1

PHY5501/ PHY8501
Modern Characterization Techniques
for Materials Physics

Lecture 7
X ray diffraction
Prof YU Kin Man
e-mail: [email protected]
Tel: 3442-7813
Office: P6422
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Lecture 7: Outline
 Review on crystallography
─ Lattice and crystal structure
─ Miller indices
 Diffraction
─ Braggs law
─ Reciprocal lattice
 X-ray diffraction
─ X-ray source and characteristic x-rays
─ Diffraction intensity─structure factor
 Powder diffraction analysis
─ Phase identification
─ Grain size and strain
─ Texture
─ Rocking curve
 Advanced XRD techniques
─ Grazing incident
─ High resolution https://www.youtube.com/watch?v=C1cYJthlBZY
 Other advanced x-ray techniques https://www.youtube.com/watch?v=3aU4adBx2ok
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Review: crystal lattice

y
 An infinite array of points
in space.
B C D E
α
 Each point has identical b
surroundings to all others. O a A x
 Arrays are arranged
exactly in a periodic
manner.

■ A crystal lattice is a set of infinite, arranged points related to

each other by transitional symmetry.
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Review: lattices & lattice translation vectors

■ Lattice translation vectors a1, a2… describe how to move around a crystal
■ A translation by any combination of the vectors will lead to another equivalent
point and leaves the lattice unchanged─translation symmetry
■ a1, a2…are the basis vectors and the choice of the basis vector is not unique.
■ Equivalent points have the same environment in the same orientation.
r’
2 dimension (2D): 𝒂′𝟐
b2
′
𝒓 = 𝒓 + 𝑢1 𝒂𝟏 + 𝑢2 𝒂𝟐
a2 𝒂′𝟏
u1, u2 are integers
a1 b1
𝒂𝒏 , 𝒂′𝒏 are primitive translation vectors (defined a minimum area) while 𝒃𝒏 are not

3 dimension (3D): 𝒓′ 𝒓′ = 𝒓 + 𝑢1 𝒂𝟏 + 𝑢2 𝒂𝟐 + 𝑢3 𝒂𝟑
or 𝒓′ = 𝒓 + 𝑢1 𝒂 + 𝑢2 𝒃 + 𝑢3 𝒄
For n dimensions:
Lattice translation vectors an are
𝒓′ =r+σ𝑛 𝑢𝑛 𝒂𝒏 a3 a2
primitive if there is no other cell of
volume < |𝒂𝟏 ∙ 𝒂𝟐 × 𝒂𝟑| that can
r a1 build the lattice
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Review: Bravais Lattice

 In 1850, Auguste Bravais showed that there are only 14
different ways of arranging identical points in 3D space so
that the points are equivalent in their surroundings. These
arrangement are later called the Bravais Lattices.
 A Bravais Lattice is defined as an infinite array of points
which appears exactly the same when viewed from any one
of the lattice points.
 A Bravais Lattice consists of all points with position vector 𝐫 of the form 𝒓 =
𝑢1𝐚+ 𝑢2𝐛 + 𝑢3𝐜 where 𝐚 , 𝐛 , 𝐜 are any three non-coplanar primitive translation
vectors and 𝑢𝑖 range through all integer values.
 There are only 7 different shapes of unit
cell which can be stacked together to
completely fill a 3 dimensional space
without overlapping. This gives the 7
crystal systems with 14 Bravais lattices in
which all crystal structure can be classified.
 The systems are defined according to the
relationship between the 6 lattice constants:
a, b, c, ( or a1, a2 a3)a, b, and g.
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Crystal systems and Bravais lattices

Crystal System Conventional Unit Cell Bravais Lattices
𝑎≠𝑏≠𝑐
Triclinic Primitive (P)
𝛼≠𝛽≠𝛾
𝑎≠𝑏≠𝑐
Monoclinic Primitive, Base-centered (C)
𝛼 = 𝛽 = 90º ≠ 𝛾
Primitive, Base-centered,
𝑎≠𝑏≠𝑐
Orthorhombic Body-centered (I) , Face-
𝛼 = 𝛽 = 𝛾 = 90º
centered (F)
𝑎=𝑏≠𝑐
Tetragonal Primitive, Body-centered
𝛼 = 𝛽 = 𝛾 = 90º
𝑎=𝑏=𝑐 Primitive, Body-centered,
Cubic
𝛼=𝛽=𝛾 Face-centered
Trigonal/ 𝑎=𝑏=𝑐
Primitive
Rhombohedral 120º > 𝛼 = 𝛽 = 𝛾 ≠ 90º
𝑎=𝑏≠𝑐
Hexagonal Primitive
𝛼 = 𝛽 = 90º, 𝛾 = 60º
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14 Bravais lattices
Ortho- Tetra- Trigonal/ Hexa-
Triclinic Monoclinic Cubic
rhombic gonal rhombodedral gonal

