AZn4Ga5Se12 (A = K, Rb, or Cs): Infrared Nonlinear Optical Materials with Simultaneous Large Second Harmonic Generation Responses and High Laser-Induced Damage Thresholds

Despite the fact that nonlinear optical (NLO) crystals such as AgGaS₂ and AgGaSe₂ have been widely used in the infrared (IR) range due to their large second harmonic generation (SHG) coefficients and wide range of IR transparency windows, the small laser-induced damage threshold (LIDT) remains a great issue hindering their high-power applications. Herein, three noncentrosymmetric (NCS) chalcogenides AZn₄Ga₅Se₁₂ (A = K, Rb, or Cs) are successfully obtained through an appropriate flux method after the extensive design and synthesis of the A/Zn/Ga/Q system. Single-crystal X-ray diffraction data demonstrate that they adopt trigonal space group R3 (No. 146) with three-dimensional diamond-like frameworks composed of [M₉Se₂₄] layers (M = Zn or Ga) stacking in the same direction and filled by charge-balancing A⁺ cations. Noticeably, they all exhibit strong powder SHG responses (2.8-3.7 × AgGaS₂) and amazing LIDTs (19.2-23.4 × AgGaS₂). In addition, theoretical calculations are performed to further determine the relationship between NCS structures and NLO properties. This work provides effective solutions for overcoming the trade-off between strong SHG and high LIDT in IR-NLO materials.