UNIT 5 SOLID STATE

Structure
5.1 Introduction
Objectives
5.2 Definition of Terms Used in Crystal Systems
Lattice
Basis
Unit Cell
5.3 Bravais Lattices and Crystal Systems
Cubic System Geometry
Bravais Lattice
5.4 Crystal Planes and Miller Indices
5.5 X-rays and Crystal Structure
Principles of Diffraction
Bragg Law and Bragg Equation
5.6 Experimental Method for the Determination of Crystal Structure
Powder Method
Some Experimental Findings
5.7 Determination of Unit Cell
Number of Net Atoms in a Cubic Unit Cell
Density Calculation
Experimental Method
5.8 Nature of Bonds in Solids
5.9 lonic, Covalent and Molecular Crystals
lonic Crystals
Covalent Crystals
Molecular Crystals
5.10 Commonly Encountered Metallic Structures
5.1 1 Semiconductors
Intrinsic Semiconductors
Extrinsic Semiconductors
5.12 Summary
5.13 Terminal Questions
5.14 Answers
- - -- - ---
-

5.1 INTRODUCTION

In the earlier units,, we had drawn a comparison amongst the three states of matter-solid,
liquid and.gas. These states of matter were described in terms of a few physical'properties
like "solids are denser than liquids and gases" or "it takes enormous pressure to compress a
solid even by a fraction of its volume", etc. However, instead of defining the states of matter
in terms of the physical properties, it is much more useful to think in terms of the binding
forces (ionic, covalent, van der Waals, etc.,) involved in a particular state imparting
different properties to solids, liquids and gases. Thus, solid state could be defined as a state
of a substance in which the neighbouring particles (molecules, atoms or ions) are close
enough for van der Waals forces to operate. As a consequence, the motion of the molecules
is restricted with respect to its neighbours.
The solids can be of two types - crystalline and amorphous. Let us explain what a
crystalline solid is. Those solids which are formed due to regulal repetition of identical
building blocks are called crystals. It is like having a collection of identical bricks which
could be arranged in some regular fashion to construct a wall. On the other hand, theie are
solids which do not appear to have any regular internal arrangemeqt in every part and thus
do not show regular shape; these are called amorphous solids. Amorphous solid means a
solid without regular form. Glass, polyethylene as in plastic bags, etc., are common
examples of amorphous substances. Though the study of amorphous substances is also quite
useful and interesting, we shall confine ourselves to the study of the crystalline solids in this
unit.
Different crystalline structures are associated with different physical properties. Hence, we
discuss crystal forms and crystal structure determination method in this unit. Further, the
theories'of metallic bonding and semiconductors are also explained with particular reference
to electrical conduction. The information obtained from crystal structure studies could help us
in understanding the physical and chemical properties of solids.
 Objectives
After studying this unit, you should be able to:
define lattice, basis, unit cell, primitive and nonprimitve cells,
describe the seven crystal systems and the fourteen Bravais latt~ces,
identify the face, corner, edge, face-centre and body-centre in a cube,
r
state the crystal planes in terms of Miller indices,
state Bragg law,
describe the determination of crystal structure by X-ray diffraction method,
determine the type of unit cell based on experimental and calculated values of density,
explain the types of bonds in solids,
discuss the structures of some ionic, covalent and metallic crystals, and,
describe the types of semiconductors.

5.2 DEFINITION OF TERMS USED IN CRYSTAL

SYSTEMS

Atom is In general =;lse tn this We h&e already seen that a crystal is defined in terms of a regular and repetitive
unit; it stands for an atom or an Ion arrangement of particles (atoms/molecules/ions) in space. In order to pndefstaad crystak
'
or a molecule. and their structures, we encounter a few new terms. These terms form akind of
crystallographic language. Let us now look at the definitions of some of these terms.
5.2.1 Lattice
Lattice is defined as an arrangement of geometrical points in a definite pattern in space
A parallel net-like arrangement of
points in space is known as lattice. (Fig. 5.la). It resembles a scaffold (a framework) erected for the construction of a building
Putting it in a simpler way, one can define.a lattice as a regular periodic arrangement of
. . points in space.

m)
bsis (with two .toms), c) c r p ! stmetare.
Fig. 5.1 :Representation ofa) lattice in two
~wingtbebPGiSof1woatomsinrddootsYekepiO.

5.2.2 Basis
Whenever there is a group of atoms When atoms tire attached regularly to each lattice point, it forms a crystal. However. instead
around a lattice pointl then the basis of an atom, we can have a group of atoms attached to each lattice point. The group is called
is defined.
a basis (Fig. 5. l b). The basis consists of the atoms, their spacings and internal bond angles.
62 Every basis is identical in compositbn, arrangement and orientation. Fig. 5.lc shows the
crystal structure where you can recognise the basis and imagine the lattice. For a large Solid State
number of crystals, the basis has only a small number of atoms but in a few instances, the
basis exceeds 1000 atoms. For example, the basis in iodine crystal is I 2 molecule whereas in
the ice crystal, H i 0 molecule is the basis.

5.2.3 Unit Cell

The unit cell is the fundamental unit in a crystal. The repetitive arrangement of unit cells in Identical repetition of basis about
three dimensions produces a crystal just as a wall is built from identical bricks. In other each 1at:ice point in three
dimensions gives a crystal structure.
words, a unit cell is the smallest unit of a crystal which on translational displacement in
three dimensions will produce the crystal. A unit cell chosen to represent the crystal may be
quite different in sizt and shape from another unit cell which may represent the crystal
equally well. The main point is that whatever the unit cell may be, it should be the simplest
representation and, when repeated in three dimensions, it should produce the crystal.

