Structures and energetics of carbon bridged C 60 clusters

The structures and energetics of carbon bridged C₆₀ clusters (C ₆₀ ) _n C_m have been studied by simulated annealing technique within the tight-binding molecular-dynamics. The “sp² addition” ball-and-chain dimers exhibit odd-even alternations over the number of chain atoms, with the dimers containing even chain atoms more stable against dissociation than their immediate neighbors containing odd chain atoms. In addition to the usual “sp² addition” dimers, a pentagon-linked C₁₂₁ isomer and a hexagon-linked C₁₂₂ isomer are also found to be stable. Based on our tight-binding calculations, trimers and larger clusters can be simply regarded as being made up of independent or weakly interacting dimers, if the C-C₆₀ joints on a single cage are not too close to each other. Large C₆₀ clusters connected by chains each containing only one or two carbon atoms have similar stability to that of constituent dimers, indicating the possibility to form stable C₆₀-carbon polymers. Received 17 January 2001 and Received in final form 26 February 2001     

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.     

Properties of diamondlike films obtained in a barrier discharge at atmospheric pressure

Diamondlike films are synthesized from gaseous hydrocarbons in a barrier discharge at atmospheric pressure. The films were investigated using transmission electron microscopy, electron diffraction, and infrared spectroscopy. A technique for determining the quantitative characteristics of the films (hydrogen content, ratio of different types of carbon-carbon bonds and hydrocarbon groups) using standard samples is described. The highest-quality films were obtained from methane (ratio of hydrogen to carbon atoms H/C=1.04, fraction of diamondlike to graphitelike bonds sp ³: sp ²=100%: 0%) and from a mixture of acetylene and hydrogen in the ratio 1:19 (H/C=0.73, sp ³: sp ²=68%: 32%). Zh. Tekh. Fiz. 67, 100–104 (August 1997)     

Synthesis of carbon nitride films by direct current plasma assisted pulsed laser deposition

Carbon nitride films were deposited by pulsed laser ablation of a graphite target under a nitrogen atmosphere at room temperature. A direct current discharge apparatus was used to supply active nitrogen species during the deposition of carbon nitride films. The composition and bonding structure of carbon nitride films were determined by Fourier-transform infrared (FTIR) spectroscopy and X-ray photoelectron spectroscopy. The incorporation of nitrogen atoms in the films is greatly improved by the using of a dc glow discharge. The ratio N/C can reach 0.34 at the discharge voltage of 400 V. Six peaks centered at 1025 cm^-1, 1226 cm^-1, 1381 cm^-1, 1534 cm^-1, 1629 cm^-1, and 2200 cm^-1 can be clearly distinguished from the FTIR spectra of the deposited films, which indicates the existence of C–N, C=N, and C≡N bonds. The fraction of sp² C, C≡N bonds, and C=N bonds in the deposited films increases with increasing discharge voltage. Deconvolution results of C 1s and N 1s spectra also indicate that nitrogen atoms in the films are chemically bonded to sp¹ C, sp² C, and sp³ C atoms. Most of the nitrogen atoms are bonded to sp² C atoms. Increasing the discharge voltage leads to a decrease of the fraction of nitrogen atoms bonded to sp² C and the fraction of amorphous carbon; however, it leads to an increase of the fraction of nitrogen atoms bonded to sp³ C and the fraction of sp² C and sp³ C atoms bonded to nitrogen atoms. Received: 7 June 2000 / Accepted: 19 February 2001 / Published online: 27 June 2001     

Polarons in linear chains of fullerenes

Polaron states in linear chains of fullerenes are studied with the use of the generalized model of Su-Shrieffer-Heeger (SSH) for the intermolecular and intramolecular degrees of freedom. Electron charge distributions over the molecular surface and Jahn-Teller distortions of carbon atoms in C₆₀ are calculated self-consistently for linear C₆₀ polymer and C ₆₀ ⁻ polyanion chains. A polaron band narrowing is examined. It is shown that the polymerization of C₆₀ molecules in phase transitions may be caused by the cooperative Jahn-Teller effect. Pis’ma Zh. éksp. Teor. Fiz. 64, No. 8, 521–525 (25 October 1996) Published in English in the original Russian Journal. Edited by Steve Torstveit.     

