SOLID STATE PHYSICS-1

Muhammad Rizwan Department of Physics University of Wah

STRUCTURE OF SOLIDS
Can be classified under several criteria based on atomic arrangements, electrical properties, thermal properties, chemical bonds etc. Using electrical criterion: Conductors, Insulators, Semiconductors Using atomic arrangements: Amorphous, Polycrystalline, Crystalline.

Amorphous Solids
No regular long range order of arrangement in the atoms. Example: Polymers, cotton candy, common window glass, ceramic. Can be prepared by rapidly cooling molten material. Rapid minimizes time for atoms to pack into a more thermodynamically favorable crystalline state.

Amorphous Solids

Continuous random network structure of atoms in an amorphous solid

Polycrystalline Solids
Atomic order present in sections (grains) of the solid. Different order of arrangement from grain to grain. Grain sizes = hundreds of m. An aggregate of a large number of small crystals or grains in which the structure is regular, but the crystals or grains are arranged in a random fashion.

Polycrystalline Solids

Crystalline Solids
Atoms arranged in a 3-D long range order. Single crystals emphasizes one type of crystal order that exists as opposed to polycrystals.

The Basis
(or basis set)

The set of atoms which, when placed at each lattice point, generates the Crystal Structure.

Crystal Structure Primitive Lattice + Basis

Translate the basis through all possible lattice vectors

T = n1a1 + n2a2 + n3a3 to get the Crystal Structure

 The periodic lattice symmetry is such that the

atomic arrangement looks the same from an arbitrary vector position r as when viewed from the point

r' = r + T

(1)

where T is the translation vector for the lattice:

T = n1a1 + n2a2 + n3a3

Mathematically, the lattice & the vectors a1,a2,a3 are

Primitive
if any 2 points r & r' always satisfy (1) with a suitable choice of integers n1,n2,n3.

2 Dimensional Lattice Translation Vectors

Consider a 2-dimensional lattice (figure). Let the

2 Dimensional Translation Vector be Rn = n1a + n2b

(Sorry for the notation change!!)

a & b are 2 d Primitive Lattice Vectors, n1, n2 are integers. Once a & b are specified by the lattice geometry & an origin is chosen, all symmetrically equivalent points in the lattice are determined by the translation vector Rn. That is, the lattice has translational symmetry. Note that the choice of Primitive Lattice vectors is not unique! So, one could equally well take vectors a & b' as primitive lattice vectors.

Point D(n1, n2) = (0,2) Point F(n1, n2) = (0,-1)

2-Dimensional Unit Cells Unit Cell

The smallest component of the crystal (group of
atoms, ions or molecules), which, when stacked together with

pure translational repetition, reproduces the whole crystal.

b
S

a
S S

S
S

S
S

S
S S

Unit Cell
The smallest component of the crystal (group of atoms,
ions or molecules), which, when stacked together with pure

translational repetition, reproduces the whole crystal.

The choice of unit cell is not unique!

S S S

Primitive Unit Cells

Note that, by definition, the Primitive Unit Cell must

contain ONLY ONE lattice point.

There can be different choices for the Primitive Lattice Vectors, but the Primitive Cell volume must be independent

of that choice.

A 2 Dimensional Example!
P = Primitive Unit Cell NP = Non-Primitive Unit Cell

Unit Cells Types A unit cell is the smallest component of the crystal that reproduces the whole crystal when stacked together.
Primitive (P) unit cells contain only a single lattice point. Internal (I) unit cell contains an atom in the body center. Face (F) unit cell contains atoms in the all faces of the planes composing the cell. Centered (C) unit cell contains atoms centered on the sides of the unit cell.

Primitive

Face-Centered

Body-Centered

End-Centered

Combining 7 Crystal Classes (cubic, tetragonal, orthorhombic, hexagonal, monoclinic, triclinic, trigonal) with 4 unit cell types (P, I, F, C) symmetry allows for only 14 types of 3-D lattice.

Crystal Lattices
Bravais Lattices
(BL)

Non-Bravais Lattices
(non-BL)

All atoms are the same kind

All lattice points are equivalent

Atoms are of different kinds.

