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通过局部位点对称性的破坏增强CsAgBiCl双钙钛矿中镧系元素的近红外发光

Boosting Near-Infrared Luminescence of Lanthanide in Cs AgBiCl Double Perovskites via Breakdown of the Local Site Symmetry.

作者信息

Pei Yifan, Tu Datao, Li Chenliang, Han Siyuan, Xie Zhi, Wen Fei, Wang Luping, Chen Xueyuan

机构信息

CAS Key Laboratory of Design and Assembly of Functional Nanostructures, Fujian Key Laboratory of Nanomaterials, State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian, 350002, China.

College of Chemistry and Materials Science, Fujian Normal University, Fuzhou, Fujian, 350117, China.

出版信息

Angew Chem Int Ed Engl. 2022 Jul 25;61(30):e202205276. doi: 10.1002/anie.202205276. Epub 2022 Jun 8.

Abstract

Currently, lanthanide (Ln )-doped near-infrared (NIR)-emitting double perovskites (DPs) suffer from low photoluminescence quantum yield (PLQY). Herein, we develop a new class of NIR-emitting DPs based on Ln -doped Cs (Na/Ag)BiCl . Benefiting from the Na -induced breakdown of local site symmetry in the Cs AgBiCl DPs, effective NIR emissions of Ln are realized through Bi sensitization. Specifically, 7.3-fold and 362.9-fold enhanced NIR emissions of Yb and Er are achieved in Cs Ag Na BiCl DPs relative to those in Na-free Cs AgBiCl counterparts, respectively. The optimal absolute NIR PLQYs for Yb and Er in Cs Ag Na BiCl DPs are determined to be 19.0 % and 4.3 %, respectively. Raman spectroscopy and first-principles density functional theory calculations verify the sublattice distortion in Cs (Na/Ag)BiCl DPs via Na doping. These findings provide fundamental insights into the design of efficient NIR-emitting Ln -doped DPs for versatile optoelectronic applications.

摘要

目前,掺杂镧系元素(Ln)的近红外(NIR)发射双钙钛矿(DPs)的光致发光量子产率(PLQY)较低。在此,我们基于掺杂Ln的Cs(Na/Ag)BiCl开发了一类新型的近红外发射双钙钛矿。受益于Na诱导的CsAgBiCl双钙钛矿中局部位点对称性的破坏,通过Bi敏化实现了Ln的有效近红外发射。具体而言,相对于无Na的CsAgBiCl对应物,CsAgNaBiCl双钙钛矿中Yb和Er的近红外发射分别增强了7.3倍和362.9倍。CsAgNaBiCl双钙钛矿中Yb和Er的最佳绝对近红外PLQY分别确定为19.0%和4.3%。拉曼光谱和第一性原理密度泛函理论计算通过Na掺杂验证了Cs(Na/Ag)BiCl双钙钛矿中的亚晶格畸变。这些发现为设计用于多功能光电子应用的高效近红外发射掺杂Ln双钙钛矿提供了基本见解。

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