Synthesis and Characterization of ZnO Ellipsoid-like Nanostructures

"ZnO ellipsoid-like structures assembled by ZnO nanrods were fabricated from common ZnO whiskers by autoclave tests and pyrolysis integrated method. X-ray diffraction, scanning electron microscopy, transmission electron microscopy, selected area electron diffraction, and high resolution transmission electron microscopy studies reveal ZnO ellipsoidal structures are single-crystals and formed from direct oriented attachment of nanorods. Raman and room temperature photoluminescence spectra are also discussed."     

The Development of Highly Sensitive and Selective Immunosensor Based on Antibody Immobilized ZnO Nanorods for the Detection of D‐Dimer

ZnO nanorods were grown on gold coated glass substrate by low temperature aqueous chemical growth method. Scanning electron microscopy (SEM) and X‐ray diffraction (XRD) techniques were used for the characterization of ZnO nanorods. ZnO nanorods are highly dense, uniform, well aligned and perpendicular‐oriented to the substrate. ZnO nanorods exhibited good crystal quality. The well aligned ZnO nanorods were potentially used for the development of selective and sensitive immunosensor for the detection of D‐dimer by immobilizing antibody on stabilized lipid films. The ZnO nanorods based immunosensor responded to a wide range of D‐dimer concentrations with fast response time of ca. 20 s.     

一种在固体基底上制备高度取向氧化锌纳米棒的新方法

采用廉价、低温的方法，在修饰过ZnO纳米粒子膜的ITO基底上成功制备出具有 高长径比、高度取向的ZnO纳米棒阵列，用扫描电子显微镜(SEM)，X射线衍射(XRD) ，高分辨透射电子显微镜(HRTEM)以及拉曼光谱对制备出的ZnO纳米棒的结构和形貌 进行了表征，测试结果表明，ZnO纳米棒是单晶，属于六方晶系，与基底直，上仍 沿(001)晶面择优生长的特征，并且ZnO纳米棒基本上无氧空位的存在，统计结果显 示，水热反应2h后90%以上的ZnO纳米棒直径为120～190nm，长度为4μm     

Various shaped-ZnO nanocrystals via low temperature synthetic methods: Surfactant and pH dependence

ZnO nanocrystals, rod-, carnation-, and flower-like structures, have been synthesized in a high yield through low-temperature synthetic methods. Well-aligned ZnO nanorods having hexagonal wurtzite structure were grown on the ZnO thin films assembled by a spin-coating method. The morphologies of ZnO seed films are affected by pHs of sol–gel solutions, resulting smaller sizes and homogeneous roughness at higher pHs and higher number of spin-coating times. The carnation-like structures, average size of about 2–3 μm, were assembled by tens of uniform ZnO nanosheet petals of ∼50 nm in thickness when a different volume ratio of the precursory solution was used. ZnO nanocrystals on the facets of the compact ZnO nanorods have grown to linear nanorods having an average diameter of ∼500 nm and length of ∼2 μm. Furthermore, a noticeable difference in the growth of ZnO nanocrystals in the presence of various surfactants, polyvinylpyrrolidone, polyvinylsulphonic acid, and polyethyleneimine, has been observed and discussed.     

Structural,optical and magnetic characterization of ZnO nanorods synthesized using hydrothermal technique at low temperature

Pure ZnO nanorods were grown from aqueous solutions at low temperature (90 °C) by hydrothermal growth technique on sapphire (0001) substrate coated with ZnO thin film. X-ray diffraction results show that these nanorods crystallize in the wurtzite structure having space group P6₃mc and that they are oriented along the c-axis. Raman and photo-luminescence studies show the presence of oxygen vacancies in the ZnO nanorods. The ZnO nanorods show room temperature ferromagnetism.     

