硝酸铟诱导的电沉积氧化锌纳米柱光学性质裁剪

为在新型太阳能电池等光电器件中应用ZnO纳米结构,需要对ZnO纳米结构阵列的几何形貌及光电物理性质进行裁剪与操控。采用电化学沉积路线制备ZnO纳米柱阵列,In(NO3)3与NH4NO3两种盐类被溶入在传统Zn(NO3)2主电解液中。对ZnO纳米柱阵列进行扫描电子显微镜、透射反射光谱、光致发光光谱测试,分析其形貌与光电物理性质。随着引入的In(NO3)3浓度的增加,ZnO纳米柱阵列的平均直径随之由57 nm减小至30 nm。同时ZnO纳米柱的阵列密度也可降低,进而增大纳米柱间距至41 nm。由于新的盐类的引入,ZnO纳米柱的光学带隙由3.46 eV蓝移至3.55 eV。随着电解液中In(NO3)3的增加,ZnO纳米柱的斯托克斯位移由198 meV减小至154 meV,ZnO纳米柱中的非辐射复合可以得到一定程度的抑制。通过在主电解液中引入In(NO3)3与NH4NO3两种盐类,可对ZnO纳米柱的直径、密度、间距、透射反射率、光学带隙、近带边发射与非辐射复合进行操控与裁剪。     

ZnO spheres and nanorods formation: their dependence on agitation in solution synthesis

ZnO nanostructures including nanorods, dense, and partially hollow spheres were synthesized via a solution synthesis method with temperature ranging from 65 to 95 °C. Scanning electron microscopy (SEM) revealed that the diameter of the spheres is in the range of 200–500 nm. Transmission electron microscopy (TEM) showed that some of the spheres are hollow or partially hollow. Powder X-ray Diffraction (XRD) and TEM-Selected area electron diffraction (SAED) analysis showed that the spheres consist of polycrystalline nanoparticles. It was found for the first time that the agitation during the synthesis plays a critical role on morphology of the ZnO nanostructures formed in solution. The oriented attachment of nanocrystals without agitation during the synthesis could guide the nanocrystals to form an ordered nanorod structure. However, the disordered aggregation of the nanocrystals under shear force resulted in a spherical morphology. It was also found that the composition of spheres is different from that of nanorods: the spheres consist of both ZnO and Zn(OH)₂, but nanorods consist of single-crystal ZnO only. Zn(OH)₂ presented in the spheres could decompose to ZnO by calcination, resulting in the formation of hollow spheres.     

Effect of zinc nitrate concentration on the structural and the optical properties of ZnO nanostructures

ZnO nanorods and nanodisks were formed on indium-tin-oxide-coated glass substrates by using an electrochemical deposition method. Scanning electron microscopy images showed that the ZnO nanorods were transformed into nanodisks with increasing Zn(NO₃)₂ concentration. X-ray diffraction patterns showed that the ZnO nanostructures had wurzite structures. The full widths at half maxima of the near band-edge emission peak of photoluminescence spectra at 300 K for ZnO nanorods were small, indicative of the high quality of the nanorods. These results indicate that the structural and the optical properties of ZnO nanostructures vary by changing Zn(NO₃)₂ concentration.     

Low-temperature growth and ethanol-sensing characteristics of quasi-one-dimensional ZnO nanostructures

ZnO nanorods, nanobelts, nanowires, and tetrapod nanowires were synthesized via thermal evaporation of Zn powder at temperatures in the range 550-600 °C under flow of Ar or Ar/O₂ as carrier gas. Uniform ZnO nanowires with diameter 15-25 nm and tetrapod nanowires with diameter 30-50 nm were obtained by strictly controlling the evaporation process. Our experimental results revealed that the concentration of O₂ in the carrier gas was a key factor to control the morphology of ZnO nanostructures. The gas sensors fabricated from quasi-one-dimensional (Q1D) ZnO nanostructures exhibited a good performance. The sensor response to 500 ppm ethanol was up to about 5.3 at the operating temperature 300 °C. Both response and recovery times were less than 20 s. The gas-sensing mechanism of the ZnO nanostructures is also discussed and their potential application is indicated accordingly.     

