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As integrated circuits continue to scale toward the atomic limit, bottom-up processes, such as epitaxial growth, have come to feature prominently in their fabrication. At the same time, chemistry has developed highly tunable molecular semiconductors that can perform the functions of ultimately scaled circuit components. Hybrid techniques that integrate programmable structures comprising molecular components into devices however are sorely lacking. Here we demonstrate a wafer-scale process that directs the localization of a conductive polymer, Mw = 20 kg mol-1 polyaniline, from dilute solutions into 50 nm vertical nanogap device architectures using electric-field-driven self-assembly. The resulting metal-polymer-metal junctions were characterized by electron microscopy, Raman spectroscopy and transport measurements demonstrating that our technique is highly selective, assembling conductive polymers only in electrically activated nanogaps. Our results represent a step toward scalable hybrid nanoelectronics that seamlessly integrate established lithographic top-down fabrication with bottom-up synthesized molecular functional circuit components.
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We have studied the magnetization dynamics of single Py(t) (t= 20 nm, 50 nm) and trilayer [Py(50)/Pd(tPd)/Py(20)] nanowire arrays fabricated over large areas using deep ultraviolet lithography technique. The dynamic properties are sensitive to the field orientation and magnetic film thicknesses. A single resonant mode corresponding to the excitations at the bulk part of the wire is detected in all the single-layer nanowire arrays. Furthermore, the spacer layer thickness influenced the dynamic properties in trilayer samples due to the different coupling mechanisms. A single resonant mode is observed intPd= 2 nm trilayer nanowires with a sharp frequency jump from 13 GHz to 15 GHz across the reversal regime. This indicates the exchange coupling and the coherence in magnetization precession in the ferromagnetic layers. On the other hand, wires with 10 nm-spacer display two well-resolved modes separated by â¼3 GHz with a gradual change in frequency across the reversal regime from-26mT to-46mT, indicating the presence of long-range dipolar interactions instead of exchange coupling. The spacer layer of the proposed spin-valve-type structure can be tailored for desired microwave splitters or combiners.
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Superconducting hybrid structures based on single nanowires are a new type of nanoscale devices with peculiar transport characteristics. Control over the nanowire structure is essential for understanding hybrid electronic phenomena arising in such complex systems. In this work, we report a technique for the fabrication of cobalt nanowires by template-assisted electrodeposition using iR compensation, which allows revealing the fundamental dependence of the preferred direction of nanowire growth on the deposition potential. Long coarse-grained cobalt nanowires with a diameter of 70 nm have been implemented into Nb/Co/Nb hybrid structures. We demonstrate that using electrode fabrication techniques that do not contaminate the surface of the nanowire leads to a high quality of devices with low-resistance interfaces. Low-temperature resistivity of 4.94±0.83 µΩ cm and other transport characteristics of Co nanowires are reported. The absence of long-range superconducting proximity effect for Nb/Co/Nb systems with different nanowire length is discussed.
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In recent years, 1D nanostructure-based devices have achieved widespread usage in various fields, such as sensors, energy harvesters, transistors, and electrodes owing to their exceptional and distinct properties. The pioneering work of Dr. R. S. Wagner at Bell Laboratories in 1964 introduced the vapor-liquid-solid (VLS) process, a powerful synthesis method. Since then, numerous synthesis techniques, including sol-gel, hydrothermal, chemical vapor deposition (CVD), physical vapor deposition (PVD), and more, have been developed. These methods have enabled researchers to effectively control the shape (length and diameter) and material properties of nanowires. However, it was only about two decades ago that nanowires started to be widely utilized as key components in functional devices, primarily due to the lack of proper integration methods. Although dozens of integration techniques have been developed, none have emerged as a predominant choice, with each method presenting its own set of advantages and limitations. Therefore, this work aims to categorize these methods based on their working principles and provide a comprehensive summary of their pros and cons. Additionally, state-of-the-art devices that capitalize on the integration of 1D nanomaterials are introduced.
