Citation: Jindan Zhang, Zhenghong Li, Chi Li, Mengqi Zhu, Shicheng Tang, Kaicong Cai, Zhibin Cheng, Chulong Liu, Shengchang Xiang, Zhangjing Zhang. Revealing a new doping mechanism of spiro-OMeTAD with tBP participation through the introduction of radicals into HTM[J]. Chinese Chemical Letters, ;2025, 36(3): 110046. doi: 10.1016/j.cclet.2024.110046 shu

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

Jindan Zhang ^{a, d, 1,} ,
Zhenghong Li ^{a, 1} ,
Chi Li ^{a, 1} ,
Mengqi Zhu ^a ,
Shicheng Tang ^a ,
Kaicong Cai ^{b, c} ,
Zhibin Cheng ^a ,
Chulong Liu ^a ,
Shengchang Xiang ^a ,
Zhangjing Zhang ^{a, **,}

a.
College of Chemistry and Materials Science, Fujian Key Laboratory of Polymer Materials, Fujian Normal University, Fuzhou 350117, China
b.
College of Chemistry and Materials Science, Fujian Key Laboratory of Advanced Materials Oriented Chemical Engineering, Fujian Normal University, Fuzhou 350117, China
c.
Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry, Xiamen University, Xiamen 361005, China
d.
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, China

^**

zhangjindan@fjnu.edu.cn

zzhang@fjnu.edu.cn

Received Date: 10 December 2023
Revised Date: 24 April 2024
Accepted Date: 24 May 2024
Available Online: 25 May 2024

Figures(5)

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(C₂H₅)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 ΔE 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.
- Perovskite solar cells,
- Hole transport layer,
- Dopants,
- Spiro-OMeTAD oxidation,
- Hole mobility conductivity
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