Regioisomeric Polymer Semiconductors Based on Cyano-Functionalized Dialkoxybithiophenes: Structure–Property Relationship and Photovoltaic Performance

Qingqing Bai; Jun Huang; Han Guo; Suxiang Ma; Jie Yang; Bin Liu; Kun Yang; Huiliang Sun; Han Young Woo; Li Niu; Xugang Guo

doi:10.1007/s12209-022-00323-0

Transactions of Tianjin University ›› 2022, Vol. 28 ›› Issue (5) : 385 -397. DOI: 10.1007/s12209-022-00323-0

Research Article

Regioisomeric Polymer Semiconductors Based on Cyano-Functionalized Dialkoxybithiophenes: Structure–Property Relationship and Photovoltaic Performance

Qingqing Bai ¹^,²
, Jun Huang ²
, Han Guo ²
, Suxiang Ma ²
, Jie Yang ²
, Bin Liu ²
, Kun Yang ²
, Huiliang Sun ¹^,²^,³^,^h
, Han Young Woo ⁴^,^j
, Li Niu ¹^,^k
, Xugang Guo ²^,^m

Author information +

¹ Center for Advanced Analytical Science, School of Chemistry and Chemical Engineering, Guangzhou University, 510006, Guangzhou, China

² Department of Materials Science and Engineering, Southern University of Science and Technology, 518055, Shenzhen, China

³ State Key Laboratory of Luminescent Materials and Devices, South China University of Technology, 510640, Guangdong, China

⁴ Department of Chemistry, Korea University, 136-713, Seoul, South Korea

^h Huiliang@gzhu.edu.cn

^j hywoo@korea.ac.kr

^k lniu@gzhu.edu.cn

^m guoxg@sustech.edu.cn

Huiliang Sun received his PhD from Changchun Institute of Applied Chemistry, Chinese Academy of Sciences in 2017. He was a postdoc with Prof. Xugang Guo at SUSTech and Prof. Junwu Chen at South China University of Technology from 2017 to 2019 and a visiting postdoc in Henry Yan Group at Hong Kong University of Science and Technology from 2019 to 2020. Currently, he is a f ull professor at Guangzhou University and visiting professor at SUSTech. His research focuses on the design and synthesis of organic polymer semiconductors and their application in solar cells and thin film transistors.

Han Young Woo received his PhD in Chemistry from the Korea Advanced Institute of Science and Technology (KAIST), Republic of Korea, in 1999. After postdoctoral training at the University of California, Santa Barbara (UCSB) in USA, he joined the Pusan National Universit y as an assistant professor. In 2015, he moved to Korea University and he is currently a professor in the Department of Chemistry, Korea University. His current research studies focus on conjugated polymers and polyelectrolytes for applications in organic optoelectronic devices and fluorescent chemo and bio sensors.

Li Niu is a Professor at Guangzhou Key Laboratory of Sensing Materials andDevices, Center for Advanced Analytical Science, School of Chemistry and Chemical Engineering, Guangzhou University. He received his Ph.D. from Changchun Institute of Applied Chemistry, Chinese Academy of Sciences in 1998. He worked as a p ostdoctor at Abo Akademi University from 1999 to 2003. He worked at Changchun Institute of Applied Chemistry, Chinese Academy of Sciences from 2003 to 2020. He is editorial board member of Analytical Chemistry, Electrochemistry, and Chemosensors. His research focuses on interface electrochemistry, material electrochemistry, electrochemical sensing and analytical instrumentation design, etc.

Xugang Guo joined Mark D. Watson Group at the University of Kentucky in 2006 and obtained his PhD in Chemistry in 2009. From 2009 to 2012, he carried out his postdoctoral training with Profs. Tobin J. Marks and Antonio Facchetti at Northwestern University. Currently, he is a full professor in Department of Materials Science and Engineering at SUSTech. His research interests include synthesis and application of organic and polymeric semiconductors.

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Abstract

Cyano substitution is vital to the molecular design of polymer semiconductors toward highly efficient organic solar cells. However, how regioselectivity impacts relevant optoelectronic properties in cyano-substituted bithiophene systems remain poorly understood. Three regioisomeric cyano-functionalized dialkoxybithiophenes BT_HH, BT_HT, and BT_TT with head-to-head, head-to-tail, and tail-to-tail linkage, respectively, were synthesized and characterized in this work. The resulting polymer semiconductors (PBDTBTs) based on these building blocks were prepared accordingly. The regiochemistry and property relationships of PBDTBTs were investigated in detail. The BT_HH moiety has a higher torsional barrier than the analogs BT_HT and BT_TT, and the regiochemistry of dialkoxybithiophenes leads to fine modulation in the optoelectronic properties of these polymers, such as optical absorption, band gap, and energy levels of frontier molecular orbitals. Organic field-effect transistors based on PBDTBT_HH had higher hole mobility (4.4 × 10⁻³ cm²/(V·s)) than those (ca. 10⁻⁴ cm²/(V·s)) of the other two polymer analogs. Significantly different short-circuit current densities and fill factors were obtained in polymer solar cells using PBDTBTs as the electron donors. Such difference was probed in greater detail by performing space-charge-limited current mobility, thin-film morphology, and transient photocurrent/photovoltage characterizations. The findings highlight that the BT_HH unit is a promising building block for the construction of polymer donors for high-performance organic photovoltaic cells.

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Keywords

Cyano substitution / Regioselectivity / Organic photovoltaic cells / Polymer semiconductors / Mobility

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Qingqing Bai, Jun Huang, Han Guo, Suxiang Ma, Jie Yang, Bin Liu, Kun Yang, Huiliang Sun, Han Young Woo, Li Niu, Xugang Guo. Regioisomeric Polymer Semiconductors Based on Cyano-Functionalized Dialkoxybithiophenes: Structure–Property Relationship and Photovoltaic Performance. Transactions of Tianjin University, 2022, 28(5): 385-397 DOI:10.1007/s12209-022-00323-0

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