Synthesis of carbon nanotubes on diamond-like carbon by the hot filament plasma-enhanced chemical vapor deposition method

Carbon nanotubes (CNTs) have attracted considerable attention as possible routes to device miniaturization due to their excellent mechanical, thermal, and electronic properties. These properties show great potential for devices such as field emission displays, transistors, and sensors. The growth of CNTs can be explained by interaction between small carbon patches and the metal catalyst. The metals such as nickel, cobalt, gold, iron, platinum, and palladium are used as the catalysts for the CNT growth. In this study, diamond-like carbon (DLC) was used for CNT growth as a nonmetallic catalyst layer. DLC films were deposited by a radio frequency (RF) plasma-enhanced chemical vapor deposition (RF-PECVD) method with a mixture of methane and hydrogen gases. CNTs were synthesized by a hot filament plasma-enhanced chemical vapor deposition (HF-PECVD) method with ammonia (NH₃) as a pretreatment gas and acetylene (C₂H₂) as a carbon source gas. The grown CNTs and the pretreated DLC films were observed using field emission scanning electron microscopy (FE-SEM) measurement, and the structure of the grown CNTs was analyzed by high resolution transmission scanning electron microscopy (HR-TEM). Also, using energy dispersive spectroscopy (EDS) measurement, we confirmed that only the carbon component remained on the substrate.     

Uniform arrays of carbon nanotubes applied in the field emission devices

Carbon nanotubes(CNTs)were grown into anodic aluminum oxide(AAO)channels by chemical vapor deposition(CVD)using C2H2/N2mixtures as feeding gas,which can be used as field emitters.The bottom surface of AAO template was etched slightly and the tips of CNTs were explored as the field emission arrays which were uniform and vertical.Field emission characterization showed a low turn-on field about 3.25 V/m and high emission current about 30 mA/cm2with the electric field about 4 V/m.These superior field emission characteristics could be attributed to low density of vertical CNTs and higher conductivity of the substrate.     

单晶LaB6场发射阵列的电化学腐蚀工艺

 六硼化镧（LaB₆）场发射尖锥阵列的刻蚀工艺是制备LaB₆场发射阵列阴极的关键。在(111)面单晶LaB₆基片上,用等离子体增强化学气相沉积法制备氮化硅层做掩膜,光刻后采用电化学腐蚀方法对基片进行刻蚀,得到具有一定高度的LaB₆尖锥场发射阵列。讨论了单晶LaB₆的电化学腐蚀机理。改变各种电化学腐蚀参数,包括电解液成分、电解液浓度、阳极所加电压,用电子扫描显微镜观察样品形貌。结果发现H₃PO₄是刻蚀单晶LaB₆的理想电解液,它克服了过去电化学实验中经常遇到的尖锥各向异性问题。随着电解液浓度或阳极电压的增大,尖锥高度增加,但是基底表面变得更为粗糙。另一方面,阳极电压太小时,有横向刻蚀现象产生,不利于提高发射体的场增强因子。此外,在二极管结构中初步测试了LaB6尖锥场发射阵列的电流发射特性,在真空度2×10^-4 Pa、极间距离0.1 mm、阳极电压900 V下,发射电流达到13 mA。     

碳纳米管场致发射中的空间电荷效应

采用微波等离子体化学气相沉积(MWPCVD)方法成功制备以碳纳米管束为单元的场致发射阵列,获得很好的场致发射电流发射特性,在电流密度较大时,发现I-V特性偏离由Fowler-Nordheim公式计算出的结果。采用Electron Beam Simulation(EBS)软件进行模拟分析发现:在电流密度较低时,I-V特性能很好与F-N公式吻合。但碳纳米管尖端电流密度大于106A/cm2时,碳纳米管尖端处的有效电场强度受空间电荷的影响比较明显,进而对碳纳米管的场致发射特性显现出不可忽略的影响,此时碳纳米管的发射电流密度开始受到空间电荷的限制。     

A comparative study of field-emission from different one dimensional carbon nanostructures synthesized via thermal CVD system

Different one dimensional (1D) carbon nanostructures, such as carbon nanonoodles (CNNs), carbon nanospikes (CNSs) and carbon nanotubes (CNTs) have been synthesized via thermal chemical vapour deposition (TCVD) technique. The different 1D morphologies were synthesized by varying the substrate material and the deposition conditions. The as-prepared samples were characterized by X-ray diffraction (XRD), field emission scanning electron microscope (FESEM) and transmission electron microscope (TEM). FESEM and TEM images showed that the diameters of the CNNs and CNTs were ∼40 nm while the diameters of the CNSs were around 100 nm. Field emission studies of the as-prepared samples showed that CNSs to be a better field emitter than CNNs, whereas CNTs are the best among the three producing large emission current. The variation of field emission properties with inter-electrode distance has been studied in detail. Also the time dependent field emission studies of all the nanostructures have been carried out.     

