Birefringent materials play indispensable roles in modulating the polarization of light and are vital in the laser science and technology. Currently, the design of birefringent materials operating in the deep-ultraviolet region (DUV, λ ≤200 nm) is still a great challenge. In this work, we developed a new DUV birefringent crystal LiBO₂ based on [BO₂]^∞ infinite chains in the Li-B-O system, which simultaneously achieves the shortest UV cutoff edge (164 nm) and the largest birefringence (≥0.168 at 266 nm) among all the reported borate-based DUV birefringent materials. Single crystals of LiBO₂ with dimensions up to Ø55 × 34 mm³ were grown by the Czochralski method, providing access to large-sized single crystal with low cost. Moreover, it has a high laser damage threshold and stable physicochemical properties. These outstanding characters unambiguously support that LiBO₂ can be an excellent birefringent material for DUV application.

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.