Optical response of small-diameter semiconducting carbon nanotubes under exciton-surface-plasmon coupling

We analyze the optical response of small-diameter (?1 nm) semiconducting carbon nanotubes under the exciton-surface-plasmon coupling. Calculated optical absorption lineshapes exhibit the significant 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 believe this effect may be used for the development of carbon nanotube based tunable optoelectronic device applications in areas such as nanophotonics and cavity quantum electrodynamics.     

Excitons in optical spectra of boron-nitride (BN) nanotubes

Exciton effects are studied in single-wall boron-nitride nanotubes. The Coulomb interaction dependence of the band gap, the optical gap, and the binding energy of excitons are discussed. The optical gap of the (5,0) nanotube is about 6 eV at the on-site interaction U=2t with the hopping integral t=1.1 eV. The binding energy of the exciton is 0.50 eV for these parameters. This energy agrees well with that of other theoretical investigations. We find that the energy gap and the binding energy are almost independent of the geometries of nanotubes. This novel property is in contrast with that of the carbon nanotubes, which show metallic and semiconducting properties depending on the chiralities.     

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.     

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.     

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.     

Quadratic electro-optic effect in the nonconjugated conductive polymer iodine-doped trans-polyisoprene, an organic nanometallic system

Thin films of 1,4-trans-polyisoprene have been prepared on various substrates from toluene solution and characterized using Fourier transform infrared (FTIR) spectroscopy, optical absorption spectroscopy and X-ray diffraction before and after doping with iodine. The optical absorption spectrum at low doping shows two peaks: one at 4.2 eV and the other at 3.2 eV. X-ray diffraction indicates an increase of (111) and (122) peak intensities upon doping. Quadratic electro-optic measurements have been made using field-induced birefringence. The Kerr coefficients as measured (3.5×10⁻¹⁰ m/V ² at 633 nm and 2.5×10⁻¹⁰ m/V ² at 1.55 μm) are exceptionally large, and they have been attributed to the subnanometer-size metallic domains formed upon doping and charge transfer.     

Characterization of luminescent chromophore obtained from silica spheres

Blue light emitting chromophores have been separated from silica spheres by soaking them into acetone for 120 days. The luminescent chromophores were not obtained from other solvents, including ether, methanol, ethanol, 2-propanol, chloroform and tetrahydrofuran. According to the Fourier transform infrared spectrum, the luminescent material is composed of C–OH, –CH₂, –CH₃, C=O, and Si–O–Si. UV–visible absorption peak of the chromophore is at 5.17 eV (240 nm). Field emission scanning electron microscope images show small cracks on the surface of aged spheres. The luminescence peak was at 2.81 eV (441 nm) for excitation energy between 3.88 and 3.35 eV and slightly shifted toward lower energy for excitation energy lower than 3.35 eV. The deconvoluted luminescent spectrum shows two emission bands at 3.08 and 2.74 eV, which are well-matched the oxygen deficient center model. Compared to the absorption peak (5.17 eV) and the emission peak (2.81 eV), large Stokes shift (2.36 eV) is observed.     

拓扑缺陷对单壁碳纳米管电子结构及其光学光谱的影响

应用密度泛函理论计算了半导体型单壁碳纳米管(7,0)和(8,0)以及其发生镜像对称和非镜像对称Stone-Wales形变、形成异质结(7,0)—(8,0)情况下的能带结构、吸收光谱、反射光谱,并对计算结果进行了比较。研究发现： 引入拓扑缺陷态后,碳纳米管的能带结构发生了明显的变化,费米能级在不同缺陷情况下移动方向不一致;碳管的吸收和反射明显减弱且吸收峰和反射峰在低能区发生红移现象;在光子能量约为E=13 eV处各碳管的吸收谱和反射谱中均出现一特征峰,并且在引入缺陷以后该特征峰向高能区移动。文章对计算结果进行了分析和探讨,可望利用这种拓扑缺陷的引入而产生的光电特性来设计碳管光电器件。     

Electronic structures and transport properties of sulfurized carbon nanotubes

The electronic and transport properties of side-walled sulfurized (8, 0) zigzag carbon nanotube were investigated by using density functional theory coupled with a non-equilibrium Green function approach. It is found that the adsorption of the sulfur chains largely reduces the bandgap of the semiconducting (8, 0) carbon nanotube, even changing it into a metallic one. More importantly, the transmission eigenstates around the Fermi level are contributed by not only the sulfur chains but also the complex system made of the sulfur chains and the single-walled carbon nanotube. Our results provide a method to improve the conductivity and utilization rate of the surface in the electrodes of supercapacitor which are made of the carbon nanotubes.     

