The Crystal Structure 1

1.1 INTRODUCTION
Intermolecular attraction is minimum in the gaseous state and this disappears completely when
the gas is ideal. The interaction is stronger in liquids and is strongest in solids. Thermal motion
of the molecules increases or decreases by raising or lowering of temperature. The attractive
interaction between the molecules tries to keep them together and the thermal motion is opposed
to that. Hence, it is possible to change a substance from one state to another by changing its
temperature. If a liquid is allowed to cool slowly, the molecules will arrange themselves in an
orderly manner and this will finally result in a crystalline solid. If, on the other hand, cooling is
rapid, the molecules will not be able to arrange themselves in order. Rapid densification will give
a glass or an amorphous solid. It is not true that the molecules and atoms in a solid have rigidly
fixed coordinates. But they move only a small distance about their equilibrium positions. In this
book, we are concerned with crystalline solids and the word solid and crystalline solid will be used
synonymously.
What is the stable state of a given material will depend on its free energy. The stable state
will be the one that has the lowest free energy under the given conditions. Free energy A is
related to internal energy U and entropy S of the system as
A = U ST ...(1.1)
Internal energy is lowered by an orderly arrangement of the atoms, molecules or ions as that
will lead to maximum energy of interaction. But this will minimise the entropy. Since internal
energy and entropy make opposite contribution to free energy, the state of matter will be
determined by the relative contributions of U and ST to A. If interaction is strong, U is highly
negative and ST can overcome the contribution of the former only at high temperatures. Such a
substance will remain as a solid even at a relatively high temperature.
The basic feature of a crystalline solid is the regular arrangement of the atoms and molecules.
At the macro level, this translates into crystals having sharp boundaries with clear cut shapes. It
is these beautiful shapes of natural crystals that attracted human attention for ages. This beautiful
shape and colour added to their value as gems.
Early study of crystals began with the observation of their shapes and this is known as
Geometric Crystallography. The description of crystal symmetry in terms of point lattice began in
the mid-nineteenth century. This was followed by X-ray crystal structure determination following
the work of Laue and Bragg on X-ray diffraction by crystals. In the second quarter of the twentieth
century, the presence of lattice defects and their role in determining the properties of crystals
were recognised. We shall not try to follow the development of the subject in a chronological
order as the development of knowledge in an area of science does not take place in the same
2 Solid State Chemistry

logical way as one would like to see it. But only after enough knowledge gets accumulated that
a subject is put in a logical perspective. Here we shall follow the rational rather than the
chronological course of development of the subject.
Crystal lattice
It is easy to imagine a crystal as a periodic
arrangement of points as shown in figure 1.1. A point
may represent an atom or a group atoms arranged
around it in a real crystal. Let us begin with a single
point. Repeated translation of this point through a
fixed distance = (a periodic translation) will generate
a linear array of points. This movement is denoted
^
by a translation vector t1. If we add a second
^
translation t2, it will generate periodically repeating
points on a plane and this is known as a plane lattice.
^
If a third translation t3 is added, we get a three
dimensional arrangement of the points that is called Figure 1.1: A two dimensional plane lattice
a space lattice.
The lattice points are imaginary. In a real crystal, they are occupied by atoms or groups of
atoms that are arranged in a regular fashion about the lattice points. This atom or the group of
atoms is the basis and the arrangement of the imaginary points is the lattice. The real crystal is
then:
basis + lattice = crystal.
A two dimensional pattern as is usually found on a curtain cloth or a wall paper is analogous
to a two dimensional crystal lattice. We can have an array of squarely arranged points
(Figure 1.2a) or the points may be arranged along inclined lines (Figure 1.2b). We can select a
single motif and place this motif in the same way about each lattice points. This will give two
different patterns (Figure. 1.2c and 1.2d). By selecting a different motif, we may get a still different
pattern and a large number of patterns can be generated from a limited number of motifs and
lattice arrangements.
Unit cell
We have seen that two noncollinear translations give rise to a plane lattice and introducing a third
translation (not on the same plane) generates a space lattice. Since any line joining two lattice
points is a translation and there can be wide choice of translation, the question arises as to which
two translation should one select to describe a plane lattice. A few such combinations are shown
in figure 1.3. It is seen that they generate two dimensional units called unit cell. Combination of
^ ^ ^ ^
t 1, t 2 or t 3, t 4 leads to cells having only one lattice point per cell. These are known as primitive
^ ^
unit cell. The combination t 5, t 6 generates a double cell. There can be many more multiple cells. The
unit cell of a lattice can be primitive or multiple. A repetition of the two dimensional unit cell by
translation in two directions generates the plane lattice. This may be extended to three dimensional
lattice that may be generated by translation of a three dimensional unit cell.
The Crystal Structure 3

(a) (c)

(b)
(d)

Figure 1.2: Two different plain lattices with identical motif leading to two different patterns

t3

t4 t6

t5
t2

t1

Figure 1.3: Different combinations of translation and the unit cell

The three translations are selected along the c
three edges of the chosen unit cell. The choice of a
unit cell for real crystal is done based on the
convenience and conventions. It can be a primitive
cell or a multiple cell. The three selected axes along
the edges of the unit cell are called the
crystallographic axes a, b and c and the angles between
them , and as shown in figure 1.4.
As has already been said, the early years of
study of solids were concerned mostly with crystal b a
b
geometry. This was followed by the study of crystal g
symmetry. Bravais in 1848 had shown that all
structures can be generated by using only 14 types
a
of space lattice (14 types of unit cell).
These 14 types of unit cells will give rise to Figure 1.4: A unit cell showing the edges and
230 types of lattice structures (space group) by the angles
performing such symmetry operations as
4 Solid State Chemistry

