Large‐Area 3D Hierarchical Superstructures Assembled from Colloidal Nanoparticles

Assembling nanosized building blocks into macroscopic 3D complex structures is challenging. Here, nanosized metal and semiconductor building blocks with a variety of sizes and shapes (spheres, stars, and rods) are successfully assembled into a broad range of hierarchical (nanometer to micrometer) assemblies of functional materials in centimeter size using butterfly wings as templates. This is achieved by the introduction of steric hindrance to the assembly process, which compensates for attraction from the environmentally sensitive hydrogen bonds and prevents the aggregation of nanosized building blocks. Of these materials, Au nanostar assemblies show a superior enhancement in surface‐enhanced Raman scattering (SERS) performance (rhodamine 6G, 1506 cm^?1) under 532, 633, and 780 nm excitation—this is 3.1–4.4, 3.6–3.9, and 2.9–47.3 folds surpassing Au nanosphere assemblies and commercial SERS substrates (Q‐SERS), respectively. This method provides a versatile route for the assembly of various nanosized building blocks into different 3D superstructures and for the construction of hybrid nanomaterials and nanocomposites.     

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.     

Layer-by-layer assembly of nanowires for three-dimensional, multifunctional electronics

We report a general approach for three-dimensional (3D) multifunctional electronics based on the layer-by-layer assembly of nanowire (NW) building blocks. Using germanium/silicon (Ge/Si) core/shell NWs as a representative example, ten vertically stacked layers of multi-NW field-effect transistors (FETs) were fabricated. Transport measurements demonstrate that the Ge/Si NW FETs have reproducible high-performance device characteristics within a given device layer, that the FET characteristics are not affected by sequential stacking, and importantly, that uniform performance is achieved in sequential layers 1 through 10 of the 3D structure. Five-layer single-NW FET structures were also prepared by printing Ge/Si NWs from lower density growth substrates, and transport measurements showed similar high-performance characteristics for the FETs in layers 1 and 5. In addition, 3D multifunctional circuitry was demonstrated on plastic substrates with sequential layers of inverter logical gates and floating gate memory elements. Notably, electrical characterization studies show stable writing and erasing of the NW floating gate memory elements and demonstrate signal inversion with larger than unity gain for frequencies up to at least 50 MHz. The ability to assemble reproducibly sequential layers of distinct types of NW-based devices coupled with the breadth of NW building blocks should enable the assembly of increasing complex multilayer and multifunctional 3D electronics in the future.     

Highly efficient visible light photocatalysis of novel CuS/ZnO heterostructure nanowire arrays

Here, a facile approach for the fabrication of CuS nanoparticle (NP)/ZnO nanowire (NW) heterostructures on a mesh substrate through a simple two-step solution method is demonstrated. Successive ionic layer adsorption and reaction (SILAR) was employed to uniformly deposit CuS NPs on the hydrothermally grown ZnO NW array. The synthesized CuS/ZnO heterostructure NWs exhibited superior photocatalytic activity under visible light compared to bare ZnO NWs. This strong photocatalytic activity under visible light is due to the interfacial charge transfer (IFCT) from the valence band of the ZnO NW to the CuS NP, which reduces CuS to Cu(2)S. After repeated cycles of photodecolorization of Acid Orange 7 (AO7), the photocatalytic behavior of CuS/ZnO heterostructure NWs exhibited no significant loss of activity. Furthermore, our CuS/ZnO NWs/mesh photocatalyst floats in solution via partial superhydrophobic modification of the NWs.     

Glycerol and ethylene glycol co-mediated synthesis of uniform multiple crystalline silver nanowires

The large scale synthesis of multiple crystalline silver nanowires (NWs) with uniform diameter were carried out by using glycerol and ethylene glycol (EG) as co-mediated solvents in the presence of poly(vinyl pyrrolidine) (PVP). Experimental results and structural characterizations reveal that Ag NWs are evolved from the multiple crystalline seeds initially generated by the reduction of AgNO₃ with EG and glycerol. Owing to the different reduction ability and viscosity of EG and glycerol, which play an important role for controlling the nucleation at the beginning of reaction, glycerol with high viscosity slows down the migration velocity of Ag⁰ in favor of forming the uniform Ag NWs with small diameter (40 nm) in the presence of PVP molecules selectively adsorbed on the surface of Ag seeds. The yield of the Ag NWs is dependent on the volume ratio of EG and glycerol. In the absence of EG, large amount of Ag nanoparticles (NPs) and few Ag NWs were created. In contrast, Ag nanorods and polyhedral particles are prepared in the case of no glycol added. This paper provides a new approach for the large scale synthesis of Ag NWs with uniform diameter by simply adjusting the solvent components. Furthermore, V-shaped Ag nanostructure was obtained and the possible growth mechanism was discussed.     

