Optimizing the Nonlinear Optical Performance of an A-N-M-Q (A: Alkali Metal; N: d¹⁰ Metal; M: Main Group Metal; Q: Chalcogen) System

Exploring new infrared nonlinear optical (IR NLO) materials with superior overall properties is scientifically and technically important. However, large second-order harmonic generation (SHG) efficiencies and high laser-induced damage thresholds (LIDT) are incompatible, which makes realizing this goal a challenge. The IR NLO performance of an A-NIIB-MIIIA-Q (Q: chalcogen) system was optimized by simultaneously modulating A/(M + N) and M/N ratios (A: alkali metal; N, M: tetra-coordinated metals), and SHG–LIDT balance was achieved. Three new sulfides, KCd3Ga5S11 (1), RbCd4Ga3S9 (2), and Cs2Cd2Ga8S15 (3), containing the same CdS4 and GaS4 but with different A/(Ga + Cd) and Ga/Cd ratios were obtained. Among these compounds, compound 3 exhibits both the largest SHG efficiency (0.5 × AgGaS2) and LIDT (35 × AgGaS2), which can be ascribed to the Ga/Cd modulation for enhancing the NLO functional motif distortions and SHG efficiency as well as the A/(Ga + Cd) modulation for enlarging the band gap and LIDT. Remarkably, compound 3 is the first phase-matchable IR NLO material in the A-NIIB-MIIIA-Q family. This article proposes a novel avenue to explore infrared nonlinear materials with superior comprehensive properties by modulating the A/(M + N) and M/N ratios.