fastmethod
method(in
(inmost
mostcases)
cases)
**Do
Donot
notdepend
dependon oncrystalline
crystallinequality
qualityof
ofthe
thefilms
films(can
(canalso
alsobe
beused
usedin
inamorphous
amorphous
layers).
layers).

Quantification
Quantificationof:
of:

**Layer
Layerthickness
thicknessin
inthin
thinfilms
filmsand
andsuperlattices: nm~~11μm
superlattices:11nm μm(±
(±0.5-1%).
0.5-1%).
**Layer density and porosity (± 1-2%).
Layer density and porosity (± 1-2%).
**Interface
Interfaceroughness:
roughness:0.1
0.1––10
10nmnm(model
(modeldependent;
dependent;reproducibility
reproducibility~~3%).
3%).
**Layer
Layerdensity
densitygradients
gradients(variations
(variations>>2%).
2%).
**Interface
Interface roughness correlationin
roughness correlation insuperlattices
superlatticesand
andmultilayers.
multilayers.

Alternative techniques:

* Thickness: optical methods (TEM, SEM) poor contrast issues.

* Density: RBS (issues for ultra thin layers).
* Interface roughness: AFM (surface only – not buried interfaces).
80

40
 X-ray fluorescence methods
Bulk materials:

Which elements are present down to ppm levels?

Liquids:
What is the elemental composition (%) ?

Fast, accurate.

Liquids, solids, amorphous, crystalline materials.

Multilayered systems:

81

X-ray fluorescence (XRF)

Data: Panalytical (www.panalytical.com)

K
Ti-Kα1 Mn-Kβ1
Kα2 Kβ1
Kα1 Fe-Kα1
Intensity (a.u.)

K-Kα1 Ba-Lα1
LI
Fe-Kβ1
LII
LIII K-Kβ1
Lβ1
Lα1 Lα2
MI
MII
MIII
MIV
MV
Energy (keV)
• •Typical
Transition notation: Typicalplot:
plot:Intensity
Intensityvs.
vs.Energy.
Energy.
• •Line
Lineposition
positionassociated
associatedtotoelement
elementandandspecific
specifictransition
transition
• •Line
Line positions: fingerprint ofthe
positions: fingerprint of
IUPAC: theelement.
element.
• •Element identification Na-U or Be-U.
<element><“hole” shell><“originating” shell> Element identification Na-U or Be-U.
• •Peak
Ex.: Cr-KLIII Peakassignment
assignmentuses usesdatabase
databaseand andsearch/match.
search/match.
• •Peak
Peakarea/height:
area/height:composition
composition(sub(subppm
ppmtoto100%).
100%).
• •Peak
Siegbahn: <element><“hole” shell><α,β,γ, etc.> Peakoverlap
overlaprequires
requiresdeconvolution.
deconvolution.
• •Composition
Ex.: Cr-Kα1 Compositiondetermination
determinationrequires
requiresstandards,
standards,calibration.
calibration.
• •Fast
Fastdata
dataacquisition
acquisition(seconds
(secondstoto½½hr).hr).
(for LIII to K transition in Cr) • •Solids, liquids, powders, thin films,…
Solids, liquids, powders, thin films,…
• •Minimum
Minimumor ornonosample
samplepreparation
preparationrequired.
required.
82

41
 EDXRF and WDXRF
Peak assignment:
Energy Dispersive XRF (EDXRF) search/match software

X-ray Sample
Concentration:
tube down to sub-ppm

r
Secondary target t ec to
De
Wavelength Dispersive XRF (WDXRF)
Sample
Energy resolution:
5-20 eV (WDXRF)
Collimator 150-300 eV (EDXRF)

Detector
X-ray An
al y
tube zer
c rys
tal 2θ
Data: Horiba Jobin Yvon
http://www.jyinc.com/Spain/esdivisions/XRay/tutorial.htm
83

