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     

Zipper dynamics of surfactant nanotube Y junctions

We investigate the formation of Y junctions in surfactant nanotubes connecting vesicles. Based on experimental observations of the surfactant flow on the nanotubes, we conclude that a Y junction propagates with a zipperlike mechanism. The surfactants from two nanotube branches undergo 1:1 mixing at the junction, and spontaneously form the extension of the third nanotube branch. Taking into account the tension driven surfactant flow, we develop a model for the Y junction dynamics that is in quantitative agreement with the experimental data.     

Single-Walled Carbon Nanotubes Acting as Controllable Transport Channels

The motion and equilibrium distribution of water molecules adsorbed inside neutral and negatively charged singlewalled carbon nanotubes (SWNTs) have been studied using molecular dynamics simulations (MDSs) at room temperature based on CHARMM (Chemistry at HARvard Molecular Mechanics) potential parameters. We find that water molecules have a conspicuous electropism phenomenon and regular tubule patterns inside and outside the charged tube wall. The analyses of the motion behaviour of water molecules in the radial and axial directions show that by charging the SWNT, the adsorption efficiency is greatly enhanced, and the electric field produced by the charged SWNTs prevents water molecules from flowing out of the nanotube. However, water molecules can travel through the neutral SWNT in a fluctuating manner. This indicates that by electrically charging and uncharging the SWNTs, one can control the adsorption and transport behaviour of polar molecules in SWNTs for using as a stable storage medium or long transport channels. The transport velocity can be tailored by changing the charge on the SWNTs, which may have a further application as modulatable transport channels.     

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.     

Initial growth of single-walled carbon nanotubes on supported iron clusters: a molecular dynamics study

Molecular dynamics simulations were used to study the initial growth of single-walled carbon nanotubes (SWNTs) on a supported iron cluster (Fe₅₀). Statistical analysis shows that the growth direction of SWNTs becomes more perpendicular to the substrate over time due to the weak interaction between carbon nanotube and the substrate. The diameter of the nanotube also increases with the simulation time and approaches the size of the supported iron cluster.     

Formation of single-wall carbon nanotubes in Ar and nitrogen gas atmosphere by using laser furnace technique

The formation of single-wall carbon nanotubes (SWNTs) by using laser vaporization technique in different ambient gas atmosphere was investigated. SWNTs were prepared with Rh/Pd (1.2/1.2 atom%)-carbon composite rod in Ar and nitrogen gas atmosphere, respectively. Raman spectra of raw carbon materials including SWNTs and photoluminescence mapping of dispersed SWNTs in a surfactant solution demonstrate that the diameter distribution of SWNTs prepared in Ar atmosphere is narrower than those obtained by using CVD technique (e.g. HiPco nanotube), even when the ambient temperature is as high as 1150 ^○C. It was also found that nitrogen atmosphere gives wider diameter distribution of SWNTs than that obtained with Ar atmosphere. Furthermore, the relative yield of fullerenes (obtained as byproducts) is investigated by using HPLC (high-performance liquid chromatography) technique. It was found that the relative yield of higher fullerenes becomes lower, when nitrogen is used as an ambient gas atmosphere. Based on these experimental findings, a plausible formation mechanism of SWNTs is discussed.     

Diameter-dependent relaxation dynamics of 1D excitons in single-walled carbon nanotubes

We have studied 1D exciton relaxation dynamics in semiconducting single-walled carbon nanotubes (SWNTs) by femtosecond pump–probe experiments. The time evolution of change in transmittance ΔT/T induced by photo-excitation varies depending on the tube diameter. The decay time decreases with a decrease in the tube diameter. Pressure measurements have been conducted to explore the relaxation mechanism. The deformation potential estimated from the pressure dependence of photoluminescence spectra increases with decreasing tube diameter. This means that the exciton–phonon interaction becomes stronger in the smaller diameter tubes. The diameter dependences of decay time and deformation potential suggest that the exciton–phonon interaction plays an important role in exciton nonradiative relaxation process in semiconducting SWNTs.     

