Efficient vertical charge transport in polycrystalline halide perovskites revealed by four-dimensional tracking of charge carriers.

Fast diffusion of charge carriers is crucial for efficient charge collection in perovskite solar cells. While lateral transient photoluminescence microscopies have been popularly used to characterize charge diffusion in perovskites, there exists a discrepancy between low diffusion coefficients measured and near-unity charge collection efficiencies achieved in practical solar cells. Here, we reveal hidden microscopic dynamics in halide perovskites through four-dimensional (directions x, y and z and time t) tracking of charge carriers by characterizing out-of-plane diffusion of charge carriers. By combining this approach with confocal microscopy, we discover a strong local heterogeneity of vertical charge diffusivities in a three-dimensional perovskite film, arising from the difference between intragrain and intergrain diffusion. We visualize that most charge carriers are efficiently transported through the direct intragrain pathways or via indirect detours through nearby areas with fast diffusion. The observed anisotropy and heterogeneity of charge carrier diffusion in perovskites rationalize their high performance as shown in real devices. Our work also foresees that further control of polycrystal growth will enable solar cells with micrometres-thick perovskites to achieve both long optical path length and efficient charge collection simultaneously.

Effects of photon recycling and scattering in high-performance perovskite solar cells.

Efficient external radiation is essential for solar cells to achieve high power conversion efficiency (PCE). The classical limit of 1/2n2 (n, refractive index) for electroluminescence quantum efficiency (ELQE) has recently been approached by perovskite solar cells (PSCs). Photon recycling (PR) and light scattering can provide an opportunity to surpass this limit. We investigate the role of PR and scattering in practical device operation using a radiative PSC with an ELQE (13.7% at 1 sun) that significantly surpasses the classical limit (7.4%). We experimentally analyze the contributions of PR and scattering to this strong radiation. A novel optical model reveals an increase of 39 mV in the voltage of our PSC. This analysis can provide design principles for future PSCs to approach the Shockley-Queisser efficiency limit.