Photovoltaic devices based on metal halide perovskites are rapidly improving in efficiency. Once the Shockley–Queisser limit is reached, charge-carrier extraction will be limited only by radiative bimolecular recombination of electrons with holes. Yet, this fundamental process, and its link with material stoichiometry, is still poorly understood. Here we show that bimolecular charge-carrier recombination in methylammonium lead triiodide perovskite can be fully explained as the inverse process of absorption. By correctly accounting for contributions to the absorption from excitons and electron-hole continuum states, we are able to utilise the van Roosbroeck–Shockley relation to determine bimolecular recombination rate constants from absorption spectra. We show that the sharpening of photon, electron and hole distribution functions significantly enhances bimolecular charge recombination as the temperature is lowered, mirroring trends in transient spectroscopy. Our findings provide vital understanding of band-to-band recombination processes in this hybrid perovskite, which comprise direct, fully radiative transitions between thermalized electrons and holes.

An understanding of charge-carrier recombination processes is essential for the development of hybrid metal halide perovskites for photovoltaic applications. We show that typical measurements of the radiative bimolecular recombination constant in CHNHPbI are strongly affected by photon reabsorption that masks a much larger intrinsic bimolecular recombination rate constant. By investigating a set of films whose thickness varies between 50 and 533 nm, we find that the bimolecular charge recombination rate appears to slow by an order of magnitude as the film thickness increases. However, by using a dynamical model that accounts for photon reabsorption and charge-carrier diffusion we determine that a single intrinsic bimolecular recombination coefficient of value 6.8 × 10 cms is common to all samples irrespective of film thickness. Hence, we postulate that the wide range of literature values reported for such coefficients is partly to blame on differences in photon out-coupling between samples with crystal grains or mesoporous scaffolds of different sizes influencing light scattering, whereas thinner films or index-matched surrounding layers can reduce the possibility for photon reabsorption. We discuss the critical role of photon confinement on free charge-carrier retention in thin photovoltaic layers and highlight an approach to assess the success of such schemes from transient spectroscopic measurement.

The addition of large hydrophobic cations to lead halide perovskites has significantly enhanced the environmental stability of photovoltaic cells based on these materials. However, the associated formation of two-dimensional structures inside the material can lead to dielectric confinement, higher exciton binding energies, wider bandgaps and limited charge-carrier mobilities. Here we show that such effects are not detrimental to the charge transport for carefully processed films comprising a selfassembled thin layer of quasi-two-dimensional (2D) perovskite interfaced with a 3D MAPbI 3 perovskite layer. We apply a combination of time-resolved photoluminescence and photoconductivity spectroscopy to reveal the charge-carrier recombination and transport through the film profile, when either the quasi-2D or the 3D layers are selectively excited. Through modeling of the recorded dynamics, we demonstrate that while the charge-carrier mobility is lower within the quasi-2D region, charge-carrier diffusion to the 3D phase leads to a rapid recovery in photoconductivity even when the quasi-2D region is initially photoexcited. In addition, the blue-shifted emission originating from quasi-2D regions overlaps significantly with the absorption spectrum of the 3D perovskite, allowing for highly effective "heterogeneous photon recycling". We show that this combination fully compensates for the adverse effects of electronic confinement, yielding quasi-2D perovskites with highly efficient charge transporting properties.

Semiconducting polycrystalline thin films are cheap to produce and can be deposited on flexible substrates, yet high-performance electronic devices usually utilize single-crystal semiconductors, owing to their superior charge-carrier mobilities and longer diffusion lengths. Here we show that the electrical performance of polycrystalline films of metal-halide perovskites (MHPs) approaches that of single crystals at room temperature. Combining temperature-dependent terahertz conductivity measurements and ab initio calculations we uncover a complete picture of the origins of charge-carrier scattering in single crystals and polycrystalline films of CH 3 NH 3 PbI 3 . We show that Fröhlich scattering of charge carriers with multiple phonon modes is the dominant mechanism limiting mobility, with grain-boundary scattering further reducing mobility in polycrystalline films. We reconcile the large discrepancy in charge-carrier diffusion lengths between single crystals and films by considering photon reabsorption. Thus, polycrystalline films of MHPs offer great promise for devices beyond solar cells, including light-emitting diodes and modulators.

The production of highly efficient single‐ and multijunction metal halide perovskite (MHP) solar cells requires careful optimization of the optical and electrical properties of these devices. Here, precise control of CH3NH3PbI3 perovskite layers is demonstrated in solar cell devices through the use of dual source coevaporation. Light absorption and device performance are tracked for incorporated MHP films ranging from ≈67 nm to ≈1.4 µm thickness and transfer‐matrix optical modeling is utilized to quantify optical losses that arise from interference effects. Based on these results, a device with 19.2% steady‐state power conversion efficiency is achieved through incorporation of a perovskite film with near‐optimum predicted thickness (≈709 nm). Significantly, a clear signature of photon reabsorption is observed in perovskite films that have the same thickness (≈709 nm) as in the optimized device. Despite the positive effect of photon recycling associated with photon reabsorption, devices with thicker (>750 nm) MHP layers exhibit poor performance owing to competing nonradiative charge recombination in a “dead‐volume” of MHP. Overall, these findings demonstrate the need for fine control over MHP thickness to achieve the highest efficiency cells, and accurate consideration of photon reabsorption, optical interference, and charge transport properties.