Effect of Fluorine Substitution on Photovoltaic Properties of Benzothiadiazole鈥揅arbazole Alternating Copolymers

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• 作者：Tomokazu Umeyama ; Yusuke Watanabe ; Evgenia Douvogianni ; Hiroshi Imahori
• 刊名：Journal of Physical Chemistry C
• 出版年：2013
• 出版时间：October 17, 2013
• 年：2013
• 卷：117
• 期：41
• 页码：21148-21157
• 全文大小：452K
• 年卷期：v.117,no.41(October 17, 2013)
• ISSN：1932-7455

文摘

To investigate the effect of fluorine substitution on molecular and film structures, optical, electrochemical, and photovoltaic properties of a moderate bandgap polymer, poly(2,7-carbazole-alt-dithienylbenzothiadiazole) (PCDTBT) with deep HOMO energy level, a fluorinated analogue of PCDTBT (i.e., PCDTBT-F) has been developed for the first time by replacing two hydrogen atoms on benzothiadiazole (BT) units with two fluorine atoms. An analogous polymer, PCBBBT-F with additional hexylthiophenes between the thiophene and carbazole of PCDTBT-F, has also been prepared to overcome the poor solubility of PCDTBT-F. The PCBBBT-F film showed wide absorption bands in UV and visible regions with an optical bandgap of 1.82 eV that is smaller than that of PCDTBT (1.89 eV), whereas the film of PCDTBT-F exhibited blue-shifted absorption with a bandgap of 1.96 eV due to the low molecular weight arising from the deficient solubility. The HOMO energy level of PCDTBT-F is lower than that of PCDTBT, owing to the electron-withdrawing fluorination of the BT unit, whereas PCBBBT-F exhibited a higher HOMO level than PCDTBT, implying that the additional incorporation of electron-donating hexylthiophenes negated the fluorination effect. A bulk heterojunction (BHJ) polymer solar cell (PSC) that employed PCDTBT-F or PCBBBT-F as an electron donor and a fullerene derivative [70]PCBM as an electron acceptor yielded lower power conversion efficiencies of 1.29 and 1.98%, respectively, than that of PCDTBT (6.16%) due to the unfavorable film structures of PCDTBT-F:[70]PCBM resulting from the poor solubility and low molecular weight, as well as low crystallinities and limited exciton lifetimes, of the fluorinated polymers. These results provide valuable information on the elaborate design of PCDTBT-based polymers for the PSC applications.