Diffraction from crystals

Recap of Bragg’s law and Miller indices

Crystal structures are determined using diffraction techniques. The wavelength of the probe
(X-rays, neutrons, electrons) must be comparable to the interatomic spacing ∼ 1Å = 10ିଵ଴ m
= 0.1 nm.

Bragg’s law
W. L. Bragg (1915 Nobel Prize; UCL Quain Professor 1915-25) proposed a simple
geometrical construction for deriving the condition for constructive interference of X-rays.

Lattice planes are assumed to reflect X-rays (specular geometry, i.e. angle of incidence ߠ ൌ
angle of reflection). Interference is constructive when the path difference AO+OB ൌ ʹߨ݊,
where ݊ is an integer, i.e. when

ʹ݀ •‹ ߠ ൌ ݊ߣ

This is Bragg’s law and it is valid also for diffraction of neutrons and electrons.

X-rays are EM waves and are scattered primarily by the electrons in the solid so the
scattering power of atoms increases with the atomic number ܼ (i.e. number of electrons). It is
more difficult to detect light atoms, especially when together with heavy atoms in the solid.
௛௖
X-rays with ߣ ‫ͳ ׽‬% have energies ‫ ܧ‬ൌ ݄ߥ ൌ ∼ 10 keV and a penetration depth of ‫ߤ ׽‬m.
ఒ

Neutrons are scattered by nuclei via the strong nuclear force. Scattering strength does not
have a monotonic dependence on atomic number; neutrons are therefore good for studying
light elements. Neutrons also interact magnetically with magnetic moments of atoms and can
be used to determine magnetic structure of materials.

Neutrons typically penetrate millimetres into the materials and have energies of order
௣మ ௛
∼ 100 meV for ∼ 1 Å ቀ‫ ܧ‬ൌ ǡߣ ൌ ቁ.
ଶ௠ ௣

Electrons are scattered by atomic electrons much more strongly than X-rays and therefore
penetrate only a few nanometres into the material. They are useful for studying surface
structures. For ߣ ‫ͳ ׽‬%, the electron energy ‫ ܧ‬ൎ ͳͲͲ‡.

2-1
Miller indices
To understand diffraction data we need to identify and label different families of lattice
planes. Each family of lattice planes:

- contains all lattice points

- has the same density of lattice points per plane
- has a characteristic inter-plane spacing ݀

We label families of planes using Miller indices (ℎ݈݇) determined in the following way:

- take any lattice plane and find its intercepts ݉ଵ , ݉ଶ and ݉ଷ with the crystallographic
axes in terms of the corresponding lattice parameters
ଵ ଵ ଵ
- take reciprocals , ,
௠భ ௠మ ௠య
- scale all reciprocals by a common factor to get a set of three smallest integers; these
are the ℎ, ݇, ݈ values1

Example:

planes

݉ଵ = 1 1/݉ଵ = 1 ×2→ ℎ =2
݉ଶ = 2 1/݉ଶ = 1/2 × 2 → ݇ = 1
݉ଷ = ∞ 1/݉ଷ = 0 × 2 → ݈ = 0

i.e. these are the (210) planes.

Crystallographic directions are labelled as [‫ ]ݓݒݑ‬where ‫ݑ‬, ‫ ݒ‬and ‫ ݓ‬are the smallest integers
such that the vector ‫܉ݑ‬ଵ + ‫܉ݒ‬ଶ + ‫܉ݓ‬ଷ points in desired direction (e.g. see vector [210]
above).
{ℎ݈݇} denotes sets of planes equivalent by symmetry.
〈ℎ݈݇〉 denotes sets of directions equivalent by symmetry.
e.g., for a cubic system the planes (110), (101), ൫110൯ … ∈ {110} and the directions
[210], [120], [102] … ∈ 〈210〉. Negative numbers are denoted with a bar, e.g. 1ത = −1.

1
Note that the Miller indices depend on the particular choice of primitive vectors. By convention, the body-
centred and face-centred cubic Bravais lattices are described in terms of their conventional cubic cells, i.e. as
simple cubic lattices with bases.

