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.     

ZnO纳米棒阵列和薄膜的同步外延生长及其光电化学性能

使用化学气相沉积法在a面蓝宝石衬底上同步外延生长氧化锌(ZnO)竖直纳米棒阵列和薄膜,研究了阵列和薄膜的光电化学性能。结果表明,纳米结构中的竖直单晶纳米棒有六棱柱形和圆柱形,其底部ZnO薄膜使竖直纳米棒互相联通。与ZnO纳米薄膜的比较表明,这种纳米结构具有优异的光电化学性能,其入射光电流效率是ZnO纳米薄膜的2.4倍;光能转化效率是ZnO纳米薄膜的5倍。这种纳米结构优异的光电化学性能,可归因于其高表面积-体积比以及其底部薄膜提供的载流子传输通道。本文分析了这种纳米结构的生长过程,提出了协同生长机理：Au液化吸收气氛中的Zn原子生成合金,合金液滴过饱和后ZnO开始成核,随后在衬底表面生成了ZnO薄膜。同时,还发生了Zn自催化的气-固(VS)生长和Au催化的气-液-固(VLS)生长,分别生成六棱柱纳米棒和圆柱形纳米棒,制备出底部由薄膜连接的竖直纳米棒阵列。     

Photovoltaic properties of a ZnO nanorod array affected by ethanol and liquid-crystalline porphyrin

A vertically aligned array of ZnO nanorods, fabricated on conductive ITO substrate in aqueous solution, was characterized by scanning electron microscopy (SEM), x-ray diffraction (XRD), and UV-visible transmission spectroscopy. Surface photovoltage (SPV) techniques based on a lock-in amplifier and a Kelvin probe were both employed to study the photogenerated charges in the system. The effects of ethanol solvent and a liquid-crystalline porphyrin, [5-(para-dodecyloxy)phenyl-10,15,20-tri-phenyl] porphyrin (DPTPP), on the photovoltage enhancement in the ZnO nanorod array were studied via SPV comparison between different irradiation directions on the system. We demonstrate that the ethanol adsorption could induce the space charge region to expand towards the ZnO/ITO interface. In the absence of ethanol, the ZnO nanorod array with the DPTPP adsorption showed enhanced SPV with reduced attenuation rate of photogenerated charge carriers. We found that the separation of photogenerated charges could be further improved by coating the surface with DPTPP and ethanol together. Furthermore, the SPV spectra patterns of the composite system with opposite incident-light directions reveal that the DPTPP molecules adsorbed just at the surface of ZnO nanorods adopt a more monomeric alignment in contrast to the aggregative state in the DPTPP bulk.     

Electrodeposition of template free hierarchical ZnO nanorod arrays via a chloride medium

We have successfully grown template and buffer free ZnO nanorod films via chloride medium by controlling bath temperature in a simple and cost effective electrochemical deposition method. Thin films of ZnO nano-rods were obtained by applying a potential of ?0.75 V by employing Ag/AgCl reference electrode for 4 h of deposition time. The CV measurements were carried out to determine potential required to deposit ZnO nanorod films whereas chronoamperometry studies were carried out to investigate current and time required to deposit ZnO nanorod films. The formation of ZnO nanorod has been confirmed by scanning electron microscopy (SEM) and Raman spectroscopy. Low angle XRD analysis confirms that ZnO nanorod films have preferred orientation along (101) direction with hexagonal wurtzite crystal structure. The SEM micrographs show nice surface morphology with uniform, dense and highly crystalline hexagonal ZnO nanorods formation. Bath temperature has a little influence on the orientation of nanorods but has a great impact on their aspect ratio. Increase in bath temperature show improvement in crystallinity, increase in diameter and uniform distribution of nanorods. Compositional analysis shows that the amount of oxygen is ~49.35 % and that of Zn is ~50.65 %. The optical band gap values were found to be 3.19 and 3.26 eV for ZnO nanorods prepared at bath temperature 70 and 80 °C respectively. These results indicate that by controlling the bath temperature band gap of ZnO nanorods can be tailored. The obtained results suggest that it is possible to synthesize ZnO nanorod films by a simple, cost effective electrodeposition process which can be useful for opto-electronic devices fabrication.     

Efficient dye-sensitized solar cells based on the combination of ZnO nanorods and microflowers

Well-aligned ZnO nanorod films were grown onto transparent conducting substrates by using an aqueous solution route. The presence of some reflections in the X-ray diffraction pattern of the ZnO films indicates the vertical alignment of the nanorods along the c axis of the wurtzite hexagonal structure. Well-aligned ZnO nanorods were observed by scanning electron microscopy. The presence of top ZnO microflower layers over the ZnO nanorod film was observed for all growth times studied. The ZnO nanorods with ZnO microflower top layers were applied as photoelectrodes in dye-sensitized solar cells. Higher photocurrent densities and photovoltages were observed with longer nanorod growth times. The high performance of the dye-sensitized solar cells might be associated to the combination of ZnO nanorods and microflowers in the same photoelectrode.     