EDXRF and WDXRF

EDXRF WDXRF

Dispersive system Energy Wavelength

Raw data Intensity vs. Energy (keV) Intensity vs. Detector angle (2θ).
Basic set up
• X-ray tube • X-ray tube
• (Secondary Target) • Sample
• Sample • Collimator ( for // beam)
• Detector • Analyzer Crystal
• Detector (+ goniometer)
Elemental Range Na – U Be – U
Detection limit Good for heavier elements (less optimum for Good for all range
light elements)
Sensitivity Good for heavier elements (less optimum for Moderate for light elements. Good for heavy
light elements) elements.
Resolution Good for heavy elements (less optimum for Good for light elements (less optimum for heavy
light elements) elements)
Cost Moderate Relatively expensive
Measurement Simultaneous • Sequential (moving detector on goniometer)
• Simultaneous (fixed detector)
Moving parts No Crystal, goniometer
Detector Solid state detector • Gas-filled (for Be – Cu)
• Scintillation (for Cu – U).
Qualitative analysis Peak area Peak height
84

42
 Basic EDXRF system configuration
Automatic
16 samples
changer

Ta or Ag Filter
collimator
Automatic
Si (Li) secondary
detector target
changer

Automatic * *X-ray
X-raytube:
tube:Rh
Rh(side
(sidewindow)
window)3.3mA,
3.3mA,60kV.
60kV.
filter
* *Secondary
Secondarytargets:
targets:Gd,
Gd,Sn,
Sn,Ag,
Ag,Ge,
Ge,Fe,
Fe,Ti.
Ti.
changer
Automatic * *Filter:
Filter:Gd
Gd(6(6mil),
mil),Sn
Sn(4(4mil),
mil),Ag
Ag(2(2mil).
mil).
x-ray tube
position * *Detector
Detectorcollimators:
collimators:Ag,
Ag,Ta.
Ta.
Two configurations:
changer * *Samples:
--- direct collimated Samples:
--- secondary target 16
16samples
samplesup
upto
to2’’
2’’diameter,
diameter,or
or
2”
2”square
squaremounts,
mounts,or or
1.25”
1.25”diameter
diameter(inserts).
(inserts).
* *Detector: Si (Li) 30mm 2 active area.
Detector: Si (Li) 30mm active area.
2
CMM instrument: Kevex Analyst 770 XRF system * *Energy
Energyresolution
resolution~~165
165eV.
eV.
85

XRF application
“Spectroscopy investigation of icons
The Virgin and the Child, Unknown author
painted on canvas” Museum of the Serbian Orthodox Church, Belgrade
Lj. Damjanovic et al, Belgrade
http://www.srs.ac.uk/scienceandheritage/prese
ntations/Olgica_Marjanovic.pdf

XRF and IR results show

Surface sample: pigments and binders
• Original made of Au. widely used in the XIX
• Restoration with Au imitation century confirming that the
Schlagmetal (Cu and Zn). work is from late XIX to XX
•Fe: natural Fe-Al-silicate red centuries
bole used for gilding the icon.

Frame sample: Cu
and Zn (no Au)
-> Schlagmetal

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43
 X-ray analysis summary
Information • % of crystallinity and amorphous contents
contents • Identification and quantification of phases and mixtures
• Chemical information (if crystalline)
• Texture (type and strength) and fraction of random grains
• Grain / crystallite size (> 2 nm)
• Strain (> 10-5)
• Stress (type, direction and value)
• Relative crystallographic orientation * Semiconductors
• Lattice constants and unit cell type * Coatings
• Structure determination
* Pharmaceutical
• Thickness (1.5 nm – 3 mm)
• Roughness (including buried interfaces) Cements
• Density and porosity * Metals
• Relative fraction of domains * Ceramics
• Defects and dislocation densities * Geology
• Mosaic tilts and sizes * Archeology
•…
* Biosciences
Detection limits > 0.1 – 0.5 w% * Forensics
Depth information Up to 20 – 50 mm (typical) * Medical applications
> 10 nm and variable with glancing angle XRD * Nanotechnology
Lateral resolution ~ a few cm (typical) * Polymers
10 mm (microdiffraction) – 5 cm * Food science
* Combustion
Angular resolution 0.1o 2q (typical powder diffraction)
0.003o 2q (high resolution methods)
* Energy
*…
Sample requirement Mostly non destructive
Sample sizes from ~ 50 mm to many cm
No vacuum compatibility required
Solids, liquids, gels
87