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The objective of this study was to evaluate the effectiveness of trimethylsilane (TMS) plasma nanocoatings in protecting silver nanowires (AgNWs) from degradation and thus to improve their stability. TMS plasma nanocoatings at various thicknesses were deposited onto AgNWs that were prepared on three different substrates, including glass, porous styrene-ethylene-butadiene-styrene (SEBS), and poly-L-lactic acid (PLLA). The experimental results showed that the application of TMS plasma nanocoatings to AgNWs induced little increase, up to ~25%, in their electrical resistance but effectively protected them from degradation. Over a two-month storage period in summer (20-22 °C, 55-70% RH), the resistance of the coated AgNWs on SEBS increased by only ~90%, compared to a substantial increase of ~700% for the uncoated AgNWs. On glass, the resistance of the coated AgNWs increased by ~30%, versus ~190% for the uncoated ones. When stored in a 37 °C phosphate-buffered saline (PBS) solution for 2 months, the resistance of the coated AgNWs on glass increased by ~130%, while the uncoated AgNWs saw a ~970% rise. Increasing the TMS plasma nanocoating thickness further improved the conductivity stability of the AgNWs. The nanocoatings also transformed the AgNWs' surfaces from hydrophilic to hydrophobic without significantly affecting their optical transparency. These findings demonstrate the potential of TMS plasma nanocoatings in protecting AgNWs from environmental and aqueous degradation, preserving their electrical conductivity and suitability for use in transparent electrodes and wearable electronics.
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The aqueous zinc-ion batteries (ZIBs) have gained increasing attention because of their high specific capacity, low cost, and good safety. However, side reactions, hydrogen evolution reaction, and uncontrolled zinc dendrites accompanying the Zn metal anodes have impeded the applications of ZIBs in grid-scale energy storage. Herein, the poly(3,4-ethylenedioxythiophene) (PEDOT) nanowires as an interfacial layer on the Zn anode (Zn-PEDOT) are reported to address the above issues. Our experimental results and density functional theory simulation reveal that the interactions between the Zn2+ and S atoms in thiophene rings of PEDOT not only facilitate the desolvation of hydrated Zn2+ but also can regulate the diffusion of Zn2+ along the thiophene molecular chains and induce the dendrite-free deposition of Zn along the (002) surface. Consequently, the Zn||Cu-PEDOT half-cell exhibits highly reversible plating/stripping behavior with an average Coulombic efficiency of 99.7% over 2500 cycles at 1 mA cm-2 and a capacity of 0.5 mAh cm-2. A symmetric Zn-PEDOT cell can steadily operate over 1100 h at 1 mA cm-2 (1 mAh cm-2) and 470 h at 10 mA cm-2 (2 mAh cm-2), outperforming the counterpart bare Zn anodes. Besides, a Zn-PEDOT||V2O5 full cell could deliver a specific capacity of 280 mAh g-1 at 1 A g-1 and exhibits a decent cycling stability, which are much superior to the bare Zn||V2O5 cell. Our results demonstrate that PEDOT nanowires are one of the promising interfacial layers for dendrite-free aqueous ZIBs.
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This research addresses challenges with silver nanowires (Ag NWs) as transparent conductive electrodes (TCEs) and heaters in commercial devices. Here, zinc oxide nanoparticles (ZnO NPs) are first reported as a protective layer for Ag NWs. Multi-physics simulations confirm enhanced thermal stability due to improved heat dissipation, temperature distribution, and thermal conductivity from ZnO. When Ag NWs are surrounded by air, heat transfers mainly through convection and radiation because of air's low conduction coefficient. Encasing Ag NWs in ZnO enhances heat transfer to the ZnO surface, accelerating cooling and dissipating more heat into the atmosphere via convection. The results show composite's efficiency in the Joule effect, maintaining a consistent temperature of 78 °C for 700 s after 500 bending cycles, a significant improvement over Ag NWs operating for only 5 s at 80 °C. Additionally, the composite film exhibited exceptional performance, including a sheet resistance of 9.8 Ω sq-1 and an optical transmittance of 96.96 %, outperforming Ag NWs, which have a sheet resistance of 12 Ω sq-1 and a transmittance of 94.11%. The combination of enhanced electrical, thermal, and mechanical stability, along with impressive optical properties, makes Ag NWs/ZnO NPs a promising candidate for transparent conductive electrode materials in various applications.
