Plasmonic Heterodimers with Binding Site‐Dependent Hot Spot for Surface‐Enhanced Raman Scattering

A novel plasmonic heterodimer nanostructure with a controllable self‐assembled hot spot is fabricated by the conjugation of individual Au@Ag core–shell nanocubes (Au@Ag NCs) and varisized gold nanospheres (GNSs) via the biotin–streptavidin interaction from the ensemble to the single‐assembly level. Due to their featured configurations, three types of heterogeneous nanostructures referred to as Vertice, Vicinity, and Middle are proposed and a single hot spot forms between the nanocube and nanosphere, which exhibits distinct diversity in surface plasmon resonance effect. Herein, the calculated surface‐enhanced Raman scattering enhancement factors of the three types of heterodimers show a narrow distribution and can be tuned in orders of magnitude by controlling the size of GNSs onto individual Au@Ag NCs. Particularly, the Vertice heterodimer with unique configuration can provide extraordinary enhancement of the electric field for the single hot spot region due to the collaborative interaction of lightning rod effect and interparticle plasmon coupling effect. This established relationship between the architecture and the corresponding optical properties of the heterodimers provides the basis for creating controllable platforms which can be exploited in the applications of plasmonic devices, electronics, and biodetection.     

Bimetallic Nanostructures as Active Raman Markers: Gold‐Nanoparticle Assembly on 1D and 2D Silver Nanostructure Surfaces

It is demonstrated that bimetallic silver–gold anisotropic nanostructures can be easily assembled from various nanoparticle building blocks with well‐defined geometries by means of electrostatic interactions. One‐dimensional (1D) silver nanowires, two‐dimensional (2D) silver nanoplates, and spherical gold nanoparticles are used as representative building blocks for bottom‐up assembly. The gold nanoparticles are electrostatically bound onto the 1D silver nanowires and the 2D silver nanoplates to give bimetallic nanostructures. The unique feature of the resulting nanostructures is the particle‐to‐particle interaction that subjects absorbed analytes to an enhanced electromagnetic field with strong polarization dependence. The Raman activity of the bimetallic nanostructures is compared with that of the individual nanoparticle blocks by using rhodamine 6G solution as the model analyte. The Raman intensity of the best‐performing silver–gold nanostructure is comparable with the dense array of silver nanowires and silver nanoplates that were prepared by means of the Langmuir–Blodgett technique. An optimized design of a single‐nanostructure substrate for surface‐enhanced Raman spectroscopy (SERS), based on a wet‐assembly technique proposed here, can serve as a compact and low‐cost alternative to fabricated nanoparticle arrays.     

Fabrication of nanostructure on a polymer film using atomic force microscope

SPM based lithographic techniques have been developed to pattern various substrates such as metals, semiconductors, and organic/polymer films due to its simplicity and high spatial precision nanostructure. Fabrication of nanostructure using polymeric materials is a key technique for the development of nanodevices. Here, we report the fabrication of nanostructures from polyacrylicacid (PAA) and polymethacrylicacid (PMAA) film on a silicon substrate using atomic force microscope (AFM). The formation of the nanopattern from the polymer film was studied using electrostatic nanolithography and the optimization of the conditions for nanopatterning of the polymer film was investigated with respect to the applied potential and translational speed of the AFM tip. The nanostructure of size 28 nm was created using the biased AFM tip on the PMAA film coated on Si(100) substrate and found that this method is a direct and reliable method to produce uniform nanostructures on a polymer film.     

