Characteristic Feature Size Research Articles

Microstructure-dependent particulate filtration using multifunctional metallic nanowire foams.

The COVID-19 pandemic has shown the urgent need for the development of efficient, durable, reusable and recyclable filtration media for the deep-submicron size range. Here we demonstrate a multifunctional filtration platform using porous metallic nanowire foams that are efficient, robust, antimicrobial, and reusable, with the potential to further guard against multiple hazards. We have investigated the foam microstructures, detailing how the growth parameters influence the overall surface area and characteristic feature size, as well as the effects of the microstructures on the filtration performance. Nanogranules deposited on the nanowires during electrodeposition are found to greatly increase the surface area, up to 20 m2 g-1. Surprisingly, in the high surface area regime, the overall surface area gained from the nanogranules has little correlation with the improvement in capture efficiency. However, nanowire density and diameter play a significant role in the capture efficiency of PM0.3 particles, as do the surface roughness of the nanowire fibers and their characteristic feature sizes. Antimicrobial tests on the Cu foams show a >99.9995% inactivation efficiency after contacting the foams for 30 seconds. These results demonstrate promising directions to achieve a highly efficient multifunctional filtration platform with optimized microstructures.

Nanoelectronics—Beyond CMOS Computing [Guest Editorial

The six articles in this special section provide a broad perspective on future computing paradigms based on nanoelectronic technology. Nanoelectronics, as the word implies, is literally electronics at the nanoscale, i.e., with characteristic feature sizes less than 50 nm. By most measures, the semiconductor microelectronics industry today is the largest and most successful example of nanoelectronics and nanotechnology in general, where current transistor technology is below 3-nm gate lengths for the most advanced technologies, and the volume of semiconductor industry revenue exceeds US$450 billion. Semiconductor sales, in turn, power portable electronics, personal computers, mainframes, and multiple other industries.

Reconfigurable Three‐Dimensional Mesotructures of Spatially Programmed Liquid Crystal Elastomers and Their Ferromagnetic Composites

AbstractReversible programming of 3D soft mesostructures is desired for many applications including soft robotics and biomedical devices. The large, reversible shape changes of liquid crystal elastomers (LCEs), which result from the coupling between the alignment of liquid crystal (LC) molecules and the macroscopic deformation of polymer networks, have attracted much attention for such applications. Here, a facile and versatile strategy is introduced to create reconfigurable, freestanding 3D mesostructures of LCEs and magnetic LCE composites that are inaccessible with existing techniques via spatially programming LC molecules through mechanical buckling. Demonstrations include experimental and theoretical results of more than 20 reconfigurable 3D LCE mesostructures of diverse configurations, from coils and spirals to structures that resemble fences and frameworks, with characteristic feature sizes and thicknesses ranging from micro to macro. The large, reversible shape‐switching behaviors of these structures over multiple cycles are also demonstrated. An LCE gripper is shown to grab/release objects of both regular and irregular geometries. Furthermore, a robot of ferromagnetic LCE composites that simultaneously responds to magnetic and thermal stimuli for diverse biomimetic behaviors, especially crawling underneath a narrow crack, illustrates the integration of other functional materials to LCEs for multifunctional systems.

Revealing Three-Dimensional Morphology in Nanoporous Gold Using Three-Dimensional X-Ray Fresnel Coherent Diffractive Imaging Tomography

Abstract Nanoporous metals fabricated by dealloying have a unique bi-continuous, sponge-like porous structure with ultra-high surface area. The unique properties of these materials, especially nanoporous gold, have numerous potential applications in sensors and actuators and in energy-related applications such as catalytic materials, super-capacitors, and battery supports. The degree of porosity and size of the metal ligaments are critical parameters that determine many properties and thus govern the functionalities of nanoporous metals in many applications including energy storage and conversion. We used Fresnel coherent diffractive imaging combined with tomographic reconstruction to quantify the nanoscale three-dimensional spatial distribution and homogeneity of the porosity and ligament size within a bulk sample of nanoporous gold. The average porosity and its standard deviation along the axial direction through the sample were determined, as well as the characteristic feature size and its standard deviation. The result shows that free corrosion is an effective way to create homogeneous nanoporous metals with sample sizes on the order of 1 µm.

