Lecture 19

Part 4: Solid State-Band Theory and

Conductivity
 Molecular Orbitals of Polylithium

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 Band Theory
• When two atomic orbitals combine they
produce both a bonding and an antibonding
molecular orbital
• When many atomic orbitals combine they
produce a band of bonding molecular orbitals
and a band of antibonding molecular orbitals
• The band of bonding molecular orbitals is
called the valence band
• The band of antibonding molecular orbitals is
called the conduction band
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The band of molecular orbitals in lithium metal.
Sodium According to Band Theory

Conduction band:
empty 3s antibonding

No gap

Valence band:
full 3s bonding

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 Magnesium

3s bonding and antibonding should be full

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 Magnesium

Conduction band:
empty

No gap: conductor

Valence band:
full

Conductor
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Copper
• As the half-filled 4s orbitals
of an increasing number of
Cu atoms overlap, their
energies are split into a half-
filled valence band.
• Electrons can move from the
filled half (purple) to the
slightly higher energy upper
half (red), where they are
free to migrate from one
empty orbital to another.
 Solids: Conductors, Insulators and
Semiconductors
Conduction Band: white

Band gap
No gap

Valence Band
in red

Conductor Insulator Semiconductor

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Electrical conductivity in a conductor, semiconductor, and insulator.

conductor insulator

semiconductor
 Band Gap
• At absolute zero, all the electrons will occupy
the valence band
• As the temperature rises, some of the
electrons may acquire enough energy to
jump to the conduction band
• The difference in energy between the
valence band and conduction band is called
the band gap
– the larger the band gap, the fewer electrons
there are with enough energy to make the jump

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 Solids: Conductors, Insulators and
Semiconductors

Diamond
Graphite

Band gap = 5.5 eV

≈ 530 kJ/mol
No gap

Conductor Insulator
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 Allotropes of Carbon
• Diamond: high thermal conductivity,
extremely strong, insulator
• Graphite: high thermal conductivity,
conductor
– electrodes for electrolysis and batteries;
essentially pencil “lead”

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 Diamond

• Diamond has a three-dimensional network

structure in which each carbon is singly-bonded
to four others with sp3 hybridization.
• Diamond is a covalent network solid
– each carbon covalently bonded to 4 others.
• Diamonds are the hardest substance known.
– must break carbon-carbon bonds
• Diamonds have a melting point of 3550°C.
– must break carbon-carbon bonds

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 Orbital Diagram of the
sp3 Hybridization of C

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 Methane Formation with sp3 C

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Structure of Diamond

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Structure of Graphite

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 Types of Band Gaps and
Conductivity

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 Band Gap and Conductivity
• The more electrons at any one time that a substance has in
the conduction band, the better conductor of electricity it is
• If the band gap is ~0, then the electrons will be almost as
likely to be in the conduction band as the valence band and
the material will be a conductor
– metals
– the conductivity of a metal decreases with temperature
• If the band gap is small, then a significant number of the
electrons will be in the conduction band at normal
temperatures and the material will be a semiconductor
– graphite
– the conductivity of a semiconductor increases with temperature
• If the band gap is large, then effectively no electrons will be
in the conduction band at normal temperatures and the
material will be an insulator

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 Solids: Conductors, Insulators and
Semiconductors

Band Gap for Semiconductors

Diamond 5.5 eV
Si 1.1 eV
Ge 0.67 eV Band gap

Semiconductor
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Some semiconducting
materials and associated
bandgaps (eV)
GaAs

GaAs
 Doping Semiconductors
• Doping is adding impurities to the semiconductor’s
crystal to increase its conductivity
• Goal is to increase the number of electrons in the
conduction band
• n-type semiconductors do not have enough electrons
themselves to add to the conduction band, so they are
doped by adding electron-rich impurities
• p-type semiconductors are doped with an electron-
deficient impurity, resulting in electron “holes” in the
valence band. Electrons can jump between these
holes in the valence band, allowing conduction of
electricity.

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Effect of doping silicon.

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Crystal structures and band
representations of doped
semiconductors.
 Semiconductors
• Semiconducting elements form the basis of
solid state electronic devices.

– When silicon is doped with phosphorus, it

becomes an n-type semiconductor, in
which electric current is carried by
electrons.

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 Semiconductors
• Semiconducting elements form the basis of
solid state electronic devices.
– When silicon is doped with boron, it
becomes a p-type semiconductor, in
which an electrical current is carried by
positively charged holes

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 Diodes

• When a p-type semiconductor adjoins an n-

type semiconductor, the result is an p-n
junction
• Electricity can flow across the p-n junction in
only one direction – this is called a diode
• This also allows the accumulation of
electrical energy – called an amplifier

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The p-n junction.
p-n junction

Forward bias

Reverse bias
A p-n junction as a
rectifier.

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 Light Emitting Diodes
• Another important kind of diode is the light-emitting diode (LED). Whenever
an electron makes a transition from the conduction band to the valence band
(effectively recombining the electron and hole) there is a release of energy in
the form of a photon (Figure). In some materials the energy levels are spaced
so that the photon is in the visible part of the spectrum. In that case, the
continuous flow of current through the LED results in a continuous stream of
nearly monochromatic light.

Figure: Schematic of an LED. A photon is

released as an electron falls from the
conduction band to the valence band. The
band gap may be large enough that the
photon will be in the visible portion of the
spectrum.

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Unit cell of a High Temperature Superconductor

high
temperature
superconductor

YBa2Cu3O7
 The levitating power of a superconducting oxide.

rare earth magnet

superconducting ceramic disk

liquid nitrogen

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