Resistive-switching crossbar memory based on Ni-NiO core-shell nanowires

Resistive-switching memory (RRAM) is an emerging nanoscale device based on the localized metal-insulator transition within a few-nanometer-sized metal oxide region. RRAM is one of the most promising memory technologies for the ultimate downscaling of nonvolatile memory. However, to develop memory arrays with densities approaching 1 Tb cm(-2) , bottom-up schemes based on synthesis and assembly of metal oxide nanowires (NWs) must be demonstrated. A RRAM memory device based on core-shell Ni-NiO NWs is presented, in which the Ni core plays the role of the metallic interconnect, while the NiO shell serves as the active switching layer. A resistance change of at least two orders of magnitude is shown on electrical operation of the device, and the metal-insulator switching is unequivocally demonstrated to take place in the NiO shell at the crossing between two NWs or between a NW and a gold electrode strip. Since the fabrication of the NW crossbar device is not limited by lithography, this approach may provide a basis for high-density, low-cost crossbar memory with long-term storage stability.     

Si/a-Si core/shell nanowires as nonvolatile crossbar switches

Radial core/shell nanowires (NWs) represent an important class of nanoscale building blocks with substantial potential for exploring fundamental electronic properties and realizing novel device applications at the nanoscale. Here, we report the synthesis of crystalline silicon/amorphous silicon (Si/a-Si) core/shell NWs and studies of crossed Si/a-Si NW metal NW (Si/a-Si x M) devices and arrays. Room-temperature electrical measurements on single Si/a-Si x Ag NW devices exhibit bistable switching between high (off) and low (on) resistance states with well-defined switching threshold voltages, on/off ratios greater than 10(4), and current rectification in the on state. Temperature-dependent switching experiments suggest that rectification can be attributed to barriers to electric field-driven metal diffusion. Systematic studies of Si/a-Si x Ag NW devices show that (i) the bit size can be at least as small as 20 nm x 20 nm, (ii) the writing time is <100 ns, (iii) the retention time is >2 weeks, and (iv) devices can be switched >10(4) times without degradation in performance. In addition, studies of dense one-dimensional and two-dimensional Si/a-Si x Ag NW devices arrays fabricated on crystalline and plastic substrates show that elements within the arrays can be independently switched and read, and moreover that bends with radii of curvature as small as 0.3 cm cause little change in device characteristics. The Si/a-Si x Ag NW devices represent a highly scalable and promising nanodevice element for assembly and fabrication of dense nonvolatile memory and programmable nanoprocessors.     

Microstructure evolution and development of annealed Ni/Au contacts to GaN nanowires

The development of Ni/Au contacts to Mg-doped GaN nanowires (NWs) is examined. Unlike Ni/Au contacts to planar GaN, current-voltage (I-V) measurements of Mg-doped nanowire devices frequently exhibit a strong degradation after annealing in N(2)/O(2). This degradation originates from the poor wetting behavior of Ni and Au on SiO(2) and the excessive void formation that occurs at the metal/NW and metal/oxide interfaces. The void formation can cause cracking and delamination of the metal film as well as reduce the contact area at the metal/NW interface, which increases the resistance. The morphology and composition of the annealed Ni/Au contacts on SiO(2) and the p-GaN films were investigated by scanning electron microscopy (SEM), energy-dispersive x-ray spectroscopy (EDS) and x-ray diffraction (XRD) measurements. Adhesion experiments were performed in order to determine the degree of adhesion of the Ni/Au films to the SiO(2) as well as observe and analyze the morphology of the film's underside by SEM. Device degradation from annealing was prevented through the use of a specific adhesion layer of Ti/Al/Ni deposited prior to the nanowire dispersal and Ni/Au deposition. I-V measurements of NW devices fabricated using this adhesion layer showed a decrease in resistance after annealing, whereas all others showed an increase in resistance. Transmission electron microscopy (TEM) on a cross-section of a NW with Ni/Au contacts and a Ti/Al/Ni adhesion layer showed a lack of void formation at the contact/NW interface. Results of the XRD and TEM analysis of the NW contact structure using a Ti/Al/Ni adhesion layer suggests Al alloying of the Ni/Au contact increases the adhesion and stability of the metal film as well as prevents excessive void formation at the contact/NW interface.     