Sonochemical synthesis of hierarchical ZnO nanostructures

This work is about fabrication of ZnO nanostructures (ZnO-NS) via a simple sonochemical method. The chemicals used for the synthesis of various shaped ZnO are Zn salt, sodium hydroxide and ammonia solution without other structure directing agent or surfactant needed. This method is feasible and green, as it does not require high temperature and/or highly toxic chemicals. The shape of the ZnO-NS can be tuned by adjusting the ultrasound energy dissipated via varying the ultrasonication time from 5 to 60 min. It was found that uniform ZnO nanorods with diameter around 50 nm were formed after 15 min of ultrasonication while flowerlike ZnO-NS was formed after 30 min. This method produces high quality ZnO-NS with controllable shapes, uniformity, and purity.     

Growth of ZnO nanostructures by vapor–liquid–solid method

Zinc oxide nanorods have been grown by vapor–liquid–solid (VLS) catalytic growth. The optical properties and structures properties of the grown ZnO nanostructures have been studied by photoluminescence, high resolution X-ray diffraction and scanning electron microscopy. The results show that the formation of ZnO nanostructures is strongly influenced by the growth conditions and used substrates. It was found that oriented ZnO nanorods are grown more easily on a substrate with a similar crystalline structure as ZnO. By optimizing growth conditions, oriented-ZnO nanorods grown on Si(001) substrate with a diameter of around 300 nm and lengths of 20 to 35 μm have been achieved, and they show excellent optical properties. Laser action has been observed at room temperature by using optical pumping. PACS 81.05.Dz; 81.10.Bk; 81.16.Hc     

Controllable vertically aligned ZnO nanorods on flexible polyethylene naphthalate (PEN) substrate using chemical bath deposition synthesis

Zinc oxide (ZnO) nanorods were successfully grown on polyethylene naphthalate substrates with a seed layer using a wet chemical bath deposition method at a low temperature. Using various precursor concentrations, the diameter, length, and density of the ZnO nanorods were controlled, and their optical and crystallinity properties were investigated. X-ray diffraction and field emission scanning electron microscopy were used to examine the structure and morphology of the ZnO nanorods. The obtained ZnO nanorods were hexagonal and grew vertically from the substrate in the (002) direction along the c-axis. The low compressive strain values confirmed the high-quality crystal structure of the synthesized ZnO nanorods. A 0.050 M precursor concentration resulted in nanorods with a uniform diameter along their entire length and diameters ranging from 10 nm to 40 nm. The photoluminescence results indicated that the ZnO nanorods grown using a 0.050 M precursor concentration exhibited the sharpest and most intense PL peaks in the UV range compared with the other samples. Therefore, the precursor concentration considerably influenced the growth of the ZnO nanorods. These ZnO nanorods can be greatly applied for the development of flexible, elastic electronic, and optoelectronic devices.     

Aqueous chemical growth of free standing vertical ZnO nanoprisms,nanorods and nanodiskettes with improved texture co-efficient and tunable size uniformity

Tuning the morphology, size and aspect ratio of free standing ZnO nanostructured arrays by a simple hydrothermal method is reported. Pre-coated ZnO seed layers of two different thicknesses (≈350 nm or 550 nm) were used as substrates to grow ZnO nanostructures for the study. Various parameters such as chemical ambience, pH of the solution, strength of the Zn²⁺ atoms and thickness of seed bed are varied to analyze their effects on the resultant ZnO nanostructures. Vertically oriented hexagonal nanorods, multi-angular nanorods, hexagonal diskette and popcorn-like nanostructures are obtained by altering the experimental parameters. All the produced nanostructures were analysed by X-ray powder diffraction analysis and found to be grown in the (002) orientation of wurtzite ZnO. The texture co-efficient of ZnO layer was improved by combining a thick seed layer with higher cationic strength. Surface morphological studies reveal various nanostructures such as nanorods, diskettes and popcorn-like structures based on various preparation conditions. The optical property of the closest packed nanorods array was recorded by UV-VIS spectrometry, and the band gap value simulated from the results reflect the near characteristic band gap of ZnO. The surface roughness profile taken from the Atomic Force Microscopy reveals a roughness of less than 320 nm.     

