Chapter 4

Crystal lattice and waves — the

reciprocal lattice

• Quantum mechanics → particle-wave-dualism

• basic question:
what is the effect of the periodic crystal lattice on a wave transmitted through a
solid?

• examples for such waves:

– mobile electrons in the solid

– lattice vibrations (phonons)
– irradiation with light, x-rays, neutrons

• most important process:

incident or transmitted waves are partially reflected at (parallel) lattice planes.

• effects are strong when the wavelength λ is of the order of the lattice constant or
the distance between parallel lattice planes.

Figure 4.1: Wavelength versus particle energy,

for photons, neutrons and electrons. [from Kit-
tel, Introduction to solid state physics (1996);
Fig.2.1].

59
60 Chapter 4 Crystal lattice and waves — the reciprocal lattice

• discussion of x-ray- or neutron diffration:

Figure 4.2: [from

Kleiner, lecture notes
(2002); Abb.40-01].

– condition for constructive interference of waves, which are scattered from

different lattice points: the Bragg Law

Figure 4.3: Derivation of the Bragg equation 2d · sin Θ = nλ; d is the spacing of parallel
atomic planes and 2πn is the difference in phase between reflections from successive
planes. The reflecting planes have nothing to do with the surface planes bounding the
particular specimen. [from Kittel, Introduction to solid state physics (1996); Fig.2.2].

– let’s assume the angle between the incident wave and the lattice plane is Θ.
– the retardation (’Gangunterschied’) between two waves which are scattered
on neighboring lattice planes is 2 · d · sin Θ.
– constructive interference occurs for

2 · d · sin Θ = nλ with n = ±1, ±2, . . . (Bragg law) (4.1)

 61

Notes:

• the Bragg reflection can only occur for λ ≤ 2d;

if λ À d (e.g. for visible light): process described by index of refraction

• photons:
not electrically charged → mostly relatively weak interaction
Bragg reflection requires much shorter wavelength → x-rays
energy of photons from x-rays (keV) À typical energy in a solid (meV. . . eV)
each lattice plane reflects only 10−3 to 10−5 of the incident radiation.
→ 103 to 105 lattice planes may contribute to the Bragg-reflected beam.

• electrons:
electrically charged → very strong interaction,
absorption in the lattice planes close to the surface of a crystal
for wavelengths in the Å-regime: electron energy ≈ 100 eV

• neutrons:
not electrically charged, but carry a magnetic moment:
→ relatively weak interaction,
reach far into the crystal,
’see” also magnetic properties (e.g. magnetic ordering)
for wavelengths in the Å-regime: Energy ≈ 0.1 eV
corresponds to typical energies in a solid
→ neutron (almost) ideally suited for spectroscopy with energy- and
momentum-resolution.
→ Disadvantage: requires large crystals (≈mm3 ) which are often not
available
• elekcrons and lattice vibrations in a crystal:
kinetic properties (energy-momentum-relation) are strongly modified,
when the Bragg law is fulfilled:
generation of standing waves → imobile elektrons/phonons

• Bragg law is a consequence of the lattice;

further modification is due to the structure of the Basis
62 Chapter 4 Crystal lattice and waves — the reciprocal lattice

Scattered wave amplitude (for x-rays)

Figure 4.4: The difference in path length of the incident wave ~k at the points O und ~r
is r sin ϕ, and the difference in phase angle is (2πr sin ϕ)/λ, which is equal to ~k · ~r. For
the diffracted wave the difference in phase angle is −~k 0 ·~r. The total difference in phase
angle is (~k − ~k 0 ) · ~r, and the wave scattered from the volume element dV at location ~r
has the phase factor exp[i(~k − ~k 0 ) · ~r] [from Kittel, Einführung in die Festkörperphysik
(1999); Fig.2.6].

• phase difference between waves scattered at ”0” and at the volume element ”dV ”:
~ ~0
ei(k−k )·~r

• amplitude of the wave which is scatterd in dV is proportional to the local electron

concentration n(~r).
⇒ total scattered amplitude:
Z Z
i(~k−~k0 )~
r ~
F = dV n(~r)e ≡ dV n(~r)e−i∆k~r
crystalvol. crystalvol.

where we defined the scattering vector as ∆~k = ~k 0 − ~k.