Wettability control of a transparent substrate using ZnO nanorods

This paper presents a simple way of controlling the wettability of a structured surface with ZnO nanorods on a transparent substrate. A combination of ZnO nanostructures and stearic acid was used to create superhydrophobic surfaces with the potential properties of being self-cleaning, waterproof, and antifog. ZnO nanorods were uniformly covered on glass substrates through a simple hydrothermal method with varying growth time which affects the surface morphology. When a substrate is dipped into 10 mM stearic acid in ethanol for 24 h, chemisorption of the stearic acid takes place on the ZnO nanorod surface, after which the hydrophilic ZnO nanorod surfaces are modified into hydrophobic ones. The contact angle of a water droplet on this superhydrophobic ZnO nanorod surface increased from 110 degrees to 150 degrees depending on the growth time (from 3 to 6 h) with a high transparency of above 60%. In addition, the water contact angle can be made to as low as 27 degrees after exposing the substrate to 10-mW/cm2 UV for 1 h.     

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.     

ZnO films and nanorod/shell arrays electrodeposited on PET-ITO electrodes

In this work, ZnO films, nanorod and nanorod/shell arrays were synthesized on the surface of PET-ITO electrodes by electrochemical methods. ZnO films with high optical transmittance were prepared from a zinc nitrate solution using a pulsed current technique with a reduced pulse time (3 s). The X-ray diffraction pattern of ZnO film deposited on PET-ITO electrode showed that it has a polycrystalline structure with preferred orientations in the directions [0 0 2] and [1 0 3]. ZnO nanorods were synthesized on electrochemical seeded substrate in an aqueous solution containing zinc nitrate and hexamethylenetetramine. In order to increase the stability of PET-ITO electrode to electrochemical and chemical stresses during ZnO nanorods deposition the surface of the electrode was treated with a 17 wt% NH₄F aqueous solution. Electrochemical stability of PET-ITO electrode was evaluated in a solution containing nitrate ions and hexamethylenetetramine. ZnO nanorod/shell arrays were fabricated using eosin Y as nanostructuring agent. Photoluminescence spectra of ZnO nanorod and ZnO nanorod/shell arrays prepared on the surface of PET-ITO electrode were discussed comparatively. By employing the 1.5 μm-length ZnO nanorod/shell array covered with a Cu₂O film a photovoltaic device was fabricated on the PET-ITO substrate.     

Epitaxial growth of ZnO layers using nanorods with high crystalline quality

Epitaxial ZnO films were grown on c-plane sapphire substrates by metal-organic chemical vapor deposition using a ZnO multi-dimensional structure having the sequence of ZnO film/ZnO nanorods/sapphire. The vertically well-aligned one-dimensional ZnO nanorods were grown epitaxially on the sapphire substrate with in-plane alignment under suitable growth conditions and then used as seeds for the subsequent epitaxial ZnO layer. For the transition of the ZnO structures from the nanorods to the film, the growth temperature and working pressure were controlled, while keeping the other conditions fixed. The growth of the ZnO films on the well-aligned ZnO nanorods results in homoepitaxial growth with the identical orientation relationship along the in-plane direction as well as the same c-axis orientation. The microstructural analysis of the multi-dimensional structure and analysis of the microstructural evolution from the one-dimensional nanorods to the two-dimensional film were conducted using transmission electron microscopy.     

Synthesis,microstructure and photoluminescence of well-aligned ZnO nanorods on Si substrate

Well-aligned zinc oxide (ZnO) nanorods were densely grown on Si substrate using ZnO thin-film seed layer without any catalysts and/ or additives by a simple solid–vapour phase thermal sublimation technique. The growth mechanism can be interpreted as self-catalyst of zinc particles based on vapour–solid (VS) mechanism. High-resolution transmission electron microscopy (HRTEM) image and selected area electron diffraction (SAED) pattern confirmed that the single-crystalline growth of the nanorods were preferentially along c-axis of hexagonal crystal system. High-crystal quality ZnO nanorods with strong near band edge emission centred at 380 nm can be achieved on Si substrate by the introduction of sufficient oxygen during the nanorod growth processing.     

