Photophysics of polymer-wrapped single-walled carbon nanotubes

Single-walled carbon nanotubes (SWNTs) are successfully dispersed in two conjugated polymer poly(9,9-dioctylfluorenyl-2,7-diyl) (PFO) and poly[2-methoxy-5- (2’-ethyl-hexyloxy)-1,4-phenylene vinylene] (MEHPPV) solutions. Steady-state and time-resolved photoluminescence spectroscopy in the near-infrared and visible spectral regions are used to study the interaction of the dispersed carbon nanotube and the wrapped polymer in the nano-hybrids. The SWNTs infrared emission is the signatures of the separation of single semiconducting tubes, the lifetime of the photoluminescence of these tubes is bi-exponential with the first component varying from 6 ps (in MEHPPV wrapped SWNTs) to 14 ps (in PFO wrapped SWNTs), while the second component of the decay for all samples is in the range of 30-40 ps, revealing the intrinsic lifetime of the SWNTs. The study of the photoluminescence of the nano-hybrids in the visible spectral range shows, in the case of the PFO, a relatively strong quenching, the photoluminescence lifetime for the hybrid is more than 100 ps shorter than the one of the pristine polyfluorene solution. For the MEHPPV-SWNT hybrid an opposite behavior is revealed with the photoluminescence lifetime surprisingly longer than the polymer solution. The possible mechanism for the interaction of the two conjugated polymers and the SWNTs is discussed in terms of their electronic band structure.     

Molecular dynamics simulation on mechanicalproperty of carbon nanotube torsional deformation

In this paper torsional deformation of the carbon nanotubes is simulated by molecular dynamics method. The Brenner potential is used to set up thesimulation system. Simulation results show that the carbon nanotubes can bear larger torsional deformation, for the armchair type (10,10) single wall carbon nanotubes, with a yielding phenomenon taking place when the torsional angle is up to 63$^{\circ}$(1.1rad). The influence of carbon nanotube helicity in torsional deformation is very small. The shear modulus of single wall carbon nanotubes should be several hundred GPa, not 1\,GPa as others reports.     

Photon antibunching in the photoluminescence spectra of a single carbon nanotube

We report the first observation of photon antibunching in the photoluminescence from single carbon nanotubes. The emergence of a fast luminescence decay component under strong optical excitation indicates that Auger processes are partially responsible for inhibiting two-photon generation. Additionally, the presence of exciton localization at low temperatures ensures that nanotubes emit photons predominantly one by one. The fact that multiphoton emission probability can be smaller than 5% suggests that carbon nanotubes could be used as a source of single photons for applications in quantum cryptography.     

Optical transition energies for carbon nanotubes from resonant Raman spectroscopy: environment and temperature effects

This Letter reports the laser energy dependence of the Stokes and anti-Stokes Raman spectra of carbon nanotubes dispersed in aqueous solution and within solid bundles, in the energy range 1.52-2.71 eV. The electronic transition energies (E(ii)) and the radial breathing mode frequencies (omega(RBM)) are obtained for 46 different (18 metallic and 28 semiconducting) nanotubes, and the (n,m) assignment is discussed based on the observation of geometrical patterns for E(ii) versus omega(RBM) graphs. Only the low energy component of the E(M)(11) value is observed from each metallic nanotube. For a given nanotube, the resonant window is broadened and down-shifted for single wall carbon nanotube (SWNT) bundles compared to SWNTs in solution, while by increasing the temperature, the E(S)(22) energies are redshifted for S1 [(2n+m) mod 3=1] nanotubes and blueshifted for S2 [(2n+m) mod 3=2] nanotubes.     

