Introduction to

High Resolution X-Ray Diffraction of

Epitaxial Thin Films

Scott A Speakman, Ph.D.

MIT Center for Materials Science and Engineering

617-253-6887
[email protected]
http://prism.mit.edu/xray
What is an epitaxial film?

• Traditionally, an epitaxial film is a lattice-matched semiconductor thin

film grown on a semiconductor single crystal substrate
– The lattice of the film is nearly identical to the lattice of the substrate
– When the film grows, its lattice changes (strains) in order to match the lattice
of the substrate
– The atomic bonding across the substrate and film is “perfectly” matched

The lattice of the film (red) The lattice of the epitaxial film (red)
is almost the same as the distorts to minimize the strain energy
substrate (blue) where it bonds to the substrate (blue)

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A greater variety of functionally epitaxial films
are now produced on a regular basis
• A common modern definition for epitaxy is “a single crystal layer that grows
with a particular orientation determined by the single crystal substrate”
– This definition does not require the film and substrate to be lattice matched, but they
must still be similar enough to interact and have a defined relationship

• A liberal definition of epitaxy would be “Any film which resembles a single

crystal in its lattice structure and properties”
– This definition lessens the importance of the relationship between the film and
substrate. This definition would consider a single crystal layer grown on a glass
(amorphous) substrate to still be epitaxial, whereas other definitions would not.

• Definitions depending on the relationship between the film and substrate:

– Homoepitaxial film: the film and substrate are the same material
– Heteroepitaxial film: the film and substrate are different materials
• Some definitions would still require the film and substrate to have similar
structures so that they are lattice matched

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There are functionally two different types of
heteroepitaxial thin films
• In traditional heteroepitaxial thin films, the film and the substrate have very
similar crystal structures and lattice parameters
– There is a strong relationship between the film and substrate, in terms of:
• Bonding across the interface
• Geometric similarity between their crystal structures and orientation
– Examples: AlGaInP on GaAs, Si(Ge) on Si,

• Many newer types of heteroepitaxial thin films sometimes include films with
different crystal structures than the substrates
– The film and substrate structures might belong to different crystal systems: for
example, a cubic film growing on a hexagonal substrate
– The geometric relationship between the film and substrate is more complex
– These films tend to have less lattice strain and higher defect concentration,
particularly mosaicity, because the relationship between the film and substrate is
weaker.
– Examples: GaN on Al2O3, BiFeO3 on LaAlO3, Pb(Zr,Ti)O3 on MgO
– I have not yet found a good term to describe these types of films

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There are different modes of epitaxy depending on
the geometric relationship between the film and
substrate structures
• Commensurate: the primitive film lattice coincides
with all symmetry equivalent substrate lattice points

• Coincident: the lattice points of the film coincide Different examples of

with some, but not all, of the equivalent substrate commensurate epitaxy,
showing how the film lattice
lattice points (black) correlates to the
– Type I: every lattice point of the film coincides with substrate lattice (red)
substrate lattice points. However, not every substrate
lattice point has a coincident film lattice point. The film
tends to match with lines of substrate lattice points
– Type II: only some of the film lattice points lie on
substrate lattice lines.

• Incommensurate: even though the thin film has

grown as an effective single crystal without any
Different examples of coincident
grain boundaries, there is no direct correlation epitaxy, showing how the film
between the film lattice and the substrate lattice lattice (black) correlates to the
substrate lattice (red)

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HRXRD and XRR are both used to study thin films and
benefit from the same optics, so we often consider
them together
HRXRD can measure: XRR can measure:
• Structural Information • Thickness
– Composition • Surface and Interface Roughness
– Thickness • Density or composition of the
– Superlattice period topmost layer
• Defects
– Mismatch
– Relaxation
– Misorientation
– Dislocation Density
– Mosaic Spread
– Curvature
– Inhomogeneity
– Surface Damage

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Relaxation (Lattice Strain)

Relaxed Film Strained Film

• If the film is mismatched to the substrate, then the film might be strained so
that the lattice parameters in the lateral direction (ie within the plane of the
film) are forced to match the lattice parameters of the substrate
• This distorts the unit cell of the film
– A formerly cubic unit cell is now tetragonal
• Determine the degree of relaxation
– No relaxation (fully strained)- the lateral lattice parameters of the film are strained to
be identical to the substrate
– Fully relaxed- the lateral lattice parameters of the film are equal to the bulk values–
they have not been distorted at all