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Transformation of lignin to syngas can turn waste into treasure yet remains a tremendous challenge because of its naturally evolved stubborn structure. In this work, light-driven reforming of natural lignin in water for green syngas production is explored using Pt-decorated InGaN nanowires. Syngas is yielded from the continuous evolution of â¢CH3 and â¢OH from photocatalytic reforming of lignin in water. Together with the superior optoelectronic attributes of Pt-decorated InGaN nanowires, the evolution rate of syngas approaches to 43.4 mol·g-1·h-1 with tunable H2/CO ratios and a remarkable turnover number (TON) of 150, 543mol syngas per mol Pt. Notably, the architecture demonstrates a high light efficiency of 12.1% for syngas generation under focused light without any extra thermal input. Outdoor test ascertains the viability of producing syngas with the only inputs of natural lignin, water, and sunlight, thus presenting a low-carbon route for synthesizing transportation fuels and value-added chemicals.
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In this study, a novel synthesis of ultrathin, highly uniform colloidal bismuth sulfohalide (BiSX where X = Cl, Br, I) nanowires (NWs) and NW bundles (NBs) for room-temperature and solution-processed flexible photodetectors are presented. High-aspect-ratio bismuth sulfobromide (BiSBr) NWs are synthesized via a heat-up method using bismuth bromide and elemental S as precursors and 1-dodecanethiol as a solvent. Bundling of the BiSBr NWs occurs upon the addition of 1-octadecene as a co-solvent. The morphologies of the BiSBr NBs are easily tailored from sheaf-like structures to spherulite nanostructures by changing the solvent ratio. The optical bandgaps are modulated from 1.91 (BiSCl) and 1.88 eV (BiSBr) to 1.53 eV (BiSI) by changing the halide compositions. The optical bandgap of the ultrathin BiSBr NWs and NBs exhibits blueshift, whose origin is investigated through density functional theory-based first-principles calculations. Visible-light photodetectors are fabricated using BiSBr NWs and NBs via solution-based deposition followed by solid-state ligand exchanges. High photo-responsivities and external quantum efficiencies (EQE) are obtained for BiSBr NW and NB films even under strain, which offer a unique opportunity for the application of the novel BiSX NWs and NBs in flexible and environmentally friendly optoelectronic devices.
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High-entropy alloys have raised great interest in recent years because of their potential applications for multi-electron reactions owing to their diverse active sites and multielement tunability. However, the difficulty of synthesis is an obstacle to their development due to phase separation often exists. In addition, it's a challenge to precisely control morphology in harsh conditions, thus leading to nanoparticles in many cases. We report a facile method to obtain PdPtPbSnNi HEA NWs by solvothermal synthesis method that no existing phase separation. PdPb nucleation plays a role in the formation of the high-entropy structure that serves as a PdPb nucleus for Sn, Ni, and Pt reduction subsequently, thus forming a single phase and an orderly-arranged nanowire structure. Significantly, the optimized PdPtPbSnNi NWs exhibit excellent catalytic activity and stability for both EOR and MOR which is 4.36 A mgPd+Pt-1 and 4.34 A mgPd+Pt-1, respectively. This study highlights a novel strategy for morphology tuning, providing a prospect for designing superior high-entropy nano-catalysts for multi-step reactions.
