PHY322: Solid State Physics

Lecture 3: X-ray Diffraction

MR. H. KHUDZE
 Diffraction

Diffraction is bending of waves when they pass

through an aperture or around an obstacle with
aperture or size (d) that is comparable to the
wavelength () of the wave (ie., when d  ).
 X-ray diffraction
X-rays are electromagnetic (EM) waves of very
short wavelength (in the order of 1Å).
The energy of the wave decreases with increasing
wavelength.
X-ray diffraction is the bending of X-rays when they
pass through an aperture.
Grating cannot diffract X-rays because  of X-rays is
very small. However, when X-rays are incident on a
crystal, they are diffracted from atomic planes of
the crystal.
 X-ray diffraction….
Atomic planes are like mirrors for atomic plane
reflection (see Figure 1).

X-ray source 1

2
A
 

  dhkl
B C
O

Figure 1: Diffraction of x-rays

 Bragg’s law

 Reflection continues until diffraction is completed.

If  is the incident wavelength, then the diffracted
beam will have the same wavelength in the same
medium.
The diffracted waves can interfere but they must be
in coherent (phase difference must be constant
with time)
 Bragg’s law….
 Rays 1 and 2 travel along different paths, so there is
path difference and there will be phase difference.
 In crystals there is periodic arrangement of atoms,
consequently, dhkl remains constant (where hkl are
𝑎
Miller indices). For a cubic crystal, dhkl = 2 2 2
ℎ +𝑘 +𝑙
 Path difference =OA + OB= dhkl sin + dhkl sin
=2 dhkl sin
If the detector is placed where path difference is /2,
then the detector will detect the intensity of minima
due to destructive interference.
If path difference is , then there will be constructive
interference.
 Bragg’s law….
For constructive interference, intensity and path
difference must be integral multiples of wavelength
. Either fix  and vary  (by using a monochromatic
X-ray beam), or fix  and vary  to satisfy the
condition:
2 dhkl sin=n , for n=1, 2, 3, ….. (1)

This is Bragg’s law, and n is the order of diffraction.

This equation can be used to calculate dhkl and
determine the crystal structure.
 Diffraction angle
 Angle between incident and diffracted rays.
Incident wave

Diffracted wave
B B
B

Undeviated wave

Figure 2: Angle between incident and diffracted rays

 Diffraction angle =2B

 Bragg’s angle = B
 Bragg’s law is a consequence of periodicity.
 X-ray diffraction pattern
 X-ray pattern intensity versus diffraction angle
 B is limited to 0-90o.
 As dhkl increases, diffraction angle decreases.
Intensity

0

Figure 3: Variation of intensity with diffraction angle.
 The observed peaks are due to Bragg’s law.
 Example
A beam of X-rays of wavelength 1.5 Å is incident on
the surface of a crystal. The second fringe is
observed when the incident angle is 48.6o. Calculate
the spacing of the atoms in the crystal.
Solution:
From Eq.(1),

= n = 2∗1.5∗ 10−10
dhkl 2 sin  2∗sin 48.6 0
=2Å
 Reciprocal lattice
Every crystal is associated with two types of
crystals: i) direct and ii) reciprocal
Direct lattice: points are arranged according to their
positions. Thus, the direct lattice is defined in
position space. It has a unit of length [L]
Reciprocal lattice: lattice points are arranged
according to their wave vector (k) or momentum
(ħk). Consequently, the reciprocal lattice is defined
in momentum space or Fourier Space. It has
reciprocal unit of length [L] -1.
 Reciprocal lattice….
Position and momentum lattices are inversely
related, or are conjugate of each other.
Wave vector is the number of waves per unit
wavelength. It describes the direction in which the
wave is propagating. The wave number k is given
by:
2 (3)
k=

 Potential energy in position space.
 KE in momentum space.
 Reciprocal lattice….

