Structure‐Prediction‐Oriented Synthesis of Thiophosphates as Promising Infrared Nonlinear Optical Materials

Oriented synthesis of functional materials is a focus of attention in material science. As one of the most important function materials, infrared nonlinear optical materials with large second harmonic generation effects and broad optical bandgap are in urgent need. In this work, directed by the theoretical structure prediction, the first series of non‐centrosymmetric (NCS) alkali‐alkaline earth metal [PS4]‐based thiophosphates LiCaPS4 (Ama2), NaCaPS4 (P21), KCaPS4 (Pna21), RbCaPS4 (Pna21), CsCaPS4 (Pna21) were successfully synthesized. Comprehensive characterizations reveal that ACaPS4 could be regarded as promising IR NLO materials, exhibiting wide bandgap (3.77‐3.86 eV), moderate birefringence (0.027‐0.064 at 1064 nm), high laser‐induced damage threshold (LIDT, ~10 × AGS), and suitable phase‐matching second harmonic generation responses (0.4‐0.6 × AGS). Structure‐properties analyses illustrate that the Ca‐S bonds show non‐ignorable covalent feature, and [PS4] together with [CaSn] units play dominant roles to determine the bandgap and SHG response. This work indicates that Li‐, Na‐ and K‐ analogs may be promising infrared nonlinear optical material candidates, and this is the first successful case of “prediction to synthesis” involving infrared (IR) nonlinear optical (NLO) crystals in the thiophosphate system and may provide a new avenue to the design and oriented synthesis of high‐performance function materials in the future.