Field Emission Properties of Multi-walled Carbon Nanotubes Grown on Silicon Nanoporous Pillar Array

"Multi-walled carbon nanotubes (CNTs) were grown on a silicon nanoporous pillar array (Si-NPA) by thermal chemical vapor deposition. Surface morphologies and microstructure of the resultant were studied by a field emission scanning electron microscope, Raman spectrum, transmission electron microscope, and highresolution transmission electron microscopy. The composition of samples was determined by energy dispersive X-ray spectroscopy (EDS). The results showed that a great deal of CNTs, with diameter in the range of 20-70 nm, incorporated with Si-NPA and a large scale nest array of CNTs/Si-NPA (NACNT/Si-NPA) was formed. EDS analysis showed that the composition of carbon nanotubes was carbon. Field emission measurements showed that a current density of 5 mA/cm2 was obtained at an electric field of 4.26 V/1m, with a turn-on field of 1.3 V/1m. The enhancement factor calculated according to the Fowler-Nordheim theory was ?11,000. This excellent field emission performance is attributed to the unique structure and morphology of NACNT/Si-NPA, especially the formation of a nest-shaped carbon nanotube array. A schematic drawing that illustrates the experimental configuration is given. These results indicate that NACNT/Si-NPA might be an ideal candidate cathode for potential applications in flat panel displays."     

纳米CaCO3负载过渡金属CVD法制备多壁碳纳米管的研究

以纳米碳酸钙粉体为载体,用浸渍法制备了可用于化学气相沉积(CVD)法制备碳纳米管的高产率催化剂.应用FESEM,HRTEM,TEM,XRD和激光拉曼谱对产物进行了表征.结果表明,由于纳米碳酸钙具有较大的比表面积,可高密度地承载催化剂活性组分.在碳纳米管生长初期,处于缓慢分解状态的纳米碳酸钙才能有效地起到载体作用,且反应温度为700～750℃时,碳纳米管的产率较高.Fe-Co双金属催化剂在700℃,催化生长60min后,可增重10倍,而且产物中无定形碳含量极少.纳米碳酸钙载体易于提纯,用质量分数为30%的硝酸超声提纯粗产品1h,可使纯度提高到97%,且不破坏碳纳米管结构.     

二组元酞菁固相混合法裂解合成直立碳纳米管

通过向两种金属酞菁的混合物添加一定量的硫粉,在800～950 ℃裂解合成了大面积的直立碳纳米管。采用场发射扫描电镜(FE-SEM)、高分辨透射电镜(HRTEM)和拉曼光谱对产物进行了观察和表征,结果显示：所合成的碳纳米管(直径为15～35 nm,长度为200～800 nm)管身平直,具有很好的石墨化程度,且杂质很少。采用两种金属酞菁((M(Ⅱ)Pc, M=Fe, Co))进行混合裂解时,既可以提供碳源,而且可以产生相当均匀的催化剂颗粒,有利直立碳纳米管的沉积。这种将两种酞菁进行固相混合裂解的方法,相当安全高效,有利于大规模生产直立碳纳米管。     

铬酸及硝酸混合液处理以增强碳纳米管场发射

为了修饰碳纳米管(CNTs)的表面型态及改变碳纳米管的表面结构, 进一步增强碳纳米管的场发射特性, 使用铬酸及硝酸的混合溶液对碳纳米管进行后处理. 采用SEM、TEM、Raman 和EDS测试手段对样品的形貌、表面成份组成和微观结构特征进行了表征. 场发射(FE)的数据显示, 经过铬酸及硝酸的混合溶液处理20 min的碳纳米管场发射电流比未经任何处理的碳纳米管场发射电流明显增加一个数量级以上, 场发射电流增强的主要原因为样品上的碳纳米管的表面型态的改变, 造成碳纳米管场发射增强因子茁的增大. 与单独使用硝酸溶液后处理比较, 使用铬酸及硝酸的混合溶液对碳纳米管进行后处理可以得到较高的场发射电流及较低的起始电场. 铬酸及硝酸的混合溶液处理方法能经济且有效增强碳纳米管的场发射特性.     

