Fabrication Of Nanostructures Research Articles

Fabrication and regulation of self-assembled nanostructures of benzene-1,3,5-tricarboxamide derivatives

A variety of supramolecular structures of benzene-1,3,5-tricarboxamide derivatives (BTAs), such as helixes and nanosheets, have been fabricated. However, how to regulate the self-assembly behavior through molecular design and control of experimental conditions, and thus to form supramolecular structures with different morphologies is still a topic that needs to be further explored. In this paper, two kinds of BTAs with different end groups, i.e. terpyridine and carboxyl were synthesized, which are referred to as L and A, respectively. Their self-assembly behaviors in DMF/aqueous solution were investigated by adding the DMF solution of BTAs into the aqueous solution dropwise. It was found that the two BTAs exhibited different self-assembly behaviors. L self-assembled into helical nanowires and nanosheets in the mixed media at lower and higher metal ion concentrations. However, A formed multilayer vesicles and nanotubes at lower and higher concentrations of A molecules. Such a difference was ascribed to their different molecular structures and therefore the different amphiphilicity. The more hydrophobic L molecules could escape from DMF droplets and self-assembled with the help of supramolecular interactions. The more amphiphilic A molecules were prone to adsorb at the oil/water interface to form layered films. The relative strength of coordination interaction determined the self-assembly behavior of L and the formation of helical nanowires and nanosheets, and the packing mode of A molecules at the oil/water interface determined the formation of vesicles and nanotubes. In addition, the formed vesicles of A were responsive to pH.

Efficient fabrication of high-quality hybrid periodic nanostructures on 4H-SiC using a single-step vector femtosecond laser processing

Femtosecond lasers are widely recognized for generating laser-induced periodic surface structures (LIPSS) on various materials. Moreover, the homogeneous low spatial frequency LIPSS (H-LSFL) can be achieved by employing linear scanning with polarized femtosecond laser pulses and precise control of parameters, such as fluence and scanning speed. Unlike traditional LSFLs, these H-LSFLs are characterized by uniform structures. This study demonstrates the high-precision fabrication of hybrid periodic nanostructures, specifically H-LSFL with vertically aligned HSFL (high-spatial frequency LIPSS) on 4H-SiC using azimuthally polarized femtosecond laser beams. The experimental results revealed that the rapid fabrication of two parallel line patterns featuring hybrid periodic nanostructures can be achieved in a single scanning pass. Furthermore, a beam expander was employed to reduce the laser’s focal spot size, increasing the distribution of HSFL concerning H-LSFL as the distance between line segments decreased.

Hierarchically Porous Vanadium-Based Cathode Materials for High-Performance Na-Ion Batteries

Sodium-ion batteries (SIBs) have emerged as a promising alternative to lithium-ion batteries (LIBs) in sectors requiring extensive energy storage. The abundant availability of sodium at a low cost addresses concerns associated with lithium, such as environmental contamination and limited availability. However, SIBs exhibit lower energy density and cyclic stability compared to LIBs. One of the key challenges in improving the performance of SIBs lies in the electrochemical properties of the cathode materials. Among the various cathodes utilized in SIBs, sodium vanadium phosphates (NVPs) and sodium vanadium fluorophosphates (NVPFs) are particularly advantageous. These vanadium-based cathodes offer high theoretical capacity and are cost-effective. Commercialization of SIBs with NVPF cathodes has already begun. However, the poor conductivity of these cathode materials leads to a short cycle life and inferior rate performance. Various synthesis methods have been explored to enhance the conductivity, including heteroatom doping (N, S, and Co), surface modification, the fabrication of porous nanostructures, and composite formation with conductive carbon materials. In particular, cathodes with interconnected hierarchical micro- and nano-porous morphologies have shown promise. This review focuses on the diverse synthesis methods reported for preparing hierarchically porous cathodes. With increased attention, particular emphasis has been placed on carbon composites of NVPs and NVPFs. Additionally, the synthesis of vanadium pentoxide-based cathodes is also discussed.

Thermally Stable Oxide-Capsulated Metal Nanoparticles Structure for Strong Metal-Support Interaction via Ultrafast Laser Plasmonic Nanowelding.

