Crystal Structures

Books: 1. Introduction to Solid State Physics-Charles Kittel

2. Elementary Solid State Physics-M. Ali Omar
3. Principles of Electronic Materials and Devices

Introduction:
A solid appears as a continuous rigid body. However, all solids are
composed of discrete basic units-atoms. These atoms are not
distributed randomly, but are arranged in a highly ordered manner
relative to each other. Such a group of ordered atoms is referred to
as a crystal.

The atoms in some solids appear to be randomly arranged, i.e., the

crystalline structure is absent. Such noncrystalline solid is called
amorphous solids.
 Relation of the external form of crystals to the form of the
elementary building blocks

Fig: The building blocks are

identical in (a) and (b), but
different crystal faces are
developed, (c) Cleaving a
crystal of rocksalt.
 Crystal, Single Crystal and Polycrystal
Crystal: A solid is said to be a crystal if the atoms are arranged in such a way
that their positions are exactly periodic. In other words, a crystalline solid is
as solid in which the atoms bond with each other in a regular pattern to
form a periodic collection (array) of atoms.

Here a= distance between any two nearest neighbors along the x direction
b= distance between any two nearest neighbors along the y direction
x and y axes are not necessarily orthogonal.

It follows from the periodicity that the atoms A,B,C, etc., are equivalent, In other words,
to an observer located at any of these atomic sites, the crystal appears exactly the same.
 Crystal, Single Crystal and Polycrystal (Cont..)
Example: Nearly all metals, many ceramics and semiconductors, and
various polymers are crystalline solids. The crystal structure of Cu is
shown in Fig. 1.3.
 Crystal, Single Crystal and Polycrystal (Cont..)
Single Crystal: When the periodicity of the atomic pattern extends
throughout a certain piece of material, one speaks of a single
crystal.

Polycrystal: In polycrystalline materials the periodicity of structure

is interrupted at so called grain boundaries.
 Perfect/Ideal Crystal
 A perfect crystal maintains the periodicity (or repititivity) in both the
x and y directions from - to +. There is therefore a long-range
order in a crystal.

 An ideal crystal is constructed by the infinite repetition in space of

identical structural units.

 In the simplest crystals (Cu, Ag, Fe, Al, and the Alkali metals) the
structural unit is a single atom. Often the structural unit is several
atoms or molecule, upto perhaps 100 in inorganic crystals and
10,000 in protein crystals.
A crystal possesses periodicity/translational symmetry
A crystal possesses translational symmetry meaning that if the crystal is
translated by any vector joining two atoms, say R in Fig.1.1, the crystal
appears exactly the same as it did before translation.

In other words, the crystal remains invariant under any such

translation.
One cannot prepare a perfect crystal due to:
(i) As the atoms near the surface see an environment different
from the environment seen by atoms deep within the crystal, the
periodicity is interrupted there which results in the presence of a
kind of imperfection on the surface.

(ii) Because of the thermal vibrations of atoms around their

equivalent positions for T>00K, the crystal is always distorted to a
lesser or greater degree, depending on T.

(iii) An actual crystal always contains some foreign atoms, i,.e.,

impurities. Even with the best crystal growing techniques, some
impurities remain.
Note: All Crystals can be described in terms of a lattice and a basis.
The Crystal Lattice:
In Crystallography, one replaces each atom by a geometrical point located at
the equilibrium position of that atom. When all the atomic sites have been
replaced by lattice sites, the result is pattern of points having the same
geometrical properties as the crystal. This geometrical pattern is the crystal
lattice or simply the lattice.
In other words, a lattice is an infinite periodic array of geometric points in
space, without any atoms.

Basis: The structure of all crystals is described in terms of a lattice with a

group of atoms attached to each lattice point. The group of atoms is called
the basis.
When we place (or attached) a basis of atoms (or molecules) identically to
each lattice point, we obtain the actual crustal structure. The original relation
is
Lattice + Basis = Crystal Structure
In Fig. 1.31, each lattice point has one Cu atom and the basis is a
single Cu atom.
In Fig. 4, The crystal structure is formed by the addition of the basis
(b) to every lattice point of the lattice (a). By looking at (c), you can
recognize the basis and then you can abstract the space lattice.
 Bravais and Non-Bravais Lattice
There are two classes of lattice: the Bravais and the non-Bravais.
 In a Bravais lattice, all lattice points are equivalent, hence by necessity all
atoms in the crystal are of the same kind.
 In a non-Bravais lattice, some of the lattice points are nonequivalent.