Solution-processed flexible polymer solar cells with silver nanowire electrodes

The conventional anode for organic photovoltaics (OPVs), indium tin oxide (ITO), is expensive and brittle, and thus is not suitable for use in roll-to-roll manufacturing of OPVs. In this study, fully solution-processed polymer bulk heterojunction (BHJ) solar cells with anodes made from silver nanowires (Ag NWs) have been successfully fabricated with a configuration of Ag NWs/poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS)/polymer:phenyl-C(61)-butyric acid methyl ester (PCBM)/Ca/Al. Efficiencies of 2.8 and 2.5% are obtained for devices with Ag NW network on glass and on poly(ethylene terephthalate) (PET), respectively. The efficiency of the devices is limited by the low work function of the Ag NWs/PEDOT:PSS film and the non-ideal ohmic contact between the Ag NW anode and the active layer. Compared with devices based on the ITO anode, the open-circuit voltage (V(oc)) of solar cells based on the Ag NW anode is lower by ~0.3 V. More importantly, highly flexible BHJ solar cells have been firstly fabricated on Ag NWs/PET anode with recoverable efficiency of 2.5% under large deformation up to 120°. This study indicates that, with improved engineering of the nanowires/polymer interface, Ag NW electrodes can serve as a low-cost, flexible alternative to ITO, and thereby improve the economic viability and mechanical stability of OPVs.     

Femtosecond laser irradiation induced heterojunctions between carbon nanofibers and silver nanowires for a flexible strain sensor

We report the direct joining of carbon nanofibers(CNFs)to silver nanowire(Ag NWs)by controlled irradiation with femtosecond(fs)laser pulses.Two separate types of nano-junction dependent on joint geometry,laser fluence and irradiation time are identified in irradiated mixtures.In one type of junction,the tip of an Ag NW is melted and flows to form a bond with an adjacent CNF.The second type of junction occurs without significant heating of the Ag NW and involves the softening and flow of carbon in the CNF in response to the transfer of plasmonic energy from the Ag NW into the CNF.Bonding in a T-type joint configuration can be of either kind depending on the relative orientation of the incident optical field and the long axis of the Ag NW.FDTD simulations were used to explore this effect for different joint geometries and laser polarization.The electrical properties of a heterojunction involving a single Ag NW-CNF structure have been measured,and it is found that the junction resistance can be reduced by six orders of magnitude after laser joining.Finally,we have investigated the properties of a strain sensor based on an Ag NW-CNF hybrid nanowire network and find that this device can exhibit high sensitivity.This sensitivity occurs as nano-junctions induced by fs laser irradiation greatly reduces the initial resistance.This laser-based technique for direct nanojoining of CNF and Ag NWs may enable the design of robust nanowire structures for application in a variety of new devices.     

Topotaxial fabrication of vertical Aux Ag1-x nanowire arrays: plasmon-active in the blue region and corrosion resistant

Topotaxial growth of Au(x) Ag(1-x) alloy nanowires (NWs) by postepitaxial deposition of Ag vapor on Au NWs and investigation of their plasmonic properties are reported. Ag vapor is supplied onto the epitaxially grown Au NWs, topotaxially turning them into Au(x) Ag(1-x) alloy NWs. The original geometries and alignments of the Au nanostructures are well preserved, while the composition of the alloy NWs is controlled by varying the Ag vapor supply time. The Au(0.5) Ag(0.5) NWs show high surface-enhanced Raman scattering (SERS) activity comparable to that of Ag NWs as well as highly increased oxidation resistance. The plasmon-active wavelength range of the Au(0.5) Ag(0.5) NW is significantly extended to the blue region compared to Au NWs. The Au(x) Ag(1-x) alloy NWs that have plasmonic activity in the blue region in addition to high corrosion resistance will make a superb material for practical plasmonic devices including SERS sensors and optical nanoantennas.     

