Majher Jackson D, Gray Matthew B, Liu Tianyu, Holzapfel Noah P, Woodward Patrick M
Department of Chemistry and Biochemistry, The Ohio State University, 100 W. 18th Avenue, Columbus, Ohio 43210, United States.
Inorg Chem. 2020 Oct 5;59(19):14478-14485. doi: 10.1021/acs.inorgchem.0c02248. Epub 2020 Sep 22.
Here, we present the synthesis and crystal structure of RbInCl prepared from air stable reagents via a two-step process that proceeds through the intermediate RbInCl·HO. RbInCl crystallizes with the RbYCl structure type (2/), which can be derived from the double perovskite structure by noncooperative tilting of isolated [InCl] octahedra. Despite this lowering of symmetry, the optical properties are similar to the cubic double perovskite CsNaInCl. Partial substitution of In with Sb in RbInCl results in intense cyan-green photoluminescence originating from localized 5s to 5s5p electronic transitions of [SbCl] polyatomic anions. In comparison with the cubic double perovskite phosphor CsNaInCl:Sb, the octahedral tilting distortion increases the electronic isolation of the In/Sb-centered octahedra thus facilitating electron and hole localization on Sb sites, leading to bright photoluminescence. The distorted crystal structure also leads to a larger Stokes shift (1.29 eV) and a corresponding red shift of the emission peak (λ = 522 nm) compared to the more symmetric CsNaInCl:Sb (Stokes shift ≈ 0.94 eV, λ = 445 nm).
在此，我们展示了通过两步法由空气稳定的试剂制备的RbInCl的合成及晶体结构，该两步法通过中间产物RbInCl·HO进行。RbInCl以RbYCl结构类型（2/）结晶，它可通过孤立的[InCl]八面体的非协同倾斜从双钙钛矿结构衍生而来。尽管对称性降低，但光学性质与立方双钙钛矿CsNaInCl相似。在RbInCl中用Sb部分替代In会导致强烈的蓝绿色光致发光，其源于[SbCl]多原子阴离子从局域的5s到5s5p的电子跃迁。与立方双钙钛矿荧光粉CsNaInCl:Sb相比，八面体倾斜畸变增加了以In/Sb为中心的八面体的电子隔离，从而促进电子和空穴在Sb位点的局域化，导致明亮的光致发光。与更对称的CsNaInCl:Sb（斯托克斯位移≈0.94 eV，λ = 445 nm）相比，扭曲的晶体结构还导致更大的斯托克斯位移（1.29 eV）及发射峰相应的红移（λ = 522 nm）。
