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.     

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.     

Observation of excitons in one-dimensional metallic single-walled carbon nanotubes

Excitons are generally believed not to exist in metals because of strong screening by free carriers. Here we demonstrate that excitonic states can in fact be produced in metallic systems of a one-dimensional character. Using metallic single-walled carbon nanotubes as a model system, we show both experimentally and theoretically that electron-hole pairs form tightly bound excitons. The exciton binding energy of 50 meV, deduced from optical absorption spectra of individual metallic nanotubes, significantly exceeds that of excitons in most bulk semiconductors and agrees well with ab initio theoretical predictions.     

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.     

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.     

Direct observation of dark excitons in micelle-wrapped single-wall carbon nanotubes

We have performed electroabsorption spectroscopy on micelle-wrapped single-wall carbon nanotubes. In semiconducting nanotubes, many oscillating structures composed of the increase and decrease of absorption are observed in the spectra in the region of the first and second absorption bands, E11 and E22. The spectral shape is reproduced mainly by the second-derivative curve of the absorption spectrum, which indicates the presence of nearly degenerate bright and dark excitonic states.     

Exciton States and Linear Optical Spectra of Semiconducting Carbon Nanotubes under Uniaxial Strain

Considering the exciton effect, the linear optical spectra of semiconducting single-walled carbon nanotubes （SWNTs） under uniaxial strain are theoretically studied by using the standard formulae of Orr and Ward [Mol. Phys. 20（1971）513]. It is found that due to the wrapping effect existing in the semiconducting zigzag tubes, the excitation energies of the linear optical spectra show two different kinds of variations with increasing uniaxial strain, among which one decreases such as tube （11,0）, and the other increases firstly and then decreases such as tube （10,0）. These variations of the linear optical spectra are consistent with the changes of the exciton binding energies or the （quasi）continuum edge of these SWNTs calculated in our previous work, which can be used as a supplemented tool to detect the deformation degree of an SWNT under uniaxial strain.     

Surface exciton-plasmons and optical response of small-diameter carbon nanotubes

We study theoretically the interactions of excitonic states with surface electromagnetic modes of small-diameter (≲1 nm) semiconducting single-walled carbon nanotubes. We show that these interactions can result in strong exciton-surface-plasmon coupling. The exciton absorption lineshape exhibits the line (Rabi) splitting ∼0.1–0.3 eV as the exciton energy is tuned to the nearest interband surface plasmon resonance of the nanotube so that the mixed strongly coupled surface plasmon-exciton excitations are formed. We discuss possible ways to bring the exciton in resonance with the surface plasmon. The exciton-plasmon Rabi splitting effect we predict here for an individual carbon nanotube is close in its magnitude to that previously reported for hybrid plasmonic nanostructures artificially fabricated of organic semiconductors deposited on metallic films. We expect this effect to open up paths to new tunable optoelectronic device applications of semiconducting carbon nanotubes.     

Determination of the exciton binding energy in single-walled carbon nanotubes

We report that measurements of the Raman intensity versus applied voltage are sensitive to filling of the density of states and enable us to measure the second band gap in specific semiconducting single-walled carbon nanotubes (SWNTs). Raman scattering preferentially selects sets of SWNTs whose excitonic transitions are resonant with the incident or scattered photon energies. Simultaneous measurement of the electronic gap and exciton resonance allows us to infer binding energies for the exciton of 0.49+/-0.05 and 0.62+/-0.05 eV for tubes of (10, 3) and (7, 5), respectively. Metallic SWNTs exhibit no excitonic feature.     

Direct observation of deep excitonic states in the photoluminescence spectra of single-walled carbon nanotubes

Low-energy, dark excitonic states have recently been predicted to lie below the first bright (E11) exciton in semiconducting single-walled carbon nanotubes [Phys. Rev. Lett. 93, 157402 (2004)10.1103/PhysRevLett.93.157402]. Decay into such deep excitonic states is implicated as a mechanism which reduces photoluminescence quantum yields. In this study we report the first direct observation of deep excitons in SWNTs. Photoluminescence (PL) microscopy of suspended semiconducting single-walled carbon nanotubes (SWNTs) reveals weak emission satellites redshifted by approximately 38-45 and approximately 100-130 meV relative to the main E11 PL emission peaks. Similar satellites, redshifted by 95-145 meV depending on nanotube species, were also found in PL measurements of ensembles of SWNTs in water-surfactant dispersions. The relative intensities of these deep exciton emission features depend on the nanotube surroundings.     