Structural phenomena in glassy carbon induced by cobalt ion implantation

Glassy carbon (GC) was implanted by 150 keV Co⁺ ions to the doses of 1×10¹⁶ (low dose) and 1×10¹⁷ ions/cm² (high dose). The low dose implantation results in GC structure disordering with formation of amorphous carbon (a-C). Analysis of Rutherford backscattering (RBS) and Raman spectra has revealed 15 at.% of sp³-bonded C atoms in the a-C structure. The in-pane size of sp² clusters was estimated to be 1.1 nm. On the contrary, the high dose ion implantation results in ordering of the a-C structure. Content of the sp³ atoms in a-C was reduced to about 5% and, respectively, the in-plane sp² cluster size was increased up to 2.8 nm. Together with the a-C structure ordering the Raman spectra identifies formation of transpolyacetylene (TPA)-like chains after the high-dose Co⁺ implantation. In parallel, RBS suggests an enhanced diffusion of the implanted cobalt within the modified carbon layer. Correlation of the RBS and Raman results argues a driving role of cobalt diffusion in the TPA-like chains formation and a-C ordering. Great surface roughening observed after the high dose Co⁺ implantation suggests also the pronounced cobalt clustering causing large flux of “free volume” to the surface.     

Mechanism of three-dimensional polymerization of fullerite C60 at high pressures

A series of polycrystalline phases corresponding to different stages of three-dimensional polymerization and destruction of C₆₀ molecules has been synthesized by heating fullerite C₆₀ under a pressure P=12.5 GPa. The structure of the phases can be identified as fcc, and the lattice period decreases with increasing heating temperature. A model of three-dimensional polymerization in which the lattice parameter is a continuous function of the fraction of covalently bonded molecules is proposed. The model makes it possible to estimate the number of atoms in the sp ³ state. The hardness of the polymerized fcc phases is studied on the basis of percolation of rigidity. It is shown experimentally that the period a≈13.8 Å is the threshold for the formation of a three-dimensionally rigid C₆₀ polymer. It is found that the thermal stability of the strongly and weakly polymerized phases is qualitatively different. Pis’ma Zh. éksp. Teor. Fiz. 64, No. 11, 755–759 (10 December 1996)     

Density-functional study of Si<Subscript><Emphasis Type="Italic">n</Emphasis></Subscript>C<Subscript><Emphasis Type="Italic">n</Emphasis></Subscript> (<Emphasis Type="Italic">n</Emphasis> = 10–15) clusters

Density-functional theory with generalized gradient approximation for the exchange-correlation potential has been used to calculate the structural and electronic properties of Si _n C _n (n = 10–15) clusters. We find that the Si _n C _n clusters prefer cagelike structures. An extensive isomer search shows that the lowest-energy arrangements are those in which the silicon atoms and the carbon atoms form two distinct subunits. It is found that the carbon atoms favor to form fullerene-like structure due to the sp ²-like bond. The silicon atoms are trying to cope with an unfavorable sp ² environment, but distorted tetrahedra still show up somewhere of the cagelike structures. On the basis of the lowest-energy geometries obtained, the binding energy, HOMO–LUMO gap, Mulliken charge, ionization potential and electron affinity of the clusters have been computed and analyzed. An electronic charge transfer from the Si-populated to the C-populated regions is observed.     

