Variation of Tetrahedrons and Cations Regulates LIDTs in 3D‐DL Structure MIR‐NLO Crystals

The incomplete understanding of the relationship between structural changes and laser‐induced damage thresholds (LIDTs) in mid‐infrared nonlinear‐optical (MIR‐NLO) crystals considerably restricts the design and synthesis of MIR‐NLO crystals with high LIDTs. This review summarizes the structures of 87 types of three‐dimensional diamond‐like (3D‐DL) structure MIR‐NLO crystals and their LIDTs. Specifically, their LIDTs were measured under specific pump laser conditions (approximately 1.06 µm). These 3D‐DL structure MIR‐NLO crystals were first categorized into three major categories according to their optical band gaps: 1.17 eV ≤ E g ≤ 2.33 eV, 2.34 eV ≤ E g ≤ 3.50 eV, 3.51 eV ≤ E g ≤ 4.66 eV. Within each major category, they were subsequently discussed in the order of structural types (β‐ZnS structure, defect β‐ZnS structure, A‐ions‐substituted β‐ZnS structure, α‐ZnS structure, defect α‐ZnS structure, and A‐ions‐substituted α‐ZnS structure). The final statistical results reveal that the types of tetrahedrons and cations, their arrangement patterns, and dimensional reduction effects across different structures all play a decisive role in the magnitude of LIDT improvement.