Fabrication and Electrical Characterization of Densified Carbon Nanotube Micropillars for IC Interconnection

Closely packed carbon nanotube (CNT) bundles are expected to have higher conductivity than copper and could potentially replace copper for electrical and thermal conductors in IC chips. However, it is extremely difficult, if not impossible, to controllably grow closely packed CNT bundles. We report on a novel postgrowth capillary densification method, which results in dramatic increase of CNT site density. Bare CNT pillars are densified approximately 15 times. High-density CNT micropillars and micrologs with round cross sections were fabricated from CNTs coated with parylene prior to densification. These CNT micropillars and micrologs could be used as basic building blocks for future IC interconnection. Electrical characterization results show that the densification process does not mitigate the electrical conducting performance of CNTs.      

Electron field emission characteristics of different surface morphologies of ZnO nanostructures coated on carbon nanotubes

The optimal carbon nanotube (CNT) bundles with a hexagonal arrangement were synthesized using thermal chemical vapor deposition (TCVD). To enhance the electron field emission characteristics of the pristine CNTs, the zinc oxide (ZnO) nanostructures coated on CNT bundles using another TCVD technique. Transmission electron microscopy (TEM) images showed that the ZnO nanostructures were grown onto the CNT surface uniformly, and the surface morphology of ZnO nanostructures varied with the distance between the CNT bundle and the zinc acetate. The results of field emissions showed that the ZnO nanostructures grown onto the CNTs could improve the electron field emission characteristics. The enhancement of field emission characteristics was attributed to the increase of emission sites formed by the nanostructures of ZnO grown onto the CNT surface, and each ZnO nanostructure could be regarded as an individual field emission site. In addition, ZnO-coated CNT bundles exhibited a good emission uniformity and stable current density. These results demonstrated that ZnO-coated CNTs is a promising field emitter material.     

Evaluation and visualization of the percolating networks in multi-wall carbon nanotube/epoxy composites

In this study, epoxy-based nanocomposites containing multi-wall carbon nanotubes (CNTs) were produced by a calendering approach. The electrical conductivities of these composites were investigated as a function of CNT content. The conductivity was found to obey a percolation-like power law with a percolation threshold below 0.05 vol.%. The electrical conductivity of the neat epoxy resin could be enhanced by nine orders of magnitude, with the addition of only 0.6 vol.% CNTs, suggesting the formation of a well-conducting network by the CNTs throughout the insulating polymer matrix. To characterize the dispersion and the morphology of CNTs in epoxy matrix, different microscopic techniques were applied to characterize the dispersion and the morphology of CNTs in epoxy matrix, such as atomic force microscopy, transmission electron microscopy, and scanning electron microscopy (SEM). In particular, the charge contrast imaging in SEM allows a visualization of the overall distribution of CNTs at a micro-scale, as well as the identification of CNT bundles at a nano-scale. On the basis of microscopic investigation, the electrical conduction mechanism of CNT/epoxy composites is discussed.     

Vibration Damping of Carbon Nanotube Assembly Materials

Vibration reduction is of great importance in various engineering applications, and a material that exhibits good vibration damping along with high strength and modulus has become more and more vital. Owing to the superior mechanical property of carbon nanotube (CNT), new types of vibration damping material can be developed. This paper presents recent advancements, including our progresses, in the development of high‐damping macroscopic CNT assembly materials, such as forests, gels, films, and fibers. In these assemblies, structural deformation of CNTs, zipping and unzipping at CNT connection nodes, strengthening and welding of the nodes, and sliding between CNTs or CNT bundles are playing important roles in determining the viscoelasticity, and elasticity as well. Toward the damping enhancement, strategies for micro‐structure and interface design are also discussed.

     

An assessment of the science and technology of carbon nanotube-based fibers and composites

This paper examines the recent advancements in the science and technology of carbon nanotube (CNT)-based fibers and composites. The assessment is made according to the hierarchical structural levels of CNTs used in composites, ranging from 1-D to 2-D to 3-D. At the 1-D level, fibers composed of pure CNTs or CNTs embedded in a polymeric matrix produced by various techniques are reviewed. At the 2-D level, the focuses are on CNT-modified advanced fibers, CNT-modified interlaminar surfaces and highly oriented CNTs in planar form. At the 3-D level, we examine the mechanical and physical properties CNT/polymer composites, CNT-based damage sensing, and textile assemblies of CNTs. The opportunities and challenges in basic research at these hierarchical levels have been discussed.     

