Introduction to crystallography

The unitcell
The resiprocal space and unitcell
Braggs law
Structure factor Fhkl and atomic scattering factor fzθ
The specimen

Introduction to crystallography
We divide materials into two categories:

• Amorphous materials
• The atoms are ”randomly” distributed in space
• Not quite true, there is short range order
• Examples: glass, polystyrene (isopor)

• Crystalline materials
• The atoms are ordered
• Short range and long range order
• Deviations from the perfect order are of
importance for the properties of the materials.

Why do we see facets on the surface

The specimen

Introduction to crystallography
The specimen

Basic aspects of crystallography

• Crystallography describes and characterise the structure of
crystals
• Basic concept is symmetry
• Translational symmetry: if you are standing at one point in a
crystal, and move a distance (vector) a the crystal will look
exactly the same as where you started.

2D
a a a a
b
1D

a a a a
The specimen

The lattice
• described as a set of mathematical points in space
• each of these points represents one or a group of atoms,
basis
Basis

+ Lattice
a a a

= crystal structure
a a a
The specimen

Axial systems
z The point lattices can be described by 7 axial
systems (coordinate systems)

c Axial system Axes Angles

α Triclinic a≠b≠c α≠β≠γ≠90o

β b y
Monoclinic a≠b≠c α=γ=90o ≠ β
γ
a Orthorombic a≠b≠c α= β=γ=90o
Tetragonal a=b≠c α= β=γ=90o
x Cubic a=b=c α= β=γ=90o
Hexagonal a1=a2=a3≠c α= β=90o
γ=120o
Rhombohedral a=b=c α= β=γ ≠ 90o
The specimen

Bravais lattice
The point lattices can be described
by 14 different Bravais lattices

Hermann and Mauguin symboler:

P (primitiv)
F (face centred)
I (body centred)
A, B, C (bace or end centred)
R (rhombohedral)
The specimen

Unit cell
• The crystal structure is described by specifying a repeating element and its translational periodicity
• The repeating element (usually consisting of many atoms) is replaced by a lattice point and all lattice points have the
same atomic environments.
• The unit cells are the smallest building blocks.
• A primitive unit cell has only one lattice point in the unit cell.

Repeating element, basis

c
α
β b
γ Lattice point
a
The specimen

Exaples of materials with a face centered

cubic lattice

Copper
The specimen

Exaples of materials with a face centered

cubic lattice

Silicon
The specimen

Exaples of materials with a face centered

cubic lattice

ZnS
The specimen

What about other symmetry elements?

• We have discussed translational symmetry, but there are also other
important symmetry operations:
• Mirror planes
• Rotation axes
• Inversion
• Screw axes
• Glide planes
• The combination of these symmetry operations with the Bravais
lattices give the 230 space groups
The specimen
Space groups
• Crystals can be classified
according to 230 space groups.
• Details about crystal description
can be found in International
Tables for Crystallography.
• Criteria for filling Bravais
point lattice with atoms.
• A space group can be referred to
by a number or the space group
symbol (ex. Fm-3m is nr. 225)
• Structural data for known crystalline
phases are available in “books” like
“Pearson’s handbook of
crystallographic data….” but also
electronically in databases like “Find it”
or f.ex. “Crystallography open
database”:
http://www.crystallography.net/cod/ .
• Pearson symbol like cF4 indicate the
axial system (cubic), centering of the
lattice (face) and number of atoms in
the unit cell of a phase (like Cu).
The specimen

Lattice planes
• Miller indexing system z

• Crystals are described in the axial system

of their unit cell
c/l

• Miller indices (hkl) of a plane is found a/h b/k

from the interception of the plane with 0
the unit cell axis (a/h, b/k, c/l).
y
x
• The reciprocal of the interceptions are Z
rationalized if necessary to avoid fraction
numbers of (h k l) and 1/∞ = 0 (110)

Y
• Planes are often described by their
normal Z Z
(001)
X
(111)
• (hkl) one single set of parallel planes (010)
• {hkl} equivalent planes Y Y
(100)
X X
The specimen

Directions
z
wc
• The indices of directions (u, v and w) can be found from
the components of the vector in the axial system a, b, c. [uvw]
c
b
a vb
• The indices are scaled so that all are integers and as small ua
as possible y
x
• Notation
• [uvw] one single direction or zone axis Zone axis [uvw]
• <uvw> geometrical equivalent directions
(hkl)

• [hkl] is normal to the (hkl) plane in cubic axial systems

uh+vk+wl= 0
The specimen

Reciprocal vectors, planar distances

–The normal of a plane is given by the vector: • The reciprocal lattice is defined by the vectors :
g hkl  ha *  k b*  l c* a *  (b  c ) / V
b *  (c  a ) / V
–Planar distance between the planes {hkl} is
given by: c*  (a  b) / V

d hkl  1 / g hkl a*=(bcsinα)/V

b*=(casinβ)/V
–Planar distance (d-value) between planes
{hkl} in a cubic crystal with lattice parameter c*=(absinγ)/V
a:
a
d hkl 
h2  k 2  l 2
Interaction with sample

Elastic scattering
Why do we want a monochromatic wave in diffraction studies?

