ZnO纳米棒水热法生长与表征

采用两步法在FTO导电玻璃衬底上制备ZnO纳米棒,首先利用浸渍-提拉法在FTO导电玻璃衬底上制备ZnO晶种层,然后把有ZnO晶种层的FTO衬底放入盛有生长溶液的反应釜中利用水热法制备ZnO纳米棒.研究了生长溶液的浓度、生长温度和生长时间对所制备的对ZnO纳米棒阵列的微结构和光致发光性能的影响,利用X射线衍射(XRD)、扫描电子显微镜(SEM)和光致发光谱(PL)研究了ZnO样品的结构、形貌和光学性质.实验结果表明:所制备的ZnO纳米棒呈现六方纤锌矿结构,沿(002)晶面择优取向生长,纳米棒的平均直径约为100 nm,长度约为2.5 μm.所制备的ZnO纳米棒在390 nm附近具有很强的紫外发光峰和在550 nm附近有较弱的宽绿光发光峰.     

Selective Growth of Vertical-aligned ZnO Nanorod Arrays on Si Substrate by Catalyst-free Thermal Evaporation

By thermal evaporation of pure ZnO powders, high-density vertical-aligned ZnO nanorod arrays with diameter ranged in 80–250 nm were successfully synthesized on Si substrates covered with ZnO seed layers. It was revealed that the morphology, orientation, crystal, and optical quality of the ZnO nanorod arrays highly depend on the crystal quality of ZnO seed layers, which was confirmed by the characterizations of field-emission scanning electron microscopy, X-ray diffraction, transmission electron microscopy, and photoluminescence measurements. For ZnO seed layer with wurtzite structure, the ZnO nanorods grew exactly normal to the substrate with perfect wurtzite structure, strong near-band-edge emission, and neglectable deep-level emission. The nanorods synthesized on the polycrystalline ZnO seed layer presented random orientation, wide diameter, and weak deep-level emission. This article provides a C-free and Au-free method for large-scale synthesis of vertical-aligned ZnO nanorod arrays by controlling the crystal quality of the seed layer.     

Growth temperature dependent properties of ZnO nanorod arrays on glass substrate prepared by wet chemical method

In this work, ZnO nanorod arrays were grown on glass substrate by the wet chemical method, and the effect of synthesis temperature on the properties was investigated. The grown nanorods were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), Raman and Photoluminescence (PL) measurements. XRD pattern showed that nanorod prepared at 80 °C and 90 °C has high crystallinity with wurtzite structure and orientated along the c-axis. However, nanorods were not formed at 60 °C and 70 °C due to less energy supply for the growth of the ZnO. FE-SEM results showed that the morphology and the size of ZnO can be effectively controlled. In particular, as the temperature increased, diameter of the nanorod was increased while length decreased. Raman scattering spectra of ZnO nanorod arrays revealed the characteristic E₂^high mode that is related to the vibration of oxygen atoms in the wurtzite ZnO. Room-temperature PL spectra of the ZnO nanorods revealed a near-band-edge (NBE) emission peak. The NBE (UV light emission) band at ~383 nm might be attributed to the recombination of free exciton. The narrow full-width at half-maximum (FWHM) of the UV emission indicated that ZnO nanorods had high crystallinity.     

Room-temperature nonequilibrium growth of controllable ZnO nanorod arrays

In this study, controllable ZnO nanorod arrays were successfully synthesized on Si substrate at room temperature (approx. 25°C). The formation of controllable ZnO nanorod arrays has been investigated using growth media with different concentrations and molar ratios of Zn(NO₃)₂ to NaOH. Under such a nonequilibrium growth condition, the density and dimension of ZnO nanorod arrays were successfully adjusted through controlling the supersaturation degree, i.e., volume of growth medium. It was found that the wettability and electrowetting behaviors of ZnO nanorod arrays could be tuned through variations of nanorods density and length. Moreover, its field emission property was also optimized by changing the nanorods density and dimension.     

