ZnO纳米线薄膜的合成参数、表面形貌和接触角关系研究

水浴法合成ZnO纳米线薄膜的工艺参数直接影响其表面形貌, 并使其接触角及润湿性能发生变化. 本文仿真分析了轮廓算数平均偏差、偏斜度、峭度、相关长度等特征参数对随机粗糙表面特性的影响规律; 改变生长时间、种子层溶液和生长液的浓度, 批量制备了表面形貌不同的ZnO纳米线薄膜; 提出了取样长度的确定方法, 并基于扫描电镜图像和Matlab图像处理算子对ZnO纳米线薄膜表面形貌的特征参数进行了提取; 将表面形貌高度和水平方向的特征参数引入Wenzel模型, 分析了合成参数、表面形貌特征参数与接触角的影响关系. 结果表明, 合成参数变化时, 选择取样长度5.0 μm为宜; 生长液浓度大于0.125 mol/L时, ZnO纳米线之间发生重结晶, 并呈现疏水性; 改变种子层溶液浓度和生长时间, 均得到超亲水表面. 上述结论可用于不同氧化酶、细胞等在ZnO纳米线薄膜上的有效吸附及相应传感器测试性能的进一步提高. 关键词： ZnO纳米线 水浴合成 表面形貌 接触角     

ZnO薄膜的性质对水热生长ZnO纳米线阵列的影响

用水热法在ZnO薄膜上制备了直径、密度及取向可控的ZnO纳米线阵列。ZnO薄膜是通过原子层沉积(ALD)方法制备并在不同温度下退火处理得到的,退火温度对ZnO薄膜的晶粒尺寸、结晶质量和缺陷性质有很大的影响。而ZnO薄膜的性质对随后生长的ZnO纳米线的直径、密度及取向能起到调节控制的作用。通过扫描电子显微镜(SEM)、X射线衍射(XRD)仪和光致发光(PL)测试对ZnO薄膜和ZnO纳米线进行了表征。最后得到的垂直取向的ZnO纳米线阵列适合在发光二极管和太阳能电池等领域使用。     

Effect of seed layer on the growth of well-aligned ZnO nanowires

We demonstrate that vertical well-aligned crystalline ZnO nanowire arrays were grown on ZnO/glass substrates by a low-temperature solution method. Different thicknesses of ZnO seed layers on glass substrates were prepared by radio-frequency sputtering. In this work it was found that the morphology of ZnO nanowires strongly depends on the thickness of ZnO seed layers. The average diameter of nanowires is increased from 50 to 130 nm and the nanowire density is decreased from 110 to 60 μm⁻² while the seed layer thickness is varied from 20 to 1000 nm. The improved control of the morphology of ZnO nanowire arrays may lead to an enhanced carrier collection of hybrid polymer photovoltaic devices based on ZnO.     

Control growth of catalyst-free high-quality ZnO nanowire arrays on transparent quartz glass substrate by chemical vapor deposition

ZnO nanowire arrays have been successfully synthesized on transparent quartz glass substrate by chemical vapor deposition technique. Our work demonstrates the critical role of the growth temperature and the buffer layer on the effective control of the morphology of ZnO nanowires. A proper growth temperature and the thicker buffer layer could promise the good alignment and high density of the nanowires. The room-temperature photoluminescence spectrum shows that the buffer layer has also great effects on optical properties of ZnO nanowire arrays. The integrated intensity ratio [I_UV/I_{Visible band}] of the ZnO UV emission peak to visible band emission decreases with the increase of the thickness of the buffer layers. The obtained nanowire arrays have transmittance of above 50% in the visible region.     

Controllable hydrothermal synthesis of ZnO nanowires arrays on Al-doped ZnO seed layer and patterning of ZnO nanowires arrays via surface modification of substrate

ZnO nanowire (NW) arrays are assembled on the Al-doped ZnO (AZO) seed layer by a hydrothermal process. Effects of the temperature and growth time of the hydrothermal process on morphological and photoluminescence properties of the as-assembled ZnO NW arrays are characterized and studied. Results indicate that the length and diameter of the ZnO NWs increase with a lengthening of the growth time at 80 °C and the hydrothermal temperature has a significant effect on the growth rate and the photoluminescence properties of the ZnO NW arrays. The patterned AZO seed layer is fabricated on a silicon substrate by combining a sol-gel process with an electron-beam lithography process, as well as a surface fluorination technique, and then the ZnO NW arrays are selectively grown on those patterned regions of the AZO seed layer by the hydrothermal process. Room-temperature photoluminescence spectra of the patterned ZnO NW arrays shows that only a strong UV emission at about 380 nm is observed, which implies that few crystal defects exist inside the as-grown ZnO NW arrays.     