Growth of carbon nanotubes on stainless steel substrates by DC-PECVD

We report on the fabrication of carbon nanotubes (CNTs) on Ni-coated stainless steel (SUS) substrates by using dc plasma enhanced chemical vapor deposition. The synthesized CNTs have the diameter of about 30 nm and the length of about 1.2 μm. To verify the effects of SUS substrates on the growth of CNTs, CNTs had also been grown on Ni-coated Si substrates. CNTs grown on the SUS substrates were more uniform compared with those grown on the Si substrates. Field emission properties of the CNT films were measured in the diode configuration, and the turn-on electric field of 3.87 V/μm and field enhancement factor β of about 1737 were obtained from the synthesized CNTs at the gap of 500 μm between the SUS substrate and the anode. These results have not only clarified the effects of the substrate on the growth of CNTs, but also shown the potential of CNTs in field emission applications, especially CNT-based cold-cathode X-ray tubes.     

Carbon nanotube as the core of conical carbon fiber: fabrication,characterization and field emission property

Conical carbon fibers (CCFs) with carbon nanotubes (CNTs) as their cores were grown on graphite substrates with a chemical vapor deposition method. The CNT-cored CCFs were about several tens of micrometers in length. In the interaction with a probe system, the CNT core filaments demonstrated good mechanical strength. Furthermore, field emission currents around 100 μA were also attained from individual CNTs. The growth mechanism of this CNT/CCF combined structure is briefly discussed. Our method has provided a convenient and inexpensive approach to mass assembling CNTs to a carbon substrate. PACS 81.05.Uw; 81.15.Gh; 79.70.+q     

Effects of total CH4/Ar gas pressure on the structures and field electron emission properties of carbon nanomaterials grown by plasma-enhanced chemical vapor deposition

The effects of total CH₄/Ar gas pressure on the growth of carbon nanomaterials on Si (1 0 0) substrate covered with CoO nanoparticles, using plasma-enhanced chemical vapor deposition (PECVD), were investigated. The structures of obtained products were correlated with the total gas pressure and changed from pure carbon nanotubes (CNTs) through hybrid CNTs/graphene sheets (GSs), to pure GSs as the total gas pressure changed from 20 to 4 Torr. The total gas pressure influenced the density of hydrogen radicals and Ar ions in chamber, which in turn determined the degree of how CoO nanoparticles were deoxidized and ion bombardment energy that governed the final carbon nanomaterials. Moreover, the obtained hybrid CNTs/GSs exhibited a lower turn-on field (1.4 V/μm) emission, compared to either 2.7 V/μm for pure CNTs or 2.2 V/μm for pure GSs, at current density of 10 μA/cm².     

Titanium buffer layer for improved field emission of CNT based cold cathode

Carbon nanotube (CNT) based cold cathodes are considered to be the most promising material for fabrication of next generation high-performance flat panel displays and vacuum microelectronic devices. Adhesion of CNTs with the substrate and the contact resistance between them are two of the important issues to be addressed in CNT based field emission (FE) devices. Here in this work, a buffer layer of titanium (Ti) is deposited prior to the catalyst deposition and the growth was carried out using chemical vapor deposition (CVD) technique. There was significant increase in emission current density from 10 mA/cm² to 30 mA/cm² at the field of 4 V/μm by the use of titanium buffer layer due to much less dense growth of CNTs of smaller diameter. Field emission results suggest that the adhesion of the CNTs to the substrate has improved. The titanium buffer layer has also lowered the contact resistance between the CNTs and the substrate because of which a stable emission of 30 mA for a longer duration was obtained.     

