Energy Bands in Solids

Lecture 1.2

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 Electrons revolve around a positively charged nucleus in
discrete orbits (K, L, M or n=1, 2, 3 respectively) with specific
levels of energy.
 Electrons positions are fixed as such, however, an electron can
jump to higher or lower energy level by absorption or emission
of energy respectively.
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Wave mechanical model
• Electron position is
Wave-mechanical described in terms of a
atom model probability distribution.

• Electron energy is quantized

into both shells and
subshells — each electron is
characterized by four
quantum numbers.

Bohr Model

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 Note: here ε = E0
i.e. the binding energy
  is the distance at which the interaction energy is zero,
  is the depth of the potential well & is a measure of the bonding energy between
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Bonding Forces

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 Different types of chemical bonding in solids
Ionic bonding in NaCl Covalent bonding in the Si crystal

Ionic Bonding Co-valent Bonding

• Na (Z = 11) gives up its outermost shell electron to • Exhibited by the Silicon lattice semiconductors.
Cl (Z=17) atom, thus the crystal is made up of ions • Each atom surrounded by four nearest neighbors,
with the electronic structures of the inert atoms Ne each having four electrons in the outermost orbit.
and Ar. • Each atom shares its valence electrons with its
• Note: the ions have net electric charges after the four nearest neighbors.
electron exchange ion has a net positive charge, • Bonding forces arise from a quantum mechanical
having lost an electron, and ion has a net negative interaction between the shared electrons.
charge, having acquired an electron. • Both electrons belong to each bond, are
• Thus, an electrostatic attractive force is established, indistinguishable, and have opposite spins.
and the balance is reached when this equals the net • No free electrons available at 0 K, however, by
repulsive force. thermal or optical excitation, electrons can be
• Note: all the electrons are tightly bound to the excited out of a covalent bond and can participate
atom. in current conduction important feature of
• Since there are no loosely bound electrons to semiconductors.
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participate in current flow NaCl is a good insulator.
Metallic Bonding

• In metals, the outer shell is filled by no more than three electrons (loosely
bound and given up easily) great chemical activity and high electrical
conductivity.

• Outer electron(s) contributed to the crystal as a whole solid made up of

ions with closed shells immersed in a sea of free electrons, which are free to
move about the crystal under the influence of an electric field.

• Coulomb attraction force between the ions and the electrons hold the
lattice together.

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 Metals, Semiconductors, and Insulators
Insulator Semiconductor Metal

Typical band
Structures at 0 K

• For electrons to move under an applied electric field, there must be states
available to them.

• A completely filled band cannot contribute to current transport; neither can a

completely empty band.

• Thus, semiconductors at 0 K are perfect insulators.

• With thermal or optical excitation, some of these electrons can be excited from the
valence band to the conduction band, and then they can contribute to the current
transport process.
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• At temperatures other than 0 K, the magnitude of the band gap separates an
insulator from a semiconductor, FOR e.g., AT 300 K
Eg (Diamond) = 5 eV (insulator),
Eg (Silicon) = 1.12 eV (semiconductor).

• Number of electrons available for conduction can be increased greatly in

semiconductors by reasonable amount of thermal or optical energy.

• In metals, the bands are either partially filled or they overlap thus,
 electrons and empty states coexist
 great electrical conductivity.
Energy Gap
• Distinguishing feature among metals, insulators, and semiconductors.

• Determines the absorption/emission spectra, the leakage current, and the

intrinsic conductivity.

• Unique value for each semiconductor (e.g. 1.12 eV for Si, 1.42 eV for GaAs)
function of temperature.

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 Energy Bands in Solids

• Electrons are restricted to sets of discrete energy levels within atoms, with large gaps
among them where no energy state is available for the electron to occupy.

• Electrons in solids also are restricted to certain energies and are not allowed at other
energies.

• Difference in the solid, the electron has a range (or band) of available energies.

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• The influence of neighboring atoms on the energy levels of a particular atom can
be treated as a small perturbation, giving rise to shifting and splitting of energy
states into energy bands.

• The discrete energy levels of the isolated atom spread into bands of energies in
the solid because
i) in the solid, the wave functions of electrons in neighboring atoms
overlap, thus, it affects the potential energy term and the boundary
conditions in the Schrödinger equation, and different energies are
obtained in the solution, and

ii) an electron is not necessarily localized at a particular atom.

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 Electronic structure and energy levels in a Si atom

Electronic structure and energy levels in a Si atom:

(a) The orbital model of a Si atom showing the 10 core electrons (n = 1 and 2), and the 4
valence electrons (n = 3);
(b) Energy levels in the coulombic potential of the nucleus are also shown schematically.
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Hybridization

 The negative part of the p orbital cancels the 𝑠-type wave function, while the
positive part enhances it, thereby leading to a "directed" bond in space.
 These linear combinations of atomic orbitals (LCAO) or "hybridized" sp3
orbitals point symmetrically in space along the 4 tetragonal directions.

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 Linear combinations of atomic orbitals (LCAO)
Wavefunction of the two atoms

Coulombic potential wells of two atoms close to each other

Isolated atoms
Nearby atoms

* When 2 atoms are brought together leads to 2 distinct "normal" modes—a higher
energy antibonding orbital, and a lower energy bonding orbital.
* Electron probability density is high in the region between the ion cores (covalent
"bond"), leading to lowering of the bonding energy level and the cohesion of the crystal.
* When N atoms brought together, there will be N distinct LCAO, and N closely spaced
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 Energy band Formation- Silicon
Si
Atomic number: 14
Electronic Configuration:

sp3 Hybrization

The core levels (n = 1,2) in Si are completely filled with electrons. At the actual atomic spacing
of the crystal, the 2 N electrons in the 3s subshell and the 2 N electrons in the 3p subshell
undergo sp3 hybridization, and all end up in the lower 4N stales (valence band), while the
higher-lying 4 N states (conduction band) are empty, separated by a band gap.
 Energy Band Formation- Carbon

Carbon
Atomic number: 6
Electronic Configuration:
1s2 2s2 2p2

sp2 Hybrization

* Electron wave functions begin to overlap as isolated atoms are brought together to form
a solid.
* Various interactions occur, and, at the proper interatomic spacing for the crystal, the
forces of attraction and repulsion find a balance.
* Due to Pauli exclusion principle, the discrete energy levels of individual atoms split into
bands belonging to the pair instead of to individual atoms.
* In a solid, due to large number of atoms, the split energy levels for essentially continuous
bands of energy.
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 Activity

1. Give examples Ionic, Covalent and Metallic materials

2. Animation Video *a
https://nanohub.org/resources/8815/download/BS_band_v1.gif

*a Saumitra Raj Mehrotra, Gerhard Klimeck (2010), "Electronic band structure,"

https://nanohub.org/resources/8814.
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