UNIT 1: CRYSTAL STRUCTURES

Solid materials may be classified according to the regularity with which atoms or ions are arranged
with respect to one another. A crystalline material is one in which the atoms are situated in a repeating or
periodic array over large atomic distances; that is, long-range order exists, such that upon solidification, the
atoms will position themselves in a repetitive three-dimensional pattern, in which each atom is bonded to its
nearest-neighbor atoms. All metals, many ceramic materials, and certain polymers form crystalline structures
under normal solidification conditions. When describing crystalline structures, atoms (or ions) are thought
of as being solid spheres having well-defined diameters. This is termed the atomic hard sphere model in
which spheres representing nearest-neighbor atoms touch one another.

Fig 1: Hard sphere model of a simple cubic unit cell

In different states of matter, we can define four types of atomic or ionic arrangements:

1. No Order: In monoatomic gases, such as argon (Ar) or plasma created in a fluorescent tube light, atoms
or ions have no orderly arrangement. These materials randomly fill up whatever space is available to
them.
2. Short-Range Order (SRO): A material displays short-range order (SRO) if the special arrangement
of the atoms extends only to the atoms nearest neighbors. Each water molecule in steam has a short-
range order due to the covalent bonds between the hydrogen and oxygen atoms; that is, each oxygen
atom is joined to two hydrogen atoms, forming an angle of 104.5O between the bonds. However, the
water molecules in steam have no special arrangement with respect to each others position. A similar
situation exists in materials known as inorganic glasses. Many polymers also display short-range atomic
arrangements.
3. Long-Range Order (LRO): Most metals and alloys, semiconductors, ceramics, and some polymers
have a crystalline structure in which the atoms or ions display long range order (LRO); the special
atomic arrangement extends over much larger length scales>100 nm. The atoms or ions in these
materials form a regular repetitive, grid like pattern, in three dimensions. We refer to these materials as
crystalline materials. If a crystalline material consists of only one crystal, we refer to it as a single
crystal material. Single crystal materials are useful in many electronic and optical applications. For
example, computer chips are made from silicon in the form of large (up to 12-inch diameter) single
crystals. A polycrystalline material is comprised of many crystals with varying orientations in space.
These crystals in a polycrystalline material are known as grains. Many crystalline materials we deal
with in engineering applications are polycrystalline (e.g., steels used in construction, aluminum alloys
for aircrafts, etc.)
4. Liquid crystals (LCs): LCs are polymeric materials that have a special type of order. Liquid crystal
polymers behave as amorphous materials (liquid-like) in one state. However, when an external stimulus
(such as an electric field or a temperature change) is provided, some polymer molecules undergo
alignment and form small regions that are crystalline, hence the name liquid crystals.
.
Lattice, Basis and Crystal structure:

A lattice is a collection of points called lattice points that are arranged in a periodic pattern so that
the surroundings of each point in the lattice are identical. A lattice may be one, two, or three dimensional.
Lattice is a purely mathematical construct and is infinite in extent. A group of one or more atoms, located
in a particular way with respect to each other and associated with each lattice point, is known as the motif
or basis. We obtain a crystal structure by adding the lattice and basis (i.e. crystal structure = lattice + basis).

The unit cell is the subdivision of a lattice that still retains the overall characteristics of the entire
lattice. By stacking identical unit cells, the entire lattice can be constructed. There are seven unique
arrangements, known as crystal systems, which can be used to fill up a three-dimensional space. These are
cubic, tetragonal, orthorhombic, rhombohedral (also known as trigonal), hexagonal, monoclinic, and
triclinic. Although there are seven crystal systems, we have a total of 14 distinct arrangements of lattice
points. These unique arrangements of lattice points are known as the Bravais lattices.

Note that although we have only 14 Bravais lattices, we can have many more bases. Since crystal
structure is derived by adding lattice and basis, we have hundreds of different crystal structures. We will
assume that each lattice point has only one atom (i.e., the basis is one), unless otherwise stated. This
assumption allows us to refer to the terms lattice and the crystal structure interchangeably.

