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Workshop08 X-Ray Handouts PDF
Workshop08 X-Ray Handouts PDF
Characterization Workshop
Sponsors:
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
h0
h0
Fluorescence
h1
V) h2 Photoelectron
25 (ke e-
125 0. 1
E
e-
X Auger electron
UV Visible
rays rays Interaction
2 nm ~30 m volume h: photon
1 0
0. 0 10 m) 20 e-: electron
(n 50 m 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) - o energy
energyhh o; ;
incident
incidentphoton
o
hh (a)eeabsorbs
- absorbsincident
incidentenergy
energyhh (b) o
photon (excited o
(b)outer
outershell
shelle-e-cascade
cascadedown
(excitedphotoelectron);
interacts - o down
interactswith
witheewith
- withnono photoelectron); filling
(b) fillingthe
theholes
holescausing
(b) part of the energy is emittedatat
energy part of the energy is emitted causing
energyloss
lossand
andnonophase
phase secondary
different 1 and secondaryphotons
photons
change
change differentenergy
energyhh different
1 and different emission 2).).
phase.
phase. emission(h(h 2
Auger
Augerelectron
electronemission:
emission:
Photoelectron (a)
(a)incident 0 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
hh0 energy is used to eject electron e- with
- nd - levelstotofill
fillthe
the
0 energy is used to eject electron e with hole
kinetic energy = h
kinetic energy = ho B.E.(bindingenergy).
B.E.(binding energy). holeand
andaaphoton
photonisisemitted;
emitted;
(c)
(c)the
theemitted
o photon isisabsorbed by valance
emitted photon absorbed by valance
ee-,-,which
whichionizes
ionizesandandleaves
leavesthetheatom.
atom.
3
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
2/d
origin
Fundaments of diffraction
Real space
F Reciprocal space
2/d
origin
3
Fundaments of diffraction
Real space
F Reciprocal space
origin
Fundaments of diffraction
Real space F Reciprocal space
k1
q
2
k0 (= radius)
2 d sin = n q = k1 k0
Elastic (Thompsons)
scattering q: scattering vector
q = (4 /) sin
Paul P. Ewald
81888-1985
18621942 1890-1971
4
Fundaments of diffraction
Real space Reciprocal space
Detector
scan 2/ scan Rocking
curve scan:
(2) (2/) Rocking curve () to scattering
(sample) scan vector
Diffracted () 2/ scan:
beam
Scattering (2/) radial, // to
vector Detector Scan:
am scattering
be around
ent vector
id Ewalds sphere
2 In
c
hkl
(2)
q k1
hk
l
k0
Fundaments of diffraction
Real space Reciprocal space
Detector
scan 2/ scan Defects, material quality
Rocking
Mosaicity curve scan:
(2) (2/) Rocking () to scattering vector
curve scan Texture
Texture strength
Diffracted () 2/ scan:
beam
Scattering (2/) radial,
vector Detector Scan:
am
// to scattering
be around Ewalds
nt
vector
cid
e
Phase analysis sphere
2 In Grain size analysis hkl
(2)
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
Crystalline? Amorphous?
Strain?
12
6
Bragg-Brentano focusing configuration
Single crystal
Receiving monochromator
Focus slit ()
X-ray
source
Divergence Detector
slit
Secondary
Optics:
Scatter and soller slits
Focusing
circle Detector
(variable during specimen
measurement) rotation
(2)
Angle of
incidence
()
Diffractometer circle
13
(fixed during measurement)
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 (2)
grazing
grazing Angle of Sample
Sample height
height
incidence
incidence
incidence positioning
positioning isis critical
critical
()
analysis
analysis Diffractometer circle
14
(fixed during measurement)
7
Instrumentation: powder diffraction
Soller Divergence
slits slit
s am
Cu ple
x-ray
source 2 2
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 2 ~ 0.2O
15
8
Crystallite size analysis
Scherrers equation:
Not accounting for peak
k* broadening from strain and
Size = defects
cos () * (FWHM)
Peak
Peakwidth
width(FWHM)
(FWHM)
___ Measurement
___ Fit
Peak
Peakposition
position2
2
17
Imax
It does not take into
account the lower part ()I FWHM (deg)
max
of the profile
18
9
Peak shape analysis
Peak fit:
Gaussian
Lorentzian
Pearson-VII (sharp peaks)
Pseudo-Voigt
(round peaks) Measurement
___ Measurement
___ Fit
19
D: deconvolution parameter
Measurement
D : 1 (~ Lorentzian)
Instrument function = (meas) (instr)
D : 2 (~ Gaussian)
2 = (meas)2 (instr)2
D : 1.5
1.5 = (meas)1.5 (instr)1.5
10
Potential artifacts in size determination
FWHM: Assume:
D = (meas)D (instr)D Instrument resolution ~ 0.15o
2 = 40o
Measured Size, nm Size, nm Size, nm Cu radiation
peak D=1 D = 1.5 D=2
width (o) (Lorentzian) (Gaussian)
21
No strain
(2)
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()
(FWHM)*cos()==k/(size)
k/(size)++(strain)*sin()
(strain)*sin()
(FWHM)*cos()
Williamson-Hall
Method
Acta Metall. 1 (1953) 22.
