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The Shockley-Queisser limit is the detailed-balance efficiency bound for an ideal single-junction solar cell with radiative recombination under specified illumination and optical conditions. Below-gap photons are not absorbed and excess energy of above-gap photons is thermalized; radiative emission further limits the output voltage. The often quoted unconcentrated terrestrial maximum is roughly one third, not an illumination-independent universal percentage.

A multi-junction solar cell places a high-gap junction before lower-gap junctions, dividing the spectrum so photons generate carriers in a better-matched absorber. This reduces transmission and thermalization losses and can exceed the single-junction bound without violating its assumptions: there is now more than one junction. In a two-terminal series stack, all junctions carry the same current, so the lowest photocurrent limits the whole device. Current matching uses bandgap choice, absorber thickness, optical management and sometimes lateral area to make the generated currents comparable for the intended spectrum. Independently contacted junctions need not share the same current.^[ref]

The Shockley-Queisser limit is a radiative detailed-balance limit for a single-junction photovoltaic device under specified illumination and temperature. Its idealized absorber collects above-gap photons, thermalizes their excess energy and loses carriers only through the radiative processes required by absorptance and emission. Sub-gap photons are not harvested. A favorable gap balances current loss at large gap against voltage loss at small gap.^[ref]

For a step-like absorber,The dark radiative current decreases rapidly with gap, so the qualitative ordering for the supplied absorbers isThe curve rises beneath the diagonal $V=E_g/q$. The deficit $\Delta V=E_g/q-V_{\mathrm{OC}}^{\mathrm{rad}}$ reflects finite-temperature carrier statistics and the entropy associated with absorption and emission, including angular dilution of sunlight. Under ordinary unconcentrated illumination it is of order a few tenths of a volt, with a weaker gap dependence than $V_{\mathrm{OC}}$ itself. In a fixed blackbody-sun model its absolute value grows modestly with increasing gap, while its fraction of $E_g/q$ decreases. Above-gap thermalization is an efficiency loss but is not, by itself, the definition of this voltage deficit.

A measured perovskite device can have a larger deficit from nonradiative recombination and contact losses. The gaps alone do not determine those material-specific losses or a unique numerical voltage: solar spectrum, concentration, cell temperature and optical emission geometry must also be specified.

A solar cell uses the photovoltaic effect to turn photon energy into electrical work. In a semiconductor, above-gap photon absorption generates an electron in the conduction band and an electron hole in the valence band. A p-n junction, together with selective electrical contacts, collects the two carrier species at opposite terminals. Carrier diffusion and the built-in electric field help separate them before electron-hole recombination. Illumination maintains different quasi-Fermi levels for electrons and electron holes; their splitting, divided by $e$, sets the available terminal voltage in an ideal device. The equilibrium built-in potential alone cannot continuously deliver work.

For an ideal junction, the illuminated output current density isHere $J_{\mathrm{sc}}$ is the photogenerated short-circuit current density and $J_0$ the diode saturation current. The useful operating point maximizes $VJ$, rather than either current or voltage separately. With solar-cell fill factor $\mathrm{FF}=P_{\max }/(V_{\mathrm{oc}}{I}_{\mathrm{sc}})$,Series resistance, shunts, incomplete photon absorption and nonradiative recombination reduce the attainable efficiency.

The Shockley-Queisser limit removes these avoidable losses but retains the following physical constraints. There is one semiconductor junction with one band gap; each absorbed above-gap photon yields at most one collected electron-hole pair; carriers thermalize to the cell temperature; and the inverse optical process produces unavoidable radiative recombination. If ${\Phi }_{\odot }(E)$ is the incident photon flux per unit energy, ideal photon absorption givesThe same ability to absorb light requires the junction to emit it. At a forward voltage $V$, the emitted photon population has a chemical potential $eV$; in the ordinary nondegenerate limit the resulting recombination current is the exponential diode term above. Maximizing $VJ$ with this radiative $J_0$, and then choosing $E_g$, gives the limiting efficiency.

A small band gap collects many photons but gives a low voltage and large thermalization losses. A large band gap permits a larger voltage but transmits too much of the incident spectrum. Below-gap photons are lost to transmission, excess photon energy above the gap becomes heat, and radiative emission and its associated entropy loss keep $e{V}_{\mathrm{oc}}$ below $E_g$. The optimum single-junction conversion is roughly thirty percent under ordinary unconcentrated sunlight; the precise ceiling depends on spectrum, cell temperature and optical geometry. The original detailed-balance calculation gave about $30\%$ at $E_g\simeq 1.1\mathrm{eV}$ under its specified assumptions.^[ref] Multiple junctions and optical concentration change the assumptions and consequently change the bound.

The Shockley-Queisser limit is the radiative conversion-efficiency bound for an ideal single-junction solar cell, with one collected electron-electron hole pair per absorbed above-gap photon, carrier thermalization, and radiative recombination required by the reverse optical process. Photons below the band gap are not absorbed, while excess photon energy above it is thermalized. Maximizing the electrical power over the operating electric potential difference and then the band gap gives a ceiling of roughly thirty percent for ordinary unconcentrated sunlight; its precise value depends on the incident spectrum, cell temperature and emission geometry. The original calculation by William Shockley and Hans-Joachim Queisser obtained approximately $30\%$ at $1.1\mathrm{eV}$ for a $6000\mathrm{K}$ blackbody source and a cell at $300\mathrm{K}$.^[ref]