Vertically aligned cadmium chalcogenide nanowire arrays on muscovite mica: a demonstration of epitaxial growth strategy

We report a strategy for achieving epitaxial, vertically aligned cadmium chalcogenide (CdS, CdSe, and CdTe) nanowire arrays utilizing van der Waals epitaxy with (001) muscovite mica substrate. The nanowires, grown from a vapor transport process, exhibited diameter uniformity throughout their length, sharp interface to the substrate, and positive correlation between diameter and length with preferential growth direction of [0001] for the monocrystalline wurtzite CdS and CdSe nanowires, but of [111] for zinc blende CdTe nanowires, which also featured abundant twinning boundaries. Self-catalytic vapor-liquid-solid mechanism with hydrogen-assisted thermal evaporation is proposed to intepret the observations. Optical absorption from the as-grown CdSe nanowire arrays on mica at 10 K revealed intense first-order exciton absorption and its longitudinal optical phonon replica. A small Stokes shift (～1.3 meV) was identified, suggesting the high quality of the nanowires. This study demonstrated the generality of van der Waals epitaxy for the growth of nanowire arrays and their potential applications in optical and energy related devices.     

A generic approach for embedded catalyst-supported vertically aligned nanowire growth

We demonstrate a general approach for growing vertically aligned, single-crystalline nanowires of any material on arbitrary substrates by using plasma-sputtered Au/Pd thin films as a catalyst through the vapor-liquid-solid process. The high-energy sputtered Au/Pd atoms form a reactive interface with the substrate forming nanoclusters which get embedded in the substrate, thus providing mechanical stability for vertically aligned nanowire growth. We demonstrate that our approach for vertically aligned nanowire growth is generic and can be extended to various complex substrates such as conducting indium tin oxide.     

Growth of ZnO nanowires on a patterned Au substrate

ZnO nanowires were site-selectively deposited on the catalytic gold-patterned substrates using a vapor transport process at low temperature. We observed that Au-Zn phase played an important role in initiating the ZnO nucleation, which was identified from the TEM observation of the interface between the substrate and ZnO nanowires. And then further growth of the nanowires on the ZnO surface was driven by the reaction of the Zn vapor and O₂ gas in vapor-solid growth mode. Finally, it was concluded that the site-specific deposition of ZnO nanowires was ascribed to the vapor-liquid-solid mechanism of Au, Zn vapor, and Au-Zn phases at the initial stage of ZnO nucleation.     

Elastic property of vertically aligned nanowires

An atomic force microscopy (AFM) based technique is demonstrated for measuring the elastic modulus of individual nanowires/nanotubes aligned on a solid substrate without destructing or manipulating the sample. By simultaneously acquiring the topography and lateral force image of the aligned nanowires in the AFM contacting mode, the elastic modulus of the individual nanowires in the image has been derived. The measurement is based on quantifying the lateral force required to induce the maximal deflection of the nanowire where the AFM tip was scanning over the surface in contact mode. For the [0001] ZnO nanowires/nanorods grown on a sapphire surface with an average diameter of 45 nm, the elastic modulus is measured to be 29 +/- 8 GPa.     

Aligned nanowire growth using lithography-assisted bonding of a polycarbonate template for neural probe electrodes

This research presents a fabrication method of vertically aligned nanowires on substrates using lithography-assisted template bonding (LATB) towards developing highly efficient electrodes for biomedical applications at low cost. A polycarbonate template containing cylindrical nanopores is attached to a substrate and the nanopores are selectively opened with a modified lithography process. Vertically aligned nanowires are grown by electrochemical deposition through these open pores on polyimide film and silicon substrates. The process of opening the nanopores is optimized to yield uniform growth of nanowires. The morphological, crystalline, and electrochemical properties of the resulting vertically aligned nanowires are discussed using scanning electron microscopy (SEM), x-ray diffraction (XRD), and electrochemical analysis tools. The potential application of this simple and inexpensive fabrication technology is discussed in the development of neural probe electrodes.     

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.     

