Sol-gel assisted ZnO nanorod array template to synthesize TiO(2) nanotube arrays

A TiO(2) nanotube array with a large surface area is fabricated on a glass substrate using a ZnO nanorod array and sol-gel process, and the structural characteristics of the TiO(2) nanotube array are investigated. The well-aligned ZnO nanorod array, which is deposited on ZnO seed layer coated glass substrates by the wet-chemical route, is used as a template to synthesize TiO(2)/ZnO composite nanostructures through the sol-gel process. Then, by selectively removing the ZnO template, a TiO(2) nanotube with contours of the ZnO nanorods is fabricated on the ZnO seed layer coated glass. The resultant TiO(2) nanotubes are 1.5?μm long and 100-120?nm in inner diameter, with a wall thickness of ～10?nm. In addition, by adjusting the experimental parameters, such as the dip-coating cycle number or heating rate, porous TiO(2) thick films can also be obtained.     

Enhanced photoelectrochemical performance of bridged ZnO nanorod arrays grown on V-grooved structure

Bridged ZnO nanorod arrays on a V-grooved Si(100) substrate were used as the photoanode of a photoelectrochemical (PEC) cell for water splitting. Photolithography followed by reactive ion etching was employed to create a V-grooved structure on a Si substrate. ZnO nanorod arrays were grown via a hydrothermal method. The light trapping and PEC properties are greatly enhanced using the bridged ZnO nanorod arrays on a V-grooved Si substrate compared with those on a flat one. Increased short circuit photocurrent density (J(SC), 0.73?mA?cm(-2)) and half-life time (1500?s) are achieved. This improved J(SC) and half-life time are 4 times and 10 times, respectively, higher than those of the ZnO nanorod arrays grown on a flat substrate. The overall PEC cell performance improvement for the V-groove grown ZnO array is attributed to the reduced light reflection and enhanced light trapping effect. Moreover, V-groove ZnO showed stronger adhesion between ZnO nanorod arrays and the substrate.     

Growth of well-aligned ZnO nanorod arrays on Si substrates by thermal evaporation of Cu-Zn alloy powders

Well-aligned ZnO nanorod arrays with uniform diameters and lengths have been fabricated on a Si substrate by simple thermal evaporation of Cu-Zn alloy powders in the presence of oxygen without using a template, catalyst, or pre-deposited ZnO seed layer. The ZnO nanorods are characterized by X-ray diffraction, electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy and the growth mechanism is suggested. The nanorods have a single-crystal hexagonal structure and grow along the (0001) direction. Their diameters range from 200 to 400 nm and the lengths are up to several micrometers. The photoluminescence (PL) and Raman spectra disclose the optical properties of the products. The PL spectra show intense near-band ultraviolet emission at 378 nm from the nanorod arrays. The well-aligned ZnO nanorod arrays have a low turn-on field of 6.1 V/microm, suggesting good field emission properties. The simple synthesis methodology in conjunction with the good field emission and optical properties make the study both scientifically and technologically interesting.     

Substrate-free growth, characterization and growth mechanism of ZnO nanorod close-packed arrays

ZnO nanorod close-packed arrays are successfully fabricated in a substrate-free manner by a citric acid assisted annealing process at a low growth temperature of 400?°C. Each nanorod of ZnO nanorod close-packed arrays grows along the [0001] direction and is single crystalline with an average diameter of 50?nm, and an average length of 0.5?μm. The aspect ratio is 10. The ZnO nanorod close-packed arrays show a strong exciton absorption peak at 372?nm in UV-visible absorption spectra, exhibiting a blue-shift relative to the bulk exciton absorption (387?nm). Finally, a new growth mechanism is proposed for the substrate-free preparation of ZnO nanorod close-packed arrays by a citric acid assisted annealing process.     

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.     

Temperature induced hierarchical growth of ZnO microcrystal

Unique ZnO microcrystal composed of hierarchical nanorod arrays was successfully prepared by a surfactant-free process in aqueous solution under moderate temperature. The products were characterized by X-ray powder diffraction (XRD) and scanning electron microscopy (SEM). The as-prepared ZnO microstructures are of hexagonal phase and high purity. On the basis of SEM images and parallel experiments, a possible formation mechanism for this ZnO microcrystal with hierarchical nanorod arrays is proposed and the reaction temperatures are found to have great influence on inducing secondary nucleation and the hierarchical growth. In addition, the optical properties of the ZnO samples were also investigated by the photoluminescence (PL) spectrometer.     