Strong metal-support interaction (SMSI) has drawn much attention in heterogeneous catalysts due to its stable and excellent catalytic efficiency. However, construction of high-performance oxide-capsulated metal nanostructures meets great challenge in materials thermodynamic compatibility. In this work, dynamically controlled formation of oxide-capsulated metal nanoparticles (NPs) structures is demonstrated by ultrafast laser plasmonic nanowelding. Under the strong localized electromagnetic field interaction, metal (Au) NPs are dragged by an optical force toward oxide NPs (TiO2). Intense energy is simultaneously injected into this heterojunction area, where TiO2 is precisely ablated. With the embedding of metal into oxide, optical force on Au gradually turned from attractive to repulsive due to the varied metal-dielectric environment. Meanwhile, local ablated oxides are redeposited on Au NP. Upon the whole coverage of metal NP, the implantation behavior of metal NP is stopped, resulting in a controlled metal-oxide eccentric structure with capsulated oxide layer thickness ≈0.72-1.30nm. These oxide-capsulated metal NPs structures can preserve their configurations even after thermal annealing in air at 600°C for 10min. This ultrafast laser plasmonic nanowelding can also extend to oxide-capsulated metal nanostructure fabrication with broad materials combinations (e.g., Au/ZnO, Au/MgO, etc.), which shows great potential in designing/constructing nanoscale high-performance catalysts.

Self‐Assembly of Polyoxometalate Clusters into Nanostructures with Different Dimensions

AbstractSelf‐assembly of polyoxometalate (POM) clusters offers a viable method for constructing nanostructures with tailored properties. Over the past few decades, POMs‐based nanostructures of varying dimensions, such as nanowires, nanobelts, nanosheets, and other superstructures, have been constructed. Additionally, these nanostructures show broad prospects in optical, electrochemical, catalytic, and mechanical applications. Particularly noteworthy are surface modifications, such as surfactant encapsulation, which yield amphiphilic POMs. These modifications render the POMs compatible with organic systems, significantly broadening their morphological and functional applicability. This concept provides an overview of recent advancements in nanostructures based on self‐assembly of surfactant encapsulated POM clusters, encompassing one‐dimensional (1D), two‐dimensional (2D), and three‐dimensional (3D) structures. Through surfactant encapsulation, POM clusters can be rendered compatible with various solvents, facilitating the formation of hybrid assemblies with diverse morphologies and unique properties. The structures, formation mechanisms, and properties of these sub‐nanometer assemblies are discussed from both experimental and theoretical perspectives. This concept aims to provide a new insight into the design and fabrication of nanostructures based on POM clusters.

Fabrication of Large-Area Nanostructures Using Cross-Nanoimprint Strategy.

Nanostructures with sufficiently large areas are necessary for the development of practical devices. Current efforts to fabricate large-area nanostructures using step-and-repeat nanoimprint lithography, however, result in either wide seams or low efficiency due to ultraviolet light leakage and the overflow of imprint resin. In this study, we propose an efficient method for large-area nanostructure fabrication using step-and-repeat nanoimprint lithography with a composite mold. The composite mold consists of a quartz support layer, a soft polydimethylsiloxane buffer layer, and multiple intermediate polymer stamps arranged in a cross pattern. The distance between the adjacent stamp pattern areas is equal to the width of the pattern area. This design combines the high imprinting precision of hard molds with the uniform large-area imprinting offered by soft molds. In this experiment, we utilized a composite mold consisting of three sub-molds combined with a cross-nanoimprint strategy to create large-area nanostructures measuring 5 mm × 30 mm on a silicon substrate, with the minimum linewidth of the structure being 100 nm. Compared with traditional step-and-flash nanoimprint lithography, the present method enhances manufacturing efficiency and generates large-area patterns with seam errors only at the micron level. This research could help advance micro-nano optics, flexible electronics, optical communication, and biomedicine studies.

