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     

Strong lithium-polysulfide anchoring effect of amorphous carbon for lithium–sulfur batteries

Solving the shuttle effect caused by lithium polysulfide (LPS) dissolution is important in lithium−sulfur batteries. The anchoring of LPSs to carbon combined with sulfur is a method of suppressing the shuttle effect. This first-principles study is the first to report that amorphous carbon offers the best ability to anchor LPSs. The adsorption energies of LPSs on amorphous carbon are at least six times higher than those on graphene and at least two times higher than those on pyridinic-N doped graphene. The LPSs adsorbed on amorphous carbon undergo significant molecular distortion and/or partial dissociation due to the S-to-C electron transfer of 1.2–1.8 e per molecule, as well as the formation of strong bonds between both the Li and S atoms and the sp- and sp²-site C atoms. We propose an amorphous carbon−graphite hybrid anchoring material, because amorphous carbon can strongly capture LPSs and graphite can act as an electron channel.     

A new study on the catalytic mechanism of Fe-based alloys in diamond formation by Mössbauer spectroscopy

M?ssbauer spectroscopy has been used to systemically study the catalytic mechanism of Fe-based alloys in diamond formation at high temperature–high pressure (HTHP) for the first time. M?ssbauer spectra reveal the magnetic state of the 3d electrons of a Fe atom in the Fe-based alloy catalyst during diamond formation at HTHP. During carburization at lower temperatures than that required for diamond formation and diamond formation in the diamond-stability region using Fe-based alloys as a catalyst, both the quadrupole splitting QS and the isomer shift IS change from negative to positive, especially reaching a state in which they are zero. It was indicated that the state of the 3d-shell electrons of the iron atom changes greatly during carburization and diamond formation and that the incomplete 3d sub-bands of Fe atoms in the catalyst alloys could be filled up in proper order by electrons of interstitial carbon atoms. During diamond formation, the unpaired 3d-shell electrons of an iron atom in the Fe-based alloy absorb and interact with 2P_z electrons of the carbon atoms. There exist a Fe–C bonding and an electron charge transfer stage. The 2P_z electrons of the carbon atoms could be dragged into the metal atoms in the catalyst alloy and would make a transition of triangular (sp²π) hybridization of valence electrons to tetrahedral (sp³) hybridization of valence electrons (a transition of sp²π bonds of graphite to sp³ bonds of diamond), resulting in a transition of graphite structure to diamond. Although the conclusion of this study is strictly applicable only to Fe-based alloy catalysts, it could be considered more general because of the chemical similarities between the transition elements used as solvent catalysts for diamond synthesis. Received: 2 March 2001 / Accepted: 20 August 2001 / Published online: 2 October 2001     

Simulations of structures of amorphous SixC1−x films

Amorphous Si_xC_1−x films possess the potential to improve wear performance in humid atmospheres and at higher temperatures. But some experimental work on the films showed that silicon contents greatly influenced their microstructures and mechanical properties. Therefore, simulations of molecular dynamics were carried out to predict structures of the Si_xC_1−x films at different silicon contents. The results show that the sp³/sp² ratio of all the films increases, but the stiffness of the films is decreasing with an increase in silicon contents. Moreover, silicon atoms are almost surrounded by carbon atoms, which is in agreement with the experiments.     

Clustering and polymerization of Li15C60

The structural and electronic properties of lithium intercalated fullerides (of which Li₁₅C₆₀ is the most representative) are still puzzling and unclear. Above 520 K, x-ray/neutron diffraction shows an fcc phase in which the 15 Li atoms clusterize in the octahedral interstices. However, at lower temperatures, a change in the crystalline symmetry and also in the electronic properties takes place as observed from ¹³C, ⁷Li/⁶Li NMR and x-ray diffraction measurements. X-ray diffraction data suggest the presence of two different stable structures: a tetragonal monomeric and an orthorhombic polymerised phase. Detailed ¹³C magic angle spinning NMR experiments in the latter phase indicate sp ³ bondings among the carbon atoms, whereas the relative (sp ²/sp ³) intensities, together with x-ray data, suggest the C₆₀ polymerization to be a [2+2] cycloaddition. Multiple quantum NMR experiments on ⁷Li confirm the presence of lithium clusters, as observed by x-ray diffraction in the high temperature phase, also at lower temperatures. However, the inferred cluster size is significantly smaller than that suggested by the stoichiometry. The distortion in the low-T structure of L₁₅C₆₀ is supposed to induce the migration of Li atoms from octahedral to tetrahedral voids, thus accounting for the lower number of Li atoms in the clusters. Further evidence of this scenario is obtained also from preliminary measurements of line shapes and T ₁ relaxation times, which exhibit a multiexponential recovery with very different constants that are hardly compatible with a single family of Li atom sites.     