(i) translation, (ii) rotation, (iii) translation + rotation and (iv) reflection. It was shown by Federov
and independently by Barlow that it is not possible to have arrangement of lattice points other
than than these 230 types that can repeat itself infinitely in three dimensions.
The 14 types of Bravais lattices are shown in figure 1.5.

sc bcc fcc hexagonal

Simple bcc
tetragonal orthorhombic

rhombohedral monoclinic triclinic

Figure 1.5: Fourteen types of Bravais lattice

All real crystals belong to anyone of the 230 space groups. The imaginary lattice points are
occupied by atoms or groups of atoms. Table 1.1 shows the classification and the geometric
properties of the various Bravais lattices.
Table 1.1: Classification of the fourteen Bravais lattices

System Space Lattice Condition

Cubic simple cubic a = b = c

body centered cubic = = = 90
face centered cubic

Hexagonal hexagonal prism a = b c

= = 90;
= 120

Tetragonal tetragonal prism a = b c

tetragonal bcc prism = = = 90

(Contd.)
The Crystal Structure 5

Orthorhombic rectangular prism a b c

bc rectangular prism = = = 90
fc rectangular prism
base centered prism

Rhombohedral rhombohedron a = b = c
= = 90

Monoclinic parallelopiped a b c
bc parallelopiped = = 90;
90

Triclinic triclinic parallelopiped a b c

1.2 CRYSTAL PLANES AND MILLER INDICES

In a real crystal, the lattice points are occupied by atoms. One can think of a very large number
of lattice planes and one set of parallel planes can be distinguished from another set by their
orientation. Miller indices are the labels used to distinguish one set of parallel planes from another.
It is a set of three numbers h k l that defines a set of parallel planes in a crystal.
The following procedure is generally followed to determine the Miller indices.
1. Choose an origin;
2. Find out the intercept that the first such plane makes with the three crystallographic axes;
3. Obtain their reciprocals;
4. Eliminate fractions.
The set of numbers thus generated in relation with the axes a, b and c are h, k and l
respectively. A set of parallel planes are labelled by a set of hkl numbers. Different set of parallel

planes have different hkl or Miller indices. This is illustrated in figure 1.6. Here, the plane nearest
1 1 1
to the origin and cutting the b axis at , the a axis at and the c axis at is shown. This
2b 3a 2c
1 1 1
makes intercept along a axis, intercept along b axis and along c axis.
3 2 2
c

b
b
a

a
Figure 1.6: (322) set of planes
6 Solid State Chemistry

We can write
a b c
intercept 1/3 1/2 1/2
reciprocal 3 2 2
Hence this plane and a set of parallel planes separated by a distance d have the Miller
indices (322).
It should be noted that a point on a paper actually represents line of points when one
considers the three dimensional lattice. Hence on the plane of paper a line of points actually
represents a plane.
The major advantage of the Miller indices is that it permits to express interplanar distance
dhkl of a set of hkl planes in terms of lattice parameters a, b, c, , and .
For a cubic crystal
a
dhkl =
h + k2 + l2
2
e j
1.3 DIFFRACTION OF X-RAYS
In 1912, von Laue first suggested that since the lattice points in a real crystal are occupied by
atoms, the crystal lattice should act as a three-dimensional diffraction grating for X-rays. This
should happen because X-rays have wavelength of the dimension of interplanar distances in a
real crystal. Shortly after this, W.L. Bragg showed that wavelength of the X-ray undergoing
diffraction by a crystal is related to the interplanar distances by the famous Braggs equation.

1.3.1 Braggs Law of Diffraction

Let there be a set of lattice planes consisting of an array of atoms as shown in figure 1.7. The
X-ray beam incident on a plane at angle will be reflected from the plane such that the angle of
c c c

2a
a
b b
a b
2a
a 2a
a a a
(100) (010) (001)
c c
c
3a
3a 3a
2a
a
a 2a 3a
b b a 2a 3a b

3a 3a
a
a a
(111) (101) (011)

Figure 1.7: Different sets of crystal planes in a cubic crystal

The Crystal Structure 7

reflection is also and a part of the intensity will pass though the crystal undeviated from its
path. Reflection is caused by the interaction of the electromagnetic radiation with the electrons of
the atoms in the lattice. In order that the intensity of the reflection is sufficiently strong, reflected
waves from the successive planes separated by dhkl should be in phase.
From figure 1.8, it is seen that the path difference of the waves from successive planes is
2d sin . In order that the waves travelling from successive planes are in phase the condition
n = 2dhkl sin (1.2)
should be satisfied. This is Braggs condition of reflection and is known as Braggs law.
Path diff. = BC + BD
nl = 2AB sin q
= 2d sin q
A
q

q q

C B D

Figure 1.8: Diffraction of X-ray from a set of planes

1.4 RECIPROCAL LATTICE

The concept of reciprocal lattice is very useful in X-ray crystallography. It was Ewald who
developed the relation between the diffracted X-ray beams. The crystal, instead of being seen as
different sets of parallel planes, may be represented by a normal drawn perpendicular to each set
of parallel planes from a common point as origin. The length of the normal is proportional to
1/dhkl. This length and direction of the normal is used to represent a set of parallel planes. If a
point is placed at the end of each such normal, an array of points is generated. Each point then
represents a set of parallel equidistant lattice planes and hence, each point is represented by a set
of Miller indices (hkl) of the crystal. This array of points is known as the reciprocal lattice. The
reciprocal lattice vector dhkl has a direction same as the normal to the dhk l planes and its magni-
tude is 1/dhkl. We see that the arrangements of the points in the reciprocal lattice has the same
symmetry as the lattice points of the real crystal.
The concept of reciprocal lattice is particularly helpful in understanding diffraction of X-
rays by crystal planes. Let us rewrite the Braggs equation in reciprocal lattice as

