Fabrication and Optical Properties of Periodic Ag Nano‐Pore and Nano‐Particle Arrays with Controlled Shape and Size over Macroscopic Length Scales

A facile and economical route to preparation of highly ordered sliver pore or particle arrays with controlled pore‐shape and size extended over cm² areas is described. The substrates are prepared at planar and curved surfaces via sphere‐imprinted polymer (PDMS) templating using polystyrene spheres with diameters of 820, 600, or 430 nm. Nano‐pore arrays are created by sputtering 80 nm of Ag directly onto the templates and nano‐particle arrays are prepared by electrode‐less deposition of Ag from Tollen's reagent. The shape of the nano‐pore or particles in the array conformed to that of the imprint of the sphere on the template. Stretching the flexible template enable creation of cuboid shaped nano‐voids and nano‐particles following Ag deposition. Diffuse reflectance from the spherical Ag nano‐cavity arrays showed absorbance maxima at wavelengths comparable similar to the diameter of the templating sphere, whereas reflectance from the cuboid arrays, showed little correlation with the sphere diameter. The cuboid nano‐particle arrays showed the most intense visible absorption which is red‐shifted compared to the spherical arrays. White light diffraction from the arrays, observed by rotating 1 cm² substrates relative to a fixed light source, reflected exactly the symmetry axes of the periodic nano‐features in the arrays demonstrating the remarkable macroscopic order of the periodic structures. Raman spectra of 1‐benzenethiol adsorbed at the arrays indicated SERS enhancements from the substrates are attributed mainly to surface nano‐roughness with only moderate contributions from the periodically corrugated structures. Despite excitation at the major resonance dip in the reflectance spectrum, a weak, localized rim dipole mode is found to elicit a small increase in the SERS enhancement factor for the 430 nm diameter spherical arrays. FDTD studies of nano‐void arrays provided insights into v arious factors affecting the SERS experiment and confirmed the array's plasmonic spectra are dominated by propagating plasmon modes under microscope excitation/collection angles.     

Rapid,Controllable Fabrication of Regular Complex Microarchitectures by Capillary Assembly of Micropillars and Their Application in Selectively Trapping/Releasing Microparticles

A simple strategy to realize new controllable 3D microstructures and a novel method to reversibly trapping and releasing microparticles are reported. This technique controls the height, shape, width, and arrangement of pillar arrays and realizes a series of special microstructures from 2‐pillar‐cell to 12 cell arrays, S‐shape, chain‐shape and triangle 3‐cell arrays by a combined top down/bottom up method: laser interference lithography and capillary force‐induced assembly. Due to the inherent features of this method, the whole time is less than 3 min and the fabricated area determined by the size of the laser beam can reach as much as 1 cm², which shows this method is very simple, rapid, and high‐throughput. It is further demonstrated that the ‘mechanical hand’‐like 4‐cell arrays could be used to selectively trap/release microparticles with different sizes, e.g., 1.5, 2, or 3.5 μm, which are controlled by the period of the microstructures from 2.5 to 4 μm, and 6 μm. Finally, the ‘mechanical hand’‐like 4‐cell arrays are integrated into 100 μm‐width microfluidic channels prepared by ultraviolet photolithography, which shows that this technique is compatible with conventional microfabrication methods for on‐chip applications.     

Solvent‐Assisted Micromolding of Biohybrid Hydrogels to Maintain Human Hematopoietic Stem and Progenitor Cells Ex Vivo

Array‐format cell‐culture carriers providing tunable matrix cues are instrumental in current cell biology and bioengineering. A new solvent‐assisted demolding approach for the fabrication of microcavity arrays with very small feature sizes down to single‐cell level (3 µm) of very soft biohybrid glycosaminoglycan–poly(ethylene glycol) hydrogels (down to a shear modulus of 1 kPa) is reported. It is further shown that independent additional options of localized conjugation of adhesion ligand peptides, presentation of growth factors through complexation to gel‐based glycosaminoglycans, and secondary gel deposition for 3D cell embedding enable a versatile customization of the hydrogel microcavity arrays for cell culture studies. As a proof of concept, cell‐instructive hydrogel compartment arrays are used to analyze the response of human hematopoietic stem and progenitor cells to defined biomolecular and spatial cues.     