2-2
Reciprocal space and the reciprocal lattice
As with many problems involving periodic functions, it is often convenient to transform the
problem from real space to Fourier space or “reciprocal space”. We will see later that the
diffraction pattern of any solid is simply proportional to the square of the Fourier transform of
its electron density. It is therefore convenient to define the Fourier space analogue of the
crystalline lattice, known as the reciprocal lattice.

To see its usefulness, consider a plane wave

‫ ݁ܣ‬௜‫ ܚ⋅ܓ‬. We can represent its direction and
plane of
periodicity by a vector ‫݇( = ܓ‬௫ , ݇௬ , ݇௭ ) in k- constant
phase
space. This “wavevector space”, spanned by
all possible values of ݇௫ , ݇௬ and ݇௭ is known
as reciprocal space.

Note that the phase factor ݁ ௜‫ ܚ⋅ܓ‬is the same

for any set of parallel planes perpendicular to
ଶగ
‫ ܓ‬and separated by ߣ = . We could therefore associate a point ‫ ܓ‬in reciprocal space with
|‫|ܓ‬
ଶగ
sets of parallel planes perpendicular to ‫ ܓ‬and with spacing ݀ = .
|‫|ܓ‬

The set of all wavevectors ‫ ܓ‬that yield plane waves with the periodicity of a given Bravais
lattice is known as its reciprocal lattice. We will label all such wavevectors ۵ and they
correspond to all wavevectors satisfying ݁ ௜۵⋅‫ ݁ = ܚ‬௜۵⋅(‫ܚ‬ା ) for all lattice vectors, i.e.

݁ ௜۵⋅ = 1 or۵ ⋅ = 2ߨ × integer

In practice, for a given Bravais lattice with = ݊ଵ ‫܉‬ଵ + ݊ଶ ‫܉‬ଶ + ݊ଷ ‫܉‬ଷ, the reciprocal lattice (RL)
is generated by all ۵ = ℎ‫܊‬ଵ + ݇‫܊‬ଶ + ݈‫܊‬ଷ where ℎ, ݇ and ݈ are integers from −∞ to ∞ and the
primate lattice vectors ‫܊‬௜ are given by

2ߨ 2ߨ 2ߨ
‫܊‬ଵ = ‫܉‬ଶ × ‫܉‬ଷ ‫܊‬ଶ = ‫܉‬ଷ × ‫܉‬ଵ ‫܊‬ଷ = ‫܉ × ܉‬ଶ
ܸ ܸ ܸ ଵ

and ܸ ≡ ‫܉‬ଵ ⋅ (‫܉‬ଶ × ‫܉‬ଷ ), its magnitude |ܸ| being the volume of the primitive unit cell of the
direct lattice.

Check for yourself that ‫܉‬௜ and ‫܊‬௝ satisfy ‫܉‬௜ ⋅  ‫܊‬௝ = 2ߨߜ௜௝ (where ߜ௜௝ = 1 if ݅ = ݆ and 0 if ݅ ≠ ݆)
and therefore that ۵ ⋅ = 2ߨ × integer is satisfied for all ۵ and .

The reciprocal lattice of a Bravais lattice is also a Bravais lattice and its reciprocal is the
direct lattice.

(ଶగ)య
The volume of the primitive unit cell of the reciprocal lattice ‫܊‬ଵ ⋅ (‫܊‬ଶ × ‫܊‬ଷ ) = , where ܸ௣௖
௏೛೎
is the primitive cell volume of the direct lattice.

The units of reciprocal space vectors [۵] = [ ]ିଵ = mିଵ.

When ℎ, ݇ and ݈ have no common factor, ۵ = ℎ‫܊‬ଵ + ݇‫܊‬ଶ + ݈‫܊‬ଷ is perpendicular to lattice
ଶగ
planes with Miller indices (ℎ݈݇) and |۵| corresponds to the interplane spacing ݀; i.e. the Miller

2-3
indices of a lattice plane correspond to the ℎ, ݇, ݈ coordinates of the shortest reciprocal
lattice vector normal to that plane.