Fig. S;t :Choice of unit cell.

Fig. 5.2 shows four rows of spheres-represent~ng atoms-in a closely packed structure in
two dimensions. If we join the centres or any other points, say, gaps between the spheres, of
differont atoms in successive thr~crows, we get a cell of the tjpe a, b or c. All the other
rows of atoms are a repetition of the first three rows. It is immaterial whether the unit cell
chosen is a, b or c, but it is the simplest representation which on repetition in two . -
dimensions will produce the entire assembly as shown in Fig. 5.2. The si!uation.in a crystal
is somewhat similar to the above except that the u n ~ cell
t and the resulting crystal are three
dimensional. Thus, we can say that the simplest repeating unit in a crystal is called a unit
cell
It is true that the unit cell must have some regularity in stru~iure.Does any type ~f regular
shape constitute a unit cell? The answer is no. To understand this, let us consider the.
covering of a floor space by tiles without leaving a gap. Can we use any type of t~les-

Fig. 5.3 :Of aU the reguk polygons, only triangles, squares and hexagons can fill a floor space without gap.
F i - i n space is deaoted by grey 63
 triangular, square, pentagonal, hexagonal, heptagonal or octagonal? Agains the answer 1s no.
You can cover the floor space completely with triangular, square or hexagonal tiles but not
with pentagonal, heptagonal or octagonal tiles (Fig. 5.3). Note the gaps in the interior floor
space when pentagonal, heptagonal or octagonal tiles are used.

Jusc as tiles with specific shapes are useful in covering the floor space completely, unit cells
with specific symmetry properties constitute the crystal lattice. The course on Spectroscopy
deals with symmetry properties in detail.

SAQ I
What is the essential characteristic d a qnit cell?

- -

5.3 RRAVAIS LATTICES AND CRYSTAL SYSTEMS

A parallelepiped is a three The basic shape of a rrnit cell is described by a parallelepiped. (Fig. 5.4a).
dimensiooal model of a
parallelogram. A unit cell has three coordinate axes, a, b and c (note the bold letters). The cell-edge
lengths in the threc axes are a, b and c (note the italicised letters), respectively (Fig. 5.4b).
The cell-edge lengths (a, b and c) are
the repeat distances in a unit cell. The angles between a and b axes, b and c axes and c and a axes are y , a and P,
Any point in a unit cell can be respectively. The quantities a, b and c are called lattice parameters or unit cell parameters.
represented by coordinates wh~chare
fractions of a, b and c.

Fig. 5.4 :a) parallelepiped; b) three coordinate axes, cell-edge lengths and the angles between axes.

Based on the relationships among the axial angles and the edge-lengths, there are seven
crystal systems as given in Table 5.1.

Table 5.1 :The Seven Crystal Systems

Systems Axes Angles Examples

Cubic a=b=c a = ~ = Y = 9 0 ~ NaCI, CsCl

Tetragonal a=b# c a=p=y=900 Ti02 (rul~le)

Orthorhomb~c a f b f c a=p=y=900 CdS04, HgBr?

Rhombohedra1 a=b=c o=S=y#9o0 CaCOl (calcite)

Hexagonal a=b#c a = b = 90'; y = 120° SiOz
MonGl~nic a f b f c a =y = sdO;p f 90° KIOJ, NaHCO?
Triclinic a f b f c a f S f Y NaHS04, CuF:

5.3.1 Cubic System Geometry

Of the seven crystal systems, we are particularly interested in cubic system due to its
simplicity and symmetry. A cube has the same value for all the three lattice paramete?
(a b = c). We must understand the geometry of a cube. For this purpose, imagine that
 you m sitting in a cubical room. Each wall (including floor and ceiling) of your room is .Solid State
called a fpce. A cubical room has six faces-four walls, the ceiling and the floor. You can
consider the ceiling and the floor as horizontal walls! For a cubic crystal, the celledge ,

lengths are he =me dong the throe

Each point where three faces of a cube (or three wal$ in your room) meet is called a axes and ere represented as a.
corner. A cube has eight comers and these are indicated by A to H in Fig. 5.5a.
Each face h& four corners. By joining the corners of a face diagonally, two face diagonals
are obtained. For example, in Fig. 5..5b, the lines AC and BD (obtained by joining A and C Len,& of face diagod, AC
or B and D, respectively) are two of the twelve face diagonals in a cube. The centre point of =m
a face where the two face diagonals meet is called a face-centre; one of the six face-centres =2JZ
is indicated by M in Fig. 5.5b.' In U C G , /ACG -; 90".
(See Rg. 5 . 5 ~ )
Length of the body diagonal, AG
=dzT3
=JZ?Tz
=a&

Fig. 5.5 :a) Eight corners in a cube indicated by letters A to H--each comer is marked by red dot; twelvc
edges indicated by number 1 to 12; b) bottom face ABCD of the cube shown; !4C and BD are the face
diagonals and M is face-centre; c) The right-angled AACC.

By joining any two corners which are not in the same face,% body diagonal is obtainzd.
There are. four body diagonals in a cube--AG, BH; FFn and EC in Fig. 5.5a. All the body
diagonals meet at the body-centre. The .definitions of face, corner, edge, face-centre and
body-centre apply to other crystal systems also.