Electron field emission characteristics of different surface morphologies of ZnO nanostructures coated on carbon nanotubes

The optimal carbon nanotube (CNT) bundles with a hexagonal arrangement were synthesized using thermal chemical vapor deposition (TCVD). To enhance the electron field emission characteristics of the pristine CNTs, the zinc oxide (ZnO) nanostructures coated on CNT bundles using another TCVD technique. Transmission electron microscopy (TEM) images showed that the ZnO nanostructures were grown onto the CNT surface uniformly, and the surface morphology of ZnO nanostructures varied with the distance between the CNT bundle and the zinc acetate. The results of field emissions showed that the ZnO nanostructures grown onto the CNTs could improve the electron field emission characteristics. The enhancement of field emission characteristics was attributed to the increase of emission sites formed by the nanostructures of ZnO grown onto the CNT surface, and each ZnO nanostructure could be regarded as an individual field emission site. In addition, ZnO-coated CNT bundles exhibited a good emission uniformity and stable current density. These results demonstrated that ZnO-coated CNTs is a promising field emitter material.     

Local feedback mode of scanning electrochemical microscopy for electrochemical characterization of one-dimensional nanostructure: theory and experiment with nanoband electrode as model substrate

Local feedback mode is introduced as a novel operation mode of scanning electrochemical microscopy (SECM) for electrochemical characterization of a single one-dimensional (1D) nanostructure, for example, a wire, rod, band, and tube with 1-100-nm width and micrometer to centimeter length. To demonstrate the principle, SECM feedback effects under diffusion limitation were studied theoretically and experimentally with a disk probe brought near a semi-infinitely long band electrode as a geometrical model for a conductive 1D nanostructure. As the band becomes narrower than the disk diameter, the feedback mechanism for tip current enhancement is predicted to change from standard positive feedback mode, to positive local feedback mode, and then to negative local feedback mode. The negative local feedback effect is the only feedback effect that allows observation of a 1D nanostructure without serious limitations due to small lateral dimension, available tip size, or finite electron-transfer rate. In line-scan and approach-curve experiments, an unbiased Pt band electrode with 100-nm width and 2.6-cm length was detectable in negative local feedback mode, even using a 25-microm-diameter disk Pt electrode. Using a 2-microm-diameter probe, both well-defined and defected sites were observed in SECM imaging on the basis of local electrochemical activity of the nanoband electrode. Noncontact and spatially resolved measurement is an advantage of this novel SECM approach over standard electrochemical approaches using electrodes based on 1D nanostructure.     

Engineering optical response through gold bowtie nanoantennas array

We propose the coupled gold bowtie nanoantennas array and investigate its plasmonic properties theoretically. The bowtie antenna consists of a pair of opposing truncated cones. We calculate the transmission spectra and the electric field distributions. The evolution of the transmission spectrum with the gap width of the bowtie, the diameter of the tip of the cone and the distance between adjacent bowties is directly visualized. Furthermore, the sensitivity of the antennas array to dielectric constant changes of the environment is also investigated in detail. We show the electric field distribution of this nanostructure and find that E_x is mainly located at the corners of the cross section, especially at the extremity of the cone. As for the E_y, the electric field enhancement localizes at the external edges and the gap of the bowtie. Our work elucidates further the plasmonic interactions can be useful in the design of optimized, sensitive optical sensors, and the enhancement of the fluorescence of molecules.     

Fabrication of high performance surface enhanced Raman scattering substrates by a solid-state ionics method

Silver nanostructures were prepared by a solid-state ionics method using fast ionic conductor RbAg(4)I(5) films under a direct current electric field (DCEF). The surface morphology of the silver nanostructures grown under different constant current fields was characterized by scanning electron microscopy (SEM). Rhodamine 6G (R6G) aqueous solutions were used as probe molecules to detect the Raman enhancement performance of the silver nanostructure substrates. The effect of external electric field current intensity on the surface morphology of the silver nanostructures during the preparation was studied in detail. The enhancement effect of the silver nanostructure surface enhanced Raman scattering (SERS) substrates with different surface morphologies toward R6G was determined. We found that disordered silver nanowires (DSNW), ordered silver nanowires (OSNW), densely arranged silver nanobamboo arrays (SNBA) and compactly arranged silver nanobud clusters (SNBC) were respectively obtained when the constant current intensity was 3?μA, 5?μA, 8?μA and 12?μA under the same vacuum evaporation plating conditions. The limiting concentrations of R6G for these SERS substrates were found to be 10(-7)?mol?l(-1), 10(-13)?mol?l(-1), 10(-13)?mol?l(-1) and 10(-16)?mol?l(-1), respectively.     

