Polymer saturable absorber materials in the 1.5 microm band using poly-methyl-methacrylate and polystyrene with single-wall carbon nanotubes and their application to a femtosecond laser

We report saturable absorber materials in the 1.5 microm band that consist of poly-methyl-methacrylate (PMMA) and polystyrene (PS) polymers with single-wall carbon nanotubes (SWNTs). A very uniform dispersion of SWNT in PMMA and PS polymers has been realized by using chlorobenzene or tetrahydrofuran as a dispersion solvent. These materials, which are as thick as 1 mm, are easily optically polished on both surfaces. This was difficult to achieve with previous thin-film materials. By incorporating PMMA/SWNT as a saturable absorber, a 171 fs pulse is successfully generated in a passively mode-locked fiber laser.     

碳纳米管熔接金电极的分子动力学模拟

利用分子动力学模拟方法,研究了单壁碳纳米管与Au电极的高温熔接. 模拟结果表明,用端口吸附了Au团簇的碳纳米管在高温下能很好地与Au电极熔接. 首先将Au团簇放置于碳纳米管开口处进行高温退火,退火温度在1100 K左右,Au团簇部分Au原子进入碳纳米管管内,吸入碳纳米管中的Au原子形成壳层螺旋结构的Au纳米线,管外Au团簇呈无定形结构. 然后将吸附了Au团簇的碳纳米管与Au电极进行熔接,高温退火后,碳纳米管与Au电极表面之间形成了稳固的熔接,熔接最佳温度在800 K左右. 关键词： 碳纳米管 金电极 分子动力学模拟     

Fast detection of the metallic state of individual single-walled carbon nanotubes using a transient-absorption optical microscope

In spite of the outstanding properties of single-walled carbon nanotubes (SWNTs), the coexistence of metallic and semiconducting SWNTs as a result of synthesis has hindered their electronic and photonic applications. We demonstrate a pump-probe microscopy method for fast, contact-free mapping of metallicity in individual SWNTs. We employ the phase of transient absorption as a contrast to discriminate metallic and semiconducting SWNTs. Furthermore, we have clarified the phase dependence on the pump or probe wavelengths and the energy structure of SWNTs. Our imaging method holds the potential of serving as a high-speed metallicity-mapping tool to assist the development of SWNT-based nanoelectronics.     

Single-walled carbon nanotube fibers, films and balls

Well-defined fibers and films of single-walled carbon nanotubes (SWNTs) with high purity and narrow diameter distributions were obtained from the strand-like raw soot produced by a dc arc-discharge method. These architectures made up of SWNTs have very uniform smooth surfaces. When the strand-like product was placed on a silicon substrate, dipped into water, treated ultrasonically, and then dried in air, another interesting architecture, an SWNT ball, was obtained. This ball-like structure could also be found on the surface of purified SWNTs. We propose that the surface tension of water and the interaction between SWNTs and silica sphere played the key role in the ball (SWNTs outside and silica sphere inside) formation process.     

Photoluminescence from single-walled carbon nanotubes: a comparison between suspended and micelle-encapsulated nanotubes

Single-walled carbon nanotubes (SWNTs) are luminescent. Up to now, two preparation methods, both of which isolate individual SWNTs, have enabled the detection of nanotube bandgap photoluminescence (PL): encapsulation of individual SWNTs into surfactant micelles and direct growth of individual SWNTs suspended in air between pillars. This paper compares the PL obtained from suspended SWNTs to published PL data obtained from encapsulated SWNTs. We find that emission peaks are blueshifted by 28 meV on average for the suspended nanotubes as compared to the encapsulated nanotubes. Similarly, the resonant absorption peaks at the second set of van Hove singularities are blueshifted on average by 16 meV. Both shifts depend weakly on the particular chirality and diameter of the SWNT. PACS 78.67.Ch; 78.55.-m     

Relaxed GexSi1−x layer formation with reduced dislocation density grown by ultrahigh vacuum chemical vapor deposition

A mixture of as-grown single-wall carbon nanotubes (SWNTs) and a monochlorobenzene (MCB) solution of polymethylmethacrylate (PMMA) was sonicated and homogenized. As a result, SWNTs were separated from carbonaceous impurities and metal particles, which enabled us to purify the SWNTs by filtration. We also found that the number of short (about 1-μm) SWNTs and thin bundles of SWNTs increased. The thin bundles contained one to three SWNTs. These short, thin SWNTs suspended in the MCB solution of PMMA were spin-coated onto a Si wafer, and could be dispersed on it. Received: 18 July 2000 / Accepted: 20 July 2000 / Published online: 6 September 2000     

Coating of carbon nanotubes on flexible substrate and its adhesion study

The primary goal of this project was to develop a flexible transparent conductor with 100 Ω/sq and 90% transmittance in the wavelength range of 400-700 nm on a flexible substrate. The best result achieved so far was 110 Ω/sq at 88% transmittance using purified single-walled carbon nanotubes (SWNTs) coated on a polyethylene naphthalate (PEN) substrate. The secondary goal was to simplify the overall coating procedure; we successfully reduced the process from five (prior art method) to three steps utilizing a sonication method. We also found that the use of metallic SWNTs significantly improved the conductivity and transmittance compared with the use of mixed SWNTs, i.e., unseparated SWNTs. Furthermore, a possible adhesion mechanism between SWNTs and the surface of PEN was studied; we concluded that a π-π stacking effect and a hydrophobic interaction are the major contributing factors for SWNTs to adhere to the surface of the substrate.     

