A facile solution-processing strategy toward well-ordered one-dimensional nanostructures of conjugated polymers via a non-solvent vapor treatment was demonstrated, which resulted in enhancements to the charge transport characteristics of the polymers. The amount of crystalline poly(3-hexylthiophene) (P3HT) nanofibers was precisely controlled by simply varying the exposure time of solutions of P3HT solutions to non-solvent vapor. The effects of non-solvent vapor exposure on the molecular ordering and morphologies of the resultant P3HT films were systematically investigated using ultraviolet-visible (UV-vis) spectroscopy, polarized optical microscopy (POM), grazing incidence X-ray diffraction (GIXRD), and atomic force microscopy (AFM). The non-solvent vapor facilitates the π–π stacking in P3HT to minimize unfavorable interactions between the poor solvent molecules and P3HT chains. P3HT films deposited from the non-solvent vapor-treated P3HT solutions exhibited an approximately 5.6-fold improvement in charge carrier mobility as compared to that of pristine P3HT films (7.8 × 10−2 cm2 V−1 s−1 vs. 1.4 × 10−2 cm2 V−1 s−1). The robust and facile strategy presented herein would be applicable in various opto-electronics applications requiring precise control of the molecular assembly, such as organic photovoltaic cells, field-effect transistors, light-emitting diodes, and sensors.

Charge transport in π-conjugated polymer films involves π-π interactions within or between polymer chains. Here, we demonstrate a facile solution processing strategy that provides enhanced intra- and interchain π-π interactions of the resultant polymer films using a good solvent additive with low volatility. These increased interactions result in enhanced charge transport properties. The effect of the good solvent additive on the intra- and intermolecular interactions, morphologies, and charge transport properties of poly(3-hexylthiophene) (P3HT) films is systematically investigated. We found that the good solvent additive facilitates the self-assembly of P3HT chains into crystalline fibrillar nanostructures by extending the solvent drying time during thin-film formation. As compared to the prior approach using a nonsolvent additive with low volatility, the solvent blend system containing a good solvent additive results in enhanced charge transport in P3HT organic field-effect transistor (OFET) devices [from ca. 1.7 × 10 to ca. 8.2 × 10 cm V s for dichlorobenzene (DCB) versus 4.4 × 10 cm V s for acetonitrile]. The mobility appears to be maximized over a broad spectrum of additive concentrations (1-7 vol %), indicative of a wide processing window. Detailed analysis results regarding the charge injection and transport characteristics of the OFET devices reveal that a high-boiling-point solvent additive decreases both the contact resistance ( R) and channel resistance ( R), contributing to the mobility enhancement of the devices. Finally, the platform presented here is proven to be applicable to alternative good solvent additives with low volatility, such as chlorobenzene (CB) and trichlorobenzene (TCB). Specifically, the mobility enhancement of the resultant P3HT films increases in the order CB (bp 131 °C) < DCB (bp 180 °C) < TCB (bp 214 °C), suggesting that solvent additives with higher boiling points provide resultant films with preferable molecular ordering and morphologies for efficient charge transport.

High environmental stability of organic field-effect transistors is achieved by the use of conjugated polymer/paraffin blends.

Long-range alignment of conjugated polymers is as critical as polymer chain packing for achieving efficient charge transport in polymer thin films used in electronic and optoelectronic devices. Here, the present study reports a facile, scalable strategy that enables the deposition of macroscopically aligned polymer semiconductor nanowire (NW)-array films with highly enhanced charge carrier mobility, using a modified controlled evaporative self-assembly (MCESA) technique. Organic field-effect transistors (OFETs) based on highly oriented poly­(3-hexylthiophene) (P3HT)-NW films exhibit more than 10-fold enhancement of carrier mobility, with the highest mobility of 0.13 cm2 V–1 s–1, compared to the OFETs based on pristine P3HT films. Significantly, large-area aligned P3HT NW-films, which are deposited over 12 arrays of transistors on a 4 in. wafer by an MCESA coating, result in lower device performance variation (i.e., standard deviation ≈ ±0.0172 (16%) cm2 V–1 s–1) as well as an excellent average device performance (i.e., average charge mobility ≈ 0.11 cm2 V–1 s–1), compared to those obtained using the conventional CESA coating, overcoming a critical challenge in the field of OFETs.

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