Density-controlled growth of aligned ZnO nanowires sharing a common contact: a simple, low-cost, and mask-free technique for large-scale applications

An effective, low cost, simple, and mask-free pathway is demonstrated for achieving density control of the aligned ZnO nanowires grown for large-scale applications. By a slight variation of the thickness of the thermally evaporated gold catalyst film, a significant change in the density of aligned ZnO nanowires has been controlled. The growth processes of the nanowires on an Al(0.5)Ga(0.5)N substrate has been studied based on the wetting behavior of gold catalyst with or without source vapor, and the results classify the growth processes into three categories: separated dots initiated growth, continuous layer initiated growth, and scattered particle initiated growth. This study presents an approach for growing aligned nanowire arrays on a ceramic substrate with the simultaneous formation of a continuous conducting electrode at the roots, which is important for device applications, such as field emission.     

Crystal orientation-ordered ZnS nanowire bundles

We report a novel approach for growing aligned and orientation-ordered ZnS nanowires. Our method relies on a buffer layer of CdSe grown on a Si(111) substrate, on which ZnS nanowires are grown. The growth process of the nanowire bundles is presented. The technique demonstrated could be an effective pathway for growing patterned, aligned, size-controlled, and orientation-ordered ZnS nanowires.     

采用高分子自组装ZnO纳米线及其形成机理

介绍了一种能在各种晶面的硅衬底上制备垂直于衬底取向生长的ZnO纳米线阵列的新方法. 该法采用高分子络合和低温氧化烧结反应, 以聚乙烯醇(PVA)高分子材料作为自组装络合载体来控制晶体成核和生长. 首先通过PVA侧链上均匀分布的极性基团羟基(—OH)与锌盐溶液中的Zn²⁺离子发生络合作用, 然后滴加氨水调节络合溶液pH值为8.5±0.1, 使络离子Zn²⁺转变为Zn(OH)₂, 再将硅片浸入此溶液中, 从而在硅衬底表面得到较均匀的Zn(OH)₂纳米点, 随后在125 ℃左右Zn(OH)₂纳米点通过热分解转化为ZnO纳米点, 其后在420 ℃烧结过程中衬底上的ZnO纳米点在PVA高分子网络骨架对其直径的限域下逐渐取向生长成ZnO纳米线, 并且烧结初期PVA碳化形成的碳通过碳热还原ZnO为Zn, 再在氧气氛中氧化为ZnO的方式在纳米线顶端形成了催化活性点, 促进了纳米线顶端ZnO的吸收. 烧结后碳逐渐氧化被完全去除. 采用场发射扫描电镜(FE-SEM)、透射电镜(TEM, HR-TEM)和X射线衍射(XRD)对纳米线的分析结果表明, ZnO纳米线在硅衬底上分布均匀, 具有六方纤锌矿结构, 并且大多沿[0001]方向择优取向生长, 直径为20～80 nm, 长度可从0.5至几微米. 提出了聚合物控制ZnO结晶和形貌的网络骨架限域模型以解释纳米线的生长行为.     

Patterned growth of vertically aligned ZnO nanowire arrays on inorganic substrates at low temperature without catalyst

We report an approach for growing aligned ZnO nanowire arrays with a high degree control over size, orientation, dimensionality, uniformity, and possibly shape. Our method combines e-beam lithography and a low temperature hydrothermal method to achieve patterned and aligned growth of ZnO NWs at <100degreesC on general inorganic substrates, such as Si and GaN, without using catalyst. This approach opens up the possibility of applying ZnO nanowires as sensor arrays, piezoelectric antenna arrays, two-dimensional photonic crystals, IC interconnects, and nanogenerators.     

Enhanced nucleation, growth rate, and dopant incorporation in ZnO nanowires

Pure and Co-doped ZnO nanowire arrays were grown on polished silicon substrates with high rates via an electrochemical technique. A negative potential applied to the substrate not only enhances the nucleation density on polished substrates more than 4 orders of magnitude but also increases the growth rate by 35 times over that obtained in the absence of the potential. Furthermore, incorporation of metallic dopants in ZnO nanowires was demonstrated in the low-temperature process. This fast growth technique provides a route to fabrication of low-cost highly oriented ZnO nanowires on polished substrate for industrial applications.     

