Charge influence and growth mechanism of ZnO nanorods

We demonstrate the influence of charges near the substrate surface on vertically aligned ZnO nanorod growth. ZnO nanorods were fabricated on n-type GaN with and without H+ treatments by catalyst-free metal-organic chemical vapor deposition. The ZnO nanorods grown on n-GaN films were vertically well-aligned and had a well-ordered wurtzite structure. However, the ZnO did not form into nanorods and the crystal quality was very degraded as they were deposited on the H+ treated n-GaN films. The charge influence was also observed in the ZnO nanorod growth on sapphire substrates. These results implied that the charges near the substrate surface dominantly affected on the crystalization and formation of ZnO nanorods.     

Charge influence and growth mechanism of ZnO nanorods

We demonstrate the influence of charges near the substrate surface on vertically aligned ZnO nanorod growth. ZnO nanorods were fabricated on n-type GaN with and without H+ treatments by catalyst-free metal-organic chemical vapor deposition. The ZnO nanorods grown on n-GaN films were vertically well-aligned and had a well-ordered wurtzite structure. However, the ZnO did not form into nanorods and the crystal quality was very degraded as they were deposited on the H+ treated n-GaN films. The charge influence was also observed in the ZnO nanorod growth on sapphire substrates. These results implied that the charges near the substrate surface dominantly affected on the crystallization and formation of ZnO nanorods.     

Structural and photoluminescence characterization of vertically aligned multiwalled carbon nanotubes coated with ZnO by magnetron sputtering

Zinc oxide (ZnO) nanostructures are very attractive in various optoelectronic applications such as light emitting devices. A fabrication process of these ZnO nanostructures which gives a good crystalline quality and being compatible with that of micro-fabrication has significant importance for practical application. In this work ZnO films with different thicknesses were deposited by RF-sputtering on vertically aligned multiwalled carbon nanotube (MWCNTs) template in order to obtain ZnO nanorods. The obtained hybrid structures (ZnO/MWCNTs) were characterized by scanning electron microscopy, X-ray diffraction, transmission electron microscopy, and time resolved photoluminescence spectroscopy (PL). Results show that the ZnO/MWCNTs have a nanorod structure like morphology with a good crystalline quality of the deposited ZnO on the MWCNTs. PL measurements reveal an enhancement of the band edge signal of ZnO/MWCNTs which is three times of magnitude higher compared to the ZnO film deposited on silicon. Moreover, the intensity enhancement varies as function of the ZnO thickness. Such hybrid structures are promising for optoelectronic application, such as blue-violet sources.     

Structural engineering of thin films of vertically aligned TiO2 nanorods

Self-assembled and vertically aligned rutile titania nanorods and thin films with a preferred [002] axial orientation were grown on substrates of fluorine-doped tin dioxide, using a hydrothermal method. Each nanorod was made of a bundle of densely packed and ultra fine nano-fibers growing along the [002] direction. The results show that ethanol substitution of water as solvent is highly effective in promoting the one-dimensional growth of the rutile nanorods and increasing their packing density in the thin films, which offers a simple-but-effectual leverage to monitor the nanorod structures for varied applications.     

Elemental vapor-phase synthesis of nanostructured zinc oxide

We systematize experimental data on the elemental vapor-phase synthesis of zinc oxide nanocrystal arrays on substrates. This process may yield nanostructures differing in shape and dimensions, in particular, well-aligned ZnO nanorod arrays. A model is proposed in which aligned zinc oxide nanorod arrays may grow by the vapor-liquid-solid (VLS) mechanism, and liquid zinc nanodroplets forming on the substrate surface at the beginning of the process catalyze one-dimensional growth. The VLS process is accompanied by zinc oxide deposition onto the lateral surface of the nanorods from the vapor phase. The relative rates of these processes influence the shape of the nanorods and the thickness of the polycrystalline underlayer. Optimizing the deposition conditions, one can grow uniform arrays of aligned high-quality ZnO nanorods with no catalysts and with no special substrate preparation steps.     

