Effect of annealing on the optical absorption spectra of single-walled carbon nanotubes

The thermal stability of initial and purified samples of single-walled carbon nanotubes prepared through gas-phase disproportionation of carbon monoxide CO in the presence of iron particles under high pressure (the HiPCO method) is investigated using optical absorption spectroscopy and thermogravimetry. An analysis of the optical absorption spectra demonstrates that thermal oxidation of the initial material proceeds rather rapidly and uniformly owing to the catalytic effect caused by the presence of iron particles in the sample. The destruction of the carbon nanotubes contained in the as-prepared and purified samples begins at temperatures of ～250 and ～300°C, respectively. It is shown that single-walled metallic nanotubes undergo faster oxidation as compared to the single-walled semiconducting nanotubes.     

Ultra-fast optical spectroscopy of micelle-suspended single-walled carbon nanotubes

We present results of wavelength-dependent ultra-fast pump–probe experiments on micelle-suspended single-walled carbon nanotubes. The linear absorption and photoluminescence spectra of the samples show a number of chirality-dependent peaks and, consequently, the pump–probe results sensitively depend on the wavelength. In the wavelength range corresponding to the second van Hove singularities (VHSs) we observe subpicosecond decays, as has been seen in previous pump–probe studies. We ascribe these ultra-fast decays to intraband carrier relaxation. On the other hand, in the wavelength range corresponding to the first VHSs, we observe two distinct regimes in ultra-fast carrier relaxation: fast (0.3–1.2 ps) and slow (5–20 ps). The slow component, which has not been observed previously, is resonantly enhanced whenever the pump photon energy resonates with an interband absorption peak, and we attribute it to interband carrier recombination. Finally, the slow component is dependent on the pH of the solution, which suggests an important role played by H⁺ ions surrounding the nanotubes. PACS 78.47.+p; 78.67.Ch; 73.22.-f     

Quasiparticle energies,excitonic effects and optical absorption spectra of small-diameter single-walled carbon nanotubes

We present a first-principles study of the effects of many-electron interactions on the optical properties of single-walled carbon nanotubes. Motivated by recent experiments, we have carried out ab initio calculations on the single-walled carbon nanotubes (3, 3), (5, 0) and (8, 0). The calculations are based on a many-body Greens function approach in which both the quasiparticle (single-particle) excitation spectrum and the optical (electron–hole excitation) spectrum are determined. We show that the optical spectrum of both the semiconducting and metallic nanotubes studied exhibits important excitonic effects due to their quasi-one-dimensional nature. Binding energies for excitonic states range from zero for the metallic (5, 0) tube to nearly 1 eV for the semiconducting (8, 0) tube. Moreover, the metallic (3, 3) tube possesses exciton states bound by nearly 100 meV. Our calculated spectra explain quantitatively the observed features found in the measured spectra. PACS 78.67.Ch; 71.35.Cc; 73.22.-f     

Comparative X-ray absorption investigation of fluorinated single-walled carbon nanotubes

The C 1s and F 1s X-ray absorption spectra of pristine and fluorinated single-walled carbon nanotubes with different fluorine contents and nanodiamond as a reference compound have been measured with the aim of characterizing single-walled carbon nanotubes and their products formed upon treatment of the nanotubes with molecular fluorine at a temperature of 190°C. The spectra obtained have been analyzed by thoroughly comparing with the previously measured spectra of highly oriented pyrolytic graphite and fluorinated multiwalled carbon nanotubes and the spectrum of nanodiamond. It has been established that the fluorination of single-walled and multiwalled carbon nanotubes leads to similar results and is characterized by the attachment of fluorine atoms to carbon atoms on the lateral surface of the nanotube with the formation of the σ(C-F) bonds due to the covalent mixing of F 2p and C 2p _z π valence electron states.     

Excitonic effects and optical spectra of single-walled carbon nanotubes

Many-electron effects often dramatically modify the properties of reduced dimensional systems. We report calculations, based on an ab initio many-electron Green's function approach, of electron-hole interaction effects on the optical spectra of small-diameter single-walled carbon nanotubes. Excitonic effects qualitatively alter the optical spectra of both semiconducting and metallic tubes. Excitons are bound by approximately 1 eV in the semiconducting (8,0) tube and by approximately 100 meV in the metallic (3,3) tube. These large many-electron effects explain the discrepancies between previous theories and experiments.     

Nonlinear optical and optical limiting properties of individual single-walled carbon nanotubes

A large number of individual single-walled carbon nanotubes (SWNTs) were obtained by dilution of nanotube dispersions in N-methyl-2-pyrrolidone (NMP). Up to 70% individual SWNTs are contained in the NMP dispersions with concentrations of less than 4.0×10^-3 mg/mL. The nonlinear optical and optical limiting properties of SWNT dispersions were studied by using the Z-scan technique at 532 nm. As the concentration of SWNTs is increased, the nonlinear extinction (NLE) and optical limiting effects improve significantly, while the limiting thresholds decrease gradually. The individual SWNTs show similar NLE effect to zinc phthalocyanine nanoparticles, while also exhibiting larger NLE coefficients than Mo₆S_4.5I_4.5 nanowires.     

