Mineralization of semiconductor nanocrystals on peptide-coated bionanotubes and their pH-dependent morphology changes

While various mineralizing peptides have been applied to grow metal nanoparticles on bionanotube templates, the semiconductor nanoparticle growth on nanotubes has not extensively been explored yet. In this paper, various semiconductor nanocrystals were grown on the bionanotubes surfaces with controlled sizes. When three synthetic peptides, which recognize and selectively bind Ge, Ti, and Cu ions, respectively, were incorporated on template bionanotube surfaces, highly crystalline and monodisperse Ge, TiO2, and Cu2S nanocrystals were grown on the tube surfaces. The sizes of these nanocrystals could be tuned as a function of pH, and larger semiconductor nanocrystals were grown as the pH of growth solutions was increased. All of these nanocrystals from smaller sizes to larger sizes had the same crystallinity. This peptide-controlled nanocrystal growth technique will be very useful to prepare semiconductor nanowires as building blocks for future microelectronics, whose band gaps can be tuned by the sizes of coated semiconductor nanoparticles via their quantum confinement effect. The novelty of this approach in the electronic device fabrication is that the semiconductor nanocrystal size control can be achieved by controlling peptide configurations via pH change, and this control may tune electronic structures and band gaps of the resulting semiconductor nanowires.     

Ag-catalyzed growth of Ge nanostructures via the thermal evaporation of Ge powder

The Ag-catalyzed growth of straight Ge nanowires (GeNWs), serrated Ge nanobelts (GeNBs), and hexagonal Ge nanotowers (GeNTs) by thermal evaporation of Ge powder at 950 degrees C in Ar was studied. The growth of GeNWs and GeNBs at 550-600 degrees C followed the top-growth mode via the vapor-solid-solid process, while that of GeNTs at 700-750 degrees C followed the bottom-growth mode via the vapor-liquid-solid process. This result shows that the growth mode of Ge nanostructures catalyzed by Ag nanoparticles is temperature-dependent. The larger size of AgGe droplets assembled at high temperatures is beneficial to the growth of GeNTs with the bottom-growth mode. In addition, the growth mechanisms of Ge nanostructures are discussed.     

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.     

Direct printing of silver nanoparticles by an agarose stamp on planar and patterned substrates

In this study, we have used an agarose stamp to conduct direct printing of silver nanoparticles, nanowires and nanoplates on both planar and structured substrates. Nanoparticle solution could be first coated on an agarose stamp, and then transferred to a planar substrate. Micro-patterns comprising metal nanoparticles could be printed on planar substrates without the formation of residual layers. Thus a three-dimensional metal microstructure could be easily fabricated. The patterning of electrodes by printing Ag nanowires directly on TiO(2) was also demonstrated to fabricate resistive random access memory (RRAM) devices by all-solution-processing methods. By using a flat agarose stamp, the patterns printed on the microstructured substrates were quite different from those on the nanostructured substrates. On the microstructured substrates, direct printing could print silver nanoparticles onto the protrusion surface, and could print silver layers as thick as several microns, useful for high conductivity electrodes. On the substrates with nanostructures such as photonic crystals or nano-gratings, direct printing could transfer nanoparticles into the grooves or cavities only due to the contact of the agarose stamp with the groove or concavity surface. A new approach to fabricate metal wire grid polarizers was further demonstrated. A nanoporous agarose stamp has a good potential for printing using nanoparticle suspension.     

Selective growth of Ge nanowires by low-temperature thermal evaporation

High-quality single-crystalline Ge nanowires with electrical properties comparable to those of bulk Ge have been synthesized by vapor-liquid-solid growth using Au growth seeds on SiO(2)/Si(100) substrates and evaporation from solid Ge powder in a low-temperature process at crucible temperatures down to 700?°C. High nanowire growth rates at these low source temperatures have been identified as being due to sublimation of GeO from substantial amounts of GeO(2) on the powder. The Ge nanowire synthesis from GeO is highly selective at our substrate temperatures (420-500?°C), i.e., occurs only on Au vapor-liquid-solid growth seeds. For growth of nanowires of 10-20?μm length on Au particles, an upper bound of 0.5?nm Ge deposition was determined in areas of bare SiO(2)/Si substrate without Au nanoparticles.     