5.3.2 Bravais Lattice

Some crystal systems, may have one or more types of lattices depending on the number of
lattice points. If there are lattice points only at the eight comers of a unit cell, it is called a
simple or prirnitivelP) cell. A cell which ha$ lattice points at the eight corners and the six face
centres iscalled a face-centred ( F ) cell. A cell that has eight lattice points at the corners and
two more at the centres ofa pair of any two opposite faces is called an end-centred (C) cell.
If a cell has eight lattice points at the corners and one at the body centre, it is called a body- A non-~ra~ais
Lttlce structure IS
centred (I) celi. The unit cells of the type F, C and I are called nonprimitive cells. Based on composed of two or more
the presence of lattice points in the seven crystal systems, there are fourteen Bravais lattices;
these are given in Fig. 5.6. 65
I
 Cubic

Simple (P) Body-centred (I) Face-centred { F )

Tetragonal
-

Simple (P) Bodysentred (I) Simple (P) Endentred (C)

Orthorhombic

Simple (P) Body-centred (I) Facecentred (F) Endcentred (C)

Hexagonal (P) lriclinic

Rhombohedral

F
ig.5.6 :Fourteen Bmv& Lattices.

Of these Bravais lattices, we shall consider simple cubic (sc), body-centred cubic (bcc) and
face-centred cubic Ucc) lattices only. In the next section, let us see how to represent the
crystal planes.
SAQ 2
Describe the following : simple cubic, body-centred cubic and faa-centred cubic crystals.
. .

5.4 CRYSTAL PLANES AND MILLER INDICES

Crystal planes are represented .by certain numbers known as Miller indices. These indices
are determined in the following way :
i) Find the intercepts of a crystal plane on the axes, a, b and c in terms of cell-edge
lengths Q, b and c. Suppose that a crystal plane makes intercepts 3a, 2b, 2c as shown in
.Fig. 5.7.
 Fig. 5.7 :Miller indices.

~ i )Divide the intercepts by the respective cell-edge lengths (aD and cj. For the crystal
3a 26 2c .
plane in Fig. 5.7, this step g~ves -* --* i.e., 3,2,2 as the answer.
+-

a b c
iii) Take the reciprocal of the above numbers. Corresponding to Fig. 5.7, this step gives
-1 1 1
9- 9 - as the answer.
3 2 2
iv) Finally reduce the above fractions to the smallest integers having the same ratio. Write
these numbers enclosed in parantheses without comma signs; these are the Miller
indices of the given crystal plane. For the illustration in Fig. 5.7, the Miller indices are
(233); this is to be pronounced as two three three plane.
Miller indices are generally represented as (hkf). You will notice that the Miller indices are

_
defined in such a way that all equivalent and parallel pland are represented by the same set
26 2c
3 3
-
of Miller indices. Thus, planes whose intercepts are 3a, 2b,2c ora, 9 - 'br 9 ~ ~ 6fit, 6 ,.
etc. are all represented by a set of Miller indices (233).
If a face is parallel to en axis, theoretically the corresponding intercept is equal to m. To
illustrate this, Ict us draw a crystal plane of a cubic cell which makes intercepts a, m, w.
That is, the plane is parallel to b and e axes. Applying the above steps in order, we get the
1
Miller indices for this plane as (100). Remember b equal to zero. Th6 origin (0)and
, ,h-*
-
the axes directions are shown in Fig. 5.8a. The (100) plane is indicated in Fig. 5.8b.
Similarly, corresponding to the planes with intercepts Q, Q, 00 and Q, Q, u, the Miller indices
are (1 10) and (1 1I), respectively; these are shown in Figs. 5.8 c and d, respectively.

Fig. 5.8 :a) The prigin, 0,the axes and the cell-edq length a in r cubk ceU; b) (100) plsne; c) (110) p h ;
d) (111) we.
 -.
We can calculate the distance between the adjacent planes labelled by the same Miller
indices (hkl), but no generalised formula can be written. The actual formula in a particular
case would depend upon the crptal structure. For example, the distance d h k ~between the
(hko planes of a cubic lattice is given by,
a
dhk~ = ... (5.1)
d h 2 + k2 l2 +
where a is the cell-edge length of the cell.and (hkl) are the Miller indices. Thus, in
sodium chloride crystal, the ceil-edge length is 5.63 X 10-"m. The distance between (1 11)
planes is given by Eq. 5.1,

+
d l 2 l 2-b l 2 d3
Eq. 5.1 could be used only for cubic crystals. For an orthorhombic cell, the equation for d m
turns out to be,

Using Eq. 5.2, work out the following SAQ.

SAQ 3
An orthorhombic crystal has the following parameters:
a -- 8.2 X lo--'" m; b = 9.4 X 10." m; c -- 7.5 X m.
What is the distance between (123) planes?

- - -- - - -

5.5 X-RAYS AND CRYSTAL STRUCTURE

Crystal structur.es are wually.determined with the help of X-rays. In addition to X-rays,
other forms of radiations having similar properties-like a beam of neutrons or electrons-
could also be used. However, our discussion will be limited to the use of X-rays only. We
know that X-rays are electromagnetic radiations of wavelengths much shorter' than either
visible or ultraviolet light. In 1911, Ewall showed that whenever the wavelength of
radiation is of the same order of magnitude as the size of the particle in a material, the
radiation would be diffracted by the particle. In 1912, Laue suggested that since the order of
the magnitude of the wavelength of X-rays and the crystal lattice distances are the same, we
should expect diffraction of X-rays by crystals. This was soon confirmed experimentallyby
Friedrich and Knipping.,Let us explain the principle of diffraction, in general, and the
diffraction of X-rays by crystals, in p'articular.

5.5.1 Principles of Diffraction

The amplitude is directly related to Diffraction pattern arises due to interference of waves. When the waves are in phase, the
the intensity of the beam. intensity is increased, (this is known as constructive interference; Fig. 5.9a); when !hey are
out of phase (known as destructive interference), the intensity is decreased (Fig. 5.9b). If
there are two waves starting from a common source, their phase difference will be directly
proportiooal to their path difference.

