K^(+)掺杂双钙钛矿Cs_(2)AgInCl_(6)的发光性质  

Luminescence properties of K^(+)doped double perovskite Cs_(2)AgInCl_(6)

作　　者：徐锦锃 高辉 陈国庆[1,2] 王可可 胡金辉 XU Jinzeng;GAO Hui;CHEN Guoqing;WANG Keke;HU Jinhui(School of Science,Jiangnan University,Wuxi,Jiangsu 214122,China;Jiangsu Provincial Research Center of Light Industrial Optoelectronic Engineering and Technology,Wuxi,Jiangsu 214122,China)

机构地区：[1]江南大学理学院,无锡214122 [2]江苏省轻工光电工程技术研究中心,无锡214122

出　　处：《无机化学学报》2024年第2期405-411,共7页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金(No.12275344,62375112)资助。

摘　　要：采用固相球磨法制备了K^(+)掺杂双钙钛矿Cs_(2)AgInCl_(6)纳米材料,该方法无需配体辅助,绿色环保。通过X射线衍射和拉曼光谱对晶体结构进行研究,通过激发光谱、发射光谱和时间分辨光谱对其发光性能进行研究。结果表明,Cs_(2)AgInCl_(6)为立方晶体,属于Fm3m空间群,由于宇称禁戒跃迁,其荧光量子产率(PLQY)低,小于0.1%。低于60%的K^(+)掺杂主要取代Ag^(+)的位置,引起Cs_(2)AgInCl_(6)的晶格膨胀,消除了晶格结构的反演对称性,打破了宇称禁戒跃迁,掺杂后Cs_(2)AgInCl_(6)的光致发光强度显著增强。K^(+)的最佳掺杂比例为40%,Cs_(2)Ag_(0.6)K_(0.4)InCl_(6)材料发射中心波长为640 nm,半高宽为180 nm,平均荧光寿命达到29.2 ns,PLQY达到10.5%。当K^(+)掺杂比例超过60%,K^(+)开始取代Cs+的位置,产物发生相变,出现立方相的Cs_(2-x)K_(1+x+y)AgyInCl_(6)和单斜相的Cs_(2-x)K_(1+x)InCl_(6)产物,这些产物由于强电子-声子耦合,非辐射复合占据主导地位。K^(+)doped double perovskite Cs_(2)AgInCl_(6) nanomaterial was prepared by solid phase ball milling method,which is environmentally friendly without ligands.The crystal structure was studied by X-ray diffraction and Raman spectrum,and the luminescence properties were studied by excitation spectrum,emission spectrum,and timeresolved spectrum.The results show that the Cs_(2)AgInCl_(6) is a cubic crystal,which belongs to Fm3m space group.Due to parity-forbidden transition,the photoluminescence quantum yield(PLQY)is low,less than 0.1%.When K^(+)doping is less than 60%,it mainly replaces Ag^(+),which causes lattice expansion of Cs_(2)AgInCl_(6),eliminates inversion symmetry of lattice structure,breaks parity forbidden transition,and enhances photoluminescence intensity of Cs_(2)AgInCl_(6).The optimal doping ratio was 40%,the center wavelength of Cs_(2)Ag_(0.6)K_(0.4)InCl_(6) was 640 nm,the halfheight width was 180 nm,the average fluorescence lifetime was 29.2 ns and the PLQY reached 10.5%.When the doping ratio of K^(+)exceeds 60%,K+begins to replace the position of Cs^(+),which results in the presence of cubic phase Cs_(2-x)K_(1+x-y)AgyInCl_(6) and monoclinic phase Cs_(2-x)K_(1+x)InCl_(6).These products are dominated by non-radiative recombination due to strong electron-phonon coupling.

关 键 词：双钙钛矿 K^(+)掺杂 宇称禁戒跃迁 球磨法 

分 类 号：O614.24[理学—无机化学] O614.341[理学—化学]