In Situ Synthesis and Alignment of Au Nanoparticles within Hexagonally Packed Cylindrical Domains of Diblock Copolymers in Bulk

We present a simple method to prepare hexagonally packed metallic nanocylinders based on gold nanoparticles embedded in a copolymeric matrix. The gold nanoparticles are generated selectively within the P4VP-rich cylindrical domains of a polystyrene-b-poly-4-vinylpyridine (PS-b-P4VP) diblock copolymer. In order to achieve this selectivity, a gold precursor (HAuCl4) is coupled to the pyridine blocks of a spherical PS327-b-P4VP27 block copolymer. In consequence, the hybrid block copolymer is able to self-assemble in a hexagonally packed cylinders morphology. The application of mechanical oscillatory shear improved markedly the alignment of these nanocylinders, while simultaneously the gold precursor was reduced in situ into gold nanoparticles. Following rheological characterization in the linear viscoelastic regime, a set of alignment parameters were comprehensively selected and checked with a series of transmission electron microscopy (TEM) micrographs. An optimal temperature of alignment was found after systematic evaluation of samples sheared at different temperatures. The block copolymer exhibited an increase in the domain period as a consequence of chain rearrangements around the newly formed gold nanoparticles. The hexagonally packed morphology was preserved, and under the optimal conditions single grain sizes showed significant improvement to macroscale order in comparison to nonaligned samples. In contrast to current multistep lithographic techniques, the present method constitutes a simple path to produce three-dimensional organic−inorganic conductive nanowires with periodicities at the macroscopic level.