SnO2 nanorod arrays: low temperature growth, surface modification and field emission properties

SnO(2) nanorod arrays have been deposited on 4 inch SiO(2)/Si and Si wafers and stainless steel substrates by plasma-enhanced chemical vapor deposition without any high temperature treatment or additional catalysis. The SnO(2) nanorods grow up from seed nanocrystals along the [110] preferential direction by a self-catalyzed vapor-solid growth mechanism. The surface of the SnO(2) nanorods was modified by ZnO, Pt and Ni nanocrystals. After surface modification, the field emission properties of the SnO(2) nanorod arrays are improved. The Ni nanocrystal with sharp tips and edges act as additional field emission sites to SnO(2) nanorods and thus the Ni/SnO(2)/SiO(2)/Si outperforms other samples due to the synergistic effects of good conductivity and hierarchical sharp apexes. The field enhancement factor of the Ni/SnO(2)/SiO(2)/Si increased around 3 times while the turn-on field of 8.0 V μm(-1) is about one third of the SnO(2)/SiO(2)/Si device.     

Fabrication and characterization of silicon wire solar cells having ZnO nanorod antireflection coating on Al-doped ZnO seed layer

In this study, we have fabricated and characterized the silicon [Si] wire solar cells with conformal ZnO nanorod antireflection coating [ARC] grown on a Al-doped ZnO [AZO] seed layer. Vertically aligned Si wire arrays were fabricated by electrochemical etching and, the p-n junction was prepared by spin-on dopant diffusion method. Hydrothermal growth of the ZnO nanorods was followed by AZO film deposition on high aspect ratio Si microwire arrays by atomic layer deposition [ALD]. The introduction of an ALD-deposited AZO film on Si wire arrays not only helps to create the ZnO nanorod arrays, but also has a strong impact on the reduction of surface recombination. The reflectance spectra show that ZnO nanorods were used as an efficient ARC to enhance light absorption by multiple scattering. Also, from the current-voltage results, we found that the combination of the AZO film and ZnO nanorods on Si wire solar cells leads to an increased power conversion efficiency by more than 27% compared to the cells without it.     

Effect of ZnO seed layers on the solution chemical growth of ZnO nanorod arrays

High density ZnO nanorod arrays were grown on Si substrates coated with ZnO seed layers via aqueous solution route. The ZnO seed layers were deposited on the substrate using DC reactive sputtering and RF magnetron sputtering. It was found that ZnO seed layer with (1 0 3) preferred orientation, prepared using DC reactive sputtering, did not facilitate the formation of ZnO nanorods in the solution grown process. Prior seeding of the surface by ZnO layer with (0 0 2) preferred orientation, deposited using RF magnetron sputtering, leads to nucleation sites on which ZnO nanorod arrays can grow in a highly aligned fashion. ZnO nanorods with well-defined hexagonal facets (0 0 2) were grown almost vertically over the entire substrate. The uniformity and alignment of the nanorod arrays are strongly related to the properties of underneath ZnO seed layers.     

Growth of ZnO Nanorods by the Chemical Solution Method with Assisted Electrical Field

Zinc oxide (ZnO) nanorod arrays on the ZnO-coated seed substrates were prepared by the solution chemical method from Zn(NO₃)₂/NaOH under an assisted electrical field. The influence of the electrical field on ZnO nanorod growth was primarily explored, and the positive effects of the electrical field were demonstrated by adding polyethylene glycol in growth solution. It has been proved that the electrical field enhances ion adsorption to the substrate and lowers the nucleation energy barrier by increasing charge intensity; meanwhile, it produces H⁺ through oxidation of OH⁻ and increases properly the degree of solution supersaturation near the substrate surface. XRD results show that the nanorods grown under the electrical field primarily have a zincite structure. With increasing precursor concentration, the average diameter and length of ZnO nanorods increase. The maximum rod growth rate at a given concentration of Zn²⁺ ion occurs at a specific temperature.     

