Oxide Template Research Articles

Highly Sensitive ZnO/Au Nanosquare Arrays Electrode for Glucose Biosensing by Electrochemical and Optical Detection.

The fabrication of a ZnO/Au nanosquare-array electrode was successfully carried out for the detection of glucose concentration in biomedical applications. The fabrication of the ZnO/Au nanosquare array using an ultra-thin alumina mask (UTAM) based on the imprinted anodic aluminum oxide (AAO) template and the direct current (DC) sputtering method was able to produce a very well-ordered nanosquare arrangement with a side size of 300 nm and a thickness of 100 nm. Tests were done to evaluate the performance of the electrode by means of cyclic voltammetry (CV) which showed that the addition of glucose oxidase (GOx) increased the sensitivity of the electrode up to 1180 ± 116 μA mM-1cm-2, compared with its sensitivity prior to the addition of GOx of 188.34 ± 18.70 mA mM-1 cm-2. A iox/ired ratio equal to ~1 between the peaks of redox reactions was obtained for high (hyperglycemia), normal, and low (hypoglycemia) levels of glucose. The ZnO/Au nanosquare-array electrode was 7.54% more sensitive than the ZnO/Au thin-film electrode. Furthermore, finite-difference time-domain (FDTD) simulations and theoretical calculations of the energy density of the electric and magnetic fields produced by the ZnO/Au electrode were carried out and compared to the results of CV. From the results of CV, FDTD simulation, and theoretical calculations, it was confirmed that the ZnO/Au nanosquare array possessed a significant optical absorption and that the quantum effect from the nanosquare array resulted in a higher sensitivity than the thin film.

Customizing 2.5D Out-of-Plane Architectures for Robust Plasmonic Bound-States-in-the-Continuum Metasurfaces.

Bound states in the continuum (BICs) have a superior ability to confine electromagnetic waves and enhance light-matter interactions. However, the quality-factor of quasi-BIC is extremely sensitive to structural perturbations, thus the BIC metasurfaces usually require a very-high precision nanofabrication technique that greatly restricts their practical applications. Here, distinctive 2.5D out-of-plane architectures based plasmonic symmetry protected (SP)-BIC metasurfaces are proposed, which could deliver robust quality factors even with large structural perturbations. The high-throughput fabrication of such SP-BIC metasurfaces is realized by using the binary-pore anodic aluminum oxide template technique. Moreover, the deep neural network (DNN) is adapted to conduct multiparameter fittings, where the 2.5D hetero-out-of-plane architectures with robust high quality-factors and figures of merit are rapidly predicted and fabricated. Finally, owning to its large second-order surface sensitivity, the desired 2.5D hetero-out-of-plane architecture demonstrates a detection limit of endotoxin as low as 0.01 EU mL-1 , showing a good perspective of biosensors and others.

Selenium-transition metal supported on a mixture of reduced graphene oxide and silica template for water splitting.

Exploration of economical, highly efficient, and environment friendly non-noble-metal-based electrocatalysts is necessary for hydrogen and oxygen evolution reactions (HER and OER) but challenging for cost-effective water splitting. Herein, metal selenium nanoparticles (M = Ni, Co & Fe) are anchored on the surface of reduced graphene oxide and a silica template (rGO-ST) through a simple one-pot solvothermal method. The resulting electrocatalyst composite can enhance mass/charge transfer and promote interaction between water molecules and electrocatalyst reactive sites. NiSe2/rGO-ST shows a remarkable overpotential (52.5 mV) at 10 mA cm-2 for the HER compared to the benchmark Pt/C E-TEK (29 mV), while the overpotential values of CoSeO3/rGO-ST and FeSe2/rGO-ST are 246 and 347 mV, respectively. The FeSe2/rGO-ST/NF shows a low overpotential (297 mV) at 50 mA cm-2 for the OER compared to RuO2/NF (325 mV), while the overpotentials of CoSeO3-rGO-ST/NF and NiSe2-rGO-ST/NF are 400 and 475 mV, respectively. Furthermore, all catalysts indicate negligible deterioration, indicating better stability during the process of HER and OER after a stability test of 60 h. The water splitting system composed of NiSe2-rGO-ST/NF||FeSe2-rGO-ST/NF electrodes requires only ∼1.75 V at 10 mA cm-2. Its performance is nearly close to that of a noble metal-based Pt/C/NF||RuO2/NF water splitting system.

