反应源温度对ZnO纳米线阵列定向性及发光性能的影响

以Au薄膜为催化剂、ZnO与碳混合粉末为反应源,采用碳热还原法在单晶Si衬底上制备了ZnO纳米线阵列.通过扫描电子显微镜( SEM)、X射线衍射仪(XRD)、荧光分光光度计对样品的表征,研究了反应源温度对ZnO纳米线阵列的定向性和光致发光性能的影响.样品在源温度920℃条件下沿(002)方向择优生长,定向性最好,温度过低不利于ZnO纳米线阵列密集生长,而温度过高导致Zn原子二次蒸发,因而也不利于纳米线阵列的定向和择优生长;样品在源温度880℃有最强的近紫外带边发射,表明温度过高和过低都不利于ZnO晶体结构的优化;由于ZnO纳米线在缺氧氛围下生长,氧空位是缺陷存在的主要形式,因此所有样品都有较强的绿光发射.温度升高导致纳米线生长速度提高而增加了氧空位缺陷数量,从而使样品绿峰强度增强并在源温度920℃时达最大值,但温度的进一步升高可导致ZnO纳米线表面Zn元素的蒸发而降低氧空位缺陷的数量,从而抑制绿峰强度.     

Direct synthesis of high-density lead sulfide nanowires on metal thin films towards efficient infrared light conversion

We report chemical-vapor-deposition (CVD) synthesis of high-density lead sulfide (PbS) nanowire arrays and nano pine trees directly on Ti thin films, and the fabrication of photovoltaic devices based upon the PbS nanowires. The as-grown nanowire arrays are largely vertically aligned to the substrates and are uniformly distributed over a relatively large area. Field effect transistors incorporating single PbS nanowires show p-type conduction and high mobilities. These catalytic metal thin films also serve as photocarrier collection electrodes and greatly facilitate device integration. For the first time, we have fabricated Schottky junction photovoltaic devices incorporating PbS nanowires, which demonstrate the capability of converting near-infrared light to electricity. The PbS nanowire devices are stable in air and their external quantum efficiency shows no significant decrease over a period of 3?months in air. We have also compared the photocurrent direction and quantum efficiencies of photovoltaic devices made with different metal electrodes, and the results are explained by band bending at the Schottky junction. Our research shows that PbS nanowires are promising building blocks for collecting near-infrared solar energy.     

图形化硅纳米线阵列的制备

本文主要研究了在常态(常温、常压等)条件下,利用金属催化化学腐蚀方法在硅片表面上大面积制备排列整齐、取向一致的硅纳米线阵列.同时,出于对后续制作硅纳米线传感器考虑,利用微电子标准加工工艺,以氮化硅做掩膜,通过选择合适的实验参数,在硅片表面选择性生长纳米线阵列,得到图形化的硅纳米线阵列.     

The controlled growth of GaN nanowires

This paper reports a scalable process for the growth of high-quality GaN nanowires and uniform nanowire arrays in which the position and diameter of each nanowire is precisely controlled. The approach is based on conventional metalorganic chemical vapor deposition using regular precursors and requires no additional metal catalyst. The location, orientation, and diameter of each GaN nanowire are controlled using a thin, selective growth mask that is patterned by interferometric lithography. It was found that use of a pulsed MOCVD process allowed the nanowire diameter to remain constant after the nanowires had emerged from the selective growth mask. Vertical GaN nanowire growth rates in excess of 2 mum/h were measured, while remarkably the diameter of each nanowire remained constant over the entire (micrometer) length of the nanowires. The paper reports transmission electron microscopy and photoluminescence data.     

Synthesis of Free‐Standing Metal Sulfide Nanoarrays via Anion Exchange Reaction and Their Electrochemical Energy Storage Application

Metal sulfides are an emerging class of high‐performance electrode materials for solar cells and electrochemical energy storage devices. Here, a facile and powerful method based on anion exchange reactions is reported to achieve metal sulfide nanoarrays through a topotactical transformation from their metal oxide and hydroxide pre‐forms. Demonstrations are made to CoS and NiS nanowires, nanowalls, and core‐branch nanotrees on carbon cloth and nickel foam substrates. The sulfide nanoarrays exhibit superior redox reactivity for electrochemical energy storage. The self‐supported CoS nanowire arrays are tested as the pseudo‐capacitor cathode, which demonstrate enhanced high‐rate specific capacities and better cycle life as compared to the powder counterparts. The outstanding electrochemical properties of the sulfide nanoarrays are a consequence of the preservation of the nanoarray architecture and rigid connection with the current collector after the anion exchange reactions.     