Direct Synthesis of Ultrathin Pt Nanowire Arrays as Catalysts for Methanol Oxidation

High‐performance electrocatalysts are of critical importance for fuel cells. Morphological modulation of the catalyst materials is a rare but feasible strategy to improve their performance. In this work, Pt nanowire arrays are directly synthesized with a template‐less wet chemical method. The effects of surface functionalization and the reduction kinetics are revealed to be vital to the nanowire growth. The growth mechanism of the Pt nanowires is studied. By adjusting the concentration of the organic ligands, Pt nanowire arrays with tunable surface roughness can be obtained on various substrate surfaces. Such arrays avoid the contact resistance of randomly packed particles and allow open diffusion channels for reactants and products alike, making them excellent electrocatalysts for the methanol oxidation reaction. In particular, Pt nanowire arrays with rough surface have a mass activity of 1.24 A mg_Pt^?1 at 1.12 V (vs Ag/AgCl), 3.18‐fold higher than that of the commercial Pt/C catalysts. It also shows more resistant against poisoning, as indicated by the higher I_f/I_b ratio (2.06), in comparison to the Pt/C catalysts (1.30).     

Excellent Anti‐Icing Abilities of Optimal Micropillar Arrays with Nanohairs

Anti‐icing abilities are achieved on surfaces of micropillar arrays with nanohairs that are fabricated by methods of soft replication and crystal growth, i.e., different micropillar arrays with the similar nanohairs, different nanohairs with the same micropillar arrays. It is demonstrated that an optimal micropillar array with nanohairs contributes an excellent anti‐icing or antifogging property at low temperature below zero. As a result, the longest icing delay time is achieved effectively up to ≈9839 s at −10 °C on the optimal surface. As for the optimal surface in humidity, the condensed droplets merge into each other, and meanwhile jump off easily. Accordingly, a largest dry area is up to ≈90.5% at −5 °C in ≈1020 s after breeze action. It is attributed to the stability of less liquid–solid fraction on an optimal surface under low temperature, in addition to cooperation between micropillar arrays and nanohairs in sizes. This finding provides an insight into the design of structure size on micro–nanostructured surface for anti‐icing/antifogging ability effectively, which can be extended into the applications in some surfaces of systems, e.g., microdevices worked in cold or humid environment.     

Physical Deposition Improved SERS Stability of Morphology Controlled Periodic Micro/Nanostructured Arrays Based on Colloidal Templates

An effective and inexpensive method is developed to fabricate periodic arrays by sacrificial colloidal monolayer template route by chemical deposition and further physical deposition. By a colloidal template induced precursor solution dipping strategy, different periodic arrays of semi‐hollow sphere array, inverse opal with monolayer pore arrays and hole arrays are obtained under different conditions. After magnetron sputtering deposition, their morphologies are changed to novel micro/nanostructured arrays of honeycomb‐shaped arrays, hollow cavity arrays, and regular network arrays due to multiple direction deposition of sputtering deposition and shadow effect. After coating a gold thin layer, these periodic micro/nanostructured arrays are used as SERS active substrates and demonstrate a very stable SERS performance compared with periodic arrays achieved by direct colloidal template‐induced chemical deposition. Additionally, a honeycomb‐shaped array displays better SERS enhancement than that of a hollow cavity array or a regular network array. After optimization of honeycomb‐shaped arrays with different periodicities, an array with periodicity of 350 nm demonstrates much stronger SERS enhancement and possesses a low detection limit of 10^?11 M R6G. Such stable SERS performance is useful for practical application in portable Raman detecting devices to detect organic molecules.     