Effects of Metal-Organic Chemical Vapour Deposition grown seed layer on the fabrication of well aligned ZnO nanorods by Chemical Bath Deposition

Well aligned, long and uniform ZnO nanorods have been reproducibly fabricated adopting a two-steps Metal-Organic Chemical Vapour Deposition (MOCVD) and Chemical Bath Deposition (CBD) fabrication approaches. Thin (< 100 nm) ZnO buffer layers have been seeded on silicon substrates by MOCVD and ZnO layers have been subsequently grown, in form of well textured nanorods, using CBD. It has been found that the structure and thickness of the seed layer strongly influence the final morphology and the crystal texturing of ZnO nanorods as well as the CBD growth rate. There is, in addition, a strong correlation between morphologies of CBD grown ZnO nanorods and those of the seed layer underneath. Thus, nanorods deposited over low temperature MOCVD buffer layers are less homogeneous in lateral dimensions and poorly vertically oriented. On the contrary, higher temperature nano-dimensional ZnO seeds favour the CBD growth of almost mono-dimensional homologue nanorods, with an adequate control of the lateral transport of matter. The nanorod aspect ratio values decrease upon increasing the deposition temperatures of the seed layers. Moreover, the nanorods length can be tailored either by adjusting the CBD growth time or by changing concentration of the N,N,N′,N′-tetramethylethylenediamine ligand used in the CBD process. In particular, at high concentrations, the CBD process is faster with a greater global aspect ratio in agreement with a preferential one-dimensional growth of the ZnO nanostructures. Finally, these ZnO nanorod arrays possess good optical quality in accordance to the photoluminescence properties.     

Directed assembly of gold nanorods using aligned electrospun polymer nanofibers for highly efficient SERS substrates

Nonspherical metal nanoparticles are very attractive plasmonic nanostructures owing to the facile tunability of the plasmonic properties and the presence of sharp corners and edges, which act as electromagnetic hot spots for surface enhanced Raman scattering (SERS). However, such anisotropic nanostructures exhibit strong polarization dependence in their plasmonic properties, exhibiting significantly higher SERS intensity in certain orientations. In this paper, we demonstrate a facile strategy to achieve directed assembly of aligned gold nanorods using highly aligned electrospun nanofibers. We believe that the interstices between the nanofibers act as micro-and nanochannels, resulting in hydrodynamic drag forces on the gold nanorods, thus inducing massive alignment of the same on the nanofibers. Apart from exhibiting nearly 50 times higher SERS intensity compared to a planar SERS substrate with randomly oriented nanorods, our results highlight the importance of the orientation of anisotropic nanostructures. Finite difference time domain (FDTD) simulations employed to understand the electromagnetic field distribution around an aligned nanorod array showed excellent agreement with the experimental observations.     

Aligned silver nanorod arrays as substrates for surface-enhanced infrared absorption spectroscopy

Preferentially aligned silver nanorod arrays prepared by oblique angle vapor deposition were evaluated as substrates for surface-enhanced infrared absorption (SEIRA) spectroscopy. These nanorod arrays have an irregular surface lattice and are composed of tilted, cylindrically shaped nanorods that have an average length of 868 nm +/- 95 nm and an average diameter of 99 nm +/- 29 nm. The overall enhancement factor for chemisorbed organic films of para-nitrobenzoic acid (PNBA) deposited onto the Ag nanorod arrays analyzed by external reflection SEIRA was calculated to be 31 +/- 9 compared to infrared reflection-absorption spectroscopy (IRRAS) obtained from a 500 nm Ag film substrate. This enhancement is attributed to the unique optical properties of the nanorod arrays as well as the increased surface area provided by the nanorod substrate. SEIRA reflection-absorbance intensity was observed with both p- and s-polarized incident radiation with angles of incidence ranging from 25 degrees to 80 degrees . The largest intensity was achieved with p-polarization and incident angles larger than 75 degrees . Polarization-dependent ultraviolet/visible/near-infrared (UV/Vis/NIR) spectra of the nanorod arrays demonstrate that the red-shifted surface plasmon peaks of the elongated nanorods may be partially responsible for the observed SEIRA response. The SEIRA detection limit for the Ag nanorod arrays was estimated to be 0.08 ng/cm(2). Surface-enhanced Raman scattering (SERS) and SEIRA analysis of chemisorbed PNBA utilizing the same nanorod substrate is demonstrated.     

