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PHY 3307 SOLID STATE PHYSICS I

Compiled by H. Abdulsalam
© 2019

Compiled by H. Abdulsalam © 2019 i


Table of Contents

Table of Contents...........................................................................................................................................i
Table of Tables.............................................................................................................................................iii
Table of Figures ...........................................................................................................................................iv
CHAPTER ONE ........................................................................................................................................... 1
1.0 CRYSTAL STRUCTURE................................................................................................................ 1
1.1 Introduction................................................................................................................................... 1

1.2 Crystal lattice ................................................................................................................................ 1

1.3 Unit cell .......................................................................................................................................... 2

1.4 Primitive Cell ................................................................................................................................ 3

1.5 Lattice constant............................................................................................................................. 3

1.6 Crystal Systems and Bravais Lattices......................................................................................... 3

1.7 Atomic radius ................................................................................................................................ 5

1.7.1 Types of Radius with Respect to Types of Bonds............................................................... 6

1.7.2 Periodic Trends of Atomic Radius ...................................................................................... 7

1.8 Packing density ............................................................................................................................. 8

1.9 Lattice planes ................................................................................................................................ 8

1.10 Atom Positions in Cubic Unit Cells ......................................................................................... 8

1.11 Directions in Cubic Unit Cells ................................................................................................. 9

1.12 Miller Indices........................................................................................................................... 10

1.13 Interplanar Distance............................................................................................................... 11

1.14 Principal Metallic Crystal Structures ................................................................................... 13

1.14.1 Body-Centered Cubic (BCC) Crystal Structure .............................................................. 14

1.14.2 Face-Centered Cubic (FCC) Crystal Structure ............................................................... 15

1.14.3 Hexagonal Close-Packed (HCP) Crystal Structure ......................................................... 16

1.15 Exercise 1................................................................................................................................. 17

CHAPTER TWO ........................................................................................................................................ 18


2.0 X-RAY DIFFRACTION ON CRYSTALLINE STRUCTURES................................................ 18
2.1 Diffraction of X-rays................................................................................................................... 18

2.2 Diffraction of X-rays and Bragg’s Law .................................................................................... 19

2.3 Powder Diffraction ..................................................................................................................... 21

2.4 Reciprocal Lattice....................................................................................................................... 22

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2.4.1 Diffraction condition and Reciprocal Lattice................................................................... 23

2.5 Atomic Scattering Factors.......................................................................................................... 24

2.6 Exercise 2..................................................................................................................................... 24

CHAPTER THREE.................................................................................................................................... 26
3.0 BONDING IN SOLIDS AND IMPERFECTION IN SOLIDS ................................................... 26
3.1 Crystal Bonding .......................................................................................................................... 26

3.1.1 Ionic Bonding ...................................................................................................................... 27

3.1.2 Covalent Bonding................................................................................................................ 28

3.1.3 Metallic bonding ................................................................................................................. 28

3.2 Bond lengths ................................................................................................................................ 29

3.3 Bond Energies ............................................................................................................................. 30

3.4 Imperfections in Solids or Crystal defects ................................................................................ 30

3.4.1 Point Defects........................................................................................................................ 30

3.4.2 Line Defects ......................................................................................................................... 31

3.5 Exercise 3..................................................................................................................................... 32

4.0 LATTICE VIBRATIONS .............................................................................................................. 33


4.1 Introduction................................................................................................................................. 33

4.2 One-dimensional lattice.............................................................................................................. 33

4.3 Diatomic1D lattice....................................................................................................................... 36

4.4 Phonon ......................................................................................................................................... 38

4.5 Debye theory of specific heat ..................................................................................................... 38

Exercise 4 ................................................................................................................................................ 40

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Table of Tables

Table 1.1 Classifications of Space Lattices by Crystal System.......................................................4


Table 3.1 Some bonds with their respective bond lengths and bond energies ..............................29
Table 4.1 Debye Temperatures of several substances....................................................................40

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Table of Figures

Figure 1.1 Lattice and basis..............................................................................................................1


Figure 1.2 Space lattice of ideal crystalline solid.............................................................................2
Figure 1.3 A parallelepiped..............................................................................................................2
Figure 1.4 Unit cell showing axial lengths a, b, and c and the interracial angles ............................3
Figure 1.5 The 14 Bravais conventional unit cells grouped according to crystal system. The dots
indicate lattice points that, when located on faces or at corners, are shared by other identical
lattice unit cells. ................................................................................................................................5
Figure 1.6 Covalent radii..................................................................................................................6
Figure 1.7 Ionic radii........................................................................................................................7
Figure 1.8 Metallic radii from metallic bonding ..............................................................................7
Figure 1.9 Periodic Trend in atomic radii ........................................................................................7
Figure 1.10 lattice plane, lattice points and unit cell........................................................................8
Figure 1.11 (a) Rectangular x, y, and z axes for locating atom positions in cubic unit cells. (b)
Atom positions in a BCC unit cell. ...................................................................................................9
Figure 1.12 Some directions in cubic unit cells ...............................................................................9
Figure 1.13 A Miller index of a plane cutting intercepts 4a, 6b, 3c on crystallographic axes......11
Figure 1.14 Miller indices of some important planes of cubic lattices ..........................................11
Figure 1.15 Interplanar spacing for set of planes (hkl) ..................................................................13
Figure 1.16 Principal metal crystal structure unit cells: (a) body-centered cubic,(b) face-centered
cubic, (c) hexagonal close-packed. .................................................................................................13
Figure 1.17 BCC unit cells: (a) atomic-site unit cell, (b) hard-sphere unit cell, and(c) isolated unit
cell. ..................................................................................................................................................14
Figure 1.18 BCC unit cell showing relationship between the lattice constant and the atomic radius
.........................................................................................................................................................15
Figure 1.19 FCC unit cells: (a) atomic-site unit cell, (b) hard-sphere unit cell, and (c) isolated unit
cell. ..................................................................................................................................................16
Figure 1.20 FCC unit cell showing relationship between the lattice constant a and atomic radius
R Since the atoms touch across the face diagonals, ........................................................................16
Figure 2.0.1 Bragg Diffraction.......................................................................................................19
Figure 2.0.2 Debye-Scherrer Powder Diffraction ..........................................................................21
Figure 2.0.3 Direct Lattice Vector .................................................................................................23
Figure 3.1 Graph of energy against interatomic distance...............................................................26
Figure 3.2 Ionic bonding ..............................................................................................................27
Figure 3.3 Covalent bonding.........................................................................................................28
Figure 3.4 Metallic bonding ..........................................................................................................29
Figure 3.5 Impurities Defects........................................................................................................31
Figure 4.1 One-dimensional crystal lattice ....................................................................................33
Figure 4.2 .......................................................................................................................................35
Figure 4.3 A diatomic lattice.........................................................................................................37
Figure 4.4 .......................................................................................................................................37
Figure 4.5 .......................................................................................................................................38

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CHAPTER ONE

1.0 CRYSTAL STRUCTURE

1.1 Introduction
The properties of crystalline solids are determined by the symmetry of the crystalline
lattice, because both electronic and phononic systems, which determine, respectively, the electric,
magnetic and thermal response of solids, are very sensitive to the regular atomic order of
materials and to any (local or non-local) perturbation of it. The crystalline structure can be
revealed by the macroscopic form of natural or artificially-grown crystals, or can be inferred from
the resulting debris after cleaving a crystalline material. Non-crystalline materials have no long-
range order, but at least their optical properties are similar to that of crystalline materials because
the wavelength of the incident photons is much larger than the lattice constant of crystals and so,
photons “see” an effective homogeneous medium. Other properties of non-crystalline materials
are derived based on concepts proper to crystalline solids and, therefore, the crystal structure is
extremely important in understanding the properties of solid state materials. The macroscopic,
perfect crystal is formed by adding identical building blocks (unit cells) consisting of atoms or
groups of atoms. A unit cell is the smallest component of the crystal that, when stacked together
with pure translational repetition, reproduces the whole crystal. The periodicity of the crystalline
structure that results in this way is confirmed by x-ray diffraction experiments. The figures below
illustrate crystals in which the basis consists of (a) one atom and (b) two atoms.