碳纳米管中封装富勒烯的机理

利用经典分子动力学模型,发现C60进入单壁碳纳米管(SWNTs)形成(C60)n@SWNTs的吸入和俘获机理.揭示了吸入和俘获势垒只局域于SWNTs的管口区,而在SWNTs的管内区,C60沿管轴方向的运动几乎不受力.最后,系统地计算了吸入和俘获势垒随SWNTs管径的变化,发现只有当SWNTs的管径大于阈值1238nm时才能吸入C 关键词： 富勒烯相关材料 碳纳米管 类虹吸作用     

Standing or lying C70s encapsulated in carbon nanotubes with different diameters

Single-walled carbon nanotubes (SWNTs) encapsulating C₇₀s, so-called C₇₀ peapods, were synthesized in high yield by a vapor-phase doping method. Raman spectra, high resolution transmission electron microscopy (HRTEM), and selected area electron diffraction (SAED) measurement indicate that the tube diameter is one of the important factors to determine the orientation of C₇₀ molecules inside the SWNTs. SWNTs with different diameters give different alignment of C₇₀ molecules. The lying orientation is favorable over the standing orientation in thin nanotube, i.e. 1.36 nm nanotubes, whereas the standing orientation is favorable in thick nanotubes, i.e. 1.49 and 1.61 nm nanotubes.     

Selective aggregation of single-walled carbon nanotubes using the large optical field gradient of a focused laser beam

We demonstrate the selective aggregation of single-walled carbon nanotubes by photon forces, using the large optical field gradient of a laser focused through a high numerical aperture objective lens. The nanotubes, dispersed in an aqueous solution with a surfactant, are detected via Raman scattering from the confocal volume of the optical trap. By using a visible-light laser for both trapping and detection, the dynamics of the radial breathing mode signal taken at short intervals shows an increase of a single breathing mode over time, indicating the increase in the density of only one species of tube in the focal volume. This result represents a significant step toward the development of techniques for the arbitrary manipulation and sorting of nanotubes by optical fields.     

Computational analysis of effect of modification on the interfacial characteristics of a carbon nanotube-polyethylene composite system

In this study, the non-covalent association of single-walled nanotube (SWNT) with polyethylene (PE) molecule and the influence of sidewall modification on the interfacial bonding between the SWNTs and polymer were investigated using molecular mechanics (MM) and molecular dynamics (MD) simulations. The model of interaction between the initially separated PE and SWNT fragments, which can be either wrapping or filling, was computed. The possible extension of polymers wrapping or filling SWNTs can be used to structurally bridge the SWNTs and polymers to significantly improve the load transfer between them when SWNTs are used to produce nanocomposites. The interfacial bonding characteristics between the single-walled nanotubes, on which -COOH, -CONH₂, -C₆H₁₁, or -C₆H₅ groups have been chemically attached, and the polymer matrix were also investigated by performing pullout simulations. The results show that appropriate functionalization of nanotubes at low densities of functionalized carbon atoms drastically increase their interfacial bonding and shear stress between the nanotubes and the polymer matrix, where chemisorption with -C₆H₅ groups to as little as 5.0% of the nanotube carbon atoms increases the shear stress by about 1700%. Furthermore, this suggests the possibility to use functionalized nanotubes to effectively reinforce other kinds of polymer-based materials as well.     

Nematic nanotube gels

We report the creation of nematic nanotube gels containing large domains of isolated, oriented, half-micron-long, single-wall carbon nanotubes (SWNTs). We make them by homogeneously dispersing surfactant coated SWNTs at low concentration in an N-isopropyl acrylamide gel and then inducing a volume-compression transition. These gels exhibit hallmark properties of a nematic: birefrigence, anisotropy in optical absorption, and disclination defects. We also investigate the isotropic-to-nematic transition of these gels, and we describe the physical properties of their ensuing nematic state, including a novel buckling of sample walls. Finally, we provide a simple model to explain our observations.     

Selective interaction between nanotubes and perylene‐based surfactant

We recently reported a significant deviation in the photoluminescence intensities of HiPco nanotubes solubilized with a perylene‐based surfactant, C16 , compared to bile salt surfactants. For C16 , the photoluminescence emission of chiralities (9,5), (10,3), and (11,1) is enhanced by up to 430%. Resonant Raman spectroscopy is less sensitive to bundling state and also yields disparate chirality intensity ratios: The (11,0) zigzag tube signal increases by 100% compared to (8,6), (9,4), and (10,2) after suspension with C16 . We also report the change in photoluminescence intensity distribution after the swelling of bile salt suspended nanotubes with a series of small organic chromophores in DCM. These changes are attributed to chromophore‐induced surfactant reorganization, resulting in better nanotube individualization. The chirality for which the PL intensity is most enhanced is (11,1) for all chromophores, a chirality also increased by 300% in the C16 ‐solubilized sample. Conjointly, these measurements indicate that both preferential solubilization and enhanced debundling contribute to the PL intensity distribution in the C16 ‐solubilized nanotube sample. This has wide ranging implications for the design of chirally selective surfactants and the demonstration of their selectivity, which is typically only shown through luminescence measurements. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Electrochemical functionalization of multi-walled carbon nanotubes for solvation and purification