Fig. 5.9 :Two waves (shown by dotted and solid l i w s ) ghring rioe to a resu#nnt (shown by red d o u r ) :a)
cmdrudve ioterference (in-phase b a v e - m amptihade); b) dedmctive intcrtemce (out-of-phase
68
w8vc--smrOerpaptiade). .
The bending of light round the edges of an obstacle is called diffraction. Consider a beam of
light pasiing througn two slits (SI and SZ),cut near to each other on a screen and falling on
a second screen p l a d beyond the slits (Fig. 5.10). A series of dark and bright bands are
observed on the screen, which are due to the cqnstructive and destructive interference of the
two beams passing through the two slits. When their amplitudes are in-phase, the intensity
is enhanced and when their amplitudes are out-of-phase, the intensity is decreased. Whether
the beams are in-phase or out-of-phase will depend on the path differencebetween the two
rays.

Light beam

Fig. 5.10 :laphPse aud out-of-phpse w a v a

5.5.2 Bragg Law and Bragg Equation

If the path differencebetween the two rays is an integral multiple (n = 1,2,3,. . . ) of the
wavelength of X-rays, then the two rays will be in-phase and the diffraction pattern will be
bright (i.e., with enhanced intensity). This is called Bragg law. W e d mathematically, for a
bright diffraction pattern,
path difference = n A ... (5.3)
Bragg derived an equation Eq 5.9) for X-ray diffraction of crystals. This equation is named
after him. Some of the assumptions made by Bragg in deriving Eq. 5.9 are given below : The bright and dark spots which
The incident waves are reflected by parallel planes of atoms in a crystal such that the appear on a photographic film are
angle of incidence. is equal to the angle of reflection. This is called specular (mirror- called diffraction pattern; it should
like) refledion. not be confused with diffraction
• Each plane reflects only a fraction of incident radiation. phenomenon which is just the
When the reflections lrom parallel planes interfere constructively, the diffraction bending of light around the edges of
an obstacle.
pattern arises.
The wavelength of the X-rays is not changed on reflection; i.e., X-rays undergo elastic
scattering on the lattice planes. Using geometric considerations, Bragg equation can be
derived easily.
Two parallel beams PA and QC are incident at an angle 8 on the parallel planes EF and
GH (Fig. 5.1 1). The perpendicular distance (AC) between the two planes is d. The beams
are reflected along AR and CS at an angle 8. The path difference between the two sets of
incident and reflected beams (PAR and QCS) is the extra distance travelled by QCS as
compared to PAR. To calculate the path difference, draw AB I QC and AD I CS.

Fig. 5.11 :The taddent and tht reReded beams and the two -1 lattice
69
 +
Path difference = (QC CS) - (PA AR) +
+ +
= (QB BC) (CD + DS) - (PA AR) +
=BC+CD ... (5.4)
[ ': QB = PA and DS = AR, being opposite sides of the rectangles shown
by the shaded portiotls in Fig. 5.1 1 1.

Since AC IGH, /ACG = 90" = /ACB + /BCG = &B+

' 8
[ :' /QCG and /BCG are same as 8 ]
/ACB = 90' - 8
In the right-angled AABC, /BAS + /ACB + /CBA = 180°
+
Using Eq. 5.5, LBAC (!XO - 6) + 90" = 180"
/BAC = 180" - (180" - 8 ) = 8
BC
Also, -= sin 8 or BC = AC sir] 8
AC
Since, AC = d, RC = d sin 8

Similarly, we can prove that CD=dsin 8

Using Eqs. 5.4, 5.6 and 5.7,

path difference = 2d sin 8 -
Again substitut:.~gin Eq. 5.3, we get,

Bragg equation assumes that incident

nA = 2dsin 6
X-rays are reflected specu!arly Eq. 5.9 is known as Bras equation. It is useful in crystal structure determination. In this
(m~rrorlike)such that the angle of
incidence is equal to the angle of
equation, A is the wavelength of X-rays used, d is the distance or the spacing between the
reflection. This assumption is planes. 'Ile value of n gives the order of reflection.
convincing only hecause it explains If n = 1, it is first-order reflection.
*ha -rncrimental results.
If n = 2, it is second-order reflection and so on.
After reading the above section you should be able to hive the following SAQ.

SAQ 4
If the separation between the lattice layers in:a crystal is 404 pin and the wavelength of
X-rays used'is 154 pm, what would be the angle of incidence at which reflection would
occur? Assume n 7 1.

15.6 EXPERIMENTAL METHODS FOR THE

DETERMINATION OF CRYSTAL STRUCTURE
In any method of cry:tal structwe determination, we must find out 6 as well as the intensity
of the diffracted beanr. There are bas~callythree methods-hue, powder and the rotating
crystal-which ace used for the determination of the above quantities. In this section we
shall discuss the outline of powder method only.

5.6.1 Powder Method

Ili this method, we use a powdered sample containing microcrystals wmch are ra~r,lomly
oriented. There are enough of microcrystals which will have the proper orientation lor
diffraction. The diffraction beam corresponding to each scattering fans out in the form of a
cone, the axis of which lies along the incident beam as shown in Fig. 5.12. This gives rise to
bright rings on a circular photographic film and is known as powder pattern. The X-ray
--
 Solid State

Cone of
diffracted rays

Fig. 5.12 :Powder method.

powder pattern for sodium chloride is shown in Fig. 5,13. Using powder method, the
interplanar spacing can be found out since both h and 0 are known.

=- 3 WI=;M 8
N'mm dm"
- d d
8 2
V1

cr
0
3

Fig. 5.13 :X-ray powder panern for sodium chloride.