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Dislocations

• Interface dislocations may form to relieve lattice strain between

a film and substrate with a large amount of mismatch
• Slip dislocations are created by plastic deformation due to
thermal or mechanical strain in the layer
– Slip dislocations create a broadened rocking curve and diffuse scatter
𝛽2
– In the Hirsch model, Dislocation density 𝜌 =
9𝑏2
• β is the broadening of the rocking curve in radians
• b is the Burgers vector in cm

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Mosaic Spread

• Mosaicity is created by slight misorientations of different

crystals as they nucleate and grow on the substrate. When the
crystals join, they form low energy domain boundaries.

In the ideal case, each nuclei If the nuclei (red) are slightly
(red) is perfectly oriented. When misaligned, then low angle domain
the crystals grow and meet, there boundaries will be formed.
is perfect bounding between the
crystallites and therefore there is
no grain boundary

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Curvature

• The film and substrate may become slightly curved rather than
perfectly flat
– This may be the result of deposition process, thermal expansion
mismatch between the film and substrate, etc

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Inhomogeneity or Gradients

• Both compositional and strain gradients can be identified and

quantified.

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There are several levels between films with perfect
epitaxy or ideal polycrystalline randomness
Perfect Epitaxy Single crystal film in perfect registry with a substrate. There are no
defects in the film or the substrate.
Nearly perfect Single crystal film in nearly perfect registry with a substrate. Both
epitaxy film and substrate contain a low concentration of defects. Most
defects are dislocations in the film.
Textured Film consists of mosaic domains in nearly perfect registry with the
epitaxial* substrate. All domain boundaries are very low angle/low energy.
There is nearly perfect bonding across domain boundaries.
Strongly textured Film consists of grains with nearly perfect preferential orientation of
polycrystalline all principle axes. This orientation is often strongly correlated to the
substrate. Misorientation parameter for texture is small.
Textured Film consists of grains with a preferred orientation for 3 principle
polycrystalline axes or only along 1 axis out-of-plane.
Polycrystalline Film consists of randomly oriented grains.
Amorphous Film does not have long-range crystalline order.

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 What techniques can be used to learn what type
of information about these films
Thickness Composition Lattice Strain/ Defects Orientation Residual Crystallite
Relaxation Stress Size
Perfect Epitaxy XRR, HRXRD, RC Assume 100% Assume HRXRD -- --
HRXRD none
Nearly perfect XRR, HRXRD, RC HRXRD RC HRXRD -- --
epitaxy HRXRD
Textured XRR, HRXRD HRXRD, IP- RC HRXRD -- --
epitaxial* HRXRD GIXD
Strongly textured XRR XRPD, IP- IP-GIXD XRPD, IP-GIXD, IP-GIXD XRPD, IP-
polycrystalline GIXD IP-GIXD PF GIXD
Textured XRR XRPD, -- XRPD, PF Psi XRPD,
polycrystalline GIXD or IP- GIXD OR GIXD
GIXD IP-GIXD
Polycrystalline XRR XRPD, -- XRPD, PF Psi XRPD,
GIXD GIXD GIXD
Amorphous XRR -- -- -- -- -- --

XRR- X-Ray Reflectivity RC- Rocking Curve IP-GIXD- in-plane grazing incidence XRD
HRXRD- High Resolution XRD using XRPD- Bragg-Brentano powder diffraction PF- pole figure
coupled scan or RSM GIXD- grazing incidence XRD Psi- sin2psi using parellel beam

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HRXRD data usually measures scattered X-ray
intensity as a function of omega and/or 2theta