电沉积种子层化学控制生长氧化锌纳米棒和纳米管

采用水溶液法在电沉积的ZnO种子层上制备了高度取向的ZnO纳米棒阵列,并通过碱溶液化学腐蚀法获得了ZnO纳米管。对ZnO纳米棒和纳米管的溶液生长和腐蚀过程进行了分析。结果表明,种子层的结构和性能对ZnO纳米棒有着重要的影响,在-700 mV电位下沉积的种子层薄膜均匀性好,生长的纳米棒密度大、与基底垂直性好;碱溶液对纳米棒的腐蚀具有选择性,通过控制腐蚀液的浓度和时间,可获得中空的ZnO纳米管。     

Effects of substrates and seed layers on solution growing ZnO nanorods

Oriented ZnO nanorods were fabricated in a two-step approach, including the synthesis of seed layer on different substrates and the growth of ZnO nanorods in aqueous solutions of zinc nitrate and hexamethylenetetramine at low temperature. The effects of seed layer synthesized by different methods, sol–gel method and electrochemical deposition method, on the orientation and morphologies of ZnO nanorods were compared in detail. The optimal parameters for the growth of highly oriented ZnO nanorod arrays were found and the forming mechanism was also disclosed. Furthermore, as an application of the ZnO nanorod film, dye-sensitized solar cells based on it were successfully fabricated. The cell performances of ZnO nanorods grown on ED-ZnO seed layer deposited at −700 mV were higher than those with SG-ZnO seed layer due to good nanostructure.     

ZnO/CuO hetero-hierarchical nanotrees array: hydrothermal preparation and self-cleaning properties

ZnO/CuO heterohierarchical nanotrees array has been prepared via a simple hydrothermal approach combined with thermal oxidation method on Cu substrates. Scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray diffractometer(XRD) are employed to characterize and analyze the as-synthesized samples. The results demonstrate that the secondary growth of ZnO nanorods enclose with CuO nanowires, leading to the formation of ZnO/CuO heterohierarchical nanotrees array. The hierarchical nanostructures have isotropic crystal symmetry and they have no 6-fold (or 4-fold or 2-fold) symmetry as general epitaxial growth. Enlightened by the similarity with microstructure of lotus, the wettability of ZnO/CuO heterohierarchical nanotrees array has been investigated. It is revealed that as-prepared ZnO/CuO nanotrees array after silanization present remarkable superhydrophobic performance, which is attributed to the trapped air and hierarchical roughness. Furthermore, their wettability could be manipulated by the morphologies of hierarchical ZnO nanorods. At the optimal condition, the greatest static angle of water droplet on the obtained heterohierarchical nanotrees array could reach almost 170°, and this substrate could be used as self-cleaning surface.     

氨水溶液制备ZnO纳米晶阵列的研究

以氨水和硝酸锌为前躯体，采用低温水溶液法在涂敷ZnO晶种层的玻璃衬底上外延生长了ZnO纳米棒晶阵列。应用SEM、TEM、SAED和XRD表征了ZnO纳米晶的形貌和结构。讨论了该组成体系水溶液法纳米棒外延生长的机理及其对棒晶形貌的影响。通过对水溶液pH值的原位二次调整，制备出了ZnO纳米管和表面绒毛状的棒晶阵列，基于生长机理探讨了它们的形成原因，为实现不同形貌ZnO纳米晶阵列的优化控制提供了可能的技术途径。结果表明，不同形貌的ZnO均属沿c轴择优取向的六方纤锌矿结构。     

Micro-Raman and photoluminescence study of urchin-like ZnO structure assembled with nanorods synthesized by hydrothermal method

Urchin-like ZnO structures assembled with nanorods have been synthesized by cetyltrimethylammonium bromide-assisted hydrothermal method. The as-obtained products were characterized by powder X-ray diffraction, field-emission scanning electron microscopy for the study of crystal structure and morphology. The ZnO urchin is constructed of well-assembled nanorods of length ~3 μm range and diameter ~20 nm. Micro-Raman study shows characteristic Raman-active mode of hexagonal ZnO at 439 cm⁻¹ and also mode related to defects at ~581 cm⁻¹. The ZnO urchin assembled with nanorods possessed band edge emission at 3.085 eV and defect related visible emission at 2.97, 2.57, and 2.36 eV.     