The mechanical response of cellular materials with spinodal topologies

The mechanical response of cellular materials with spinodal topologies is numerically and experimentally investigated. Spinodal microstructures are generated by the numerical solution of the Cahn-Hilliard equation. Two different topologies are investigated: ‘solid models,’ where one of the two phases is modeled as a solid material and the remaining volume is void space; and ‘shell models,’ where the interface between the two phases is assumed to be a solid shell, with the rest of the volume modeled as void space. In both cases, a wide range of relative densities and spinodal characteristic feature sizes are investigated. The topology and morphology of all the numerically generated models are carefully characterized to extract key geometrical features and ensure that the distribution of curvatures and the aging law are consistent with the physics of spinodal decomposition. Finite element meshes are generated for each model, and the uniaxial compressive stiffness and strength are extracted. We show that while solid spinodal models in the density range of 30–70% are relatively inefficient (i.e., their strength and stiffness exhibit a high-power scaling with relative density), shell spinodal models in the density range of 0.01–1% are exceptionally stiff and strong. Spinodal shell materials are also shown to be remarkably imperfection insensitive. These findings are verified experimentally by in-situ uniaxial compression of polymeric samples printed at the microscale by Direct Laser Writing (DLW). At low relative densities, the strength and stiffness of shell spinodal models outperform those of most lattice materials and approach theoretical bounds for isotropic cellular materials. Most importantly, these materials can be produced by self-assembly techniques over a range of length scales, providing unique scalability.

Morphology formation in binary mixtures upon gradual destabilisation.

Spontaneous liquid-liquid phase separation is commonly understood in terms of phenomenological mean-field theories. These theories correctly predict the structural features of the fluid at sufficiently long time scales and wavelengths. However, these conditions are not met in various examples in biology and materials science where the mixture is slowly destabilised, and phase separation is strongly affected by critical thermal fluctuations. We propose a mechanism of pretransitional structuring of a mixture that approaches the miscibility gap and predict scaling relations that describe how the characteristic feature size of the emerging morphology decreases with an increasing quench rate. These predictions quantitatively agree with our kinetic Monte Carlo and molecular dynamics simulations of a phase-separating binary mixture, as well as with previously reported experimental observations. We discuss how these predictions are affected by non-conserved order parameters (e.g., due to chemical reactions or alignment of liquid-crystalline molecules), hydrodynamics and active transport.

Correlation between topology and elastic properties of imperfect truss-lattice materials

Recent advances in additive manufacturing at small scales has revealed the exceptional mechanical properties that can be achieved by truss-lattice materials. This study investigates the response of four topologically distinct truss-lattice architectures to the inclusion of defects in order to elucidate how defects influence the elastic properties of these materials. Numerical results from finite element models of periodic beam networks with missing building blocks are compared to both analytical continuum models with a micromechanical basis and to experiments with characteristic feature sizes on the nano and micro scales. Notably, this comparison reveals that the elastic properties of highly connected lattice-truss materials respond to defects in the same manner as homogeneous materials.

Freestanding 3D Mesostructures, Functional Devices, and Shape-Programmable Systems Based on Mechanically Induced Assembly with Shape Memory Polymers.

Capabilities for controlled formation of sophisticated 3D micro/nanostructures in advanced materials have foundational implications across a broad range of fields. Recently developed methods use stress release in prestrained elastomeric substrates as a driving force for assembling 3D structures and functional microdevices from 2D precursors. A limitation of this approach is that releasing these structures from their substrate returns them to their original 2D layouts due to the elastic recovery of the constituent materials. Here, a concept in which shape memory polymers serve as a means to achieve freestanding 3D architectures from the same basic approach is introduced, with demonstrated ability to realize lateral dimensions, characteristic feature sizes, and thicknesses as small as ≈500, 10, and 5 µm simultaneously, and the potential to scale to much larger or smaller dimensions. Wireless electronic devices illustrate the capacity to integrate other materials and functional components into these 3D frameworks. Quantitative mechanics modeling and experimental measurements illustrate not only shape fixation but also capabilities that allow for structure recovery and shape programmability, as a form of 4D structural control. These ideas provide opportunities in fields ranging from micro-electromechanical systems and microrobotics, to smart intravascular stents, tissue scaffolds, and many others.