Atomic‐Layer‐Deposition‐Assisted Formation of Carbon Nanoflakes on Metal Oxides and Energy Storage Application

Nanostructured carbon is widely used in energy storage devices (e.g., Li‐ion and Li‐air batteries and supercapacitors). A new method is developed for the generation of carbon nanoflakes on various metal oxide nanostructures by combining atomic layer deposition (ALD) and glucose carbonization. Various metal oxide@nanoflake carbon (MO@f‐C) core‐branch nanostructures are obtained. For the mechanism, it is proposed that the ALD Al₂O₃ and glucose form a composite layer. Upon thermal annealing, the composite layer becomes fragmented and moves outward, accompanied by carbon deposition on the alumina skeleton. When tested as electrochemical supercapacitor electrode, the hierarchical MO@f‐C nanostructures exhibit better properties compared with the pristine metal oxides or the carbon coating without ALD. The enhancement can be ascribed to increased specific surface areas and electric conductivity due to the carbon flake coating. This peculiar carbon coating method with the unique hierarchical nanostructure may provide a new insight into the preparation of ‘oxides + carbon’ hybrid electrode materials for energy storage applications.     

Sub-threshold signal processing in arrays of non-identical nanostructures

Weak input signals are routinely processed by molecular-scaled biological networks composed of non-identical units that operate correctly in a noisy environment. In order to show that artificial nanostructures can mimic this behavior, we explore theoretically noise-assisted signal processing in arrays of metallic nanoparticles functionalized with organic ligands that act as tunneling junctions connecting the nanoparticle to the external electrodes. The electronic transfer through the nanostructure is based on the Coulomb blockade and tunneling effects. Because of the fabrication uncertainties, these nanostructures are expected to show a high variability in their physical characteristics and a diversity-induced static noise should be considered together with the dynamic noise caused by thermal fluctuations. This static noise originates from the hardware variability and produces fluctuations in the threshold potential of the individual nanoparticles arranged in a parallel array. The correlation between different input (potential) and output (current) signals in the array is analyzed as a function of temperature, applied voltage, and the variability in the electrical properties of the nanostructures. Extensive kinetic Monte Carlo simulations with nanostructures whose basic properties have been demonstrated experimentally show that variability can enhance the correlation, even for the case of weak signals and high variability, provided that the signal is processed by a sufficiently high number of nanostructures. Moderate redundancy permits us not only to minimize the adverse effects of the hardware variability but also to take advantage of the nanoparticles' threshold fluctuations to increase the detection range at low temperatures. This conclusion holds for the average behavior of a moderately large statistical ensemble of non-identical nanostructures processing different types of input signals and suggests that variability could be beneficial for signal processing. We demonstrate also that circuits composed of coupled non-identical nanoparticles can act as elementary nano-oscillators that show synchronization properties for sub-threshold stimuli. The results obtained should be of conceptual interest for the design of reliable signal processing schemes with non-identical nanostructures.     

Field ion source development for neutron generators

An ion source based on the principles of electrostatic field desorption is being developed to improve the performance of existing compact neutron generators. The ion source is an array of gated metal tips derived from field electron emitter array microfabrication technology. A comprehensive summary of development and experimental activities is presented. Many structural modifications to the arrays have been incorporated to achieve higher tip operating fields, while lowering fields at the gate electrode to prevent gate field electron emission which initiates electrical breakdown in the array. The latest focus of fabrication activities has been on rounding the gate electrode edge and surrounding the gate electrode with dielectric material. Array testing results have indicated a steady progression of increased array tip operating fields with each new design tested. The latest arrays have consistently achieved fields beyond those required for the onset of deuterium desorption (∼20 V/nm), and have demonstrated the desorption of deuterium at fields up to 36 V/nm. The number of ions desorbed from an array has been quantified, and field desorption of metal tip substrate material from array tips has been observed for the first time. Gas-phase field ionization studies with ∼10,000 tip arrays have achieved deuterium ion currents of ∼50 nA. Neutron production by field ionization has yielded ∼10² n/s from ∼1 mm² of array area using the deuterium-deuterium fusion reaction at 90 kV.     

