The excitation of one-dimensional plasmons in Si and Au-Si complex atom wires

An atom-scale quantum wire array at the Au adsorbed Si(111) surface is studied by electron energy loss spectroscopy. Clear one-dimensional metallicity is verified by the observation of low-energy plasmonic excitation which exhibits a strong anisotropic dispersion. Our theoretical analysis using a quantum-mechanical nonlocal response theory shows that the plasmons are most probably supported in conductive channels made of Si honeycomb wires rather than those made of Au-Si complex wires.     

Control of surface migration of gold particles on Si nanowires

On the surface of silicon nanowires (SiNWs) synthesized by gold (Au)-catalyzed chemical vapor deposition (CVD), Au particles 5-20 nm in diameter are formed if the growth conditions are within a specific range. We studied the mechanism of Au particle formation by growing SiNWs under different conditions, specifically by dynamically changing the growth parameters during the growth process. We show that insufficient supply of Si source to the Au-Si eutectic on top of the SiNWs enhances the migration of Au atoms on the surface of SiNWs in the form of Au-Si eutectic, which is precipitated on the surface as Au particles during cooling. We also show that using Au-Si eutectic on the surface of SiNWs as a catalyst enables one-step growth of branched SiNWs.     

Surface energy driven agglomeration and growth of single crystal metal wires

We introduce a novel wire growth technique that involves simply heating a multilayer film specifically designed to take advantage of the different surface energies of the substrate and film components. In all cases the high surface energy component is extruded as a single crystal nanowire. Moreover we demonstrate that patterning the bilayer film generates localized surface agglomeration waves during the anneal that can be exploited to position the grown wires. Examples of Au and Cu nanowire growth are presented, and the generalization of this method to other systems is discussed.     

The morphology of axial and branched nanowire heterostructures

We present an extensive investigation of the epitaxial growth of Au-assisted axial heterostructure nanowires composed of group IV and III-V materials and derive a model to explain the overall morphology of such wires. By analogy with 2D epitaxial growth, this model relates the wire morphology (i.e., whether it is kinked or straight) to the relationship of the interface energies between the two materials and the particle. This model suggests that, for any pair of materials, it should be easier to form a straight wire with one interface direction than the other, and we demonstrate this for the material combinations presented here. However, such factors as kinetics and the use of surfactants may permit the growth of straight double heterostructure nanowires. Finally, we demonstrate that branched nanowire heterostructures, also known as nanotrees, can be successfully explained by the same model.     

Crystal structure control in Au-free self-seeded InSb wire growth

In this work we demonstrate experimentally the dependence of InSb crystal structure on the ratio of Sb to In atoms at the growth front. Epitaxial InSb wires are grown by a self-seeded particle assisted growth technique on several different III-V substrates. Detailed investigations of growth parameters and post-growth energy dispersive x-ray spectroscopy indicate that the seed particles initially consist of In and incorporate up to 20?at.% Sb during growth. By applying this technique we demonstrate the formation of zinc-blende, 4H and wurtzite structure in the InSb wires (identified by transmission electron microscopy and synchrotron x-ray diffraction), and correlate this sequential change in crystal structure to the increasing Sb/In ratio at the particle-wire interface. The low ionicity of InSb and the large diameter of the wire structures studied in this work are entirely outside the parameters for which polytype formation is predicted by current models of particle seeded wire growth, suggesting that the V/III ratio at the interface determines crystal structure in a manner well beyond current understanding. These results therefore provide important insight into the relationship between the particle composition and the crystal structure, and demonstrate the potential to selectively tune the crystal structure in other III-V compound materials as well.     

Shape-controlled Au particles for InAs nanowire growth

We present a study of InAs nanowire (NW) growth with shape-controlled Au seed particles. In comparison to more conventional spherical particles, the highly faceted, shaped Au particles are found to enhance the initial growth kinetics of InAs NWs at identical growth conditions. Analysis of the NWs after growth by transmission electron microscopy and energy-dispersive spectroscopy suggests that while In diffuses into the bulk of the shaped Au particles, in accordance with the vapor-liquid-solid (VLS) growth mechanism, the surface faceting is preserved. A key difference is that the shaped Au particles are characterized by a thicker In shell on their surfaces than the spherical Au particles, indicating that increased adsorption of In leads to the observed growth rate enhancement. On the basis of these results, we propose that our picture of VLS growth in regards to liquefaction and droplet formation is incomplete and that the initial particle morphology can be used to tailor NW growth.     

