CHAPTER 1

Crystal Structures
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Objectives

By the end of this Lecture you should:

➢be able to identify a unit cell

➢know that there are 7 possible unit cell shapes
➢be able to define cubic, tetragonal, orthorhombic and
hexagonal unit cell shapes
 1.1 INTRODUCTION

• WHAT IS SOLID STATE PHYSICS?

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 Solid State Physics

The branch of physics that studies the properties of materials in

the solid state, it deals with the physical properties of solids,
especially:
the electrical, thermodynamic, and structural properties of
crystalline solids, such as semiconductors.
• The properties are deduced from Schrödinger’s equation. For a collection of
atomic nuclei and electrons interacting with electrostatic forces.
 What is the point?

• Understanding the electrical properties of solids is right at the heart of

modern society and technology.

• The entire computer and electronics industry relies on tuning of a

special class of material, the semiconductor for instance, which lies
right at the metal-insulator boundary. Solid state physics provides a
background to understand what goes on in semiconductors and
nanomaterials.
 Why study crystal structures?

❑ When we look around much of what we see is non-crystalline (organic things like
wood, paper, sand; concrete walls, etc. → some of the things may have some
crystalline parts!).
❑ But, many of the common ‘inorganic’ materials are ‘usually*’ crystalline:
◘ Metals: Cu, Zn, Fe, Cu-Zn alloys
◘ Semiconductors: Si, Ge, GaAs
◘ Ceramics: Alumina (Al2O3), Zirconia (Zr2O3), SiC, SrTiO3 (Strontium titanate)
❑ Also, the usual form of crystalline materials (say a Cu wire or a piece of alumina)
is polycrystalline and special care has to be taken to produce single crystals
❑ The crystal structure directly influences the properties of the material
1.2 STRUCTURE OF SOLIDS

Can be classified under several criteria:

•Using electrical criterion: Conductors, Insulators,

Semiconductors
•Using atomic arrangements: Amorphous,
Polycrystalline, Crystalline.
 The Three General Types of Solids
Single Crystal
Polycrystalline
Amorphous

Each type is characterized by the size of

the ordered region within the material.

An ordered region is a spatial volume in which atoms or

molecules have a regular geometric arrangement or periodicity.
Types of Solids
Amorphous: lacks a systematic
atomic arrangement

SiO2

9
 Crystalline Solids
• We will deal with crystalline solids, that is
solids with an atomic structure based on a
regular repeated pattern.

• Many important solids are crystalline.

Carbon, Diamond, Silicon, Germanium etc…
1.3 Crystalline State
A perfect crystal is a periodic arrangement of atoms in y

space from - to +
a is the nearest neighbors b is the nearest neighbors
distance in the y direction b
distance in the x direction R
C

A B a x

Periodicity → Atoms A, B, and C are equivalent . From each site

the crystal appears the same

Crystal possesses a translational symmetry

 Crystal = Lattice + Motif
Motif or Basis:
an entity (typically an atom or a group of atoms) associated with each lattice point

Lattice ➢ the underlying periodicity of the crystal

Motif ➢ Entity associated with each lattice points

Lattice ➢ how to repeat

Motif ➢ what to repeat

Lattice Crystal
Translationally periodic Translationally periodic
arrangement of points arrangement of motifs
1.4 BASIC DEFINITIONS
• The structure of an Ideal Crystal can be described in
terms of a mathematical construction called a Lattice.
A Lattice ≡
• A 3-dimensional periodic array of points in space. Auguste Bravais
• The Crystal Structure is defined once both the lattice 1811-1863
& the basis are specified. That is 1850: 14 lattices
Crystal Structure
≡ Lattice + Basis
Space Lattice A lattice is also called a Space Lattice

An array of points such that every point has identical

surroundings

In Euclidean space  infinite array

 We can have 1D, 2D or 3D arrays (lattices)

 Basic Definitions, cont’d Bravais lattice: all lattice
points are equivalent

Lattice ⎯⎯→

Basis ⎯⎯⎯→

⎯ Crystal
Structure
Example ▪ Does the array of points at the centers of the Carbon atoms in the
graphene sheet as shown below form a lattice?

Part of the hexagonal array of C atoms which forms

the Graphene structure
The answer is NO!

Not all carbon positions

form a lattice
 As atoms A & B do not
have identical surrounding
both cannot be lattice
points
There are two classes of lattices: the Bravais and the non-Bravais. In a Bravais lattice all
lattice points are equivalent and hence by necessity all atoms in the crystal are of the same
kind. In a non-Bravais lattice, some of the lattice points are non-equivalent.
The lattice is defined by fundamental translation vectors. For example, the position
vector of any lattice site of the two dimensional lattice can be written as:
  
T = n1a1 + n2 a2

   
T = n1a1 + n2 a2 + n3 a3

where a1 and a2 are the two vectors shown , and n1,n2 is a pair of integers whose values
depend on the lattice site.
 
