Growth parameters and shape specific synthesis of silicon nanowires by the VLS method

In this paper the effect of varying temperature, pressure and chemical precursors on the vapour–liquid–solid (VLS) growth of silicon nanowires (Si NWs) have been investigated. Some aspects of nucleation and growth mechanisms are discussed. Control on Si NW morphology by varying the choice of gaseous precursor (silane or dichlorosilane) at elevated temperatures is reported.     

Synthesis and characterization of silicon-doped gallium oxide nanowires for optoelectronic UV applications

Silicon-doped gallium oxide nanowires have been synthesized by thermal methods using either a mixture of gallium oxide and silicon powders or metallic gallium with silicon powder as precursor materials. The growth mechanism has been found to be a vapour–liquid–solid (VLS) or vapour–solid (VS) process, respectively, depending on the precursor used. In the former case, silicon oxide droplets at the end of the nanowires have been observed. Their possible role during the growth of the nanostructures is discussed. Structural and morphological characterization of the doped nanowires has been performed by transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The results show a high crystalline quality and a uniform distribution of silicon along the nanowires. Room temperature cathodoluminescence (CL) in the SEM shows that slight variations in the composed UV–blue emission band appear due to the influence of Si impurities in the oxygen vacancy defect structure.     

单晶ZnO纳米线的合成和生长机理研究

用化学气相输运(CVT)方法合成了直径在20～120nm呈单晶结构的ZnO纳米线.利用场发射扫描电 镜(FESEM)、高分辨透射电镜(HRTEM)以及选区电子衍射(SAED)等技术对ZnO纳米线的生长机理和结构进行 了系统研究,结果表明,纳米线的成核与Au Zn合金催化颗粒的饱和度有直接的关系,先饱和的颗粒上纳米线首 先成核.纳米线顶端合金颗粒组成的变化是导致纳米线生长终止的重要原因,大量纳米线的生长不是同时进行 的.本工作提供了支持纳米线气液固(V L S)生长机理的新实验证据,提出了氧化物纳米线的生长机理.     

Applications of electron microscopy to the characterization of semiconductor nanowires

We review our current progress on semiconductor nanowires of β-Ga₂O₃, Si and GaN. These nanowires were grown using both vapor–solid (VS) and vapor–liquid–solid (VLS) mechanisms. Using transmission electron microscopy (TEM) we studied their morphological, compositional and structural characteristics. Here we survey the general morphologies, growth directions and a variety of defect structures found in our samples. We also outline a method to determine the nanowire growth direction using TEM, and present an overview of device fabrication and assembly methods developed using these nanowires. PACS 61.14.-x; 81.07.-b; 61.14.Lj; 81.05.-t     

锡催化剂助生长法制备孪晶ZnO纳米线及其结构表征

用SnO和Zn的均匀混合物在高温下共烧通过VLS机制制备出孪晶ZnO纳米线的均匀结构。SEM图像显示孪晶ZnO纳米线的直径在100~200nm之间,长度在几十微米到几百微米之间的范围内,有的甚至达到了毫米级,产率也非常的高。TEM图像中ZnO孪晶纳米线顶端的金属Sn颗粒表明了孪晶结构的Sn催化生长。高分辨电子图谱显示了氧化锌纳米线孪晶结构的特征。电子衍射分析发现孪晶氧化锌的晶带轴的方向是[0110],孪晶面为(1013),并且通过明场像和暗场像分析了孪晶纳米线的晶格关系,确定了孪晶纳米线的汽-液-固(VLS)生长机制。     

ZnO–SnO2 branch–stem nanowires based on a two-step process: Synthesis and sensing capability

ZnO–SnO₂ branch–stem nanostructures were realized on a basis of a two-step process. In step 1, SnO₂-stem nanowires were synthesized. In step 2, ZnO-branch nanowires were successfully grown on the SnO₂-stem nanowires through a simple evaporation technique. We have pre-deposited thin Au layers on the surface of SnO₂ nanowire stems and subsequently evaporated Zn powders on the nanowires. The ZnO branches, which sprouted from the SnO₂ stems, had diameters in a range of 30–35 nm. As-synthesized branches were of single crystalline hexagonal ZnO structures. Since the branch tips were comprised of Au-containing nanoparticles, the Au-catalyzed vapor–liquid–solid growth mechanism was more likely to control the growth process of the ZnO branches. To test a potential use of ZnO–SnO₂ branch–stem nanostructures in chemical gas sensors, their sensing performances with respect to NO₂ gas were investigated, showing the promising potential in chemical gas sensors.     