Synthesis of vertically aligned ultra-long ZnO nanowires on heterogeneous substrates with catalyst at the root

The synthesis of ultra-long high-quality ZnO nanowires with uniform size and orientation on heterogeneous substrates is highly desirable, not only for investigating the fundamental properties of ZnO nanowires, but also for fabricating integrated functional nanodevices. Here we present a novel and general technique for growing vertically aligned ultra-long ZnO nanowires on various substrates. More importantly, the metal catalyst is experimentally determined not at the tip ends of the nanowires but at the junction area between the nanowires and the underlying substrate. Based on detailed analysis and control group results, we then propose a three-stage growth mechanism, in which vapor-liquid-solid growth and vapor-solid growth compete with each other to become dominant.     

Twin-free uniform epitaxial GaAs nanowires grown by a two-temperature process

We demonstrate vertically aligned epitaxial GaAs nanowires of excellent crystallographic quality and optimal shape, grown by Au nanoparticle-catalyzed metalorganic chemical vapor deposition. This is achieved by a two-temperature growth procedure, consisting of a brief initial high-temperature growth step followed by prolonged growth at a lower temperature. The initial high-temperature step is essential for obtaining straight, vertically aligned epitaxial nanowires on the (111)B GaAs substrate. The lower temperature employed for subsequent growth imparts superior nanowire morphology and crystallographic quality by minimizing radial growth and eliminating twinning defects. Photoluminescence measurements confirm the excellent optical quality of these two-temperature grown nanowires. Two mechanisms are proposed to explain the success of this two-temperature growth process, one involving Au nanoparticle-GaAs interface conditions and the other involving melting-solidification temperature hysteresis of the Au-Ga nanoparticle alloy.     

Bidirectional growth of indium phosphide nanowires

We present a bidirectional growth mode of InP nanowires grown by selective-area metalorganic vapor-phase epitaxy (SA-MOVPE). We studied the effect of the supply ratio of DEZn ([DEZn]) on InP grown structure morphology and crystal structures during the SA-MOVPE. Two growth regimes were observed in the investigated range of the [DEZn] on an InP(111)B substrate. At low [DEZn], grown structures formed tripod structures featuring three nanowires branched toward the [111]A directions. At high [DEZn], we obtained hexagonal pillar-type structures vertically grown on the (111)B substrate. These results show that the growth direction changes from [111]A to [111]B as [DEZn] is increased. We propose a growth mechanism based on the correlation between the incident facet of rotational twins and the shapes of the grown structures. Our results bring us one step closer to controlling the direction of nanowires on a Si substrate that has a nonpolar nature. They can also be applied to the development of InP nanowire devices.     

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.     

Controlled growth of vertically aligned ZnO nanowires with different crystal orientation of the ZnO seed layer

A novel synthesis and growth method achieving vertically aligned zinc oxide (ZnO) nanowires on a silicon dioxide (SiO(2)) coated silicon (Si) substrate is demonstrated. The growth direction of the ZnO nanowires is determined by the crystal structure of the ZnO seed layer, which is formed by the oxidation of a DC-sputtered Zn film. The [002] crystal direction of the seed layer is dominant under optimized thickness of the Zn film and thermal treatment. Vertically aligned ZnO nanowires on SiO(2) coated Si substrate are realized from the appropriately thick oxidized Zn seed layer by a vapor-solid growth mechanism by catalyst-free thermal chemical vapor deposition (CVD). These experimental results raise the possibility of using the nanowires as functional blocks for high-density integration systems and/or photonic applications.     

Ledge-flow-controlled catalyst interface dynamics during Si nanowire growth

Self-assembled nanowires offer the prospect of accurate and scalable device engineering at an atomistic scale for applications in electronics, photonics and biology. However, deterministic nanowire growth and the control of dopant profiles and heterostructures are limited by an incomplete understanding of the role of commonly used catalysts and specifically of their interface dynamics. Although catalytic chemical vapour deposition of nanowires below the eutectic temperature has been demonstrated in many semiconductor-catalyst systems, growth from solid catalysts is still disputed and the overall mechanism is largely unresolved. Here, we present a video-rate environmental transmission electron microscopy study of Si nanowire formation from Pd silicide crystals under disilane exposure. A Si crystal nucleus forms by phase separation, as observed for the liquid Au-Si system, which we use as a comparative benchmark. The dominant coherent Pd silicide/Si growth interface subsequently advances by lateral propagation of ledges, driven by catalytic dissociation of disilane and coupled Pd and Si diffusion. Our results establish an atomistic framework for nanowire assembly from solid catalysts, relevant also to their contact formation.     

