Tuning Hot Carrier Cooling Dynamics by Dielectric Confinement in Two-Dimensional Hybrid Perovskite Crystals

by Jun Yin, Partha Maity, Rounak Naphade, Bin Cheng, Jr-Hau He, Osman M. Bakr, Jean-Luc Brédas, Omar F. Mohammed
Year: 2019 DOI: 10.1021/acsnano.9b04085 / ACS Nano, 13, 12621–12629 (2019)


ACS Nano, 13, 12621–12629 (2019)


​Hot carrier (HC) cooling is a critical photophysical process that significantly influences the optoelectronic performance of hybrid perovskite-based devices. The hot carrier extraction at the device interface is very challenging because of its ultrashort lifetime. Here, ultrafast transient reflectance spectroscopy measurements and time-domain ab initio calculations show how the dielectric constant of the organic spacers can control and slow the HC cooling dynamics in single-crystal 2D Ruddlesden–Popper hybrid perovskites. We find that (EA)2PbI4 (EA = HOC2H4NH3+) that correspond to a high dielectric constant organic spacer has a longer HC cooling time compared to that of (AP)2PbI4 (AP = HOC3H6NH3+) and (PEA)2PbI4 (PEA = C6H5C2H4NH3+). The slow HC relaxation process in the former case can be ascribed to a stronger screening of the Coulomb interactions, a small nonradiative internal conversion within the conduction bands, as well as a weak electron–phonon coupling. Our findings provide a strategy to prolong the hot carrier cooling time in low-dimensional hybrid perovskite materials by using organic spacers with reduced dielectric confinement.

DOI: 10.1021/acsnano.9b04085



2D Hybrid Perovskites Dielectric confinement Hot carrier cooling Nonadiabatic molecular dynamics Electron−phonon coupling