Determination of the texture of arrays of aligned carbon nanotubes from the angular dependence of the X-ray emission and X-ray absorption spectra

The properties of materials containing carbon nanotubes depend on the degree of alignment and the internal structure of nanotubes. It is shown that the degree of misorientation of carbon nanotubes in samples can be evaluated from the measurements of the angular dependences of the carbon X-ray emission and carbon X-ray absorption spectra. The CK _α emission and CK X-ray absorption spectra of the array of multiwalled carbon nanotubes synthesized by catalytic thermolysis of a mixture of fullerene and ferrocene are measured. A comparison of the calculated model dependences of the relative intensities of the π and σ bands in the spectra with the experimental results makes it possible to evaluate the degree of misorientation of nanotubes in the sample and their internal texture.     

Band structure and CK α emission of ultrathin nanotubes

An attempt is made to calculate the energy bands and spectra of the characteristic CK _α emission of small-diameter carbon nanotubes. The calculated spectra for the nanotubes are compared with similar spectra for graphite monolayers used as a test object and with known experimental results for nanotubes. It is concluded that the x-ray emission spectra can be used to identify thin carbon nanotubes. A classification of solid-phase carbon is proposed which takes into account the position of carbon nanotubes in the family of allotropic carbon forms. The type of hybridization of the electrons in the carbon atom is used as the criterion for classification.     

Effect of passivating Al<Subscript>2</Subscript>O<Subscript>3</Subscript> thin films on MnO<Subscript>2</Subscript>/carbon nanotube composite lithium-ion battery anodes

MnO₂/carbon nanotube composite electrodes for Li-ion battery application were directly coated with ultrathin thicknesses of aluminum oxide film by atomic layer deposition (ALD). The non-reactive Al₂O₃ layer not only provides a stable film to protect the manganese oxide and carbon nanotubes from undesirable reaction with the electrolyte but also restrains the volume change strain of manganese oxide during cycling. The first cycle Coulombic efficiency of coated samples was increased to different extents depending on the coating thickness. In the following cycles, the coated electrodes denote high specific capacity, good capacity retention ability, and perfect rate charge/discharge performance.     

X-Ray Spectral Studies of the Interface Interaction in CuO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>/MWCNTs Nanocomposite

Results of a comprehensive study of the interface interaction of a nanostructured CuO_x and multiwalled carbon nanotubes (MWCNTs) in CuO_x/MWCNT nanocomposite by X-ray absorption spectroscopy (XANES, NEXAFS) and X-ray photoelectron spectroscopy (XPS) methods using a synchrotron radiation are presented. It is established that a nanostructured CuO_x in CuO_x/MWCNT nanocomposite is predominantly formed by CuO and has the form of flakelike particles 200–500 nm in size uniformly dispersed over an array of nanotubes. A chemical interaction of CuO_x and nanotubes with formation of covalent carbon–oxygen bonds, which does not lead to a significant destruction of the outer layers of carbon nanotubes, is observed at the interfaces of the nanocomposite.     

Orientation ordering of N<Subscript>2</Subscript> molecules in vertically aligned CN<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> nanotubes

Arrays of vertically aligned nitrogen-doped carbon (CN _x ) nanotubes have been synthesized by decomposition of aerosol mixture of acetonitrile and ferrocene at 850°C. Nitrogen concentration in the outer shells of the CN _x nanotubes was found from X-ray photoelectron spectroscopy (XPS) data to reach ∼6%. The XPS N 1s spectra and N 1s near-edge X-ray absorption fine structure (NEXAFS) spectra identified three chemical forms of nitrogen in the CN _x nanotube arrays: pyridine-like, graphitic, and molecular nitrogen. The π ^* resonance of molecular nitrogen showed clear polarization dependence that indicates predominant orientation of N₂ molecules along the nanotubes axis. The estimated range of the polar angle distribution of the N₂ molecules orientation in the CN _x nanotube array amounts to 15°.     

Preparation of Co<Subscript>3</Subscript>O<Subscript>4</Subscript> hollow microsphere/graphene/carbon nanotube flexible film as a binder-free anode material for lithium-ion batteries

A flexible Co₃O₄ hollow microsphere/graphene/carbon nanotube hybrid film is successfully prepared through a facile filtration strategy and a subsequent thermally treated process. The composition, morphology, and structure of the as-prepared film are characterized by X-ray diffraction, X-ray photoelectron spectrometer, scanning electron microscopy, and transmission electron microscopy. Based on the morphology characterizations on the hybrid film, the Co₃O₄ hollow microspheres are uniformly and closely attached on three-dimensional (3D) graphene/carbon nanotubes (GR/CNTs) network, which decreases the agglomeration of Co₃O₄ microspheres effectively. In this hybrid film, the 3D GR/CNT network which enhances conductance as well as prevents aggregation is a benefit to help Co₃O₄ to exert its lithium storage capabilities sufficiently. When used as a binder-free anode material for lithium-ion batteries, the hybrid film delivers excellent electrochemical properties involving reversible capacity (863 mAh g^?1 at a current density of 100 mA g^?1) and rate performance (185 mAh g^?1 at a current density of 1600 mA g^?1).     

