Revealing a new doping mechanism of spiro-OMeTAD with tBP participation through the introduction of radicals into HTM  

作　　者：Jindan Zhang Zhenghong Li Chi Li Mengqi Zhu Shicheng Tang Kaicong Cai Zhibin Cheng Chulong Liu Shengchang Xiang Zhangjing Zhang 

机构地区：[1]College of Chemistry and Materials Science,Fujian Key Laboratory of Polymer Materials,Fujian Normal University,Fuzhou 350117,China [2]College of Chemistry and Materials Science,Fujian Key Laboratory of Advanced Materials Oriented Chemical Engineering,Fujian Normal University,Fuzhou 350117,China [3]Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry,Xiamen University,Xiamen 361005,China [4]State Key Laboratory of Structural Chemistry,Fujian Institute of Research on the Structure of Matter,Chinese Academy of Sciences,Fuzhou 350002,China

出　　处：《Chinese Chemical Letters》2025年第3期170-176,共7页中国化学快报(英文版)

基　　金：supported by the National Natural Science Foundation of China(Nos.52001066,21805039,22375045,22373015 and 22271046);the Natural Science Foundation of Fujian Province(No.2023J01500);Young teacher training program of Fujian Normal University(No.SDPY2023013).

摘　　要：Although lots of efforts have been devoted on new less hygroscopic dopants to address problems in hole transport materials(HTM),the long-time post-oxidation and the volatilization of 4-tert-butylpyridine(tBP)are still issues.A new doping mechanism for spiro-OMeTAD by disulfiram(TETD)is revealed in this work.Owing to its disulfide bond,TETD can be activated easily to produce reactive sulfur for the rapid oxidation of spiro-OMeTAD in the absence of oxygen with formation of[spiro-OMeTAD•]+[SC(S)N(C_(2)H_(5))_(2)]^(-).Thus,in this situation,the Li+ion has the opportunity to coordinate tBP and fix each other in HTM film.DFT calculations suggest that the resulting favorable energy(with a△E of−1.29 eV)must come from the mutual interactions among Li^(+),TFSI^(−),and tBP,which is different from the well-known doping process that tBP would not participate in the doping reaction.As a result,the introduction of a new radical into the HTM greatly reduce device performance fluctuations due to the environmental dependence and inhibit tBP volatilizing for enhanced long-term stability.

关 键 词：Perovskite solar cells Hole transport layer DOPANTS Spiro-OMeTAD oxidation Hole mobility conductivity 

分 类 号：O62[理学—有机化学] TM914.4[理学—化学]