Controlled Growth of One-Dimensional Oxide Nanomaterials

This article reviews the recent developments in the controlled growth of one-dimensional （1D） oxide nanomaterials, including ZnO, SnO2, In203, Ga203, SiOx, MgO, and Al203. The growth of 2D oxide nanomaterials was carried out in a simple chemical vapor transport and condensation system. This article will begin with a survey of nanotechnology and 1D nanomaterials achieved by many researchers, and then mainly discuss on the controlled growth of ID oxide nanomaterials with their morphologies, sizes, compositions, and microstructures controlled by altering experimental parameters, such as the temperature at the source material and the substrate, temperature gradient in the tube furnace, the total reaction time, the heating rate of the furnace, the gas flow rate, and the starting material. Their roles in the formation of various morphologies are analyzed and discussed. Finally, this review will be concluded with personal perspectives on the future research directions of this area.     

Soft-template mediated synthesis of GaOOH nanorod-shelled microspheres and thermal conversion to beta-Ga2O3

Micrometer-scale hollow spheres self-assembled by GaOOH nanorods were synthesized under hydrothermal conditions using gallium nitrate and sodium hydroxide as starting materials. The structures and morphologies of the products were studied by X-ray diffraction and scanning electron microscopy. Time-dependent experiments revealed three stages involved in the process of reaction including the initial stage of formation of surfactant vesicles which can be considered as soft templates, followed by the nucleation of GaOOH nanoclusters, and the assembling and growth of nanorods under the modulation of the spherical vesicles. The growth kinetics of the GaOOH nanorods was systematically investigated. Based on the experimental observation, a template-mediated assembling mechanism was proposed. We further demonstrated that the GaOOH nanorods could be converted to gallium oxide (beta-Ga2O3) nanorods by calcination without changing the spherical morphology of the assemblies.     

Controlled growth of well-aligned GaS nanohornlike structures and their field emission properties

Here, we report the synthesis of vertically aligned gallium sulfide (GaS) nanohorn arrays using simple vapor-liquid-solid (VLS) method. The morphologies of GaS nano and microstructures are tuned by controlling the temperature and position of the substrate with respect to the source material. A plausible mechanism for the controlled growth has been proposed. It is important to note that the turn-on field value of GaS nanohorns array is found to be the low turn-on field 4.2 V/μm having current density of 0.1 μA/cm(2). The striking feature of the field emission behavior of the GaS nanohorn arrays is that the average emission current remains nearly constant over long time without any degradation.     

The morphology and growth mechanism of TiC whisker prepared by chemical vapour deposition

TiC whiskers with good quality and high yield are prepared by a modified chemical vapour deposition (CVD). The whisker morphology and factors affecting its formation have been investigated. Various whisker morphologies such as Wool-, Hassock-, Cluster-, bar-, Hedgehog-, and bamboo-like, are observed under different conditions. The morphologies of TiC whiskers are markedly affected by the gas flow rate and the C/Ti ratio, which is supposed to be related to concentration variation and the formation of Ni-Ti eutectic liquid phase. The growth characteristics of TiC whiskers are also affected by the stability of deposition parameters. It is found that in the course of whisker growth on nickel substrate, the well known VLS mechanism is not necessarily dominant. It is effective in the initial stage, but then might change to the VS mechanism with the dissipation of liquid droplets at the whisker tips. The deposition temperature plays an important role in changing from the VLS to the VS mechanism.     

Unconventional gallium oxide nanowires

Zigzag and helical beta-Ga(2)O(3) one-dimensional nanostructures were produced by thermal evaporation of gallium oxide in the presence of gallium nitride. High-resolution TEM analysis indicates that each individual zigzag nanostructure has a periodic arrangement of three distinct blocks: two structurally perfect blocks mirrored with respect to each other on the (002) plane, and one stacking-fault-rich block sandwiched between them. In a zigzag nanostructure, the growth orientation of a beta-Ga(2)O(3) crystal changes alternately in three blocks. The zigzag nanostructure as a whole has the [001] axial direction. In addition to zigzag nanostructures, single-crystalline helical nanowires were also obtained.     