Biosensing by Densely Packed and Optically Coupled Plasmonic Particle Arrays

Densely packed plasmonic particle arrays are investigated for biosensing applications. Such particle arrays exhibit interparticle optical coupling creating a strong field between the particles, which is useful for sensing purposes. The sensor properties, such as bulk sensitivity, layer sensitivity, and the depth of sensitivity are investigated with the aid of a multiple multipole program. Sensitivity to the analyte with low concentration is also examined by a dynamic adsorption processes. The detectable concentration limit of streptavidin within 3000 s in the detection system is expected from the signal‐to‐noise to be less than 150 pM .     

Phase Modulation of (1T‐2H)‐MoSe2/TiC‐C Shell/Core Arrays via Nitrogen Doping for Highly Efficient Hydrogen Evolution Reaction

Tailoring molybdenum selenide electrocatalysts with tunable phase and morphology is of great importance for advancement of hydrogen evolution reaction (HER). In this work, phase‐ and morphology‐modulated N‐doped MoSe₂/TiC‐C shell/core arrays through a facile hydrothermal and postannealing treatment strategy are reported. Highly conductive TiC‐C nanorod arrays serve as the backbone for MoSe₂ nanosheets to form high‐quality MoSe₂/TiC‐C shell/core arrays. Impressively, continuous phase modulation of MoSe₂ is realized on the MoSe₂/TiC‐C arrays. Except for the pure 1T‐MoSe₂ and 2H‐MoSe₂, mixed (1T‐2H)‐MoSe₂ nanosheets are achieved in the N‐MoSe₂ by N doping and demonstrated by spherical aberration electron microscope. Plausible mechanism of phase transformation and different doping sites of N atom are proposed via theoretical calculation. The much smaller energy barrier, longer H? Se bond length, and diminished bandgap endow N‐MoSe₂/TiC‐C arrays with substantially superior HER performance compared to 1T and 2H phase counterparts. Impressively, the designed N‐MoSe₂/TiC‐C arrays exhibit a low overpotential of 137 mV at a large current density of 100 mA cm^?2, and a small Tafel slope of 32 mV dec^?1. Our results pave the way to unravel the enhancement mechanism of HER on 2D transition metal dichalcogenides by N doping.     

FeP@C Nanotube Arrays Grown on Carbon Fabric as a Low Potential and Freestanding Anode for High‐Performance Li‐Ion Batteries

An anode of self‐supported FeP@C nanotube arrays on carbon fabric (CF) is successfully fabricated via a facile template‐based deposition and phosphorization route: first, well‐aligned FeOOH nanotube arrays are simply obtained via a solution deposition and in situ etching route with hydrothermally crystallized (Co,Ni)(CO₃)_0.5OH nanowire arrays as the template; subsequently, these uniform FeOOH nanotube arrays are transformed into robust carbon‐coated Fe₃O₄ (Fe₃O₄@C) nanotube arrays via glucose adsorption and annealing treatments; and finally FeP@C nanotube arrays on CF are achieved through the facile phosphorization of the oxide‐based arrays. As an anode for lithium‐ion batteries (LIBs), these FeP@C nanotube arrays exhibit superior rate capability (reversible capacities of 945, 871, 815, 762, 717, and 657 mA h g⁻¹ at 0.1, 0.2, 0.4, 0.8, 1.3, and 2.2 A g⁻¹, respectively, corresponding to area specific capacities of 1.73, 1.59, 1.49, 1.39, 1.31, 1.20 mA h cm⁻² at 0.18, 0.37, 0.732, 1.46, 2.38, and 4.03 mA cm⁻², respectively) and a stable long‐cycling performance (a high specific capacity of 718 mA h g⁻¹ after 670 cycles at 0.5 A g⁻¹, corresponding to an area capacity of 1.31 mA h cm⁻² at 0.92 mA cm⁻²).     