Carbon nanotube bags: catalytic formation, physical properties, two-dimensional alignment and geometric structuring of densely filled carbon tubes

The catalytic CVD synthesis, using propyne as carbon precursor and Fe(NO3)3 as catalyst precursor inside porous alumina, gives carbon nanotube (CNT) bags in a well-arranged two-dimensional order. The tubes have the morphology of bags or fibers, since they are completely filled with smaller helicoidal CNTs. This morphology has so far not been reported for CNTs. Owing to the dense filling of the outer mother CNTs with small helicoidal CNTs, the resulting CNT fibers appear to be stiff and show no sign of inflation, as sometimes observed with hollow CNTs. The fiber morphology was observed by raster electron microscopy (REM), transmission electron microscopy (TEM), and atomic force microscopy (AFM). The carbon material is graphitic as deduced from spectroscopic studies (X-ray diffraction, Raman and electron energy-loss spectroscopy (EELS)). From M?ssbauer studies, the presence of two different oxidation states (Fe0 and FeIII) of the catalyst is proven. Geometric structuring of the template by two different methods has been studied. Inkjet catalyst printing shows that the tubes can be arranged in defined areas by a simple and easily applied technique. Laser-structuring creates grooves of nanotube fibers embedded in the alumina host. This allows the formation of defined architectures in the microm range. Results on hydrogen absorption and field emission properties of the CNT fibers are reported.     

Enhancement of Field Emission Characteristics for Multi-Walled Carbon Nanotubes Treated with a Mixed Solution of Chromic Trioxide and Nitric Acid

A simple acid treatment method was applied to functionalize the surface and to modify the structures of multi-walled carbon nanotubes (CNTs) grown on silicon substrates using a mixed solution of chromic trioxide (CrO₃) and nitric acid (HNO₃). Scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectroscopy, and energy dispersive spectrometer (EDS) were employed to investigate the mechanism causing the modified field emission (FE) properties of the CNT films. After 20 min of CrO₃+HNO₃ treatment, the emitted currents were enhanced by more than one order of magnitude compared with those of the untreated CNTs. This large increase in emitted current can be attributed to the favorable surface morphologies, open-ended structures, and highly curved CNT surfaces in the CNT films. These factors altogether caused an increase in the field enhancement factors of CNTs. We also demonstrated that using a mixed solution of CrO₃+HNO₃ post-treatment exhibited a higher emission current and a lower turn-on electric field than in the CNTs treated with HNO₃. The method provides a simple, economical, and effective way to enhance the CNT field emission properties.     

CNTs/TiO2多孔复合膜的组装及光催化性能

提出了一种在掺氟的SnO2(FTO)导电玻璃上组装碳纳米管(CNTs)/Fe-Ni/TiO2多孔复合膜光催化剂的新方法.采用喷涂热解法(SPD)将掺杂镍和铁的含有嵌段聚合物P123的二氧化钛前驱体溶胶涂覆在FTO导电玻璃上,制备Fe-Ni/TiO2多孔膜,再采用化学气相沉积法(CVD)在Fe-Ni/TiO2膜上原位生长CNTs,得到CNTs/Fe-Ni/TiO2多孔复合膜光催化剂.CNTs/Fe-Ni/TiO2复合膜具有多级孔结构特征,在TiO2表面原位生长的CNTs不但具有较好的石墨化结构,且CNTs较均匀地分布在整个膜层的孔中.考察了CNTs/Fe-Ni/TiO2复合膜光催化剂的结构和性能,并通过降解甲基橙溶液评价了复合膜的光催化活性.结果表明,CNTs的复合及铁和镍的掺杂等改性显著提高了TiO2膜材料的光催化活性.     