PH-Controlled Dealloying Route to Hierarchical Bulk Nanoporous Zn Derived from Metastable Alloy for Hydrogen Generation by Hydrolysis of Zn in Neutral Water

Dealloyed nanoporous metals made of very-reactive elements have rarely been reported. Instead, reactive materials are used as sacrificial components in dealloying. The high chemical reactivity of nonprecious nanostructured metals makes them suitable for a broad range of applications such as splitting water into H2 gas and metal hydroxide. On the other hand, the same high chemical reactivity hinders the synthesis of nanostructured metals. Here we use a pH-controlled dealloying strategy to fabricate bulk nanoporous Zn with bulk dimensions in the centimeter range via the selective removal of Al from metastable face-centered cubic bulk Zn20Al80 at. % parent alloys. The corresponding bulk nanoporous Zn exhibits a hierarchical ligament/pore architecture characterized by primary ligaments and pores with an average feature size in the submicrometer range. These primary structures are made of ultrafine secondary ligaments and pores with a characteristic feature size in the range of 10–20 nm. Our bulk nanoporous Zn can split water into H2 and Zn(OH)2 at ambient temperature and pressure and continuously produce H2 at a constant rate of 0.08 mL/min per gram of Zn over 8 h. We anticipate that in this hierarchical bulk architecture, the macropores facilitate the flow of water in the bulk of the material, while the mesopores and ultrafine ligaments provide a high surface area for the reaction of water with Zn. The bulk nanoporous Zn/water system can be used for on-board or on-demand H2 applications, during which H2 is produced when needed, without prior storage of this gas compressed in cylinders as it is currently the case.

(Invited) In Situ Dealloying of Bulk Mg2sn in Mg-Ion Half Cell As an Effective Route to Nanostructured Sn for High Performance Mg-Ion Battery Anodes

Nanostructured Sn as negative electrode material in Mg-ion batteries suffers from very slow magnesiation kinetics when its nanoscale feature sizes are not in the sub-100 nm range. Herein, we use electrochemical experiments in combination finite element modeling (FEM) to demonstrate a cost-effective route to nanostructured Sn for high performance Mg-ion battery anodes. Using FEM we found that antagonistic stresses developed during dealloying of Mg2Sn induce pulverization of the dealloyed material and formation of nanostructured Sn with characteristic feature size in the sub-100 nm range. These results were further confirmed through electrochemical experiments using a Mg half-cell consisting of bulk Mg2Sn particles with average characteristic size larger than 10 μm as the working electrode, cycled versus Mg metal as counter and reference electrodes, and all-phenyl complex (APC) electrolyte. Ex situ electron microscopy and diffraction techniques were used to study the working electrode material in the pristine, demagnesiated and re-magnesiated forms. The results suggest that the starting micrometer-sized Mg2Sn particles are converted into nanostructured β-Sn with characteristic sizes ranging from 10‒50 nm during the first demagnesiation. Electrochemical performance of the in situ formed nanostructured Sn was further investigated during subsequent (de)magnesiation cycles in combination with electrochemical impedance spectroscopy (EIS). EIS studies suggest the formation of passive films on the Mg2Sn electrode. A reversible capacity of 300 mAh/g was demonstrated over 150 cycles at the rate of C/5 after application of a combined sequence of regular galvanostatic cycling with an oxidative pulse to control the passive film formation. This work is expected to open new avenues for cost-effective routes to high performance alloy-type Mg-ion battery anodes without complex nanosynthesis steps.

In Situ Dealloying of Bulk Mg2Sn in Mg-Ion Half Cell as an Effective Route to Nanostructured Sn for High Performance Mg-Ion Battery Anodes

Nanostructured Sn as negative electrode material in Mg-ion batteries suffers from very slow magnesiation kinetics when its nanoscale feature sizes are not in the sub-100 nm range. Herein, we use electrochemical experiments in combination finite element modeling (FEM) to demonstrate a cost-effective route to nanostructured Sn for high performance Mg-ion battery anodes. Using FEM we found that antagonistic stresses developed during dealloying of Mg2Sn induce pulverization of the dealloyed material and formation of nanostructured Sn with the characteristic feature size in the sub-100 nm range. These results were further confirmed through electrochemical experiments using a Mg half-cell consisting of bulk Mg2Sn particles with an average characteristic size larger than 10 μm as the working electrode, cycled versus Mg metal as counter and reference electrodes, and all-phenyl complex (APC) electrolyte. Ex situ electron microscopy and diffraction techniques were used to study the working electrode material in the...

A scale space approach for estimating the characteristic feature sizes in hierarchical signals

The temporal and spatial data analysed in, for example, ecology or climatology, are often hierarchically structured, carrying information in different scales. An important goal of data analysis is then to decompose the observed signal into distinctive hierarchical levels and to determine the size of the features that each level represents. Using differences of smooths, scale space multiresolution analysis decomposes a signal into additive components associated with different levels of scales present in the data. The smoothing levels used to compute the differences are determined by the local minima of the norm of the so‐called scale‐derivative of the signal. While this procedure accomplishes the first goal, the hierarchical decomposition of the signal, it does not achieve the second goal, the determination of the actual size of the features corresponding to each hierarchical level. Here, we show that the maximum of the scale‐derivative norm of an extracted hierarchical component can be used to estimate its characteristic feature size. The feasibility of the method is demonstrated using an artificial image and a time series of a drought index, based on climate reconstructions from long tree ring chronologies. © 2018 John Wiley & Sons, Ltd.

