Course Information

• Course : CHEM 405

• Course Title: Solid State Chemistry

• Class Time: Wednesday 11:00 – 2:00

pm

• Semester: Fall 2024-2025

• Credits: 2 Credits

• Room:

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 Lecturer Information

•Instructor’s Name: Dr. khadija Hijazi

•Email Address: [Link]@[Link]

•Available on: Monday and Wednesday at Debbieh Campus

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 Course Syllabus
This course covers Bonding in solids; crystal structures; x-ray diffraction;
electron models; band theory; crystal defects; electrical, thermal, optical
and magnetic properties of solid state materials from a chemical
perspective; fabrication techniques and modern applications.

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 Course Content

Week Lecture
1,2 Introduction to Crystal Structures.
2,3 Lattice Geometry.
4,5 Crystal Structure Analysis.
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Exam 1 (6th week assessment)
6,7 Defects in Solids.
8 Bonding in Solids.
9 Electrical properties.
10 Magnetic properties.
11 Optical properties.

12 Exam 2 (12th week assessment)

12,13 Thermal properties.
13,14 Fabrication techniques.
15 Final Exam
 Assessment
The final course grade will be based on Midterm Exams, assignments and a Final
Exam.

The approximate percent weight of each is given below:

Exam 1: 30 %
Exam 2: 30 %
Final Exam: 40 %

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 Physical Chemistry II
(CHEM 349)

 Dr. khadija Hijazi

 Lecture 1
 Date: Monday, September 2, 2024
 Chapter 1

Introduction to Crystal Structures

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 What is Solid State Chemistry

Is the study of structure , synthesis, bonding, reactivity, and physical

properties of solids.

® interdisciplinary overlap with condensed matter, mineralogy,

crystallography, metallurgy, ceramics, and materials science.

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 Brief history and important contributions from solid state
chemistry
1. X-ray crystallography in the early 1900’s by William L Bragg
2. platinum-based catalysts for petroleum processing in the 1950’s
3. High-purity silicon, a core component of microelectronic devices in
the 1960’s
4. Microwave dielectrics (wireless communications) in the 1970’s
5. High temperature superconductivity in the 1980’s
6. Giant magnetoresistive materials in the 1990’s
7. Nano-, energy storage and generation, and functional materials in
the 2000’s

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 Solid State Chemistry, a sub-discipline of Chemistry, primarily
involves the study of extended solids
 Except for helium, all substances form a solid if sufficiently cooled at 1 atm.
 The vast majority of solids form one or more crystalline phases, where the
atoms, molecules, or ions form a regular repeating array (unit cell).
 The primary focus will be on the structures of metals, ionic solids, and
extended covalent structures, where extended bonding arrangements dominate.
 The properties of solids are related to its structure and bonding.
 In order to understand or modify the properties of a solid, we need to
know the structure of the material.
 Crystal structures are usually determined by the technique of X-ray
crystallography.

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 What is Crystallography?

is a branch that deals with the study of all possible types of

crystals and the physical properties of crystalline solids by

the determination of their actual structure by using X-rays,

neutron beams and electron beams.

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 Matter exists in three states: solids, liquids and gases.

 All these states are composed of atoms and molecules.

 When we focus the solids, they are classified into many types

based on several properties like:

electrical, mechanical, magnetic, optical, etc.,.

 The main reason for these different properties of solids is their

crystal structure.

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 CLASSIFICATION OF SOLIDS
Solids can broadly be classified into two types based on the
arrangement of units of matter.
The units of matter may be atoms, molecules or ions.
They are,
Crystalline solids and
Non-crystalline (or) Amorphous solids

SOLID MATERIALS
AMORPHOUS
CRYSTALLINE POLYCRYSTALLINE
(Non-crystalline)

Single Crystal

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 CRYSTALLINE SOLIDS
 A substance is said to be crystalline when the arrangement of
units of matter is regular and periodic.

 A crystalline material has directional properties and therefore

called as anisotropic substance (i.e., the physical properties of
solids are different in different directions).

 A crystal has a sharp melting point.

 It possesses a regular shape and if it is broken, all broken pieces

have the same regular shape.

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 CRYSTALLINE SOLIDS

 A crystalline material can either be a single (mono) crystal or

a polycrystal.

 A single crystal consists of only one crystal, whereas the

polycrystalline material consists of many crystals separated by
well-defined boundaries.

