Bravais Lattices

In the previous cases, we have associated to each crystal system a primitve cell.

Each of these primitive cells defines a lattice type.

There are other types of lattices, based on non primitive cells, which cannot be
related to the previous ones.
In total, we have 14 types of lattices in 3D. These are called the Bravais Lattices
Let us exhamine these lattices in detail

Four lattice centering types

No.

Type

Description

Primitive

Lattice points on corners

only. Symbol: P.

Face Centered

Lattice points on corners as

well as centered on
faces. Symbols: A (bc
faces); B (ac faces); C
(ab faces).

All-Face Centered

Lattice points on corners as

well as in the centers of
all faces. Symbol: F.

Body-Centered

Lattice points on corners as

well as in the center of
the unit cell body.
Symbol: I.
2

The 14 Bravais lattices

P
P

C
C

F
P

I
P

Crystal System & 14 Bravais Lattices

Mystery of the missing entries in the Bravais List

A cell with two centered faces must be of type F (all face centered)

( , 0, )

(0, , )

( , , 0)

(0, , )

( , 0, )

, ,

( , , 0)

, ,

, ,

, ,

Mystery of the missing entries in the Bravais List

A cell with is at the same time body centered and face centered can be always
reduced to a face centered cell

c
(0, , )

( , 1, 1)

( , , )

( , 0, )

, ,

, ,

, ,

, ,

, ,

, ,

Mystery of the missing entries in the Bravais List!

1

Cubic

Cube

Hence Cannot be called Cubic

What we choose
P
I
F

But then Cubic crystals need not have any 4-fold axes!!
(cubic lattices do need to have!)

Hence even though this lattice remains as it is it is called Simple Tetragonal

(which is smaller in size)

Mystery of the missing entries in the Bravais List!

2

Tetragonal

Square Prism (general height)

What we choose
P

Smaller sized Body Centred Cell is chosen

FCT = BCT
Face Centred Tetragonal = Body Centred Tetragonal

Mystery of the missing entries in the Bravais List!

2

Tetragonal

Square Prism (general height)

What we choose
P

Smaller sized Simple Cell is chosen

CCT = ST
C Centred Tetragonal = Simple Tetragonal

Mystery of the missing entries in the Bravais List!

4

Hexagonal

120 Rhombic Prism

Putting a lattice point at body centre

destroys the 6-fold axis

Hence body centred

hexagonal lattice NOT
possible
10

Mystery of the missing entries in the Bravais List!

P
4

Hexagonal

120 Rhombic Prism

Putting lattice points at face centres

destroys the 6-fold axis

11

Mystery of the missing entries in the Bravais List!

P
4

Hexagonal

120 Rhombic Prism

Putting a lattice point at face centre

destroys the 6-fold axis

12

Mystery of the missing entries in the Bravais List!

& what we dont

Cubic F Tetragonal I
(not chosen)

As the FCC lattice has higher symmetry than the BCT cell
(the one with higher symmetry is chosen)

13

Some example of the allowed and disallowed transfers

Crystal system

Bravais lattices

1. Cubic

2. Tetragonal

3. Orthorhombic

4. Hexagonal

5. Trigonal

6. Monoclinic

7. Triclinic

C
C

14

Space groups
A crystallographic space group is the set of geometrical symmetry operations
that take a three dimensional periodic object into itself.
We have seen so far the 32 crystallographic point groups: combinations of either
simple rotations or inversion axes, compatible with the periodic nature of the
lattice.
Combing these groups with the 14 Bravais lattices we obtain 73 space groups.
These are called symmorphic space groups.
Crystal Class

Bravais Lattices

Point Groups

Triclinic

1, 1

Monoclinic

P, C

2, m, 2/m

Orthorhombic

P, C, F, I

222, mm2, mmm

Trigonal

P, R

3, 3,32, 3m, 3m

Hexagonal

6, 6, 6m , 622, 6mm, 62m, 6mmm

Tetragonal

P, I

4, 4, 4m , 422, 4mm, 42m, 4mmm

Cubic

P, F, I

23, m3,43m, m3m

15

Space groups

However, we can replace the proper or improper axes by screw axes of the same
order and mirror planes by glide planes. Combining all possible symmetry
elements with the 14 bravais lattices, we generate the 230 possible space groups.

Important: when introducing symmetry elements with translational components,

we do not have any more the restriction that all symmetry elements must meet in
a point.

16

Asymmetric unit
This is the smallest part of the unit cell which will generate the whole cell when
applying to it the symmetry operations.
Examples of asymmetric units
Triclinic
P1

Monoclinic
P2

C2

C2/c

17

Examples of asymmetric units

Tetragonal

Orthorombic
P222

Immm

P4

Hexagonal
P

Cubic
Fm m

Fm m

18

Diagrams from International Table of Crystallography:

Triclinic system

19

Diagrams from International Tables for Crystallography:

Triclinic system

20

Diagrams from International Tables for Crystallography :

Monoclinic system

21

Diagrams from International Tables for Crystallography:

Monoclinic system

22

Diagrams from International Tables for Crystallography:

Orthorhombic system

23

Diagrams from International Tables for Crystallography:

Tetragonal system

24

Diagrams from International Tables for Crystallography:

Cubic system

25

The 230 space groups

26

Asymmetric units:
http://cci.lbl.gov/asu_gallery/

Space Group Diagrams and Tables:

http://img.chem.ucl.ac.uk/sgp/large/sgp.htm/

27

The exact choice of the asymmetric unit is in reality arbitrary!

28

Wigner-Seitz cells
The 14 Bravais Lattices are compatible with cells that are different from
those conventionally associated with them.
Apart from parallelepipeds, there are other classes of polyhedra which can
fill up the space by translation
One of them is obtained by the Dirichlet construction:
1.
2.
3.

