Controllable synthesis of branched ZnO/Si nanowire arrays with hierarchical structure

A rational approach for creating branched ZnO/Si nanowire arrays with hierarchical structure was developed based on a combination of three simple and cost-effective synthesis pathways. The crucial procedure included growth of crystalline Si nanowire arrays as backbones by chemical etching of Si substrates, deposition of ZnO thin film as a seed layer by magnetron sputtering, and fabrication of ZnO nanowire arrays as branches by hydrothermal growth. The successful synthesis of ZnO/Si heterogeneous nanostructures was confirmed by morphologic, structural, and optical characterizations. The roles of key experimental parameters, such as the etchant solution, the substrate direction, and the seed layer on the hierarchical nanostructure formation, were systematically investigated. It was demonstrated that an etchant solution with an appropriate redox potential of the oxidant was crucial for a moderate etching speed to achieve a well-aligned Si nanowire array with solid and round surface. Meanwhile, the presence of gravity gradient was a key issue for the growth of branched ZnO nanowire arrays. The substrate should be placed vertically or facedown in contrast to the solution surface during the hydrothermal growth. Otherwise, only the condensation of the ZnO nanoparticles took place in a form of film on the substrate surface. The seed layer played another important role in the growth of ZnO nanowire arrays, as it provided nucleation sites and determined the growing direction and density of the nanowire arrays for reducing the thermodynamic barrier. The results of this study might provide insight on the synthesis of hierarchical three-dimensional nanostructure materials and offer an approach for the development of complex devices and advanced applications.     

Preparation of highly ordered ZnO nanowire arrays by paired-cell deposition

Highly ordered ZnO nanowire arrays were fabricated by paired cell method into nanoporous anodic alumina oxide (AAO) template. ZnO nanowires were uniformly assembled into the ordered channels of the AAO template. TEM and selected-area electron diffraction patterns indicated that the ZnO nanowires grow as a single crystal. The factors influencing the final filled density of ZnO nanowires, including the solution concentration and the diffusing temperature are discussed briefly. In addition, the possible mechanism is also proposed to account for the growth of the ZnO nanowires in the AAO template. This result has established that this paired cell method makes it possible to grow single-crystalline ZnO nanowires in the AAO template under appropriate conditions.     

Homoepitaxial regrowth habits of ZnO nanowire arrays

ABSTRACT: Synthetic regrowth of ZnO nanowires [NWs] under a similar chemical vapor transport and condensation [CVTC] process can produce abundant ZnO nanostructures which are not possible by a single CVTC step. In this work, we report three different regrowth modes of ZnO NWs: axial growth, radial growth, and both directions. The different growth modes seem to be determined by the properties of initial ZnO NW templates. By varying the growth parameters in the first-step CVTC process, ZnO nanostructures (e.g., nanoantenna) with drastically different morphologies can be obtained with distinct photoluminescence properties. The results have implications in guiding the rational synthesis of various ZnO NW heterostructures.     

Size-selected growth of transparent well-aligned ZnO nanowire arrays

This paper reports the effect of precursor concentration, growth temperature, and growth time on the size and density of ZnO nanowire arrays (ZNAs). The well-aligned ZNAs were grown on indium tin oxide substrate using a facile chemical bath deposition method. The results showed that the ZnO nanowires could be tailored to the desired sizes with a simple variation of the growth parameters. Optical transmission spectra revealed a sufficient transparency of the ZNAs, qualifying them for photovoltaic and other optoelectronic applications. An inverted hybrid solar cell was fabricated using the ZNAs as the electron collecting layer, and the solar cell exhibited a power conversion efficiency of 0.91%.     

Controllable electrochemical synthesis of La/ZnO hierarchical nanostructures and their optical and magnetic properties

Here we presented a facile electrochemical deposition route for the controllable preparation of La³⁺/ZnO hierarchical nanostructures, such as flower-like nanostructures consisted of nanorods, flower bundles, and hexagonal nanorods with nests at the top. These prepared La³⁺/ZnO deposits were characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, UV-vis spectrophotometer, and photoluminescence spectroscopy. The formation process of La³⁺-doped ZnO and the growth mechanisms of La³⁺/ZnO hierarchical nanostructures were discussed. The UV and PL spectra measurements show that the surface morphologies of La³⁺/ZnO deposits have an obvious effect on their optical properties and we can easily adjust their optical properties as well as La³⁺/ZnO nanostructures by changing electrochemical deposition parameters. In addition, the magnetic properties of La³⁺/ZnO deposits were also investigated.     

