Direct growth of aligned carbon nanotubes on bulk metals

There are several advantages of growing carbon nanotubes (CNTs) directly on bulk metals, for example in the formation of robust CNT-metal contacts during growth. Usually, aligned CNTs are grown either by using thin catalyst layers predeposited on substrates or through vapour-phase catalyst delivery. The latter method, although flexible, is unsuitable for growing CNTs directly on metallic substrates. Here we report on the growth of aligned multiwalled CNTs on a metallic alloy, Inconel 600 (Inconel), using vapour-phase catalyst delivery. The CNTs are well anchored to the substrate and show excellent electrical contact with it. These CNT-metal structures were then used to fabricate double-layer capacitors and field-emitter devices, which demonstrated improved performance over previously designed CNT structures. Inconel coatings can also be used to grow CNTs on other metallic substrates. This finding overcomes the substrate limitation for nanotube growth which should assist the development of future CNT-related technologies.     

炭纤维表面生长碳纳米管

采用化学气相沉积工艺在炭纤维表面生长了碳纳米管,并观察了它的微观形貌,且对其影响因素进行了初步研究.结果表明:纤维表面的纵向沟槽可以负载催化剂粒子,是生长碳纳米管的物理基础;催化剂的浓度太高,金属粒子容易团聚长大,所得碳纳米管的管径较大;而催化剂浓度太低,则不能在炭纤维整个表面均匀生长碳纳米管;最佳的催化剂溶液的浓度是0.05mol/L的硝酸钴.比较了铁、钴、镍三种过渡金属催化剂,从形成的碳纳米管的质量来看,钴催化剂最佳.     

Formation of isolated carbon nanofibers with hot-wire CVD using nanosphere lithography as catalyst patterning technique

Recently the site-density control of carbon nanotubes (CNTs) has attracted much attention as this has become critical for its many applications. To obtain an ordered array of catalyst nanoparticles with good monodispersity nanosphere lithography (NSL) is used. These nanoparticles are tested as catalyst sites in hot-wire chemical vapor deposition (HWCVD) of carbon nanostructures. Aside from using NSL also nickel (Ni) nano-islands are made by thermal annealing of a thin Ni film and tested as catalyst sites. Multiwall CNTs, isolated carbon nanofibres, and other nanostructures have been deposited using HWCVD. Tungsten filaments held at ~ 2000 °C are used to decompose a mixture of ammonia, methane and hydrogen. The structures have been characterized with Scanning Electron Microscopy, High Resolution Transmission Electron Microscopy, Raman spectroscopy and Rutherford Backscattering Spectroscopy.     

平直碳纳米纤维与螺旋碳纳米纤维的共同生长

研究了采用乙醇催化燃烧法制备的碳纳米纤维的形貌和结构，并且讨论了平直碳纳米纤维与螺旋碳纳米纤维分别对应的生长机制。分析结果表明在特定的实验条件下，可以制备出平直碳纳米纤维与螺旋碳纳米纤维的共生材料。螺旋碳纳米纤维的生长机制是基于催化剂颗粒的各向异性。本实验方法具有制备工艺简单，碳源无毒性，制备过程无环境污染等特点，因而有望实现大量生产。     

Microstructure and growth mechanism of SiC whiskers on carbon/carbon composites prepared by CVD

The SiC whiskers of good quality are expected to act as the reinforcing element in the ceramic coatings for C/C composites. Using CH₃SiCl₃(MTS) and H₂ as the precursors, SiC whiskers were prepared on the surface of C/C composites by chemical vapor deposition (CVD) at normal atmosphere pressure. XRD, SEM and TEM analyses show that the whiskers are β-SiC structure and their diameters are several-hundred nanometers. With the descending MTS concentration in the depositing room, the purity of the as-prepared whiskers increases and the diameters of the whiskers decrease. The investigation of growth mechanism shows the CVD-SiC whiskers grown up by the vapor–solid (VS) growth process.     

CVD growth of carbon nanotubes on catalyst patterns generated with AFM lithography

We obtain carbon nanotubes (CNTs) by chemical vapor deposition (CVD) using ethanol as carbon source. CNTs are grown on linear and rectangular patterns containing Co–Mo catalysts. These patterns were generated with a combination of dip-pen and ‘scratching’ lithography performed with Atomic Force Microscopy (AFM). In this procedure, a gold thin film deposited on porous alumina substrates is first scratched and subsequently a solution of Co and Mo acetates in ethanol is painted on the scratched area with a syringe mounted on the AFM instrument. CVD growth temperature of CNTs is of about 750°C with an ethanol exposure time of 30 min. In the linear patterns a dense film of CNTs is obtained with average lengths of 1 μm and in the rectangular patterns CNTs grow with diameters of about 50 nm. Sample analysis is performed with scanning electron microscopy (SEM) and AFM.     

