(NH₄)₃B₁₁PO₁₉F₃: a deep-UV nonlinear optical crystal with unique [B₅PO₁₀F]_∞ layers

Deep-ultraviolet (DUV) nonlinear optical (NLO) crystals that can extend the output range of coherent light below 200 nm are pivotal materials for solid-state lasers. To date, KBe₂BO₃F₂ (KBBF) is the only usable crystal that can generate DUV coherent light by direct second harmonic generation (SHG), but the layered growth habit and toxic ingredients limit its application. Herein, we report a new fluoroborophosphate, (NH₄)₃B₁₁PO₁₉F₃ (ABPF), containing four different functional units: [BO₃], [BO₄], [BO₃F] and [PO₄]. ABPF exhibits a KBBF-like structure while eliminating the limitations of KBBF crystal. The unique [B₅PO₁₀F]_∞ layers enhance ABPF's performance; for example, it has a large SHG response (1.2 × KDP) and a sufficient birefringence (0.088 at 1064 nm) that enables the shortest phase-matching wavelength to reach the DUV region. Meanwhile, the introduction of strong B-O-P covalent bonds decreases the layered growth habit. These findings will enrich the structural chemistry of fluoroborophosphate and contribute to the discovery of more excellent DUV NLO crystals.