Low-temperature growth of ZnO nanorods by chemical bath deposition

Aligned ZnO nanorod arrays were synthesized using a chemical bath deposition method at normal atmospheric pressure without any metal catalyst. A simple two-step process was developed for growing ZnO nanorods on a PET substrate at 90-95 degrees C. The ZnO seed precursor was prepared by a sol-gel reaction. ZnO nanorod arrays were fabricated on ZnO-seed-coated substrate. The ZnO seeds were indispensable for the aligned growth of ZnO nanorods. The ZnO nanorods had a length of 400-500 nm and a diameter of 25-50 nm. HR-TEM and XRD analysis confirmed that the ZnO nanorod is a single crystal with a wurtzite structure and its growth direction is [0001] (the c-axis). Photoluminescence measurements of ZnO nanorods revealed an intense ultraviolet peak at 378.3 nm (3.27 eV) at room temperature.     

One-dimensional ZnO nanostructure arrays: synthesis and characterization

One-dimensional ZnO nanostructure arrays such as nanowires, nanonails, and nanotrees, have been synthesized by oxygen assisted thermal evaporation of metallic zinc on a quartz substrate over a large area. Morphological evolution of ZnO nanostructures at different time scales and different positions of the substrates have been studied by electron microscopy. A self-catalyzed vapor-liquid-solid (VLS) process is believed to be responsible for the nucleation and subsequently a vapor-solid process is operative for further longitudinal growth. The photoluminescence spectrum showed a weak UV and a broad green emission peak at 3.25 and 2.49 eV, respectively. The latter was attributed to the presence of zinc interstitial defects. Electrical resistivity as a function of temperature showed activated mechanisms to be present. The electrical response of the ZnO nanonail arrays to different gases (CO, NO2, and H2S) indicated that there could be possible application as gas sensors for this material.     

Controlled growth of semiconducting oxides hierarchical nanostructures

Semiconducting ZnO hierarchical nanostructure, where ZnO nanonails were grown on ZnO nanowires, has been fabricated under control experiment with a mixture of ZnO nanopowders and Sn metal powders. Sn nanoparticles are located at or close to the tips of the nanowires and the growth branches, serving as the catalyst for the vapor-liquid-solid growth mechanism. The morphology and microstructure of ZnO nanowire and nanonail were measured by scanning electron microscopy and high-resolution transmission electron microscopy. The long and straight ZnO nanowires grow along [0001] direction. ZnO nanonails are aligned radially with respect to the surface the ZnO nanowire. The long axis direction of nanonails forms an angle of ∼30° to the [0001] direction.     

Comparative structure and optical properties of Ga-, In-, and Sn-doped ZnO nanowires synthesized via thermal evaporation

ZnO nanowires doped with a high concentration Ga, In, and Sn were synthesized via thermal evaporation. The doping content defined as X/(Zn + X) atomic ratio, where X is the doped element, is about 15% for all nanowires. The nanowires consist of single-crystalline wurtzite ZnO crystal, and the average diameter is 80 nm. The growth direction of vertically aligned Ga-doped nanowires is [001], while that of randomly tilted In- and Sn-doped nanowires is [010]. A correlation between the growth direction and the vertical alignment has been suggested. The broaden X-ray diffraction peaks indicate the lattice distortion caused by the doping, and the broadening is most significant in the case of Sn doping. The absorption and photoluminescence of Sn-doped ZnO nanowires shift to the lower energy region than those of In- and Ga-doped nanowires, probably due to the larger charge density of Sn.     

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.     