P
Simple/Primitive

I
Body Centered

F
Face Centered

C
Base Centered
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Crystal structure=lattice+basis
 Each lattice point can be an atom, group of atoms and molecules in the
crystal─basis.
 In a real crystal the lattice point is replaced by a basis and every basis is identical
in composition, arrangement and orientation

b
a +
2 D lattice basis crystal
defect

𝒓𝒋
If rj for the element B is 0, position of element A 𝒓𝒋 = 𝑥𝑗 𝒂 + 𝑦𝑗 𝒃

In 3D: 𝒓𝒋 = 𝑥𝑗 𝒂 + 𝑦𝑗 𝒃 + 𝑧𝑗 𝒄 where 0 𝑥𝑗 , 𝑦𝑗 , 𝑧𝑗  1

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Crystal Structure

The atoms do not necessarily lie at lattice points but basis must be in the
same orientation

3D

lattice basis Crystal structure

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Crystal planes: 3-D

In a 3D crystal lattice we can identify multiple sets of equally spaced parallel
planes

Each group of planes forms a set and are a property of the lattice

How do we define the planes?

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Miller indices for planes

Miller Indices are a symbolic vector representation for the orientation of an
atomic plane in a crystal lattice and are defined as the reciprocals of the
fractional intercepts which the plane makes with the crystallographic axes.

 Method z
─ If the plane passes through the origin,
select an equivalent plane or move the
Miller Indices
origin. (0, 0, 1/2) (1 1 2)
─ Determine the intercepts of the plane
along each of the three
(0, 1,0)
crystallographic directions. 0 y
─ Take the reciprocals of the intercepts
(1, 0, 0)
(if the plane does not intersect one of
the axes, the intercept is at infinity and
the inverse is zero). x
─ Enclose in parentheses (…) X Y Z
Intercepts 1 1 1/2
Reciprocals 1 1 2
Miller Indices for Planes: example

z
z
(0, 0, 0)
(0, 0, 1) y
Miller Indices Miller Indices
(1, 0, 0) (1, 1,0) ത
(2 2 1) (1 0 1)

x (0, 0, -1)
(0, 1/2,0) (0, 1,-1)
y
(1/2, 0, 0)

X Y Z
x
X Y Z
Intercepts 1 ∞ -1

Intercepts 1/2 1/2 1 Reciprocals 1 0 -1

Reciprocals 2 2 1 Miller Indices 1 0 1ത

ത)
(1 0 1
 Miller Indices for Planes: example

X Y Z
(0, 0, 2)
Intercepts 1 -1 2
Reciprocals 1 -1 ½
2 -2 1
Miller Indices
(2 2ത 1)

(2 2ത 1)
(0, -1,0)
X Y Z
y Reciprocals 2 -2 1
Intercepts ½ -1/2 1

(1, 0, 0)
x
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Family of planes and interplanar distances

z
 In some situation when the unit cell has
rotational symmetry, nonparallel planes may (110)
be equivalent by virtue of this symmetry.
 These plane are grouped together and called
a family of planes and is expressed by a curly d110
bracket {hkl}
 Examples in a cubic system:
100 : 100 , 010 , 001 , 1ത 00 , 01ത 0 , 001ത
(100)
111 : 111 , 111ത , 11ത 1 , 1ത 11 , 11ത 1ത , 1ത 1ത 1 d100
y
, 1ത 11ത , 1ത 1ത 1ത z
z

(0 1ത 0) (111)
(010)
ത
(111) x
y
̶y y

x x
 For an orthorhombic crystal, 𝛼 = 𝛽 = 𝛾 = 90𝑜 , it can be shown that :
1 ℎ2 𝑘 2 𝑙 2
2 = 2+ 2+ 2
𝑑ℎ𝑘𝑙 𝑎 𝑏 𝑐
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Plane separation dhkl