For ۵௛௞௟ with ℎ, ݇ and ݈ that do have a common factor, the planes with spacing

2ߨ
݀௛௞௟ =
|۵௛௞௟ |

are not all lattice planes, but there will be a set of lattice planes with ݀ = ݊ ⋅ ݀௛௞௟ where ݊ is
an integer.

planes with spacing

lattice planes with

spacing

ௗ
We can then rewrite Bragg’s law as 2 ቀ ቁ sin ߠ = ߣ or
௡

2݀௛௞௟ sin ߠ = ߣ
ଶగ
Since ݀௛௞௟ = |۵ , we have an easy way of calculating the interplane distances, e.g., for
೓ೖ೗ |
భ
ଶగ
cubic crystals |۵௛௞௟ | = (ℎଶ + ݇ ଶ + ݈ ଶ )మ ( ) and
௔

௖௨௕௜௖
ܽ
݀௛௞௟ =
√ℎଶ + ݇ ଶ + ݈ଶ

2-4
Examples of reciprocal lattices:

3D orthorhombic lattice

Direct lattice: ‫܉‬ଵ ⊥ ‫܉‬ଶ ⊥ ‫܉‬ଷ , ܽଵ ≠ ܽଶ ≠ ܽଷ

Reciprocal lattice:
ଶగ‫܉‬మ ×‫܉‬య ଶగ ଶగ‫܉‬య ×‫܉‬భ ଶగ ଶగ‫܉‬భ ×‫܉‬మ ଶగ
‫܊‬ଵ = = ‫܉‬ො , ‫܊‬ଶ = = ‫܉‬ො , ‫܊‬ଷ = = ‫܉‬ො
|‫܉‬భ ⋅ (‫܉‬మ ×‫܉‬య )| ௔భ ଵ |‫܉‬భ ⋅ (‫܉‬మ ×‫܉‬య )| ௔మ ଶ |‫܉‬భ ⋅ (‫܉‬మ ×‫܉‬య )| ௔య ଷ

where ‫܉‬ො௜ is a unit vector in the direction of ‫܉‬௜ .

2D hexagonal lattice

ଵ √ଷ
Direct lattice: ‫܉‬ଵ = ܽ‫ܠ‬, ‫܉‬ଶ = ܽ ቀ− ‫ ܠ‬+ ‫ܡ‬ቁ
ଶ ଶ

Reciprocal lattice (assume ‫܉‬ଷ ⊥ ‫܉‬ଵ , ‫܉‬ଶ ):

ଶగ‫܉‬మ ×‫܉‬య ଶగ ଶ √ଷ ଵ
‫܊‬ଵ = = ቀ ‫ ܠ‬+ ‫ܡ‬ቁ
|‫܉‬భ ⋅ (‫܉‬మ ×‫܉‬య )| ௔ √ଷ ଶ ଶ

ଶగ‫܉‬మ ×‫܉‬య ଶగ ଶ
‫܊‬ଵ = = ‫ܡ‬
|‫܉‬భ ⋅ (‫܉‬మ ×‫܉‬య )| ௔ √ଷ

i.e., the reciprocal lattice of a 2D hexagonal lattice is a 2D hexagonal lattice rotated

by 30⁰ with respect to the direct lattice.

1D lattice

Direct lattice primitive vector: ‫܉‬ଵ

Reciprocal lattice: (assume ‫܉‬ଷ ⊥ ‫܉‬ଵ ⊥ ‫܉‬ଶ )

ଶగ
‫܊‬ଵ = ‫܉‬ො
௔భ ଵ

BCC/FCC lattice

The reciprocal lattice of BCC is FCC and vice versa (see homework exercise).

2-5
Laue condition for diffraction
The Bragg formulation of diffraction assumed specular reflection (angle of incidence = angle
of reflection) of X-rays from lattice planes. The von Laue approach assumes the crystal is
made of identical atoms (or sets of atoms) at lattice sites that scatter X-rays elastically, i.e.
without change in energy (wavelength) of the X-rays.