Synthesis and magnetic properties of Cu-doped ZnO nanowire arrays

Arrays of Cu-doped ZnO nanowires were successfully fabricated by electrodeposition of Zn²⁺ and Cu²⁺ into anodic aluminum oxide template and post-oxidation annealing in air atmosphere. The transmission electron microscopy result shows that the nanowires are uniform, about 100 nm in diameter and with the aspect ratio of up to 40. Selected area electron diffraction and X-ray diffraction results indicate that the nanowires are in hexagonal wurtzite structure. Magnetization measurements show that the Zn_1−xCu_xO (x = 0.07 and 0.11) nanowires exhibit room-temperature ferromagnetism and the enhancement of the ferromagnetism is revealed for the Zn_0.93Cu_0.07O nanowires annealed in vacuum.     

Highly stable field emission properties from well-crystalline 6-Fold symmetrical hierarchical ZnO nanostructures

Herein, we report the growth, characterization and field emission application of well-crystalline 6-fold symmetrical hierarchical ZnO nanostructures grown on silicon substrate by thermal evaporation process. The detailed morphological characterizations revealed that the prepared material possess six-fold structures in which ZnO nanoneedles are symmetrically grown on each facets of core hexagonal ZnO nanorods in such a manner that they made beautiful 6-fold symmetrical hierarchical structure. The detailed structural studies confirmed that the grown hierarchical structures possess well-crystallinity with wurtzite hexagonal phase. The room-temperature photoluminescence (PL) spectrum exhibited a strong UV emission confirming good optical properties. The Raman-scattering revealed the wurtzite hexagonal phase for as-grown hierarchical structures. The field emission properties of the 6-fold symmetrical hierarchical ZnO nanostructures were tested and a turn-on voltage equal to 2.8 kV, corresponds to emission current of 65 nA, was observed. A threshold voltage of 4.6 kV with a maximum emission current of about 9.36 µA was also recorded. A high emission current stability profile over a period of ~7000 s was noted for the fabricated FE device.     

Effects of preparing conditions on the electrodeposition of well-aligned ZnO nanorod arrays

By using a potentiostatic electrodeposition method, well-aligned ZnO nanorod arrays (ZNAs) were synthesized under different conditions. The effects of preparing conditions on the electrodeposition of ZNAs were systematically studied by scanning electron microscopy (SEM), X-ray diffraction (XRD) and absorbance spectroscopy. It is indicated that the electrodeposition parameters, such as electrodeposition potential, electrolyte pH, concentration of precursors, temperature of solution and electrodeposition time, have significant influence on the morphology, diameter, density and growth rate of ZNAs. The ZNAs, with well-defined crystallization, can be only obtained when the applied potential is controlled from −0.4 to −1.0 V. The growth temperature has great impact on the morphology of ZnO nanostructure but it is weakly related to the band gap (E_g) of ZNAs. The rod diameters can be monitored to some extent only by changing the concentration of the precursors. The electrolyte pH value has relative influence on the diameter of ZNAs. With the growth time increasing, ZNAs with high aspect ratio can be gained.     

Electrodeposition of CdSe coatings on ZnO nanowire arrays for extremely thin absorber solar cells

We report on electrodeposition of CdSe coatings onto ZnO nanowire arrays and determine the effect of processing conditions on material properties such as morphology and microstructure. CdSe-coated ZnO nanowire arrays have potential use in extremely thin absorber (ETA) solar cells, where CdSe absorbs visible light and injects photoexcited electrons into the ZnO nanowires. We show that room-temperature electrodeposition enables growth of CdSe coatings that are highly crystalline, uniform, and conformal with precise control over thickness and microstructure. X-ray diffraction and transmission electron microscopy show nanocrystalline CdSe in both hexagonal and cubic phases with grain size ∼5 nm. Coating morphology depends on electrodeposition current density. Uniform and conformal coatings were achieved using moderate current densities of ∼2 mA cm⁻² for nanowires with roughness factor of ∼10, while lower current densities resulted in sparse nucleation and growth of larger, isolated islands. Electrodeposition charge density controls the thickness of the CdSe coating, which was exploited to investigate the evolution of the morphology at early stages of nucleation and growth. UV–vis transmission spectroscopy and photoelectrochemical solar cell measurements demonstrate that CdSe effectively sensitizes ZnO nanowires to visible light.     

