Linear unit BN2: a novel birefringence-enhanced fundamental module with sp orbital hybridization

Abstract

Inorganic planar π-conjugated groups are advantageous to generate large birefringence in optical functional materials, and many excellent materials contain CO₃, BO₃ or B₃O₆, such as CaCO₃, α/β-BaB₂O₄ (α/β-BBO), and KBe₂BO₃F₂ (KBBF). In view of their microscopic structures, the common characteristics are the planar structures, which are regarded as birefringence-enhanced fundamental modules (FMs). Nowadays, exploring novel birefringence-enhanced FMs is becoming a burning issue. Herein, we investigated the birefringence-enhanced FMs in B–N systems and found that the BN₂ linear unit could produce great birefringence. Through the investigation based on the Inorganic Crystal Structure Database, some compounds with the BN₂ linear group were screened out with the formulas A₃BN₂ (A = Li, Na), A₃BN₃ (A = Mg, Ca), and Ba₃(BN₂)₂. Particularly, Ca₃(BN₂)N exhibits a great birefringence of about 0.411 at 1064 nm, which is 3.5, 2.5 and 2.0 times those of the most commercially used birefringent crystals α-BaB₂O₄ (Δn = 0.116 at 1064 nm), CaCO₃ (Δn = 0.164 at 1064 nm) and YVO₄ (Δn = 0.208 at 1064 nm), respectively. To find the origins of the optical properties of compounds with the BN₂ linear group, the first-principles, REDA and polarizability anisotropy analysis methods were used. Owing to the structural arrangement and the polarization anisotropy of the BN₂ linear group, it can influence the birefringence significantly. This work will provide a general way for exploring birefringence-enhanced FMs in B–N compounds.