Effect of nickel on the structure and bond type in amorphous diamond-like carbon films

Experimental data are presented from studies of the structure and bond type of carbon atoms in amorphous carbon-nickel films deposited from pulsed vacuum-arc discharge plasma sources. X-ray photoelectron spectroscopy was used. The characteristics of the plasmon loss spectra depend significantly on the deposition parameters. Carbon exists in a mixed sp²+sp³ hybridized state in the carbon–nickel films. The ratio of sp³/sp² carbon bonds increases when the nickel content is reduced (from 5.5 to 1.0 atomic %) and the deposition angle is increased. The structure closest to that of diamond was with a substrate bias voltage of –80 to –100 V and a deposition angle of 90°.     

Observation of oriented 23 S 1 helium atoms in a sodium-helium plasma irradiated by polarization-modulated laser radiation

An experiment on the observation of spin polarization of metastable helium atoms interacting with optically oriented sodium atoms under continuous rf discharge conditions is described. Laser radiation with alternating-sign circular polarization, tuned to the resonance excitation of the 3² S _1/2–3² P _1/2 transition in Na atoms, is used as the source for optical pumping of ground-state sodium atoms. Pis’ma Zh. éksp. Teor. Fiz. 65, No. 5, 385–387 (10 March 1997)     

Thermal conductivity of nonlinear waves in disordered chains

We present computational data on the thermal conductivity of nonlinear waves in disordered chains. Disorder induces Anderson localization for linear waves and results in a vanishing conductivity. Cubic nonlinearity restores normal conductivity, but with a strongly temperature-dependent conductivity κ(T). We find indications for an asymptotic low-temperature κ ∼ T ⁴ and intermediate temperature κ ∼ T ² laws. These findings are in accord with theoretical studies of wave packet spreading, where a regime of strong chaos is found to be intermediate, followed by an asymptotic regime of weak chaos (Laptyeva et al, Europhys. Lett. 91, 30001 (2010)).     

Absolutely Singular Dynamical Foliations

Let A ³ be the product of the automorphism of T ² and of the identity on T ¹. A small perturbation g of A ³ among volume preserving diffeomorphisms will have an invariant family of smooth circles Γ forming a continuous foliation of T ³. Corresponding to the vector bundle tangent to the circles Γ there is a “central” Lyapunov exponent of (g, volume), which is nonzero for an open set of ergodic g's. This surprising result of Shub and Wilkinson is complemented here by showing that the volume on T ³ has atomic conditional measures on the Γ's: there is a finite k such that almost every Γ carries $k$ atoms of mass 1/k. Received: 26 September 2000 / Accepted: 8 December 2000     

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.     

Properties of carbon films with high conductivity anisotropy

Carbon films with high conductivity anisotropy were obtained via sputtering a graphite target with an accelerated argon ion beam. The film structure was studied using Raman spectroscopy (combination scattering spectroscopy), transmission high-resolution electron microscopy, chemical analysis, X-ray photoelectron spectroscopy, and tunnel spectroscopy. We found conductivity anisotropy along and across the film chains of the order of 10⁴, which is associated with a high content of linear carbon chains with sp hybridization of bonding orbitals.     

Electronic structure of linear chains of fullerenes

The band structure of linear chains of fullerene molecules is calculated as a function of the intermolecular π-electron overlap integral T, which increases under increasing external pressure. Chains consisting of neutral (C₆₀) and charged (C ₆₀ ⁻ ) molecules are studied. It is shown that there is a sharp transition from a metal (or narrow-gap semiconductor) to an insulator (with band gap ∼1 eV)with increasing T. The proposed model makes it possible to describe the formation of solid-carbon struc-tures, containing chains of covalently bound fullerene molecules, with different pressure-dependent semiconductor properties. Pis’ma Zh. éksp. Teor. Fiz. 65, No. 8, 647–650 (25 April 1997)     

Progress in pion-decay channelling: Refractory bcc metals at high and low temperatures

By means of π⁺/μ⁺ channelling, positive pions (π⁺) implanted intoTa, Mo, andW are investigated up to high temperatures. A striking observation is that the channelling effect disappears in a rather narrow temperature interval centred at 0.26 (Ta) to 0.51 (W) of the melting temperature. From studies of π⁺ trapping by oxygen atoms inTa estimates for the low-temperature π⁺ diffusivity inTa [D _π(23K)=1.4·10^−10±0.3 m²s⁻¹,D _π(47K)=5.7·10^−10±0.3 m²s⁻¹] as well as for the binding enthalpy of π⁺ to 0 atoms (H _B=7·10⁻² eV) have been obtained. The diffusion data are in reasonable agreement with the theory of phonon-assisted tunnelling.     