Enhanced Magnetism in Highly Ordered Magnetite Nanoparticle‐Filled Nanohole Arrays

A new approach to develop highly ordered magnetite (Fe₃O₄) nanoparticle‐patterned nanohole arrays with desirable magnetic properties for a variety of technological applications is presented. In this work, the sub‐100 nm nanohole arrays are successfully fabricated from a pre‐ceramic polymer mold using spin‐on nanoprinting (SNAP). These nanoholes a then filled with monodispersed, spherical Fe₃O₄ nanoparticles of about 10 nm diameter using a novel magnetic drag and drop procedure. The nanohole arrays filled with magnetic nanoparticles a imaged using magnetic force microscopy (MFM). Magnetometry and MFM measurements reveal room temperature ferromagnetism in the Fe₃O₄‐filled nanohole arrays, while the as‐synthesized Fe₃O₄ nanoparticles exhibit superparamagnetic behavior. As revealed by MFM measurements, the enhanced magnetism in the Fe₃O₄‐filled nanohole arrays originates mainly from the enhanced magnetic dipole interactions of Fe₃O₄ nanoparticles within the nanoholes and between adjacent nanoholes. Nanoparticle filled nanohole arrays can be highly beneficial in magnetic data storage and other applications such as microwave devices and biosensor arrays that require tunable and anisotropic magnetic properties.     

Conductivity Tuning via Doping with Electron Donating and Withdrawing Molecules in Perovskite CsPbI3 Nanocrystal Films

Doping of semiconductors enables fine control over the excess charge carriers, and thus the overall electronic properties, crucial to many technologies. Controlled doping in lead‐halide perovskite semiconductors has thus far proven to be difficult. However, lower dimensional perovskites such as nanocrystals, with their high surface‐area‐to‐volume ratio, are particularly well‐suited for doping via ground‐state molecular charge transfer. Here, the tunability of the electronic properties of perovskite nanocrystal arrays is detailed using physically adsorbed molecular dopants. Incorporation of the dopant molecules into electronically coupled CsPbI₃ nanocrystal arrays is confirmed via infrared and photoelectron spectroscopies. Untreated CsPbI₃ nanocrystal films are found to be slightly p‐type with increasing conductivity achieved by incorporating the electron‐accepting dopant 2,3,5,6‐tetrafluoro‐7,7,8,8‐tetracyanoquinodimethane (F₄TCNQ) and decreasing conductivity for the electron‐donating dopant benzyl viologen. Time‐resolved spectroscopic measurements reveal the time scales of Auger‐mediated recombination in the presence of excess electrons or holes. Microwave conductance and field‐effect transistor measurements demonstrate that both the local and long‐range hole mobility are improved by F₄TCNQ doping of the nanocrystal arrays. The improved hole mobility in photoexcited p‐type arrays leads to a pronounced enhancement in phototransistors.     

Nanostructuring of Nickel Hydroxide via a Template Solution Approach for Efficient Electrochemical Devices

Nanostructuring is a key approach in enhancing the performance of electrochemical devices. In this work, nanostructuring is achieved by the electrodeposition of nickel hydroxide nanowire arrays, with both open‐ended and close‐ended structures, through anodized aluminium oxide (AAO) templates that are directly fabricated on indium tin oxide/glass substrates. The open‐ended and close‐ended nanostructures are compared together with identically fabricated thin films to show the effects of nanostructuring. Open‐ended nanowire arrays demonstrated the best electrochemical activity with superior transmittance modulation and faster activation, while the thin film showed the worst performance. In comparing with the close‐ended structures, enhanced performance is observed for the open‐ended structures despite the use of less material for the latter. This demonstrates that in designing nanostructures or porous materials, it is important for the porosity to have both interconnectivity and exposure to the electrolyte in electrochemical reactions.     

Zinc Sulfide Nanostructure Arrays: ZnS Nanostructure Arrays: A Developing Material Star (Adv. Mater. 5/2011)

Semiconductor nanostructure arrays are of great scientific and technical interest because of the strong non‐linear and electro‐optic effects that occur due to carrier confinement in three dimensions. The use of such nanostructure arrays with tailored geometry, array density, and length‐diameter‐ratio as building blocks are expected to play a crucial role in future nanoscale devices. With the unique properties of a direct wide‐bandgap semiconductor, such as the presence of polar surfaces, excellent transport properties, good thermal stability, and high electronic mobility, ZnS nanostructure arrays has been a developing material star. The research on ZnS nanostructure arrays has seen remarkable progress over the last five years due to the unique properties and important potential applications of nanostructure arrays, which are summarized here. Firstly, a survey of various methods to the synthesis of ZnS nanostructure arrays will be introduced. Next recent efforts on exploiting the unique properties and applications of ZnS nanostructure arrays are discussed. Potential future directions of this research field are also highlighted.     

