Head-to-Head Linkage Containing Dialkoxybithiophene-Based Polymeric Semiconductors for Polymer Solar Cells with Large Open-Circuit Voltages

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• 作者：Jun Huang ; Yumin Tang ; Ke Gao ; Feng Liu ; Han Guo ; Thomas P. Russell ; Tingbin Yang ; Yongye Liang ; Xing Cheng ; Xugang Guo
• 刊名：Macromolecules
• 出版年：2017
• 出版时间：January 10, 2017
• 年：2017
• 卷：50
• 期：1
• 页码：137-150
• 全文大小：884K
• ISSN：1520-5835

文摘

High degree of polymer backbone planarity is achieved by incorporating intramolecular noncovalent sulfur···oxygen interaction, which also affords good solubility by attaching alkoxy chains at the 3,3′-positions of bithiophene. However, the applications of the resulting polymers are plagued by their high-lying HOMOs due to the strong electron-donating alkoxy chains, resulting in small open-circuit voltages (V_ocs) in polymer solar cells. Herein, a novel head-to-head linkage containing 3,3′-dialkoxy-4,4′-dicyano-2,2′-bithiophene (BTCNOR) is invented. Single-crystal X-ray diffraction shows direct evidence of noncovalent sulfur···oxygen interaction and coplanar backbone of BTCNOR. Very low-lying HOMOs (−5.5 to −5.6 eV) of the corresponding polymers with high degree of backbone planarity and good solubility are achieved by introducing strong electron-withdrawing cyano group onto the dialkoxybithiophene. The cyano offsets the effect of the electron-donating alkoxy chain, rendering the new BTCNOR as a weak donor unit. With this approach, polymer solar cells fabricated from BTCNOR-based polymers deliver very large V_ocs (0.9–1.0 V). By varying the BTCNOR side chains, the highest power conversion efficiency of 7.13% is obtained. Diverse characterization techniques are performed to elucidate the structure–property correlations of the new BTCNOR-based semiconductors. The results demonstrate that incorporating strong electron-withdrawing groups into the highly electron-rich dialkoxybithiophene can lead to improved optoelectrical property. The study offers a promising materials design strategy for high-performance organic electronics.