Polymeric Janus nanorods via anodic aluminum oxide templating.

We report a novel method for the fabrication of polymeric Janus nanorods via sequential polymerization from anodic aluminum oxide (AAO) templates. Dual compositions can be incorporated into individual nanorods and endow versatile potential applications. This fabrication strategy paves the way for constructing multifunctional nanostructures and brings together different materials in a single entity.

A new and versatile template towards vertically oriented nanopillars and nanotubes.

Vertically oriented nanostructures bring unparalleled high surface area, light trapping capability, and high device density to electronic, optoelectronic, and energy storage devices. However, general methods to prepare such structures remain sparse and are typically based on anodized metal oxide templates. Here, we demonstrate a new approach: using vertically oriented tetraaniline nanopillar arrays as templates for creating nanopillars and nanotubes of other materials. The tetraaniline templates are scalable and easy to prepare. Vertical arrays of a variety of materials can be created by directly coating them onto the tetraaniline nanopillars via vapor, solution, or electrodeposition. Since the tetraaniline template is encased within the target material, it does not require post-deposition removal, thus enabling vertical structure formation of sensitive materials. Conversely, removal of the encased tetraaniline template provides vertically oriented nanotube arrays in a lost-wax-type operation. The resulting vertical structures exhibit a high degree of orientation and height uniformity, with tunable feature size, spacing, and array density. Furthermore, the deposition location and shape of the vertical arrays can be patterned at a resolution of 3 μm. Collectively, these attributes should broaden the material repertoire for vertically oriented structures, and lead to advancements in energy storage, electronics, and optoelectronics.

Large-scale synthesis of 2D-silica (SiOx) nanosheets using graphene oxide (GO) as a template material.

Graphene oxide (GO) was used in this study as a template to successfully synthesize silicon oxide (SiOx) based 2D-nanomaterials, adapting the same morphological features as the GO sheets. By performing a controlled condensation reaction using low concentrations of GO (<0.5 wt%), the study shows how to obtain 2D-nanoflakes, consisting of GO-flakes coated with a silica precursor that were ca. 500 nm in lateral diameter and ca. 1.5 nm in thickness. XPS revealed that the silanes had linked covalently with the GO sheets at the expense of the oxygen groups present on the GO surface. The GO template was shown to be fully removable through thermal treatment without affecting the nanoflake morphology of the pure SiOx-material, providing a methodology for large-scale preparation of SiOx-based 2D nanosheets with nearly identical dimensions as the GO template. The formation of SiOx sheets using a GO template was investigated for two different silane precursors, (3-aminopropyl) triethoxysilane (APTES) and tetraethyl orthosilicate (TEOS), showing that both precursors were capable of accurately templating the graphene oxide template. Molecular modeling revealed that the choice of silane affected the number of layers coated on the GO sheets. Furthermore, rheological measurements showed that the relative viscosity was significantly affected by the specific surface area of the synthesized particles. The protocol used showed the ability to synthesize these types of nanoparticles using a common aqueous alcohol solvent, and yield larger amounts (∼1 g) of SiOx-sheets than what has been previously reported.

Plasmon Resonances in 1D Nanowire Arrays and 3D Nanowire Networks of Topological Insulators and Metals.

