Low temperature and cost-effective growth of vertically aligned carbon nanofibers using spin-coated polymer-stabilized palladium nanocatalysts

We describe a fast and cost-effective process for the growth of carbon nanofibers (CNFs) at a temperature compatible with complementary metal oxide semiconductor technology, using highly stable polymer–Pd nanohybrid colloidal solutions of palladium catalyst nanoparticles (NPs). Two polymer–Pd nanohybrids, namely poly(lauryl methacrylate)-block-poly((2-acetoacetoxy)ethyl methacrylate)/Pd (LauMA_x-b-AEMA_y/Pd) and polyvinylpyrrolidone/Pd were prepared in organic solvents and spin-coated onto silicon substrates. Subsequently, vertically aligned CNFs were grown on these NPs by plasma enhanced chemical vapor deposition at different temperatures. The electrical properties of the grown CNFs were evaluated using an electrochemical method, commonly used for the characterization of supercapacitors. The results show that the polymer–Pd nanohybrid solutions offer the optimum size range of palladium catalyst NPs enabling the growth of CNFs at temperatures as low as 350 °C. Furthermore, the CNFs grown at such a low temperature are vertically aligned similar to the CNFs grown at 550 °C. Finally the capacitive behavior of these CNFs was similar to that of the CNFs grown at high temperature assuring the same electrical properties thus enabling their usage in different applications such as on-chip capacitors, interconnects, thermal heat sink and energy storage solutions.     

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。     

含铁碳纳米纤维的制备与表征

在聚丙烯腈的N,N-二甲基甲酰胺和四氢呋喃的混合溶剂中添加聚二茂铁硅烷,通过溶液的静电纺丝,制备了含聚二茂铁硅烷微相分离的微纳前驱体纤维,经预氧化和炭化,得到负载Fe的碳纳米纤维膜;利用SEM、SEM-EDS和XPS分别对纳米纤维的形貌、尺寸、结构和组成进行了表征。     

低碳钢基体表面氧乙炔碳化焰法沉积纳米炭纤维

低碳钢经浓硝酸浸蚀预处理后,调节氧乙炔火焰成碳化焰,预处理过的低碳钢基体表面火焰沉积获得纳米炭纤维涂层。采用扫描电镜、X射线衍射和显微激光拉曼光谱等先进分析手段对其形态和结构进行了表征。研究发现纳米炭纤维相互缠绕弯曲,石墨化程度高,直径为80nm~100nm、长度为4μm~5μm,形态短而粗。纳米炭纤维相互排列紧密但与基体结合力弱易从低碳钢表面脱落,浓硝酸浸蚀预处理的低碳钢表面在火焰中形成大量氧化铁颗粒,催化纳米炭纤维成核生长。     

Low temperature growth of SWNTs on a nickel catalyst by thermal chemical vapor deposition

Single-walled carbon nanotubes (SWNTs) have been grown on a silica-supported monometallic nickel (Ni) catalyst at temperatures ranging from as low as 450 °C to 800 °C. Different spectroscopic techniques, such as Raman, photoluminescence emission (PLE), and ultra violet-visible-near infrared (UV-vis-NIR) absorption spectroscopy were used to evaluate the diameter and quality of the SWNTs grown over the Ni catalyst at different temperatures. The analysis revealed that high quality SWNTs with a very narrow diameter distribution were obtained at a growth temperature of 500 °C. In the PLE and absorption spectra, differences were observed between the SWNTs grown on Ni and those grown on cobalt (Co). This result expands the potential of growing a specific (n, m) tube species with relatively high abundance by tuning the catalyst composition. Furthermore, the prerequisites for the low temperature growth of SWNTs over a monometallic transition metal catalyst have been elucidated.      