Bio-inspired fabrication of well-oriented ZnO nanorod arrays film and its superhydrophobicity and superhydrophilicity

A highly oriented ZnO nanorod array film was fabricated on glass substrate by combinations of Sol–Gel and hydrothermal. The film exhibits perfect superhydrophobicity with a contact angle of 155° and a glide angle of 4° after being surface modified by fluoroalkylsilane, which is similar with wings’ property and structures of large yellow spots mosquitoes. Interestingly, the ZnO nanorods film were converted from superhydrophobicity into superhydrophilicity under ultraviolet light for 2 h due to the decomposition of fluoroalkyl chain of fluoroalkylsilane and the photosensitivity of ZnO surface. The transition mechanisms of wettability are discussed on the basis of correlated theories.     

Controlled one-step fabrication of highly oriented ZnO nanoneedle/nanorods arrays at near room temperature

Highly oriented ZnO nanoneedle/nanorods arrays have been fabricated by direct oxidation of zinc foil in alkaline zincate ion solution at near room temperature (20 degrees C for nanoneedles, 30 degrees C for nanorods).     

Morphosynthesis of hierarchical hydrozincite with tunable surface architectures and hollow zinc oxide

Hydrozincite (Zn5(CO3)2(OH)6) microspheres with a tunable surface architecture have been successfully synthesized via a homogeneous precipitation method under solvothermal conditions. For a smooth hydrozincite microsphere, various building blocks such as nanocubes, nanorods, and nanosheets are arranged to cover a spherical surface by concisely controlling reaction time and the volume of ethylene glycol. Hexagonal Zn5(CO3)2(OH)6 with nanostep structures are also prepared without any additives. The hollow ZnO microspheres with a porous surface have been successfully fabricated via a solution-based method by the room-temperature treatment of filled Zn5(CO3)2(OH)6 microspheres composed of nanocubes. A possible growth mechanism of these hollow ZnO microspheres is proposed. The similar filled ZnO microspheres can also be obtained by a direct pyrolysis of Zn5(CO3)2(OH)6 microspheres composed of nanocubes at 450 degrees C.     

Fine-tuning the synthesis of ZnO nanostructures by an alcohol thermal process

A simple and efficient alcohol thermal technique was applied to control the growth of the dimensions and morphology of ZnO nanostructures under mild conditions, where surfactant was not necessary. The size of ZnO nanocrystals increased with growth temperature and they transformed into nanorods with different aspect ratios through tuning the reaction time. The length of nanorods increased significantly with the reaction time, but their thickness only slightly increased. The as-prepared ZnO nanocrystals were monocrystalline and the growth orientation of ZnO nanorods was [001]. Photoluminescence measurements showed a blue shift in violet emission with a reduction in crystal size and revealed the quantum confinement effect. Electron irradiation induced structural damage was observed in the ZnO nanorods synthesized at 120 degrees C. Experimental results proved that the possible growth mechanism of ZnO nanostructures was oriented attachment.     

Hybrid polymer/zinc oxide photovoltaic devices with vertically oriented ZnO nanorods and an amphiphilic molecular interface layer

We report on the effect of nanoparticle morphology and interfacial modification on the performance of hybrid polymer/zinc oxide photovoltaic devices. We compare structures consisting of poly-3-hexylthiophene (P3HT) polymer in contact with three different types of ZnO layer: a flat ZnO backing layer alone; vertically aligned ZnO nanorods on a ZnO backing layer; and ZnO nanoparticles on a ZnO backing layer. We use scanning electron microscopy, steady state and transient absorption spectroscopies, and photovoltaic device measurements to study the morphology, charge separation, recombination behavior and device performance of the three types of structures. We find that charge recombination in the structures containing vertically aligned ZnO nanorods is remarkably slow, with a half-life of several milliseconds, over 2 orders of magnitude slower than that for randomly oriented ZnO nanoparticles. A photovoltaic device based on the nanorod structure that has been treated with an amphiphilic dye before deposition of the P3HT polymer yields a power conversion efficiency over four times greater than that for a similar device based on the nanoparticle structure. The best ZnO nanorod:P3HT device yields a short circuit current density of 2 mAcm(-2) under AM1.5 illumination (100 mW cm(-2)) and a peak external quantum efficiency over 14%, resulting in a power conversion efficiency of 0.20%.     