Scaling behavior of nanoimprint and nanoprinting lithography for producing nanostructures of molybdenum disulfide

Top-down lithography techniques are needed for manufacturing uniform device structures based on emerging 2D-layered materials. Mechanical exfoliation approaches based on nanoimprint and nanoprint principles are capable of producing ordered arrays of multilayer transition metal dichalcogenide microstructures with a high uniformity of feature dimensions. In this study, we present a study on the applicability of nanoimprint-assisted shear exfoliation for generating ultrathin monolayer and few-layer MoS2 structures as well as the critical limits of feature dimensions produced via such nanoimprint and nanoprint-based processes. In particular, this work shows that give a lateral feature size of MoS2 structures that are pre-patterned on a bulk stamp, there exists a critical thickness or aspect ratio value, below which the exfoliated layered structures exhibit major defects. To exfoliate a high-quality, uniform monolayer or few-layer structures, the characteristic lateral feature sizes of such structures need to be in the sub-100 nm regimes. In addition, the exfoliated MoS2 flakes of critical thicknesses exhibit prominent interlayer twisting features on their cleaved surfaces. Field-effect transistors made from these MoS2 flakes exhibit multiple (or quasi-analog-tunable) charge memory states. This work advances the knowledge regarding the limitations and application scope of nanoimprint and nanoprint processes in manufacturing nano/microstructures based on layered materials and provides a method for producing multi-bit charge memory devices.

3-Dimensional Plasmonic Substrates Based on Chicken Eggshell Bio-Templates for SERS-Based Bio-Sensing

A simple technique is presented to fabricate stable and reproducible plasmonic substrates using chicken eggshell as bio-templates, an otherwise everyday waste material. The 3-dimensional (3D) submicron features on the outer shell (OS), inner shell (IS), and shell membrane (SM) regions are sputter coated with gold and characterized for surface-enhanced Raman scattering (SERS) performance with respect to coating thickness, enhancement factor (EF), hot-spots distribution, and reproducibility. The OS and IS substrates have similar EF (2.6 × 106 and 1.8 × 106, respectively), while the SM provides smaller EF (1.5 × 105) due to its larger characteristic feature size. The variability from them (calculated as relative standard deviation, %RSD) are less than 7, 15, and 9 for the OS, IS, and SM substrates, respectively. Due to the larger EF and better signal reproducibility, the OS region is used for label-free sensing and identification of Escherichia coli and Bacillus subtilis bacteria as an example of the potential SERS applications. It is demonstrated that the detection limit could reach the level of single bacterial cells. The OS and IS regions are also used as templates to fabricate 3D flexible SERS substrates using polydimethylsiloxane and characterized. The simple, low-cost, and green route of fabricating plasmonic substrates represents an innovative alternative approach without the needs for nanofabrication facilities. Coupled with hyperspectral Raman imaging, high-throughput bio-sensing can be carried out at the single pathogen level.

Enhanced Thermal Conduction Through Nanostructured Interfaces

ABSTRACTInterfaces dominate heat conduction in nanostructured systems, and much work has focused on methods to enhance interfacial conduction. These approaches generally address planar interfaces, where the heat flux vector is everywhere normal to the interface. Here, we explore a nanostructured interface geometry that uses nonplanar features to enhance the effective interfacial conductance beyond what is possible with planar interfaces. This interface consists of interdigitating Al pillars embedded within SiO2 with characteristic feature size ranging from 100 to 800 nm. The total sidewall surface area is modulated to highlight the impact of this additional channel by changing the pillar-to-pillar pitch between 1.6 µm and 200 nm while maintaining the same Al:SiO2 fill fraction. Using optical pump-probe thermoreflectance measurements, we show that the effective conductance of an ~65 nm thick fin layer monotonically increases with decreasing and that the conductance for = 200 nm is more than twice the prediction for a layered stack with the same volume ratio and a planar interface. Through a combination of Boltzmann transport modeling and finite element calculations, we explore the impact of the pitch and the pillar aspect ratio on effective thermal conductance. This analysis suggests that the concept of nanostructured interfaces can be extended to interfaces between diffusive and quasiballistic media in highly scaled devices. Our work proposes that the controlled texturing of interfaces can facilitate interfacial conduction beyond the planar interface regime, opening new avenues for thermal management at the nanoscale.