多孔纳米碳纤维的制备及其在超级电容器中的应用研究

利用溶胶凝胶燃烧法制备了碱金属氧化物掺杂的铜催化剂,并使用这种催化剂在不同的温度、掺杂比例下通过热CVD法合成出了具有多孔分叉结构的纳米碳纤维.通过TEM、HRTEM、BET和激光拉曼光谱等手段对产物进行表征,显示这种纳米碳纤维的比表面积可高达1162m2/g,远高于普通的碳电极材料,并且具有非常丰富的中孔结构,克服了常规碳纳米纤维在应用中表现出的相对有效利用面积不大,比电容不高等缺陷,具备做电极材料的潜力.在将其应用于超级电容器电极材料后,利用二次电池测试仪及电化学工作站对其进行了循环伏安曲线及恒流充放电曲线的测试,结果显示这种纳米碳纤维具有良好的电化学电容行为,电极的可逆性良好,并且比电容值高达203F/g.这些发现将有助于碳纳米材料可控制备的研究,并且提供了一种有一定应用潜力的超级电容器电极材料.     

On the role of activation mode in the plasma- and hot filaments-enhanced catalytic chemical vapour deposition of vertically aligned carbon nanotubes

Catalytic chemical vapor deposition (CCVD) with different activation modes (thermal; hot filaments-enhanced; direct current plasma-enhanced and both hot filament and direct current plasma-enhanced) are achieved in order to grow vertically aligned carbon nanotubes (VA CNTs). By widely varying the power of the different activation sources of the gas (plasma, hot filaments, substrate heating) while keeping identical the substrate temperature (973 K) and the catalyst preparation, the results point out the important role of ions in the nucleation of carbon nanotubes (CNTs), as well as the etching behaviour of highly activated radicals such as H˙ in the selective growth of vertically aligned films of CNTs. Moreover, it is demonstrated that, within the deposition conditions (temperature, pressure, flow rate) used in this study, oriented carbon nanotubes can be grown only when both ions, mainly generated by the gas discharge plasma, and highly reactive radicals, mainly formed by the hot filaments, are produced in the gas phase. We propose that highly energetic ions are needed to nucleate the carbon nanotubes by increasing the carbon concentration gradient whereas the highly reactive radicals allow the selective growth of vertically aligned CNTs by preventing carbon deposition on the whole surface through chemical etching of edge carbons in graphene sheets.     

常温生长类金刚石薄膜的实验研究

利用射频等离子体增强化学气相沉积(RFPECVD)工艺在常温下实现在不锈钢、硅片、玻璃等基底上大面积沉积类金刚石(DLC)膜.薄膜表面光滑致密,与衬底的结合力较高.用Raman,FTIR,SEM,EDX研究了薄膜的形貌、结构与组分.用栓-盘摩擦磨损试验机测试了薄膜的摩擦系数.通过优化沉积参数,所沉积的DLC膜在与100Cr6钢球对磨时摩擦系数低于0.01.在摩擦过程中DLC膜的磨损机制借助SEM进行了研究.     

Fabrication of a room temperature hydrogen sensor based on thin film of single-walled carbon nanotubes doped with palladium nanoparticles

A new sensor for the detection of hydrogen at parts per million (ppm) levels was fabricated by coating a thin film of palladium-doped activated single-walled carbon nanotube on the inner wall of a glass tube. The response of the sensor was based on the changes in the impedance of the sensor upon the adsorption of hydrogen molecules. The linear dynamic range of the sensor was from 1 to 50?ppm. The relative standard deviation of six replicate analyses of 5?ppm of H₂ was 2.1% and the limit of detection was 0.73?ppm for H₂ species. Humidity, methane and hydrogen sulphide did not have any serious effect on hydrogen recognition. Also, no interfering effect was observed when 20-fold excess (mass/mass) of carbon dioxide or carbon monoxide was present with hydrogen.     

直接在金属基片上生长超长宏观定向碳纳米管

在水辅助氧化作用下，直接在金属镍片上生长出宏观上定向生长的螺旋状碳纳米管，其长度达到7mm，直径在100-200nm，测试其场发射特性，开启场强为1．6V／μm，最大发射电流密度可达6mA／cm^2。     

喷雾热解法制备高产率石墨/炭纳米纤维及其特征研究

基于石墨/炭纳米纤维(GNFs)的克量级(>1 g)制备及其特征表征,通过苯的喷雾热解制备了GNFs,并采用XRD,TEM及SEM对GNFs进行了表征.结果表明:高产率GNFs的最佳生长条件是:喷管内径～0.52mm,苯液流量～5 mL/min,反应温度～750℃,载气H2流量～1 500 mL/min.所制GNFs的典型长度和直径分别为～60um和～250 nm,大部分GNFs样品呈现螺圈/螺旋纤维状.喷雾热解生长模式中GNFs的产率为克量级(1.45 g)/产程.     

