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PHYSICIST CHEMIST
Solid state band Molecular orbital
Valence band, VB HOMO
Conduction band, CB LUMO
Fermi energy, EF Chemical potential
Bloch orbital, delocalized Molecular orbital, localized
n-doping Reduction, pH scale base
p-doping Oxidation, pH scale acid
Band gap, Eg HOMO-LUMO gap
Direct band gap Dipole allowed
Indirect band gap Dipole forbidden
Phonon or lattice vibration Vibrational mode
Peierls distotion Jahn-Teller effect
ELEMENTARY BAND THEORY
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Valence electrons from the atoms spread throughout the entire
structure
Molecular orbitals are extended over all the constituent atoms
A large number of overlapping atomic orbitals lead to molecular
orbitals with very similar energies = continuous band
The bands are separated by band gaps (energy values where there
are no available levels)
Electronic Structure of Solids
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Band Theory
3d
4s
4p
1 atom NA atoms
Energies of electrons are quantized = can possess only allowed
energies, can occupy only allowed levels, cannot enter forbidden band
gaps.
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Molecular orbital  Electronic band
N atomic orbitals combine to form bonding and antibonding
molecular orbitals, N energy levels.
Large rings - cyclic boundary condition
A rough rule of thumb: the separation of the energy levels in the
dimer corresponds to about half width of the energy band.
Electronic Bands
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Bands arise from many MO’s of slightly different energies different
degree of bonding
The bottom of the band – the lowest energy MO, all bonding
character
The top – the highest energy MO with all anti-bonding
character
The rest of the band is formed from all the MO’s with
intermediate bonding character between the two extremes
Electronic Structure of Solids
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Crystal Orbitals in 1D - Nodes
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Crystal Orbitals
N atoms in the chain = N energy levels and N
electronic states (MO)
The wavefunction for each electronic state:
Ψk = Σ eikna χn
Where:
a is the lattice constant (spacing between atoms)
n identifies the individual atoms within the chain
χn represents the atomic orbitals
k is a quantum number that identifies the
wavefunction and the phase of the orbitals
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Bonding
Antibonding
Bloch functions, crystal orbitals
simple example:
infinite one-dimensional array of s-
orbitals
k = wavevector gives the phase of the
AOs as well as the wavelength of the
electron wavefunction (crystal
momentum)
a = lattice constant
n = orbital counter
Large number of discreet levels =
band
Band Theory
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Band Theory Antibonding orbitals
Bonding orbitals
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Filling Bands by Electrons
N atoms, 1 electron on each
N levels in a band
Occupied by pairs of electrons
N/2 levels filled
N/2 levels empty
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Bands in Metals
3s
3p
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Bandwidth or Band Dispersion
Energy difference between the highest and lowest level
Bandwidth increases with better orbital overlap
•shorter interatomic distance
•closer energy match
•topology
•density, oxides more diffuse than halides, wider bands
•localization of electrons – narrow bands
Bandwidth arising from sigma > pi > delta overlap
Core orbitals – narrow bands (0.1 eV), 4f in lanthanides
Valence orbitals, s, p – wide bands (10 eV)
Wide bands = Large intermolecular overlap = delocalized eNarrow
bands = Weak intermolecular overlap = localized e-
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Bandwidth or Band Dispersion
energy difference
between the highest
and lowest level
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Different types of orbitals
(symmetry) form separate bands
s, p, d bands
distinct bands with a band gap
overlaping bands
depends on the separation of the
orbitals and strength of the
interaction between the atoms
Strong interaction = wide bands and
a greater overlap.
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Two dimensional lattice
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Two dimensional lattice
Band structure
of a square lattice of H atoms
(dHH = 2.0 Å)
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Density of states
a) MO diagram with translational symmetry taken into account
b) Density of states (DOS, N(E) dE)
Number of levels available for electrons at different energies per unit volume
of the solid. DOS is zero in the band gap
a) b)
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Rutile TiO2 Band Structure
Ti eg
Ti t2g
O 2p
O 2s
Band structure – spaghetti (a) and DOS (b)
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Contributions to
the total DOS of rutile
(a) Ti and O
(b) Ti d-orbitals, t2g and eg
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Classification of solids
Molecular solids – N2, C6H6, I2, …
Van der Waals forces, little change from the gas phase, electronic
bands correspond to empty and filled MOs of the individual
molecules.