2 1 d hkl
sin hkl = = (1.3)
dhkl 2

Here, we have tried to relate the magnitude of the reciprocal lattice vector to diffraction
angle and the wavelength of the X-ray. In order to see the geometric consequence of this equation,
let us imagine a sphere of radius 1/ = AO as shown in figure 1.9.
8 Solid State Chemistry

shkl

2q
A q q
q C O

Figure 1.9: Relation between reciprocal lattice point and X-ray diffraction

Let AO also be the direction of the X-ray beam incident on the crystal plane at C, the centre
of the sphere. If is the Braggs angle, the reflected beam will strike the sphere (shown as a circle
here) at the point P making an angle 2 with the passing beam. It should be noted that the angle
between the incident beam and AP is .
Since 2 sin hk l/ = 1/dhk l, we can see that 1/dhk l = OP. Thus, the point P is the reciprocal
lattice point for the set of planes from which the X-ray beam is reflected. Also, since the Braggs
diffraction conditions are satisfied, the diffracted beam will touch the sphere (circle in the picture)
at point P. The same will be the case with other set of parallel planes except that they will strike
the sphere at some other point which are the reciprocal lattice points for the respective set of
planes. The three-dimensional sphere is called the sphere of reflection or Ewald sphere.

1.5 POWDER METHOD

The most common method of determining the structure of a crystalline solid is X-ray diffraction.
There are many experimental variations. Complete determination of the crystal structure by
locating the coordinates of all the atoms requires a good single crystal of, at least, about 1 mm
size. But most substances crystallize as polycrystalline solids which means that each particle is
made of a number of randomly oriented tiny crystals. Growing a single crystal needs some
Diffracted beam

2q
X-ray
O
2q

Diffracted beam

Figure 1.10: Diffraction of X-ray by randomly oriented crystals

The Crystal Structure 9

special techniques and is not always easy. However, it is possible to get important structural
information by recording the X-ray diffraction pattern of the powdered polycrystalline samples.
This is commonly known as the powder method.
Synthetic chemists prepare many solid materials in the laboratory. Before proceeding fur-
ther, one would like to know whether the desired structure has been formed. This is done by
recording the X-ray powder diffraction pattern of the material and comparing this with that of
the known pattern. Extensive powder diffraction data have been compiled in the ASTM X-Ray
Data Files that makes such comparison possible. Moreover, the powder diffraction patterns can
provide important structural information such as the type of Bravais lattice, size of the unit cell
and the space group. In the case of a simple crystal, it is even possible to determine the coordi-
nates of all the atoms by analyzing these patterns. No surprise that this method has become a
useful tool of the solid state chemists. If a set of Miller planes satisfy the Braggs condition, the
reflected beam will emerge making an angle 2 with the undeflected beam. Since the crystals are
randomly oriented, the same Miller planes in another crystal may satisfy Braggs condition, but
the deflected beam at angle 2 may have a different direction as shown in the figure 1.10. Since
the number of crystals is very large, all kind of orientations are possible and the diffracted X-ray
will form a cone with angle 4.

1.5.1 Debye-Scherrer Method

Debye and Scherrer devised a specially designed camera that used photographic film for detect-
ing the diffracted X-ray beams. The finely powdered sample in the shape of a thin rod is mounted
vertically inside the camera which is surrounded by a strip of photographic film. The rod-like
shape of the powdered sample is achieved by filling the powder in a short capillary made of glass
or some polymer. The crystals inside the tube are randomly oriented. Hence planes with different
Miller indices will satisfy the Braggs condition of reflection of X-ray. So as not to miss any set
of parallel planes fulfilling the reflection condition, the rod is slowly rotated by a motor. In
randomly oriented crystals, there are innumerable orientations of the same set of planes making
the angle hkl with the incident X-ray beam. Hence the reflected X-ray will appear as a cone that
makes an angle 2hkl with the direction of the beam. This cone will strike the wall of the camera
in the form of a circle that will be registered in the thin strip of the film as two lines equidistant
from the centre of the circle (see figure 1.11).
If S is the measured distance between the centre of the two lines (part of the circle), then
S
4hkl = radians
R
This gives
S 180
hkl = degree
4R
Thus, by measuring S, the corresponding value of can be found out. The interplanar
distance dhkl can be found out using Braggs equation.
180
Since = 57.3, calculations can be simplified if the radius of the camera is made 57.3 mm

or its integral multiple. Then S can be measured in mm and can be easily converted to in degree.
This is the reason why cameras are made either of 57.3 mm or 114.6 mm radius.
The main disadvantages of the Debye-Scherrer method are: (i) the precision is limited by the
measurement of S, (ii) the time of exposure is large, often several hours, (iii) measurement of the
10 Solid State Chemistry

intensity of the lines is not very satisfactory and it is time consuming. For these reasons, this
method is hardly used in recent times and has been replaced by the automatic X-ray powder
diffractometer. We shall not discuss here the different sources of error while recording the
X-ray diffraction pattern using the Debye-Scherrer camera as it is rarely used nowadays.

Diffraction
cones

X-ray in X-ray out

Film

(a)

(b)

Figure 1.11: Diffraction from a powdered sample using Debye-Scherrer camera: (a) diffracted
cones and (b) the part of the cones as pairs of lines in the uncoiled film

1.5.2 The Powder Diffractometer

In this instrument, the powder sample in the form of a thin circular disc of about 15 mm diameter
1-2 mm thickness is placed on a holder standing vertically. The holder can be rotated about an
axis perpendicular to the table. The X-ray beam is allowed to fall on the sample making an angle
with the surface. An X-ray photon counter rotates in a circle around the sample detecting all the
reflected beams in turn. For better focussing of the reflected beam on the detector, the sample is
rotated at a speed half of that of the detector. The detector converts the intensity into current and
the diffraction angles is plotted as 2 against the current on a strip-chart recorder. As an example,
the diffraction pattern of potassium bromide crystals is shown in figure 1.12.
This method is fast and is much more precise both in terms of and intensity measurement.

