GaN nanowires: CVD synthesis and properties

The growth of GaN nanowires from Ga and NH₃ sources in the flow of Ar carrier gas using a chemical vapor deposition (CVD) system was systematically studied. The substrates used were Si(111) and Si(100). Fabricated nanowires were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy (EDX). We investigated the influence of growth temperature, catalyst used, Ga amount, and the ratio of Ar and NH₃ flow rates on the morphology and properties of GaN nanowires. We found that the best results were obtained for a growth temperature of 950 °C. Optimal catalysts were Au and metallic Ni, while the use of nickel nitrate was found to lead to formation of SiO_x nanowire bunches in addition to GaN nanowires. For the optimal temperature and catalyst used, the influence of the Ga to N ratio on the nanowire growth was studied. It was found that different types of nanostructures are observed in relatively Ga-rich and in relatively N-rich conditions. Growth mechanisms of different types of nanowires, including the stacked-cone nanowires and the microscale structures formed by lateral growth under N-rich conditions, are discussed.     

Coherent Growth of InP/InAsP/InP Nanowires on a Si (111) Surface by Molecular-Beam Epitaxy

Results obtained in a study of the growth of InP/InAsP/InP nanowires on the Si (111) surface are presented. Using a special procedure of substrate preparation immediately before the growth made it possible to obtain a nanowire coherency with the substrate of nearly 100%. A high-intensity emission from nanostructures of this kind was observed at a wavelength of ~1.3 μm at room temperature.     

Growth of GaInAs/AlInAs heterostructure nanowires for long-wavelength photon emission

We investigated the growth of GaInAs/AlInAs heterostructure nanowires on InP(111)B and Si(111) substrates in a metalorganic vapor phase epitaxy reactor. Au colloids were used to deposit Au catalysts 20 and 40 nm in diameter on the substrate surfaces. We obtained vertical GaInAs and AlInAs nanowires on InP(111)B surfaces. The GaInAs nanowires capped with GaAs/AlInAs layers show room-temperature photoluminescence. The peak exhibits a blue-shift when the Ga content in the core GaInAs nanowire is increased. For the GaInAs/AlInAs heterostructure growth, it is possible to change the Ga content sharply but Al also exists in the GaInAs layer regions. We also found that the ratios of Ga and Al contents to In content tend to increase and the axial growth rate to decrease along the nanowire toward the top. We were also able to make vertical GaInAs nanowires on Si(111) surfaces after a short growth of GaP and InP.     

Morphology of self-catalyzed GaN nanowires and chronology of their formation by molecular beam epitaxy

GaN nanowires are synthesized by plasma-assisted molecular beam epitaxy on Si(111) substrates. The strong impact of the cell orientation relative to the substrate on the nanowire morphology is shown. To study the kinetics of growth, thin AlN markers are introduced periodically during NW growth. These markers are observed in single nanowires by transmission electron microscopy, giving access to the chronology of the nanowire formation and to the time evolution of the nanowire morphology. A long delay precedes the beginning of nanowire formation. Then, their elongation proceeds at a constant rate. Later, shells develop on the side-wall facets by ascending growth of layer bunches which first agglomerate at the nanowire foot.     

Measurement of mechanical properties of one-dimensional nanostructures with combined multi-probe platform

New materials and nanostructures with superior mechanical and electronic properties are emerging for development of novel devices. Their engineering application requires accurate mechanical characterization, which, in turn, requires novel experimental techniques. In this paper, we report a recently developed multi-probe mechanical testing system and a few of its typical applications in studying mechanical behaviors of one-dimensional (1D) nanostructures, which include analyzing clamping strength of electron beam induced deposition (EBID) for Si nanowires and the tungsten substrate, retrieving Young’s modulus of a Si nanowire using tunable resonance method, and investigating thermal fatigue behavior of nanoscale interconnect lines bearing alternating current. We find this testing system can be easily used for clamping, loading, and measuring various 1D nanostructures.     

Si/InGaN core/shell hierarchical nanowire arrays and their photoelectrochemical properties

Three-dimensional hierarchical nanostructures were synthesized by the halide chemical vapor deposition of InGaN nanowires on Si wire arrays. Single phase InGaN nanowires grew vertically on the sidewalls of Si wires and acted as a high surface area photoanode for solar water splitting. Electrochemical measurements showed that the photocurrent density with hierarchical Si/InGaN nanowire arrays increased by 5 times compared to the photocurrent density with InGaN nanowire arrays grown on planar Si (1.23 V vs RHE). High-resolution transmission electron microscopy showed that InGaN nanowires are stable after 15 h of illumination. These measurements show that Si/InGaN hierarchical nanostructures are a viable high surface area electrode geometry for solar water splitting.     

