Versatile solution for growing thin films of conducting polymers.

The method employed for depositing nanostructures of conducting polymers dictates potential uses in a variety of applications such as organic solar cells, light-emitting diodes, electrochromics, and sensors. A simple and scalable film fabrication technique that allows reproducible control of thickness, and morphological homogeneity at the nanoscale, is an attractive option for industrial applications. Here we demonstrate that under the proper conditions of volume, doping, and polymer concentration, films consisting of monolayers of conducting polymer nanofibers such as polyaniline, polythiophene, and poly(3-hexylthiophene) can be produced in a matter of seconds. A thermodynamically driven solution-based process leads to the growth of transparent thin films of interfacially adsorbed nanofibers. High quality transparent thin films are deposited at ambient conditions on virtually any substrate. This inexpensive process uses solutions that are recyclable and affords a new technique in the field of conducting polymers for coating large substrate areas.

Morphological and dimensional control via hierarchical assembly of doped oligoaniline single crystals.

Single crystals of doped aniline oligomers are produced via a simple solution-based self-assembly method. Detailed mechanistic studies reveal that crystals of different morphologies and dimensions can be produced by a "bottom-up" hierarchical assembly where structures such as one-dimensional (1-D) nanofibers can be aggregated into higher order architectures. A large variety of crystalline nanostructures including 1-D nanofibers and nanowires, 2-D nanoribbons and nanosheets, 3-D nanoplates, stacked sheets, nanoflowers, porous networks, hollow spheres, and twisted coils can be obtained by controlling the nucleation of the crystals and the non-covalent interactions between the doped oligomers. These nanoscale crystals exhibit enhanced conductivity compared to their bulk counterparts as well as interesting structure-property relationships such as shape-dependent crystallinity. Furthermore, the morphology and dimension of these structures can be largely rationalized and predicted by monitoring molecule-solvent interactions via absorption studies. Using doped tetraaniline as a model system, the results and strategies presented here provide insight into the general scheme of shape and size control for organic materials.

Applications of oligomers for nanostructured conducting polymers.

This Feature Article provides an overview of the distinctive nanostructures that aniline oligomers form and the applications of these oligomers for shaping the nanoscale morphologies and chirality of conducting polymers. We focus on the synthetic methods for achieving such goals and highlight the underlying mechanisms. The clear advantages of each method and their possible drawbacks are discussed. Assembly and applications of these novel organic (semi)conducting nanomaterials are also outlined. We conclude this article with our perspective on the main challenges, new opportunities, and future directions for this nascent yet vibrant field of research.

Nanoscale morphology, dimensional control, and electrical properties of oligoanilines.

While nanostructures of organic conductors have generated great interest in recent years, their nanoscale size and shape control remains a significant challenge. Here, we report a general method for producing a variety of oligoaniline nanostructures with well-defined morphologies and dimensionalities. 1-D nanowires, 2-D nanoribbons, and 3-D rectangular nanoplates and nanoflowers of tetraaniline are produced by a solvent exchange process in which the dopant acid can be used to tune the oligomer morphology. The process appears to be a general route for producing nanostructures for a variety of other aniline oligomers such as the phenyl-capped tetramer. X-ray diffraction of the tetraniline nanostructures reveals that they possess different packing arrangements, which results in different nanoscale morphologies with different electrical properties for the structures. The conductivity of a single tetraaniline nanostructure is up to 2 orders of magnitude higher than the highest previously reported value and rivals that of pressed pellets of conventional polyaniline doped with acid. Furthermore, these oligomer nanostructures can be easily processed by a number of methods in order to create thin films composed of aligned nanostructures over a macroscopic area.

A general synthetic route to nanofibers of polyaniline derivatives.

Nanofibrous mats of a wide variety of polyaniline derivatives can be synthesized without the need for templates or functional dopants by simply introducing an initiator into the reaction mixture of a rapidly mixed reaction between monomer and oxidant.

Aligned carbon nanotube, graphene and graphite oxide thin films via substrate-directed rapid interfacial deposition.

A procedure for depositing thin films of carbon nanostructures is described that overcomes the limitations typically associated with solution based methods. Transparent and conductively continuous carbon coatings can be grown on virtually any type of substrate within seconds. Interfacial surface tension gradients result in directional fluid flow and film spreading at the water/oil interface. Transparent films of carbon nanostructures are produced including aligned ropes of single-walled carbon nanotubes and assemblies of single sheets of chemically converted graphene and graphite oxide. Process scale-up, layer-by-layer deposition, and a simple method for coating non-activated hydrophobic surfaces are demonstrated.

Toward an understanding of the formation of conducting polymer nanofibers.

Introducing small amounts of additives into polymerization reactions to produce conducting polymers can have a profound impact on the resulting polymer morphology. When an oligomer such as aniline dimer is added to the polymerization of aniline, the nanofibers produced are longer and less entangled than those typically observed. The addition of aniline dimer can even induce nanofiber formation under synthetic conditions that generally do not favor a nanofibrillar morphology. This finding can be extended to both the synthesis of polythiophene and polypyrrole nanofibers. The traditional oxidative polymerization of thiophene or pyrrole only produces agglomerated particles. However, when minute amounts of thiophene or pyrrole oligomers are added to the reaction, the resulting polymers possess a nanofibrillar morphology. These results reveal important insights into a semirigid rod nucleation phenomenon that has hitherto been little explored. When polyaniline nucleates homogeneously, surface energy requirements necessitate the formation of ordered nuclei which leads to the directional polymerization of aniline. This ultimately leads to the one-dimensional nanofibrillar morphology observed in the final product. The synthetic procedures developed here are simple, scalable, and do not require any templates or other additives that are not inherent to the polymer.