Crystal System Unit Cell Characteristics dhkl

𝑎=𝑏=𝑐 1 ℎ2 + 𝑘 2 + 𝑙 2
Cubic =
𝛼 = 𝛽 = 𝛾 = 90o 𝑑2 𝑎2
𝑎=𝑏≠𝑐 1 ℎ2 + 𝑘 2 𝑙 2
Tetragonal = + 2
𝛼 = 𝛽 = 𝛾 = 90o 𝑑2 𝑎2 𝑐
𝑎≠𝑏≠𝑐 1 ℎ2 𝑘 2 𝑙 2
Orthorhombic = + +
𝛼 = 𝛽 = 𝛾 = 90o 𝑑2 𝑎2 𝑏2 𝑐 2
𝑎=𝑏≠𝑐 1 4 ℎ2 + ℎ𝑘 + 𝑘 2 𝑙2
Hexagonal = + 2
𝛼 = 𝛽 = 90o, 𝛾 = 60o 𝑑2 3 𝑎2 𝑐
𝑎≠𝑏≠𝑐 1 1 ℎ2 𝑘 2 𝑠𝑖𝑛2 𝛽 𝑙 2 2ℎ𝑙𝑐𝑜𝑠𝛽
Monoclinic = + + 2−
𝛼 = 𝛽 = 90º ≠ 𝛾 𝑑 2 𝑠𝑖𝑛2 𝛽 𝑎2 𝑏2 𝑐 𝑎𝑐
𝑎=𝑏=𝑐
Trigonal/ 1 ℎ2 + 𝑘 2 + 𝑙 2 𝑠𝑖𝑛2 𝛼 + 2 ℎ𝑘 + 𝑘𝑙 + ℎ𝑙 𝑐𝑜𝑠 2 𝛼 − 𝑐𝑜𝑠𝛼
120o >𝛼=𝛽=𝛾 =
Rhombohedral o
𝑑2 𝑎2 1 − 3𝑐𝑜𝑠 2 𝛼 + 2𝑐𝑜𝑠 3 𝛼
≠ 90
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Review: diffraction
 Diffraction is a wave phenomenon in which the apparent bending and spreading
of waves occur when they meet an obstacle.
 Diffraction occurs with all waves including electromagnetic waves, such as light
and radio waves as well as sound waves, water waves and matter waves.
 The simplest demonstration of diffraction is the double-slit diffraction
experiment.

 Interference pattern (fringes)

 Wider separation between
the fringes with smaller slit
separation.
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Diffraction from a particle and solid

 Single Particle  Solid (a matrix of particles)
─ The particle scatters the incident ─ For a crystalline solid, the scattered
beam in all directions. beams may add in a few directions
to produce unique pattern.

f  
i ( k r  t )
 scattered  e
r
f = atomic form factor (scattering power of atom)
 =amplitude
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Electromagnetic spectrum

X-rays are well suited to probe crystal structure

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X-ray crystallography: a short history

 1895: Röntgen discovered X-rays and led
to the development of the field of X-ray
Wilhelm Röntgen diffraction crystallography (Röntgen was
(1845-1923) the first recipient of the Nobel prize in
physics, in 1901)
 Max von Laue developed the use of X-
ray diffraction (Nobel Prize, 1914)
Max von Laue  Typical X-ray wavelength ~ 0.1nm which
(1879-1960) is similar to interatomic spacing in
crystals
 1913-1914 :The Braggs together
developed the principles for the analysis
of crystal structure by means of X-rays
and shared the 1915 Nobel Prize in
physics
Sir William Henry Bragg, Sir William Lawrence Bragg,
FRS (1862 -1942) FRS (1890 -1971)
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Diffraction
When a wave incident on a crystal (periodic arrays of atoms)

a a

When l<2a: wave either passes through crystal (k unchanged) or for a

particular incident angle will be diffracted
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Bragg’s law
 When a monochromatic x-ray beam is incident on the surface of a crystal,
the reflection takes places only when the angle of incidence has certain
values.
 Bragg considered crystals as a set of parallel planes of atoms. The incident
beam is reflected partially at each of these planes.
 The reflected rays are collected by a detector at a distance.
 According to physical optics, the interference is constructive only if the
difference between the paths of any two consecutive rays is an
integral multiple of the wavelength.
 The path difference D

D  nl  OC  OD q O’ q
n  1,2,3,.. integers
C D
2d sin θ = 𝑛𝜆
O
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Bragg’s law
2
d1
sin θ1  l
 The incident beam, the normal
n to the reflection plane, and the
diffracted beam are always co-
2
d2
sin θ 2 l
planar.
n
 The angle between the diffracted
beam and the transmitted beam
q1 q1
is always 2q (usually measured).
d1
 sin 𝜃 cannot be more than unity;
q2
this requires
𝑛𝜆 < 2𝑑, for 𝑛 = 1, 𝜆 < 2𝑑
 This is why we cannot use
visible light.
Note: The smaller the spacing d, the higher
the angle of reflection q.
 The diffracted beams from any set of lattice planes can only occur at the
angles predicted by the Bragg law.
 The set of lattice planes is then represented by the diffracted beam, or
diffracted spots.
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The reciprocal lattice 𝜆

