Isaac W. Moran

Nanoimprint Lithography for Functional Three-Dimensional Patterns

Nanoimprint lithography (NIL) is viewed as an alternative nanopatterning technique to traditional photolithography, allowing micrometer-scale and sub-hundred-nanometer resolution as well as three-dimensional structure fabrication. In this Research News article we highlight current activities towards the use of NIL in patterning active or functional materials, and the application of NIL in patterning materials that present both chemistry and structure/topography in the patterned structures, which provide scaffolds for subsequent manipulation. We discuss and give examples of the various materials and chemistries that have been used to create functional patterns and their implication in various fields as electronic and magnetic devices, optically relevant structures, biologically important surfaces, and 3D particles.

High-resolution soft lithography of thin film resists enabling nanoscopic pattern transfer

Soft UV-imprint lithography at sub-micron dimensions was achieved in thin films of photopolymer resist. The imprinting was enabled by overcoming resist absorption by polydimethylsiloxane (PDMS) through surface treatment with a layer of (heptadecafluoro-1,1,2,2-tetrahydrodecyl)dimethylchlorosilane. Characterization of the composite molds was done by X-ray photoelectron spectroscopy, nanoindentation, and contact angle measurements. PDMS molds treated with fluoroalkylsilane layer were used to imprint into thin films (70-630 nm) of UV curable resins consisting of either polyurethanes or acrylates, replicating with high fidelity features over the surface of wafer substrates. The use of these highly conformal PDMS molds allowed the patterning of functional materials including gold and aluminium by a simple imprint lithographic technique. This is the first report of the use of modified PDMS surfaces in an imprint process that enables the transfer of sub-micron patterns to underlying layers for device structure fabrication. The patterned features were studied with atomic force microscopy, scanning electron microscopy, and optical microscopy.

Silylcarborane Acrylate Nanoimprint Lithography Resists

The synthesis of a novel silylcarborane acrylate monomer is reported as well as its application as an etch-resistant component for the formulation of imprint layers for UV nanoimprint lithography (NIL). By introduction of 10% by weight of the silylcarborane acrylate monomer into NIL resist formulations, the oxygen plasma etch rate of the resulting film was reduced by nearly a factor of 2. When used in NIL, the patterned resist layer had excellent oxygen plasma etch resistance, leading to effective image transfer to the underlying poly(hydroxyethyl methacrylate) lift-off layer. The latter allowed for the fabrication of metallic interdigitated electrode patterns via a NIL/lift-off process. This work demonstrates the robustness of silylcarborane-containing resists and paves the way for the investigation of new, high-resolution patterning methods.

Direct Passivation of Hydride-Terminated Silicon (100) Surfaces by Free-Radically Tethered Polymer Brushes

A simple and effective means for passivating crystalline silicon is reported by the use of free-radical polymerization (FRP) to directly graft polymer chains to a hydride-terminated surface (Si-H). Complete surface coverage and passivation was achieved in approximately 24 h at 60 degrees C or 30 min at 90 degrees C. Mechanistic studies determined that chain attachment followed a hydride-transfer-based grafting-to mechanism. The grafting process is compatible with a variety of monomers and was used to assemble polymer brush layers (2-12 nm thick), with grafting densities ranging from 0.02 to 0.65 chains/nm2 rivaling densities typically obtained by grafting-from scenarios. This new passivation route provides a uniquely accessible means to covalently anchor dense polymer brushes to silicon surfaces without the need for functionalization of the polymer chain ends or the substrate.

Functionally Decoupled Soft Lithography for Patterning Polymer Brushes

Easy soft imprint nanolithography (ESINL) is employed in the patterning of multiple olymer brushes. This new approach to soft lithography is found to be uniquely effective at patterning brushes both prior to and subsequent to grafting of the polymer chains. Silicon substrates are grafted with polystyrene, polymethylmethacrylate, and polyhydroxyethylmethacrylate using surface-initiated atom transfer radical polymerization assisted by activators generated by electron transfer (ARGET-ATRP) and characterized by contact angle measurements, infrared spectroscopy, and ellipsometry. Line grating features of 3 cm × 3 cm with critical dimensions in the range of 410-480 nm are imprinted directly over grafted brush layers or over assembled monolayers of initiator molecules and transferred to the active layer by reactive ion etching. In all cases the grating pattern is accurately reproduced in the brush layer as confirmed by atomic force microscopy, demonstrating the capability of the technique to generate large-area nanoscale patterns on a range of surface types and functionalities.