含Fe、Co、Ni的LDHs为催化剂前体生长碳纳米管

分别以具有相似Fe、Co、Ni含量的层状双金属氢氧化物（LDHs）为催化剂前体,用化学气相沉积的方法生长碳纳米管（CNTs）。 催化剂由LDHs焙烧还原得到。 通过X射线衍射（XRD）、扫描电子显微镜（SEM）、透射电子显微镜（TEM）及拉曼光谱（Raman）测试技术对LDHs及其焙烧产物的结构、CNTs的形貌和结构进行了研究。 结果表明,3种催化剂生长的CNTs均为多壁结构;其中Co催化剂活性较低,生长CNTs的管径较细、石墨化程度较高;Ni催化剂的活性较高,生长CNTs的密度较大、管壁较厚、石墨化程度较差;Fe催化剂的活性介于Co和Ni之间。 催化剂活性及CNTs的密度可以由生长CNTs的结构来解释。     

含Fe、Co、Ni的层状双金属氢氧化物为催化剂前体生长碳纳米管

分别以具有相似Fe、Co、Ni含量的层状双金属氢氧化物(LDHs)为催化剂前体,用化学气相沉积的方法生长碳纳米管(CNTs).催化剂由LDHs焙烧还原得到.通过X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)及拉曼光谱(Raman)测试技术对LDHs及其焙烧产物的结构、CNTs的形貌和结构进行了研究.结果表明,3种催化剂生长的CNTs均为多壁结构;其中Co催化剂活性较低,生长CNTs的管径较细、石墨化程度较高;Ni催化剂的活性较高,生长CNTs的密度较大、管壁较厚、石墨化程度较差;Fe催化剂的活性介于Co和Ni之间.催化剂活性及CNTs的密度可以由生长CNTs的结构来解释.     

Improvement of field emission properties from screen‐printed CNTs cathodes by heat treatment in a C2H2/H2 gas mixture

We developed a posttreatment method for the screen‐printed carbon nanotubes (CNTs) cathode to improve its field emission characteristics. The treatment was carried out at 500 °C and 20 kPa for 20 min in the atmosphere of C₂H₂/H₂ (volume ratio 1:2). After the treatment, the field emission characteristics were greatly improved. The turn‐on field lowered from 5.0 to 1.6 V/µm, and the emission current density increased from 2 × 10^?4 to 1.0 mA/cm² at the electric field of 2.6 V/µm. In the mean time, the emission site density and uniformity were significantly increased. Scanning electron microscope images revealed that a new top layer of CNTs film has re‐grown on the surface of the printed CNTs cathode during the treatment. This new re‐grown CNTs layer contributes to the drastic enhancement of field emission from the printed cathode. This heat‐treatment technique is very promising for practical application of CNTs in field emission display. Copyright © 2006 John Wiley & Sons, Ltd.     

Bulk synthesis of linear carbon chains confined inside single-wall carbon nanotubes by vacuum discharge

Carbyne, an infinite carbon chain, has attracted much interest and induced significant controversy for many decades. Recently, the presence of linear carbon chains (LCCs), which were confined stably inside double-wall carbon nanotubes (DWCNTs) and multiwall carbon nanotubes (MWCNTs), has been reported. In this study, we present a novel method to produce LCCs in a film of carbon nanotubes (CNTs). Our transmission electron microscopy and Raman spectroscopy revealed the formation of a bulk amount of LCCs after electric discharge of CNT films, which were used as field emission cathodes. The LCCs were confined inside single-wall CNTs as well as DWCNTs. Furthermore, two or three LCCs in parallel with each other are encapsulated when the inner diameter of CNT is larger than approximately 1.1 nm.     

Influence of high vacuum annealing treatment on some properties of carbon nanotubes

Carbon nanotubes (CNTs) were synthesized using a chemical vapour deposition (CVD) method. The properties of CNTs before and after vacuum annealing treatment were studied using scanning electron microscopy (SEM), scanning tunneling microscopy/spectroscopy (STM/STS) and thermogravimetric analysis (TG). Field emission characteristics of the raw and vacuum heated (up to 650°C) carbon nanotube films (CNTFs) were measured in a diode system. Emissive properties of the CNTFs depend on an annealing process during which structural changes in the nanotube walls take place. The structural changes, related to saturation of dangling bonds, influence a rate of oxidation process and also improve the emissive field properties.     