Some latticeof different kinds. Some Atoms are points arent equivalent. A combination of 2 equivalent. lattice points are notor more BL

2 d examples

Conventional & Primitive Unit Cells

Unt Cell Types
Primitive
A single lattice point per cell
The smallest area in 2 dimensions, or The smallest volume in 3 dimensions

Conventional
(Non-primitive)
More than one lattice point per cell
Volume (area) = integer multiple of that for primitive cell

Simple Cubic (sc)

Conventional Cell = Primitive cell

Body Centered Cubic (bcc)

Conventional Cell Primitive cell

Conventional Unit Cells

A Conventional Unit Cell just fills space when translated through a subset of Bravais lattice vectors. The conventional unit cell is larger than the primitive cell, but with the full symmetry of the Bravais lattice.
The size of the conventional cell is given by the lattice constant a.

FCC Bravais Lattice

The full cube is the Conventional Unit Cell for the FCC Lattice

Conventional & Primitive Unit Cells Face Centered Cubic Lattice

Primitive Unit Cell
(Shaded)

Primitive Lattice Vectors

Lattice Constant

a1 = ()a(0,1,0) a2 = ()a(1,0,1) a3 = ()a(1,1,0)

Note that the ais are

Conventional Unit Cell

(Full Cube)

NOT Mutually Orthogonal!

Conventional & Primitive Unit Cells Body Centered Cubic Lattice

Primitive Unit Cell

Primitive Lattice Vectors

Note that the ais are

Lattice Constant Conventional Unit Cell
(Full Cube)

a1 = ()a(1,1,-1) a2 = ()a(-1,1,1) a3 = ()a(1,-1,1) NOT mutually orthogonal!

It can be shown that, in 2 Dimensions, there are

Five (5) & ONLY Five Bravais Lattices!

Classification of Crystal Structures

Crystallographers showed a long time ago that, in 3 Dimensions, there are

14 BRAVAIS LATTICES + 7 CRYSTAL SYSTEMS

This results in the fact that, in 3 dimensions, there are only 7 different shapes of unit cell which can be stacked together to completely fill all space without overlapping. This gives the 7 crystal systems, in which all crystal structures can be classified. These are:

The Cubic Crystal System (SC, BCC, FCC) The Hexagonal Crystal System (S) The Triclinic Crystal System (S) The Monoclinic Crystal System (S, Base-C) The Orthorhombic Crystal System (S, Base-C, BC, FC) The Tetragonal Crystal System (S, BC) The Trigonal (or Rhombohedral) Crystal System (S)
21

22

Some concepts
Number of atoms per unit cell Corner atom = 1/8 per unit cell Body centered atom = 1 Face centered atom = 1/2
3a
Face diagonal=

Body diagonal=

2a

Coordination Number
For a Bravais Lattice,

The Coordinaton Number

The number of lattice points closest to a given point
(the number of nearest-neighbors of each point).

Because of lattice periodicity, all points have the same number of nearest neighbors or coordination number.
(That is, the coordination number is intrinsic to the lattice.)

Examples
Simple Cubic (SC) coordination number = 6 Body-Centered Cubic coordination number = 8 Face-Centered Cubic coordination number = 12
Crystal Structure 24

Atomic Packing Factor

(or Atomic Packing Fraction)
For a Bravais Lattice,

The Atomic Packing Factor (APF)

the volume of the atoms within the unit cell divided by the volume of the unit cell.

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 nearestneighbor sphere.

1- CUBIC CRYSTAL SYSTEMS

3 Common Unit Cells with Cubic Symmetry

Simple Cubic (SC)

Body Centered Cubic (BCC)

Face Centered Cubic (FCC)

3 Common Unit Cells with Cubic Symmetry

The Simple Cubic (SC) Lattice

The SC Lattice has one lattice point in its unit cell, so its unit cell is a primitive cell.
In the unit cell shown on the left, the atoms at the corners are cut because only a portion (in this case 1/8) belongs to that cell. The rest of the atom belongs to neighboring cells. The Coordinatination Number of the SC Lattice = 6.

c a
28

Simple Cubic Structure (SC)

Rare due to poor packing (only Po has this structure) Close-packed directions are cube edges.
Coordination # = 6 (# nearest neighbors)

1 atom/unit cell

Simple cubic(P)
Number of atoms per unit cell Coordination number Atomic packing factor

