Dark Self-Healing Mediated Negative Photoconductivity of Lead-Free Cs3Bi2Cl9 Perovskite Single Crystal

TL;DR

This study reveals that lead-free Cs3Bi2Cl9 perovskite single crystals exhibit negative photoconductivity and light-induced degradation, with electronic trap states affecting their optoelectronic properties, contrasting with typical positive photoconductivity in similar materials.

Contribution

First demonstration of negative photoconductivity and degradation in lead-free Cs3Bi2Cl9 perovskite single crystals, highlighting unique optoelectronic behavior and trap state formation.

Findings

Negative photoconductivity observed under illumination

Light-activated metastable trap states identified

Comparable or superior detector performance metrics

Abstract

Halide perovskites are recently emerged as one of the frontline optoelectronic materials for device applications and have been extensively studied in past few years. Among these while, lead-based materials were most widely explored, investigation of optical properties of lead-free perovskites is limited. Being optically active, these materials were expected to show light-induced enhanced photoconductivity and the same was reported for lead halide perovskite single crystals. However, on contrary, herein, light-induced degradation of bismuth halide perovskite Cs3Bi2Cl9 single crystals is reported which was evidenced by negative photoconductivity with slow recovery. The femtosecond transient reflectance (fs-TR) spectroscopy studies further revealed these electronic transport properties were due to the formation of light-activated metastable trap states within the perovskite crystal. The figure of merits of Cs3Bi2Cl9 single-crystal detectors such as responsivity (17 mA/W), detectivity (6.23 X 10power 11 Jones) and the ratio of current in dark to light (~7160) was calculated and it is found that they are comparable or higher to reported perovskite single crystals based positive photodetectors. This observation for lead-free perovskite single crystals which were optically active but showed retroactive photocurrent on irradiation remained unique for such materials.