The Solid State

To understand the solid state, we must first understand how matter exists

Matter : "anything that occupies space and has weight“

(original definition made in the 18th century when little was known about "matter“)

The "Scientific Revolution" was just getting started in the 18th century and
science was referred to as "Natural Philosophy"

We will delve into the “building-blocks" of matter and how solids originate

Initial knowledge concerning physics and chemistry; some ability in mathematics

 Early workers knew that matter existed in three forms, i.e., solids, liquids and gases
Water was studied extensively because it was easy to freeze and boil
Differences between the three states of matter :
how these states differ physically from one another
The major difference is a matter of energy, the solid having the least energy of all
The gaseous state : molecules are free to roam (e.g., steam)
"a state of matter in which the substance expands readily to fill any containing vessel“
The liquid state : molecules are bound together (condensation of steam to water)
They are still free to move in 3Ds but still have to be confined in a container in the same
manner as the gaseous state
Important differences : translational degrees of freedom are restricted
(since the molecules are much closer together and can interact with one another giving
the liquid state its unique properties)
The molecules of a liquid are not free to flow in any of the three directions, but are bound
by intermolecular forces
The solid state : molecules are bound & ordered into a tight-knit structure
On removing more energy from the liquid, it finally reaches a temperature where it
"freezes", i.e., it converts to a solid (water to ice)
Molecular sense  the molecules become ordered they form a lattice-like framework
The solid differs from the other states of matter in
that a long range ordering of atoms or molecules has appeared
To achieve long range order in any solid, one must stack atoms or molecules in a
symmetrical way to completely fill all of the space available. This is not a trivial matter
since solids require that all of the atoms be arranged in a symmetrical pattern in 3D.
Thus, if we could actually see these atoms in a solid, we would find that they are
composed of specific "building blocks", called "propagation models" or “units"
Due to the symmetry criteria, only certain types of propagation models / shapes
(3D models available) can be used to form a symmetrical solid

Atomic forms / propagation models suitable for forming the solid state

Tetrahedral Hexagonal Cubic

4 atoms per unit 6 atoms per unit 8 atoms per unit
Only even-numbered sets of atoms are suitable
Odd-numbered units of 5, 7, or 9 atoms per unit can not be used
(such units cannot be fit together in a 3D which has long range order and symmetry)
 Kinds of solids :
Homogeneous (composed from atoms that are all the same) and
Heterogeneous (composed from different atoms)
Building of a solid structure :
Solid structures are based on the largest atom present, as well as how it
stacks together (its valence) in space filling-form

For most inorganic compounds, this is the oxygen atom, e.g., oxides, silicates,
phosphates, sulfates, borates, tungstates, vanadates, etc.

Few exceptions : chalcogenides, halides, hydrides, etc.

(even in those compounds, the structure is based upon aggregation of the
largest atom, e.g.., the sulfur atom in ZnS)

Consider propagation units in their space-filling aspects

These are solid state building blocks that we can stack in a symmetrical form to infinity

Tetrahedron (4)
Octahedron (6)
Basic propagation units found in solids
Hexagon (6 or 8)
Cube (8)
 Solid State Sciences Many areas of overlap & interest
Solid state physics, solid state chemistry (SSC), materials science
ceramics & ceramic engineering, mineralogy and metallurgy
SSC is been recognized as a separate branch of physical science and
arguably it is the most central of the solid state sciences
SSC is concerned with the synthesis, structure, properties and applications
of solid materials
Materials are usually inorganic (mainly non-molecular), but not exclusively so;
Metals ; Organic solids ; Minerals (natural occurrance)
Materials are usually crystalline, but not exclusively so; Glasses

Crystalline
Regular or periodic arrangement
Long-range order (low energy state)

Solids

Amorphous
Random arrangement
Short-range order (~ a few atomic diameter)
e.g. glass, plastics, rubber
 Single e.g. diamond, quartz, mica
crystals

Crystal

Polycrystalline
Small crystallites e.g. metals & ceramics
(grains)

The branch of science which deals with the study of geometrical forms and
physical properties of crystalline solids is called crystallography.

It is necessary to understand the strong correlation between the structure of

a material and its physical properties
 Every crystal structure represents
an ordered arrangement of identical chemical units in space
If every such chemical unit is replaced by a point identically, it results in a
collection of points having an ordered arrangement in space

Crystal Lattice or Direct Lattice
lattice point or lattice position (points) ; basis or motif (chemical unit)
As lattice points form an ordered array in space, any such lattice point can be represented by
a vector (rn1n2n3) which itself is made up of three non coplanar translation vectors (a, b and c)
which are used to describe the lattice
Vectors a, b and c are considered
from a common origin at one lattice pt.
n1, n2 and n3 are a set of three
numbers representing one lattice pt.

