SOLID STATE

CHEMISTRY

Submitted by:
Saksham Saxena
13102066
 INTRODUCTION
• Solid-state chemistry, also sometimes referred
to as materials chemistry, is the study of the
synthesis, structure, and properties of solid
phase materials, particularly, but not necessarily
exclusively of, non-molecular solids. 
•  It therefore has a strong overlap with solid-state

physics, mineralogy, crystallography, ceramics, 
metallurgy, thermodynamics, materials
science and electronics with a focus on the
synthesis of novel materials and their
characterization.
 HISTORY
• Applications discovered in the 20th century
include zeolite and platinum-based catalysts for
petroleum processing in the 1950s
• High-purity silicon as a core component of
microelectronic devices in the 1960s
• The invention of X-ray crystallography in the early
1900s by William Lawrence Bragg enabled further
innovation.
• Carl Wagner's work on oxidation rate theory, counter
diffusion of ions, and defect chemistry. Because of
this, he has sometimes been referred to as the Father
of solid state chemistry.
SYNTHETIC METHODS
• Oven techniques- Bulk solids are prepared
using tube furnaces or ovens consisting of a
tantalum tube through which an electric current is
passed can be used for even higher temperatures
up to 2000 °C. Such high temperatures are at
times required to induce diffusion of the
reactants.
• Melt methods- Melting the reactants together
and then annealing the solidified melt. If volatile
reactants are involved the reactants are often put
in an ampoule that is evacuated -often while
keeping the reactant mixture cold e.g. by keeping
the bottom of the ampoule in liquid nitrogen- and
then sealed. The sealed ampoule is then put in an
oven and given a certain heat treatment.
• Solution methods- It is possible to use solvents to
prepare solids by precipitation or by evaporation.
At times the solvent is used hydrothermally, i.e.
under pressure at temperatures higher than the
normal boiling point. A variation on this theme is
the use of flux methods, where a salt of relatively
low melting point is added to the mixture to act as
a high temperature solvent in which the desired
reaction can take place.
• Air and moisture sensitive materials- Many solids
are hygroscopic and/or oxygen sensitive.
Many halides e.g. are very 'thirsty' and can only be
studied in their anhydrous form if they are handled
in a glove box filled with dry (and/or oxygen-free)
gas, usually nitrogen.
 CRYSTAL structure
• In mineralogy and crystallography, a crystal
structure is a unique
arrangement of atoms, ions
 or molecules in a
in a crystalline liquid or 
solid.
  INSULIN CRYSTALS

Why study crystal structures?

• description of solid
• comparison with other similar materials -
classification
• correlation with physical properties
CRYSTALS ARE EVERYWHERE
CRYSTAL LATTICE
• The crystal lattice can be thought of as an array of
'small boxes' infinitely repeating in all three
spatial directions.
• Unit cell is the smallest unit of volume that
contains all of the structural and symmetry
information to build-up the macroscopic structure
of the lattice by translation.
The unit cell is a box
with:
• 3 sides - a, b, c
• 3 angles - , , 
SEVEN UNIT CELLS SHAPES
The unit cells fall into seven categories, which differ
in the three unit-cell edge lengths (a, b, and c) and
three internal angles
•Cubic a=b=c ===90°
•Tetragonal a=bc ===90°
•Orthorhombic abc ===90°
•Monoclinic abc ==90°,   90°
•Triclinic abc     90°
•Hexagonal a=bc ==90°, =120°
•Rhombohedral a=b=c ==90°
BRAVIAS UNIT CELLS
Five of the seven crystal systems and their unit cells can be
derived from cubic by structural distortions.
 2D example - rocksalt
(sodium chloride, NaCl)

We define lattice points ; these are points with

identical environments
Choice of origin is arbitrary - lattice points need not be atoms
- but unit cell size should always be the same.
This is also a unit cell -
it doesn’t matter if you start from Na or Cl
- or if you don’t start from an atom
In 2D, this is a unit cell
In 3D, it is NOT
TYPES OF UNIT CELLS
1. SIMPLE CUBIC CELL:
• atom at each corner of the unit cell.
• Each atom at a lattice point is then shared
equally between eight adjacent cubes, and
the unit cell therefore contains in total one
atom (1⁄8 × 8).
2. BODY CENTRED CUBIC(BCC):
The body-centered cubic system (cI) has one
lattice point in the center of the unit cell in
addition to the eight corner points. It has a net
total of 2 lattice points per unit cell (1⁄8 × 8 + 1).
3. FACE-CENTRED CUBIC:
The face-centered cubic system (cF) has lattice
points on the faces of the cube, that each gives
exactly one half contribution, in addition to the
corner lattice points, giving a total of 4 lattice points
per unit cell (1⁄8 × 8 from the corners plus 1⁄2 × 6
from the faces).
IONIC CRYSTALS
 INTRODUCTION
• A class of crystal consisting of a lattice of ions held
together by electrostatic interactions; they exhibit
strong absorption of infrared radiation and have
planes along which they cleave easily.
• Stability of ionic solids depends on lattice energy,
which is released in the form of heat when two
ions are brought together to form a solid. Lattice
energy is the sum of all the interactions within the
crystal.
• The properties of ionic crystals reflect the strong
interactions that exist between the ions. They are
very poor conductors of electricity, have strong
absorption of infrared radiation, and are easily
cleaved. These solids tend to be quite hard and
have high melting points.
NaCl Crystal Structure
• Face-centered cubes of both ions offset by a half a
unit cell in one direction.
• Many alkali metals have this same geometry.
• Coordination number - 6
This animation shows the NaCl lattice
In the red is Cl-
In the blue is Na+
 CsCl Crystal Structure
• Chloride ions form simple cubes with cesium
ions in the center (Figure 7-7).
• The cesium ion is able to fit in to center hole.
• Co-ordination number- 8
This animation shows the CsCl lattice, only the
teal Cs+ (the Cs sublattice), and only the gold
Cl- (the Cl sublattice). 
TiO2 (The rutile structure)
• Distorted TiO6 octahedral
• Ti has a C.N. of 6, octahedral coordination
• O has a C.N. of 3
Rationalization of Structure of
Crystalline Solids

• Predicting coordination number from radius ratio (r+/r-).

