Systematically moving the alkyl-chain branching position away from the polymer backbone afforded two new thieno[3,2-b]thiophene-diketopyrrolopyrrole (DPPTT-T) polymers. When used as donor materials in polymer:fullerene solar cells, efficiencies exceeding 7% were achieved without the use of processing additives. The effect of the position of the alkyl-chain branching point on the thin-film morphology was investigated using X-ray scattering techniques and the effects on the photovoltaic and charge-transport properties were also studied. For both solar cell and transistor devices, moving the branching point further from the backbone was beneficial. This is the first time that this effect has been shown to improve solar cell performance. Strong evidence is presented for changes in microstructure across the series, which is most likely the cause for the photocurrent enhancement.

We present the synthesis and characterization of two novel thiazole-containing conjugated polymers (PTTTz and PTTz) that are isostructural to poly(3-hexylthiophene) (P3HT). The novel materials demonstrate optical and morphological properties almost identical to those of P3HT but with HOMO and LUMO levels that are up to 0.45 eV deeper. An intramolecular planarizing nitrogen−sulfur nonbonding interaction is observed, and its magnitude and origin are discussed. Both materials demonstrate significantly greater open circuit voltages than P3HT in bulk heterojunction solar cells. PTTTz is shown to be an extremely versatile donor polymer that can be used with a wide variety of fullerene acceptors with device efficiencies of up to 4.5%. It is anticipated that this material could be used as a high-open circuit voltage alternative to P3HT in organic solar cells.

We describe a spectroelectrochemical approach to accelerated electrochemical stability studies of conjugated polymers under oxidative stress. The polaron stabilities of alternating copolymers based on (i) thiophene and thiazole, namely PTTz, and (ii) bithiophene and thiazole, namely PTTTz, are compared in neat films with that of P3HT. P3HT is found to be the most stable whilst PTTz is found to be the least stable.

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