Growth of vertically aligned ZnO nanorods using textured ZnO films

A hydrothermal method to grow vertical-aligned ZnO nanorod arrays on ZnO films obtained by atomic layer deposition (ALD) is presented. The growth of ZnO nanorods is studied as function of the crystallographic orientation of the ZnO films deposited on silicon (100) substrates. Different thicknesses of ZnO films around 40 to 180 nm were obtained and characterized before carrying out the growth process by hydrothermal methods. A textured ZnO layer with preferential direction in the normal c-axes is formed on substrates by the decomposition of diethylzinc to provide nucleation sites for vertical nanorod growth. Crystallographic orientation of the ZnO nanorods and ZnO-ALD films was determined by X-ray diffraction analysis. Composition, morphologies, length, size, and diameter of the nanorods were studied using a scanning electron microscope and energy dispersed x-ray spectroscopy analyses. In this work, it is demonstrated that crystallinity of the ZnO-ALD films plays an important role in the vertical-aligned ZnO nanorod growth. The nanorod arrays synthesized in solution had a diameter, length, density, and orientation desirable for a potential application as photosensitive materials in the manufacture of semiconductor-polymer solar cells.

PACS

61.46.Hk, Nanocrystals; 61.46.Km, Structure of nanowires and nanorods; 81.07.Gf, Nanowires; 81.15.Gh, Chemical vapor deposition (including plasma-enhanced CVD, MOCVD, ALD, etc.)     

Influence of Y-doped induced defects on the optical and magnetic properties of ZnO nanorod arrays prepared by low-temperature hydrothermal process

ABSTRACT: One-dimensional pure zinc oxide (ZnO) and Y-doped ZnO nanorod arrays have been successfully fabricated on the silicon substrate for comparison by a simple hydrothermal process at the low temperature of 90°C. The Y-doped nanorods exhibit the same c-axis-oriented wurtzite hexagonal structure as pure ZnO nanorods. Based on the results of photoluminescence, an enhancement of defect-induced green-yellow visible emission is observed for the Y-doped ZnO nanorods. The decrease of E2(H) mode intensity and increase of E1(LO) mode intensity examined by the Raman spectrum also indicate the increase of defects for the Y-doped ZnO nanorods. As compared to pure ZnO nanorods, Y-doped ZnO nanorods show a remarked increase of saturation magnetization. The combination of visible photoluminescence and ferromagnetism measurement results indicates the increase of oxygen defects due to the Y doping which plays a crucial role in the optical and magnetic performances of the ZnO nanorods.     

Effects of dye etching on the morphology and performance of ZnO nanorod dye-sensitized solar cells

Dye-sensitized solar cells based on electrodeposited ZnO nanorod arrays were fabricated and tested. Field-emission scanning electron microscopy (FESEM) and X-ray powder diffraction (XRD) were used to identify the characters of ZnO nanorod arrays. The effects of dye etching on the morphology and performance of ZnO nanorod dye-sensitized solar cells were studied. It was found that the surfaces of ZnO nanorods were both etched by dye solutions, no matter N3 or N719. Compared with N3, N719 had a larger damage to the structure of ZnO nanorod photoanode, and the photoelectric conversion efficiency of cells decreased quickly with the sensitizing time increasing. In a certain range, the increasing length of ZnO nanorods can clearly improve the photoelectric conversion efficiency of cells.     

Seedless Pattern Growth of Quasi-Aligned ZnO Nanorod Arrays on Cover Glass Substrates in Solution

A hybrid technique for the selective growth of ZnO nanorod arrays on wanted areas of thin cover glass substrates was developed without the use of seed layer of ZnO. This method utilizes electron-beam lithography for pattern transfer on seedless substrate, followed by solution method for the bottom-up growth of ZnO nanorod arrays on the patterned substrates. The arrays of highly crystalline ZnO nanorods having diameter of 60 ± 10 nm and length of 750 ± 50 nm were selectively grown on different shape patterns and exhibited a remarkable uniformity in terms of diameter, length, and density. The room temperature cathodluminescence measurements showed a strong ultraviolet emission at 381 nm and broad visible emission at 585–610 nm were observed in the spectrum.     

