Achieving Short‐Wavelength Phase‐Matching Second Harmonic Generation in Boron‐Rich Borosulfate with Planar [BO3] Units

Abstract Ultraviolet (UV) nonlinear optical (NLO) crystals which can produce short‐wavelength lasers via a direct second harmonic generation (SHG) process are of great importance in modern laser technology. Currently, the exploration of UV NLO crystals in borosulfates is nearly stagnant since the non‐phase matching (PM) property lies on the small birefringence induced by the intrinsically small optical anisotropy of the tetrahedral groups. Herein, for the first time, the planar [BO 3 ] units were introduced into borosulfates leading to a boron‐rich borosulfate (NH 4 ) 2 B 4 SO 10 with unprecedented [B 4 SO 10 ] ∞ layers and evidently enhanced birefringence. To the best of our knowledge, it achieves the shortest SHG PM wavelength of 252 nm in all reported borosulfates with deep UV cutoff edge (184 nm), large SHG response (1.1×KDP at 1064 nm and 0.15×β‐BBO at 532 nm) and large birefringence (0.053 at 1064 nm) and is easy to grow single crystals via simple chemical vapor deposition method. These results confirm the feasibility of utilizing planar [BO 3 ] units to optimize birefringence of borosulfates, and also open up broad prospects for UV NLO crystals in boron‐rich borosulfates.