One-pot synthesis of ferromagnetic Fe2.25W0.75O4 nanoparticles as a magnetically recyclable photocatalyst

ZnO nanostructures, including nanowires, nanorods, and nanoneedles, have been deposited on GaAs substrates by the two-step chemical bath synthesis. It was demonstrated that the O₂-plasma treatment of GaAs substrates prior to the sol?Cgel deposition of seed layers was essential to conformally grow the nanostructures instead of 2D ZnO bunches and grains on the seed layers. Via adjusting the growth time and concentration of precursors, nanostructures with different average diameter (26?C225?nm), length (0.98?C2.29???m), and density (1.9?C15.3?×?10⁹?cm^?2) can be obtained. To the best of our knowledge, this is the first demonstration of ZnO nanostructure arrays grown on GaAs substrates by the two-step chemical bath synthesis. As an anti-reflection layer on GaAs-based solar cells, the array of ZnO nanoneedles with an average diameter of 125?nm, a moderate length of 2.29???m, and the distribution density of 9.8?×?10⁹ cm^?2 has increased the power conversion efficiency from 7.3 to 12.2?%, corresponding to a 67?% improvement.     

Enhanced photocatalytic activity of Cu-doped ZnO nanorods

Cu-doped ZnO nanorods with different Cu concentrations were synthesized through the vapor transport method. The synthesized nanorods were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM) and UV–vis spectroscopy. The XRD results revealed that Cu was successfully doped into ZnO lattice. The FE-SEM images showed that the undoped ZnO has needle like morphology whereas Cu-doped ZnO samples have rod like morphology with an average diameter and length of 60–90 nm and 1.5–3 μm respectively. The red shift in band edge absorption peak in UV-vis absorbance spectrum with increasing Cu content also confirm the doping of Cu in ZnO nanorods. The photocatalytic activity of pure and Cu-doped ZnO samples was studied by the photodegradation of resazurin (Rz) dye. Both pure ZnO and the Cu-doped ZnO nanorods effectively removed the Rz in a short time. This photodegradation of Rz followed the pseudo-first-order reaction kinetics. ZnO nanorods with increasing Cu doping exhibit enhanced photocatalytic activity. The pseudo-first-order reaction rate constant for 15 % Cu-doped ZnO is equal to 10.17×10^?2min^?1 about double of that with pure ZnO. The increased photocatalytic activity of Cu-doped ZnO is attributed to intrinsic oxygen vacancies due to high surface to volume ratio in nanorods and extrinsic defect due to Cu doping.     

水浴法制备ZnO纳米棒及其场发射性能

用硝酸锌(Zn(NO3)2·6H2O)与六亚甲基四胺(C6H12N4)以等浓度配制成反应溶液,通过水浴法制备出了形貌可控的棒状ZnO纳米结构,讨论了不同反应浓度及衬底对ZnO表面形貌的影响.样品的XRD和扫描电子显微镜分析结果表明,所得产物均为六方纤锌矿结构,在有晶种层的衬底上制备出的ZnO纳米棒沿(001)方向并垂直于衬底表面生长.随着反应浓度的增加,ZnO纳米棒的直径增大,长径比减小.样品的场发射性能测试表明,反应溶液浓度为0.005 mol/L,以铜膜为晶种层的硅衬底上制备出的场发射阴极具有较好的场发射性能.     

Influence of solution parameters for the fast growth of ZnO nanostructures by laser-induced chemical liquid deposition

ZnO nanorods, nanoneedles, nanoparticles, and nanoballs were synthesized on fused quartz substrates upon irradiation of a droplet of methanolic zinc acetate dihydrate solution by an infrared (IR) continuous wave CO₂ laser for a few seconds. The addition of monoethanolamine and water to the solution improved the alignment of the nanorods and had a significant effect on the volume and morphology of the deposits. An increase of the zinc acetate concentration was found to lead to an increase of the thickness and area covered by the initial ZnO seed layer on which the nanostructures grew. By investigating the crystal structure of the deposits using X-ray and electron diffraction, we were able to show that the nanorods grow along the c axis with a high crystalline quality. Raman and photoluminescence spectroscopy confirmed the high quality of the grown ZnO nanostructures. As a matter of fact, their photoluminescence spectra are dominated by an intense UV emission around 390 nm.     