Examples
Metallic crystals: Cu, Ag, Al, Mg, etc,
Non-metallic crystals: C, Si, Ge, etc 15
 SINGLE CRYSTAL
 Single crystals have a periodic atomic structure across its
whole volume.
 At long range length scales, each atom is related to every other
equivalent atom in the structure by translational or rotational
symmetry

Single Pyrite
Crystal

Single Crystals
Amorphous
Solid

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 POLYCRYSTALLINE SOLIDS

 Polycrystalline materials are made up of an aggregate of many small single

crystals (also called crystallites or grains).
 Polycrystalline materials have a high degree of order over many atomic or
molecular dimensions.
 Grains (domains) are separated by grain boundaries. The atomic order can
vary from one domain to the next.
 The grains are usually 100 nm - 100 microns in diameter.
 Polycrystals with grains less than 10 nm in diameter are nanocrystalline

Polycrystalline
Pyrite form
(Grain)

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 NON CRYSTALLINE SOLIDS (Amorphous)
 In amorphous solids, the constituent particles are not arranged
in an orderly manner. They are randomly distributed.
They do not have directional properties and so they are called
as `isotropic’ substances (i.e., the physical properties are the same
in all directions).
 They have wide range of melting point and do not possess a
regular shape.
Examples:
Glass, Plastics, Rubber etc.,

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ATOMIC ARRANGEMENT IN CRYSTALS

(a) mono (or) single crystals

(b) polycrystalline solids
(c) amorphous solids
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 CRYSTAL LATTICE
y
• An infinite array of points in

space, B C D E
b α
• Each point has identical

surroundings to all others. O a A x

• Arrays are arranged in a regular

and periodic manner.

• The Space lattice is otherwise

called the Crystal lattice

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 BASIS

 A crystal structure is formed by associating every lattice

point with an unit assembly of atoms or molecules identical in
composition, arrangement and orientation.

 This unit assembly is called the ‘basis’.

 When the basis is repeated with correct periodicity in all

directions, it gives the actual crystal structure.

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 CRYSTAL STRUCTURE

= +

Crystal structure = Lattice + Basis

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A two-dimensional Bravais lattice with
different choices for the basis

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 Unit Cell in 2D

• The smallest component of the crystal (group of atoms,

ions or molecules), which when stacked together with
pure translational repetition reproduces the whole
crystal.

S S

S S S
S S S S

S S S

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Unit Cell in 3D

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Three common Unit Cells in 3D

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 Unit Cell

• The unit cell and, consequently, the

entire lattice, is uniquely determined
by the six lattice constants: a, b, c, α,
β and γ.

• Only 1/8 of each lattice point in a

unit cell can actually be assigned to
that cell.

• Each unit cell in the figure can be

associated with 8 x 1/8 = 1 lattice
point.

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 PRIMITIVE CELL

It is the smallest unit cell in volume constructed

by primitives. It consists of only one full atom

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 PRIMITIVE & NON PRIMITIVE CELL

 A primitive cell is one, which has got the points or

atoms only at the corners of the unit cell.

 If a unit cell consists of more than one atom, then it is

not a primitive cell.

 Example for primitive cell: Simple Cubic unit cell.

 Examples for non-primitive cell: BCC and FCC unit cell.

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 CRYSTALS SYSTEMS

A three dimensional space lattice is generated by

repeated translation of three translational vectors a, b and
c.

Crystals are grouped under seven systems on the basis

of the shape of the unit cell.

The seven crystal systems are distinguished from one

another by their lattice parameters .

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 CRYSTALS SYSTEMS

The seven systems are,

 Cubic
 Tetragonal
 Orthorhombic
 Trigonal (rhombohedral)
 Hexagonal
 Monoclinic and
 Triclinic

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 CRYSTALS SYSTEMS

The space lattices formed by unit cells are marked by the

following symbols:

 Primitive lattice: P  having lattice points only at the

corners of the unit cell.

 Body centered lattice: I  having lattice points at the

corners as well as at the body centre of the unit cell.

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 CRYSTALS SYSTEMS

 Face centered lattice: F  having lattice points at the

corners as well as at the face centers of the unit cell.

 Base or side centered lattice: C  having lattice points

at the corners as well as at the top and bottom base
centers of the unit cell.

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 BRAVAIS LATTICES

Bravais in 1948 showed that 14 types of unit cells

under seven crystal systems are possible. They are

commonly called as ‘Bravais lattices’.

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35
 Calculation of Number of Atoms per Unit cell

1. Simple Cubic or Primitive cubic

 In primitive cubic unit cell has atoms only at its corner. Each
atom at a corner is shared between eight unit cells. Therefore, only
(1/8) of an atom (or molecule or ion) actually belongs to a particular
unit cell.
 Since each unit cell has 8 atoms on its corners, The total number of
atoms in one unit cell = 8 x (1/8) = 1 atom.