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Core-shell gallium nitride (GaN)-based nanowires offer noteworthy opportunities for innovation in high-frequency opto- and microelectronics. This work delves deeply into the physical properties of crystalline GaN nanowires with aluminum and hafnium oxide shells. Particular attention is paid to partial coverage of nanowires, resulting with exceptional properties. First, the crystal lattice relaxation is observed by X-ray diffraction, photoluminescence, and Raman spectroscopy measurements. A high potential of partial coverage for optoelectronic applications is revealed with photo- and cathodoluminescence spectra along with an exploration of their temperature dependency. Next, the study focuses on understanding the mechanisms behind the observed enhancement of the luminescence efficiency. It is confirmed that nanowires are effectively protected against photoadsorption using partial coatings. This research advances the frontiers of nanotechnology, investigating the benefits of partial coverage, and shedding light on its complex interaction with cores.
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Selective CO2 photoreduction to value-added multi-carbon (C2+) feedstocks, such as C2H4, holds great promise in direct solar-to-chemical conversion for a carbon-neutral future. Nevertheless, the performance is largely inhibited by the high energy barrier of C-C coupling process, thereby leading to C2+ products with low selectivity. Here we report that through facile surface immobilization of a 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIM-BF4) ionic liquid, plasmonic Cu nanowires could enable highly selective CO2 photoreduction to C2H4 product. At an optimal condition, the resultant plasmonic photocatalyst exhibits C2H4 production with selectivity up to 96.7% under 450 nm monochromatic light irradiation, greatly surpassing its pristine Cu counterpart. Combined in situ spectroscopies and computational calculations unravel that the addition of EMIM-BF4 ionic liquid modulates the local electronic structure of Cu, resulting in its enhanced adsorption strength of *CO intermediate and significantly reduced energy barrier of C-C coupling process. This work paves new path for Cu surface plasmons in selective artificial photosynthesis to targeted products.
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In this study, we present a novel method for fabricating semi-transparent electrodes by combining silver nanowires (AgNW) with titanium nitride (TiN) layers, resulting in conductive nanocomposite coatings with exceptional electromechanical properties. These nanocomposites were deposited on cellulose nanopaper (CNP) using a plasma-enhanced pulsed laser deposition (PE-PLD) technique at low temperatures (below 200 °C). Repetitive bending tests demonstrate that incorporating AgNW into TiN coatings significantly enhances the microstructure, increasing the electrode's electromechanical robustness by up to four orders of magnitude compared to commercial PET/ITO substrates. Furthermore, the optical and electrical conductivities can be optimized by adjusting the AgNW network density and TiN synthesis temperature. Our results also indicate that the nanocomposite electrodes exhibit improved stability in air and superior adhesion compared to bare AgNW coatings.
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An experimental characterization of cupric oxide nanowire (CuO NW) growth from thermally oxidized, microstructured Cu thin films is performed. We have systematically studied the influence of the thickness and dimension of Cu layers on the synthesis of CuO NW. The objective was to determine the optimum Cu geometries for increased CuO NWs growth to bridge the gap between adjacent Cu structures directly on the chip for gas sensing applications. Thresholds for CuO-NW growth regarding film thickness and lateral dimensions are identified based on SEM images. For a film thickness of 560 nm, NWs with lengths > 500 nm start to grow from the edges of Cu structures with an area ≥ 4 µm2. NWs growing from the upper surface were observed for an area ≥ 16 µm2. NW growth between adjacent thermally oxidized thin films was analyzed. The study provides information on the most relevant parameters of CuO NWs growth, which is mandatory for integrating CuO NWs as gas sensor components directly on microchips. Based on this result, the gap size of the structure was varied to find the optimum value of 3 µm.