𝑑=
 Bragg’s Law shows that there is a 2 sin 𝜃
reciprocal relationship between the
plane spacing d and the diffraction angle
q, we can therefore relate the diffraction
pattern to the crystal lattice by a
mathematical construct, the
reciprocal lattice.
 The reciprocal lattice is a set of
imaginary points in which the direction
of a vector from one point to another
corresponds to a direction normal to a
plane in a real lattice
 We can view the pattern created from X-
ray diffraction as a new lattice that we
can use to gain information about the
crystal lattice.
X-ray diffraction pattern for a single alum
crystal - wiki.brown.edu
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The Reciprocal Lattice

 Crystal planes (hkl) in the z
real-space or direct lattice 𝐺റℎ𝑘𝑙
are characterized by the y
n̂hkl
normal vector 𝒏 ෝ 𝒉𝒌𝒍 and the
interplanar spacing 𝒅𝒉𝒌𝒍 . x d hkl

 In the reciprocal lattice, the position of the lattice point in the reciprocal space
is given by the vector
 2 This vector is parallel to the [hkl] direction but has
Ghkl  nˆhkl
d hkl magnitude 2/dhkl, which is a reciprocal distance

 The reciprocal lattice is composed of all points lying at positions 𝑮𝒉𝒌𝒍 from the
origin, so that there is one point in the reciprocal lattice for each set of planes
(hkl) in the real-space lattice.
 So why do we need the reciprocal lattice?
─ The reciprocal lattice simplifies the interpretation of diffraction data from
crystals.
─ The reciprocal lattice facilitates the calculation of wave propagation in the
crystal (lattice vibrations, electron waves, … etc.)
 2D Reciprocal Lattice
 Direct (Real) Space  Reciprocal Space

n01
d11

n12 (12)
n11
n10 (01) (11)
d12
d01 2𝜋
(01)
planes 𝑑01
o 2𝜋 (10)
𝑑10
d10

 Pick some point as an origin

 lay out the normal to every family of parallel planes in the direct lattice
 set the length of each normal equal to 2 X the reciprocal of the
interplanar spacing for its particular set of planes
 place a point at the end of each normal
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X-ray diffraction (XRD)

 The lattice structure determines the

position of the lines.
 The basis determines the relative
intensity.
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X-ray source

A typical Coolidge tube

 X-rays are produced whenever high-speed electrons collide with a metal target.
 A source of electrons – hot W filament, a high accelerating voltage (30-50kV)
between the cathode (W) and the anode, which is a water-cooled block of Cu or
Mo containing desired target metal.
 The x-ray output is the shape characteristic x-ray lines of the anode metal on a
continuum of bremsstrahlung radiation
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X-ray production

As some e- approach the nucleus

and are slowed down and pulled
into a new direction, consequently
some energy is released in the form
of X-rays called Bremsstrahlung.
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X-ray source: characteristic x-rays

Characteristic x-ray line energy= 𝐸𝑓𝑖𝑛𝑎𝑙 − 𝐸𝑖𝑛𝑖𝑡𝑖𝑎𝑙
Relative intensities of major x-ray lines
𝐾𝛼1 = 100 𝐿𝛼1 = 100 𝑀𝛼1,2 = 100
𝐾𝛼2 = 50 𝐿𝛼2 = 50 𝑀𝛽 = 60
𝐾𝛽1 = 15 − 30 𝐿𝛽1 = 50
𝐾𝛽2 = 1 − 10 𝐿𝛽2 = 250
𝐾𝛽3 = 6 − 15 𝐿𝛽3 = 1 − 6
𝐿𝛽4 = 3 − 5
𝐿𝛾1 = 1 − 10

 If an incoming electron has sufficient kinetic

energy for knocking out an electron of the K
shell (the inner-most shell), it may excite
the atom to an high-energy state (K state).
Ka1  One of the outer electron falls into the K-
Ka2 shell vacancy, emitting the excess energy
as a x-ray photon.
 Characteristic x-ray energy:
𝐸𝑥−𝑟𝑎𝑦 = 𝐸𝑓𝑖𝑛𝑎𝑙 − 𝐸𝑖𝑛𝑖𝑡𝑖𝑎𝑙
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X-ray Absorption Edge

