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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]

The exciton binding energy is the positive energy needed to separate a bound Electron and electron hole into the relevant unbound scattering states. Compare the exciton energy $E_X$ with the continuum threshold $E_{\mathrm{cont}}$ at the same total crystal momentum and for the same energy bands. The negative internal energy eigenvalue $-E_B$ and the positive separation cost $E_B$ are different sign conventions for related quantities. An exciton may move freely through a perfect crystal while remaining internally bound: “free exciton” does not mean an unbound pair.

For the ideal Wannier-Mott exciton in energy bands whose edges occur at the same crystal momentum, the pair excitation energy, measured from the unexcited crystal, isHere $\hslash \mathbf{K}$ is the pair's total crystal momentum; the last term is center of mass kinetic energy. For a permitted photon absorption transition with negligible recoil energy, $\hslash \omega \simeq E_g-E_{B,n}$. An electric-dipole selection rule and a nonzero transition matrix element are still needed: a bound state need not produce an observable spectral line. If the relevant energy band edges have different values of crystal momentum, a phonon can also be needed to conserve crystal momentum; subtracting a binding scale from a band gap alone does not specify the optical threshold.

For example, the lowest internal bound state in this hypothetical model costs $1.489115\mathrm{eV}$ to create optically, yet needs only $0.010885\mathrm{eV}$ more to dissociate. The large creation energy and the small exciton binding energy answer different physical questions. An electron-hole recombination event can instead release excitation energy by photon emission or to other degrees of freedom; an emitted photon need not reproduce the original absorption energy if relaxation intervened.

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.