Eu P S : The First Rare-Earth Chalcogenophosphate Exhibiting Large Second-Harmonic Generation Response and High Laser-Induced Damage Threshold.

Metal chalcogenophosphates are receiving increasing interest, specifically as promising infrared nonlinear optical (NLO) candidates. Here, a rare-earth chalcogenophosphate Eu P S crystallizing in the monoclinic noncentrosymmetric space group Pn was synthesized using a high-temperature solid-state method. Its structure features isolated [P S ] dimer, and two types of EuS bicapped triangular prisms. Eu P S exhibits a phase-matchable second-harmonic generation (SHG) response ≈0.9×AgGaS @2.1 μm, and high laser-induced damage threshold of 3.4×AgGaS , representing the first rare-earth NLO chalcogenophosphate. The theoretical calculation result suggests that the SHG response is ascribed to the synergetic contribution of [P S ] dimers and EuS bicapped triangular prisms. This work provides not only a promising high-performance infrared NLO material, but also opens the avenue for exploring rare-earth chalcogenophosphates as potential IR NLO materials.