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.     

Simple, large-scale patterning of hydrophobic ZnO nanorod arrays

Here we describe a simple, versatile technique to produce large-scale arrays of highly ordered ZnO nanorods. Patterning of three distinct ZnO crystal morphologies is demonstrated through use of different ZnO seed layers. Array formation is accomplished through a simple variation on nanosphere lithography that imprints a thickness variation across a PMMA mask layer. The area of exposed seed layer is controlled through etching time in an oxygen plasma. Subsequent hydrothermal growth from the patterned seed layer produces high-quality ZnO crystals in uniform arrays. The high uniformity of the patterned array is shown to induce a high contact angle hydrophobic state even without the need for chemical modification of the ZnO surface. This technique provides a straightforward way to integrate the optical and electrical properties of high-quality ZnO nanorods with the tunable fluidic properties at the surface of well-ordered arrays.     

The incorporation of preformed metal nanoparticles in zinc oxide thin films using aerosol assisted chemical vapour deposition

The feasibility of Aerosol Assisted Chemical Vapour Deposition (AA-CVD) has been investigated for the growth of zinc oxide (ZnO) films containing preformed metal nanoparticles. The deposition parameters were first established for ZnO thin films, by varying the heating configuration, substrate temperature and deposition time. Films were characterised using Scanning Electron Microscopy and X-Ray Diffraction. As-deposited films, grown at 250 °C, were mostly amorphous and transformed to highly crystalline Wurtzite ZnO at higher substrate temperatures (400-450 °C). A change in the preferential orientation of the films was observed upon changing (i), the substrate temperature or (ii), the heating configuration. Following this, the applicability of the AA-CVD process for the incorporation of preformed nanoparticles (platinum and gold) in ZnO thin films was investigated. It was found that surface agglomeration occurred, such that the ZnO films were capped with an inhomogeneous coverage of the metal. These layers were characterised using Transmission Electron Microscopy and Electron Diffraction. A possible mechanism for the formation of these metal surface clusters is presented.     

Selective protein adsorption on ZnO thin films for biofunctional nano-platforms

The immobilization of albumin and lysozyme by spontaneous adsorption on ZnO films, deposited by metal-organic chemical vapour deposition (MOCVD), has been investigated. Quartz crystal microbalance with dissipation monitoring and X-ray photoelectron spectroscopy analyses show that, at physiological pH, the two proteins exhibit different adsorption behaviours, namely albumin irreversibly adsorbs up to coverage of a half of monolayer, while lysozyme does not. Indeed, the high isoelectric point (IEP) of ZnO favors immobilization of biomolecules with lower IEP, assisted by electrostatic attraction in the proper pH range. This selective protein adsorption behaviour results very promising for ZnO nanoplatforms, consisting of hexagonally patterned ZnO nanoring arrays and SiO2 areas, obtained by colloidal template-catalyst assisted MOCVD.     

Grafted polymeric nanostructures patterned bottom-up by colloidal lithography and initiated chemical vapor deposition (iCVD)

Colloidal lithography is a popular non-conventional process which uses two-dimensional self-assembled monolayer arrays of colloidal nanoparticles as masks for “top-down” techniques such as etching or sputtering. Initiated Chemical Vapor Deposition (iCVD) is a surface controlled process which offers unprecedented opportunity for producing polymer brushes patterned through a colloidal template by grafting to substrates with dangling vinyl bonds. We demonstrate a generic “bottom-up” process as an inexpensive and simple technique for creating well-ordered arrays of functional patterned polymeric nanostructures. These patterns were produced from p(butyl acrylate) and p(hydroxyethyl methacrylate), and are robustly tethered to the underlying substrate as demonstrated by their ability to withstand aggressive solvent.     

Fabrication of the selective-growth ZnO nanorods with a hole-array pattern on a p-type GaN:Mg layer through a chemical bath deposition process

ZnO nanorod arrays were effectively selective-grown on a p-type GaN:Mg layer through chemical bath deposition (CBD) at a low temperature hydrothermal synthesis (85 °C) with a ZnO seed layer. The 5 μm-diameter hole-array patterns of the ZnO seed layer were grown on a p-type GaN:Mg layer in aqueous solution with a mercury lamp illumination. The diameter and the height of ZnO nanorods were measured as the values of 500 nm and 3 μm, respectively. The growth orientation, surface morphology, and aspect ratio of the ZnO nanorods can be controlled and formed on the hole-array patterned ZnO seed layer. The peak wavelength of the photoluminescence spectrum was measured at 384 nm.     