Bottom-up growth of carbon nanotube multilayers: unprecedented growth

An unusual growth phenomenon, with no precedent in vapor-phase thin film growth, is described here, for the case of the growth of stacked multiple layers of vertically aligned carbon nanotubes(1-6) on solid substrates. As multiple layers of ordered nanotubes are sequentially deposited from the vapor onto the substrate, each layer nucleates and grows from the original substrate surface at the bottom of the existing multiple stacks of nanotubes. In contrast to conventional understanding of thin film deposition,(7) the mechanism here has similarities to porous oxide film formation on surfaces.(8) The stacked layers of aligned nanotubes act as fully permeable membranes for the downward diffusion of growth precursor vapors, allowing growth to occur at the buried solid interface. The preexisting multiple nanotube stacks lift up to accommodate the vertical growth of fresh layers, allowing the formation of nanotube towers extending in millimeter lengths. Our results provide evidence for a new growth phenomenon, characterized by selective, interface-driven, bottom-up growth of self-assembled nanowires at buried interfaces, covered with weakly adhering thick porous membranes.     

Influence of seed layers on the vertical growth of ZnO nanowires

We synthesized vertically aligned ZnO nanowires on SiO₂ wafer <100> using the Au, ZnO and Au/ZnO seed layers through the physical vapor deposition process. The growth direction of ZnO nanowire was controlled by using the three different seed layers. From the XRD results, we observed the highest intensity of the (002) peak on the Au/ZnO seed layer among the three seed layers. The SEM images show that all of the ZnO nanowires have an average diameter of about 100 ~ 200 nm and a length of about 5 μm, and the nanowires grown on the Au/ZnO seed layer are oriented the most perpendicularly to the substrate surface. From the PL analysis, we observed that the intensity of broad emissions at 400-600 nm relating the green emission for the ZnO nanowires on the Au/ZnO seed layer was much weaker than that for the ZnO nanowires on the ZnO seed layer. The experiment results indicate that the selection of seed layers is important to grow nanowires vertically for the application of nanoscale devices.     

Efficient strategy to Cu/Si catalyst into vertically aligned carbon nanotubes with bamboo shape by CVD technique

Bamboo-shaped vertically aligned carbon nanotubes (bs-VACNTs) were fabricated on Cu/Si catalyst by chemical vapour deposition (CVD) technique under the atmospheric pressure. The catalytic material (Cu/Si) played a vital role in attaining bs-VACNTs, which is synthesized by drop cast method in a cost-effective manner. Using this catalytic support, we have achieved the tip growth bs-VACNTs at low temperature with well graphitization. The as-grown carbon material was then characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), energy dispersive X-ray spectroscopy (EDX) analyzer, high-resolution transmission electron microscope (HRTEM) and Raman spectroscopy. XRD technique confirms the formation of hexagonal graphitic carbon planes of carbon nanotubes (CNTs). The surface morphology of the material was characterized by SEM, which clearly infer vertically aligned CNTs. The nature, diameter and crystallinity were noticed by HRTEM and Raman spectroscopy, respectively. Further, we have also studied the electrochemical properties of the bs-VACNTs and it seems to be proved as highly electroconductive when compared to multi-walled carbon nanotubes (MWCNTs).     

Effect of ZnO seed layer on the catalytic growth of vertically aligned ZnO nanorod arrays

We have grown vertically aligned ZnO nanorods and multipods by a seeded layer assisted vapor–liquid–solid (VLS) growth process using a muffle furnace. The effect of seed layer, substrate temperature and substrate material has been studied systematically for the growth of high quality aligned nanorods. The structural analysis on the aligned nanorods shows c-axis oriented aligned growth by homoepitaxy. High crystallinity and highly aligned ZnO nanorods are obtained for growth temperature of 850–900 °C. Depending on the thickness of the ZnO seed layer and local temperature on the substrate, some region of a substrate show ZnO tetrapod, hexapods and multipods, in addition to the vertically aligned nanorods. Raman scattering studies on the aligned nanorods show distinct mode at ∼438 cm⁻¹, confirming the hexagonal wurtzite phase of the nanorods. Room temperature photoluminescence studies show strong near band edge emission at ∼378 nm for aligned nanorods, while the non-aligned nanorods show only defect-emission band at ∼500 nm. ZnO nanorods grown without the seed layer were found to be non-aligned and are of much inferior quality. Possible growth mechanism for the seeded layer grown aligned nanorods is discussed.     