Figure 1.1 Lattice and basis


The group of atoms or molecules that forms, by infinite repetition, the macroscopic crystal is
called basis. The basis is positioned in a set of mathematical/abstract points that form the lattice
(also called Bravais lattice). So, a crystal is a combination of a basis and a lattice. Although
usually the basis consists of only few atoms, it can also contain complex organic or inorganic
molecules (for example, proteins) of hundreds and even thousands of atoms.

1.2 Crystal lattice


A crystal lattice is the arrangement of these atoms, or groups of atoms, in a crystal. These
atoms or groups of atoms are commonly referred to as points within a crystal lattice site. Thus,
think of a crystal lattice site as containing a series of points arranged in a specific pattern with
high symmetry. Note that these points don't indicate the position of an atom in a crystal, they are
simply points 'in space' oriented in such a way to build a lattice structure. In other words, a
crystal lattice is a set of infinite, arranged points related to each other by transitional symmetry. In
crystal lattice each lattice point is surrounded by other points. The number of nearest neighbors in

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a packing is known as coordination number. The outlines for such patterns are called lattices.
Lattices are comprised of the intersections of three parallel planes. The planes intersect producing
three-dimensional figures which have six faces (like a cube) these are set in three sets of parallel
planes, thus making a figure known as a parallelepiped.

Figure 1.2 Space lattice of ideal crystalline solid


A parallelepiped is classified as a three-dimensional object which is composed of six faces, all of
which are parallelograms. Recall that a parallelogram has opposite sides parallel and equal. We
may state that the relation between a parallelepiped and a parallelogram is similar to that between
rectangle (or square) and cuboids (or cube).An image of a parallelepiped is shown below.

Figure 1.3 A parallelepiped

1.3 Unit cell


The size and shape of the unit cell can be described by three lattice vectors a, b, and c,
originating from one corner of the unit cell (Figure 1.4). The axial lengths a, b, and c and the
interracial angles α, β, and γ are the lattice constants of the unit cell. The interracial angles α, β,
and γ are the angles between b and c, c and a, and a and b, respectively In other words, the unit
cell of a mineral is the smallest divisible unit of mineral that possesses the symmetry and
properties of the mineral. It is a small group of atoms arranged in a “box” with parallel sides that
is repeated in three dimensions to fill space. It has three principal axes (a, b and c) and three inter
axial angles (i.e. and ). A unit cells fulfill the following requirements:
i. A repetitive arrangement (pure translation) of them can build up the whole crystal without
overlaps/gaps.
ii. There is no further partition of the unit cell that could itself be used as a unit cell.

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Figure 1.4 Unit cell showing axial lengths a, b, and c and the interracial angles

1.4 Primitive Cell


A unit cell with lattice points at its corners only is called primitive cell. Thus, there is only
one lattice point to each primitive cell. It is also defined as the smallest unit cell in volume of
space lattice. Basis vectors are set of linearly independent vectors a, b and c, which can be used to
define a unit cell. Primitive basis vectors: A set of linearly independent vectors that define a
primitive cell is called primitive basis vectors.
1.5 Lattice constant
The lattice constant, or lattice parameter, refers to the physical dimension of unit cells in a
crystal lattice. Lattices in three dimensions generally have three lattice constants, referred to as a,
b, and c (magnitudes of the primitive translation vectors). However, in the special case of cubic
crystal structures, all of the constants are equal and we only refer to a. Similarly, in hexagonal
crystal structures, a and b constants are equal, and we only refer to a and c constants. A group of
lattice constants could be referred to as lattice parameters. However, the full set of lattice
parameters consist of the three lattice constants and the three angles between them.
1.6 Crystal Systems and Bravais Lattices
Crystal system is a method of classifying crystalline substances on the basis of their unit
cell. There are seven unique crystal systems. The simplest and most symmetric, the cubic (or
isometric) system, has the symmetry of a cube. The other six systems, in order of decreasing
symmetry, are hexagonal, tetragonal, Trigonal (also known as rhombohedral), orthorhombic,
monoclinic and triclinic. These crystal systems are listed in table 1.1.Many of the seven crystal
systems have variations of the basic unit cell. In 1848, the French physicist and crystallographer
Auguste Bravais (1811-1863) established that in three-dimensional space only fourteen different
Bravais lattices may be constructed and in two dimensions there are five distinct Bravais lattices.
The Bravais lattices are the distinct lattice types which when repeated can fill the whole space.
The lattice can therefore be generated by three primitive translation vectors, , and and a
set of integers and so that each lattice point, identified by a vector R, can be obtained
from:

These fourteen lattices are further classified as shown in the Table 1.1 where
and are the magnitudes of the primitive translation vectors and and

are the angles between the unit vectors. All crystalline materials recognized till now fit in one of
these arrangements. These Bravais lattices are illustrated in Figure 1.5.

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Table 1.1 Classifications of Space Lattices by Crystal System
Crystal system Axial lengths and interaxial angles Space lattice

1. Cubic Three equal axes at right angles  Simple cubic


 Body-centered cubic
 Face-centered cubic

2. Tetragonal Three axes at right angles, two  Simple tetragonal


equal
 Body-centered tetragonal

3. Orthorhombic Three unequal axes at right angles  Simple orthorhombic


(Trigonal)
 Body-centered
orthorhombic
 Base-centered
orthorhombic
 Face-centered
orthorhombic

4. Rhombohedral Three equal axes, equally inclined Simple rhombohedral

5. Hexagonal Two equal axes at 120, third axis at right angles Simple hexagonal

6. Monoclinic Three unequal axes, one pair not at right angles  Simple monoclinic
 Base-centered monoclinic

7. Triclinic  Simple triclinic


Three unequal axes, unequally inclined and none
at right angles

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Figure 1.5 The 14 Bravais conventional unit cells grouped according to crystal system. The dots indicate
lattice points that, when located on faces or at corners, are shared by other identical lattice unit cells.

1.7 Atomic radius


Atomic radius is generally stated as being the total distance from an atom’s nucleus to the
outermost orbital of electron. In simpler terms, it can be defined as something similar to the radius
of a circle, where the center of the circle is the nucleus and the outer edge of the circle is the
outermost orbital of electron. Atomic radii are useful for determining many aspects of chemistry
such as various physical and chemical properties. The effective nuclear charge (Zeff) of an atom is
the net positive charge felt by the valence electron. Some positive charge is shielded by the core
electrons therefore the total positive charge is not felt by the valence electron. Zeff greatly affects

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the atomic size of an atom. So as the Zeff decreases, the atomic radius will grow as a result
because there is more screening of the electrons from the nucleus, which decreases the attraction
between the nucleus and the electron. Since Zeff decreases going down a group and right to left
across the periodic table, the atomic radius will increase going down a group and right to left
across the periodic table.

1.7.1 Types of Radius with Respect to Types of Bonds


The radii of atoms are determined by the bonds they form. An atom will have different
radii depending on the bond it forms; so there is no fixed radius of an atom.
Covalent Radius
When a covalent bond is present between two atoms, the covalent radius can be
determined. When two atoms of the same element are covalently bonded, the radius of each atom
will be half the distance between the two nuclei because they equally attract the electrons. The
distance between two nuclei will give the diameter of an atom, but you want the radius which is
half the diameter.
Covalent radii will increase in the same pattern as atomic radii. The reason for this trend is that
the bigger the radii, the further the distance between the two nuclei. The covalent radius depicted
in Figure 1.6 will be the same for both atoms because they are of the same element as shown by
X.

Figure 1.6 Covalent radii

Ionic Radius
The ionic radius is the radius of an atom forming ionic bond or an ion. The radius of each
atom in an ionic bond will be different than that in a covalent bond. This is an important concept.
The reason for the variability in radius is due to the fact that the atoms in an ionic bond are of
greatly different size. One of the atoms is a cation, which is smaller in size, and the other atom is
an anion which is a lot larger in size. So in order to account for this difference, one most get the
total distance between the two nuclei and divide the distance according to atomic size. The bigger
the atomic size, the larger radius it will have. This is depicted in Figure 1.7, where the cation is
displayed on the left as X+, and clearly has a smaller radius than the anion, which is depicted as
Y- on the right.

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Figure 1.7 Ionic radii

Metallic Radius
The metallic radius is the radius of an atom joined by metallic bond. The metallic radius is
half of the total distance between the nuclei of two adjacent atoms in a metallic cluster. Since a
metal will be a group of atoms of the same element, the distance of each atom will be the same
(Figure 1.8).