s Detector
X-ray tube

w
2q

• The incident angle, w, is defined between the X-ray source and the sample.
• The diffracted angle, 2q, is defined between the incident beam and detector angle.
• Type of scans:
– A Rocking Curve is a plot of X-ray intensity vs. Omega
– A Detector Scan plots X-ray intensity vs. 2Theta without changing Omega.
– A Coupled Scan is a plot of scattered X-ray intensity vs 2Theta, but Omega also changes in a way
that is linked to 2Theta so that Omega= ½*2Theta + offset
• A coupled scan is used to measure the Bragg diffraction angle
Diffraction patterns are produced by the coherent
scattering of light by atoms in crystalline materials.
• Diffraction occurs when each object in a periodic array scatters radiation
coherently, producing concerted constructive interference at specific angles.
• Atoms in a crystal are a periodic array of coherent scatterers.
– The wavelength of X rays are similar to the distance between atoms.
– Diffraction from different planes of atoms produces a diffraction pattern, which
contains information about the atomic arrangement within the crystal
– The strong peak of intensity that is produced by the coherent scattering of the
atomic arrangement in a crystal is called the Bragg diffraction peak.
• The substrate and film layers can be considered to produce separate
plan waves
– These plane waves from the substrate and each film layer will interact, producing
additional peaks of intensity that will contain microstructural (rather than atomic)
information
• X Rays are also reflected, scattered incoherently, absorbed, refracted, and
transmitted when they interact with matter.
Bragg’s law is a simplistic model to understand
what conditions are required for diffraction.
s
[hkl]

l  2d hkl sin B q q

dhkl dhkl
• For parallel planes of atoms, with a space dhkl between the planes, constructive interference
only occurs when Bragg’s law is satisfied.
– In our diffractometers, the X-ray wavelength l is fixed.
– Consequently, a family of planes produces a diffraction peak only at a specific angle q.
– The space between diffracting planes of atoms determines peak positions.
• Additionally, the plane normal [hkl] must be parallel to the diffraction vector s
– Plane normal [hkl]: the direction perpendicular to a plane of atoms
– Diffraction vector s: the vector that bisects the angle between the incident and diffracted beam
A coupled scan of a single crystal produces only one
family of Bragg peaks in the diffraction pattern.

[100] [110] [200]

s s s
2q

At 20.6 °2q, Bragg’s law The (110) planes would diffract at 29.3 The (200) planes are parallel to the (100)
fulfilled for the (100) planes, °2q; however, they are not properly planes. Therefore, they also diffract for this
producing a diffraction peak. aligned to produce a diffraction peak crystal. Since d200 is ½ d100, they appear at
(the perpendicular to those planes does 42 °2q.
not bisect the incident and diffracted
beams). Only background is observed.
HRXRD can be used to measure several
characteristics of epitaxial thin films
• Rocking curves are primarily used to study defects such as dislocation
density, mosaic spread, curvature, misorientation, and inhomogeneity
– In lattice matched thin films, rocking curves can also be used to study layer thickness,
superlattice period, strain and composition profile, lattice mismatch, ternary
composition, and relaxation
• Coupled scans are used to study lattice mismatch, ternary composition,
relaxation, thickness and superlattice period
– Lattice mismatch, composition, and relaxation all affect the position of the Bragg
peak. A single coupled scan can be used to study the film is only one of these is
unknown- otherwise, multiple coupled scans are required for analysis
• Reciprocal space maps provide the most complete amount of information and
are necessary for the analysis of strained films
• X-Ray Reflectivity can give information on
– Thickness, interface roughness, and composition or density
– XRR works with non-epitaxial and even non-crystalline thin films

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 A coupled diffraction scan will give information
on the d-spacing and thickness
Substrate peak
Thickness Film
fringes peak [400]
s

d004
2q

• Coupled scan: omega and 2-theta change in coupled manner so the direction being measured (ie
diffraction vector, s) does not change
• The peak position will give the d-spacing for the Bragg peak
– This will provide information on anything that changes the lattice parameter of the unit cell, such as composition
or strain/relaxation
– If both parameters are unknown, then multiple measurements will be required to calculate their values
– This will only provide measurement of the lattice parameter in one direction
• The width of the film’s Bragg peak can be used to quantify the film thickness
– The thickness fringes can also be use to quantify the film thickness

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The sample can be tilted to measure Bragg
peaks with different crystallographic directions
[400]
• A symmetric scan requires that
s
omega= ½ 2Theta, so that the
2q
diffraction vector s will be normal to
the surface of the sample

[220] [220] • In order to measure different

s s crystallographic directions in the
sample, the sample can be tilted
– This is called an asymmetric scan

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A rocking curve (omega scan) produces observed
intensity from planes that are not perfectly parallel
[400] [400] [400]
s s s
2q 2q 2q

