Modification of the optical and structural properties of ZnO nanowires by low-energy Ar+ ion sputtering

The effects of low-energy (≤2 kV) Ar⁺ irradiation on the optical and structural properties of zinc oxide (ZnO) nanowires (NWs) grown by a simple and cost-effective low-temperature technique were investigated. Both photoluminescence spectra from ZnO NW-coated films and cathodoluminescence analysis of individual ZnO NWs demonstrated obvious evidences of ultraviolet/visible luminescent enhancement with respect to irradiation fluence. Annihilation of the thinner ZnO NWs after the ion bombardment was appreciated by means of high-resolution scanning electron microscopy and transmission electron microscopy (TEM), which results in an increasing NW mean diameter for increasing irradiation fluences. Corresponding structural analysis by TEM pointed out not only significant changes in the morphology but also in the microstructure of these NWs, revealing certain radiation-sensitive behavior. The possible mechanisms accounting for the decrease of the deep-level emissions in the NWs with the increasing irradiation fluences are discussed according to their structural modifications.     

Growth and formation mechanism of sea urchin-like ZnO nanostructures on Si

Sea urchin-like nanostructures of ZnO consisting of ZnO nanowires with blunt faceted ends were grown on Si (100) substrates by oxidation of metallic Zn at 600 °C. ZnO nanowires having a diameter of 30–60 nm and length of 2–4 Μm were in similar shape with uniform diameter along its entire length with well faceted blunt ends. X-ray diffraction and transmission electron microscope analysis showed that the as-grown nanostructures were highly crystalline with wurtzite hexagonal structure having lattice constants of a=b=3.25 å and c=5.21 å. Room temperature photoluminescence (PL) measurements showed a weak near band-edge emission at 380 nm, but a strong green emission at 500–530 nm. A model for vapor-solid (VS) growth mechanism of ZnO nanowires was presented, in which nucleation of ZnO is crucial for the growth of the nanostructures.     

SURFACE MODIFICATION OF HYDROTHERMALLY GROWN ZnO NANOSTRUCTURES WITH PROCESS PARAMETERS

ZnO nanorods (NRs) were hydrothermally synthesized by using equimolar zinc nitrate hydrate (Zn(NO₃)₂ [sdot] 6H₂O) and hexamethylenetetramine (C₆H₁₂N₄) solutions. The shape of the nanostructures, obtained by aqueous method, was greatly influenced by the growth temperature and the molar concentrations. NRs grown at higher temperature (90°C) have rounded tips, whereas nanostructures of hexagonal flat-end shape were obtained at 75°C. Hardly any nanostructures were observed by further reducing the temperature to 60°C. In addition, solutions with higher molarity favored the appearance of nanoflowers. Scattered ZnO NRs were observed on silicon substrate, whereas aligned ZnO nanowires (NWs) 50–70 nm in diameter were obtained at 75°C by introducing sputtered ZnO film as a seed layer. High-resolution transmission electron microscopy (HRTEM) confirmed the growth of ZnO nanowires along [001] direction. A band-edge luminescence along with a broad visible spectrum was observed for the ZnO nanowires.     

Synthesizing vertical porous ZnO nanowires arrays on Si/ITO substrate for enhanced photocatalysis

In this work, porous ZnO nanowires arrays (NWAs) which are perpendicular to the substrate were synthesized using facile and simple hydrothermal process approaches. The surface of ZnO nanowires (NWs) was increased by chemical electroless etching many macropores on them, which results in better photocatalytic activity, which is 1.73 times in terms of the rate constant for methyl orange (MO) degradation for porous ZnO NWAs compared with ZnO NWAs. The absorption of the vertical porous ZnO NWAs was considerably enhanced in the visible region. The optical band-gap became slightly narrower from 3.24 eV (ZnO NWAs) to 3.22 eV (porous ZnO NWAs). Thus, the vertical porous ZnO NWAs can be employed for various applications, such as gas sensor, photocatalyst, and solar cell.     

Enhanced optical confinement and lasing characteristics of individual urchin-like ZnO microstructures prepared by oxidation of metallic Zn

We prepared urchin-like micron-sized ZnO cavities with high optical quality by oxidizing metallic Zn and proposed the mechanism that resulted in the growth of the urchin-like microstructures. The photoluminescence spectra of the ZnO microstructures had a predominant excitonic emission at room temperature. The lasing properties of the urchin-like ZnO microstructures were investigated systematically through excitation power- and size-dependent photoluminescence measurements. The results showed that a low lasing threshold with high quality factors could be achieved because of the high reflectivity of the optical reflectors formed by the tapered nanowires. The unique optical characteristics may facilitate the development of high-efficiency random lasers.     