Comparison with other techniques

X-ray analysis methods Other techniques

Sample o No vacuum compatibility required (except o Surface analysis and electron microscopy
preparation XRF on vacuum). techniques will require vacuum compatibility
and vacuum o “Any” sample size (depends on the and in many cases sample preparation.
compatibility goniometer size/weight capability). o Optical techniques will do analysis on air.
o Rough surfaces acceptable (parallel beam
configuration).
o No sample preparation required (prep
recommended for the detection of unknown
phases or elements in XRD/XRF).
Composition ¾ ~ 0.1 w % (XRF > ppm); may require ¾ XPS: > 0.01 – 0.1 at % (may require depth
and impurity standards. profiling).
determination ¾ XRD: also phase information and % of ¾ SIMS: > 1 ppm (requires sputtering depth
and crystallinity. profiling).
quantification ¾ Data averaged over large lateral area. ¾ EDS: > 0.1 – 1 w % over small volume 1μm3.
¾ Little with phase information; averages over
small lateral areas (< 100 μm).
Lattice o Better than within 10-5 o TEM: estimates ~ 10-3
constants
Thickness in ¾ HR-XRD or XRR: direct measurement (no ¾ RBS: > 10 nm (requires modeling).
thin films modeling for single or bi-layers). ¾ Ellipsometry: requires modeling.
¾ Requires flat interfaces. ¾ TEM: requires visual contrast between layers.
Grain size o Measures Crystallite Size. o SEM: grain size distribution averaged over
o Typically ~ 1-2 nm – microns, requires small area.
size/strain assumptions/ modeling. o TEM/SEM: “number average” size.
o “Volume average” size.

88

44
 Comparison with other techniques
X-ray analysis methods Other techniques

Texture o Type and distribution averaged over large
sample volume.
Residual Stress ¾ 10 MPa, averaged over large sample
volume (large number of grains).
¾ Needs crystallinity.
¾ Measures strain and obtains stress from
Hooke’s law.
¾ Averages macro and micro stresses over
large area of a layer.
Depth ¾ Phase, grain sizes, texture and stress
dependent “depth profiling” – requires x-ray information
information depth modeling
Surface or ¾ XRR: interface roughness 0.01 – 5 nm,
Interface including buried interfaces
roughness
Defects ¾ Misfit dislocations (HR-XRD).
¾ Point defects (diffuse scattering with
model).
¾ Extended defects (powder XRD with
model).
¾ Average over larger sample area (> mm).
Instrument cost ¾ Portable instruments ~ $ 60 K.
¾ Average well-equipped: ~ $ 200 – 300 K.
¾ Top of the line ~ $ 500 K (including
microdiffraction and 2D detectors).
o EBSD: within grain sizes dimensions, better
sensitivity at the surface.
¾ Wafer curvature: No need for crystallinity.
Direct measurement of stress, but only
interlayer stress between film and substrate
(macrostress).
¾ Surface analysis depth profiling:
compositional depth profiles.
¾ SPM: top surface only; rsm~ 0.01-100 nm.
¾ TEM: accurate identification of defects and
their densities; average over small sample
area. Sample preparation may introduce
artifacts.
¾ Surface analysis instruments > $ 500 K.
¾ Electron microscopes ~ $ 300 K – 1 M.
¾ RBS ~ $ 2 M.
¾ Raman, ellipsometry > $ 100 K.
89