• In a rocking curve, the detector is set at a specific Bragg angle and the sample is tilted.
• A perfect crystal will produce a very sharp peak, observed only when the crystal is properly
tilted so that the crystallographic direction is parallel to the diffraction vector s
– The RC from a perfect crystal will have some width due to instrument broadening and the intrensic width
of the crystal material

• Defects like mosaicity, dislocations, and curvature create

disruptions in the perfect parallelism of atomic planes
– This is observed as broadening of the rocking curve
– The center of the rocking curve is determined by the d-spacing
of the peaks

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Double-Axis vs Triple-Axis Diffractometry
• There are two instrumental configurations for HRXRD
• In both experiments, the monochromator provides a conditioned beam
• In the double-axis experiment, the detector does not discriminate between
different diffraction angles 2theta.
– All Bragg angles are measured simultaneously (over a limited range)
– The sample is rotated about its omega axis (changing the incident angle) to produce a
Rocking Curve (intensity vs omega)
• In the triple-axis experiment, a slit or analyzer crystal determines the angular
acceptance of the detector.
– While a rocking curve (intensity vs omega) can be measured, it is more common to
collect data by using a coupled scan
• As the sample is rotated about omega, the detector is rotated at twice the rate so
that 2Theta=2*Omega, producing a coupled omega-2theta scan
– Reciprocal space maps are collected by collecting coupled scans at different omega
offsets, where 2Theta= 2*Omega - offset
• This separates the effects of strains and tilts on the measurement and permits the
measurement of diffuse scatter

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 Rocking Curve Schematic: double- vs triple-axis
A Si(Ge) film on Si was scanned by rotating omega while keeping the detector stationary

Double
Si
Axis
detector
Si(Ge)

In a double-axis measurement, the

detector can see several different
Mono- angles of 2Theta- so both the Si and
chroma
Incident Si(Ge) peaks are observed
tor
beam 32.717 33.142 33.567 33.992 34.417 34.842 35.267 35.692 36.117 36.541

Omega

Triple Analyzer Si
Axis
detector

In a triple-axis measurement, the

analyzer (a crystal or a slit) constrains
Mono-
chroma the detector so that only one 2Theta
Incident tor angle is observed- in this case, the Si
beam peak 32.726 33.151 33.576 34.001 34.426 34.851 35.276 35.701 36.126 36.551

Omega

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Rocking Curve with Double-Axis

• Traditional double-axis diffractometry uses a single reference crystal

to condition the X-ray beam.
– This crystal is the same material as the sample
– The rocking curve is a correlation of the rocking curves of the two crystals
– very sensitive to strains and strain gradients in the specimen
• The reference crystal configuration is not practical for a research
environment
– Instead, use a 2x or 4x monochromator to provide a more highly conditioned
beam to the sample
– This allows the rocking curve to be collected by a wide variety of materials
• Double-axis rocking curves are easily simulated using fundamental X-
ray scattering theory

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Double-axis rocking curves work best for lattice
matched thin films
• A range of Bragg angles are collected simultaneously without angular discrimination
– The detector can only cover a limited angular range with suffering defocusing effects
– The Bragg angle of the substrate and film peaks should be about the same
• The rocking curve peak position is determined by the Bragg angle and the tilt of the planes
– Diffraction is observed when Omega= ½*2Theta + Tilt
– Differences in the Bragg angle (differences in the d-spacing of the crystallographic planes) are resolved
by differences in the rocking curve peak position
– Differences in tilt of the crystallographic planes are also resolved by differences in the rocking curve
peak position
– Tilts and dilations cannot be distinguished using rocking curves
• The rocking curve width and shape is a product of the material and defects
– A perfect crystal has an intrinsic width (FWHM) for that material
– Different planes of a crystal also have different intrinsic peak widths
– Defects cause the rocking curve to broaden beyond the intrinsic width for the Bragg peak
– Multiple defects are separated by measuring multiple rocking curves, indentifying systematic trends:
• Between symmetric and asymmetric scans
• Rotating the sample
• Changing the beam size
• Changing beam position