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The chemical bath deposition (CBD) process enables the deposition of ZnO nanowires (NWs) on various substrates with customizable morphology. However, the hydrogen-rich CBD environment introduces numerous hydrogen-related defects, unintentionally doping the ZnO NWs and increasing their electrical conductivity. The oxygen-based plasma treatment can modify the nature and amount of these defects, potentially tailoring the ZnO NW properties for specific applications. This study examines the impact of the average ion energy on the formation of oxygen vacancies (VO) and hydrogen-related defects in ZnO NWs exposed to low-pressure oxygen plasma. Using X-ray photoelectron spectroscopy (XPS), 5 K cathodoluminescence (5K CL), and Raman spectroscopy, a comprehensive understanding of the effect of the oxygen ion energy on the formation of defects and defect complexes was established. A series of associative and dissociative reactions indicated that controlling plasma process parameters, particularly ion energy, is crucial. The XPS data suggested that increasing the ion energy could enhance Fermi level pinning by increasing the amount of VO and favoring the hydroxyl group adsorption, expanding the depletion region of charge carriers. The 5K CL and Raman spectroscopy further demonstrated the potential to adjust the ZnO NW physical properties by varying the oxygen ion energy, affecting various donor- and acceptor-type defect complexes. This study highlights the ability to tune the ZnO NW properties at low temperature by modifying plasma process parameters, offering new possibilities for a wide variety of nanoscale engineering devices fabricated on flexible and/or transparent substrates.
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The direct generation of conducting paths within an insulating surface represents a conceptually unexplored approach to single-layer electrical conduction that opens vistas for exciting research and applications fundamentally different from those based on specific layered materials. Herein we report surface channels with single-layer -COOH functionality patterned on insulating n-octadecyltrichlorosilane monolayers on silicon that exhibit unusual ionic-electronic conduction when equipped with ion-releasing silver electrodes. The strong dependence of charge transport in such channels on their lateral dimensions (nanosize, macro-size), the type (p, n) and resistivity (doping level) of the underlying silicon substrate, the nature of the insulating spacer layer between the conducting channel and the silicon surface, and the postpatterning chemical manipulation of channel's -COOH functionality allows designing channels with variable resistivities, ranging from that of a practical insulator to some unexpectedly low values. The unusually low resistivities displayed by channels with nanometric widths and micrometer-millimeter lengths are attributed primarily to enhanced electronic transport within ultrathin nanowire-like silver metal films formed along their conductive paths. Function-structure correlations derived from a comprehensive analysis of electrical, atomic force microscopy, and Fourier transform infrared spectral data suggest an unconventional mode of conduction in these channels, which has yet to be elucidated, apparently involving coupled ionic-electronic transport mediated and enhanced by interfacial electrical interactions with charge carriers located outside the conducting channel and separated from those carrying the measured current. These intriguing findings hint at effects akin to Coulomb pairing in the proposed mechanisms of excitonic superconductivity in interfacial nanosystems structurally related to the present metalized surface channels.
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Manipulation of excitonic emission in two-dimensional (2D) materials via the assembly of van der Waals (vdW) heterostructures unlocks numerous opportunities for engineering their photonic and optoelectronic properties. In this work, we introduce a category of mixed-dimensional vdW heterostructures, integrating 2D materials with one-dimensional (1D) semiconductor nanowires composed of vdW layers. This configuration induces spatially distinct localized excitonic emissions through a tailored interfacial heterolayer atomic arrangement. By precisely adjusting both the axial and sidewall facet orientations of bottom-up grown PbI2 vdW nanowires and by transferring them onto 1L WSe2 flakes, we establish vdW heterointerfaces with either perpendicular or parallel interatomic arrangements. The edge-standing heterojunction, featuring perpendicular PbI2 layers atop WSe2, promotes efficient charge transfer through the edges and coupled localized states, leading to an enhanced redshifted excitonic emission. Conversely, the layer-by-layer heterointerface, where PbI2 layers are in parallel contact with WSe2, exhibits substantial quenching due to deep midgap states in a type-II alignment, as evidenced by power-dependent measurements and first-principle calculations. Our results introduce a method for actively manipulating excitonic emissions in 2D transition metal dichalcogenides (TMDs) through edge engineering, highlighting their potential in the development of various quantum devices.
