Cover Picture: Fabrication and Electrical and Mechanical Properties of Carbon Nanotube Interconnections (Adv. Funct. Mater. 11/2005)

The fabrication of carbon nanotube (CNT) structures, including simple tube–tube connections, crossed junctions, T‐junctions, zigzag structures, and even nanotube networks, has been achieved by cutting and soldering CNTs using electron‐beam‐induced deposition of amorphous carbon (a‐C), as detailed in the work of Peng and co‐workers on p. 1825. These CNT structures have been constructed with a high degree of control, and it is found that the electric conductance and mechanical strength of the junctions can be improved by the deposition of a‐C and by increasing the contact area of the junctions. Individual carbon nanotubes (CNTs) have been cut, manipulated, and soldered via electron‐beam‐induced deposition of amorphous carbon (a‐C) and using a scanning tunneling microscope inside a transmission electron microscope. All CNT structures, including simple tube–tube connections, crossed junctions, T‐junctions, zigzag structures, and even nanotube networks, have been successfully constructed with a high degree of control, and their electrical and mechanical properties have been measured in situ inside the transmission electron microscope. It is found that multiple CNTs may be readily soldered together with moderate junction resistance and excellent mechanical resilience and strength, and the junction resistance may be further reduced by current‐induced graphitization of the deposited a‐C on the junction.     

Shaping Carbon Nanotubes and the Effects on Their Electrical and Mechanical Properties

A method is developed and shown to be able to shape a carbon nanotube (CNT) into a desired morphology while maintaining its excellent electrical and mechanical properties. Single, freestanding nanotubes are bent by a scanning tunneling microscopy probe, and their morphology is fixed by electron‐beam‐induced deposition (inside a transmission electron microscope) of amorphous carbon on the bent area. It is shown that the mechanical strength of the bent CNT may be greatly enhanced by increasing the amount of carbon glue or the deposition area, and the electrical conduction of the nanotube shows hardly any dependence on the bending deformation or on the deposition of amorphous carbon. Our findings suggest that CNTs might be manipulated and processed as interconnections between electronic devices without much degradation in their electrical conductance, and be used in areas requiring complex morphology, such as nanometer‐scale transport carriers and nanoelectromechanical systems.     

Nondestructive determination of the depth of planar p-n junctions by scanning electron microscopy

A method was developed for measuring nondestructively the depth of planar p-n junctions in simple devices as well as in integrated-circuit structures with the electron-beam induced current (EBIC) by scanning parallel to the junction in a scanning electron microscope (SEM). The results were found to be in good agreement with those obtained by the commonly used destructive method of lapping at an angle to the junction and staining to reveal the junction.     

Template Synthesis of Aligned Carbon Nanotube Arrays using Glucose as a Carbon Source: Pt Decoration of Inner and Outer Nanotube Surfaces for Fuel‐Cell Catalysts

A facile method is developed to synthesize aligned arrays of open‐ended carbon nanotubes (CNTs) via in situ glucose polymerization in the inner pores of anodic aluminum oxide templates under hydrothermal conditions, followed by carbonization at high temperature. Pt nanoparticles are decorated on the surfaces of the as‐prepared CNTs using the incipient wet method based on the use of NaBH₄ as a reductant. Characterization of the resulting structures by transmission electron microscopy and field‐emission scanning electron microscopy demonstrates that the Pt nanoparticles are anchored on both the inner and outer walls of CNTs, thus giving rise to a shell–core–shell‐like nanotube composite. The electrocatalytic properties of the Pt–CNT–Pt electrodes are investigated for methanol oxidation by cyclic voltammetry and chronoamperometric measurements. It is found that the hybrid electrodes show superior catalytic performance compared to commercial carbon‐black‐supported Pt. The increased catalytic efficiency of Pt might be a result of the unique morphology of these structures.     

