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 gt;105 cm amp; 8722;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 onemicrosecond 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. Thiswork reveals the critical role of cation disorder in these systems on both absorption characteristics and charge carrier kinetic