Role of VI/II ratio on the growth of ZnO nanostructures using chemical bath deposition

In this paper the growth process and morphological evolution of ZnO nanostructures were investigated in a series of experiments using chemical bath deposition. The experimental results indicate that the morphological evolution depends on the reaction conditions, particularly on OH⁻ to Zn²⁺ ratio (which directly affects the pH). For low VI/II ratios, quasi-spherical nanoparticles of an average diameter 30 nm are obtained, whereas for larger VI/II ratios, nanorods with an average diameter less than 100 nm are produced, which indicates that by systematically controlling the VI/II ratio, it is possible to produce different shapes and sizes of ZnO nanostructures. A possible mechanism for the nanostructural change of the as-synthesized ZnO from particle to rod was elucidated based on the relative densities of H⁺ and OH⁻ in the solution.     

氧化锌纳米棒的生长过程研究

利用高分子聚乙烯吡咯烷酮(PVP)和乙酸锌的配合物作为前驱体,在300 ℃温度下煅烧,并制备了氧化锌纳米棒。生成的产物用XRD,TEM,SAED等测试方法进行了表征。为了研究氧化锌纳米棒的生长过程,我们通过控制制备前驱体所需原料的比例不变,改变在300 ℃温度下煅烧的时间,分别为0.5, 3, 12和24 h,来观察生成产物的形貌特征。实验发现在110 ℃温度下干燥的前驱体中已经有氧化锌微晶生成;在300 ℃温度下煅烧0.5 h后就出现了明显的由几个纳米大小的微晶所组成的氧化锌纳米棒;煅烧3 h后的产物是结构非常完整的径直单晶ZnO纳米棒;12和24 h煅烧前驱体生成的ZnO纳米棒长度有所增加,ZnO的量基本保持不变。实验发现氧化锌的生长是沿着c轴方向,但是在横向也有生长方向。     

Fabrication of needle-like ZnO nanorods arrays by a low-temperature seed-layer growth approach in solution

Uniform, large-scale, and well-aligned needle-like ZnO nanorods with good photoluminescence and photocatalysis properties on Zn substrates, have been successfully fabricated using a simple low-temperature seed-layer growth approach in solution (50 °C). The formation of ZnO seed-layer by the anodic oxidation technique (AOT) plays an important role in the subsequent growth of highly oriented ZnO nanorods arrays. Temperature also proved to be a significant factor in the growth of ZnO nanorods and had a great effect on their optical properties. X-ray diffraction (XRD) analysis, selected-area electron diffraction (SAED) pattern and high-resolution TEM (HRTEM) indicated that the needle-like ZnO nanorods were single crystal in nature and that they had grown up preferentially along the [0001] direction. The well-aligned ZnO nanorods arrays on Zn substrates exhibited strong UV emission at around 380 nm at room temperature. To investigate their potential as photocatalysts, degradation of pentachlorophenol (PCP) in aqueous solution was carried out using photocatalytic processes, with comparison to direct photolysis. After 1 h, the degradation efficiencies of PCP by direct photolysis and photocatalytic processes achieved 57% and 76% under given experimental conditions, respectively. This improved degradation efficiency of PCP illustrates that ZnO nanorods arrays on Zn substrates have good photocatalytic activity. This simple low-temperature seed-layer growth approach in solution resulted in the development of an effective and low-cost fabrication process for high-quality ZnO nanorods arrays with good optical and photocatalytic properties that can be applicable in many fields such as photocatalysis, photovoltaic cells, luminescent sensors, and photoconductive sensors. PACS 81.07.Bc; 81.10.Dn; 81.15.Pq; 82.50.Hp; 85.60.Jb     

