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

Abstract

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 (Vocs) 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 ...