Current‐Induced Restructuring and Chemical Modification of N‐Doped Multi‐walled Carbon Nanotubes

Multi‐walled carbon nanotubes (MWCNTs) have long been anticipated as candidates for electrical components in an increasingly miniaturized electronics industry due to their inherent electrical properties. It is possible to manipulate and control these properties by introducing dopants such as N, B, and P. Although some current‐induced structural changes in MWCNTs have been observed, no systematic study has been carried out to explore the correlation of changes in the internal structure with the electronic behavior of doped‐MWCNTs in terms of the current densities present. In situ transmission electron microscopy (TEM) investigations are presented here of individual, N‐doped MWNCT (N‐MWCNTs) using the in situ TEM/scanning tunneling microscopy (TEM/STM) Nanofactory© holder. It is observed for the first time that N‐MWCNTs not only undergo current‐induced structural transformation; i.e., from the typical bamboo structure of N‐MWCNTs to the stacked cones, but also—and most importantly—the complete removal of the dopant causes a significant change in the electronic behavior. This has serious implications for the use of doped CNTs as electronic components, especially since tremendous efforts are being made to synthesize CNTs with controlled dopant concentrations.     

Structural characteristics of carbon nanostructures synthesized by ECR-CVD

In this study, carbon nanotubes (CNTs) and nanoparticles were synthesized by an electron cyclotron resonance-chemical vapor deposition (ECR-CVD) system. Results show that both high- and low-aspect-ratio CNTs and nanoparticles are found. The CNTs range in length from tens of nanometers to micrometers, and in outer diameter from about 5 to 50 nm. Transmission electron microscope (TEM) images show that the faceted nanoparticles exhibit polyhedral or onion or irregularly profiled fullerene structures, and the CNTs growth is from the interlayers lamination. The surface sheet resistance and average surface roughness of the CNT films are about 360 Ω per square and 7-17 nm, respectively. When the CNT sample has a higher amount of nanoparticles, the current density will be increased.     

Beam to String Transition of Vibrating Carbon Nanotubes Under Axial Tension

State‐of‐the‐art nanoelectromechanical systems have been demonstrated in recent years using carbon nanotube (CNT) based devices, where the vibration of CNTs is tuned by tension induced through external electrical fields. However, the vibration properties of CNTs under axial tension have not been quantitatively determined in experiments. Here, a novel in situ method for precise and simultaneous measurement of the resonance frequency, the axial tension applied to individual CNTs and the tube geometry is demonstrated. A gradual beam‐to‐string transition from multi‐walled CNTs to single‐walled CNTs is observed with the crossover from bending rigidity dominant regime to extensional rigidity dominant regime occur much larger than that expected by previous theoretical work. Both the tube resonance frequency under tension and transition of vibration behavior from beam to string are surprisingly well fitted by the continuum beam theory. In the limit of a string, the vibration of a CNT is independent of its own stiffness, and a force sensitivity as large as 0.25 MHz (pN)^?1 is demonstrated using a 2.2 nm diameter single‐walled CNT. These results will allow for the designs of CNT resonators with tailored properties.     

纳米碳管新用途：石棉纤维的屏蔽

本文报道了对石棉纤维外围生长的纳米碳管的观察和研究，利用电子显微镜可以看到，以直径为几十纳米的柱形石棉纤维表面为基可通过电弧放电的方法在石棉纤维表面生长屏蔽碳管，内部的石棉纤维及其外部的碳管均经过Ｘ射线能量损失谱的成份分析及选区电子衍射的结构分析加以证实。本文还对以石棉纤维为基体的碳管生长机制进行了探讨。     

