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.     

Fabrication and photoluminescence properties of graphite fiber/ZnO nanorod core-shell structures

Graphite fiber/ZnO nanorod core-shell structures were synthesized by thermal evaporation process. The core-shell hybrid architectures were comprised of ZnO nanorods grown on the surface of graphite fiber. In addition, Hollow ZnO hierarchical structure can be obtained by oxidizing the graphite fiber. Room temperature photoluminescence (PL) of the as-made graphite fiber/ZnO nanorod structures shows two UV peaks at around 3.274 eV and 3.181 eV. The temperature-dependent photoluminescence spectra demonstrate the two UV emissions are attributed to the intrinsic optical transitions and extrinsic defect-related emissions in ZnO. These hybrid structures may be used as the building block for fabrication of nanodevices.     

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.     

ZnO and conjugated polymer bulk heterojunction solar cells containing ZnO nanorod photoanode

Hybrid solar cells based on poly(3-hexylthiophene) (P3HT) and ZnO nanoparticle bulk heterojunctions (BHJ) combined with ZnO nanorod arrays were fabricated and analyzed. The dispersion of ZnO nanoparticles in P3HT is assisted by dye molecules, which function as a surface modifier for ZnO nanoparticles to improve compatibility between ZnO nanoparticles and P3HT. Compared to the ZnO nanorod/P3HT devices, the optimized cells with the ZnO nanoparticles dispersed in P3HT can significantly increase the short-circuit current and the overall power conversion efficiency from 1.36 mA cm(-2) to 2.51 mA cm(-2) and from 0.18% to 0.45% with 625 nm long ZnO nanorod arrays, respectively. The novel scheme of using the light-absorbing dye molecules both as light absorber and as surfactant for ZnO nanoparticles presents a facile route towards forming bulk heterojunction hybrid solar cells based on semiconducting nanomaterials and conjugated polymers.     

Morphology-tuned growth of ZnO microstructures

Morphology-tuned ZnO microcrystals can be prepared by oxidizing zinc metal substrates in aqueous solution using hydrothermal technique. Some typical ZnO growth morphologies such as nanorod superstructures, nanorod arrays, microspheres, hierarchical nanostructures, and split crystals have been chemically fabricated. These microscopic shapes can be finely controlled by selecting Zn(NO₃)₂ concentration and solvent. A conceptual model was proposed to explain the formation of the as-prepared ZnO structures by selecting proper kinetic environments. This one-step, wet-chemical approach is controllable and reproducible, which can be conveniently transferred to industrial applications.     

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.     

The Interplay of Growth Mechanism and Properties of ZnO Nanostructures for Different Applications (Small 44/2023)

This review provides a background on the structure and properties of ZnO nanostructures. ZnO nanostructures are advantageous for many applications in sensing, photocatalysis, functional textiles, and cosmetic industries, which are described in this review. Previous work using UV Visible (UV–vis) spectroscopy and scanning electron microscopy (SEM) for ZnO nanorod growth analysis in-solution and on a substrate for determination of optical properties and morphology is discussed, as well as their results in determining the kinetics and growth mechanisms. From this literature review, it is understood that the synthesis process greatly affects nanostructures and properties; and hence, their applications. In addition, in this review, the mechanism of ZnO nanostructure growth is unveiled, and it is shown that by having greater control over their morphology and size through such mechanistic understanding, the above-mentioned applications can be affected. The contradictions and gaps in knowledge are summarized in order to highlight the variations in results, followed by suggestions for how to answer these gaps and future outlooks for ZnO nanostructure research.     

Effect of surface modifications on ZnO nanorod arrays electrode for dye-sensitized solar cells

High quality, large area and well-oriented ZnO nanorod arrays electrodes were successfully synthesized on conductive transparent oxide substrates by low-temperature hydrothermal methods for dye-sensitized solar cells. Aiming at getting further enhancement and study the effect of the surface modification on cell performance, ZnO thin film and ZnO nanoparticles are carried out to modify the as-grown ZnO nanorod arrays. The morphology, structure and photoluminescence property of the modified ZnO electrodes are characterized in detail. Furthermore, the I-V characterization result shows that these modification methods have distinct influences on the performance of the cell based on ZnO nanorod arrays electrode. The overall conversion efficiency can be optimized by choosing the suitable modification route.     

Fabrication and Wettability of ZnO Nanorod Array

ZnO nanorod arrays were prepared in an open system by using a simple aqueous solution method. Spindle-like, wimble-like, tower-like and hexagonal rod-like ZnO rods were obtained under different conditions. ZnO nanorod arrays with different morphology and size were studied by X-ray diffraction (XRD), scanning electron microscopy (SEM), and contact angle measurement (CAM). The size of ordered zinc oxide rods can be controlled by temperature of water bath, because this temperature can influences growing speeds in different crystal directions. Some additives, such as urea and thiourea, were introduced into reaction solution to improve quality of arrays. Surface character of ZnO nanorod arrays can be changed from hydrophilic to hydrophobic, which was proved to be dependence on size of air grooves on surface.     

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.     

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。     

ZnO nanostructures as efficient antireflection layers in solar cells

An efficient antireflection coating (ARC) can enhance solar cell performance through increased light coupling. Here, we investigate solution-grown ZnO nanostructures as ARCs for Si solar cells and compare them to conventional single layer ARCs. We find that nanoscale morphology, controlled through synthetic chemistry, has a great effect on the macroscopic ARC performance. Compared with a silicon nitride (SiN) single layer ARC, ZnO nanorod arrays display a broadband reflection suppression from 400 to 1200 nm. For a tapered nanorod array with average tip diameter of 10 nm, we achieve a weighted global reflectance of 6.6%, which is superior to an optimized SiN single layer ARC. Calculations using rigorous coupled wave analysis suggest that the tapered nanorod arrays behave like modified single layer ARCs, where the tapering leads to impedance matching between Si and air through a gradual reduction of the effective refractive index away from the surface, resulting in low reflection particularly at longer wavelengths and eliminating interference fringes through roughening of the air-ZnO interface. According to the calculations, we may further improve ARC performance by tailoring the thickness of the bottom fused ZnO layer and through better control of tip tapering.     

