Wave Diffraction and Reciprocal

Lattice

1
❑ Diffraction of Waves by Crystals
▪ the Bragg Laws
❑ Scattered wave amplitude
❑ Reciprocal Lattice
❑ Brillouin Zones
❑ Fourier Analysis of the Basis
▪ structural factor
▪ atomic form factor
2
 Diffraction of Waves by Crystals
Bragg Law
We study crystal structure through the diffraction of photons, neutrons, and electrons
(Fig. 1). The diffraction depends on the crystal structure and on the wavelength.

Figure 1 Wavelength versus particle energy,

for photons, neutrons, and electrons.

3
 Bragg Law of Diffraction
➢ W. L. Bragg presented a simple explanation of the law of diffraction
beams from a crystal.
➢ The incident waves are reflected specularly (mirror-like) from parallel
planes of atoms in the crystals. In the specular reflection, the angle of
incidence is equal to the angle of reflection.
➢ The diffracted beams are found when the reflections from parallel
planes of atoms interfere constructively.
➢ Elastic scattering is considered here that the energy of x-rays is not
changed upon reflection.

4
Figure 2 Derivation of the Bragg equation here 2𝑑 sin 𝜃 = 𝑛𝜆 is the spacing of parallel
atomic planes and is 2𝜋𝑛 the difference in phase between reflections from successive
planes. The reflecting planes have nothing to do with the surface planes bounding the
particular specimen.
5
 Diffraction of Waves by Crystals

Constructive
interference of the
radiation from
successive planes
occurs when the path
difference is an
integral number 𝑛 of
wavelengths 𝜆, so that The Bragg law:
2𝑑 sin 𝜃 = 𝑛𝜆 (1)
6
 XRD
The Bragg law:
2𝑑 sin 𝜃 = 𝑛𝜆

500

400
(111) (220)

Intensity (cps)
300
(311)
200

100

0
10 15 20 25 30 35 40 45 50 55 60
2θ(o)

Single Crystal Silicon Powder

7
 A Monochromator Set-up

(110)

n=1 n=2 n=3

2 (d/n) sin = 

Figure 3 Sketch of a monochromator which by Bragg reflection selects a narrow spectrum of x-

ray or neutron wavelengths from a broad spectrum incident beam. The upper part of the figure
shows the analysis (obtained by reflection from a second crystal) of the purity of a 1.16 Å beam
of neutrons from a calcium fluoride crystal monochromator. (After G. Bacon.) 8
 Silicon Diamond Crystal Structure

Figure 4 X-ray
diffractometer recording of
powdered silicon, showing a
counter recording of the
diffracted beams. (Courtesy
of W. Parrish.) X-ray Powder diffraction pattern of Si 9
Standard flat orientations for different semiconductor wafers
10
 SCATTERED WAVE AMPLITUDE
(a)

The Bragg derivation of the diffraction

condition (1) gives a neat statement of the
condition for the constructive interference of
(b) waves scattered from the lattice points.
We need a deeper analysis to determine
the scattering intensity from the basis of atoms,
(c) which means from the spatial distribution of
electrons within each cell.

11
 From (1, 3), a crystal is invariant under any translation of the form 𝐓 =
𝒖𝟏 𝐚𝟏 + 𝒖𝟐 𝐚𝟐 + 𝒖𝟑 𝐚𝟑 , where 𝑢1 , 𝑢2 , 𝑢3 are integers and 𝑎1 , 𝑎2 , 𝑎3 are
the crystal axes. Any local physical property of the crystal is
invariant under 𝐓, such as the charge concentration, electron number
density, or magnetic moment density.

Fourier Analysis
Electron number density 𝑛 𝐫 is a periodic function of 𝐫 ,
𝑛 𝐫+𝐓 =𝑛 𝐫 (2)
▪ Such periodicity creates an ideal situation for Fourier analysis.
▪ The most interesting properties of crystals are directly related to the
Fourier components of the electron density.
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 We consider first a function n(x) in one dimension with period a in
the direction x. We expand n(x) in a Fourier series of sines and cosines:

1-D 𝑛 𝑥 = 𝑛0 + ෍ 𝐶𝑝 cos 2𝜋𝑝𝑥 Τ𝑎 + 𝑆𝑝 sin 2𝜋𝑝𝑥 Τ𝑎 𝑝>0

𝑝>0 (3)
where the 𝑝 are positive integers and 𝐶𝑝 , 𝑆𝑝 are real constants, called the
Fourier coefficients of the expansion.
The factor 2𝜋Τ𝑎 in the arguments ensures that n(x) has the period a:

𝑛 𝑥 + 𝑎 = 𝑛0 + ෍ 𝐶𝑝 cos 2𝜋𝑝𝑥 Τ𝑎 + 2𝜋𝑝 + 𝑆𝑝 sin 2𝜋𝑝𝑥 Τ𝑎 + 2𝜋𝑝

= 𝑛0 + ෍ 𝐶𝑝 cos 2𝜋𝑝𝑥 Τ𝑎 + 𝑆𝑝 sin 2𝜋𝑝𝑥 Τ𝑎 =𝑛 𝑥

𝑝>0 (4)
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 We say that 2𝜋𝑝Τ𝑎 is a point in the reciprocal lattice or Fourier space of
the crystal. In one dimension these points lie on a line. The reciprocal lattice
points tell us the allowed terms in the Fourier series (4) or (5). A term is
allowed if it is consistent with the periodicity of the crystal, as in Fig. 5.