ZnO/MoO3/Al(OH)3阻燃聚丙烯材料的制备及性能

采用水热法制备了一维材料ZnO和MoO_3纳米线(nanowires,NWs),并通过SEM和XRD对纳米线的形貌和结构进行了表征。将一维纳米线和纳米氢氧化铝(ATH)与聚丙烯(PP)熔融共混制备了ZnO/MoO_3/Al(OH)_3/PP复合材料(NWs/ATH/PP)。利用TGA、极限氧指数(LOI)测定仪和锥形量热仪(CCT)表征了复合材料的热稳定性和燃烧性能,利用万能材料试验机测试了复合材料的力学性能。结果表明:当添加质量分数3.75%ZnO纳米线、质量分数3.25%MoO_3纳米线和质量分数21.00%纳米ATH时,NWs/ATH/PP复合材料的初始分解温度较纯PP增加了17.8℃,残重率为24.6%,峰值热释放速率(PHRR)和总热释放量(THR)分别下降了54.3%和25.7%,LOI提高7.1%。SEM结果显示:NWs/ATH/PP的残炭表面致密、连续且平整。     

ZnO nanowires decoration on carbon fiber via hydrothermal synthesis for paper-based friction materials with improved friction and wear properties

Two-step growth of ZnO nanowires (NWs) on carbon fiber (CF) surface via hydrothermal synthesis was studied and their application in the preparation of paper-based friction materials by wet-forming process was also investigated. SEM and EDS results showed a dense and uniform ZnO NWs layer with vertical alignment was well established on surface of CFs. UV–vis spectra and XRD characterization further confirmed the formation of ZnO NWs on CFs surface. In comparison with control sample (paper-based friction material containing pristine CFs), the modified sample (paper-based friction material containing modified CFs) exhibited higher and more stable dynamic friction coefficient and greater wear resistance. It was concluded that the CFs@ZnO NWs had excellent tribological properties and was highly promising for wet paper-based friction material.     

Synthesis and Characterization of ZnO Nanowire–CdO Composite Nanostructures

ZnO nanowire–CdO composite nanostructures were fabricated by a simple two-step process involving ammonia solution method and thermal evaporation. First, ZnO nanowires (NWs) were grown on Si substrate by aqueous ammonia solution method and then CdO was deposited on these ZnO NWs by thermal evaporation of cadmium chloride powder. The surface morphology and structure of the synthesized composite structures were analyzed by scanning electron microscopy, X-ray diffraction and transmission electron microscopy. The optical absorbance spectrum showed that ZnO NW–CdO composites can absorb light up to 550 nm. The photoluminescence spectrum of the composite structure does not show any CdO-related emission peak and also there was no band gap modification of ZnO due to CdO. The photocurrent measurements showed that ZnO NW–CdO composite structures have better photocurrent when compared with the bare ZnO NWs.     

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.     

Well-aligned ZnO nanowires with excellent field emission and photocatalytic properties

Well-aligned ZnO nanowires (NWs) were successfully synthesized on Si(100) by the process of carbothermal reduction and vapor-liquid-solid method. Scanning electron microscopy and transmission electron microscopy results confirmed that ZnO NWs were single crystalline wurtzite structures and grew along the [0001] direction. The influences of substrate temperature and total pressure on the growth were discussed. The well-aligned ZnO NWs show good field emission properties, and the emitter constructed of pencil-like ZnO NWs exhibited a low turn-on field (3.82 V μm(-1)) and a high field enhancement factor (β = 2303). Finally, we demonstrated that the as-prepared ZnO NWs with small diameter on the substrate have good photocatalytic activity toward degradation of methylene blue. Using ZnO NWs with Au nanoparticles (NPs) would decrease the recombination rate of hole-electron pairs due to the great shift of the Fermi level to the conduction band. Hence, adding Au NPs was a promising method to enhance the photocatalytic performance of ZnO NWs. It is significant that photocatalyst fabricated by ZnO NWs can apply to the degradation of organic pollution, and solve the environmental issues.     