80 70 60 50 40 30 20
2q

Figure 1.12: Powder diffraction pattern of potassium bromide

The Crystal Structure 11

1.5.3 Indexing the Powder Patterns

Identifying every d value in the powder pattern of a pure solid substance with as set of Miller
indices hkl is known as indexing of a powder pattern. This is done using the equations that relate
the lattice parameters for the cyrstal a, b, c and , , with dhkl.
Indexing is simple for cubic crystals and not difficult for tetragonal and hexagonal crystals,
but may be quite difficult for crystals of low symmetry like those with monoclinic or triclinic unit
cells. For cubic crystals,
a2 = (h2 + k2 + l2)d2hkl (1.4)
Since = is constant for a given substance, it is possible to choose the hkl values for all d values
in such a way so that the right hand side of the above equation gives a constant value. Thus the
lattice parameter = of the cubic crystal can be found out. Rearranging the above equation, we get
a2
2
= h2 + k2 + l2 (1.5)
d
The value of = is chosen such that =2/d2 is an integer for all the observed values of d. This
makes indexing easier.
An alternative to this numerical method of indexing is a graphical technique. According to
this method, some d values are calculated with assumed values of a using equation (1.5) for
different hkl. Values of a between 0 to 20 are sufficient. a is then plotted against d using a
20 20 cm chart paper giving a number of straight lines each corresponding to a set of hkl. A strip
of chart paper is cut and the experimental d values are marked using the same scale as used in
the chart paper. The strip is then slid over the chart paper (see figure 1.13) so that each and every
mark on it coincides with one of the straight lines of some hkl. The hkl values for each d is thus
identified.
For indexing a tetragonal crystal, one can use the equation
1 h2 + k 2 l2
= + (1.6)
2
d hkl a2 c2
When l = 0,
2 a2
d hk0 = (1.7)
h2 + k 2
This equation makes it possible to find out a for those planes with l = 0. After getting a,
value of c can be found out using equation (1.6) for the rest of the lines. A graphical method for
indexing tetragonal crystals was devised by Hull and Davey.
For a hexagonal system, the equation used is
1 4 2 2 l2
2 = (h + hk + K ) + (1.8)
d hkl 3a 2 c2
When l = 0, it becomes
2 3 a2
d hk0 = (1.9)
4 h + hk + k 2
2

which is used for finding a. Knowing a, c can be found out using equation (1.8). Powder patterns
of crystals of low symmetry are difficult to index and will not be considered here.
12 Solid State Chemistry

321 222
400 311
410 310
330 221
411 300
331
420 220 211 210 200 111 110 100
20.00

15.00

d=0

10.00

a,

5.00

0
5.00 10.00 15.00 20.00
d,

Figure 1.13: Indexing a cubic crystal using graphical method

What is measured in the diffraction pattern are the angles 2 and the intensity of the peaks.
Larger the angle, more accurately it can be measured. Large angles correspond to higher hkl
planes. Hence, the lattice parameter calculated for the high hkl planes is more accurate. For
example, let us say that we have calculated the lattice parameter a for a cubic crystal using
equation (1.4) for each hkl. Instead of averaging these values of a, it will make more sense if we
average only those values that have been calculated for the large hkl planes. If it is suspected that
the instrument itself is a source of inaccuracy, the sample may be mixed with some crystalline
solid for which the d values are accurately known. These lines can then be used for calibration.
Accurate measurement of density of the crystal is very useful as it helps in finding out the
number of formula units per unit cell. For this, the number of formula units per unit cell is
assumed and the mass of an unit cell is calculated from the atomic weight of the elements. The
volume of the unit cell is calculated from the lattice constants obtained from X-ray diffraction.
The Crystal Structure 13

Density (x-ray) is calculated as

nm N
xray = g/cm3
volume
where n is the number of formula units, m is the mass (in amu) of the formula unit, N is Avogadro
number. This density known as X-ray density is then compared with the density measured by any
standard experimental method. A comparison of the two densities will give the correct number
of formula units per unit cell.
Intensity of the Lines
Intensity of the diffracted lines depend on the scattering power of the atoms that occupy a Miller
plane. Higher the number of electrons in the atom, higher is its scattering power. This is so
because the scattering of the electromagnetic radiation takes place by interaction with electrons.
Planes that have heavy atoms will give more intense diffraction lines, whereas it is difficult to
detect very light atoms by X-ray diffraction because of their poor scattering power.
It is easy to predict the powder pattern of a solid with cubic unit cell. Let us take the
example of a solid having one kind of atom such as a metal. A primitive cubic structure is
expected to show the diffraction lines corresponding to all possible hkl values. But two cubic
metals, tungsten and copper show diffraction patterns that are quite different. Copper that has
a fcc unit cell gives reflection corresponding to (111), (200), (220), (311), (222), (400), (331) etc.
whereas the powder pattern of bcc tungsten gives X-ray diffraction lines for planes (110), (200),
(211), (220), (301), (222), (321) .... This marked difference between the two diffraction patterns can
be understood by considering the fcc and bcc lattice as consisting of two interpenetrating primi-
tive cubic sublattices A and B in two diffeent ways. The distance travelled by parallel X-ray beams
from the same hkl planes of the two sublattices is not equal and there will be a path difference
between the two waves. If the path difference is an integral multiple of the X-ray wavelength ,
the two waves will superimpose giving high intensity to the diffracted beam. We say the two
waves are in phase. If the two waves are out of phase, they will interfere destructively and no
diffraction line will be observed. The phase difference is
phase difference = 2(hx + ky + lz)
where the atom of B sublattice is located at the point (ax + by + cz) assuming the atom of A
sublattice as the origin. Note that the plane under consideration in both the sublattice is the same
hkl plane. When the phase difference is radians, the amplitudes of the two waves interfere
destructively and if the atoms at the two sublattices are the same (with identical scattering
1
power), the intensity will completely vanish. If the unit cell is bcc, x = y = z = and the phase
2
difference = (h + k + l). Hence all reflections for planes for which h + k + l is odd will vanish.
The systematic absence of the lines for planes for which (h + k + l) is odd indicates the cubic
crystal as bcc. It will only show those lines for which (h + k + l) is an even number. No such
restriction exists for a primitive cubic unit cell.
It can be similarly shown that for fcc unit cell, (h, k, l) should either be all even or all odd
in order that the waves from both sublattices are in phase. So, a fcc metal will show only those
lines for which (h, k, l) are all even or all odd. In the light of this discussion, the difference
between the X-ray diffraction patterns of copper and tungsten can be appreciated.
Let us next consider the X-ray powder diffraction patterns of two similar fcc binary crystals
KCl and NaCl. Their diffraction patterns are shown in figure 1.14.
14 Solid State Chemistry