Self-assembled tungsten oxide nanowires by electron beam assisted rapid thermal annealing

We report on the fabrication of WO₃ nanowires on Si (100) substrate using nickel catalyzed electron beam assisted rapid thermal annealing process. A 7 nm thick W layer deposited on the nickel coated substrate was annealed under high vacuum using electron beam (3 keV) for 30, 60 and 90 s. The nickel activates the growth of tungsten nanowires with a high aspect ratio and subsequently is oxidized due to the high refractory nature of tungsten under exposure to oxygen gas. The resulting changes in surface morphology, oxidization state and elemental composition of WO₃ nanowires were investigated systematically. The oxidization of metallic tungsten nanowire was found to depend on the annealing time.     

Growth and optical properties of aluminum-doped zinc oxide nanostructures on flexible substrates in flexible electronics

Undoped ZnO nanowire arrays and Al-doped ZnO nanostructures with nanowires and nanosheets were successfully synthesized on a polyethylene terephthalate substrate using the rapid hydrothermal synthesis. These undoped ZnO nanowire arrays showed close alignment with highly c-axis oriented and well-defined hexagonal facets (001). The coexistence of the nanowires and nanosheets was observed during the introduction of Al ions. The number of nanosheets increased due to the Al doping concentration and the lack of surface energy. The diameter of the nanosheets and the length of nanowire arrays also increased as a function of the growth time. Room-temperature photoluminescence spectra show that the ZnO:Al nanostructures on the ZnO seeded polyethylene terephthalate substrate yield low level of the defect density compared to the ZnO seeded glass substrate to remove post annealing process.     

Hydrothermal synthesis of one-dimensional single-crystalline rutile TiO2 nanostructures and their application in dye-sensitized solar cells

One-dimensional (1D) TiO2 nanowire arrays are fabricated on transparent conducting substrates via a low temperature hydrothermal route for application in dye-sensitized solar cells (DSSCs). The as-prepared sample on fluorine-doped tin oxide (FTO) substrate is found to be single-crystalline rutile TiO2 structures from X-ray and electron diffractions. The length and diameter of the nanowires depend mainly on the growth time and temperature. With increasing the reaction time, the growth rate becomes slower and the interface adhesion between the growth nanowires and the substrate becomes weaker. In the same time the adjacent nanowires aggregate to larger the apparent diameter of the nanowire making the gaps among the nanowires to disappear at last. The nanowires exhibit flower-like morphology on the non-conducting surface of FTO substrate. By using TiO2 nanowire arrays with 2 microm long on FTO substrate as the photoanode in DSSCs, an overall light conversion efficiency of 1.58% is achieved with an open circuit voltage of 0.714 V, a short circuit current density of 4.68 mA cm(-2), and a fill factor of 0.472.     

Synthesis and properties of copper phthalocyanine nanowires

Copper phthalocyanine (CuPc) nanowires were fabricated by organic vapor deposition. The nanowires were studied by scanning electron microscopy, X-ray diffraction, and absorption spectroscopy. The effect of the nature of substrate (glass, Si, indium tin oxide, fluorine doped tin oxide) and its temperature on the morphology and properties of the fabricated nanowires was studied. Deposition of a thin CuPc film before the nanostructure growth ensured high yield of CuPc nanowires for all the substrates except Si. The nanowire size and crystal structure were mainly determined by the substrate temperature, with α-CuPc nanowires obtained at the lowest temperature (∼ 190 °C) and β-CuPc nanowires obtained at higher temperatures (above 200 °C).     

ZnO nanowire growth by electric current heating method: A study on the effect of substrate temperature

In this study, we report the growth of ZnO nanowire on quartz glass substrates with Au-catalyst assistance by electric current heating of ZnO ceramic bar. The effect of substrate temperature on the properties of ZnO nanostructures has been investigated systematically. Structural analysis indicates that the grown ZnO crystals belong to hexagonal phase with preferential growth along (0 0 2) orientation. Scanning electron microscopic studies reveal the aligned ZnO nanowires were grown at 800 °C. The typical length and diameter of nanowires are in the uniform ranges of 4–20 μm and 20–100 nm, respectively, showing their high aspect ratio of about 1000. We have made an attempt to discuss about the change in ZnO nanostructures with different substrate temperatures and the possible mechanism for the growth of nanowires. Optical reflectance studies show the infrared reflectivity was controlled through the substrate temperature.     

