Double Free:A Promising Route toward Moisture-Stable Hypotoxic Hybrid Perovskites  

作　　者：Guang-Ning Liu Ruo-Yu Zhao Rang-Dong Xu Cuncheng Li Guo-Cong Guo 

机构地区：[1]School of Chemistry and Chemical Engineering,University of Jinan,Jinan,Shandong 250022 [2]State Key Laboratory of Structural Chemistry,Fujian Institute of Research on the Structure of Matter,Chinese Academy of Sciences,Fuzhou,Fujian 350002

出　　处：《CCS Chemistry》2022年第4期1273-1283,共11页中国化学会会刊（英文）

基　　金：the financial support by the Natural Science Foundation of Shandong Province(no.ZR2020MB014);the National Natural Science Foundation of China(no.21201080);the Fund of State Key Laboratory of Structural Chemistry;the Jinan Research Leader’s Studio(no.2019GXRC053)for financial support.

摘　　要：The moisture instability and toxicity of lead have hindered the development of lead organometal halide perovskites(Pb-OHPs).Similar to Pb-OHPs,OHPs based on Pb-free elements,including Group VA metals Bi and Sb(denoted as M),exhibit optoelectronic properties due to their isoelectronic configuration and close chemistry of the lone-pair ns^(2) state.However,M-OHPs are mostly based on hydrophilic protonated organic countercations and possess low structural dimensionalities,which affect the moisture stability and disrupt continuous carrier transport,respectively.Herein,we demonstrate a“double-free”strategy to realize the rational synthesis of moisture-stable hypotoxic hybrid perovskites.A hydrogen-bond-free alkylated countercation was assembled with Pb-free OHP bearing an extended structure in one molecule.As a proof of concept,two double-free M-OHPs are synthesized,which show greatly improved moisture and photostability compared to their corresponding hydrogen-bond OHPs and the extensively studied MA_(3)M_(2)X_(9)(MA=CH_(3)NH_(3)^(+)).The photoconduction behaviors of both double-free OHPs display short rise and decay recovery time and exhibit excellent photocurrent reproducibility.Importantly,(1-methyl-4-phenylpyridin-1-ium)BiI_(4)(Me4ppi-BiI_(4))displays a comparable switching on/off ratio with MA_(3)Bi_(2)I_(9),and can endure 75% relative humidity(RH)for at least 243 days.The photophysical property measurements and theoretical calculations show that this remarkable photoconversion performance results from the relatively low exciton binding energy and greatly improved carrier mobility and concentration.

关 键 词：bismuth halide crystal structure hydrogen-bond-free inorganic-organic hybrid PHOTOCONDUCTOR 

分 类 号：O62[理学—有机化学]