Growth mechanism and elemental distribution of beta-Ga2O3 crystalline nanowires synthesized by cobalt-assisted chemical vapor deposition

Long beta-Ga2O3 crystalline nanowires are synthesized on patterned silicon substrates using chemical vapor deposition technique. Advanced electron microscopy indicates that the as-grown beta-Ga2O3 nanowires are consisted of poly-crystalline (Co, Ga)O tips and straight crystalline beta-Ga2O3 stems. The catalytic cobalt not only locates at the nanowire tips but diffuses into beta-Ga2O3 nanowire stems several ten nanometers. A solid diffusion growth mechanism is proposed based on the spatial elemental distribution along the beta-Ga2O3 nanowires at nanoscale.     

碳热还原法合成AIN晶须及其生长机理

以Al2O3和石墨为原料，采用碳热还原法制备AIN晶须.研究了矿化剂的种类及温度等工艺对AIN晶须合成的影响结果表明，以CaF2和B2O3为矿化剂的AIN品须是以VLS机制生长的，高温下VLS机制可以转变为VS机制，同时存在两维成核及螺位错生长过程，晶须生长方向大多呈{101n}，（n=0，1，2，3）及{121m}，（m=0，1；2）的晶面生长     

升华再结晶法制备AIN晶须及其生长特性

以AIN粉体为原料，加入适量的CaO-B2O3矿化剂，采用升华再结晶法制备AIN晶须．初步探讨了反应器及其合成温度对产物种类的影响，研究了晶须的结构特征及其生长机理．结果表明，初期的合成产物包括AIN晶柱、晶须和非晶AIN纤维，以VLS机制生长：后期产物为AIN晶须，表现为VS生长机制：XRD及TEM分析表明，晶须大多呈现沿｛2110｝、｛101l｝和｛0001｝，l＝0、1、2、3的晶面生长．多数晶须宏观生长轴向平行于这些晶面的法线，而部分晶须由于发生斜生长，导致宏观生长轴向与这些晶面的法线斜交．     

Synthesis, Growth Mechanism, and Applications of Zinc Oxide Nanomaterials

This article reviews recent progresses in growth mechanism, synthesis, and applications of zinc oxide nano-materials （mainly focusing on one-dimensional （1D） nanomaterials）. In the first part of this article, we briefly introduce the importance, the synthesis methods and growth mechanisms, the properties and applications of ZnO 1D nanomaterials. In the second part of this article, the growth mechanisms of ZnO 1D nanomaterials will be discussed in detail in the framework of vapor-liquid-solid （VLS）, vapor-solid （VS）, and aqueous solution growth （ASG） approaches. Both qualitative and quantitative information will be provided to show how a controlled synthesis of ZnO 1D nanomaterials can be achieved. In the third part of this article, we present recent progresses in our group for the synthesis of ZnO 1D nanomaterials, and the results from other groups will only be mentioned briefly. Especially, experiment designing according to theories will be elaborated to demonstrate the concept of controlled synthesis. In the fourth part of this article, the properties and potential applications of ZnO 1D nanomaterials will be treated. Finally, a summary part will be presented in the fifth section. The future trend of research for ZnO 1D nanomaterials will be pointed out and key issues to be solved will be proposed.     

Growth time-dependent density and surface evolution of silicon nanowires in a vapor-liquid-solid process

Single crystalline silicon nanowires (SiNWs) were grown on Si(100) substrate using a gold (Au)-catalyzed vapor-liquid-solid (VLS) approach. The dependence of the growth time (i.e., the time of exposure to the Si source) on the density and surface evolution of the grown SiNWs is considered. It was observed that the density of grown SiNWs on Si substrate increased with increasing growth time. The highest density (approximately 1.1 x 10(6) mm(-2)) was reached at 4 hr. Upon further exposure to the Si source, we observed that the density was maintained for up to 9 hr. We suggest that the increased Si chemical potential in Au-Si droplets with increased growth time enhanced the SiNW growth rate at the interfaces between Au-Si droplets and SiNWs, and enhanced the transition of the NWs from the existing Au-Si droplets onto Si substrate. This allows the SiNW density to increase with increased growth time of up to 4 hr. Moreover, we examined the influence of the growth time on surface evolution including Au diffusion, facet and taper formation, and vapor-solid (VS) growth of the SiNWs. To explain the behavior of the grown SiNWs in the VLS process, we propose a combined model using the VLS and VS growth mechanisms.     