One-step formation of core-shell sulfide-oxide nanorod arrays from a single precursor

Densely packed and well-aligned coaxial (core-shell) CdS-CdO and ZnS-ZnO nanorod arrays were prepared with a one-step, non-catalytic, template-free metalorganic chemical vapour deposition (MOCVD) process by using single-source molecular precursors Cd(O-EtXan)(2) and Zn(O-EtXan)(2), respectively (O-EtXan = S(2)COCH(2)CH(3)). Data from pyrolysis gas chromatography/mass spectrometry of the precursors revealed the sequence of formation, namely sulfide core first and oxide shell later, with the first formed sulfide nanorods serving as the template for subsequent in?situ oxide shell coating. The coaxial CdS-CdO and ZnS-ZnO nanorod arrays were formed at collection temperatures of 180 and 200?°C, respectively. At a slightly higher collection temperature of 250?°C, coaxial ZnS-ZnO nanowires were also obtained. The coaxial nanostructure was characterized and confirmed with high-resolution transmission electron microscopy. In a photoluminescence study, near band edge emissions at around 530?nm, a composite emission of the two near band edge emissions of 524?nm of CdS and 551?nm of CdO, were observed for the coaxial CdS-CdO nanorod sample, while defect-induced emissions at around 470?nm were observed for both coaxial ZnS-ZnO nanorod and nanowire samples. A more stable oxide shell not only protects the sulfide core but also provides possible surface passivation beneficial to enhanced photoluminescence. The present work demonstrates the feasibility of growth of coaxial one-dimensional nanostructures from single-source precursors that contain all the necessary constituent elements in one compound.     

Conversion of a Bi nanowire array to an array of Bi-Bi2O3 core-shell nanowires and Bi2O3 nanotubes

A template-based heat-treatment method has been developed to convert metal nanowire arrays into arrays of metal-metal oxide core-shell nanowires and single-crystalline metal oxide nanotubes. This process is demonstrated by kinetically controlling the conversion of single-crystalline Bi nanowires to Bi-Bi(2)O(3) core-shell nanowires via a multistep, slow oxidation method, and then controlling their further conversion to a single-crystalline Bi(2)O(3) nanotube array via fast oxidation. This process can conveniently be extended to fabricate a free-standing, easily oxidized metal-metal oxide nanowire and metal oxide nanotube array, which may have future applications in nanoscale optics, electronics, and magnetics.     

Writing and Functionalisation of Suspended DNA Nanowires on Superhydrophobic Pillar Arrays

Nanowire arrays and networks with precisely controlled patterns are very interesting for innovative device concepts in mesoscopic physics. In particular, DNA templates have proven to be versatile for the fabrication of complex structures that obtained functionality via combinations with other materials, for example by functionalisation with molecules or nanoparticles, or by coating with metals. Here, the controlled motion of the a three‐phase contact line (TCL) of DNA‐loaded drops on superhydrophobic substrates is used to fabricate suspended nanowire arrays. In particular, the deposition of DNA wires is imaged in situ, and different patterns are obtained on hexagonal pillar arrays by controlling the TCL velocity and direction. Robust conductive wires and networks are achieved by coating the wires with a thin layer of gold, and as proof of concept conductivity measurements are performed on single suspended wires. The plastic material of the superhydrophobic pillars ensures electrical isolation from the substrate. The more general versatility of these suspended nanowire networks as functional templates is outlined by fabricating hybrid organic–metal–semiconductor nanowires by growing ZnO nanocrystals onto the metal‐coated nanowires.     

Rational Synthesis of Metal Nanotubes and Nanowires from Lamellar Structures

A generic method has been developed for the synthesis of crystalline metal nanowires or nanotubes (such as bismuth nanotubes, tungsten nanowires) from lamellar structures. In a typical process, lamellar surfactant/inorganic composite precursors are first prepared by reacting cationic or anionic surfactants with inorganic species under appropriate conditions. After treating these precursors by hydrothermal pyrolysis, or other processes, crystalline metallic nanotubes or nanowires are obtained.     

交流电化学沉积FeCo合金纳米线阵列及其磁性能研究

采用二步阳极氧化法制备孔结构高度有序的多孔氧化铝(AAO)模板。在不同Fe2+/Co2+摩尔比的电解液中,利用交流电化学沉积,在模板孔内成功制备了FeCo合金纳米线阵列。分别采用透射电子显微镜(TEM),场发射扫描电子显微镜(FE-SEM),X射线衍射仪(XRD)和震动样品磁强计(VSM)对样品的形貌,结构及磁学性能进行了表征。结果表明,制备的FeCo合金纳米线排列有序,粗细均匀;其直径与模板孔径一致,填充率较高,且具有明显的[110]择优取向。VSM测试结果表明,不同溶液浓度下制备的FeCo合金纳米线阵列均具有良好的垂直磁各向异性,易磁化轴沿着纳米线轴线方向。随着电解液Fe2+/Co2+摩尔比的不同,可在一定范围内对FeCo合金纳米线阵列的磁性进行调控,并对其原因进行了讨论。     