1/8 X 8 = 1

Simple cubic

Number of atoms per unit cell Coordination number Atomic packing factor

1/8 X 8 = 1

Simple cubic
Number of atoms per unit cell Coordination number Atomic packing factor 1/8 X 8 = 1

6 0.52

Simple Cubic (SC) Lattice

Atomic Packing Factor
a = 2r APF SC = V atoms = 0.52 V unit cell

33

The Body Centered Cubic (BCC) Lattice

The BCC Lattice has two lattice points per unit cell so the BCC unit cell is a non-primitive cell. Every BCC lattice point has 8 nearestneighbors. So (in the hard sphere model) each atom is in contact with its neighbors only along the body-diagonal directions. Many metals (Fe,Li,Na..etc), including the alkalis and several transition elements have the BCC structure.

c a
34

Body centered cubic(I)

Number of atoms per unit cell Coordination number Atomic packing factor 1/8 X 8 + 1 = 2

Body centered cubic

Number of atoms per unit cell Coordination number Atomic packing factor 1/8 X 8 + 1 = 2

Body centered cubic

Number of atoms per unit cell Coordination number Atomic packing factor 1/8 X 8 + 1 = 2

8 0.68

BCC Structure

Body Centered Cubic (BCC) Lattice

Atomic Packing Factor
4R a= 3 V atoms = 0.68 V unit cell

APF BCC

(0.433a)

Crystal Structure

39

 APF for a body-centered cubic structure = 0.68

Atomic Packing Factor: BCC

3a
a

2a
Close-packed directions: R atoms unit cell APF = 2 a 4 length = 4R = volume atom volume unit cell
40

3a

p ( 3 a/4 ) 3

3 a3

Elements with the BCC Structure

c- The Face Centered Cubic (FCC) Lattice

In the FCC Lattice there are atoms at the corners of the unit cell and at the center of each face.
The FCC unit cell has 4 atoms so it is a non-primitive cell. Every FCC Lattice point has 12 nearest-neighbors. Many common metals (Cu,Ni,Pb..etc) crystallize in the FCC structure.

Crystal Structure

42

Face centered cubic(F)

Number of atoms per unit cell Coordination number Atomic packing factor
1/8 X 8 + 1/2 X 6 = 4

Face centered cubic

Number of atoms per unit cell Coordination number Atomic packing factor
1/8 X 8 + 1/2 X 6 = 4

12

Face centered cubic

Number of atoms per unit cell Coordination number Atomic packing factor
1/8 X 8 + 1/2 X 6 = 4

12 0.74*

*Highest packing possible in real structures

FCC Structure

Face Centered Cubic (FCC) Lattice

Atomic Packing Factor

4R a= 3

APF BCC FCC

V atoms 0.74 = = 0.68 V unit cell

Unit cell contains: 6 x 1/2 + 8 x 1/8 = 4 atoms/unit cell atoms unit cell APF =
Crystal Structure

4 3

p ( 2 a/4 ) 3 a3

volume atom volume unit cell 47

Atomic Positions
Z (0,0,1)

(1/2,1/2,1)

(0,1,1)

(1/2,1/2,1/2)
(1/2,0,1/2) Y (0,0,0)

Hexagonal Close-Packed Structure (HCP)

ABAB... Stacking Sequence

3D Projection
A sites

2D Projection
Top layer

B sites
A sites

Middle layer Bottom layer

a
Coordination # = 12 APF = 0.74 c/a = 1.633 6 atoms/unit cell

ex: Cd, Mg, Ti, Zn

49

FCC & BCC: Conventional Cells With a Basis

Alternatively, the FCC lattice can be viewed in terms of a conventional unit cell with a 4-point basis.

Similarly, the BCC lattice can be viewed in terms of a conventional unit cell with a 2- point basis.

2- HEXAGONAL CRYSTAL SYSTEMS

In a Hexagonal Crystal System, three equal coplanar axes intersect at an angle of 60, and another axis is perpendicular to the others and of a different length.

The atoms are all the same.

Crystal Structure

Hexagonal Close Packed (HCP) Lattice

The HCP lattice is not a Bravais lattice, because orientation of the environment of a point varies from layer to layer along the c-axis.