Photo-induced absorption in the pump probe spectroscopy of single-walled carbon nanotubes

Femtosecond pump probe spectroscopy is employed to study the photo-induced absorption feature in the single-walled carbon nanotube transient spectrum. The two advantages of the experiment, a chirality enriched sample and tuning the pump wavelength to the resonance of a specific nanotube species, greatly facilitate the identification of the photo-induced absorption signal of one tube species. It is found that a photo-induced absorption feature is located at one radial breathing mode to the blue side of the E11 state. This finding prompts a new explanation for the origin of the photo-induced absorption: the transition from the ground state to a phonon coupled state near the E ii state. The explanation suggests a superposition mechanism of the photo-bleach and photo-induced absorption signals, which may serve as a key to the interpretation of the complex pump probe transient spectrum of carbon nanotubes. The finding sheds some light on the understanding of the complex non-radiative relaxation process and the electronic structure of single-walled carbon nanotubes.     

Luminescence decay and the absorption cross section of individual single-walled carbon nanotubes

The absorption cross section of highly luminescent individual single-walled carbon nanotubes is determined using time-resolved and cw luminescence spectroscopy. A mean value of approximately 1 x 10(-17) cm2 per carbon atom is obtained for (6,5) tubes excited at their second optical transition, and corroborated by single tube photothermal absorption measurements. Biexponential luminescence decays are systematically observed, with short and long lifetimes around 45 and 250 ps. This behavior is attributed to the band edge exciton fine structure with a dark level lying a few meV below a bright one.     

Nonlinear optical properties and phase-relaxation processes in single-walled carbon nanotubes

We have investigated third-order nonlinear optical properties of bundled and isolated semiconducting single-walled carbon nanotubes (SWNTs) by means of Z-scan method, pump-probe method, and two-beam time-resolved degenerate four-wave mixing (DFWM) method. The figures of merit Im χ⁽³⁾/α in both bundled and isolated SWNTs samples were found to be enhanced with increasing tube diameter. The measured Im χ⁽³⁾/α value in the bundled SWNTs was an order of magnitude smaller than that in the isolated SWNTs. Both population relaxation time T₁ and phase-relaxation time T₂ for bundled samples were smaller than those in the isolated samples. These experimental results can be explained by an increase in nonradiative recombination rate and phase-relaxation rate in the bundled sample. The phase-relaxation time T₂ is considered to have a significant role in the enhancement of Im χ⁽³⁾/α.     

Direct measurement of the lifetime of optical phonons in single-walled carbon nanotubes

Time-resolved anti-Stokes Raman spectroscopy has been applied to probe the dynamics of optical phonons created in single-walled carbon nanotubes by femtosecond laser excitation. From measurement of the decay of the anti-Stokes Raman signal in semiconducting nanotubes of (6,5) chiral index, a room-temperature lifetime for G-mode phonons of 1.1+/-0.2 ps has been determined. This lifetime, which reflects the anharmonic coupling of the G-mode phonons to lower-frequency phonons, is important in assessing the role of nonequilibrium phonon populations in high-field transport phenomena.     

Electron-electron interaction effects on the optical excitations of semiconducting single-walled carbon nanotubes

We report correlated-electron calculations of optically excited states in ten semiconducting single-walled carbon nanotubes with a wide range of diameters. Optical excitation occurs to excitons whose binding energies decrease with increasing nanotube diameter, and are smaller than the binding energy of an isolated strand of poly-(paraphenylene vinylene). The ratio of the energy of the second optical exciton polarized along the nanotube axis to that of the lowest exciton is smaller than the value predicted within single-particle theory. The experimentally observed weak photoluminescence is an intrinsic feature of semiconducting nanotubes.     

Anisotropic optical properties of mechanically aligned single-walled carbon nanotubes in polymer

We have prepared aligned single-walled carbon nanotubes in polymer by mechanical stretching. The polarized absorption and Raman spectra of the aligned samples have been investigated. The optical transitions in nanotubes strongly depend on the angle between the polarization of the incident light and the nanotube axis: the absorbance measured at the peak energy shows a maximum at =0°, and they are suppressed at =90°. Raman spectra also show strong polarization dependence, which is mainly determined by the dependence of the oscillator strength of optical transitions in nanotubes. PACS 71.35.Cc; 78.30.-j; 78.67.Ch; 73.22.-f     

Large optical nonlinearity of semiconducting single-walled carbon nanotubes under resonant excitations

We measured third-order nonlinear susceptibility (chi(3)) spectra in semiconducting single-walled carbon nanotubes (SWNTs) by the Z-scan method. |Imchi(3)| is remarkably enhanced under resonant excitation to the lowest interband transition, reaching 4.2 x 10(-6) esu and 1.5 x 10(-7) esu in SWNTs grown by the laser ablation and HiPco methods, respectively. A comparison of the transient absorption changes evaluated by degenerate and nondegenerate pump-probe measurements suggests that the resonant enhancement of |Imchi(3)| is dominated by a coherent process rather than by saturation of absorption.     