AFM tip-based fabrication of silicon nanostructures with reduced subsurface amorphous layers

Atomic force microscopy (AFM) tip-based nanofabrication is a feasible method to create nanofeatures on a variety of materials. Surface/subsurface integrity is important for qualifying surface performances. However, while machining on crystalline materials, subsurface amorphous layers are inevitably produced because of the large stress in the contact area between the sharp tip and the workpiece surface, which would reduce the mechanical performance of the surface. In this work, multi-pass reciprocating cutting (MPRC) was implemented to reduce the subsurface amorphous layer (SAL) of a single crystal silicon. The mechanism was studied by experiments and molecular dynamic simulation. Results showed the thickness of the amorphous layer can be greatly decreased to a low value and the tip wear can be reduced as well by the MPRC method. On this basis, by optimizing the machining parameters of the MPRC method, nanogrooves with varied depths but few subsurface amorphous phases were successfully fabricated.

P‐207: Enhancing OLED Optical Characteristics through Simple Fabrication of High Aspect Ratio Nanostructures based on photosensitive photopolymer for External Light Extraction

Investigated nano‐pillar‐based light extraction methods for OLEDs. Explored photosensitive photopolymer (SU‐8) based random nanostructure's impact on light extraction efficiency. Achieved 85% visible spectrum transmittance, highest efficiency with minimal unetched structure thickness. Compared to OLEDs lacking nano‐pillar structure, saw up to 38% improved quantum efficiency and 40% enhanced power efficiency. Insights aid in optimizing these structures for OLED advancement.

Tunability of impedance spectroscopy, electrical conductivity and optical properties of Cu-doped TiO2 nanostructures for optoelectronic device application

This paper details the successful fabrication of Cu-doped TiO2 nanostructures using a co-precipitation method. A thorough analysis of the structural and electrical characteristics of the nanostructure samples was carried out. It was found that all synthesized samples exhibited an anatase TiO2 structure. The XRD pattern indicated an average crystalline size of 23.19 nm for Cu-doped TiO2 nanostructures, whereas TiO2 nanostructures showed a size of 11.78 nm. The UV-Visible spectrum indicated a noticeable absorption band shift towards longer wavelengths, coupled with an increased absorption rate of light. Analysis of electrical conductivity showcased temperature-dependent variations in conductivity at high frequencies. Impedance spectroscopy unveiled improved conductivity upon the integration of Cu into TiO2 nanostructures. Nonetheless, at 300 K, copper doping resulted in a decline in electrical conductivity, whereas at elevated temperatures, Cu doping showed a increase in conductivity for the nanostructures samples. These findings underscore the potential and applicability of the nanostructures, showcasing improved AC conductivity and electrical characteristics, making them promising for various electrical applications.

Fabrication of porous copper oxide nanostructure on nickel foam electrode by a co-precipitation method for non-enzymatic glucose detection

A novel porous copper oxide nanostructure on nickel foam (CuO/NF) electrode has been successfully prepared through a co-precipitation way. The porous CuO structure and nickel foam can be integrated into a three-dimensional ordered and hierarchal CuO electrode sensor. The porous CuO structure contains many loosely packed nanoparticles and the nanochannels, which are beneficial for providing more active sites for electrocatalytic oxidation–reduction reactions. The Cu(III)/Cu(II) pair plays an essential role, which completes the charge transfer during the electrochemically catalyzed reaction. Two Cu(III) ions obtain two electrons from one molecule of glucose, which completes two electron transfers to produce one molecule of gluconic acid lactone. The results of the actual detection of Fetal Bovine Serum indicate that the CuO/NF electrode produced could be utilized for the determination of actual samples.

