Crystal Structure of Solids

Dr. Sukanta De
Books for Solid state physics Course: -

Introduction to Solid State Physics by Charles Kittel

Solid State Physics By A J Dekker

Solid State Physics By Ashcroft and Mermin


How do atoms assemble into solid structures?
Crystalline Solids : Atoms are arranged in regular manner , form 3-D
pattern. (by 3-D repetition of a certain pattern unit.)
PERI ODI C ARRANGEMENT OF ATOMS/I ONS OVER LARGE ATOMI C
DI STANCES

Leads to structure displaying
LONG-RANGE ORDER that is
Measurable and Quantifiable
All metals, many ceramics, and some polymers
When the periodicity of the pattern extends throughout a
certain piece of material Single Crystal
When the periodicity of the pattern interrupted at grain boundary
and grain size is at least several Angstroms
Polycrystalline materials
If the grain size is comparable to the size of pattern unit
Amorphous materials
Materials Lacking Long range order
Example: Ceramic GLASS and many plastics
POLYCRYSTALLINE MATERIALS
Nuclei form during solidification, each of which grows into crystals
Ideal Crystal
An ideal crystal is a periodic array of structural units,
such as atoms or molecules.
It can be constructed by the infinite repetition of
these identical structural units in space.
Structure can be described in terms of a lattice, with
a group of atoms attached to each lattice point. The
group of atoms is the basis.
Bravais Lattice
An infinite array of discrete points with an
arrangement and orientation that appears
exactly the same, from any of the points the
array is viewed from.
A three dimensional Bravais lattice consists of
all points with position vectors R that can be
written as a linear combination of primitive
vectors. The expansion coefficients must be
integers.

Lattice - infinite, perfectly periodic array of
points in a space
Not a lattice:
We abstracted points from the shape:
Now we abstract further:
Now we abstract further:
This is a UNIT CELL
Now we abstract further:
This is a UNIT CELL
Represented by two lengths and an angle




.or, alternatively, by two vectors
Basis vectors and unit cells
T = ma + nb
a and b are the basis vectors for the lattice
a
b
T
In 3-D:
a
b
a, b, and c are the basis vectors for the lattice
c
In 3-D:
T = m
1
a + m
2
b + m
3
c
a
b
T
a, b, and c are the basis vectors for the lattice
c
Crystal Systems Some Definitional
information
7 crystal systems of varying
symmetry are known
These systems are built by changing
the lattice parameters:
a, b, and c are the edge
lengths
o, |, and are interaxial
angles
Fig. 3.4, Callister 7e.
Unit cell: smallest repetitive volume which contains
the complete lattice pattern of a crystal.
Crystal Systems
Crystal structures are divided
into groups according to unit
cell geometry (symmetry).
CRYSTAL SYMMETRY
Symmetry defines the order resulting from how atoms
are arranged and oriented in a crystal
The definite ordered arrangement of the faces and edges
of a crystal known as Crystal Symmetry
The Symmetry Operation is one that leaves the crystal
and its environment invariant. i.e., actions which result in
no change to the order of atoms in the crystal structure
Imagine that this object will be rotated (maybe)
Was it?
The object is obviously symmetricit has
symmetry
The object is obviously symmetricit has symmetry

Can be rotated 90 w/o detection
so symmetry is really
doing nothing
Symmetry is doing nothing - or at least doing
something so that it looks like nothing was done!
What kind of symmetry does this object have?
What kind of symmetry does this object have?
4
What kind of symmetry does this object have?
4
m
What kind of symmetry does this object have?
4
m
What kind of symmetry does this object have?
4
m
What kind of symmetry does this object have?
4
m
4mm
Another example:
Another example:
6
m
6mm
Why Is Symmetry Important?
Identification of Materials
Prediction of Atomic Structure
Relation to Physical Properties
Optical
Mechanical
Electrical and Magnetic
Symmetry operations performed about a point or a line are
called point group symmetry operations
Point group symmetry elements exhibited by crystals
are

1. The inversion (centre of symmetry)
2. Reflection symmetry (The mirror reflection)
3. Rotation Symmetry
Inversion
1
1
A crystal will possess an inversion
centre if for every lattice point
given by a position vector r there
will be a corresponding lattice point
at the position -r
Crystallographic symmetry
element : Centre of Symmetry
In this operation, the reflection of a structure at a mirror plane m
passing through a lattice point leaves the crystal unchanged. The
mirror plane may or may not be composed of the atoms lying on
the concerned imaginary plane.
Reflection Symmetry
Crystallographic symmetry
element : Plane of Symmetry
Rotational Symmetry
If a crystal left invariant after a rotation about an axis ,
is said to possess rotational symmetry.