Figure 5 A periodic function

n(x) of period a, and the
terms 2𝜋𝑝Τ𝑎 that may appear
in the Fourier transform
𝑛 𝑥 = σ 𝑛𝑝 exp 𝑖 2𝜋𝑝𝑥Τ𝑎 .

14
 It is convenient to write the series (4) in the compact form

1-D 𝑛 𝑥 = ෍ 𝑛𝑝 exp 𝑖 2𝜋𝑝𝑥 Τ𝑎 (5)

𝑝
where the sum is over all integers 𝑝: positive, negative, and zero. The
coefficients 𝑛𝑝 now are complex numbers. To ensure that 𝑛 𝑥 is a real
function, we require ∗
∗
𝑛 −𝑝 = 𝑛 𝑝 (6)
𝑛−𝑝 = 𝑛𝑝 ,
∗
for then the sum of the terms in 𝑝 and −𝑝 is real. The asterisk on 𝑛−𝑝 denotes
the complex conjugate of 𝑛−𝑝 .
Proof With φ = 2𝜋𝑝𝑥 Τ𝑎, the sum of the terms in 𝑝 and −𝑝 in (5) is real if (6)
is satisfied. The sum is
𝑛𝑝 cos 𝜑 + 𝑖 sin 𝜑 + 𝑛−𝑝 cos 𝜑 − 𝑖 sin 𝜑 (7)
= 𝑛𝑝 + 𝑛−𝑝 cos 𝜑 + 𝑖 𝑛𝑝 − 𝑛−𝑝 sin 𝜑
which in turn is equal to the real function 15
 (7)
𝑛𝑝 cos 𝜑 + 𝑖 sin 𝜑 + 𝑛−𝑝 cos 𝜑 − 𝑖 sin 𝜑
= 𝑛𝑝 + 𝑛−𝑝 cos 𝜑 + 𝑖 𝑛𝑝 − 𝑛−𝑝 sin 𝜑
The real function
2𝑅𝑒 𝑛𝑝 cos 𝜑 − 2𝐼𝑚 𝑛𝑝 sin 𝜑 (8)
if (6) is satisfied. Here 𝑅𝑒 𝑛𝑝 and 𝐼𝑚 𝑛𝑝 are real and denote the real
and imaginary parts of 𝑛𝑝 . Thus the number density 𝑛 𝑥 is a real function, as
desired.

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 The extension of the Fourier analysis to periodic functions 𝑛 𝒓 in three
dimensions is straightforward. We must find a set of vectors 𝐆 such that
3-D (9)
𝑛 𝐫 = ෍ 𝑛𝑮 exp 𝑖𝐆 ∙ 𝐫
𝐆
is invariant under all crystal translations 𝐓 that leave the crystal invariant. It
will be shown below that the set of Fourier coefficients 𝑛𝐆 determines the
x-ray scattering amplitude.

17
Inversion of Fourier Series
We now show that the Fourier coefficient 𝑛𝑝 in the series (5) is given by
𝑎 To prove this identity eq. (10)
1-D 𝑛𝑝 = 𝑎−1 න 𝑑𝑥 𝑛 𝑥 exp −𝑖 2𝜋𝑝𝑥 Τ𝑎 (10)
0

Substitute (5) in (10) to obtain 𝒏 𝒙 is now substituted by eq. (5)

𝑎
𝑛𝑝 = 𝑎−1 ෍ 𝑛𝑝′ න 𝑑𝑥 exp −𝑖 2𝜋 𝑝′ − 𝑝 𝑥 Τ𝑎 (11)
0
𝑝′

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If 𝑝′ ≠ 𝑝 the value of the integral is
𝑎 𝑖2𝜋 𝑝 ′ −𝑝
𝑒 − 1 = 0,
𝑖2𝜋 𝑝′ − 𝑝
because 𝑝′ − 𝑝 is an integer and exp 𝑖2𝜋 integer = 1. For the term 𝑝′ = 𝑝
the integrand is exp 𝑖0 = 1, and the value of the integral is 𝑎, so that 𝑛𝑝 =
𝑎−1 𝑛𝑝 𝑎 = 𝑛𝑝 , which is an identity, so that (10) is an identity.
As in (10), the inversion of (9) gives

(12)
3-D 𝑛𝐆 = 𝑉𝑐−1 න 𝑑𝑉 𝑛 𝐫 exp −𝑖𝐆 ∙ 𝐫 .
cell
Here 𝑉𝑐 is the volume of a cell of the crystal.