5.6.2 Some Experimental Findings

Some noteworthy features in crystal structure determination by X-ray diffraction are given
below:

11 appears that a set of planes 1s retlecting the X-ray beam.

The reflection takes place only for certain values of 8; these values of 0 must satisfy
. Bragg equation (Eq. 5.9).
It is a common practice to set n = 1 in Eq. 5.9, unless specified otherwise. Higher
order reflections (n > 1 ) are weak.

The x-ray diffraction method leads us to the value of cell-edge length which can be used to
detfrmine the density of the crystal.

5.7 DETERMINATION OF UNIT CELL

The comparison between the experimental and the theoretical values of density could help
us in determining the cubic cell type. First let us calculate the number of atoms belonging to
a unll cell in each type of cubic cell.

5.7.1
..
Number of Net Atoms in a Cubic Unit Cell
An atom at the hody-centre of a unit cell belongs to that cell only (Fig. 5.14a). An atom on
the face-centre of a unit cell is shared by unit cells (Fig. 5.14b) and thus, only half of
such an atom belongs to one unit cell. An atom at the edge-centre of a unit cell is shared by
four unit cells (Fig. 5.14~);one-fourth of an atom in the edge-centre belongs to one unll
cell. But an atom at the corner of a unit cell will be shared by eight unit cells as shown in
Fig. 5.14d. Hence, we can say that one eighth of an atom in a corner belongs to a particular
unit-cell. Using this background, let us calculate the number of net atoms present per u n ~ t -
lor a ~ l r i 1 ~ l e ~ uface-centered
c ~ b l l 6b, cubic or body-centred cubic structure.
 Fig. 5.14 :a) An atom at the body-ceotre of a mit ceU; b) An atom at the face-centre shared by two unit
cells; c) An atom at the edge-centre shored by four unit cells! d) An atom in the comer shared by eigM
unit cells.
The number of net atoms per unit 0 In a simple cubic cell, there are atoms only at the eight corners; and hence, a simple
cell are one, two and four in simple 1
cubic, bcc and fcc structures. cubic structure has only one net atom (8 X -8
= I) per unit cell.
. On the other hand, in a bcc structure, there are atoms in the eight corners and'the
1
+
centre of the cell; hence, there are two net atoms [(8 X - ) 1 = 21 per unit cell of a
8
bcc structure.
Finally, for a fcc structure, there are atoms in the eight corners and six face centres.
1 I
+
That is, a fcc structure has four net atoms [(8 X - ) (6 X -) = 1 3 = 41 per
8 2
+
unit cell.
The density of a crystal depends on the number of atoms, their mass and the volume of the
unit cell. Let us no& see the calculation of the densities of these three types of unit cells.

5.7.2 Density Calculation

Mass
It is known that density = - ...
Volume
In this unit, the cell-edge lenghs'apd X-ray measurements give us the celledge length. If the celledge length is a m, (i.e, a metre)
the distance between the planes are then the volume of the unit cell = a' m' ... (5.1 1)
given in m or pm units; but it is
0
usual to rtate such data in A unit also. The mass of an atom of the substance is obtained by dividing the mass of one mole atoms [i.e.,
atomic mass (w) in kg mol '1 by Avogardo constant ( N A, which is a equal to
6.022 X lo'.' mol I).
w kg mol-' w
Mass of on atom = -- = -kg ...
NA mol N\
A simple cubic structure has only one atom per unit cell; hence. mass of unit cell of a simple
cubic crystal js given by Eq. 5.12. Substituting the proper values from Eqs 5.1 1 and 5.12 in
Eq.5,10, we get,
the density
of a simple
cubic cell
} = -
W
kg m-j ... (5.13)

Since, simple cubic, bcc and fcc unit cells have one, two and four atoms per unit cell, the
densities of bcc and fcc are given by :
Density of a bcc cell, = 7 2w kg m-3
NAa
4w
Density of a fcc cell = 7 kg m-j
NAa
nw
In general, the density of a cubic unit cell (p) = 7
NAa
kg m-j ... (5.16)
where n is the number of net atoms per unit cell.
Rearranging Eq. 5.16, we get,

5.7.3 Experimental Method

The cell-edge length (a) and the density (p) of a crystal are experimentally determined. These
values are substituted in Eq. 5.17 and n is calculated. Depending on whether n = 1 or 2 or 4,
the unit cell is simple cubic or bcc or fcc. Let us work out an example.
Nickel metal packs in a cubic unit cell with a cell-edge length (a) of 3.524 X lo-'' m. The
density (p) of nickel is 8.90 X lo3kg m-3. Let us find out the unit cell type for nickel. Since
atomic mass of nickel is 58.7, w = 0.0587 kg mol-I
First we have to calculate n using Eq. 5.17

- 8.90 X lo3kg m-3 X 6.022 X loz3mol-I X (3.524 X lo-" m13

0.0587 kg mol-'
= 4 (rounded to the nearest whole number).
Since there are four atoms per unit cell, nickel has a fcc lattice.
In the following section, we shall study the nature of bonds responsible for holding the solid
together. Before that attempt the following SAQ.
SAQ 5
Tungsten forms bcc cbtals. Its celledge length IS 3.16 X 10-'%. Find the density of
tungsten:

5.8 NATURE OF BONDS IN SOLIDS

There are basically two theories or models to explain the nature of bonds in solids. One is
known as bond model and the other as band model. These two names may sound new;
however, they are the same two approaches that we have already studied (in Units 4 and 5
of Atoms and Molecules course) in connection with the formation of a molecule by the
combination of two or more atoms. Thus the bond model is the same as the valence bond
apprpach. Here we consider a crystal as a three dimensional arrangment of atoms and each
of these atoms has valence electrons which can form normal chemical bonds with
neighbouring atoms. These bonds may be ionic, covalent or van der Waals in character. In
the other approach, which is called the band model, we follow the molecular orbital
treatment. All the nuclei with their core electrons are considered as a fixed periodic array
-
States n l Matter
over which the valence electrons are spread out. It is like pouring of electron cement over a
fixed arrangement of nuclear bricks. We have already read about ibnic bond, covalent
bond, hydrogen bond, etc., in Unit 3 of Atoms and Molecules course. We shall now study
metallic bonding in terms of the above two models.