The axis is called Axis of Symmetry


The axis is called `n-fold, axis if the angle of
rotation is 360
0
/n .
If equivalent configuration occurs after rotation of 180,
120 and 90, the axes of rotation are known as two-fold, three-
fold and four-fold axes of symmetry respectively.
If n=1, the crystal has to be rotated through an angle
= 360, about an axis to achieve self coincidence.
Such an axis is called an `identity axis. Each
crystal possesses an infinite number of such axes.
Symmetry the rules behind the
shapes
Symmetry elements For a simple Cubic Lattice
One CENTRE OF SYMMETRY
Plane of Symmetry:
There are three planes of symmetry parallel to the faces of
the cube and six diagonal planes of symmetry
9

p
l
a
n
e
s

o
f

S
y
m
m
e
t
r
y

If n=4, for every 90 rotation, coincidence is achieved and the axis
is termed `tetrad axis.It is discussed already that a cube has `three
tetrad axes.
If n=3, the crystal has to be rotated through an angle = 120
about an axis to achieve self coincidence. Such an axis is called is
`triad axis. In a cube, the axis passing through a solid diagonal
acts as a triad axis. Since there are 4 solid diagonals in a cube, the
number of triad axis is four.
If n=2, the crystal has to be rotated through an angle = 180
about an axis to achieve self coincidence. Such an axis is called a
`diad axis.Since there are 12 such edges in a cube, the number of
diad axes is six.
Total 13 axes of rotational symmetry for a Cube
(a) Centre of symmetry 1
(b) Planes of symmetry 9
(Straight planes -3,Diagonal planes -6)
(c) Diad axes 6
(d) Triad axes 4
(e) Tetrad axes 3
----
Total number of symmetry elements = 23
----
Thus the total number of symmetry elements of a cubic structure is 23.
SYMMETRICAL ELEMENTS OF CUBE
N-fold axes with n=5 or n>6 does not occur
in crystals
Adjacent spaces must be completely filled (no gaps, no overlaps).
ABSENCE OF 5 FOLD SYMMETRY
We have seen earlier that the crystalline solids show only
1,2,3,4 and 6-fold axes of symmetry and not 5-fold axis of
symmetry or symmetry axis higher than 6.

The reason is that, a crystal is a one in which the atoms or
molecules are internally arranged in a very regular and
periodic fashion in a three dimensional pattern, and
identical repetition of an unit cell can take place only
when we consider 1,2,3,4 and 6-fold axes.

P Q
R
S
a


MATHEMATICAL VERIFICATION
Let us consider a lattice P Q R S as shown in figure
Let this lattice has n-fold axis of symmetry and the
lattice parameter be equal to a.
Let us rotate the vectors Q P and R S through an
angle u = 360
0
/n , in the clockwise and anti clockwise
directions respectively.
After rotation the ends of the vectors be at x and y.
Since the lattice PQRS has n-fold axis of symmetry,
the points x and y should be the lattice points.
P Q
R
S
a


x
y
Further the line xy should be parallel to the line PQRS.
Therefore the distance xy must equal to some integral
multiple of the lattice parameter a say, m a.
i.e., xy = a + 2a cos u = ma (1)

Here, m = 0, 1, 2, 3, ..................

From equation (1),

2a cos u = m a a
i.e., 2a cos u = a (m - 1)

(or) cos u = (2)

Here,
N = 0, 1, 2, 3, .....

2 2
1 N m
=

since (m-1) is also an integer, say N.

We can determine the values of u which are allowed in a
lattice by solving the equation (2) for all values of N.