Improve photocurrent quantum efficiency of carbon nanotube by chemical treatment

High photocurrent quantum efficiency (QE) of carbon nanotubes (CNTs) is important to their photovoltaic applications. The ability of photocurrent generation of CNTs depends on their band structure and surface state. For given CNTs, it is possible to improve the QE of photocurrent by chemical modification. Here, we study the effects of simple chemical treatment on the QE of CNTs by measuring the photocurrent of macroscopic CNT bundles. The QE of the H₂O₂-treated CNT bundle reaches 5.28% at 0.1 V bias voltage at a laser (λ = 473 nm) illumination, which is 85% higher than that of the pristine sample. But the QE of the CNTs treated in concentrated HNO₃ is lower than that of the pristine sample. It shows that moderate chemical treatment can enhance the photocurrent QE and excessive chemical treatment will decrease the QE because of introducing lots of structural defects.     

改变基底合成不同形貌碳纳米管宏观结构

采用化学气相沉积法,选用不同基底和表面涂层合成了碳纳米管垂直阵列薄膜、管束和条带三种碳纳米管宏观结构,并用扫描电镜（SEM）和透射电镜（TEM）进行了表征。结果表明：在石英涂层上合成的定向碳纳米管薄膜厚度达毫米级;在表面有Al2O3涂层的不锈钢基底上可合成碳纳米管垂直阵列薄膜和不同尺寸宏观管束结构;在表面有SiO2涂层...     

Processing and tensile characterization of composites composed of carbon nanotube-grown carbon fibers

The growth of carbon nanotubes (CNTs) on carbon fibers was conducted via chemical vapor deposition. A solution approach has been used to distribute nickel particles on the fiber, and the carbon source was a methane gas. The resulting CNTs are about 10 μm in length and 50 nm in outer diameter. After CNT growth, a fiber bundle was impregnated with an epoxy resin to form a unidirectional composite. Tensile tests were carried out, and the induced fracture surface was examined by microscopes. Three types of CNT fracture during fiber pullout are discussed. The results show that fracture in the CNT/fiber joint is the major mode. Pullout of CNTs was also observed. While pullout of fibers leaves micro-scale holes, pullout of CNTs leaves nano-scale holes. The multi-scale fracture behavior generates new parameters for material design and processing. Some concepts regarding the microstructural design for this special composite are discussed.     

Process intensification by CO2 for high quality carbon nanotube forest growth: Double-walled carbon nanotube convexity or single-walled carbon nanotube bowls?

Introduction of CO₂ is a facile way to tune the growth of vertically aligned double- or single-walled carbon nanotube (CNT) forests on wafers. In the absence of CO₂, a double-walled CNT convexity was obtained. With increasing concentration of CO₂, the morphologies of the forests transformed first into radial blocks, and finally into bowl-shaped forests. Furthermore, the wall number and diameter distribution of the CNTs were also modulated by varying the amount of CO₂. With increasing CO₂ concentration, CNTs with fewer wall number and smaller diameter were obtained. The addition of CO₂ is speculated to generate water and serve as a weak oxidant for high quality CNT growth. It can tune the growth rate and the morphologies of the forests, prevent the formation of amorphous carbon, and reduce the wall number of the CNTs.     

Flexible High‐Conductivity Carbon‐Nanotube Interconnects Made by Rolling and Printing

Applications of carbon nanotubes (CNTs) in flexible and complementary metal‐oxide‐semiconductor (CMOS)‐based electronic and energy devices are impeded due to typically low CNT areal densities, growth temperatures that are incompatible with device substrates, and challenges in large‐area alignment and interconnection. A scalable method for continuous fabrication and transfer printing of dense horizontally aligned CNT (HA‐CNT) ribbon interconnects is presented. The process combines vertically aligned CNT (VA‐CNT) growth by thermal chemical vapor deposition, a novel mechanical rolling process to transform the VA‐CNTs to HA‐CNTs, and adhesion‐controlled transfer printing without needing a carrier film. The rolling force determines the HA‐CNT packing fraction and the HA‐CNTs are processed by conventional lithography. An electrical resistivity of 2 mΩ · cm is measured for ribbons having 800‐nm thickness, while the resistivity of copper is 100 times lower, a value that exceeds most CNT assemblies made to date, and significant improvements can be made in CNT structural quality. This rolling and printing process could be scaled to full wafer areas and more complex architectures such as continuous CNT sheets and multidirectional patterns could be achieved by straightforward design of the CNT growth process and/or multiple rolling and printing sequences.     

