Strong absorption and ultrafast localisation in NaBiS2 nanocrystals with slow charge-carrier recombination

I-V-VI2 ternary chalcogenides are gaining attention as earth-abundant, nontoxic, and air-stable absorbers for photovoltaic applications. However, the semiconductors explored thus far have slowly-rising absorption onsets, and their charge-carrier transport is not well understood yet. Herein, we investigate cation-disordered NaBiS2 nanocrystals, which have a steep absorption onset, with absorption coefficients reaching >10(5) cm(-1) just above its pseudo-direct bandgap of 1.4 eV. Surprisingly, we also observe an ultrafast (picosecond-time scale) photoconductivity decay and long-lived charge-carrier population persisting for over one microsecond in NaBiS2 nanocrystals. These unusual features arise because of the localised, non-bonding S p character of the upper valence band, which leads to a high density of electronic states at the band edges, ultrafast localisation of spatially-separated electrons and holes, as well as the slow decay of trapped holes. This work reveals the critical role of cation disorder in these systems on both absorption characteristics and charge-carrier kinetics. Ternary chalcogenides are gaining interest as nontoxic, stable solar absorbers. Here, the authors investigate NaBiS2, finding cation disorder to be a critical parameter that enables its high absorption strength and unusual charge-carrier kinetics.

Automated summary

Ternary chalcogenides such as NaBiS2 are promising materials for solar energy applications. This study reveals the importance of cation disorder in achieving high absorption strength and unusual charge-carrier kinetics in NaBiS2 nanocrystals.