Quantized bimolecular auger recombination of excitons in single-walled carbon nanotubes

Auger-like exciton-exciton annihilation in isolated single-walled carbon nanotubes (SWNTs) has been studied by femtosecond transient absorption spectroscopy. We observe a quantization of the Auger recombination process and extract dynamics for 2 and 3 electron-hole pair excited states. We further demonstrate that Auger recombination in SWNTs is a two-particle process involving strongly bound excitons and not a three-particle Auger process involving unbound electrons and holes. We thus provide explicit experimental evidence for one-dimensional discrete excitons in SWNTs.     

Novel single-walled carbon nanotubes periodically embedded with four- and eight-membered rings

Based on experimental results, we obtain five types of single-walled carbon nanotube (SWNT) clusters with different chirality indices and diameters using density functional theory (DFT). We then obtain the corresponding SWNTs by using periodic boundary conditions. Studies of the stability and electronic properties show that the stability of the novel SWNTs is independent of the chirality index and relates only to the tube diameter; larger diameters correspond to more stable SWNTs. The electronic properties all show metallic characteristics independent of the chirality indices and tube diameters, thereby promoting the application of metallic-type SWNTs.     

缺陷对单壁碳纳米管熔化与预熔化的影响

利用分子动力学模拟研究了具有几种常见缺陷的单壁碳纳米管的熔化与预熔化性质. 研究结果表明, 类似于纳米颗粒和聚合物, 碳纳米管发生熔化时的Lindemann指数为003, 远低于晶体熔化的判据01—015 使用Lindemann指数, 得出标准碳纳米管的熔化温度为4800K左右, 而带缺陷的碳纳米管的熔化总是从缺陷处开始, 并且缺陷会影响碳纳米管局部的熔化温度, 导致局部预熔化. Stone-Wales缺陷在2600K引起碳纳米管的局部熔化,空位缺陷导致的局部熔化温度在3200K, 而具有硅替位缺陷的碳纳米管在3800K以下具有很好的热稳定性. 关键词： 熔化 预熔化 缺陷 碳纳米管     

Dynamics of individual single-walled carbon nanotubes in water by real-time visualization

Individual single-walled carbon nanotubes (SWNTs) in aqueous suspension are visualized directly by fluorescence video microscopy. The fluorescent tagging is simple, biocompatible, and does not modify the SWNTs. The dynamics of individual SWNTs in water are observed and quantified for the first time. We measure the confined rotational diffusion coefficient and find it in reasonable agreement with predictions based on confined diffusion of dilute Brownian rods. We determine the critical concentration at which SWNTs in suspensions start interacting. By analyzing the fluctuating shape of SWNTs in the 3 to 5 microm range, we determine that their persistence length ranges between 32 and 174 microm, in agreement with theoretical estimates; thus, commonly available SWNTs in liquids can be considered as rigid Brownian rods in the absence of imposed external fields or self-attractive forces.     

Assembly of single-walled carbon nanotubes on patterns of Au nanoparticles

We report on the assembly of single-walled carbon nanotubes (SWNTs) and gold nanoparticles (NPs) hybrid structure without any surface modification of SWNTs on patterns of Au nanoparticles (NPs). Microscale Au NP patterns were created on composite self-assembled monolayer (SAM) templates of octadecanethiol (ODT) and octanedithiol (OD) through self-assembly of Au NPs via the thiol-Au chemical bond onto the OD region. On such templates, we observed extensive adhesion and strong affinity of SWNTs on the Au NPs and no SWNT on ODT. We also examined systematically the adhesion of SWNTs on ODT with varying coverage of vapour-deposited Au. We observed little SWNT attachment even when there are high-density of Au clusters on the ODT SAM. Extensive adhesion of SWNTs is observed only when the coverage of ODT by Au is almost complete. Dynamic contact angle measurements of dichlorobenzene on the ODT/Au substrates revealed a direct correlation between the surface wettability and the SWNT assembly on a molecular template.     

