Magnetically Assembled Multisegmented Nanowires and Their Applications

Here we report a cost effective and versatile way of synthesizing and assembling multi‐functional (e.g., gold‐polypyrrole‐nickel‐gold) nanowires. Multisegmented nanowires were synthesized using electrodeposition method for precise control over segment dimensions for proper expression of material functionality. The nanowires were integrated on microfabricated electrodes using magnetic dipole interactions between the ferromagnetic segment in the nanowire and the ferromagnetic electrodes. The electrical properties of multisegmented nanowires showed semiconducting behavior with the activation energy of ca. 0.27 eV for the conducting polymer segment of the nanowire. These nanowire devices showed response towards light and exposure to ammonia, demonstrating their potential use as photonic device and gas sensor, respectively.     

Formation of nanowire striations driven by Marangoni instability in spin-cast polymer thin films

Parallel striations made of silver nanowires were formed through the Marangoni instability induced during spin casting of poly(2-vinyl pyridine)/silver nanowire/chloroform solutions. The striation patterns of the silver nanowires resembled those obtained from spin casting of the corresponding neat polymer solutions, indicating essentially the same driving mechanism (i.e., the Marangoni instability). The silver nanowires were found to concentrate in the valleys of the striation pattern to balance the nonuniform surface tension distribution in the polymer thin film. The resulting nanowire striation patterns were found to depend on polymer concentration, rotational speed, and nanowire loading. Interestingly, this nanowire striation phenomenon was found to be independent of the substrate characteristics, hydrophobic or hydrophilic.     

Magnetic cobalt nanowire thin films

Two-dimensional (2D) and three-dimensional (3D) magnetic cobalt nanowire thin films with tunable 3-10 nm wire diameters have been electrodeposited using mesoporous silica templates containing 2D hexagonal or 3D cubic pore channels. As compared to bulk cobalt films, the cobalt nanowire thin films exhibit enhanced coercivities and controllable magnetic anisotropy through tuning of the mesostructure and dimension of the nanowires. Such novel magnetic nanowire thin films may provide a new platform for high-density information storage applications.     

Inorganic semiconductor nanowires: rational growth, assembly, and novel properties

Rationally controlled growth of inorganic semiconductor nanowires is important for their applications in nanoscale electronics and photonics. In this article, we discuss the rational growth, physical properties, and integration of nanowires based on the results from the authors' laboratory. The composition, diameter, growth position, and orientation of the nanowires are controlled based on the vapor-solid-liquid (VLS) crystal growth mechanism. The thermal stability and optical properties of these semiconductor nanowires are investigated. Particularly, ZnO nanowires with well-defined end surfaces can function as room-temperature ultraviolet nanolasers. In addition, a novel microfluidic-assisted nanowire integration (MANI) process was developed for the hierarchical assembly of nanowire building blocks into functional devices and systems.     

钼硫碘纳米线结构特性和化学改性的理论研究

 采用第一性原理密度泛函理论研究了纳米线结构的钼硫碘材料. 结构的理论模拟结果显示, 钼硫碘纳米线机械性能很高, 且其形变过程中显示出一种特殊的磁滞现象. 形成能、投影态密度以及电荷密度的计算结果显示, 使用电负性接近硫的碳元素可对钼硫碘纳米线化学改性同时不失去其良好的结构性能和电子性能. 该结果为化学改性钼硫碘纳米线材料应用于催化提供了依据. 这些钼硫碘纳米线材料将在纳米电子学、纳米机械学、催化、纳米限域等研究中有潜在应用.     

Symmetry controlled spin polarized conductance in au nanowires

The fact that the resistance of propagating electrons in solids depends on their spin orientation has led to a new field called spintronics. With the parallel advances in nanoscience, it is now possible to talk about nanospintronics. Many works have focused on the study of charge transport along nanosystems, such as carbon nanotubes, graphene nanoribbons, or metallic nanowires, and spin dependent transport properties at this scale may lead to new behaviors due to the manipulation of a small number of spins. Metal nanowires have been studied as electric contacts where atomic and molecular insertions can be constructed. Here we describe what might be considered the ultimate spin device, namely, a Au thin nanowire with one Co atom bridging its two sides. We show that this system has strong spin dependent transport properties and that its local symmetry can dramatically change them, leading to a significant spin polarized conductance.     