Morphology control of 1D ZnO nanostructures grown by metal-organic chemical vapor deposition

The morphology of ZnO nanostructures grown by metal-organic chemical vapor deposition under various growth conditions was examined by scanning electron microscopy. An increase in the growth temperature resulted in the formation of 1D nanostructures with diameters decreasing with increasing temperature. Vertically aligned nanorods with a needle-like tip shape were grown on a previously deposited homo-seed layer. Also the seed layer reduced the growth temperature of 1D nanorods. Low-temperature growth posterior to nanorod growth resulted in the formation of nanorods with an inverted graded diameter.     

Large field enhancement at electrochemically grown quasi-1D Ni nanostructures with low-threshold cold-field electron emission

Ni nanorod arrays have been vertically grown on a Ta-coated Si substrate via an electrodeposition process through the nanopores of a porous alumina membrane. Field emission studies of the samples are performed which show a considerable low-threshold field around 5 V μm(-1). The field emission mechanism followed Fowler-Nordheim tunneling due to large field enhancement at the emitter tips. Low-dimensional structures of the nanorod tips provided the large geometrical field enhancement and thus produce a high enough local or barrier field for low-threshold cold-field electron emission. The cost-effective synthesis of vertically aligned Ni nanorods on an Si substrate and low-threshold field emission properties can provide a potential alternative to conventional carbon-based field emitters for low power panel applications.     

Growth of vertically aligned InGaN nanorod arrays on p-type Si substrates for heterojunction diodes

InGaN nanorod arrays have been grown by molecular beam epitaxy on bare and high-temperature AIN-buffered Si(111) substrates. It has been found that well vertically aligned InGaN nanorod arrays can be grown by using the high-temperature AIN buffer layer. On bare Si substrate, high-resolution transmission electron microscopy revealed an amorphous SiNx layer generated at the interface, and the thickness and flatness of the SiNx layer may affect the relative alignment of the nanorods with the substrate. By using the high-temperature AIN buffer layer, the interface quality was improved, and uniform InGaN nanorods could be grown. N-InGaN nanorods/p-Si heterostructure diodes were fabricated, which exhibit well rectifying behavior with a low turn on voltage of 1.2 eV and an on/off ratio of 7.2 at 2.5 V.     

A novel, substrate independent three-step process for the growth of uniform ZnO nanorod arrays

We report a three-step deposition process for uniform arrays of ZnO nanorods, involving chemical bath deposition of aligned seed layers followed by nanorod nucleation sites and subsequent vapour phase transport growth of nanorods. This combines chemical bath deposition techniques, which enable substrate independent seeding and nucleation site generation with vapour phase transport growth of high crystalline and optical quality ZnO nanorod arrays. Our data indicate that the three-step process produces uniform nanorod arrays with narrow and rather monodisperse rod diameters (∼ 70 nm) across substrates of centimetre dimensions. X-ray photoelectron spectroscopy, scanning electron microscopy and X-ray diffraction were used to study the growth mechanism and characterise the nanostructures.     