Consider elastic scattering of a plane

EM wave ݁ ௜‫ ܚ⋅ܓ‬by an atom at ‫ܚ‬. Relative
to the wave scattered by an atom at the O
origin, it picks up an additional phase
ଶగ
difference Δ߶ = (݈ଵ + ݈ଶ ). wave
ఒ
fronts
ଶగ
Since |‫ ܓ| = |ܓ‬ᇱ | = (elastic
ఒ
scattering), Δ߶ = (‫ ܓ‬− ‫ ܓ‬ᇱ ) ⋅ ‫ ≡ ܚ‬− ⋅ ‫ܚ‬,
where = ‫ ܓ‬ᇱ − ‫ ܓ‬is the scattering vector (aka momentum transfer vector2).

If the atoms are separated by lattice vectors ௜ , scattering from all atoms will be in phase if
⋅ = 2ߨ × integer for all ௜ . This is satisfied for all

=۵

This is the Laue condition for diffraction.

Equivalence of Bragg and Laue conditions

۵ is always perpendicular to the (ℎ݈݇) planes
ଶగ
with spacing ݀ = . Therefore, when the Laue
ห۵ห
condition is satisfied, is also normal to the
scattering planes. Since |‫ ܓ| = |ܓ‬ᇱ |, we have the
usual Bragg (specular) geometry. Thus,
starting from the Laue condition, we have

2ߨ
|۵| = | | = 2|‫ |ܓ‬sin ߠ =
݀
ଶగ
Using |‫= |ܓ‬ and rearranging gives 2݀ sin ߠ = ߣ, i.e. Bragg’s condition.
ఒ

Ewald sphere

The Laue condition for diffraction is very restrictive. In practice, to access the different lattice
points in reciprocal space, we have to rotate the crystal (and/or the beam). The Ewald
construction gives a useful visual representation of what’s required to satisfy the Laue
condition.
Let’s fix the incoming beam direction to be horizontal, as in the figure below. As we rotate
the crystal around the different axes, its lattice and therefore its reciprocal lattice rotate with
it. For a certain X-ray wavelength ߣ, the magnitude of ‫( ܓ‬and ‫ ܓ‬ᇱ ) is fixed and therefore all

2
The name momentum transfer comes from the fact that ℏ‫ ܓ‬corresponds to the momentum of the X-ray
photon and therefore ℏ is the change in the momentum of the scattered photon.

2-6
possible scattering vectors ൌ ‫ ܓ‬ᇱ െ ‫ ܓ‬lie on the surface of a sphere—the Ewald sphere—of
radius |‫|ܓ‬. The Laue condition can then be satisfied if the orientation of the crystal with
respect to the incident beam is such that a reciprocal lattice point at some ۵௛௞௟ lies on the
Ewald sphere. Then, for an appropriate position of the detector (i.e. when the detector is
positioned at an angle ʹߠ that satisfies the Bragg law for ݀௛௞௟ ൌ ʹߨȀ|۵௛௞௟ |), diffraction will be
observed.

Calculation of scattered intensities

The Bragg and Laue conditions give us the general requirement for constructive interference
of waves diffracted by a crystalline lattice. To calculate the scattered intensities, we need to
add up the scattering amplitudes from each atom in the basis, or more precisely, from the
electron distributions of each atom, as it is the electrons that interact with the X-rays.

solid

incident
wave
O
scattered
wave

Consider a general solid. Assume amplitude of wave scattered from volume ܸ݀ is

proportional to ݊(‫ ܸ݀)ܚ‬where ݊(‫ )ܚ‬is the local electron density. As before, the additional
phase difference picked up by the wave (compared to that scattered at the origin) ȟ߶ ൌ
(‫ ܓ‬െ ‫ ܓ‬ᇱ ) ‫ ܚ ڄ‬ൌ െ ‫ܚ ڄ‬, therefore the total amplitude of the EM wave scattered in direction ‫ ܓ‬ᇱ is
proportional to the integral

‫ ) (ܨ‬ൌ න ݊(‫ି ݁)ܚ‬௜ ‫ܚڄ‬

ܸ݀
௦௢௟௜ௗ

2-7
This integral is known as the scattering amplitude. It is just the Fourier transform of the
electron density function ݊(‫)ܚ‬. If we could measure ‫ ) (ܨ‬for all the different (i.e. different
direction of ‫ ܓ‬− ‫ ܓ‬ᇱ ) we could obtain the electron distribution directly by inverse Fourier
transform of ‫) (ܨ‬. Unfortunately, ‫ ) (ܨ‬is a complex function and experimentally we can only
measure the diffracted intensity ‫|ܨ| ∝ ܫ‬ଶ , thereby losing the information about the phase of
‫) (ܨ‬.

