Hot carrier cooling mechanisms in halide perovskites.

Halide perovskites exhibit unique slow hot-carrier cooling properties capable of unlocking disruptive perovskite photon-electron conversion technologies (e.g., high-efficiency hot-carrier photovoltaics, photo-catalysis, and photodetectors). Presently, the origins and mechanisms of this retardation remain highly contentious (e.g., large polarons, hot-phonon bottleneck, acoustical-optical phonon upconversion etc.). Here, we investigate the fluence-dependent hot-carrier dynamics in methylammonium lead triiodide using transient absorption spectroscopy, and correlate with theoretical modeling and first-principles calculations. At moderate carrier concentrations (around 10 cm), carrier cooling is mediated by polar Fröhlich electron-phonon interactions through zone-center delayed longitudinal optical phonon emissions (i.e., with phonon lifetime τ around 0.6 ± 0.1 ps) induced by the hot-phonon bottleneck. The hot-phonon effect arises from the suppression of the Klemens relaxation pathway essential for longitudinal optical phonon decay. At high carrier concentrations (around 10 cm), Auger heating further reduces the cooling rates. Our study unravels the intricate interplay between the hot-phonon bottleneck and Auger heating effects on carrier cooling, which will resolve the existing controversy.