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Compiled by H. Abdulsalam

© 2019

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

2.0 X-RAY DIFFRACTION ON CRYSTALLINE STRUCTURES................................................ 18

2.1 Diffraction of X-rays................................................................................................................... 18

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

CHAPTER THREE.................................................................................................................................... 26

3.0 BONDING IN SOLIDS AND IMPERFECTION IN SOLIDS ................................................... 26

3.1 Crystal Bonding .......................................................................................................................... 26

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

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

Table of Tables

Table 3.1 Some bonds with their respective bond lengths and bond energies ..............................29

Table 4.1 Debye Temperatures of several substances....................................................................40

Table of Figures

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

CHAPTER ONE

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.

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.

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

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.

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.

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.

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

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.

Table 1.1 Classifications of Space Lattices by Crystal System

Crystal system Axial lengths and interaxial angles Space lattice

Body-centered cubic

Face-centered cubic

equal

Body-centered tetragonal

(Trigonal)

Body-centered

orthorhombic

Base-centered

orthorhombic

Face-centered

orthorhombic

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

Three unequal axes, unequally inclined and none

at right angles

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.

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

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.

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.

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.

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).

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.

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

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.

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

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

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.

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.

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

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 .

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).

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

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.

From fig 1.15:

, and

Therefore:

Figure 1.15 Interplanar spacing for set of planes (hkl)

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.

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.

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.

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.

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

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:

CHAPTER TWO

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.

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,

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.

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.

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

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.

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.

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:

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.

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

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.

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

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

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 .

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

satisfy he condition

2.17

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.

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.

CHAPTER THREE

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.

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

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.

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

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,

n8valence electrons respectively, the covalent binding is accompanied by a ionic contribution.

The resulting bond is called polar covalent bond.

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.

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)

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

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.

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.

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.

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.

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.

CHAPTER FOUR

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.

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

Likewise

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

Again and

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.

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.

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.

ii. Phase and group velocity.

The phase velocity is defined 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.

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.

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.

Compiled by H. Abdulsalam © 2019 36

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

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

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.

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.

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

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.

Table 4.1 Debye Temperatures of several substances.

Substance Debye Substance Debye Substance Debye

Temperature(K) Temperature(K) Temperature(K)

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.