On the disorder of the Cl atom position in and its probable effect on the magnetic properties of (CuCl)LaNb2O7

The magnetic susceptibility of (CuCl)LaNb2O7 shows a spin gap despite the Cu(2+) ions in each CuClO2 layer forming a square lattice. To account for this observation, we explored implications of the disorder of the Cl-atom position in (CuCl)LaNb2O7 by considering possible ordered structures of CuCl4O2 octahedra in each CuClO2 layer, by identifying various spin exchange interactions of a CuClO2 layer and by estimating the relative strengths of these interactions in terms of spin dimer analysis. We then probed what kind of spin lattice is required for each CuClO2 layer to have a spin gap on the basis of the classical spin approximation. Our study suggests that the CuCl4O2 octahedra of each CuClO2 layer should be arranged such that the resulting spin lattice does not have uniform chains but ring clusters containing an even number of Cu atoms. Implications of this conclusion were discussed on the basis of the recently reported neutron scattering and magnetization studies of (CuCl)LaNb2O7.     

TiO2纳米线的制备及其光电性能研究

利用在钛箔表面沉积一层TiO₂纳米粒子作为晶种，与NaOH反应，制备了一维物质TiO₂纳米线。并用XRD、SEM、TEM、HRTEM及EDS等分析手段对TiO₂纳米线的成分、形貌、结构进行表征。结果表明，采用该方法制得的TiO₂纳米线直径在20～50 nm左右、长度可达几微米。反应温度能显著影响所得纳米线的形貌。研究了TiO₂纳米线的光电化学性能。随反应温度的升高TiO₂纳米线光电转换效率增大。     

Magnetic field assisting DC electrodeposition: general methods for high-performance Ni nanowire array fabrication

One-dimensional magnetic nanowires are generally thought to show fine axial magnetism for their special high aspect ratio of the shape. However, the magnetic nanowire arrays fabricated by DC electrodeposition in template pores always show a low squareness in parallel to the nanowire direction. We developed two general and simple methods to improve the squareness of the as-fabricated Ni nanowire arrays parallel to the nanowire direction. The nanowires are found to be polycrystalline. The magnetism of the nanowire is also analyzed based on the microstructure.     

Hunting for a maximum highly-energetic facet that interplays with spatial charge storage for enhanced catalytic activity

Exposure of highly-energetic facets challenges one's capabilities of designing new substances at the atomic level and of exploiting novel physicochemical properties. We report herein on TiO(2) microspheres with a maximum exposure of the highly-energetic facet (001). Intriguingly, these microspheres were fabricated by bundles of adjacent nanowires that grow roughly parallel along the c-axis from sphere centres to outward surfaces. In between these nanowires, there existed nanoscale boundary cavities. Reducing the nanowire diameter led to a lattice expansion, and meanwhile nanoscale boundary cavities in between nanowires were tailored to possess an optimum charge storage at a nanowire diameter of 6.2 nm. This charge storage could suppress the combination of photo-generated holes and electrons. Furthermore, owing to the lattice expansion, photo-generated holes were promoted to transfer along the c-axial to the highly-energetic facet (001) to produce reactive hydroxyl radicals. As a consequence, under UV-light irradiation, microspheres with a nanowire diameter of 6.2 nm showed a maximum photocatalytic activity among all nanowire diameters. When the microspheres were broken into segments, the catalytic activities were further enhanced and even superior to commercial P25, because of sufficient utilization of incident light. The methodology reported in this work is fundamentally important, and may offer opportunities for exploring highly-energetic facets of micro-architectures that interplay with spatial charge storage to active novel surface activities, potentially useful in various catalytic applications.     

Comparable Studies of Adsorption and Magnetic Properties of Ferrite MnFe_2O_4 Nanoparticles,Porous Bulks and Nanowires

The spinel ferrites MnFe2O4 nanowires were synthesized by hydrothermal route,porous MnFe2O4 and nanoparticles morphologies were synthesized by sol-gel method with egg white.The structures,morphologies,magnetic properties and adsorption properties of these obtained ferrites with different morphologies were studied contrastively.Results show that the obtained samples exhibit ferromagnetic properties.This realizes convenient magnetic separation from solution when they are used in the treatment of organic dyes ...     