Enhancement of UV emission in ZnO nanorods by growing additional ZnO layers on the surface

Ultraviolet (UV) photoluminescence emission from ZnO nanorod arrays was greatly enhanced by growing additional thin ZnO layers on the surface after thermal reduction of the nanorods. Appropriate selection of additives based on the shape of the original ZnO samples was found to be an important factor in designing the solution composition for growing the additional ZnO layers. This is because the additives modify the growth rates with respect to crystallographic planes. Adding ethylene glycol to the solution was effective for rod-shaped ZnO nanorods in enhancing the UV emission, whereas adding polyethylenimine was better for plate-like particles. These results can be explained by the presence of non-luminescent regions near the surface, where UV emission is thought to be suppressed by non-radiative surface centers. Growing additional layers on side planes increases the volume of the optically active region of ZnO nanorods, with a lower transmittance loss; thus, it effectively enhances the UV emission intensity.     

Microstructural,chemical and textural characterization of ZnO nanorods synthesized by aerosol assisted chemical vapor deposition

ZnO nanorods were synthesized by aerosol assisted chemical vapor deposition onto TiO₂ covered borosilicate glass substrates. Deposition parameters were optimized and kept constant. Solely the effect of different nozzle velocities on the growth of ZnO nanorods was evaluated in order to develop a dense and uniform structure. The crystalline structure was characterized by conventional X-ray diffraction in grazing incidence and Bragg–Brentano configurations. In addition, two-dimensional grazing incidence synchrotron radiation diffraction was employed to determine the preferred growth direction of the nanorods. Morphology and growth characteristics analyzed by electron microscopy were correlated with diffraction outcomes. Chemical composition was established by X-ray photoelectron spectroscopy. X-ray diffraction results and X-ray photoelectron spectroscopy showed the presence of wurtzite ZnO and anatase TiO₂ phases. Morphological changes noticed when the deposition velocity was lowered to the minimum, indicated the formation of relatively vertically oriented nanorods evenly distributed onto the TiO₂ buffer film. By coupling two-dimensional X-ray diffraction and computational modeling with ANAELU it was proved that a successful texture determination was achieved and confirmed by scanning electron microscopy analysis. Texture analysis led to the conclusion of a preferred growth direction in [001] having a distribution width Ω = 20° ± 2°.     

Growth specificity of vertical ZnO nanorods on patterned seeded substrates through integrated chemical process

A simple and cost effective method has been employed for the random growth and oriented ZnO nanorod arrays over as-prepared and patterned seeded glass substrates by low temperature two step growth process and growth specificity by direct laser writing (DLW) process. Scanning electron microscopy (SEM) images and X-ray diffraction analysis confirm the growth of vertical ZnO nanorods with perfect (0 0 2) orientation along c-axis which is in conjunction with optimizing the parameters at different reaction times and temperatures. Transmission electron microscopy (TEM) images show the formation of vertical ZnO nanorods with diameter and length of ∼120 nm and ∼400 nm respectively. Photoluminescence (PL) spectroscopic studies show a narrow emission at ∼385 nm and a broad visible emission from 450 to 600 nm. Further, site-selective ZnO nanorod growth is demonstrated for its high degree of control over size, orientation, uniformity, and periodicity on a positive photoresist ZnO seed layer by simple geometrical (line, circle and ring) patterns of 10 μm and 5 μm dimensions. The demonstrated control over size, orientation and periodicity of ZnO nanorods process opens up an opportunity to develop multifunctional properties which promises their potential applications in sensor, piezoelectric, and optoelectronic devices.     

Initiated chemical vapor deposition of responsive polymeric surfaces

Organic materials can exhibit responsive behavior, including swelling upon exposure to a specific chemical analyte or displaying a switch surface energy in response to a change to external stimuli. The initiated Chemical Vapor Deposition (iCVD) of responsive surfaces facilitates their integration into novel devices and into roll-to-roll processing. Incorporating responsive organic layers into devices creates the ability to transduce chemical or biological events into optoelectronic signals. Additionally, ultrathin, responsive layers enable the design of novel membranes for separation and purification. This work describes the ability to synthesize thermally responsive organic layers by initiated Chemical Vapor Deposition (iCVD).     

Effects of seed layer patterns on the structural characteristics of hydrothermally grown ZnO nanorods

We investigated the effects of surface pattern size and shape on the characteristics of hydrothermally grown ZnO nanorods. For this purpose, the structural characteristics of ZnO nanorods were examined using X-ray diffraction and scanning electron microscopy. The sputtered ZnO seed layer was patterned using photolithography techniques on a Si substrate. ZnO nanorods with a [0001] texturing structure were successfully grown on selective areas by hydrothermal processes. In our experiments, however, it was observed that the diameter and the texture of the ZnO nanorods were strongly influenced by the size of the surface pattern.     