Total energy is conserved, KE and PE are inversely

related (as KE increases, PE decreases).
If an electron is completely free, it will have KE only.
 Reasons for needing a reciprocal
lattice
It is difficult to visualise the crystal plane as the order
of the plane increases.
For instance, it is difficult to visualise the plane (003)
z

(003)

 As hkl increase, dhkl decreases.

 Wave scattering

The Bragg derivation of the derivation gives a neat

statement of the condition for constructive
interference of waves scattered from lattice points.
A deeper analysis is required to determine the
scattering intensity from the basis of atoms, which
means from the spatial distribution of electrons in
within each cell.
 Fourier analysis can be applied in such an analysis.
 Wave scattering: Fourier analysis
In three dimensions, the lattice vectors can be
expressed as:
T=u1a1+u2a2+u3a3 (4)
Where a1, a2 and a3 are the primitive translation
vectors, and (u1,u2,u3) are integers whose values
depend on a particular lattice site.

Figure 5: Lattice vectors in three dimensions.

Wave scattering: Fourier analysis….
 A crystal is invariant (does not change) under any
translation T=u1a1+u2a2+u3a3
 Any local physical property of the crystal such as charge
concentration, electron number density, or magnetic
moment density is invariant under T.
 Most important in this analysis is that the number density
n(r) is a periodic function of r with periods a1, a2 and a3 in
the directions of the three crystal axes respectively.
 Due to this periodicity, we have:
n(r + T)= n(r)
 This periodicity creates an ideal situation for application of
Fourier analysis.
 Fourier series formula
A periodic function f can be expressed in Fourier
series as:
∞ 2πn𝑥 2πn𝑥
𝑓 𝑥 = a0 + ∑ 𝑎n cos + 𝑏n sin
L L
𝑛 =1

Where [-L, L] is the interval in which f(x) is defined, 𝑎n

and 𝑏n are Fourier coefficients, and n=1,2,3,…
Fourier series formula….
 Wave scattering: Fourier analysis….

Fourier analysis can be extended to periodic

functions n(r) in three dimensions. In this case, we
must to find a set of vectors G such that:

(5)

For further Fourier analysis of the electron

concentration, we need to find the vectors G
in the Fourier summation.
 Brillouin zone

Brillouin gave the statement of the diffraction

condition that is most widely used in solid state
physics, useful in the description of electron
band theory and of elementary excitations of
other types.
A Brillouin zone is a Wigner-Seitz primitive
cell in the reciprocal lattice.
 Wigner-Seitz primitive cell
Wigner-Seitz primitive cell: the locus of points in space that
are closer to that lattice point than to any of the other
lattice points with smallest volume.
Wigner-Seitz primitive cell may be constructed as shown
in Figure 6.

Figure 6: Construction of a Wigner-Seitz primitive unit cell

 Brillouin Zones
Brillouin zone gives a clear geometric interpretation of the
diffraction condition 2k.G=G2. When we divide this equation by 4,
we obtain:

 We can now work in the reciprocal space of the k’s

and G’s:
1) Select a reciprocal vector G from the origin to a
reciprocal lattice point
2) Construct a plane normal to this vector at its
midpoint. This plane forms part of a zone boundary
Brillouin Zones….
 Brillouin Zones….

 The set of planes that are perpendicular bisectors of the reciprocal

lattice vectors is of general importance in the theory of wave
propagation in crystals: A wave vector drawn from the origin ends
on any of these planes will satisfy the condition for diffraction. These
planes divide the Fourier space of crystal into fragments as shown in
Figure 5b for a square lattice.
 The central square is a primitive cell of the reciprocal
lattice.
 The central cell is of special importance in the theory of solids,
and it is called the first Brillouin zone
 Brillouin Zones….