Microstructural and optical characteristics of solution-grown Ga-doped ZnO nanorod arrays

Highly oriented Ga-doped zinc oxide (ZnO) nanorod arrays have been prepared on a ZnO-buffered silicon substrate in an aqueous solution, which is a mixture of methenamine (C(6)H(12)N(4)), zinc nitrate hexahydrate (Zn(NO(3))(2)·6H(2)O), and gallium nitrate hydrate (Ga(NO(3))(3)·xH(2)O). The microstructure characteristics and optical properties of the nanorod arrays were analyzed using different characterization techniques including field-emission scanning electron microscopy (FESEM), x-ray photoelectron spectroscopy (XPS), and photoluminescence (PL). The experimental results show that the morphology, density, and surface compositions of ZnO nanorod arrays are sensitive to the concentration of gallium nitrate hydrate. The PL spectra of all ZnO nanorod arrays show three different emissions, including UV (ultraviolet), yellow, and NIR (near infrared) emissions. With the increase in the Ga doping level, the luminescence quality of ZnO nanorods has been improved. The peak of UV emission has a small redshift, which can be ascribed to the combined effect of size and Ga doping. Furthermore, Ga doping has caused defects that respond to NIR emission.     

Synthesis and photoluminescence properties of the ZnO@SnO<Subscript>2</Subscript> core–shell nanorod arrays

The ZnO@SnO₂ core–shell nanorod arrays have been synthesized. As the cores, ZnO nanorod arrays were first prepared by aqueous chemical growth method. Then using a simple liquid-phase deposition method, SnO₂ was deposited on the ZnO nanorod arrays. Scanning electron microscopy, transmission electron microscopy, and X-ray diffraction were used to characterize the morphologies and structures of the products. Photoluminescence properties were also investigated. It was found that the ZnO@SnO₂ core–shell nanorod arrays showed enhanced UV and green emissions when compared with the bare ZnO nanorod arrays.     

Controllable synthesis of vertically aligned ZnO nanorod arrays in aqueous solution

High-density well-aligned ZnO nanorod array was successfully synthesized on a large-area magnetron sputtering deposited Al doped ZnO film-coated Si (AZO/Si) substrate via a convenient solution method. X-ray diffraction and scanning electron microscopy show that the nanorods are well-oriented perpendicular to the substrate. The influences of the reaction temperature, time, on the size and shapes of the as-prepared ZnO nanorods (ZNs) samples have been studied. The length and diameter of the nanorods became bigger when a longer reaction time was used. When the temperature is elevated to 130 degrees C, a new conical ZNs was synthesized. Room-temperature photoluminescence (PL) spectra of all the ZnO products showed a strong ultraviolet (UV) emission. The photoluminescence from free excitons of the ZNs synthesized at higher temperature reflects the high purity and nearly defect free structure of nanorods. The well-aligned feature of the nanorod array is attributed to the nanorods' epitaxial growth from the AZO films.     

Structure and photoluminescence of S-doped ZnO nanorod arrays

Vertically aligned S-doped ZnO nanorod arrays have been successfully synthesized by hydrothermal method at 90 °C for 2 h. The obtained nanorod is ～ 70 nm in diameter and 1.2 μm in length. The XRD pattern and the Raman spectra indicate that the S-doped nanorod arrays are orientated at [001] and are single crystals with hexagonal wurtzite structure. The photoluminescence (PL) spectra show that S-doped ZnO nanorod arrays exhibit a relative weak ultraviolet (UV) emission, a violet emission and a strong green emission. The effects of S-doping on the structure and photoluminescence of ZnO nanorod arrays are discussed in detail.     

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.     