111
200

220
311
222
400
331
420
422
511
333
440
531
600
442
620
533
622

444

711
511
640
(b)
(a)

200

220

222
400
420
422

440
600
442
620
622
444
640
642
Figure 1.14: X-ray powder patterns (a) KCl and (b) NaCl
The first thing that strikes us is that the angles (given by the position of the lines) due to
the same set of Miller planes are slightly larger in NaCl. This is because the NaCl unit cell is
slightly smaller than that of KCl. The more striking difference is the absence of certain lines like
(111), (311), (511) etc. in KCl although these lines are present in powder pattern of NaCl. From
systematic absence rules for fcc crystals, we know that the lines with mixed indices should be
absent for both NaCl and KCl. This is indeed so. Further, for NaCl we see that the successive
orders of (111) planes (these are 111, 222, 333, 444 etc.) are alternately weak and strong. For
example, the reflection from (111) is weak and that from (222) is strong and so on. We know that
in the binary fcc compounds like NaCl or KCl, the (111) planes are alternately occupied by Na+
(or K+) and Cl ions. If the scattered waves from two or more such planes containing only sodium
are in phase and intensify the reflection, the planes containing sodium will be out of phase with
planes containing chlorine and will interfere destructively thus diminishing the intensity. This is
the reason why (111) reflection in NaCl is weak and (222) reflection is strong. For KCl, the
alternate (111) planes have potassium and chlorine. These two ions have the same number of
electrons and identical scattering power. So far as X-ray is concerned, K+ and Cl are identical.
Since the radiation scattered by these planes are out of phase, the reflected waves will get completely
annihilated and the reflections from (111), (333) etc. will not be seen.
X-ray scattering power of an atom f is proportional to the number of electrons in the atom.
One need not consider the scattering power of all the infinite number of atoms in a crystal. It is
enough to consider the atoms of one unit cell. We must know the location of the atoms in a unit
cell. This will enable us to determine what is called the structure factor (Fhkl) for a reflection hkl.

Fhkl = f1 e 2i( hx1 + ky1 + lz1 ) +. . . + f n e 2i( hxn + kyn + lzn ) (1.10)
where N is the number of atoms in the unit cell and xnynzn defines the coordinate of an atom.
Taking the position of a cation as the origin, NaCl crystal will have in its unit cell Na+ at 000,
11 1 1 11 111 1 1 1 1
0 , 0 and 0 and Cl ions at , 00 , 0 and 00 . Putting these coordinates
22 2 2 22 222 2 2 2 2
and simplifying, we get

Fhkl = [ fNa+ + fCl e i( h + k + l ) ][ e 0 + e i( h + k ) + e i( h + l) + e i( k + l ) ] (1.11)

The Crystal Structure 15

Since ein is +1 when n is even and 1 when n is odd, the Miller indices hkl with all even
or all odd will make the terms within the second square brackets in equation (1.11) equal to 4.
With mixed hkl, this part of the equation becomes zero. So the structure factor for NaCl is

Fhkl = 4 [ fNa+ + fCl] e i( h + k + l ) (1.12)

which can be further simplified as
Fhkl = 4(fNa+ + fCl) when h, k, l are all even, and
Fhkl = 4(fNa+ fCl) when h, k, l are all odd.
2
Intensity of the reflected X-ray beam is proportional to Fhkl . This means that if the cation
and the anion had the same scattering power, all reflections with h, k, l all odd will vanish as it
happens in the case of KCl. These lines appear as weak reflections for NaCl because of the
unequal scattering power of sodium and chloride ions.
The powder method is inadequate for locating the coordinates of every single atom in a
complex solid that needs single crystal X-ray structure determination. This is beyond the scope
of this book.

1.5.4 Use of X-ray Powder Patterns

Despite all its limitations, X-ray powder method has become the most important tool for chemists
who study solid materials, metals and inorganic solids in particular. It is most commonly used
to find out if the desired phase is present in a synthesized or natural material by comparing its
X-ray pattern with those of the known materials of similar composition. The presence of any
impurity phase can be detected by this method. In a solid state reaction to synthesize some
ceramic material, it can be used to check the completion of the reaction. For simple structures, it
allows to determine the unit cell type and size, the number of formula units per unit cell and in
some simple cases, even intensity analysis is possible. Its one limitation is that the lines become
broad and finally disappear as the particle size decreases. The most appropriate size of the
particles should be between 100 nm to 103 nm. Another shortcoming is its inability to identify
hydrogen atoms thus severely restricting its application to organic compounds.