The first Brillouin zone is the smallest volume

completely enclosed by planes that are
perpendicular bisectors of the reciprocal lattice
vectors drawn from the origin.
Brillouin zones are not historically part of the
language of x-ray diffraction analysis of crystal
structures but the zones are an essential component
of the electronic energy-band structure of the crystals.
 Reciprocal lattice vectors

There is a powerful abstract procedure to do

this. This procedure constitutes much of the
theoretical basis of solid state physics, where
Fourier analysis if frequently applied.
 Reciprocal lattice vectors….
We can construct the axis vectors b1, b2 and b3 of
the reciprocal lattice as follows:
𝐚2 X 𝐚3
𝐛1 = 2 ;
𝐚1 . 𝐚2 X 𝐚3

𝐚3 X 𝐚1
𝐛2 = 2 ;
𝐚1 . 𝐚2 X 𝐚3
(6)
𝐚 1 x 𝐚2
𝐛3 = 2
𝐚1 . 𝐚2 x 𝐚3
If a1, a2 and a3 are primitive vectors then b1, b2 and
b3 are primitive vectors of the reciprocal lattice.
 Reciprocal lattice vectors….
Each vector of the reciprocal lattice is orthogonal
to two axis vectors of the crystal lattice.
Consequently, the vectors b1, b2 and b3 have the
property that that:
𝐛𝑖. 𝒂𝑗 = 2𝑖𝑗 (7)
Where  𝑖𝑗 = 1 if i=j, and  𝑖𝑗 = 0 if ij.
Points in the reciprocal lattice are mapped by the
set of vectors defined as:
G=v1b1+ v2b2 + v3b3
(8)
Where v1, v2 and v3 are integers.
 Reciprocal lattice vectors….
Vectors G in the Fourier series are reciprocal
vectors presented in Eq. (6), so that the Fourier
series representation of the electron density has
the desired invariance under any crystal
translation: T=u1a1+ u2a2 + u3a3
 It follows from Eq.(5) that:
n 𝐫 + 𝐓 = ∑ G 𝑛G exp i𝐆. 𝒓 exp i𝐆. 𝑻 (9)
 However, exp i𝐆. T =1, because:
𝑒𝑥𝑝 i𝐆. 𝑻 = exp i v1b1+ v2b2 + v3b3 . u1a1+ u2a2 + u3a3
= exp 2i v1u1+ v2u2 + v3u3 (10)
 Reciprocal lattice vectors….

The argument of the exponential is of the form

2i times an integer, since v1u1+ v2u2 + v3u3 is an
integer. Consequently, based on Eq. (5), we have the
desired invariance n(r+T)=n(r).
Every crystal structure has two lattices associated
with it, the crystal lattice and the reciprocal lattice.
A diffraction pattern of a crystal is a map of the
reciprocal lattice of the crystal.
A microscopic image, if resolved on a fine scale, is a
map of the crystal structure in real space.
 Reciprocal lattice vectors

 Two lattices are related by Eq. (6).

The reciprocal lattice is a lattice in the Fourier space
associated with the crystal.
Wavevectors are drawn in the Fourier space, so that
each position in the Fourier space may have a
meaning as a description of a wave. Nevertheless,
there is a special significance to the points defined
by G’s associated with the crystal structure.
 Primitive unit cell
In the case of a rectangular two dimensional lattice, the
unit cell is the rectangle, whose sides are the vectors a1
and a2. If the unit cell is translated by all the lattice
vectors expressed by Equation (8), the area of the whole
lattice is covered once and only once. A primitive unit cell
is a unit cell with the smallest area which produces this
coverage (a primitive unit cell contains exactly one lattice
point).
In the two dimensional case the area of the unit cell is
given by:
S=|a1 x a2| (11)
In three dimensional case, the volume V of the unit cell is
given by: V= a1. a2 x a3 (12)
Reciprocal lattice simple cubic
crystal
Reciprocal lattice simple cubic
crystal….
 Diffraction conditions

 Theorem: the set of reciprocal lattice vectors G

determines the possible x-ray reflection.
The difference in phase factors is exp[i(k-k’).r]
between beams scattered from volume elements r
apart.
Wave vectors of the incoming and outgoing beams
are k and k’
Diffraction conditions….
 Diffraction conditions….

