Bright triplet excitons in lead halide perovskites

TL;DR

This paper demonstrates that the lowest exciton in lead halide perovskites is optically active, leading to brighter emission and faster photon rates, challenging the traditional view of dark excitons in inorganic semiconductors.

Contribution

The study reveals that lead halide perovskites have bright lowest excitons due to spin-orbit coupling and the Rashba effect, providing a new understanding of their optical properties.

Findings

Lowest exciton in lead halide perovskites is bright.

Perovskites emit photons 20 to 1,000 times faster than other nanocrystals.

Bright excitons explain anomalously high emission rates.

Abstract

Nanostructured semiconductors emit light from electronic states known as excitons[1]. According to Hund's rules[2], the lowest energy exciton in organic materials should be a poorly emitting triplet state. Analogously, the lowest exciton level in all known inorganic semiconductors is believed to be optically inactive. These 'dark' excitons (into which the system can relax) hinder light-emitting devices based on semiconductor nanostructures. While strategies to diminish their influence have been developed[3-5], no materials have been identified in which the lowest exciton is bright. Here we show that the lowest exciton in quasi-cubic lead halide perovskites is optically active. We first use the effective-mass model and group theory to explore this possibility, which can occur when the strong spin-orbit coupling in the perovskite conduction band is combined with the Rashba effect [6-10]. We then apply our model to CsPbX3 (X=Cl,Br,I) nanocrystals[11], for which we measure size- and composition-dependent fluorescence at the single-nanocrystal level. The bright character of the lowest exciton immediately explains the anomalous photon-emission rates of these materials, which emit 20 and 1,000 times faster[12] than any other semiconductor nanocrystal at room[13-16] and cryogenic[17] temperatures, respectively. The bright exciton is further confirmed by detailed analysis of the fine structure in low-temperature fluorescence spectra. For semiconductor nanocrystals[18], which are already used in lighting[19,20], lasers[21,22], and displays[23], these optically active excitons can lead to materials with brighter emission and enhanced absorption. More generally, our results provide criteria for identifying other semiconductors exhibiting bright excitons with potentially broad implications for optoelectronic devices.