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Triple-Axis coupled omega-2Theta scans
• The triple axis diffractometer observes a narrowly defined region of 2Theta angle
– Use a slit with an opening between 3deg to 0.1deg
– Use an analyzer crystal with an effective opening of ??
• A rocking curve collected on a triple-axis diffractometer will observe data for one
specific diffraction peak, rather than all diffraction peaks within a certain range
– You can measure tilt independent of strain (dilation) and get defect information for each
individual layer
– Tilt and strain could not be indepently resolved using a single double-axis rocking curve
• A single coupled scan is resolving differences in the d-spacing values of the
crystallographic planes
– d-spacing responds to mismatch, composition, relaxation
– Can resolve these contributes whereas rocking curve cannot
– Triple-axis provides much better resolution of multilayers with modest amount of defects
(threading dislocations, etc) compared to double-axis
• A common strategy is to collect an omega-2theta scan, identify peak positions,
then collect the rocking curve for each diffraction peak

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 Rocking Curve Schematic: double- vs triple-axis
A Si(Ge) film on Si was scanned by rotating omega while keeping the detector stationary

Double
Si
Axis
detector
Si(Ge)

In a double-axis measurement, the

detector can see several different
Mono- angles of 2Theta- so both the Si and
chroma
Incident Si(Ge) peaks are observed
tor
beam 32.717 33.142 33.567 33.992 34.417 34.842 35.267 35.692 36.117 36.541

Omega

Triple Analyzer Si
Axis
detector

In a triple-axis measurement, the

analyzer (a crystal or a slit) constrains
Mono-
chroma the detector so that only one 2Theta
Incident tor angle is observed- in this case, the Si
beam peak 32.726 33.151 33.576 34.001 34.426 34.851 35.276 35.701 36.126 36.551

Omega

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 Triple-Axis Rocking Curve vs Coupled Scan
A Si(Ge) film on Si was scanned using a rocking curve and a coupled Omega-2Theta Scan

Rocking Analyzer Si
Curve
detector

In the triple-axis rocking curve, the

analyzer (a crystal or a slit) constrains
Mono-
chroma the detector so that only one 2Theta
Incident tor angle is observed- in this case, the Si
beam peak 32.726 33.151 33.576 34.001 34.426 34.851 35.276 35.701 36.126 36.551

Omega

Si
Coupled

2Theta
Scan
Si(Ge)

In the triple-axis coupled scan, 2Theta

Mono- changes with Omega so that peaks with
chroma different 2Theta positions but identical tilts
Incident tor can be observed- so the Si(Ge) and Si peaks 32.726 33.151 33.576 34.001 34.426 34.851 35.276 35.701 36.126 36.551

Omega-2Theta
beam are both observed as long they are parallel

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The Triple-Axis Coupled Scan Allows you to discern
more complicated detail in a measurement

32.877 33.117 33.357 33.597 33.837 34.077 34.317 34.557 34.797 35.037
32.877 33.117 33.357 33.597 33.837 34.077 34.317 34.557 34.797 35.037
Omega
Omega-2Theta
Sim (Sample 1)

• The double-axis rocking curve a Si • The triple-axis coupled Omega-

wafer coated with 5 slightly relaxed 2Theta scan of the same Si wafer
Si(Ge) layers of varying Ge coated with 5 slightly relaxed Si(Ge)
concentration layers of varying Ge concentration
• The Ge concentrations were 10, 20, • A rocking curve in triple-axis mode
30, 40, and 50%. can be collected for each individual
• Each Ge layer was 500nm thick. peak to determine the tilt variation of
each individual Si(Ge) layer

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Triple-Axis Diffractometry: coupled scans vs
Reciprocal Space Maps
• Coupled scan collects data as omega-2Theta or 2Theta-omega
– The detector angle 2Theta is moved at twice the rate as the sample rotation about omega
– 2Theta=2*omega+tilt
– This will observe peaks with different Bragg angles, but only for one specific tilt
– If the epilayers are tilted with respect to the substrate, then a single coupled scan cannot
observe both subtrate and film peaks
– In order to observe possible data, must collect coupled scans for a range of tilts: this is the
Reciprocal Space Map
• The Reciprocal Space Map collects several omega-2Theta coupled scans, but each
coupled scan is collected with a slightly different tilt (offset) in the omega
direction
– When the scan is collected, 2Theta still moves at twice the rate as the sample rotation so
that 2Theta=2*Omega + tilt
– The tilt value is slightly different for each coupled scan that is collected
– This is equivalent to what we did on the previous slide when we collected the rocking
curve for each Si(Ge) peak that we observed– instead the reciprocal space map produces a
complete map of Omega-2Theta vs Tilt (omega)

