A study of the influence of structural imperfection on the electronic structure of carbon nanotubes by x-ray spectroscopy and quantum-chemical methods

It is demonstrated that the CK _α x-ray fluorescence spectra of carbon nanotubes synthesized by electric-arc evaporation of graphite and the spectra of carbon nanotubes produced using catalytic decomposition of hydrocarbons differ in the intensity of the short-wavelength lines. In order to interpret the obtained data, the electronic structures of perfect and defect-containing nanotubes are calculated in the framework of the tight-binding method with optimized parameters. The density of localized states that correspond to the observed increase in the intensity of the fluorescence spectrum of catalytic nanotubes can be obtained in the case when 15–20% of the total number of carbon atoms are absent in the carbon network. It is shown that defects of this type can bring about a decrease in the band gap of the nanotubes.     

Study of the electronic structure and properties of 13C-isotope-based composites

The morphology and electronic structure of ¹³C-isotope-based graphite composites were studied by transmission electron microscopy (TEM), x-ray diffraction, and x-ray fluorescence spectroscopy. High-resolution TEM images showed that composites contain several forms of carbon particles. According to an x-ray diffraction analysis, the size of graphene stacks of graphite particles is 20 and 40 Å. The CK _α x-ray fluorescence spectra of the initial ¹³C isotope powder and composites based on it detected an increase in the density of high-energy occupied states in comparison with the graphite spectrum. Ab initio quantum chemical calculation of the structure of C₁₅₀ graphene showed that the increase in the density of states stems from the electrons of dangling bonds of boundary carbon atoms of particles ～20 Å in size. Electrical properties of ¹³C-isotope-based samples were studied by analyzing the temperature dependence of the conductivity. It was assumed that the change in the logarithmic dependence of the conductivity observed at liquid-helium temperatures to the linear dependence as the temperature increases is caused by carrier transfers between the disordered graphene layers forming a nanocomposite.     

Electrical conductivity of double-walled carbon nanotubes in the framework of the Hubbard model

The electrical conductivity of double-walled carbon nanotubes of the “armchair” type with the ABAB packing of layers is investigated theoretically. The temperature dependences of the longitudinal electrical conductivity σ(T) for a number of double-walled carbon nanotubes, such as the (3, 3)@(8, 8), (5, 5)@(10, 10), (8, 8)@(13, 13), (10, 10)@(15, 15), and (15, 15)@(20, 20) nanotubes, are obtained in the framework of the Hubbard model with the use of the Green’s function method. It is revealed that the dependences of the electrical conductivity for single-walled and double-walled carbon nanotubes exhibit different behavior in the temperature range from 30 to 60 K. In particular, the dependence of the electrical conductivity for the double-walled carbon nanotubes flattens out in this temperature range.     

Current-conducting properties of paper consisting of multiwall carbon nanotubes

Electrical conductivity σ(T) of the paper consisting of multiwalled carbon nanotubes (MWCNTs) is studied in the temperature range 4.2-295 K, and its magnetoresistivity ρ(B) at various temperatures in magnetic fields up to 9 T is analyzed. The temperature dependence of the paper electrical conductivity σ(T) exhibits two-dimensional quantum corrections to the conductivity below 10 K. The dependences of negative magnetoresistivity ρ(B) measured at various temperatures are used to estimate the wavefunction phase breakdown length L _φ of conduction electrons and to obtain the temperature dependence L _φ = constT ^?p/2, where p ≈ 1/3. Similar dependences of electrical conductivity σ(T), magnetoresistivity ρ(B), and phase breakdown length L _φ(T) are detected for the initial MWCNTs used to prepare the paper.     

Thermoelectric properties of SnzCo8Sb24 skutterudites

Sn-filled CoSb₃ skutterudite compounds were synthesized by the induction melting process. Formation of a single δ-phase of the synthesized materials was confirmed by X-ray diffraction analysis. The temperature dependences of the Seebeck coefficient, electrical resistivity and thermal conductivity were examined in the temperature range of 300-700 K. Positive Seebeck and Hall coefficients confirmed p-type conductivity. Electrical resistivity increased with increasing temperature, which shows that the Sn-filled CoSb₃ skutterudite is a degenerate semiconductor. The thermal conductivity was reduced by Sn-filling because the filler atoms acted as phonon scattering centers in the skutterudite lattice. The lowest thermal conductivity was achieved in the composition of Sn_0.25Co₈Sb₂₄.     