 Here the lattice sites A, B and C are equivalent to each other.

 The lattice sites A’, B’ and C’ are equivalent to each other.
 But the two sites A and A’ are not equivalent to each other, as the
lattice is not invariant under a translation by AA’.
Remarks:
 A non-Baravais lattice is sometimes referred to as a lattice with a
basis, the basis referring to the set of atoms stationed near each site
of a Baravais lattice. In Fig. 1.2, the basis is the two atoms A and A’,
or any other equivalent set.

 The non-Bravais lattice may be regarded as a combination of two or

more interpenetrating Bravais lattice with fixed orientations relative
to each other. Thus the points A,B, C, etc., one Bravais lattice, while
the points A’,B’,C’ etc., form another.
Basis Vectors:
Consider the lattice shown in Fig. 1.3.

Let us choose the origin of coordinates at a certain lattice point, say A. Now
the position vector of any lattice point (called the lattice vector) can be
written as,
Rn=n1a+n2b (1.1)
Here a and b are the two vectors,
(n1,n2) is a pair of integers whose values depend on the lattice point.
For the point D, (n1,n2)=(0,2)
B,(n1,n2)=((1,0), and
F, (n1,n2)=(0,-1)
The two vectors a and b (which must be noncolinear) form a set of
basis vectors for the lattice.
In terms of a and b, the positions of all lattice points can be
conveniently expressed by the use of (1.1), Rn=n1a+n2b (1.1)
The set of all vectors expressed by this equation is called the lattice
vectors.

 The choice of basis vectors is not unique. Thus one can equally
will take the vectors a and b’(=a+b) as a bass. Other possibilities
are also evident.
 The Unit Cell
The area of the parallelogram whose sides are the basis vectors a and b is
called a unit cell of the lattice (Fig. 1.3).

 If a unit cell is translated by all the lattice vectors of Eq. (1.1), the area of
the whole lattice is covered once and only once.

 The unit cell is usually the smallest area, the repetition of which produce
the whole lattice.
 The lattice may be viewed as composed of a large number of equivalent
unit cells placed side by side, like a mosaic pattern.
 The Unit Cell (Cont..)

 The choice of a unit cell for one and the same lattice is not
unique, since the choice of basis vectors is not unique.
 Thus the parallelogram formed by a and b’ is also an acceptable
unit cell.

Remarks:
(i) All unit cells have the same area, i.e., the area of the unit cell is
unique.

(ii) Each unit cell has only one lattice point.

[The unit cell formed by ab has four points at its corners, but
each of these points is shared by four adjacent cells].
 Two-Dimensional Lattice Types
There is an unlimited number of possible lattices because there is no
natural restriction on the lengths a, b of the lattice translation vectors and
on the angles  between them.
There are five distinct lattice types in two dimensions, the oblic lattice and
the four special lattices: Square, Hexagonal, Rectangular and Centered
Rectangular.

Oblic Lattice: All pairs of vectors a, b are

translation vectors of the lattice.
Two-Dimensional Lattice Types (Cont..)
 Primitive versus nonprimitive Cells

The unit cell discussed above is called a primitive cell (a, b, c are primitive
axis). A primitive cell is a minimum volume cell (unit cell); it will fill all space
by the action of suitable crystal translation operations.
It is sometimes more convenient to deal with a unit cell which is larger, and
which exhibits the symmetry of the lattice more clearly. The idea is
illustrated in Fig. 1.4.

The vectors a1, a2 can be chosen as a basis set, in which case the unit cell is
the parallelogram.
 Primitive versus nonprimitive Cells (Cont..)

However, the lattice may be also arranged as a set of adjacent rectangles,

where we take the vectors a and b as basis vectors. The unit cell is then
the area s2 formed by these vectors. It has one lattice point at its center,
in addition to the points at the corner. This cell is a nonprimitive unit cell.

Note: The area of the nonprimitive cell is an integral multiple of the

primitive cell. In Fig. 4, the multiplication factor is two.
 Three Dimestions
All the previous statements for two dimensions can be
extended to three dimensions in a straight forwards manner.

