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Gold double-ring structures synthesized from block copolymer corpuscle templates.

Organic and inorganic nanorings have recently attracted considerable attention from theoretical, experimental, and devices viewpoints, since the quantum size effects and large surface-to-volume ratio of the nanometer-sized rings contribute to their unique properties, like magnetic, optical, electrical, or chemical sensing. Many efficient approaches have been developed to make nanorings using lithography, template-based methods, colloidal lithography, capillary force lithography, and self-assembly of block copolymers. The self-organization of block copolymers (BCPs) that can be used as templates to fabricate well-defined nanostructures is an attractive strategy among these methods, due to the tunability in size and shape, the ease of processing without introducing disruptive technologies, and the use of functionalities. In particular, BCP micelles have been used to make a rich variety of metal and metal oxide nanostructures. Among them, spherical micelles consisting of an insoluble core and a soluble corona, in which only one of the blocks is dissolved in a preferential solvent, are the most common shape and can be transferred onto a solid substrate with a kinetically frozen dimple-type structure. Selective binding between the metal precursors and one of the blocks takes place by electrostatic interactions, metal coordination reactions with a polar functional group, and p complexation with olefin groups. Subsequent chemical or plasma treatment leads to the formation of periodic metal nanoring arrays. For example, Wang et al. demonstrated the fabrication process of gold (Au) nanoring arrays by immersing a reverse polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP) micellar thin film into a solution mixture of Au precursor (HAuCl4) and hydrogen chloride, with subsequent reduction of the Au salts by plasma treatment. Zu et al. reported a more general approach to make metal or metal oxide nanorings using a salt precipitation reaction. Selective swelling of minor blocks in a metal-incorporated micellar film led to the formation of metal or metal oxide nanoring structures. As a direct approach, toroidal micelles in solution or ascasted films were used as effective templates for metal nanorings. After polyisoprene-block-poly(2-vinylpyridine) was dissolved in a good solvent for both blocks, the gradual addition of a preferential solvent for the P2VP minor component resulted in the formation of toroidal micelles. Subsequent loading of Au precursors onto the micellar templates and the reduction of Au salts provides an efficient way to make uniform-sized Au nanorings. Recently, our group reported fabrication of gold ring arrays by controlling the loading time of gold precursors within block copolymer templates on a surface-modified substrate. However, the examples mentioned above showed metal or metal oxide single-ring structures due to the morphologies of copolymer templates. Herein, we demonstrate a novel method for making Au double-ring structures using corpuscle-like PS-b-P2VP templates spin-coated onto a surface-modified silicon substrate. The fabrication processes are illustrated in Scheme 1 and