A two-step route to synthesize highly oriented ZnO nanotube arrays

Large-scale and highly oriented ZnO nanotube arrays are synthesized on transparent conductive glass substrates by a two-step route. First, ZnO nanorod arrays were prepared by electrochemical deposition from an aqueous solution of zinc nitrate. Then, hollow ZnO nanotubes were obtained by the selective dissolution of the electrodeposited ZnO nanorods in potassium hydroxide solution. Field emission scanning electron microscopy (FESEM) and X-ray powder diffraction (XRD) have been used to characterize the morphology and structure of the derived products. The effect of the concentration of alkali, dissolution time, and temperature on the formation process and morphologies of ZnO nanotube arrays has been discussed.     

Microcontact Printing of Organic Self-Assembled Monolayers for Patterned Growth of Well-Aligned ZnO Nanorod Arrays and their Field-Emission Properties

This paper describes a simple method for preparing well-aligned ZnO nanorod arrays in a more tunable fashion, which enables the synthesis of nanorods directly in various patterns and the easy control of the array density. This method is based on a combination of the microcontact printing process for patterning and a solution approach for depositing ZnO nanorods. The growth behavior between the contact and noncontact areas is investigated. Different formation mechanisms are proposed, and it is found that the key difference between nanorod and microrod forms was the ZnO seed layer and the van der Waals force at specific conditions. The role of self-assembled monolayers of octadecyl-trichloro-silane in the reaction solution is also discussed. Wettability of the surfaces is assessed by measuring the water contact angle, and the results show significant variation with surface morphology, from 17.6° to 123.6°. The lowest turn-on applied field strength is 4.65 V/μm at the current density of 10 μA/cm², which is achieved by the lowest array density of nanorods. The field-emission characteristics of the nanorods are found to be highly reproducible. The results could be valuable for the application of field-emission-based devices using ZnO nanorod arrays as cathode materials.     

氧化锌纳米棒阵列对芳纶的改性

利用湿化学方法在芳纶Ⅲ表面预制氧化锌(ZnO)晶种层,再在晶种膜的基础上制备出了垂直生长的ZnO纳米棒阵列。采用X射线衍射(XRD)、场发射扫描电镜(FE-SEM)和微脱黏试验对纤维表面的组成、形貌及复合材料的界面黏结性能进行了研究。结果表明:纤维表面生长的ZnO纳米棒阵列属于六方纤锌矿晶相,纳米棒垂直生长在纤维表面,增大了与基体的接触面积,能够使纤维更好地与环氧树脂基体间发生界面结合,进而有效改善芳纶Ⅲ-环氧复合材料的界面黏接强度。     

Structural and optical properties of ZnO nanorods by electrochemical growth using multi-walled carbon nanotube-composed seed layers

We reported the enhancement of the structural and optical properties of electrochemically synthesized zinc oxide [ZnO] nanorod arrays [NRAs] using the multi-walled carbon nanotube [MWCNT]-composed seed layers, which were formed by spin-coating the aqueous seed solution containing MWCNTs on the indium tin oxide-coated glass substrate. The MWCNT-composed seed layer served as the efficient nucleation surface as well as the film with better electrical conductivity, thus leading to a more uniform high-density ZnO NRAs with an improved crystal quality during the electrochemical deposition process. For ZnO NRAs grown on the seed layer containing MWCNTs (2 wt.%), the photoluminescence peak intensity of the near-band-edge emission at a wavelength of approximately 375 nm was enhanced by 2.8 times compared with that of the ZnO nanorods grown without the seed layer due to the high crystallinity of ZnO NRAs and the surface plasmon-meditated emission enhancement by MWCNTs. The effect of the MWCNT-composed seed layer on the surface wettability was also investigated.     