ZnO 1-D nanostructures: Low temperature synthesis and characterizations

ZnO is one of the most important semiconductors having a wide variety of applications in photonic, field emission and sensing devices. In addition, it exhibits a wide variety of morphologies in the nano regime that can be grown by tuning the growth habit of the ZnO crystal. Among various nanostructures, oriented 1-D nanoforms are particularly important for applications such as UV laser, sensors, UV LED, field emission displays, piezoelectric nanogenerator etc. We have developed a soft chemical approach to fabricate well-aligned arrays of various 1-D nanoforms like nanonails, nanowires and nanorods. The microstructural and photoluminescence properties of all the structures were investigated and tuned by varying the synthesis parameters. Field emission study from the aligned nanorod arrays exhibited high current density and a low turn-on field. These arrays also exhibited very strong UV emission and week defect emission. These structures can be utilized to fabricate efficient UV LEDs.     

Formation of aligned ZnO nanotube arrays by chemical etching and coupling with CdSe for photovoltaic application

High density aligned ZnO nanotube (NT) arrays were synthesized using a facile chemical etching of electrochemically deposited ZnO nanorods (NRs). The influence of etching time and solution concentration on the ZnO NT formation was investigated. Moreover, cadmium selenide (CdSe) nanoparticles as sensitizers were assembled onto the ZnO NT and NR arrays for solar cell application. A conversion efficiency (η) of 0.44% was achieved for CdSe/ZnO NT-based solar cell under the white light illumination intensity of 85 mW/cm². An 8% enhancement in η was observed between the CdSe/ZnO NT-based and NR-based solar cell due to the enhancement of the photocurrent density. ZnO NT arrays have been proved to have a superior ability as compared with ZnO NR arrays when employed as a semiconductor film.     

Amorphous silicon thin film solar cells deposited entirely by hot-wire chemical vapour deposition at low temperature (< 150 °C)

Amorphous silicon n-i-p solar cells have been fabricated entirely by Hot-Wire Chemical Vapour Deposition (HW-CVD) at low process temperature < 150 °C. A textured-Ag/ZnO back reflector deposited on Corning 1737F by rf magnetron sputtering was used as the substrate. Doped layers with very good conductivity and a very less defective intrinsic a-Si:H layer were used for the cell fabrication. A double n-layer (µc-Si:H/a-Si:H) and µc-Si:H p-layer were used for the cell. In this paper, we report the characterization of these layers and the integration of these layers in a solar cell fabricated at low temperature. An initial efficiency of 4.62% has been achieved for the n-i-p cell deposited at temperatures below 150 °C over glass/Ag/ZnO textured back reflector.     

Seeded growth of ZnO nanorods from NaOH solutions

Perpendicularly aligned arrays of corrugated ZnO nanorods were grown onto gold patterned LiTaO₃ substrates, coated with a sputtered ZnO seed layer. During the growth process, these substrates were held submerged in an aqueous solution comprising a 1:40 mol ratio mix of zinc nitrate hexahydrate to sodium hydroxide. The substrates were placed in a custom apparatus residing in an autoclavable storage bottle. Scanning electron micrographs, which were taken at different deposition intervals, suggest that the growth mechanism of ZnO nanorods initiates with the etching of the ZnO sputtered seed layer into hexagonal bases (> 500 nm across), from where multiple protrusions (40 nm-100 nm in width) grow atop these hexagonal bases. Such nanoprotrusions later coalesce into larger nanorods. Uniformly distributed high density corrugated nanorods, with proximal spacing between adjacent nanorods of approximately 20 nm-50 nm, were observed over the entire surface.     

Hierarchical Metal/Semiconductor Nanostructure for Efficient Water Splitting

A hierarchically patterned metal/semiconductor (gold nanoparticles/ZnO nanowires) nanostructure with maximized photon trapping effects is fabricated via interference lithography (IL) for plasmon enhanced photo‐electrochemical water splitting in the visible region of light. Compared with unpatterned (plain) gold nanoparticles‐coated ZnO NWs (Au NPs/ZnO NWs), the hierarchically patterned Au NPs/ZnO NWs hybrid structures demonstrate higher and wider absorption bands of light leading to increased surface enhanced Raman scattering due to the light trapping effects achieved by the combination of two different nanostructure dimensions; furthermore, pronounced plasmonic enhancement of water splitting is verified in the hierarchically patterned Au NPs/ZnO NWs structures in the visible region. The excellent performance of the hierarchically patterned Au NPs/ZnO NWs indicates that the combination of pre‐determined two different dimensions has great potential for application in solar energy conversion, light emitting diodes, as well as SERS substrates and photoelectrodes for water splitting.     