Nano-sized particles formed by pulsed discharge of powders

Exploding wire and pulsed wire discharge are effective methods to form nano-sized particles. They are based on evaporation of thin metal wires by applied large electric current as the principle to form particles. Many kinds of wires have been used to form nano-sized particles so far. However, materials which are not sufficiently ductile to form thin wires are unsuitable for the methods. We have developed a method for powders to be held between electrodes by using heat-shrinkable tubes and discharged for evaporation. Nano-sized intermetallic NiAl compound particles were synthesized from mixed powders of Al and Ni. Si powder could be discharged by sealing with a thin Al wire, and nano-sized Si particles were formed. Utilizing this technique, various metal powders can be used for raw materials in pulsed discharge.     

Secondary ion mass spectrometry of vapor-liquid-solid grown, Au-catalyzed, Si wires

Knowledge of the catalyst concentration within vapor-liquid-solid (VLS) grown semiconductor wires is needed in order to assess potential limits to electrical and optical device performance imposed by the VLS growth mechanism. We report herein the use of secondary ion mass spectrometry to characterize the Au catalyst concentration within individual, VLS-grown, Si wires. For Si wires grown by chemical vapor deposition from SiCl 4 at 1000 degrees C, an upper limit on the bulk Au concentration was observed to be 1.7 x 10(16) atoms/cm(3), similar to the thermodynamic equilibrium concentration at the growth temperature. However, a higher concentration of Au was observed on the sidewalls of the wires.     

Control of Si nanowire growth by oxygen

Semiconductor nanowires formed using the vapor-liquid-solid mechanism are routinely grown in many laboratories, but a comprehensive understanding of the key factors affecting wire growth is still lacking. In this paper we show that, under conditions of low disilane pressure and higher temperature, long, untapered Si wires cannot be grown, using Au catalyst, without the presence of oxygen. Exposure to oxygen, even at low levels, reduces the diffusion of Au away from the catalyst droplets. This allows the droplet volumes to remain constant for longer times and therefore permits the growth of untapered wires. This effect is observed for both gas-phase and surface-bound oxygen, so the source of oxygen is unimportant. The control of oxygen exposure during growth provides a new tool for the fabrication of long, uniform-diameter structures, as required for many applications of nanowires.     

Coexistence of Vapor–Liquid–Solid and Vapor–Solid–Solid Growth Modes in Pd‐Assisted InAs Nanowires

During the growth of InAs nanowires from Pd catalyst particles on InAs(111)A substrates, two distinct classes of nanowires are observed with smooth or zigzagged sidewalls. It is shown that this is related to a bimodal distribution of the wire‐tip diameter: above a critical diameter wires grow with smooth sidewalls, and below with zigzagged morphology. Transmission electron microscopy analysis shows that the catalyst particles at the tip of zigzagged wires are smooth and have a higher aspect ratio than those at the tip of smooth wires. Zigzagged wires grow from liquid particles in the vapor–liquid–solid (VLS) mode whereas the smooth ones grow from solid particles in the vapor–solid–solid (VSS) mode.     

Condensation and crystal morphology of bismuth aerosols

Condensation aerosols of bismuth were prepared in the heat-pulse cloud chamber at various wall temperatures by flash evaporation of metal into argon at atmospheric pressure. The particles nucleate from the vapour in the liquid state only. When prepared at low wall temperatures the droplets solidify to tapered twins with an asymmetrically sited protuberance. At wall temperatures approaching the melting point of the metal the morphology of the smaller particles is affected by thermal ageing. Complex multiple twins occur, as well as twins of simpler, rhombohedral shape. A solidification mechanism is proposed for the tapered particles, by which the freshly nucleated crystal, growing at the surface of the droplet with an emergent corner, experiences a twinning shear under the influence of fluctuating stresses imposed by the particle motion. The crystal growth rate is thereby enhanced unidirectionally, and the particle becomes elongated as a result of the volumetric expansion.     

