Revealing unusual bandgap shifts with temperature and bandgap renormalization effect in phase-stabilized metal halide perovskites

Hybrid organic-inorganic metal halide perovskites are emerging materials in photovoltaics, whose bandgap is one of the most crucial parameters governing their light harvesting performance. Here we present temperature and photocarrier density dependence of the bandgap in two phase-stabilized perovskite thin films (MA0.3FA0.7PbI3 and MA0.3FA0.7Pb0.5Sn0.5I3) using photoluminescence and absorption spectroscopy. Contrasting bandgap shifts with temperature are observed between the two perovskites. By utilizing X-ray diffraction and in situ high pressure photoluminescence spectroscopy, we show that the thermal expansion plays only a minor role on the large bandgap blueshift due to the enhanced structural stability in our samples. Our first-principles calculations further demonstrate the significant impact of thermally induced lattice distortions on the bandgap widening and reveal that the anomalous trends are caused by the competition between the static and dynamic distortions. Additionally, both the bandgap renormalization and band filling effects are directly observed for the first time in fluence-dependent photoluminescence measurements and are employed to estimate the exciton effective mass. Our results provide new insights into the basic understanding of thermal and charge-accumulation effects on the band structure of hybrid perovskites.