Attachment-driven morphology evolvement of rectangular ZnO nanowires

The rectangular cross-sectional ZnO nanowires were synthesized in a solution method. An attachment-driven growth mechanism was proposed for the morphology evolvement of ZnO nanocrystals from nanoparticles to nanoplates and eventually to nanowires. Due to the pileup attachment of the nanoplates to recrystallize into nanowires, unique one-dimensional (1D) ZnO nanowires with the rectangular cross section were obtained, which is different from those nanowires in the previous reports. It is the first time the evidence that "oriented attachment" can occur not only for nanoparticles but also for nanoplates was obtained, suggesting that "oriented attachment" is an intrinsic behavior for nanosized materials. According to the growth model proposed based on the direct TEM observations, ZnO nanocrystals can be easily controlled as nanoparticles, nanoplates, or nanowires by tuning the synthetic parameters.     

Growth of large-area aligned molybdenum nanowires by high temperature chemical vapor deposition: synthesis, growth mechanism, and device application

Large-area aligned Mo nanowires have been grown on stainless steel substrates by high-temperature chemical vapor deposition with the use of Mo metal. The detailed physical and chemical growth processes regarding the formation of the nanowires have been investigated using mass spectroscopy, thermogravimetry, and differential scanning calorimetry analysis, as well as structure analysis by electron microscopy. In reference to Gibbs energy calculation, our study reveals that the growth relies on the decomposition of MoO2 vapors through condensation of its vapor at high substrate temperatures. The aligned growth is a result of competing growth with the nanowires normal to the substrate surface reaching the final growth front. The field emission measurement and the vacuum luminescent tube study show that the Mo nanowires have potential application as electron emitters.     

Synthesis and Characterization of ZnO Nanowires

Zinc oxide is a wide bandgap (3.37 eV) semiconductor with a hexagonal wurtzite crystal structure. ZnO prepared in nanowire form may be used as a nanosized ultraviolet light-emitting source. In this study, ZnO nanowires were prepared by vapor-phase transport of Zn vapor onto gold-coated silicon substrates in a tube furnace heated to 900 ?C. Gold serves as a catalyst to capture Zn vapor during nanowire growth. Size control of ZnO nanowires has been achieved by varying the gold film thickness…     

硫化锌与硫化锌/氧化锌异质结纳米线的化学气相沉积法制备与表征

介绍一种利用石墨还原快速制备大量硫化锌纳米线的方法,并分别合成了超晶格型、双轴型、核/壳型的硫化锌/氧化锌异质结纳米线。所合成的硫化锌纳米线存在六方纤锌矿和立方闪锌矿两种晶型,纳米线长度达几十微米,直径在20-50 nm,直径均匀且产量很高。在具有双轴型的硫化锌/氧化锌异质结中,首次发现具有超结构特征的氧化锌。HRTEM分析表明,硫化锌/氧化锌超晶格异质结界面为ZB-ZnS(111)∥ZnO(0001),而核/壳型异质结界面为W-ZnS(0001)∥ZnO(0001),这三个晶面分别为各自晶体的极性面,即所合成的硫化锌/氧化锌异质结中极性面相互平行。对ZnS 和ZnS/ZnO 异质结的生长机制进行了探讨,并对硫化锌纳米线与硫化锌/氧化锌异质结的光学性质进行了分析。     

Molten gallium as a catalyst for the large-scale growth of highly aligned silica nanowires

The vapor-liquid-solid (VLS) process is a fundamental mechanism for the growth of nanowires, in which a small size (5-100 nm in diameter), high melting point metal (such as gold and iron) catalyst particle directs the nanowire's growth direction and defines the diameter of the crystalline nanowire. In this article, we show that the large size (5-50 microm in diameter), low melting point gallium droplets can be used as an effective catalyst for the large-scale growth of highly aligned, closely packed silica nanowire bunches. Unlike any previously observed results using gold or iron as catalyst, the gallium-catalyzed VLS growth exhibits many amazing growth phenomena. The silica nanowires tend to grow batch by batch. For each batch, numerous nanowires simultaneously nucleate, grow at nearly the same rate and direction, and simultaneously stop growing. The force between the batches periodically lifts the gallium catalyst upward, forming two different kinds of products on a silicon wafer and alumina substrate. On the silicon wafer, carrot-shaped tubes whose walls are composed of highly aligned silica nanowires with diameters of 15-30 nm and length of 10-40 microm were obtained. On the alumina substrate, cometlike structures composed of highly oriented silica nanowires with diameters of 50-100 nm and length of 10-50 microm were formed. A growth model was proposed. The experimental results expand the VLS mechanism to a broader range.     

