Rational Design of a Rare‐Earth Oxychalcogenide Nd₃[Ga₃O₃S₃][Ge₂O₇] with Superior Infrared Nonlinear Optical Performance

Abstract

Inorganic chalcogenides have been studied as the most promising infrared (IR) nonlinear optical (NLO) candidates for the past decades. However, it is proven difficult to discover high-performance materials that combine the often-incompatible properties of large energy gap (E_g ) and strong second harmonic generation (SHG) response (d_eff ), especially for rare-earth chalcogenides. Herein, centrosymmetric Cs₃ [Sb₃ O₆ ][Ge₂ O₇ ] is selected as a maternal structure and a new noncentrosymmetric rare-earth oxychalcogenide, namely, Nd₃ [Ga₃ O₃ S₃ ][Ge₂ O₇ ], is successfully designed and obtained by the module substitution strategy for the first time. Especially, Nd₃ [Ga₃ O₃ S₃ ][Ge₂ O₇ ] is the first case of breaking the trade-off relationship between wide E_g (>3.5 eV) and large d_eff (>0.5 × AgGaS₂ ) in rare-earth chalcogenide system, and thus displays an outstanding IR-NLO comprehensive performance. Detailed structure analyses and theoretical studies reveal that the NLO effect originates mainly from the cooperation of heteroanionic [GaO₂ S₂ ] and [NdO₂ S₆ ] asymmetric building blocks. This work not only presents an excellent rare-earth IR-NLO candidate, but also plays a crucial role in the rational structure design of other NLO materials in which both large E_g and strong d_eff are pursued.