– A hard sphere treatment of the ions.
– Treats bonding as purely ionic.
– Simply, as the M+ ratio increases, more anions can
pack around it.
Thermodynamics of Ionic Crystal
Formation
• A compound tends to adopt the crystal structure
corresponding to lowest Gibbs energy.
M+(g) + X-(g)  MX(s)
G = H - TS (standard state), 2nd term can be
ignored
• Lattice enthalpy
MX(s)  M+(g) + X-(g) HL (standard molar
enthalpy change)
Currently, we are interested in lattice formation.
The Born-Haber Cycle
• A special thermodynamic
cycle that includes lattice
formation as one step.
• The cycle has to sum up to
zero if written appropriately.
Lattice Enthalpy Calculations
• Considering only Coulombic contributions
– The electrostatic potential energy between each
pair.
z A z B  e2 
U   
r0  4 o 
zA, zB = ionic charges in electron units
r0 = distance between ion centers
e = electronic charge
4o = permittivity of a vacuum
e2/ 4o = 2.307  10-28 J m
Calculation would be performed on each cation/anion
pair (nearest neighbor).
Lattice Enthalpy Calculations

• A more accurate equation depicts the Coulombic

interactions over the entire crystal.
N Ae2  z A z B 
U    
4 o  r0 
NA = Avogadro’s constant
A = Madelung’s constant, value specific to a
crystal type (in table). This is a sum of all the
geometric factors carried out until the
interaction become infinitesimal.
IMPERFECTION IN SOLIDS
• The properties of some materials are profoundly
influenced by the presence of imperfections.
• It is important to have knowledge about the types
of imperfections that exist and the roles they play
in affecting the behavior of materials.
• Crystals are invariably imperfect because defects
leads to a reduction of free energy.
• Creation of defects increase enthalpy and
entropy. According to:

G  H  TS
Atom Purity and Crystal Perfection
• If we assume a perfect crystal structure
containing pure elements, then anything that
deviated from this concept or intruded in this
uniform homogeneity would be an imperfection.
1. There are no perfect crystals.
2. Many material properties are improved by
the presence of imperfections and
deliberately modified (alloying and doping).
 DEFECTS IN CRYSTALS

 Point defects
 Line defects
 Surface Imperfections

PROPERTIES

Structure sensitive Structure Insensitive

E.g. Yield stress, Fracture toughness E.g. Density, elastic modulus

CLASSIFICATION OF DEFECTS BASED ON DIMENSIONALITY

0D 1D 2D 3D
(Point defects) (Line defects) (Surface / Interface) (Volume defects)

Surface Twins
Vacancy Dislocation
Interphase Precipitate
Impurity Disclination
boundary
Faulted
Frenkel Dispiration Grain
region
defect boundary
Twin Voids /
Schottky
boundary Cracks
defect
Stacking Thermal
faults vibration
Anti-phase
boundaries
 SYMMETRY ASSOCIATED DEFECTS

Translation Rotation Screw

Atomic
Dislocation Disclination Dispiration Level

SYMMETRY ASSOCIATED DEFECTS

Mirror Rotation Inversion

Twins Multi-atom
 Vacancy
Non-ionic Interstitial
Impurity
crystals
Substitutional
0D
(Point defects) Frenkel defect
Ionic
Other ~
crystals
Schottky defect

 Imperfect point-like regions in the crystal about the

size of 1-2 atomic
diameters
 Vacancy

 Missing atom from an atomic site

 Atoms around the vacancy displaced
 Tensile stress field produced in the vicinity

Tensile Stress
Fields
 Relative
size
Interstitial
Compressive
Impurity Stress
Fields
Substitutional

Compressive stress
fields

 SUBSTITUTIONAL IMPURITY Tensile Stress

 Foreign atom replacing the parent atom in the crystal Fields
 E.g. Cu sitting in the lattice site of FCC-Ni
 INTERSTITIAL IMPURITY
 Foreign atom sitting in the void of a crystal
 E.g. C sitting in the octahedral void in HT FCC-Fe
 Ionic Crystals

 Overall electrical neutrality has to be maintained

Frenkel defect

 Cation (being smaller get displaced to interstitial voids

 E.g. AgI, CaF2
 Schottky defect

 Pair of anion and cation vacancies

 E.g. Alkali halides
 Other defects due to charge balance
 If Cd2+ replaces Na+ → one cation vacancy is created

Defects due to off stiochiometry

 ZnO heated in Zn vapour → ZnyO (y >1)

 The excess cations occupy interstitial voids
 The electrons (2e) released stay associated to the interstitial cation
 FeO heated in oxygen atmosphere → FexO (x <1)
 Vacant cation sites are present
 Charge is compensated by conversion of ferrous to ferric ion:
Fe2+ → Fe3+ + e
 For every vacancy (of Fe cation) two ferrous ions are converted to
ferric ions → provides the 2 electrons required by excess oxygen