Amazing x-ray samples

Pieces from Egyptian mummy
Powder from Inca ruins
Corrosion in pipes from IL water supply
Rocks from Mississippi river
Mud from a cadaver’s shoes
Dove chocolate
Corn starch
Train tracks
Heavy machinery valves
100 μm micro chips
10 μm superconductor single crystal
Next generation CPU processors
Micro extraction from Dutch paintings
Virus, bacteria, DNA, proteins
Powder from Mars terrain
Gasoline, electrical car battery
Bone implants
Pork tissue
90

45
 Amazing x-ray samples
W. C. Roetgen wife’s hand (1895)
© Science and Society Picture Library / Science Museum

A. Bertha Roetgen
(1833-1919)

Wedding ring

It “frightened Bertha terribly”

as a “premonition of death” W.C. Roetgen
After Boston Globe 11/6/95 (1845-1923)
1st Physics Nobel
91

Quick guide to our x-ray analysis instruments (1)

X-ray analysis instrumentation available as user facility in the FS-MRL

Instrument Set up Applications

• Source: Cu Kα1, line or point focus. • High resolution XRD capabilities.

• High resolution configuration. • Rocking curve.
• 4 or 2 reflection Ge monochromator (12 or 30 • Single crystals, epitaxial systems.
Panalytical arc-sec parallel beam). • Reciprocal space mapping.
X’pert (#1) • 3 reflection Ge analyzer crystal (12 arc-sec • Reflectivity.
parallel beam). • Curvature, wafer mapping, miscut, diffuse scattering.
• Eulerian cradle. • Topography.
• Proportional detectors. • Glancing angle.
• Parallel beam applications.
• Max sample size: 10 cm diameter x 2 cm thick.
• Source: Cu Kα1+Kα2, line or point focus. •.Phase, size, strain, stress, texture, crystallinity
• Crossed slit collimator (variable aperture). •.Parallel beam applications
• X-ray lens. •.Bragg-Brentano applications
Panalytical • Programmable divergence slit. •.General thin film analysis
X’pert (#2) • Eulerian Cradle. •.Glancing/grazing angle
• Parallel plate collimator and flat graphite •.Max sample size: 10 cm diameter x 2 cm thick
monochromator
• Programmable receive and scatter slits and
graphite monochromator.
• Proportional detectors.

92

46
 Quick guide to our x-ray analysis instruments (2)
X-ray analysis instrumentation available as user facility in the FS-MRL
Instrument Set up Applications

• Source: Cu Kα1+Kα2, line focus. • Phase, size, strain, crystallinity.

Rigaku • Bragg-Brentano focusing configuration. • Bragg-Brentano applications.
D/Max b • Theta/2theta goniometer. • Rietveld analysis.
• Divergence, soller, scatter and receiving slits. • Mostly for powder, bulks and thin film with small preferred
• Curved graphite monochromator. orientation.
• Scintillation detector.
• Source: Mo point focus. • Single crystal orientation.
Rigaku • Four circle sample stage (manual). • Miscut information.
Laue • Polaroid film camera detection system. • Crystallographic alignment prior to crystal cutting.

• Source: Cu Kα1+Kα2, line focus. • Ideal for powder and soft samples (horizontal load).
Bruker / • Bragg-Brentano focusing configuration. • Phase, size, strain, crystallinity.
Siemens • Theta / theta goniometer. • Bragg-Brentano applications.
D5000 • Horizontal sample load. • Rietveld analysis.
(Fall 2008) • No sample movement required during analysis. • Mostly for powder, bulks and thin film with small preferred
• Divergence, scatter and receiving slits. orientation.
• Scintillation detector.
•.Source: Rh (side window) 3.3mA, 60kV •.Elemental identification: Na – U.
Kevex •.6 secondary targets, 2 detector collimators, 3 •.Liquids, solids, powder samples.
Analyst 700 filters. •.Composition: > ppm (some standards available).
XRF •.Si (Li) solid state detector.
•.Energy resolution 165 meV.
93