BiOCl nano/microstructures on substrates: Synthesis and photocatalytic properties

Bismuth oxycholoride (BiOCl) nano/microstructures, including flake and nanowire arrays, were successfully synthesized on Anodic Aluminum Oxide (AAO) templates via sol-gel combined with the vacuum air-extraction method. The flakes are almost vertically aligned on the surface, but nanowires at a lower sol concentration are aligned along the channels. A possible formation mechanism is proposed. Furthermore, the photocatalytic activity of the BiOCl nano/microstructures is investigated by photocatalytic decomposition of Rhodamine B (Rh B) dye under UV-Visible light irradiation. Compared with the BiOCl flake-like film on the glass substrate, where the flakes are horizontally oriented on the surface, the vertically aligned flake and nanowire arrays on AAO templates, have higher photocatalytic efficiency.     

On the role of activation mode in the plasma- and hot filaments-enhanced catalytic chemical vapour deposition of vertically aligned carbon nanotubes

Catalytic chemical vapor deposition (CCVD) with different activation modes (thermal; hot filaments-enhanced; direct current plasma-enhanced and both hot filament and direct current plasma-enhanced) are achieved in order to grow vertically aligned carbon nanotubes (VA CNTs). By widely varying the power of the different activation sources of the gas (plasma, hot filaments, substrate heating) while keeping identical the substrate temperature (973 K) and the catalyst preparation, the results point out the important role of ions in the nucleation of carbon nanotubes (CNTs), as well as the etching behaviour of highly activated radicals such as H˙ in the selective growth of vertically aligned films of CNTs. Moreover, it is demonstrated that, within the deposition conditions (temperature, pressure, flow rate) used in this study, oriented carbon nanotubes can be grown only when both ions, mainly generated by the gas discharge plasma, and highly reactive radicals, mainly formed by the hot filaments, are produced in the gas phase. We propose that highly energetic ions are needed to nucleate the carbon nanotubes by increasing the carbon concentration gradient whereas the highly reactive radicals allow the selective growth of vertically aligned CNTs by preventing carbon deposition on the whole surface through chemical etching of edge carbons in graphene sheets.     

Acoustic charge transport in GaN nanowires

We present acoustic charge transport in GaN nanowires (GaN NWs). The GaN NWs were grown by molecular beam epitaxy (MBE) on silicon(111) substrates. The nanowires were removed from the silicon substrate, aligned using surface acoustic waves (SAWs) on the piezoelectric substrate LiNbO(3) and finally contacted by electron beam lithography. Then, a SAW was used to create an acoustoelectric current in the GaN NWs which was detected as a function of radio-frequency (RF) wave frequency and its power. The presented method and our experimental findings open up a route towards new acoustic charge transport nanostructure devices in a wide bandgap material such as GaN.     

Synthesis and characterization of cadmium telluride nanowire

CdTe nanowires with controlled composition were cathodically electrodeposited using track-etched polycarbonate membrane as scaffolds and their material and electrical properties were systematically investigated. As-deposited CdTe nanowires show nanocrystalline cubic phase structures with grain sizes of up to 60 nm. The dark-field images of nanowires reveal that the crystallinity of nanowires was greatly improved from nanocrystalline to a few single crystals within nanowires upon annealing at 200?°C for 6?h in a reducing environment (5%?H(2)+95%?N(2)). For electrical characterization, a single CdTe nanowire was assembled across microfabricated gold electrodes using the drop-casting method. In addition to an increase in grain size, the electrical resistivity of an annealed single nanowire (a few 10(5)?Ω?cm) was one order of magnitude greater than in an as-deposited nanowire, indicating that crystallinity of nanowires improved and defects within nanowires were reduced during annealing. By controlling the dopants levels (e.g.?Te content of nanowires), the resistivity of nanowires was varied from 10(4) to 10(0)?Ω?cm. Current-voltage (I-V) characteristics of nanowires indicated the presence of Schottky barriers at both ends of the Au/CdTe interface. Temperature-dependent I-V measurements show that the electron transport mode was determined by a thermally activated component at T>-50?°C and a temperature-independent component below -50?°C. Under optical illumination, the single CdTe nanowire exhibited enhanced conductance.