1.6 CRYSTAL DEFECTS

So far in this chapter we have considered the crystal lattice in which all the sites meant for some
atoms are occupied appropriately. In the NaCl structure, for example, every site meant for so-
dium are occupied by sodium and the same is true for chlorine atoms. It did not happen that a
chlorine atom occupied a site that is meant for a sodium atom. Such a crystal is called a perfect
or an ideal crystal. A perfect arrangement gives the crystal the highest possible negative value of
lattice energy and hence apparently such a structure should be most stable. Stability, however,
is determined by free energy G which for a solid may be taken as A, the Helmholtz free energy
expressed as
A = U TS
Further, we can write lattice energy UL in place of internal energy U. This equation tells us
that A = UL will be minimum only when T = 0 K, i.e., when the contribution of entropy towards
free energy is zero. Entropy of an disordered (imperfect) crystal is higher than that of an ordered
crystal. Thus, at any temperature other than 0 K, two factors will contribute to free energy.
16 Solid State Chemistry

Perfection in the crystal will minimize the free energy by making the internal energy UL more
negative, and the contribution from entropy ST will try to minimize the same by making the
crystal more imperfect thus increasing S. The equilibrium structure at any temperature other than
0 K will have some disorder or imperfection. We see that the presence of defects in a crystal is
a thermodynamic requirement for stability. The main defects in a crystal are of three types: point
defects, dislocations and grain boundaries.

1.6.1 Point Defects

The simplest type of point defect in a crystal is a vacancy. When a lattice site that normally is to
be occupied by an atom or an ion is left vacant, we have a point defect known as vacancy and
it has the symbol V. If the vacant site was supposed to be occupied by an atom X in the crystal,
the symbol is VX meaning the vacancy occurs at a site that is meant for an X atom.
If an atom or ion is removed from its normal position in the lattice and is placed at an
interstitial site, the point defect is known as an interstitial. If M is the atom that is at an interstitial
site, it is given the symobl Mi. Similarly, there may be an interstitial Xi which means an X atom
instead of being present at its normal site, occupies an interstitial site.
If an atom A in a crystal of composition AB instead of being present at a site meant for it
goes to occupy a site which is normally occupied by an atom B, the point defect is called a
misplaced atom. The symbol for this is BA. Here the letter B is the site for atom B and the subscript
^
shows the atom that is occupying the site. It goes without saying that AA and BB mean normal
lattice sites but AB and BA mean misplaced atoms.
A crystal may have in it a variety of point defects but which type will predominate depends
on the energetics of defect formation.
Many crystals show combination of defects i.e., one type of defect is associated with an
equivalent number of defects of another type. Such combination defects are particularly important
in ionic crystals for maintaining overall charge neutrality of the crystal. Two such defects of
particular importance are the Frenkel and Schottky defects.
When an atom or ion is removed from its normal site and placed at an interstitial site, the
crystal has simultaneously a vacancy and one interstitial. This combination is known as a Frenkel
defect.
In a crystal, when a cation vacancy exists with an equivalent number of anion vacancies
necessary for its charge neutrality, the combination is known as Schottky defect. Frenkel and
Schottky defects are shown in figure 1.15.

+ + + + + +

+ + + + +
+
+ + + + + +

+ + + + +

+ + + + + +
( a) (b )

Figure 1.15: (a) Frenkel defect and (b) Schottky defect in an ionic crystal
The Crystal Structure 17

The formation of Schottky defect is accompanied by the creation of an equivalent number

of new lattice sites or removal of the ions to the gas phase from the lattice.
The presence of foreign atoms constitutes another type of point defect. These atoms or ions
can be present either in interstitial or in substitutional positions. In an ionic crystal, the introduc-
tion of a foreign atom is dependent on its ionic radius and electronic structure. Sometimes, it is
possible for the same ion to enter the lattice both interstitially and substitutionally. Substitution
of a lattice ion by an impurity ion of different charge will disturb the charge balance. In order to
maintain the charge neutrality of the lattice, such substitution may be accompanied either by the
creation of a lattice vacancy or by the change of the oxidation state of an ion in the lattice.
Substitution of Ag+ by Cd2+ in AgCl leads to the former, whereas substitution of Ni2+ by Li+ in
NiO lattice gives rise to the latter. These two cases are illustrated below, one creating a cation
vacancy, and the other a valence defect. Here Ni3+ is known as a valence defect.

Ag+ Cl Ag+ Cl Ni2+ O2 Ni2+ O2

Cl Cd2+ Cl Ag+ O2 Ni3+ O2 Ni2+
Ag+ Cl Cl Ni2+ O2 Li+ O2
Cl Ag+ Cl Ag+ O2 Ni2+ O2 Ni2+
Vacancy produced by Valence defect produced
Cd2+ substitution by Li+ substitution
Unlike the inherent thermodynamic defects, the impurity defects can be deliberately added
in a controlled way that is known as doping. This helps in modifying the properties of the solid.
There is another type of defect that very much influences the electronic properties of the
solid. These are the electronic defects. Let us assume that a solid has an anion vacancy. The anion
vacancy is the site that normally should have been occupied by an anion. Hence this site (sur-
rounded by cations) has a strong positive potential and can trap electrons. It will need some
energy to free the trapped electron. When sodium chloride is heated in sodium vapour, we see
that is acquires a yellow colour. The heating in excess sodium creates new lattice sites for sodium.
To maintain the structure, an equal number of chloride sites are also created, but the latter are
vacant. The electron of the sodium atom that is ionized in the NaCl matrix is trapped by the
chloride ion vacancy. This trapped electron can be freed into the crystal by absorbing visible light
and hence the colour. A trapped electron at an anion vacancy is an electronic defect and it is
known as F centre (from German Farbe meaning colour). In fact, many of the point defects may
have a charge different from the normal charge of the original site due to trapped electrons or
holes. These electrons and holes can be released to the conduction band or to the valence band
of the solid and this will modify its electronic properties.
The symbols of the point defects then should also include the information of the charge that
they carry. It is more convenient to talk of an effective charge. The effective charge of a point defect
is taken as the difference of its charge from the charge of the ion that normally occupies that site.
Let us illustrate this with some examples.
Let us say that there is a cation vacancy in the MgO lattice. This vacant site was originally
occupied by a Mg2+ ion that had a charge +2. Now it has zero charge and hence its effective
charge is 2. We write the symbol V Mg, where the superscript stands for two negative effective
charges. If the cation vacancy captures a hole, its effective charge becomes uninegative and the
symbol used is VMg. If it captures another hole, it will have a real charge +2, but a zero effective
X
charge and will be denoted as VMg . An oxygen vacancy with zero charge is having two effective
18 Solid State Chemistry