19
 Reciprocal Lattice Vector
To proceed further with the Fourier analysis of the electron concentration
we must find the vectors 𝐆 of the Fourier sum σ𝐆 𝑛𝑮 exp 𝑖𝐆 ∙ 𝐫 as in (9).
We construct the axis vectors 𝐛1 , 𝐛2 , 𝐛3 of the reciprocal lattice:
𝐚2 × 𝐚3 𝐚3 × 𝐚1 𝐚1 × 𝐚2
𝐛1 = 2𝜋 ; 𝐛2 = 2𝜋 ; 𝐛3 = 2𝜋 . (13)
𝐚1 ∙ 𝐚2 × 𝐚3 𝐚1 ∙ 𝐚2 × 𝐚3 𝐚1 ∙ 𝐚2 × 𝐚3

If a1, a2, a3 are primitive vectors of the crystal lattice, then b1, b2, b3 are
primitive vectors of the reciprocal lattice. Each vector defined by (13) is
orthogonal to two axis vectors of the crystal lattice. Thus b1, b2, b3 have the
property 𝐛𝑖 ∙ 𝑎𝑓 = 2𝜋𝛿𝑖𝑗 , (14)
where 𝛿𝑖𝑗 = 1 if 𝑖 = 𝑗 and 𝛿𝑖𝑗 = 0 if 𝑖 ≠ 𝑗
20
 Points in the reciprocal lattice are mapped by the set of vectors
𝐆 = 𝒗𝟏 𝐛𝟏 + 𝒗𝟐 𝐛𝟐 + 𝒗𝟑 𝐛𝟑 (15)
where v1, v2, v3 are integers. A vector G of this form is a reciprocal lattice
vector.
The vectors G in the Fourier series (9) are just the reciprocal lattice
vectors (15), for then the Fourier series representation of the electron density
has the desired invariance under any crystal translation 𝐓 = 𝒖𝟏 𝐚𝟏 + 𝒖𝟐 𝐚𝟐 +
𝒖𝟑 𝐚𝟑 . From (9),

𝑛 𝐫 + 𝐓 = ෍ 𝑛𝑮 exp 𝑖𝐆 ∙ 𝐫 exp 𝑖𝐆 ∙ 𝐓 (16)

𝐆

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But exp 𝑖𝐆 ∙ 𝐓 = 𝟏, because
exp 𝑖𝐆 ∙ 𝐓 = exp 𝑖 𝒗𝟏 𝐛𝟏 + 𝒗𝟐 𝐛𝟐 + 𝒗𝟑 𝐛𝟑 ∙ 𝒖𝟏 𝐚𝟏 + 𝒖𝟐 𝐚𝟐 + 𝒖𝟑 𝐚𝟑
= exp 𝑖2𝜋 𝑣1 𝑢1 + 𝑣2 𝑢2 + 𝑣3 𝑢3
The argument of the exponential has the form 2𝜋𝑖 times an integer,
because 𝑣1 𝑢1 + 𝑣2 𝑢2 + 𝑣3 𝑢3 is an integer, being the sum of products of
integers. Thus by (9) we have the desired invariance, 𝑛 𝐫 + 𝐓 =
𝑛 𝐫 = σ 𝑛𝑮 exp 𝑖𝐆 ∙ 𝐫 .

This result proves that the Fourier representation of a function

periodic in the crystal lattice can contain components 𝑛𝑮 expሺ𝑖𝐆 ∙
𝐫ሻ only at the reciprocal lattice vectors 𝐆 as defined by (15).
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❑ Every crystal has two lattices associated with it: the crystal lattice,
and the reciprocal lattice.
➢ A diffraction pattern of a crystal is, as we shall show, a map of the
reciprocal lattice of the crystal. A microscope image, if it could be
resolved on a fine enough scale, is a map of the crystal structure
in real space.
➢ A diffraction pattern of a crystal is, as we shall show, a map of the
reciprocal lattice of the crystal. A microscope image, if it could be
resolved on a fine enough scale, is a map of the crystal structure
in real space. The two lattices are related by the definitions (13).
Thus when we rotate a crystal in a holder, we rotate both the
direct lattice and the reciprocal lattice.

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 ➢ Vectors in the direct lattice have the dimensions of [length];
vectors in the reciprocal lattice have the dimensions of [l/length].
❑ The reciprocal lattice is a lattice in the Fourier space associated with
the crystal.

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Gold
FCC
 Si
Diamond
 50
45 Silicon
40
35
Intensity (a.u.)

30
25 (311)
20 (111)
(220)
15
10
5
0
10 20 30 40 50 60 70 80
2 (Degree)