If our solid is a crystal, ݊(‫ )ܚ‬will have the periodicity of the crystal, i.e. ݊(‫ ܚ(݊ = )ܚ‬+ ).
Additionally, when the diffraction condition is satisfied = ۵ and

‫(ܨ‬۵) = ܰ න ݊(‫ି ݁)ܚ‬௜۵⋅‫ܵܰ ≡ ܸ݀ ܚ‬۵

௖௘௟௟

Where ܰ is the number of unit cells in the crystal and ܵ۵ is known as the structure factor.
The entire function ݊(‫ )ܚ‬of a crystal is therefore encoded in a set of discrete complex
numbers ܵ۵ .

It is convenient to separate ݊(‫ )ܚ‬into contributions from individual atoms at positions ‫ܚ‬௝ , i.e.
݊(‫∑ = )ܚ‬௕௔௦௜௦
௝ ݊௝ ൫‫ ܚ‬− ‫ܚ‬௝ ൯ = ∑௕௔௦௜௦
௝ ݊௝ ൫ૉ௝ ൯ where ૉ௝ = ‫ ܚ‬− ‫ܚ‬௝ is the position vector relative to the
centre of atom. Then,

௕௔௦௜௦

ܵ۵ = ෍ න ݊௝ ൫ૉ௝ ൯݁ ି௜۵⋅ૉ ݁ ି௜۵⋅‫ܚ‬ೕ ܸ݀

௝ ௖௘௟௟

௕௔௦௜௦

= ෍ ݁ ି௜۵⋅‫ܚ‬ೕ න ݊௝ ൫ૉ௝ ൯݁ ି௜۵⋅ૉ ܸ݀

௝ ௖௘௟௟

or
௕௔௦௜௦

ܵ۵ = ෍ ݂௝ ݁ ି௜۵⋅‫ܚ‬ೕ
௝

where ݂௝ = ∫௖௘௟௟ ݊௝ ൫ૉ௝ ൯݁ ି௜۵⋅ૉ ܸ݀ is the atomic form factor, the amplitude scattered by the
atom.

݂௝ (۵) contains information about the structure of the atom (remember, ݊(‫| = )ܚ‬Ψ|ଶ ). Most of
the electron density remains unchanged when atoms are integrated into a crystal and
therefore we can use the ݂௝ calculated for isolated atoms. Atoms have spherical symmetry
and so do the ݂௝ . If we assume atoms are point-like, i.e. its electron density distribution can
be represented as a delta function ݊(ૉ) = ܼߜ(ૉ), then ݂ = ܼ, the atomic number. In reality,
݂௝ (۵) decreases with |۵| and tends to zero as |۵| → ∞ (e.g., see Kittel’s book). To
determine the crystal structure accurately we need to measure as many (ℎ݈݇) reflections as
possible but this becomes difficult for larger (ℎ݈݇) (larger with |۵|) since ݂௝ (۵) → 0.

2-8
Example

Diffraction from the FCC lattice

We are now ready to treat the diffraction from a structure with a multi-atom basis. The
FCC structure has four lattice points per conventional unit cell. We can decompose
this structure into a simple cubic lattice with a four atom basis:
௔ ௔ ௔ ௔ ௔ ௔
(0,0,0), ቀ , , 0ቁ , ቀ , 0, ቁ and ቀ0, , ቁ
ଶ ଶ ଶ ଶ ଶ ଶ

The reciprocal lattice of a simple cubic lattice is also a simple cubic lattice with
ଶగ
reciprocal lattice vectors ۵ = (ℎ, ݇, ݈). The structure factor is therefore
௔

