Hybrid perovskites have emerged as exceptional semiconductors for optoelectronic applications. Here, we control the cation alloying to push optoelectronic performance through alteration of the charge carrier dynamics in mixed-halide perovskites. In contrast to single-halide perovskites, we find high luminescence yields for photo-excited carrier densities far below solar illumination conditions. Using time-resolved spectroscopy we show that the charge-carrier recombination regime changes from second to first order within the first tens of nanoseconds after excitation. Supported by microscale-mapping of the optical bandgap and elemental composition, electrically-gated transport measurements and first-principles calculations, we demonstrate that spatially-varying energetic disorder in the electronic states causes local charge accumulation, creating p- and n-type photo-doped regions, which unearths a strategy for efficient light emission at low charge-injection in solar cells and LEDs.
Organic-inorganic perovskites such as CH3NH3PbI3 are highly promising materials for a variety of optoelectronic applications, with certified power conversion efficiencies in solar cells already exceeding 21% and promising applications in light-emitting diodes, lasers and photodetectors also emerging. A key enabling property of the perovskites is their high photoluminescence quantum efficiency, suggesting that these materials could in principle approach the thermodynamic device efficiency limits in which all recombination is radiative. However, non-radiative recombination sites are present which vary heterogeneously from grain to grain and limit device performance.
Here, I will present results where we probe the local photophysics of neat CH3NH3PbI3 perovskite films using confocal photoluminescence (PL) measurements and correlate the observations with the local chemistry of the grains using energy-dispersive X-ray spectroscopy (EDX) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). We investigate the connection between grains that are bright or dark in emission and the local Pb:I ratios at the surface and through the grains. We also examine how the photophysics, local chemistry and non-radiative decay pathways change slowly over time under illumination. Our results reveal a “photo-induced cleaning” arising from a redistribution of iodide content in the films, giving strong evidence for photo-induced ion migration. These slow transient effects appear to be related to anomalous hysteresis phenomena observed in full solar cells. I will discuss how immobilizing ions, reducing trap densities and achieving homogenous stoichiometries could suppress hysteresis effects and lead to devices approaching the efficiency limits.
Conference Committee Involvement (4)
Physics, Simulation, and Photonic Engineering of Photovoltaic Devices X
23 January 2021 | San Francisco, California, United States
Physics, Simulation, and Photonic Engineering of Photovoltaic Devices IX
4 February 2020 | San Francisco, California, United States
Physics, Simulation, and Photonic Engineering of Photovoltaic Devices VIII
5 February 2019 | San Francisco, California, United States
Physics, Simulation, and Photonic Engineering of Photovoltaic Devices VII
31 January 2018 | San Francisco, California, United States