Beer Lambert Law: 𝐼 = 𝐼𝑜 𝑒 −𝛼𝑥
𝛼
Mass absorption coefficient: 𝜇𝑚𝑎𝑠𝑠 =
𝜌𝑚

𝐼𝑜 =initial intensity
𝐼 =transmitted intensity
a= linear absorption
(attenuation) coefficient
x= thickness
𝜌𝑚 =mass density
 31

Characteristic x-ray and filters

 32

Characteristic x-ray and filters

Element Ka1 (Å) Ka2 (Å) Kb (Å) K absorption Excitation
edge (Å) potential (kV)
Ag 0.56084 0.56380 0.49707 0.4859 25.52
Mo 0.7093 0.71359 0.632288 0.632288 20.0
Cu 1.54056 1.54439 1.392218 1.392218 8.98
Ni 1.65791 1.66175 1.50014 1.4881 8.33
Co 1.78896 1.79285 1.62079 1.6082 7.71

 Accurate XRD measurements

requires a single x-ray line as
the probe.
2d sin θ = 𝜆
 For example, for a Cu anode,
Kb line can be eliminated by
a Ni filter
X-ray data booklet:
http://xdb.lbl.gov/
 33

Diffraction intensity

+
lattice basis Crystal structure
𝐼ℎ𝑘𝑙 ∝ 𝐹ℎ𝑘𝑙 2

Structure Factor: 𝐹ℎ𝑘𝑙 = ෍ 𝑓𝑗 𝑒𝑥𝑝 2𝜋𝑖(ℎ𝑢𝑗 + 𝑘𝑣𝑗 + 𝑙𝑤𝑗 )

𝑏𝑎𝑠𝑖𝑠
where 𝑓𝑗 is the atomic scattering factor, and is dependent on atomic number
𝑢𝑗 ,𝑣𝑗 , 𝑤𝑗 are the fractional distances within the unit cell
ℎ, 𝑘, 𝑙 is the Miller indices of the plane
𝜆
Atomic scattering factor: 𝑓 𝜃 ∝ 𝜃 𝑍
sin
2

where Z is the atomic number of the atom

 Denser atoms scatter with greater intensity
 Intensity decreases as the scattering angle
increases
 34

Structure factor: BCC crystal

 We can consider the BCC structure as a
simple cubic lattice with a two atom
basis, with atoms at [000] and [½½½]

𝐹ℎ𝑘𝑙 = ෍ 𝑓𝑗 𝑒𝑥𝑝 2𝜋𝑖(ℎ𝑢𝑗 + 𝑘𝑣𝑗 + 𝑙𝑤𝑗 )

𝑏𝑎𝑠𝑖𝑠

1 1 1
𝐹ℎ𝑘𝑙 = 𝑓𝑒𝑥𝑝 𝑖0 + 𝑓𝑒𝑥𝑝 2𝜋𝑖( ℎ + 𝑘 + 𝑙)
2 2 2
𝐹ℎ𝑘𝑙 = 𝑓 1 + 𝑒𝑥𝑝 𝑖𝜋(ℎ + 𝑘 + 𝑙)
(1Τ2 1Τ2 1Τ2)
2𝑓 if ℎ + 𝑘 + 𝑙 𝑖𝑠 𝑒𝑣𝑒𝑛
 Hence: 𝐹ℎ𝑘𝑙 = ቊ
0 if ℎ + 𝑘 + 𝑙 𝑖𝑠 𝑜𝑑𝑑
(000)
 For a monatomic BCC crystal diffraction
from (111), (003), (201), (221), etc. are
missing and these are the forbidden
diffractions
 35

Structure factor: FCC crystal

Four atoms at positions, (uvw):

D A(0,0,0), B(½,0,½), C(½,½,0), D(0,½,½)

𝐹ℎ𝑘𝑙 = ෍ 𝑓𝑗 𝑒𝑥𝑝 2𝜋𝑖(ℎ𝑢𝑗 + 𝑘𝑣𝑗 + 𝑙𝑤𝑗 )

𝑏𝑎𝑠𝑖𝑠

𝐹ℎ𝑘𝑙 = 𝑓 ෍ 𝑒𝑥𝑝 2𝜋𝑖(ℎ𝑢𝑗 + 𝑘𝑣𝑗 + 𝑙𝑤𝑗 )

𝑏𝑎𝑠𝑖𝑠
ℎ 𝑙 ℎ 𝑘 𝑘 𝑙
= 𝑓 exp 2𝜋𝑖 0 + exp 2𝜋𝑖 + + exp 2𝜋𝑖 + + exp 2𝜋𝑖 +
2 2 2 2 2 2
= 𝑓 1 + 𝑒 𝑖𝜋(ℎ+𝑙) + 𝑒 𝑖𝜋(ℎ+𝑘) + 𝑒 𝑖𝜋(𝑘+𝑙)

4f h, k, l all odd or all even e.g. (111), (220), (222), etc.

