Solid State Physics 355

Topic 1

Symmetry & Crystal

Structures

Crystals

Atoms that are bound together, do so in a

way that minimizes their energy.

This most often leads to a periodic

arrangement of the atoms in space.

If the arrangement is purely periodic we

say that it is crystalline.

Crystal = Lattice + Basis

Unit Cell

The three interior angles formed between unit cell

edges are called:
alpha, between edges a2 & a3
(beta, between edges a1 & a3)
(gamma, between edges a1 & a2)
In the FCC rhombohedral standard reduced cell, it can
be shown that = = = 60. Note that a cube is a just
a special rhombohedron, with = = = 90.

Face-centered Cubic Lattice

In the Face Centered
Cubic (FCC) unit cell
there is one basis atom
at each corner and one
basis atom in each face.
There are 4 atoms per
unit cell:
(1/8)8 + (1/2)6 = 4.

(x y)
2
a

a2 (y z)
2
a

a3 (z x)
2
a1

0 a1 a2 a3

The simplest primitive

cell is actually
rhombohedral. Its
volume is that of the
cubic, as we might
expect.

BaTiO3

Body-centered Cubic Lattice

In the Body Centered Cubic (BCC)

unit cell there is one host atom (lattice
point) at each corner of the cube and
one host atom in the center of the
cube: Z = 2

Symmetry Operations
Translational
Reflection

at a plane
Rotation about an axis
Inversion through a point
Glide

(=reflection + translation)
Screw (=rotation + translation)

Rotations

Mirror Symmetry

Inversion

2D - Point Groups

Point and Space Groups

7

crystal systems
14 Bravais lattices
230 non-Bravais lattices

Space Groups
32

2
3
3
7
5
5
7

point symmetries
triclinic
monoclinic
orthorhombic
tetragonal
cubic
trigonal
hexagonal

Crystal Directions

100 [100], [010], [001], [ 1 00], [0 1 0], [00 1 ]

Crystal Planes

Crystal Planes: Miller Indices

Procedure for finding Miller indices in four-index notation:

1. Find the intersections, r and s, of the plane with any two of the basal plane
axes.
2. Find the intersection t of the plane with the c axis.
3. Evaluate the reciprocals 1/r, 1/s, and 1/t.
4. Convert the reciprocals to smallest set of integers that are in the same ratio.
5. Use the relation i = -(h+ k), where h is associated with a1, k is associated
with a2, and i is associated with a3.
6. Enclose all four indices in parentheses: (h k i l)

Example: What is the designation, using four

Miller indices, of the lattice plane shaded
pink in the figure?
The plane intercepts the a1, a3, and c axes
at r = 1, u = 1, and t = , respectively.
The reciprocals are
1/r = 1
1/u = 1
1/t = 0
These are already in integer form.
We can write down the Miller indices as (h
k i l) = (1 k 1 0), where the k index is
undetermined so far.
Use i = (h + k). That is, k = 2.
The designation of this plane is (h k i l) =

(12 10)

Why are planes in a lattice important?

(A) Determining crystal structure
Diffraction methods directly measure the distance between parallel planes of lattice
points. This information is used to determine the lattice parameters in a crystal
and measure the angles between lattice planes.
(B) Plastic deformation
Plastic (permanent) deformation in metals occurs by the slip of atoms past each
other in the crystal. This slip tends to occur preferentially along specific lattice
planes in the crystal. Which planes slip depends on the crystal structure of the
material.
(C) Transport Properties
In certain materials, the atomic structure in certain planes causes the transport of
electrons and/or heat to be particularly rapid in that plane, and relatively slow away
from the plane.
Example: Graphite
Conduction of heat is more rapid in the sp2 covalently bonded lattice planes than in
the direction perpendicular to those planes.
Example: YBa2Cu3O7 superconductors
Some lattice planes contain only Cu and O. These planes conduct pairs of
electrons (called Cooper pairs) that are responsible for superconductivity. These
superconductors are electrically insulating in directions perpendicular to the Cu-O
lattice planes.

