Hole Exciton model

for
Semiconductor ANISH KUMAR R
MS220002CY
NIT-SIKKIM
The Hole-Exciton Model in semiconductor physics is a theoretical framework used to understand and describe the behavior of
holes and excitons in semiconductors. To understand this model, let's break it down into its two main components: holes and
excitons.

Holes:
• In semiconductors, when an electron gains enough energy to move from the valence band (the highest energy electron band) to
the conduction band (the lowest energy electron band), it leaves behind an empty space in the valence band. This "missing"
electron is referred to as a hole.

• Holes behave as if they were positively charged particles, even though they are technically the absence of an electron. This
concept is known as the "hole charge carrier."

• Holes can move through the semiconductor lattice just like electrons, and their motion is responsible for electrical conduction
in p-type (positive) semiconductors.
Excitons:
• An exciton is a bound state of an electron and a hole in a semiconductor material. It forms when an electron in the conduction
band is attracted to a nearby hole in the valence band due to their opposite charges.
• The electron and hole in an exciton are held together by the Coulombic attraction between them, creating a quasi-particle with a
net zero charge.
• Excitons can exist in different energy states, and they can recombine, releasing energy in the form of photons (emission of
light). This property makes excitons important in the context of optoelectronic devices like light-emitting diodes (LEDs) and
lasers.

The hole-exciton model is particularly useful in explaining various phenomena in semiconductors, including the absorption and
emission of light, as well as the behavior of charge carriers in these materials. This model plays a significant role in the design and
understanding of semiconductor devices and is crucial in fields like solid-state physics and semiconductor technology.

The electron–hole pair shown on the left can migrate through a solid
lattice as the excitation hops from molecule to molecule. The mobile
excitation is called an exciton.
Excitons are often treated in the two limiting cases:

(i) The electron and the hole jump together from molecule to molecule as they migrate. A migrating excitation of this kind is called
a Frenkel exciton. Frenkel excitons typically occur in insulators and organic semiconductors with relatively narrow allowed
energy bands and accordingly, rather heavy Effective mass.

(ii) The electron and hole can also be on different molecules, but in each other’s vicinity. A migrating excitation of this kind, which
is now spread over several molecules (more usually ions), is a Wannier exciton.Wannier-Mott excitons are considered as
hydrogen-like quasiparticles. The wavefunction of the bound state then is said to be hydrogenic, resulting in a series of energy
states in analogy to a hydrogen atom.

Wannier–Mott exciton, bound electron-hole pair that is

Frenkel exciton, bound electron-hole pair where the not localized at a crystal position. This figure
hole is localized at a position in the crystal schematically shows diffusion of the exciton across the
represented by black dots lattice.
Frenkel exciton:

• In materials with a relatively small dielectric constant, the Coulomb interaction between an electron and a hole may be strong
and the excitons thus tend to be small, of the same order as the size of the unit cell. Molecular excitons may even be entirely
located on the same molecule, as in fullerenes.

• Frenkel excitons are typically found in alkali halide crystals and in organic molecular crystals composed of aromatic molecules,
such as anthracene and tetracene.

• Another example of Frenkel exciton includes on-site d-d excitations in transition metal compounds with partially filled d-shells.
While d-d transitions are in principle forbidden by symmetry, they become weakly-allowed in a crystal when the symmetry is
broken by structural relaxations or other effects.

• Absorption of a photon resonant with a d-d transition leads to the creation of an electron-hole pair on a single atomic site,
which can be treated as a Frenkel exciton.
Wannier–Mott exciton:

• In semiconductors, the dielectric constant is generally large. Consequently, electric field screening tends to reduce the Coulomb
interaction between electrons and holes.

• The result is a Wannier–Mott exciton, which has a radius larger than the lattice spacing. Small effective mass of electrons that is
typical of semiconductors also favors large exciton radii.

• As a result, the effect of the lattice potential can be incorporated into the effective masses of the electron and hole. Likewise,
because of the lower masses and the screened Coulomb interaction, the binding energy is usually much less than that of a
hydrogen atom, typically on the order of 0.01eV.

• Wannier–Mott excitons are typically found in semiconductor crystals with small energy gaps and high dielectric constants, but
have also been identified in liquids, such as liquid xenon. They are also known as large excitons.
3D semiconductors:

In a bulk semiconductor, a Wannier exciton has an energy and radius associated with it, called exciton Rydberg energy and
exciton Bohr radius respectively. For the energy, we have

2D semiconductors:

In 2D materials, the system is quantum confined in the direction perpendicular to the plane of the material. The reduced
dimensionality of the system has an effect on the binding energies and radii of Wannier excitons. In fact, excitonic effects are
enhanced in such systems.
For a simple screened Coulomb potential, the binding energies take the form of the 2D hydrogen atom
0D semiconductors:(quantum dots)

The analysis for quantum dots is more complicated due to the variation of the size and shape of the quantum dots. Generally
speaking, the exciton binding energy is much higher in the case of quantum wells and dots as compared to bulk materials due to
electron and hole confinement in quantum structures. Accompanying the increase in exciton binding energy is a reduction of the
exciton Bohr radius. While reports in the open literature indicate a variety of results for various quantum dot shapes and sizes, a
general consensus is that the binding energy in quantum dots increases as the size of the dot decreases. The dashed line in Fig
represents the exciton binding energy in a bulk GaN material, and the solid line represents the change in the exciton binding
energy as a function of the quantum dot radius. Again, the behavior of the binding energy in Fig seems to be universal for most
quantum dot materials. While optical absorption from excitons in quantum dots has not been reported, perhaps due to the
significantly small optical length, theoretical results indicate that excitons in quantum dots could have large oscillator strengths

Variation of change in exciton binding energy

as a function of dot size for GaN.
Three-dimensional nanocrystals:
Three-dimensional nanocrystals of semiconducting materials containing 103 to 105 atoms are called quantum dots. They can be
made in solution or by depositing atoms on a surface, with the size of the nanocrystal being determined by the details of the
Synthesis. A quantitative but approximate treatment that leads to the energy of the exciton begins with the following hamiltonian
for a spherical quantum dot of radius R:

where the first two terms are the kinetic energy operators for the electron and hole, and the third term is the potential energy of
interaction between electron and hole, which are located at positions re and rh from the centre of the sphere.

Solving the Schrödinger equation in this case is not a trivial task, but the final expression for the energy of the exciton, Eex, is
relatively simple

As expected, we see that the energy of the exciton decreases with increasing radius of the quantum dot.
Thank You!