Electronic band structure

 The electronic band structure of a solid describes allowed and

forbidden energy (range of energy) for an electron within the
solid.

 Band theory derives these bands and band gaps by examining the
allowed quantum mechanical wave functions for an electron in a
large, periodic lattice of atoms or molecules.

 Band theory successfully describes many physical properties of

solids, such as electrical resistivity and optical absorption, and
forms the foundation of the understanding of all solid-state
devices (transistors, solar cells, etc.).
Why bands and band gaps occur??

 The electrons of a single, isolated atom occupy atomic orbitals.

 Each orbital forms at a discrete energy level.
 When multiple atoms join together to form into a molecule, their
atomic orbitals combine to form molecular orbitals, each of
which forms at a discrete energy level. The electrons are no more
localized to their particular parent atoms.
 As more atoms are brought together, the molecular orbitals
extend larger and larger, and the energy levels of the molecule
will become increasingly dense.
 Eventually, the collection of atoms form a solid and the energy
levels are so close that they can be considered to form a
continuum.
 Band gaps are essentially leftover ranges of energy not covered
by any band, a result of the finite widths of the energy bands.
 The bands have different widths, with the widths depending
upon the degree of overlap in the atomic orbitals from which
they arise.
 For example, the bands associated with core orbitals (such as 1𝑠
electrons) are extremely narrow due to the small overlap
between adjacent atoms. As a result, there tend to be large band
gaps between the core bands.
 Higher bands involve larger and larger orbitals with more
overlap, becoming progressively wider and wider at high energy
so that there are no band gaps at high energy
Band formation in Si crystal
Orbital model of
a Si atom
Energy levels in the
coulombic potential
of the nucleus
• Si (Z = 14)
• Electronic configuration
in the ground state is
1𝑠 2 2𝑠 2 2𝑝6 3𝑠 2 3𝑝2
 No of core electrons
(n = 1 and 2) is 10
 No of valence electrons
(n = 3) is 4
𝒆𝟐
𝑼𝒄𝒐𝒖𝒍𝒐𝒎𝒃 = −𝜶
𝟒𝝅𝜺𝟎 𝒓
α= 1.736, Madelung Constant
 3𝑠 orbital is spherically symmetric with no angular dependence,
and is positive everywhere.
 It can hold 2 electrons with opposite spin according to the Pauli
Exclusion principle.
 There are 3𝑝-orbitals which are mutually perpendicular.
 These are shaped like dumbbells with a positive lobe and a
negative lobe.
 The 3p subshell can hold up to 6 electrons, but in the case of Si
has only 2.
 Interestingly, in a Si crystal when we bring individual atoms very
close together, the 𝑠- and 𝑝-orbitals overlap so much that they
lose their distinct character, and lead to four mixed 𝑠𝑝3 orbitals.
 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.
When two atoms comes closer under Coulombic potential, the Schrodinger
equation for such an interacting system gives the composite two-electron wave
functions are LCAO.

LCAO have two normal modes

(1) a higher energy antibonding orbital
(2) a lower energy bonding orbital
The bonding orbital has a higher value of the wave function (and therefore higher
is the electron probability density) than the antibonding state in the region
between the two nuclei.
 In a solid, many atoms are brought together, so that the split energy
levels form essentially continuous bands of energies.
Consider band formation in Si crystal
• Each isolated silicon atom has an electronic structure
1s22s22p63s23p2 in the ground state
• Each atom has available two 1s states, two 2s states, six 2p states,
two 3s states, six 3p states, and higher states
• If we consider N atoms, there will be 2N, 2N, 6N, 2N, and 6N states
of type 1s, 2s, 2p, 3s, and 3p, respectively
• As the interatomic spacing decreases, these energy levels split into
bands, beginning with the outer (n = 3) shell.
• As the "3s“ and "3p" bands grow, they merge into a single band
composed of a mixture of energy levels.
• This band of "3s-3p" levels contains 8N available states.
Continue…..
• As the distance between atoms approaches the equilibrium
interatomic spacing of silicon, this band splits into two bands
separated by an energy gap Eg.
• The upper band (called the conduction band) contains 4N
states, as does the lower (valence) band.
• Thus, apart from the low-lying and tightly bound "core"
levels, the silicon crystal has two bands of available energy
levels separated by an energy gap Eg wide, which contains no
allowed energy levels for electrons to occupy.
• This gap is called a "forbidden band," since in a perfect
crystal it contains no electron energy states.
Continue…..
Let us calculate the electron occupancy in different energy levels
• The lower “1s" band is filled with the 2N electrons which originally
resided in the collective 1s states of the isolated atoms.
• Similarly, the 2s band and the 2p bands will have 2N and 6N electrons
in them, respectively.
• However, there were 4N electrons in the original isolated n = 3 shells
(2N in 3s states and 2N in 3p states).These 4N electrons must occupy
states in the valence band or the conduction band in the crystal.
• At 0 K the electrons will occupy the lowest energy states available to
them.
• In the case of the Si crystal, there are exactly 4N states in the valence
band available to the 4N electrons.
• Thus at 0 K, every state in the valence band will be filled, while the
conduction band will be completely empty of electrons.
• This arrangement of completely filled and empty energy bands has an
important effect on the electrical conductivity of the solid.
Formation of a silicon crystal from isolated silicon atoms.
Metals, Semiconductors, and Insulators
• Every solid has its own characteristic energy band structure.
• This variation in band structures is responsible for the wide range
of electrical characteristics observed in various materials.

Fig.2 The range of conductivities of solids.

Solids Band Gap, 𝐸𝑔 Example
Metals Overlap Au, Ag, Fe, Co, Ni
Insulators > 4 eV Dimond (5.47 eV), Fused Silica
(7.21 eV), Mica (7.8 eV)
Semiconductors < 4 eV Si (1.1 eV), Ge (0.67 eV), GaAs
(1.43 eV), GaN (3.4 eV)
Q. Why Si is insulator at 0 K???
• The silicon band structure is such that the valence band is
completely filled with electrons at 0 K and the conduction
band is empty.
• There can be no charge transport within the valence band,
since no empty states are available into which electrons can
move.
• There are no electrons in the conduction band, so no charge
transport can take place there either.
• Thus silicon has a high resistivity typical of insulators.

Semiconductor materials at 0 K have basically the same

structure as insulators—a filled valence band separated from an
empty conduction band by a band gap containing no allowed
energy states.