Controlling the Nonlinear Optical Behavior and Structural Transformation with A‐Site Cation in α‐AZnPO4 (A = Li, K)

Abstract Regulating the crystal structure by A‐site cation substitution is one of the effective methods to explore high‐performance nonlinear optical (NLO) materials. Herein, two non‐centrosymmetric (NCS) compounds, α‐MZnPO 4 (M = Li, K) with short UV absorption edges 221 and 225 nm, are obtained by performing A‐site cation substitution method. It is noteworthy that α‐LiZnPO 4 (α‐LZPO) achieves >10 times second harmonic generation (SHG) response (2.3 × KDP) enhancement compared with that of α‐KZnPO 4 (α‐KZPO) (0.2 × KDP), which is the only case among phosphates with different A‐site cations. By structural comparison, it is found that the A‐site cations play important roles for anion rearrangements, and further the structure features of the two compounds by designing two suppositional crystal models as well as performing other theoretical calculations are analyzed. The study confirms the feasibility to design promising NLO materials with strengthen SHG response and structural stability in orthophosphate system.