Ionic solids – NaCl, CaF2, NiO, …
Charge transfer from cations to anions, energy bands made up from
the atomic orbitals of cations and anions.
NaCl: 3p of Cl is the top filled band, 3s of Na is the lowest empty
band.
Covalent solids – diamond, Si, …..
Overlap of orbitals and electron sharing between adjacent atoms.
Filled bands are made up from bonding MOs, empty bands are
made up from antibonding MOs.
Metallic solids – Cu, Mg, W, TiO, ….
Simple metals – Na
Very strong overlap of atomic orbitals on adjacent atoms, arising
bands are very broad, 3s, 3p, and 3d merge into a single wide band,
electrons move freely, little attraction to the atomic cores.
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Ionic solids
Example NaCl, Eg = 9 eV
i = ions in the gas phase
ii = ions in the lattice,
Madelung potential,
filled levels stabilized by positive
potential of cations,
empty levels destabilized
iii = polarization energy
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The distinction between metallic and non-metallic solids
- the orbitals filling
Metallic behavior – a partially filled band, no gap between
the top filled level (Fermi level) and the lowest empty one
Non-metallic behavior – a completely filled level (the
valence band) and an empty one (the conduction band)
separated by a band gap
Metallic and Non-metallic Solids
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Fermi level
EF = the thermodynamic chemical potential for electrons in the solid
Metals – boundary between filled and unfilled levels
The Fermi-Dirac distribution function:
f(E) = 1/[1 + exp{(E – EF)/kT}]
The Fermi level cuts a band in a metal
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Fermi Level
Ef occupation probability ½
Levels
E < Ef occupied
E > Ef empty
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Fermi Level
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In the filled band every electron is matched by another - no
overall net motion of electric charge
For conduction to occur electrons have to be excited up to
the conduction band by overcoming an activation energy
and hence, the conduction of these compounds increases
with temperature
Metallic and Non-metallic Solids
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Metallic and Non-metallic Solids
Semiconductors and Insulators
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Band gap = the minimum photon energy required to excite an
electron up to the conduction band from the valence band
The band gap size determines a semiconductor or an insulator
Insulators - a completely filled valence band separated from
the next empty energy band by a large, forbidden gap
Diamond = insulator, a very large band gap of 6 eV
very few electrons have sufficient energy to be promoted and
the conductivity is negligibly small
Conductivity of insulators increases with temperature
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Band Gap Energies, kJ mol1
NaCl 840
Diamond 480
ZnO 315
CdO 210
B 170
Si 125
Ge 85
Te, InAs 40
PbTe, InSb 20
α-Sn (grey) 8
Mg, Al, Cu, β-Sn (white)…… 0
1 eV = 1.60210 10−19 J 1 eV (molekula)−1 = 1 eV  NA = 96 485 J mol−1
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Electrical Conductivity
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Bands in Graphite
Graphite is a conductor
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Bands in Diamond
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Semiconductors - a similar band structure to insulators but
the band gap is small, some electrons have sufficient
thermal energy to be promoted up to the empty conduction
band.
Two types of conduction mechanism in semiconductors:
- Electrons promoted into the conduction band = negative
charge carriers, move towards a positive electrode under
an applied potential.
- The holes these electrons leave behind = positive holes.
Holes move when an electron enters them - new positive
hole. The positive holes move in an opposite direction to the
electrons.
Semiconductors
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Fermi level
a gap between the filled and
empty states in a
semiconductor/insulator
Semiconductors
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INTRINSIC
Intrinsic semiconductors are pure materials with the band structure.
The number of electrons in the conduction band is determined only
by the size of the band gap and the temperature (more electrons
with small band gap and high temperature).
EXTRINSIC
Extrinsic semiconductors are materials where the conductivity is
controlled by adding dopants with different numbers of valenece
electrons to that of the original material.
Semiconductors
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Semiconductors
A direct band gap
(InAs, GaAs)
the band edges aligned in k, so that a
electron can transit from the valence
band to the conduction band, with
the emission of a photon, without
changing considerably the
momentum.
