Fine tuning the HOMO energy levels of polythieno[3,4-b]thiophene derivatives by incorporation of thiophene-3,4-dicarboxylate moiety for photovoltaic applications

To lower the HOMO (highest occupied molecular orbital) energy level of polythieno[3,4-b]thiophene (∼−4.5 eV), a series of ester-functionalized polythieno[3,4-b]thiophene derivatives (P1–P3) were designed and synthesized by Stille cross coupling reaction. The resulting copolymers exhibited broad and strong absorption bands from visible to near infrared region with low optical band gaps of 1.23–1.42 eV. Through cyclic voltammetry measurements, it was found that the HOMO energy levels of the copolymers gradually decreased with increasing the content of the thiophene-3,4-dicarboxylate moiety, i.e. −4.91 eV for P1, −5.00 eV for P2, and −5.11 eV for P3. Preliminary photovoltaic properties of the copolymers blended with [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) as electron acceptor were investigated. Among the three copolymers, P1 exhibited the best photovoltaic performance with an open circuit voltage (Voc) of 0.54 V, a short circuit current density (Isc) of 3.3 mA/cm2, a fill factor (FF) of 0.57, and a power conversion efficiency (PCE) of 1.02%. A high Voc up to 0.71 V was achieved in the solar cell based on a P3:PCBM blend.

Graphical abstractFigure optionsDownload full-size imageDownload as PowerPoint slideHighlights► We introduce thiophene-3,4-dicarboxylate into polythieno[3,4-b]thiophene's backbone. ► The HOMO gradually decreased with increasing the content of thiophene-3,4-dicarboxylate. ► Photovoltaic properties of copolymers were investigated. ► A relatively high Voc of 0.71 V was achieved.