The 1D nanowire arrays and 3D nanowire networks of topological insulators and metals have been fabricated by template-assisted deposition of Bi2Te3 and Ni inside anodic aluminum oxide (AAO) templates, respectively. Despite the different origins of the plasmon capabilities of the two materials, the results indicate that the optical response is determined by plasmon resonances, whose position depends on the nanowire interactions and material properties. Due to the thermoelectric properties of Bi2Te3 nanowires, these plasmon resonances could be used to develop new ways of enhancing thermal gradients and their associated thermoelectric power.

Tuning of the Titanium Oxide Surface to Control Magnetic Properties of Thin Iron Films

We describe the magnetic properties of thin iron films deposited on the nanoporous titanium oxide templates and analyze their dependance on nanopore radius. We then compare the results to a continuous iron film of the same thickness. Additionally, we investigate the evolution of the magnetic properties of these films after annealing. We demonstrate that the M(H) loops consist of two magnetic phases originating from the iron layer and iron oxides formed at the titanium oxide/iron interface. We perform deconvolution of hysteresis loops to extract information for each magnetic phase. Finally, we investigate the magnetic interactions between the phases and verify the presence of exchange coupling between them. We observe the altering of the magnetic properties by the nanopores as a magnetic hardening of the magnetic material. The ZFC-FC (Zero-field cooled/field cooled) measurements indicate the presence of a disordered glass state below 50 K, which can be explained by the formation of iron oxide at the titanium oxide-iron interface with a short-range magnetic order.

Superhydrophobic Mechano-Bactericidal Surface with Photodynamic Antibacterial Capability

Bacterial invasion and proliferation on various surfaces pose a serious threat to public health worldwide. Conventional antibacterial strategies that mainly rely on bactericides exhibit high bacteria-killing efficiency but might trigger the well-known risk of antibiotic resistance. Here, we report a superhydrophobic mechano-bactericidal surface with photodynamically enhanced antibacterial capability. First, bioinspired nanopillars with polycarbonate as the bulk material were replicated from anodized alumina oxide templates via a simple hot-pressing molding method. Subsequently, a facile bovine serum albumin phase-transition method was used to introduce chlorin e6 onto the nanopillar-patterned surface, which was then perfluorinated to render the surface superhydrophobic. Benefiting from its strong liquid super-repellency and photodynamically enhanced mechano-bactericidal properties, the superhydrophobic nanopillar-patterned surface exhibits 100% antibacterial efficiency after 30 min visible light irradiation (650 nm, 20 mW cm-2). More strikingly, the surface exhibited impressive long-lasting antimicrobial performance, maintaining a very high bactericidal efficiency (≥99%) even after 10 cycles of bacterial contamination tests. Also, the superhydrophobic nanopillar-patterned surface displays good hemocompatibility with a much lower than the 5% hemolysis rate. Overall, this work offers a new method for significantly enhancing the antibacterial efficiency of structural antimicrobial surfaces without involving any bactericidal agents, and this functional surface shows great potential in the field of advanced medical materials and hospital surfaces.

Influence of natural convection on the electrodeposition of copper nanowires in anodic aluminium oxide templates

Templated electrodeposition is a versatile method for preparing metal nanostructures. Among the various parameters of this process, the effect of convection on the deposition process is less explored. The present work is devoted to the experimental and theoretical study of the influence of natural convection near nanoporous anodic aluminium oxide templates on the deposition of nanowires. Electrochemical deposition of copper nanowires was carried out with vertical templates parallel to the gravitational acceleration at various overpotentials. A model of nanowire electrodeposition was developed based on the Navier‒Stokes and diffusion equations. The length profiles of the nanowires, experimentally measured using scanning electron microscopy, were compared with the results of the numerical simulation. The simulation results were also compared with current-time transients recorded during metal electrodeposition into nanopores. In addition, an analytical expression has been proposed to describe the evolution of the deposition current density into nanopores under natural convection conditions.