Figure 1.8 Metallic radii from metallic bonding

1.7.2 Periodic Trends of Atomic Radius


An atom gets larger as the number of electronic shells increase; therefore the radius of
atoms increases down a certain group in the periodic table of elements. In general, the size of an
atom will decrease from left to the right of a certain period.

Figure 1.9 Periodic Trend in atomic radii


Vertical Trend: The radius of atoms increases as you go down a certain group.

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Horizontal Trend: The size of an atom will decrease as you move from left to the right of a
period.
Exceptions: Because the electrons added in the transition elements are added in the inner electron
shell and at the same time, the outer shell remains constant, the nucleus attracts the electrons
inward. The electron configuration of the transition metals explains this phenomenon. This is why
Ga is the same size as its preceding atom and why Sb is slightly bigger than Sn.
1.8 Packing density
A packing density or Atomic packing fraction (APF) of a packing in some space is the fraction of
the space filled by the figures making up the packing. In packing problems, the objective is
usually to obtain a packing of the greatest possible density.

1.9 Lattice planes


In crystallography, a lattice plane of a given Bravais lattice is a plane (or family of parallel
planes) whose intersections with the lattice (or any crystalline structure of that lattice)
are periodic (i.e. are described by 2d Bravais lattices) and intersect the Bravais lattice;
equivalently, a lattice plane is any plane containing at least three non collinear Bravais lattice
points. All lattice planes can be described by a set of integer Miller indices, and vice versa (all
integer Miller indices define lattice planes). Conversely, planes that are not lattice planes
have aperiodic intersections with the lattice called quasicrystals

Figure 1.10 lattice plane, lattice points and unit cell

1.10 Atom Positions in Cubic Unit Cells


To locate atom positions in cubic unit cells, we use rectangular x, y, and z axes. In
crystallography the positive x axis is usually the direction coming out of the paper, the positive y
axis is the direction to the right of the paper, and the positive z axis is the direction to the top Fig.
1.10. Negative directions are opposite to those just described. Atom positions in unit cells are
located by using unit distances along the x, y, and z axes, as indicated in Fig. 1.11a. For example,
the position coordinates for the atoms in the BCC unit cell are shown in Fig. 1.11b. The atom
positions for the eight corner atoms of the BCC unit cell are

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The center atom in the BCC unit cell has the position coordinates . For simplicity
sometimes only two atom positions in the BCC unit cell are specified which are and
. The remaining atom positions of the BCC unit cell are assumed to be understood. In the
same way the atom positions in the FCC unit cell can be located.

Figure 1.11 (a) Rectangular x, y, and z axes for locating atom positions in cubic unit cells. (b) Atom
positions in a BCC unit cell.

1.11 Directions in Cubic Unit Cells


Often it is necessary to refer to specific directions in crystal lattices. This is especially
important for metals and alloys with properties that vary with crystallographic orientation. For
cubic crystals the crystallographic direction indices are the vector components of the direction
resolved along each of the coordinate axes and reduced to the smallest integers.

Figure 1.12 Some directions in cubic unit cells


To diagrammatically indicate a direction in a cubic unit cell, we draw a direction vector
from an origin, which is usually a corner of the cubic cell, until it emerges from the cube surface
Figure. 1.12. The position coordinates of the unit cell where the direction vector emerges from the
cube surface after being converted to integers are the direction indices. The direction indices are
enclosed by square brackets with no separating commas. For example, the position coordinates of
the direction vector OR in Figure1.12a where it emerges from the cube surface are (1, 0, 0), and
so the direction indices for the direction vector OR are [100]. The position coordinates of the
direction vector OS Figure 1.12a are (1, 1, 0), and so the direction indices for OS are [110]. The

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position coordinates for the direction vector OT (Figure 1.12b) are (1, 1, 1), and so the direction
indices of OT are [111].

The position coordinates of the direction vector OM, Fig. 1.12c are and since
the direction vectors must be integers, these position coordinates must be multiplied by 2 to obtain
integers. Thus, the direction indices of OM become . The position
coordinates of the vector ON Figure1.12d are A negative direction index is written
with a bar over the index. Thus, the direction indices for the vector ON are . Note that to
draw the direction ON inside the cube the origin of the direction vector had to be moved to the
front lower-right corner of the unit cube (Figure 1.12d). The letters u, v, ware used in a general
sense for the direction indices in the x, y, and z directions, respectively, and are written as [uvw]. It
is also important to note that all parallel direction vectors have the same direction indices.
Directions are said to be crystallographically equivalent if the atom spacing along each direction
is the same. For example, the following cubic edge directions are crystallographic equivalent
directions:

Equivalent directions are called indices of a family or form. The notation is used to
indicate cubic edge directions collectively. Other directions of a form are the cubic body
diagonals and the cubic face diagonals .

1.12 Miller Indices


A plane in a crystal is specified in terms of Miller indices. To find the Miller indices of a
plane, following procedure is used.
(i) Determine the intercepts of the plane on crystal axes in terms of fundamental vectors a, b and
c.
(ii) Take the reciprocal of these numbers in order. Reduce them to three smallest integers having
the same ratio.
(iii) Enclose these numbers in parentheses as (h k l).
The Miller indices (h k l) denote a set of parallel planes.
For example consider a plane with intercepts 4a, 6b and 3c on the crystal axes. In terms of axial
units, the intercepts are 4, 6, 3. The reciprocals of these numbers are . By multiplying each
of these numbers with lowest common multiple 12, these are reduced to smallest integers 3, 2, 4.
The Miller indices of the plane are (324).

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Figure 1.13 A Miller index of a plane cutting intercepts 4a, 6b, 3c on crystallographic axes

If a plane intersects the crystal axes on the negative side of origin, the corresponding index
is negative. By convention a minus sign is placed above the corresponding index. A plane
intercepting the crystal axes at – 4a, 2b, – c, has Miller indices (1 2 4). Miller indices of some
important planes of cubic lattices are shown in the Figure 1.14

Figure 1.14 Miller indices of some important planes of cubic lattices

1.13 Interplanar Distance


The interplanar spacing or interplanar distance is the perpendicular distance between two
successive planes on a family (hkl). It is commonly indicated as dhkl and corresponds to the
reciprocal of the length of the corresponding vector in reciprocal space.
To find the interplanar spacing d for the set of planes with Miller indices (hkl), take the
origin on any one plane of this set and erect axes in the directions of crystal axes a, band c. The
interplanar spacing d for the planes of indices (hkl) is equal to the distance from origin to the
nearest plane of the set under question. The distance d is measured along the normal drawn from
origin to the plane (hkl). Let the normal to the plane make angles and with a-axis, b-axis
and c-axis respectively. The plane (hkl) intersects a-axis at a/h, b-axis at b/k and c-axis at c/l.

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From fig 1.15:

, and

For orthogonal axes,

Therefore:

For a cubic system where :

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Figure 1.15 Interplanar spacing for set of planes (hkl)

1.14 Principal Metallic Crystal Structures


Most elemental metals (about 90 percent) crystallize upon solidification into three densely
packed crystal structures: body-centered cubic (BCC) (Figure 1.16a), face-centered cubic (FCC)
(Figure 1.16b) and hexagonal close-packed (HCP) (Figure 1.16c). The HCP structure is a denser
modification of the simple hexagonal crystal structure shown in Figure 1.5. Most metals
crystallize in these dense-packed structures because energy is released as the atoms come closer
together and bond more tightly with each other. Thus, the densely packed structures are in lower
and more stable energy arrangements. The extremely small size of the unit cells of crystalline
metals that are shown in Figure 1.4 should be emphasized. The cube side of the unit cell of body-
centered cubic iron, for example, at room temperature is equal to 0.287 × 10-9 m, or 0.287
nanometer (nm). Therefore, if unit cells of pure iron are lined up side by side, in 1 mm there will
be:

Since

Figure 1.16 Principal metal crystal structure unit cells: (a) body-centered cubic,(b) face-centered cubic,
(c) hexagonal close-packed.

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Let us now examine in detail the arrangement of the atoms in the three principal crystal
structure unit cells. Although an approximation, we shall consider atoms in these crystal structures
to be hard spheres. The distance between the atoms (interatomic distance) in crystal structures can
be determined experimentally by x-ray diffraction analysis. For example, the interatomic distance
between two aluminum atoms in a piece of pure aluminum at is 0.2862 nm. The radius of
the aluminum atom in the aluminum metal is assumed to be half the interatomic distance, or 0.143
nm.