The chemical modification of multi-walled carbon nanotubes using electrolysis is described. It is found that the evolution of the halogens chlorine or bromine on an anode made from a foil of carbon nanotubes couples halogen atoms to the nanotube lattice. Furthermore, oxygen bearing functional groups, such as hydroxyl and carboxyl groups, are formed at the same time aiding solvation of the nanotubes in water or alcohol without any surfactant. Impurities and low grade modified nanotubes remain insoluble. The halogenated carbon nanotubes can be converted with sodium amide or triphenylmethyllithium to add the corresponding functional groups.     

碳纳米管阵列水渗透性质的研究

碳纳米管阵列组成的碳纳米管分子膜在生物学分子器件等方面有重要应用. 本文利用分子动力学方法计算研究水分子对(11, 11)碳纳米管阵列的渗透过程. 结果发现, 只有当阵列间隙面积大于57.91 Ų时, 水分子才能进入阵列间隙中, 并揭示了碳管内部、阵列间隙内水分子结构随相邻碳管间距变化的演化趋势以及管内外水分子电偶极矩的分布特性.     

形变碳纳米管选择通过性的分子动力学研究

本文采用分子动力学方法, 研究了基团修饰后形变碳纳米管的水分子通过性和离子选择性. 结果表明, 形变碳纳米管的短径与修饰基团的种类、修饰率及修饰位置有关. 不同粗细碳纳米管均存在临界短径, 小于临界短径的形变碳纳米管具有对氯离子和钠离子的选择性, 同时水分子通过速率与本征碳纳米管相比未明显变小. 分析系统平均力势表明, 离子选择性来源于不同短径碳纳米管管口的通过势垒. 对于实际制备中较宽孔径分布的碳纳米管, 可以通过基团修饰等方法调控其短径, 提高其离子选择性.     

Collapse of single-wall carbon nanotubes is diameter dependent

We present classical molecular dynamics simulations demonstrating that single-wall carbon nanotube (SWNT) bundles collapse under hydrostatic pressure. The collapse pressures obtained as a function of nanotube diameter are in excellent quantitative agreement with new data presented here for small diameter (d approximately 0.8 nm) SWNTs, and the majority of previously published results, although there remain some unreconciled contradictions in the literature. The collapse pressure is found to be independent of the nanotube chirality, and a lower limit on the largest SWNT that remains inflated at atmospheric pressure is established (d>4.16 nm).     

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.     

Donor doping of single-walled carbon nanotubes by filling of channels with silver

The channels of single-walled carbon nanotubes (SWNTs) are filled with metallic silver. The synthesized nanocomposites are studied by Raman spectroscopy and optical absorption spectroscopy, and these data indicate a substantial modification of the electronic structure of the nanotubes upon their filling. Moreover, X-ray photoelectron spectroscopy shows that the incorporation of the metal leads to a change in the work function of SWNTs due to the Fermi level upshift and to the transfer of an electron density from inserted nanoparticles to the nanotube walls. Thus, the filling of the channels with silver results in donor doping of the nanotubes.     

单壁碳纳米管受限空间内水的分布

碳纳米管管腔作为分子物质的纳米通道,其储存或输送水的能力具有重要研究价值.为了研究碳纳米管管腔受限空间对水分子团簇结构和分布的影响,本文采用分子动力学方法探究了管径、手性和温度对单壁碳纳米管管腔内水的结构和分布的影响.结果表明:在常温下,管径尺寸范围为1.018—1.253 nm的单壁碳纳米管管内易形成有序的多元环水结构,此范围以外碳纳米管管内难以形成水的有序结构;且随着管径尺寸增大,多元环水呈现由三元环至六元环的结构变化;范德瓦耳斯势分布分析表明,在上述管径范围内,水分子趋向于贴近碳纳米管管壁分布而形成水的有序结构.对比管径尺寸差别较小的碳纳米管,其手性对多元环水结构影响不大.多元环水结构的稳定性表现出温度依赖性,管径较大的碳纳米管内的多元环水的有序结构更易随温度升高而消失.