Giulia Longo

Inorganic–organic hybrid lead halide perovskites are emerging optoelectronic materials for solar cell application. However, the toxicity concerns and poor stability largely hamper their practical applications. For these reasons, the search for “perovskite‐inspired” alternatives, having the same advantages but overcoming the drawbacks of the lead‐based one, has become an important sector in the field. Among the candidates, Bi 3+ and Sb 3+ containing materials are of great interest, due to their electronic structures resembling the Pb 2+ . Bismuth/antimony chalcohalides have been known for a long time as the potential absorber in photovoltaics, even if their performances are still low. Interestingly, pnictogen chalcohalides can be the stepping stone toward numerous quaternary compounds, including some perovskite structures. The understanding of the fundamental properties and the current limitations of both the starting ternary compounds and the final quaternary materials can allow the achievement of improved photovoltaic absorbers, stable, and efficient. In this review, the fundamental properties and device performances of many ternary pnictogen chalcohalides and the derived quaternary compounds are summarized, focusing on the different preparation strategies.