Electrodeposition of Cu-doped ZnO nanowire arrays and heterojunction formation with p-GaN for color tunable light emitting diode applications

Copper-doped zinc oxide (ZnO:Cu) nanowires (NWs) were electrochemically deposited at low temperature on fluor-doped tin oxide (FTO) substrates. The electrochemical behavior of the Cu–Zn system for Cu-doped ZnO electrodeposition was studied and the electrochemical reaction mechanism is discussed. The synthesized ZnO arrayed layers were investigated by using SEM, XRD, EDX, photoluminescence and Raman techniques. X-ray diffraction analysis demonstrates a decrease in the lattice parameters of Cu-doped ZnO NWs. Structural analyses show that the nanomaterial is of hexagonal structure with the Cu incorporated in ZnO NWs probably by substituting zinc in the host lattice. Photoluminescence studies on pure and Cu-doped ZnO NWs shows that the near band edge emission is red-shifted by about 5 or 12 nm depending on Cu(II) concentration in the electrolytic bath solution (3 or 6 μmol l⁻¹). Cu-doped ZnO NWs have been also epitaxially grown on Mg doped p-GaN single-crystalline layers and the (ZnO:Cu NWs)/(p-GaN:Mg) heterojunction has been used to fabricate a light-emitting diode (LED) structure. The emission was red-shifted to the visible violet spectral region compared to pure ZnO. The present work demonstrates the ability of electrodeposition to produce high quality ZnO nanowires with tailored optical properties by doping. The obtained results are of great importance for further studies on bandgap engineering of ZnO, for color-tunable LED applications and for quantum well preparation.     

Cytotoxic effects of ZnO hierarchical architectures on RSC96 Schwann cells

The alteration in intracellular Zn²⁺ homeostasis is attributed to the generation of intracellular reactive oxygen species, which subsequently results in oxidative damage of organelles and cell apoptosis. In this work, the neurotoxic effects of ZnO hierarchical architectures (nanoparticles and microspheres, the prism-like and flower-like structures) were evaluated through the 3-(4, 5-dimethylthiazol-2-yl)-2, 5-diphenyltetrazolium bromide assay using RSC96 Schwann cells as the model. Cell apoptosis and cell cycle were detected using flow cytometry. The concentration of Zn²⁺ in the culture media was monitored using atomic absorption spectrometry. The results show that ZnO nanoparticles and microspheres displayed significant cytotoxic effects on RSC96 Schwann cells in dose- and time-dependent manners, whereas no or low cytotoxic effect was observed when the cells were treated with the prism-like and flower-like ZnO. A remarkable cell apoptosis and G2/M cell cycle arrest were observed when RSC96 Schwann cells were exposed to ZnO nanoparticles and microspheres at a dose of 80 μg/mL for 12 h. The time-dependent increase of Zn²⁺ concentration in the culture media suggests that the cytotoxic effects were associated with the decomposition of ZnO hierarchical architecture and the subsequent release of Zn²⁺. These results provide new insights into the cytotoxic effects of complex ZnO architectures, which could be prominently dominated by nanoscale building blocks.     

Fabrication and characterization of hexagonally patterned quasi-1D ZnO nanowire arrays

Quasi-one-dimensional (quasi-1D) ZnO nanowire arrays with hexagonal pattern have been successfully synthesized via the vapor transport process without any metal catalyst. By utilizing polystyrene microsphere self-assembled monolayer, sol–gel-derived ZnO thin films were used as the periodic nucleation sites for the growth of ZnO nanowires. High-quality quasi-1D ZnO nanowires were grown from nucleation sites, and the original hexagonal periodicity is well-preserved. According to the experimental results, the vapor transport solid condensation mechanism was proposed, in which the sol–gel-derived ZnO film acting as a seed layer for nucleation. This simple method provides a favorable way to form quasi-1D ZnO nanostructures applicable to diverse fields such as two-dimensional photonic crystal, nanolaser, sensor arrays, and other optoelectronic devices.     