If rn1n2n3 are so selected that n1, n2 and n3 are all integers lying between + and 
(primitive lattice)
But if rn1n2n3 are so selected that n1, n2 and n3 may be both integers and fractions
for different lattice points (non-primitive lattice)
By changing vectors, the same lattice may be described as primitive or non-primitive

A lattice represents an imaginary situation but it becomes a reality to form

a crystal structure when a basis is attached identically to each lattice point

Logical relation : Lattice + Basis = Crystal Structure

Lattice translation operation
Defined as the displacement of a crystal parallel to itself by a crystal translation vector

T = ua + vb + wc : u, v, w are arbitrary integers

r = r + T : Any two lattice points are connected by a vector of this form

Unit cell of a lattice

Smallest unit of the lattice which, on continuous repetition, generates the complete lattice
It may be primitive or non-primitive depending on the vector used

Wigner-Seitz cell An oblique lattice in 2D

Connect a given lattice point to all nearby lattice points
Draw normals at the midpoints of lines connecting the lattice points
The smallest vol occupied by these normals is the W-S primitive cell

The choice of a conventional unit cell is a matter of convenience

Surface / face (usually planar); edge (intersection of two faces) ; interfacial angle
Basic laws regarding forms of the crystals (derived from external nature)
I. Steno’s law of the constancy of interfacial angles
The angles between the corresponding faces on various crystals of the same substance
are constant

II. Haüy’s law of rational intercepts

The regular external form of crystals is
a reflection of the inner regular order of
the arrangement of the building units
A crystal is made up of
innumerable smaller crystals

If the intercepts made by a face on the three non-coplanar axes are a, b, and c and
if any other face cuts the three axes with intercepts x, y, and z, then
x : y : z = pa : qb : rc where, p, q, r = small integers (1, 2, 3 …)

All faces cut a given axis at distances from the origin which bear a simple ratio to one another
These ratios (p : q : r) characterize and represent any plane of the crystal
The coefficients (p, q, r) are called Weiss indices
Miller indices (hkl) : Obtained by taking reciprocals of the coefficients p, q, r and when
necessary the ratio is multiplied by the least common multiple

III. Law of constancy of symmetry

Symmetry in crystals may be with respect to a plane, a line or a point
 Miller indices of planes : (hkl) Intercepts : (a/h b/k c/l)

Set of planes : {hkl} e.g., {100} represents (100), (010) & (001)
planes in a cubic crystal
Direction of a plane : [hkl]

<hkl> denotes the set of all directions that are equivalent to [hkl] by symmetry

Miller indices of planes in hexagonal crystals are an exception

where four indices are often used (hkil)

Origin at solid circle

Positive a directions indicated by arrows

 a
For cubic system d hkl 
h2  k 2  l 2

1 h2  k 2 l 2
For tetragonal system 2
 2
 2
d hkl a c

1 h2 k 2 l 2
For orthorhombic system 2
 2 2 2
d hkl a b c
 Utility of interplanar distances
If we can determine dhkl experimentally, the constancy of the quantity

d hkl h 2  k 2  l 2 will (i) determine the value of a

(ii) indicate the cubic system the crystal belongs

1 1
Simple cubic lattice d100 : d110 : d111  1: :  1: 0.707 : 0.577
2 3

Face-centred 1 1 1
cubic lattice
d200 : d220 : d111  : :  1: 0.707 :1.154
2 2 2 3

Body-centred 1 1 1
cubic lattice d200 : d110 : d222  : :  1:1.414 : 0.577
2 2 2 3
 Diffraction of X-rays by crystals

Bragg’s equation : 2d sin   n ; n  1, 2,3

d 
Alternatively,   2   sin  hkl  2d hkl sin  hkl
n
Diffraction pattern of a cubic system

a
d hkl 
h2  k 2  l 2
a
2 sin  hkl
h k l
2 2 2

2
sin 2 hkl 
4a 2
h 2
 k2  l2 
2
sin  hkl  K  h  k  l
2 2 2 2
 Where K 
4a 2

Assign consecutive integral values (0, 1, 2, …) to h, k, and l

Calculate a series of dhkl and sin 
Interplanar distances and the corresponding expected angles of diffraction
Primitive cubic lattice
221
hkl 100 110 111 200 210 211 220 300 310 311 222 320
dhkl a a/2 a/3 a/2 a/5 a/6 a/22 a/3 a/10 a/11 a/12 a/13
sin2  K 2K 3K 4K 5K 6K 8K 9K 10K 11K 12K 13K
sin2   7, 15, 23, 28 etc. (these can’t be written in the form of h2 + k2 + l2)

Body-centered cubic lattice

221
hkl 100 110 111 200 210 211 220 300 310 311 222 320
dhkl a/2 a/2 a/6 a/22 a/10 a/12
sin2  2K 4K 6K 8K 10K 12K