Synthesis of 1D regular arrays of gold nanoparticles and modeling of their optical properties

Self-organized formation of uniform coating of semiconductor substrate by metal nanoparticles offers a convenient and efficient access to large-scale arrays of uniform metal-semiconductor nanostructures. We used a cheap and facile method of photoinduced chemical gold deposition from an aqueous or alcohol gold salt solution onto semiconductor surface (GaAs, InP). By controlling of both the solution composition and the deposition conditions, gold particles of 10-50 nm in diameter were obtained and the gold covering degree of the semiconductor surface was varied in a wide range. Morphology of the nano/micro structures formed was characterized by atomic force microscopy and scanned electron microscopy with local element analysis. The investigations show that the semiconductor surface patterning can be used for the selective deposition of gold nanoparticles, because they are located predominantly at the tops of the microrelief. We have used specially textured by the anisotropic chemical etching microrelief surfaces of semiconductor single crystal as templates and have obtained nanoparticle arrays in the shape of 1D systems of near parallel quasiperiodical wires. For the periodic 1D array of metal nanowires built into the air-semiconductor interface the spectral and angular dependencies of the transmittance/reflectance of the polarized light have been obtained theoretically using differential formalism. These dependencies demonstrate non-monotonic behaviour at surface plasmon polariton excitation conditions and show possibility of designing functional subwavelength devices.     

Water-soluble organo-silica hybrid nanowires

There has been growing interest in the past decade in one-dimensional (1D) nanostructures, such as nanowires, nanotubes or nanorods, owing to their size-dependent optical and electronic properties and their potential application as building blocks, interconnects and functional components for assembling nanodevices. Significant progress has been made; however, the strict control of the distinctive geometry at extremely small size for 1D structures remains a great challenge in this field. The anisotropic nature of cylindrical polymer brushes has been applied to template 1D nanostructured materials, such as metal, semiconductor or magnetic nanowires. Here, by constructing the cylindrical polymer brushes themselves with a precursor-containing monomer, we successfully synthesized hybrid nanowires with a silsesquioxane core and a shell made up from oligo(ethylene glycol) methacrylate units, which are soluble in water and many organic solvents. The length and diameter of these rigid wires are tunable by the degrees of polymerization of both the backbone and the side chain. They show lyotropic liquid-crystalline behaviour and can be pyrolysed to silica nanowires. This approach provides a route to the controlled fabrication of inorganic or hybrid silica nanostructures by living polymerization techniques.     

One-Dimensional （1D） ZnS Nanomaterials and Nanostructures

One-dimensional （1D） nanomaterials and nanostructures have received much attention due to their potential interest for understanding fundamental physical concepts and for applications in constructing nanoscale electric and optoelectronic devices. Zinc sulfide （ZnS） is an important semiconductor compound of Ⅱ-Ⅵ group, and the synthesis of 1D ZnS nanomaterials and nanostructures has been of growing interest owing to their promising application in nanoscale optoelectronic devices. This paper reviews the recent progress on 1D ZnS nanomaterials and nanostructures, including nanowires, nanowire arrays, nanorods, nanobelts or nanoribbons, nanocables, and hierarchical nanostructures etc. This article begins with a survey of various methods that have been developed for generating 1D nanomaterials and nanostructures, and then mainly focuses on structures, synthesis, characterization, formation mechanisms and optical property tuning, and luminescence mechanisms of 1D ZnS nanomaterials and nanostructures. Finally, this review concludes with personal views towards future research on 1D ZnS nanomaterials and nanostructures.     