具有有序宏观结构纳米碳纤维的制备及其性能应用

以CH4为碳源,金属Ni为催化剂,采用化学气相沉积法（CVD）在有序宏观基体材料（SiO2纤维,Al2O3纤维）上制备出纳米碳纤维。利用场发射扫描电镜（FE—SEM）、透射电镜（TEM）、拉曼光谱（Raman）以及热重分析（TG）对产物进行了微观形貌和结构的检测。结果表明,所制备的纳米碳纤维具有取向性,能够在有序宏观基体材料上形成致密有序的纳米碳纤维层;与Al2O3纤维相比,SiO2纤维更易于生成高质量的纳米碳纤维;所制备的纳米碳纤维遵循顶端生长模式。此外,采用纳米碳纤维作模板可以原位合成出具有有序宏观结构的纳米LaMnO3,它能明显降低碳黑颗粒的起燃温度,具有潜在的应用前景。     

Thermometer for between 0.01 and 4 K using a carbon resistor

We present an original mounting for a carbon resistor. This device, when used as a thermometer, has displayed very good cooling ability and excellent reproducibility down to 10 mK.     

Controlled growth of carbon nanofibers using plasma enhanced chemical vapor deposition: Effect of catalyst thickness and gas ratio

The characteristics of carbon nanofibers (CNFs) grown, using direct current plasma enhanced chemical vapor deposition system reactor under various acetylene to ammonia gas ratios and different catalyst thicknesses were studied. Nickel/Chromium-glass (Ni/Cr-glass) thin film catalyst was employed for the growth of CNF. The grown CNFs were then characterized using Raman spectroscopy, field emission scanning electron microscopy and transmission electron microscopy (TEM). Raman spectroscopy showed that the Ni/Cr-glass with thickness of 15 nm and gas ratio acetylene to ammonia of 1:3 produced CNFs with the lowest I_D/I_G value (the relative intensity of D-band to G-band). This indicated that this catalyst thickness and gas ratio value is the optimum combination for the synthesis of CNFs under the conditions studied. TEM observation pointed out that the CNFs produced have 104 concentric walls and the residual catalyst particles were located inside the tubes of CNFs. It was also observed that structural morphology of the grown CNFs was influenced by acetylene to ammonia gas ratio and catalyst thickness.     

Low temperature synthesis of spherical nano-diamond

Thin film nano-diamonds have been synthesised using CH₄/H₂ mixture by micro-wave plasma enhanced CVD (MW-PECVD) at a substrate temperature as low as 250°C. These are found to be spherically shaped, homogeneously distributed on the film surface (size ～100?nm) and are related to ball-like or ballas-like nano-diamonds. With the increment of temperature from 200°C to 250°C, these spherical structures are found to form in increasing number density, but the same could not be grown with the variation of power and pressure. However, the bulk material is found to improve in crystallinity with the increment of pressure and highly polycrystalline nano-diamonds (111), along with Graphitic [(100), (004)] inclusions, have been grown using a gas pressure of 70?Torr and 500?W of MW power. The preliminary results on FE-SEM, Raman and HR-TEM studies are discussed here. Further developments of the material and characterisation are in progress.     

Quantitative elucidation of the rapid growth and growth saturation of millimeter-scale vertically aligned carbon nanotubes by hot-filament chemical vapor deposition

We report the rapid synthesis of millimeter-long vertically-aligned carbon-nanotubes (VACNTs) by hot-filament chemical-vapor-deposition without the use of water vapor. The growth rate increased initially up to ~ 190 μm/min but decreased thereafter resulting in the growth of up to 2.2 ± 0.2 mm in 23 ± 2 min. A thermodynamic model driven by a carbon-concentration gradient can account for very rapid initial growth with Arrhenius-type exponential temperature dependence. Another model devised for the quantitative elucidation of the monotonic decrease in growth-rate and quasi saturation of VACNT growth confirmed that the growth kinetics of VACNTs are controlled by the concomitant contribution of a diffusion-limited precursor supply and reaction-driven catalyst deactivation.     