1.14.1 Body-Centered Cubic (BCC) Crystal Structure


First, consider the atomic-site unit cell for the BCC crystal structure shown in Figure
1.17a. In this unit cell the solid spheres represent the centers where atoms are located and clearly
indicate their relative positions. If we represent the atoms in this cell as hard spheres, then the unit
cell appears as shown in Figure 1.17b. In this unit cell we see that the central atom is surrounded
by eight nearest neighbors and is said to have a coordination number of 8. If we isolate a single
hard-sphere unit cell, we obtain the model shown in Figure 1.17c. Each of these cells has the
equivalent of two atoms per unit cell. One complete atom is located at the center of the unit cell,
and an eighth of a sphere is located at each corner of the cell, making the equivalent of another
atom. Thus there is a total of:

The atoms in the BCC unit cell contact each other across the cube diagonal, as indicated in
Figure 1.18, so that the relationship between the length of the cube side a and the atomic radius R
is:

Or

Figure 1.17 BCC unit cells: (a) atomic-site unit cell, (b) hard-sphere unit cell, and(c) isolated unit cell.

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Figure 1.18 BCC unit cell showing relationship between the lattice constant and the atomic radius

If the atoms in the BCC unit cell are considered to be spherical, an atomic packing factor
(APF) can be calculated by using the equation:

Using this equation, the APF for the BCC unit cell (Figure 1.18a) is calculated to be68 percent.
That is, 68 percent of the volume of the BCC unit cell is occupied by atoms and the remaining 32
percent is empty space. The BCC crystal structure is not a close-packed structure since the atoms
could be packed closer together. Many metals such as iron, chromium, tungsten, molybdenum,
and vanadium have the BCC crystal structure at room temperature.

1.14.2 Face-Centered Cubic (FCC) Crystal Structure


Consider next the FCC lattice-point unit cell of Figure 1.19a. In this unit cell there is one
lattice point at each corner of the cube and one at the center of each cube face. The hard-sphere
model of Figure 1.19b indicates that the atoms in the FCC crystal structure are packed as close
together as possible. The APF for this close packed structure is 0.74 as compared to 0.68 for the
BCC structure, which is not close-packed. The FCC unit cell as shown in Figure 1.19c has the
equivalent of four atoms per unit cell. The eight corner octants account for one atom
and the six half-atoms on the cube faces contribute another three atoms, making a total of four
atoms per unit cell. The atoms in the FCC unit cell contact each other across the cubic face
diagonal, as indicated in Figure 1.20, so that the relationship between the length of the cube side a
and the atomic radius R is:

Or

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Figure 1.19 FCC unit cells: (a) atomic-site unit cell, (b) hard-sphere unit cell, and (c) isolated unit cell.

Figure 1.20 FCC unit cell showing relationship between the lattice constant a and atomic radius R Since
the atoms touch across the face diagonals,

The APF for the FCC crystal structure is 0.74, which is greater than the 0.68 factor for the
BCC structure. The APF of 0.74 is for the closest packing possible of “spherical atoms.” Many
metals such as aluminum, copper, lead, nickel, and iron at elevated temperatures (912 to 1394 oC)
crystallize with the FCC crystal structure.
1.14.3 Hexagonal Close-Packed (HCP) Crystal Structure
The third common metallic crystal structure is the HCP structure shown in Figure 1.21.
Metals do not crystallize into the simple hexagonal crystal structure shown in Figure 1.5 because
the APF is too low. The atoms can attain a lower energy and a more stable condition by forming
the HCP structure of Figure 1.21. The APF of the HCP crystal structure is 0.74, the same as that
for the FCC crystal structure since in both structures the atoms are packed as tightly as possible.
In both the HCP and FCC crystal structures each atom is surrounded by 12other atoms, and thus
both structures have a coordination number of 12.
The isolated HCP unit cell is shown in Figure 1.21c and has the equivalent of six atoms
per unit cell. Three atoms form a triangle in the middle layer, as indicated by the atomic sites in
Fig. 1.21a. There are six -atom sections on both the top and bottom layers, making an equivalent
of two more atoms . Finally, there is one-half of an atom in the center of both the
top and bottom layers, making the equivalent of one more atom. The total number of atoms in the
HCP crystal structure unit cell is thus: .
The ratio of the height c of the hexagonal prism of the HCP crystal structure to its basal side a is
called the c/a ratio (Figure 1.20a). The c/a ratio for an ideal HCP crystal structure consisting of
uniform spheres packed as tightly together as possible is 1.633.Cadmium and zinc have c/a ratios
Compiled by H. Abdulsalam © 2019 16
higher than ideality, which indicates that the atoms in these structures are slightly elongated along
the c axis of the HCP unit cell. The metals magnesium, cobalt, zirconium, titanium, and beryllium
have c/a ratios less than the ideal ratio. Therefore, in these metals the atoms are slightly
compressed in the direction along the c axis.

Fig. 1.21HCP unit cells: (a) atomic-site unit cell, (b) hard-sphere unit cell, and(c) isolated unit cell.
1.15 Exercise 1
1. Iron at 20oC is BCC with atoms of atomic radius 0.124 nm. Calculate the lattice constant a for the
cube edge of the iron unit cell.
2. Calculate the atomic packing factor (APF) for the BCC unit cell, assuming the atoms to be hard
spheres.
3. Calculate the volume of the zinc crystal structure unit cell by using the following data: pure zinc
has the HCP crystal structure with lattice constants a = 0.2665 nm and c = 0.4947 nm.
4. Briefly define or explain the following terms:
i. Bravais Lattice,
ii. Primitive Unit Cell,
iii. Packing Fraction,
iv. Coordination Number.
5. Draw the following direction vectors in cubic unit cells:
(a)
(b)
(c)
d)

6. Determine the direction indices of the cubic direction shown in Figure below:

Compiled by H. Abdulsalam © 2019 17


CHAPTER TWO

2.0 X-RAY DIFFRACTION ON CRYSTALLINE STRUCTURES

2.1 Diffraction of X-rays


The direct observation of the periodicity of atoms in a crystalline material relies on the X-
ray or particle (electron or neutron) diffraction/scattering on these spatially periodic structures,
since the wavelength of the incident beam is in these cases comparable to the typical interatomic
distance of a few Å. Optical diffraction is not suitable for this purpose since the wavelength of
photons is much too long (about 1 µm) in comparison to the lattice constant (a few Angstroms). In
a diffraction experiment, both the X-ray or particle source and the detector are placed in vacuum
and sufficiently far away from the sample such that, for monochromatic radiation, the incident
and outgoing X-rays or particle beams can be approximated by plane waves. The X-rays can be
used in either transmission or reflection configurations. The diffraction picture offers information
regarding the symmetry of the crystal along a certain axis. In particular, the positions of the spots
give information about the lattice and the intensity analysis reveal the composition of the basis.
The X-rays penetrate deeply in the material, so that many layers contribute to the
reflected intensity and the diffracted peak intensities are very sharp (in angular distribution). To
obtain sharp intensity peaks of the scattered radiation, the X-rays should be reflect specularly by
the atoms in one plane.

For X-rays, the wavelength is determined from the relation:

But, , therefore

Where E is the energy of electron, proton or neutron, c is speed of light, is wavelength of the x-
ray and h is Planck constant.

X-rays are scattered mostly by the electronic shells of atoms in a solid, since the nuclei are too
heavy to respond. Electrons can also have de Broglie wavelengths similar to the lattice constants
of crystals. In this case,

And the wavelength is given by:

Where m is the mass of electron, proton or neutron

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When a wave interacts with the crystal, the plane wave is scattered by the atoms in the
crystal each atom acting like a point source (Huygens’ Principle). Because a crystal structure
consists of a lattice and a basis, the X-ray diffraction is a convolution of diffraction by the lattice
points and diffraction by the basis. Generally, the latter term modulates the diffraction by the
lattice points. In particular, if each lattice point acts as a coherent point source, each lattice plane
acts as a mirror.