Many body shake up in X-ray photoemission from bundles of lithium-intercalated single-walled carbon nanotubes

We present a model to describe the asymmetric features of X-ray photoemission spectra from bundles of clean and Li-intercalated single-walled carbon nanotubes due to shake up processes in both metallic and semiconducting bands, with energy gaps below ∼1 eV. Using the tight binding method, we determine the effect of the suddenly created core hole - in the 1s-state of a carbon atom - on the many electron states of π and π^∗ bands. We compute the energy distributions of many body excitations created at the expense of the photoelectron energy in (10, 10) and (16, 0) tubes, thus, obtaining an merit function for the X-ray photo-peak, resulting from the superposition of a symmetric and an asymmetric components. The latter describes to the average behavior of shake up electrons in tubes of different chirality and changes with the concentration of dopants.     

Electronic structure and optical properties of LaNiO3: First-principles calculations

Using a first-principles method, we investigate the electronic structure and optical properties of rhombohedral LaNiO₃. The total density of states shows that there is no band gap and bulk LaNiO₃ is metallic. There is a strong hybridization between Ni and O orbits near the Fermi level, suggesting that the metallic nature of LaNiO₃ mainly originates from Ni 3d states and La atoms have no noticeable contribution to this. The absorption coefficient of LaNiO₃ is one order of magnitude less than that of nickel in the lower energy region (0–5 eV), and the interband optical transitions are mainly derived from O 2p and Ni 3d states. In reflectivity spectrum of LaNiO₃, there are three main reflectance peaks located at 0 eV, 15.6 eV and 22.9 eV, respectively. In the visible–ultraviolet energy range, the reflectivity of LaNiO₃ remarkably decreases with the increasing photon energy and the value is always smaller than that of nickel in the region.     

Transition from a Tomonaga-Luttinger liquid to a fermi liquid in potassium-intercalated bundles of single-wall carbon nanotubes

We report on the first direct observation of a transition from a Tomonaga-Luttinger liquid to a Fermi-liquid behavior in potassium-intercalated mats of single-wall carbon nanotubes. Using high resolution photoemission spectroscopy, an analysis of the spectral shape near the Fermi level reveals a Tomonaga-Luttinger liquid power law scaling in the density of states for the pristine sample and for low dopant concentration. As soon as the doping is high enough to achieve a filling of the conduction bands of the semiconducting tubes, a distinct transition to metallic single-wall carbon nanotube bundles with the scaling behavior of a normal Fermi liquid occurs.     

Ab initio density functional theory investigation of Li-intercalated silicon carbide nanotube bundles

We present the results of ab initio density functional theory calculations on the energetic, and geometric and electronic structure of Li-intercalated (6,6) silicon carbide nanotube (SiCNT) bundles. Our results show that intercalation of lithium leads to the significant changes in the geometrical structure. The most prominent effect of Li intercalation on the electronic band structure is a shift of the Fermi energy which occurs as a result of charge transfer from lithium to the SiCNTs. All the Li-intercalated (6,6) SiCNT bundles are predicted to be metallic representing a substantial change in electronic properties relative to the undoped bundle, which is a wide band gap semiconductor. Both inside of the nanotube and the interstitial space are susceptible for intercalation. The present calculations suggest that the SiCNT bundle is a promising candidate for the anode material in battery applications.     

Synthesis, integration, and electrical properties of individual single-walled carbon nanotubes

High-quality single-walled carbon nanotubes (SWNTs) are synthesized by chemical vapor deposition (CVD) of methane on silicon-dioxide substrates at controlled locations using patterned catalytic islands. With the synthesized nanotube chips, microfabrication techniques are used to reliably contact individual SWNTs and obtain low contact resistance. The combined chemical synthesis and microfabrication approaches enable systematic characterization of electron transport properties of a large number of individual SWNTs. Results of electrical properties of representative semiconducting and metallic SWNTs are presented. The lowest two-terminal resistance for individual metallic SWNTs (≈5 μm long) is ≈16.5 kΩ measured at 4.2 K. Received: 17 May 1999 / Accepted: 18 May 1999 / Published online: 14 July 1999     

Polarization component of cohesion energy in single-wall carbon nanotube-DNA complexes

Within the framework of a quantum mechanical model, the polarization component of the energy of cohesion of an ionized DNA molecule to the surface of a nanotube has been calculated. Neglecting the polarization of the DNA, and in the absence of external screening, the binding energy is ∼0.47 eV per elementary charge. The effective nanotube screening parameter is ∼2 and cannot be reduced to classical expressions for metallic and dielectric screening. Published in Russian in Pis’ma v Zhurnal éksperimental’noĭ i Teoreticheskoĭ Fiziki, 2006, Vol. 84, No. 6, pp. 411–415. The article was translated by the authors.     