Epitaxial growth of the zinc oxide nanorods, their characterization and in vitro biocompatibility studies

Here, we have synthesized Zinc Oxide (ZnO) nanorods at room temperature using zinc acetate and hexamethylenetetramine as precursors followed by characterization using X-ray diffraction (XRD), fourier transform infra red spectroscopy, scanning electron microscopy (SEM) and transmission electron microscopy. The growth of the synthesized ZnO was found to be very close to its hexagonal nature, which is confirmed by XRD. The nanorods were grown perpendicular to the long-axis and grew along the [001] direction, which is the nature of ZnO growth. The morphology of the synthesized ZnO nanorods was also confirmed by SEM. The size of the nanorod was estimated to be around 20-25?nm in diameter and approximately 50-60?nm in length. Our biocompatibility studies using synthesized ZnO showed no significant dose- or time-dependent increase in the formation of free radicals, accumulation of peroxidative products, antioxidant depletion or loss of cell viability on lung epithelial cells.     

N-Type Field-Effect Transistors Using Multiple Mg-Doped ZnO Nanorods

Nanorod field-effect transistors (FETs) that use multiple Mg-doped ZnO nanorods and a SiO₂ gate insulator were fabricated and characterized. The use of multiple nanorods provides higher on-currents without significant degradation in threshold voltage shift and subthreshold slopes. It has been observed that the on-currents of the multiple ZnO nanorod FETs increase approximately linearly with the number of nanorods, with on-currents of ~1 muA per nanorod and little change in off-current (~4times10^-12). The subthreshold slopes and on-off ratios typically improve as the number of nanorods within the device channel is increased, reflecting good uniformity of properties from nanorod to nanorod. It is expected that Mg dopants contribute to high n-type semiconductor characteristics during ZnO nanorod growth. For comparison, nonintentionally doped ZnO nanorod FETs are fabricated, and show low conductivity to compare with Mg-doped ZnO nanorods. In addition, temperature-dependent current-voltage characteristics of single ZnO nanorod FETs indicate that the activation energy of the drain current is very low (0.05-0.16 eV) at gate voltages both above and below threshold     

Effect of pulsed electromagnetic field on growth and structure properties of ZnO nanorod arrays

Well-aligned ZnO nanorod arrays had been prepared by hydrothermal methods assisted with pulsed electromagnetic field (PEMF). The effects of pulsed electromagnetic field on growth and structure properties of ZnO nanorod arrays were studied in detail. XRD and SEM analysis showed ZnO nanorod arrays had bigger length to diameter ratio and better verticality on the substrate. And the Raman analysis showed well-aligned ZnO nanorod arrays have highly crystallized wurtzite structure with much fewer defects after a pulsed electromagnetic field was introduced. At last, a possible mechanism of pulsed electromagnetic field acted on nanorod arrays was proposed.     

ZnO nanorod/CdS nanocrystal core/shell-type heterostructures for solar cell applications

ZnO/CdS core/shell nanorod arrays were fabricated by a two-step method. Single-crystalline ZnO nanorod arrays were first electrochemically grown on SnO(2):F (FTO) glass substrates. Then, CdS nanocrystals were deposited onto the ZnO nanorods, using the successive ion layer adsorption and reaction (SILAR) technique, to form core/shell nanocable architectures. Structural, morphological and optical properties of the nanorod heterojunctions were investigated. The results indicate that CdS single-crystalline domains with a mean diameter of about 7 nm are uniformly and conformally covered on the surface of the single-crystalline ZnO nanorods. ZnO absorption with a bandgap energy value of 3.30 ± 0.02 eV is present in all optical transmittance spectra. Another absorption edge close to 500 nm corresponding to CdS with bandgap energy values between 2.43 and 2.59 eV is observed. The dispersion in this value may originate in quantum confinement inside the nanocrystalline material. The appearance of both edges corresponds with the separation of ZnO and CdS phases and reveals the absorption increase due to CdS sensitizer. The photovoltaic performance of the resulting ZnO/CdS core/shell nanorod arrays has been investigated as solar cell photoanodes in a photoelectrochemical cell under white illumination. In comparison with bare ZnO nanorod arrays, a 13-fold enhancement in photoactivity was observed using the ZnO/CdS coaxial heterostructures.     