In‐situ Observations of Nanoscale Effects in Germanium Nanowire Growth with Ternary Eutectic Alloys

Vapour‐liquid‐solid (VLS) techniques are popular routes for the scalable synthesis of semiconductor nanowires. In this article, in‐situ electron microscopy is used to correlate the equilibrium content of ternary (Au_0.75Ag_0.25–Ge and Au_0.65Ag_0.35–Ge) metastable alloys with the kinetics, thermodynamics and diameter of Ge nanowires grown via a VLS mechanism. The shape and geometry of the heterogeneous interfaces between the liquid eutectic and solid Ge nanowires varies as a function of nanowire diameter and eutectic alloy composition. The behaviour of the faceted heterogeneous liquid–solid interface correlates with the growth kinetics of the nanowires, where the main growth facet at the solid nanowire–liquid catalyst drop contact line lengthens for faster nanowire growth kinetics. Pronounced diameter dependent growth kinetics, as inferred from liquid–solid interfacial behaviour, is apparent for the synthesised nanowires. Direct in‐situ microscopy observations facilitates the comparison between the nanowire growth behaviour from ternary (Au–Ag–Ge) and binary (Au–Ge) eutectic systems.     

Ultrasonic-assisted synthesis of Au nanobelts and nanowires

Au one-dimensional (1D) nanostructures, including nanobelts and nanowires, have been synthesized in an ethylene glycol (EG)/polyvinylpyrrolidone (PVP) system by a simple and convenient seed-mediated growth method. The nanobelts and nanowires have aspect ratios up to 600, a length distribution ranging from several to tens of microns, and an average width of 100 nm. In this method, we used an ultrasonic process to promote the formation of Au seeds, which largely determines the morphology of final product. Additionally, we have found that the ultrasonic process significantly increases the fabrication yield of 1D nanostructures. Further experimental results show strong polarization dependence of Surface-Enhanced Raman Scattering (SERS) on a single Au 1D nanostructure. This convenient, versatile and low-cost synthesis method can be applied to 1D nanostructures composed from a range of materials, making it widely applicable to many areas of modern science and technology.     

Deterministic Assembly of Single Sub-20 nm Functional Nanoparticles Using a Thermally Modified Template with a Scanning Nanoprobe

A deterministic assembly technique for single sub-20 nm functional nanoparticles is developed based on nanostructured templates fabricated by hot scanning nanoprobes. With this technique, single nanoparticles including quantum dots, polystyrene fluorescent nanobeads, and gold nanoparticles are successfully assembled into 2D arrays with high yields. Experimental and theoretical analyses show that the key for the high yields is the hot-probe-based template fabrication technique, which creates geometrical nanotraps and modifies their surface energy simultaneously. In addition to single nanoparticle patterning, further experiments demonstrate that this technique is also capable of building complex nanostructures, such as nanoparticle clusters with well-defined shapes and heterogeneously integrated nanostructures consisting of quantum dots and silver nanowires. It opens the door to many important applications.     

Solvothermal fabrication of uniform silver nanowires

Conventional polyol synthesis has been widely used for the preparation of silver nanostructures with different morphologies. However, there is a drawback that it is difficult to control the reaction parameters for shape-controlled synthesis of silver nanostructures, such as the rate of the addition of silver ions to the solution. In this paper, we combine polyol process and solvothermal method for easily synthesizing silver nanostructures. Importantly, the introduction of cuprous chloride (CuCl) to the reaction leads to increasing the population of twinned Ag seeds (required for wire growth) at the expense of that of single Ag seeds. Silver nanowires (Ag NWs) with uniform width (~80?nm in width) can be obtained in the presence of poly(vinyl pyrrolidone) (PVP). Some other parameters, such as the reaction temperature and molar ratios of the repeating unit of PVP to AgNO₃ (R), also have been discussed. A possible mechanism is put forward to understand the evolution of silver nanostructures.     