Metallic Bonding
According to the bond theory, the metallic solids can be considered as having simple
covalent bonds between adjacent atoms. However,in these cases, the number of electron
pairs available for bond formation is less than the number of orbitals available. Hence,
when such substances are placed under an applied electric field, the electrons from the filled
orbitals can easily flow into the vacant orbitals, thus making them highly conducting.

In the band theory of metals, a crystalline metallic solid is considered as a single giant
molecule: Linear combination of atomic orbitals on ali the atoms is taken to give molecular
orbitals of the solid just as in the case of simple diatomic molecule. It is also assumed that
there is negligible overlap of inner shell atomic orbitals and the energies of these remain
practically the same as atomic orbitals on isolated atoms. However, the outer orhitals do
combine to give molecular orbitals of bonding and antibondixg character. Suppose that a
crystal of sodium contains N atoms, where PI is of the order of 10". Neglecting the innei
orbitals, there are N number of 3s orbitals on all the atoms in the crystal which can
combine to give N molecular orbitals or delocalised crystal orbitals. Since each molecular
orbital can hold 2 electrons, the total number of electrons which these orbitals can hold is
2N. The actual number of electrons is however only N, since each atom is contributing only
one 3s electron. Hence, only half of the molecular orbitals will be occupied by the electrons
and half will remain vacant. Further, since there are N molecular orbitals and the total
energy difference between the highest and the lowest orbital is very small, the energy
separation between the adjacent molecular orbitals would be very small. For all practical
purposes we can consider these molecular orbitals as forming a continuous band of energy
rather than separate energy levels. Thus we have a situation where a band of vacant energy
levels lie very near to a band of occupied energy levels. Therefore, the electrons present in
the occupied lower energy levels can easily move out to vacant band. This is the reason
given for metals being good conductors of electricity. In the next section, we shall study the
structures of ionic, covalent and molecular crystals.

5.9 IONIC, COVALENT AND MOLECULAR CRYSTALS

In this section.we shall consider the structures of some crystals, which have either ionic or
covalent bonds; examples are also given for crystals having~ovalentbonding with van der
Waals attraction or hydrogen bonding.

5.9.1 Ionic Crystals

As examples for io*nic crystals, we shall consider caesium chloride and sodium chloride
which have bcc and fcc structures, respectively.\

bcc Structure
The structure of a bcc crystal can be defined in terms of unit cell-edge length and two
unique positions in the cell. Consider a crystal like CsCl which has bcc structure and has
Unit cell-edge length must connect two different ions in lattice positions. Suppose the centre of a cube is occupied by Cs' ion;
equivalent points If there is an atom then, this is one of the unique positibns of the crystal. It is unique because there is no other
at the corner of a unit-cell, similar point within the cell which is one cell-edge length away and which can be occupied by
atoms must be present at all the
cornen. If there is an atom at a face- another Cs' ion. Now if one of the corners of the cube is occupied by a chloride ion, then
centre, the opposite facecentre also all the eight corners of the cube must be occupied by chloride ions. This is so because each
must have the similar atom. of the corners is one unit cell-edge length away from its nearest neighbours and if one
corner is occupied by Cl- ion, its immediate neighbours which are unit cell-edge length
away must also be occupied by chloride ions. We can say that any one corner position is
unique in the sense that once you associate an atom with this position, then all the other
corners automatically get associated with the similar atoms. Thus, once these two positions
are defined, the whole crystal gets &fined'(~i~. 5.15).
 Solid Slatr

0 CI-
@ cs'

Fig. 5.15 : CsCl structure

Since CsCl crystal has one Cs' ion at the centre and eight CI- ions at the corners, it has one
I
Cs' ion and one CI- ion (8 X - = I) belonging to one'unit cell as per discussion in
8
Subsec. 5.7.1. That is, each CsCl unit cell has one formula unit.
fcc Structure
In a fcc structure, there are four unique positions; once these positions are defined, the rest
of the crystal gets completely described. These are the centres of jhree adjacent faces and
one corner. Once one corner, is occupied by an atom, all other corners will have similar
atoms. Further, if one atom occupies the centre of one face, the centre of the opposite face
would also be occupied by sii:.;lar atom. Thus, by describing the atoms which odcupy the
centres of adjacent three faces, we know the atoms occupying the centres of all the six faces
Similarly, all the eight corners are described, once we know the atom occupying one of the
corner positions. Thus, the whole crystal is described. Sodium chloride is one such example.
It can be Considered to be composed of two interpenetratingfcc lattices, one made up of
sodium ions and the other made up of chloride ions (Fig. 5.16).

A unit cell of sodium chloride can be

considered to be made up of
onefcc unit cell of sodium ions
and
onefcc unit cell of chloride ions.
Since each suchfcc unit cell has four
atoms (or ions), sodium chloride
crystal h p four NaCl formula units
per unit cell.

Fig. 5.16 :'Structure of sodium chloride.

The sodium ion lattice is shifted in all the three dimensions by half cell-edge length from the
chloride ion lattice. A unit cell of NaCl contains four formula units.

