Enhanced performance of quasi-solid-state dye-sensitized solar cells by branching the linear substituent in sensitizers based on thieno[3,4-c]pyrrole-4,6-dione.

Thieno[3,4-c]pyrrole-4,6-dione-based organic sensitizers with triphenylamine (FNE38 and FNE40) or julolidine (FNE39 and FNE41) as electron-donating unit have been designed and synthesized. A linear hexyl group or a branched alkyl chain, the 2-ethylhexyl group, is incorporated into molecular skeleton of the dyes to minimize intermolecular interactions. The absorption, electrochemical, and photovoltaic properties for these sensitizers were then systematically investigated. It is found that the sensitizers have similar photophysical and electrochemical properties, such as absorption spectra and energy levels, owing to their close chemical structures. However, the quasi-solid-state dye-sensitized solar cells (DSSCs) based on the two types of sensitizers exhibit very different performance parameters. Upon the incorporation of the short ethyl group on the hexyl moiety, enhancements in both open-circuit voltage (V(oc)) and short-circuit current (J(sc)) are achieved for the quasi-solid-state DSSCs. The V(oc) gains originating from the suppression of charge recombination were quantitatively investigated and are in good agreement with the experimentally observed V(oc) enhancements. Therefore, an enhanced solar energy conversion efficiency (η) of 6.16%, constituting an increase by 23%, is achieved under standard AM 1.5 sunlight without the use of coadsorbant agents for the quasi-solid-state DSSC based on sensitizer FNE40, which bears the branched alkyl group, in comparison with that based on FNE38 carrying the linear alkyl group. This work presents a design concept for considering the crucial importance of the branched alkyl substituent in novel metal-free organic sensitizers.