Suppose the amplitude of the wave scattered from

a volume element is proportional to the local
electron concentration n(r).

k
k

K’

Figure 8: Schematic representation of the k, k’ and k.

 Diffraction conditions….

k measures the change in wave vector, and is

called the scattering vector.

When the scattering vector k is equal to a

particular reciprocal lattice vector G,
k = G (16)
 Diffraction conditions….

In elastic scattering, a photon of energy ħ is

conserved so that frequency ’=ck’ of the emergent
beam is equal to the frequency of the incident
beam. Therefore, the magnitudes k and k’ are
equal, and k2=k’2. This result also holds for elastic
scattering of electron and neutron beams.
 Diffraction conditions….
 From Eq.(16), k + G =k’. So, the diffraction condition
can be written as k2=k + G2, or

2k.G+G2=0 (17)
If G is a reciprocal lattice vector, then –G is also a
reciprocal vector. With this substitution, Eq.(22) can
be expressed as:
2k.G=G2 (18)
 Diffraction conditions….
Eq. (18) is usually used a condition for diffraction. It
is another statement of the Bragg condition.
The spacing d(hkl) between parallel planes that are
normal to the direction G=hb1+kb2+lb3 is d(hkl)=
2/G. The integers hkl that define G are not
necessarily the same as the indices of an actual
crystal plane since hkl may contain a common factor
n, while as the common factor was eliminated from
the definition of Miller indices.
 Diffraction conditions….
Consider a vector wave k incident on a plane, and
the reciprocal lattice vector G that is perpendicular
to the plane (Figure 9). The wave undergoes
reflection emerging as wave vector k’. From Eq.(16),
G=k.
Planes

k

k k’

Figure 9: Schematic representation of the k, k’ and k.

 Diffraction conditions….
 Eq. (16) can be re-written as:
2 k G cos  = G2 (19)
Where k (=2/) and G (= 2/d(hkl)) are respectively the
magnitudes of the vectors k and G, and  is the angle
between the two vectors. But k =G, and so, from Figure
9, =/2 + .
This implies that,
cos  =cos (/2+)=cos (/2) cos -sin (/2) sin  =-sin 
Therefore Eq.(24) can be expressed as:
2 (2/) sin =2/d(hkl)
Or, 2 d(hkl) sin =  (20)
 Diffraction conditions….

So, we obtain the Bragg condition:

2d sin = n (21)

Where d is the spacing between adjacent parallel

planes with indices, h/n, k/n and l/n.
 Laue equations….
The original result of diffraction theory that k=G
can be expressed in another way to obtain what are
known as Laue equations.
Laue equations are valuable due to their geometric
representation.
If we take the scalar product of both k and G
successively with a1, a2, and a3.
From Eqs. (6) and (7), we obtain: a1. k=2v1,
a2. k=2v2, and a3. k=2v3.
 Interpretation of Laue equations
a1. k=2v1 shows that k lies on a cone about the
direction of a1.
a2. k=2v2, shows that k lies on a cone about
the direction of a2.
a3. k=2v3 shows that k lies on a cone about the
direction of a3.
Consequently, at reflection, k must satisfy all the
three equations.
Interpretation of Laue equations….

Figure 10 shows the Edward construction which

helps visualization of the nature of accident that
must occur to satisfy the diffraction conditions in
three dimensions.
Interpretation of Laue equations….
 Exercise

1) Derive Laue equations.

