Solid State Chemistry

(CYT644)
4 Credits: 3 (theory) - 1 (Tutorial)

Dr. Sumanta Kumar Meher

Materials Electrochemistry & Energy Storage (MEES) Lab
Department of Chemistry
CONTENTS

 Introduction to Crystal Structures

 Methods to Characterise Solids

 Synthesis and Fabrication of Solids

 Defects in Solids

 Porous and Nanostructured Solids

BOOKS:
1. Solid State Chemistry and its Applications, Anthony R. West, Wiley.

2. Principles of the Solid State, H.V. Keer, Wiley–Blackwell.

3. Solid State Chemistry: Techniques, A. K. Cheetham and P. Day, Wiley.
 Classification of Solids by Atomic Arrangement
(Crystalline and Amorphous Solids)

• Particles making up a solid (ionic/molecular/covalent/metallic) are held by

strong attractive forces between them

• In solids, positions of the atoms, molecules, or ions are considered rather

than their motion.

Constituents of a solid can be arranged in two general ways

 Repeating long range three-dimensional structure  crystal lattice 
produces a crystalline solid
 Aggregate short-range order  Non crystalline/amorphous solids/glass

Obsidian Diamond
 Crystalline Solids

 Distinctive internal structures  distinctive flat surfaces/faces

 Faces intersect at angles  reflect the regular repeating arrangement of the
components (atoms/molecules/ions) in space
 Well-defined melting points  components have same neighbor at same
distance (regularity creates same local environment)
 Intermolecular forces are uniform  same amount of thermal energy is
needed to break all of the interactions simultaneously

• Repeating patterns of components in three dimensions  crystal lattice  An

infinite array of points in space, in which each point has identical surroundings
to all others
• Basic repeating unit  unit cell  The smallest component of the crystal,
which when stacked together with pure translational repetition reproduces the
whole crystal
• Entire crystal  smallest identical units stacked together  crystal
Unit Cell ??
Basis/Motiff (atom/group of atoms)

Conventional cell

Primitive Cell
Unit Cell
 Bravais Lattice (5 nos.) in 2D
a
oblique
b a  b;   90o

rectangular
a  b;  = 90o

square centered rectangular

hexagonal
a = b;  = 90o a  b;  = 90o
a = b;  = 120o
a' = b'; '  90o, 120o
Bravais Lattice (14 nos.) in 3D; 7 Crystal Systems

4 types of Unit Cell

P = Primitive
I = Body-Centered
F = Face-Centered
C = Side Centered
Crystal Systems
Bravais Lattice (set of point in space) + Basis/Motiff (atom/group of atoms
at every lattice point)

Crystal System/Structure

Bravais Lattice (FCC) + Basis/Motiff (Au, Al, Cu, Pt etc.)  FCC

Bravais Lattice (FCC) + Basis/Motiff (molecule: CH4)  FCC

Bravais Lattice (FCC) + Basis/Motiff (ion pair: Na+ Cl–)  Rock salt

Bravais Lattice (FCC)

+ Basis/Motiff (atom pair: C–C)
 Diamond (cubic)
 4 fold rotation axes (passing through pairs of opposite face
4 centers, parallel to cell axes): TOTAL = 3

4 3
3-fold rotation axes (passing through cube
body diagonals): TOTAL = 4

The symmetry element : n  Rotation about

the axis by 360/n degrees gives an identical
orientation and the operation is repeated n
times before the original configuration is
regained
The seven crystal systems
Five of the seven crystal systems can be derived from cubic crystal by
structural distortions

7 Crystal Systems
 Counting atoms or ions in a unit cell

 Atom lying on a face of a unit cell  shared by two adjacent unit cells
 counted as 1/2 atom per unit cell
 Atom lying on the edge of a unit cell  shared by four adjacent unit cells
 contributes 1/4 atom per unit cell
 Atom at the corner of a unit cell  shared by all eight adjacent unit cells
 contributes 1/8 atom per unit cell
 Atom lying entirely within a unit cell  contributes 1atom per unit cell
 NaCl (Face Centered Cubic)

 Cl– ions occupy the corners and face centers

 Na+ occupy body centre and edge centers
 Each Na+ is surrounded by six Cl– and each Cl– is surrounded by 6 Na+
NaCl has 6:6 coordination
Number of NaCl units per unit cell

Cl–
6 at the face center contribute ½ per unit cell : 6 × ½ = 3
8 at the corner contribute 1/8 per unit cell : 8 × 1/8 = 1
Total number of Cl– ions = 4

Na+
12 at the face center contribute 1/4 per unit cell : 12 × 1/4 = 3
One at the body center contributes fully = 1 x 1 = 1
Total number of Na+ ions = 4

Therefore total NaCl units in one unit cell = 4

CsCl (Body Centered Cubic)

Each Cs+ is surrounded by 8 Cl– at the corners of its cube

Each Cl- is surrounded by 8 Cs+ at the corners of its cube
(8:8 coordination)

8 at the corner contribute 1/8 per unit cell : 8 × 1/8 = 1

One at the body center contributes fully = 1 x 1 = 1

Therefore total CsCl units in one unit cell = 1

Holes (Tetrahedral and Octahedral)
ZnS (Zinc Blende)

Zn

 Zn atoms at the corners and at the center of each face of the FCC
structure

 S atoms occupy tetrahedral sites; coordination number = 4

 4 S atoms occupy only half (4 out of 8) of tetrahedral sites

(alternate tetrahedral sites are filled)
 Stoichiometry of ZnS is 1:1 (4 Zn and 4 S)
 Ex. GaAs, CuCl, CuBr, CuI, AgI, BeS
ZnS (Wurtzite)
S