Construction of FeS2‐Sensitized ZnO@ZnS Nanorod Arrays with Enhanced Optical and Photoresponse Performances

FeS₂‐sensitized ZnO@ZnS nanorod arrays are fabricated by a two‐step solution immersion and a subsequent sulfurization. The material properties including structure, morphology, and photoluminescence are investigated by a variety of characterization methods. As compared with ZnO@ZnS core/shell structure, FeS₂‐sensitized ZnO@ZnS nanorod arrays show improved optical absorption property with the extension of the absorption edge into the range of visible light. The photoresponse performance of FeS₂‐sensitized Zno@ZnS is also enhanced as the photocurrent density at 1.0 V is dozens of times larger than that of ZnO@ZnS nanorods. The cause for the difference in such material properties of these two materials is discussed. In this work, a new method for sensitizing wide bandgap ZnO@ZnS nanorod arrays with improved light response performance is presented.     

Bio‐Inspired Bright Structurally Colored Colloidal Amorphous Array Enhanced by Controlling Thickness and Black Background

Inspired by Steller's jay, which displays angle‐independent structural colors, angle‐independent structurally colored materials are created, which are composed of amorphous arrays of submicrometer‐sized fine spherical silica colloidal particles. When the colloidal amorphous arrays are thick, they do not appear colorful but almost white. However, the saturation of the structural color can be increased by (i) appropriately controlling the thickness of the array and (ii) placing the black background substrate. This is similar in the case of the blue feather of Steller's jay. Based on the knowledge gained through the biomimicry of structural colored materials, colloidal amorphous arrays on the surface of a black particle as the core particle are also prepared as colorful photonic pigments. Moreover, a structural color on–off system is successfully built by controlling the background brightness of the colloidal amorphous arrays.     

Configurable Low‐Cost Plotter Device for Fabrication of Multi‐Color Sub‐Cellular Scale Microarrays

The construction and operation of a low‐cost plotter for fabrication of microarrays for multiplexed single‐cell analyses is reported. The printing head consists of polymeric pyramidal pens mounted on a rotation stage installed on an aluminium frame. This construction enables printing of microarrays onto glass substrates mounted on a tilt stage, controlled by a Lab‐View operated user interface. The plotter can be assembled by typical academic workshops from components of less than 15 000 Euro. The functionality of the instrument is demonstrated by printing DNA microarrays on the area of 0.5 cm² using up to three different oligonucleotides. Typical feature sizes are 5 μm diameter with a pitch of 15 μm, leading to densities of up to 10⁴–10⁵ spots/mm². The fabricated DNA microarrays are used to produce sub‐cellular scale arrays of bioactive epidermal growth factor peptides by means of DNA‐directed immobilization. The suitability of these biochips for cell biological studies is demonstrated by specific recruitment, concentration, and activation of EGF receptors within the plasma membrane of adherent living cells. This work illustrates that the presented plotter gives access to bio‐functionalized arrays usable for fundamental research in cell biology, such as the manipulation of signal pathways in living cells at subcellular resolution.     

Flexible Photodetector Arrays Based on Patterned CH3NH3PbI3−xClx Perovskite Film for Real‐Time Photosensing and Imaging

The quest for novel deformable image sensors with outstanding optoelectronic properties and large‐scale integration becomes a great impetus to exploit more advanced flexible photodetector (PD) arrays. Here, 10 × 10 flexible PD arrays with a resolution of 63.5 dpi are demonstrated based on as‐prepared perovskite arrays for photosensing and imaging. Large‐scale growth controllable CH₃NH₃PbI_3?xCl_x arrays are synthesized on a poly(ethylene terephthalate) substrate by using a two‐step sequential deposition method with the developed Al₂O₃‐assisted hydrophilic–hydrophobic surface treatment process. The flexible PD arrays with high detectivity (9.4 × 10¹¹ Jones), large on/off current ratio (up to 1.2 × 10³), and broad spectral response exhibit excellent electrical stability under large bending angle (θ = 150°) and superior folding endurance after hundreds of bending cycles. In addition, the device can execute the functions of capturing a real‐time light trajectory and detecting a multipoint light distribution, indicating that it has widespread potential in photosensing and imaging for optical communication, digital display, and artificial electronic skin applications.     