以Y/Ni为催化剂制备的单壁碳纳米管的拉曼光谱研究

采用电弧放电法以Y/Ni为催化制备了单壁碳纳米管（SWNTs），对样品进行了扫描电镜、透射电镜和拉曼光谱的研究。所制备的样品中单壁碳纳米管的含量较高。对单壁碳纳米管的共振拉曼散射增强效应进行了观察，随激光波长的不同，单壁碳纳米管的拉曼光谱也随之变化，尤其是低频区径向呼吸模的变化比较明显。利用布里渊区折叠法计算了单壁碳纳米管的电子态密度曲线，根据SWNTs电子态密度尖峰之间的能量差、管子的直径和呼吸模频率建立了一个图表，并对SWNTs的呼吸模进行了归属。分析结果表明：样品中单壁碳纳米管的直径分布在0.79-1.76nm范围，金属管和半导体管均存在，并且直径在1.45nm附近的碳管居多。     

Curvature-induced condensation of lithium confined inside single-walled carbon nanotubes: First-principles calculations

We carry out first-principles calculations to explore the potential energy profiles of Li confined inside single-walled carbon nanotubes (SWNTs) and the subsequent condensation processes. We found that Li has high mobility around tube axis with the energy barrier less than 47 meV, whereas the diffusion barrier along radial direction is as higher as 380 meV. This characterizes the condensation of Li atoms when placed randomly into SWNTs, resulting in nanowires with single or multi-shelled morphologies depending on the diameter of SWNTs. The charge transfer from Li nanowires to SWNTs is significant, indicating stronger couplings between them.     

Viscoelasticity of single wall carbon nanotube suspensions

We investigate the viscoelastic properties of an associating rigid rod network: aqueous suspensions of surfactant stabilized single wall carbon nanotubes (SWNTs). The SWNT suspensions exhibit a rigidity percolation transition with an onset of solidlike elasticity at a volume fraction of 0.0026; the percolation exponent is 2.3+/-0.1. At large strain, the solidlike samples show volume fraction dependent yielding. We develop a simple model to understand these rheological responses and show that the shear dependent stresses can be scaled onto a single master curve to obtain an internanotube interaction energy per bond approximately 40k(B)T. Our experimental observations suggest SWNTs in suspension form interconnected networks with bonds that freely rotate and resist stretching. Suspension elasticity originates from bonds between SWNTs rather than from the stiffness or stretching of individual SWNTs.     

Selective removal of metallic SWNTs using microwave radiation

We report new method for selectively removing the metallic CNTs from semiconducting CNTs in a powder using high-power microwave radiation in the infrared and radio frequency range of the electromagnetic spectrum. SWNTs in a powder film were heated in a 2.5 GHz microwave oven for a few minutes, and the metallic nanotubes burned more rapidly than the semiconducting nanotubes. Raman data showed that the ratio of metallic to semiconducting nanotubes decreased dramatically after exposure to microwave radiation. Using their more rapid absorption of the radiation energy of the microwaves, we achieved the selective removal of metallic SWNTs from semiconducting SWNTs. This method results in the high-purity of semiconducting SWNTs necessary for sensor and electronic applications.     

Hydrostatic-pressure induced phase transition of phonons in single-walled nanotubes

We study the effect of the hydrostatic pressure on the phonons in single-walled carbon nanotubes (SWNTs) in a magnetic field. We calculate the magnetic moments of the phonons using a functional integral technique, and find that the phonons in SWNTs undergo a pressure-induced phase transition from the paramagnetic phase to the diamagnetic phase under hydrostatic pressure 2 GPa. We explain the mechanism of generating this phase transition.     

Sample-specific and ensemble-averaged magnetoconductance of individual single-wall carbon nanotubes

We discuss magnetotransport measurements on individual single-wall carbon nanotubes (SWNTs) with low contact resistance, performed as a function of temperature and gate voltage. We find that the application of a magnetic field perpendicular to the tube axis results in a large magnetoconductance of the order of e2/h at low temperature. We demonstrate that this magnetoconductance consists of a sample-specific and of an ensemble-averaged contribution, both of which decrease with increasing temperature. The observed behavior resembles very closely the behavior of more conventional multichannel mesoscopic wires, exhibiting universal conductance fluctuations and weak localization. A theoretical analysis of our experiments will enable us to reach a deeper understanding of phase-coherent one-dimensional electronic motion in SWNTs.     

Resonant Raman scattering of the smallest single-walled carbon nanotubes

We report optical properties of the smallest single-walled carbon nanotubes (SWNTs) with a diameter of only 3 A. These ultrasmall SWNTs are fabricated in the elliptical nanochannels of an AlPO-11 (AEL) single crystal. Polarized and resonant Raman scattering unambiguously revealed that these 0.3 nm SWNTs are of (2,2) armchair symmetry. Interestingly, the (2,2) armchair tube has two metastable ground states corresponding to two slightly different lattice constants in the axial direction: one state is metallic and the other is semiconducting.     

CVD synthesis and purification of single-walled carbon nanotubes on aerogel-supported catalyst

Single-walled carbon nanotubes (SWNTs) were synthesized by disproportionation of carbon monoxide on an aerogel-supported Fe/Mo catalyst. A simple acidic treatment followed by an oxidation process produced a high purity (>99%) of SWNTs. The nanotubes obtained are bundled SWNTs and free of amorphous-carbon coating. Several factors that affect the yield and the quality of the SWNTs were also studied. This method shows great promise for large-scale production of SWNTs. Received: 30 August 2001 / Accepted: 3 December 2001 / Published online: 4 March 2002