For example, if N = 0, cos u = 0 i.e., u = 90
o

n = 4.
In a similar way, we can get four more rotation axes
in a lattice, i.e., n = 1, n = 2, n = 3, and n = 6.
Since the allowed values of cos u have the limits 1
to +1, the solutions of the equation (2) are not
possible for N > 2.
Therefore only 1, 2, 3, 4 and 6 fold symmetry axes
can exist in a lattice.
Crystal Structure 53
Lattice Sites in Cubic Unit Cell
Crystal Structure 54
Crystal Directions
Fig. Shows
[111] direction

We choose one lattice point on the line as an
origin, say the point O. Choice of origin is
completely arbitrary, since every lattice point is
identical.
Then we choose the lattice vector joining O to
any point on the line, say point T. This vector
can be written as;

R = n
1
a + n
2
b + n
3
c

To distinguish a lattice direction from a lattice
point, the triple is enclosed in square brackets [
...] is used.[n
1
n
2
n
3
]
[n
1
n
2
n
3
] is the smallest integer of the same
relative ratios.
Crystal Structure 55
210
X = 1 , Y = , Z = 0
[1 0] [2 1 0]
X = , Y = , Z = 1
[ 1] [1 1 2]
Examples
Crystal Structure 56
Negative directions
When we write the
direction [n
1
n
2
n
3
] depend
on the origin, negative
directions can be written
as


Y direction
(origin) O
- Y direction
X direction
- X direction
Z direction
- Z direction
] [
3 2 1
n n n
] [
3 2 1
n n n
Crystal Structure 57
X = -1 , Y = -1 , Z = 0 [110]
Examples of crystal directions
X = 1 , Y = 0 , Z = 0 [1 0 0]
Crystal Structure 58
Crystal Planes
Within a crystal lattice it is possible to identify sets of
equally spaced parallel planes. These are called
lattice planes.
b
a
b
a
The set of
planes in
2D lattice.
Crystal Structure 59
Miller Indices
Miller Indices are a symbolic vector representation for the
orientation of an atomic plane in a crystal lattice and are defined
as the reciprocals of the fractional intercepts which the plane
makes with the crystallographic axes.

To determine Miller indices of a plane, take the following steps;

1) Determine the intercepts of the plane along each of the three
crystallographic directions

2) Take the reciprocals of the intercepts

3) If fractions result, multiply each by the denominator of the
smallest fraction

Crystal Structure 60
Axis
X Y Z
Intercept
points
1
Reciprocals
1/1 1/ 1/
Smallest
Ratio
1 0 0
Miller ndices (100)
Example-1
(1,0,0)
Crystal Structure 61
Axis
X Y Z
Intercept
points
1 1
Reciprocals
1/1 1/ 1 1/
Smallest
Ratio
1 1 0
Miller ndices (110)
Example-2
(1,0,0)
(0,1,0)
Crystal Structure 62
Axis
X Y Z
Intercept
points
1 1 1
Reciprocals
1/1 1/ 1 1/ 1
Smallest
Ratio
1 1 1
Miller ndices (111)
(1,0,0)
(0,1,0)
(0,0,1)
Example-3
Crystal Structure 63
Axis
X Y Z
Intercept
points
1/2 1
Reciprocals
1/() 1/ 1 1/
Smallest
Ratio
2 1 0
Miller ndices (210)
(1/2, 0, 0)
(0,1,0)
Example-4
Crystal Structure 64
Axis
a b c
Intercept
points
1
Reciprocals 1/1 1/ 1/()
Smallest
Ratio
1 0 2
Miller ndices (102)
Example-5
Crystal Structure 65
Axis
a b c
Intercept
points
-1
Reciprocals 1/-1 1/ 1/()
Smallest
Ratio
-1 0 2
Miller ndices (102)
Example-6
Crystal Structure 66
Miller Indices
Reciprocal numbers are:
2
1
,
2
1
,
3
1
Plane intercepts axes at c b a 2 , 2 , 3
Indices of the plane (Miller): (2,3,3)
(100)
(200)
(110)
(111)
(100)
Indices of the direction: [2,3,3]
a
3
2
2
b
c
[2,3,3]
Crystal Structure 67
Example-7
Crystal Structure 68
Indices of a Family or Form
Sometimes when the unit cell has rotational symmetry, several
nonparallel planes may be equivalent by virtue of this symmetry, in
which case it is convenient to lump all these planes in the same
Miller Indices, but with curly brackets.
Thus indices {h,k,l} represent all the planes equivalent to the
plane (hkl) through rotational symmetry.
) 1 1 1 ( ), 1 1 1 ( ), 1 1 1 ( ), 1 1 1 ( ), 11 1 ( ), 1 1 1 ( ), 1 11 ( ), 111 ( } 111 {
) 00 1 ( ), 1 00 ( ), 0 1 0 ( ), 001 ( ), 010 ( ), 100 ( } 100 {