Electrophoretic Build‐Up of Alternately Multilayered Films and Micropatterns Based on Graphene Sheets and Nanoparticles and their Applications in Flexible Supercapacitors

Graphene nanosheets and metal nanoparticles (NPs) have been used as nano‐building‐blocks for assembly into macroscale hybrid structures with promising performance in electrical devices. However, in most graphene and metal NP hybrid structures, the graphene sheets and metal NPs (e.g., AuNPs) do not enable control of the reaction process, orientation of building blocks, and organization at the nanoscale. Here, an electrophoretic layer‐by‐layer assembly for constructing multilayered reduced graphene oxide (RGO)/AuNP films and lateral micropatterns is presented. This assembly method allows easy control of the nano‐architecture of building blocks along the normal direction of the film, including the number and thickness of RGO and AuNP layers, in addition to control of the lateral orientation of the resultant multilayered structures. Conductivity of multilayered RGO/AuNP hybrid nano‐architecture shows great improvement caused by a bridging effect of the AuNPs along the out‐of‐plane direction between the upper and lower RGO layers. The results clearly show the potential of electrophoretic build‐up in the fabrication of graphene‐based alternately multilayered films and patterns. Finally, flexible supercapacitors based on multilayered RGO/AuNP hybrid films are fabricated, and excellent performance, such as high energy and power densities, are achieved.     

Hierarchical Metal/Semiconductor Nanostructure for Efficient Water Splitting

A hierarchically patterned metal/semiconductor (gold nanoparticles/ZnO nanowires) nanostructure with maximized photon trapping effects is fabricated via interference lithography (IL) for plasmon enhanced photo‐electrochemical water splitting in the visible region of light. Compared with unpatterned (plain) gold nanoparticles‐coated ZnO NWs (Au NPs/ZnO NWs), the hierarchically patterned Au NPs/ZnO NWs hybrid structures demonstrate higher and wider absorption bands of light leading to increased surface enhanced Raman scattering due to the light trapping effects achieved by the combination of two different nanostructure dimensions; furthermore, pronounced plasmonic enhancement of water splitting is verified in the hierarchically patterned Au NPs/ZnO NWs structures in the visible region. The excellent performance of the hierarchically patterned Au NPs/ZnO NWs indicates that the combination of pre‐determined two different dimensions has great potential for application in solar energy conversion, light emitting diodes, as well as SERS substrates and photoelectrodes for water splitting.     

Massive assembly of ZnO nanowire-based integrated devices

Although a directed assembly strategy has been utilized for the massive assembly of various nanowires and nanotubes (NWs/NTs), its application has usually been limited to rather small-diameter NWs/NTs prepared in solution. We report two complementary methods for the massive assembly of large-size ZnO nanowires (NWs). In the solution-phase method, ZnO NWs were assembled and aligned selectively onto negatively charged surface patterns in solution. In addition, the substrate bias voltage and capillary forces can be used to further enhance the adsorption rate and degree of alignment of ZnO NWs, respectively. In the direct-transfer method, a NW film grown on a solid substrate was placed in close proximity to?a?molecule-patterned substrate, and ultrasonic vibration was applied so that the NWs were directly transferred and aligned onto the patterned substrate. The solution-phase and direct-transfer methods are complementary to each other and suitable for the assembly of NWs?prepared in solution and on solid substrates, respectively.     

Development of ultra-high density silicon nanowire arrays for electronics applications

This article reviews our recent progress on ultra-high density nanowires (NWs) array-based electronics. The superlattice nanowire pattern transfer (SNAP) method is utilized to produce aligned, ultra-high density Si NW arrays. We fi rst cover processing and materials issues related to achieving bulk-like conductivity characteristics from 10 20 nm wide Si NWs. We then discuss Si NW-based fi eld-effect transistors (FETs). These NWs & NW FETs provide terrifi c building blocks for various electronic circuits with applications to memory, energy conversion, fundamental physics, logic, and others. We focus our discussion on complementary symmetry NW logic circuitry, since that provides the most demanding metrics for guiding nanofabrication. Issues such as controlling the density and spatial distribution of both p-and n-type dopants within NW arrays are discussed, as are general methods for achieving Ohmic contacts to both p-and n-type NWs. These various materials and nanofabrication advances are brought together to demonstrate energy effi cient, complementary symmetry NW logic circuits.     

