Advances in lead-free double perovskite nanocrystals, engineering band-gaps and enhancing stability through composition tunability.

In this topical review, we have focused on the recent advances made in the studies of lead-free perovskites in the bulk form and as nanocrystals. Substitution of lead in halide perovskites is essential to overcome the toxicity concerns and improve the relatively low stability of these materials. In lead-free double perovskites the unit cell is doubled and two divalent lead cations are replaced by mono and trivalent cations. The current main challenge with the double perovskite metal halides lies in overcoming their inherently indirect and disallowed optical transitions. In this review, we have discussed the recent discoveries made in the synthesis of these materials and highlighted how nanocrystals can serve as model systems to explore the schemes of cationic exchange, doping and alloying for engineering the electronic structure of double perovskites. In nanocrystals, the quantum confinement effects can modify the electronic structure and the resulting optical transition, thus increasing the absorption cross-section and emission, which are important properties for optoelectronic devices. Lastly, the enlarged surface to volume ratio in the nanocrystals adds a surface energy term that may enhance the stability of the metastable crystallographic phases. We have reviewed how the nanocrystal can provide information on phases that are inherently stable and investigated how the facile exchange reactions can help in achieving material compositions that are impossible to achieve by any other way. Finally, based on our recent synthetic experience, we have emphasized the similarities between lead-based and lead-free perovskite nanocrystals; we hope that our insight along with a summary of recent progress in this fast-growing field will help to expand the interest in lead-free perovskites towards a greener and brighter future.