Crystal Structure 69
Coordinaton Number

Coordinaton Number (CN) : The Bravais lattice points
closest to a given point are the nearest neighbours.

Because the Bravais lattice is periodic, all points have
the same number of nearest neighbours or coordination
number. It is a property of the lattice.

A simple cubic has coordination number 6; a body-
centered cubic lattice, 8; and a face-centered cubic
lattice,12.
Atomic Packing Factor

Atomic Packing Factor (APF) is defined as the
volume of atoms within the unit cell divided by
the volume of the unit cell.
Crystal Structure 71
1-CUBIC CRYSTAL SYSTEM
Simple Cubic has one lattice point so its primitive cell.
In the unit cell on the left, the atoms at the corners are cut
because only a portion (in this case 1/8) belongs to that cell.
The rest of the atom belongs to neighboring cells.
Coordinatination number of simple cubic is 6.
a- Simple Cubic (SC)
a
b
c
APF for a simple cubic structure = 0.52
APF =
a
3
4
3
t (0.5a)
3
1
atoms
unit cell
atom
volume
unit cell
volume
Atomic Packing Factor (APF)
APF =
Volume of atoms in unit cell*
Volume of unit cell
*assume hard spheres
Adapted from Fig. 3.23,
Callister 7e.
close-packed directions
a
R=0.5a
contains (8 x 1/8) =
1 atom/unit cell
Here: a = R
at
*2
Where R
at
is the handbook atomic
radius

Crystal Structure 73
b-Body Centered Cubic (BCC)


BCC has two lattice points so BCC
is a non-primitive cell.

BCC has eight nearest neighbors.
Each atom is in contact with its
neighbors only along the body-
diagonal directions.

Many metals (Fe,Li,Na..etc),
including the alkalis and several
transition elements choose the
BCC structure.
a
b
c
Atomic Packing Factor: BCC
a
APF =
4
3
t ( 3 a/4 )
3
2
atoms
unit cell
atom
volume
a
3
unit cell
volume
length = 4R =
Close-packed directions:
3 a
APF for a body-centered cubic structure = 0.68
a
R
Adapted from
Fig. 3.2(a), Callister 7e.
a 2
a 3
Crystal Structure 75
c- Face Centered Cubic (FCC)
There are atoms at the corners of the unit cell and at the center of
each face.
Face centered cubic has 4 atoms so its non primitive cell.
Many of common metals (Cu,Ni,Pb..etc) crystallize in FCC
structure.
Crystal Structure 76
3 - Face Centered Cubc
Atoms are all same.
APF for a face-centered cubic structure = 0.74
Atomic Packing Factor: FCC
The maximum achievable APF!
APF =
4
3
t ( 2 a/4 )
3
4
atoms
unit cell
atom
volume
a
3
unit cell
volume
Close-packed directions:
length = 4R = 2 a
Unit cell contains:
6 x 1/2 + 8 x 1/8
= 4 atoms/unit cell
a
2 a
Adapted from
Fig. 3.1(a),
Callister 7e.
(a = 2\2*R)
Crystal Structure 78
Atoms Shared Between: Each atom counts:
corner 8 cells 1/8
face centre 2 cells 1/2
body centre 1 cell 1
edge centre 2 cells 1/2

lattice type cell contents
P 1 [=8 x 1/8]
I 2 [=(8 x 1/8) + (1 x 1)]
F 4 [=(8 x 1/8) + (6 x 1/2)]
C 2 [=(8 x 1/8) + (2 x 1/2)]
Unit cell contents
Counting the number of atoms within the unit cell
Theoretical Density,
where n = number of atoms/unit cell
A = atomic weight
V
C
= Volume of unit cell = a
3
for cubic
N
A
= Avogadros number
= 6.023 x 10
23
atoms/mol
Density = =
V
C
N
A
n A
=
Cell Unit of Volume Total
Cell Unit in Atoms of Mass