Laser patterning of Zn for ZnO nanostructure growth: Comparison between laser induced forward transfer in air and in vacuum

This study reports patterning of surfaces with Zn using the laser induced forward transfer (LIFT) technique and subsequent chemical growth of ZnO thin films. The LIFT process is performed both in vacuum and in air and yields a Zn pattern on the receiving substrate. These Zn patterns were used as precursors to chemically grown ZnO thin films, and the morphology of these films was investigated and compared. Inspection of the films grown from the in-vacuum deposited pattern revealed the aligned growth of ZnO nanorods (NRs), in the regions where the Zn precursor was deposited, while no substantial ZnO growth was observed outside the precursor patterns. The ZnO films grown from the in-air deposited patterns show different growth behaviour; the precursor pattern is not well preserved and the surface morphology reveals flower-type ZnO nanorods. The difference in morphology of the seeding Zn patterns deposited under the two environments (vacuum versus air) directly translates into different morphology ZnO features, chemically grown from these patterns (nanorod versus flower growth).     

Synthesis, microstructure and photoluminescence of well-aligned ZnO nanorods on Si substrate

Well-aligned zinc oxide (ZnO) nanorods were densely grown on Si substrate using ZnO thin-film seed layer without any catalysts and/or additives by a simple solid–vapour phase thermal sublimation technique. The growth mechanism can be interpreted as self-catalyst of zinc particles based on vapour–solid (VS) mechanism. High-resolution transmission electron microscopy (HRTEM) image and selected area electron diffraction (SAED) pattern confirmed that the single-crystalline growth of the nanorods were preferentially along c-axis of hexagonal crystal system. High-crystal quality ZnO nanorods with strong near band edge emission centred at 380 nm can be achieved on Si substrate by the introduction of sufficient oxygen during the nanorod growth processing.     

Controllable synthesis and photoluminescence properties of ZnO nanorod and nanopin arrays

Well-aligned ZnO nanorods and nanopins are synthesized on a silicon substrate using a one-step simple thermal evaporation of a mixture of zinc and zinc acetate powder under controlled conditions. A self-assembled ZnO buffer layer was first obtained on the Si substrate. The structure and morphology of the as-synthesized ZnO nanorod and nanopin arrays are characterized using X-ray diffraction, and scanning and transmission electron microscopies, energy-dispersive X-ray spectroscopy, and photoluminescence spectroscopy. The influence of the background atmosphere on the two ZnO nanostructures has been studied. Two different growth mechanisms are mentioned to interpret the formation of ZnO nanorod and nanopin arrays in our work. The room-temperature PL features the ZnO nanorods exhibit only sharp and strong ultraviolet (UV) emission emissions, which confirms the better crystalline and optical quality than the ZnO nanopins.     

Fabrication of vertically aligned ultrafine ZnO nanorods using metal-organic vapor phase epitaxy with a two-temperature growth method

We report the fabrication of vertically aligned ultrafine ZnO nanorods using metal-organic vapor phase epitaxy and applying a two-temperature growth method. First, thick nanorods were grown vertically on the substrate at a lower temperature. Then, ultrafine ZnO nanorods with an average diameter of 17.7?nm were grown from the tips of the thick nanorods at a higher temperature. The direction of the ultrafine ZnO nanorods followed that of the preformed vertically aligned thick nanorods. Electron microscopy revealed that the ultrafine nanorods were single crystals and the growth direction was along the c axis. Excellent photoluminescence characteristics of the nanorods were confirmed.     

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.     

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.     

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.     

Fabrication of ZnS/ZnO hierarchical nanostructures by two-step vapor phase method

A simple two-step vapor phase method is presented to fabricate ZnS/ZnO hierarchical nanostructures in bulk quantities. That is ZnS nanobelts were first synthesized and then used as substrate for growth of ZnO nanorod arrays. Investigation results demonstrate that the polar surfaces of ZnS nanobelts could induce a preferred asymmetric growth of ZnO nanorods on the side surfaces. But it is believed that if the local concentration of ZnO was high enough, ZnO nanorods could also grow symmetrically on the top/bottom surface of the ZnS nanobelts. The optical property of the products was also recorded by means of photoluminescence (PL) spectroscopy.     

Silver nanoisland induced synthesis of ZnO nanostructures by vapor phase transport

ZnO nanostructures including nanorod and nanotower were synthesized on Ag nanoisland coated Si substrate by thermal evaporation and vapor phase transport at atmospheric pressure. The as-prepared ZnO nanorods and nanotowers were single crystal growing along [0001] direction. The growth of ZnO nanostructures strongly depended on the surface morphology of the nanoisland Ag film deposited by electroless nanoelectrochemistry. The growth mechanism of the ZnO nanostructures was proposed on the basis of experimental data. A strong room-temperature photoluminescence in ZnO nanostructures has been demonstrated. The growth technique would be of particular interest for direct integration in the current silicon-technology-based optoelectronic devices.     

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.