Characterization of dense arrays of chemiresistor vapor sensors with submicrometer features and patterned nanoparticle interface layers

The performance of arrays of small, densely integrated chemiresistor (CR) vapor sensors with electron-beam patterned interface layers of thiolate-monolayer-protected gold nanoparticles (MPNs) is explored. Each CR in the array consists of a 100-μm(2) interdigital electrode separated from adjacent devices by 4 μm. Initial studies involved four separate arrays, each containing four CRs coated with one of four different MPNs, which were calibrated with five vapors before and after MPN-film patterning. MPNs derived from n-octanethiol (C8), 4-(phenylethynyl)-benzenethiol (DPA), 6-phenoxyhexane-1-thiol (OPH), and methyl-6-mercaptohexanoate (HME) were tested. Parallel calibrations of MPN-coated thickness-shear-mode resonators (TSMR) were used to derive partition coefficients of unpatterned films and to assess transducer-dependent factors affecting responses. A 600-μm(2) 4-CR array with four different patterned MPN interface layers, in which the MPN derived from 7-hydroxy-7,7-bis(trifluoro-methyl)heptane-1-thiol (HFA) was substituted for HME, was then characterized. This is the smallest multi-MPN array yet reported. Reductions in the diversity of the collective response patterns are observed with the patterned films, but projected vapor discrimination rates remain high. The use of such arrays as ultralow-dead-volume detectors in microscale gas chromatographic analyzers is discussed.     

Synthesis and characterization of SnS/ZnO nanocomposite by chemical method

SnS nanorods and SnS/ZnO nanocomposite have been synthesized by chemical method. Structure and phase purity of the samples were confirmed by powder X-ray diffraction. Transmission electron microscope image of SnS nanorods showed the average diameter of nanorods was about 85 nm and length was several micrometers. Transmission electron microscope image of SnS/ZnO nanocomposite showed the average particle size of ZnO nanoparticle was about 12 nm. The formation of SnS/ZnO nanocomposite was confirmed by elemental analysis using energy dispersive X-ray spectroscopy. From the microRaman spectrum of SnS/ZnO nanocomposite, it was observed that the intensity of B_2g mode of SnS nanorods decreased dramatically compared to that of pure SnS nanorods, since the surface of the SnS nanorods were coated with ZnO nanoparticles. Both direct and indirect band gap transitions were observed for SnS nanorods from the optical absorption spectrum and the optical absorption spectrum of SnS/ZnO nanocomposite showed absorption in the visible region.     

Site-specific multi-stage CVD of large-scale arrays of ultrafine ZnO nanorods

Multi-stage growth of ZnO nanorod arrays has been carried out by Au-assisted chemical vapor deposition (CVD) in order to better understand and more precisely control the growth behaviors. It is evidenced that Au-catalyzed vapor-liquid-solid (VLS) growth only dominates the initial site-specific nucleation of the nanorods, while the subsequent growth is governed by a vapor-solid (VS) epitaxy mechanism. The sequential VLS and VS behaviors permit the fabrication of large-scale highly ordered arrays of ZnO nanorods with precisely tunable diameters and embedded junctions by controlling reactant concentration and nanorod top morphology. Based on the above results, two routes to fabricate ultrafine ZnO nanorod arrays are proposed and stepwise nanorod arrays with ultrafine top segment (~10 nm in diameter) have been achieved. Temperature-dependent photoluminescence (PL) and spatial resolved PL were carried out on the nanorod arrays and on individual nanorods, indicating high quality optical properties and tunable light emission along the length of the stepwise nanorods.     

Effect of thicknesses of copper catalyst and oxide sublayer on morphology of ZnO nanorods

The influence of thicknesses of a ZnO sublayer and a copper catalyst film on the morphology of ZnO nanorods grown by carbothermal synthesis on α-Al₂O₃(11–20) substrates has been studied. An increase in the Cu catalyst film thickness leads to a growth in the diameters, heights, and surface density of nanorods. As the ZnO sublayer thickness is increased, the average diameter of nanorods also increases, while their lengths and surface density decrease. The effect of elevated temperatures on the thermal decomposition of ultrathin Cu films deposited on α-Al₂O₃ substrates has been studied. The photoluminescence characteristics of nanorod arrays have been measured at high levels of optical pumping. An increase in the pumping level to 250–280 kW/cm² leads to superluminescence of the nanorods.