Direct synthesis of ZnO nanowire arrays on Zn foil by a simple thermal evaporation process

ZnO nanowire arrays were synthesized on zinc foil by a simple thermal evaporation process at relatively low temperature. Morphology and size controlled synthesis of the ZnO nanostructures was achieved by variation of the synthesis temperature, reaction time and the surface roughness of the substrate. A gas-solid and self-catalytic liquid-solid mechanism is proposed for the growth of nanowires at different temperatures. High-resolution transmission electron microscopy (HRTEM) showed that the as-grown nanowires were of single crystal hexagonal wurtzite structure, growing along the [101] direction. Photoluminescence exhibited strong UV emission at ～382?nm and a broad green emission at ～513?nm with 325?nm excitation. Raman spectroscopy revealed a phonon confinement effect when compared with results from bulk ZnO. The nanowire arrays also exhibited a field emission property.     

A hot-wire chemical vapor deposition (HWCVD) method for metal oxide and their alloy nanowire arrays

A concept for synthesizing nanowire arrays of transition metal oxides and their alloys using hot wire chemical vapor deposition (HWCVD) is discussed. Here, unlike conventional HWCVD, the hot filaments act as the source of the metal for the synthesis of one dimensional nanostructures. In the present concept, the chemical vapor transport of metal oxides generated by heating the filaments in low amounts of oxygen, onto substrates maintained at lower temperatures leads to the formation of metal oxide nanowires. Experiments performed using tungsten and molybdenum filaments showed that the nucleation density of the resulting metal oxide nanowires could be varied by varying the substrate temperature. Experiments performed using a magnesium source inside the reactor, in addition to tungsten filaments, resulted in the formation of MgWO₄ nanowires. This clearly indicates the possibility of either doping the metal oxide nanowires or alloying during synthesis.     

Synthesis of metal chalcogenide nanodot arrays using block copolymer-derived nanoreactors

Soluble metal chalcogenide precursors are used to fabricate arrays of metal chalcogenide nanodots by spin-coating. Nanodots are formed after thermal decomposition of the precursors, which are collected in patterned nanowell arrays. These arrays are derived from block copolymer patterns and may consist of the polymer itself or result from etching to transfer the pattern to an inorganic substrate. Etching provides enhanced control over nanowell shape and the morphology of the resulting metal chalcogenide array.     

Modification of SiO2 nanowires with metallic nanocrystals from supercritical CO2

Through hydrogen reduction of metal precursors in supercritical CO2, Cu, and Pd, nanocrystals were deposited onto SiO2 nanowires to form different types of nanostructured materials, including nanocrystal-nanowire, spherical aggregation-nanowire, shell-nanowire composites, and "mesoporous" metals supported by the framework of nanowires. This supercritical fluid deposition technique is an attractive approach for modifying nanowires because of its generality and simplicity; the modified nanowires could be useful as catalysts and for further fabrication of multifunctional composites.     

Seed-layer controlled synthesis of well-aligned ZnO nanowire arrays via a low temperature aqueous solution method

A simple and controllable method has been developed to synthesize well-aligned ZnO nanowire arrays on silicon and glass substrates in aqueous solution. A thin ZnO seed-layer coated with colloidal ZnO nanocrystals was introduced to control the density and orientation of ZnO nanowires. X-ray diffraction (XRD) and scanning electron microscopy (SEM) result show the high dense and well-aligned character of ZnO nanowires. The photoluminescence (PL) reveals the high crystal quality of the nanowires. It was found that the ZnO seed-layer can effect the size distribution, density and crystal structure of the nanowires. The growth mechanism of ZnO nanowires was also discussed.     

Growth of Arrayed Nanorods and Nanowires of ZnO from Aqueous Solutions

A novel approach to the rational fabrication of smart and functional metal oxide particulate thin films and coatings is demonstrated on the growth of ZnO nanowires and oriented nanorod arrays. The synthesis involves a template‐less and surfactant‐free aqueous method, which enables the generation of, at large‐scale, low‐cost, and moderate temperatures, advanced metal oxide thin films with controlled complexity. The strategy consists of monitoring of the nucleation, growth, and aging processes by means of chemical and electrostatic control of the interfacial free energy. It enables the control of the size of nano‐, meso‐, and microcrystallites, their surface morphology, orientations onto various substrates, and crystal structure.     