Inducing imperfections in germanium nanowires

Nanowires with inhomogeneous heterostructures such as polytypes and periodic twin boundaries are interesting due to their potential use as components for optical,electrical,and thermophysical applications.Additionally,the incorporation of metal impurities in semiconductor nanowires could substantially alter their electronic and optical properties.In this highlight article,we review our recent progress and understanding in the deliberate induction of imperfections,in terms of both twin boundaries and additional impurities in germanium nanowires for new/enhanced functionalities.The role of catalysts and catalyst-nanowire interfaces for the growth of engineered nanowires via a three-phase paradigm is explored.Three-phase bottom-up growth is a feasible way to incorporate and engineer imperfections such as crystal defects and impurities in semiconductor nanowires via catalyst and/or interfacial manipulation."Epitaxial defect transfer"process and catalyst-nanowire interfacial engineering are employed to induce twin defects parallel and perpendicular to the nanowire growth axis.By inducing and manipulating twin boundaries in the metal catalysts,twin formation and density are controlled in Ge nanowires.The formation of Ge polytypes is also observed in nanowires for the growth of highly dense lateral twin boundaries.Additionally,metal impurity in the form of Sn is injected and engineered via third-party metal catalysts resulting in above-equilibrium incorporation of Sn adatoms in Ge nanowires.Sn impurities are precipitated into Ge bi-layers during Ge nanowire growth,where the impurity Sn atoms become trapped with the deposition of successive layers,thus giving an extraordinary Sn content (＞6 at.％) in Ge nanowires.A larger amount of Sn impingement (＞9 at.％) is further encouraged by utilizing the eutectic solubility of Sn in Ge along with impurity trapping.     

Fabrication, structural characterization and photoluminescence of Q-1D semiconductor ZnS hierarchical nanostructures

Quasi-one-dimensional semiconductor ZnS hierarchical nanostructures have been fabricated by thermal evaporation of a mixture of ZnS nanopowders and Sn powders. Sn nanoparticles are located at or close to the tips of the nanowires (or nanoneedles) and served as the catalyst for quasi-one-dimensional ZnS nanostructure growth by a vapour-liquid-solid mechanism. The morphology and microstructure of the ZnS hierarchical nanostructures were measured by scanning electron microscopy and high-resolution transmission electron microscopy. The results show that a large number of ZnS nanoneedles were formed on the outer shells of a long and straight ZnS axial nanowire. The ZnS axial nanowires grow along the [001] direction, and ZnS nanoneedles are aligned over the surface of the ZnS nanowire in the radial direction. The room temperature photoluminescence spectrum exhibits a UV weak emission centred at 337?nm and one blue emission centred at 436?nm from the as-synthesized single-crystalline semiconductor ZnS hierarchical nanostructures.     

Morphology control of self-catalyzed germanium nanostructures with graphitic carbon shell

The crystalline germanium nanowires (GeNWs) with a uniform graphitic carbon shell were prepared via a conventional low-pressure chemical vapor deposition method without any external catalyst. The GeNWs grown at low temperature (Tg < 500 degrees C) have a uniform diameter with a large expect ratio of more than 10(3). With increasing the growth temperature (Tg > 500 degrees C), however, the nanowire morphology is dramatically changed into a hybrid structure where highly dense Ge nanoparticles (GeNPs) with a diameter of 5-10 nm are attached onto the Ge nanowires. The nanostructures consist of crystalline Ge-core and very thin graphitic carbon shell. The possible mechanism of anisotropic growth and the control of morphological transition from uniform nanowires to NW/NP hybrid structures are discussed and demonstrated.     

Selenium nanowires and nanotubes synthesized via a facile template-free solution method

Trigonal selenium (t-Se) nanowires and nanotubes were successfully prepared on a large scale via an environment-friendly synthetic process, in which no templates or surfactants were employed. These t-Se nanowires having a width of 70-100 nm and length up to tens of micrometers were synthesized in absolute ethanol at room temperature, while t-Se nanotubes with outer diameter ranging from 180 to 350 nm were obtained at 85 °C in water system. SEM and TEM analyses of the samples obtained at different stages indicated that the formation of these t-Se 1D nanostructures was governed by a “solid-solution-solid” growth process. The amorphous Se (a-Se) nanoparticles were initially generated and then would transform into crystal seeds for the subsequent growth of nanowires or nanotubes. Detailed experiments found that temperature and solvents as well as concentrations of starting materials were crucial to the formation of final morphology.     