sin()
Intercept
Intercept~~1/(size)
1/(size)
Slope
Slope~~micro
microstrain
strain
FWHMstrain = 4*(strain)*tan
23
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(-p)
(mainassumption) exp(-p)2->->Use
UseScherrers
Scherrersequation
equation
Jones
Jonesmethod:
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
2(o)
Software:
MDIs Jade + 8.0
25
(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 ; b= 2.86285 ; c= 14.17281
(Rietveld = 90o = 90o = 120o
refinement): Unit cell volume: 100.6 ()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 , Ni-Li: 2.8729 ,
* Pattern Indexing distances Ni-Ni: 2.8629 , Co-O: 1.9570 ,
(Rietveld): Co-Ni: 2.8629 , Co-Li: 2.8729
* Cell Refinement Li-O: 2.1117 , Li-Li: 2.8629 ,
* Pattern Simulation O-O: 2.7983
* RIR w% quantification Quantitative 82.9 w% LiNi0.7Co0.3O2, 17.1 w% C
Co
* Rietveld structure refinement analysis:
Crystallite size: > 1000
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: MDIs Jade + 8.0
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
Whole pattern R
fitted
H A
15
X-ray parallel beam methods
Near surface
Glancing / grazing angle applications.
region Phase, stress gradients (depth profiles)
31
Detector
Parallel
rotation
beam
(2)
Angle of specimen
incidence
()
Excellent
Excellentfor
forglancing
glancingangle
angle
(fixed)
(fixed )applications
applications 32
16
Instrumentation: thin film, texture, stress analysis
Parallel plate collimator Primary optics Optional
configurations option 1: filter or
Crossed-slit attenuator
collimator
X-ray source:
Top view ple Cu, line or point focus
sam
2
0.27o- Crossed slits
parallel (slit+mask) Primary optics option 2:
plates x-ray lenses
collimator Vertical mask
Ji/JTa = 11
-TaN
scans t = 500 nm
Intensity (a.u.)
fN = 0.125 Ts = 600 C
2
Data:
(002) Shin,
Petrov et al,
Intensity (a.u.)
30 eV, = 0.75
-TaN
20 eV, = 0.60
Cube
Cubeon oncube
cube -TaN
epitaxy:
epitaxy:
8.5 eV, = 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
2 (deg) 0 50 100 150 200 250 300 350
(deg) 34
17
Glancing angle x-ray analysis
Inc
ide m
nt
x bea
surface -ra -ray
normal y be t edx
am rac
(fixed) Diff
grains
-Type of radiation
- Angle of incidence
- Material (Z, A, , )
36
18
X-ray penetration and information depths
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 fordepth
depthprofiling
profilingatat
differentincidences.
different incidences.
Very
Verygood
good2
2resolution
resolutionand
andwell-
well-
known
knownmathematical
mathematicalformalism.
formalism.
Slightlylower
Slightly lower2
2resolution:
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
Poly-Si
(~ 100 nm)
Substrate Substrate
Si(001)
substrate
Glancing
angle
Conventional
2/ 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
2
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
x-ray s
ource Angle of
incidence:
ScN(220)
0.50
Depth from surface ()
GIXS from a
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
fromaa2/
2/scan
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
2 sample
detector
urce
(111) x-ray so
1
Inverse
pole
figures
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
r 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 (parallel to
O O equatorial plane)
S
OW = r tan(/2) OS = 2 r tan(/2)
45
Tilt
= 0, 90o
100 : [100],[100]
Example: (100) cubic crystal (111) Pole figure
-1 -1 1 -1 1 1 Azimuth
= 45o, 135o,
Pole figure plot 225o, 315o
111
1 -1 1 Tilt = 54.7o
hkl : [100],[111]
23
Basics of pole figure analysis
Surface
hkl (100) Pole figure
Azimuth
= 30o,
normal 001 010
150o, 270o
Tilt = 54.7o
100 : [111],[100]
Example: (111) cubic crystal (111) Pole figure -1 1 1
Azimuth
= 90o,
Pole figure plot 210o, 330o
111
1 -1 1 1 1-1
Tilt = 0, 70.5o
hkl : [111],[111]
: [111],[110]
47
Conventional 2/ scan:
Si
Cu(111)
Grains:
56 nm
Cu(222)
48
24
Fiber texture analysis
(111) Pole figure:
Example: Cu thin film = 70.53o
on Si (001) substrate
Conventional 2/ scan:
Si
Cu(111)
=0
Grains:
56 nm
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?
