Robust, large area, superhydrophobic surfaces with feature sizes approaching 10 nm are fabricated by block‐copolymer‐based thin‐film patterning. We show that tuning the nanostructure shape and aspect ...ratio dramatically influences the surface wetting properties, with proper control crucial for achieving superhydrophobicity.
Nanometre-scale features with special shapes impart a broad spectrum of unique properties to the surface of insects. These properties are essential for the animal's survival, and include the low ...light reflectance of moth eyes, the oil repellency of springtail carapaces and the ultra-adhesive nature of palmtree bugs. Antireflective mosquito eyes and cicada wings are also known to exhibit some antifogging and self-cleaning properties. In all cases, the combination of small feature size and optimal shape provides exceptional surface properties. In this work, we investigate the underlying antifogging mechanism in model materials designed to mimic natural systems, and explain the importance of the texture's feature size and shape. While exposure to fog strongly compromises the water-repellency of hydrophobic structures, this failure can be minimized by scaling the texture down to nanosize. This undesired effect even becomes non-measurable if the hydrophobic surface consists of nanocones, which generate antifogging efficiency close to unity and water departure of droplets smaller than 2 μm.
Despite numerous organic semiconducting materials synthesized for organic photovoltaics in the past decade, fullerenes are widely used as electron acceptors in highly efficient bulk-heterojunction ...solar cells. None of the non-fullerene bulk heterojunction solar cells have achieved efficiencies as high as fullerene-based solar cells. Design principles for fullerene-free acceptors remain unclear in the field. Here we report examples of helical molecular semiconductors as electron acceptors that are on par with fullerene derivatives in efficient solar cells. We achieved an 8.3% power conversion efficiency in a solar cell, which is a record high for non-fullerene bulk heterojunctions. Femtosecond transient absorption spectroscopy revealed both electron and hole transfer processes at the donor-acceptor interfaces. Atomic force microscopy reveals a mesh-like network of acceptors with pores that are tens of nanometres in diameter for efficient exciton separation and charge transport. This study describes a new motif for designing highly efficient acceptors for organic solar cells.
Materials providing broadband light antireflection have applications as highly transparent window coatings, military camouflage, and coatings for efficiently coupling light into solar cells and out ...of light-emitting diodes. In this work, densely packed silicon nanotextures with feature sizes smaller than 50 nm enhance the broadband antireflection compared with that predicted by their geometry alone. A significant fraction of the nanotexture volume comprises a surface layer whose optical properties differ substantially from those of the bulk, providing the key to improved performance. The nanotexture reflectivity is quantitatively well-modelled after accounting for both its profile and changes in refractive index at the surface. We employ block copolymer self-assembly for precise and tunable nanotexture design in the range of ~10-70 nm across macroscopic solar cell areas. Implementing this efficient antireflection approach in crystalline silicon solar cells significantly betters the performance gain compared with an optimized, planar antireflection coating.
Self-assembly is a powerful paradigm, wherein molecules spontaneously form ordered phases exhibiting well-defined nanoscale periodicity and shapes. However, the inherent energy-minimization aspect of ...self-assembly yields a very limited set of morphologies, such as lamellae or hexagonally packed cylinders. Here, we show how soft self-assembling materials-block copolymer thin films-can be manipulated to form a diverse library of previously unreported morphologies. In this iterative assembly process, each polymer layer acts as both a structural component of the final morphology and a template for directing the order of subsequent layers. Specifically, block copolymer films are immobilized on surfaces, and template successive layers through subtle surface topography. This strategy generates an enormous variety of three-dimensional morphologies that are absent in the native block copolymer phase diagram.
