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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.