碳纳米管阵列拉曼光谱的对比研究

利用热化学气相沉积技术制备碳纳米管阵列,并对不同工艺下获得的一系列定向碳纳米管阵列进行了拉曼光谱的对比研究。研究发现：碳纳米管阵列一阶拉曼光谱的G峰中心和D峰中心都会向低波数方向发生红移。并且阵列中碳管的一致性、准直性越好,红移的波数就越多。除了谱峰以外,D线和G线的积分强度比I_D / I_G也能够反映所研究的碳材料的有序度和完整性。I_D / I_G越低,说明该碳纳米管阵列的石墨化越好,无定形碳杂质越少。     

Superior capacitive characteristics of RuO2 nanorods grown on carbon nanotubes

Carbon nanotubes (CNTs) were used as the electric double layer capacitor (EDLC) material and were synthesized by using thermal chemical vapor deposition (TCVD). To enhance the EDLC capacity, the ruthenium dioxide (RuO₂) nanorods were grown on CNTs by using metal organic chemical vapor deposition (MOCVD). The synthesized CNTs were the principal part and template, and the RuO₂ nanorods were grown outwardly from CNTs. The increase of effective specific area between electrode and electrolyte played an important role in enhancing the capacitance. Different concentrations of KOH were used as electrolyte to measure the capacitance to find the variation of capacitance. Moreover, the RuO₂/CNT composites demonstrated a stable cycle life. The results showed that the RuO₂/CNT composites were a promising supercapacitor device material.     

Aligned growth and alignment mechanism of carbon nanotubes by hot filament chemical vapor deposition

Carbon nanotubes (CNTs) growth on Inconel sheets was carried out using hot filament chemical vapor deposition (HFCVD) in a gas mixture of methane and hydrogen. Scanning electron microscopy, transmission electron microscopy and field electron emission (FEE) measurement were applied to study the structure and FEE properties of the deposited CNTs. The effect of bias voltage and substrate surface roughness on the growth of vertically aligned carbon nanotubes was investigated. Well-aligned CNTs were synthesized by bias enhanced HFCVD. The results show that a bias of −500 V generates the best alignment. It has been observed that at the early growth stage, aligned and non-aligned CNTs are growing simultaneously on the unscratched sheets, whereas only aligned CNTs are growing on the scratched sheets. The results indicate that tip growth is not necessary for the electric field to align the CNTs, and larger catalyst particles created by scratching before the heat treatment can induce alignment of CNTs at the early growth stage. In addition, tree-like CNTs bundles grown on the scratched substrates exhibit better FEE performances than dense carbon nanotube forest grown on the unscratched substrates due to the reduced screen effect.     

生长温度对碳纳米管阴极场发射性能的影响

碳纳米管(Carbon Nanotubes,CNTs)场发射平面显示器(Field Emission Display,FED)与其他显示器比较显示了其独特优点,被认为是未来理想的平面显示器之一。碳纳米管阴极作为器件的核心部分,其性能的好坏直接影响显示器的性能。针对30~60英寸(76.2~152.4cm)大屏幕显示器所用的厚膜工艺,即采用丝网印刷法制备了碳纳米管阴极阵列,研究了化学气相沉积法在不同温度下生长的CNTs的场发射电流-电压特性,找到了适合FED用碳纳米管的最佳生长温度。结果表明生长温度越高(750℃),CNTs场发射性能越好。并用荧光粉阳极测试这些CNTs的场发射发光显示效果,验证了上述结论。     

Field emission characteristics of carbon nanotubes post-treated with high-density Ar plasma

The field emission characteristics of carbon nanotubes (CNTs) grown by thermal chemical vapor deposition (CVD) and subsequently surface treated by high-density Ar plasma in an inductively coupled plasma reactive ion etching (ICP-RIE) with the various plasma powers were measured. Results indicate that, after treated by Ar plasma with power between 250 and 500 W, the emission current density of the CNTs is enhanced by nearly two orders of magnitude (increased from 0.65 to 48 mA/cm²) as compared to that of the as-grown ones. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were employed to investigate the structural features relevant to the modified field emission properties of CNTs. The SEM images of CNTs subjected to a 500 W Ar plasma treatment exhibit obvious damages to the CNTs. Nevertheless, the turn-on fields decreased from 3.6 to 2.2 V/μm, indicating a remarkable field emission enhancement. Our results further suggest that the primary effect of Ar plasma treatment might be to modify the geometrical structures of the local emission region in CNTs. In any case, the Ar plasma treatment appears to be an efficient method to enhance the site density for electron emission and, hence markedly improving the electric characteristics of the CNTs.     