Insights into the writing process of the mask-free nanoprinting fluid force microscopy technology

Platelets are activated immediately when contacting with non-physiological surfaces. Minimization of surface-induced platelet activation is important not only for platelet storage but also for other blood-contacting devices and implants. Chemical surface modification tunes the response of cells to contacting surfaces, but it requires a long process involving many regulatory challenges to transfer into a marketable product. Biophysical modification overcomes these limitations by modifying only the surface topography of already approved materials. The available large and random structures on platelet storage bags do not cause a significant impact on platelets because of their smallest size (only 1–3 μm) compared to other cells. We have recently demonstrated the feasibility of the mask-free nanoprint fluid force microscope (FluidFM) technology for writing dot-grid and hexanol structures. Here, we demonstrated that the technique allows the fabrication of nanostructures of varying features including grid, circle, triangle, and Pacman-like structures. Characteristics of nanostructures including height, width, and cross-line were analyzed and compared using atomic force microscopy imaging. Based on the results, we identified several technical issues, such as the printing direction and shape of structures that directly altered nanofeatures during printing. Importantly, both geometry and interspace governed the degree of platelet adhesion, especially, the structures with triangular shapes and small interspaces prevent platelet adhesion better than others. We confirmed that FluidFM is a powerful technique to precisely fabricate a variety of desired nanostructures for the development of platelet/blood-contacting devices if technical issues during printing are well controlled.

Graphene Quantum Dots as Hole Extraction and Transfer Layer Empowering Solar Water Splitting of Catalyst-Coupled Zinc Ferrite Nanorods.

Despite the narrow band gap energy, the performance of zinc ferrite (ZnFe2O4) as a photoharvester for solar-driven water splitting is significantly hindered due to its sluggish charge transfer and severe charge recombination. This work reports the fabrication of a hybrid nanostructured hydrogenated ZnFe2O4 (ZFO) photoanode with enhanced photoelectrochemical water-oxidation activity through coupling N-doped graphene quantum dots (GQDs) as a hole transfer layer and Co-Pi as a catalyst. The GQDs not only reduce the surface-mediated nonradiative electron-hole pair recombination but also induce a built-in interfacial electric field leading to a favorable band alignment at the ZFO/GQDs interface, helping rapid photogenerated hole separation and serving as a conducting hole transfer highway, improve the hole transportation into the Co-Pi catalyst for enhanced water oxidation reaction kinetics. The optimized ZFO/GQD/Co-Pi hybrid photoanode delivers a 23-fold photocurrent enhancement at 1.23 V versus the reversible hydrogen electrode (RHE) and a significant 360 mV reduction in the onset potential, reaching 0.65 VRHE compared with the ZFO photoanode under 1 sun illumination in a neutral electrolytic environment. This investigation underscores the mechanism of synergistic interplay between the hole transport layer and cocatalyst in boosting the solar-illuminated water-splitting activity of the ZFO photoanode.

Revealing the Influence of Molecular Chemisorption Direction on the Reaction Selectivity of Dehalogenative Coupling on Au(111): Polymerization versus Cyclization.

The control of reaction selectivity is of great interest in chemistry and depends crucially on the revelation of key influencing factors. Based on well-defined molecule-substrate model systems, various influencing factors have been elucidated, focusing primarily on the molecular precursors and the underlying substrates themselves, while interfacial properties have recently been shown to be essential as well. However, the influence of molecular chemisorption direction on reaction selectivity, as a subtle interplay between molecules and underlying substrates, remains elusive. In this work, by a combination of scanning tunneling microscopy imaging and density functional theory calculations, we report the influence of molecular chemisorption direction on the reaction selectivity of two types of dehalogenative coupling on Au(111), i.e., polymerization and cyclization, at the atomic level. The diffusion step of a reactive dehalogenated intermediate in two different chemisorption directions was theoretically revealed to be the key to determining the corresponding reaction selectivity. Our results highlight the important role of molecular chemisorption directions in regulating the on-surface dehalogenative coupling reaction pathways and products, which provides fundamental insights into the control of reaction selectivity by exploiting some subtle interfacial parameters in on-surface reactions for the fabrication of target low-dimensional carbon nanostructures.

Hierarchical Ni3V2O8@N-Doped Carbon Hollow Double-Shell Microspheres for High-Performance Lithium-Ion Storage.