Advances in carbon-nanotube assembly

Iijima's observation in 1991 of fullerene-like materials by high-resolution transmission electron microscopy heralded the beginning of the carbon nanotube (CNT) era. A wealth of theoretical predictions and experimental verifications about CNTs have disclosed remarkable size- and structure-dependent properties that are attractive for various potential applications, ranging from conducting wires in molecular devices to fillers in nanocomposites. Many of these applications require assembly (alignment and/or patterning) of CNTs into hierarchical arrays over large-scale areas with controllable shape, location, orientation, and density of the nanotubes. Efforts from both the scientific and engineering points of view have been made to address this issue, beginning shortly after the discovery of CNTs. We review here the development of CNT-assembly techniques under the two rubrics of synthetic assembly and post-synthetic assembly, with emphasis given to the post-synthetic approach. Preliminary to the survey of assembly techniques, we also discuss the characterization techniques that have been widely used for the challenging tasks of visualizing and quantifying CNT assembly.     

Elaboration of single wall carbon nanotubes-based gas sensors: Evaluating the bundling effect on the sensor performance

In this article, carbon nanotube (CNT)-based sensors have been prepared using dispersion techniques. Sensors are obtained from a dispersion of CNTs using either chloroform as a solvent or sodium dodecylbenzene sulfonate as a surfactant. These sensors are prepared by drop-cast deposition of the solutions on interdigitated electrodes. The organic solvent processing leads to CNT layers where carbon nanotubes are obtained as larger bundles, whereas smaller bundles and individual tubes are predominantly formed in the surfactant processing. Under gas exposure (NO₂), both sensors respond to low gas concentrations; however, the sensing layers composed of larger bundles of CNTs present a slightly different behaviour (in terms of rapid stabilisation and sensitivity) compared to those made of individual CNTs.     

Experimental-computational study of shear interactions within double-walled carbon nanotube bundles

The mechanical behavior of carbon nanotube (CNT)-based fibers and nanocomposites depends intimately on the shear interactions between adjacent tubes. We have applied an experimental-computational approach to investigate the shear interactions between adjacent CNTs within individual double-walled nanotube (DWNT) bundles. The force required to pull out an inner bundle of DWNTs from an outer shell of DWNTs was measured using in situ scanning electron microscopy methods. The normalized force per CNT-CNT interaction (1.7 ± 1.0 nN) was found to be considerably higher than molecular mechanics (MM)-based predictions for bare CNTs (0.3 nN). This MM result is similar to the force that results from exposure of newly formed CNT surfaces, indicating that the observed pullout force arises from factors beyond what arise from potential energy effects associated with bare CNTs. Through further theoretical considerations we show that the experimentally measured pullout force may include small contributions from carbonyl functional groups terminating the free ends of the CNTs, corrugation of the CNT-CNT interactions, and polygonization of the nanotubes due to their mutual interactions. In addition, surface functional groups, such as hydroxyl groups, that may exist between the nanotubes are found to play an unimportant role. All of these potential energy effects account for less than half of the ~1.7 nN force. However, partially pulled-out inner bundles are found not to pull back into the outer shell after the outer shell is broken, suggesting that dissipation is responsible for more than half of the pullout force. The sum of force contributions from potential energy and dissipation effects are found to agree with the experimental pullout force within the experimental error.     

Macroscopic carbon nanotube assemblies: preparation, properties, and potential applications

As classical 1D nanoscale structures, carbon nanotubes (CNTs) possess remarkable mechanical, electrical, thermal, and optical properties. In the past several years, considerable attention has been paid to the use of CNTs as building blocks for novel high-performance materials. In this way, the production of macroscopic architectures based on assembled CNTs with controlled orientation and configurations is an important step towards their application. So far, various forms of macroscale CNT assemblies have been produced, such as 1D CNT fibers, 2D CNT films/sheets, and 3D aligned CNT arrays or foams. These macroarchitectures, depending on the manner in which they are assembled, display a variety of fascinating features that cannot be achieved using conventional materials. This review provides an overview of various macroscopic CNT assemblies, with a focus on their preparation and mechanical properties as well as their potential applications in practical fields.     

沉积条件对碳纤维表面碳纳米管生长的影响

采用化学气相沉积(CVD)法在碳纤维(CF)表面原位生长碳纳米管(CNTs)。考察了不同催化剂、沉积温度、氢气流量以及样品距进气口距离等工艺参数对CNTs-CF生长的影响。利用SEM和高分辨透射电子显微镜(HRTEM)对CNTs-CF形貌和微结构进行了表征和分析。结果表明:在CF表面原位生长的CNTs为多壁结构,其中以Ni为催化剂得到的CNTs直径小、分布均匀;在600~750℃温度范围内,随着温度的升高,CNTs直径和长度减小,产量降低;随着氢气流量的增加,CNTs直径和长度均增加;距进气口30cm,在CF表面得到的CNTs覆盖率高、直径小且分布窄,有利于制备高质量CNTs。     

Influence of shape and size on the alignment of multi-wall carbon nanotubes under magnetic fields

The influence of the shape and size of carbon nanotubes (CNTs) on the alignment of multi-wall CNTs was investigated. A CNT suspension with polyethylenimine (PEI) added as a dispersant showed stable dispersion. Stable CNT dispersion had a relatively high zeta potential value compared with poor dispersion. In addition, a strong magnetic field of 12 T was applied to the CNT suspension to investigate the alignment behavior of the CNTs. Good alignment of the CNTs according to the direction of the magnetic field was obtained. The degree of alignment depended on the shape and size of the CNTs, with the thick, straight CNTs showing better alignment than the thin, curved CNTs.     

