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

Yin, Jun; Maity, Partha; Naphade, Rounak; Cheng, Bin; He, Jr-Hau; Bakr, Osman M; Brédas, Jean-Luc; Mohammed, Omar F · ACS Nano · 2019

basic_science · Level V

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Abstract

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 <i>ab initio</i> 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)<sub>2</sub>PbI<sub>4</sub> (EA = HOC<sub>2</sub>H<sub>4</sub>NH<sub>3</sub><sup>+</sup>) that correspond to a high dielectric constant organic spacer has a longer HC cooling time compared to that of (AP)<sub>2</sub>PbI<sub>4</sub> (AP = HOC<sub>3</sub>H<sub>6</sub>NH<sub>3</sub><sup>+</sup>) and (PEA)<sub>2</sub>PbI<sub>4</sub> (PEA = C<sub>6</sub>H<sub>5</sub>C<sub>2</sub>H<sub>4</sub>NH<sub>3</sub><sup>+</sup>). 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.