Fabrication and functionalization of periodically aligned metallic nanocup arrays using colloidal lithography with a sinusoidally wrinkled substrate.

We propose a general strategy for fabricating ultrasmall attoliter-sized (10(-18) L) one-dimensional (1D) aligned nanocup arrays embedded in poly(dimethylsiloxane) (PDMS) films based on a combination of colloidal soft-lithography and wrinkle processing. The nanocup consists of a metallic shell (silver-single or double-layer silver/gold type) with a thickness of several tens of nanometers and whose diameter was ca. 500 nm and cavity depth was ca. 250 nm. First, monodisperse polystyrene (PS) colloids (d = 500 nm) were arranged onto a sinusoidally wrinkled PDMS substrate. Then, the colloid particle arrays were transferred onto another flat PDMS substrate, and a metal film was vacuum deposited over the array to form a nanostructured surface consisting of half-shell metal-coated colloid particle arrays. After the metal-coated PS array was gently transferred onto another soft PDMS substrate prepared by nonthermal curing, the attached films were thermally cured. After that, both films were carefully separated to selectively transfer the metal-coated PS particle arrays, since the metallic shell on the PS surface can adhere to the soft PDMS. Finally, the PS colloids were removed by plasma etching, leaving behind the 1D hemispherical metallic shells, called here the "metallic nanocup array structure". This structure was evaluated by performing atomic force microscopy, scanning electron microscopy, and X-ray photoelectron spectroscopy measurements. We further demonstrate chemical modification of the inner nanocup surface through construction of a self-assembled monolayer, and we also fill them with nanomaterials (silica nanoparticles) to demonstrate their application to size-selecting devices. The obtained metallic nanocup arrays could be components in a new class of chemical and/or biological nanoreactors with small reaction vessels, surface-enhanced Raman scattering (SERS)-based sensors, and size separators for nanoparticles.