(GPa)

d spacing
d hkl

n
h

a2

b2

Example
The lattice constant for aluminum is
4.041 angstroms. What is d220?

c2

Answer
Aluminum has an fcc structure, so a = b = 4.041

d hkl

1
h2 k 2
a

1
22 22
2

4.041

1.43 angstroms

Interstitials
FCC

BCC

What types/sizes of atoms or ions can fit in a given interstitial

site?
Answer:
1.

2.
3.
4.

Calculate the effective radius of the void space using

trigonometry AND the hard-sphere model with the radius r for
the host atom (for metals) or ions (for ionic crystals).
Any element with atomic/ionic radius less than or equal to can
occupy that interstitial site.
If the element has radius larger than , then it will cause some
distortion to the crystal structure
The increased energy due to distortion will limit the number of
interstitial sites that can be occupied (example: carbon in iron).

Examples of common structures:

(1) The Sodium Chloride (NaCl) Structure
(LiH, MgO, MnO, AgBr, PbS, KCl, KBr)
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
Atom positions:
Cl : 000 ; 0; 0; 0
Na: ; 00; 00; 00
Each atom has 6 nearest
neighbours of the opposite
kind

Often described as 2 interpenetrating

FCC lattices

NaCl structure
Crystal

LiH

4.08

MgO

4.20

MnO

4.43

NaCl

5.63

AgBr

5.77

PbS

5.92

KCl

6.29

KBr

6.59

(2) The Cesium Chloride (CsCl) structure

(CsBr, CsI, RbCl, AlCo, AgZn, BeCu, MgCe, RuAl, SrTl)

The CsCl structure is BCC

The basis consists of one Cs
atom and one Cl atom, with
each atom at the center of a
cube of atoms of the opposite
kind
There is on unit of CsCl in
each unit cube
Atom positions:
Cs : 000
Cl : (or vice-versa)
Each atom has 8 nearest
neighbours of the opposite
kind

CsCl structure
Crystal

BeCu

2.70

AlNi

2.88

CuZn

2.94

CuPd

2.99

AgMg

3.28

LiHg

3.29

NH4Cl

3.87

TlBr

3.97

CsCl

4.11

TlI

4.20

Why are the a values smaller for the CsCl structures

than for the NaCl (in general)?

Closed-packed structures

(or, what does stacking fruit have to do with solid state physics?)

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
(from Kittel)

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)

(3) The Hexagonal Closed-packed (HCP) structure

Be, Sc, Te, Co, Zn, Y, Zr, Tc, Ru, Gd,Tb, Py, Ho, Er, Tm, Lu, Hf, Re, Os, Tl

The HCP structure is made up of stacking spheres in a ABABAB

configuration
The HCP structure has the primitive cell of the hexagonal lattice, with a
basis of two identical atoms
Atom positions: 000, 2/3 1/3 (remember, the unit axes are not all
perpendicular)
The number of nearest-neighbours is 12.

Conventional HCP unit cell

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]
FCC
HCP

(CCP)
(looking along [111]
direction

ABAB
sequence

ABCABC
sequence

HCP and FCC structures

The hexagonal-closed
packed (HCP) and FCC
structures both have the
ideal packing fraction of
0.74 (Kepler figured this
out hundreds of years ago)
The ideal ratio of c/a for
this packing is
(8/3)1/2 = 1.633

Crystal

c/a

He

1.633

Be

1.581

Mg

1.623

Ti

1.586

Zn

1.861

Cd

1.886

Co

1.622

1.570

Zr

1.594

Gd

1.592

Lu

1.586

Amorphous Materials
Glass
The continuous
random network
structure
of amorphous
silicon dioxide,
notice that
each Si atom
(gold spheres)
has 4 bonds, and
each oxygen
atom (red
spheres) has 2
bonds.