Au–Pd catalyzed growth of carbon nanofibers mat

Carbon nanofibers (CNFs) mat was synthesized from Au–Pd catalyst at 700 °C for 60 min in 10 kPa of the gas mixture of C₂H₂, H₂ and Ar by thermal chemical vapor deposition (CVD). Fine Au–Pd catalyst as admixture on the growth substrate of SiO₂ was adopted for the growth of CNFs mat. Fine Pd particles without Au particles were detected at the top/inside of as-grown CNFs by TEM-EDS analysis. The Au component within Au–Pd particles with ca. 1.5 nm did not contribute to the CNF growth. On the other hand, the growth scale of individual CNF was ranged from 5 to 150 nm in diameter and less than 100 μm in length, by controlling H₂ or Ar concentration in carbon source gas of C₂H₂/Ar or C₂H₂/H₂/Ar. It seemed that Ar gas accelerated the growth of the CNFs mat and the length of each CNF was increased with increasing the supplying amount of H₂. In contrast, H₂ induced the lower growth density of CNFs mat and the decrease in the diameter of those. The CNFs mainly grow through adsorption and decomposition of acetylene on the surface of Au–Pd catalyst and precipitation of carbon on the surface of those.     

沉积条件对CVD碳纤维生长的影响

用CH4、H2或包含NH3的混合气体为反应气体,利用负偏压增强热丝化学气相沉积方法在沉积有过渡层(Ta或Ti)和催化剂层(NiFe)的Si衬底上制备碳纤维,并用扫描电子显微镜研究了它们的生长和结构,结果发现不同的沉积条件对碳纤维的生长和结构有很大的影响。在无辉光放电的条件下,衬底温度较低时碳纳米管或纤维生长困难;提高衬底温度,能够弯曲生长;在辉光放电的条件下,则呈现定向生长的特点。     

Influence of co-catalyst on growth of carbon nanotubes using alcohol catalytic CVD method

This paper describes the influence of a co-catalyst on growth of carbon nanotubes (CNTs) by alcohol catalytic chemical vapour deposition (ACCVD) method. Silicon wafers covered with thermal oxide or polycrystalline diamond thin film were used as substrates. Ni thin film supported with Al, Cu or Ti was used as a catalyst. The films were deposited by pulsed laser deposition technique. Comparison of the various types of the co-catalyst (Al, Cu, Ti) leads to the conclusion that Cu co-catalyst is suitable for producing very thin single wall carbon nanotubes (SWCNTs) and combination of Al and Ni provide a good condition to the catalytic growth of CNTs. In addition, we observed also the influence of the various diffusion barriers (thermal oxide and polycrystalline diamond) on growth of CNTs. Prepared samples were analysed by Raman spectroscopy (RS) and scanning electron microscopy (SEM).     

Influence of CVD conditions on the growth of carbon microcoils with circular cross-sections

The pyrolysis of C₂H₂ over a Ni powder catalyst in the atmosphere of H₂, H₂S and various inert gases was used to synthesize carbon microcoils (CMCs). The influences of the CVD conditions, esp. the gas flow rate of N₂, Ar, H₂O, or H₂ as well as reaction time on the growth of the CMCs, whose coiled fibers have circular cross-sections (circular CMCs), were investigated.     

Improvement of the electrical conductivity of carbon fibers through the growth of carbon nanofibers

In this work, carbon nanofibers (CNFs) were synthesized on carbon fiber (CF) surfaces precoated with metal-doped mesoporous silica films. Fe, Ni, and Co were doped in the mesoporous silica films and played the role of catalysts for the decomposition of acetylene to grow CNFs on the CF surfaces. The chemical composition and surface structure of CFs before and after the growth of the CNFs were investigated by EDX, N2 full isotherms, and SEM. The electrical property of the CFs was investigated using a four-probe volume resistivity tester. The SEM results indicated that the CNFs with diameters of 20-100 nm grew uniformly and densely on the CF surfaces. The diameter and length distributions of the CNFs were found to be dependent on the metal that was doped in the mesoporous silica films. The electrical properties of the CFs were enhanced after the CNFs' growth on the CF surfaces, and the CNFs grown over the Ni catalyst with the narrowest diameter distribution gave the lowest volume resistivity to the CFs.     

Technology of ZnO nanofibers based devices

In the presented work, the possibility of fabrication of ZnO single- and multi-nanofiber structures using a standard microelectronic device technology were studied. An innovative fabrication step, namely, selective wet chemical nanofibers etching through a photoresist mask, was used to define the active area, along with mesa etch in the Si/SiO₂ substrate. Test structures in the configuration of a resistor and Schottky diode with chemically active electrospun ZnO nanofibers were prepared. The Ti/Au ohmic and Pt Schottky contacts were fabricated using a lift-off photolithography process. Optical and scanning electron microscopy studies were done to characterize ZnO nanofibers and topography of contacts. The measurements made for electrical characterization showed linear I–V dependence and saturation of the current for single ZnO nanofiber structures.     