Growth characteristics of hierarchical ZnO structures prepared by one-step aqueous chemical growth

By varying the initial precursor concentrations of (KOH/Zn(NO₃)₂ 6H₂O) without addition of surfactants, the branched nanostructures with different growth characteristics can be obtained. In this study, the growth behavior of the three-dimensional hierarchical structure arrays varied from randomly oriented to well-defined sixfold symmetry by altering pH value of the solution and the related effect of erosion phenomenon have been illustrated. In summary, the hierarchical structures with different morphologies can be obtained on preformed Zn microtips through a simple one-step solution method.     

Electrochemical route to the synthesis of ZnO microstructures: its nestlike structure and holding of Ag particles

Abstract

A simple and facile electrochemical route was developed for the shape-selective synthesis of large-scaled series of ZnO microstructures, including petal, flower, sphere, nest and clew aggregates of ZnO laminas at room temperature. This route is based on sodium citrate-directed crystallization. In the system, sodium citrate can greatly promote ZnO to nucleate and directly grow by selectively capping the specific ZnO facets because of its excellent adsorption ability. The morphology of ZnO is tuned by readily adjusting the concentration of sodium citrate and the electrodeposition time. Among the series structures, the remarkable ZnO nestlike structure can be used as a container to hold not only the interlaced ZnO laminas but also Ag nanoparticles in the center. The special heterostructures of nestlike ZnO holding Ag nanoparticles were found to display the superior properties on the surface-enhanced Raman scattering. This work has signified an important methodology to produce a wide assortment of desired microstructures of ZnO.

PACS

81 Materials science 81.07.-b nanoscale materials and structures Fabrication Characterization 81.15.-z Methods of deposition of films Coatings Film growth and epitaxy.     

Growth and optical properties of ZnO nanorod arrays on Al-doped ZnO transparent conductive film

ZnO nanorod arrays (NRAs) on transparent conductive oxide (TCO) films have been grown by a solution-free, catalyst-free, vapor-phase synthesis method at 600°C. TCO films, Al-doped ZnO films, were deposited on quartz substrates by magnetron sputtering. In order to study the effect of the growth duration on the morphological and optical properties of NRAs, the growth duration was changed from 3 to 12 min. The results show that the electrical performance of the TCO films does not degrade after the growth of NRAs and the nanorods are highly crystalline. As the growth duration increases from 3 to 8 min, the diffuse transmittance of the samples decreases, while the total transmittance and UV emission enhance. Two possible nanorod self-attraction models were proposed to interpret the phenomena in the sample with 9-min growth duration. The sample with 8-min growth duration has the highest total transmittance of 87.0%, proper density about 75 μm⁻², diameter about 26 nm, and length about 500 nm, indicating that it can be used in hybrid solar cells.     

Direct selective growth of ZnO nanowire arrays from inkjet-printed zinc acetate precursor on a heated substrate

Inkjet printing of functional materials has drawn tremendous interest as an alternative to the conventional photolithography-based microelectronics fabrication process development. We introduce direct selective nanowire array growth by inkjet printing of Zn acetate precursor ink patterning and subsequent hydrothermal ZnO local growth without nozzle clogging problem which frequently happens in nanoparticle inkjet printing. The proposed process can directly grow ZnO nanowires in any arbitrary patterned shape, and it is basically very fast, low cost, environmentally benign, and low temperature. Therefore, Zn acetate precursor inkjet printing-based direct nanowire local growth is expected to give extremely high flexibility in nanomaterial patterning for high-performance electronics fabrication especially at the development stage. As a proof of concept of the proposed method, ZnO nanowire network-based field effect transistors and ultraviolet photo-detectors were demonstrated by direct patterned grown ZnO nanowires as active layer.     