Broadband and wide-angle antireflection subwavelength structures of Si by inductively coupled plasma etching using dewetted nanopatterns of Au thin films as masks

We report the broadband and wide-angle antireflection subwavelength structures (SWSs) on silicon (Si) substrate by inductively coupled plasma (ICP) etching using gold (Au) nanopatterns as etch masks. The reflectance depends strongly on the etched profile of Si SWSs which is influenced by both thermal dewetting and etching conditions. The size, shape, and array geometry of nano-sized patterns, which are produced via the thermal dewetting of Au thin films, are optimized under proper heat treatment. The etched depth and shape of Si nano tips are controlled additionally by ICP power, thus achieving the efficient antireflection characteristics. The optimized Si SWS with the tapered structure and sharp tips at high ICP power leads to a significantly low reflectance value of < 1% at wavelengths of 350-1100 nm. Furthermore, it exhibits a wide-angle antireflection property of < 7.5% at incident angles of 8-70° over a wide wavelength range of 300-1100 nm.     

Selective area growth of GaN nanowires using metalorganic chemical vapor deposition on nano-patterned Si(111) formed by the etching of nano-sized Au droplets

We report on the selective area growth of GaN nanowires (NWs) on nano-patterned Si(111) substrates by metalorganic chemical vapor deposition. The nano-patterns were fabricated by the oxidation of Si followed by the etching process of Au nano-droplets. The size of formed nano-pattern on Si(111) substrate was corresponding to the size of Au nano-droplet, and the diameter of GaN NWs grown was similar to the diameter of fabricated nano-pattern. The interesting phenomenon of using the nano-patterned Si(111) substrates is the formation of very clear substrate surface even after the growth of GaN NWs. However, in the case of GaN NWs grown using Au nano-droplets, there was several nanoparticles including GaN bulk grains on the Si(111) substrates. The smooth surface morphology of nano-patterned Si(111) substrates was attributed to the presence of SiO₂ layer which prevents the formation of unnecessary GaN particles during the GaN NW growth. Therefore, we believe that nano-patterning method of Si(111) which was obtained by the oxidation of Si(111) substrate and subsequent Au etching process can be utilized to grow high-quality GaN NWs and its related nano-device applications.     

Contactless measurement of surface dominated recombination in gold- and aluminum-catalyzed silicon vapor-liquid-solid wires

Carrier lifetimes of Si micro/nanowires grown by the vapor-liquid-solid method are measured using an extension of the classic contactless photoconductivity decay method. The samples measured consist of a thin aggregated film of oxide passivated wires on a fused silica carrier. Au catalyzed wires in the 392-730 nm diameter range are studied. Recombination in these wires is controlled by the surface or near surface effects, not bulk Au impurities. The lifetimes of Au- and Al-catalyzed wires of comparable diameter are measured. The Al wires are found to have slightly longer lifetimes than those grown with Au at a comparable diameter. Across all samples, the lifetimes measured range was from 0.2 to 1.0 ns. The surface controlled nature of the recombination measured implies larger diameter wires will offer better performance in devices that rely on minority carrier transport.     

Some aspects of substrate pretreatment for epitaxial Si nanowire growth

We report on the influence of the surface pretreatment for vapor-liquid-solid growth of epitaxial silicon nanowires with gold catalyst and silane precursor on Si(111) substrates. In this paper we make it obvious that a thin native oxide layer on the Si substrate-as is present under most technological conditions-or a thin layer of oxide formed on top of the catalytic gold particle restrain nucleation and nanowire growth. High resolution transmission electron microscopy, and electron energy loss spectroscopy were utilized to demonstrate Si diffusion from the substrate through the catalytic Au layer and further the formation of a thin oxide layer atop. Based on this observation we present a sample pretreatment practice, making the catalyst insensitive for further oxide formation, thereby preserving epitaxy for nanowire synthesis.     

One Step Synthesis of Gold‐Loaded Radial Mesoporous Silica Nanospheres and Supported Lipid Bilayer Functionalization: Towards Bio‐Multifunctional Sensors

A simple synthetic route is developed to achieve gold functionalized radial mesoporous silica nanoparticles (Au‐MsNP) synthesized by a one step procedure fully compatible with basic conditions required for the preparation of monodispersed nanospheres. In a second step, Au‐MsNP particles have been coated with phospholipid bilayers in order to design an advanced biofunctional platform with the gold metallic nanoparticles previously grown into the pore channels and responsible for a plasmonic activity relevant for biosensing. The size of Au‐MsNP is checked by dynamic light scattering while zeta potential measurements reflect their surface charge. The particle morphology is characterized by transmission and scanning electron microscopy and the Si/Au ratios are obtained from energy dispersive X‐ray analysis. The textural properties of Au‐MsNP, specific surface area and pore size, are determined from N₂ adsorption. The supported bilayers are achieved from vesicles of different phospholipids incubated with Au‐MsNP particles. The coating efficiency is investigated by zeta potential and cryo‐ transmission electron microscopy. The plasmonic activities of bare Au‐MsNP particles and coated lipid bilayer Au‐MsNP platform are evidenced for two model systems: direct adsorption of bovine serum albumin and molecular recognition events between avidin molecules and biotin receptors integrated in the supported lipid bilayer.     