𝐹ℎ𝑘𝑙 = ቊ
0 h, k, l mixed (210), (112), (320), etc.
 36

Structure factor
BCC Al

For monatomic BCC crystals:

2f if h + k + l is even
𝐹ℎ𝑘𝑙 = ቊ
0 if h + k + l is odd

(111), (003), (201), (221), etc. are missing

For FCC crystals:

4f h, h, l all odd or all even
𝐹ℎ𝑘𝑙 = ቊ
0 h, k, l mixed

(210), (112), (320), etc. are missing

 37

X-ray powder diffraction

X-ray powder diffraction (XRD) is a rapid

analytical technique primarily used for phase
identification of a crystalline material and can
provide information on unit cell dimensions. Bragg-Brentano geometry
Samples can be powder, sintered pellets, thin
film coatings on substrates, etc.
 The sample holder and the x-ray detector are
mechanically linked.
 If the sample holder turns q, the detector turns
2q, so that the detector is always ready to
detect the Bragg diffracted beam.
 x-ray detectors (e.g. Geiger counters) are
used instead of the film to record both the
position and intensity of the x-ray peaks
 38

XRD: powder diffraction

 39

XRD: single crystal case

A single crystal specimen in a Bragg-Brentano diffractometer would produce
only one family of peaks in the diffraction pattern
 40

XRD: polycrystalline case

A polycrystalline sample should contain thousands of crystallites.
Therefore, all possible diffraction peaks should be observed.

 For every set of planes, there will be some crystallites that are properly
oriented to satisfy Bragg’s law
 In powder diffraction, the basic assumption is that all grains (crystallites)
are randomly oriented, so for every set of planes there is an equal number
of crystallites that will diffract.
 41

XRD patterns (diffractogram)

 A cone along the sphere corresponds to a single Bragg angle 2-theta

─ The tens of thousands of randomly oriented crystallites in an ideal
sample produce a Debye diffraction cone.
 The linear diffraction pattern is formed as the detector scans through an arc
that intersects each Debye cone at a single point; thus giving the appearance
of a discrete diffraction peak.
 42

XRD: common applications

 Phase Composition of a Sample

─ Quantitative Phase Analysis: determine the relative amounts of
phases in a mixture by referencing the relative peak intensities
 Unit cell lattice parameters and Bravais lattice symmetry
─ Index peak positions
─ Lattice parameters can vary as a function of composition, and
therefore give you information about, alloying, doping, solid solutions,
strains, etc.
 Residual Strain (macrostrain)
 Epitaxy/Texture/Orientation
 Crystallite Size and Microstrain
─ Indicated by peak broadening
─ Other defects (stacking faults, etc.) can be measured by analysis of
peak shapes and peak width
 43

XRD: Phase Identification

The most common use of XRD is for phase identification since the diffraction
pattern for every phase is as unique as your fingerprint
 Phases with the same chemical composition can have drastically
different diffraction patterns
 Use the position and relative intensity of a series of peaks to match
experimental data to the reference patterns in the database

 By accurately measuring peak

positions over a long range of
2q, you can determine the unit
cell lattice parameters of the
phases in your sample
 Effects such as alloying,
substitutional doping,
temperature and pressure, etc.
can create changes in lattice
parameters that you may want
to quantify.
 44

XRD powder patterns: JCPDS Card

Joint Committee on Powder Diffraction Standards (JCPDS), now The International
Centre for Diffraction Data (ICDD) collects over 300,000 diffraction patterns
Quality of data

1. file number
2. three strongest lines
3. lowest-angle line
4. chemical formula
and name
5. data on diffraction
method used
6. crystallographic
data
7. optical and other
data
8. data on specimen
9. data on diffraction
pattern
 45

Example: alloy composition analysis

(0002) Diffraction peaks of ZnO1-xSx alloy 1 4 ℎ2 + ℎ𝑘 + 𝑘 2 𝑙2
= + 2
Increasing x 𝑑2 3 𝑎2 𝑐

Jaquez et al., J. Appl. Phys. 118, 215702 (2015)

 Wurtzite ZnO (c=0.52 nm) and ZnS (c=0.626 nm)