Interface-Driven Phenomena in Solids: Thermodynamics, Kinetics and Chemistry

The study of materials interfaces dates back over a century. In solid systems and from an engineering perspective, free surfaces and internal (grain and/or phase) boundaries influence a wide range of properties, such as thermal, electrical and optical transport, and mechanical ones. The properties and the role of interfaces has been discussed extensively in various reviews such as by Sutton and Balluffi. As the characteristic feature size of a materials system (i.e., grain size) is decreased to the nanometer scale, interface-driven physics is expected to dominate due to the increased density of such planar defects. Moreover, interfacial attributes, thermodynamics, and mobility play a key role in phase transformations, such as solidification dynamics and structural transitions in solids, and in homogenization and microstructural evolution processes, such as grain growth, coarsening, and recrystallization. In summary, the set of articles published in this special topic titled: “Interface-Driven Phenomena in Solids: Thermodynamics, Kinetics and Chemistry” covers topics related to microstructure evolution, segregation/adsorption phenomena and interface interactions with other materials defects.

Utilizing dynamic laser speckle to probe nanoscale morphology evolution in nanoporous gold thin films.

This paper demonstrates the use of dynamic laser speckle autocorrelation spectroscopy in conjunction with the photothermal treatment of nanoporous gold (np-Au) thin films to probe nanoscale morphology changes during the photothermal treatment. Utilizing this spectroscopy method, backscattered speckle from the incident laser is tracked during photothermal treatment and both the characteristic feature size and annealing time of the film are determined. These results demonstrate that this method can successfully be used to monitor laser-based surface modification processes without the use of ex-situ characterization.

Nanoporous gold as a neural interface coating: effects of topography, surface chemistry, and feature size.

Designing neural interfaces that maintain close physical coupling of neurons to an electrode surface remains a major challenge for both implantable and in vitro neural recording electrode arrays. Typically, low-impedance nanostructured electrode coatings rely on chemical cues from pharmaceuticals or surface-immobilized peptides to suppress glial scar tissue formation over the electrode surface (astrogliosis), which is an obstacle to reliable neuron-electrode coupling. Nanoporous gold (np-Au), produced by an alloy corrosion process, is a promising candidate to reduce astrogliosis solely through topography by taking advantage of its tunable length scale. In the present in vitro study on np-Au's interaction with cortical neuron-glia co-cultures, we demonstrate that the nanostructure of np-Au achieves close physical coupling of neurons by maintaining a high neuron-to-astrocyte surface coverage ratio. Atomic layer deposition-based surface modification was employed to decouple the effect of morphology from surface chemistry. Additionally, length scale effects were systematically studied by controlling the characteristic feature size of np-Au through variations in the dealloying conditions. Our results show that np-Au nanotopography, not surface chemistry, reduces astrocyte surface coverage while maintaining high neuronal coverage and may enhance neuron-electrode coupling through nanostructure-mediated suppression of scar tissue formation.

Gyroid‐Structured 3D ZnO Networks Made by Atomic Layer Deposition

3D continuous ZnO morphologies with characteristic feature sizes on the 10 nm length scale are attractive for electronic device manufacture. However, their synthesis remains a challenge because of the low crystallization temperature of ZnO. Here, we report a method for the robust and reliable synthesis of fully crystalline 3D mesoporous ZnO networks by means of atomic layer deposition (ALD) of ZnO into a self‐assembled block copolymer template. By carefully optimizing the processing conditions we are able to synthesize several‐micrometer‐thick layers of mesoporous ZnO networks with a strut width of 30 nm. Two 3D mesoporous morphologies are manufactured: a periodic gyroid structure and a random worm‐like morphology. Exploiting the ALD property to conformally coat complex surfaces of high aspect ratio, the channel network of a 3D continuous channel network of a self‐assembled block copolymer is replicated into ZnO. X‐ray photoemission spectroscopy and x‐ray diffraction measurements reveal that the chemical composition of the mesoporous structures is uniform and consists of wurtzite‐ZnO throughout the film. Scanning electron microscopy reveals an average pore dimension of 30 nm. The potential of this material for a hybrid photovoltaic application is demonstrated by the manufacture of a poly(3‐hexylthiophene)/ZnO solar cell.

ChemInform Abstract: Viewing Spin Structures with Soft X‐Ray Microscopy

AbstractReview: 102 refs.