Preparation of well-aligned carbon nanotubes/silicon nanowires core-sheath composite structure arrays in porous anodic aluminum oxide templates

The well-aligned carbon nanotubes (CNTs) arrays with opened ends were prepared in ordered pores of anodic aluminum oxide (AAO) template by the chemical vapor deposition (CVD) method. After then, silicon nanowires (SiNWs) were deposited in the hollow cavities of CNTs. By using this method, CNTs/SiNWs core-sheath composite structure arrays were synthesized successfully. Growing structures and physical properties of the CNTs/SiNWs composite structure arrays were analyzed and researched by the scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray diffraction spectrum (XRD), respectively. The field emission (FE) behavior of the CNTs/SiNWs composite structure arrays was studied based on Fowler-Nordheim tunneling mechanism and current-voltage (/-V) curve. And the photoluminescence (PL) was also characterized. Significantly, the CNTs/SiNWs core-sheath composite structure nanowire fabricated by AAO template method is characteristic of a metal/semiconductor (M/S) behavior and can be     

Quantitative analysis of electron field-emission characteristics of individual carbon nanotubes: the importance of the tip structure

Electron field-emission measurements on individual carbon nanotubes (CNTs) were performed inside the transmission electron microscope (TEM). The field-emission characteristics of CNTs with different tip structures were compared, and their field conversion factor and emission area were studied systematically. It was found that the field-emission characteristics of a CNT depend sensitively on its tip structure, and in particular an opened CNT was shown to be superior to a capped CNT. High-resolution TEM observations revealed that the tip of an opened CNT may, in general, be regarded as being composed of irregular shaped graphitic sheets, and these graphitic sheets have been found to improve dramatically the field-emission characteristics, but the sharp edge may result in larger error in the calculated emission area. The influence of uncertainty in the work function of the CNTs on the field conversion factor and emission area calculation was also investigated.     

液相法制备取向ZnO纳米线阵列的场发射特性(英文)

采用水热合成工艺,在不同条件下制备了不同的一维取向ZnO纳米线阵列样品.用X射线衍射仪(XRD)、扫描电镜(SEM)及透射电镜(TEM)对样品的晶体结构和形貌等进行了表征,对样品的场发射特性进行了分析和比较,并用Fowler-Nordheim方程对影响ZnO纳米线场发射的因素进行了研究.结果表明,具有较低生长密度分布、较高的长径比和较尖锐生长端的ZnO纳米线阵列样品具有较好的场发射特性.     

A catalytic gas diffusion layer for improving the efficiency of a direct methanol fuel cell

The efficiency of a single direct methanol fuel cell (DMFC) with Pt–Ru decorated carbon nanotubes directly grown on carbon cloth (Pt–Ru/CNTs/CC) as a catalytic gas diffusion layer (GDL) at the anode was evaluated by polarization analysis. Pt–Ru nanoparticles were electrodeposited on dense carbon nanotubes directly grown on carbon cloth in ethylene glycol containing sulfuric acid solutions. The presence of relatively well dispersed Pt–Ru nanoparticles (4–6 nm) on the surfaces of CNTs was confirmed by transmission electron microscopy. Two more GDLs, one with dense CNTs but without the presence of Pt–Ru nanoparticles and the other with neither CNTs nor catalysts, were also prepared for comparison purpose. For quantitatively evaluating the performance of the catalytic GDL, three identical membrane–electrode-assemblies were prepared and laminated with different GDLs before they were used to construct DMFCs for performance test. It was found via polarization analyses the catalytic GDL was able to promote the peak specific power density of the DMFC by 27% at ambient temperature.     