 As x increases, the lattice parameter increases
 Bragg law: 𝜆 = 2𝑑 sin 𝜃 increasing 𝑑 means decreasing 𝜃.
 Vegard's law: lattice parameter of a solid solution of two constituents
𝑐𝑍𝑛𝑂1−𝑥 𝑆𝑥 = 𝑥𝑐𝑍𝑛𝑆 + (1 − 𝑥)𝑐𝑍𝑛𝑂
 Composition 𝑥 can be derived from the measured lattice parameter 𝑐.
 46

XRD: crystallite size

Crystallites smaller than ~120 nm create broadening of diffraction peaks
 this peak broadening can be used to quantify the average crystallite size of
nanoparticles using the Scherrer equation
─ contributions due to instrument broadening should be known by using a
standard sample (e.g. a single crystal)
Cu Ka1 Cu Ka2 Cu Kb1
2 2 2
𝐵𝑚𝑒𝑎𝑠 = 𝐵𝑔𝑟𝑎𝑖𝑛 + 𝐵𝑖𝑛𝑠𝑡𝑟 keV 8.0478 8.028 9.572
𝐵𝑖𝑛𝑠𝑡𝑟 ~0.01° l (Å) 1.5408 1.544 1.295
2 2
𝐵𝑚𝑒𝑎𝑠 ≈ 𝐵𝑔𝑟𝑎𝑖𝑛

𝐾𝜆
Scherrer equation: 𝐵 2𝜃 =
𝐿 cos 𝜃
where B is the 2𝜃 FWHM peak broadening in
radian, 𝜆 is the wavelength of the x-ray
used, L is the grain size and K~0.9
 47

Crystallinity: example
GaSbxN1-x ; x~0.04 grown at different temperature

𝐾𝜆 800
𝐵 2𝜃 =
𝐿 cos 𝜃

600

Grain size
o
400 T =470 C
L~30 nm g

o
T =285 C
~12 nm g

200
o
T =135 C
g
~8 nm
o
amorphous T =90 C
g
0
25 30 35 40
Two-theta (deg.)
 48

XRD: lattice strain

do

No Strain 2q

d1

Uniform Strain: (d1-do)/do 2q

Peak moves, no shape changes
Dq a Dd a strain

Non-uniform Strain

d1constant
Peak broadens 2q
Dd
Broadeing b  D 2q  2 tan q
d
 49

Preferred orientation (texture)

 In common polycrystalline materials,
the grains may not be oriented
randomly (not the grain shape, but the
orientation of the unit cell of each
grain,↑).
 This kind of ‘texture’ arises from all
sorts of treatments, e.g. casting, cold
working, annealing, etc.
 If the crystallites (or grains) are not
oriented randomly, the diffraction cone
will not be a complete cone.
 “texturing” may affect the properties
due to anisotropic nature. Grain

Random orientation
Preferred orientation
 50

XRD: texturing
Ba0.92Ca0.08TiO3 piezoelectric ceramic

Haugen et al., J. Appl. Phys. 116(13):134102 (2014)

 51

Preferred orientation
Preferred orientation of crystallites can create a variation in diffraction peak
intensities that can be
 qualitatively analyzed using a 1D diffraction pattern (powder pattern)
 quantitatively analyzed by a pole figure which maps the intensity of a single
peak as a function of tilt and rotation of the sample

Random
Textured
 52

Preferred orientation

Texture PbTiO3 (001)  MgO (001)

highly c-axis oriented
PbTiO3 (PT) simple tetragonal

X-ray diffraction  scan patterns from (a) X-ray diffraction q-2q scan profile of a PbTiO3
PbTiO3 (101) and (b) MgO (202) reflections thin film grown on MgO (001) at 600°C.
 53

X-ray rocking curve

 Performs a θ-2θ scan and fix the θ-2θ geometry where a strong diffraction peak
is observed
 A rocking curve scan is then acquired by varying the orientation of the sample
by an angle Δω around its equilibrium position (rocking), while keeping the
detector position fixed.
 The width of this peak W (FWHM)
will be determined by several Detector
factors: X-ray tube s
─ The mean spread in
orientation for the set of planes
belonging to the chosen Bragg

reflection. 2q
─ the lateral size of the
crystalline domains, similar to
the Scherrer broadening
described for θ-2θ scans, but
depends here on the lateral
size of the crystallites.
 54

Rocking curve (omega scan)

[400] [400] [400]
s s s

2q 2q 2q

 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 intrinsic 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
 55

Example: Rocking curve

AlGaN/GaN high-electron-mobility transistors on Si(111) substrate

 AlGaN has a different

structure with Si and when
grown on Si the crystal quality
is poor
 GaN is used as a buffer layer
to relieve the crystalline
defects.
 RC analysis shows that with
increasing GaN thickness, the
quality of the film improves
and the mobility increases