positive charges and will be represented as VO. If it captures one electron, its effective charge
will be unipositive and the symbol for it is VO . If it captures a second electron, its effective charge
will be zero and the symbol is VOX , although its true charge is 2. Similarly, the charge of other
types of point defects should be included in the symbol. Thus, if a bivalent metal ion goes to a
normally unoccupied interstitial site, the effective charge of the interstitial site becomes +2 be-
cause originally this site did not have any charge. In this case, however, the real charge too is +2.
The inclusion of the effective charge in the notation of the point defects is important as complete
balance of effecticve charge will have to be maintained in writing balanced equations for defect
reactions.

1.6.2 Defect Equations

It should be remembered that the total effective positive and negative charges should be equal
in a crystal. In writing an equation involving point defects, the following rules should be
followed.
1. The ratio of the number of regular cationic and anionic sites in a solid is constant. If the
crystal has a NaCl structure, this ratio is unity. If the solid crystallizes with the fluorite
structure, this ratio is 1: 2. This will be so even if the solid is non-stoichiometric. This
means that if we create a Na lattice site, we are obliged also to create a Cl lattice site
even if that site is to be kept vacant.
2. Defect equation may include creation of new lattice sites as well as elimination of the
existing lattice sites i.e., the total number of lattice sites may change.
3. The total mass balance should be maintained which means the total number of each type
of atoms on both sides of the equation should be the same.
4. The total effective charge should be same on both sides, i.e., a charge balance should be
maintained.
Next, let us try to write some defect equations following the rules stated above. Here only
stoichiometric compounds will be considered. Non-stoichiometeric oxides will be considered later.
Let us first consider Schottky defects in a stoichiometric oxide MO. The equation for the
formation of a Schottky defect can be written as

MM + OO l VM + VO + MM + OO
The regular lattice sites on the right hand side means that the formation of Schottky defect
requires that new lattice sites are created. Cancelling common terms, we write

O l VM

+ VO
where O stands for a perfect lattice. Here we have assumed that the doubly charged vacancies
predominate. It is obvious that the doubly charged vacancies can capture or release electrons and
can either become singly charged or neutral. If these species are to be included in the equation,
the corresponding electrons or holes are also to be added.
A Frenkel defect is created by transferring a regular ion to an interstitial site. Suppose the
interstitial ion is a cation as is generally the case, we can write

MM l VM + Mi
assuming that the doubly charged interstitials and vacancies predominate.
The Crystal Structure 19

We have considered the important types of point defect. Next we shall look into the concen-
tration of the thermodynamic defects under specific conditions. The equilibrium concentration of
the inherent thermodynamic defects is dependent on temperature. It is possible to calculate this
concentration at any given temperature provided the energy required for their formation is known.
Here we shall derive the equations that relate the defect concentration to temperature.

1.6.3 Vacancy Concentration in a Metal

The change of an ideal crystal at constant volume and temperature to a defect crystal with vacant
lattice sites will be accompanied by a change in Helmholtz free energy such that
A = U TS (1.13)
where A, U and S are the respective changes in free energy, internal energy and entropy. At
equilibrium, the change in free energy with the change in the number of vacancies n will be zero.
We can write
FG aAfIJ
H n K T ,V
= 0 (1.14)

If is the energy needed to create a vacancy,

U = n. (1.15)
Neglecting the contribution to entropy by the vibration of the atoms which in any case
is small, the entropy of the defect structure will be essentially its configurational entropy
( Sconf. = S). Hence,
S = k ln w (1.16)
where k is the Boltzmann constant and w the thermodynamic probability which is equal to the
number of ways n vacant sites and (N n) occupied sites can be arranged among the N available
lattice sites. This will give
N!
w =
N n !n! a f (1.17)

Substituting this in equation (1.16) and applying Stirlings approximation, we get

a f a
S = k N ln N N n ln N n n ln n f (1.18)
It is now possible to write

a
A = n kT N ln N N n ln N n n ln nf a f (1.19)
Differentiating A with respect to n and equating to zero (condition of equilibrium concen-
tration of defects), we get

= kT

n
a f a
N n ln N n n ln n f
This will give
N n
= kT ln
n
and
n FG IJ
N n
= exp
kT H K (1.20)
20 Solid State Chemistry

Since N >> n,
n FG IJ
N
= exp
H kT K
If EV is the energy necessary to create one mole of vacancy, then
EV = Avogadros number and
n E FG IJ
N
= exp V
RT H K (1.21)

Thus, knowing the energy of fromation of vacancies, it is possible to calculate the number
of vacancies per mole of metal atoms at a given temperature.

