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Improving polarizability is an important strategy for designing high‐performance mid‐infrared (mid‐IR) nonlinear optical (NLO) materials. The substitution of equivalent or aliovalent atoms can manipulate the polarizability by adjusting the symmetry of the polyhedron. Herein, the Li+ and Cd2+ are introduced into the Cu3PS4 as the equivalent and aliovalent dopants for the Cu site. As a result, Li+ can significantly improve the bandgap (Eg) of LixCu3−xPS4 from 2.38 to 2.88 eV, leading to a higher laser‐induced damage threshold (LIDT) of 4.9 times than AgGaS2 (AGS) with a comparable second harmonic generation (SHG) response of AGS (26−45 µm). Interestingly, Cd2+ can improve the SHG response and enlarge the Eg simultaneously. As a result, Cd0.4Cu2.2PS4 has a large SHG response of 10 × AGS at 2050 nm (26−45 µm) and a LIDT of 2.6 × AGS. Theoretical calculations reveal that lattice vacancies induced by Cd2+ significantly boost polarizability compared to LixCu3−xPS4 with no vacancy, leading to a strong NLO response. [ABSTRACT FROM AUTHOR]

Oxychloride phosphors that contain active ions coordinated with both oxygen and chloride ions have garnered significant attention, but the application of oxychloride phosphors is yet limited because of their demanding synthesis condition of vacuum or reducing atmosphere. Herein, we synthesize a new serial oxychlorides of La 9 W 6 O 30 Cl (LWOC) and Er3+/Yb3+, Ho3+/Yb3+, Tm3+/Yb3+ doped LWOC through molten salt shielding method (MSS) in air, which is more efficient compared to the traditional method in vacuum. The compound of LWOC crystallizes in the tetragonal system space group P 4 2 / nmc (No. 137) with cell parameters a = b = 10.0445(1) Å, c = 12.6826(4) Å, V = 1279.57(5) Å3 and Z = 11. The asymmetric unit of LWOC includes three La atoms, one unique W atom, two disordered W atoms with occupancy factors of 0.16(5) and 0.84(5), respectively, one Cl atom and six O atoms. Under the excitation of 980 nm laser, all the Er3+/Yb3+, Ho3+/Yb3+ and Tm3+/Yb3+ co-doped LWOC phosphors have excellent upconversion (UC) luminescence with bright visible light emission. A fluorescence intensity ratio (FIR) type temperature sensor is developed by using LWOC: Er3+, Yb3+ phosphor as sensing media, which has a maximum relative temperature sensitivity (S r) of 0.90 % K−1 at 300 K. • Oxychloride crystals were synthesized in air by molten salt shielding (MSS) method for the first time. • The effect of oxygen defect on crystal color is explained. • An optical temperature sensing device that can work in real environment is prepared. [ABSTRACT FROM AUTHOR]