Absorption spectra of high purity metallic and semiconducting single-walled carbon nanotube thin films in a wide energy region

Absorption spectra of high purity metallic and semiconducting single-walled carbon nanotubes separated by the density-gradient ultracentrifugation method have been measured in the wide energy region from 1 meV to 5 eV. In the high purity metallic nanotube sample, a strong and broad absorption band has been observed at 0.06 eV. This observation suggests that the optical properties of even high purity metallic nanotube bundles cannot be explained by the simple Drude conduction model. We discuss the origin of these absorption bands for metallic and semiconducting nanotube samples by considering the existence of a small energy gap in metallic nanotube bundles and plasmon resonance.     

Polarized absorption spectra of single-walled 4 A carbon nanotubes aligned in channels of an AlPO(4)-5 single crystal

We report the polarized optical absorption spectra of single-walled 4 A carbon nanotubes arrayed in the channels of an AlPO (4)-5 single crystal. When the light electric field (E) is polarized parallel to the tube direction (c), the spectra display a sharp peak at 1.37 eV, with two broadbands at 2.1 and 3.1 eV. In the E perpendicular c configuration, the tube is nearly transparent in the measured energy region 0.5-4.1 eV. The optical dipole selection rules are discussed, and the absorption bands are assigned to the dipole transitions between the Van Hove singularities. The measured absorption spectra agreed well with the ab initio calculations of band structure based on the local density function approximation.     

超细0.4nm直径单壁碳管的光学特性

由于纳米碳管的优异机械特性及其丰富多采的光学和电学特性，它自1991年被发现以来一直受到科学家的青睐，纳米碳管研究已成为当今世界上发展最迅速，竞争最激烈的科学前沿领域之一。怎样才能把纳米碳管做得更细小，尺寸更均匀以及如何使众多的纳米碳管排列规整，一直是纳米碳管研究中的难题。我们利用多孔的沸石晶体作为载体，首次成功地研制出了尺寸均一，排列规整的超细单壁纳米碳管，这些超细纳米碳管具有独特的性能，低温下（＜20K）甚至呈现出前所未有的一维超导现象。详细介绍了这些超细单壁纳米碳管的制备过程，并着重介绍其在可见光区的光吸收，光发射以及二次谱波的倍频特性。     

Electronics and Structural Properties of Single-Walled Carbon Nanotubes Interacting with a Glucose Molecule：ab initio Calculations

The adsorption of glucose molecule on single-walled carbon nanotubes (SWCNTs) is investigated by density functional theory calculations. Adsorption energies and equilibrium distances are evaluated, and glucose binding to the typical semiconducting and metallic nanotubes with various diameters and chirality are compared. We also investigated the role of the structural defects on the adsorption capability of the SWCNTs. We could observe larger adsorption energies for the larger diameters semiconducting CNTs, while the story is paradoxical for the metallic CNTs. The obtained results reveal that the adsorption energy is significantly higher for nanotubes with higher chiral angles. Finally, the adsorption energies are calculated for defected nanotubes for various configurations such as glucose molecule approaching to the pentagon, hexagon, and heptagon sites in the tube surface. We find that the respected defects have a minor contribution to the adsorption mechanism of the glucose on SWNTs. The calculation of electron transfers and the density of states supports that the electronic properties of SWCNTs do not change significantly after the gluycose molecular adsorption. Consequently, one can predict that presence of glucose would neither modify the electronic structure of the SWCNTs nor direct to a change in the conductivity of the intrinsic nanotubes.     

Electronics and Structural Properties of Single-Walled Carbon Nanotubes Interacting with a Glucose Molecule: ab initio Calculations

The adsorption of glucose molecule on single-walled carbon nanotubes(SWCNTs)is investigated by density functional theory calculations.Adsorption energies and equilibrium distances are evaluated,and glucose binding to the typical semiconducting and metallic nanotubes with various diameters and chirality are compared.We also investigated the role of the structural defects on the adsorption capability of the SWCNTs.We could observe larger adsorption energies for the larger diameters semiconducting CNTs,while the story is paradoxical for the metallic CNTs.The obtained results reveal that the adsorption energy is significantly higher for nanotubes with higher chiral angles.Finally,the adsorption energies are calculated for defected nanotubes for various configurations such as glucose molecule approaching to the pentagon,hexagon,and heptagon sites in the tube surface.We find that the respected defects have a minor contribution to the adsorption mechanism of the glucose on SWNTs.The calculation of electron transfers and the density of states supports that the electronic properties of SWCNTs do not change significantly after the gluycose molecular adsorption.Consequently,one can predict that presence of glucose would neither modify the electronic structure of the SWCNTs nor direct to a change in the conductivity of the intrinsic nanotubes.     