Growth of carbon nanotubes from C<Subscript>60</Subscript>

Carbon nanotubes can be obtained from a multitude of molecular precursors in chemical vapor deposition (CVD) processes. Here we demonstrate that the use of C₆₀ as the carbon feedstock gas in an iron-catalyzed thermal CVD experiment leads to the formation of films of multi-walled carbon nanotubes. The critical role of the diameter of the catalyst particles in determining the efficiency of nanotube growth is clearly demonstrated. Electron microscopy and Raman spectroscopy were employed for the characterisation of the nanotube material. The structural properties of the individual nanotubes show distinctive differences to acetylene-grown multi-walled nanotubes. PACS 81.07.De; 81.10.Bk     

Influence of the inhomogeneity of local magnetic parameters on the curves of magnetization in an ensemble of Fe<Subscript>3</Subscript>C ferromagnetic nanoparticles encapsulated in carbon nanotubes

Methods have been proposed and tested for analyzing local magnetic parameters in a system of single-domain ferromagnetic nanoparticles using their magnetization curves. The magnetic inhomogeneity in ensembles of Fe₃C nanoparticles encapsulated in carbon nanotubes has been investigated. It has been established that the Fe₃C nanoparticles encapsulated in carbon nanotubes are characterized by two-modal distribution functions of the local magnetic anisotropy energy. The particle distribution over the blocking temperature is reconstructed from the experimental temperature dependence of the coercive force. The allowance made for the inhomogeneity of the local magnetic parameters of the Fe₃C nanoparticles, which were studied by the proposed methods, explains the discrepancy between the magnetic anisotropy energy determined by the method of the magnetization approaching saturation and the magnetic anisotropy energy estimated from the coercive force of single-domain nanoparticles.     

Spatial dependence of the dichroism of photoemission of Fe<Subscript>1/4</Subscript>TiTe<Subscript>2</Subscript> upon excitation with circularly polarized radiation

This paper reports on the results of the experimental investigation into the angular dependence of the photoemission of the valence band (the angle-resolved photoelectron spectrum) for the Fe_1/4TiTe₂ single crystal upon excitation with circularly polarized radiation. The angle-resolved photoelectron spectrum is studied in the vicinity of the Γ point of the Brillouin zone in the two directions ΓK and ΓM with the highest symmetry. The measurements are performed in noncoplanar geometry. The circular dichroism in the photoemission angular distribution is observed over the entire ranges of energies and angles. The magnitude of the dichroism depends on the choice of the band, the binding energy, and the polar angle and varies from 0 at the Γ point to 20%.     

Electrical conduction mechanism in Fe<Subscript>70</Subscript>Pd<Subscript>30</Subscript> catalyzed multi-walled carbon nanotubes

Carbon nanotubes (CNTs) are synthesized by the catalytic decomposition of acetylene using low pressure chemical vapour deposition method (LPCVD) at 800 °C and at a chamber pressure of 10 Torr over a supported catalyst film of Fe₇₀Pd₃₀. Morphology of these CNTs is studied using Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM) and High Resolution Transmission Electron Microscopy (HRTEM). From HRTEM image of these multi-walled carbon nanotubes (MWNTs), it is clear that these MWNTs do not possess a co-axial cylindrical structure, but are composed of imperfect and broken graphite cylinders of different sizes. The average diameter and length of the nanotubes varies between 20–70 nm and 5–60 μm respectively. Electrical transport measurements of these MWNTs are studied over a temperature range of 298–4.2 K. The results have been interpreted in terms of variable-range hopping (VRH) over the entire temperature range of 298–4.2 K. Three-dimensional variable-range hopping (VRH) is suggested for the temperature range (298–125 K), while two-dimensional VRH is observed for the temperature range (125–4.2 K).     