5.9.2 Covalent Crystals

In covalent crystals, definite covalent bonds join all the atoms in the crystal. The structure
of a covalent crystal is related to the number of valence electrons, the nature of orbitals
involved in bond formation and their orientation. One of the most commonly cited
 examples is that of diamond (Fig. 5.1 7). Each carbon atom in diamond is tetrahedrally
bonded to four neighbouring carbon atoms. This is so since each carbon has four sp'
hybridised orbitals pointing towards the corners of a regular tetrahedron. These orbitals
overlap with the similar set of orbitals on the neighbouring atoms. Crystals thus formed are
hard and h e a c t i v e .

Fig. 5. 18 : Structure of iodine crystal-the

Fig. 5.17 :Structure of diamond. basis is 12 molecule.

Let us now see another type of covalent crystals known as molecular crystals.

5.9.3 Molecular Crystals

In molecular crystals, the moleculesare held together due to van der Waals interaction.
These crystals acquire the structure which has the minimum energy maintaining the original
shape of the discrete molecules. Iodine (Fig. 5.18) and carbon dioxide crystals are examples
, ..
of this type.

There is a class of crystals which have hydrogen bonding between the molecules. An
example of this type is ice. In ice. each oxygen atom is tetrahedrally surrounded by four
hydrogen atoms, two being linked through covalent bonds in the same molecule and the other
two through hydrogen bonds to different water molecules. In the next section, we shall
illustrate the four main types of crystal structures in metals.

SAQ 6 *
The deoslty of potasium bromide is ,2326 x 10' kglm-'. Its cell edge-length 15
6.54 X 10 "' m. It has a cuhlc structure. ~in&ut$@ether it hap
structure. "c $3 *
,,,--

5.10 COMMONLY ENCOUNTERED METALLIC

STRUCTURES d
b2

Most of the metals crystallise in one of the four basic structures-- simple cuh~c,body-
centred cublc (bcc), hexagonal closest packed (hcp) and tace-centred cubic (or cubic
hcp and structures,each layer closest packed-ccp). Simple cubic structure is not yery common except perhaps for
of atoms is closely packed as the polonium metal which packs in this structure. Alkali metals, Ba, V, Cr, Mo, etc., crystallise
name suggests. in bcc structure. The number of nearest neighbours (coordination number) is 8 in bcc
arrangement.
The unit cell with ccp arrangement is
called fcc unit cell,
Each atom in hcp and ccp arrangements touches three atoms in the plane above, three in the
plane below and six in the same plane. Thus, in both the cases, the coordination number is
76
 12. Further, in ccp and hcp structures,74%of the total space is filled with atoms. The difference Solid State
between the hcp and ccp structures (Figs. 5.19 a and b) is in the arrangementof the third
layer of atoms with respect to the first layer. Metals like Be, Mg, Co, Zn pack in the hcp
structure, whereas those like Ag, Au, Cu, Ni crystallise in ccp arrangement. .

Fig.5.19 :a) kp---thc a t o a in the tbW hycr are stmignt above those in the first k y e r d c d
ABAB .,. b) c&p -tbc .toma h thc thbd hyw srmngcd ha^ those in
tbc tlrst-alkd MCABC ..- amagemmt.

5.1 1 SEMICONDUCTORS

Semiconductorsare solids which are insulators under normal conditions but become The addition of impurities to a
conductors when heated or doped with impurities. The electrical conductivity of a semiconductor is called doping.
semiconductor increases with temperature. The semiconductors can be broadly classified
into two types. Let us consider them one by one.
' -
5.1 1.1 Intrinsic Semiconductors
Intrinsic semiconductors are pure substances which conduct elixtricity when heated. In an
intrinsic semiconductor, the energy gap between the highest filled band and the next empty
one is very small. Pdre germanium, pure grey tin, etc., are intrinsic semiconductors. At
absolute zero, they are insulators. But increase ln temperature promotes some electrons
from filled to next higher band across the gap; so they become conductors. The number of
excited electrons increases as the temperature increases; so their conductivity increases with
increase in temperature.

5.11.2 Extrinsic Semiconductors

Semiconductors with impurities are called extrinsic semiconductors. They can further be
classified into n-type and p-type semiconductors.
n-type Semiconductors
When a semiconductor is doped with an impurity having more valence electrons than those
id the semiconductor, a n-type semiconductor is produced. Such an impurity can donate
electron(s)(tothe valence band of the semiconductor, and is called a donor. Phosphorus,
arsenic or antimony (each having five valence electrons) are examples of donor impurities
added to gemanium or silicon (each semiconductor having four valence electrons). The
addition of donor impurity to the semiconductor provides additional energy levels and if
they are rightly related to the bands of the semiconductor, conductivity may result. That is,
if the impurity contains a full energy level just below that of an empty band in the
semiconductor, the electrons from the impurity go to empty band in the semiconductor,
hence, it becomes negatively charged (n-type). Upto certain temperature, the conductivity of ;
a n-type semiconductor increases with increase in tempenturc. 1
ptype Semiconductors
When the impurity used for doping has less valence electrons than the semiconductor, the
~mpuritycan accept electron(s) from the valence band of the semiconductor. Such an
impurity is called acceptor. The addition of boron, aluminium, gallium or indium (each
hav~ng,three valence electrons) to silicon or germanium (each semiconductor having four
valence electrons\ ic, an example of this type. The essential feature is that the impurity must
contain an empty energy level just above a full band in the semiconductor; the electrons
from the full band in the semiconductor will pass to the empty level of the impurity.
Passage of electrons from the semiconductor to impurity makes the former positively
charged @-type). The effect of temperature on the conductivity of a p-type semiconductor is
similar to that of n-type sem~conductor.