Ex: Cr (BCC)
A = 52.00 g/mol
R = 0.125 nm
n = 2
a = 4R/\3 = 0.2887 nm
a
R
=
a
3
52.00 2
atoms
unit cell
mol
g
unit cell
volume atoms
mol
6.023 x 10
23

Theoretical Density,

theoretical

actual

= 7.18 g/cm
3
= 7.19 g/cm
3
The Concept of the reciprocal lattice devised to tabulate two
important properties of crystal planes: Their slopes and their inter
planer distance.

The reciprocal space lattice is a set of imaginary points
constructed in such a way that the direction of vector from one
point to another coincides with the direction of a normal to the
real space planes and the separation of those points (absolute
value of the vector) is equal to the reciprocal of the real inter-
planer distance.
Reciprocal Lattice Vectors
The electronic number density is a periodic function in
space with a period equal to the lattice translation
vector T, i.e.

This means that one can use a Fourier series
expansion to represent in 1D n(x) as


where:


) ( ) ( r T r n n = +
| |
a px i
p
p
p
p p
e n a px S a px C n x n
/ 2
0
0
) / 2 sin( ) / 2 cos( ) (
t
>

t + t + =
}
=
t
a
a px i
a
p
e x dxn n
0
/ 2
1
) (
In 3D, we have


The set of reciprocal lattice vectors that lead to electron
density invariant under lattice translations is found from the
condition:


The reciprocal lattice vectors that satisfy the above
requirement are of the form

where v
1
, v
2
and v
3
are integers and




}
=

=

a
i
V
i
e dVn n e n n
c
0
1
) ( ) (
r G
G
r G
G
G
r r
1 ) ( ) (
) (
= =

= +
+ T G T G r G
G
G
T r G
G
G
r T r
i i i i
e when n e e n e n n
3 3 2 2 1 1
b b b G v v v + + =
( )
ij j i
k j i
k j
i
z y x i to = =

t = 2 , , , 2 a b
a a a
a a
b
HW:

Reciprocal of a reciprocal lattice is the direct lattice


Crystal Structure 97
Wigner-Seitz Method
A simply way to find the primitive
cell which is called Wigner-Seitz
cell can be done as follows;

1. Choose a lattice point.
2. Draw lines to connect these
lattice point to its neighbours.
3. At the mid-point and normal to
these lines draw new lines.


The volume enclosed is called as a
Wigner-Seitz cell.
Crystal Structure 98
Wigner-Seitz Cell - 3D


X-ray Diffraction
/ hc E =
Typical interatomic distances in solid are of the order of an angstrom.
Thus the typical wavelength of an electromagnetic probe of such distances
Must be of the order of an angstrom.
Upon substituting this value for the wavelength into the energy equation,
We find that E is of the order of 12 thousand eV, which is a typical X-ray
Energy. Thus X-ray diffraction of crystals is a standard probe.
X-Rays to Determine Crystal Structure
X-ray
intensity
(from
detector)
u
u
c
d =
n
2 sin u
c
Measurement of
critical angle, u
c
,
allows computation of
planar spacing, d.
Incoming X-rays diffract from crystal planes.
Adapted from Fig. 3.19,
Callister 7e.
reflections must
be in phase for
a detectable signal!
spacing
between
planes
d
u

u
extra
distance
traveled
by wave 2
2 2 2
hkl
a
d
h k l
=
+ +
For Cubic Crystals:
h, k, l are Miller Indices
Figure 3.34 (a) An x-ray diffractometer. (Courtesy of Scintag,
Inc.) (b) A schematic of the experiment.
X-Ray Diffraction Pattern
Adapted from Fig. 3.20, Callister 5e.
(110)
(200)
(211)
z
x
y
a
b
c
Diffraction angle 2u
Diffraction pattern for polycrystalline o-iron (BCC)
I
n
t
e
n
s
i
t
y

(
r
e
l
a
t
i
v
e
)

z
x
y
a
b
c
z
x
y
a
b
c
Energies of Interactions Between Atoms
Ionic bonding
NaCl
Covalent bonding
Comparison of ionic and covalent bonding
Metallic bonding
Van der waals bonding
Hydrogen bonding
What kind of forces hold the atoms together in
a solid?
Energies of Interactions Between Atoms
The energy of the crystal is lower than that of the free
atoms by an amount equal to the energy required to pull
the crystal apart into a set of free atoms. This is called the
binding (cohesive) energy of the crystal.