Face-centered cubic lattice

221
hkl 100 110 111 200 210 211 220 300 310 311 222
dhkl a/3 a/2 a/22 a/11 a/12
sin2  3K 4K 8K 11K 12K
Additional Slides
 Systematic absences in non-primitive lattice types
Lattice type Coordinates of lattice points Systematic
absence
P 0,0,0 None
A 0,0,0; 0,½,½ k+l=2n+1
B 0,0,0; ½,0,½ h+l=2n+1
C 0,0,0; ½,½,0 h+k=2n+1
F 0,0,0; 0,½,½; ½,0,½; ½,½,0 h,k,l neither all
odd nor all even
I 0,0,0; ½,½,½ h+k+l=2n+1
 Lattice planes & d-spacings  how many are possible?
Usually large, but finite!
First,  of X-ray beam places a lower limit on the d-spacings that may be
experimentally observed
n 
d   sin  max  1
2sin  2

For CuK α ,  0.77
2
For smaller d-spacings, target metal must be changed (e.g., Mo)

Second, Miller indices can have only integral values (i.e., h,k,l= 0, 1, 2, …)
Target K1 K2 K(avg.) Filter

Cr
Fe
Cu 1.5405 1.5443 1.5418 Ni
Mo 0.7093 0.7135 0.7107 Nb
Ag
 Why crystals do have defects/Imperfections?
A perfect crystal ? only at T= 0 K

Defect<<< 1% diamond or quartz

Why imperfect ? reduction of free energy

H= Energy requirement

S= Increase in entropy

Configurational entropy [Boltzmann formula]

S  k ln W W 1023
 Types of Defect Description
1. Point Defects
(a) Schottky defect Atom/group of atoms missing from correct lattice site;
movement to the surface

(b) Frenkel defect Atom displaced to interstitial site creating nearby vacancy

(c) Interstitials Extra atom in an interstitial site

2. Line Defects
(a) Edge dislocation Row of atoms marking edge of a crystallographic plane
extending only part way in the crystal
(b) Screw dislocation Row of atoms about which a normal crystallographic
plane appears to spiral
3. Plane Defects
(a) Lineage boundary Boundary between two adjacent perfect regions in the
same crystal that are slightly tilted with respect to each other
(b) Grain boundary Boundary between two crystals in a polycrystalline solid
(c) Stacking fault Boundary between two parts of a closest packing
having alternate stacking sequences
Schottky defect
Movement of ions in pairs
(cation+anion) both
<Stoichiometric defect>
<Macroscopic charge neutrality is maintained>
Volume of the crystal increases
(density decreases)
<A careful density measurement can decide the nature of the defect>
U p /2 kT
ns  Ne
N= total number of atoms
ns= number of Schottky defects produced
Up= energy required to remove a pair of
atoms/ions
Occurs mainly in highly ionic compounds
where the positive and negative ions are
of a similar size and hence
CN is high (usually 8 or 6)
e.g., NaCl, CsCl, KCl, KBr
Frenkel defect
Movement of an ion to an interstitial position
(usually cations move)
[Metal ions are generally smaller than the
anions. So it is more common to find the
positive ions occupying interstitial positions]
No appreciable change in density (or volume)
n f  NNi eUi /2kT
Ni= total number of interstitial positions
nf= number of Frenkel defects formed
Ui= energy required to displace an atom from
its proper position to an interstitial position
Defect is favoured by a large difference in
size between the positive and negative ions,
consequently
CN is usually low (4 or 6)
e.g., ZnS, AgCl, AgBr, AgI
Properties of solids

Crystal, crystal planes, law of rational indices, Calculation of fraction occupied

for simple cubic, bcc, and fcc. Miller indices. Bragg's law and its applications
for the determination of crystal structure for cubic system single crystal. Crystal
structures of NaCl and KCl.
Crystalline solids
Ionic (Coulombic)
Covalent
Other (metallic, H-bonds, dipole-dipole forces, London dispersion forces)
 Types of Solids: Example Crystalline Structures

Simple Cubic Body-Centered Cubic Face-Centered Cubic

FCC
structure: Na+
NaCl

Cl-
 Types of Solids: Example Crystalline Structures
Graphite Diamond
Planar sp2 bonding Tetrahedral sp3 bonding
(good lubricant) (very hard!)

Vertical p-bonds Bond angle = 109.5º

 Electronic structure of solids : Band Theory
Differences between M’s, S’s, I’s depend on :
 (ohm1 cm1 )
 The band structure of each
M   104 to 106
 Whether the VB’s are full or
only partly full I   10-15
 The magnitude of any energy gap S   105 to 103
between full & empty bands (arbitrary boundary)

Band structure of (a) and (b) metals, (c) semimetals, (d) semiconductors and
(e) insulators. Purple shading: empty energy levels; blue: occupied levels