Pressure‐Induced Structural Evolution and Bandgap Optimization of Lead‐Free Halide Double Perovskite (NH(4))(2)SeBr(6)

Lead‐free halide double perovskites (HDPs) are promising candidates for high‐performance solar cells because of their environmentally‐friendly property and chemical stability in air. The power conversion efficiency of HDPs‐based solar cells needs to be further improved before their commercialization in the market. It requires a thoughtful understanding of the correlation between their specific structure and property. Here, the structural and optical properties of an important HDP‐based (NH(4))(2)SeBr(6) are investigated under high pressure. A dramatic piezochromism is found with the increase in pressure. Optical absorption spectra reveal the pressure‐induced red‐shift in bandgap with two distinct anomalies at 6.57 and 11.18 GPa, and the energy tunability reaches 360 meV within 20.02 GPa. Combined with structural characterizations, Raman and infrared spectra, and theoretical calculations using density functional theory, results reveal that, the first anomaly is caused by the formation of a Br‐Br bond among the [SeBr(6)](2−) octahedra, and the latter is attributed to a cubic‐to‐tetragonal phase transition. These results provide a clear correlation between the chemical bonding and optical properties of (NH(4))(2)SeBr(6). It is believed that the proposed strategy paves the way to optimize the optoelectronic properties of HDPs and further stimulate the development of next‐generation clear energy based on HDPs solar cells.