Bias-independent growth of carbon nanowalls by microwave electron-cyclotron resonance plasma CVD

The investigations reported here describe the synthesis of carbon nanowalls (CNWs) by microwave electron-cyclotron resonance (ECR) plasma-assisted chemical vapour deposition (PACVD) process without an application of external bias to the substrate during growth. CNWs were grown on silicon (Si) substrates using hydrogen (H₂)/methane (CH₄) plasma at 650°C substrate temperature. Nickel (Ni) was used as a catalyst for the synthesis of CNWs. To the best of our knowledge, this is the first report that describes the bias-independent growth of CNWs using the ECR PACVD process. Formation of CNWs is confirmed by scanning electron microscopy and Raman spectroscopy. The discussion part also includes a possible growth mechanism for CNWs in terms of the role of surface plasmons.     

Self-assembled palladium nanoparticles on carbon nanofibers

Carbon nanofibers containing palladium nanoparticles were prepared simply by electrospinning a polymer solution containing palladium chloride and the subsequent thermal treatment in argon. It is demonstrated that palladium oxide formed in air stabilization transforms into nanoparticles through an interaction with carbon materials. Since the palladium nanoparticles covering the outer surface of nanofibers homogeneously are small enough to have high catalytic activity, this material could find applications as efficient catalysts and hydrogen sensors.     

Highly conducting doped poly-Si deposited by hot wire CVD and its applicability as gate material for CMOS devices

Highly conducting p- and n-type poly-Si:H films were deposited by hot wire chemical vapor deposition (HWCVD) using SiH₄+H₂+B₂H₆ and SiH₄+H₂+PH₃ gas mixtures, respectively. Conductivity of 1.2×10² (Ω cm)⁻¹ for the p-type films and 2.25×10² (Ω cm)⁻¹ for the n-type films was obtained. These are the highest values obtained so far by this technique. The increase in conductivity with substrate temperature (T_s) is attributed to the increase in grain size as reflected in the atomic force microscopy results. Interestingly conductivity of n-type films is higher than the p-type films deposited at the same T_s. To test the applicability of these films as gate contact Al/poly-Si/SiO₂/Si capacitor structures with oxide thickness of 4 nm were fabricated on n-type c-Si wafers. Sputter etching of the poly-Si was optimized in order to fabricate the devices. The performance of the HWCVD poly-Si as gate material was monitored using C–V measurements on a MOS test device at different frequencies. The results reveal that as deposited poly-Si without annealing shows low series resistance.     

Synthetic hierarchical nanostructures: growth of carbon nanofibers on microfibers by chemical vapor deposition

In this paper the synthesis of three-dimensional hierarchical nanostructures by pyrolysis of acetylene to grow carbon nanofibers (CNFs) on carbon microfibers (CMFs) and glass microfibers (GMFs) is reported. The morphology and structure of the as-prepared CNFs were studied by scanning electron microscopy and high-resolution transmission electron microscopy. CNFs grown on both substrates typically exhibited two types of morphology: the coil-like CNFs with frequent change in orientation and the relatively straight and long CNFs with parallel graphene sheets. The ethanol pretreatment was effective at improving the yield and distribution of the as-grown CNFs on CMFs, but showed an adverse effect to the CNF growth on GMFs. The influence of different substrates and growth temperatures on CNF morphology and the possible growth mechanism for the observed microstructures was discussed.     

CVD synthesis of carbon nanotubes

Abstracts are not published in this journal This revised version was published online in November 2006 with corrections to the Cover Date.     

纳米炭纤维的表面润湿行为

采用动态渗透法研究了不同结构的纳米炭纤维(Carbonnanofibers,CNF)表面润湿性以及在不同溶剂中润湿性的变化和表面改性对其润湿性的影响。结果表明,生长条件如催化剂组成、碳源等对CNF的表面性质有显著影响,并最终决定其在溶剂中的润湿能力。以Fe/γ-Al2O3为催化剂,以C2H4为碳源得到的CNF在水中的润湿性能最差;而以Ni/γ-Al2O3为催化剂,CO为碳源得到的CNF在环己烷中的润湿性能最好。CNF在不同溶剂中的相对接触角测定表明CNF是一种表面非极性较强的材料。设CNF在润湿性能最好的环己烷中的接触角为0°,则CNF在水,丙酮,乙醇中的相对接触角分别为81.6°,45.2°,24.8°。不同的表面改性手段可对CNF的表面性质进行调变以控制其在不同溶剂中的润湿行为。在浓硝酸中液相氧化可提高其对水溶液和环己烷的润湿性能;在氩气中的高温热处理可提高其对水溶液的润湿性能,但降低了对环己烷的润湿能力;而在过氧化氢溶液中的处理则同时降低了对水溶液以及环己烷的润湿能力。