Three dimensional architectures of ultra-high density semiconducting nanowires deposited on chip

We report a "clean" and fast process, utilizing supercritical carbon dioxide, for producing ultrahigh densities, up to 10(12) nanowires per square centimeter, of ordered germanium nanowires on silicon and quartz substrates. Uniform mesoporous thin films were employed as templates for the nucleation and growth of unidirectional nanowire arrays orientated almost perpendicular to a substrate surface. Additionally, these nanocomposite materials display room-temperature photoluminescence (PL), the energy of which is dependent on the diameter of the encased nanowires. The ability to synthesis ultrahigh-density arrays of semiconducting nanowires on-chip is a key step in future "bottom-up" fabrication of multilayered device architectures for nanoelectronic and optoelectronic devices.     

Temperature-controlled growth of ZnO nanowires and nanoplates in the temperature range 250-300 degrees C

Starting from a mixture of Zn and BiI3, we grew nanowires and nanoplates on an oxidized Si substrate at relatively low temperatures of 250 and 300 degrees C, respectively. The ZnO nanowires had diameters of approximately 40 nm and grew along the [110] direction rather than the conventional [0001] direction. The nanoplates had thicknesses of approximately 40 nm and lateral dimensions of 3-4 microm. The growth of both the nanowires and nanoplates is dominated by the synergy of vapor-liquid-solid (VLS) and direction conducting. Analysis of photoluminescence spectra suggested that the nanoplates contain more oxygen vacancies and have higher surface-to-volume ratios than the nanowires. The present results clearly demonstrate that the shapes of ZnO nanostructures formed by using BiI3 can be controlled by varying the temperature in the range 250-300 degrees C.     

Preparation and Photoluminescence of ZnO Nanorods Arrays

A high-density well-aligned Zinc Oxide nanorod array was synthesized on Si (100) substrate by a simplevapor deposition under normal pressure using neither a catalyst and nor pre-deposition of ZnO film. Various different morphologies were obtained in different deposition regions. Si substrate put over the Zn source was the key factor in getting a well-aligned sample. Field emission scanning electron microscope (FESEM) observations and X-ray diffraction were carried out to characterize the surface morphology and crystalline quality of the samples. The growth mechanism is discussed. The photoluminescence properties of the ZnO samples were also investigated. It is suggested that the green band is related to oxygen vacancies and thekinetic process involving transition from shallow donor to deep acceptor level.     

Control of the ZnO nanowires nucleation site using microfluidic channels

We report on the growth of uniquely shaped ZnO nanowires with high surface area and patterned over large areas by using a poly(dimethylsiloxane) (PDMS) microfluidic channel technique. The synthesis uses first a patterned seed template fabricated by zinc acetate solution flowing though a microfluidic channel and then growth of ZnO nanowire at the seed using thermal chemical vapor deposition on a silicon substrate. Variations the ZnO nanowire by seed pattern formed within the microfluidic channel were also observed for different substrates and concentrations of the zinc acetate solution. The photocurrent properties of the patterned ZnO nanowires with high surface area, due to their unique shape, were also investigated. These specialized shapes and patterning technique increase the possibility of realizing one-dimensional nanostructure devices such as sensors and optoelectric devices.     

三维分级结构ZnO的制备及光催化性能

以聚乙烯醇/醋酸锌复合纳米纤维为模板, 采用模板辅助共沉积技术制备了三维尖晶石型ZnO纳米线/纳米纤维分级结构, 并采用SEM, XRD对其形貌和晶型结构进行了表征. 在光催化降解乙醛性能实验中, 三维分级结构ZnO表现出比纳米粒子和纤维更好的光催化性能. 这主要归因于ZnO纳米线的次级结构和开放的三维网络结构更有利于乙醛分子和氧分子的扩散和传输, 从而提高了乙醛的光降解速率.