ELEKTRONIKOS PAGRINDAI 2008 1

2. STRUCTURE AND BAND THEORY OF SOLIDS

Objectives:
Gain knowledge about structure of solids and crystal lattices of semiconductors.
Studies of band models of metals, semiconductors and insulators.

Content of the topic:

1. Types of bonds in solids.
2. Crystal lattices.
3. Imperfections of crystal structures.
4. Energies of electrons in solids.
5. Electrons effective mass.
6. Band models of metals, semiconductors and insulators.

VGTU EF ESK [email protected]

 ELEKTRONIKOS PAGRINDAI 2008 2

Interaction of atoms in solids

Many important properties of solids and existence of crystals are

predetermined by forces between atoms.
Attractive forces and bonds between atoms arise in solids. Attractive forces
have electrostatic nature.
Four types of bonds (ionic, covalent, metallic and molecular) can exist in
solids.
In covalent binding the atoms share one or more pairs of
electrons. The shared electrons circulate around the
nuclei. They spent more time between the nuclei than
they do on the outside. The result is an effective
negative charge between the positive nuclei. This
charge attracts the nuclei.
Carbon, silicon and germanium atoms can form covalent
crystals, having diamond type crystal lattices.
In the diamond type crystal lattice each atom shares
electron pairs with the four other atoms adjacent to it.

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Interaction of atoms in solids

Because attractive force is electrostatic force, it

increases, if the distance between acting charges
decreases: 2
q
Fatr =
4 r 2
with a small distance between atoms, the
repulsion force arises and increases rapidly, if the
distance between atoms decreases. The repulsive
force is due to crowding of electrons into too small
volume.

At some distance r0 between interacting atoms the sum of the attractive and
repulsive forces becomes zero. So, atoms of a solid tend to take
positions in which the distance between them is r0. It is possible if the
atoms of solids are in a regular array.
Three types of solids exist: amorphous, crystalline and polycrystalline solids.
Further we will concentrate our attention on the crystalline solids or crystals.

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Crystal lattices

The essential characteristic of crystal structures of solids

is regularity in arrangement of atoms. According to this
real crystals are modelled by crystal lattices. In a crystal
lattice every atom has identical surroundings in three
dimensional space.
Crystal lattices consist of unit cells.
If atoms are dislocated only in the lattice nodes or
points, we have a simple (primitive) lattice. The
simple cubic lattice has nodes lying only at the
intersections of the network of axes.
The body-centred (volume-centred) cubic lattice
has additional nodes at the cube centres. The
base-centred cubic lattice has additional nodes at
the centres of bases. Lastly, the face-centred cubic
lattice has additional nodes at the centres of the
cube faces.
centred cubic lattices are at the same time
primitive lattices.

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 ELEKTRONIKOS PAGRINDAI 2008 5

Crystal lattices

there are lattices that can be arranged only by translation of groups of atoms.
Such a group of atoms is called a crystal lattice basis (base).
The translation of the basis gives a lattice consisting of interpenetrating sublattices.
One of them is displaced from the other.
The simple semiconductors (silicon and germanium) have the diamond type crystal
lattice.
The basis of a diamond lattice consists of two atoms.
The crystal lattice of a simple semiconductor may be represented as two
face-centred cubic lattices; one is put into another and shifted by 1/4 of the
space diagonal of the unit cell.
Each atom of a simple semiconductor is surrounded by four others that occupy the
corners of a regular tetrahedron.

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Crystal lattices

A three-dimensional model of the silicon structure is too cumbersome for most

discussions.
It may be replaced by a two-dimensional representation.

The compound semiconductors have zinc

blend or sphalerite lattice.
Each atom of the compound semiconductor
is surrounded by four atoms of another
element.

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Structure of crystals. Crystallographic indices

The disposition of nodes and the crystal properties along different directions
are different. Therefore it is necessary to find a convenient way to specify the
orientation of crystal planes and directions.
We can describe the disposition of a node by three coordinates x = ma, y = nb,
and z = pc. But, if the lattice constants a, b, c are known, it is enough to specify
integers m, n, p. The set of the integers in double square brackets [[m n p]] is
the crystallographic index of the node.

The direction in the crystal can be specified

by the vector, going from the origin of the co-
ordinate system.

The direction is determined by the first node

in the direction of the vector and is indicated
by the bracketed index of the node: [m n p].

