Synthesis, Optoelectronic Properties, and Charge Carrier Dynamics of Colloidal Quasi-two-dimensional Cs3Bi2I9 Perovskite Nanosheets

TL;DR

This study synthesizes colloidal quasi-2D Cs3Bi2I9 nanosheets, investigates their optoelectronic properties, and analyzes charge carrier dynamics, revealing an indirect bandgap, phonon-assisted recombination, and stable polaron formation.

Contribution

It presents a novel synthesis of colloidal quasi-2D Cs3Bi2I9 nanosheets and provides detailed insights into their charge carrier dynamics and optoelectronic properties.

Findings

Indirect bandgap of 2.07 eV confirmed by spectroscopy and DFT.

Observation of broad cathodoluminescence indicating phonon- and trap-assisted recombination.

Detection of slow exciton relaxation suggesting stable polaron formation.

Abstract

Non-toxicity and stability make two-dimensional (2D) bismuth halide perovskites better alternatives to lead-based ones for optoelectronic applications and catalysis. In this work, we synthesize sub-micron size colloidal quasi-2D Cs3Bi2I9 perovskite nanosheets and study their generation and relaxation of charge carriers. Steady-state absorption spectroscopy reveals an indirect bandgap of 2.07 eV, which is supported by the density functional theory calculated band structure. The nanosheets do not show detectable photoluminescence at room temperature at band-edge excitation which is attributed to the indirect bandgap. However, cathodoluminescence spanning a broad range from 500 nm to 750 nm with an asymmetric and Stokes-shifted spectrum is observed, indicating the phonon- and trap-assisted recombination. We study the ultrafast charge carrier dynamics in Cs3Bi2I9 nanosheets using a femtosecond transient absorption spectroscopy. The samples are excited with pump energies higher than their bandgap, and the results are interpreted in terms of hot carrier generation (<1 ps), thermalization with local phonons (~1 ps), and cooling (>30 ps). Further, a relatively slow relaxation of excitons (>3 ns) at the band edge suggests the formation of stable polarons which decay nonradiatively by emitting phonons.