Radhakrishnan et al., Appl. Phys. Lett. 97, 232107 (2010)

 56

Grazing incident XRD (GIXRD)

Grazing incidence X-ray diffraction (GID, GIXRD) uses small incident angles for
the incoming X-ray (<5o), so that diffraction can be made surface sensitive. It is
used to study surfaces and layers because wave penetration is limited. Distances
are on the order of nanometers.

 kept constant ~0.2 to 4o

 Conventional Bragg-Brentano configuration: 2q- scans probe only grains

aligned parallel to the surface
 Parallel-beam glazing incidence configuration: 2q scans probe grains in all
directions
 57

GIXRD: x-ray penetration

2q Glancing angle 2q

Grain orientation Directions ⊥ surface Various directions
Depth resolution Constant, tens of mm  Few nm-mm, depth profiling possible
by varying 
 Surface sensitive
 Ideal for ultra thin films (nm)
Best configuration Bragg-Brentano Parallel beam
Parallel beam
 58

GIXRD: example
 59

High resolution XRD (HRXRD)

 60

HRXRD: applications
Commonly used for measuring single crystals, epitaxial films, heterostuctures,
superlattices, quantum dot, etc:
 Lattice distortions within 10-5.
 Rocking curve analysis
 Strain relaxation and lattice parameter measurements.
 Alloy composition and superlattice periods.
 Interface smearing in heterostructures (dynamical simulation).
 61

HRXRD
Example: strained InxGa1-xAs on GaAs (001) substrate

Strain, layer thickness and composition x can be obtained

 62

Web Resources
Videos:

XRD https://www.youtube.com/watch?v=lwV5WCBh9a0 (tutorial)

https://www.youtube.com/watch?v=C1cYJthlBZY
https://www.youtube.com/watch?v=3aU4adBx2ok
Bremsstrahlung https://www.youtube.com/watch?v=UkywJG9QPuE
Characteristic https://www.youtube.com/watch?v=FjeF1xQHdwk
Lattice structure: http://www.youtube.com/watch?v=Rm-
i1c7zr6Q&list=TLyPTUJ62VYE4wC1snHSChDl0NGo9IK-Nl
Synchrotron: https://www.youtube.com/watch?v=_UGOJW3yPSk
https://www.youtube.com/watch?v=l4NSF-gkKCU
 63

Other x-ray techniques

 Reciprocal space mapping
─ Accurate lattice parameters in and out
of plane
─ Strain and composition gradients
─ Strain relaxation
─ Mosaic size and rotation
─ Misfit dislocation density
─ Nanostructure dimensions,
─ Lattice disorder and diffuse scattering.
 X-ray absorption (XAS):
─ Typically require a synchrotron
radiation source
─ Measures the local bonding
environment of a certain element in a
material
─ Information such as bond angle, bond
length, coordination number, bind type,
bond distortion, etc. can be obtained
 64

Synchrotron radiation
 65

Synchroton Facilities

Advanced photon source

The Australian Synchrotron

 66

Interference of photoelectron waves

Interference of outgoing and incoming part of photoelectron modulates absorption
coefficient
2.3

ℎ𝜔 > 𝐸𝑎𝑏𝑠 2.2

Correction factor=c/cexp
2.1

2.0

1.9

1.8

0 2 4 6 8 10 12 14
k (Å)

 Advantages: Atomic-species specific, local bonding environment

(length, angle, disorder, neighbor)
 Disadvantages: very short range (<~5-6 Å), sensitive to multiple
scattering, overlapping edges...
 67

EXAFS
2.5 Cu K-edge for Cu metal foil c
(
k
)
SN
f
(k
)
kR


sin(
2
kR(
k
))
l
ee 2
0 j
j
j
2
j
j j

2
R/
j (
k
) 
22
k
j
2

2.0
For each coordination shell j:
1.5 m0d Rj, Nj, 2j are the sought distance, coord. number
md

Extended x-ray absorption and variance of distance (disorder)

1.0 X-ray fine structure (EXAFS)
fj(k)=|fj(k)|eij(k) is the scattering amplitude
absorption
0.5
near edge λ is the electron free path,
structure
(XANES) S02 accounts for many-electron excitations.
0.0
9000 9200 9400 9600
First nearest neighbor
photon energy (eV)
8
4
2 6 4th NN
|FT(ck2)|
3rd NN
2

0
ck

4
-2 2nd NN

-4 2
-6
2 4 6 8 10 12 14 0
-1
0 2 4 6 8
photoelectron wave number (Å )
distance (Å)