Recommended literature
Basic applications of x-ray diffraction:
Basic applications of x-ray diffraction:
“X-ray diffraction – a practical approach”, C. Suryanarayana and M.G. Norton.
“X-ray diffraction – a practical approach”, C. Suryanarayana and M.G. Norton.
“Introduction to X-Ray Powder Diffractometry”, R. Jenkins and R. Snyder,
“Introduction to X-Ray Powder Diffractometry”, R. Jenkins and R. Snyder,
Wiley-Interscience; 1996.
Wiley-Interscience; 1996.
“X-ray characterization of materials”, E. Lifshin, Wiley-VCH, 1999.
“X-ray characterization of materials”, E. Lifshin, Wiley-VCH, 1999.
Sample Preparation Methods:
Sample Preparation Methods:
“A practical guide for the preparation of specimens for x-ray fluorescence and x-
“A practical guide for the preparation of specimens for x-ray fluorescence and x- “X-Ray Diffraction and the Identification and Analysis of Clay Minerals”, D.M.
ray diffraction analysis”, V.E. Buhrke, R. Jenkins and D.K. Smith; Wiley-VCH,
ray diffraction analysis”, V.E. Buhrke, R. Jenkins and D.K. Smith; Wiley-VCH, Moore and R.C. Reynolds, Oxford University Press, 1997.
1998.
1998.
Rietveld Analysis:
Rietveld Analysis:
“The Rietveld Method” ed. By R.A. Young, Oxford Press, 2000.
“The Rietveld Method” ed. By R.A. Young, Oxford Press, 2000.
Thin Analysis by X-ray:
Thin Analysis by X-ray:
“Thin Films Analysis by X-ray Scattering”, M.Birkholz, Wiley-VCH, 2006
“Thin Films Analysis by X-ray Scattering”, M.Birkholz, Wiley-VCH, 2006
High-resolution X-ray analysis:
High-resolution X-ray analysis:
“X-ray scattering from semiconductors”, P. Fewster, Imperial College, 2001.
“X-ray scattering from semiconductors”, P. Fewster, Imperial College, 2001.
“High Resolution X-Ray Diffractometry And Topography”, D.K. Bowen and B.
“High Resolution X-Ray Diffractometry And Topography”, D.K. Bowen and B. Two-dimensional XRD (with areal detectors):
K. Tanner, CRC, 1998.
K. Tanner, CRC, 1998.
“High-Resolution X-Ray Scattering: From Thin Films to Lateral Nanostructures
“High-Resolution X-Ray Scattering: From Thin Films to Lateral Nanostructures 19 (2004) 110 -118.
(Advanced Texts in Physics)”, U. Pietsch, V. Holy and T. Baumbach, Springer;
(Advanced Texts in Physics)”, U. Pietsch, V. Holy and T. Baumbach, Springer;
2004.
2004.
Industrial applications of x-ray analysis:
Industrial applications of x-ray analysis:
“Industrial Applications of X-Ray Diffraction” by F. Smith (Editor), CRC, 1999.
“Industrial Applications of X-Ray Diffraction” by F. Smith (Editor), CRC, 1999. Klug and L.E. Alexander, Wisley-Interscience, 1974.
“X-Ray Metrology in Semiconductor Manufacturing”, D.K. Bowen and B.K.
“X-Ray Metrology in Semiconductor Manufacturing”, D.K. Bowen and B.K.
Tanner, CRC, 2006.
Tanner, CRC, 2006.
Glancing/grazing incidence methods and reflectometry:
Glancing/grazing incidence methods and reflectometry:
“Thin film and surface characterization by specular X-ray reflectivity”, E.
“Thin film and surface characterization by specular X-ray reflectivity”, E.
Chason and T. M. Mayer, Critical Reviews in Solid State and Materials
Chason and T. M. Mayer, Critical Reviews in Solid State and Materials
Sciences, 22 (1997) 1 – 67.
Sciences, 22 (1997) 1 – 67.
“Review on grazing incidence X-ray spectrometry and reflectometry”, K.N.