ி஼஼
ܵ௛௞௟ = ෍ ݂௝ ݁ ି௜۵⋅‫ܚ‬ೕ = ݂൫1 + ݁ ି௜గ(௛ା௞) + ݁ ି௜గ(௞ା௟) + ݁ ି௜గ(௛ା௟) ൯
௝

= ݂൫1 + (−1)௛ା௞ + (−1)௞ା௟ + (−1)௛ା௟ ൯

4݂if ℎ݈݇are all even or all odd

=ቄ
0 otherwise

So, in order of increasing ℎଶ + ݇ ଶ + ݈ ଶ (i.e. increasing |۵|), we have

ℎ݈݇ ி஼஼
ܵ௛௞௟ ℎଶ + ݇ ଶ + ݈ ଶ
100 0 1
110 0 2
111 4f 3
200 4f 4
210 0 5
211 0 6
220 4f 8
221 0 9
300 0 9

Note that the ۵ vectors with non-zero intensity generate a BCC lattice (as expected,
since the reciprocal lattice of FCC is BCC!).

Similarly, for BCC we find that

஻஼஼ 2݂if ℎ + ݇ + ݈ = even

ܵ௛௞௟ =ቄ
0 if ℎ + ݇ + ݈ = odd

The missing peaks for certain (ℎ݈݇), e.g. (100) for FCC and BCC, are known as
missing orders. They are due to destructive interference by atoms in the basis. For
example, for the FCC structure, when Bragg’s law is satisfied for the (100) planes, the
atoms in the planes half-way between contribute a phase difference of ߨ and thus
contributes scattered amplitude that is exactly out-of-phase.

2-9
Structure determination from powder diffraction
X-ray powder diffraction is one of the most common methods for determining the structure of
materials.

The powder sample ensures that as long as ʹߠ is chosen to satisfy Bragg’s law for some
(݄݈݇), there will be some powder grains oriented correctly for specular ‘reflection’ of the X-
ray beam. The experiment then consists of scanning the angle ʹߠ and recording the
scattered intensity on the detector. Often neither the structure nor the lattice parameters are
known and therefore the simple procedure is to apply Bragg’s law on a trial and error basis
until a good fit is obtained.

Example

Let’s assume we want to find out whether a particular diffraction pattern corresponds to a
simple cubic or BCC structure.
௔
For a cubic material, we have ݀ ൌ . Therefore, Bragg’s law ʹ݀ •‹ ߠ ൌ ߣ gives
ξ௛ మ ା௞ మ ା௟మ

ߣଶ ଶ
sinଶ ߠ ൌ (ℎ ൅ ݇ ଶ ൅ ݈ ଶ )
Ͷܽଶ

If experimentally, the peaks in intensity are observed at ʹߠ values ʹߠଵ ǡ ʹߠଶ ǡ ʹߠଷ …etc, then we
first need to index the observed reflections (i.e. identify their ݄݈݇ values). Since the lattice
parameter ܽ is also unknown, we eliminate it by taking ratios of the nth to 1st peak, which
according to the equation above should be given by

sinଶ ߠ௡ (ℎଶ ൅ ݇ ଶ ൅ ݈ ଶ )௡
=
sinଶ ߠଵ (ℎଶ ൅ ݇ ଶ ൅ ݈ ଶ )ଵ

To distinguish between simple cubic and BCC, we calculate the (ℎଶ ൅ ݇ ଶ ൅ ݈ ଶ ) ratios for all
allowed (݄݈݇) reflections for the two structures and then compare these to the experimental
sinଶ ߠ ratios. For the simple cubic structure, all (݄݈݇) are allowed, whereas for BCC, only
those with ℎଶ ൅ ݇ ଶ ൅ ݈ ଶ = even give non-zero intensity, therefore we have

2-10
 Simple cubic BCC
ℎ݈݇ ℎଶ + ݇ ଶ + ݈ ଶ (ℎଶ + ݇ ଶ + ݈ ଶ )௡ ℎ݈݇ ℎ + ݇ ଶ + ݈ଶ
ଶ (ℎଶ + ݇ ଶ + ݈ ଶ )௡
(ℎଶ + ݇ ଶ + ݈ ଶ )ଵ (ℎଶ + ݇ ଶ + ݈ ଶ )ଵ
100 1 1 110 2 1
110 2 2 200 4 2
111 3 3 211 6 3
200 4 4 220 8 4
210 5 5 310 10 5
211 6 6 222 12 6
220 8 8 321 14 7