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Platinum (Pt) has been widely used as cathodic electrocatalysts for the hydrogen evolution reaction (HER) but unfortunately neglected as an anodic electrocatalyst for the oxygen evolution reaction (OER) due to excessively strong bonding with oxygen species in water splitting electrolyzers. Herein we report that fine control over the electronic-structure and local-coordination environment of Pt-rich PtPbCu nanowires (NWs) by doping of iridium (Ir) lowers the overpotential of the OER and simultaneously suppresses the overoxidation of Pt in IrPtPbCu NWs during water electrolysis. In light of the one-dimensional morphology featured with atomically dispersed IrOx species and electronically modulated Pt-sites, the IrPtPbCu NWs exhibit an enhanced OER (175 mV at 10 mA cm-2) and HER (25 mV at 10 mA cm-2) electrocatalytic performance in acidic media and yield a high turnover frequency. For OER at the overpotential of 250 mV, the IrPtPbCu NWs show an enhanced mass activity of 1.51 A mg-1Pt+Ir (about 19 times higher) than Ir/C. For HER at the overpotential of 50 mV, NWs exhibit a remarkable mass activity of 1.35 A mg-1Pt+Ir, which is 2.6-fold relative to Pt/C. Experimental results and theoretical calculations corroborate that the doping of Ir in NWs has the capacity to suppress the formation of Ptx>4 derivates and ameliorate the adsorption free energy of reaction intermediates during the water electrolysis. This approach enabled the realization of a previously unobserved mechanism for anodic electrocatalysts.
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A fundamental challenge in artificial superhydrophobic papers is their poor resistance to mechanical abrasion, which limits their practical application in different fields. Herein, a robust and multifunctional superhydrophobic paper is successfully fabricated via a facile spraying method by combining silver nanowires and fluorinated titania nanoparticles through a common paper sizing agent (alkyl ketene dimer) onto paper. It is shown that the surface of the paper-based material presents a three-dimensional network structure due to the cross-linking of silver nanowires with a high aspect ratio. Further hydrophilic and hydrophobic performance test results show that it exhibits exceptional water repellency, with a desirable static contact angle of 165° and roll-off angle of 6.2°. The superhydrophobic paper showcases excellent mechanical durability and maintains its superhydrophobicity even after enduring 130 linear sandpaper abrasion cycles or high-velocity water jetting impact benefited from interfacial van der Waals and hydrogen bonding. Simultaneously, the robust superhydrophobic surface can effectively prevent the penetration of acid or alkali solutions, as well as UV light, resulting in excellent chemical stability. Additionally, the superhydrophobic paper offers supplementary features such as self-cleaning, electrical conductivity, and antibacterial capability. Further development of this strategy paves a way toward next-generation superhydrophobic paper composed of nanostructures and characterized by multiple (or additional) functionalities.
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Among the experimental realization of fault-tolerant topological circuits are interconnecting nanowires with minimal disorder. Out-of-plane indium antimonide (InSb) nanowire networks formed by merging are potential candidates. Yet, their growth requires a foreign material stem usually made of InP-InAs. This stem imposes limitations, which include restricting the size of the nanowire network, inducing disorder through grain boundaries and impurity incorporation. Here, we omit the stem allowing for the growth of stemless InSb nanowire networks on an InP substrate. To enable the growth without the stem, we show that a preconditioning step using arsine (AsH3) is required before InSb growth. High-yield of stemless nanowire growth is achieved by patterning the substrate with a selective-area mask with nanohole cavities, containing restricted gold droplets from which nanowires originate. Interestingly, these nanowires are bent, posing challenges for the synthesis of interconnecting nanowire networks due to merging failure. We attribute this bending to the non-homogeneous incorporation of arsenic impurities in the InSb nanowires and the interposed lattice-mismatch. By tuning the growth parameters, we can mitigate the bending, yielding large and single crystalline InSb nanowire networks and nanoflakes. The improved size and crystal quality of these nanostructures broaden the potential of this technique for fabricating advanced quantum devices.