Type?
Direction (s)?
Stress gradients?
51
o
+45
o
+30o
Diffracting planes +15
0
o
-15
o
-30o
-45
Interplanar spacing d (Angstroms)
o
-60
d/d = [(1+)/E] sin2
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 Sin2 and RIM methods.
and scan methods.
1.168
0.0 0.2 0.4 0.6 0.8 New glancing angle method (texture).
2
sin () 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 sin2 method
Film Normal
unstressed L,
Incident Reflected
X-rays X-rays
a stressed
a
film surface a0
Diffracting planes
4.55 HfN1.05/SiO2
a ao 1+ 2
4.54 = -0.03074 = = sin 2
ao E E
= 4.54521
a ()
a
4.53 a =
a o
E
[(1 + ) sin 2
]
2 + a o = sin 2 +
2
sin 2 = 2
4.52 1+ ao = + = 4.533
1+
4.51 E
0.0 0.2 0.4 0.6 0.8 1.0 = = 1.47 GPa (Compressive)
2 + (1 + )
sin2 53
Data: Petrov et al, UIUC
b Accurate measurements of a, b, c, , ,
Detailed peak shapes: defects, mosaicity.
a c
+
a
a Film / substrate epitaxial systems:
a 54
27
Instrument resolution in reciprocal space
Dif
Beam angular divergence, frac
te eam
db nt b
i de
detector acceptance and eam
I nc
diffractometer sampling volume sample
Angular
acceptance
of the
secondary
optics
Primary beam
2 divergence
Diffractometer (from primary optics)
sampling
volume
Ewald sphere
55
28
Instrumentation: high-resolution configuration
Hybrid
Mirror x-ray
(2-bounce monochromator +
X-ray mirror)
source
ple
sam
slit
3-bounce 2 =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 Xpert #2 XRD system
57
29
High resolution x-ray analysis
High resolution 2/ 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)
Data: Sardela
asubstrate 59
Sample: Highland, Cahill, Coleman et at, UIUC
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 q001 Mosaicity
(diffuse
scattering)
film
q110
0.1 nm-1
Si1-xGex 0.1 nm-1
Si1-xGex
on Si(001) on Si(001)
Data: Sardela et al
61
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? q
Si(001) substrate Si1-xGex
Defects?
q// 62
31
High resolution reciprocal space mapping
High resolution 2/ 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? q
Si(001) substrate Si1-xGex
Defects?
q// 63
[001]
0.1 nm-1
Data: Sardela
Sample: Zuo, UIUC
[110]
64
32
High resolution reciprocal lattice map
Strained Si
= - 0.77% Strained Si (top layer)
// = 0.64 % Si substrate Relaxed Si1-xGex
Si(001) substrate
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
Analyzer streaks
[001]
0.1 nm-1
Data: Sardela
Sample: Zuo, UIUC
[110]
66
33
High resolution reciprocal lattice map
Analyzer streaks
68
34
The shape of the reciprocal lattice point
Changes in
sca
lattice parameter
n
(radial direction)
Lateral sub-grain
004 boundaries
224
(along q//)
can Mosaicity,
)s
[001] /2 curvature,
( 24 orientation
G2
CTR, finite (circumferential
000 direction)
layer
thickness,
superlattice
(along q)
[110]
69
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 c One sharp interface
(density e variation:
function at interface)
R ~ -4
Log Reflectivity R
Angle , or 2
72
36
X-ray reflectivity information content
critical = (2)1/2
Critical angle: density, porosity Refractive index = 1-+i
Thickness fringes:
angular separation gives total superlattice thickness
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
Data
Best fit
76
38
X-ray reflectivity data fitting
2.2 nm
(+ 10 %)
simulation
Data
1.8 nm
(- 10 %)
simulation
77
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
Quantification
Quantificationof:
of:
**Layer
Layerthickness
thicknessin
inthin
thinfilms
filmsand
andsuperlattices: nm~~11m
superlattices:11nm m(
(0.5-1%).
0.5-1%).
**Layer density and porosity ( 1-2%).
Layer density and porosity ( 1-2%).
**Interface
Interfaceroughness:
roughness:0.1
0.110
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:
40
X-ray fluorescence methods
Bulk materials:
Fast, accurate.
