Effect of pulsed ion irradiation on the electronic structure of multi-walled carbon nanotubes

The effect of pulsed ion irradiation and vacuum annealing on the ratio of sp ²- and sp ³-hybridized orbitals of carbon atoms in the layers of oriented multi-walled carbon nanotubes has been studied by analyzing the photoemission spectra of the C1s core level and the valence band of carbon, which were obtained using the equipment of the BESSY II Russian-German beamline of synchrotron radiation and a Riber analytical system. It has been shown that the ion irradiation leads to a significant decrease in the fraction of atoms with the sp ³ hybridization of electrons. On the contrary, the annealing reduces the fraction of the sp ³-component in the spectra of carbon. Typical features of the valence band of multi-walled carbon nanotubes in the annealed and irradiated states have been established.     

Effect of concurrent electron irradiation on the structure of deposited carbon films

Carbon films 110–180 nm thick are fabricated on nickel substrates by the ion sputtering of graphite with simultaneous electron irradiation and subsequent ion irradiation. Irradiation leads to the formation of bonds in the films in various proportions due to the sp and sp ³ hybridization of orbitals (sp-and sp ³-bonds). Ion irradiation induces, to a greater extent, the formation of sp bonds, while concurrent electron irradiation increases the portion of sp ³ bonds. Electron and ion irradiation increases the film microhardness which reaches a value of 12 GPa. A model of the kinetics of creating carbon allotropes in a deposited film is proposed, which is based on the competition between the formation and breakage of carbon bonds during hybridization of different types. Electron and ion irradiation influence the probabilities of the formation and breakage of carbon bonds in the deposited film. The model provides a qualitative interpretation of the observed content ratios of carbon phases in the deposited film.     

Correlation of sp and sp fraction of carbon with electrical, optical and nano-mechanical properties of argon-diluted diamond-like carbon films

In the present work the correlation of electrical, optical and nano-mechanical properties of argon-diluted diamond-like carbon (Ar-DLC) thin films with sp³ and sp² fractions of carbon have been explored. These Ar-DLC thin films have been deposited, under varying C₂H₂ gas pressures from 25 to 75 mTorr, by radio frequency-plasma enhanced chemical vapor deposition technique. X-ray photoelectron spectroscopy studies are performed to estimate the sp³ and sp² fractions of carbon by deconvoluting C 1s core level spectra. Various electrical, optical and nano-mechanical parameters such as conductivity, I-V characteristics, optical band gap, stress, hardness, elastic modulus, plastic resistance parameter, elastic recovery and plastic deformation energy have been estimated and then correlated with calculated sp³ and sp² fractions of carbon and sp³/sp² ratios. Observed tremendous electrical, optical and nano-mechanical properties in Ar-DLC films deposited under high base pressure conditions made it a cost effective material for not only hard and protective coating applications but also for electronic and optoelectronic applications.     

Nitrogen 1s electron binding energy assignment in carbon nitride thin films with different structures

Carbon nitride thin films deposited by dc unbalanced magnetron sputtering have been analyzed by high-resolution X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. The XPS data show that N 1s binding states depend on substrate temperature (T_s). By comparison with the Raman spectra, N 1s binding states are assigned in which nitrogen atoms are mainly bound to sp² and sp³ carbon atoms at T_s = 100°C, whereas at T_s = 500°C nitrogen atoms are mainly bonded to sp², sp³ and sp¹ carbon atoms.     

Structure of carbinoid nanotubes and carbinofullerenes

Molecular mechanics methods have been used to calculate the geometrically optimized structure of carbinoid layers, carbinoid nanotubes, and carbinofullerenes consisting of carbine chains linked by atoms in sp ² and/or sp ³ hybridization states. Energy characteristics of carbinoid nanostructures have been calculated by semi-empirical quantum-mechanical methods. A structural classification of framework carbinoid nanostructures has been proposed. The dependence of specific binding energies of carbinoid nanostructures on the ratio sp ²/sp and their geometrical sizes has been determined.     

Structural modifications of diamond like carbon films induced by MeV nitrogen ion irradiation

Diamond-like carbon (DLC) films were deposited on Si(1 0 0) substrates using plasma deposition technique. The deposited films were irradiated using 2 MeV N⁺ ions at fluences of 1×10¹⁴, 1×10¹⁵ and 5×10¹⁵ ions/cm². Samples have been characterized by using Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and high-resolution transmission electron microscopy (HRTEM). Analysis of Raman spectra shows a gradual shift of both D and G band peaks towards higher frequencies along with an increase of the intensity ratio, I(D)/I(G), with increasing ion fluence in irradiation. These results are consistent with an increase of sp² bonding. XPS results also show a monotonic increase of sp²/sp³ hybridization ratio with increasing ion fluence. Plan view TEM images show the formation of clusters in the irradiated DLC films. HRTEM micrographs from the samples irradiated at a fluence of 5×10¹⁵ ions/cm² show the lattice image with an average interplanar spacing of 0.34 nm, revealing that the clusters are graphite clusters. The crystallographic planes in these clusters are somewhat distorted compared to the perfect graphite structure.     