碳纳米管对Ni60激光熔覆层的耐蚀性影响

利用自动送粉激光熔覆技术,在A3钢表面进行了Ni60合金添加碳纳米管的激光熔覆实验,采用静态浸泡法对相同工艺条件下获得的纯Ni60熔覆层和碳纳米管/镍基熔覆层的耐腐蚀性进行研究,在光学显微镜下观察样品表面腐蚀形貌,并对碳纳米管/镍基熔覆层的腐蚀机理进行了分析.结果表明:当碳纳米管的含量为0.3 wt%时,碳纳米管/镍基激光熔覆层的耐腐蚀性能最好,与纯Ni60激光熔覆层相比,耐腐蚀性提高1倍多.碳纳米管/镍基激光熔覆层耐腐蚀的原因在于熔覆层保留的碳纳米管使熔覆层更加致密,隔离了腐蚀介质,促进了镍基合金的钝化,从而提高了熔覆层的耐蚀性;同时,熔覆层中保留下来的碳纳米管和被分解的碳纳米管与金属基体形成碳化物,作为增强相均匀弥散在熔覆层中,它们的存在阻止了腐蚀坑的长大,因而蚀坑较小,耐腐蚀性得到提高.     

Effect of rapid thermally nitrided titanium films contacting silicided and nonsilicided junctions

The effect of rapid thermally nitrided titanium films contacting silicided (titanium disilicided) and nonsilicided junctions has been studied in the temperature range of 800 to 900°C. The rapid thermal nitridation of titanium films used as diffusion barriers between aluminum and silicon, has a major impact on shallow junction complementary metal oxide semiconductor technologies. During the process of rapid thermal nitridation, the dopants in the junctions undergo a redistribution and affect the electrical properties of shallow junction structures. This work focuses on using novel contact resistance structures to measure the variation in electrical parameters for rapid thermally nitrided titanium films annealed at different temperatures. The self-aligned silicide (salicide) junctions in this study were formed using rapid thermally annealed titanium films. Electrical contact resistance testers were used to measure the interface contact resistance between the salicide and silicon, as well as between the metal and the salicide. The results show that the interface contact resistance to the p⁻ diffused salicided junctions increases with rapid thermal nitridation of the additional titanium film, whereas the interface contact resistance to the n⁻ diffused salicided junction shows a decrease. Further, as a function of the rapid thermal annealing temperature (for fixed titanium thickness), the nonsalicided diffusions show an increase in the interface contact resistance. The boron profiles at the TiSi₂/Si interface obtained using secondary ion mass spectroscopy show an excellent qualitative agreement with the electrical results for each of the conditions discussed. The films were also characterized using Rutherford back-scattering spectrometry and transmission electron microscopy and the results show good agreement with the measured variation in electrical parameters. These results also show that as the anneal temperature is increased, the TiN thickness increases, further the change in the silicide/silicon interface position with the nitridation of the additional titanium layer was verified. This work was carried out when the author was working at AT&T Bell Labs     

Poly(ϵ‐caprolactone)‐Functionalized Carbon Nanotubes and Their Biodegradation Properties

Biodegradable poly(?‐caprolactone) (PCL) has been covalently grafted onto the surfaces of multiwalled carbon nanotubes (MWNTs) by the “grafting from” approach based on in‐situ ring‐opening polymerization of ?‐caprolactone. The grafted PCL content can be controlled easily by adjusting the feed ratio of monomer to MWNT‐supported macroinitiators (MWNT‐OH). The resulting products have been characterized with Fourier‐transform IR (FTIR), NMR, and Raman spectroscopies, transmission electron microscopy (TEM), and scanning electron microscopy (SEM). After PCL was coated onto MWNT surfaces, core/shell structures with nanotubes as the “hard” core and the hairy polymer layer as the “soft” shell are formed, especially for MWNTs coated with a high density of polymer chains. Such a polymer shell promises good solubility/dispersibility of the MWNT–PCL nanohybrids in low‐boiling‐point organic solvents such as chloroform and tetrahydrofuran. Biodegradation experiments have shown that the PCL grafted onto MWNTs can be completely enzymatically degraded within 4 days in a phosphate buffer solution in the presence of pseudomonas (PS) lipase, and the carbon nanotubes retain their tubelike morphologies, as observed by SEM and TEM. The results present possible applications for these biocompatible PCL‐functionalized CNTs in bionanomaterials, biomedicine, and artificial bones.     