陀螺状氮化镓基材料的制备和表征

以碳球为硬模板,通过溶剂热与NH3后处理相结合的方法合成出了具有陀螺状结构形貌的Ga0.97N0.9O0材料.通过X射线衍射(XRD)、场发射扫描电子显微镜(FE-SEM)、X射线能谱(EDS)对所制备的样品进行了表征,同时对其生长机理进行了简要的探讨.     

Conversion between hexagonal GaN and beta-Ga(2)O(3) nanowires and their electrical transport properties

We have observed that the hexagonal GaN nanowires grown from a simple chemical vapor deposition method using gallium metal and ammonia gas are usually gallium-doped. By annealing in air, the gallium-doped hexagonal GaN nanowires could be completely converted to beta-Ga(2)O(3) nanowires. Annealing the beta-Ga(2)O(3) nanowires in ammonia could convert them back to undoped hexagonal GaN nanowires. Field effect transistors based on these three kinds of nanowires were fabricated, and their performances were studied. Because of gallium doping, the as-grown GaN nanowires show a weak gating effect. Through the conversion process of GaN nanowires (gallium-doped) --> Ga(2)O(3) nanowires --> GaN nanowires (undoped) via annealing, the final undoped GaN nanowires display different electrical properties than the initial gallium-doped GaN nanowires, show a pronounced n-type gating effect, and can be completely turned off.     

Structure characteristics of AlN whiskers fabricated by the carbo-thermal reduction method

With Al2O3 and graphite as raw materials, CaF2 and B2O3 as additives, AlN whiskers were fabricated by a carbo-thermal reduction method. The fabrication mechanism and growth characteristics of AlN whiskers were investigated. At the beginning of the high-temperature fabrication, AlN whiskers grew by the vapour/liquid/solid (VLS) mechanism, and defects existed on the surfaces of the whiskers. In later stages, the VLS mechanism possibly changed to a vapour/solid (VS) mechanism, and the defects disappeared. The orientation of most AlN whiskers was normal to (n=0, 1, 2, 3), and normal to (n=0, 1, 2). The growth processes of both two-dimensional nucleation and screw dislocations existed at the same time. © 1998 Kluwer Academic Publishers     

Morphology control of layer-structured gallium selenide nanowires

Layer-structured group III chalcogenides have highly anisotropic properties and are attractive materials for stable photocathodes and battery electrodes. We report the controlled synthesis and characterization of layer-structured GaSe nanowires via a catalyst-assisted vapor-liquid-solid (VLS) growth mechanism during GaSe powder evaporation. GaSe nanowires consist of Se-Ga-Ga-Se layers stacked together via van der Waals interactions to form belt-shaped nanowires with a growth direction along the [11-20], width along the [1-100], and height along the [0001] direction. Nanobelts exhibit a variety of morphologies including straight, zigzag, and saw-tooth shapes. These morphologies are realized by controlling the growth temperature and time so that the actual catalysts have a chemical composition of Au, Au-Ga alloy, or Ga. The participation of Ga in the VLS catalyst is important for achieving different morphologies of GaSe. In addition, GaSe nanotubes are also prepared by a slow growth process.     

Synthesis of In2O3 nanostructures: from pyramidal monuments, nanotowers to nanopencils

We report on the synthesis of In2O3 nanostructures grown at three different growth temperatures by using the thermal evaporation method. The obtained nanostructural morphologies of In2O3 were characterized by field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), and X-ray diffraction (XRD). In2O3 nanopencils and pyramidal monument-like structures were reported. The reaction temperature and the difference of temperature between the central heating zones and the product deposition zones, the reaction time, and the surface energies of different growth planes are all responsible for the final crystalline morphologies of the In2O3 nanostructures. A growth mechanism proposed to elucidate the kinetic factors leading the growth of In2O3 nanostructures. The obtained results may not only assist the investigation of new approaches of preparing various nanostructures for potential technical applications and how to modulate the desired morphology, but also give a deeper understanding of the fundamental physical and chemical processes of CVD methods.     

