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Solids: Conductors, Insulators

and Semiconductors
• Conductors: mostly metals
• Insulators: mostly nonmetal materials
– we’ll study allotropes of carbon and study
their properties
• Semiconductors: metalloids

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Solids: Conductors, Insulators
and Semiconductors
Conduction Band: white

Band gap
No gap
Valence Band
in red

Conductor Insulator Semiconductor 2


Bonding in Metals
• The electron-sea model is a simple
depiction of a metal as an array of positive
ions surrounded by delocalized valence
electrons.
– Metals are good conductors of electricity because
of the mobility of these delocalized valence
electrons.

– A metal also conducts heat well because the mobile


electrons can carry additional kinetic energy.
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Bonding in Metals

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Bonding in Metals
• Molecular orbital theory gives a more
detailed picture of the bonding in metals.

– Because the energy levels in a metal


crowd together into bands, this picture
of metal bonding is called band theory.

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Bonding in Metals
• Molecular orbital theory gives a more
detailed picture of the bonding in metals.

– According to band theory, the electrons in a


crystal become free to move when they are
excited to the unoccupied orbitals of a
band.

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Bonding in Metals
• Molecular orbital theory gives a more
detailed picture of the bonding in metals.

– In a metal, this requires little energy


since the unoccupied orbitals lie just above
the occupied orbitals of highest energy.

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Bonding In
Metals:
Lithium
according to
Molecular
Orbital
Theory
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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 11
Solids: Conductors, Insulators
and Semiconductors
Conduction Band: white

Band gap
No gap
Valence Band
in red

Conductor Insulator Semiconductor 12


Allotropes of Carbon
• Diamond: high thermal conductivity,
extremely strong, insulator
• Graphite: high thermal conductivity,
conductor
– electrodes for electrolysis and batteries;
essentially pencil “lead”
• Fullerenes: discovered in 1986, amazing
possibilities

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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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Structure of Diamond

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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.
• Why do diamonds conduct heat?
– Metals conduct heat because the the mobile electrons can
carry additional kinetic energy.
– Diamonds are insulators and have no mobile electrons.
– Diamonds conduct heat through high frequency (= high
energy) vibrations that transmit over long distances
• Diamonds conduct heat 4 times better than copper!

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Graphite
• Graphite has a layered structure, in which
the carbon atoms in each layer bond to three
other carbons with sp2 orbitals.
• Graphite’s primary use is in the
manufacture of electrodes for electrolysis
and batteries.
– Of the covalent network solids, only graphite
conducts electricity.
– This is due to the delocalization of the resonant p
electrons in graphite’s sp2 hybridization. 17
Structure of Graphite

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Fullerenes
• The fullerenes are a family of molecules with a
closed cage of carbon atoms arranged in
pentagons and hexagons. Each carbon is sp2
hybridized.
– The most symmetrical member is
buckminsterfullerene, C60.
– Buckminsterfullerenes show potential for
applications in superconductivity and catalytic
activity.

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Buckminsterfullerene
Figure 13.25:
A frame
model
of C60.
By permission of Dr.
Richard Smalley, Rice

University

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Solids: Conductors, Insulators
and Semiconductors
Diamond
Graphite

Band gap = 5.5 eV


≈ 530 kJ/mol
No gap

Conductor Insulator 21
Solids: Conductors, Insulators
and Semiconductors
Band Gap for Semiconductors

Diamond 5.5 eV
Si 1.1 eV
Band gap
Ge 0.67 eV

Semiconductor 22
Semiconductors
• Metalloids: semiconducting elements
– low electrical conductivity at room temperature
– Electrical conductivity increases with temp.
• Gap between valence and conduction band
is intermediate in size

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Semiconductors
• Semiconducting elements form the basis of
solid state electronic devices.
– Metalloids (such as silicon or germanium) are
semiconducting elements whose electrical
conductivity increases as temperature increases.
– A striking property of these elements is that their
conductivities increase markedly when they are
doped with small quantities of other elements.

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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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Semiconductors
• Semiconducting elements form the basis of
solid state electronic devices.
– Joining a p-type semiconductor to an n-
type semiconductor produces a p-n
junction, which can function as a rectifier.
– A rectifier is a device that allows current to
flow in one direction, but not the other.

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Figure 13.29: Effect of doping silicon.

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Figure 13.30:
A p-n junction as a
rectifier.

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