The electronic structure of In1−x Ga x P alloy by the recursion method

Summary The electronic structure calculation of In_1−x Ga _x P alloy using the recursion method is reported. A five-orbitals,sp ³ s ^*, per atom model is used in the tight-binding representation of the Hamiltonian. The local densities of states are calculated for In, Ga and P sites in a cluster of 216 atoms. The results are in reasonably good agreement with previous calculations. To speed up pubblication, the authors of this paper have agreed to not receive the proofs for correction.     

Structural,optical and electrical properties of sulfur-incorporated amorphous carbon films

Amorphous carbon–sulfur (a-C:S) composite films were prepared by vapor phase pyrolysis technique. The structural changes in the a-C:S films were investigated by electron microscopy. A powder X-ray diffraction (XRD) study depicts the two-phase nature of a sulfur-incorporated a-C system. The optical bandgap energy shows a decreasing trend with an increase in the sulfur content and preparation temperature. This infers a sulfur incorporation and pyrolysis temperature induced reduction in structural disorder or increase in sp ² or π-sites. The presence of sulfur (S 2p) in the a-C:S sample is analyzed by the X-ray photoelectron spectroscopy (XPS). The sp ³/sp ² hybridization ratio is determined by using the XPS C 1s peak fitting, and the results confirm an increase in sp ² hybrids with sulfur addition to a-C. The electrical resistivity variation in the films depends on both the sulfur concentration and the pyrolysis temperature.     

Possibilities of C 1s XPS and N(E) C KVV Auger spectroscopy for identification of inherent peculiarities of diamond growth

The interaction of C-atoms and CH_n-radicals with uncleaned and argon cleaned silicon substrate and with diamond surface after H-treatment have been studied in situ by XPS and Auger spectroscopy. It was found the formation of a new chemical surface state of carbon atoms in the case of carbon atoms and radicals interaction with cleaned silicon. The same chemical state was revealed on the H-treated diamond surface. Graphite-like structure of carbon atoms was observed on the surface of unlearned silicon and H-treated diamond after interaction with carbon atoms and radicals. N(E) C KVV Auger spectrum for the new chemical state of carbon atoms significantly differs from typical spectra for sp²- and sp³-bonded carbon materials. The high energy part of this spectrum was interpreted under the hypothesis of sp³-bonded carbon atoms but with shifted fermi level position.     

Doping induced diode behavior with large rectifying ratio in graphyne nanoribbons device

By applying nonequilibrium Green's functions (NEGF) in combination with density functional theory (DFT), the electronic transport properties of α-armchair graphyne nanoribbons (α-AGyNR) device are investigated, in which the left electrode is doped by Boron (B) atoms and the right electrode is doped by Nitrogen (N) atoms. B and N doping atoms that are substituted in SP and SP² sites result in four devices named as A (sp–sp), B (sp²–sp²), C (sp²–sp) and D (sp–sp²). The current–voltage characteristics of these systems reveal that the proposed devices have a striking nonlinear feature that leads to formation of a p–n junction which results rectifying behavior. The results show that the rectification characteristics are strongly dependent on the site of doping atoms. In A and D devices the rectification ratio (RR) can reach to 10³ in the bias region from 0.2 V to 0.6 V while in B and C devices the RR can be enlarged to 10⁴ in the same bias region. Unlike the most of the previous proposed molecular rectifiers that are vertical hetero structures, the proposed rectifier in this work is in-plane or two dimensional structures. The results provide a new insight and a novel effective pathway for developing applicable high-performance Graphyne-based rectifiers.