Selective growth of ZnO nanowires on substrates patterned by photolithography and inkjet printing

Zinc oxide nanowires (ZnO NWs) were grown by a two-step growth method, involving the deposition of a patterned ZnO thin seeding layer and the chemical vapor deposition (CVD) of ZnO NWs. Two ways of patterning the seed layer were performed. The seeding solution containing ZnO precursors was deposited by sol–gel/spin-coating technique and patterned by photolithography. In the other case, the seeding solution was directly printed by inkjet printing only on selected portion of the substrate areas. In both cases, crystallization of the seed layer was achieved by thermal annealing in ambient air. Vertically aligned ZnO NWs were then grown by CVD on patterned, seeded substrates. The structure and morphology of ZnO NWs was analyzed by means of X-ray diffraction and field emission scanning electron microscopy measurements, respectively, while the vibrational properties were evaluated through Raman spectroscopy. Results showed that less-defective, vertically aligned, c-axis oriented ZnO NWs were grown on substrates patterned by photolithography while more defective nanostructures were grown on printed seed layer. A feature size of 30 µm was transferred into the patterned seed layer, and a good selectivity in growing ZnO NWs was obtained.     

Growth and characterization of type-II ZnO/ZnTe core-shell nanowire arrays for solar cell applications

Large area, well-aligned type-II ZnO/ZnTe core-shell nanowire arrays have been fabricated on an a-plane sapphire substrate. The ZnO nanowires were grown in a furnace by chemical vapor deposition with gold as catalyst and then were coated with a ZnTe shell on the ZnO nanowires surface by a metal-organic chemical deposition chamber. The morphology and size distribution of the ZnO/ZnTe core-shell nanowire arrays were studied by scanning electron microscopy (SEM) and the crystal structure was examined by x-ray diffraction (XRD). Transmission measurement was used to study the optical properties of the core-shell nanowires. The results indicated that the ZnO/ZnTe core-shell nanowire arrays have good crystalline quality. In addition, it was found that the nanowire arrays have good light absorption characteristics and these properties make it suitable for making photovoltaic devices.     

Growth of ZnO nanorods by aqueous solution method with electrodeposited ZnO seed layers

ZnO nanorod arrays on ZnO-coated seed layers were fabricated by aqueous solution method using zinc nitrate and hexamethylenetetramine at low temperature. The seed layers were coated on ITO substrates by electrochemical deposition technique, and their textures were dominated by controlling the deposition parameters, such as deposition potential and electrolyte concentration. The effects of the electrodeposited seed layers and the growing parameters on the structures and properties of ZnO nanorod arrays were primarily discussed. The orientation and morphology of both the seed layer and successive nanorods were analyzed by using X-ray diffraction (XRD), SEM and TEM. The results show that the seed layer deposited at −700 mV has evenly distributed crystallites and (0 0 2) preferred orientation; the density of resultant nanorods is high and ZnO nanorods stand completely perpendicular onto substrates. Meanwhile, the size of nanorods quite also depends on the growth solution, and the higher concentration of growth solution primary leads to a large diameter of the ZnO nanorods.     

Pulsed-laser deposition and characterization of ZnO nanowires with regular lateral arrangement

We report on the high-pressure pulsed-laser deposition growth of periodic arrays of free-standing single zinc oxide nanowires with uniform hexagonal arrangement and cross-section with thickness of less than 100 nm. In order to achieve the wire alignment, we prepared an ordered array of catalytic gold seed particles by a nanosphere lithography mask transfer technique using monodisperse spherical polystyrol nanoparticles. These templates were investigated by scanning electron microscopy and atomic force microscopy prior to nanowire growth. X-ray diffraction revealed the epitaxial relationships between the nanostructures and the a-plane sapphire substrate and excellent crystal quality. The optical properties of the ZnO nanowire arrays were measured by cathodoluminescence. PACS 61.82.Rx; 81.05.-t; 81.05.Dz; 81.10.-h     