Visible fluorescence induced by the metal semiconductor transition in composites of carbon nanotubes with noble metal nanoparticles

We show that single-walled carbon nanotube (SWNT) bundles emit visible fluorescence in the presence of noble metal nanoparticles and nanorods in the solid state. Conductivity measurements with metallic nanotubes, isolated from pristine SWNTs, show that they become semiconducting in the presence of the metal nanoparticles. Nanoparticle binding increases the defects in the nanotube structures which is evident in the Raman spectra. The metal-semiconductor transition removes the nonradiative decay channels of the excited states enabling visible fluorescence. Nanotube structures are imaged using this emission with resolution below the classical limits.     

Surface functionalization by low-energy electron processing of molecular ices

Low-energy electron processing of condensed molecular films (also called ices) is an efficient method to induce functionalization of a substrate, and thereby to modify and adjust its electronic and chemical properties. This method takes advantage of a resonant mechanism specific to low-energy electrons (by opposition to photons), the dissociative electron attachment (DEA), the key process allowing the chemical selectivity to be directly and easily controlled by the kinetic energy of the processing electrons. The functionalization procedure is described and illustrated by high resolution electron energy loss spectroscopy (HREELS) results on the induced anchoring of CH₂CN organic chains on synthetic diamond by electron irradiation at 2 eV of condensed acetonitrile. The range of application of the proposed functionalization method is worth to be extended to other organic/inorganic interfaces, such as organic layers on metallic and semiconducting substrates.     

Characterizations of n-type ferromagnetic GaMnN thin film grown on GaN/Al2O3 (0 0 0 1) by metal-organic chemical vapor deposition

A high-quality ferromagnetic GaMnN (Mn=2.8 at%) film was deposited onto a GaN buffer/Al₂O₃(0 0 0 1) at 885 °C using the metal-organic chemical vapor deposition (MOCVD) process. The GaMnN film shows a highly c-axis-oriented hexagonal wurtzite structure, implying that Mn doping into GaN does not influence the crystallinity of the film. No Mn-related secondary phases were found in the GaMnN film by means of a high-flux X-ray diffraction analysis. The composition profiles of Ga, Mn, and N maintain nearly constant levels in depth profiles of the GaMnN film. The binding energy peak of the Mn 2p_3/2 orbital was observed at 642.3 eV corresponding to the Mn (III) oxidation state of MnN. The presence of metallic Mn clusters (binding energy: 640.9 eV) in the GaMnN film was excluded. A broad yellow emission around 2.2 eV as well as a relatively weak near-band-edge emission at 3.39 eV was observed in a Mn-doped GaN film, while the undoped GaN film only shows a near-band-edge emission at 3.37 eV. The Mn-doped GaN film showed n-type semiconducting characteristics; the electron carrier concentration was 1.2×10²¹/cm³ and the resistivity was 3.9×10⁻³ Ω cm. Ferromagnetic hysteresis loops were observed at 300 K with a magnetic field parallel and perpendicular to the ab plane. The zero-field-cooled and field-cooled curves at temperatures ranging from 10 to 350 K strongly indicate that the GaMnN film is ferromagnetic at least up to 350 K. A coercive field of 250 Oe and effective magnetic moment of 0.0003 μ_B/Mn were obtained. The n-type semiconducting behavior plays a role in inducing ferromagnetism in the GaMnN film, and the observed ferromagnetism is appropriately explained by a double exchange mechanism.     

Effect of Al-doping on optical and electrical properties of spray pyrolytic nano-crystalline CdO thin films

CdO and Al-doped CdO nano-crystalline thin films have been prepared on glass at 300 °C substrate temperature by spray pyrolysis. The films are highly crystalline with grain size (18–32 nm) and found to be cubic structure with lattice constant averaged to 0.46877 nm. Al-doping increased the optical transmission of the film substantially. Direct band gap energy of CdO is 2.49 eV which decreased with increasing Al-doping. The refractive index and dielectric constant varies with photon energy and concentration of Al as well. The conductivity of un-doped CdO film shows metallic behavior at lower temperature region. This behavior dies out completely with doping of Al and exhibits semiconducting behavior for whole measured temperature range. Un-doped and Al-doped CdO is an n-type semiconductor having carrier concentration is of the order of ∼10²¹ cm⁻³, confirmed by Hall voltage and thermo-power measurements.     

Optical characterization of CuIn5S8 crystals by ellipsometry measurements

Optical properties of CuIn₅S₈ crystals grown by Bridgman method were investigated by ellipsometry measurements. Spectral dependence of optical parameters; real and imaginary parts of the pseudodielectric function, pseudorefractive index, pseudoextinction coefficient, reflectivity and absorption coefficients were obtained from the analysis of ellipsometry experiments performed in the 1.2–6.2 eV spectral region. Analysis of spectral dependence of the absorption coefficient revealed the existence of direct band gap transitions with energy 1.53 eV. Wemple–DiDomenico and Spitzer–Fan models were used to find the oscillator energy, dispersion energy, zero-frequency refractive index and high-frequency dielectric constant values. Structural properties of the CuIn₅S₈ crystals were investigated using X-ray diffraction and energy dispersive spectroscopy analysis.