Multilayered systems:
81
K
Ti-K1 Mn-K1
K2 K1
K1 Fe-K1
Intensity (a.u.)
K-K1 Ba-L1
LI
Fe-K1
LII
LIII K-K1
L1
L1 L2
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><,,, etc.> Peakoverlap
overlaprequires
requiresdeconvolution.
deconvolution.
Composition
Ex.: Cr-K1 Compositiondetermination
determinationrequires
requiresstandards,
standards,calibration.
calibration.
Fast
Fastdata
dataacquisition
acquisition(seconds
(secondstotohr).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 2
Data: Horiba Jobin Yvon
http://www.jyinc.com/Spain/esdivisions/XRay/tutorial.htm
83
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
2diameter,
diameter,or
or
2
2square
squaremounts,
mounts,or or
1.25
1.25diameter
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
Frame sample: Cu
and Zn (no Au)
-> Schlagmetal
86
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
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 ~ 0.1 w % (XRF > ppm); may require XPS: > 0.01 0.1 at % (may require depth
and impurity standards. profiling).
determination XRD: also phase information and % of SIMS: > 1 ppm (requires sputtering depth
and crystallinity. profiling).
quantification Data averaged over large lateral area. EDS: > 0.1 1 w % over small volume 1m3.
Little with phase information; averages over
small lateral areas (< 100 m).
Lattice o Better than within 10-5 o TEM: estimates ~ 10-3
constants
Thickness in HR-XRD or XRR: direct measurement (no RBS: > 10 nm (requires modeling).
thin films modeling for single or bi-layers). Ellipsometry: requires modeling.
Requires flat interfaces. 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 o EBSD: within grain sizes dimensions, better
sample volume. sensitivity at the surface.
Residual Stress 10 MPa, averaged over large sample Wafer curvature: No need for crystallinity.
volume (large number of grains). Direct measurement of stress, but only
Needs crystallinity. interlayer stress between film and substrate
Measures strain and obtains stress from (macrostress).
Hookes law.
Averages macro and micro stresses over
large area of a layer.
Depth Phase, grain sizes, texture and stress Surface analysis depth profiling:
dependent depth profiling requires x-ray information compositional depth profiles.
information depth modeling
Surface or XRR: interface roughness 0.01 5 nm, SPM: top surface only; rsm~ 0.01-100 nm.
Interface including buried interfaces
roughness
Defects Misfit dislocations (HR-XRD). TEM: accurate identification of defects and
Point defects (diffuse scattering with their densities; average over small sample
model). area. Sample preparation may introduce
Extended defects (powder XRD with artifacts.
model).
Average over larger sample area (> mm).
Instrument cost Portable instruments ~ $ 60 K. Surface analysis instruments > $ 500 K.
Average well-equipped: ~ $ 200 300 K. Electron microscopes ~ $ 300 K 1 M.
Top of the line ~ $ 500 K (including RBS ~ $ 2 M.
microdiffraction and 2D detectors). Raman, ellipsometry > $ 100 K.
89
45
Amazing x-ray samples
W. C. Roetgen wifes hand (1895)
Science and Society Picture Library / Science Museum
A. Bertha Roetgen
(1833-1919)
Wedding ring
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 K1+K2, 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
Residual stress and stress gradients:
Basic applications of x-ray diffraction: Residual stress and stress gradients:
Basic applications of x-ray diffraction: Residual Stress: Measurement by Diffraction and Interpretation, I. C. Noyan
X-ray diffraction a practical approach, C. Suryanarayana and M.G. Norton. Residual Stress: Measurement by Diffraction and Interpretation, I. C. Noyan
X-ray diffraction a practical approach, C. Suryanarayana and M.G. Norton. and J. B. Cohen, Springer-Verlag, 1987.
Introduction to X-Ray Powder Diffractometry, R. Jenkins and R. Snyder, and J. B. Cohen, Springer-Verlag, 1987.
Introduction to X-Ray Powder Diffractometry, R. Jenkins and R. Snyder, Residual stress/strain analysis in thin films by X-ray diffraction, I.C.
Wiley-Interscience; 1996. Residual stress/strain analysis in thin films by X-ray diffraction, I.C.
Wiley-Interscience; 1996. Noyan, T.C. Huang and B.R. York, Critical Reviews in Solid State and Materials
X-ray characterization of materials, E. Lifshin, Wiley-VCH, 1999. Noyan, T.C. Huang and B.R. York, Critical Reviews in Solid State and Materials
X-ray characterization of materials, E. Lifshin, Wiley-VCH, 1999. Sciences, 20 (1995) 125 177.
