Yang Xin, Wang Xu-Dong, Li Wen-Guang, Huang Yu-Hua, Wang Ling-Bin, Liu Jia-Min, Jiang Long, Kuang Dai-Bin
Key Laboratory of Bioinorganic and Synthetic Chemistry of Ministry of Education, Lehn Institute of Functional Materials, Guangdong Basic Research Center of Excellence for Functional Molecular Engineering, School of Chemistry, Institute of Green Chemistry and Molecular Engineering, Sun Yat-Sen University, Guangzhou 510275, China.
Key Laboratory of Bioinorganic and Synthetic Chemistry of Ministry of Education, Lehn Institute of Functional Materials, Guangdong Basic Research Center of Excellence for Functional Molecular Engineering, School of Chemistry, Institute of Green Chemistry and Molecular Engineering, Sun Yat-Sen University, Guangzhou 510275, China; State Key Laboratory of Optoelectronic Materials and Technologies, Sun Yat-Sen University, Guangzhou 510275, China.
Sci Bull (Beijing). 2024 Dec 30;69(24):3849-3859. doi: 10.1016/j.scib.2024.08.041. Epub 2024 Sep 2.
Low-dimensional lead halide materials have proved to be intrinsically stable semiconductor materials. However, the development of one-dimensional (1D) perovskites or perovskitoids with both robust water stability and high optoelectronic performance still faces significant challenges. Here, we report a new class of 1D (TzBIPY)PbX (X = Cl, Br, I) perovskitoids featuring a π-conjugated diamine cation (TzBIPY = 2,5-di(pyridin-4-yl)thiazolo[5,4-d]thiazole). The TzBIPY cation with delocalized electrons directly contributes to the electronic structure and hence reduces the band gap. Especially, the Br-based material exhibits enhanced carrier separation and transport capacity, benefiting from the improved electronic conjugation together with a type II intramolecular heterojunction between conjugated organic cations and Pb-X octahedra. The (TzBIPY)PbBr photodetector exhibits an impressive photocurrent on/off ratio of 8.1 × 10, which is much superior to the previous three-dimensional (3D) perovskite benchmark. Additionally, the π-conjugated cations serve as dense protective shields for vulnerable Pb-X inorganic lattice against being attacked by water, thus demonstrating exceptional stability even immersed in water for over 3000 h.
低维铅卤化物材料已被证明是本质上稳定的半导体材料。然而，开发具有强大水稳定性和高光电性能的一维（1D）钙钛矿或类钙钛矿仍然面临重大挑战。在此，我们报道了一类新型的1D（TzBIPY）PbX（X = Cl、Br、I）类钙钛矿，其具有一个π共轭二胺阳离子（TzBIPY = 2,5-二（吡啶-4-基）噻唑并[5,4-d]噻唑）。具有离域电子的TzBIPY阳离子直接影响电子结构，从而减小带隙。特别地，基于溴的材料表现出增强的载流子分离和传输能力，这得益于改善的电子共轭以及共轭有机阳离子与Pb-X八面体之间的II型分子内异质结。（TzBIPY）PbBr光电探测器表现出令人印象深刻的8.1×10的光电流开/关比，这远优于先前的三维（3D）钙钛矿基准。此外，π共轭阳离子作为致密的保护屏障，防止易受攻击的Pb-X无机晶格受到水的侵蚀，因此即使浸入水中超过3000小时仍表现出卓越的稳定性。
