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Structural Modulation from Cu3PS4 to Cu5Zn0.5P2S8 - Single-Site Aliovalent-Substitution-Driven Second-Harmonic-Generation Enhancement

MetadataDetails
Publication Date2021-03-12
JournalInorganic Chemistry
AuthorsBang-Jun Song, Zuju Ma, Bingxuan Li, Xintao Wu, Hua Lin
InstitutionsTan Kah Kee Innovation Laboratory, Yantai University
Citations22

Diamond-like (DL) chalcophosphates, which possess the merits of impressive second-harmonic-generation (SHG) responses, strong laser-induced damage thresholds, and low melting points, are highly desirable for IR nonlinear-optical (NLO) applications. Herein, a new quaternary DL chalcophosphate, Cu<sub>5</sub>Zn<sub>0.5</sub>P<sub>2</sub>S<sub>8</sub>, is successfully discovered, taking known Cu<sub>3</sub>PS<sub>4</sub> as the template via a single-site aliovalent-substitution strategy. It crystallizes in the orthorhombic system with noncentrosymmetric space group <i>Pmn</i>2<sub>1</sub>, and the 3D DL structure is built by corner-shared [(Cu/Zn)S<sub>4</sub>], [CuS<sub>4</sub>], and [PS<sub>4</sub>] tetrahedra. Compared with its parent Cu<sub>3</sub>PS<sub>4</sub>, Cu<sub>5</sub>Zn<sub>0.5</sub>P<sub>2</sub>S<sub>8</sub> exhibits a good phase-matching capability and a sharply enhanced SHG effect (10Cu<sub>3</sub>PS<sub>4</sub>) benefiting from partial Zn substitution. Moreover, the structure-performance relationships have been illustrated by means of theoretical investigations. Such an aliovalent-substitution strategy based on known DL semiconductors might be widely applied for the discovery of high-performance IR NLO crystals.

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