Selective growth of ZnO nanorods for gas sensors using ink-jet printing and hydrothermal processes

Selective growth of ZnO nanorod arrays with well-defined areas was developed to fabricate the NO₂ gas sensor. The seed solution was ink-jet printed on the interdigitated electrodes. Then, vertically aligned ZnO nanorods were grown on the patterned seed layer by the hydrothermal approach. The influences of seed-solution properties and the ink-jet printing parameters on the printing performance and the morphology of the nanorods were studied. Round micropattern (diameter: 650 μm) of ZnO nanorod arrays is demonstrated. The dimensions and positions of the nanorod arrays can be controlled by changing the printed seed pattern. The effects of nanorod structure and nanorod size on the gas-sensing capability of ZnO nanorod gas sensors were demonstrated. Due to the high surface-to-volume ratios of the nanorod-array structure, the ZnO nanorod gas sensor can respond to 750 ppb NO₂ at 100 °C. The sensors without baking treatment exhibit the typical response of a p-type semiconductor. However, only the response of n-type semiconductor oxides was observed after the annealing treatment at 150 °C for 2 h.     

InGaN/GaN multiple quantum wells grown on nonpolar facets of vertical GaN nanorod arrays

Uniform GaN nanorod arrays are grown vertically by selective area growth on (left angle bracket 0001 right angle bracket) substrates. The GaN nanorods present six nonpolar {1?100} facets, which serve as growth surfaces for InGaN-based light-emitting diode quantum well active regions. Compared to growth on the polar {0001} plane, the piezoelectric fields in the multiple quantum wells (MQWs) can be eliminated when they are grown on nonpolar planes. The capability of growing ordered GaN nanorod arrays with different rod densities is demonstrated. Light emission from InGaN/GaN MQWs grown on the nonpolar facets is investigated by photoluminescence. Local emission from MQWs grown on different regions of GaN nanorods is studied by cathodoluminescence (CL). The core-shell structure of MQWs grown on GaN nanorods is investigated by cross-sectional transmission electron microscopy in both axial and radial directions. The results show that the active MQWs are predominantly grown on nonpolar planes of GaN nanorods, consistent with the observations from CL. The results suggest that GaN nanorod arrays are suitable growth templates for efficient light-emitting diodes.     

Morphological transformations induced by Co impurity in ZnO nanostructures prepared by rf-sputtering and their physical properties

Growth of uniform and vertically well aligned nanorods is a difficult process and becomes more complicated in case of ZnO nanorods on silicon (Si) substrate due to thermal instability of the Si substrate and large lattice mismatch (~?40%) between the substrate and the ZnO nanorods array. Growth of ZnO nanorods assisted by metal ion via rf-sputtering is a good technique; however, it needs many parameters to be controlled for desired growth and morphology of nanostructures. In this work, we report the morphological transformations of ZnO nanostructured thin film by simply controlling the concentration of Cobalt (Co) impurity in sputtering target. With the introduction of Co ions in ZnO matrix, the initial coalescence grain structure (pyramidal morphology) changes into columnar grains and as the concentration of Co ions increases further, a highly oriented ZnO nanorods array is obtained. The possible mechanism with the help of schematic diagram is also proposed for the morphological transformation of ZnO nanostructures. The vertically aligned nanorods show good optical properties as well as robust ferromagnetism at room temperatures. It has also been observed that with the dopant conc. increasing there was a significant decrease in the band gap energy. The structure and morphology of rf-sputtered nanostructured thin films were investigated by X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy and selected area electron diffraction. Interestingly, with Co conc. increasing in ZnO matrix results in decreasing LO modes in Raman spectroscopy. It can have strong influence on the magnetic properties of the material. The good optical and strong ferromagnetic properties of the ZnO nanorods, suggest its possible applications in the fields of lasers, spintronics and medical applications.     

Freezing a water droplet on an aligned Si nanorod array substrate

When a water droplet is dried on a vertically aligned Si nanorod array surface, the nanorods are bundled together. To understand how bundles are formed, a water droplet is frozen rapidly on a Si nanorod array surface observed under a cryo-SEM (scanning electron microscope). The nanorods in the precursor film form similar bundles as those dried in air. But the nanorods under the apparent frozen water droplet are only slightly deformed. We propose that the bundling of nanorods is caused by non-uniform water-nanorod interaction, which could happen either during the water spreading or drying process. Therefore, controlling the liquid-nanostructure interaction could minimize the bundling. In addition, the rapid freezing process does not preserve the water inside the nanochannels, and almost all the water forms ice on top of the nanorod surface, either as a planar interface or as particles, depending on the locations. The separated ice-nanorod interface will have potential applications in chemical separation and crystal growth.     

