Pressure-Induced Indirect-Direct Bandgap Crossover and Bandgap Engineering in Ductile Semiconductor Ag3PO4 with Negative Linear Compressibility

摘要: Silver orthophosphate (Ag3PO4) has aroused widespread interest since the discovery of visible-light-driven photocatalysis activity. However, its indirect bandgap nature at ambient becomes an obstacle to improve the photocatalysis efficiency and use in other application fields. In this study, the indirect-to-direct bandgap crossover was found during the pressure-induced phase transition from cubic to trigonal phase in Ag3PO4. The observed bandgap narrowing could be partially retained after pressure was released to ambient conditions, accelerating to efficiently utilize the solar spectrum. Moreover, Ag3PO4 was ductile like metals. Unexpectedly, this ion-conducting and ductile semiconductor photocatalyst further exhibited the negative linear compressibility (NLC) at pressure range of 7.5-25 GPa. This work, combining experimental and theoretical tools, provides an insight into the modulation mechanism of the electronic structure for silver-based semiconductors, and may broaden the applications of Ag3PO4.