Raman spectroscopy of carbon nanotubes

The use of Raman spectroscopy to reveal the remarkable structure and the unusual electronic and phonon properties of single wall carbon nanotubes (SWNTs) is reviewed comprehensively. The various types of Raman scattering processes relevant to carbon nanotubes are reviewed, and the theoretical foundations for these topics are presented. The most common experimental techniques used to probe carbon nanotubes are summarized, followed by a review of the novel experimental findings for each of the features in the first order and second order Raman spectra for single wall carbon nanotubes. These results are presented and discussed in connection with theoretical considerations. Raman spectra for bundles of SWNTs, for SWNTs surrounded by various common wrapping agents, and for isolated SWNTs at the single nanotube level are reviewed. Some of the current research challenges facing the field are briefly summarized.     

单壁BC3纳米管晶格动力学研究

基于力常数模型计算了一系列扶手椅型、锯齿型和手性单壁BC₃纳米管的声子色散关系.描述了单壁BC₃纳米管结构的表征方式,比较详细地给出了其结构、对称性和晶格动力学分析.基于数值计算结果,讨论了拉曼活性模和红外活性振动模的频率与管径的关系.由分析结果做出推断,BC₃纳米管的拉曼光谱和红外光谱比单壁碳纳米管更为复杂. 关键词： 3纳米管')" href="#">BC₃纳米管 声子色散关系 晶格动力学     

Mono-dispersed single-walled carbon nanotubes made by using arc-burning method in nitrogen atmosphere

Single-walled carbon nanotubes made by using arc-burning technique in nitrogen atmosphere were dispersed in sodium cholate (SC) solution, and the diameter and chirality distribution of semiconductive SWNTs was investigated by UV-VIS-NIR and Raman spectroscopy, and photoluminescence mapping technique. In the typical formation condition, the diameter distribution of them is found to be relatively narrow (1.2 nm–1.4 nm in diameter), less chirality dependent, almost the same as the diameter distribution of SWNTs obtained by using laser-furnace technique.     

Charge‐transfer behavior of polyaniline single wall carbon nanotubes nanocomposites monitored by resonance Raman spectroscopy

Highly dispersed nanocomposites of polyaniline(PANI) and oxidized single wall carbon nanotubes(SWNTs) have been prepared using dodecylbenzenesulfonic acid as dispersant. The materials were characterized via resonance Raman and electronic absorption spectroscopies. The behavior of the composites as a function of the applied potential was also investigated using in situ Raman electrochemical measurements. The results obtained at E_laser = 1.17 eV suggest that a charge‐transfer process occur between PANI and semiconducting nanotubes for samples where the metallic tubes are previously oxidized. The spectroelectrochemical data show that the presence of SWNTs prevents the oxidation of PANI rings. Copyright © 2010 John Wiley & Sons, Ltd.     

Electronic excitation energy transfer between CdS quantum dots and carbon nanotubes

Stationary and transient photoluminescence of CdS quantum dots deposited on silicon substrates and carbon nanotubes is investigated. The photoluminescence spectrum of quantum dots on a silicon substrate is dominated by a band originating from electron transitions between the quantum-confinement levels in the dots. When the quantum dots are deposited on carbon nanotubes, the intensity of this band decreases significantly. Furthermore, the kinetics of the photoluminescence decay becomes faster, which brings evidence of an additional channel for the quantum-dot deexcitation. The analysis of the experimental data demonstrates that the Förster energy transfer from CdS quantum dots to carbon nanotubes is most probably responsible for this channel. The efficiency of this process exceeds 60%.     

Physical and mechanical characterization of nanocomposites with carbon nanotubes functionalized with the matrix polymer

Single wall carbon nanotubes (SWNT) are functionalized with poly(vinyl alcohol) (PVA). The functionalized nanotubes are homogeneously dispersed in a PVA solution. Nanocomposite films with low SWNT content (0.1 to 1%) are produced by the wet-casting method. X-ray diffraction shows that the PVA crystallinity was not affected by the presence of the SWNT. The improvement in tensile modulus and strength at such low reinforcement loadings is indicative of good interfacial bonding between the functionalized nanotubes and the polymer matrix.     