Dynamics and spectra of excited states of water-micellar suspensions of single-walled carbon nanotubes

The dynamics of the photoinduced differential absorption and excited-state bleaching spectra of single-walled carbon nanotubes suspended in a micellar solution were studied in the spectral range from 40 to 1000 nm within a time interval from 70 fs to 150 ps under excitation by 50-fs pulses with photon energies 2 and 4 eV. The bleaching and absorption bands were observed in the spectra; the positions of the bleaching peaks were independent of the photon energy of the exciting femtosecond pulse in the range 2–4 eV. It was established that, for delay times shorter than 1 ps, the shape of the differential spectrum of excited nanotubes coincided with the shape of the second derivative of the absorption spectrum of unexcited nanotubes in the frequency range of exciting pulse above 18000 cm^?1 (the range of absorption bands of metallic nanotubes). In the frequency range below 16000 cm^?1 (the range of absorption peaks of semiconducting nanotubes), the bleaching peaks in the differential spectrum of excited nanotubes undergo a high-frequency shift of 200–300 cm^?1 with respect to the second-derivative spectrum of unexcited nanotubes. The excited-state relaxation rate constants were measured. They are well approximated by the exponential dependences and depend on the probe-pulse wavelength. An assumption was made about the nature of the observed spectra of excited nanotubes and about the excitation relaxation.     

Strongly localized states in a single carbon nanotube with polymer molecules

A single-walled carbon nanotube (SWCNT) with conjugated polymer molecules is analyzed via optical spectroscopy. The presence of strongly localized excitonic states in the SWCNT is confirmed using time-integrated photoluminescence (PL). The PL spectrum exhibits extremely narrow width (~0.8 meV) which is attributed to the strong confinement of the states by polymer molecules. In addition, I observed that the excited states are gradually filled as a function of the excitation power, which supports the localized excitonic behavior. Only the ground excitonic state is observed at low excitation powers, but three additional PL peaks appear as the excitation power is increased. Especially, the power-dependent PL spectrum shows a blueshift and increased width, which can be elucidated in terms of quantum confined stark effect and the screening of induced electric fields. Overall, I demonstrate that the presence of polymer molecules induces several localized states in a single SWCNT.     

Measurement of the optical Stark effect in semiconducting carbon nanotubes

A strong optical Stark effect has been observed in (6,5) semiconducting single-walled carbon nanotubes by femtosecond pump-probe spectroscopy. The response is characterized by an instantaneous blueshift of the excitonic resonance upon application of pump radiation at photon energy well below the band gap. The large Stark effect is attributed to the enhanced Coulomb interactions present in these one-dimensional materials.     

New features in the anti‐Stokes and Stokes Raman spectra of single‐walled carbon nanotubes that are highly separated into their semiconducting and metallic nanotube components

Surface‐enhanced Raman scattering studies were performed using nonresonant (514.5 nm) and resonant (676.4 nm) optical excitations on single‐walled carbon nanotubes thoroughly separated into semiconducting (pure 99%) and metallic (pure 98%) components. Regardless of the support (Au or Ag), the metallic nanotubes do not present an anomalous anti‐Stokes Raman emission. Regardless of whether an on‐resonant or off‐resonant optical excitation is used, only the semiconducting nanotubes produce an abnormal anti‐Stokes Raman emission that grows when increasing the excitation light intensity or temperature. The Raman studies under light polarized relative to the main nanotube axis demonstrate that only semiconducting nanotubes are sensitive toward changes in the polarization of the excitation light. Copyright © 2014 John Wiley & Sons, Ltd.     

Surface-enhanced and normal stokes and anti-stokes Raman spectroscopy of single-walled carbon nanotubes

Surface enhancement factors of at least 10(12) for the Raman scattering of single-walled carbon nanotubes in contact with fractal silver colloidal clusters result in measuring very narrow Raman bands corresponding to the homogeneous linewidth of the tangential C-C stretching mode in semiconducting nanotubes. Normal and surface-enhanced Stokes and anti-Stokes Raman spectra are discussed in the framework of selective resonant Raman contributions of semiconducting or metallic nanotubes to the Stokes or anti-Stokes spectra, respectively, of the population of vibrational levels due to the extremely strong surface-enhanced Raman process, and of phonon-phonon interactions.