Two Covalent Ultraviolet Nonlinear Optical Crystals

Nonlinear optical (NLO) crystals are the vital components of laser science and technology, as they can convert lasers in common wavelengths into new wavelength bands for ultraviolet (UV), IR, and even terahertz laser output. Known UV NLO crystals mainly focus on crystals containing cations, but covalent crystals have rarely been reported. Here we report two covalent NLO crystals, B₂O₃ I and B₂O₃ II. According to the first‐principles calculations, B₂O₃ I and II have extremely short absorption edges of about 134 nm and 141 nm, large NLO coefficients of d₂₂=1.38 pm/V and d₂₄=0.702 pm/V, as well as sufficient birefringences of 0.037 and 0.031, respectively. Notably, the absorption edges are almost the shortest among NLO crystals. Meanwhile, the NLO coefficients are evidently larger than that of another well‐known covalent NLO crystal α‐SiO₂ and are comparable to those of the commercial UV NLO crystal LiBO₃ with Li⁺ cation. Furthermore, the birefringences are significantly larger than that of α‐SiO₂, which are favorable to the phase matching for both crystals. These results reveal that B₂O₃ I and B₂O₃ II are excellent candidates for UV NLO applications. In‐depth calculations are carried out to reveal the origin of excellent NLO properties. These covalent crystals provide a new direction for the research of UV NLO crystals.