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.     

Tight-binding study of Si2Cn (n = 3 to 42) fullerene-like or nanodiamonds microclusters: are Si atoms isolated or adjacent?

We studied in tight-binding approximation involving sp^ν hybridization (ν=2,3), some Si₂C_n (n=3 to 42) microclusters. We then investigated, on one hand, fragments of fullerene-like structures (sp²), and on the other hand, nanodiamonds (sp³) of adamantane-type or a 44-atom nanodiamond (with 2 inner atoms which are assumed to play the role of bulk atoms). We compared the stabilities, i.e. the electronic energies of these clusters, according to the various positions of the 2 Si atoms. Results are very different in the two kinds of hybridization. Besides, they can be analysed according to two different points of view: either the clusters are considered as small particles with limited sizes, or they are assumed to be used as models in order to simulate the Si-atom behaviour in very larger systems. In sp² hybridization (fullerene-like geometries), the most stable isomer is always encountered when the 2 Si atoms build a Si₂ group, and this result holds for both viewpoints quoted above. Conversely, in sp³ hybridization (nanodiamonds), since Si atoms “prefer” sites having the minimum connectivity, they are never found in adjacent sites. We see that with a simple and fast computational method we can explain an experimental fact which is very interesting such as the relative position of two heteroatoms in the cluster. This enhances the generality and the fecondity in the tight binding approximation due essentially to the link between this model and the graph theory, link based on the topology of the clusters.     

XeO3和XeOF2与三种不同杂化方式N原子的Xe···N非共价作用的理论研究

本文采用密度泛函理论和二级微扰理论方法研究了XeO₃和XeOF₂与一系列不同杂化含氮给体配合物之间的相互作用. 含氮给体与XeO₃和XeOF₂之间的相互作用能在6.5∽19.9 kcal/mol之间. 相互作用强弱顺序为sp³>sp²>sp,且XeO₃比XeOF₂高. 约化密度梯度图证明,对于sp²和sp³杂化的给体,空间位阻效应在相互作用中起着一定的影响. 能量成分分析发现,Xe···N作用主要的吸引部分是静电相互作用. 在XeO₃配合物中,极化能的占比大于色散,而在XeOF₂配合物中则相反. 除表面静电势(V_s)外,其他5个相互作用参数之间的线性相关系数均较大.     

Cluster-Type Structure of Amorphous Smooth Hydrocarbon CD<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> Films (<Emphasis Type="Italic">x</Emphasis> ~ 0.5) from T-10 Tokamak

Structure of smooth hydrocarbon CD _x films with a high deuterium ratio x ~ 0.5 redeposited from T-10 tokamak D-plasma discharges (NRC Kurchatov Institute, Moscow) has been studied. For the first time, small and wide angle X-ray scattering technique using synchrotron radiation and neutron diffraction have been employed. A fractal structure of CD _x films is found to consist of mass-fractals with rough border, surface fractals (with rough surface), plane scatterers and linear chains forming a branched and highly cross-linked 3D carbon network. The found fractals, including sp² clusters, are of typical size ~1.60 nm. They include a C₁₃ fragment consisting of three interconnected aromatic rings forming a minimal fractal sp² aggregate 9 × C₁₃. These graphene-like sp² clusters are interconnected and form a 3D lattice which can be alternatively interpreted as a highly defective graphene layer with a large concentration of vacancies. The unsaturated chemical bonds are filled with D, H atoms, linear sp² C=C, C=O, and sp³ structural elements like C-C, C-H(D), C-D_2,3, C-O, O-H, COOH, C _x D(H) _y found earlier from the infrared spectra of CD _x films, which are binding linear elements of a carbon network. The amorphous structure of CD _x films has been confirmed by the results of earlier fractal structure modeling, as well as by researches with X-ray photoelectron spectroscopy which allow finding a definite similarity with the electron structure of their model analogues — polymeric a-C:H and a-C:D films with a disordered carbon network consisting of atoms in sp³ + sp² states.     

Release of a diamond-like film on a nickel surface irradiated simultaneously with carbon ions and electrons

Nickel samples at temperatures of 300–1000°C have been irradiated simultaneously with 10-to 30-keV C⁺ ions and 1-to 5-keV electrons. The release of implanted carbon atoms on the surface of a sample with the formation of a transparent carbon film with the prevailing sp ³ hybridization has been observed. The thickness of the film is several tens of nanometers. The formation of films is attributed to the acceleration of the formation of carbon structures in samples irradiated by accelerated electrons.     

Bonding character of lithium atoms adsorbed on a graphene layer

This work uses first-principles calculations to investigate the aspects of the bonding character of lithium atoms adsorbed on a graphene layer. The presented results are in contradiction to other results that have recently appeared in the specialized literature, although they confirm some previous claims. In particular, a discussion of the characteristics of the bonding between lithium and carbon atoms and whether they interact via an sp² or an sp³ hybridization is intended to clarify the problem. It is also found that the carbon-lithium bond is not purely covalent but instead presents a significant ionic character. The local geometry is governed by the π-acceptor character of lithium atoms which occupy reverse positions relative to the carbon atoms as compared to the positions of hydrogen in graphane.     

