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Bonding in Solids: Electronic Properties

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Band Structure: What is it and what is it good for?

What is the electronic band structure?

For an extended solid the band structure plays the same
role that an MO diagram does for a molecule.
Why is it important to determine and understand the
electronic band structure?
• It is the link between crystal structure, bonding and
chemical and physical properties.
• It helps us understand the following properties:
 Electronic conductivity
 Optical and magnetic properties, including color
 Catalytic Activity

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Band Theory of Solids

• To explain the properties of metals, insulators and semiconductors, the
periodic potential experienced by electrons must be considered.
• The periodic potential U that arises from interaction of electrons with
the periodic array of ions in a crystal is shown in the figure.

• For a free electron, U =0.

• Negative potentials imply bound
electrons.
• Solution of the Schrodinger equation
for a periodic potential results in
energy bands and bandgaps, as shown
in the figure.
• Only electrons that are in the highest
energy band close to the Fermi level
can move freely in the solid.

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Band Theory of Solids

• When two atoms approach each other, the wave functions of the
outermost electrons overlap.
• Taking hydrogen as an example the two 1s orbitals, which have the same
energy when the atoms are far apart, split into two states of different
energy. The same happens to the 2s state as shown in figure (a).
• If six atoms are brought together, each state splits into six states of
different energy as shown in figure (b).

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Band Theory of Solids

• If N atoms are brought together, the overlap of the wave functions lead
to N states of different energy (i.e. the number of states equals the
number of atoms).
• A sample of solid material contains a large
number of atoms (e.g. in 1cm3 of Cu, there are
~ 1023 atoms), each state splits into energy
levels so close together that energy bands are
formed.
• Each band consists of essentially a continuous
range of allowed energies.
• The energy bands are separated by energy
gaps known as bandgaps. The width of a band
depends on the lattice spacing.

• The properties of a solid are determined by the energy of the bands, the
extent to which they are occupied by electrons, and the size of the band
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Conductors, Insulators and Semiconductors

• We can now address the question of why some solids are
conductors, while others are insulators or semiconductors.
 For good conductors, the highest energy band occupied by
electrons is partially filled.

 Taking sodium as an example, the 1s, 2s and 2p bands are full. For
a sample of N sodium atoms, the 3s band has 2N available states
but there are only N electrons (one 3s electron/atom) to fill the
3s band. Consequently, the 3s band is only half-filled.

 If a potential difference is applied across the sample, the

electrons in the partially filled band can easily move to states of
higher energy available.

 It is therefore easy for a current to flow, making sodium a good

conductor.
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Conductors
Conductor: Partially filled band

Example: Sodium
Partially filled band

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Sodium energy bands 7

Insulators
• In the case of insulators the highest
band occupied by electrons, called the Insulator
valence band, is completely filled.
 The next band, is called the conduction
band, is completely empty and there is a
bandgap of typically 5 to 10eV between
the valence and conduction bands.

 At room temperature (~300K),

electrons have an average kinetic energy
of ~ 0.04eV and can therefore not move
to conduction band.

 Such materials are therefore insulators.

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Semiconductors
• The band structure of pure (intrinsic) semiconductors is similar
to that of an insulator except that the valence and conduction
bands are separated by a smaller bandgap Eg of typically 1eV
(e.g. Eg for Si is 1.11eV at 300K).
• At room temperature a few electrons have sufficient energy to
overcome the bandgap. At higher temperatures, more electrons
are able to do so resulting in lower resistivity. The resistivity of
semiconductors generally decrease with increasing temperature
(resistivity of Si is -.07/oC and that of Ge is -0.05/oC) in
contrast with that of metals which generally increases.

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Conductors, Insulators and Semiconductors

Metal (Cu) Semiconductor (Si) Insulator (Al2O3)

Empty 4p 
(conduction)
Empty  
Band gap (conduction)
Empty  
(conduction)
partially     Band gap
Band gap
Ef,  filled 4s  Ef Ef
Fermi  (conduction)
level Filled (valence) Filled (valence)

Band gap Band gap Band gap

filled               Filled                Filled               
3p, 2p, 2s, 1p,  (deep valence) (deep valence)
1s (valence)

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Some semiconducting materials and associated bandgaps (eV)

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Doped Semiconductors: n-type semiconductors

• The band structure and conductivity of intrinsic
semiconductors can be modified by the controlled
addition of ‘impurity’ atoms (typically 1 to 10 ppm). This
process is known as doping.
• Silicon is an important semiconductor material with 4
valence electrons.
• When silicon is doped with arsenic (or some other
element that has 5 valence electrons) the arsenic atoms
occupy silicon sites in the lattice.
• Four valence electrons from each arsenic atom form
covalent bonds with adjacent silicon atoms but the fifth
electron can move relatively freely as in a conductor. This
increases the conductivity of the doped silicon sample.
• Silicon that has been doped with a pentavalent atom such
as arsenic is known as an n-type semiconductor because
conduction is due to negative charges (electrons).
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n-type semiconductors

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p-type semiconductors
• If silicon is doped with a trivalent element such as gallium
(Ga), the three valence electrons form covalent bonds
with adjacent silicon atoms, but a vacancy (hole) exists at
the gallium site.
• An electron from a silicon atom can move into the hole at
the gallium site leaving a hole at the silicon site. This hole
can then be filled by an electron from another silicon
atom , etc. The hole is equivalent to a positive charge.
This increases the conductivity of the doped silicon
sample.
• Silicon doped with trivalent atoms are p-type
semiconductors. Conduction is due to positive holes.
• Note that both n-type and p-type semiconductors are
electrically neutral.
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p-type semiconductors

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Semiconductor Doping: Energy Band Picture

• In doped semiconductors, ‘impurity’ states are formed
between the valence and conduction bands.
• In n-type semiconductors the ‘impurity’ energy level lies
very close (~ 0.05eV for silicon compared to thermal
energy of 0.04eV at 300K) to the conduction band.
Electrons are readily promoted to the conduction band
from the ‘impurity‘ level which is, therefore, known as the
donor level.
• In p-type semiconductors the ‘impurity’ level lies just
above the valence band. Electrons are readily accepted
from the valence band leaving holes behind. The ‘impurity’
levels are therefore known as acceptor levels.

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Semiconductor Doping: Energy Band Picture

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Semiconductor Devices
 Semiconductor doping is used to produce well-defined
regions of different conductivities in a semiconductor
material.
 This led to the development of semiconductor devices such
as the diode and transistor, and miniaturization of
electronic circuitry which has revolutionized the electronics
industry.
 In 1965, Gordon Moore predicted that the number of
transistors on a chip would double every year. In 1986, the
386 processor contained 275,000 transistors. The Pentium
4 processor contains 42,000,000 transistors.
 Ultimately the maximum density of components will be
determined by quantum effects in the semiconductor
materials.
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Semiconductor Devices
 A diode consists of a semiconductor
substrate which has been doped so that
one end is p-type and the other n-type.
 In the absence of a voltage across the
diode, some electrons from the n-type
region drift into the p-type region where
they combine with holes. The n-type
region is left with a positive charge.
 Similarly, holes drift from the p-type
region into the n-type region combining
with electrons. The p-type region is left
with a negative charge.
 A potential difference is established
which prevents further diffusion of
holes and electrons.

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Semiconductor Devices - Transistors

 a transistor consists of one type of doped semiconductor (n-type or p-
type) sandwiched between two doped semiconductors of the opposite
type.

Arrow shows direction of conventional current flow during

normal operation
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