Radio-frequency transmission properties of carbon nanotubes in a field-effect transistor configuration

In this letter, the radio-frequency (RF) transmission properties of single-walled carbon nanotubes (CNTs) have been characterized up to the frequency of 12 GHz in a carbon nanotube field-effect transistor (CNFET) configuration using a two-port S-parameter method for the first time. The RF characteristics of the CNTs were measured from the drain to the source of the CNFET. A resistance, inductance, and capacitance model has been proposed, and the element values have been extracted. Without the effect of the parasitics, the RF signal transmission in the CNTs presents no degeneration even at 12 GHz. The capacitive contact between CNTs and metal electrodes is reported.     

An inner-feedback-style traveling-wave tube oscillator

A new concept of inner-feedback-style traveling wave tube oscillator, which is based on a traveling-wave tube having a partial reflector located at near the junction between the slow-wave structure and the output coupler and a mechanical tuner connected to the input coupler, is proposed. Simulations by CHIPIC code show that the inner-feedback-style traveling wave tube oscillator having 100W of power, about 10% of electron efficiency and a tunable band of 73.35?C73.91 GHz may be achieved. Compared with Backward Wave Oscillators (BWOs), the new devices have similar ability for tuning, and have much higher electron efficiency, suggesting much more potential as a Terahertz source.     

Preparation of Short Carbon Nanotubes and Application as an Electrode Material in Li‐Ion Batteries

A new approach is developed for cutting conventional micrometer‐long entangled carbon nanotubes (CNTs) to short ca. 200 nm long segments with excellent dispersion. CNTs with different lengths are used as anode materials in Li‐ion batteries. The reversible capacity of the Li‐ion batteries is increased and the irreversible capacity is decreased upon shortening the length of the CNTs. The reason for this is that the insertion/extraction of Li ions is easier into/from short CNTs as compared to long CNTs because of the shortened length and the presence of lateral defects. Moreover, short CNTs have a lower electrical resistance and Warburg prefactor, resulting in better rate performance at high current densities. The present study suggests that short segments of CNTs obtained by cutting long CNTs may possess novel properties that may be useful for a wide variety of applications.     

A Pyrenylpropyl Phosphonic Acid Surface Modifier for Mitigating the Thermal Resistance of Carbon Nanotube Contacts

Efforts to utilize the high intrinsic thermal conductivity of carbon nanotubes (CNTs) for thermal transport applications, namely for thermal interface materials (TIMs), have been encumbered by the presence of high thermal contact resistances between the CNTs and connecting materials. Here, a pyrenylpropyl‐phosphonic acid surface modifier is synthesized and applied in a straight forward and repeatable approach to reduce the thermal contact resistance between CNTs and metal oxide surfaces. When used to bond nominally vertically aligned multi‐walled CNT forests to Cu oxide surfaces, the modifier facilitates a roughly 9‐fold reduction in the thermal contact resistance over dry contact, enabling CNT‐based TIMs with thermal resistances of 4.6 ± 0.5 mm² K W^?1, comparable to conventional metallic solders. Additional experimental characterization of the modifier suggests that it may be used to reduce the electrical resistance of CNT‐metal oxide contacts by similar orders of magnitude.     