树形结构Si/ZnO纳米线阵列的制备及光学性能

用一种低成本的方法制备出了树形结构Si/ZnO纳米线阵列。首先在室温条件下用金属辅助化学腐蚀法在Si(100)衬底上制备了Si纳米线阵列,Si纳米线的直径尺寸及分布都很均匀,通过改变腐蚀时间,能够得到高度不同的Si纳米线阵列。利用磁控溅射在Si纳米线表面制备一层ZnO薄膜,然后利用水热法在Si纳米线阵列上生长了ZnO纳米线。通过扫描电子显微镜(SEM)、能谱分析仪(EDS)和光致发光(PL)测试对样品进行了表征。通过这种方法制备的Si/ZnO复合结构在太阳能电池、光催化等领域有潜在应用价值。     

Sol-gel synthesis of sub-50 nm ZnO nanowires on pulse laser deposited ZnO thin films

A simple synthesis route to high-quality sub-50 nm ZnO nanowires is reported, utilizing ZnO thin films grown by pulse laser deposition (PLD) as seed layers. Depending upon the PLD growth conditions, the surface morphology of the ZnO nanowires on ZnO film was distinctively different whereas the diameters were almost the same. With the increase of the concentration of zinc nitrate/methenamine solution from 0.002 to 0.02 M, the average diameter of the ZnO nanowire increased but remained sub-50 nm. The grown ZnO nanowires showed a high crystallinity with a low defect density confirmed by a sharp photoluminescence spectrum.     

海胆状ZnO纳米线阵列的制备及其光学性能

采用一种低成本的有效方法制备出了有序排列的海胆状ZnO纳米线阵列。首先利用自组装的方法得到了单层的聚苯乙烯(PS)小球,以其为模板用水热法在小球表面生长ZnO纳米线,得到了由PS小球和ZnO纳米线构成的海胆状结构。纳米线的直径均一,长度可通过水热反应时间进行控制。利用这种方法制备的一维ZnO纳米结构在传感器、太阳能电池及光催化领域有潜在的应用价值。     

Growth of vertically aligned one-dimensional ZnO nanowire arrays on sol–gel derived ZnO thin films

Vertically aligned one-dimensional ZnO nanowire arrays have been synthesized by a hydrothermal method on sol–gel derived ZnO films. Sol–gel derived ZnO films and corresponding ZnO nanowire arrays have been characterized by X-ray diffraction and field-emission scanning electron microscopy. The effect of sol–gel derived ZnO film surface on the morphology of ZnO nanowire arrays has been investigated. The authors suggest from our investigation that sol–gel derived ZnO films affect the growth of one-dimensional ZnO nanostructures. Not only crystalline ZnO films but also amorphous ones can act as a scaffold for ZnO nucleus. Tilted ZnO micro-rods are grown on ZnO gel films, whereas vertically aligned ZnO nanowire arrays are grown on nanometer-sized ZnO grains. The average diameter of ZnO nanowire arrays are correlated strongly with the grain size of sol–gel derived ZnO films.     

Alignment-controlled hydrothermal growth of well-aligned ZnO nanorod arrays

ZnO nanorod arrays (ZNAs) were prepared via a two-step seeding and solution hydrothermal growth process. Effects of preparing parameters such as seed layer, colloid concentration, substrate and precursor concentration, on the alignment control of ZNAs were systematically investigated. The deviation angle of ZnO nanorods was measured to evaluate the alignment of arrays. Results show that seed layer not only controls the vertical orientation of ZNAs, but also the compactness of ZNAs. Altering colloid concentration and substrate can influence the microstructure of ZnO seed layer and affect the ordered alignment of ZNAs. The precursor concentration has an insignificant effect on the alignment of ZNAs but has great impact on the morphology of ZNAs. Alignment-controlled and well-aligned ZnO nanorods with different diameter and aspect ratio can be obtained by properly controlling the preparing parameters. A growth mechanism was proposed for the growth of ZnO nanorods.     