Transition metal oxides (TMOs) are highly dense in energy and considered as promising anode materials for a new generation of alkaline ion batteries. However, their electrode structure is disrupted due to significant volume changes during charging and discharging, resulting in the short cycle life of batteries. In this paper, the hierarchical Ni3V2O8@N-doped carbon (Ni3V2O8@NC) hollow double-shell microspheres were prepared and used as electrode materials for lithium-ion batteries (LIBs). The utilization efficiency and ion transfer rate of Ni3V2O8 were improved by the hollow microsphere structure formed through nanoparticle self-assembly. Furthermore, the uniform N-doped carbon layer not only enhanced the structural stability of Ni3V2O8, but also improved the overall electrical conductivity of the composite. The Ni3V2O8@NC electrode has an initial discharge capacity of up to 1167.3 mAh g-1 at a current density of 0.3 A g-1, a reversible capacity of up to 726.5 mAh g-1 after 200 cycles, and still has a capacity of 567.6 mAh g-1 after 500 cycles at a current density of 1 A g-1, indicating that the material has good cycle stability and high-rate capability. This work presents new findings on the design and fabrication of complex porous double-shell nanostructures.

Fabrication of manganese ferrite-reduced graphene oxide nanostructure as an electrode material for high performance supercapacitor

Fabrication of manganese ferrite-reduced graphene oxide nanostructure as an electrode material for high performance supercapacitor

An outstanding photocatalytic performance of CNTs based nanocomposite of ternary metal oxides towards cationic and anionic dyes and pharmaceutical drug

Currently, hetero-metallic oxides and their nanocomposites with 1D materials have a tremendous role in photocatalytic applications, mainly for the removal of organic effluents, due to their higher potential of electron-hole pair migration and separation than pure metal oxide NPs. The present work reports the fabrication of ternary metal oxides nanostructure (WO3·Ag2O·CuO) and its nanocomposite with carbon nanotubes (WO3·Ag2O·CuO/CNTs) using a facile approach i.e. ultra-sonication. The photocatalytic removal efficacy of fabricated nanocomposite i.e. WO3.Ag2O.CuO/CNTs along its counterpart (WO3·Ag2O·CuO) was evaluated using a model cationic dye (Methylene blue, MB), an anionic dye (Congo red, CR), and an analgesic drug (Paracetamol). The catalytic experiment was performed under natural sunlight upon light irradiation of about 90 min and using 30 mg of photocatalyst for all chosen effluents. The obtained results deduced that WO3·Ag2O·CuO/CNTs nanocomposite showed catalytic efficiency of about 97 % for MB, 87 % for CR, and 93 % for Paracetamol while it was about 80 % for MB, 74 % for CR, and 79 % for drug using WO3·Ag2O·CuO as photocatalyst. The rate constant values of nanocomposite for the removal of MB, CR, and Paracetamol are 0.037 min−1, 0.023 min−1, and 0.027 min−1 respectively. The remarkable degradation performance of WO3·Ag2O·CuO/CNTs nanocomposite as compared to ternary metal oxide (WO3·Ag2O·CuO) was due to its high charge separation, high surface area, and availability of large number of active sites for the adsorption of pollutant molecules. Hence, WO3·Ag2O·CuO/CNTs nanocomposite could be a competent photocatalyst for the removal of variety of industrial effluents i.e. organic dyes and pharmaceutical drugs etc.

Conventional sintering of nano-crystalline Yttria-Stabilized Zirconia enables high-strength, highly translucent and opalescent dental ceramics

Development of restorative materials capable of mimicking optical and mechanical performance of natural teeth is a quest in aesthetic density. Yttria-Stabilized Zirconia (YSZ) ceramics represent one of the most popular choices for dental restorations, owing to their biocompatibility, white colour, and the possibility to use CAD-CAM technologies. In particular, YSZ doped with 3 mol. % yttria (3YSZ) is popular because it presents high strength. Nonetheless, the limited light transmission of commercially available high strength 3YSZ does not meet the requirements of highly aesthetic cases. On the other side, YSZ presenting a larger portion of yttria are more translucent but exhibit modest strength. Here, we report on fabrication of dense zirconia nanostructures in bulk form via conventional pressure-less sintering at temperatures down to 1100–1200 °C, achieving highly translucent and strong 3YSZ with significant opalescent behaviour. Both Hall−Petch and inverse Hall-Petch relationship were observed in 3YSZ samples with average grain size in the range of 250 nm and 55 nm, demonstrating the importance of grain size control to enhance both optical and mechanical properties of zirconia ceramics, simultaneously. Maximum biaxial strength of 1980 ± 260 MPa, in-line light transmission of 38% in the visible spectrum and opalescence approaching that of enamel were obtained at optimum grain size of 80 ± 5 nm. The notable optical properties are linked to the miniaturization of the residual pores and refinement of grain size towards the nanoscale while the superior mechanical strength is justified by the activation of different energy dissipation processes at nano and macroscale.