Micromechanical properties of poly(butylene terephthalate) nanocomposites with single- and multi-walled carbon nanotubes

Polymer nanocomposites with carbon nanotubes (CNT) are becoming important structural materials because of their superior mechanical properties and easy processability. The objective of the work is to investigate the influence of small amounts of single walled carbon nanotubes (SWCNT), as well as multi-walled carbon nanotubes (MWCNT), on the microhardness of a thermoplastic polymer such as poly(butylene terephthalate) (PBT). The nanocomposites were obtained by introducing the CNT into the reaction mixture during the synthesis of PBT. The polymers without carbon nanotubes (reference material) and with carbon nanotubes were synthesized using an in-situ polycondensation reaction process. Weight percentages ranging from 0.01 to 0.2 wt% of the single walled and from 0.01 to 0.35 wt% of the multi-walled nanotubes were dispersed in 1,4-butanediol (BD) by ultrasonication and by ultra high speed stirring. The nanocomposites were extruded followed by injection molding. The samples were characterized by electron microscopy and microindentation hardness techniques. The variations of the micromechanical properties (indentation hardness) of the nanocomposites with nanotube content and with temperature are discussed in the light of the stress transfer between the polymer matrix and nanotubes, the degree of dispersion, the nature of the tubes and other structural parameters.     

ESR Investigations on Polyethylene–Fluorine Functionalized Single Wall Carbon Nanotubes Composites

Electron spin resonance investigations on nanocomposites obtained by dispersing fluorinated single walled carbon nanotubes within polyethylene are reported. Three resonance lines assigned to uncoupled electronic spins confined within magnetic impurities, amorphous carbon, and single wall carbon nanotubes have been observed. The temperature dependence of these lines is analyzed in detail and used to assign each component of the as-recorded ESR spectrum to a precise component of the nanocomposite. Magnetic impurities are originating from catalysts residues (in our case, Fe impurities). Surprisingly, the narrowest line is due to paramagnetic defects (amorphous carbon) while the broad line originates from electrons delocalized over conducting nanotubes. The broadening of this line reflects a bottleneck in the relaxation mechanism, triggered by the interaction of the uncoupled electrons localized on carbon nanotubes with the magnetic impurities.     

Elastic exciton-exciton scattering in photoexcited carbon nanotubes

We report on original nonlinear spectral hole-burning experiments in single wall carbon nanotubes that bring evidence of pure dephasing induced by exciton-exciton scattering. We show that the collision-induced broadening in carbon nanotubes is controlled by exciton-exciton scattering as for Wannier excitons in inorganic semiconductors, while the population relaxation is driven by exciton-exciton annihilation as for Frenkel excitons in organic materials. We demonstrate that this singular behavior originates from the intrinsic one-dimensionality of excitons in carbon nanotubes, which display unique hybrid features of organic and inorganic systems.     

Effect of hydrogen on the growth and morphology of single wall carbon nanotubes synthesized on a FeMo/MgO catalytic system

Single wall carbon nanotubes were synthesized from thermal pyrolysis of methane on a FeMo/MgO catalyst by radio frequency catalytic chemical vapor deposition (RF-CVD) using argon as a carrier gas. Controlled amounts of hydrogen (H₂/CH₄=0-1 v/v) were introduced in separate experiments along with the carbon source. The properties and morphology of the synthesized single wall carbon nanotubes were monitored by transmission electron microscopy, Raman scattering, and thermogravimetric analysis. The nanotubes with the highest crystallinity were obtained with H₂/CH₄=0.6. By monitoring the Radial Breathing Modes present in the Raman spectra of the single-wall carbon nanotube samples, the variation of the structural and morphological properties of the carbon nanotubes with the flow level of hydrogen, reflect changes of the catalyst systems induced by the presence of hydrogen.     

Electronic Properties of Aluminum Doped Carbon Nanotubes with Stone Wales Defects: Density Functional Theory

Physics of the Solid State - Al-doped single wall carbon nanotube with Stone Wales defect was theoretically analyzed, two different orientations of chiral (8, 4) carbon nanotubes was doped among...     

