Temperature Dependence of the Energy Levels of Methylammonium Lead Iodide Perovskite from First-Principles.

Title Temperature Dependence of the Energy Levels of Methylammonium Lead Iodide Perovskite from First-Principles.
Authors W.A. Saidi; S. Poncé; B. Monserrat
Journal J Phys Chem Lett
DOI 10.1021/acs.jpclett.6b02560
Abstract

Environmental effects and intrinsic energy-loss processes lead to fluctuations in the operational temperature of solar cells, which can profoundly influence their power conversion efficiency. Here we determine from first-principles the effects of temperature on the band gap and band edges of the hybrid pervoskite CH3NH3PbI3 by accounting for electron-phonon coupling and thermal expansion. From 290 to 380 K, the computed band gap change of 40 meV coincides with the experimental change of 30-40 meV. The calculation of electron-phonon coupling in CH3NH3PbI3 is particularly intricate as the commonly used Allen-Heine-Cardona theory overestimates the band gap change with temperature, and excellent agreement with experiment is only obtained when including high-order terms in the electron-phonon interaction. We also find that spin-orbit coupling enhances the electron-phonon coupling strength but that the inclusion of nonlocal correlations using hybrid functionals has little effect. We reach similar conclusions in the metal-halide perovskite CsPbI3. Our results unambiguously confirm for the first time the importance of high-order terms in the electron-phonon coupling by direct comparison with experiment.

Citation W.A. Saidi; S. Poncé; B. Monserrat.Temperature Dependence of the Energy Levels of Methylammonium Lead Iodide Perovskite from First-Principles.. J Phys Chem Lett. 2016;7(24):52475252. doi:10.1021/acs.jpclett.6b02560

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