Titanium-assisted growth of silica nanowires: from surface-matched to free-standing morphologies

We report on an oxide-assisted growth technique for silica nanowires which allows tuning the growth from surface-matched nanowires to free-standing morphologies based on growth control by Ti in the role of a catalyst and surfactant. Using an adjustable Ti concentration, we grew silica nanowires with lengths ranging from 100 nm up to several millimetres whose defect chemistry was analysed by electron microscopy tools, monochromatic cathodoluminescence imaging and time resolved photoluminescence spectroscopy. The knowledge of the luminescence properties and the related defect occurrence along with their spatial distribution is pivotal for advancing silica nanowire growth in order to realize successful device designs based on self-assembled Si/SiO(x) nanostructures. We demonstrate a core-shell structure of the grown nanowires with a highly luminescent 150 nm thick shell and outstandingly fast decaying dynamics (≈1 ns) for glass-like materials. The conjunction of the observed efficient and stable luminescences with their attributed decaying behaviours suggests applications for silica nanowires such as active and passive optical interconnectors and white light phosphors. The identification of a time domain difference for the spectral regime from 2.3 to 3.3 eV, within the confined spatial dimensions of a single nanowire, is very promising for future, e.g. data transmission applications, employing silica nanowires which exhibit achievable compatibility with commonly applied silicon-based electronics. A qualitative growth model based on silica particle diffusion and Ti-assisted seed formation is developed for the various types of segregated silica nanowires which extends commonly assumed oxide-assisted growth mechanisms.     

The influence of surface oxide on the growth of metal/semiconductor nanowires

We report the critical effects of oxide on the growth of nanostructures through silicide formation. Under an in situ ultrahigh vacuum transmission electron microscope, it is observed from the conversion of Si nanowires into the metallic PtSi grains epitaxially through controlled reactions between lithographically defined Pt pads and Si nanowires. With oxide, instead of contact area, single crystal PtSi grains start forming either near the center between two adjacent pads or from the ends of Si nanowires, resulting in the heterostructure formation of Si/PtSi/Si. Without oxide, transformation from Si into PtSi begins at the contact area between them, resulting in the heterostructure formation of PtSi/Si/PtSi. The nanowire heterostructures have an atomically sharp interface with epitaxial relationships of Si(20-2)//PtSi(10-1) and Si[111]//PtSi[111]. Additionally, it has been observed that the existence of oxide significantly affects not only the growth position but also the growth behavior and the growth rate by two orders of magnitude. Molecular dynamics simulations have been performed to support our experimental results and the proposed growth mechanisms. In addition to fundamental science, the significance of the study matters for future processing techniques in nanotechnology and related applications as well.     

van der Waals epitaxy of InAs nanowires vertically aligned on single-layer graphene

Semiconductor nanowire arrays integrated vertically on graphene films offer significant advantages for many sophisticated device applications. We report on van der Waals (VDW) epitaxy of InAs nanowires vertically aligned on graphene substrates using metal-organic chemical vapor deposition. The strong correlation between the growth direction of InAs nanowires and surface roughness of graphene substrates was investigated using various graphene films with different numbers of stacked layers. Notably, vertically well-aligned InAs nanowire arrays were obtained easily on single-layer graphene substrates with sufficiently strong VDW attraction. This study presents a considerable advance toward the VDW heteroepitaxy of inorganic nanostructures on chemical vapor-deposited large-area graphenes. More importantly, this work demonstrates the thinnest epitaxial substrate material that yields vertical nanowire arrays by the VDW epitaxy method.     

Investigation of initial growth of ZnO nanowires and their growth mechanism

ZnO nanowires were synthesized on Si substrates by a simple metal vapor deposition method without any catalysts. The initial growth and the growth mechanism of the ZnO nanowires were studied using scanning and transmission electron microscopy. We found that the ZnO nanowires grew on the Si substrate via a self-seeding vapor-solid mechanism. The growth process of the ZnO nanowires consisted of four steps: self-seeding, one-dimensional epitaxial growth of the nanowires on the seeds by a base-growth mode, further acceleration of nanowire growth with additional seeding, and active formation of the nanowires.     