NaCl is more stable than a collection of free Na and Cl.
Ge crystal is more stable than a collection of free Ge.
Cl
Na NaCl
Types of Bonding Mechanisms
It is conventional to classify the bonds between
atoms into different types as

Ionic
Covalent
Metallic
Van der Waals
Hydrogen

All bonding is a consequence of the electrostatic interaction between
the nuclei and electrons.

Ionic bonding is the electrostatic force of attraction between
positively and negatively charged ions (between non-metals
and metals).

All ionic compounds are crystalline solids at room
temperature.

NaCl is a typical example of ionic bonding.
Metallic elements have only up to the valence electrons in their outer
shell.

When losing their electrons they become positive ions.

Electronegative elements tend to acquire additional electrons to
become negative ions or anions.
Na Cl
When the Na
+
and Cl
-
ions approach each other closely
enough so that the orbits of the electron in the ions begin
to overlap with each other, then the electron begins to
repel each other by virtue of the repulsive electrostatic
coulomb force. Of course the closer together the ions are,
the greater the repulsive force.





Pauli exclusion principle has an important role in repulsive
force. To prevent a violation of the exclusion principle, the
potential energy of the system increases very rapidly.

Covalent bonding takes place between atoms with small differences
in electronegativity which are close to each other in the periodic
table (between non-metals and non-metals).

The covalent bonding is formed when the atoms share the outer
shell electrons (i.e., s and p electrons) rather than by electron
transfer.

Noble gas electron configuration can be attained.


Each electron in a shared pair is attracted to both nuclei
involved in the bond. The approach, electron overlap, and
attraction can be visualized as shown in the following figure
representing the nuclei and electrons in a hydrogen molecule.
e
e
Comparison of Ionic and Covalent
Bonding
Metallic bonding is found in metal
elements. This is the electrostatic
force of attraction between positively
charged ions and delocalized outer
electrons.

The metallic bond is weaker than the
ionic and the covalent bonds.

A metal may be described as a low-
density cloud of free electrons.

Therefore, metals have high electrical
and thermal conductivity.
+
+
+
+
+
+
+
+
+
These are weak bonds with a typical strength of 0.2 eV/atom.

Van Der Waals bonds occur between neutral atoms and
molecules.

Weak forces of attraction result from the natural fluctuations in
the electron density of all molecules that cause small
temporary dipoles to appear within the molecules.

It is these temporary dipoles that attract one molecule to
another. They are called van der Waals' forces.
The shape of a molecule influences its ability to form temporary
dipoles. Long thin molecules can pack closer to each other than
molecules that are more spherical. The bigger the 'surface area' of
a molecule, the greater the van der Waal's forces will be and the
higher the melting and boiling points of the compound will be.
Van der Waal's forces are of the order of 1% of the strength of a
covalent bond.

Homonuclear molecules,
such as iodine, develop
temporary dipoles due to
natural fluctuations of electron
density within the molecule
Heteronuclear molecules,
such as H-Cl have permanent
dipoles that attract the opposite
pole in other molecules.
These forces are due to the electrostatic attraction between
the nucleus of one atom and the electrons of the other.

Van der waals interaction occurs generally between
atoms which have noble gas configuration.

van der waals
bonding
A hydrogen atom, having one electron, can be covalently bonded to
only one atom. However, the hydrogen atom can involve itself in an
additional electrostatic bond with a second atom of highly
electronegative character such as fluorine or oxygen. This second
bond permits a hydrogen bond between two atoms or strucures.
The strength of hydrogen bonding varies from 0.1 to 0.5 ev/atom.

Hydrogen bonds connect water
molecules in ordinary ice.
Hydrogen bonding is also very
important in proteins and
nucleic acids and therefore in
life processes.