Raman scattering spectroscopy of inclusions of carbon in Al<Subscript>2</Subscript>O<Subscript>3</Subscript> films and its solid solutions with HfO<Subscript>2</Subscript>

We apply Raman scattering spectroscopy to study the nature of carbon inclusions in Al₂O₃ and (HfO₂) _x (Al₂O₃)_{1 ? x} films deposited using volatile complex compounds. Raman spectra of the films under investigation contain D and G vibrational modes, which indicate that carbon clusters of the sp ² configuration tend to form in the films. We estimate the size of clusters from the integrated intensity ratio I _D /I _G and find it to be in the range of 14–20 Å. The content of hydrogen in carbon clusters is calculated from the height of the photoluminescence pedestal and is found to vary from 14 to 30 at % depending on the regime of the film’s synthesis.     

Fabrication and characterization of CdS-sensitized TiO<Subscript>2</Subscript> nanotube photoelectrode

CdS quantum dot (Qd)-sensitized TiO₂ nanotube array photoelectrode is synthesised via a two-step method on tin-doped In₂O₃-coated (ITO) glass substrate. TiO₂ nanotube arrays are prepared in the ethylene glycol electrolyte solution by anodizing titanium films which are deposited on ITO glass substrate by radio frequency sputtering. Then, the CdS Qds are deposited on the nanotubes by successive ionic layer adsorption and reaction technique. The resulting nanotube arrays are characterized by scanning electron microscopy, X-ray diffraction (XRD) and UV–visible absorption spectroscopy. The length of the obtained nanotubes reaches 1.60 μm and their inner diameter and wall thickness are around 90 and 20 nm, respectively. The XRD results show that the as-prepared TiO₂ nanotubes array is amorphous, which are converted to anatase TiO₂ after annealed at 450 °C for 2 h. The CdS Qds deposited on the TiO₂ nanotubes shift the absorption edge of TiO₂ from 388 to 494 nm. The results show that the CdS-sensitized TiO₂ nanotubes array film can be used as the photoelectrode for solar cells.     

First-principle study of interaction of molecular hydrogen with BC<Subscript>3</Subscript> composite single-walled nanotube

The physisorption of molecular hydrogen in BC₃ composite single-walled nanotube, investigated using density functional theory, was compared with single-walled carbon nanotube. Both external and internal adsorption sites of these two nanotubes have been studied with the hydrogen molecular axis oriented parallel to the nanotube wall. The calculated results show that: ([see full textsee full text]) the physisorption energies of a H₂ molecule are larger for BC₃(8,0) composite nanotube than for C(8,0) nanotube at all adsorption sites examined. ([see full textsee full text]) For these two nanotubes, the physisorption energies are larger for hydrogen bound inside the nanotubes than for adsorption outside the nanotubes. The different behavior between these two nanotubes is explained by the contour plots of electron density and charge-density difference of them. The present computations suggest that BC₃ nanotube may be a better candidate for hydrogen storage than carbon nanotube.     

Electrical and resonance properties of magnetically inhomogeneous La<Subscript>0.775</Subscript>Sr<Subscript>0.225</Subscript>MnO<Subscript>3−δ</Subscript> films

Electrical properties and magnetic-resonance spectra are studied in La_0.775Sr_0.225MnO_3?δ thin films obtained on SrTiO₃ single-crystal substrates through magnetron sputtering. Below 250 K, the essential influence of the intensity of an electric current flowing through a film on the electrical resistance of the sample is observed. It is experimentally shown that as the current density is increased in the low-temperature range, the semiconducting conduction transforms into metallic conduction. Arguments are advanced in favor of the hypothesis that the strong sensitivity of the film properties to external factors is caused by the coexistence of ferromagnetic metallic and charge-or orbital-ordered phases in a sample.     

Absorption by CS<Subscript>2</Subscript> molecules on “hot” band emission lines from a TEA CO<Subscript>2</Subscript> laser

We have measured absorption of emission from a TEA CO₂ laser, lasing on hot band lines, in pure CS₂ and a mixture of CS₂ with air, and we have determined the optimal lines for optical excitation. Numerical modeling has shown that as the peak intensity of the pump radiation is increased, we observe absorption saturation, the extent of which decreases as the pressure increases. The major factor responsible for absorption saturation is the “rotational bottleneck” effect. Depending on the peak intensity of the radiation, addition of a buffer gas can lead to an increase or decrease in the absorption. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 1, pp. 61–66, January–February, 2007.     