Patterning materials efficiently at the smallest length scales is a longstanding challenge in nanotechnology. Electron-beam lithography (EBL) is the primary method for patterning arbitrary features, ...but EBL has not reliably provided sub-4 nm patterns. The few competing techniques that have achieved this resolution are orders of magnitude slower than EBL. In this work, we employed an aberration-corrected scanning transmission electron microscope for lithography to achieve unprecedented resolution. Here we show aberration-corrected EBL at the one nanometer length scale using poly(methyl methacrylate) (PMMA) and have produced both the smallest isolated feature in any conventional resist (1.7 ± 0.5 nm) and the highest density patterns in PMMA (10.7 nm pitch for negative-tone and 17.5 nm pitch for positive-tone PMMA). We also demonstrate pattern transfer from the resist to semiconductor and metallic materials at the sub-5 nm scale. These results indicate that polymer-based nanofabrication can achieve feature sizes comparable to the Kuhn length of PMMA and ten times smaller than its radius of gyration. Use of aberration-corrected EBL will increase the resolution, speed, and complexity in nanomaterial fabrication.
The extreme technological complexity associated with continued dimensional scaling of the photolithographic patterning process to sub-50 nm dimensions has forced the semiconductor industry to seek ...increasingly innovative alternative approaches. One unconventional method under preliminary consideration involves using self-assembling block copolymer films as high-resolution patterning materials for defining integrated circuit (IC) elements. While these materials are attractive because of their ability to define nanometer-scale dimensions, their ultimate utility as a viable patterning method remains in question because of issues relating to pattern roughness and defectivity. In this issue, Prof. Paul Nealey and co-workers at the University of Wisconsin present compelling first demonstrations of experimental methods by which polymer self-assembly can generate the pattern elements essential for IC fabrication.
Cells have the remarkable ability to sense the mechanical stiffness of their surroundings. This has been studied extensively in the context of cells interacting with planar surfaces, a conceptually ...elegant model that also has application in biomaterial design. However, physiological interfaces are spatially complex, exhibiting topographical features that are described over multiple scales. This report explores mechanosensing of microstructured elastomer surfaces by CD4⁺ T cells, key mediators of the adaptive immune response. We show that T cells form complex interactions with elastomer micropillar arrays, extending processes into spaces between structures and forming local areas of contraction and expansion dictated by the layout of microtubules within this interface. Conversely, cytoskeletal reorganization and intracellular signaling are sensitive to the pillar dimensions and flexibility. Unexpectedly, these measures show different responses to substrate rigidity, suggesting competing processes in overall T cell mechanosensing. The results of this study demonstrate that T cells sense the local rigidity of their environment, leading to strategies for biomaterial design.
Superhydrophobic coatings repel liquids by trapping air inside microscopic surface textures. However, the resulting composite interface is prone to collapse under external pressure. Nanometer-size ...textures should facilitate more resilient coatings owing to geometry and confinement effects at the nanoscale. Here, we use in situ x-ray diffraction to study the collapse of the superhydrophobic state in arrays of approximately 20 nm-wide silicon textures with cylindrical, conical, and linear features defined by block-copolymer self-assembly and plasma etching. We reveal that the superhydrophobic state vanishes above critical pressures which depend on texture shape and size. This phenomenon is irreversible for all but the conical surface textures which exhibit a spontaneous, partial reappearance of the trapped gas phase upon liquid depressurization. This process is influenced by the kinetics of gas-liquid exchange.
Structural evolutions are crucial for determining the performance of high-voltage lithium, manganese-rich layered cathodes. Moreover, interface between electrode and electrolyte plays a critical role ...in governing ionic transfer in all-solid-state batteries. Here, we unveil two different types of porous structure in Li1.2Ni0.2Mn0.6O2 cathode with LiPON solid-state electrolyte. Nanopores are found near the cathode/electrolyte interface at pristine state, where cation mixing, phase transformation, oxygen loss, and Mn reduction are also found. In situ Li+ extraction induces the evolution of nanovoids, initially formed near the interface then propagated into the bulk. Despite the development of nanovoids, layered structure is conserved, suggesting the nature of nanopores and nanovoids are different and their impact would be divergent. This work demonstrates the intrinsic interfacial layer, as well as the dynamic scenario of nanovoid formation inside high-capacity layered cathode, which helps to understand the performance fading in cathodes and offers insight into the all-solid-state battery design.
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