2.2 Diffraction of X-rays and Bragg’s Law


In 1913 Bragg found that crystalline solids have remarkably characteristic patterns of
reflected x-ray radiation. In crystalline materials, for certain wavelengths and incident directions,
intense peaks of scattered radiation were observed. Bragg accounted for this by regarding a crystal
as made out of parallel planes of atoms, spaced by distance d apart. The conditions for a sharp
peak in the intensity of the scattered radiation were that:
 The x-rays should be specularly reflected by the atoms in one plane;
 The reflected rays from the successive planes interfere constructively.
Let us consider a crystal made up of equidistant parallel planes of atoms with the inter-planer
spacing dhkl. Further, consider a monochromatic x-ray beam of wavelength having a common
wave front, falls at an angle on the planes as shown in figure 2.1 below.

Figure 2.0.1 Bragg Diffraction

Each atom scatters the x-rays more or less uniformly in all directions, but because of the periodic
arrangement of atoms the scattered radiation from all atoms in a set of planes is in phase where
they interfere constructively. In all other directions, there is destructive interference.
Consider two of the incoming x-ray OA and O'E inclined at an angle with the topmost
plane of the crystal and are scattered in the directions AP and EP', also at an angle with that
plane. Since the path length of the rays OAP and O'EP' are the same, they arrive at P and P'
respectively in phase with each other and again form a common wavefront. This is the condition
for scattering in phase by single plane of the crystal.
Now, let us consider X-ray scattering from two adjacent planes and as shown in
figure 2.1. If EB and ED are parallel to the incident and scattered wavefront respectively, the total
path OCP’’ is longer than the path O’EP' by an amount

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Now, from the right angle triangle EBC and EDC, we have

If two consecutive planes scattered in phase with each other then we know that the path difference
must be equal to an integral multiple of wavelength, i.e. where gives the
order of reflection. Thus the condition for constructive interference by a set of equidistant parallel
planes in a crystal is given by:

The integer n is known as the order of the corresponding reflection (or order of interference).
There are a number of various setups for studying crystal structure using x-ray diffraction. In most
cases, the wavelength of radiation is fixed, and the angle is varied to observe diffraction peaks
corresponding to reflections from different crystallographic planes. Using the Bragg law one can
then determine the distance between the planes.
Thus constructive diffraction occurs for certain discrete value of for which the Bragg’s
condition is satisfy, as the maximum value of sine of any given angle is one i.e.

That is, must not be greater than twice the interplaner spacing, otherwise no diffraction will
occur. This observation is an example of X-ray wave interference, commonly known as X-ray
diffraction (XRD), and was direct evidence for the periodic atomic structure of crystals postulated
for several centuries. Although Bragg's law was used to explain the interference pattern of X-rays
scattered by crystals, diffraction has been developed to study the structure of all states of matter
with any beam, e.g., ions, electrons, neutrons, and protons, with a wavelength similar to the
distance between the atomic or molecular structures of interest. For certain specific wavelengths
and incident angles, intense peaks of reflected radiation (known as Bragg peaks) were produced.
The concept of Bragg diffraction applies equally to neutron diffraction and electron diffraction
processes. When x-rays are incident on an atom, they make the electronic cloud move as does any
electromagnetic wave. The movement of these charges reradiates waves with the same frequency
(blurred slightly due to a variety of effects); this phenomenon is known as Rayleigh scattering
(or elastic scattering). The scattered waves can themselves be scattered but this secondary
scattering is assumed to be negligible. A similar process occurs upon scattering neutron waves
from the nuclei or by a coherent spin interaction with an unpaired electron. These re-emitted wave
fields interfere with each other either constructively or destructively (overlapping waves either
add together to produce stronger peaks or subtract from each other to some degree), producing a
diffraction pattern on a detector or film. The resulting wave interference pattern is the basis of
diffraction analysis.

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2.3 Powder Diffraction
Powder diffraction is a scientific technique using X-ray, neutron, or electron diffraction on
powder or microcrystalline samples for structural characterization of materials. An instrument
dedicated to performing such powder measurements is called a powder diffractometer. Powder
diffraction stands in contrast to single crystal diffraction techniques, which work best with a
single, well-ordered crystal. A diffractometer produces waves at a known frequency, which is
determined by their source. The source is often x-rays, because they are the only kind of energy
with the correct frequency for inter-atomic-scale diffraction. However, electrons and neutrons are
also common sources, with their frequency determined by their de Broglie wavelength. When
these waves reach the sample, the atoms of the sample act just like a diffraction grating,
producing bright spots at particular angles. By measuring the angle where these bright spots
occur, the spacing of the diffraction grating can be determined by Bragg's law. Because the
sample itself is the diffraction grating, this spacing is the atomic spacing. The distinction between
powder and single crystal diffraction is the degree of texturing in the sample. Single crystals have
maximal texturing, and are said to be anisotropic. In contrast, in powder diffraction, every
possible crystalline orientation is represented equally in a powdered sample, the isotropic case.
X-ray Powder Diffraction (PXRD) operates under the assumption that the sample is
randomly arranged. Therefore, a statistically significant number of each plane of the crystal
structure will be in the proper orientation to diffract the X-rays. Therefore, each plane will be
represented in the signal. In practice, it is sometimes necessary to rotate the sample orientation to
eliminate the effects of texturing and achieve true randomness.
There are twomain types of powder diffraction experiments; automated powder
diffractometer experiments yielding (digital) computer output and Debye-Scherrer experiments
providing (analog) film output. the Debye-Scherrer method is the use of wave scattering on a
sample which is not single crystalline, but is powdered. In this case, the incoming wave can
scatter off of any one of many small crystallites which may be oriented in any possible direction.
In spirit this technique is similar to the rotating crystal method in that there is always some angle
at which a crystal can be oriented to diffract the incoming wave. A figure of the Debye-Scherrer
setup is shown in Fig. 2.2.Using Bragg’s law, given the wavelength of the incoming wave, we can
deduce the possible spacing s between lattice planes.

Figure 2.0.2 Debye-Scherrer Powder Diffraction

Diffraction of X-rays or neutrons by polycrystalline samples is one of the most important,


powerful and widely used analytical techniques available to materials scientists. For most
Compiled by H. Abdulsalam © 2019 21
crystalline substances of technological importance, the bulk properties of a powder or a
polycrystalline solid, averaged throughout the sample, are required; in general a single-crystal
data, even if they can be obtained, are usually of little interest except for determination of the
crystal structure or for studying some other fundamental physical property. In the main, powder
diffraction is a means to an end, in that it frequently forms part of a wider investigation of
physical, chemical or mechanical properties of materials. It is also interdisciplinary in nature, a
technique which is equally applicable to a study of the behaviour of semiconductors and
superconductors, for example, as to alloys, catalysts, minerals, pharmaceutical substances or
polymers. Indeed, as will be evident from this review, powder diffraction transcends the
traditional, and increasingly artificial, subject areas of science. The basic difference between
coherent scattering from planes of atoms of spacing d in a single crystal and a random powder is
that diffracted beams from individual crystallites in the latter generate cones with semi-angle 2 ,
where

is the wavelength of the radiation used. In the reciprocal space representation, the lattices
associated with individual crystallites are oriented randomly and points given by the position
vector, :

In the single crystal case become spheres of radius for random powder, where
are vectors defining the reciprocal unit cell and hkl are Miller indices, which are proportional to
direction cosine of the planes in question thus:

In a powder-diffraction experiment, a 1-dimensional representation of diffracted intensity as a


function of the radial distance d*is normally obtained. Two types of experiment are possible,
angle dispersive, in which monochromatic radiation is used, and energy dispersive for which the
scattering angle is fixed. In some applications, the variation of intensity as a function of d *is all
that is required. In others, it is necessary to reconstruct the 3-dimensional lattice.

2.4 Reciprocal Lattice


A reciprocal lattice represents the Fourier transform of a Bravais lattice. In normal usage, this first
lattice whose transform is represented by the reciprocal lattice is usually a periodic spatial
function in real-space and is also known as the direct lattice. Reciprocal lattice is the set of wave
vectors for which the corresponding plane waves have the periodicity of the Bravais
lattice . Thus we are looking for all waves that remain unchanged when being shifted by
any reciprocal lattice vector . Reciprocal lattice provides a simple geometrical basis for
understanding:
a) All things of "wave nature" (like behavior of electron and lattice vibrations in crystals.
b) The geometry of x-ray and electron diffraction patterns

Compiled by H. Abdulsalam © 2019 22


2.4.1 Diffraction condition and Reciprocal Lattice
Later von Layer introduced a different approach for x ray diffraction. He regarded a crystal as
composed of identical atoms placed at the lattice sites and assumed that each atom
canreradiatetheincidentradiationinalldirections.Sharppeaksareobserved
onlyinthedirectionsandatwavelengthsforwhichthex-raysscatteredfrom all lattice points interfere
constructively.