A Facile One‐Step Approach for Constructing Multidimensional Ordered Nanowire Micropatterns via Fibrous Elastocapillary Coalescence

Nanowire (NW) based micropatterns have attracted research interests for their applications in electric microdevices. Particularly, aligning NWs represents an important process due to the as‐generated integrated physicochemical advantages. Here, a facile and general strategy is developed to align NWs using fibrous elastocapillary coalescence of carbon nanotube arrays (ACNTs), which enables constructing multidimensional ordered NW micropatterns in one step without any external energy input. It is proposed that the liquid film of NW solution is capable of shrinking unidirectionally on the top of ACNTs, driven by the dewetting‐induced elastocapillary coalescence of the ACNTs. Consequently, the randomly distributed NWs individually rotate and move into dense alignment. Meanwhile, the aggregating and bundling of ACNTs is helpful to produce carbon nanotube (CNT) yarns connecting neighboring bundles. Thus, a micropatterned NW network composed of a top‐layer of horizontally aligned NWs and an under‐layer of vertical ACNT bundles connected by CNT yarns is prepared, showing excellent performance in sensing external pressure with a sensitivity of 0.32 kPa^?1. Moreover, the aligned NWs can be transferred onto various substrates for constructing electronic circuits. The strategy is applicable for aligning various NWs of Ag, ZnO, Al₂O₃, and even living microbes. The result may offer new inspiration for fabricating NW‐based functional micropatterns.     

Fabry–Perot Microcavity Modes in Single GaP/GaNP Core/Shell Nanowires

Semiconductor nanowires (NWs) are attracting increasing interest as nanobuilding blocks for optoelectronics and photonics. A novel material system that is highly suitable for these applications are GaNP NWs. In this article, we show that individual GaP/GaNP core/shell nanowires (NWs) grown by molecular beam epitaxy on Si substrates can act as Fabry‐Perot (FP) microcavities. This conclusion is based on results of microphotoluminescence (μ‐PL) measurements performed on individual NWs, which reveal periodic undulations of the PL intensity that follow an expected pattern of FP cavity modes. The cavity is concluded to be formed along the NW axis with the end facets acting as reflecting mirrors. The formation of the FP modes is shown to be facilitated by an increasing index contrast with the surrounding media. Spectral dependence of the group refractive index is also determined for the studied NWs. The observation of the FP microcavity modes in the GaP/GaNP core/shell NWs can be considered as a first step toward achieving lasing in this quasidirect bandgap semiconductor in the NW geometry.     

Silver Nanowire Embedded Colorless Polyimide Heater for Wearable Chemical Sensors: Improved Reversible Reaction Kinetics of Optically Reduced Graphene Oxide

Optically reduced graphene oxide (ORGO) sheets are successfully integrated on silver nanowire (Ag NW)‐embedded transparent and flexible substrate. As a heating element, Ag NWs are embedded in a colorless polyimide (CPI) film by covering Ag NW networks using polyamic acid and subsequent imidization. Graphene oxide dispersed aqueous solution is drop‐coated on the Ag NW‐embedded CPI (Ag NW‐CPI) film and directly irradiated by intense pulsed light to obtain ORGO sheets. The heat generation property of Ag NW‐CPI film is investigated by applying DC voltage, which demonstrates unprecedentedly reliable and stable characteristics even in dynamic bending condition. To demonstrate the potential application in wearable chemical sensors, NO₂ sensing characteristic of ORGO is investigated with respect to the different heating temperature (22.7–71.7 °C) of Ag NW‐CPI film. The result reveals that the ORGO sheets exhibit high sensitivity of 2.69% with reversible response/recovery sensing properties and minimal deviation of baseline resistance of around 1% toward NO₂ molecules when the temperature of Ag NW‐CPI film is 71.7 °C. This work first demonstrates the improved reversible NO₂ sensing properties of ORGO sheets on flexible and transparent Ag NW‐CPI film assisted by Ag NW heating networks.     

