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The initially empty energy band above the band gap in the simple semiconductor description. Excited Electrons in it can carry electric current; they can also bind to valence band electron holes as excitons.

An electron hole is an unoccupied Electron quantum state in an otherwise nearly full energy band, often the valence band. “Filled” refers to occupation of the allowed quantum states, not to filling all space with a continuous fluid of Electrons. Each state, including its spin label, can hold at most one Electron by the Pauli exclusion principle. The almost full energy band and its few missing occupants are therefore simpler to describe as a background plus a few electron holes. The electron hole is a quasiparticle, not a Positron inserted into the crystal.

Removing an Electron of electric charge $-e$ changes the background's electric charge by $+e$. Thus an electron hole carries positive electric charge relative to that background. Promoting an Electron into the conduction band creates an electron hole without changing the whole crystal's electric charge: $(-e)+(+e)=0$. An unbound pair still consists of two separate charge carriers; only a bound state of their relative motion is an exciton.

The local cartoon explains why a vacancy can move: when a neighboring Electron fills it, another vacancy appears where that Electron was. The vacancy has moved opposite to that particular transfer of an Electron. In an extended Bloch state, use crystal momentum instead of imagining a permanently empty atomic site. For a completely filled energy band the summed electric current vanishes. Omitting one Electron with group velocity ${\mathbf{v}}_v$ removes its contribution $-e{\mathbf{v}}_v$, leaving a contribution $+e{\mathbf{v}}_v$. This fixes both the positive electric charge and the velocity convention of the electron hole.

More precisely, near a parabolic valence band maximum, set its energy $E_v(0)$ as reference and define the electron hole wave vector by ${\mathbf{k}}_h=-{\mathbf{k}}_v$. ThenThe occupied Electron branch has negative curvature there, while the electron hole branch has positive effective mass $m_h^{\ast }$. The velocity equality compares the electron hole with the missing Bloch state's group velocity; it does not contradict the opposite vacancy motion in a local transfer cartoon. The sign conventions are listed in Phys 460 Lecture 17.

An Electron filling an electron hole removes both excitations relative to the filled-band background. Their electric charges cancel, consistent with charge conservation; the remaining Electrons are still present. The released energy can leave through photon emission or other channels, including phonons. Formation of an exciton instead retains the excited Electron and electron hole as a bound pair; recombination removes the pair. A valence band Electron filling a nearby vacancy merely moves the electron hole and does not remove the total vacancy count.

An exciton is a bound state of an Electron and an electron hole. Their opposite electric charges attract through the Coulomb potential, producing a neutral quasiparticle with internal relative motion and motion of its center of mass. In a semiconductor, promoting an Electron from the valence band into the conduction band leaves an electron hole; the pair can occupy either an exciton bound state or an unbound scattering state. Merely creating the two charge carriers does not establish binding. A neutral exciton can transport excitation energy without transporting net electric charge. Coupling this material excitation strongly to a photon can form a polariton.

The striking optical consequence is that an exciton optical transition can absorb a photon with less energy than the threshold for creating unbound Electrons and electron holes. The difference is the exciton binding energy, not an extra one-electron energy band inside the band gap. The Wannier-Mott exciton supplies a useful large-radius model; the Frenkel exciton describes the opposite, tightly localized limit.^[ref]

A Wannier-Mott exciton has an internal wave function extending over many unit cells. Its simplest model assumes a three-dimensional bulk crystal, approximately parabolic valence band and conduction band, positive isotropic scalar effective masses $m_e^{\ast },m_h^{\ast }$, a constant scalar relative permittivity ${ϵ}_r$, and a dilute pair population. Replace microscopic crystal forces by those effective masses and dielectric screening, and neglect exchange corrections and coupling to phonons. These assumptions must hold on the spatial and energy scales of the particular exciton.

With relative coordinate $\mathbf{r}={\mathbf{r}}_e-{\mathbf{r}}_h$, the internal Hamiltonian operator is the three-dimensional hydrogen atom problem with a reduced mass and a screened Coulomb potential:Here $e$ is the elementary charge, ${ϵ}_0$ the vacuum permittivity, and $\hslash$ the reduced Planck constant. The internal energy eigenvalues, radius scale, and exciton binding energies areThe principal quantum number is $n=1,2,\dots$. This reduction and these scales are derived in Excitons in Semiconductor Quantum Dots by Matjaž Humar (§3, printed pp. 5–6, equations (13)–(26)).

To check the scales by dimensional analysis, write $C=e^2/(4\pi {ϵ}_0{ϵ}_r)$, which has units of energy times length. Then $a_B^{\ast }={\hslash }^2/(\mu C)$ is a length and $R^{\ast }=\mu C^2/(2{\hslash }^2)$ is an energy. Rescaling $r=a_B^{\ast }\rho$ makes $H_{\mathrm{rel}}/R^{\ast }=-{\nabla }_{\rho }^2-2/\rho$, the dimensionless hydrogen atom operator. The Bohr radius $a_B^{\ast }$ is a wave function scale, not the radius of a classical orbit; for this model's lowest internal bound state, the mean separation is $3a_B^{\ast }/2$.

For the diagrams' hypothetical inputs $m_e^{\ast }=0.10m_0$, $m_h^{\ast }=0.40m_0$, ${ϵ}_r=10$ and $E_g=1.500\mathrm{eV}$, where $m_0$ is the free Electron mass, independent substitution gives $\mu =0.080m_0$, $a_B^{\ast }\simeq 6.615\mathrm{nm}$ and $R^{\ast }\simeq 10.885\mathrm{meV}$. Here electronvolts express energy. The exciton binding energies for $n=1,2,3$ are approximately $10.885$, $2.721$ and $1.209\mathrm{meV}$. These are model calculations, not measured material parameters. The large-radius approximation additionally requires $a_B^{\ast }$ to be much larger than the crystal's unit cell length scale. In a thin layer, with anisotropic effective masses, or with spatially varying dielectric screening, this three-dimensional formula is not generally valid.