Ultra-thin graphene edges at the nanowire tips: a cascade cold cathode with two-stage field amplification

A multistage field emitter based on graphene-linked ZnO nanowire array is realized by means of spin-coating a graphene dispersion (reduced graphene oxide) over a nanostructured platform followed by plasma modification. Spin-coating leads to interlinking of graphene sheets between the neighboring nanowires whereas plasma etching in the subsequent step generates numerous ultra-sharp graphene edges at the nanowire tips. The inherent tendency of graphene to lay flat over a plane substrate can easily be bypassed through the currently presented nanostructure platform based technique. The turn-on and threshold field significantly downshifted compared to the individual components in the cascade emitter. Through the facile electron transfer from nanowires to graphene due to band bending at the ZnO-graphene interface together with multistage geometrical field enhancement at both the nanowire and graphene edges remain behind this enriched field emission from the composite cold cathode. This strategy will open up a new direction to integrate the functionalities of both the graphene array and several other inorganic nanostructure array for practical electronic devices.     

Field emission characteristics from tapered ZnO nanostructures grown onto vertically aligned carbon nanotubes

Zinc oxide (ZnO) nanostructures were grown on vertically aligned carbon nanotubes (CNTs) using thermal chemical vapor deposition (CVD) to enhance the field emission characteristics. The shape of ZnO nanostructure was tapered. Scanning electron microscopy (SEM) image showed the ZnO nanostructures were grown onto CNT surface uniformly. The field electron emission of pristine CNTs and ZnO-coated CNTs were measured. The results showed that ZnO nanostructures grown onto CNTs could improve the field emission characteristics. The ZnO-coated CNTs had a threshold electric field at about 3.1 V/μm at 1.0 mA/cm². The results demonstrated that the ZnO-coated CNT is an ideal field emitter candidate material. The stability of the field emission current was also tested.     

Broadband bowtie belt nanoantennas

In this article, we study a linear array of bowtie nanoantennas placed between two metallic strips that can work from 800 to 1420 nm (600 nm linewidth), with an electric field enhancement factor close to 20. We study the dynamical change of the position of the electric field enhancement amongst different elements in the array and, at the same time, the effects of dispersion on the scalability of the array elements. A systematic analysis and methodology to produce an array that can operate over a large bandwidth whilst maintaining the electric field enhancement without significant variation is provided.     

The fabrication and properties of field emission display based on ZnO tetrapod-liked nanostructure

ZnO tetrapod-liked nanostructure with fine crystalline structure and high purity was synthesized via CVD method. Each branch of the nanotetrapod was 50-200 nm in diameter and the nanotetrapod structure exhibited a high aspect ratio. Cathode emission materials with this nanostructure were employed to fabricate field emission display with 72 × 72 pixel array. The as-obtained device showed an ideal field emission property with a threshold electric field of 4.1 V/μm and an emission current density of 1 mA/cm² when the electric field reached 11.5 V/μm. The field enhancement factor of the nanotetrapods was calculated to be 1852. Using proper circuit drive, dynamic Chinese characters can be successfully displayed in the device.     

Catalyst-free growth of pyramidal zinc sulfide nanostructure arrays on single walled carbon nanotubes

Uniform and ordered pyramidal zinc sulfide (ZnS) nanostructure arrays have been fabricated on the single walled carbon nanotube (SWNT) films by chemical vapor deposition without using any metal catalyst. Each ZnS pyramid has a 100 nm-sized base, a uniform length of 600 nm, and a sharp tip of 10 nm. The control of interspatial distance between ZnS nanostructures was achieved by creation of selective growth on the SWNTs in voids with the assistance of a close-packed silica particle monolayer as a template. Furthermore, this kind of morphology control of nanostructure arrays can play an important role for potential applications, such as high efficiency of field emission because of the strong correlation between shapes and functionalities of nanostructures.     