Growth of germanium nanowires on silicon(111) substrates by molecular beam epitaxy

Heteroepitaxial growth of Ge nanowires was carried out on Si(111) substrates by MBE. Au seeds were used as precursor for the VLS growth of the nanowires. Even if the Au droplets do not act as catalyst for the dissociation of gas, they are local preferential areas where the energetic barrier of Ge nucleation is lowered compare to the remaining non activated surface. Two sets of Au seeds were used as precursors for the VLS process. The first set have an average diameter of 125 nm and the second of 25 nm. In-situ RHEED monitoring showed a Au wetting layer between these seeds before the nanowires growth as well as at the end of the Ge nanowires growth. It means that the wetting layer acted as a surfactant from the Si(111) surface to the Ge grown layer between the nanowires. Analysis of SEM images brought the fact that the diffusion of gold from the droplets on the surface and the sidewalls of the nanowires via the Ostwald ripening is a key parameter of the growth of the nanowires.     

Controlled growth and characterization methods of semiconductor nanomaterials

One-dimensional (1D) semiconductor nanomaterials attract much attention because they are ideal systems for investigation and studying the relationship between properties and structures and having extensive application future in the high technical field. They are expected to play an important role in fabrication of the next generation nanocircuits, nanotools, nanowires lasers, photon tunneling devices, near-field photo-waveguide devices, etc. This article described controlled growth, characterization of structures and morphologies and properties of 1D semiconductor nanomaterials based on our previous works. This article is organized into two parts: The first part is complicated nanostructures of semiconductors, which includes coaxial nanocables, heterostructure nanowires and nanowires with metal-semiconductor junction behavior, hierarchical structures, doping of the nanowires and nanobelts, porous materials and periodically twined nanowires and asymmetrical polytypic nanobelts. The second part contains semiconductor nanoarrays based on anodic alumina membrane (AAM) templates. Finally, we propose that further investigation of the influence of nanomaterial morphologies on properties and how to design the morphology of nanostructures to meet the property requirements of nanodevices are our future research directions in this field.     

Synthesis and applications of one-dimensional semiconductors

Nanoscale inorganic materials such as quantum dots (0-dimensional) and one-dimensional (1D) structures, such as nanowires, nanobelts and nanotubes, have gained tremendous attention within the last decade. Among the huge variety of 1D nanostructures, semiconducting nanowires have gained particular interest due to their potential applications in optoelectronic and electronic devices. Despite the huge efforts to control and understand the growth mechanisms underlying the formation of these highly anisotropic structures, some fundamental phenomena are still not well understood. For example, high aspect-ratio semiconductors exhibit unexpected growth phenomena, e.g. diameter-dependent and temperature-dependent growth directions, and unusual high doping levels or compositions, which are not known for their macroscopic crystals or thin-film counterparts.This article reviews viable synthetic approaches for growing high aspect-ratio semiconductors from bottom-up techniques, such as crystal structure governed nucleation, metal-promoted vapour phase and solution growth, formation in non-metal seeded gas-phase processes, structure directing templates and electrospinning. In particular new experimental findings and theoretical models relating to the frequently applied vapour-liquid-solid (VLS) growth are highlighted. In addition, the top-down application of controlled chemical etching, using novel masking techniques, is described as a viable approach for generating certain 1D structures. The review highlights the controlled synthesis of semiconducting nanostructures and heterostructures of silicon, germanium, gallium nitride, gallium arsenide, cadmium sulphide, zinc oxide and tin oxide. The alignment of 1D nanostructures will be reviewed briefly. Whilst specific and reliable contact procedures are still a major challenge for the integration of 1D nanostructures as active building blocks, this issue will not be the focus of this paper. However, the promising applications of 1D semiconductors will be highlighted, particularly with reference to surface dependent electronic transduction (gas and biological sensors), energy generation (nanomechanical and photovoltaic) devices, energy storage (lithium storage in battery anodes) as well as nanowire photonics.