Temperature-triggered self-assembly of ZnO: from nanocrystals to nanorods to tablets

ZnO nanocrystals, nanorods, and tablets were prepared at 110, 140, and 180 degrees C in a water-ethanol system. Nanorods (~2 x 40 nm) arranged in serpentine morphologies formed by the oriented coalescence of anhedral ZnO nanocrystals (~3.5 nm diameter), while tabular ZnO grew by [1210] textural attachment of the nanorods. The development of these crystal habits is believed to proceed via a dissolution and growth mechanism mediated by a transient amorphous phase. Materials synthesized at intermediate temperatures (125 and 160 degrees C) possessed microstructures containing mixed crystal forms in the expected orientation relationship. Photoluminescent spectra of the nanocrystals and nanorods showed blue shifts of 0.16 and 0.13 eV with respect to the bulk ZnO band gap (3.26 eV) due to quantum confinement, with the narrow emission peaks typical of particles possessing uniform size and shape. The larger tablets displayed a less energetic emission (3.10 eV) ascribed to exciton-exciton collisions.     

基底对电沉积制备ZnO纳米棒阵列的影响

采用恒电位电沉积方法, 在未经修饰的ITO导电玻璃基底上通过控制实验条件制备出不同形貌的纳米ZnO结构, 而在经过ZnO纳米粒子膜修饰后的ITO导电玻璃基底上, 制备出透明、高取向、粒径小于30 nm的ZnO纳米棒阵列. 用扫描电子显微镜(SEM)、X射线衍射(XRD)以及透射光谱对制备出的ZnO纳米棒阵列的结构、形貌和透明性进行了表征. 测试结果表明, ZnO纳米棒阵列的平均直径为21 nm, 粒径分布窄, 约18～25 nm, 择优生长取向为[001]方向, 垂直于基底生长. 当入射光波长大于400 nm时, ZnO纳米棒阵列的透光率大于95%.     

胶带表面优异防覆冰性能

通过在普通胶带表面黏结聚甲基丙烯酸甲酯(PMMA)微米球,再通过水热法在微米球表面制备规则的ZnO纳米棒结构,经氟化处理后得到了具有柔性、大面积、低温超疏水和防冰性能的薄膜.低温环境中,液滴在这种复合的微纳米结构表面可以实现结冰延迟.经历结冰-融化循环后,液滴的界面未发生明显变化,证明了该结构的可靠性.这种抗结冰的薄膜是建立在胶带和PMMA基础之上的,在风电、高压线缆以及冰箱制造工业中具有良好的应用前景.     

氧化锌纳米棒微结构光电极的制备

通过两步法,即首先热分解醋酸锌制备氧化锌晶种层,在晶种的诱导下,再采用低温水热法在氟掺杂的SnO₂导电玻璃(fluorine-doped tin oxide, FTO)基底导电面上成功制备出高取向性的氧化锌纳米棒阵列光电极。系统研究了前驱液浓度、溶液pH值、反应时间等实验条件对光电极微结构的影响。实验结果表明在一定变化范围内,随着前驱液浓度和溶液pH值的增大,纳米棒的直径增大;随着反应时间的延长,纳米棒的长度增长。将氧化锌纳米棒阵列薄膜制作成染料敏化太阳电池(dye-sensitized solar cell, DSSC)的光电极,并对电池的I-V特性进行了表征。     

微观尺度高分子协同组装ZnO纳米片

以醇水混合体系作为反应介质,六水合硝酸锌和尿素为原料,聚乙烯吡咯烷酮(PVP)作为模板剂,经水热过程合成了由纳米片组装的花状微球碱式碳酸锌前驱体,经热处理得到相应的氧化锌(ZnO)产物。采用X射线衍射(XRD)和环境扫描电镜(SEM)对样品进行了表征,结果表明产物为六方纤维矿结构的ZnO,单分散花状微球直径约为2 μm,尺寸均一,组装成微球的纳米片构筑单元厚度为20 nm。红外分析表明PVP与Zn²⁺之间的化学配位作用发生在侧环的内酰基C=O键上的O位与Zn²⁺之间,研究表明PVP用量影响组装过程,在相同实验条件下,用聚乙二醇(PEG)代替PVP的模板作用,得到了粒径较大的纳米片组装的微球(φ～15 μm),在此基础上探讨了高分子结构对晶体生长和组装机制的影响。