Comparison between ZnO nanowires grown by chemical vapor deposition and hydrothermal synthesis

Vertically aligned zinc oxide nanowires (NWs) were synthesized by two different techniques: chemical vapor deposition (CVD) and hydrothermal synthesis. To compare the effects of different growth conditions, both F-doped SnO₂ (FTO) coated-glass and silicon wafers were used as substrates. Before NWs growth, all the substrates were covered with a ZnO seed layer film obtained with the same procedure, which acts as nucleation site for the subsequent growth of the nanowires both during CVD and hydrothermal synthesis. We studied the influence of the two synthesis techniques and the growth duration on the final morphology, orientation, and density of the ZnO NWs using electron microscopy and X-ray diffraction, while the NWs optical quality was addressed by UV–Vis spectroscopy. By discussing advantages and disadvantages of both synthesis methods, we finally show that the application purpose often drives the choice of the NWs growth process and the substrate to be used.     

Synthesis of ZnO nanowires on aluminum flake by aqueous method

ZnO nanowires are grown on aluminum flake at low temperature by using a simple aqueous solution method. X-Ray Diffraction (XRD), Scanning Electron Microscopy (SEM) and Transmission Electron Microscope (TEM) are applied to determine the as-grown ZnO nanowires morphology and crystal structures. The results show that the ZnO nanowires have wurtzite structure, and the diameter and length of the nanowire are 30 nm and more than 1.5 μm, respectively. Photoluminescence spectroscopy (PL) and Raman spectrum reveal the nanowires have good optical properties with low tensile stress. Meanwhile, photoelectrochemical cell (PEC) study verifies that ZnO nanowires as photoanodes are relatively stable in the photo-oxidation process, which could be a promising technique for practical applications.     

Growth of self-assembled ZnO nanowire arrays

This paper reports on ZnO nanowires arrays synthesized using Sn as a catalyst. The Sn particles were produced from the reduction of SnO₂ powders via a vapour-solid growth process. Control of growth conditions led to the formation of ZnO nanowire arrays, radial nanowire ‘flowers’ and uniaxial fuzzy nanowires. ZnO nanowire–nanobelt junctions were also grown by changing the growth direction. As-grown nanowire arrays could be fundamental materials for investigating physical and chemical properties at nano-scale dimensions.     

Structures of nanowires with Zn-ZnO:CuO junctions for detecting ethanol vapors

The synthesis of ZnO-ZnO:CuO structures in the form of overlapping layers of nanowires of pure and copper oxide-doped zinc oxide is described. These structures are tested as ethanol vapor sensors. The following two-stage method is used to form ZnO:CuO nanowires. At the first stage, ZnO nanowires are formed by chemical deposition from a solution. At the second stage, arrays of ZnO nanowires are coated with a copper-containing layer. The CuO content on the surface of ZnO nanowires is changed by varying the number of immersions in a Cu(NO₃)₂ solution. The formed structures are studied by scanning electron microscopy, X-ray diffraction, and energy dispersive X-ray analysis. The interaction of the grown sensor structures with ethanol vapors is analyzed by measuring the potential difference between the layers of pure zinc oxide and copper oxide-modified zinc oxide in the temperature range 190–300°C. The response of the sensor is investigated at various ethanol vapor concentrations and detection temperatures.     

ZnO three-dimensional hedgehog-like nanostructure: synthesis,growth mechanism and optical enhancement

The 3D hedgehog-like ZnO nanostructures were synthesized on Si substrate through chemical vapor deposition process. The morphology and structure of the products were characterized by X-ray diffraction, Raman spectroscopy, scanning electron microscopy, as well as transmission electron microscopy. The ZnO 3D hedgehog-like architectures were found to consist of a central nucleus and multiple side-growing nanowires with diameter of 100–250 nm and length up to 10 µm. The growth mechanism of the hedgehog-like ZnO nanostructures was studied. It revealed a three-step process during the entire growth. Finally, room temperature photoluminescence spectra of ZnO 3D nanostructures showed that the center excitation would render much stronger PL emission intensity. Furthermore, simulation results indicated that the enhanced emission came from light-trapping-induced excitation light field enhancement.     

One step synthesis of vertically aligned ZnO nanowire arrays with tunable length

Length control of ZnO nanowire arrays is a valuable concern for both fundamental research and future device application. In this article, vertically aligned ZnO nanowire arrays were synthesized by a seed layer catalyzed vapor phase transport method in a single experiment cycle. The length of these nanowire arrays exhibits a quasi-continuous evolution. It was found that the type and flow rate of carrier gas have a significant influence on the length modulation of ZnO arrays along the tube. A feasible route to tune the length of ZnO nanowire arrays from several micrometers to nearly 100 μm could be achieved by adjusting proper deposition position and carrier gas.