• now we employ the periodicity of the crystal:

electron density n(~r) is invariant under lattice translation T~ : n(~r + T~ ) = n(~r)
⇒ n(~r) can be represented as a 3D-Fourierseries:
X ~
n(~r) = nG~ · eiG~r
G
 63

• task:
determine G~ (=”reciprocal lattice vector”)
in such a way that n(~r + T~ ) = n(~r) is valid.
~ = v1~b1 + v2~b2 + v3~b3 with integer v1 , v2 , v3 and:
• solution: G

~b1 = 2π ~a2 × ~a3

|~a1 · (~a2 × ~a3 )|
~b2 ~a3 × ~a1
= 2π
|~a1 · (~a2 × ~a3 )|
~b3 ~a1 × ~a2
= 2π
|~a1 · (~a2 × ~a3 )|

The vektors ~b1 , ~b2 , ~b3 are the axis verctors of the ”reciprocal lattice”

• With the above choice of ~b1 , ~b2 , ~b3 we obtain:

~bi~aj = 2πδij , (with i, j = 1, 2, 3)

X ~ ~
X ~ ~~
n(~r + T~ ) = nG~ eiG(~r+T ) = nG~ eiG~r eiGT
~
G ~
G
X ~ r i2πn
X ~
iG~
= nG~ e e = nG~ eiG~r · 1 = n(~r)
~
G ~
G

q.e.d.
⇒ scattered amplitude
Z X
~ ~ ~
F = dV n(~r)e−i∆k~r = nG~ ei(G−∆k)~r
crystalvol. ~
G

– for ∆~k = G:
~ F = V ol · n ~
G

– for ∆~k 6= G:
~ F ≈0

⇒ scattered x-rays image reciprocal lattice!

64 Chapter 4 Crystal lattice and waves — the reciprocal lattice

Bragg condition and Brillouin zones

Question Is it possible to construct a lattice in ~k-space in such a way that on
the boundaries of the lattice cells Bragg reflection takes place?
If yes, we have found a particularly simple graphic representation
of the (wave-)physic in solids
Answer yes, this is possible; leads to the Brillouin zones
detailed derivation:

• for elastic (x-ray-)scattering: ~ω = ~ω 0 (energy conservation):

• in this case: Bragg condition corresponds to 2~k G

~ = G2 . With ~ω = ~ω 0 :
⇒ |~k| = |~k 0 | due to ω = ck
⇒ k 2 = (k 0 )2
⇒ (~k + G)
~ 2 = k 02 due to ~k + G
~ = ~k 0
⇒ 2~k G
~ + G2 = 0
⇒ 2~k G
~ = G2 since −G
~ is also a reciproal lattice vector

• draw in ~k-space a line from a reciprocal lattice point ”0” to another lattice point;
~ (see figure below)
this shall be a reciprocal lattice vector G
~ a line perpendicular to G
• draw halfway at G/2 ~

• for vector ~k ending at this line, the Bragg condition is fulfilled:

Figure 4.5: Vectors used for derivation of Bragg condition

µ ¶2 Ã !2
G ~
G G~ G2 ~ ~
+ h2 = k 2 ; + ~h = ~k ⇒ h2 = ~k − = k2 + − kG
2 2 2 4
µ ¶2
G G2 ~ ~
⇒ + k2 + − kG = k2
2 4
G2 ~ ~
⇒ = kG q.e.d.
2
• Note: analogous construction was used in real space,
eads to the Wigner-Seitz cell
 65

• Width of diffraction maximum.

We suppose that in a linear crystal there are identical point scattering centers at
every lattice point ρ~m = m~a, where m is
Pan integer. The total scattered radiation
amplitude will be proportional to F = exp[−im~a ·∆~k]. The sum over M lattice
points is
1 − exp[−iM~a · ∆~k]
F = (4.2)
1 − exp[−i~a · ∆~k]
by the use of the series
M −1
X 1 − xM
xm = . (4.3)
m=0
1−x
The scattered intensity is proportional to |F |2 .
~ (~a · ∆~k)
sin2 12 M
2
|F | = (4.4)
sin2 1 (~a · ∆~k)
2

We know that a diffraction maximum appears when (~a · ∆~k) = 2πn, where n is
an integer. We change ∆~k slightly and define ε in (~a · ∆~k) = 2πn + ε such that
~ (~a · ∆~k). It can be shown that
ε gives the position of the first zero in sin2 21 M
ε = 2π/M ~ , so that the width of the diffraction maximum is proportional to 1/M
and can be extremely narrow for macroscopic values of M . The same holds for a
3- dimensional crystal.