Figure 2.0.3 Direct Lattice Vector


To find the condition of constructive interference we consider two waves scattered in figure 2.3
separated by a direct lattice vector . The x-rays incident are from infinity, along direction with
wavelength and wave vector , Assuming the scattering is elastic, i.e. the x-rays are
scattered in direction with same wavelength so that the wave vector . The path
difference between the x-ray scattered from the two atoms should be an integer number of
wavelengths. Therefore, as is seen from figure #, the condition of constructive interference is

Where n is an integer. Multiplying both sides of Eqn 2.10 by leads to a condition on the
incident and scattered wave vectors:

Defining the scattering wave vector , the diffraction condition can be written as the
diffraction condition can be written as

Where is, by definition, such a vector for which

A set of vectors which satisfies this condition form a reciprocal lattice. Vectors are called
reciprocal lattice vectors. A reciprocal lattice is defined with reference to a particular Bravais
lattice which is determined by a set of lattice vectors . The Bravais lattice that determines a

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particular reciprocal lattice is referred as the direct lattice, when viewed in relation to its
reciprocal.
There is an algorithm for constricting the reciprocal lattice from the direct lattice. Let ,
and be a set of primitive vectors of the direct lattice. Then the reciprocal lattice can be
generated using primitive vectors , and .

Where is the volume of the unit cell, so that:

In order to proof that the vectors built in this way satisfy condition (2.13), we first note that the
satisfy he condition

Where is the Kronecker symbol defined by

2.17

Indeed, since we obtain

This proofs Eqn (2.13).

2.5 Atomic Scattering Factors


The coherent scattering of X-rays from an atom may be described in terms of the atomic
scattering factor f, which is the ratio of the amplitude of the radiation scattered by the atom of to
the amplitude of the radiation which an electron would scatter under the same conditions
according to classical theory. The scattering factor depends on the scattering amplitude of an
individual atom, on the Bragg angle and the type of radiation involved. The atomic scattering
factors are measures of the scattering power of individual atoms. Each element has a different
atomic scattering factor, which represents how strongly x-rays interact with those atoms. The
scattering factor has two components: f1 and f2, which describe the dispersive and absorptive
components. In other words, f2 describes how strongly the material absorbs the radiation, while f1
describes the non-absorptive interaction; which leads to refraction. It is also obvious that the X-
ray scattering power will depend on the number of electrons in the particular atom. The X-ray
scattering power of an atom decreases with increasing scattering angle and is higher for heavier
atoms. A plot of scattering factor f in units of electrons versus shows this behavior. Note

that for zero scattering angle the value of f equals the number of electrons.
Exercise 2
1. Using an appropriate diagram, show that: , where is the wavelength of X-ray, is
the order of diffraction, d is the interplanar spacing and is the angle of diffraction.

Compiled by H. Abdulsalam © 2019 24


2. Determine the second and third order angles through which an X-ray of wavelength 0.440Å be
reflected from the cube face of a rock salt crystal (d = 2.814Å).
3. What is Rayleigh scattering or elastic scattering?
4. Explain the difference between powder diffraction and x-ray diffraction on single crystals.
5. Briefly define or explain Atomic Scattering Factors
6. Give the conditions for a sharp peak in the intensity of the scattered radiation.

Compiled by H. Abdulsalam © 2019 25


CHAPTER THREE

3.0 BONDING IN SOLIDS AND IMPERFECTION IN SOLIDS

3.1 Crystal Bonding


The stability of solid state materials is assured by the existing interactions (attractive and
repulsive) between the atoms in the crystal. The crystal itself is definitely more stable than the
collection of the constituent atoms. This means that there exist attractive interatomic forces and
that the energy of the crystal is lower than the energy of the free atoms. On the other hand,
repulsive forces must exist at small distance in order to prevent the collapse of the material. One
measure of the strength of the interatomic forces is the so-called cohesive energy of the crystal,
defined as the difference between the energy of free atoms and the crystal energy. Similarly, the
cohesive energy per atom is defined as the ratio between the cohesive energy of the crystal
and the number of atoms. Typical values of the cohesive energy per atom range from one (1) to
ten (10) eV/atom, with the exception of inert gases, where the cohesive energy is about 0.1 eV per
atom. In particular, the cohesive energy determines the melting temperature of solid state
materials. Crystals with have weak crystal bindings, while the others are
characterized by strong crystal bindings.

Figure 3.1 Graph of energy against interatomic distance


As shown in the figure 3.1, the potential/binding energy U, which describes the interaction
between two atoms, approach 0 (or infinity) for an interatomic distance R → ∞ (or to 0), and has a
minimum at a certain distance . It is composed of an attractive energy part, dominant at
, and a repulsive energy part that prevails at . Then, the most stable state of the
system, which occurs at the lowest possible energy, is characterized by the cohesive energy ,
the corresponding interatomic distance, , being known as the equilibrium interatomic
distance. The equilibrium interatomic distance has typical values of , which implies that
the stability of the crystal is determined by short-range forces.
The interatomic force, defined as

Compiled by H. Abdulsalam © 2019 26


is negative (attractive) for , and positive (repulsive) for . The attractive and
repulsive forces, which have different origins, cancel each other at the equilibrium interatomic
distance.
The general form of the potential energy is

The repulsive force between atoms in the solid has the same origin in all crystals: Pauli exclusion
principle, which forbids two electrons to occupy the same orbital (the same quantum state). The
repulsive force is characterized (see the formula above) by the power-law expression

The repulsive potential is short-ranged and thus it is effective only for nearest neighbors. The
attractive forces create bonds between atoms/molecules in the solid, which guarantee the crystal
stability and are of different types depending on the crystal. Only the outer (valence) electrons
participate in the bonding. There are several types of bonding, depending on the mechanism
responsible for crystal cohesion: ionic, covalent and metallic, which give rise to strong crystal
bindings, and hydrogen bonding and van der Waals interaction, which determine weak crystal
bindings. Electronegativity is the average of the first ionization energy and the electron affinity.
It measures the ability of an atom or molecule to attract electrons in the context of a chemical
bond. In general, the electronegativity increases with the group number in the periodic element
table, from the first to the seventh group (elements in the eight group have complete shells).
3.1.1 Ionic Bonding
Ionic bonding is a type of chemical bond that involves the electrostatic attraction between
oppositely charged ions, and is the primary interaction occurring in ionic compounds. The ions
are atoms that have gained one or more electrons (known as anions, which are negatively
charged) and atoms that have lost one or more electrons (known as cations, which are positively
charged). This transfer of electrons is known as electrovalence in contrast to covalence. In the
simplest case, the cation is a metal atom and the anion is a nonmetal atom, but these ions can be
of a more complex nature, e.g. molecular ions like NH4+ or SO42−. In simpler words, an ionic bond
is the transfer of electrons from a metal to a non-metal in order for both atoms to obtain a full
valence shell.

Figure 3.2 Ionic bonding

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3.1.2 Covalent Bonding
The covalent bonding forms in molecules composed of identical particles. The outer
electron levels of atoms, which are close to each other, can interact and this interaction leads to a
sharing of electrons between the atoms. One pair of electrons shared single covalent bond while
two pairs of electrons shared double covalent bond and so on. The shared electrons are said to be
delocalized i.e. they do not belong to any particular atom. Generally, covalent bonding occurs
between non-metallic atoms. For examples: H2, CO2, C6H12O6 and other molecules

Figure 3.3 Covalent bonding


Single hydrogen atom (left) and two hydrogen atoms forming a covalent bond with a shared
electron pair (right).
C, Si and Ge form crystals in which the covalent binding is dominant, the van der Waals
contribution to the cohesion energy, also encountered in crystals from a single element, being
negligible. However, in crystals with a basis composed of two atoms A and B, with n and,
n8valence electrons respectively, the covalent binding is accompanied by a ionic contribution.
The resulting bond is called polar covalent bond.

