Superhydrophobic Polymer Topography Design Assisted by Machine Learning Algorithms.

Superhydrophobic surfaces have been largely achieved through various surface topographies. Both empirical and numerical simulations have been reported to help understand and design superhydrophobic surfaces. Many such successful surfaces have also been achieved using bioinspired and biomimetic designs. Despite this, identifying the right surface texture to meet the requirements of specific applications is not a straightforward task. Here, we report a hybrid approach that includes experimental methods, numerical simulations, and machine learning (ML) algorithms to create design maps for superhydrophobic polymer topographies. Two design objectives to investigate superhydrophobic properties were the maximum water contact angle (WCA) and Laplace pressure. The design parameters were the geometries of an isotropic pillar structure in micrometer and sub-micrometer length scales. The finite element method (FEM) was validated by the experimental data and employed to generate a labeled dataset for ML training. Artificial neural network (ANN) models were then trained on the labeled database for the topographic parameters (width W, height H, and pitch P) with the corresponding WCA and Laplace pressure. The ANN models yielded a series of nonlinear relationships between the topographic design parameters and the WCA and Laplace pressure and substantial differences between the micrometer and sub-micrometer length scales. Design maps that span the topography design parameters provide optimal design or tradeoff parameters. This research demonstrates the potential of ANN as a rapid design tool for surface topography exploration.

Versatile pattern generation of periodic, high aspect ratio Si nanostructure arrays with sub-50-nm resolution on a wafer scale.

We report on a method of fabricating variable patterns of periodic, high aspect ratio silicon nanostructures with sub-50-nm resolution on a wafer scale. The approach marries step-and-repeat nanoimprint lithography (NIL) and metal-catalyzed electroless etching (MCEE), enabling near perfectly ordered Si nanostructure arrays of user-defined patterns to be controllably and rapidly generated on a wafer scale. Periodic features possessing circular, hexagonal, and rectangular cross-sections with lateral dimensions down to sub-50 nm, in hexagonal or square array configurations and high array packing densities up to 5.13 × 107 structures/mm2 not achievable by conventional UV photolithography are fabricated using this top-down approach. By suitably tuning the duration of catalytic etching, variable aspect ratio Si nanostructures can be formed. As the etched Si pattern depends largely on the NIL mould which is patterned by electron beam lithography (EBL), the technique can be used to form patterns not possible with self-assembly methods, nanosphere, and interference lithography for replication on a wafer scale. Good chemical resistance of the nanoimprinted mask and adhesion to the Si substrate facilitate good pattern transfer and preserve the smooth top surface morphology of the Si nanostructures as shown in TEM. This approach is suitable for generating Si nanostructures of controlled dimensions and patterns, with high aspect ratio on a wafer level suitable for semiconductor device production.

Large area, facile oxide nanofabrication via step-and-flash imprint lithography of metal-organic hybrid resins.

Step-and-flash imprint lithography (S-FIL) is a wafer-scale, high-resolution nanoimprint technique capable of expansion of nanoscale patterns via serial patterning of imprint fields. While S-FIL patterning of organic resins is well known, patterning of metal-organic resins followed by calcination to form structured oxide films remains relatively unexplored. However, with calcination shrinkage, there is tremendous potential utility in easing accessibility of arbitrary nanostructures at 20 nm resolution and below. However, barriers to commercial adoption exist due to difficulties in formulating polymerizable oxide precursors with good dispensability, long shelf life, and resistance to auto-homopolymerization. Here we propose a solution to these issues in the form of a versatile resin formulation scheme that is applicable to a host of functional oxides (Al2O3, HfO2, TiO2, ZrO2, Ta2O5, and Nb2O5). This scheme utilizes a reaction of metal alkoxides with 2-(methacryloyloxy)ethyl acetoacetate (MAEAA), a polymerizable chelating agent. Formation of these inorganic coordination complexes enables remarkable resistance to auto-homopolymerization, greatly improving dispensability and shelf life, thus enabling full scale-up of this facile nanofabrication approach. Results include successively imprinted fields consisting of 100 nm linewidth gratings. Isothermal calcination of these structures resulted in corresponding shrinkage of 75-80% without loss of mechanical integrity or aspect ratio, resulting in 20 nm linewidth oxide nanostructures.

High resolution UV roll-to-roll nanoimprinting of resin moulds and subsequent replication via thermal nanoimprint lithography.

UV roll-to-roll nanoimprinting at high resolution is still a relatively unexplored field of study with far-reaching application potential. One enabling technology that is particularly worthy of attention is mass production of high resolution resin moulds via UV roll-to-roll nanoimprinting at such high throughput and low cost that they can be used only once and disposed of or recycled economically. Low cost, high resolution resin moulds can greatly improve the production cost profile for a number of applications in biomedicine, nanofluidics, data storage and electronics with relatively low unit values but which require one or more nanoscale lithography steps. In this report, UV roll-to-roll nanoimprinting was employed to fabricate high fidelity resin moulds with nanoscale as well as mixed micro- and nanoscale features down to 50 nm feature diameter, at up to 120 cm(2) area and at 10 m min(-1) throughput. UV roll-to-roll nanoimprinted resin moulds were subsequently segmented out, employed in a batch mode thermal nanoimprinting process, and characterized to study performance and demonstrate viability. The results show that high resolution mixed nanostructures can be faithfully replicated in PMMA on silicon substrates with minimal volumetric shrinkage. Process details and challenges specific to roll-to-roll fabrication of resin moulds are discussed at length, particularly with respect to the curvature uniformity of the imprint roller.

Direct patterning of TiO2 using step-and-flash imprint lithography.

Although step-and-flash imprint lithography, or S-FIL, has brought about tremendous advancement in wafer-scale fabrication of sub-100 nm features of photopolymerizable organic and organo-silicon-based resists, it has not been successful in direct patterning of inorganic materials such as oxides because of the difficulties associated with resist formulation and its dispensing. In this paper, we demonstrate the proof-of-concept S-FIL of titanium dioxide (TiO(2)) carried by an acrylate-based formulation containing an allyl-functionalized titanium complex. The prepolymer formulation contains 48 wt % metal precursor, but it exhibits low enough viscosity (∼5 mPa·s) to be dispensed by an automatic dispensing system, adheres and spreads well on the substrate, is insensitive to pattern density variations, and rapidly polymerizes when exposed to broadband UV radiation to give a yield close to 95%. Five fields, each measuring 1 cm × 1 cm, consisting of 100 nm gratings were successively imprinted. Heat-treatment of the patterned structures at 450 °C resulted in the loss of organics and their subsequent shrinkage without the loss of integrity or aspect ratio and converted them to TiO(2) anatase nanostructures as small as 30 nm wide. With this approach, wafer-scale direct patterning of functional oxides on a sub-100 nm scale using S-FIL can become a distinct possibility.