多壁碳纳米管结构与其电化学容量之间关系的研究

采用化学气相沉积法,通过改变催化剂的成分、碳源、反应和后处理条件来制 备不同管径、管长、石墨化程度的多壁碳纳米管。经电化学容量性能测试、透射电 子显微镜观察和N_2吸附等结构表征,发现管径分布为30.0～40.0 nm、管长越短、 石墨化程度越低、比表面积越大、孔容越大的多壁碳纳米管具有更好的电化学容量 。     

Surface functionalization of multiwalled carbon nanotubes with poly(3,4-propylenedioxythiophene) and preparation of its random copolymers: new hybrid materials

Multiwalled carbon nanotubes (MWNTs) were functionalized with poly(3,4-propylenedioxythiophene) (PProDOT) using a simple “chemical grafting” approach. After the conventional acid oxidation (AO) process, the MWNT-COOH was converted to the acyl chloride functionalized MWNTs (MWNT-COCl) by treating them with thionyl chloride. The MWNT-COCl were further reacted with a functionalized monomer based on 3,4-propylenedioxythiophene (ProDOT-OH), followed by oxidative polymerization to prepare the MWNT-g-PProDOT hybrid. The monomer-functionalized MWNTs was further copolymerized with thiophene to prepare conducting copolymers on carbon nanotubes (CNTs). Fourier-transformed infrared spectrophotometry was employed to characterize the change in surface functionalities, which revealed that the PProDOT was covalently grafted to the MWNTs, while TGA was used to study the weight gain due to the functionalization. UV–Vis absorption spectra revealed the functionalization of the conjugated polymer by showing the typical absorption band. The morphology micrographs of the grafted PProDOT on MWNTs as evidenced by field emission scanning electron microscopy and transmission electron microscopy showed apparent effect on the structure and appearance of the MWNTs by growing thicker as expected from surface modification. Using the facile route developed in this study, CNTs can be easily fabricated with other types of polymers for several applications.     

Controlled Nanofiber Composed of Multi‐Wall Carbon Nanotube/Poly(Ethylene Oxide)

We have successfully fabricated poly(ethylene oxide) (PEO) nanofibers containing embedded multi‐wall carbon nanotubes (MWCNTs). An initial dispersion of the MWCNTs in distilled water was achieved using sodium dodecyl sulfate. Subsequently, the dispersion was decanted into a PEO solution, which enabled separation of the MWCNTs and their individual incorporation into the PEO nanofibers on subsequent electrospinning. Initially, the carbon nanotube (CNT) rods were randomly oriented, but owing to the sink‐like flow in the electrospinning wedge, they became gradually oriented along the streaming direction, in order that oriented CNTs were obtained on entering the electrospun jet. Individual MWCNTs became embedded in the nanofibers, and were mostly aligned along the fiber axis. Evidence of load transfer to the nanotubes in the composite nanofiber was observed from the field‐emission scanning electron microscopy, transmission electron microscopy and conductivity data.     

Two types of carbon nanocomposites: Graphite encapsulated iron nanoparticles and thin carbon nanotubes supported on thick carbon nanotubes, synthesized using PECVD

In this work, graphite encapsulated Fe nanoparticles and thin carbon nanotubes (CNTs) supported on the pristine CNTs, respectively, were synthesized using plasma enhanced chemical vapor deposition via efficiently controlling the flow rate of discharging CH₄ and H₂ gas. The properties of the obtained hybrid materials were characterized with superconducting quantum interference and field emission measurements. The results showed that the encapsulated Fe nanoparticles had diameters ranging from 1 to 30 nm, and this hybrid nanocomposite exhibited a ferromagnetic behavior at room temperature. Thin CNTs with an average diameter of 6 nm were attached to the surface of the prepared CNTs, which exhibited a lower turn-on field and higher emission current density than the pristine CNTs. The Fe nanoparticles either encapsulated with graphite or used as catalyst for thin CNTs growth were all originated from the pyrolysis of ferrocene.