2) Consider a plane (hkl) in a crystal lattice.
Prove that the reciprocal lattice vector
G=v1b1+ v2b2 + v3b3 is perpendicular to this
plane.
Instrumentation
Diffractometer
 Two Circle Diffractometer

 For polycrystalline Materials

 Four Circle Diffractometer
 For single crystals

[Link]/
Hong et al., Nuclear Instruments and Methods in Physics Research A 572 (2007) 942
 Powder Diffractometer
 For powdered crystals
 Diffraction Methods

Method Wavelength Angle Specimen

Laue Variable Fixed Single Crystal

Rotating Fixed Variable (in Single

Crystal part) Crystal

Powder Fixed Variable Powder

 Rotating crystal method
In rotating crystal method, a single crystal is
mounted at a point of cylindrical shape in such a
way that x-rays are incident on the crystal at right
angles.
A cylindrical photographic film is placed around the
crystal which then rotated about the axis in a
chosen direction.
The axis of the photographic film is aligned with the
axis of rotation of the crystal.
Rotating crystal method….
 Rotating crystal method….
As the crystal rotates, lattice points come at positions
that satisfy the Bragg condition. At some particular
positions, lattice points are correctly at Bragg’s angle
for reflection of x-ray beam and at this instant,
diffraction beam will be formed.
The diffraction beam is located the surface of an
imaginary cone when the film is laid out from the
cylinder, flatten it, the diffraction spots lie on the film in
horizontal lines.
By recording the diffraction pattern, both angle and
intensities for different crystal orientation can be
obtained, and the shape and size of the unit cell of the
crystal can be determined.
 Rotating crystal method….
If the wavelength of the x-rays is  and the angle of
diffraction is  at which reflection occurs, then the
interplanar spacing d can be calculated by using the
Bragg equation.
 For a simple cube,
𝑎
𝑑=
ℎ2 + 𝑘 2 + 𝑙2
 Powder method
It is usually difficult to get a single crystal. In view
of this, a power can be used instead.
It is important to ensure that every possible crystal
orientation is equally represented. Sample consists
of a large number of crystallites with different
orientations.
 Powder method….
The wavelength of x-rays is fixed but angle of incidence
is variable.
Tiny crystal are oriented in random directions with
respect to the incident x-rays. So, when x-rays fall on
the sample , and some of the crystals will be correctly
oriented with the x-ray beam and produce diffraction
pattern. For instance, in particular planes, say, (100)
planes can reflect the incident beam and other crystals
will be correctly oriented for the other planes such as
(110) and so on and so forth.
Consequently, in Powder method, every set of lattice
planes will be capable of reflection as all the
orientations of crystal are available on the sample.
 Powder method….
If the sample consists of many randomly oriented
single crystals, the diffraction beams are observed
to lie on the surface of several cones. These cones
may merge in all directions, in forward and
backward as shown in Figure 3.
 Powder method….
Diffracted rays are record on a circular strip (Figure
5).
 Powder method….
The cones of distracted radiation intersect the
cylindrical strips of film inline or arc and when the
strips is unrolled and made flat, the shows
diffraction lines as shown in Figure 6.
 Powder method….
Each diffraction line is made up of a large number
of small spots. Each line is formed by a separate
crystal particle. The spots are so close together that
they appear as a continuous line.
The lines are generally curved as cone of diffracted
rays cut the strip in a curved line but at 2θ= 900 ,
the line will be straight.
From the measured position of a given diffraction
line on the film, the angle diffraction can be
determined.
 Powder method….

From knowledge of the wavelength λ of x-rays, we

can calculate the inter planar spacing (d) of
reflecting lattice planes.
 Advantages of the powder method

1) Simplicity of sample preparation

2) Rapidity of measurement
3) Ability to analyse mixed phases (such as soil
samples).
4) Determination of structure in situ.
 Neutron diffraction
Neutrons are very penetrating, probably due to the
fact that have no electric charge, so they do not
interact with the atomic electrons. Nevertheless,
Nevertheless, they do have a magnetic moment
that allows them to interact with magnetic nuclei.
 Neutron diffraction was proposed in 1934, to
exploit de Broglie’s hypothesis about the wave
nature of matter. Use de Broglie’s equation λ = h/p
to calculate the momentum (p) and energy (En) of a
neutron whose wavelength is comparable to atomic
spacing.
 Neutron diffraction….
p2 h2
En = =
2mn 2mn 2

Where h is Plank’s constant and mn is mass of

neutron.
 Thanks

THE END

Next: Heat Capacities