Structural,electrical, and rheological properties of palladium/silver bimetallic nanoparticles prepared by conventional and ultrasonic-assisted reduction methods

Polyvinylpyrrolidone stabilized Pd/Ag bimetallic nanoparticles (NPs) with average particle sizes of 9 and 6 nm were synthesized by simultaneous reduction in the presence and absence of ultrasound waves, respectively. The prepared NPs were characterized by six methods including X-ray diffraction (XRD), transmission electron microscopy (TEM), high resolution-TEM (HRTEM), UV–vis spectroscopy, scanning tunneling microscopy (STM), and energy dispersive X-ray (EDX) analysis. The rheological properties of Pd/Ag NPs in ethylene glycol as a base fluid with various mass fractions of NPs from 2% to 5% at different temperatures were studied experimentally and theoretically. The experimental results showed that viscosity of Pd/Ag NPs in ethylene glycol increases with increasing particle mass fraction and decreases with increasing temperature. A maximum of 31.58% increase in viscosity of ethylene glycol at 20 °C was observed when 5% Pd/Ag NPs was added. Measurement of the electrical conductivity of nanofluids of Pd/Ag bimetallic NPs in distilled water at different mass fractions and temperatures was performed. A 3841% increase in electrical conductivity of distilled water at 25 °C was observed when 1% Pd/Ag NPs was added. Both the rheological and electrical properties of Pd/Ag bimetallic NPs were measured in ethylene glycol and distilled water, respectively for the first time.     

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.     

Multivalent assembly of ultrasmall nanoparticles: One-, two-, and three-dimensional architectures of 2 nm gold nanoparticles

The assembly of nanoparticles (NPs) into complex structures is a fundamental topic in nanochemistry. Although progress has been made in this respect, the classical treatment of NPs as hard building blocks that lack the ability to anisotropically “bond” to each other limits the construction of more complex assemblies. More importantly, extension of methods of assembly of robust NPs to the assembly of ultrasmall ones with size below 2 nm is still challenging. Here we report the controlled self-assembly of ∼2 nm gold NPs into one-dimensional (1D) nanochain, two-dimensional (2D) nanobelt and three-dimensional (3D) nanocomet architectures by kinetically controlling the diffusion of ultrasmall gold NPs with anisotropic surfaces in solution. This process is presumed to allow selective ligand exchange with linkers at different binding sites on the NP surface, and results in “multivalent” interactions between NPs. Different from the assembly of “hard building blocks”, our results demonstrate the significance of surface effects for ultrasmall NPs (or clusters) in determining the structure of complex self-assemblies, and suggest the possibility of assembling these “molecule-like” ultrasmall nanocrystals into novel complex materials on a nanoscale approaching that of real atoms or molecules.      

Comparison of the top-down and bottom-up approach to fabricate nanowire-based silicon/germanium heterostructures

Silicon nanowires (NWs) and vertical nanowire-based Si/Ge heterostructures are expected to be building blocks for future devices, e.g. field-effect transistors or thermoelectric elements. In principle two approaches can be applied to synthesise these NWs: the ‘bottom-up’ and the ‘top-down’ approach. The most common method for the former is the vapour-liquid-solid (VLS) mechanism which can also be applied to grow NWs by molecular beam epitaxy (MBE). Although MBE allows a precise growth control under highly reproducible conditions, the general nature of the growth process via a eutectic droplet prevents the synthesis of heterostructures with sharp interfaces and high Ge concentrations. We compare the VLS NW growth with two different top-down methods: The first is a combination of colloidal lithography and metal-assisted wet chemical etching, which is an inexpensive and fast method and results in large arrays of homogenous Si NWs with adjustable diameters down to 50 nm. The second top-down method combines the growth of Si/Ge superlattices by MBE with electron beam lithography and reactive ion etching. Again, large and homogeneous arrays of NWs were created, this time with a diameter of 40 nm and the Si/Ge superlattice inside.     

Enhanced absorptive characteristics of metal nanoparticle-coated silicon nanowires for solar cell applications

The optical properties of metal nanoparticle (NP)-coated silicon nanowires (Si NWs) are theoretically investigated using COMSOL Multiphysics commercial software. A geometrical array of periodic Si NWs coated with metal NPs is proposed. The simulation demonstrates that light absorption could be enhanced significantly in a long wavelength region of the solar spectrum, based upon the localized surface plasmons generated around metal NPs. Various metal NPs, such as Au, Ag, and Al, are all found to increase their light absorption while in contact with Si NWs, in which the Au NPs show the best result in light enhancement. This theoretical work might prove useful in providing a fundamental understanding toward improving further the efficiency of Si wired solar cells.     