Sciences, 20 (1995) 125 177.
Sample Preparation Methods:
Sample Preparation Methods: X-ray analysis of clay minerals:
A practical guide for the preparation of specimens for x-ray fluorescence and x- X-ray analysis of clay minerals:
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, 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, Moore and R.C. Reynolds, Oxford University Press, 1997.
1998. Moore and R.C. Reynolds, Oxford University Press, 1997.
1998.
X-ray fluorescence:
Rietveld Analysis: X-ray fluorescence:
Rietveld Analysis: Quantitative x-ray spectrometry, R. Jenkins, R.W. Gould and D. Gedcke,
The Rietveld Method ed. By R.A. Young, Oxford Press, 2000. Quantitative x-ray spectrometry, R. Jenkins, R.W. Gould and D. Gedcke,
The Rietveld Method ed. By R.A. Young, Oxford Press, 2000. Marcel Dekker Inc, 1995
Marcel Dekker Inc, 1995
Quantitative x-ray fluorescence analysis theory and application, G.R. Lachance
Thin Analysis by X-ray: Quantitative x-ray fluorescence analysis theory and application, G.R. Lachance
Thin Analysis by X-ray: and F. Claisse, Willey, 1995.
Thin Films Analysis by X-ray Scattering, M.Birkholz, Wiley-VCH, 2006 and F. Claisse, Willey, 1995.
Thin Films Analysis by X-ray Scattering, M.Birkholz, Wiley-VCH, 2006
Laue methods:
High-resolution X-ray analysis: Laue methods:
High-resolution X-ray analysis: Laue Method, J.L. Amoros, Academic Press Inc., 1975.
X-ray scattering from semiconductors, P. Fewster, Imperial College, 2001. Laue Method, J.L. Amoros, Academic Press Inc., 1975.
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. Two-dimensional XRD (with areal detectors):
K. Tanner, CRC, 1998. Microdiffraction using two-dimensional detectors, B.B. He, Powder Diffraction
High-Resolution X-Ray Scattering: From Thin Films to Lateral Nanostructures Microdiffraction using two-dimensional detectors, B.B. He, Powder Diffraction
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; 19 (2004) 110 -118.
(Advanced Texts in Physics), U. Pietsch, V. Holy and T. Baumbach, Springer;
2004.
2004. Fundaments of x-ray scattering:
Fundaments of x-ray scattering:
X-ray diffraction, B.E. Warren, Addison-Wesley, 1962.
Industrial applications of x-ray analysis: X-ray diffraction, B.E. Warren, Addison-Wesley, 1962.
Industrial applications of x-ray analysis: X-ray diffraction procedures for polycrystallines and amorphous materials, H.P.
Industrial Applications of X-Ray Diffraction by F. Smith (Editor), CRC, 1999. X-ray diffraction procedures for polycrystallines and amorphous materials, H.P.
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. Klug and L.E. Alexander, Wisley-Interscience, 1974.
X-Ray Metrology in Semiconductor Manufacturing, D.K. Bowen and B.K. Elements of x-ray diffraction, B.D. Cullity, Addison-Wesley, 1978.
Tanner, CRC, 2006. Elements of x-ray diffraction, B.D. Cullity, Addison-Wesley, 1978.
Tanner, CRC, 2006. 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.
Glancing/grazing incidence methods and reflectometry: Wiley, 2001.
Glancing/grazing incidence methods and reflectometry: Coherent X-Ray Optics (Oxford Series on Synchrotron Radiation), D. Paganin,
Thin film and surface characterization by specular X-ray reflectivity, E. Coherent X-Ray Optics (Oxford Series on Synchrotron Radiation), D. Paganin,
Thin film and surface characterization by specular X-ray reflectivity, E. Oxford University Press, 2006.
Chason and T. M. Mayer, Critical Reviews in Solid State and Materials Oxford University Press, 2006.
Chason and T. M. Mayer, Critical Reviews in Solid State and Materials
Sciences, 22 (1997) 1 67.
Sciences, 22 (1997) 1 67. Web resource: www.ccp14.ac.co.uk (free x-ray data analysis programs and
Review on grazing incidence X-ray spectrometry and reflectometry, K.N. Web resource: www.ccp14.ac.co.uk (free x-ray data analysis programs and
Review on grazing incidence X-ray spectrometry and reflectometry, K.N. tutorials)
Stoev and K. Sakurai, Spectrochimica Acta B: At Spectros, 54 (1999) 41-82. tutorials)
Stoev and K. Sakurai, Spectrochimica Acta B: At Spectros, 54 (1999) 41-82.
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Acknowledgements
Sponsors:
95
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