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The internal luminescence quantum efficiency ($Q_\mathrm{i}^\mathrm{lum}$)provides an excellent assessment of the optoelectronic quality ofsemiconductors. To determine $Q_\mathrm{i}^\mathrm{lum}$ of perovskite filmsfrom the experimentally accessible external luminescence quantum efficiency($Q_\mathrm{e}^\mathrm{lum}$) it is essential to account for photon recycling,and this requires knowledge of the photon escape probability ($p_\mathrm{e}$).Here, we establish an analysis procedure based on a curve fitting model thataccurately determines $p_\mathrm{e}$ of perovskite films from photoluminescence(PL) spectra measured with a confocal microscope and an integrating spheresetup. We show that scattering-induced outcoupling of initially-trapped PLexplains commonly observed red-shifted and broadened PL spectral shapes andleads to $p_\mathrm{e}$ being more than 10% higher in absolute terms comparedto earlier assumptions. Applying our model to CH$_3$NH$_3$PbI$_3$ films withexceptionally high $Q_\mathrm{e}^\mathrm{lum}$ up to 47.4% sets a realbenchmark for $Q_\mathrm{i}^\mathrm{lum}$ at $78.0 \pm 0.5\%$, revealing thereis beyond a factor of two more scope for reducing non-radiative recombinationthan previously thought.

Revealing the internal luminescence quantum efficiency of perovskite films via accurate quantification of photon recycling