• 1. Brillouin zone is identical with the Wigner-Seitz cell in ~k-space

= smallest volume, which is entirely enclosed by planes, which intersect the lattice
vectors (drawn from the origin) perpendicularly at their midpoints)

Figure 4.6: Construction of the first Bril-

louin zone for an oblique lattice in two
dimensions. We first draw a number of
vectors from O to nearby points in the re-
ciprocal lattice. Next we construct lines
perpendicular to these vectors at their
midpoints. The smallest enclosed area is
the 1. Brillouin zone. [from Kittel, In-
troduction to solid state physics (1996);
Fig.2.10].
66 Chapter 4 Crystal lattice and waves — the reciprocal lattice

• Example of a square reciprocal lattice

Figure 4.7: Square reciprocal lattice with

reciprocal lattice vectors shown a fine
black lines. The lines shown in white
are perpendicular bisectors of the recip-
rocal lattice vectors. The central square
is the smallest volume about the origin
which is bounded entirely by white lines.
The square is the Wigner-Seitz primitive
cell of the reciprocal lattice. It is called
the 1. Brillouion zone. [from Kittel, In-
troduction to solid state physics (1996);
Fig.2.9b].

• example: linear crystal lattice

Figure 4.8: Crystal and reciprocal lattices

in one dimension. The basis vector in the
reciprocal lattice is ~b, of length equal to
2π
a
. The shortest reciprocal lattice vectors
from the origin are ~b and −~b. The perpen-
dicular bisectors of these vectors form the
boundaries of the 1. Brillouin zone. The
boundaries are at k = ± πa [from Kittel,
Introduction to solid state physics (1996);
Fig.2.11].

• Brillouin zones of higher order (example: square lattice)

Figure 4.9: [from Kleiner, Lecture Notes

(2000); Fig.46-01].
 67

• Examples of reciprocal lattices in 3D:

real space ~k-space 1. Brillouin zone

simply cubic simply cubic cube; faces at ±a(x̂, ŷ, ẑ)
body-centered cubic face-centered cubic rhomic dodecahedron
face-centered cubic body-centered cubic obtuse (’stumpfes’) octahedron

• simple cubic lattice:

primitive translation vectors in real space:

~a1 = ax̂, ~a2 = aŷ, ~a3 = aẑ

primitive translation vectors in ~k-space:

~b1 = 2π x̂, ~b2 = 2π ŷ, ~b3 = 2π ẑ

a a a
surface of the 1. Brillouin zone: planes
1 π 1 π 1 π
± ~b1 = ± x̂, ± ~b2 = ± ŷ, ± ~b3 = ± ẑ
2 a 2 a 2 a
these planes enclose a cube with edges of length 2π/a and volume
(2π/a)3 .
• body-centered cubic lattice:

Figure 4.10: primitive

basis vectors of the
body centered cubic
lattice [from Kittel,
Introduction to solid
state physics (1996);
Fig.2.12].
68 Chapter 4 Crystal lattice and waves — the reciprocal lattice

primitive translation vectoren in real space:

1 1 1
~a1 = a(−x̂ + ŷ + ẑ), ~a2 = a(x̂ − ŷ + ẑ), ~a3 = a(x̂ + ŷ − ẑ),
2 2 2
volume:
1
|~a1 · (~a2 × ~a3 )| a3
2
primitive translation vectors in ~k-space:

~b1 = 2π (ŷ + ẑ), ~b2 = 2π (x̂ + ẑ), ~b3 = 2π (x̂ + ŷ) = fcc lattice
a a a
Surface of the 1. Brillouin zone: see figure

Figure 4.11: 1. Brillouin zone of the body-centered cubic lattice: The figure is a regular
rhombic dodecahedron [from Kittel, Introduction to solid state physics (1996); Fig.2.13].
 69

• face-centered cubic lattice

Figure 4.12: Brillouin zones of the face-centered cubic lattice. The cells are in the
reciprocal space, and the reciprocal lattice is body-centered [from Kittel, Introduction
to solid state physics (1996); Fig.2.15].

Figure 4.13: Primitive basis vectors of the face-centered cubic lattice [from Kittel,
Introduction to solid state physics (1996); Fig.2.14].
70 Chapter 4 Crystal lattice and waves — the reciprocal lattice

Effect of the basis on the scattering amplitude F

– until now: we considered only the effect of the lattice on the scattering amplitude
F.

