Person:

Aizenberg, Joanna

A powerful fabrication platform for a wide range of biomimetic, high-aspect-ratio nanostructured surfaces is introduced. The principles of soft lithography are extended into a double-mold replication process, whereby a master topography is mapped onto an elastomeric inverse mold and replicated in arbitrary multiple material and stiffness gradients, and an array of modified geometries. Control of geometry via deformation of the inverse mold and control of stiffness via prepolymer mixing are discussed. New capabilities enabled by our approach include biomimetic actuation/sensor arrays with programmable biases, precisely tunable mechanical and geometric properties for optical or wetting applications, and flexible curved substrates. Indeed, flexibly anchored ciliary high-aspect-ratio nanostructures are now possible, and a proof-of-principle is described.

This paper describes the fabrication of arrays of nanostructures (rings, crescents, counterfacing split rings, cylinders, coaxial cylinders, and other structures) by a four-step process: (i) molding an array of epoxy posts by soft lithography, (ii) depositing thin films on the posts, (iii) embedding the posts in epoxy, and (iv) sectioning in a plane parallel to the plane defined by the array of posts, into slabs, with an ultramicrotome (“nanoskiving”). This work demonstrates the combination of four capabilities: (i) formation of structures that are submicrometer in all dimensions; (ii) fabrication of 3D structures, and arrays of structures, with gradients of height; (iii) patterning of arrays containing two or more materials, including metals, semiconductors, oxides, and polymers; and (iv) generation of as many as 60 consecutive slabs bearing contiguous arrays of nanostructures. These arrays can be transferred to different substrates, and arrays of gold rings exhibit plasmonic resonances in the range of wavelengths spanning 2−5 μm.

We present a reproducible, one-pot colloidal co-assembly approach that results in large-scale, highly-ordered porous silica films with embedded, uniformly-distributed, accessible gold nanoparticles. The unique coloration of these inverse opal films combines iridescence with plasmonic effects. The coupled optical properties are easily tunable either by changing the concentration of added nanoparticles to the solution before assembly or by localized growth of the embedded Au nanoparticles upon exposure to tetrachloroauric acid solution, after colloidal template removal. The presence of the selectively absorbing particles furthermore enhances the hue and saturation of the inverse opals color by suppressing incoherent diffuse scattering. The composition and optical properties of these films are demonstrated to be locally tunable using selective functionalization of the doped opals.

Arrays of high-aspect-ratio (HAR) nano- and microstructures are of great interest for designing surfaces for applications in optics, bio−nano interfaces, microelectromechanical systems, and microfluidics, but the difficulty of systematically and conveniently varying the geometries of these structures significantly limits their design and optimization for a specific function. This paper demonstrates a low-cost, high-throughput benchtop method that enables a HAR array to be reshaped with nanoscale precision by electrodeposition of conductive polymers. The method—named STEPS (structural transformation by electrodeposition on patterned substrates)—makes it possible to create patterns with proportionally increasing size of original features, to convert isolated HAR features into a closed-cell substrate with a continuous HAR wall, and to transform a simple parent two-dimensional HAR array into new three-dimensional patterned structures with tapered, tilted, anisotropic, or overhanging geometries by controlling the deposition conditions. We demonstrate the fabrication of substrates with continuous or discrete gradients of nanostructure features, as well as libraries of various patterns, starting from a single master structure. By providing exemplary applications in plasmonics, bacterial patterning, and formation of mechanically reinforced structures, we show that STEPS enables a wide range of studies of the effect of substrate topography on surface properties leading to optimization of the structures for a specific application. This research identifies solution-based deposition of conductive polymers as a new tool in nanofabrication and allows access to 3D architectures that were previously difficult to fabricate.

Formation of unwanted deposits on steels during their interaction with liquids is an inherent problem that often leads to corrosion, biofouling and results in reduction in durability and function. Here we report a new route to form anti-fouling steel surfaces by electrodeposition of nanoporous tungsten oxide (TO) films. TO-modified steels are as mechanically durable as bare steel and highly tolerant to compressive and tensile stresses due to chemical bonding to the substrate and island-like morphology. When inherently superhydrophilic TO coatings are converted to superhydrophobic, they remain non-wetting even after impingement with yttria-stabilized-zirconia particles, or exposure to ultraviolet light and extreme temperatures. Upon lubrication, these surfaces display omniphobicity against highly contaminating media retaining hitherto unseen mechanical durability. To illustrate the applicability of such a durable coating in biofouling conditions, we modified naval construction steels and surgical instruments and demonstrated significantly reduced marine algal film adhesion, Escherichia coli attachment and blood staining.

Omniphobic fluorogel elastomers were prepared by photocuring perfluorinated acrylates and a perfluoropolyether crosslinker. By tuning either the chemical composition or the temperature that control the crystallinity of the resulting polymer chains, a broad range of optical and mechanical properties of the fluorogel can be achieved. After infusing with fluorinated lubricants, the fluorogels showed excellent resistance to wetting by various liquids and anti-biofouling behavior, while maintaining cytocompatiblity.

Omniphobic surfaces that can repel fluids at temperatures higher than 100 °C are rare. Most state-of-the-art liquid-repellent materials are based on the lotus effect, where a thin air layer is maintained throughout micro/nanotextures leading to high mobility of liquids. However, such behavior eventually fails at elevated temperatures when the surface tension of test liquids decreases significantly. Here, we demonstrate a class of lubricant-infused structured surfaces that can maintain a robust omniphobic state even for low-surface-tension liquids at temperatures up to at least 200 °C. We also demonstrate how liquid mobility on such surfaces can be tuned by a factor of 1000.