Controllable growth of highly ordered ZnO nanorod arrays via inverted self-assembled monolayer template

This article presents a facile and effective approach to the controllable growth of highly ordered and vertically aligned ZnO nanorod arrays on the GaN substrate via a hydrothermal route by using the TiO(2) ring template deriving from the polystyrene microsphere self-assembled monolayer. The size of TiO(2) ring template can be flexibly tuned from 50 to 400 nm for the 500 nm polystyrene microspheres by varying the time of reactive ion etching and the concentration of TiO(2) sol. As a result, the diameter of the individual ZnO nanorods can be potentially tuned over a wide range. The combination of several characterization techniques has demonstrated that the ordered ZnO nanorods are highly uniform in diameter and height with perfect alignment and are epitaxially grown along [0001] direction. This work provides a novel and accessible route to prepare oriented and aligned ZnO nanorod arrays with high crystalline quality.     

Stress dependent band gap shift and valence band studies in ZnO nanorods

ZnO nanorods are grown on seedless and ZnO seeded glass substrates using chemical solution method and their structural, morphological, optical and valence band studies have been carried out. On seedless substrate horizontal nanorods are observed whereas for the seeded substrates vertically aligned hollow and solid nanorods grows. X-ray diffraction analysis revealed the presence of tensile stress in the vertical nanorods. Blue shift has been observed in the band gap of the vertical nanorods as compared to the horizontal nanorods which is attributed to the presence of tensile stress in the vertically aligned nanorods. Photoluminescence spectra revealed the dominance of Zinc vacancies (V(Zn)) related defects in the nanorods and oxygen defects are found to be higher in the vertically aligned nanorods as compared to the horizontal nanorods. The difference between the Fermi level and valence band maxima for horizontal, hollow vertical and solid vertical nanorods are found to be approximately 0.56 eV, approximately 0.70 eV and approximately 0.92 eV respectively indicating the possibility of p-type of conduction in the nanorods which has been attributed to presence of V(Zn) defects in the ZnO nanorods.     

Aligned 1D silicon nanostructure arrays by plasma etching

High-density aligned arrays made of one-dimensional (1D) silicon nanostructures, including nanocone, nanorod, and nanowire, are fabricated by plasma etching in a hot-filament chemical vapor deposition apparatus using the gas mixture of hydrogen, nitrogen and methane. The silicon nanocones are crystalline structure and have a uniform apex angle of about 22°. The cones can be coated in situ with an about 3 nm thick amorphous carbon film by increasing the methane concentration in source gases. With gradually decreasing the plasma intensity, the morphologies of the silicon nanostructures evolve along the nanocone–nanorod–nanowire route, and the nanowire becomes amorphous structure. The model for fabrication process of silicon nanostructures with different morphologies will also be suggested.     

The growth of CuSi composite nanorod arrays by oblique angle co-deposition, and their structural, electrical and optical properties

Different CuSi composite nanorods with 0-100?at.% Cu were fabricated by an oblique angle co-deposition technique. The effects of increasing Cu during deposition on the morphologies, structures and properties were investigated. During co-evaporation, the addition of Cu decreases the nanorod width and height but increases the nanorod tilting angle. The polarized optical transmission spectra reveal that all the nanorod samples show a remarkable anisotropic response to visible light with an eccentricity e?≈?1, whereas their optical response to NIR light depends strongly on the Cu composition, and the related eccentricity increases monotonically with the increase of Cu. The obtained amorphous Si film has a resistivity of approximately 4.9?×?10(4)?Ω?cm. The incorporation of 5-75?at.% Cu increases the electrical conductance from two to eight orders of magnitude. The improved conductance and the unique optical properties of the Si-based nanocomposites could have potential applications for Li-ion battery anode and optical design.