Silver sulfide nanoparticle assembly obtained by reacting an assembled silver nanoparticle template with hydrogen sulfide gas

A fast, simple procedure is described for obtaining an assembly of silver sulfide nanoparticles (Ag(2)S NPs) on a glass substrate through reaction of a template of an assembled layer of silver nanoparticles (Ag NPs) with hydrogen sulfide (H(2)S) gas. The Ag NP template was prepared by assembling a monolayer of spherical Ag NPs (mean diameter of 7.4?nm) on a polyethylenimine-treated glass substrate. Exposure to pure H(2)S for 10?min converted the Ag NPs of the template to Ag(2)S NPs. The resulting Ag(2)S NP assembly, which retains the template nanostructure and particle distribution, was characterized by optical absorption spectroscopy, atomic force microscopy, transmission electron microscopy (TEM), scanning high resolution TEM, energy dispersive x-ray spectroscopy and x-ray photoelectron spectroscopy. The Ag(2)S NPs have a crystal structure of monoclinic acanthite, and while they retained the spherical shape of the original Ag NPs, their mean particle size increased to 8.4?nm due to changes to the crystal structure when the Ag NPs are converted into Ag(2)S NPs. The measured optical absorption edge of the Ag(2)S NP assembly indicated an indirect interband transition with a band gap energy of 1.71?eV. The Ag(2)S NP assembly absorbed light with wavelengths below 725?nm, and the absorbance increased monotonically toward the UV region.     

Self-assembled silver nanoprisms monolayers at the liquid/liquid interface

A crown ether derivative (4′-aminobenzo-15-crown-5 hydrotetrafluoroborate) can mediate the self-assembly of silver nanoprisms at the liquid/liquid interface in the form of a stable hybrid nanocomposite film. The metallic luster of the interfacial film results from the electronic coupling of Ag nanoprisms, suggesting the formation of closely packed nanoprism thin films. The interfacial film of nanoprisms could be transferred to solid substrates as a Langmuir–Blodgett film. The properties of films were studied by UV–vis spectroscopy and transmission electron microscopy.     

Silver nanoparticles are assembled only on the two facets of the rod template

Although the focus of nano-research appears to be shifting to the creation of the secondary structures using primary nanoparticle (NP) building blocks, very complex preparation routes to assemble NPs have been reported so far. In this work, for the first time, we demonstrate that silver NPs can be organized to assemble on the two facets of the 1-dimensional rod template via facile one-step process. This method could potentially be used to prepare assembly of diverse metal, semiconductor, or metal oxide NPs in the one dimensional material form.     

ZnO nanorods arrays with Ag nanoparticles on the (002) plane derived by liquid epitaxy growth and electrodeposition process

Well-aligned ZnO nanorods (NRs) arrays with Ag nanoparticles (NPs) on the (002) plane are obtained by combining a liquid epitaxy technique with an electrodeposition process. Cyclic voltammetry study is employed to understand the electrochemical behaviors of the electrodeposition system, and potentiostatic method is employed to deposit silver NPs on the ZnO NRs in the electrolyte with an Ag⁺ concentration of 1 mM. X-ray diffraction analysis is used to study the crystalline properties of the as-prepared samples, and energy dispersive X-ray is adopted to confirm the composition at the surface of the deposited samples. Results indicate only a small quantity of silver can be deposited on the surface of the samples. Effect of the deposition potential and time on the morphological properties of the resultant Ag NPs/ZnO NRs are investigated in detail. Scanning electron microscopy images and transmission electron microscopy images indicate that the Ag NPs deposited on the (002) plane of the ZnO NRs with a large dispersion in diameter can be obtained by a single potentiostatic deposition process, while dense Ag NPs with a much smaller diameter dispersion on the top of the ZnO NRs, most of which locate on the conical tip of the ZnO NRs, can be obtained by a two-potentiostatic deposition process, The mechanism of this deposition process is also suggested.     

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.     

Characterization of silver nanoparticle in the carboxymethyl cellulose hydrogel prepared by a gamma ray irradiation

In this study, carboxymethyl cellulose (CMC) hydrogels were traditionally prepared by gamma-ray with an absorbed dose of 50 kGy from a 60Co source. The CMC hydrogels were absorbed and swelled in silver nitrate aqueous solution (0.01 M) by dipping for 1 hour, and then irradiated by gamma-ray at various doses to form silver nanoparticles (Ag NPs). The UV-Vis analysis indicated that the concentration of Ag NPs was enhanced by increasing of absorbed dose from 1 to 5 kGy in this situ reducing system. The FE-SEM and XPS measurements provided further evidence for the successful formation of Ag NPs. These CMC hydrogels stabilized Ag NPs also have been investigated for inhibiting the growth of Staphylococcus aureus and Escherichia coli strains in liquid as well as on solid growth media. The antibacterial tests indicated that the hydrogels containing Ag NPs have antibacterial activity.