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Efficiency has several denominators. Specify a steady electric current $I>0$, positive terminal electric potential difference $V_f$, and a simplified narrow emission spectrum with photon energy $E_{\gamma }$. Assume at most one radiative photon per injected Electron and electron hole pair. Let ${\eta }_{\mathrm{inj}}$ be the fraction of the electrical pair-supply rate $I/q$ reaching the active layer, ${\eta }_{\mathrm{rad}}$ the fraction of those pairs recombining radiatively, and ${\eta }_{\mathrm{ext}}$ the fraction of internally emitted photons that escape. Then counting the successive events givesDefine internal quantum efficiency here conditionally on pairs reaching the active layer: ${\eta }_{\mathrm{IQE}}={\eta }_{\mathrm{rad}}$. The internal photon yield per electrical pair is instead ${\eta }_{\mathrm{inj}}{\eta }_{\mathrm{IQE}}$. Stating this convention matters when another definition folds injection into internal quantum efficiency. The external quantum efficiency and wall-plug efficiency areThese are photon-count and energy-flow identities for the declared model. For a broad spectrum, replace $E_{\gamma }$ by the mean escaping photon energy, weighted by photon number, when computing optical power.

A stipulated example chooses $I=20\mathrm{mA}$, $V_f=3.20\mathrm{V}$, $\lambda =450\mathrm{nm}$, ${\eta }_{\mathrm{inj}}=0.90$, ${\eta }_{\mathrm{IQE}}=0.80$ and ${\eta }_{\mathrm{ext}}=0.50$. For every 100 electrical pairs, 90 reach the active layer, 72 emit internally, and 36 photons escape. Thus ${\eta }_{\mathrm{EQE}}=0.36$, not $0.80$. Using $q=1.602176634\times 10^{-19}\mathrm{C}$ givesThe dimensional analysis is transparent: $A/C={\mathrm{s}}^{-1}$, $J/s=\mathrm{W}$, and $\mathrm{CV}=\mathrm{J}$. The optical and electrical efficiencies differ because $E_{\gamma }/q=2.75520\mathrm{V}$ differs from the chosen $V_f$.

The factors suggest different improvements. Better confinement can reduce injection leakage; suppressing nonradiative recombination raises the radiative fraction; improving light extraction efficiency helps already-emitted photons escape. A photon trapped by total internal reflection has already passed the radiative step and can still be lost through absorption. Improving extraction therefore need not change the internal radiative fraction.

Shuji Nakamura's lecture cautions that why indium gallium nitride emits efficiently despite many defects was not completely settled in that account.^[ref]

As an independent consistency check on the 1994 reported values, treating its broad spectrum as monochromatic at the $450\mathrm{nm}$ peak givesThis agrees at the quoted precision with the reported $2.7\%$. Its optical/electrical power ratio is instead $1.5\mathrm{mW}/(20\mathrm{mA}\times 3.6\mathrm{V})=2.0833\%$. The first estimate uses a peak in place of a photon-number-weighted mean, so agreement is a consistency check rather than an exact reanalysis of the measured spectrum.

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.