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Defining Reciprocal Space

• dhkl is the vector drawn from the origin of

the unit cell to intersect the first
crystallographic plane in the family (hkl)
at a 90° angle
• The reciprocal vector is d*hkl= 1/dhkl
• In the reciprocal lattice, each point
represents a vector which, in turn, b*030 130 230 330

represents a set of Bragg planes 020 120 220 320

• Each reciprocal vector can be resolved 010 110 210 310

a*
into the components: 100 200 300 400

– d*hkl= ha* + kb* + lc* 0-10 1-10 2-10 3-10 4-10

0-20

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Different scan types cover different regions of
reciprocal space

• The rocking curve (omega scan) is an arc centered on the origin

• The detector scan (2theta scan) is an arc along the Ewald sphere
circumference
• The couple scan (2theta-omega scan) is a straight line pointing away
from the origin

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Effects such as strain will shift reciprocal lattice
points, preventing the collection of data with a single
scan
b* b*

a* a*

• The reciprocal space map uses multiple scans in order to observe

both the film and substrate peaks

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 Converting to reciprocal space units
• The sample was a (001) oriented wafer; the
2 theta
65.64 65.724 65.808 65.893 65.977 66.061 66.145 66.23 66.314 66.398 1.216E5
-0.439
0.391
8.433E4
5.849E4

(004) Bragg was mapped

0.35
0.33 4.057E4

0.3 2.814E4
1.951E4
0.248 0.25 1.354E4

• The [004] direction is normal to the plane

9.388E3
0.2 6.511E3

0.165 4.516E3
0.15 3.132E3

of the wafer
2.172E3
0.1
0.083 1.507E3
1.045E3
0.05
7.248E2

omega
omega

5.027E2

•[110] is a lateral direction (ie the direction

0 0
3.487E2
-0.05 2.418E2
1.677E2
-0.083
-0.1 1.163E2

within the plane of the film)

8.069E1
-0.15 5.597E1
-0.165
3.882E1
-0.2 2.692E1

• Position in qz correlates to the d-spacing of the

1.867E1
-0.248 -0.25
1.295E1
8.983E0
-0.3
6.23E0
-0.33
4.321E0

peak
-0.35
2.997E0
-0.4 2.079E0
-0.413
1.442E0

65.64 65.724 65.808 65.893 65.977 66.061 66.145 66.23 66.314 66.398

2 theta
• Position in qx correlates to tilt of planes
qx, h[ 1 1 0]
• Map of the symmetric Bragg peak can be used
to separate tilts and strain
-0.025 -0.02 -0.015 -0.01 -0.005 0 0.005 0.01 0.015 0.02 0.025 1.216E5
7.031
7.111
8.433E4
7.11
5.849E4

7.105 7.105 4.057E4

• To separate composition/mismatch and strain,

2.814E4
7.1 1.951E4

7.097 1.354E4
7.095 9.388E3
6.511E3

need to map an asymmetric peak

7.09 4.516E3
7.089
3.132E3
7.085 2.172E3
1.507E3
7.081
7.08 1.045E3
qz, l[ 0 0 1]
qz, l[ 0 0 1]

7.248E2
7.075 5.027E2
7.073
3.487E2
7.07
2.418E2
1.677E2
7.065 7.065
1.163E2
8.069E1
7.06
5.597E1
7.057
3.882E1
7.055
2.692E1

7.05 1.867E1
7.049
1.295E1
7.045 8.983E0
6.23E0
7.041
7.04 4.321E0
2.997E0
7.035 2.079E0
7.033
1.442E0

-0.025 -0.02 -0.015 -0.01 -0.005 0 0.005 0.01 0.015 0.02 0.025

qx, h[ 1 1 0]

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Symmetric vs Asymmetric

• One family of planes is parallel or nearly parallel to the surface

of the sample.
– These are the only planes examined in a symmetric scan.
– The sample is not tilted, so 2Theta=2*Omega
• Other planes can only be observed by tilting the sample
– Asymmetric scans are used to collect these other planes by tilting the
sample about omega, so 2Theta=2*Omega+tilt
– The sample can be tilted two ways:
• Grazing incidence (-) tilts the sample towards a lower omega value
• Grazing exit (+) tilts the sample towards a higher omega value
• Several properties can only be determined by collecting both
symmetric and asymmetric scans (summarized later)