Aerosol formation of Sea-Urchin-like nanostructures of carbon nanotubes on bimetallic nanocomposite particles

With the advantage of continuous production of pure carbon nanotubes (CNTs), a new simple aerosol process for the formation of CNTs was developed. A combination of conventional spray pyrolysis and thermal chemical vapor deposition enabled the formation unusual sea-urchin-like carbon nanostructures composed of multi-walled CNTs and metal composite nanoparticles. The CNTs formed were relatively untangled and uniform with a diameter of less than ~10 nm. The key to the formation of CNTs in this way was to create a substrate particle containing both a catalytic and non-catalytic component, which prevented coking. The density of the CNTs grown on the spherical metal nanoparticles could be controlled by perturbing the density of the metal catalysts (Fe) in the host non-catalytic metal particle matrix (Al). Mobility size measurement was identified as a useful technique to real-time characterization of either the catalytic formation of thin carbon layer or CNTs on the surface of the metal aerosol. These materials have shown unique properties in enhancing the thermal conductivity of fluids. Other potential advantages are that the as-produced material can be manipulated easily without the concern of high mobility of conventional nanowires, and then subsequently released at the desired time in an unagglomerated state.     

LPCVD法制备碳纳米管薄膜及其场发射性能的研究

采用低压化学气相沉积法(LPCVD)在镍片上直接制备碳纳米管(CNTs)薄膜,系统地研究了生长温度(500~800℃)对碳纳米管薄膜形貌、结构及场发射性能的影响,并对此方法的生长机理进行了分析。当温度从500℃升高到650℃时,碳纳米管的生长速率随着温度升高而增大,而温度继续上升,速率则明显减小。利用扫描电镜(SEM)和拉曼光谱仪表征和检测了碳纳米管薄膜的形貌和结构。碳纳米管的管径、长度、一致性和晶化程度随温度都有明显的变化。同时还对碳纳米管薄膜的场发射特性进行了测试,对其场发射机理进行了深入地探讨,表明温度对碳纳米管的性能有很大影响,并存在最优化的温度条件。实验结果表明碳纳米管薄膜的形貌、结构及其场发射性能可通过生长温度进行一定范围的控制。     

Direct production of carbon nanotubes decorated with Cu2O by thermal chemical vapor deposition on Ni catalyst electroplated on a copper substrate

Carbon nanotubes (CNTs) decorated with Cu₂O particles were grown on a Ni catalyst layer deposited on a Cu substrate by thermal chemical vapor deposition from liquid petroleum gas. Ni catalyst nanoparticles with different sizes were produced in an electroplating system at 45 °C using the corrosive effect of H₂SO₄ which was added to solution. These nanoparticles provide the nucleation sites for CNT growth avoiding the need for a buffer layer. The surface morphology of the Ni catalyst films and CNT growth over this catalyst was studied by scanning electron microscopy (SEM). High temperature surface segregation of the Cu substrate into the Ni catalyst layer and its exposition to O₂ at atmospheric environment, during the CNTs growth, lead to the production of CNTs decorated with about 6 nm Cu₂O nanoparticles. We used SEM to study the surface characteristics of Ni catalyst films and characteristic of grown CNTs. Raman spectroscopy, transmission electron microscopy (TEM), electron diffraction (EDX), X-ray diffraction, and X-ray photoelectron spectroscopy (XPS) revealed the formation of CNTs. The selected area electron diffraction pattern, EDX, and XPS studies show that these CNTs were decorated with Cu₂O nanoparticles. This way of fabrication is the easiest and lowest cost method.     

场致发射阴极碳纳米管的热化学气相沉积法低温生长

结合丝网印刷和过滤阴极真空电弧法、离子束溅射方法，在普通玻璃衬底上制备催化剂图案，采用低温热化学气相沉积法(CVD)生长碳纳米管/纤维(CNTs)薄膜.研究了不同种类催化剂对CNTs薄膜生长及其场发射的影响.结果表明，在a-C:Co,Ni-Cu和Cu三种催化剂上没有获得明显的CNTs，在外加电场小于4.4V/μm时没有观察到场发射；而在Ni-Fe及Ni-Cr两种催化剂上获得了大量的CNTs，并且表现出良好的场发射性能，开启电场为2.5V/μm，这种热CVD有简单、低温等优点，在CNTs场发射显示器的阴极制备中有潜在的应用价值.     

Change in Graphene Electronic Properties in the Presence of Acetone Vapor

Changes in properties of graphene grown by chemical vapor deposition (CVD) with water adsorbate removal from the graphene–SiO₂/Si substrate interface using an organic material, i.e., acetone, are studied. It is found that acetone vapor suppresses grapheme structuring under low-intensity nanosecond laser radiation (wavelength λ = 532 nm). It is found that the electron work function in graphene decreases by ～0.2 eV, which is presumably due to a decrease in the water adsorbate layer thickness at the mentioned interface.