Liu Bin-Wen, Pei Shao-Min, Jiang Xiao-Ming, Guo Guo-Cong
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, P. R. China.
University of Chinese Academy of Sciences, Beijing 100190, People's Republic of China.
Mater Horiz. 2022 May 10;9(5):1513-1517. doi: 10.1039/d2mh00060a.
Magnetic infrared (IR) nonlinear optical (NLO) materials, particularly those containing d-block metals, have attracted considerable attention due to the contributions of d-orbitals to large NLO efficiency. However, the d-d transitions from the d-block metals lead to strong optical absorption and narrow band gap, seriously hindering their practical applications. The structural flexibility of salt-inclusion systems provides a good opportunity for modulating the crystal field of magnetic ions to suppress the d-d transitions but allowing the NLO-active d-s and d-p transitions. These ideas afford a new salt-inclusion sulfide [KCl][MnGaS], which features a rare nanoporous [MnGaS] framework with tunnels of inner diameter of 9.0 Å and possesses a broad transparency (0.39-25.0 μm) and the widest band gap (3.17 eV) among all magnetic IR NLO chalcogenides. Remarkably, it exhibits a strong phase-matchable second-harmonic generation intensity (0.8 × AgGaS at 1910 nm and 3.1 × AgGaS at 1064 nm) and a high laser-induced damage threshold (12.5 × AgGaS at 1064 nm), achieving the important criteria of an advanced IR NLO material.
磁性红外（IR）非线性光学（NLO）材料，特别是那些含有d族金属的材料，由于d轨道对大的NLO效率有贡献而受到了相当大的关注。然而，d族金属的d-d跃迁导致强烈的光吸收和窄带隙，严重阻碍了它们的实际应用。盐包合物体系的结构灵活性为调节磁性离子的晶体场提供了一个很好的机会，以抑制d-d跃迁，但允许NLO活性的d-s和d-p跃迁。这些想法促成了一种新的盐包合硫化物[KCl][MnGaS]，它具有罕见的纳米多孔[MnGaS]框架，其内径为9.0 Å的隧道，并且在所有磁性红外NLO硫族化物中具有宽的透明度（0.39 - 25.0μm）和最宽的带隙（3.17 eV）。值得注意的是，它表现出强烈的可相位匹配的二次谐波产生强度（在1910 nm处为0.8×AgGaS，在1064 nm处为3.1×AgGaS）和高的激光诱导损伤阈值（在1064 nm处为12.5×AgGaS），达到了先进红外NLO材料的重要标准。
