Electron-phonon coupling in hybrid lead halide perovskites

Electron-phonon coupling in hybrid lead halide perovskites

26 May 2016 | Adam D. Wright, Carla Verdi, Rebecca L. Milot, Giles E. Eperon, Miguel A. Pérez-Osorio, Henry J. Snaith, Feliciano Giustino, Michael B. Johnston & Laura M. Herz
This study investigates the electron-phonon coupling in hybrid lead halide perovskites, focusing on the temperature dependence of emission line broadening in four common perovskite materials: formamidinium lead iodide (FAPbI₃), formamidinium lead bromide (FAPbBr₃), methylammonium lead iodide (MAPbI₃), and methylammonium lead bromide (MAPbBr₃). The research reveals that the dominant source of electron-phonon coupling near room temperature is the Fröhlich interaction with longitudinal optical (LO) phonons, while scattering from acoustic phonons is negligible. The energies of the LO phonon modes are determined to be 11.5 and 15.3 meV for lead iodide and bromide perovskites, respectively, with Fröhlich coupling constants of approximately 40 and 60 meV. These findings align well with first-principles calculations based on many-body perturbation theory, supporting the use of an electronic band-structure model for describing charge carriers in hybrid perovskites. The study also explores how the composition of perovskites affects electron-phonon coupling. It is found that bromide perovskites exhibit higher Fröhlich coupling than iodide perovskites due to their smaller high-frequency values of the dielectric function. The results demonstrate that electron-phonon coupling in hybrid lead halide perovskites follows a classic band-structure picture for polar inorganic semiconductors, dominated by Fröhlich coupling between charge carriers and LO phonons in the high-temperature regime. The analysis of the temperature-dependent emission linewidth shows that the majority of broadening at room temperature arises from interactions with optical phonons, with acoustic phonon contributions being minor. The findings support the hypothesis that the observed temperature dependence of charge-carrier mobility is not solely attributable to acoustic deformation potential scattering. The study provides a foundation for more quantitative models of charge-carrier mobility and cooling dynamics in photovoltaic devices.This study investigates the electron-phonon coupling in hybrid lead halide perovskites, focusing on the temperature dependence of emission line broadening in four common perovskite materials: formamidinium lead iodide (FAPbI₃), formamidinium lead bromide (FAPbBr₃), methylammonium lead iodide (MAPbI₃), and methylammonium lead bromide (MAPbBr₃). The research reveals that the dominant source of electron-phonon coupling near room temperature is the Fröhlich interaction with longitudinal optical (LO) phonons, while scattering from acoustic phonons is negligible. The energies of the LO phonon modes are determined to be 11.5 and 15.3 meV for lead iodide and bromide perovskites, respectively, with Fröhlich coupling constants of approximately 40 and 60 meV. These findings align well with first-principles calculations based on many-body perturbation theory, supporting the use of an electronic band-structure model for describing charge carriers in hybrid perovskites. The study also explores how the composition of perovskites affects electron-phonon coupling. It is found that bromide perovskites exhibit higher Fröhlich coupling than iodide perovskites due to their smaller high-frequency values of the dielectric function. The results demonstrate that electron-phonon coupling in hybrid lead halide perovskites follows a classic band-structure picture for polar inorganic semiconductors, dominated by Fröhlich coupling between charge carriers and LO phonons in the high-temperature regime. The analysis of the temperature-dependent emission linewidth shows that the majority of broadening at room temperature arises from interactions with optical phonons, with acoustic phonon contributions being minor. The findings support the hypothesis that the observed temperature dependence of charge-carrier mobility is not solely attributable to acoustic deformation potential scattering. The study provides a foundation for more quantitative models of charge-carrier mobility and cooling dynamics in photovoltaic devices.
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