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.     

Semi-transparent,flexible, and electrically conductive silicon mesh by capillarity-driven welding of vapor-liquid-solid-grown nanowires over large areas

Bottom-up synthesis of semiconductor nanowires (NWs) by the vapor-liquid-solid (VLS) mechanism has enabled diverse technological applications for these nanomaterials. Unlike metallic NWs, however, it has been challenging to form large-area interconnected NW networks. Here, we generate centimeter-scale meshes of mechanically and electrically interconnected Si NWs by sequentially growing, collapsing, and joining the NWs using a capillarity-driven welding mechanism. We fabricate meshes from VLS-grown NWs ranging in diameter from 20 to 100 nm and find that the meshes are three-dimensional with a thickness ranging from ~ 1 to ~ 10 microns depending on the NW diameter. Optical extinction measurements reveal that the networks are semi-transparent with a color that depends on the absorption and scattering characteristics of individual NWs. Moreover, active voltage contrast imaging of both centimeter- and micron-scale meshes reveals widespread electrical connectivity. Using a sacrificial layer, we demonstrate that the mesh can be liberated from the growth substrate, yielding a highly flexible and transparent film. Electrical transport measurements both on the growth substrate and on liberated, flexible films reveal electrical conduction across a centimeter scale with a sheet resistance of ~ 160–180 kΩ/square that does not change significantly upon bending. Given the ability to encode complex functionality in semiconductor NWs through the VLS process, we believe these meshes of networked NWs could find application as neuromorphic memory, electrode scaffolds, and bioelectronic interfaces.

     

Nucleation‐Controlled Distributed Plasticity in Penta‐twinned Silver Nanowires

A unique size‐dependent strain hardening mechanism, that achieves both high strength and ductility, is demonstrated for penta‐twinned Ag nanowires (NWs) through a combined experimental‐computational approach. Thin Ag NWs are found to deform via the surface nucleation of stacking fault decahedrons (SFDs) in multiple plastic zones distributed along the NW. Twin boundaries lead to the formation of SFD chains that locally harden the NW and promote subsequent nucleation of SFDs at other locations. Due to surface undulations, chain reactions of SFD arrays are activated at stress concentrations and terminated as local stress decreases, revealing insensitivity to defects imparted by the twin structures. Thick NWs exhibit lower flow stress and number of distributed plastic zones due to the onset of necking accompanied by more complex dislocation structures.     

Contactless monitoring of the diameter-dependent conductivity of GaAs nanowires

Contactless monitoring with photoelectron microspectroscopy of the surface potential along individual nanostructures, created by the X-ray nanoprobe, opens exciting possibilities to examine quantitatively size- and surface-chemistry-effects on the electrical transport of semiconductor nanowires (NWs). Implementing this novel approach-which combines surface chemical microanalysis with conductivity measurements-we explored the dependence of the electrical properties of undoped GaAs NWs on the NW width, temperature and surface chemistry. By following the evolution of the Ga 3d and As 3d core level spectra, we measured the position-dependent surface potential along the GaAs NWs as a function of NW diameter, decreasing from 120 to ?20 nm, and correlated the observed decrease of the conductivity with the monotonic reduction in the NW diameter from 120 to ~20 nm. Exposure of the GaAs NWs to oxygen ambient leads to a decrease in their conductivity by up to a factor of 10, attributed to the significant decrease in the carrier density associated with the formation of an oxide shell. Open image in new window     

Growth and Fabrication of High‐Quality Single Nanowire Devices with Radial p‐i‐n Junctions

Nanowires (NWs) with radial p‐i‐n junction have advantages, such as large junction area and small influence from the surface states, which can lead to highly efficient material use and good device quantum efficiency. However, it is difficult to make high‐quality core–shell NW devices, especially single NW devices. Here, the key factors during the growth and fabrication process that influence the quality of single core–shell p‐i‐n NW devices are studied using GaAs(P) NW photovoltaics as an example. By p‐doping and annealing, good ohmic contact is achieved on NWs with a diameter as small as 50–60 nm. Single NW photovoltaics are subsequently developed and a record fill factor of 80.5% is shown. These results bring valuable information for making single NW devices, which can further benefit the development of high‐density integration circuits.     