Connect a lattice point with its nearest neighbors

Trace through the mid points of the segments the planes perpendicular
to them.
The intersecting planes delimit a region of space known as the WignerSeitz cells

Examples in 2D....
29

Examples in 3D....

Construction of a Wigner-Seitz cell

in the case of a body-centered
cubic lattice

Construction of a Wigner-Seitz cell

in the case of a face-centered cubic
lattice

Crystal lattice filled with the

repetition of a Wigner-Seitz cell

As we shall see later, the Wigner-Seitz construction delimits a region in the

reciprocal space known as the first Brilllouin Zone.

30

Overview of some common crystal

structures
Closed-packed structures

There are an infinite number of ways to organize spheres to

maximize the packing fraction.
The centres
of spheres
at A, B, and
C positions

There are different ways you can pack spheres together. This
shows two ways, one by putting the spheres in an ABAB
arrangement, the other with ACAC. (or any combination of
the two works)

31

The FCC and hexagonal closed-packed structures (HCP) are formed from
packing in different ways. FCC (sometimes called the cubic closed-packed
structure, or CCP) has the stacking arrangement of ABCABCABC HCP has
the arrangement ABABAB.
[1 1 1]
[0 0 1]
HCP

ABAB
sequence

FCC
(CCP)
(looking
along [111]
direction

ABCABC
sequence

32

Cubic clos packing (fcc) packing

An enormous number of solids crystallize in
the face-centered structure, with an atom at
each lattice site.
In the cell, the direction in which the ABC
staking can be seen is the 111 direction.
The fcc structure is a Bravais lattice
An example is represented by gold.

Cube side a = 4.08

Space group: Fm3m (number 225)

33

Hexagonal close packing (same packing

density of cubic close packing)

This is described by an hexagonal unit cell

Also a great number of solids crystallize in

the hexagonal close packed structure, with an
atom at each lattice site.
In the cell, the direction in which the AB
staking can be seen is the 001 direction.

Comparison between AB and ABC stacking

The hcp structure is not a Bravais lattice!

An example is represented by metallic Co

a= 2.51 , c= 4.07
Space group: P63/mmc (number 194)
34

Diamond structure

The diamond structure consists of two

interpenetrating face-centered cubic (fcc) Bravais
lattices, displaced along the body diagonal of the
cubic cell by one quarter of the length of the diagonal

The two sublattices are colored differently, although

all atoms refer to carbon atoms
a
Cube side a = 3.57
The diamond lattice is not a bravais lattice!

Space group: Fd3m (number 227)

Also Si, Ge and -Sn crystallize in the diamond structure

35

Honeycomb net (graphene, boron nitride)

Similarly to the case of diamond, a honeycomb net,
like the case of a single graphene sheet, is not a
Bravais lattice, in the sense that each C atom cannot
be considered as a point of a 2D lattice. Instead, we
can describe it as two interpenetrated hexagonal
lattices.
The two sublattices are colored differently, although
all atoms refer to carbon atoms

The same structure of two interpenetrating sublattices

can describe a single sheet of boron nitride (BN). In
this case one sublattice is formed by B atoms, the
other by N atoms.

36

Zinc-blende structure

Strongly related to the diamond structure is the zincblende structure, named after the mineral sphalerite
(ZnS), which consists of two interpenetrating facecentered cubic Bravais lattices, displaced along the
body diagonal of the cubic cell by one quarter of the
length of the diagonal
In this case, the two sublattices, colored differently,
are made of different atoms: Zn and S
a
Cube side a = 5.41
The diamond lattice is not a bravais lattice!

Space group: F43m (number 216)

Many semiconductors (GaAs, CdTe, CdSe, etc) crystallize in the zinc-blende structure
37

Wurtzite structure

c axis

The wurtzite structure, named after the mineral

wurtzite (Zn, Fe)S, consists of two interpenetrating
hcp lattices.
In this case too, the two sublattices, colored
differently, are made of different atoms
One lattice, the blue one in the figure, is shifted
by - 38
0. 375 along the c direction
Example: ZnO

a = 3.25 , c = 5.21
Space group: P63mc (number 186)

The wurtzite lattice is obviously not a bravais lattice!

Many compounds (AgI, ZnO, CdS, CdSe, -SiC, GaN, AlN, BN, etc.) crystallize in the
wurtzite structure
The wurtzite structure is non-centrosymmetric (i.e., lacks inversion symmetry). Due to this,
wurtzite crystals can (and generally do) have properties such as piezoelectricity and 38
pyroelectricity, which centrosymmetric crystals lack

A comparison between wurtzite and zincblende

d is smaller in wurtzite than in zinc-blende

39

Fluorite structure

Antifluorite structure

It is convenient to
see this structure
in terms of
coordination
polyhedra
The fluorite structure can
be generated by starting
with a FCC lattice of
cations (A) and filling all
of the tetrahedral holes
with anions (X).

The antifluorite structure is

identical except that the
anion and cation
coordinations are reversed.

Cubic Cu2Se for example has

antifluorite crystal structure

Comparing Zinc Blende and Antifluorite structures

Zinc Blende

Antifluorite

The sphalerite structure can also be seen as derived

from the antifluorite structure, by removing of the
cations from the tetrahedral sites

Rock salt (NaCl) structure

The NaCl structure is fcc

The basis consists of one Na atom and one Cl atom,
separated by one-half of the body diagonal of a unit
cube
There are four units of NaCl in each unit cube
Each atom has 6 nearest neighbors of the opposite kind

Another example of rocksalt structure is represented by NiO

Also, it is most convenient to see this structure in terms of
coordination polyhedra

The rocksalt structure is then represented by edge-sharing NaCl6 octahedra

42