Edge‐Epitaxial Growth of InSe Nanowires toward High‐Performance Photodetectors

Semiconducting nanowires offer many opportunities for electronic and optoelectronic device applications due to their unique geometries and physical properties. However, it is challenging to synthesize semiconducting nanowires directly on a SiO₂/Si substrate due to lattice mismatch. Here, a catalysis‐free approach is developed to achieve direct synthesis of long and straight InSe nanowires on SiO₂/Si substrates through edge‐homoepitaxial growth. Parallel InSe nanowires are achieved further on SiO₂/Si substrates through controlling growth conditions. The underlying growth mechanism is attributed to a selenium self‐driven vapor–liquid–solid process, which is distinct from the conventional metal‐catalytic vapor–liquid–solid method widely used for growing Si and III–V nanowires. Furthermore, it is demonstrated that the as‐grown InSe nanowire‐based visible light photodetector simultaneously possesses an extraordinary photoresponsivity of 271 A W^?1, ultrahigh detectivity of 1.57 × 10¹⁴ Jones, and a fast response speed of microsecond scale. The excellent performance of the photodetector indicates that as‐grown InSe nanowires are promising in future optoelectronic applications. More importantly, the proposed edge‐homoepitaxial approach may open up a novel avenue for direct synthesis of semiconducting nanowire arrays on SiO₂/Si substrates.     

Controlled growth of Si nanowire arrays for device integration

Silicon nanowires were synthesized, in a controlled manner, for their practical integration into devices. Gold colloids were used for nanowire synthesis by the vapor-liquid-solid growth mechanism. Using SiCl4 as the precursor gas in a chemical vapor deposition system, nanowire arrays were grown vertically aligned with respect to the substrate. By manipulating the colloid deposition on the substrate, highly controlled growth of aligned silicon nanowires was achieved. Nanowire arrays were synthesized with narrow size distributions dictated by the seeding colloids and with average diameters down to 39 nm. The density of wire growth was successfully varied from approximately 0.1-1.8 wires/microm2. Patterned deposition of the colloids led to confinement of the vertical nanowire growth to selected regions. In addition, Si nanowires were grown directly into microchannels to demonstrate the flexibility of the deposition technique. By controlling various aspects of nanowire growth, these methods will enable their efficient and economical incorporation into devices.     

Growth condition dependence of zinc oxide nanostructures on Si substrates in an electrochemical process

Zinc oxide nanostructures were synthesized in an aqueous solution of hexamine and zinc nitrate by an electrochemical process. The effects of growth conditions, including electrical potential, growth temperature and template size, on morphology and composition of the nanostructures were systematically investigated. A negative potential enhanced the growth of single crystalline ZnO nanowire arrays while a positive potential caused nano-disks of ZnO and ZnO₂ composites to grow on the substrate. The applied negative potential also helped room temperature growth of ZnO nanowires with a reduced growth rate. Similar growth behavior was observed on a bare substrate and that with pre-defined polymer template.     

The influence of substrate orientation on the density of silicon nanowires grown on multicrystalline and single crystal substrates by electron cyclotron resonance chemical vapour deposition

The Au catalysed, vapour-liquid-solid growth of Si nanowires on Si substrates of different orientations has been studied using electron cyclotron resonance plasma-assisted chemical vapour deposition (ECRCVD). ECRCVD plasma excitation is found to strongly promote wire growth rate and density with wire diameters in excess of 200 nm under the conditions used. Substrate orientation and nanowire density are strongly correlated. This has been studied using multicrystalline as well as single crystal Si substrates. It is suggested that the Gibbs-Thomson effect can account for the behaviour of wire density with orientation. The application of an RF generated, DC self-bias of − 5 V on the substrate during growth strongly enhances wire density without affecting growth rate or diameter. A tentative model for wire growth has been proposed which is based on an initial incubation/crystallisation step, followed by silicon incorporation at the vapour-liquid interface being rate-limiting.     

Dynamics of dysprosium silicide nanostructures on Si(001) and (111) surfaces

The growth and coarsening dynamics of dysprosium silicide nanostructures are observed in real-time using photoelectron emission microscopy. The annealing of a thin Dy film to temperatures in the range of 700–1050 °C results in the formation of epitaxial rectangular silicide islands and nanowires on Si(001) and triangular and hexagonal silicide islands on Si(111). During continuous annealing, individual islands are observed to coarsen via Ostwald ripening at different rates as a consequence of local variations in the size and relative location of the surrounding islands on the surface. A subsequent deposition of Dy onto the Si(001) surface at 1050 °C leads to the growth of the preexisting islands and to the formation of silicide nanowires at temperatures above where nanowire growth typically occurs. Immediately after the deposition is terminated, the nanowires begin to decay from the ends, apparently transferring atoms to the more stable rectangular islands. On Si(111), a low continuous flux of Dy at 1050 °C leads to the growth of kinked and jagged island structures, which ultimately form into nearly equilateral triangular shapes.