Exploring Short-Wavelength Phase-Matching Nonlinear Optical Crystals by Employing KBe₂BO₃F₂ as the Template

Exploration of nonlinear optical (NLO) crystals that are competent in generating short-wavelength ultraviolet (UV, λ ≤ 266 nm, and even deep-UV, λ ≤ 200 nm) coherent light output by direct second harmonic generation (SHG) remains a formidable challenge. Herein, four UV/deep-UV NLO crystals, M₂B₄SO₁₀ (M = K, Rb, and Cs) and Rb₃B₁₁PO₁₉F₃, were successfully synthesized by evolving the KBe₂BO₃F₂ (KBBF) structure into mixed-anionic borosulfate and fluoroborophosphate systems. They display functional [B₄SO₁₀]_∞ or [B₁₁PO₁₉F₃]_∞ KBBF-type layers that are composed of [BO₃], [BO₄], and [SO₄] groups or [BO₃], [BO₄], [BO₃F], and [PO₄] groups, respectively. Experimental characterization and numerical computation results indicate that these crystals possess exceptional NLO performance, including large SHG responses (0.9-1.7 × KDP at 1064 nm and 0.1-0.3 × β-BBO at 532 nm) and adequate birefringence to fulfill the SHG phase-matching (PM) condition at 266 nm. In particular, the shortest type-I PM wavelength (λ_PM) of Rb₃B₁₁PO₁₉F₃ reaches 180 nm, which implies that Rb₃B₁₁PO₁₉F₃ can become a prospective deep-UV NLO crystal. In addition, single crystals of K₂B₄SO₁₀, Rb₂B₄SO₁₀, and Cs₂B₄SO₁₀ are easily obtained by the high-temperature solution approach. This work will facilitate the discovery of short-wavelength PM NLO crystals by using the KBBF structure as the template.