• X-rays are scattered by the electrons in a material

• Electrons are scattered by both the electron and the nuclei in a material
• The electrons are directly scattered and not by an field to field exchange as in the case for X-rays

• The diffraction theory is the same for electrons, X-rays and neutrons.
• Based on Braggs law
Interaction with sample

Braggs law

Coherent incoming Gives the angle when

wave the scattered wave is in phase.
Elastic
scattering
Interaction with sample

Deduction of Braggs law:

ψi
θ Sum ψ scattered in phase

θ d
x x

In order for the scattered waves to be in phase (resulting in constructiv interference),

the difference in the travelled distance of the waves must be a multiple of λ (i.e 2X = nλ).
X= d sinθ and hence 2d sinθ= nλ.
Interaction with sample

Effect of adding a scattering plane with d/2

ψi
θ
(001)
d/2
(002) x’ x’
θ d
x x

Imaging that the red planes represents the (001) planes in a cubic structure with the same atom (=electron) density on
the (002) plane (like in fcc and bcc structures). The (002) plane will now scatter the incoming wave and travel 1/2nλ
shorter/longer than the waves scattered from (001). The amplitude of the sum of the waves in this situation is 0 (x’=d/2
sinθ, 2x’= d sinθ and this is equal to 1/2nλ.

In this example “d“ represented the planar distance of the (001) planes and “d/2” the planar distance of the (002) plane.
This is commonly written as d001 and d002. For a cubic unitcell d001 and d002 is equivalent to d100 and d200. The latter ones
are the ones commonly tabulated in d-value tables if the intensity is not 0.
Interaction with sample

Example: Bragg angle for (002) relative to (001)

ψi
θ
(001)
d/2
(002) x’ x’
θ d
x x

Imaging that the wave length and the crystal are the same as in the previous examplered planes represents the (001)
planes in a cubic structure with the same atom (=electron) density on the (002) plane (like in fcc and bcc structures). The
(002) plane will now scatter the incoming wave and travel 1/2nλ shorter/longer than the waves scattered from (001). The
amplitude of the sum of the waves in this situation is 0 (x’=d/2 sinθ, 2x’= d sinθ and this is equal to 1/2nλ.

In this example “d“ represented the planar distance of the (001) planes and “d/2” the planar distance of the (002) plane.
This is commonly written as d001 and d002. For a cubic unitcell d001 and d002 is equivalent to d100 and d200. The latter ones
are the ones commonly tabulated in d-value tables if the intensity is not 0.
Atomic scattering factor (X-ray)
Z

Intensity of the
scattered
X-ray beam
 Structure factors
N

z
X-ray: Fg  Fhkl   f j( x ) exp( 2i(hu j  kv j  lw j ))
wjc j 1

rj
c The coordinate of atom j within the crystal unit cell is given rj=uja+vjb+wjc.
a b
uja vjb
y h, k and l are the miller indices of the Bragg reflection g (and represents the normal
x to the plane (hkl).

N is the number of atoms within the crystal unit cell. fj(n) is the x-ray scattering
factor, or x-ray scattering amplitude, for atom j.

The structure factors for x-ray, neutron and The intensity of a reflection is
electron diffraction are similar. For neutrons and proportional to: Fg Fg
electrons we need only to replace by fj(n) or fj(e) .
Example: Cu, fcc
N
• eiφ = cosφ + isinφ Fg  Fhkl   f j exp( 2 i(hu j  kv j  lw j ))
j 1
• enπi = (-1)n
• eix + e-ix = 2cosx
Atomic positions in the unit cell:
[000], [½ ½ 0], [½ 0 ½ ], [0 ½ ½ ]

Fhkl= f (1+ eπi(h+k) + eπi(h+l) + eπi(k+l))

What is the general condition
for reflections for fcc? If h, k, l are all odd then:
Fhkl= f(1+1+1+1)=4f

What is the general condition If h, k, l are mixed integers (exs 112) then
for reflections for bcc? Fhkl=f(1+1-1-1)=0 (forbidden)
 N

Example: Cu, fcc Fg  Fhkl   f j exp( 2 i(hu j  kv j  lw j ))

j 1

Atomic positions in the unit cell:

• enπi = (-1)n [000], [½ ½ 0], [½ 0 ½ ], [0 ½ ½ ]
The coordinate of atom j within the crystal unit cell is given rj=uja+vjb+wjc. (hkl): a plane

Fhkl= fCu (exp2πi(0+0+0) + exp2πi(1/2h+1/2k+0) + exp2πi(1/2h+0+1/2l) + exp2πi(0+1/2k+1/2l))

Fhkl= fCu (exp0πi + expπi(h+k) + expπi(h+l) + expπi(k+l)) : General expression for fcc
F100=fCu(1 + expπi(1+0) + exp πi(1+0) + exp πi(0+0))= fCu(1-1-1+1)= 0 If h, k, l are all odd (ex. 111) or even then:
Fhkl= f(1+1+1+1)=4f (intensity)
F200=fCu(1 + expπi(2+0) + exp πi(2+0) + exp πi(0+0))= fCu(1+1+1+1)= 4fCu
F110=fCu(1 + expπi(1+1) + exp πi(1+0) + exp πi(1+0))= fCu(1+1-1-1)= 0 If h, k, l are mixed integers (exs 110) then:
F111=fCu(1 + expπi(1+1) + exp πi(1+1) + exp πi(1+1))= fCu(1+1+1+1)=4fCu Fhkl=f(1+1-1-1)=0 (no intensity)

The fcc real space lattice results in a bcc reciprocal lattice

002
111
c* b*
a* 200