Effects of phosphorus-doping upon the electronic structures of single wall carbon nanotubes

The phosphorus-doped single wall carbon nanotube (PSWCNT) is studied by using First-Principle methods based on Density Function Theory (DFT). The formation energy, total energy, band structure, geometry structure and density of states are calculated. It is found that the formation energy of the P-doped single carbon nanotubes increases with diameters; the total energy of carbon nanotubes with the same diameter decreases as the doping rate increases. The effects of impurity position on the impurity level are discussed. It illustrates that the position of the impurity level may depend on the C-P-C bond angle. According to the above results, it is feasible to substitute a carbon atom with a phosphorus atom in SWCNT. It is also found that P-doped carbon nanotubes are N type semiconductor. Supported by the Natural Science Foundation of Fujian Province of China (Grant No. A0220001)     

Bright band gap photoluminescence from unprocessed single-walled carbon nanotubes

Unprocessed single-walled carbon nanotubes suspended in air at room temperature emit bright, sharply peaked band gap photoluminescence. This is in contrast with measurements taken from nanotubes lying on the flat surface for which no luminescence was detected. Each individual nanotube has a luminescence peak of similar linewidth ( approximately 13 meV), with different species emitting at various different wavelengths spanning at least 1.0 to 1.6 microm. A strong enhancement of photoluminescence intensity is observed when the excitation wavelength is resonant with the second Van Hove singularity, unambiguously confirming the origin of the photoluminescence.     

Frequency change by inter-walled length difference of double-wall carbon nanotube resonator

Ultrahigh frequency nanomechanical resonators based on double-walled carbon nanotubes with different wall lengths were investigated via classical molecular dynamics simulations. For a double-walled carbon nanotube resonator with a short outer wall, the free edge of the short outer wall plays an important role in the vibration of the long inner wall. For a double-walled carbon nanotube resonator with a short inner wall, the short inner wall can be considered as a flexible core, thus, the fundamental frequency is influenced by its length. By controlling the length of the inner or outer wall, various frequency devices can be realized by a single type of double-walled carbon nanotube with walls of equal length.     

Effect of carbon nanotubes dispersion on morphology, internal structure and thermal stability of electrospun poly(vinyl alcohol)/carbon nanotubes nanofibers

The current work reports the effect of multi walled carbon nanotubes and single walled carbon nanotubes dispersion on morphological, structural and thermal degradation of electrospun poly(vinyl alcohol) (PVA)/carbon nanotubes (CNTs) dispersed in sodium dodecyl sulfate (SDS) (PVA/CNTs–SDS) composites nanofibers. (PVA/CNTs–SDS) nanocomposites fibers were elaborated using the traditional electrospinning process to disperse and align CNTs into the fibers, especially for low CNTs loading fraction: 0.3 and 0.7 wt%. The morphology of the electrospun fibers was studied using the scanning electronic microscopy. The average diameter of the fibers changes significantly after the incorporation of the CNTs in the PVA. Furthermore, Fourier transform infrared spectroscopy elucidated the effect of CNTs on the crystallization of the PVA which was confirmed by X-ray diffraction analysis. Thermogravimetric analysis showed that the thermal stability of the composite fibers depends on the loading fraction and on the type of carbon nanotubes.     

Exciton resonances quench the photoluminescence of zigzag carbon nanotubes

We show that the photoluminescence intensity of single-walled carbon nanotubes is much stronger in tubes with large chiral angles--armchair tubes--because exciton resonances make the luminescence of zigzag tubes intrinsically weak. This exciton-exciton resonance depends on the electronic structure of the tubes and is found more often in nanotubes of the +1 family. Armchair tubes do not necessarily grow preferentially with present growth techniques; they just have stronger luminescence. Our analysis allows us to normalize photoluminescence intensities and find the abundance of nanotube chiralities in macroscopic samples.