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2. Body-centered cubic unit cell

 A body centered cubic (bcc) unit cell has an atom at each of its corners
and also one at its body centre. The atom at the body center wholly
belongs to the unit cell.

Thus in a body-centered cubic (bcc) unit cell:

(i) 8 corners x (1/8) per corner atom = 8 x (1/8) = 1 atom
(ii) 1 body centre atom= 1 x 1 = 1 atom
Total number of atoms per unit cell = 2 atoms.

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3. Face centered cubic

 A face-centered cubic (fcc) unit cell contains atoms at all the corners and at the
centre of all the faces of the cube.
 each atom located at the face-centre is shared between two adjacent unit cells and
only ½ of each atom belongs to a unit cell.
 Thus , in a face-centered cubic (fcc) unit cell:
(i) 8 corners x (1/8) per corner atom = 8 x (1/8) = 1 atom
(ii) 6 face-centered atoms x ½ atom per unit cell = 6 x ½ = 3 atoms
Total number of atoms per unit cell = 1 + 3 = 4 atoms

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Calculation of Number of Atoms per Unit cell

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 Atomic Radius of a Cubic Lattice

 Atomic radius (r): is the half the distance between the centers of the
nearest neighboring atom in a unit cell.
 Length of the cube edge (a): the distance between the centers of two
corners atoms of the cube.

[Link] Cubic or Primitive cubic

 The atomic radius (r) and length of the cube

(a) are related as:
a=2r
r = a/2

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2. Body-centered cubic cell

 From Fig , it is clear that :

(4 r)2 = (a √2)2+ a2= 3 a2

r = [(√3) a ] / 4

3. Face-centered cubic cell

From Fig it is clear that,

(4 r)2 = a2+ a2
16 r2 = 2 a2
r = [a / (2 √2)] = a /√8

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 Crystal Density
Let
a = side of a cubic crystal
D = density of atom
M = molar mass of atom
NA = Avogadro’s number

Mass of each atom (m) = (M/NA)

Mass of unit cell = number of atoms in unit cell x mass of each atom
=nxm
= (n x M/NA)
Volume of unit cell = a3
Therefore, density of unit cell = D= (mass / volume)
= (n x M/(NAx a3))
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 Packing Efficiency or Packing Fraction
 Packing efficiency is the percentage of total space filled by the
particles.

Packing efficiency in simple cubic lattice

 In simple cubic lattice the atoms are located only on the corners of the
cube. The particles touch each other along the edge.

 Thus, the edge length or side of the cube 'a' and the radius of each particle,
r are related as :a = 2 r
volume of the cube is = a3= 8r3 ---------(1)
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 Packing Efficiency or Packing Fraction

Packing efficiency in simple cubic lattice

We know that , each simple cubic unit cell contains only 1 atom,
Total volume of four spheres = 1x (4/3)  r3-------------(2)

Packing efficiency
=
[(Volume occupied by the four spheres in the unit cell) / (Total volume of unit cell)] x
100

Packing Efficiency = ((2) / (1)) x 100

Packing Efficiency = ((2) / (1)) x 100 = 52.4 % 44
 Packing Efficiency or Packing Fraction

Packing efficiency in hcp and ccp Structures

We know that , each unit cell in ccp structure , has effectively 4 spheres.
Total volume of four spheres = 4 x (4/3) r3-------------(2)
AC=(4r2)= a2 + a2
a= r
Packing efficiency
=
[(Volume occupied by the four spheres in the unit cell) / (Total volume of
unit cell)] x 100

Packing Efficiency = ((2) / (1)) x 100

Packing Efficiency = [(4 x (4/3) )  r3) / ((2√2r3) )) x 100 = 74 %

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Packing efficiency in Body-centred Cubic Structure

From the Figure it is clear that the atom at the centre will be in touch with the
other two atoms diagonally arranged.

In Δ EFD, b2 = a2+ a2 = 2a2

b = √2a
Now in Δ AFD, c2 = a2+ b2= a2+ 2a2
= 3 a2
c = √3 a

The length of the body diagonal c is equal to 4r , where r is the radius of

the sphere (atom) , as all the three spheres along the diagonal touch with
each other. Therefore , √3 a = 4 r
volume of the cube is = a3 = [(4/√3) r]3 -----------------(1)
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We know that , each unit cell in body-centered cubic structure , has
effectively 2 spheres.
Total volume of two spheres = 2 x (4/3)  r3-------------(2)

Packing Efficiency = ((2) / (1)) x 100

Packing Efficiency = [(2 x (4/3)  r3) / ((4/√3)r)3 ] x 100 = 68 %

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48
 Close-packing in Crystal
 Assuming that the particles are hard spheres of identical size.
 The close packing is packing of these spheres to occupy the minimum
available space in such away that the crystal has maximum density.