– now: consider a basis consisting of more than one atoms

• scattering amplitude in general:

Z X
~ ~ ~
F = dV n(~r)e−i∆k~r = nG~ ei(G−∆k)~r
crystalvol. ~
G

• finite scattering amplitude for ∆~k = G,~ i.e. for

Z Z
~r
−iG~ ~
FG~ = dV n(~r)e = N n(~r)e−iG~r =: N SG~
crystal cell

here, N is the number of unit cells in the crystal and SG~ is the ”structure
~
factor” of the reciprocal lattice vector G

• assume the basis consists of s atoms; with atom j at the location ~rj and described
by an electron density nj (~r P
− ~rj ).
We then get: n(~r) = sj=1 nj (~r − ~rj )
X Z ~
⇒ SG~ = dV nj (~r − ~rj )e−iG~r
j
crystal
X Z X
~ rj
−iG~ ~ ~
= e ρ)e−iG~ρ =
dV nj (~ e−iG~rj fj
j j
crystal

with the ”atomic form factors” fj (in general to be calculated

numerically) and ρ~ = ~r − ~rj
X ~
X
⇒ SG~ = fj e−iG~rj = fj e−2πi(v1 xj +v2 yj +v3 zj )
j j

~ = v1~b1 +v2~b2 +v3~b3 and ~ai~bk = 2πδik

since ~rj = xj~a1 +yj~a2 +zj~a3 , G
• now, we can formulate selection rules for different cases:
example 1: bcc lattice
with one atom at x1 = y1 = z1 = 0 and one at x2 y2 = z2 = 12
→ atomic form factors of both atome shall be f
½
−iπ(v1 +v2 +v3 ) 0, if v1 + v2 + v3 odd
⇒ SG = f · {1 + e }=
2f, if v1 + v2 + v3 even

→ every second reflex of the cubic unit cell is suppressed; due to destructive
interference of the wave scattered on both atoms
 71

example 2: fcc lattice

→ atoms at 000, 0 12 12 , 12 0 21 , 11
22
0
→ atomic form factor of the atoms shall be f

⇒ SG = f · {1 + eiπ(v2 +v3 ) + eiπ(v1 +v3 ) + eiπ(v1 +v2 ) }

½
4f, if all vk even or odd
=
0, if only only index is even or odd

x-ray diffraction pattern from KCl and KBr

Figure 4.14: Comparison of x-ray reflections from KCl and KBr powders. In KCl the
numbers of electrons of K+ and Cl− ions are equal. The scattering amplitudes f (K+ )
and f (Cl− ) are almost exactly equal, so that the crystal look to x-rays as if it were a
monatomic simple cubic lattice of lattice constant a/2. Only even integers occur in the
reflection indices when these are based on a cubic lattice of lattice constant a. In KBr
the form factor of Br− is quite different than that of K+ , and all reflections of the fcc
lattice are present (Courtesy of Robert van Nordstrand) [from Kittel, Introduction to
solid state physics (1996); Fig.2.17].
72 Chapter 4 Crystal lattice and waves — the reciprocal lattice

Note regarding x-ray- and neutron scattering

• Bragg condition ∆~k = G

~ can also be represented by
”Laue equation”
~ai ∆~k = 2πvi
with integer vi and i = 1, 2, 3
Geometric denotation:
∆~k lies on the common intersections of the cones about ~a, (i = 1, 2, 3)
• Ewald construction of the diffraction condition:

Figure 4.15: The points on the right-hand side are reciprocal lattice points of the
crystal. The vector ~k is drawn in the direction of the incident x-ray beam, and the
origin is chosen such that ~k terminates at any reciprocal lattice point. We draw a
sphere of radius k = 2π λ
about the origin of ~k. A diffracted beam will be formed if
this sphere intersects any other point in the reciprocal lattice. The sphere as drawn
intercepts a point connected with the end of ~k by a reciprocal lattice vector G.
~ The
diffracted x-ray beam is in the direction ~k = ~k + G.
0 ~ The angle θ is the Bragg angle
of fig.4.3. This construction is due to P.P. Ewald [adapted from Kittel, Introduction to
solid state physics (1996); Fig.2.08].
 73

• X-ray diffraction techniques

– powder diffraction:
∗ In a powder all crystal orientations are present
∗ does not require large single crystals

Figure 4.16: Principle of powder diffraction: Debye-Scherrer camera [from Bergmann-

Schaefer, Lehrbuch der Experimentalphysik (1992); Fig.2.32].
74 Chapter 4 Crystal lattice and waves — the reciprocal lattice

Figure 4.17: (a) Debye-Scherrer recording from Cu powder (b) Pattern obtained from
ore (’Erz’) using a powder diffractometer (top) and diffraction lines as suggested from
a computer-software (bottom) calcualted for reference compounds from the JCPDS
data base (Fa. Stoe & CIE GmbH, Darmstadt) [from Bergmann-Schaefer, Lehrbuch
der Experimentalphysik (1992); Fig.2.33].
 75

– Laue method
uses single crystal + ’white’ source

Figure 4.18: Experimental configuration of the Laue method [from Bergmann-Schaefer,

Lehrbuch der Experimentalphysik (1992); Fig.2.34].