Fabrication of Nanostructures Consisting of Composite Nanoparticles by Open-Air PLD

We present a two-step physical method for the fabrication of composite nanoparticle-based nanostructures. The proposed method is based on the pulsed laser deposition (PLD) technique performed sequentially in vacuum and in air. As a first step, thin-alloyed films of iron with noble metal were deposited by PLD in vacuum. The films were prepared by ablation of a mosaic target formed by equal iron and gold sectors. As a second step, the as-prepared alloyed films were ablated in air at atmospheric pressure as the laser beam scanned their surface. Two sets of experiments were performed in the second step, namely, by applying nanosecond (ns) and picosecond (ps) laser pulses for ablation. The structure, microstructure, morphology, and optical properties of the samples obtained were studied with respect to the laser ablation regime applied. The implementation of the ablation process in open air resulted in the formation of nanoparticle and/or nanoparticle aggregates in the plasma plume regardless of the ablation regime applied. These nanoparticles and/or nanoaggregates deposited on the substrate formed a complex porous structure. It was found that ablating FeAu films in air by ns pulses resulted in the fabrication of alloyed nanoparticles, while ablation by ps laser pulses results in separation of the metals in the alloy and further oxidation of Fe. In the latter case, the as-deposited structures also contain core–shell type nanoparticles, with the shell consisting of Fe-oxide phase. The obtained structures, regardless of the ablation regime applied, demonstrate a red-shifted plasmon resonance with respect to the plasmon resonance of pure Au nanoparticles.

Surface engineering by rogue wave induced by energetic carbon clusters

Swift heavy ions are effective in nanostructuring material surfaces. The irradiation of lanthanum fluoride with 30 MeV C60 leads to the creation of surface nanohillocks of size larger than the ones produced by monoatomic heavy ions. The generation of the observed nano-sized hillocks is described here by a new approach that is based on ion-induced intensive electronic excitations that create localized rogue waves. Consequently, the induced nonlinear ion-acoustic rogue waves are considered a hallmark of nanohillock formation. Plasma hydrodynamic equations produce a relationship between normalised electron number density and crystal lattice spacing. Similarities to the hillock profile suggest the crucial primary role of electron density in the fabrication of surface nanostructures.

In situ fabrication of transition metal phosphide tree-like nanostructure for energy-saving hydrogen production coupled via urea oxidation reaction

Substituting the Oxygen Evolution Reaction (OER) with the Urea Oxidation Reaction (UOR) which is a thermodynamically more favorable option, has paved the way for the production of energy-saving hydrogen as well as the purification of urea-reach waste water. In this study, a nanostructured, porous and active Ni-Cu-Mn-P electrode was created using the dynamic hydrogen bubble template (DHBT) process in different conditions. The fabricated electrodes were utilized as bi-functional electrodes for both the HER and UOR processes. The electrochemical results displayed that the Ni-Cu-Mn-P (which synthesized at current density of 2 A.cm−2) requires only 84 mV overpotential to achieve a current density of 10 mA.cm−2, in HER process, and the necessary potential value for the UOR is only 1.30 V vs RHE. Also, the favorable electrocatalytic stability for industrial applications was also confirmed. The Ni-Cu-Mn-P electrode also demonstrated satisfactory performance in the overall urea electrolysis process and the cell voltage was 1.40 V to generate 10 mA.cm−2. The excellent performance of the electrode was due to the hierarchical porous nanostructure with high active surface area and also the synergistic effect between the elements. This study introduces an effective catalyst design for energy-saving hydrogen production.