Low concentration ethanol sensor based on graphene/ZnO nanowires

Metal-oxide based gas sensors are widely used as the gas sensing elements in industrial and residential areas. Many efforts have been made to increase sensitivity and reduce the working temperature of metal-oxide based gas sensors. In this paper, ZnO nanowires (NWs) were successfully grown on graphene (Gr) nanosheets by the hydrothermal method. The synthesized Gr/ZnO NWs nanocomposite were investigated as the sensing material. Not only is the sensor response much higher, it also works in a lower working temperature toward a low concentration of ethanol in comparison with pure ZnO NWs. The optimum working temperature is reduced from 200 °C in pure ZnO NWs to 125 in Gr/ZnO NWs sensor. The maximum response of the Gr/ZnO NWs sensor is 26, which is approximately enhanced twice as much as the pure ZnO NWs sensor. The lower limit of detection (LLOD) of the proposed sensor is as low as 1 ppm ethanol vapor. The sensor was shown a high response, good selectivity, fast response toward ethanol vapor, excellent repeatability, and low sensitivity toward a high relative humidity, as well as remarkable long-term stability.     

Enhanced UV photosensitivity from rapid thermal annealed vertically aligned ZnO nanowires

We report on the major improvement in UV photosensitivity and faster photoresponse from vertically aligned ZnO nanowires (NWs) by means of rapid thermal annealing (RTA). The ZnO NWs were grown by vapor-liquid-solid method and subsequently RTA treated at 700°C and 800°C for 120 s. The UV photosensitivity (photo-to-dark current ratio) is 4.5 × 10³ for the as-grown NWs and after RTA treatment it is enhanced by a factor of five. The photocurrent (PC) spectra of the as-grown and RTA-treated NWs show a strong peak in the UV region and two other relatively weak peaks in the visible region. The photoresponse measurement shows a bi-exponential growth and bi-exponential decay of the PC from as-grown as well as RTA-treated ZnO NWs. The growth and decay time constants are reduced after the RTA treatment indicating a faster photoresponse. The dark current-voltage characteristics clearly show the presence of surface defects-related trap centers on the as-grown ZnO NWs and after RTA treatment it is significantly reduced. The RTA processing diminishes the surface defect-related trap centers and modifies the surface of the ZnO NWs, resulting in enhanced PC and faster photoresponse. These results demonstrated the effectiveness of RTA processing for achieving improved photosensitivity of ZnO NWs.     

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.     

Investigations into the impact of the substrates with ultra thin seed layers deposited by atomic layer deposition on ZnO Nanowire Arrays

ABSTRACT: The impact of various substrates and ZnO ultra thin seed layers prepared by atomic layer deposition on the geometric morphology of subsequent ZnO nanowire arrays (NWs) fabricated by the hydrothermal method was investigated. The investigated substrates included B-doped ZnO films, Indium Tin Oxide films, single crystal silicon (111), and glass sheets. Scanning electron microscopy and X-ray diffraction measurements revealed that the geometry and aligment of the NWs were controlled by surface topography of the substrates and thickness of the ZnO seed layers, respectively. According to atomic force microscopy data, we suggest that the substrate, fluctuate amplitude and fluctuate frequency of roughness on ZnO seed layers have a great impact on the alignment of the resulting NWs, wherease the influence of the seed layers' texture was negligible. Transmission Electron Microscopy and Photoluminescence spectroscopy showed that crystal defects were influenced greatly by substrates instead of seed layers.     

Preparation and electrochemical performances of ZnO nanowires as anode materials for Ni/Zn secondary battery

ZnO nanowires were synthesized by a hydrothermal route without any substrate or template. Structure analyses through XRD, SEM, TEM and HRTEM indicated that ZnO nanowires had high purity and perfect crystallinity, and grew along [0 0 0 1]. The diameter was 50-80 nm, the length was about several micrometers and length-diameter ratio was more than 100. As electrode materials of Ni/Zn batteries, ZnO nanowires showed the obviously improved cycle stability, average discharge capacity of 609 mAh g⁻¹, higher discharge voltage/lower charge voltage. Slow rate cyclic voltammetry showed that electrochemical activity of ZnO nanowires was superior to that of the conventional ZnO. The improvements of electrochemical performance were ascribed to the unique nanowire structure. During the charging/discharging cycles, nanowires were broke, grew in diameter, and changed into nanorods. Nanowires lying parallel to the anodes could suppress the growth of dendrite clusters perpendicular to the anodes.     