ZnO纳米棒阵列膜的制备及其光电化学性能研究

采用化学溶液沉积法,在ZnO纳米颗粒膜修饰的FTO导电玻璃基底上,制备了ZnO纳米棒阵列。用X射线衍射仪（XRD）、场发射扫描电子显微镜（FESEM）、透射电子显微镜（TEM）对样品进行表征。研究结果表明所制备的ZnO纳米棒为六方纤锌矿相单晶结构,沿c轴择优取向生长,平均直径约为40nm,长度约为900nm;ZnO纳米棒阵列生长致密,取向性较一致。以曙红Y敏化的ZnO纳米棒阵列膜为光阳极制作了染料敏化太阳能电池原型器件,在光照强度为100mW/cm2下,其开路电压为0.418V,短路电流为0.889mA/cm2,总的光电转换效率为0.133%。     

Positive temperature coefficient of resistance of single ZnO nanorods

ZnO nanorods were synthesized by a simple aqueous solution method. Crystal structures and morphology studies show that the ZnO nanorods are single crystalline with the growth direction aligned with the c axis of ZnO. An Au-ZnO nanorod-Au (metal-semiconductor-metal, MSM) device using the synthesized nanorod was fabricated. An electronic model with two back-to-back Schottky diodes in series with a nanorod was used to describe the electrical transport of the MSM device. A positive temperature coefficient of resistance is observed on a single ZnO nanorod from 383 to 473 K. A simple model has been proposed to explain such an abnormal behavior including the effect of the interface states and the adsorption-desorption of the water/oxygen molecules on the surface of the nanorod.     

Enhanced Piezo‐Photoelectric Catalysis with Oriented Carrier Migration in Asymmetric Au−ZnO Nanorod Array

Current photocatalytic semiconductors often have low catalytic performance due to limited light utilization and fast charge carrier recombination. Formation of Schottky junction between semiconductors and plasmonic metals can broaden the light absorption and facilitate the photon‐generated carriers separation. To further amplify the catalytic performance, herein, an asymmetric gold‐zinc oxide (Asy‐Au?ZnO) nanorod array is rationally designed, which realizes the synergy of piezocatalysis and photocatalysis, as well as spatially oriented electron?hole pairs separation, generating a significantly enhanced catalytic performance. In addition to conventional properties from noble metal/semiconductor Schottky junction, the rationally designed heterostructure has several additional advantages: 1) The piezoelectric ZnO under light and mechanical stress can directly generate charge carriers; 2) the Schottky barrier can be reduced by ZnO piezopotential to enhance the injection efficiency of hot electrons from Au nanoparticles to ZnO; 3) the unique asymmetric nanorod array structure can achieve a spatially directed separation and migration of the photon‐generated carriers. When ultrasound and all‐spectrum light irradiation are exerted simultaneously, the Asy‐Au?ZnO reaches the highest catalytic efficiency of 95% in 75 min for dye degradation. It paves a new pathway for designing unique asymmetric nanostructures with the synergy of photocatalysis and piezocatalysis.     

可见光诱导TiO2光催化及其机理研究进展

简述了二氧化钛的光催化机理。针对其禁带宽度较大,只能被小于387nm的紫外光所激发的缺点,综述了近年来国内外针对纳米TiO2可见光催化的改性方法和改性机理研究进展,包括离子掺杂、半导体复合、表面光敏化等方法。最后展望了提高纳米TiO2可见光光催化活性研究的前景。     

Induction of zinc particles on the morphology and photoluminescent property of globular Zn/ZnO core/shell nanorod heterojunction array architectures

Zn/ZnO metal/semiconductor nanostructures were successfully synthesised by a facile zinc-rich chemistry liquid-phase approach with zinc microspheres as sacrificial templates at ambient temperature. A series of globular Zn/ZnO core/shell structures and hollow microsphere architectures self-assembled by Zn/ZnO nanorod heterojunction arrays were obtained by controlling the amount of zinc particles. The structure, morphology, composition and optical properties of the products have been characterised by X-ray diffraction, scanning electron microscopy, Raman spectroscopy and photoluminescent spectroscopy. A possible growth mechanism of the Zn/ZnO nanostructures has been proposed based on the structural analysis. The growth mechanism of Zn/ZnO hollow microspheres is ascribed to Kirkendall effect. A new strong blue emission at 440 nm and a green emission around 500 nm with an enhancement over one order of magnitude compared with the pure ZnO sample have been observed. These emission bands are attributed to two kinds of mechanisms that have been discussed in detail.