3.1.3 Metallic bonding


The metallic bonding can be understood as the bonding between positively charged
metallic nuclei/ions and delocalized conduction electrons, seen as a “sea of free electrons”. It
prevails in elements in which the valence electrons are not tightly bound with the nucleus (in
metals, for example). However, in the metallic bond we cannot speak about ions, since there is no
particular electron that is “lost” to another ion. Unlike other bonding types, the metallic bonding is
collective in nature, so that no single “metallic bond” exists. It is neither intra- nor intermolecular
since no molecule can be distinguished in metals. Metallic bonding can be understood as a non
molecular, extremely delocalized communal form of covalent bonding. The delocalization is most
pronounced for s and p electrons, with l = 0 and l = 1, respectively, being much weaker for d and f
electrons, which have quantum numbers l = 2 and l = 3, respectively.

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Figure 3.4 Metallic bonding
The outer electrons are so weakly bound to metal atoms that they are free to roam across the
entire metal. This results in a lattice of positively ions in a sea of communal electrons
In metals, an atom achieves a more stable configuration by sharing all its valence electrons
with all other atoms in the crystal. The metallic bonding is encountered, for example, in alkaline
metals such as Li, K, Na, with electronic configurations that resemble those of noble gases with
an additional s electron on the outer shell. Having few electrons on their outer shells, alkali metals
have only partly filled energy levels, and therefore are electron deficient. In forming the crystal,
the wave functions of the outer s electrons overlap with those of their nearest neighbors, and the
electrons become delocalized. Their dynamics resembles that of free electrons, so that in alkaline
metals the lattice is occupied by the positively charged ions with the noble gas structure (they
occupy in fact only as much as 20% from the volume of the crystal), while the valence electrons
occupy the remaining volume.
3.2 Bond lengths
Distances between centers of bonded atoms are called bond lengths, or bond distances.
Bond lengths vary depending on many factors, but in general, they are very consistent. Of course
the bond orders affect bond length, but bond lengths of the same order for the same pair of atoms
in various molecules are very consistent. Thus, there are tables of interatomic distances or bond
lengths in some standard handbooks. Table 3.1 shows some bonds with their respective bond
lengths and bond energies.

Table 3.1 Some bonds with their respective bond lengths and bond energies
S/N Bond Length Energy S/N Bond Length Energy S/N Bond Length Energy
(kJ/mol)
(pm) (kJ/mol) (pm) (kJ/mol) (pm)

1. H--H 74 436 2. H--C 109 413 3. C=C 134 614

4. N--N 145 170 5. H--N 101 391 6. C--Br 194 288

7. O--O 148 145 8. H--O 96 366 9. C--I 214 216

10. F--F 142 158 11. H--F 92 568 12. C--S 182 272

13. Cl-Cl 199 243 14. H--Cl 127 432 15. C--F 135 488

16. Br-Br 228 193 17. H--Br 141 366 18. C--Cl 177 330

19. I--I 267 151 20. H--I 161 298 21. O=O 121 498

22. C--O 143 360 23. C--C 154 348 24. C--N 147 308

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Bond lengths are determined by X-ray diffraction of solids, by electron diffraction, and by
spectroscopic methods (study of the light absorbed or emitted by molecules). The bond lengths
ranges from the shortest of 74 pm for H-H to some 200 pm for large atoms, and the bond energies
depends on bond order and lengths. Half of the bond length of a single bond of two similar atoms
is called covalent radius. The sum of two covalent radii of two atoms is usually the single bond
length. For example, the covalent radii of H and C are 37 and 77 pm respectively. The C-H bond
is thus (37+77) 114 pm.
The bond order is the number of electron pairs shared between two atoms in the formation of the
bond. Bond order for C=C and O=O is 2.

3.3 Bond Energies


The amount of energy required to break a bond is called bond dissociation energy or
simply bond energy. Since bond lengths are consistent, bond energies of similar bonds are also
consistent. Thus, tables of bond energies are also of commonly found in handbooks. Some typical
bond lengths in picometers (1 pm = 10-12 and bond energies in kJ/mol are given here to illustrate a
general trend so that you are familiar with these quantities.
The bond energy is essentially the average enthalpy change for a gas reaction to break all the
similar bonds. For the methane molecule, C(-H)4, 435 kJ is required to break a single C-H bond
for a mole of methane, but breaking all four C-H bonds for a mole requires 1662 kJ. Thus the
average bond energy is (1662/4) 416 (not 436) kJ/mol.
Bond energy is a measure of the strength of a chemical bond. The larger the bond energy, the
stronger the bond.
There is a general trend in that the shorter the bond length, the higher the bond energy.
However, there is no formula to show this relationship, because the variation is widespread.
3.4 Imperfections in Solids or Crystal defects
Irregularity in the arrangement of constituent particles in solids is called crystal defect or
imperfection in solids. There are two types of crystal defects - Point Defects and Line Defects.
3.4.1 Point Defects
Irregularities or deviation from ideal arrangement of constituent particles around the point
or atom in a crystalline solid is known as point defects. Point Defects are divided into three types:
(i) Stoichiometric Defects (ii) Impurities Defects (iii) Non-stoichiometric Defects.
Stoichiometric Defects:
It is a type of point defects which does not disturb the stoichiometry of solid. This is also known
as Intrinsic or Thermodynamic Defects.
Impurities Defects
Defects in ionic compounds occurs because of replacement of ions by the ions of other
compound is called impurities defects.

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Figure 3.5 Impurities Defects
In NaCl; during crystallization; a little amount of SrCl 2 is also crystallized. In this process, Sr++
ions get the place of Na+ ions and create impurities defects in the crystal of NaCl. In this defect,
each of the Sr++ ion replaces two Na+ ions. Sr++ ion occupies one site of Na+ ion; leaving other
site vacant. Hence it creates cationic vacancies equal number of Sr++ ions. CaCl2, AgCl, etc. also
shows impurities defects.
Non-stoichiometric Defects
There are large numbers of inorganic solids found which contain the constituent particles in non-
stoichiometric ratio because of defects in their crystal structure. Thus, defects because of presence
of constituent particles in non-stoichiometric ratio in the crystal structure are called Non-
stoichiometric Defects.

3.4.2 Line Defects


Point defects are defects that occur only at or around a single lattice point. They are not
extended in space in any dimension. Strict limits for how small a point defect is are generally not
defined explicitly. However, these defects typically involve at most a few extra or missing atoms.
Larger defects in an ordered structure are usually considered dislocation loops. Many point
defects, especially in ionic crystals, are called centers: for example a vacancy in many ionic solids
is called a luminescence center, a color center, or F-center. These dislocations permit ionic
transport through crystals leading to electrochemical reactions.
 Vacancy defects are lattice sites which would be occupied in a perfect crystal, but are vacant. If a
neighboring atom moves to occupy the vacant site, the vacancy moves in the opposite direction to
the site which used to be occupied by the moving atom. The stability of the surrounding crystal
structure guarantees that the neighboring atoms will not simply collapse around the vacancy. In
some materials, neighboring atoms actually move away from a vacancy, because they experience
attraction from atoms in the surroundings. A vacancy (or pair of vacancies in an ionic solid) is
sometimes called a Schottky defect.
 Interstitial defects are atoms that occupy a site in the crystal structure at which there is usually not
an atom. They are generally high energy configurations. Small atoms in some crystals can occupy
interstices without high energy, such as hydrogen in palladium.

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3.5 Exercise 3
1. List the various types of crystal bonding and group them under strong crystal and weak crystal
bonding
2. State the dominant contributor to the binding energy U if: and where is
interatomic distance and is the equilibrium interatomic distance. (2 marks)
3. Briefly define Point Defect list and explain the types of point defect in solids.
4. Briefly define bond length and bond energy.

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CHAPTER FOUR

4.0 LATTICE VIBRATIONS

4.1 Introduction
When the lattice is at equilibrium each atom is positioned exactly at its lattice site. Now
suppose that an atom displaced from its equilibrium site by a small amount. Due to force acting on
this atom, it will tend to return to its equilibrium position. This results in lattice vibrations. Due to
interactions between atoms, various atoms move simultaneously, so we have to consider the
motion of the entire lattice.
4.2 One-dimensional lattice
For simplicity we consider, first, a one-dimensional crystal lattice and assume that the
forces between the atoms in this lattice are proportional to relative displacements from the
equilibrium positions.