ZnO纳米线的合成与生长机理

采用化学气相沉积系统制备ZnO纳米线,以覆盖一层约5nm厚的Ag薄膜的单晶Si(001)为衬底,纳米线的生长遵循气-液-固(VLS)机理。对得到的样品采用X射线衍射(XRD)和扫描电镜(SEM)进行晶体结构和形貌的表征。XRD结果表明衬底温度在600~700℃时生长的ZnO纳米线具有六方结构和统一的取向。通过扫描电子显微镜分析,比较了生长温度对纳米线直径和长度的影响。实验表明我们可以通过催化剂和温度来实现ZnO纳米线生长的可控。与传统的VLS生长方式不同的是在我们制备的ZnO纳米线顶端并没有看到催化剂颗粒,表明纳米线的生长方式是底部生长,我们对其生长机理进行了研究。     

Growth of ZnO nanostructures by vapor–liquid–solid method

Zinc oxide nanorods have been grown by vapor–liquid–solid (VLS) catalytic growth. The optical properties and structures properties of the grown ZnO nanostructures have been studied by photoluminescence, high resolution X-ray diffraction and scanning electron microscopy. The results show that the formation of ZnO nanostructures is strongly influenced by the growth conditions and used substrates. It was found that oriented ZnO nanorods are grown more easily on a substrate with a similar crystalline structure as ZnO. By optimizing growth conditions, oriented-ZnO nanorods grown on Si(001) substrate with a diameter of around 300 nm and lengths of 20 to 35 μm have been achieved, and they show excellent optical properties. Laser action has been observed at room temperature by using optical pumping. PACS 81.05.Dz; 81.10.Bk; 81.16.Hc     

Silicon nanowires synthesized by vapor–liquid–solid growth on excimer laser annealed thin gold film

The fabrication of Si nanowires has been demonstrated using excimer laser annealed thin gold film as the catalyst and vapor–liquid–solid (VLS) growth. Au nanoparticles with mean diameters of 12, 13 and 15 nm were formed by excimer laser annealing (ELA) of Au film with thickness of 2.5, 5 and 10 nm, respectively. The results show that the silicon nanowires (SiNWs) with desired diameter can be obtained by controlling the Au film thickness and laser power density.     

Flow assisted synthesis of highly ordered silica nanowire arrays

Silica nanowires were synthesized through a self-supplied vapor–liquid–solid (VLS) mechanism. Unlike randomly entangled nanowires on the substrate, highly ordered nanowire arrays have been successfully fabricated using a sandwich-like configuration to define and enhance the local gas-flow. As-synthesized nanowires were characterized to be amorphous silicon dioxide with Au as catalysts. The role of the sandwich-like structure and the effect of gas-flow on the alignment of silica nanowires are demonstrated.     

Thermal evaporation and solution strategies to novel nanoarchitectures of silicon carbide

Two simple methods, the thermal evaporation method and solution method, were developed to synthesize a variety of SiC nanoarchitectures. SiC nanowires, nanopyramids, and nanobones were obtained by the thermal evaporation method, while nanokelps, nanoflowers and nanocombs were achieved in the solution route. X-ray diffraction (XRD) analyses demonstrate that these SiC nanoarchitectures all have a face-centered cubic structure. The variety of the SiC nanoarchitectures is recognized caused by using different carbon and silicon sources with and without nucleation initiators, e.g., ZnS and Zn/SiO₂ in the thermal evaporation method, and different growth manners in the solution method. The vapor–solid (VS) and vapor–liquid–solid (VLS) reaction mechanisms are proposed for the formation of these different morphologies and structures of the SiC nanoarchitectures. The study on the nanoarchitectures may be helpful in the further research towards controllable formation of nanostructures and in finding potential applications for nanodevices. PACS 42.70.Nq; 68.37.-d; 78.67.Bf; 81.07.Vb; 81.15.Gh     