Swelling,thermal stability,antibacterial properties enhancement on composite hydrogel synthesized by chitosan-acrylic acid and ZnO nanowires

ABSTRACT

A series of antibacterial superabsorbents containing zinc oxide nanowires (ZnO NWs) based on chitosan (CS) and acrylic acid (AA) were prepared by one-step synthesis. Antibacterial influence of the content with ZnO NWs complex in superabsorbents on Escherichia coli and Staphylococcus aureus was studied, as well as water absorbency, swelling behavior, and thermal stability. Results showed that water absorbency for CS-co-AA composite hydrogel in water was 1000 g/g, because of the presence of ZnO NWs within CS-co-AA hydrogel facilitated the water absorbency ability. Furthermore, results also showed that the antibacterial effect of CS-co-AA composite hydrogels increased with an increase of ZnO NWs content.     

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.     

Structural and photoluminescence studies on catalytic growth of silicon/zinc oxide heterostructure nanowires

Silicon/zinc oxide (Si/ZnO) core-shell nanowires (NWs) were prepared on a p-type Si(111) substrate using a two-step growth process. First, indium seed-coated Si NWs (In/Si NWs) were synthesized using a plasma-assisted hot-wire chemical vapor deposition technique. This was then followed by the growth of a ZnO nanostructure shell layer using a vapor transport and condensation method. By varying the ZnO growth time from 0.5 to 2 h, different morphologies of ZnO nanostructures, such as ZnO nanoparticles, ZnO shell layer, and ZnO nanorods were grown on the In/Si NWs. The In seeds were believed to act as centers to attract the ZnO molecule vapors, further inducing the lateral growth of ZnO nanorods from the Si/ZnO core-shell NWs via a vapor-liquid-solid mechanism. The ZnO nanorods had a tendency to grow in the direction of [0001] as indicated by X-ray diffraction and high resolution transmission electron microscopy analyses. We showed that the Si/ZnO core-shell NWs exhibit a broad visible emission ranging from 400 to 750 nm due to the combination of emissions from oxygen vacancies in ZnO and In₂O₃ structures and nanocrystallite Si on the Si NWs. The hierarchical growth of straight ZnO nanorods on the core-shell NWs eventually reduced the defect (green) emission and enhanced the near band edge (ultraviolet) emission of the ZnO.     

Polystyrene sphere monolayer assisted electrochemical deposition of ZnO nanorods with controlable surface density

In this paper we report the zinc oxide nanorods (ZnO NRs) growth by electrochemical deposition onto polycrystalline gold electrodes modified with assemblies of polystyrene sphere monolayers (PSSMs). Growth occurs through the interstitial spaces between the hexagonally close packed spheres. ZnO NRs nucleate in the region where three adjacent spheres leave a space, being able to grow and projected over the PSSMs. The nanorod surface density (N_NR) shows a linear dependence with respect to a PS sphere diameter selected. XRD analysis shows these ZnO NRs are highly oriented along the (0 0 2) plane (c-axis). This open the possibility to have electronic devices with mechanically supported nanometric materials.     

One-dimensional ZnO nanostructure growth prepared by thermal evaporation on different substrates: Ultraviolet emission as a function of size and dimensionality

Large-scale uniform one-dimensional ZnO nanostructures were fabricated through thermal evaporation via the vapor solid mechanism on different substrates. The effects of Si (100), Si (111), SiO₂ and sapphire substrates with constant oxygen treatment on the morphology and diameter of ZnO nanostructures were investigated. It is found that the type of substrate has a great effect on the shape and diameter of the synthesized nanowires, nanorods, and nanotubes. It is noticed that the size and dimensionality were the most influential parameters on both structural and optical properties of the grown ZnO nanostructures. X-ray diffraction analysis confirms the stability of the wurtzite crystal structure for all grown ZnO nanostructures and the preferred orientation is substrate dependent. The crystallinity as well as the defects within the crystal lattice of the grown ZnO nanostructures was studied through Raman spectroscopy. The photoluminescence spectra of ZnO nanostructures grown on Si (100), Si (111), SiO₂ and sapphire substrates showed two peaks at a near-band-edge (NBE) emission in the ultraviolet region and a broad deep-level emission (DLE) around the green emission.