Synthesis of nickel nanowires (Ni-NWs) as high ferromagnetic material by electrodeposition technique

Metallic nanowires (NWs) and their different compounds display incredible prospects for their use in various applications including media storage, sensor and solar cell devices along with the biological drug delivery systems. In this research work, the metallic NWs like nickel nanowires (Ni-NWs) are synthesized successfully by employing electrodeposition process. Anodic aluminum oxide (AAO) templates are employed as a platform with copper metal coating which acts as an active cathode. The synthesized Ni-NWs are examined through various characterization techniques including X-ray diffraction (XRD), scanning electron microscope (SEM) and vibrating sample magnetometer (VSM) to study the crystal structure, surface morphology and magnetic properties, respectively. The XRD analysis shows the development of various diffraction planes like Ni (111), Ni (200), Ni (220) which confirms the formation of polycrystalline nickel NWs. The SEM analysis reveals that the range of diameter and length of nickel NWs are found to be ∼160 to 200 and ∼4 to 11 micron respectively showing high aspect ratio (ranged from ∼200 to 300). The ferromagnetic behavior of Ni-NWs is confirmed by the hysteresis loop carried out for parallel and perpendicular configurations having Hc = 100 and 206 Oe, respectively. The obtained results suggest that the synthesized Ni- NWs may be used for high-density media storage devices.

Tuning magnetostatic interaction and coercivity distributions of FeCo/Cu multilayer nanowire arrays by variation of magnetic and nonmagnetic layer aspect ratios

FeCo/Cu multilayer NW arrays are fabricated using a pulsed electrodeposition method in 50 nm pore diameter anodic aluminum oxide templates. The magnetic layer (LFeCo) and nonmagnetic layer (LCu) thicknesses range between 23–225 and 2–50 nm, respectively. These layer designations make it possible to find a thin Cu layer, in which the magnetic behavior of multilayer NWs is similar to that of alloy NWs. A threshold LCu is also obtained, representing dual behavior of the coercive field in FeCo/Cu multilayer NWs. These behaviors, in turn, are associated with an increase in magnetizing and demagnetizing interactions, as evidenced by hysteresis curve and first-order reversal curve experiments. By extracting magnetic parameters such as the average coercive field, irreversible coercive field, magnetostatic interaction distribution, and reversibility, the magnetic behavior of FeCo/Cu multilayer NWs is comprehensively explored as a function of LFeCo.

Manipulating Dual Bound States in the Continuum for Efficient Spatial Light Modulator

Spatial light modulators (SLMs) that could control diverse optical properties are highly demanded by many optoelectronic systems. Recently, the integration of nonlinear χ(2) materials and metasurfaces has been recognized as a promising strategy for next-generation SLMs. However, their modulation efficiency still encounters challenges due to low quality factor and weak light-matter interaction. Here, we demonstrate an efficient SLM by manipulating the dual bound state in continuum (BIC) with the assistance of a binary-pore anodic alumina oxide template technique. The coexistence of symmetry-protected BIC and Fabry-Pérot BIC is obtained by a desirable sandwich configuration with a BIC metasurface and EO polymer, which efficiently restrain radiative loss and generate a strong quasi-BIC resonance. The assembled SLM with large absorption and Q-factor delivers a modulation depth of 77% and an f3dB of nearly 100 MHz. This dual BIC metasurface provides potential for applications including switches, LIDAR, augmented and virtual reality, and so on.

Facile Preparation of Carbon Nanopillar Array

Carbon-based nanostructures have attracted extensive interest in obtaining advanced sensing electronic devices in environmental and biological monitoring applications as an alternative to conventional materials. Herein, the facile preparation, control of the growth, and artificial intelligence–based morphological information of the carbon nanopillar array in the Anodized Aluminum Oxide (AAO) template were investigated. A facile approach for controlling the growth of the nanostructure was proposed as a two-step anodization technique for AAO and Plasma Enhanced Chemical Vapor Deposition (PECVD) for carbon nanopillar array. It involved the competitive carbon deposition between the carbon nanopillars electrodeposited on the AAO template and at the bottom of the pores of AAO under vacuum conditions. The morphology and structure of the prepared carbon nanopillars were reported in detail. Hexagonally straight AAO nanotubes were approximately 65 nm in diameter and 360 nm in length, with 90 nm interpore distances. The AAO nanotube density is approximately 1.75x1014 cm-2. Carbon nanopillars with a width of ~60 nm were used to create a low-dimensional nanostructure. This controllable preparation leads to the facile and impressive preparation of a free-standing carbon nanopillar array, especially for various chemical sensor applications.