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 Symmetric vs Asymmetric

theta
theta
theta
omega omega omega

Mono- Mono-
chroma Mono-
chroma
Incident tor chroma
tor
beam tor

Symmetric Scan Asymmetric Scan Asymmetric Scan

Grazing Incidence (-) Grazing Exit (+)
Omega=Theta
Omega=Theta-Tilt Omega=Theta+Tilt
s
s s
ω 2θ 2θ ω
ω
2θ
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Our Triple Axis Machine

• Incident beam optics

– Mirror only (for XRR)
– Mirror + Ge(022)x4 asymmetric monochromator
– Mirror + Ge(044)x4 symmetric monochromator
• Could be tuned to Ge(022)x4 symmetric monochromator
– Slits to control the height and width the X-ray beam
• Receiving-Side Optics
– Motorized receiving slit + point detector
– Ge(022)x3 Analyzer Crystal + point detector
– Linear Position Sensitive Detector- point mode or 1D mode
– PSD in high dynamic range configuration (90deg mount) and point mode
with manual receiving slit for XRR

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HRXRD requires an Incident Beam
Monochromator
• If the incident beam contains both Kα1 and Kα2 radiation, much
of the important information from the film will be lost
• The incident beam must also have very low divergence
– The source profile of the X-ray beam will obscure broadening of the
rocking curve caused by defects in the epilayer
• The best signal is produced when the divergence of the incident
X-ray beam matches the quality of the film
– An X-ray beam with very low divergence will scatter with low efficiency
from a highly distorted film
– For example, Si-Ge multilayers often have some relaxation in each layer,
which also produces a small amount of threading dislocations. A lower
resolution (more divergence) monochromator will give a stronger signal
than a high resolution (less divergence) monochromator from such a
sample … without compromising resolution.

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Values comparing Bruker monochromators
when coupled with a Goebel Mirror
Monochromator Divergence Beam Intensity FWHM of Si(022)
(arc-seconds) (cps) (°)
None (mirror only) 108” 170,000,000 0.07
Ge(022)x4 symmetric 12” 4,500,000 0.0035
Ge(022)x4 asymmetric 25” 18,000,000 0.008
Ge(044)x4 symmetric 5” 150,000 0.0015
• The mirror refocuses the divergent beam into a pseudo-parallel beam, producing less divergence and an
intensity gain
• The pseudo-parallel beam from the mirror interacts more efficiently with the monochromator,
producing a stronger incident X-ray beam
• A 2-bounce monochromator gives good intensity and peak shape, but requires a slit to define the
spectral bandpass– so not all Kα2 is removed
• We use a 4-bounce monochromator instead– we lose some incident beam intensity, but have a
better quality beam with no Kα2 and better collimation (ie resolution)
• Using Ge instead of Si for the monochromator yields higher intensity, but costs more and has high
losses from polarization
• The asymmetric design reduces the polarization losses to give higher intensity

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This image shows a 4-bounce Ge
monochromator
• Each pair of diffracting crystals is
channel-cut from a single piece of Ge
– This prevents misorientation
between the pair of crystals
• Two sets of channel-cut crystals are
used
– The orientation between these two
sets must be precisely aligned to get
a usable X-ray beam
• Slits are used control the width of the
beam entering the first channel-cut
crystal and to control the width in-
between the two sets of channel-cut
crystals

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Historical- why omega-2Theta and why regard
as mismatch/relaxation
• HRXRD started as rocking curve (omega scans) using double-
axis instruments
• When triple axis developed to do coupled scans of omega and
2theta, it was referenced as omega-2theta
– In powder diffraction, it is referenced as 2theta-omega
• Mismatch/Relaxation
– Starting assumption is that you want fully strained lattice matched
epitaxial thin films
– Therefore, mismatch and relaxation are regarded as “defects”
– Mismatch and partial relaxation may be desired for ternary films, but the
analysis software will still often regard them as defects

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PEAK POSITIONS ARE AFFECTED BY
RELAXATION/STRAIN, COMPOSITION, AND TILT