Ni 掺杂ZnO纳米线的电子结构与磁性

采用自旋极化密度泛函理论系统研究了Ni掺杂ZnO纳米线的电子结构、磁学和光学性质.磁学性质计算结果显示六种Ni掺杂ZnO纳米线的磁性耦合体系出现了铁磁(FM)、反铁磁(AFM)和顺磁(PM)二种不同的耦合状态.能量计算结果表明Ni原子在纳米线外表面沿[0001]方向替代Zn原子时能量最低,体系的AFM耦合相对稳定,AFM体系表现出金属性.态密度计算结果显示FM耦合在费米能级附近出现了明显的自旋极化现象,发生了强烈的Ni 3d和O 2p杂化效应,掺杂产生的磁矩主要来源于Ni 3d未成对轨道电子和部分O 2p轨道电子的贡献,FM耦合表现出半金属性.另外,光学性质计算结果显示Ni掺杂ZnO纳米线的远紫外吸收峰发生了红移现象,而380 nm附近的近紫外吸收峰发生了明显的蓝移现象,在整个紫外区都表现出了优异的发光性能.以上结果表明Ni掺杂ZnO纳米线是一种很有前途的磁光电子材料.     

A controllable transformation in copper valence states and its applications

The present study revealed a surprising valence transformation of copper (Cu) in the sintering process of mixtures of copper chloride dihydrate (CuCl(2)·2H(2)O) with β-cyclodextrin (β-CD) in ambient atmosphere. Such a transformation in Cu valence states can be modulated by changing the initial molar ratio (IMR) of CuCl(2)·2H(2)O to β-CD in the mixtures. Firstly, as the value of IMR decreased, the content of cuprous chloride (CuCl) decreased, while the content of cupric oxide (CuO) increased gradually. That is to say, there is an unambiguous IMR-dependence of the contents of CuCl and CuO formed. However, such a controllable valence transformation from Cu(II) to Cu(I) to Cu(II) did not happen in nitrogen atmosphere. Secondly, the in situ composite of CuCl and CuO produced a highly ordered structure of self-assembled nanowires, intertwined, with a diameter of 30 to 50 nm. Furthermore, electronic structural analysis provided direct evidence that the Cu-Cl and Cu-O bonds in this composite material were simultaneously impaired by self-assembled growth. Finally, we noticed that the photoluminescence property of CuCl was regulated through the formation of composites with CuO. In addition, this in situ composite synthesis technique was used to modify the magnetic property of CuO. Furthermore, the anomalous ferromagnetic behaviour of the CuO nanocrystal was observed and explained. In short, this work not only demonstrates a flexible and easily controllable valence transformation of Cu, but also provides a novel approach for constructing inorganic nanocomposite materials. We believe that the implications of these findings are important and make significant contributions to the development of inorganic chemistry and material science.     

C-doped ZnO nanowires: electronic structures, magnetic properties, and a possible spintronic device

Electronic structures, magnetic properties, and spin-dependent electron transport characteristics of C-doped ZnO nanowires have been investigated via first-principles method based on density functional theory and nonequilibrium techniques of Green's functions. Our calculations show that the doping of carbon atoms in a ZnO nanowire could induce strong magnetic moments in the wire, and the electronic structures as well as the magnetic properties of the system sensitively depend on partial hydrogenation. Based on these findings, we proposed a quasi-1d tunneling magnetic junction made of a partially hydrogenated C-doped ZnO nanowire, which shows a high tunneling magnetoresistance ratio, and could be the building block of a new class of spintronic devices.     

Molecular Template Assisted Growth of Ultrathin Silicon Carbide Nanowires with Strong Green Light Emission and Excellent Field‐Emission Properties

A novel molecule template assisted chemical co‐reduction method has been successfully developed for the controlled synthesis of ultrathin β‐SiC single‐crystalline nanowires on a large scale. The ultrathin β‐SiC single‐crystalline nanowires are about 8 nm in diameter and 200–800 nm in length. The resulting thin β‐SiC single‐crystalline nanowire is new in the family of β‐SiC one‐dimensional (1D) nanostructures. A synergistic action of π‐stacking and steric hindrance result from the 1,10‐phenanthroline molecule template are proposed to explain the growth mechanism of the ultrathin β‐SiC single‐crystalline nanowires based on the experimental observation. Importantly, such ultrathin β‐SiC nanowire has shown a strong structure‐induced enhancement of photoluminescence properties and has exhibited a very strong green light emission, which can be seen by naked eye. Furthermore, the unique β‐SiC ultrathin nanowire structure exhibits a low turn‐on field (3.57 V μm^?1) and a large field‐emission current density (20 mA cm^?2). These results suggest that the ultrathin β‐SiC nanowires can be expected to find promising applications as field emitters and photoelectronic devices.     