Growth of Silver Nanowires from Controlled Silver Chloride Seeds and Their Application for Fluorescence Enhancement Based on Localized Surface Plasmon Resonance

A “Polyol” method has granted low‐cost and facile process‐controllability for silver‐nanowire (Ag‐NW) synthesis. Although homogenous and heterogeneous nucleation and growth during Ag‐NW synthesis are possible using polyol methods, heterogeneous nucleation and growth of Ag NW guarantees highly selective growth of nanostructures using silver chloride (AgCl) seeds, which provides a stable source of chloride ions (Cl?) and thermodynamic reversibility. In this paper, a microdroplet has been adopted to synthesize uniform AgCl seeds with different diameter that are used for seed‐mediated Ag‐NW synthesis. The concentration of two precursors (AgNO₃ and NaCl) in the droplets is modulated to produce different sizes of AgCl seeds, which determines the diameter and length of Ag NWs. The process of the seed‐mediated growth of Ag NWs has been monitored by observing the peak shift in the time‐resolved UV–vis extinction spectrum. Furthermore, the distinct plasmonic property of Ag NWs for transverse and longitudinal localized‐surface‐plasmon‐resonance (LSPR)‐mediated fluorescence enhancement is utilized. The high aspect ratio and sharp tips work as simple antennas that induce the enhanced fluorescence emission intensity of a fluorophore, which can be applied in the fields of biological tissue imaging and therapy.     

Controlled synthesis of germanium nanowires and nanotubes with variable morphologies and sizes

We report on the controlled growth of germanium (Ge) nanostructures in the form of both nanowire (NW) and nanotube (NT) with ultrahigh aspect ratios and variable diameters. The nanostructures are grown inside a porous anodic aluminum oxide (AAO) template by low-temperature chemical vapor deposition (CVD) assisted by an electrodeposited metal nanorod catalyst. Depending on the choice of catalytic metals (Au, Ni, Cu, Co) and germane (GeH(4)) concentration during CVD, either Ge NWs or NTs can be synthesized at low growth temperatures (310-370 °C). Furthermore, Ge NWs and NTs with two or more branches can be grown from the same stem while using AAO with branched channels as templates. Transmission electron microscopy studies show that NWs are single crystalline and that branches grow epitaxially from the stem of NWs with a crystalline direction independent of diameter. As-grown NTs are amorphous but can crystallize via postannealing at 400 °C in Ar/H(2) atmosphere, with a wall thickness controllable between 6 and 18 nm in the CVD process. The yield and quality of the NTs are critically dependent on the choice of the catalyst, where Ni appears the best choice for Ge NT growth among Ni, Cu, Co, and Au. The synthesis of structurally uniform and morphologically versatile Ge nanostructures may open up new opportunities for integrated Ge-nanostructure-based nanocircuits, nanodevices, and nanosystems.     