The combination of p-type and n-type semiconductor is called p-n junction. The p-n
junctions are used as rectifiers, solar cells, light emitting diodes and other electronic devices.

SAQ 7
Differentlate betweer~intrinsic and extrinsic scn~rconductr>rs.

---
5.12 SUMMARY

In this unit, we have briefly described those solid substances which can be classified as
crystals. We have also given a hint at the potential usefulness of crystal studies. We
summarise below what we have studied so far :
The terms-lattice, basis and unit cell-were explained.
Seven crystal systems and fourteen Bravais lattices were discussed.
Diffraction method and its utility in crystal structure determination were emphasised;
an experimental technique was then discussed.
The nature of bonding in crystals with special reference to metallic bonding was
discussed briefly.
Types of semiconductors.were stated and defined.

5.13 TERMINAL OUESTIONS

1) Show that for a simple cubic cell, the ratio of the volume occupied to the volume of the
unit cell is 0.52.
(Hint : Assume (i) atoms are spherical and (ii) they touch along the cell-edge, i.e.,
a
radius = - ).
2
2) In the following cases. mark 'L/' for correct statement and 'X' for wrong statement :
i) The Miller indices of a crystal plane which makes intercepts 2a, 3b, 2c are (232).
ii) The basis in ice crystal is H:O molecule.
iii) A cube has twelve edges.
iv) The unit cell of caesium chloride crystal contains two formula units of CsCI.

3) What are the separaiions of the planes with Miller indices ( I1 1 ), (21 1) and ( 100) in a
cubic crystal having cell-edge length of 432 pm?

4) How many net atoms are there In a fir and bcc unit cell? Arrive at the conclusior~by
geometrical arguments.

5) Identify the type of attractive forces (or bonding) mainly responsible for crystal
bonding in the following cases:
i) diamond ii) potassium bromide
iii) aluminium iv) helium
 6) Sodium crystallises in a bcc lattice with a'cell-edge length of 4.23 X lo-'" m. Calculatr Solid Slate
'the density of sodium metal.

7) The density and cell-edge length of sodium chloride are 2.163 X 10' kg m-' and
5.63 X lo-"' m, respectively. Using these data, arrive at the number of form~launits
per unit cell of sodium chloride crystal.

5.14 ANSWERS
Self Assessment Questions

1) A unit cell is the smallest unit chosen which repeats itself ii three dimensions.
2) Simple ciubic - lattice points at the eight corners only;
bcc - lattice points at the eight corners and the body-centre;
fee -- lattice points at the eight corners and the six face-centres.

4) Using Eq. 5.9,

sin 0 = 0.191
.'. 0 = sin ' 0.191
= 11°

5) Using Eq. 5.14, density of tungsten = 1.936 X lo4 kg m-'

-
6) - Let .us find out the number of formula units of KBr present in a unit cell using Eq. 5. I?.
w Molar mass of KBr = 0.1 19 kg mol - I .

2.826 X
-- 10' kg m-j% (6.54
. X lo-'Ofi)' X 6.022 X l ~ ~ ~ m o l - '
* 119 kg mol-'
=4
Since it has four formula units per unit cell, it has NaCl structure and not CsCl
structure.

7) The conductivity of an intrinsic semiconductor is due to the existence of a vacant

conduction band separated by a small energy gap from the filled valence band. An
extrinsic semiconductor owes its electrical conductivity largely to the presence of an
impurity with appropriate energy levels.

II Terminal Questions

I ) Since the spheres touch along the edge, the cell-edge length (a) is twice the radius df a
a.
sphere (r), i.e., r = - .
2
47rr3 - Ira 3
The volume of a sphere = ------ - -
3 6
1 A simple cubic lattice has one net sphere only per unit cell (Subsec. 5.7.1). Hence,
7ra3
volume occupied in a unit cell = -
6

1 But the volume of the unit cell = a'

I .'. Fraction of the volume filled =Volume occupied

unit cell volume

2) (i) X (ii) (iii) (iv) X.

3) 2.49 X 10-lo m; 1.76 X 10-'~mand 4.32 X lo-" m.
4) A jcc uhit cell has four net atoms while a bcc unit cell has two net atoms (see subsec.
5.7.1).
5) I) Co~alentbonding
11) Electrostatic forces (~oni'cbonding)
il!) Metallic bonding
iv) van der waals interaction.

7) Substitut~ngthc dens~ty( p ) , cell-edge length (a) and molar mass ( w ) of sodium chloride
in Eq. 5.17, we get,

,, r 2.163 X 10' kg m-' X (5.63 X lo-'' m)3 X 6.022 X lo2' mol

0,05845 kg mol
= 4.

Further Reading
1 ) Principles of Physical Chemirtry, Samuel H. Maron and Carl F. Prutton, Oxford and
IBH Publishing Co., New Delhi, 4th ed., 1985.
2) f'hysica? Chemistry, Gilbert W . Castellan, Narosa Publishing House, Addison-
Wesley/Narosa (Indian Student Edition), Delhi, 3rd ed., 1983.
3 ) Phy.sira1 Chemisfry, P.C. Rakshit. Sarat Book House, Calcutta, 5th ed., 1988.
4 ) Phj~sica1,Chrrnistrythrough Problems, S . K . Dogra and S. Dogra, Wiley Eastern Ltd.,
New Delhi. 1984.
5) Physical Chemistry-Principles and Problems, D.V.S. Jain and P. Jauhar, Tata
McGraw-Hill Pub. Company Ltd., New Delhi. 1990.