Copper Azide Confined Inside Templated Carbon Nanotubes

The currently used primary explosives, such as lead azide and lead styphnate, present serious health hazards due to the toxicity of lead. There is a need to replace them with equally energetic but safer‐to‐handle and more environmentally friendly materials. Copper azide is more environmentally acceptable, but very sensitive and detonates easily from electrostatic charges during handling. If the highly sensitive copper azide is encapsulated within conducting containers, such as anodic aluminum oxide (AAO)‐templated carbon nanotubes (CNTs), its sensitivity can be tamed. This work describes a technique for confining energetic copper azide within CNTs. ～5 nm colloidal copper oxide nanoparticles are synthesized and filled into the 200 nm diameter CNTs, produced by template synthesis. The Cu‐O inside the CNTs is reduced in hydrogen to copper, and reacted with hydrazoic acid gas to produce copper azide. Upon initiation, the 60 μm long straight, open‐ended CNTs guide decomposition gases along the tube channel without fracturing the nanotube walls. These novel materials have potential for applications as nano‐detonators and green primary explosives; they also offer new opportunities for understanding the physics of detonation at the nanoscale.     

Effect of molecular bending and foreign molecules on electronic properties of molecular junctions

We have investigated the charge transport properties of molecular junction using density functional theory in combination with the non-equilibrium Green's function. The charge transport behaviour and change in electronic properties of the molecular junctions formed by bending CNTs is explained by analysing molecular projected self-consistent Hamiltonian, projected density of state, transmission eigen channel, and transmission spectra. The system we used for investigation is consisting of CNTs (3, 3), & (3, 0) with conducting electrodes of Au. Because of the gradual loss in overlapping of the molecular orbitals due to bending processes the conductance decreases. The work also reveals that H₂O significantly affects the conductance of the bent CNTs by interacting with the orbitals of the CNTs and shifting orbital energies, closer to the Au Fermi energy.     

Biomimetic Carbon Nanotube Films with Gradient Structure and Locally Tunable Mechanical Property

Naturally existing materials often acquire unique functions by adopting a gradient structure with gradual change in their microstructure and related properties. Imparting such an elegant structural control into synthetic materials has been a grand challenge in the field. Here, the concept of gradient structure into macroscopic carbon nanotube (CNT) films is employed and the CNT arrangement from well‐aligned array to completely random distribution, in a continuous and smooth way, is changed. Gradient films with tailored aligned‐to‐random transition rate or multilevel hierarchical structures with repeated transition have been fabricated. Local deformation and mechanical properties are directly related to the arrangement of CNTs and can be tailored by Herman's orientation factor; in particular, the elastic modulus and stiffness span over several orders of magnitude from aligned to random regions within a single monolithic film. Controlled synthesis of macroscopic CNT gradient structures with tunable mechanical properties opens a potential route toward manufacturing biomimetic functional materials with locally optimized design.     

RF-PECVD法研究碳纳米管的生长特性

采用射频等离子体增强化学气相沉积(RF-PECVD),以Fe作为催化剂,在Si基片上生长了碳纳米管(CNT),采用扫描电子显微镜(SEM),高分辨透射电子显微镜(HR TEM)以及显微Raman光谱等对制备的CNT的形貌及结构进行了表征.结果表明:700℃和800℃温度下生长的CNT均取向无序、弯曲缠结,由整齐排列的圆...     

A rapid growth of aligned carbon nanotube films and high-aspect-ratio arrays

The remarkable properties of carbon nanotubes (CNTs) make them attractive for microelectronic applications, especially for interconnects and nanoscale devices. In this paper, we report an efficient process to grow well-aligned CNT films and high-aspect-ratio CNT arrays with very high area distribution density (>1600 μm⁻²). Chemical vapor deposition (CVD) was invoked to deposit highly aligned CNTs on Al₂O₃/Fe coated silicon substrates of several square centimeter area using ethylene as the carbon source, and argon and hydrogen as carrier gases. The nanotubes grew at a high rate of ∼100 μm/min. for nanotube films at 800°C, while the nanotube arrays grew at ∼140 μm/min. even at 750°C, due to the base growth mode. The CNTs were characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), and x-ray photoelectron spectroscopy (XPS). The results demonstrated that the CNTs are of high purity and form densely aligned arrays with controllable size and height. The as-grown CNT structures have considerable potential for thermal management and electrical interconnects for microelectronic devices.