Electrical and Magnetic Properties of Hafnium Disulfide Intercalated with Iron Atoms

Simultaneous study of the dependences of the structural parameters, electrical, and magnetic properties of hafnium disulfide intercalated iron atoms in the dependence on the intercalate concentration and temperature has been performed for the first time. The temperature dependences of the electrical resistance are shown to exhibit the activation character with the activation energies characteristic of impurity conduction. The effective magnetic moments of iron ions in Fe _x HfS₂ is found to be significantly lesser than the values of free iron ions and to decrease as the iron content increases. The character of the temperature dependences of the effective magnetic moments and negative values of the paramagnetic Curie temperatures indicate possible interactions of the antiferromagnetic type between intercalated atoms. However, the dependences of the magnetization on field for Fe_0.33HfS₂ and Fe_0.5HfS₂ obtained at T = 2 K demonstrate the hysteresis phenomenon characteristic of the ferromagnetic state. The results are discussed assuming the existence of hybridization 3d electron states of intercalated iron atoms with the electronic states of HfS₂ matrices and the competition of various exchange interaction.     

Features of electrical conductivity in an incommensurate phase of graphite intercalation compound C10HNO3

Electrical conductivity and conduction-electron spin resonance (CESR) have been studied in stage-2 acceptor α-graphite-nitric acid intercalation compound C₁₀HNO₃. It is found that the electrical conductivity σ_c along the c axis in the structurally incommensurate phase of this compound is temperature independent, whereas the electrical conductivity σ_a along carbon layers exhibits “metallic” temperature behavior. Analysis of the temperature dependences of σ_c, σ_a, and the CESR linewidth demonstrates that, in the incommensurate phase of the graphite intercalation compound, the electrical conductivity along the c axis is realized through a nonband mechanism—the transfer of free charge carriers along thin high-conductivity channels shunting the carbon layers adjacent to the intercalate.     

Characterization of fluorinated multiwalled carbon nanotubes by x-ray absorption spectroscopy

The C 1s and F 1s x-ray absorption spectra of fluorinated multiwalled carbon nanotubes with different fluorine contents and reference compounds (highly oriented pyrolytic graphite crystals and “white” graphite fluoride) were measured using the equipment of the Russian-German beamline at the BESSY II storage ring with a high energy resolution. The spectra obtained were analyzed with the aim of characterizing multiwalled carbon nanotubes and their products formed upon treatment of the nanotubes with fluorine at a temperature of 420°C. It was established that, within the probing depth (～15 nm) of carbon nanotubes, the process of fluorination occurs uniformly and does not depend on the fluorine concentration. The interaction of fluorine atoms with multiwalled carbon nanotubes in this case proceeds through the covalent attachment of fluorine atoms to graphene layers of the graphite skeleton and is accompanied by a change in the hybridization of the 2s and 2p valence electron states of the carbon atom from the trigonal (sp ²) to tetrahedral (sp ³) hybridization.     

Structural studies of thin silicon layers repeatedly implanted by carbon ions

The composition and structure of homogeneous SiC_1.4 and SiC_0.12 layers produced by multiple implantation of 40-, 20-, 10-, 5-, and 3-keV carbon ions into silicon were studied by electron microscopy, x-ray diffraction, Auger spectroscopy, and IR spectroscopy. The temperature dependences of the IR transmittance peak parameters obtained in the range 200–1400°C indicate that the increase in the number of carbon atoms that are bound to silicon atoms and are involved in absorption is caused by the formation and breaking of hexagonal, near-tetrahedral, and multiple Si-C bonds and by the decomposition of optically active strong carbon clusters. The high crystallization temperature of SiC (1200°C) in the SiC_1.4 layer is explained by the presence of stable multiple Si-C bonds and strong carbon clusters. Strong carbon clusters are shown to exist in the implanted SiC_0.12 layer, and their decomposition is found to affect the formation of tetrahedral bonds in the temperature range 1200–1400°C.     