Current density-induced emergence of soft and hard magnetic phases in Fe nanowire arrays

The capability of generating magnetically soft and hard phases in a material is important in many aspects, ranging from basic science to applications. Here, the emergence of soft and hard magnetic phases is reported in Fe nanowire (NW) arrays with a diameter of 35 nm fabricated by using a pulsed electrochemical deposition method in porous aluminum oxide templates under different current density (C d ) values in the range of 25–100 mA cm−2. The variation of C d influences the grain size, crystallinity, electrodeposition efficiency and length of the Fe NWs, as characterized by x-ray diffraction, high-resolution transmission electron microscopy, vibrating sample magnetometry and field-emission scanning electron microscopy. Increasing C d from 25 to 80 mA cm−2 results in a significant decrease in coercivity and squareness from 1590 to 900 Oe and 0.9 to 0.5, respectively, inducing the soft and hard phases along the length of Fe NWs. Further increasing the C d leads to the separation of the phases, as evidenced by first-order reversal curve analysis. From a theoretical aspect, the emergence of the soft phase may lead to the occurrence of the fanning reversal mode in the NWs, for which there is no precedent in previous experimental investigations.

Growth of type I superlattice III-V heterostructure in horizontal nanowires enclosed in a silicon oxide template

Template assisted selective epitaxy (TASE) offers an attractive monolithic integration route for III-V semiconductors on Si, benefitting from reduced defect density and versatility in its employment to create various electronic and photonic devices. This work achieves compositional and morphological control of lattice matched InGaAs quantum wells embedded in a horizontal InP nanowire grown directly from a Si seed and of the respective heterointerfaces. A series of growth experiments introducing variations of the precursor switching sequence in the growth recipe, and a subsequent scanning transmission electron microscopy and energy dispersive X-ray spectroscopy analysis, were employed to create and characterize a type I superlattice enclosed in a silicon oxide template.

Toward the Scalable Fabrication of Fully Bio-Based Antimicrobial and UVB-Blocking Transparent Polylactic Acid Films That Incorporate Natural Coatings and Nanopatterns.

Microbial transmissions via membrane surface and single-use plastic-induced pollution are two urgent societal problems. This research introduces a scalable fabrication strategy for fully biobased antibacterial and ultraviolet-B block polylactic acid (PLA) films integrating natural coatings and nanopatterns via ultrasonic atomization spray coating and thermal nanoimprinting lithography (TNIL) techniques, respectively. Tannic acid (TA) and gallic acid (GA) were formulated prior to TNIL using anode aluminum oxide template. Results reveal that TA and GA inks display intense adsorption in the UVB region. Plasma increases the hydrophilicity of PLA films for fast spreading of ink droplets. Micron-sized pillars observed on film confirm the successful structural replication. TA-coated PLA films display higher transparency than GA-coated ones. Nanopatterned PLA films have a modest antibacterial resistance of c. 45% against Escherichia coli. TA/GA coatings, however, impart PLA films with a bacterial reduction rate of over 80%. The integration of a TA or GA coating with nanopatterns further promotes the antibacterial rate up to 98%. The cytocompatibility of TA and GA demonstrates that the engineered film can potentially be applied as food packaging. Finally, a continuous mass production strategy is proposed along with an outline of the associated challenges and costs. This study provides a scalable strategy to the sustainable development of eco-benign and functional films.