The vectors a1 and a2 are called the primitive translation vectors.
Another example, in 2 dimensions:

The choice of the primitive translation vectors is not unique. One could equally well take the vectors a1
and a = a1+a2 as primitive translation vectors.
Unit cell. In the case of a rectangular two dimensional lattice the unit cell is the rectangle, whose sides are
the vectors a1 and a2.
A primitive unit cell is the unit cell with the smallest area which produces this coverage
The unit cell can be primitive and non-primitive (or conventional). In some
cases it is more convenient to deal with a unit cell which is larger, because it
exhibits the symmetry of the lattice more clearly. The unit cell in this case
is larger.
The area of the non-primitive unit cell
is an integral multiple of the primitive
unit cell.

If the lattice points are only at the corners, the

unit cell is primitive otherwise non-primitive

The unit cell that is actually used is largely a matter of

convenience, and it may contain a lattice point in its centre
(Conventional cell)
Wigner-Seitz cell: smallest possible primitive cell, which consist
of one lattice point and all the surrounding space closer to it
than to any other point. The construction of the W-S cell in the
reciprocal lattice delivers the first Brillouin zone (important for
diffraction).
• Wigner-Seitz primitive unit cell
The cell may be chosen by first picking a lattice point. Then, lines are drawn to all
nearby (closest) lattice points. At the midpoint of each line, another line (or a plane,
in 3D) is drawn normal to each of the first set of lines.

3D BCC
2D case
 in 2 Dimensions, there are ONLY Five Bravais Lattices
Parallelogram (general)
Rectangle

Centered Rectangle

120 Rhombus Square

1.4 The 14 bravais lattices and the 7 crystal systems

• In 1848, Auguste Bravais demonstrated that in a 3-

dimensional system there are fourteen possible lattices
Auguste Bravais
(1811-1863)

There are 7 crystal systems of varying symmetry. Seven unique unit cell shapes that can be
stacked together to fill three-dimensional space
These systems are built by changing the lattice parameters:
a, b, and c are the edge lengths
, , and  are inter-axial angles
Now let us consider some simple crystals
EQUIVALENT SITES (ATOMIC POSITIONS)
IN CUBIC UNIT CELLS

Simple Cubic, SC - one atom per unit cell -

corner atoms only
(0,0,0) (1,0,0) (1,1,0) (0,1,0)
(0,0,1) (1,0,1) (1,1,1) (0,1,1)
Body Centered Cubic, BCC - two per unit cell -
corner atoms as above, plus (1/2, 1/2, 1/2)
Face Centered Cubic, FCC - four per unit cell -
corner atoms as above plus
(1/2, 1/2, 0) (1/2, 0, 1/2) ( 0, 1/2, 1/2)
(1, 1/2, 1/2) (1/2, 1, 1/2) (1/2, 1/2, 1)
Lattice Sites in an Orthogonal Coordinate System
i.e. Simple Cubic
▪ Cubic

Number of Bravais lattices Conditions

simple
a1 = a2 = a3
body-centered cubic
face-centered cubic
 =  =  = 90

a a a
a a a
a a a

simple cubic body-centered Cubic face-centered cubic

▪ Tetragonal
Number of Bravais lattices Conditions

simple a1 = a2 ≠ a3
body-centered  =  =  = 90

c c
a a
a a
simple tetragonal body-centered tetragonal
▪ Orthorhombic:
Number of Bravais lattices Conditions
simple
body-centered a1 ≠ a2 ≠ a3
face-centered  =  =  = 90
base-centered

c
c c c

b b b b
a a a a

simple body-centered face-centered base-centered

▪ Hexagonal

Number of Bravais lattices Conditions

a1 = a2 ≠ a3
simple  =  = 90
 = 120

simple hexagonal
▪ Rhombohedral

Number of Bravais lattices Conditions

a1 = a2 = a3
simple
 =  =   120  90

simple rhombohedral
▪ Monoclinic
4 rectangular faces and 2 parallelogram faces

Number of Bravais lattices Conditions

simple a1 ≠ a2 ≠ a3
base-centered  =  = 90  

simple monoclinic base-centered monoclinic

▪ Triclinic

Number of Bravais lattices Conditions

a1 ≠ a2 ≠ a3
simple
    

simple triclinic
 Cubic Lattices
•To see what fraction of each atom is actually inside the unit cell, we look at “sliced” views:

•Every atom completely inside a cell is only in 1 cell.