The effect of substrate surface roughness on ZnO nanostructures growth

The ZnO nanowires have been synthesized using vapor-liquid-solid (VLS) process on Au catalyst thin film deposited on different substrates including Si(1 0 0), epi-Si(1 0 0), quartz and alumina. The influence of surface roughness of different substrates and two different environments (Ar + H₂ and N₂) on formation of ZnO nanostructures was investigated. According to AFM observations, the degree of surface roughness of the different substrates is an important factor to form Au islands for growing ZnO nanostructures (nanowires and nanobelts) with different diameters and lengths. Si substrate (without epi-taxy layer) was found that is the best substrate among Si (with epi-taxy layer), alumina and quartz, for the growth of ZnO nanowires with the uniformly small diameter. Scanning electron microscopy (SEM) reveals that different nanostructures including nanobelts, nanowires and microplates have been synthesized depending on types of substrates and gas flow. Observation by transmission electron microscopy (TEM) reveals that the nanostructures are grown by VLS mechanism. The field emission properties of ZnO nanowires grown on the Si(1 0 0) substrate, in various vacuum gaps, were characterized in a UHV chamber at room temperature. Field emission (FE) characterization shows that the turn-on field and the field enhancement factor (β) decrease and increases, respectively, when the vacuum gap (d) increase from 100 to 300 μm. The turn-on emission field and the enhancement factor of ZnO nanowires are found 10 V/μm and 1183 at the vacuum gap of 300 μm.     

Controlling growth density and patterning of single crystalline silicon nanowires

This study examines the usage of well-patterned Au nanoparticles (NPs) as a catalyst for one-dimensional growth of single crystalline Si nanowires (NWs) through the vapor-liquid-solid (VLS) mechanism. The study reports the fabrication of monolayer Au NPs through the self-assembly of Au NPs on a 3-aminopropyltrimethoxysilane (APTMS)-modified silicon substrate. Results indicate that the spin coating time of Au NPs plays a crucial role in determining the density of Au NPs on the surface of the silicon substrate and the later catalysis growth of Si NWs. The experiments in this study employed optical lithography to pattern Au NPs, treating them as a catalyst for Si NW growth. The patterned Si NW structures easily produced and controlled Si NW density. This approach may be useful for further studies on single crystalline Si NW-based nanodevices and their properties.     

Growth of amorphous SiO<Subscript>2</Subscript> nanowires on Si using a Pd/Au thin film as a catalyst

Nanowires of amorphous SiO₂ were synthesized by thermal processing of a Si(100) substrate at 1100 °C in the presence of a nitrogen flow, and using a 15 nm thick high silicon-solubility Pd/Au film as a catalyst. The substrate itself was the only source of silicon for the nanowire growth. The nanostructures produced were characterized by high resolution transmission and scanning electron microscopy and by X-ray diffraction. The nanowire growth is consistent with the vapor-liquid-solid (VLS) mechanism, with particles of Pd₂Si and Au(Pd) being observed to form from the reaction between silicon and the catalytic film, and to remain at the tip of the wires. The synthesized nanowires showed a well defined morphology which could be very interesting for lasing applications. PACS 81.05.Ys; 81.10.Bk; 85.40.Ux     

Metal catalyst-assisted growth of GaN nanowires on graphene films for flexible photocatalyst applications

We report the growth of high-areal-density GaN nanowires on large-size graphene films using a nickel (Ni) catalyst-assisted vapor-liquid-solid (VLS) method. Before the nanowire growth, the graphene films were prepared on copper foils using hot-wall chemical vapor deposition and transferred onto SiO₂/Si substrates. Then, for catalyst-assisted VLS growth, Ni catalyst layers with thickness of a few nanometers were deposited on the graphene-coated substrates using a thermal evaporator. We investigated the effect of the Ni catalyst thickness on the formation of GaN nanowires. Furthermore, the structural and optical characteristics of GaN nanowires were investigated using X-ray diffraction, transmission electron microscopy, and photoluminescence spectroscopy. The GaN nanowires grown on graphene films were transferred onto polymer substrates using a simple lift-off method for applications as flexible photocatalysts. Photocatalysis activities of the GaN nanowires prepared on the flexible polymer substrates were investigated under bending conditions.     