化学蚀刻法制备纳米硅线作为高能锂离子电池的负极

采用金属催化剂诱导化学蚀刻法首先在单晶硅片上制备出具有高长径比的纳米硅线阵列, 然后通过超声振荡法将硅线阵列破碎为纳米硅线粉体, 最后将其作为锂离子电池的负极材料, 系统研究了金属银催化剂制备过程和各向异性化学蚀刻过程对硅片表面形貌特征的影响, 发现银催化剂在蚀刻过程出现溶解/再沉积现象。通过优化AgNO₃、HF、H₂O₂等试剂的浓度, 在大面积范围内得到了高长径比的纳米硅线阵列。借助超声波的作用将硅线从硅片上切割下来, 制备成纳米硅线负极进行了充放电循环测试, 观察到标准的硅锂合金/去合金化反应平台, 前五次循环的比容量均超过1800 mAh/g。     

Growth and optical properties of In x Ga1−x P nanowires synthesized by selective-area epitaxy

Ternary Ⅲ-Ⅴ nanowires (NWs) cover a wide range of wavelengths in the solar spectrum and would greatly benefit from being synthesized as position-controlled arrays for improved vertical yield,reprodudbility,and tunable optical absorption.Here,we report on successful selective-area epitaxy of metal-particle-free vertical InxGa1-xP NW arrays using metal-organic vapor phase epitaxy and detail their optical properties.A systematic growth study establishes the range of suitable growth parameters to obtain uniform NW growth over a large array.The optical properties of the NWs were characterized by room-temperature cathodoluminescence spectroscopy.Tunability of the emission wavelength from 870 nm to approximately 800 nm was achieved.Transmission electron microscopy and energy dispersive X-ray measurements performed on crosssection samples revealed a pure wurtzite crystal structure with very few stacking faults and a slight composition gradient along the NW growth axis.     

Attenuation of protein adsorption on static and oscillating magnetostrictive nanowires

The research described here investigates the hypothesis that nanoarchitecture contained in a nanowire array is capable of attenuating the adverse host response generated when medical devices are implanted in the body. This adverse host response, or biofouling, generates an avascular fibrous mass transfer barrier between the device and the analyte of interest, disabling the implant if it is a sensor. Numerous studies have indicated that surface chemistry and architecture modulate the host response. These findings led us to hypothesize that nanostructured surfaces will inhibit the formation of an avascular fibrous capsule significantly. We are investigating whether arrays of oscillating magnetostrictive nanowires can prevent protein adsorption. Magnetostrictive nanowires were fabricated by electroplating a ferromagnetic metal alloy into the pores of a nanoporous alumina template. The ferromagnetic nanowires are made to oscillate by oscillating the magnetic field surrounding the wires. Radiolabeled bovine serum albumin, enzyme-linked immunosorbent assay (ELISA), and other protein assays were used to study protein adhesion on the nanowire arrays. These results display a reduced protein adsorption per surface area of static nanowires. Comparing the surfaces, 14-30% of the protein that absorbed on the flat surface adsorbed on the nanowires. Our contact angle measurements indicate that the attenuation of protein on the nanowire surface might be due to the increased hydrophilicity of the nanostructured surface compared to a flat surface of the same material. We oscillated the magnetostrictive wires by placing them in a 38 G 10 Hz oscillating magnetic field. The oscillating nanowires show a further reduction in protein adhesion where only 7-67% of the protein on the static wires was measured on the oscillating nanowires. By varying the viscosity of the fluid the nanowires are oscillated in, we determined that protein detachment is shear-stress modulated. We created a high shearing fluid with dextran, which reduced protein adsorption on the oscillating nanowires by 70% over nanowires oscillating in baseline viscosity fluid. Our preliminary studies strongly suggest that the architecture in the static nanowire arrays and the shear created by oscillating the nanowire arrays would attenuate the biofouling response in vivo.     

Synthesis of nanocomposites using glasses and mica as templates

Various nanocomposites were synthesized using either a silica-based glass or mica crystallites as the medium. In some cases by an oxidation or a sulfidation treatment a core-shell nanostructure could be generated. Iron-iron oxide core-shell structured nanocomposites exhibited excellent humidity sensing behaviour. Gold-gold sulfide core-shell nanorods exhibited a number of optical absorption peaks which arose because of their structural characteristics. Nanoparticles of silver and silver oxide could be aligned in a polymethylmethacrylate film by an a.c. electric field of 1 MHz frequency. The composites showed large sensitivity to relative humidity. Lead sulfide nanowires of diameter, 1.2 nm, were grown within the nanochannels of Na-4 mica. These exhibited a semiconductor to metal transition at around 300 K. This arose because of high pressure generated on the nanowires. Copper sulfide nanowires grown within the Na-4 mica channels showed metallic behaviour. Silver core-silver orthosilicate shell nanostructures developed within a silicate glass medium showed discontinuous changes in resistivity at some specific temperatures. This was explained as arising due to excitation of Lamb modes at certain pressures generated because of thermal expansion mismatch of the core and the shell phases. Optical properties of iron core-iron oxide shell nanocomposites when analysed by effective medium theory led to the result of a metal non-metal transition for particle diameters below a critical value. Similar results were obtained from optical absorption data of silver nanoparticles grown in a tetrapeptide solution.