A) Close Packing in One Dimension

 The only way is to arrange the particles in arrow touching each other.

 The number of nearest neighbored of a particle is called its

coordination number

 In one dimensional close packed arrangement, the coordination

number is 2

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 Close-packing in Crystal
B) Close Packing in Two Dimensions
 Generated by stacking the two rows of close packed spheres. This can be
done in two different ways.
i) Two dimensional Square Close Packing

 The spheres of the second row are placed exactly above those of the
first row.
 If we call the first row as ‘A’ type row, the second row is also of ‘A’ type.
We may place more rows to obtain AAAA type of arrangement.
 Each sphere is in contact with four of its neighbors. Thus two
dimensional coordination number is 4.
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 Close-packing in Crystal
ii) Two dimensional hexagonal close-packing

 The second row may be placed above the first one in a distributed
manner such that its spheres fit in the depressions of the first row.
 If the arrangement of spheres in the first row is called 'A‘ type, the one
in the second row is called 'B‘ type.
 Hence this arrangement is of ABAB type. In this arrangement there is
less free space and this packing is more efficient than the square packing.
 Each sphere is in contact with six of its neighbors and the two
dimensional coordination number is 6.
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 Close-packing in Crystal
C) Close Packing in Three Dimensions

They can be obtained by stacking two dimensional layers one above the other.

i) Simple cubic lattice

 Three dimensional close packing from two dimensional square close-

packed layers.
 The arrangement of spheres in the first layer is called ‘A’ type, all
the layers have the same arrangement.
 Thus this lattice has AAA... Type pattern.
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 Close-packing in Crystal
ii) Three dimensional close packing from two dimensional hexagonal close
packed layers

(a) Placing second layer over the first layer

 It can be observed that not all the triangular voids of the first layer
are covered by spheres of the second layer.
 When a sphere of the second layer is found above the void of first
layer a tetrahedral void ‘T’ is formed.

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 Close-packing in Crystal
iii) Three dimensional close packing from two dimensional hexagonal
close packed layers
(b) Placing second layer over the first layer

 When a sphere of the second layer is not found above the void of first
layer an octahedral void ‘O’ is formed.
 The number of these two types of voids depend upon the number of
close packed spheres.
Let the number of close packed spheres be N , then :
 The number of octahedral voids generated = N
 The number of tetrahedral voids generated = 2 N 54
Summary

 Particles are close packed in either ccp or hcp structure.

 Two types of voids are generated, octahedral and tetrahedral.

 The number of octahedral voids is equal to the number of close packed

particles.

 The number of tetrahedral voids generated is twice this number.

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 Formula of a Compound and Number of Voids filled

 In ionic solids, the bigger ions (usually anions) form the

close packed structure and smaller ions (usually cations)
occupy the voids.
 If the latter ion is small enough then tetrahedral voids are
occupied,
 if bigger, then octahedral voids are occupied.
 Not all octahedral or tetrahedral voids are occupied.
 In a given compound, the fraction of octahedral or tetrahedral
voids that are occupied, depends upon the chemical formula of
the compound.

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 Formula of a Compound and Number of Voids filled
Example: A compound formed by two elements A and B. Atoms of the
element A (as anions) make up ccp and those of the element B (as
cations) occupy the octahedral voids. What is the formula of the
compound?

Solution
 The ccp lattice is formed by the element A. Let number of atoms A= N
 The number of octahedral voids generated would be equal to the
number of atoms of B present in it.
 Since all the octahedral voids are occupied by the atoms of B, their
number would also be equal to that of the element A. (number of B = N)
 Thus, the atoms of A and B are present in equal numbers or 1:1 ratio.
 Therefore the formula of the compound is BA. 57
 Formula of a Compound and Number of Voids filled

Example: Atoms of element Q form hcp lattice and those of the

element P occupy (2/3)rd of tetrahedral voids. What is the formula
of the compound formed by elements P and Q?
Solution
 The hcp lattice is formed by the element Qand Let the number
of atoms Q in hcp arrangement = N
 The number of tetrahedral voids formed is equal to twice the number
of atoms of elements Q, number of tetrahedral voids= 2N
and only (2/3)rd of these are occupied by atoms of element P.
 Hence the ratio of the number of atoms of P and Q is 4/3 N : N
2 x (2/3) : 1 or 4 : 3
 and formula of the compound is P4Q3. 58
Structure Coordination Stacking
number pattern
Primitive
Cubic
4
AAAAA…
Body- 8
centered ABABAB…
Cubic

Hexagonal 12 ABABAB…
close packed

Cubic close 12 ABCABC…

packed

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Units Cells for Metals

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