The lattice vectors in 3D are expressed by

Rn=n1a+n2b+n3c (1.1)
Where a, b, and c are three noncolinear vectors joining the lattice point at
the origin to its nearest neighbors and n1, n2, n3 are a triplet of integers 0,
1, 2, etc., where values depends on the particular lattice point.
 Three Dimestions (Cont..)
 The vector triplet a, b, and c is the basis vector, and the
parallelepiped whose sides are these vectors is a unit cell.

 Here again the choice of primitive cell is not unique, although all
primitive cells have equal volumes.

 Also, it is sometimes convenient to deal with nonprimitive cells,

ones which have additional points either inside the cell or on its
surface.

 Finally, non-Bravais lattices in three dimensions are possible, and

are made up of two or three interpenetrating Bravais lattices.
 Three-Dimensional Lattice Types
 In 3D, the number of Bravais lattice is 14; The number of non-
Bravais lattice is 230. This reduction to 14 is a consequence of the
translational symmetry condition demanded of a lattice.
 The 14 lattices (or crystal classes) are grouped into seven crystal
systems, each specified by the shape and symmetry of the unit
cell.
 These systems are the triclinic, monoclinic, orthorhombic,
tetragonal, cubic, hexagonal, and the trigonal.
 In every case the cell is a parallelepiped whose sides are the bases
a, b, c. The opposite angles are called , , and  (Fig. 1.6).
Three-Dimensional Lattice Types (Cont..)
 A simple lattice has points only at the corners, a body-centered lattice has
one additional point at the center of the cell, and a face-centered lattice has
six additional points, one on each face.
 In all the nonsimple lattices the unit cells are nonprimitive.
 Three-Dimensional Lattice Types (Cont..)

Both Fig. 1.7 and Table 1.1 should be studied carefully, and their contents mastered.
 Elements of Symmetry
Crystal lattices can be carried into themselves by the lattice translations T
and by various other symmetry operations (such as inversion, reflection or
rotation). Each of the unit cells of the 14 Bravais lattices has one or more
types of symmetry properties.
(i) Inversion Center: A cell has an inversion center if there is a point at
which the cell remains invariant when the mathematical
transformation r-r is performed on it.
All Bravais lattices are inversion symmetric (Fig. 1.7). With every lattice
vector Rn=n1a+n2b+n3c, there is associated an inverse vector
Rn - Rn = -n1a-n2b-n3c.
A non-Bravais lattice may or may not have an inversion center, depending
on the symmetry of the basis.

Note: We have discussed the simplest symmetry elements. More complicated

elements also exist, such as rotation-reflection axes, glide planes etc.
(ii) Reflection Plane: A plane in a cell such that, when a mirror
reflection in this plane is performed, the cell remains invariant. The
triclinic has no reflection plane, the monoclinic has one plane
midway between and parallel to the bases, and so forth (Fig. 1.7).

(iii) Rotation Axis: There is an axis that passes through a lattice point
such that, if the cell is rotated around it through some angle, the cell
remains invariant. The axis is called n-fold if the angle of rotation is
2/n. The tryclinic has no axis of rotation, the monoclinic has a 2-fold
axis (=2/2=) normal to the base (Fig. 1.7).

Lattices can be found such that one-, two-, three-, four-, and six fold
rotation axes carry the lattice into itself, corresponding to rotations by
2, 2/2, 2/3, 2/4, and 2/6 radians and by integral multiples of
these rotations. The rotation axes denoted by the symbols 1, 2, 3, 4,
and 6.
We cannot find a lattice that goes into itself under other rotations,
such as by 2/5 radians or 2/7 radians.
Point groups, Space groups ans non-Bravais lattices
In a non-Bravais lattice, a cluster of atoms called the basis is assocated
with each lattice point. Therefore,
the symmetry of a non-Bravais lattice = symmetry of the basis +
symmetry of the Bravais lattice on which this basis is superimposed.

 The symmetry of the basis, called point group symmetry, refers to all
possible symmetry operations which, when applied about a fixed
point in the basis, leave the lattice invariant. Only 32 different point
groups can exist.

 When we combine the rotation symmetries of the point groups with

the translational symmetries, we obtain a space group symmetry. In
this manner one generates 72 space groups.