1.6.4 Schottky Defect Concentration in an Ionic Crystal

Let us next calculate the equilibrium concentration of Schottky defects in an ionic crystal of
stoichiometry MX. Let s be the energy necessary to create a Schottky defect. This means that this
is the energy needed to produce one cation and one anion vacancy in MX. If the total cationic site
is N and the number of action vacancy is ns, the number of occupied cationic sites will be
(N ns). The number of ways in which ns cation vacancies and (N ns) cationic sites can be
arranged in N available cationic sites is
n!
w =
b g
N ns ! ns !
(1.22)

There will be ns anion vacancy since stoichiometry is MX. The number of ways in which ns
anion vacancies and (N ns) anions can be distributed among N anionic sites is also equal to w
given by equation (1.22). The total probability W = w.w. The configurational entropy is
N!
S = 2k ln
bN n g ! n !
s s
(1.23)

which means

b g b g
S = 2k N ln N N n s ln N n s n s ln ns (1.24)
We can now write

b g b
A = ns 2kT N ln N N ns ln N ns ns ln ns g (1.25)
In order to minimize A, we differentiate the above equation with respect to ns and equate
that to zero. After rearranging the result, we get
ns FG IJ
H 2kT K
s
= exp (1.26)
N
If Es is the energy of formation of one mole of Schottky defect in the crystal MX, then
ns FG E IJ
H 2RT K
s
= exp (1.27)
N
The expression for Schottky defect concentration for crystal of composition MX2 can be
similarly deduced.
The Crystal Structure 21

1.6.5 Frenkel Defect Concentration

A crystal with Frenkel defects will have equal number of vacancies and interstitials. Let the
number of Frenkel defects be nf. If N is the total number of lattice sites, there will (N nf)
occupied sites. The number of ways in which nf vacancies (N nf) occupied sites can be arranged
in N available lattice sites gives the probability
N!
eN n j ! n !
w = (1.28)
f f

Let the total number of interstitial sites be N*. The number of ways in which nf interstitial
atoms and (N* nf) unoccupied interstitial sites can arrange gives the probability
N *!
eN * n j ! n !
w* = (1.29)
f f

Total configurational probability W = w.w* In this case,

N! N *!
S = k [ln + ln
eN n j ! n ! eN * n j ! n !
] (1.30)
f f f f

The change in free energy in forming nf number of Frenkel defects is

N! N *!
A = nf kT [ln + ln
eN n j ! n ! eN * n j ! n !
] (1.31)
f f f f

Solving
F AI
GH n JK f
= 0 (1.32)
V ,T

we get
n 2f F I
( N n f ) ( N * n f )
= exp GH kT JK f

Since nf is very much smaller than both N and N*, we get

nf f F I F I
GH JK GH JK
Ef
= exp = exp (1.33)
NN * kT kT
where Ef is the energy needed to form a mole of Frenkel defects. The concentration of the various
types of point defects present at a temperature T can be calculated if the energy of defect formation
is known.

1.6.6 Dislocations
Dislocations also known as line defects and are of two kinds. They are edge dislocation and screw
dislocation.
An edge dislocation is what would happen if a half plane is inserted into a crystal. The
dislocation extends along a line perpendicular to the plane of the paper. The structure is distorted
near the dislocation and several lattice constants are to be covered before this distortion disappears.
Edge dislocation can move along the crystal under a shear force. Suppose force is applied in
22 Solid State Chemistry

opposite directions at the two ends of a crystal. Instead of separating it into two parts that would
need a large number of bonds to be broken, atoms on one side can just move a short distance.
This will make the dislocation move along the crystal in the direction of the shear force. Movement
of the edge dislocations in the crystal are responsible for their plastic property. Edge dislocation
may form accidentally during crystal growth or may be produced by bending a crystal. Dislocation
density in a common crystal is of the order 106/cm2.

Figure 1.16: Edge dislocation

Edge dislocation are given the symbol as shown in figure 1.16 where the dislocation line
is perpendicular to the plane of the paper. Dislocations can be identified by taking electron
microscope pictures at magnification 105 or higher where the lattice planes appear as straight
lines. Dislocations show up as disruption in these straight lines.
The other type of line defect is known as screw dislocation. Screw dislocation results from
movement of one part of a crystal relative to another. The distance of movement is less than a
lattice constant and hence the coordination number of the atoms near the screw dislocation does
not change. The screw dislocation only leads to a distortion of the bonds in its vicinity. If one
moves from lattice point to lattice point around the dislocation, one will move up as if in a spiral
staircase. The name screw dislocation is derived from this (see figure 1.17). Dislocations severely
affect the mechanical properties of solids.

Figure 1.17: Screw dislocation

The Crystal Structure 23

1.6.7 Plane Defects or Grain Boundaries

So far we discussed defects that are present within a crystal. Many solids however does not exist
as a single crystal but as aggregate of a large number of small crystals or grains. These grains
have different orientations. As a result, the environment of the atoms near the boundary of two
such grains is bound to be different from what it is within a crystallite of grain. The periodicity
of the atoms will be destroyed at and near the grain boundary region and this region will be non-
crystalline. If this non-crystalline region is fairly thick, each crystal will try to force the atoms of
this region to orient themselves in accordance with its own structure. This will be so because the
irregularity in the non-crystalline region will increase the energy of the solid.
Grain boundaries may be wide-angle (figure 1.18) or small-angle depending upon the tilt of
the angle of the boundary. Small-angle grain boundaries can be treated as a series of dislocations.
When the grain boundary becomes a reflection plane, the two crystals on either side of the
reflection plane constitutes a twin.

Figure 1.18: Wide-angle grain boundary

Grain boundaries seriously affect the mechanical properties of solids. They can be removed
by heat treatment. At high temperature when the mobility of the atoms increases, some grains
grow at the expense of others and this process is known as secondary recrystallization.

SUGGESTED READING
1. Azaroff, L.V. Introduction to Solids, TMH edition, Tata McGraw-Hill, New Delhi.
2. Azaroff, L.V. and Buerger, M.J. The Powder Method in X-ray Crystallography, McGraw-Hill, 1958.
3. Epifanov, G.I. Solid State Physics, MIR, Moscow, 1979.
4. Hannay, N.B. Solid State Chemistry, Prentice-Hall, New Jersey, 1967.
5. Keer, H.V. Principles of the Solid State, Wiley Eastern, New Delhi, 1993.
6. Kittel, C. Introduction to Solid State, 3rd edition, John Wiley, 1966.
7. Megaw, H.D. Crystal Structure: A Working Approach, Saunders College Publ., 1973.