不锈钢丝网上氧化锌纳米线阵列的 可控生长及光催化性能研究

利用水热法在不锈钢丝网上制备了氧化锌纳米线阵列,借助扫描电镜（SEM）对产物的形貌进行了表征,探讨了反应物浓度和反应时间对产物形貌的影响,并以橙黄Ⅱ为目标降解物,研究了不同生长条件下氧化锌纳米线阵列的光催化降解性能。研究结果表明：硝酸锌浓度和反应时间对氧化锌纳米线阵列的密度、长度、直径和晶形有重要影响,在硝酸锌浓度为0.1 mol/L、反应时间为6 h条件下,制得的氧化锌纳米线阵列具有较佳的光催化活性,多次循环实验结果表明其稳定性较高。另外,双层叠合的氧化锌纳米线的光催化降解性能优于单层氧化锌纳米线的实验结果,其不锈钢丝网的网状结构为制备多维纳米阵列和薄膜提供了一种新的研究思路。     

Electrodeposition of ZnO nanoflake-based photoanode sensitized by carbon quantum dots for photoelectrochemical water oxidation

We report a promising simple strategy for improving the performance of the photoanode for photoelectrochemical (PEC) water oxidation. Three-dimentional hierarchical ZnO nanoflake arrays with abundant porosity and small thickness on fluorine-doped tin oxide glass substrate (FTO) was prepared with electrodeposition. The ZnO nanoflake-based photoanode exhibits superior photoresponse and PEC capability. Furthermore, the ZnO photoanode sensitized by carbon quantum dots (CQDs) can further PEC performance due to the narrower bandgap of CQDs and the improved efficiency of photogenerated electrons transfer from CQDs to ZnO nanostructures. The morphology and properties of the sample were examined by scanning electron microscopy (SEM), cross-section SEM, UV–vis spectra, X-ray photoelectron spectra (XPS), FT-IR, X-ray diffractometry (XRD) and electrical measurements.     

Parametric Study on Dimensional Control of ZnO Nanowalls and Nanowires by Electrochemical Deposition

A simple electrochemical deposition technique is used to synthesize both two-dimensional (nanowall) and one-dimensional (nanowire) ZnO nanostructures on indium-tin-oxide-coated glass substrates at 70°C. By fine-tuning the deposition conditions, particularly the initial Zn(NO₃)₂·6H₂O electrolyte concentration, the mean ledge thickness of the nanowalls (50–100 nm) and the average diameter of the nanowires (50–120 nm) can be easily varied. The KCl supporting electrolyte used in the electrodeposition also has a pronounced effect on the formation of the nanowalls, due to the adsorption of Cl⁻ ions on the preferred (0001) growth plane of ZnO and thereby redirecting growth on the (10[`1] \bar{1} 0) and (2[`1] \bar{1} [`1] \bar{1} 0) planes. Furthermore, evolution from the formation of ZnO nanowalls to formation of nanowires is observed as the KCl concentration is reduced in the electrolyte. The crystalline properties and growth directions of the as-synthesized ZnO nanostructures are studied in details by glancing-incidence X-ray diffraction and transmission electron microscopy.     

High-yield synthesis of ZnO nanowire arrays and their opto-electrical properties

In this article, ZnO nanostructures were synthesized via the hydrothermal method which used ZnCl(2) and HMTA mixed solution as the precursor. A multistep growth was adopted to improve the growth restriction of a closed system, not only the length but also the aspect ratio were increased with steps of growth, and the shape of nanorods maintained integrity. Furthermore, photoluminescence spectra which have the near-band-edge-emission (～3.37 eV) and defect-related emission show the optical properties of ZnO nanostructures. The defect-related emission intensity was greatly enhanced with the increasing surface area of ZnO nanowires. The level of the OH group was attributed to the yellow-light emission (～580 nm) and the red-shift phenomenon. In addition, we fabricated two types of ultraviolet photodetectors: a single nanowire device and a nanowire-array device, operating at a low bias (less than 5 mV). With the lower energy consumption and the weaker persistent photoconductive effect, our ultraviolet photodetectors have better performance, exhibiting a short response time and higher sensitivity.