Solid State Notes 2019

ENERGY LEVELS AND BAND STRUCTURE

Reference: Handout - "Energy Band Formation

X- ray emission spectra gives clear cut evidence of the band structure of occupied energy levels of
electrons in solids. When crystals are hit by high energy electrons, electrons are knocked out of the
innermost part of the atom (K-shell, L-shell, etc.). Transitions take place from the outer to inner shells
creating narrow discrete lines. This means that the energy levels of the outer electrons are not discrete,
but form a band. The outer electrons of a given atom strongly interact with the outer electrons of
neighbouring atoms, and through this interaction with all the other outer electrons in the crystal.
The allowed electron energies in a solid occur then in bands in which the energy is almost
continuously variable. These are separated by forbidden energy regions (gap) which correspond to
energy levels the electrons cannot attain.

Let us examine carbon (Z = 6) closely. Carbon is an element having covalent interatomic bonding with
an electronic formula of 1s22s22p2. Assume carbon as being in its crystal form (diamond) so that it
behaves as an insulator.
Atomically, the inner principal shell (1s2) is full as is the second shell (2s2) but, there are four
vacancies in the outer subshell. (2p may hold 6e-).

Assume a very large interatomic spacing so that there is no interaction which occurs between the
atoms. (See I on following graph)
As the carbon atoms are brought together level splitting occurs (outer shell energies), which results in
bands of allowed energies. (See II) The energy levels with higher l numbers split first. For even closer
spacing, as at III, the bands can overlap. Eventually, with spacing reduced even further, the energies of
the outer shell (L) electrons can lie in one of two bands, separated by a forbidden gap as at IV. Covalent
bonding also occurs at IV.

In practice it is not possible to vary the interatomic spacing, since for a crystalline solid the lattice
constant (a measure of interatomic spacing which varies with material) is fixed. Carbon in the diamond
form thus has a band structure as indicated at the spacing at IV.

The band structure is important for covalent solids since its magnitude and form determine the
peculiar electrical conducting properties of that solid.

The difference between the terms ‘shell’ and ‘band’ relate to interatomic spacing. In the theoretical case
of a single isolated atom, orbital paths are contained into shells. Bands (of energy) are formed due to
the overlapping of shells from neighbouring atoms. This is illustrated in the figure below. At ‘I’ this is a
single atom and so are referred to as ‘shells’; whereas at ‘IV’ the shells have overlapped and formed
‘bands’.
Examples of Band Gap Energies:
Semiconductor Group Band Gap eV
Material Energy
300 K 0K
Carbon ( C ) IV 5.47 5.51
Germanium (Ge) IV 0.66 0.75
Silicon ( Si ) IV 1.12 1.16

GaAs III - V 1.43 1.52

GaP III - V 2.24 2.40
 Electrical Properties of Matter from the point of view of Energy Band Structure.

Insulator - poor conductor. Energy band structure at normal lattice spacing gives rise to a band
gap between valence and conduction bands that is quite large. Energy supplied from normal applied
electric fields is insufficient to free electrons.
diamond, crystalline carbon Eg=5.47 eV

Semiconductor - fair conductor. The width of the forbidden energy gap is relatively small1eV.
Silicon and germanium are the most important (elemental) semiconductors. This energy gap is sufficient
that electrons cannot normally acquire such energy from an electric field. As temperature increases
some of these electrons acquire energy Eg and enter the conduction band. Such conduction band
electrons move readily under the influence of electric fields. The empty states in the valence band are
known as holes and also serve as carriers of electric current.

Metals - there is no forbidden energy region. The valence band merges into the conduction band.
An applied electric field can move electrons into higher energy states and conduction readily occurs.

Intrinsic Semiconductors - pure crystal, equal number of holes and electrons. Every time a covalent
bond is broken one free electron and one hole result. The illustration below is referred to next.
When a valence band electron gains sufficient energy it breaks its covalent bond becoming a free
electron leaving behind a hole in the valence band (II). The hole permits charge movement and hence
conduction by valence band electrons. A nearby valence band electron (in a covalent bond) can fill a
hole and thus create another hole with practically no exchange of energy. If it were possible one would
observe the hole (vacancy in a covalent bond) rather than the electron move. The hole acts as a positive
charge carrier since it moves in a direction opposite to an electron in an electric field. For illustrative
purposes only, both electron and hole are depicted as moving in the same direction. In REALITY the
particles flow in opposite direction to each other.
Impurity (Extrinsic) Semiconductors

n-type semiconductors - Create an excess of free electrons over holes. Replace a few atoms in the
crystal structure by an element having 5 valence electrons (Group V, pentavalent) and of comparable
size.
Phosphorus 3s23p3
Arsenic 4s24p3 (showing valence structure only)
Antimony 5s25p3
Bismuth 6s26p3

The process of adding controlled amounts of impurities to the semiconductor crystal is known as
doping. Impurities from Group V are known as donor impurities because they donate excess electrons.