“Review on grazing incidence X-ray spectrometry and reflectometry”, K.N.
Stoev and K. Sakurai, Spectrochimica Acta B: At Spectros, 54 (1999) 41-82.
Stoev and K. Sakurai, Spectrochimica Acta B: At Spectros, 54 (1999) 41-82.
Residual stress and stress gradients:
Residual stress and stress gradients:
“Residual Stress: Measurement by Diffraction and Interpretation”, I. C. Noyan
“Residual Stress: Measurement by Diffraction and Interpretation”, I. C. Noyan
and J. B. Cohen, Springer-Verlag, 1987.
and J. B. Cohen, Springer-Verlag, 1987.
“Residual stress/strain analysis in thin films by X-ray diffraction”, I.C.
“Residual stress/strain analysis in thin films by X-ray diffraction”, I.C.
Noyan, T.C. Huang and B.R. York, Critical Reviews in Solid State and Materials
Noyan, T.C. Huang and B.R. York, Critical Reviews in Solid State and Materials
Sciences, 20 (1995) 125 – 177.
Sciences, 20 (1995) 125 – 177.
X-ray analysis of clay minerals:
X-ray analysis of clay minerals:
“X-Ray Diffraction and the Identification and Analysis of Clay Minerals”, D.M.
Moore and R.C. Reynolds, Oxford University Press, 1997.
X-ray fluorescence:
X-ray fluorescence:
“Quantitative x-ray spectrometry”, R. Jenkins, R.W. Gould and D. Gedcke,
“Quantitative x-ray spectrometry”, R. Jenkins, R.W. Gould and D. Gedcke,
Marcel Dekker Inc, 1995
Marcel Dekker Inc, 1995
“Quantitative x-ray fluorescence analysis theory and application”, G.R. Lachance
“Quantitative x-ray fluorescence analysis theory and application”, G.R. Lachance
and F. Claisse, Willey, 1995.
and F. Claisse, Willey, 1995.
Laue methods:
Laue methods:
“Laue Method”, J.L. Amoros, Academic Press Inc., 1975.
“Laue Method”, J.L. Amoros, Academic Press Inc., 1975.
Two-dimensional XRD (with areal detectors):
“Microdiffraction using two-dimensional detectors”, B.B. He, Powder Diffraction
“Microdiffraction using two-dimensional detectors”, B.B. He, Powder Diffraction
19 (2004) 110 -118.
Fundaments of x-ray scattering:
Fundaments of x-ray scattering:
“X-ray diffraction”, B.E. Warren, Addison-Wesley, 1962.
“X-ray diffraction”, B.E. Warren, Addison-Wesley, 1962.
“X-ray diffraction procedures for polycrystallines and amorphous materials”, H.P.
“X-ray diffraction procedures for polycrystallines and amorphous materials”, H.P.
Klug and L.E. Alexander, Wisley-Interscience, 1974.
“Elements of x-ray diffraction”, B.D. Cullity, Addison-Wesley, 1978.
“Elements of x-ray diffraction”, B.D. Cullity, Addison-Wesley, 1978.
“Elements of Modern X-ray Physics”, J. Als-Nielsen (Author), D. McMorrow,
“Elements of Modern X-ray Physics”, J. Als-Nielsen (Author), D. McMorrow,
Wiley, 2001.
Wiley, 2001.
“Coherent X-Ray Optics (Oxford Series on Synchrotron Radiation)”, D. Paganin,
“Coherent X-Ray Optics (Oxford Series on Synchrotron Radiation)”, D. Paganin,
Oxford University Press, 2006.
Oxford University Press, 2006.
Web resource: www.ccp14.ac.co.uk (free x-ray data analysis programs and
Web resource: www.ccp14.ac.co.uk (free x-ray data analysis programs and
tutorials)
tutorials)
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 Acknowledgements
Sponsors:

Frederick Seitz Materials Research Laboratory is

supported by the U.S. Department of Energy
under grants DEFG02-07-ER46453 and DEFG02-07-ER46471

95

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