School of Chemistry and Chemical Engineering, Yangzhou University, 180 Siwangting Road, Yangzhou, Jiangsu, 250002, China.
Small. 2023 Feb;19(8):e2206910. doi: 10.1002/smll.202206910. Epub 2022 Dec 11.
Rare-earth (RE) chalcogenides have been extensively studied as infrared nonlinear optical (NLO) materials because of their nice integrated performances; however, very few RE chalcophosphates are involved for this topic. Here, three quaternary RE selenophosphates, KSmP Se (1), KGdP Se (2), and KTbP Se (3), are profoundly studied for their NLO potentials. Their noncentrosymmetric P21 structures feature RESe8-bicapped trigonal prisms and ethane-like [P Se ] - dimers built {[REP Se ]-}∞ layers. As the first studied NLO-active RE selenophosphates, 1-3 exhibit second harmonic generation (SHG)responses ≈0.34-1.08 × AgGaS at 2.10 µm and laser-induced damage thresholds (LIDTs) ≈1.43-4.33 × AgGaS , and they all show phase-matchable behaviors, indicating their wonderful balanced NLO properties. Theoretical calculations demonstrate that the synergistic effect between RESe and P Se units makes the major contribution to the SHG responses.
稀土（RE）硫属化物因其良好的综合性能而被广泛研究作为红外非线性光学（NLO）材料；然而，涉及这个主题的 RE 磷属化物却很少。在此，我们深入研究了三种四元 RE 硒磷酸盐，KSmP Se（1）、KGdP Se（2）和 KTbP Se（3），以研究它们的 NLO 潜力。它们的非中心对称 P21 结构具有 RESe8-双帽三角棱柱和类似乙烷的[P Se ]-二聚体构建的{[REP Se ]-}∞层。作为首次研究的 NLO 活性 RE 硒磷酸盐，1-3 在 2.10µm 处表现出 ≈0.34-1.08×AgGaS 的二次谐波产生（SHG）响应和 ≈1.43-4.33×AgGaS 的激光诱导破坏阈值（LIDT），它们都表现出相匹配的行为，表明它们具有出色的平衡 NLO 性质。理论计算表明，RESe 和 P Se 单元之间的协同效应是产生 SHG 响应的主要原因。