Effect of Microstructure of ZnO Nanorod Film on Humidity Sensing

In this study, a simple thick‐film humidity sensor was fabricated by coating wet‐synthesized ZnO nanorods on screen‐printing interdigitated electrodes. We investigated the influence of the coating procedure on the microstructure of ZnO nanorod films and thereby on humidity sensing. The experimental results revealed that the specific surface area (SSA) decreased and the average pore size (APS) increased with increasing the sintering time and the number of coating layer. The humidity response depended significantly on the pore properties of the ZnO nanorod films. By virtue of the incipient wetness analysis, it was found that the adsorption of water molecules on the ZnO surface led to the decrease in electrical resistance even though the ZnO was rod like, n‐type semiconductor. While tuning the pore structure of the ZnO nanorod film, the thick‐film humidity sensor might display near‐linear response in the full range of 0%–100% relative humidity (RH).     

Improving the field emission of graphene by depositing zinc oxide nanorods on its surface

Zinc oxide (ZnO) nanorods were vertically grown on the surface of graphene sheets by chemical vapor deposition, and their use in a field emission device was demonstrated. In comparison with pristine graphene, the graphene/ZnO nanorod hybrid structure exhibited efficient field emission with low turn-on field, low threshold field, high emission spot density, high field enhancement factor and excellent emitting stability. It is proposed that the introduction of mid-density ZnO nanorods on the surface of graphene sheets can increase the number of emitters, enhance tunneling probability, and lead to optimized field emission for the hybrid emitters. The results showed that the field emission properties of graphene can be tailored by growing various ZnO nanostructures on its surface.     

Effect of Aspect Ratio on Field Emission Properties of ZnO Nanorod Arrays

ZnO nanorod arrays are prepared on a silicon wafer through a multi-step hydrothermal process. The aspect ratios and densities of the ZnO nanorod arrays are controlled by adjusting the reaction times and concentrations of solution. The investigation of field emission properties of ZnO nanorod arrays revealed a strong dependency on the aspect ratio and their density. The aspect ratio and spacing of ZnO nanorod arrays are 39 and 167 nm (sample C), respectively, to exhibit the best field emission properties. The turn-on field and threshold field of the nanorod arrays are 3.83 V/μm and 5.65 V/μm, respectively. Importantly, the sample C shows a highest enhancement of factor β, which is 2612. The result shows that an optimum density and aspect ratio of ZnO nanorod arrays have high efficiency of field emission.     

Highly Uniform Epitaxial ZnO Nanorod Arrays for Nanopiezotronics

Highly uniform and c-axis-aligned ZnO nanorod arrays were fabricated in predefined patterns by a low temperature homoepitaxial aqueous chemical method. The nucleation seed patterns were realized in polymer and in metal thin films, resulting in, all-ZnO and bottom-contacted structures, respectively. Both of them show excellent geometrical uniformity: the cross-sectional uniformity according to the scanning electron micrographs across the array is lower than 2%. The diameter of the hexagonal prism-shaped nanorods can be set in the range of 90–170 nm while their typical length achievable is 0.5–2.3 μm. The effect of the surface polarity was also examined, however, no significant difference was found between the arrays grown on Zn-terminated and on O-terminated face of the ZnO single crystal. The transmission electron microscopy observation revealed the single crystalline nature of the nanorods. The current–voltage characteristics taken on an individual nanorod contacted by a Au-coated atomic force microscope tip reflected Schottky-type behavior. The geometrical uniformity, the designable pattern, and the electrical properties make the presented nanorod arrays ideal candidates to be used in ZnO-based DC nanogenerator and in next-generation integrated piezoelectric nano-electromechanical systems (NEMS).