Conductivity of single-walled carbon nanotubes

In a system of N interacting single-level quantum dots (QDs), we study the relaxation dynamics and the current–voltage characteristics determined by symmetry properties of the QD arrangement. Different numbers of dots, initial charge configurations, and various coupling regimes to reservoirs are considered. We reveal that effective charge trapping occurs for particular regimes of coupling to the reservoir when more than two dots form a ring structure with the C_N spatial symmetry. We reveal that the effective charge trapping caused by the C_N spatial symmetry of N coupled QDs depends on the number of dots and the way of coupling to the reservoirs. We demonstrate that the charge trapping effect is directly connected with the formation of dark states, which are not coupled to reservoirs due to the system spatial symmetry C_N. We also reveal the symmetry blockade of the tunneling current caused by the presence of dark states.     

Nucleation of single-walled carbon nanotubes

The nucleation pathway for single-wall carbon nanotubes on a metal surface is demonstrated by a series of total energy calculations using density functional theory. Incorporation of pentagons at an early stage of nucleation is energetically favorable as they reduce the number of dangling bonds and facilitate curvature of the structure and bonding to the metal. In the presence of the metal surface, nucleation of a closed cap or a capped single-wall carbon nanotube is overwhelmingly favored compared to any structure with dangling bonds or to a fullerene.     

Hydrogenation of single-walled carbon nanotubes

Towards the development of a useful mechanism for hydrogen storage, we have studied the hydrogenation of single-walled carbon nanotubes with atomic hydrogen using core-level photoelectron spectroscopy and x-ray absorption spectroscopy. We find that atomic hydrogen creates C-H bonds with the carbon atoms in the nanotube walls, and such C-H bonds can be completely broken by heating to 600 degrees C. We demonstrate approximately 65 +/- 15 at % hydrogenation of carbon atoms in the single-walled carbon nanotubes, which is equivalent to 5.1 +/- 1.2 wt % hydrogen capacity. We also show that the hydrogenation is a reversible process.     

Ester-functionalized soluble single-walled carbon nanotubes

We report the preparation of soluble ester- functionalized single-wall carbon nanotubes (sSWNT-COO(CH₂)₁₇CH₃). By use of solution phase IR spectroscopy we are able to compare the ratio of the carbon atoms in the SWNT backbone to the carbon atoms in the ester and amide functionalities of s-SWNTs. Received: 16 July 2001 / Accepted: 3 December 2001 / Published online: 4 March 2002     

On the vibrations of single-walled carbon nanotubes

In this paper, a detailed numerical study on the free and forced vibrations of single walled carbon nanotubes is presented. A simple and straightforward method developed such that the proximity of the mathematical model to the actual atomic structure of the nanotube is significantly retained, is used for this purpose. Both zigzag and armchair chiralities of the carbon nanotubes for clamped-free and clamped-clamped boundary conditions are analyzed and their natural frequencies and corresponding mode shapes are obtained. Results pertaining to axial, bending, and torsional modes of vibration are reported with discussions. These modes of vibration appear in the eigen-values and eigen-vectors without any distinction. The direct integration method by Newmark is used extensively along with the fast Fourier transform to identify different types of vibrational modes. In the case of zigzag nanotubes, the axial, bending, and torsional modes appear to be decoupled, whereas the armchair nanotubes show coupling between such modes.     

Flame synthesis of single-walled carbon nanotubes

Flames offer potential for synthesis of carbon nanotubes in large quantities at considerably lower costs than that of other methods currently available. This study aims to examine conditions for carbon nanotube formation in premixed flames and to characterize the morphology of solid carbon deposits and their primary formation mechanisms in the combustion environment. Single-walled nanotubes have been observed in the post-flame region of a premixed acetylene/oxygen/15 mol% argon flame operated at 6.7 kPa with Fe(CO)₅ vapor used as a source of metallic catalyst necessary for nanotube growth. Thermophoretic sampling and transmission electron microscopy were used to characterize the solid material present in the flame at various heights above burner (HAB), giving a resolution of formation dynamics within the flame system. Catalyst particle formation and growth is observed to dominate the immediate post-flame region (10–40 mm HAB). Nanotubes were observed to be present after 40 mm HAB with nanotube inception occurring as early as 30 mm HAB. Between 40 and 70 mm HAB, nanotubes are observed to coalesce into clusters. A nanotube formation ‘window’ is evident with formation limited to fuel equivalence ratios between 1.5 and 1.9. A continuum of morphologies ranging from relatively clean clusters of nanotubes to amorphous material is observed between these lower and upper limits. High-resolution TEM and Raman spectroscopy revealed nanotube bundles with each nanotube being single-walled with diameters between 0.9 and 1.5 nm.     

单壁纳米碳管的声子谱研究

通过五步旋转操作方便地得到了不同位置原子间的力常数矩阵，从而可以使对各种不同类型管的声子谱的计算变得简便. 计算表明，非螺旋的扶手椅型（n, n）管与锯齿型(n, 0)管的非简并和二重简并模式数分别为12和6(n-1)，这与从群论等方法所得结果相符. 关键词： 纳米碳管 声子谱 振动模式密度 动力学矩阵