Bottom-up nanoscale patterning and selective deposition on silicon nanowires.

We demonstrate a bottom-up process for programming the deposition of coaxial thin films aligned to the underlying dopant profile of semiconductor nanowires. Our process synergistically combines three distinct methods-vapor-liquid-solid nanowire growth, selective coaxial lithography via etching of surfaces (SCALES), and area-selective atomic layer deposition (AS-ALD)-into a cohesive whole. Here, we study ZrO2on Si nanowires as a model system. Si nanowires are first grown with an axially modulated n-Si/i-Si dopant profile. SCALES then yields coaxial poly(methyl methacrylate) (PMMA) masks on the n-Si regions. Subsequent AS-ALD of ZrO2occurs on the exposed i-Si regions and not on those masked by PMMA. We show the spatial relationship between nanowire dopant profile, PMMA masks, and ZrO2films, confirming the programmability of the process. The nanoscale resolution of our process coupled with the plethora of available AS-ALD chemistries promises a range of future opportunities to generate structurally complex nanoscale materials and electronic devices using entirely bottom-up methods.

Bottom-Up Masking of Si/Ge Surfaces and Nanowire Heterostructures via Surface-Initiated Polymerization and Selective Etching.

The fully bottom-up and scalable synthesis of complex micro/nanoscale materials and functional devices requires masking methods to define key features and direct the deposition of various coatings and films. Here, we demonstrate selective coaxial lithography via etching of surfaces (SCALES), an enabling bottom-up process to add polymer masks to micro/nanoscale objects. SCALES is a three-step process, including (1) bottom-up synthesis of compositionally modulated structures, (2) surface-initiated polymerization of a conformal mask, and (3) selective removal of the mask only from regions whose underlying surface is susceptible to an etchant. We demonstrate the key features of and characterize the SCALES process with a series of model Si/Ge systems: Si and Ge wafers, Si and Ge nanowires, and Si/Ge heterostructure nanowires.

Self-regenerating giant hyaluronan polymer brushes.

Tailoring interfaces with polymer brushes is a commonly used strategy to create functional materials for numerous applications. Existing methods are limited in brush thickness, the ability to generate high-density brushes of biopolymers, and the potential for regeneration. Here we introduce a scheme to synthesize ultra-thick regenerating hyaluronan polymer brushes using hyaluronan synthase. The platform provides a dynamic interface with tunable brush heights that extend up to 20 microns - two orders of magnitude thicker than standard brushes. The brushes are easily sculpted into micropatterned landscapes by photo-deactivation of the enzyme. Further, they provide a continuous source of megadalton hyaluronan or they can be covalently-stabilized to the surface. Stabilized brushes exhibit superb resistance to biofilms, yet are locally digested by fibroblasts. This brush technology provides opportunities in a range of arenas including regenerating tailorable biointerfaces for implants, wound healing or lubrication as well as fundamental studies of the glycocalyx and polymer physics.