Unconventional gallium oxide nanowires

Zigzag and helical beta-Ga(2)O(3) one-dimensional nanostructures were produced by thermal evaporation of gallium oxide in the presence of gallium nitride. High-resolution TEM analysis indicates that each individual zigzag nanostructure has a periodic arrangement of three distinct blocks: two structurally perfect blocks mirrored with respect to each other on the (002) plane, and one stacking-fault-rich block sandwiched between them. In a zigzag nanostructure, the growth orientation of a beta-Ga(2)O(3) crystal changes alternately in three blocks. The zigzag nanostructure as a whole has the [001] axial direction. In addition to zigzag nanostructures, single-crystalline helical nanowires were also obtained.     

Facile synthesis of three-dimensional porous graphene nanostructures from coordination complexes for supercapacitor electrode

Fabrication of hierarchical nanostructures is an important way for performance improvement and application expansion of nanomaterials. It is still a great challenge to synthesize three dimensional hierarchical graphene nanostructures with controlled secondary structures and primary building units, because it is difficult to realize effective control of graphene layer morphology and necessary arrangement of graphene. In this work, a “complex-directed” strategy has been successfully developed for the synthesis of three dimensional graphene nanostructures. Especially, the obtained three dimensional graphene nanostructures are quite regular in morphology, they can be nanorods or regular particles, composed of hollow graphene nanospheres with different layers. The morphology and the structure of these nanostructures, including primary building units and secondary structures are strongly dependent on the amount of HCl solution. The obtained three-dimensional graphene nanostructure can serve as an excellent candidate for electrode material of electric double layer capacitors (EDLCs) and present outstanding electrochemical behaviors. This is mainly due to the excellent electrical conductivity of graphene hollow nanospheres and the porous structures conducive to ion diffusion and electron transport.     

Correlated piezoelectric and electrical properties in individual ZnO nanorods

Resistivity and piezoelectric response of individual ZnO nanorods were measured using scanning force microscopy. We found a variation in resistivity of 3 orders of magnitude, from 0.1 to 155 Omegacm and in piezoelectric coefficient ranging from 0.4 to 9.5 pm/V in ZnO nanorods grown from solution at the same time on the same substrate. However, there exists a clear correlation between these two properties: nanorods with low piezoelectric response display low resistivity. The relationship is explained by the reduction of the Madelung constant due to free electrons. The results highlight that slight differences in the local environment during synthesis can cause large variation in physical properties found among similar nanostructures. These variations cannot be revealed through ensemble measurements and may contribute to the confusion in the literature of individual nanostructure properties. We demonstrate that correlating multiple physical properties on individual nanostructures provides an insight into the origin of the varying physical properties.     

Anti‐plane mechanical and in‐plane electrical fields for a finite electrode/punch on a finite piezoelectric layer

The problems of a surface electrode and a rigid punch on a finite piezoelectric layer are considered in this paper. The resultant force and the accumulated electric charge on the electrode/punch are prescribed. Closed‐form solutions for the electromechanical fields at the electrode/punch tip are obtained and are expressed in terms of the applied strain and electric field intensity factors. For infinite layer thickness, the strain and electric field intensity factors are obtained in closed‐form. For finite layer thickness, the strain and electric field intensity factors are obtained numerically by the singular integral equation technique. The effect of layer thickness on the electrode/punch tip fields is discussed. It is found that the field intensities at the electrode/punch tip can be reduced considerably by decreasing layer thickness. In addition to the single electrode/punch problem, this paper also provides a solution technique for two collinear surface electrodes/punches on a finite piezoelectric layer. The effect of the relative distance between the two electrodes/punches on the electromechanical fields in the piezoelectric layer is also discussed.