Density and thermodynamics of hydrogen adsorbed on the surface of single-walled carbon nanotubes

A method is proposed for calculating the adsorption of hydrogen in single-walled carbon nanotubes. This method involves solving the Schrödinger equation for a particle (hydrogen molecule) moving in a potential generated by the surrounding hydrogen molecules and atoms forming the wall of the carbon nanotube. The interaction potential for hydrogen molecules is taken in the form of the Silvera-Goldman empirical potential, which adequately describes the experimental data on the interaction between H₂ molecules (including the van der Waals interaction). The interaction of hydrogen molecules with carbon atoms is included in the calculation through the Lennard-Jones potential. The free energy at a nonzero temperature is calculated with allowance made for the phonon contribution, which, in turn, makes it possible to take into account the correlations in the mutual arrangement of the neighboring molecules. The dependences of the total energy, the free energy, and the Gibbs thermodynamic potential on the applied pressure P and temperature T are calculated for adsorbed hydrogen molecules. These dependences are obtained for the first time with due regard for the quantum effects. The pressure and temperature dependences of the hydrogen density m(P, T) are also constructed for the first time.     

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.     

Thermal conductivity of high-porosity biocarbon precursors of white pine wood

This paper reports on measurements of the thermal conductivity κ and the electrical conductivity σ of high-porosity (cellular pores) biocarbon precursors of white pine tree wood in the temperature range 5–300 K, which were prepared by pyrolysis of the wood at carbonization temperatures (T _carb) of 1000 and 2400°C. The x-ray structural analysis has permitted the determination of the sizes of the nanocrystallites contained in the carbon framework of the biocarbon precursors. The sizes of the nanocrystallites revealed in the samples prepared at T _carb = 1000 and 2400°C are within the ranges 12–35 and 25–70 Å, respectively. The dependences κ(T) and σ(T) are obtained for samples cut along the tree growth direction. As follows from σ(T) measurements, the biocarbon precursors studied are semiconducting. The values of κ and σ increase with increasing carbonization temperature of the samples. Thermal conductivity measurements have revealed that samples of both types exhibit a temperature dependence of the phonon thermal conductivity κ_ph, which is not typical of amorphous (and amorphous to x-rays) materials. As the temperature increases, κ_ph first varies proportional to T, to scale subsequently as ～T ^1.7. The results obtained are analyzed.     

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.     

Electrical and thermoelectric properties of nanoporous carbon

This paper reports on a study of the temperature dependences of the electrical resistivity, Hall coefficient, and thermopower of nanoporous carbon prepared from polycrystalline carbides (α-SiC, TiC, Mo₂C) and 6H-SiC single crystals in the temperature range 1.5–300 K. The structural units responsible for the character of charge transport in these materials are carbon nanoclusters measuring ～10–30 Å. The conductivity in all the samples studied was found to be p type with a high carrier concentration (n_h ～ 10²⁰ cm^?3). The behavior of the transport coefficients at low temperatures is discussed.     

Low-temperature thermal conductivity of terbium-gallium garnet

Thermal conductivity of paramagnetic Tb₃Ga₅O₁₂ (TbGG) terbium-gallium garnet single crystals is investigated at temperatures from 0.4 to 300 K in magnetic fields up to 3.25 T. A minimum is observed in the temperature dependence κ(T) of thermal conductivity at T _min = 0.52 K. This and other singularities on the κ(T) dependence are associated with scattering of phonons from terbium ions. The thermal conductivity at T = 5.1 K strongly depends on the magnetic field direction relative to the crystallographic axes of the crystal. Experimental data are considered using the Debye theory of thermal conductivity taking into account resonance scattering of phonons from Tb³⁺ ions. Analysis of the temperature and field dependences of the thermal conductivity indicates the existence of a strong spin-phonon interaction in TbGG. The low-temperature behavior of the thermal conductivity (field and angular dependences) is mainly determined by resonance scattering of phonons at the first quasi-doublet of the electron spectrum of Tb³⁺ ion.     

