Probing the Strain Direction‐Dependent Nonmonotonic Optical Bandgap Modulation of Layered Violet Phosphorus

Recent theoretical investigations have well-predicted strain-induced nonmonotonic optical band gap variations in low-dimensional materials. However, few two-dimensional (2D) materials are experimentally confirmed to exhibit nonmonotonic optical band gap variation under varying strain. Here, a strain-induced nonmonotonic optical bandgap variation in violet phosphorus (VP) nanosheets is observed, as evidenced by photoluminescence spectroscopy, which is reported in a few other 2D materials in knowledge. The optical bandgap variations are characterized to show the modulation rates of 41 and -24 meV/% with compression and tensile strains, respectively. Remarkably, first-principle calculations predict and clarify the nonmonotonic modulation accurately, highlighting its relationship with the strain direction-dependent asymmetric distribution of conduction band minimum wavefunctions, demonstrating that this unique nonmonotonic optical bandgap modulation is determined by the distinctive crystal structure of VP. This work provides a deep insight into the design of 2D materials toward optoelectronic and photoelectrochemical applications via strain engineering.