Sawtooth faceting in silicon nanowires

We observe in situ the vapor-liquid-solid (VLS) growth of Si nanowires, in UHV-CVD using Au catalyst. The nanowire sidewalls exhibit periodic sawtooth faceting, reflecting an oscillatory growth process. We interpret the facet alternation as resulting from the interplay of the geometry and surface energies of the wire and liquid droplet. Such faceting may be present in any VLS growth system in which there are no stable orientations parallel to the growth direction. The sawtooth structure has important implications for electronic mobility and scattering in nanowire devices.     

Electroluminescence from ZnO nanowires with a p-ZnO film/n-ZnO nanowire homojunction

ZnO homojunction light-emitting diodes based on ZnO nanowires were fabricated on Si(100) substrates. An N–In codoped p-type ZnO film grown by ultrasonic spray pyrolysis and an unintentionally doped n-type ZnO nanowire quasi-array grown by an easy low-temperature hydrothermal method were employed to form the homojunction diode. Under a forward bias larger than 8 V, electroluminescence, which was composed of an ultraviolet peak centered at 387 nm and a green band around 540 nm, was observed. The electroluminescence emission was contributed by the ZnO nanowires. The results reported here suggest that ZnO-based ultraviolet light-emitting devices could be realized at low cost. PACS 42.72.Bj; 73.40.Lq; 85.60.Jb     

Formation of ZnO nanowires during short durations of potentiostatic and galvanostatic anodization

Different behaviors during the formation of ZnO nanowires from a Zn foil by either potentiostatic or galvanostatic anodization are described herein. During the initial stage, 4.5 fold fewer nucleation sites are created in potentiostatic mode than galvanostatic mode. However, the nucleation sites continuously increase as anodization proceeds in the potentiostatic mode, whereas the number of nucleation sites is determined at the beginning of anodization in galvanostatic mode. Overall, the total number of nanowires produced is almost identical. The growth rate of nanowires is 0.04 μm/s for both modes. Based on the findings during anodization of a Zn foil, a sputtered film of Zn is anodized. In galvanostatic mode, the growth of well-defined nanowires is similar to that observed during anodization of the foil, whereas sparse growth of nanowire bundles is observed in potentiostatic mode. The formation of unevenly grown nanowires is ascribed to the surplus growth species, which are intensively deposited on a few nucleation sites.     

Investigation of the growth process of Si nanowires using the vapour－liquid－solid mechanism

Silicon nanowires have been grown by the thermal decomposition of silane via the vapour－liquid－solid (VLS) mechanism. Three different stages of VLS growth (eutectic alloy formation, crystal nucleation and unidirectional growth) were studied separately using a scanning electron microscope and a high-resolution transmission electron microscope. Very short silicon nanowires prepared under particular conditions provide direct evidence of the VLS mechanism on a nanometre scale. Our results will be very helpful for the controllable synthesis of Si nanowires.     

Photoluminescence and field emission of 1D ZnO nanorods fabricated by thermal evaporation

Four kinds of new one-dimensional nanostructures, celery-shaped nanorods, needle-shaped nanorods, twist fold-shaped nanorods, and awl-shaped nanorods of ZnO, have been grown on single silicon substrates by an Au catalyst assisted thermal evaporation of ZnO and active carbon powders. The morphology and structure of the prepared nanorods are determined on the basis of field-emission scanning electron microscopy (FESEM) and x-ray diffraction (XRD). The photoluminescence spectra (PL) analysis noted that UV emission band is the band-to-band emission peak and the emission bands in the visible range are attributed to the oxygen vacancies, Zn interstitials, or impurities. The field-emission properties of four kinds of ZnO nanorods have been invested and the awl-shaped nanorods of ZnO have preferable characteristics due to the smallest emitter radius on the nanoscale in the tip in comparison with other nanorods. The growth mechanism of the ZnO nanorods can be explained on the basis of the vapor–liquid–solid (VLS) processes.