Preparation and characterization of biocompatible magnetic carbon nanotubes

Magnetic carbon nanotubes consisting of multi-wall carbon nanotubes (MWNTs) core and Fe₃O₄ shell were successfully prepared by in situ thermal decomposition of Fe(acac)₃ or FeCl₃ or Fe(CO)₅ in 2-pyrrolidone containing acid treated MWNTs at 240 °C with the protection of nitrogen gas. The samples were characterized by TEM, XRD, SEAD, XPS and superconducting quantum interference device. Also, their biocompatibility was compared with naked carbon nanotubes. The results showed that after coated with Fe₃O₄ nanoparticles, the obtained magnetic carbon nanotubes show superparamagnetic characteristic at room temperature, and their blocking temperature is about 80 K. The magnetic properties of the nanotubes are relevant to the content of magnetic particles, increasing content of magnetic nanoparticles leads to higher blocking temperature and saturation magnetization. The results of antimicrobial activities to bacterial cells (Escherichia coli) showed that the MWNTs have antimicrobial activity, while the magnetic nanotubes are biocompatible even with a higher concentration than that of MWNTs.     

Carbon nanotube-epoxy composites: The role of acid treatment in thermal and electrical conductivity

Wet acid oxidation treatment methods have been widely reported as an effective method to purify and oxidize the surface of industrial multi-walled carbon nanotubes. This work examines the use of a concentrated HNO₃/H₂SO₄ mixture in an attempt to optimize the purification procedure of industrial multi-walled carbon nanotubes with diameter distribution statistics. It is shown that acid treatments of several hours are enough to purify the nanotubes. The electrical and thermal conductivities of epoxy composites containing 0.05–0.25 wt% of an acid-treated multi-walled carbon nanotube have been studied. The electrical conductivity of the composites decreases by more than three orders, whereas the thermal conductivity of the same specimen increases very modestly as a function of the filler content.     

Influence of the composition on electrical properties of low-temperature ionic conductors in the Cu1 ? x Ag x GeAsSe3 system

The chalcogenides Cu_{1 ? x} Ag _x GeAsSe₃ (x = 0.5, 0.8, 0.9) have been synthesized and their electrical properties have been studied at low temperatures. Compounds of this type are electron-ionic conductors with a mixed character of conduction. It has been shown that the substitution of copper atoms for a part of silver atoms in the AgGeAsSe₃ compound leads to a decrease in the total conductivity, a decrease in the fraction of ionic component of the conductivity, a significant increase in the polarization times, an increase in the temperature of the onset of a noticeable contribution (as compared to the electron contribution) of the ionic transport, and a decrease in the activation energy of carriers.     

Percolation conductivity of single-crystal manganite Pr1 − x Sr x MnO3 (x = 0.22; 0.24) in the phase-separation state

This paper presents an experimental study of the temperature dependences of the electrical resistivity, thermopower, and magnetoresistance of single-crystal manganite Pr_{1 ? x} Sr _x MnO₃ (x = 0.22, 0.24). The results obtained have been analyzed in terms of the theory of hopping electrical conductivity of manganites in the phase-separation state and the main postulates of percolation theory. In the 2–400-K interval, hopping conductivity with temperature-dependent activation energy has been observed. Near the Curie temperature, the monotonic exponential growth of electrical resistivity with decreasing temperature becomes distorted by formation of finite metallic clusters. For T ≤ 36 K, the conductivity of Pr_0.8Sr_0.22MnO₃ follows the Mott law.     

Effect of fluorination on electrical properties of single walled carbon nanotubes and C60 peapods in networks

We present a comparative study of fluorinated single wall carbon nanotubes and C₆₀ peapods. The fluorination was carried out by xenon difluoride treatment at moderate temperature (100 °C). The fluorination level was determined by EDX. In empty nanotubes a fluorination level of 0.8 at.% was obtained, whereas the same treatment leads to 18 at.% in peapods (corresponding to a gross stoichiometry of C₄F). TEM images show that this fluorination procedure does not affect the peapod structure. The elemental mapping carried out by EELS reveals homogenous distribution of fluorine along the carbon nanotube bundle. This chemical treatment is found to change the electrical properties of carbon nanotubes in bucky papers. Four-probe measurements indicate a conductivity decrease by up to two orders of magnitude at room temperature. The temperature dependence of the conductivity indicates a significant change in the charge carrier density of this system. Moreover, a non-linear behavior of the I–V characteristic is observed below 50 K in fluorinated peapods.