Highly Distorted [HgS4] Motif-Driven Structural Symmetry Degradation and Strengthened Second-Harmonic Generation Response in the Defect Diamond-Like Chalcogenide Hg3P2S8

• Published in: ACS applied materials & interfaces 2021-08, Vol.13 (31), p.37331-37338
• Main Authors: Xing, Wenhao, Liang, Fei, Tang, Chunlan, Uykur, Ece, Lin, Zheshuai, Yao, Jiyong, Yin, Wenlong, Kang, Bin
• Format: Article
• Language: English
• Subjects: Functional Inorganic Materials and Devices
• ISSN: 1944-8244; 1944-8252
• DOI: 10.1021/acsami.1c06933

Chalcogenides with diamond-like (DL) structures are a treasury of infrared nonlinear optical (NLO) materials. Here, a ternary Hg-based chalcogenide with a defect DL structure, Hg3P2S8, is synthesized by solid-state reaction. Driven by the highly distorted [HgS4] tetrahedra, this compound displays an interesting structural symmetry degradation from tetragonal to orthorhombic compared with its analogue Zn3P2S8. Meanwhile, the overall performances of Hg3P2S8 are quite remarkable, including a very strong phase-matchable second-harmonic generation (SHG) response (4.2 × AgGaS2), large band gap (2.77 eV), wide IR transparent range (0.45–16.7 μm), and high laser-induced damage threshold (4 × AGS). Furthermore, the theoretical analysis and local dipole moment calculations elucidate that the highly distorted [HgS4] tetrahedra contribute a lot to the enhancement of the SHG effect. This discovery will motivate the exploration of other DL Hg-based chalcogenides serving as high-performing mid-IR NLO materials.