AN EXAMINATION OF THE GROWTH MODELS FOR TiC WHISKERS MADE BY CVD

Whiskers of refractory compounds such as carbides, nitrides and oxides have been grown by many researchers by chemical vapor deposition. The growth of whiskers from the vapor phase has been suggested to occur by the vapor-solid (VS) and/or the vapor-liquid-solid (VLS) mechanisms. In the growth of TiC whiskers with nickel as the catalyst, the VLS mechanism is widely accepted as the primary initial growth mechanism in which a ternary eutectic of Ni, Ti and C is considered to provide the growth path for the whiskers. In this paper, we examine the published literature on the growth of TiC whiskers by several researchers and show that this view of the ternary eutectic may not explain the whisker growth at temperatures below the eutectic point of the Ti-Ni-C system. This paper attempts to formalize a VLS mechanism model based on a binary eutectic for the observed formation of whiskers at lower temperatures,     

四钛酸钾纤维的反应机制研究

以K2CO3、TiO2为原料,采用混炼-干燥-焙烧工艺制备出四钛酸钾纤维,通过TG—DSC、XRD、SEM等测试手段分析研究了不同TiO2/K2CO3摩尔比时的Ti4O9反应形成机制,实验证明,TiO2／K2CO3摩尔比对纤维的合成有一定的影响,并且用VLS和LS理论对纤维形成给予了解释。     

Synthesis and cathodoluminescence of beta-Ga2O3 nanowires with holes

Gallium oxide nanowires were synthesized on Si (001) substrate by chemical vapor deposition, using a Ga/Ga2O3 mixture as a precursor and Au as a catalyst. The structure of the as-synthesized products was examined by X-ray powder diffraction and high-resolution transmission electron microscopy, and found to be monoclinic beta-Ga2O3. The morphologies of the beta-Ga2O3 nanowires were characterized by scanning electron microscopy. The majority of the nanowires contain holes along their length, but a few were also found without holes. The holes are believed to be formed by the reaction of adsorbed Ga droplets on reactive terminating surfaces of the nanowires. For nanowires where these reactive surfaces are not exposed, the reaction of Ga is retarded. Cathodoluminescence (CL) of the nanowires was measured. Three emission bands centered at 376, 454, and 666 nm, respectively, were observed.     

Synthesis of flower-like CuS nanostructured microspheres using poly(ethylene glycol) 200 as solvent

CuS flower-like microspheres with the diameter of about 3-4 microm constructed by nanoflakes with thickness of about 30-40 nm have been successfully synthesized by a simple wet chemical method. In this reaction system, Poly(ethylene glycol) 200 (PEG 200) was used as solvent, CuCl2 2H2O as cuprum source, and thioacetamide (TAA) as sulfur source. The products were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and high-resolution transmission electron microscopy (HRTEM) in detail. The XRD patterns revealed that the products were pure hexagonal phase of CuS. Experiments with various parameters indicated that the reaction temperature and molar ratio of CuCl2 2H2O to thioacetamide had strong effects on the sizes and morphologies of CuS crystals. A possible growth mechanism on the formation of CuS microspheres was proposed. The PEG 200 acted as solvent, complexing agent, and soft template in this synthesis. Furthermore, optical studies of the products including UV-Vis absorption spectrum and photoluminescence spectrum have also been carried out.     

Fabrication of ZnO Nanoneedle/nanocolumn Composite Films and Annealing Induced Improvement in Their Microstructural and Photoluminescence Characteristics

ZnO nanoneedle/nanocolumn （NN/NC） composite films were grown via reactive electron beam evaporation （REBE） in the NH3/H2 gaseous mixture by using polycrystalline ZnO ceramic targets as source materials. The growth was performed at low substrate temperatures （450～500℃） without employing any metallic catalysts. As-prepared samples were then rapidly annealed in 02 ambient at a higher temperature （600℃）. Electron microscopic observations revealed the typical composite-structured morphologies of NN/NC/substrate of ZnO nanomaterials grown at 500℃. Such unique morphologies should render potential applications, for instance, as an efficient microwave absorption material utilized in the fabrication of concealed aerostat. In addition, X-ray diffraction and photoluminescence measurements showed remarkable improvement in crystal and optical qualities of ZnO NN/NC composite films after annealing.