Enhanced UV Nonlinear Optical Properties in Layered Germanous Phosphites through Functional Group Sequential Construction

This study pioneers a novel strategy for synthesizing solar-blind ultraviolet (UV) nonlinear optical (NLO) crystals through functional groups sequential construction, effectively addressing the inherent trade-offs among broad transmittance, enhanced second-harmonic generation (SHG), and optimal birefringence. We have developed two innovative van der Waals layered germanous phosphites: GeHPO₃, the first Ge(II)-based oxide NLO crystal which exhibits a black phosphorus-like structure, and K(GeHPO₃)₂Br, distinguished by its exceptional birefringence and graphene-like structure. Significantly, GeHPO₃ exhibits a remarkable array of NLO properties, including the highest SHG coefficient recorded among all NLO crystals for phase-matching and generating 266 nm coherent light via quadruple frequency conversion. It delivers a potent SHG intensity, surpassing KH₂PO₄ (KDP) by 10.3 times at 1064 nm and β-BaB₂O₄ by 1.3 times at 532 nm, complemented by a distinct UV absorption edge at 211 nm and moderate birefringence of 0.062 at 546 nm. Comprehensive theoretical analysis links these exceptional characteristics to the unique NLO-active GeO₃ ^4- units and the distinctive, highly ordered layered structures. Our findings deliver essential experimental insights into the development of Ge(II)-based optoelectronic materials and present a strategic blueprint for engineering structure-driven functional materials with customized properties.