Highly Stretchable Metallic Nanowire Networks Reinforced by the Underlying Randomly Distributed Elastic Polymer Nanofibers via Interfacial Adhesion Improvement

On‐skin electronics require conductive, porous, and stretchable materials for a stable operation with minimal invasiveness to the human body. However, porous elastic conductors that simultaneously achieve high conductivity, good stretchability, and durability are rare owing to the lack of proper design for good adhesion between porous elastic polymer and conductive metallic networks. Here, a simple fabrication approach for porous nanomesh‐type elastic conductors is shown by designing a layer‐by‐layer structure of nanofibers/nanowires (NFs/NWs) via interfacial hydrogen bonding. The as‐prepared conductors, consisting of Ag NWs and polyurethane (PU) NFs, simultaneously achieve high conductivity (9190 S cm^?1), high stretchability (310%), and good durability (82% resistance increase after 1000 cycles of deformation at 70% tensile strain). The direct contact between the Ag NWs enables the high conductivity. The synergistic effect of the layer‐by‐layer structure and good adhesion between the Ag NWs and the PU NFs enables good mechanical properties. Furthermore, without any adhesive gel/tape, the conductors can be utilized as breathable strain sensors for precise joint motion monitoring, and as breathable sensing electrodes for continuous electrophysiological signal recording.     

An advanced fabrication method of highly ordered ZnO nanowire arrays on silicon substrates by atomic layer deposition

In this work, the controlled fabrication of highly ordered ZnO nanowire (NW) arrays on silicon substrates is reported. Si NWs fabricated by a combination of phase shift lithography and etching are used as a template and are subsequently substituted by ZnO NWs with a dry-etching technique and atomic layer deposition. This fabrication technique allows the vertical ZnO NWs to be fabricated on 4 in Si wafers. Room temperature photoluminescence and micro-photoluminescence are used to observe the optical properties of the atomic layer deposition (ALD) based ZnO NWs. The sharp UV luminescence observed from the ALD ZnO NWs is unexpected for the polycrystalline nanostructure. Surprisingly, the defect related luminescence is much decreased compared to an ALD ZnO film deposited at the same time ona plane substrate. Electrical characterization was carried out by using nanomanipulators. With the p-type Si substrate and the n-type ZnO NWs the nanodevices represent p–n NW diodes.The nanowire diodes show a very high breakthrough potential which implies that the ALD ZnO NWs can be used for future electronic applications.     

Rational synthesis of p-type zinc oxide nanowire arrays using simple chemical vapor deposition

We report, for the first time, the synthesis of the high-quality p-type ZnO NWs using a simple chemical vapor deposition method, where phosphorus pentoxide has been used as the dopant source. Single-crystal phosphorus doped ZnO NWs have their growth axis along the 001 direction and form perfect vertical arrays on a-sapphire. P-type doping was confirmed by photoluminescence measurements at various temperatures and by studying the electrical transport in single NWs field-effect transistors. Comparisons of the low-temperature PL of unintentionally doped ZnO (n-type), as-grown phosphorus-doped ZnO, and annealed phosphorus-doped ZnO NWs show clear differences related to the presence of intragap donor and acceptor states. The electrical transport measurements of phosphorus-doped NW FETs indicate a transition from n-type to p-type conduction upon annealing at high temperature, in good agreement with the PL results. The synthesis of p-type ZnO NWs enables novel complementary ZnO NW devices and opens up enormous opportunities for nanoscale electronics, optoelectronics, and medicines.     

Preparation of nickel–silver core–shell nanoparticles by liquid-phase reduction for use in conductive paste

Nickel–silver (Ni–Ag) core–shell nanoparticles (NPs) were prepared by depositing Ag on Ni nanocores using the liquid-phase reduction technique in aqueous solution, and their properties were characterised using various experimental techniques. The core–shell NPs had good crystallinity, and the thicknesses of the Ag nanoshells could be tuned effectively. The oxidation resistance of the Ag surface and the electroconductive properties of the Ni core allowed these Ni–Ag core–shell NPs to be used in a conductive paste. Thick films composed of Ni–Ag core–shell NPs were screen-printed on a polycrystalline silicon substrate then sintered at temperatures ranging from 500 °C to 800 °C. Stable resistivity was obtained when the sintering temperature was higher than 650 °C, and the electrical properties of the Ni–Ag core–shell paste were close to those of pure Ag paste. Thus, the Ni–Ag NPs can partly replace pure Ag NPs in conductive pastes.