中国科学院新疆理化技术研究所潘世烈团队报道了基于结构预测的硫代磷酸盐红外非线性光学材料合成研究。相关研究成果发表在2024年6月3日出版的《德国应用化学》。

功能材料的定向合成是材料科学研究的一个热点。作为最重要的功能材料之一，迫切需要具有大二次谐波产生效应和宽光学带隙的红外非线性光学材料。

该文中，在理论结构预测的指导下，成功合成了非中心对称（NCS）碱-碱土金属[PS₄]基硫代磷酸盐LiCaPS₄ (Ama2)、NaCaPS₄ (P21)、KCaPS₄ (Pna21)、RbCaPS₄ (Pna21)、CsCaPS₄ (Pna21)。综合表征表明，ACaPS⁴具有宽频带隙（3.77-3.86eV）、中等双折射率（在1064nm处为0.027-0.064）、高激光诱导损伤阈值（LIDT，~10×AGS）和合适的相位匹配二次谐波产生响应（0.4-0.6×AGS）。结构性质分析表明，Ca-S键表现出不可忽略的共价特征，[PS₄]和[CaSn]单元在决定带隙和SHG响应方面起主导作用。

这项工作表明，Li、Na和K类似物可能是很有前途的红外非线性光学材料候选者，这是硫磷酸盐系统中涉及红外（IR）非线性光学（NLO）晶体的“预测合成”的第一个成功案例，可能为未来高性能功能材料的设计和定向合成提供新的途径。

附：英文原文

Title: Structure-Prediction-Oriented Synthesis of Thiophosphates as Promising Infrared Nonlinear Optical Materials

Author: Yi Huang, Dongdong Chu, Yong Zhang, Congwei Xie, Guangmao Li, Shilie Pan

Issue&Volume: 2024-06-03

Abstract: Oriented synthesis of functional materials is a focus of attention in material science. As one of the most important function materials, infrared nonlinear optical materials with large second harmonic generation effects and broad optical bandgap are in urgent need. In this work, directed by the theoretical structure prediction, the first series of non-centrosymmetric (NCS) alkali-alkaline earth metal [PS4]-based thiophosphates LiCaPS4 (Ama2), NaCaPS4 (P21), KCaPS4 (Pna21), RbCaPS4 (Pna21), CsCaPS4 (Pna21) were successfully synthesized. Comprehensive characterizations reveal that ACaPS4 could be regarded as promising IR NLO materials, exhibiting wide bandgap (3.77-3.86 eV), moderate birefringence (0.027-0.064 at 1064 nm), high laser-induced damage threshold (LIDT, ~10 × AGS), and suitable phase-matching second harmonic generation responses (0.4-0.6 × AGS). Structure-properties analyses illustrate that the Ca-S bonds show non-ignorable covalent feature, and [PS4] together with [CaSn] units play dominant roles to determine the bandgap and SHG response. This work indicates that Li-, Na- and K- analogs may be promising infrared nonlinear optical material candidates, and this is the first successful case of “prediction to synthesis” involving infrared (IR) nonlinear optical (NLO) crystals in the thiophosphate system and may provide a new avenue to the design and oriented synthesis of high-performance function materials in the future.

DOI: 10.1002/anie.202406576

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202406576