Low temperature synthesis of multiwalled carbon nanotubes and incorporation into an organic solar cell

ABSTRACT

Metal nanoparticle (MNP) catalysts used for the synthesis of multiwalled carbon nanotubes (MWCNTs) consisted of single metals (Fe, Ni or Co) and bimetallic mixture (CoFe, NiFe or NiCo). MWCNTs were successfully synthesised at 200 °C in 10 min using liquefied petroleum gas as carbon source with non-equilibrium plasma enhanced chemical vapour deposition (PECVD) method. The nanostructures and the morphology of the MNPs and the MWCNTs film were characterised using relevant microscopic and spectroscopic methods. The synthesised MWCNTs were used as part of the electrode material in organic solar cell (OSC) set-up. Poly (3,4-ethylenedioxythiophene): polystyrene sulfonate (PEDOT: PSS) was used as an electron transporter and poly-3-hexyl thiophene (P3HT) as an electron donor. The performance of OSC devices was tested using standard electrical measurements and solar simulator operating at 100 mW/cm². The measured power conversion efficiencies was found to be dependent on the metal catalyst used during synthesis. Among all the catalysts employed in this investigation, the best device performance was found from the synthesis of MWCNTs using Fe as a catalyst followed by Co and then Ni, respectively.     

低温等离子体增强化学气相沉积技术制备碳纳米管

由于等离子体在低温下具有高活性的特点,等离子体增强化学气相沉积(PECVD)技术可显著降低薄膜沉积的温度范围.通常条件下,高质量碳纳米管的生长要求800℃以上的基片温度,若能使该温度降到400℃以下,则对许多应用非常有利,如可以在玻璃基片上沉积碳纳米管场发射电极.目前,碳纳米管基纳电子器件的研制这一课题备受关注,如果能实现低温原位制备碳纳米管,则可能将纳电子器件与传统的微电子加工工艺结合并实现超大容量的超大规模集成电路.本文主要介绍近年来生长碳纳米管所采用的各种等离子体化学气相沉积技术,讨论影响碳纳米管生长特性的几个关键因素.     

Surface characterization of silver and palladium modified glassy carbon

In this work, the influence of silver and palladium on the surface of undoped, boron doped and phosphorus doped glassy carbon has been studied. The silver and palladium concentrations in solution, after metal deposition, were measured by atomic absorption spectrophotometer. The morphology of metal coatings was characterized by scanning electron microscopy. In order to investigate the nature and thermal stability of surface oxygen groups, temperature-programmed desorption method combined with mass spectrometric analyses, was performed. The results obtained have shown that silver and palladium spontaneously deposit from their salt solutions at the surface of glassy carbon samples. Silver deposits have dendrite structure, whilst palladium forms separate clusters. The highest amount of both silver and palladium deposits at the surface of sample containing the highest quantity of surface oxide complexes. It has been concluded that carboxyl groups and structure defects are responsible for metal reduction. Calculated desorption energies have shown that the surface modification by metal deposition leads to the formation of more stable surface of undoped and doped glassy carbon samples.     

Vapor growth of novel carbon submicro-fibers with a tile-like form and carbon nanofibers with a zigzag form

Carbon submicro-fibers with a tile-like form and carbon nanofibers with a zigzag form were grown by a CVD process using iron powder as a catalyst, H₂S as an impurity, and acetylene as the carbon source. The morphology and the microstructure were examined, and the influence of the deposition conditions on their nanostructures was discussed. The results reveal that sulfur is indispensable for the growth of these two structures. Reaction temperature and total gas-flow rates also affected the deposits and their yield significantly. At 700 °C, it is suitable to grow the tile-like structure, while at higher temperature, such as 800 °C, it is suitable to form the zigzag structure.