The degree of hybridization in paramagnetic complexes

It is argued that in a series of complexes formed by ions of the same type and having the same geometry and ligand the degree of hybridization $\text{?}{}_{\mathrm{s}}\text{?}{}_{\mathrm{\sigma }}$ tends to decrease when covalency increases. This rule which discards any sp² explanation for the ligand hybridization has been well verified through series of d⁹ and s¹ complexes. The validity of such a rule, also useful for understanding the behaviour of $\text{?}{}_{\mathrm{s}}\text{?}{}_{\mathrm{gs}}$ in some D_2h systems, outlines that ligand core polarization effects are negligible in these cases.     

Spectroscopy of homogeneous deuterated hydrocarbon films redeposited from a T-10 tokamak plasma discharge

Homogeneous deuterated hydrocarbon films redeposited from a deuterium plasma discharge inside the T-10 tokamak vacuum chamber are studied using photoluminescence methods; EXAFS, EPR, and IR spectroscopies; and temperature measurements. The photoluminescence excitation spectra of sp ³-sp ² nanostructures of tokamak films are compared with those of sp ² nanostructures of C60 fullerite films. The effect of defect states on photoluminescence and its temperature quenching is discussed. It is concluded that the model of temperature luminescence quenching for homogeneous deuterated tokamak films is similar to that for amorphous a-C:H films.     

Electrical conditioning of diamond-like carbon films for the formation of coated field emission cathodes

Diamond-like carbon (DLC) films deposited on different substrates by plasma enhanced chemical vapour deposition were investigated. Bonding states and film quality were characterized by FT-IR spectroscopy. The influence of the power of plasma and the deposition time on the sp²/sp³ ratio as well as the concentration of CH_n bonds was studied. The influence of sp²/sp³ ratio on the formation process of conducting channels in diamond-like carbon films as a result of electrical breakdown was determined. Reproducible increase of diamond-like carbon film conductivity, with initial sp²/sp³ ratio larger than 0.16, was observed after electrical breakdown.     

Ion-beam analysis of the structure and composition of nanocomposite nc-TiC/a-C:H coatings

The structure and composition of nanocomposite nc-TiC/a-C:H thin films prepared by closed-field unbalanced reactive magnetron sputtering in an argon-acetylene atmosphere have been investigated. The concentrations of carbon and heavier elements have been obtained by Rutherford backscattering and nuclear backscattering. The hydrogen concentration in the films has been determined by elastic recoil detection analysis. Based on the data obtained, a scheme has been proposed to evaluate the C:H matrix mass density and the sp ³ and sp ² fractions in the matrix.     

Photoelastic properties of graphenes

The components of the elastooptic tensor of graphenes with the sp ² hybridization of atomic orbitals for the visible and near infrared spectral regions are calculated. These components are shown to be comparable with those of lithium niobate.

     

Percolative transition in carbon-ion implanted type II<Emphasis Type="Italic">a</Emphasis> diamond

Experimental data for the conductivity of type IIa diamond specimens implanted at low temperatures with carbon ions, followed by high temperature annealing, have been analyzed using hopping and percolation theories in the vicinity of the insulator-metal transition. Near the transition it appears that conductivity occurs viasp ²-bonded graphitic clusters which are randomly distributed in thesp ³-bonded diamond matrix. A conductivity crossover between the Mott and Efros-Shklovskii VRH laws has been observed on the insulating side of the transition.     

X-ray photoelectron and X-ray Auger electron spectroscopy studies of heavy ion irradiated C60 films

The influence of 200 MeV Au ion irradiation on the surface properties of polycrystalline fullerene films has been investigated. The X-ray photoelectron and X-ray Auger electron spectroscopies are employed to study the ion-induced modification of the fullerene, near the surface region. The shift of C 1s core level and decrease in intensity of shake-up satellite were used to investigate the structural changes (like sp² to sp³ conversion) and reduction of π electrons, respectively, under heavy ion irradiation. Further, X-ray Auger electron spectroscopy was employed to investigate hybridization conversion qualitatively as a function of ion fluence.     

Infrared spectroscopic study of thermal annealing effects of hydrocarbon species on a Si surface exposed to methane plasma

We have investigated the thermal annealing effects of hydrocarbon species on the methane-plasma exposed silicon surface, investigated by in situ infrared absorption spectroscopy (IRAS) in multiple internal reflection (MIR) geometry. The proportion of types of hydrocarbon species is not remarkably changed in the hydrocarbon network that consists of sp-, sp²- and sp³-CH_X species by annealing at moderate temperatures. On the other hands, the proportion is drastically changed in the network that is mainly composed of sp³-CH_X species by annealing at moderate temperatures. It suggests that excess CH₃ species in the film is not stable against thermal annealing and would be converted to sp³-CH_1-2 species by annealing at moderate temperatures. And the data also show that sp²-CH species is more stable against the thermal annealing than sp³-hydrocarbon species.