Direct growth of horizontally aligned carbon nanotubes between electrodes and its application to field-effect transistors

This paper presents direct growth of horizontally-aligned carbon nanotubes (CNTs) between two predefined various inter-spacing up to tens of microns of electrodes (pads) and its use as CNT field-effect transistors (CNT-FETs). Using the conventional photolithography technique followed by thin film evaporation and lift off, the catalytic electrodes (pads) were prepared, consisting of Pt, Al and Fe triple layers on SiO2/Si substrate. The grown CNTs were horizontally-aligned across the catalytic electrodes on the modified gold image furnace hot stage (thermal CVD) at 800 degrees C by using an alcohol vapor as the carbon source. Scanning and transmission electron microcopies (SEM/TEM) were used to observe the structure, growth direction and density of CNTs, while Raman spectrum analysis was used to indicate the degree of amorphous impurity and diameter of CNTs. Both single- and multi-wall CNTs with diameters of 1.1-2.2 nm were obtained and the CNT density was controlled by thickness of Fe catalytic layer. Following horizontally-aligned growth of CNTs, the electrical properties of back-gate CNT-FETs were measured and showd p-type conduction behaviors of FET.     

Synthesis of multi-walled carbon nanotube bundles with uniform diameter

A new method is used to grow macroscopic multi-walled carbon nanotube (MWNT) bundles with uniform diameter in bulk quantities. The diameter of the bundles are about 15–25 μm and their length is over 500 μm. The CNTs in each bundle are closely compact and parallel to each other along the direction of the bundle axis, which have potential applications as a composite enhancer or a high-strength nanostructure. Scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Raman analysis have been used to evaluate the morphological and structural features of such nanotube-based material. The formation mechanism of the bundles is discussed.     

Microstructures and tensile behavior of carbon nanotube reinforced Cu matrix nanocomposites

Carbon nanotubes (CNTs) have been considered as an ideal reinforcement to improve the mechanical performance of monolithic materials. However, the CNT/metal nanocomposites have shown lower strength than expected. In this study, the CNT reinforced Cu matrix nanocomposites were fabricated by spark plasma sintering (SPS) of high energy ball-milled nano-sized Cu powders with multi-wall CNTs, and followed by cold rolling process. The microstructure of CNT/Cu nanocomposites consists of two regions including CNT/Cu composite region, where most CNTs are distributed, and CNT free Cu matrix region. The stress–strain curves of CNT/Cu nanocomposites show a two-step yielding behavior, which is caused from the microstructural characteristics consisting of two regions and the load transfer between these regions. The CNT/Cu nanocomposites show a tensile strength of 281 MPa, which is approximately 1.6 times higher than that of monolithic Cu. It is confirmed that the key issue to enhance the strength of CNT/metal nanocomposite is homogeneous distribution of CNTs.     

Synthesis and characterization of vertically aligned carbon nanotube forest for solid state fiber spinning

Continuous carbon nanotubes (CNT) fibers were directly spun from a vertically aligned CNT forest grown by a plasma-enhanced chemical vapor deposition (PECVD) process. The correlation of the CNT structure with Fe catalyst coarsening, reaction time, and the CNTs bundling phenomenon was investigated. We controlled the diameters and walls of the CNTs and minimized the amorphous carbon deposition on the CNTs for favorable bundling and spinning of the CNT fibers. The CNT fibers were fabricated with an as-grown vertically aligned CNT forest by a PECVD process using nanocatalyst an Al2O3 buffer layer, followed by a dry spinning process. Well-aligned CNT fibers were successfully manufactured using a dry spinning process and a surface tension-based densification process by ethanol. The mechanical properties were characterized for the CNT fibers spun from different lengths of a vertically aligned CNT forest. Highly oriented CNT fibers from the dry spinning process were characterized with high strength, high modulus, and high electrical as well as thermal conductivities for possible application as ultralight, highly strong structural materials. Examples of structural materials include space elevator cables, artificial muscle, and armor material, while multifunctional materials include E-textile, touch panels, biosensors, and super capacitors.