Donor-acceptor interfacial microstructures and fast ambipolar charge transport are pivotal in determining the device performance of inorganic-organic hybrid photovoltaics. Here, we report on a series of one-dimensional coaxial p-n junction core-shell nanohybrids formed by direct side-on attachment of carboxylated poly(3-alkylthiophene)s onto single-crystalline ZnO nanowires. The diameter of pristine ZnO nanowires is ∼30 nm, and the conjugated polymer forms a 2-10 nm shell around each nanowire. Spectroscopic studies on the resulting core-shell hybrid nanowires show an elongated conjugation length of the poly(3-alkylthiophene) backbone and fast electron transfer via ordered donor-acceptor interfaces. Hybrid nanowires in suspensions spontaneously undergo phase transitions from isotropic to nematic liquid crystalline phases via a biphasic region with increasing concentration. The unique liquid crystalline elasticity of nanohybrids results in large-area monodomain structures of aligned hybrid nanowires under simple shear flow, which are maintained in the dried film used for device fabrication. These methodologies provide a mechanism for controlling donor-acceptor interfaces and exploiting lyotropic liquid crystallinity for solution-based processing of large-area alignment of photovoltaic elements with anisotropic charge transport for hybrid photovoltaic devices.

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The sol–gel transition of conductive nanocomposites consisting of poly(3-hexylthiophene) (P3HT) and ZnO nanowires in o-dichlorobenzene (o-DCB) has been investigated rheologically. The physical gelation of P3HT in o-DCB spontaneously occurs upon adding the small amount of ZnO nanowires. The rheological properties of the P3HT/ZnO nanocomposite gels have been systematically studied by varying factors such as polymer concentration, nanowire loading, and temperature. The nanocomposite gel exhibits shear-thinning in the low shear rate range and shear-thickening in the high shear rate range. The elastic storage modulus of the nanocomposite gel gradually increases with gelation time and is consistently independent of frequency at all investigated ranges. The isothermal gelation kinetics has been analyzed by monitoring the storage modulus with gelation time, and the data are well fitted with a first-order rate law. The structural analysis data reveal that the polymer forms the crystalline layer coated on ZnO nanowires. A fringed micelle model is proposed to explain the possible gelation mechanism.