Figure 4.19: (a) Laue diffraction from Kalialaun (KAl(SO4 )2 · 12H2 O)(cubic, space
group Pa3) in [100] direction. The patterns shows clearly an absence of a 4-fold sym-
metry. This allows the unambiguous discrimination between the possible cubic Laue
classes m3 und m3m in favor of m3. (b) Laue pattern obtained from a quasi crystal
Al6 CuLi3 with 5-fold symmetry [from Bergmann-Schaefer, Lehrbuch der Experimental-
physik (1992); Fig.2.35].
76 Chapter 4 Crystal lattice and waves — the reciprocal lattice

– Single crystal diffractometry

single crystal + monochromatic source

Figure 4.20: (a) Geometry of ’Euler-Wiege’; (b) realization of the Ewald diffraction
conditions in the plane of diffraction of a ’Euler-Wiege’. [from Bergmann-Schaefer,
Lehrbuch der Experimentalphysik (1992); Fig.2.45].
 77

• Neutron diffraction:

– Diffraction pattern depends on magnetic ordering in a sample

Example: Neutron diffraction on manganese oxide (MnO)

Figure 4.21: Neutron diffraction patterns for MnO below and above the spin-ordering
temperature of 120 K, after C.G.Shull, W.A.Streuser and E.O.Wollan. The reflection
indices are based on an 8.85 Å cell at 80 K and on a 4.43 Å cell at 293 K. At the higher
temperature the Mn2+ ions are still magnetic, but they are no longer ordered [from
Kittel, Einführung in die Festkörperphysik (1999); Fig.15.20].

Figure 4.22: Ordered arrangements of

spins of the Mn2+ ions in manganese
oxide (MnO), as determined by neu-
tron diffration. The O2− ions are not
shown. [aus Kittel, Einführung in die
Festkörperphysik (1999); Fig.15.21].
78 Chapter 4 Crystal lattice and waves — the reciprocal lattice

• Effect of finite temperature on the x-ray- or neutron diffraction peaks

– finite temperature → crystal lattice oscillates

– naive view: diffraction peaks are broadened
– in fact: intensity I decreases; width of the peaks remains unchanged
2 2
– one finds: I = I0 e−kB T G /(M ω )
with M : atom mass, ω: frequency of oscillation, kB : Boltzmann
constant
exponential term is called ”Debye-Waller factor”
– ”missing” intensity goes to incoherent background

Figure 4.23: The dependence of intensity on temeperature for the (h00) x-ray reflections
of aluminium. Reflections (h00) with h odd are forbidden for an fcc structure. (After
R. M. Nicklow und R. A. Young) [from Kittel, Einführung in die Festkörperphysik
(1999); Fig.A.01].
 79

Derivation of the Debye-Waller factor

• Atom j in crystal oscillates with amplitude ~u about ~rj0 : ~rj (t) = ~rj0 + ~u(t)

• time averaging of the structure factor

¿Z À X D E X D E
~r
−iG~ ~ rj
iG~ ~r 0
iG~ ~u
iG~
hSG~ i = dV n(~r)e = fj e = fj e j e
j j

~ ~ ui − 1 h(G~
~ u) 2 i + . . .
Term heiG~u i ≈ 1 + ihG~ 2
~ ui = 0, for harmonic oscillation.
– hG~
~ u)2 i = G2 hu2 ihcos2 Θi = 1 hu2 G2 i
– h(G~ 3
with Θ: angle between G ~ and ~u and hcos2 Θi = 1
with geometric
3
averaging over a sphere

~ 1 1 2 2
⇒ heiG~u i ≈ 1 − hu2 iG2 ≈ e− 6 hu iG
6
1 2 2
scattering intensity =(amplitude)2 =I0 e− 3 hu iG
3
Mean thermal energy hU i of a harmonic oscillator: k T
2 B

1 1 3 C
⇒ hU i = chu2 i = M ω 2 hu2 i = kB T ; (ω 2 = )
2 2 2 M
solve for hu2 i
2 /(M ω 2 )
⇒ I = I0 e−kB T G
q.e.d.
80 Chapter 4 Crystal lattice and waves — the reciprocal lattice