Fig 2: The various Bravais lattices - 7 crystal system and 14 crystal structures

Lattice Parameter: The lattice parameters, which describe the size and shape of the unit cell, include the
dimensions of the sides of the unit cell and the angles between the sides. In a cubic crystal system, only the
length of one of the sides of the cube is necessary to completely describe the cell (angles of 90o are assumed
unless otherwise specified). This length is the lattice parameter a (sometimes designated as ao). The length
is often given in nanometers (nm) or Angstrom (A) units, where:
1 nanometer (nm) = 10-9m = 10-7 cm = 10
1 angstrom () = 0.1 nm = 10-10 m = 10-8 cm
An x, y, z coordinate system is established with its origin at one of the unit cell corners; each of the x, y, and
z axes coincides with one of the three parallelepiped edges that extend from this corner. The unit cell
geometry is completely defined in terms of six parameters: the three edge lengths a, b, and c, and the three
inter-axial angles , and .
 Fig 3: Lattice parameters

Face Centered Cubic (FCC): The crystal structure found for many metals has a unit cell of cubic geometry,
with atoms located at each of the corners and the centers of all the cube faces. It is aptly called the face-
centered cubic (FCC) crystal structure. Some of the familiar metals having this crystal structure are copper,
aluminum, silver, and gold. Figure 3(a) shows a hard sphere model for the FCC unit cell, whereas in figure
3(b) the atom centers are represented by small circles to provide a better perspective of atom positions.

Figure 3: (a) Hard sphere model of FCC unit cell (b) A reduced sphere unit cell of FCC
The atoms touch one another across a face-diagonal the length of which is 4R. Since the unit cell is a cube,
its volume is where a is the cell edge length. From the right triangle on the face:
2 + 2 = (4)2
Or solving for a:
a= 2R2
The FCC unit cell volume V may be computed from:
V = 3 = (22)3 = 16 3 2
Body Centered Cubic (BCC): Another common metallic crystal structure also has a cubic unit cell with
atoms located at all eight corners and a single atom at the cube center. This is called a body-centered cubic
(BCC) crystal structure. Figure 4(a) and (b) are diagrams of BCC unit cells with the atoms represented by
hard sphere and reduced-sphere models, respectively. Two atoms are associated with each BCC unit cell:
the equivalent of one atom from the eight corners, each of which is shared among eight unit cells, and the
single center atom, which is wholly contained within its cell.

Figure 4: (a) Hard sphere model of BCC unit cell (b) Reduced sphere model of BCC unit cell

From the above figure:

2 = 2 + 2 = 2 + 2 = 22
BC=22 =2

Now AC=4R and by Pythagoras theorem applied on triangle ABC:

(4)2 = (2)2 + 2
(4)2 = (22 + 2 )
4R = 32
4
=
3
Unit cell volume is given by 3
4 64 3
3 = ( )3 =
3 33
Hexagonal Close Packed (HCP): The top and bottom faces of the unit cell consist of six atoms that form
regular hexagons and surround a single atom in the center. Another plane that provides three additional
atoms to the unit cell is situated between the top and bottom planes. The atoms in this mid plane have as
nearest neighbors atoms in both of the adjacent two planes. Notice that the blackened parallelepiped is the
repeating structure in the case of HCP and not the whole hexagonal structure.

Figure 6: Reduced sphere model depicting the HCP structure and the repeating structure

Number of atoms per unit cell: Each unit cell contains a specific number of lattice points and each lattice
points may be shared by more than one unit cell. A lattice point at the corner is shared by 7 adjacent unit
cells i.e. a total of 8 unit cells; only one eighth of each corner belongs to a particular cell.
In the SC unit cell, lattice points are located only at the corners of the cube:

1
= (8 ) ( ) = 1
8

In the case of BCC unit cell, lattice points are located at the corners and the center of the cube:

1
= (8 ) ( ) + (1 )(1) = 2
8

In the case of FCC unit cell, lattice points are located at the corners and the faces of the cube:

1 1

= (8 ) (8) + (6 ) (2) =4
Co-ordination Number: The coordination number is the number of atoms touching a particular atom, or
the number of nearest neighbors for that particular atom. This is one indication of how tightly and efficiently
atoms are packed together. For ionic solids, the coordination number of cations is defined as the number of
nearest anions. The coordination number of anions is the number of nearest cations.
SC structure has a coordination number of 6
BCC structure has a coordination number of 6
FCC structure has a coordination number of 12, which is the maximum.