Of the 5 valence electrons of the donor atom, 4 have entered into covalent bonds similar to normal
atoms, the fifth electron is not bound in a bond and only experiences a weak electrostatic attraction to
the nucleus and is easily "ionized" (removed from influence of parent atom) by available thermal energy
at room temperature. By this process free electrons have been created without introducing additional
holes. The crystal has an excess of free electrons. Conduction is predominantly due to free electrons;
such a semiconductor is known as an n-type semiconductor (negative charge carriers)
Electrons majority carriers
Holes minority carriers

p-type semiconductors - It is also possible to create an excess of holes in the semiconductor crystal. To
do this introduce a small concentration of impurity atoms from Group III, these elements have three
valence electrons (trivalent)
Boron 2s22p1
Gallium 4s24p1
Indium 5s25p1
When these acceptor atoms take up positions in the crystal structure the three valence electrons enter
normal covalent bonds but one bond is incomplete. Excess holes have been created without additional
free electrons.
This is known as a p-type semiconductor (positive charge carriers)
holes majority carriers
electrons minority carriers

Energy Levels in Extrinsic Semiconductors

When donor impurities are added to a semiconductor,

allowable energy levels are introduced a very small
distance below the bottom of the conduction band.
These new levels (donor level, ED) are essentially a
discrete level because the impurity atoms are far apart in
the crystal structure. (relatively few impurity atoms, say
one impurity atom for every million normal atoms) and
hence their interaction is small.

The distance from ED to EC is a measure of the amount

of energy required to remove the excess fifth valence
electron of the impurity atom from its parent nucleus.
This energy is of the order of 0.05eV for silicon and 0.01eV for germanium.
 When acceptor impurities are added to a semiconductor
a discrete energy level is produced just above the top of
the valence band. It requires very little energy for an
electron to leave the valence band and occupy an
acceptor level.

Extrinsic Semiconductors and Temperature

In an extrinsic semiconductor at room temperature all the potential impurity contributed carriers
have been liberated and are available for conduction. As temperature increases above room value no
more impurity contributed carriers will be generated but the number of thermally generated hole-
electron pairs (due to breaking of normal covalent bonds) continues to increase until eventually the
effects of the doping have been swamped and the crystal appears as intrinsic.

Photoelectric Effect – emission of electrons from conductor surface when light of a particular
wavelength and frequency impacts on the surface. This explains photovoltaic systems and sensors.

This is contrasted with the thermionic effect in which the emission of electrons is due to high heat
being absorbed (or produced) by the substance in question. This partly explains vacuum tubes.

Albert Einstein in 1905 extended on a postulate by Max Planck that had been proposed earlier. Einstein
stated that a beam of light consists of small bundles of energy called quanta or photons.
E = hf
Energy of photon = Planck’s constant (h) x the frequency of the photon where:
h = 6.62607015  10 −34 J  s

A photon striking the surface of a conductor strikes an electron. If the collision transfers the exact
amount of energy required (an ‘all or nothing’ event) to match the surface potential, then emission
occurs.
1eV = 1.602x10−19 J
h = 4.136x10−15 eV  s Planck's constant in terms of eV.
Line Spectra and Energy Levels

‘College Physics 8ed by Young and Geller’

(a) Shows continuous spectrum – emitted by a very hot solid or liquid. All colours are emitted i.e.
incandescent light bulb.
(b) Line spectrum – emitted by heated gases characterized by defined lines produced by particular
wavelengths and frequencies.

Each element has a unique and distinct line spectra. This is how astronomers can determine the
composition of distant stars and planetary atmospheres through line spectra analysis.

Bohr speculated (later confirmed) that an orbital was characterized by an integer standing wave that
was unique to a certain energy. This describes all elements known to humankind.
When an electron is ‘excited’ (absorbs energy) to a higher energy state, it immediately tries to return
to its natural or ‘ground’ state. The path to ground state determines the unique colour emitted.
The above is in contrast to absorption spectra in which a ‘fraction of incident radiation absorbed by
the material over a range of frequencies’ determined by ‘the atomic and molecular composition of
the material. Both emission and absorption spectra are used as investigative tools in a variety of
science and engineering fields.