Two‐Dimensional Self‐Organization of an Ordered Au Silicide Nanowire Network on a Si(110)‐16 × 2 Surface

A well‐ordered two‐dimensional (2D) network consisting of two crossed Au silicide nanowire (NW) arrays is self‐organized on a Si(110)‐16 × 2 surface by the direct‐current heating of ≈1.5 monolayers of Au on the surface at 1100 K. Such a highly regular crossbar nanomesh exhibits both a perfect long‐range spatial order and a high integration density over a mesoscopic area, and these two self‐ordering crossed arrays of parallel‐aligned NWs have distinctly different sizes and conductivities. NWs are fabricated with widths and pitches as small as ≈2 and ≈5 nm, respectively. The difference in the conductivities of two crossed‐NW arrays opens up the possibility for their utilization in nanodevices of crossbar architecture. Scanning tunneling microscopy/spectroscopy studies show that the 2D self‐organization of this perfect Au silicide nanomesh can be achieved through two different directional electromigrations of Au silicide NWs along different orientations of two nonorthogonal 16 × 2 domains, which are driven by the electrical field of direct‐current heating. Prospects for this Au silicide nanomesh are also discussed.     

Spherical Nanoparticle Arrays with Tunable Nanogaps and Their Hydrophobicity Enhanced Rapid SERS Detection by Localized Concentration of Droplet Evaporation

Periodic hexagonal spherical nanoparticle arrays are fabricated by a sacrificial colloidal monolayer template route by chemical deposition and further physical deposition. The regular network‐structured arrays are first templated by colloidal monolayers and then they are changed to novel periodic spherical nanoparticle arrays by further sputtering deposition due to multiple direction deposition and shadow effect between adjacent nanoparticles. The nanogaps between two adjacent spherical nanoparticles can be well tuned by controlling deposition time. Such periodic nanoparticle arrays with gold coatings demonstrate a very stable and high sensitive surface‐enhanced Raman scattering spectroscopy (SERS) performance. The periodic nanoparticle arrays with 10 nm gaps display much stronger SERS enhancement due to electromagnetic coupling. The chemically modified nanoparticle arrays show good hydrophobicity, which shorten process of detecting probe molecules using them as SERS‐active substrates by localized concentration of droplet evaporation and a low detection limit of 10⁻¹² m R6G can be achieved without solution wasting in a short time. The hydrophobic substrate offers a simple, convenient, and economical method to examine SERS performance by rapid concentration of solution on it and it is highly helpful to improve its practical applications in portable Raman detecting devices to detect organic molecules.     

Polypyrrole Whelk‐Like Arrays toward Robust Controlling Manipulation of Organic Droplets Underwater

Whelk‐like polypyrrole (PPy) arrays film is successfully prepared by electropolymerization of pyrrole in the presence of low‐surface‐energy tetraethylammonium perfluorooctanesulfonate (TEAPFOS) as dopant. The underwater wettability of PPy whelk‐like arrays can be successfully tuned by electrical doping/dedoping of PFOS ions. Interestingly, CCl₄ droplets with microliter‐size as a representative sample are gathered together to form a larger droplet underwater at the potential of +0.8 V (vs Ag/AgCl), because PPy is in its PFOS‐doped states. Note that CCl₄ droplet can climb uphill successfully on the inclined whelk‐like arrays PPy film under the applied potential of ?1.0 V (vs Ag/AgCl), which may be attributed to wettability gradient derived from different oxidation states of PPy induced by electrochemical potential. These results may provide a simple strategy for on‐demand manipulation of organic droplets underwater at low voltage.