•Every atom along a cell face is in 2 cells. (½ in each)
•Every atom along an edge is in 4 cells. (¼ in each)
•Every atom in the corner is in 8 cells. (1/8 in each)
Shared by 8 Shared by 2
unit cells unit cells
1 atom/unit cell 2 atoms/unit cell 4 atoms/unit cell
(8 x 1/8 = 1) (8 x 1/8 + 1 = 2) (8 x 1/8 + 6 x 1/2 = 4)
42
Coordination Number
• The number of touching or nearest neighbor atoms
• SC is 6
• BCC is 8
• FCC is 12
• HCP is 12
 2-D view BCC

Illustration of coordinations in (a) SC and (b) BCC unit cells. Six atoms
touch each atom in SC, while the eight atoms touch each atom in the BCC
unit cell.
 Coordination number =12

y-z plane

x-z plane x-y plane

z
x
y
 Atomic Packing Factor
• For a Bravais Lattice,

• When calculating the APF, the volume of the atoms in the unit cell is
calculated AS IF each atom was a hard sphere, centered on the lattice point
& large enough to just touch the nearest-neighbor sphere.
Determining the Relationship between Atomic
Radius and Lattice Parameters
Atoms touch along the edge of the cube in SC structures.

a = 2r
In BCC structures, atoms touch along the body diagonal

4r
a=
3
In FCC structures, atoms touch along the face diagonal of the cube.

4r
a=
2
 Atomic Packing Factor Simple Cubic
Rare due to low packing density (only Po – Polonium -- has this structure)

a 4 3
(1)( r )
R=0.5a
Packing Factor = 3 = 0.52
3
( 2r )
 Atomic Packing Factor Body Centered Cubic : BCC
ex: Cr, W, Fe (), Tantalum, Molybdenum

Body diagonal

R
a

atoms volume
4
unit cell 2
3
 ( 3a/4 ) 3
atom 3a = 4r
APF =
volume
a3
unit cell

• APF for a body-centered cubic structure = 0.68

Atomic Packing Factor Face Centered Cubic: FCC
ex: Al, Cu, Au, Pb, Ni, Pt, Ag

2a
Unit cell contains:
6 x 1/2 + 8 x 1/8
= 4 atoms/unit cell
a
4
(4 atoms/cell)( r 3 )
Packing Factor = 3
Face diagonal a3
Since, for FCC unit cells, a = 4r/ 2
4
(4)( r 3 )
3 
Packing Factor = =  0.74
3 18
( 4r / 2 )

2a = 4 r
 Hexagonal Close-Packed Structure (HCP) ex: Cd, Mg, Ti, Zn

• ABAB... Stacking Sequence

A sites

c
B sites

A sites

a
 Some properties of equilateral triangles

All sides are equal: AB = AC = BC = a

The median, the angle bisector and the perpendicular bisector all coincide at o
All three of them again are equal: AD = BE = CF = h = 3 a
2
2 1
OA = OB = OC = R = h = a
3 3
1 1
OD = OE = OF = r = h = a
3 2 3
53
 3 3a 2
Volume of hcp unit cell = c
2
 h a/2

a
2 2
a 2 a 1 3
a = h +    h = a −   = 1−  a =
2 2
a
2 2 4 4

Distance x from an atom to the middle of the triangle

2 2 3 3 1
x= h= a = 2 a = a
3 3 4 3 3
c 1 2 2 c 8
= a −x = a − a =
2 2 2
a  =
2 3 3 a 3

c/2
a

x
 HEXAGONAL CLOSED PACKED STRUCTURE

n  Vs
APF =
Vc
3
4 3 a 4 a
Vs = 6  r substitute r =  Vs = 6   = a 3
3 2 3 8

3 3a 2  c
Volume of hcp unit cell =
2

n  Vs a 3 2 a
APF = = 2
=  = 0.74 = 74 %
Vc 3 3a 3 3 c c 8 a 3
c = or =
2 a 3 c 8
56
Summary

Atoms Coordination Packing

Structure a0 vs. r Examples
per cell Number factor

SC a = 2r 1 6 0.52
Polonium
(Po)

4 Fe,W,Mo,Nb
BCC a = r 2 8 0.68 ,Ta,K,Na,V,Z
3
r,Cr
4
a= r Fe,Cu,Au,Pt,
FCC 2 4 12 0.74
Ag,Pb,Ni

a = 2r Ti,Mg,Zn,Be,
HCP c  1.633a 6 12 0.74
Co,Zr,Cd