Temperature conditions for GaAs nanowire formation by Au-assisted molecular beam epitaxy

Molecular beam epitaxial growth of GaAs nanowires using Au particles as a catalyst was investigated. Prior to the growth during annealing, Au alloyed with Ga coming from the GaAs substrate, and melted. Phase transitions of the resulting particles were observed in?situ by reflection high-energy electron diffraction (RHEED). The temperature domain in which GaAs nanowire growth is possible was determined. The lower limit of this domain (320?°C) is close to the observed catalyst solidification temperature. Below this temperature, the catalyst is buried by GaAs growth. Above the higher limit (620?°C), the catalyst segregates on the surface with no significant nanowire formation. Inside this domain, the influence of growth temperature on the nanowire morphology and crystalline structure was investigated in detail by scanning electron microscopy and transmission electron microscopy. The correlation of the nanowire morphology with the RHEED patterns observed during the growth was established. Wurtzite GaAs was found to be the dominant crystal structure of the wires.     

Mechanism of gold-catalyzed carbon material growth

We demonstrate that nanosized Au particles have carbon solubility. Au-catalyzed carbon material growth by chemical vapor deposition undergoes a structural change, either a carbon nanowire or a single-walled carbon nanotube, depending on the catalyst particle size. This carbon material growth from Au is derived by the formation of Au-C eutectic nanosized alloy.     

Writing on Superhydrophobic Nanopost Arrays: Topographic Design for Bottom-up Assembly

A well-known property of superhydrophobic surfaces, such as an array of hydrophobic nanoposts, is to allow only limited surface contact of a liquid to the tips of the nanoposts. Herein we demonstrate that material deposition from solution, whether solid precipitation, surface adsorption or colloidal adhesion in static system, or dynamic "writing", can be limited to these specific areas of the surface when in this nonwetting state. As an example of solid precipitation, we show that nucleation of CaCO(3) results in the growth of small, uniform, amorphous deposits (which can merge and recrystallize) instead of disordered, large crystals due to the abundance of identical, small heterogeneous nucleation sites. The growth of amorphous CaCO(3) can be used to trap molecules from solution, as a potential application for controlled drug release. To demonstrate the localized surface adsorption, we show that chemical functionalization of the post tips can make them "sticky" for specific attachment of species (such as colloidal particles) from solution. The electrostatic charge and relative size ratio of the particle/post diameters control the attachment of particles to the post tips with great specificity. Dynamic conditions have also been shown for writing using droplets translated across the nonwetting surface at controlled speeds during deposition. These methods offer unprecedented control over the heterogeneous nucleation and localized growth of crystals from solution and avoid nonspecific adsorption. There is selective control of colloidal or molecular attachment to the nanopost tips, whereby the contact area, time of contact, and tip surface chemistry for reaction are all independently tunable parameters.     

High-resolution detection of Au catalyst atoms in Si nanowires

The potential for the metal nanocatalyst to contaminate vapour-liquid-solid grown semiconductor nanowires has been a long-standing concern, because the most common catalyst material, Au, is highly detrimental to the performance of minority carrier electronic devices. We have detected single Au atoms in Si nanowires grown using Au nanocatalyst particles in a vapour-liquid-solid process. Using high-angle annular dark-field scanning transmission electron microscopy, Au atoms were observed in higher numbers than expected from a simple extrapolation of the bulk solubility to the low growth temperature. Direct measurements of the minority carrier diffusion length versus nanowire diameter, however, demonstrate that surface recombination controls minority carrier transport in as-grown n-type nanowires; the influence of Au is negligible. These results advance the quantitative correlation of atomic-scale structure with the properties of nanomaterials and can provide essential guidance to the development of nanowire-based device technologies.