Comments on Close Packing

Close pack
A A A
A A

A
B A B

A
B

A A
B A

BA BA BA B A C C C
A BA BA B A C C C C A

A
A

BA BA B A B A C C C
Sequence ABABAB.. -hexagonal close pack

Sequence AAAA - simple cubic Sequence ABAB - body centered cubic

53

Sequence ABCABCAB.. -face centered cubic close pack

Crystal Structure

Miller Index For Cubic Structures

Miller index is used to describe directions and planes in a crystal. Directions - written as [u v w] where u, v, w. Integers u, v, w represent coordinates of the vector in real space. A family of directions which are equivalent due to symmetry operations is written as <u v w> Planes: Written as (h k l). Integers h, k, and l represent the intercept of the plane with x-, y-, and z- axes, respectively. Equivalent planes represented by {h k l}.

Miller Indices: Directions

z

y x
[1] Draw a vector and take components [2] Reduce to simplest integers [3] Enclose the number in square brackets x 0 0 y 2a 1 [0 1 1] z 2a 1

Negative Directions

y x
[1] Draw a vector and take components [2] Reduce to simplest integers [3] Enclose the number in square brackets x 0 0 y -a -1 z 2a 2

0 1 2

Miller Indices: Equivalent Directions

Equivalent directions due to crystal symmetry:

1: 2: 3:

[100] [010] [001]

y x 2 1

Notation <100> used to denote all directions equivalent to [100]

Directions

The intercepts of a crystal plane with the axis defined by a set of unit vectors are at 2a, -3b and 4c. Find the corresponding Miller indices of this and all other crystal planes parallel to this plane.

The Miller indices are obtained in the following three steps: 1. Identify the intersections with the axis, namely 2, -3 and 4. 2. Calculate the inverse of each of those intercepts, resulting in 1/2, -1/3 and 1/4. 3. Find the smallest integers proportional to the inverse of the intercepts. Multiplying each fraction with the product of each of the intercepts (24 = 2 x 3 x 4) does result in integers, but not always the smallest integers. 4. These are obtained in this case by multiplying each fraction by 12. 5. Resulting Miller indices is 6 4 3 6. Negative index indicated by a bar on top.

Miller Indices of Planes

z=

y x=a x y=

x [1] Determine intercept of plane with each axis a [2] Invert the intercept values 1/a

1/
0
(1 0 0)

1/

[3] Convert to the smallest integers

[4] Enclose the number in round brackets

Miller Indices of Planes

x [1] Determine intercept of plane with each axis 2a [2] Invert the intercept values 1/2a

y 2a 1/2a

2a 1/2a
1

[3] Convert to the smallest integers

[4] Enclose the number in round brackets

1
(1 1 1)

Planes with Negative Indices

x
x
[1] Determine intercept of plane with each axis a [2] Invert the intercept values [3] Convert to the smallest integers [4] Enclose the number in round brackets 1/a 1

-a -1/a
-1 1 1 1

a 1/a
-1

Equivalent Planes
(100) plane

(001) plane (010) plane

y
x Planes (100), (010), (001), (100), (010), (001) are equivalent planes. Denoted by {1 0 0}. Atomic density and arrangement as well as electrical, optical, physical properties are also equivalent.

The (111) surface Assignment Intercepts : a , a , a Fractional intercepts : 1 , 1 , 1 Miller Indices : (111)

The (210) surface Assignment Intercepts : a , a , Fractional intercepts : , 1 , Miller Indices : (210)

Crystallographic Planes z
example 1. Intercepts 2. Reciprocals 3. 4. Reduction Miller Indices a 1 1/1 1 1 (110) a 1/2 1/ 2 2 (100) b c 1/ 1/ 0 0 0 0 b 1 1/1 1 1 c 1/ 0 0

c y a x c z b

example 1. Intercepts 2. Reciprocals 3. 4. Reduction Miller Indices

y a
x b

Symmetry-equivalent surfaces
the three highlighted surfaces are related by the symmetry elements of the cubic crystal - they are entirely equivalent.
In fact there are a total of 6 faces related by the symmetry elements and equivalent to the (100) surface - any surface belonging to this set of symmetry related surfaces may be denoted by the more general notation {100} where the Miller indices of one of the surfaces is instead enclosed in curly-brackets.

Family of Planes {hkl} Ex: {100} = (100), (010), (001), (100), (010), (001)

Diamond Lattice Structure

a = lattice constant

Crystalline Structure of Diamond