Photocatalytic activity of 6.5 MeV electron-irradiated ZnO nanorods

The microwave-synthesized zinc-oxide (ZnO) nanonorods of average length of ～ 1500 nm and diameter ～ 100 nm were irradiated with 6.5 meV electrons. From sample to sample, the electron fluence was varied over the range 5×10¹⁴ to 2.5×10¹⁵ e-cm^?2. The pre- and post-electron-irradiated ZnO nanorods were characterized by X-ray diffraction, UV–VIS, EDAX, scanning electron microscopy, transmission electron microscopy, and BET methods. The results show that after electron irradiation, the ZnO nanorods could retain the hexagonal phase with the wurtzite structure; however, the average length of the ZnO nanorods reduced to ～ 800 nm. Moreover, the oxygen atoms from a fraction of ZnO molecules were dislodged, and the process contributed to the formation of Zn–ZnO mixed phase, with increased zinc to oxygen ratio. In the photo-degradation of Rhodamine-B, a significant enhancement in the photocatalytic activity of the electron-irradiated ZnO nanorods was observed. This could be attributed to the induced defects, reduced dimensions, and increased surface area of the ZnO nanorods, in addition to the formation of the Zn–ZnO phase. All these could collectively contribute to the effective separation of the photogenerated electrons from the holes on the ZnO nanorods, and therefore enhance the photocatalytic activity under UV exposure.     

Field emission from lotiform-like ZnO nanostructures synthesized via thermal evaporation method

Novel lotiform ZnO nanostructures were synthesized on silicon substrate via simple thermal evaporation. The average diameter of the ZnO nanostructures is ∼1.5 μm. The lotiform-like ZnO structures were formed by nanorods arrays with the average diameter of 70 nm. The as-grown lotiform ZnO nanostructures have excellent field-emission properties such as the low turn-on field of 3.4 V/μm, and very high emission current density of 12.4 mA/cm² at the field of 9.6 V/μm. These features make the lotiform-like ZnO nanostructures competitive candidates for field-emission-based displays. PACS 61.46.-w; 61.82.Rx; 78.67.-n; 73.63.Bd; 74.78.Na     

Surface enhanced Raman scattering and photoluminescence properties of catalytic grown ZnO nanostructures

Sword-like (diameter ranging from 40 nm to 300 nm) and needle-like zinc oxide (ZnO) nanostructures (average tip diameter ∼40 nm) were synthesized on annealed silver template over silicon substrate and directly on silicon wafer, respectively via thermal evaporation of metallic zinc followed by a thermal annealing in air. The surface morphology, microstructure, chemical analysis and optical properties of the grown samples were investigated by field emission scanning electron microscopy, X-ray diffraction, energy dispersive X-ray analysis, room temperature photoluminescence and Raman spectroscopy. The sword-like ZnO nanostructures grown on annealed silver template are of high optical quality compared to needle-like ZnO nanorods for UV emission and show enhanced Raman scattering.     

The study of low temperature hydrothermal growth of ZnO nanorods on stents and its applications of cell adhesion and viability

The hydrothermal growths of the ZnO nanorods with the densities ranging from 157 to 73 nanorods/μm² were achieved by diluting the ZnO seed solution. However, the ZnO seed nanocrystals started to agglomerate for the seed solution diluted below 1% of the original nano-crystalline solutions and resulted in the formation of clustered nanorods. With the assistance of a surfactant, Triton X-100, the nanorod density can be further reduced to 4 nanorods/μm². The diameters of the nanorods depended on the concentration of the seed solution and agitation speed of the nanorod growth solution. More diluted seed solution used and less agitation of the growth solution, the larger diameter of the nanorods was obtained. This indicated that the nanorod growth mechanism was controlled by the diffusion of reactants. With sufficient agitation of the growth solution, the nanorod can be uniformly grown with subjects on any arbitrary geometry. We have demonstrated ZnO nanorods growth on both inside and outside of biliary stents as well as on nitinol wires used as metal stents. The effect of nanorod density on the NIH 3T3 and HUVEC cells growth was also investigated in this study and the results suggested nanorod-coating to be a suitable method for controlling cell adhesion and viability on implantable devices.     

Effect of substrate temperature on the growth and luminescence properties of ZnO nanostructures

ZnO nanowires, nanorods and nanoribbons have been prepared by heating a mixture of ZnO/graphite powders using the thermal evaporation and vapor transport on Si(1 0 0) substrates without any catalyst. The nanostructures are grown as a function of substrate temperature ranging from 900 to 1300 K. These nanostructures are of the size 100–300 nm in diameter or width and several tens of micrometers in length. We studied the influence of the substrate temperature on the luminescent properties of these nanostructures. We observed a strong relationship between the substrate temperature and the green emission band in ZnO, i.e., the photoluminescence study revealed that the green emission peak of the ZnO nanostructures is suppressed relative to the band edge emission when the substrate temperature is decreased from 1300 to 900 K.