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 ELEKTRONIKOS PAGRINDAI 2008 8

Structure of crystals. Crystallographic indices

The crystallographic indices of the plane are obtained using the following
procedure:
Determine the intercepts of the plane on the three crystal axes.
Measure the distances of the intercepts from the origin in multiples of the lattice
constants.
Take the reciprocals of the intercepts.
Reduce the reciprocals to the smallest integers that are in the same ratio.

The calculation is based on the basic equations (intercept and normal forms) of a
plane:
x y z Here D is the common
+ + = 1;
m n p (hkl) denominator.

hx + ky + lz = D;
In the cubic system
the direction is
always perpendicu-
lar to the plane
having the same
indices.

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 ELEKTRONIKOS PAGRINDAI 2008 9

Imperfections in crystal structures

Real crystals differ from ideal crystals. Imperfections or defects exist in real crystals.
Lattice vibrations cause dynamic defects of the crystal lattice.
The energy of lattice vibrations is given by
... the energies of thermal vibrations of a crystal have
1
Wk = h i ni +
2
a quantum character.
The vibratory wave-particle entities are called
i
phonons.

Point defects, line defects and surface defects are the main kinds of static defects
of crystal lattices.
There are two types of the line defects: edge
dislocations and screw dislocations.

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Structure of solids. Problems

1. The diamond lattice constant is a. Find the distance between the nearest
atoms and the atomic radius.
2. Find coordinates of intersections of planes (213) ir (210) with coordinate
axes x, y and z.
3. Atomic mass A, the constant of cubic lattice a and number of atoms N in a
unit cell of a crystal are known. Derive the formula for calculation of
material density.
4. Density of silicon is 2.33103 kg/m3, its atomic mass is 28. Number of
atoms in a unit cell is 8. Find the lattice constant.

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 ELEKTRONIKOS PAGRINDAI 2008 11

Energies of electrons in solids

Let us now examine what changes in the energies of electrons occur when atoms
come together to form a solid.
Let us use simplified models for analysis. Let us begin with the strong bonding of
two sodium atoms.
A sodium atom has 11 electrons. The electronic structure of a sodium atom is
1s22s22p63s1. If the distance between the atoms is relatively great, electrons of
one atom are separated from another atom by high and wide potential barriers.

Electrons of the atom

cannot interact with
electrons of the other
one.
The height of the
potential barriers for
electrons depends on
the potential level.

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Energies of electrons in solids

... If atoms approach, widths and heights of the barriers decrease.

At d = a the conditions for electrons in the lower states are essentially
unchanged. But the state 3s belongs to both atoms. Electrons in the state 3s can
move from one atom to another. They are free (unlocalized) in the system.

If the system consists of N atoms, N

valence electrons exist.
According to the Paulis exclusion
principle only two electrons with
different spin quantum numbers can
occupy the state 3s.

Way out of this situation is found assuming that the outer electrons of each atom
in the crystal are affected by the neighbouring atoms.
The result is that the energy levels of each atom are disturbed slightly and the
discrete energy states split in the crystal to form a band of allowed energy states.

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Energies of electrons in solids

The split energy levels in solids form

allowed energy bands in which the
energy of electrons can change almost
continuously. The allowed energy bands
are separated by the forbidden regions,
forbidden energy bands or forbidden
energy gaps in which electrons cannot
exist.

Thus, the energy spectrum of electrons in solids has the band structure.
The allowed energy bands in the crystal correspond to the allowed energy
levels in the isolated atoms.

Similar results may be obtained mathematically solving the Schrodinger

equation.

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Energies of electrons in solids

Simplified mathematical model of a solid was proposed by Kronig and

Penney. It consists of a regular one-dimensional array of square-well
potentials.
According to the model the periodic field of atoms in a crystal is modelled by
the periodic function.

If the height of the barriers is zero,

the electron is free. In this case

h2 2 h2 p2 Energy spectrum of a free electron is

Wk = k = =
2m 2 m 2
2m continuous.

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Energies of electrons in solids

If the periodic barriers exist, the solution of the Schrodinger equation in the
form of the W-k or W-p diagram becomes more complicate.

Allowed bands

Forbidden
bands

The curve Wk(k) is not continuous.

According to the diagram, the allowed and forbidden energy bands exist
for an electron in a solid.