Dynamics of two-photon picosecond absorption in ZnWO<Subscript>4</Subscript> and PbWO<Subscript>4</Subscript> crystals

A method has been proposed to analyze the dynamics of interband two-photon absorption in a nonlinear medium excited by a sequence of picosecond laser pulses of variable intensity and continuous probe radiation. Induced absorption leading both to hysteresis in the dependence of the absorption on the intensity of laser pump radiation and to the opacity of crystals at the pump wavelength has been revealed in initially transparent ZnWO₄ and PbWO₄ crystals irradiated by a train of 523.5-nm pulses with a duration of 20 ps at pump intensities of 5 to 140 GW/cm². The kinetics of an increase in absorption and its subsequent relaxation at a 523.5-nm picosecond excitation of the crystals have been measured with continuous 633-nm probe radiation. An exponential component of the increase in absorption with the time constant τ = 2−3.5 and 8–9.5 μs depending on the direction of the linear polarization of pump radiation has been revealed at 300 K in ZnWO₄ and PbWO₄ crystals, respectively. The absorption relaxation kinetics in the crystals are complicated and approach an exponential at a late stage with the constant τ = 40−130 and 12–80 ms for the ZnWO₄ and PbWO₄ crystals, respectively.     

Magnetic ordering in a [Fe/Co]<Subscript>35</Subscript> BCC film studied by nuclear resonant reflectometry

An analysis of the angular dependences of nuclear resonant reflectivity time spectra for different models of magnetic ordering in films reveals an ambiguity in the magnetization direction determined from spectra measured at one orientation of the sample. This analysis explains features in the spectra of the nuclear resonant reflectivity from a MgO/[Fe(6 ML)/Co(3 ML)]₃₅/V (1 nm) film measured before and after sample rotation by 90° about the normal to the surface. It is shown that the spectrum measured only at one orientation of the sample determines only the effective azimuth angle of magnetization γ^eff. This does not exclude the occurrence of a domain structure, while the angle γ^eff does not correspond to the true direction of the preferred orientation of magnetization. The results of measurements at two orientations of the sample can be satisfactorily matched using a model that considers a coherent mixture of states with magnetization directed along the 〈110〉 axis (77%) and with a chaotic orientation of the magnetic hyperfine field B _hf in the film plane for the other nuclei.     

Systematic investigation of the reactive ion beam sputter deposition process of SiO<Subscript>2</Subscript>

Ion beam sputter deposition (IBSD) is an established physical vapour deposition technique that offers the opportunity to tailor the properties of film-forming particles and, consequently, film properties. This is because of two reasons: (i) ion generation and acceleration (ion source), sputtering (target) and film deposition (substrate) are locally separated. (ii) The angular and energy distribution of sputtered target atoms and scattered primary particles depend on ion incidence angle, ion energy, and ion species. Ion beam sputtering of a Si target in a reactive oxygen atmosphere was used to grow SiO₂ films on silicon substrates. The sputtering geometry, ion energy and ion species were varied systematically and their influence on film properties was investigated. The SiO₂ films are amorphous. The growth rate increases with increasing ion energy and ion incidence angle. Thickness, index of refraction, stoichiometry, mass density and surface roughness show a strong correlation with the sputtering geometry. A considerable amount of primary inert gas particles is found in the deposited films. The primary ion species also has an impact on the film properties, whereas the influence of the ion energy is rather small.     

Structural and magnetic properties of layered Ca<Subscript>3</Subscript>Co<Subscript>4</Subscript>O<Subscript>9</Subscript> thin films

Layered cobalt oxides Ca₃Co₄O₉ thin films have been grown directly on c-cut sapphire substrates using pulsed laser deposition. X-ray diffraction and transmission electron microscopy characterizations show that the deposited films present the expected monoclinic structure and a texture along the direction perpendicular to the Al₂O₃(001) plane. The Ca₃Co₄O₉ structure presents six variants in the film plane. Rutherford backscattering spectroscopy shows that the films are stoichiometric and that the film thickness agrees with the nominal value. The susceptibility χ of the films, recorded along the c-axis of the substrate, after field cooling and zero field cooling in an applied field of 1 kOe shows two magnetic transitions at 19 and 370 K which agree well with previous findings on single crystal samples. In turn, at low temperature (5 K), the magnetization curve along the c-axis exhibits coercive field and remanent magnetization much smaller than those reported for bulk samples, which can be related to the influence of structural variants and structural defects.     

C<Subscript>60</Subscript> fullerene decoration of carbon nanotubes

A new fully carbon nanocomposite material is synthesized by the immersion of carbon nanotubes in a fullerene solution in carbon disulfide. The presence of a dense layer of fullerene molecules on the outer nanotube surface is demonstrated by TEM and XPS. Fullerenes are redistributed on the nanotube surface during a long-term action of an electron beam, which points to the existence of a molecular bond between a nanotube and fullerenes. Theoretical calculations show that the formation of a fullerene shell begins with the attachment of one C₆₀ molecule to a defect on the nanotube surface.