Prediction of Novel van der Waals Boron Oxides with Superior Deep-Ultraviolet Nonlinear Optical Performance

Abstract

Deep-ultraviolet nonlinear optical (DUV NLO) materials are attracting increasing attention because of their structural diversity and complexity. Using the two-dimensional (2D) crystal structure prediction method combined with the first-principles calculations, here we propose layered 18-membered-ring (18MR) boron oxide B₂ O₃ polymorphs as high-performance NLO materials. 18MR-B₂ O₃ with the AA and AB stackings are potential DUV NLO materials. The superior performing 18MR-B₂ O₃ ^AB has an unprecedentedly high second harmonic generation coefficient of 1.63 pm V^-1 , the largest among the DUV NLO materials, three times larger than that of the advanced DUV NLO material KBe₂ BO₃ F₂ and comparable to that of β-BaB₂ O₄ . Its unusually large birefringence of 0.196 at 400 nm guarantees the phase-matching wavelength λ_PM to reach this material's extreme absorption edge of ≈154 nm.

Keywords: boron oxides; crystal structure prediction; deep-ultraviolet nonlinear optical material; theoretical calculations; van der Waals.