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Relaxation

Relaxed Film Strained Film

• If the film is mismatched to the substrate, then the film might be strained so
that the lattice parameters in the lateral direction (ie within the plane of the
film) are forced to match the lattice parameters of the substrate
• This distorts the unit cell of the film
– A formerly cubic unit cell is now tetragonal
• Determine the degree of relaxation
– No relaxation (fully strained)- the lateral lattice parameters of the film are strained to
be identical to the substrate
– Fully relaxed- the lateral lattice parameters of the film are equal to the bulk values–
they have not been distorted at all

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Relaxation
Strained Film
Relaxed Film

csub c'film
cfilm

afilm a'film
csub

asub asub

• asub=csub • asub=csub
• a'film ≠ c'film
• afilm=cfilm
• a'film=asub
• afilm≠asub
• (001)sub ∕ ∕ (001)film
• (001)sub ∕ ∕ (001)film
• (101)sub not parallel (101)film
• (101)sub ∕ ∕ (101)film • The Bragg angle for (001) shifts from its
• Difference in Bragg angles b/w film and theoretical position, seen in rocking curve and
substrate is by splitting of peaks in the coupled scans
Rocking Curve and multiple peaks in • Asymmetric coupled scan shows a film peak or
Coupled Scan substrate peak, but not both because they are not
parallel
• Asymmetric coupled scans show Bragg
diffraction from both film and substrate • Separation between peaks in Rocking curves
changes with the scan geometry (GE vs GI vs
sym)

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Composition

• In substitutional solid solids, the composition can vary

• Changes in the composition will change the lattice parameters,
which will change dhkl and therefore the Bragg peak positions
– Unlike relaxation, changes in composition will not change lattice tilts

asymmetric asymmetric asymmetric

symmetric symmetric symmetric

No strain No strain Strained

No change in composition Composition changed No change in composition

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Symmetric scans cannot distinguish between
strain and compositional changes
asymmetric asymmetric asymmetric
symmetric symmetric symmetric

No strain No strain Strained

No change in composition Composition changed No change in composition

• In the symmetric scan, strain and compositional changes produce

similar peak shifts
• In order to quantify both strain and composition, must combine a
symmetric scan with an asymmetric scan

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If the film is highly strained, a single coupled
asymmetric scan produce usable data
asymmetric asymmetric
symmetric symmetric

Strained film Strained film

• The typical way to collect recriprocal space maps is to vary

relative omega and collect multiple 2theta-omega coupled scans

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Defects and gradients can produce spreading
of the reciprocal space point
asymmetric asymmetric asymmetric
symmetric symmetric symmetric

Compositional gradient strain gradient defects

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Mosaic Spread can be quantified by measuring the
broadening of the lattice point in reciprocal space

Lateral correlation

• The amount of broadening of the reciprocal lattice point that is

perpendicular to the reflecting plane normal can be attributed to
mosaic spread
• The peak broadening parallel to the interface can be attributed to
lateral correlation length

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X-Ray Reflectivity (XRR)

• The same equipment that is optimized for HRXRD can also be

used for XRR analysis of thin films.
• X-ray waves reflecting from each different surfaces in a
multilayer thin film.
– The multiple reflected waves interfere with each other, producing a
reflectivity curve
– The XRR scan can be used to determine the density, thickness, and
roughness of each layer in a multilayer thin film.

This image is taken

from training
materials provided
by Bruker AXS

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The critical angle is a function of the density
and composition of the layer
• Below the critical angle, θC, the X-ray
beam is completely reflected (total Increasing Density

external reflection)
• The critical angle for a layer is a
function of its electron density
– This is a convolution of density and
composition
– If one is known, the other can be
determined using XRR
– For example, for a given composition, as
the density of the film increases the
critical angle θC often increases.

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The distance between interference fringes is a
function of the thickness of the layers
• Interference fringes are created by the phase difference between
X-rays reflected from different surfaces
• The distance between the fringes is inversely proportional to the
thickness of the layer
– Because of this, thicker films need better resolution (use a
monochromator) and thinner films need more intensity (use only the
mirror)

40nm thick

20 nm thick

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Roughness determines how quickly the
reflected signal decays
• Roughness causes X-rays to be scattered
rather than reflected
– This produces a decay in the reflected beam
intensity
– The loss of beam intensity increases with Increasing
Theta Roughness
• A rougher surface produces more
diffuse scatter, causing the reflected
beam intensity to decay more with Theta
– The diffuse scatter can be measured to look
for order in the roughness of the film.

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