An indirect band gap
(Si, Ge, AlSb)
the band edges are not aligned so the
electron doesn't transit directly to the
conduction band. In this process both
a photon and a phonon are involved.
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Two fundamental differences between extrinsic and
intrinsic semiconductors:
1) At standard temperatures extrinsic semiconductors
tend to have significantly greater conductivities than
comparable intrinsic ones.
2) The conductivity of an extrinsic semiconductor can
easily and accurately be controlled by controlling the
amount of dopant.
Materials can be manufactured to exact specifications
of conductivity.
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Metals
EF
EC
Valence
band
T > 0
E = 0
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Insulators
EF
EC
EV
Conduction
Egap
T > 0
Valence
band
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Intrinsic Semiconductors
EF
EC
EV
T > 0
Valence
band
Conduction
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Extrinsic Semiconductors
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Doping of semiconductors - introducing atoms with more
or less electrons than the parent element.
Doping is substitutional, the dopant atoms directly replace
the original atoms.
Very low levels of dopant are required, only 1 atom in 109
of the parent atoms.
Extrinsic Semiconductors
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Extrinsic Semiconductors n-type
EC
EV
EF
ED
Egap~ 1 eV
n-type Si
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Silicon - phosphorous atoms introduce extra electrons (one extra valence
electron for each dopant atom introduced as P)
The dopant atoms form a set of energy levels that lie in the band gap
between the valence and conduction bands, but close to the conduction
band.
The electrons in the dopant levels cannot move directly - there is not
enough of them to form a continuous band.
The levels act as donor levels because the electrons have enough
thermal energy to get up into the conduction band where they can move
freely.
n-type semiconductors, the negative charge carriers or electrons.
Extrinsic Semiconductors n-type
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Extrinsic Semiconductors p-type
EA
EC
EV
EF
p-type Si
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Doping with an element with one less valence electron such as Ga
For every dopant atom - an electron missing,
form a narrow, empty band consisting of acceptor levels which lie just above
the valence band, discrete levels if the concentration of gallium atoms is
small.
Electrons from the valence band have enough thermal energy to be promoted
into the acceptor levels,
electrons in the acceptor levels cannot contribute to the conductivity of the
material.
The positive holes in the valence band left behind by the promoted electrons
are able to move - p-type semiconductors, the positive holes.
Extrinsic Semiconductors p-type
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Some transition metal compounds can be conductors due to the
presence of an element in more than one oxidation state.
NiO
On oxidation - turns black and becomes a relatively good conductor
Some of the Ni2+ ions oxidized to Ni3+ and some Ni2+ ions diffuse out to
maintain charge balance leaving cation holes. The reason for the
conduction is the ability of electrons to transfer from Ni2+ to Ni3+ ions.
This basically allows the Ni3+ ions to move and black NiO is therefore a
p-type semiconductor.
Controlled Valency Semiconductors
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The transfer process is thermally controlled and therefore highly dependent
on temperature, makes controlling the conductivity difficult.
Controlled valency semiconductors rely on control of the concentration of
Ni3+ ions by controlled addition of a dopant (such as lithium).
NiO
Li+
x Ni2+
1-2x Ni3+
x O
the concentration of Li+ ions controls the conductivity
Hopping Semiconductor
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Delocalized Bands – Localized Bonds
Molecules: Mulliken overlap population Σ 2 c1 c2 S12
c1, c2 same sign = bonding
c1, c2 opposite sign = antibonding
S12 overlap integral
Solids: Overlap population-weighted density of states = crystal
orbital overlap population (COOP) – for a specific bond
COOP curves
Sign – positive = bonding, negative = antibonding
Amplitude – depends on DOS, orbital overlap, MO coefficients
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DOS and COOP for the Ti-O bonds in rutile
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DOS and COOP for the Ni-Ni bonds in Ni metal
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Peierls distortion
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Peierls distortion – maximizing bonding, lowering the DOS at the
Fermi level, bonding states down in energy, antibonding states up, a
band gap opens at the Fermi level
Destabilization
Stabilization
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Peierls distortion
Photocatalysis
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Photocatalysis
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Solar cells
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Electronic Bands in Nanoparticles
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