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 ELEKTRONIKOS PAGRINDAI 2008 16

Electrons effective mass

Let us consider an electron moving in the crystal under the influence of an

externally applied electric field.
1 dW
d W = F d x = Fvg d t vg = d /d k =W /h
F dt dW =
h dk
dk F d v d vg d2 1 d2 W 1 d2 W d k
= a= = = = =
dt h dt dt dt d k h dt d k h d k2 dt

1 d2 W F h2
a= 2 2
F= mn =
h dk mn d 2 W /d k 2

If the electron is free:

h2 2 h2 p2 d 2 W /d k 2 = h 2 / m
Wk = k = =
2m 2 m 2
2m
mn = m ... the effective mass of the free electron is the same as
its mass m.

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 ELEKTRONIKOS PAGRINDAI 2008 17

Electrons effective mass

In the allowed band the effective mass of an

electron in a crystal is not constant.
It can vary over a range from a few per cents of
the electronic rest mass m to much greater than
m.

Using the effective mass concept it is possible

to treat an electron in a solid as a classical
particle. The electron-lattice interaction is included
in the effective-mass term.
We must notice that the effective mass of an
electron in a crystal becomes negative at the top
of the allowed band. Having a negative effective
mass, the electron is accelerated in the direction of
the electric field. So, it acts as a positive charge
and is called a hole. We will see later that holes
correspond to the unoccupied electron states at
the top of the allowed band.

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Band models of solids

Let us begin with lithium. A lithium atom has 3 electrons. Its electronic
structure is given by 1s22s1.
If the distance between the lithium atoms decreases, the energy levels split,
and the allowed energy bands, corresponding to allowed energy levels,
appear.

Two electrons may be in the state 2s in an atom. So the energy band 2s is

only partially occupied by electrons. There are unoccupied levels over the
occupied levels in the band 2s.

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Band models of metals

Beryllium electronic structure is given by 1s22s2. So the state 2s in a beryllium

atom is completely occupied by electrons. But we must have in mind and
estimate that the allowed level exists over the level 2s. It is unoccupied (empty)
in isolated atoms. When atoms become closer to form a crystal, energy bands 2s
and 2s overlap. As a result the hybrid allowed energy band appears. It is only
partially occupied by electrons.
Both materials (lithium and beryllium) are conductors. So partially filled
energy band is a characteristic feature of the band structure of
conductors.
Energy levels are filled in the band up to some level WF, above which there
are many empty states.

Because properties of conductors are defined by

the processes that take place only in the
surroundings of the energy level WF, usually we use
the simplified energy diagram of conductors.

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Band models of semiconductors and insulators

Now let us take such materials as carbon C (having a diamond lattice), silicon Si
and germanium Ge. Electronic structures of atoms of these materials are given by
C: 1s22s22p2 Si: 1s22s22p63s23p2 Ge: 1s22s22p63s23p63d104s24p2
Eight electrons can occupy the levels s and p in an isolated C, Si and Ge atom. So
there are 4 unoccupied states in each atom.
When the atoms form crystals, valence electrons go into covalent bonds. Two
common electrons for each two neighbour atoms appear. As a result each atom
in a diamond crystal is linked with 8 electrons and all states in the allowed
valence band are occupied by electrons.

Conduction
band
Forbidden band

Valence
band

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Band models of solids

Diamond is insulator. Silicon and germanium are semiconductors. According to the
analysis the completely full valence band is the characteristic feature of the
band structure of insulators and semiconductors. A forbidden energy band
and an empty band, the conduction band, exist over the valence band.
The band structure of semiconductors is similar to that of insulators. These band
structures differ in the width of the forbidden band. The width of the forbidden gap
of semiconductors is much smaller than for insulators. It is of the order of 1 eV.

If the temperature increases, the vibration of the crystal lattice also increases. At
room temperature there are electrons in the valence band that can have energy to
jump to the conduction band. When electrons appear in the conduction band, we
have a situation similar to that in conductors. There are energy levels occupied by
electrons and empty states over them. So electrons in the conduction band can
carry charge in a crystal and current flow becomes possible.

It is not necessary to show the full band diagram of a

semiconductor. The properties of a semiconductor are
defined by the processes between the top of the valence
band and the bottom of the conduction band.
W = Wc Wv
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 ELEKTRONIKOS PAGRINDAI 2008 22

Electrons in solids. Problems

1. What changes in the energies of electrons occur when atoms come

together to form a solid?
Draw and explain the energy level diagrams for a conductor.
Draw and explain the energy level diagrams for semiconductor and
insulator.
The lattice constant of silicon is 0,542 nm. A unit cell contains 8 atoms. Find
the number of valence electrons in a unit volume.

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