Positive and negative effects of graphite flake and monolayer graphene oxide templates on protein crystallization

Heterogeneous template-induced nucleation is a promising way to regulate protein crystallization events and could be employed for purification processes and crystallographic studies. Protein crystallization process with graphite and graphene oxide, as heterogeneous templates, were investigated. More than 640 hanging drops with different concentrations of Lysozyme (30, 50, 70, 100 mg/mL) and NaCl (0.7, 0.9, 1.1, 1.3, 1.5 M) were crystallised at 4 °C with or without graphite/graphene oxide templates. The induction times and crystallization process were observed under the microscope. The lysozyme in the solutions with graphite flakes nucleated faster under all the conditions than the lysozyme with equal experimental conditions without templates. The crystals preferred to grow around the edge of graphite flakes than on the flat surfaces. In the droplets with monolayer graphene oxide, more crystals appeared around graphene oxide particles, and the faster or slower nucleation processes with templates were dependent on the lysozyme and NaCl concentrations. Graphene oxide templates strongly inhibited nucleation at high lysozyme concentrations but promoted nucleation at low lysozyme concentrations. Both heterogeneous templates changed the crystal morphology and the crystallization kinetics. More crystals were observed in the solution with graphite templatesthan with graphene oxide templates and without any template.

Growth of Highly-Ordered Metal Nanoparticle Arrays in the Dimpled Pores of an Anodic Aluminum Oxide Template.

A reliable, scalable, and inexpensive technology for the fabrication of ordered arrays of metal nanoparticles with large areal coverage on various substrates is presented. The nanoparticle arrays were formed on aluminum substrates using a two-step anodization process. By varying the anodization potential, the pore diameter, inter-pore spacing, and pore ordering in the anodic aluminum oxide (AAO) template were tuned. Following a chemical etch, the height of the pores in the AAO membrane were reduced to create a dimpled membrane surface. Periodic arrays of metal nanoparticles were subsequently created by evaporating metal on to the dimpled surface, allowing for individual nanoparticles to form within the dimples by a solid state de-wetting process induced by annealing. The ordered nanoparticle array could then be transferred to a substrate of choice using a polymer lift-off method. Following optimization of the experimental parameters, it was possible to obtain cm2 coverage of metal nanoparticles, like gold and indium, on silicon, quartz and sapphire substrates, with average sizes in the range of 50-90 nm. The de-wetting process was investigated for a specific geometry of the dimpled surface and the results explained for two different film thicknesses. Using a simple model, the experimental results were interpreted and supported by numerical estimations.

Rapid fabrication of large-area and uniform surface-enhanced Raman spectroscopy substrate of Au nano-hemisphere array and its application in the detection of Malachite Green in tilapia

Abstract Although surface-enhanced Raman spectroscopy (SERS) substrates have achieved high sensitivity, it is still difficult to apply these SERS protocols to the on-site detection of real samples due to the SERS substrate being fabrication-complexed, unstable, reproducible, or unable to be applied in batch production. Here, a large-scale ordered two-dimensional array of Au nano-hemispheres was developed through electron beam vaporization of Au onto the easy-available commercialized anodic aluminum oxide (AAO) template with two-layer nanostructures of different diameters. The uniform Au nano-hemisphere is reliable for SERS detection of malachite green (MG) due to the relative standard deviation (RSD) of the SERS intensities at different locations less than 10%. With the optimized excitation wavelength, solvent effect and pH environment, the linear range of MG detection spans from 10–10 to 10–6 mol/L with a limit of detection (LOD) of 4×10–10 mol/L. The enhancement factor can reach 1.2×106. After extraction with acetonitrile and dichloromethane, MG in the spiked tilapia was detected with satisfactory recovery. The results indicate that the Au nano-hemisphere array can be expected to greatly facilitate SERS practical applications in detecting harmful food additives and chemicals due to the advantages of chemical inertness, physical robustness, simple fabrication, controllability, large-area uniformity, and large-batch production.