Figure 4.1 One-dimensional crystal lattice


This is known as the harmonic approximation, which holds well provided that the displacements
are small. One might think about the atoms in the lattice as interconnected by elastic springs.
Therefore, the force exerted on n-the atom in the lattice is given by

Where C is the interatomic force (elastic) constant. Applying Newton’s second law to the motion
of the n-th atom we obtain

Where M is the mass of the atom. Note that we neglected here by the interaction of the n-th atom
with all but its nearest neighbors. A similar equation should be written for each atom in the lattice,
resulting in N coupled differential equations, which should be solved simultaneously (N is the
total number of atoms in the lattice). In addition the boundary conditions applied to the end atom
in the lattice should be taken into account.
Now let us attempt a solution of the form

Where is the equilibrium position of the n-th atom so that:

Likewise

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This equation represents a traveling wave, in which all the atoms oscillate with the same
frequency and the same amplitude A and have wave vector q. Note that a solution of the form of
Eqn 4.3 andEqn.4.5areonly possible because of the transnational symmetry of the lattice.

Now substituting Eqn.4.5 into Eqn 4.2 and canceling the common quantities (the amplitude and
the time-dependent factor) we obtain

But

Factor out from R.H.S gives:

Dividing both sides of Eqn 4.8 with gives:

Again and

Factor out from R.H.S gives:

Dividing both sides of Eqn 4.8 with gives:

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Equation 4.14 gives the relationship between the frequency of vibrations and the wave vector q,
this dispersion relation have a number of important properties.

i. Reducing to the first Brillouin zone.


The frequency (Eqn 4.14) and the displacement of the atoms (Eqn 4.3)do not change when we
change by This means that these solutions are physically identical. This allows us to set
the range of independent values of q within the first Brillouin zone, i.e.

Within this range of q the versus q is shown in Figure 4.2.

Figure 4.2

The maximum frequency is . The frequency is symmetric with respect to the sign change in q,
i.e. .This is not surprising because a mode with positive q corresponds to the wave
traveling in the lattice from the left to the right and a mode with a negative q corresponds to the
wave traveling from the right to the left. Since these two directions are equivalent in the lattice
the frequency does not change with the sign change in q.
At the boundaries of the Brillouin zone the solution represents a
standing wave
: Atoms oscillate in the opposite phases depending on whether n is even or odd.
The wave moves neither right nor left.

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ii. Phase and group velocity.
The phase velocity is defined by

And the group velocity by

The physical distinction between the two velocities is that is the velocity of the propagation of
the plane wave, where as the is the velocity of the propagation of the wave packet. The latter is
the velocity for the propagation of energy in the medium.
For the particular dispersion relation (Eqn 4.14) the group velocity is given by

As is seen from Eqn 4.17 the group velocity is zero at the edge of the zone where .
Here the
wave is standing and therefore the transmission velocity for the energy is zero.

iii. Long wavelength limit.


The long wavelength limit implies that In this limit .We can then expand the
sine in Eqn 4.14 and obtain for the positive frequencies:

We see that the frequency of vibration is proportional to the wave vector. This is equivalent to the
statement that velocity is independent of frequency. In this case

This is the velocity of sound for the one dimensional lattice which is consistent with the
expression we obtained earlier for elastic waves.

4.3 Diatomic1D lattice


Now we consider a one-dimensional lattice with two non-equivalent atoms in a unit cell. It
appears that the diatomic lattice exhibit important features different from the mono atomic case.
Figure 4.3 shows a diatomic lattice with the unit cell composed of two atoms of masses and
with the distance between two neighboring atoms a.
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Figure 4.3 A diatomic lattice
Wecantreatthemotionofthislatticeinasimilarfashionasformonoatomiclattice.However,in this case
because we have two different kinds of atoms, we should write two equations of motion:

In analogy with the mono atomic lattice we are looking for the solution in the form of traveling
mode for the two atoms:

This is written in the obvious matrix form. Substituting this solution to Eqn 4.20 we obtain

This is a system of linear homogeneous equations for the unknowns and .A non trivial
solution exists only if the determinant of the matrix is zero. This leads to the secular equation

This is a quadratic equation, which can be readily solved:

Depending on sign in this formula there are two different solutions corresponding to two different
dispersion curves, as is shown in Figure 4.4:

Figure 4.4

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The lower curve is called the acoustic branch, while the upper curve is called the optical branch.
The optical branch begins at and . Then with increasing q the frequency increases in
a linear fashion. This is why this branch is called acoustic: it corresponds to elastic waves or
sound. Eventually this curve saturates at the edge of the Brillouin zone. On the other hand, the
optical branch has a non- zero frequency at zero q and it does not change much with q.

The distinction between the acoustic and optical branches of lattice vibrations can be seen most
clearly by comparing the m at (infinite wavelength). As follows from Eqn 5.21, for the
acoustic branch and .So in this limit the two atoms in the cell have the same
amplitude and the phase. Therefore, the molecule oscillates as a rigid body, as shown in Figure
4.5 for the acoustic mode.

Figure 4.5

4.4 Phonon
Considering the regular lattice of atoms in a uniform solid material, you would expect
there to be energy associated with the vibrations of these atoms. But they are tied together with
bonds, so they can't vibrate independently. The vibrations take the form of collective modes
which propagate through the material. Such propagating lattice vibrations can be considered to be
sound waves, and their propagation speed is the speed of sound in the material. The vibrational
energies of molecules, e.g., a diatomic molecule, are quantized and treated as quantum harmonic
oscillators. The evidence on the behavior of vibrational energy in periodic solids is that the
collective vibrational modes can accept energy only in discrete amounts, and these quanta of
energy have been labeled "phonons". Like the photons of electromagnetic energy, they
obey Bose-Einstein statistics. Considering a solid to be a periodic array of mass points, there are
constraints on both the minimum and maximum wavelength associated with a vibrational mode.

4.5 Debye theory of specific heat


A theory of the specific heat capacity of solids put forward by Peter Debye in 1912, in
which it was assumed that the specific heat is a consequence of the vibrations of the atoms of the
lattice of the solid. In contrast to the Einstein theory of specific heat, which assumes that each
atom has the same vibrational frequency, Debye postulated that there is a continuous range of
frequencies that cuts off at a maximum frequency , which is characteristic of a particular solid.

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The theory leads to the conclusion that the specific heat capacity of solids is proportional to T3,
where T is the thermodynamic temperature. This result is in very good agreement with experiment
at low temperatures. A key quantity in this theory is the Debye temperature, . The Debye

temperature is characteristic of a particular solid. For example, the Debye temperature of sodium
is 150 K and the Debye temperature of copper is 315 K.
At low temperatures, the optical branch phonons have energies higher than , and
therefore, optical branch waves are not excited. Only acoustic waves contribute to the heat
capacity. For an acoustic branch , as and the Einstein model fails to include this
feature in its model. The Debye model assumes that the lattice waves are elastic waves (one
longitudinal branch and two transverse branches) and the frequency here is not a constant but a
specific distribution with a cut off frequency of ,above which no shorter wave phonons are
excited.
In the Debye model can be defined as

We may define the Debye temperature as

We get the Debye specific heat capacity as

Where is called the Debye specific heat capacity function. When

approaches the value .But, when , Debye specific heat equation


becomes as

Here, is proportional to this is known as the Debye law. At lower temperatures the Debye
approximation is best suited because almost all excited phonons belong to the long-wavelength
waves in the acoustic branches and the crystal behaves like acontinuum. The Debye temperature
is defined in a temperature-independentparameter.

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Table 4.1 Debye Temperatures of several substances.
Substance Debye Substance Debye Substance Debye
Temperature(K) Temperature(K) Temperature(K)

Aluminum 428 Iron 470 Silicon 645K

Cadmium 209 Lead 105 Silver 225K

Chromium 630 Manganese 410 Zinc 327K

Copper 343.5 Nickel 450 Carbon 2230K

Gold 165 Platinum 240 Ice 192K

Exercise 4
1. What is a phonon?
2. Consider the model one-dimensional monatomic chain of N atoms, equally spaced with separation
a, and each with the same mass m. The force constant coupling each atom to its nearest-neighbors
is C. The normal mode vibrational frequency ω(q) of a mode with wave vector q for this model is:

a. Derive an expression for the group velocity and phase velocity as a function of q
b. Using the results of part a, evaluate vg at very small values of q (q → 0).
c. Using the results of part a, evaluate vg for k at the Brillouin Zone boundary [q = (π/a)],
Briefly Discuss the physical significance of this Brillouin Zone boundary group velocity.
3. Give Einstein and Derby assumptions to specific heat.

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