Synthesis and characterisation of three-dimensional dendritic ZnO nanorods

Abstract

Intriguing ZnO three-dimensional (3D) dendritic nanorods on silicon substrates have been successfully synthesised by thermal evaporation of pure zinc powder at a relative low temperature of 478°C without any metal catalyst. ZnO dendritic nanostructure exhibits unique shape and it is composed of stems and nanorod branches. It is found that the nanorods are single crystalline wurtzite structures, and each nanorod grows along the [0001] direction. At different growth temperatures, the shapes of ZnO nanostructures can be altered. System analysis reveals that the formation and morphology of ZnO dendritic nanostructures are sensitive to the growth temperature. Finally, room temperature photoluminescence spectrum is also investigated, revealing that the ZnO dendritic nanostructure could find application in UV optoelectronic devices; the nanostructure implies some potential applications for nanoscale functional devices.     

The magnetoelectric effect in Ni-Fe alloy/ZnO nanorod array composites

Ni-Fe alloy/ZnO nanorod composites were fabricated and the magnetoelectric effect was demonstrated. The ZnO and Ni-Fe alloy serve as the piezoelectric phase and the magnetostrictive phase in the nanocomposite, respectively. Since the nanorod structure possesses the inherent nature of a large surface-to-volume ratio, it greatly enhances the interplay between the piezoelectric and magnetostrictive coupling. Besides, the substrate clamping effect can be avoided. Our newly devised composite therefore provides a different species for magnetoelectric applications. It is interesting that the magnetoelectric voltage coefficient determined by the direct measurement method can reach a value as high as 0.48?mV?cm(-1)?Oe(-1).     

Effects of surface potential on growth of ZnO nanorod arrays investigated by electric force microscopy

The electric and Kelvin force probe microscopy were used to investigate the surface potentials on the ZnO seed layer, which shows a remarkable dependence on the annealing temperature. The optimum temperature for the growth of nanorod arrays normal to the surface was found to be at 600 degrees C, which is in the range of right surface potentials and energy measured between 500 degrees C and 700 degrees C. We demonstrated from both electric and Kelvin force probe microscopy studies that surface potential controls the growth of ZnO nanorods, illustrating the fact that this is a promising technique to visualize the control of ZnO nanorod arrays by studying their surface potentials. This study will provide important understanding of growth of other nanostructures.     

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.     

Highly sensitive hydrogen detection of catalyst-free ZnO nanorod networks suspended by lithography-assisted growth

We have successfully demonstrated a ZnO nanorod-based 3D nanostructure to show a high sensitivity and very fast response/recovery to hydrogen gas. ZnO nanorods have been synthesized selectively over the pre-defined area at relatively low temperature using a simple self-catalytic solution process assisted by a lithographic method. The conductance of the ZnO nanorod device varies significantly as the concentration of the hydrogen is changed without any additive metal catalyst, revealing a high sensitivity to hydrogen gas. Its superior performance can be explained by the porous structure of its three-dimensional network and the enhanced surface reaction of the hydrogen molecules with the oxygen defects resulting from a high surface-to-volume ratio. It was found that the change of conductance follows a power law depending on the hydrogen concentration. A Langmuir isotherm following an ideal power law and a cross-over behavior of the activation energy with respect to hydrogen concentration were observed. This is a very novel and intriguing phenomenon on nanostructured materials, which suggests competitive surface reactions in ZnO nanorod gas sensors.     

电沉积氧化锌纳米柱的带隙和近带边发射蓝移

用电化学沉积方法制备了ZnO纳米柱阵列。在Zn(NO₃)₂基础电解液中加入新电解质并引入NH₄NO₃ 和Ga(NO₃)₃,实现了对ZnO纳米柱阵列的带隙、近带边发射、斯托克斯位移、直径、密度等物理性质的设计和裁剪。可在63~77 nm操控纳米柱的直径。增加电解液中的Ga(NO₃)₃浓度,阵列的密度可降低到7.0×10⁹ /cm²。新加入电解液中的盐类使ZnO纳米柱的带隙蓝移~50 meV并使光致发光图谱中的近带边发射蓝移53~73 meV以及斯托克斯位移蓝移23 meV,表明可对其非辐射复合进行抑制设计和裁剪。     

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.     

Fabrication of two-dimensional zinc oxide nanorod patterns and their application for optical diffraction grating effect

We present a novel method for fabricating two-dimensional arrays of zinc oxide (ZnO) nanorod patterns. Vertically aligned ZnO nanostructure patterns were synthesized by hydrothermal growth on a two-dimensional seed layer pattern formed by atomic layer deposition. Various characteristics of ZnO seed films were experimentally studied in order to optimize the fabrication of ZnO rod structures in terms of their uniformity and vertical alignment on the two-dimensional-patterned surfaces. Using these ZnO structures as hierarchical electrodes, we demonstrate that localized electric fields in the proximity of ZnO rod patterns can be used for periodic alignment of liquid crystal molecules, resulting in the optical diffraction grating effect. Process conditions for creating ZnO rod patterns that best enhance diffraction efficiency are further discussed. The current study is the first demonstration of hierarchical ZnO rod patterns as electrodes for optical modulation of a medium. We believe this will be beneficial for future optical applications.