We see that for the two structures differ in the value of the 7th (ℎଶ + ݇ ଶ + ݈ ଶ ) ratio and
therefore experimentally one could distinguish between them by the absence or presence of
ୱ୧୬మ ఏ೙
= 7.
ୱ୧୬మ ఏభ

For structures of lower symmetry than cubic, other peaks appear as some of the {ℎ݈݇}
planes that were equivalent by symmetry in the cubic structure are no longer symmetry
equivalent (i.e. the planes do not have the same spacing). For example, for the lattice below,
݀ଵଵ଴ ≠ ݀ഥଵଵ଴ and therefore the (110) and (1ത 10) reflections will appear at different 2ߠ angles.

Once the ℎ݈݇ values for all the reflections are known, we can calculate the lattice
parameter(s) using Bragg’s law from a given reflection (or subset of reflections).

2-11
Diffraction from powdered samples leads to rings of intensity at specific values of ʹߠ, known
as Debye-Scherrer rings.

2-12
Examples of powder diffraction patterns from cubic crystals:

(011)
ߣ = 0.154 nm, ܽ = 0.412 nm

(112)
(001)

Simple
(002)

(012)
(111)

(013)
cubic

(022)
(122)

(113)
(no restrictions)

ߣ = 0.154 nm, ܽ = 0.564 nm

(002)

(022)

(024)

Face centred
(222)

cubic
(004)
(111)

h,k,l all even or all odd

(113)

(133)

only

2-13
Brillouin zones
As for the direct lattice, we can define unit cells for the reciprocal lattice. The most important
unit cell is the Brillouin Zone (BZ), which is the Wigner-Seitz cell of the reciprocal lattice.
Recall that it is formed from perpendicular bisectors of lines from a reciprocal lattice point
(that we choose as the origin) to all nearest reciprocal lattice points. E.g., for a square
(reciprocal) lattice we have

Brillouin zone
boundary

1st Brillouin
zone

The first Brillouin zone has the same volume as the primitive unit cell of the reciprocal lattice.
Higher zones can also be defined, e.g., the 2nd BZ is formed by the perpendicular bisectors
to the next nearest neighbours, etc. All BZs have the same volume.

The Brillouin zone plays a very special role in the theory of propagation of waves in crystals
(be it electromagnetic waves, electron waves, lattice waves, etc.) and facilitates the
statement of a very general condition for diffraction of waves in crystals.

For the square lattice above, when the Laue condition ۵ = = ‫ ܓ‬ᇱ − ‫ ܓ‬is satisfied, ‫ܓ‬
terminates on the BZ boundary (BZB). This is a sufficient condition for diffraction, i.e., if a
wavevector terminates on the BZB, the wave will be diffracted.

Direct lattice Reciprocal space

BZB

Lattice planes

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Proof:

The Laue condition says that diffraction occurs when ‫ ܓ‬ᇱ − ‫ = ܓ‬reciprocal lattice vector. If
when ‫ ܓ‬ᇱ − ‫ ܓ‬is a reciprocal lattice vector, then so is when ‫ ܓ‬− ‫ܓ‬′ (in the sketch above, both
۵ଵ଴૙ and ۵ଵ଴૙ satisfy the Laue condition). Let this reciprocal lattice vector be ۵, i.e. let
‫ ܓ‬− ‫ ܓ‬ᇱ = ۵, then

‫ܓ‬ᇱ = ‫ ܓ‬− ۵

|‫ ܓ‬ᇱ |ଶ = |‫|ܓ‬ଶ + |۵|ଶ − 2‫ ⋅ ܓ‬۵

For elastic scattering considered here, |‫ ܓ‬ᇱ | = |‫ |ܓ‬and therefore

2‫ ⋅ ܓ‬۵ = |۵|ଶ

෡= ۵,
or, defining the unit vector ۵ |۵|

1
෡ = |۵|
‫⋅ܓ‬۵
2
ଵ
So, when the component of ‫ ܓ‬parallel to ۵ is |۵| (i.e., when ‫ ܓ‬lies on the Brillouin zone
ଶ
boundary), the Laue condition is satisfied and the wave will be diffracted. We will see later
the consequences of this for lattice waves and electron waves in crystals.

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