Fig 5: Illustration of co-ordination number in (a) SC and (b) BCC unit cells
Six atoms touch each atom in SC, while eight atoms touch each atom in the BCC unit cell.

Packing Factor: The packing factor is the fraction of space occupied by atoms, assuming that atoms are hard
spheres sized so that they touch their closest neighbor. The general expression for packing factor is:

( )( )
Packing factor =

SC has a packing factor of 0.52

BCC has a packing factor of 0.68
FCC has a packing factor of 0.74

( )( )
Density: =
( )( )

The found out density is the theoretical density which will vary from the actual density obtained because
of the presence of dislocations and defects.
Points, directions and planes in unit cell:
Co-ordinate of points: We can locate certain points, such as atom positions, in the lattice or unit cell by
constructing the right-handed coordinate system in Figure 6. Distance is measured in terms of the number
of lattice parameters we must move in each of the x, y, and z coordinates to get from the origin to the point
in question. The co-ordinates are written as the three distances, with commas separating the numbers.

Figure 6: Co-ordinates of selected points in the unit cell.

Directions in the unit cell: Certain directions in the unit cell are of particular importance. Miller indices for
directions are the shorthand notation used to describe these directions. The procedure for finding the Miller
indices for directions is as follows:

1. A vector of convenient length is positioned such that it passes through the origin of the coordinate system.
Any vector may be translated throughout the crystal lattice without alteration, if parallelism is maintained.
2. The length of the vector projection on each of the three axes is determined; these are measured in terms
of the unit cell dimensions a, b, and c.
3. These three numbers are multiplied or divided by a common factor to reduce them to the smallest integer
values.
4. The three indices, not separated by commas, are enclosed in square brackets, thus: [u v w]. The u, v, and
w integers correspond to the reduced projections along the x, y, and z axes, respectively.
Given example illustrates a way of determining the Miller indices of direction:

Direction A
1. Two points are 1, 0, 0, and 0, 0, 0 which are ending and starting point respectively.
2. Subtracting the relative coordinates: 1, 0, 0 - 0, 0, 0 = 1, 0, 0
3. No fractions to clear or integers to reduce
4. Result is given in terms of square brackets [100]

Direction B
1. Two points are 1, 1, 1 and 0, 0, 0
2. 1, 1, 1 - 0, 0, 0 = 1, 1, 1
3. No fractions to clear or integers to reduce
4. [111]

Direction C
1
1. Two points are 0, 0, 1 and 2 , 1, 0
1 1
2. 0, 0, 1- , 1, 0 = - , -1, 0
2 2
1
3. 2(2 , 1, 1) = -1, -2, 2

4. [1 2 2]
Planes in unit cell: Miller indices are used as a shorthand notation to identify these important planes, as
described in the following procedure:
1. Identify the points at which the plane intercepts the x, y, and z coordinates in terms of the number of
lattice parameters. If the plane passes through the origin, the origin of the system must be moved!
2. Take reciprocals of these intercepts.
3. Clear fractions but do not reduce to lowest integers.
4. Enclose the resulting numbers in parentheses ( ). Again, negative numbers should be written with a bar
over the number.
The following example shows how Miller indices of planes can be obtained.

Plane A (Note please try plane C)

1. x = 1, y = 1, z = 1
2.1/ = 1,1 = 1, 1 = 1
3. No fractions to clear
4. (111)

Plane B
1. The plane never intercepts the z axis, so z = , other intercepts are x = 1 and y = 2
2. 1 = 1, 1 =12, 1 = 0;

3. Clear the fractions: 1 = 2, 1 = 1, 1 = 0

4. (210)