Assembly of multicellular constructs and microarrays of cells using magnetic nanowires

An approach is described for controlling the spatial organization of mammalian cells using ferromagnetic nanowires in conjunction with patterned micromagnet arrays. The nanowires are fabricated by electrodeposition in nanoporous templates, which allows for precise control of their size and magnetic properties. The high aspect ratio and large remanent magnetization of the nanowires enable suspensions of cells bound to Ni nanowires to be controlled with low magnetic fields. This was used to produce one- and two-dimensional field-tuned patterning of suspended 3T3 mouse fibroblasts. Self-assembled one-dimensional chains of cells were obtained through manipulation of the wires' dipolar interactions. Ordered patterns of individual cells in two dimensions were formed through trapping onto magnetic microarrays of ellipsoidal permalloy micromagnets. Cell chains were formed on the arrays by varying the spacing between the micromagnets or the strength of fluid flow over the arrays. The positioning of cells on the array was further controlled by varying the direction of an external magnetic field. These results demonstrate the possibility of using magnetic nanowires to organize cells.     

Thermal properties of bi nanowire arrays with different orientations and diameters

The thermal properties of single-crystalline Bi nanowire arrays with different orientations and diameters were studied by differential scanning calorimeter and in situ high-temperature X-ray diffraction. Bi nanowires were fabricated by a pulsed electrodeposition technique within the porous anodic alumina membrane. The relationships between the orientation and diameter of Bi nanowires and the corresponding thermal properties are deduced solely from experimental results. It is shown that the melting point decreases with decreasing nanowire diameter, and there is an anisotropic thermal expansion property of Bi nanowires with different orientations and diameters. The transition of the thermal expansion coefficient from positive at low temperature to negative at high temperature for Bi nanowire arrays was analyzed and discussed.     

Temperature dependence of the field effect mobility of solution-grown germanium nanowires

The temperature dependence of the field effect mobility was measured for solution-grown single-crystal Ge nanowires. The nanowires were synthesized in hexane from diphenylgermane by the supercritical fluid-liquid-solid process using gold nanocrystals as seeds. The nanowires were chemically treated with isoprene to passivate their surfaces. The electrical properties of individual nanowires were then measured by depositing them on a Si substrate, followed by electrical connection with Pt wires using focused ion beam assisted chemical vapor deposition. The nanowires were positioned over TaN or Au electrodes covered with ZrO2 dielectric that were used as gates to apply external potentials to modulate the conductance. Negative gate potentials increased the Ge nanowire conductance, characteristic of a p-type semiconductor. The temperature-dependent source/drain current-voltage measurements under applied gate potential revealed that the field effect mobility increased with increasing temperature, indicating that the carrier mobility through the nanowire is probably dominated either by a hopping mechanism or by trapped charges in fast surface states.     

金、铜金属纳米棒或纳米线的AFM和SERS的研究(英文)

通过电化学氧化法制备具有不同孔径氧化铝模板 ,利用交流电镀的方法在模板中沉积金属 ,再用酸溶解模板可以得到相应尺度的金属纳米线或纳米棒的阵列 .本文利用原子力显微镜和表面增强拉曼技术分别表征了金和铜两种金属纳米线阵列 .研究结果表明 ,作为探针分子的硫氰(SCN )在金属纳米线上的碳氮三键的振动频率随纳米线直径的增大而蓝移 .这一现象可能是因为尺寸效应对纳米线的费米能级造成影响 ,使不同直径的金属纳米线电子结构存在微小的差别 .     

Phase‐Controlled Synthesis of Transition‐Metal Phosphide Nanowires by Ullmann‐Type Reactions

Transition‐metal phosphide nanowires were facilely synthesized by Ullmann‐type reactions between transition metals and triphenylphosphine in vacuum‐sealed tubes at 350–400 °C. The phase (stoichiometry) of the phosphide products is controllable by tuning the metal/PPh₃ molar ratio and concentration, reaction temperature and time, and heating rate. Six classes of iron, cobalt, and nickel phosphide (Fe₂P, FeP, Co₂P, CoP, Ni₂P, and NiP₂) nanostructures were prepared to demonstrate the general applicability of this new method. The resulting phosphide nanostructures exhibit interesting phase‐ and composition‐dependent magnetic properties, and magnetic measurements suggested that the Co₂P nanowires with anti‐PbCl₂ structure show a ferromagnetic–paramagnetic transition at 6 K, while the MnP‐structured CoP nanowires are paramagnetic with Curie–Weiss behavior. Moreover, GC‐MS analyses of organic byproducts of the reaction revealed that thermally generated phenyl radicals promoted the formation of transition‐metal phosphides under synthetic conditions. Our work offers a general method for preparing one‐dimensional nanoscale transition‐metal phosphides that are promising for magnetic and electronic applications.