SummaryEfficient fibre formation for all regioregular poly(3-alkylthiophene)s (P3ATs) with alkyl chain lengths (A) between 3 and 9 carbon atoms has been accomplished in several solvents. It was observed that for the aliphatic and (chlorinated) aromatic hydrocarbon solvents used, the solvent refractive index offers some rationale to predict the feasibility of a solvent for fibre formation. The fibres were separated from remaining non-organised polymer by centrifugation. This enabled the characterisation of the isolated fibres in function of alkyl chain length (A) with TEM, AFM, XRD and UV-Vis spectroscopy. The fibres are 20 +/− 5 nm wide and 0.5 to >4 µm long and mainly crystallize in the common type I crystal phase. The order within the fibres was probed with XRD, SAED, and UV-Vis and was found to strongly improve with increasing alkyl chain length in going from P33T to P35T, resulting in a longer conjugation length. For P35T to P39T the improvement in order is only marginal.Fibres from P37T, were found to mainly crystallize in a crystal phase slightly different from type I that we refer to as type I'. This new crystal structure has a lattice constant a that is marginally shorter than that of phase I and a slightly longer lattice constant b of 4.0 Å and thus in XRD can hardly be distinguished from phase I. It is furthermore characterized by a blue-shifted absorption band in UVVis spectroscopy. The type I' fibres were converted in normal type I fibres in the solid state at 70 °C and in solution around 50 °C.

The field‐effect transistor (FET) and diode characteristics of poly(3‐alkylthiophene) (P3AT) nanofiber layers deposited from nanofiber dispersions are presented and compared with those of layers deposited from molecularly dissolved polymer solutions in chlorobenzene. The P3AT n‐alkyl‐side‐chain length was varied from 4 to 9 carbon atoms. The hole mobilities are correlated with the interface and bulk morphology of the layers as determined by UV–vis spectroscopy, transmission electron microscopy (TEM) with selected area electron diffraction (SAED), atomic force microscopy (AFM), and polarized carbon K‐edge near edge X‐ray absorption fine structure (NEXAFS) spectroscopy. The latter technique reveals the average polymer orientation in the accumulation region of the FET at the interface with the SiO2 gate dielectric. The previously observed alkyl‐chain‐length‐dependence of the FET mobility in P3AT films results from differences in molecular ordering and orientation at the dielectric/semiconductor interface, and it is concluded that side‐chain length does not determine the intrinsic mobility of P3ATs, but rather the alkyl chain length of P3ATs influences FET diode mobility only through changes in interfacial bulk ordering in solution processed films.

The effect of poly(3-alkylthiophene) (P3AT) crystallinity in (nanofiber P3AT):PCBM photovoltaic devices on the energy of the charge-transfer state (ECT) and on the open-circuit voltage (Voc) is investigated for poly(3-butythiophene), poly(3-pentylthiophene) and poly(3-hexylhiophene). P3AT crystallinity, expressed as the crystalline nanofiber mass fraction f to the total P3AT mass in the spin-coating dispersion, is varied between ∼0.1 and ∼0.9 by temperature control. ECT, as obtained by Fourier-transform photocurrent spectroscopy decreased with f as ECT=ECT0−0.2f eV. Alkyl side-chain length only influences ECT0. Voc relates to ECT as Voc=ECT/q−0.6 V.

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