Zn

 Each Zn atom is surrounded by 4 S atoms

Each S atom is surrounded by 4 Zn atoms
 Zn and S are present in equivalent positions
Coordination of ZnS is 4:4
 S atoms form the hcp arrangement
 Zn atoms occupy tetrahedral sites
 Zn atoms occupy only half of tetrahedral sites (1 of 2)
Alternate tetrahedral sites remain vacant
Stoichiometry of the compound is 1:1 Ex. ZnO, CdS, CdTe and BeO
CaF2 (fluorite) Ca

F
 Each F ion is surrounded by 4 Ca ions
Each Ca ion is surrounded by 8 F ions
 Coordination of CaF2 is 8:4

 The stochiometry =1:2

 Ca ions form the ccp arrangement (occupy all the corner the
center of each face of the cube)
 F ions occupy tetrahedral sites
(coordination number of fluoride ion = 4)

 F ions occupy all the tetrahedral sites (2 of 2)

Ex. SrF2, BaF2, SrCl2, CdF2, HgF2, and PbF2

 Lattice Planes and Miller Indices
Lattice plane:

 Defined purely from the shape and dimensions of the unit cell.

 Entirely imaginary and provide a reference grid to which the atoms in the crystal
structure may be referred

Lattice planes (in projection) derivation of Miller indices

Interplanar Spacings
 Crystal Densities and Unit Cell Contents

The unit cell, by definition, must contain at least one formula unit, whether it be an
atom, ion pair, molecule, etc.

In centred cells, the unit cell contains more than one formula unit and more than
one lattice point.

Relation between cell volume, the number of formula units in the cell, the formula
weight (FW) and the bulk crystal density (D)

where N is Avogadro’s number. If the unit cell, of volume V, contains Z formula units,
then

V is expressed in Å3 → × 10−24 → cm−3 → D in g cm−3

Substituting for N, the equation reduces to
 Description of Crystal Structures

 Close packing
 Space-filling polyhedra

Close Packed Structures – Cubic and Hexagonal Close Packing

 Structures are usually arranged to have the maximum density

 Most efficient way of packing equal-sized spheres in three dimensions

A non-cp layer of equal-sized spheres

(CN of A = 4)

A cp layer of equal-sized spheres (CN of A = 6)

2D
3D

Alternative positions P and R for a second cp layer

Hexagonal Close Packing

. . .ABABAB. . .
Cubic Close Packing

. . .ABCABCABC. . .

Other more complex sequences with larger repeat units, e.g. …ABCACB… or
…ABAC…, occur in a few materials; some of these larger repeat units are
responsible for the phenomenon of polytypism (different polymorphs exist in different
domains of the same crystal)
In a 3D cp structure, each sphere is in contact with 12 others, and this is the
maximum coordination number possible for contacting equal-sized spheres.

A common non-cp structure is the body centred cube, e.g. in α-Fe, with a
coordination number of eight

Sometimes the atoms that form the cp array are as closely packed as possible, but
in other cases their arrangement is as in cp but the atoms are clearly not touching
 eutactic structures
For the (220) plane of an FCC lattice,
Calculate the face density and volume density if the lattice parameter is 0.361 nm.

0.361
d220 = = 0.128 nm
22 + 22 + 02

1
The number of atoms = 2 = 1
2
2𝑎 𝑎2
The area of the square = a  2 = = 0.092 nm2
2
1
Face density = = 10.8 atoms/nm2
0.092
10.85
Volume density = = 85 atoms/nm3
0.128
Discovery of X-ray (Nov. 8, 1895)
Wilhelm Röntgen
X-ray : Form of Electromagnetic radiation of very short wavelength
How short ??  How short ??  0.01 Å    100 Å

1Å

12400 eV/photon

Ionizing radiation

E = -kz2

-13.6 eV
 Vacuum S
Origin of X-ray C
I
C A E
8 Hz N
e
35,000 V T
I
L
A
Gas discharge tube (glass)
T
35,000 V (High voltage, low pressure)
I
N
G

Choke coil S
20 V C
R
E
E
N
X radiation !!!

Ba[Pt(CN)4]
Physics

 The emission can not be from the gas molecules in the tube
 The emission must be from the anode, where the electron is hitting at
a higher energy

e

e 4 N
L Cascade down
3 M to K shell
L K
2 L
e h K From 1 shell
away (n=1)
h K
E=qV
𝑚𝑣 2
= 1 K
2
Cascade of photoemission
 K

Intensity 
L

K
L


Cu K = 1.5818 Å

Identity of the element

Moseley’s X-ray plots (“Moseley’s law”) establishing the validity of atomic number, N,

Mendeleev: Periodicity is a function of

atomic mass

Mosley: Periodicity is a function of

proton number
Proton number 
 Bremstrahlung
quantized (breaking radiation)

K

scattering e-
High angle
Intensity 

L low angle
scattering e-

K
L

F (V)
F (Z)
 ℎ𝑐
Eincident = q  V = eV = Eemitted photon =

ℎ𝑐 12,400
shorter wavelength = = Å
𝑒𝑉 𝑉

Determines 

William Coolidge (Inventor of hot cathode X-ray tube)

1. Vacuum Tube  higher efficiency

2. Hot Cathode  Reduce binding energy of electron
3. Water cooled anode  Avoid low melting the anode with continuous operation
4. Pb shielding (high Z  many energy level
 lower energy photons by absorb and reemit
 Cheapest among the heaviest)
5. Be window (low Z  few no. of energy level
 less absorption and reemission  higher efficiency)
Characterizing the atomic arrangement by X-ray

 Model the atoms as mirrors  Law of specular reflection applies

incidence = reflection

 Apply interference criteria

 Constructive interference
 Destructive interference
FCC
BCC
Laue Method