金刚石延(111)面生长的第一性原理研究

利用密度泛函理论(DFT)对碳原子在镍(111)表面吸附结构进行了计算，得到了吸附能以及态密度 (density of state, DOS)分布，分析了吸附在镍(111)面的碳原子和金刚石(111)面的碳原子的分波态密度(PDOS)，结果表明吸附在镍表面的碳原子具有与金刚石表面碳原子相类似的电子结构特点，即两者都存在孤对的和成键的sp³杂化电子,进而发现吸附在镍表面的碳原子极易与金刚石表面相互作用形成稳定的类金刚石几何结构. 关键词： 密度泛函理论 化学吸附 电子结构 金刚石生长     

XPS study of the chemical bonding in hydrogenated amorphous germanium–carbon alloys

A systematic study of the chemical bonding in hydrogenated amorphous germanium–carbon (a-Ge_1-xC_x:H)alloys using X-ray photoelectron spectroscopy (XPS) is presented. The films, with carbon content ranging from 0 at. % to 100 at. %, were prepared by the rf co-sputtering technique. Raman spectroscopy was used to investigate the carbon hybridization. Rutherford backscattering spectroscopy (RBS) and XPS were used to determine the film stoichiometry. The Ge 3d and C 1s core levels were used for investigating the bonding properties of germanium and carbon atoms, respectively. The relative concentrations of C–Ge, C–C, and C–H bonds were calculated using the intensities of the chemically shifted C 1s components. It was observed that the carbon atoms enter the germanium network with different hybridization, which depends on the carbon concentration. For concentrations lower than 20 at. %, the carbon atoms are preferentially sp³ hybridized, and approximately randomly distributed. As the carbon content increases the concentration of sp² sites also increases and the films are more graphitic-like. Received: 4 May 1999 / Accepted: 24 November 1999 / Published online: 24 March 2000     

Pressure- and temperature-induced transformations in crystalline polymers of C60

The great advantage of the C₆₀ molecule is its potential for polymerization, due to which the molecule can be the building block of new all carbon materials. In addition, it contains, both sp ² and sp ³ hybridized carbon atoms, which allows synthesizing new carbon materials with desired physicochemical properties using both types of carbon bonding. The one- and two-dimensional polymeric phases of C₆₀ are prototype materials of this sort. Their properties, especially polymerization under pressure and room temperature via covalent bonding between molecules belonging to adjacent polymeric chains or polymeric layers, can be used for further development of new materials. The present review focuses on the study of the pressure-induced polymerization and thermodynamic stability of these materials and their recovered new phases by in-situ high-pressure Raman and X-ray diffraction studies. The phonon spectra show that the fullerene molecular cage in the high-pressure phases is preserved, while these polymers decompose under heat treatment into the initial fullerene C₆₀ monomer.     

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.     

Aqueous-phase exfoliation of graphite in the presence of polyvinylpyrrolidone for the production of water-soluble graphenes

Treatment of crystalline graphite fine powder with an aqueous solution of the harmless and versatile substance polyvinylpyrrolidone under sonication results in water-soluble, polymer-protected graphene single layers without oxidation or destruction of the sp² character of the carbon core. The liquid-phase extraction of graphene monolayers was evidenced by TEM and AFM techniques, while their graphitic character was checked with Raman spectroscopy. Besides PVP, the water-soluble biopolymers albumin and sodic carboxymethylcellulose were also employed successfully in the aqueous-phase exfoliation of graphite, thereby supporting the generic character of the present method using a variety of suitable polymeric extractants.     

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.     

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.     

Laser fluence dependence of the elastic properties of diamond-like carbon films prepared by pulsed-laser deposition

We studied the temperature dependence of internal friction of variety of amorphous diamond-like carbon films prepared by pulsed-laser deposition. Like the most of amorphous solids, the internal friction below 10 K exhibits a temperature independent plateau, which is caused by the atomic tunnelling states—a measure of structure disorder. In this work, we have varied the concentration of sp³ versus sp² carbon atoms by increasing laser fluence from 1.5 to 30 J/cm². Our results show that the internal friction has a nonmonotonic dependence on sp³/sp² ratio with the values of the internal friction plateaus varying between 6×10⁻⁵ and 1.1×10⁻⁴. We explain our findings as a result of a possible competition between the increase of atomic bonding and the increase of internal strain in the films, both of which are important in determining the tunneling states in amorphous solids. The importance of the internal strain in diamond-like carbon films is consistent with our previous study on laser fluence, doping, and annealing, which we will review as well. In contrast, no significant dependence of laser fluence is found in shear moduli of the films, which vary between 220 and 250 GPa.     

Carbon systems of polymerized nanotubes: Crystal and electronic structures

Molecular dynamic calculations are carried out for the (P, T) phase diagram of a covalent compound of cross-linked carbon single-wall nanotubes (SWNT) and for the structures and electronic spectra of the novel crystals of polymerized carbon nanotubes. It is shown that the transformation of covalently bonded nanotubes in a close-packed conducting structure cardinally modifies their electronic properties. The P-SWNT crystal becomes semiconducting and, upon complete transformation of sp ²-hybridized carbon atoms into sp ³-hybridized ones, it becomes an insulator.     

Thermal conductive performance of deposited amorphous carbon materials by molecular dynamics simulation

A series of diamond-like carbon (DLC) films with different microstructure were prepared by depositing carbon atoms on diamond surface with incident energy ranging from 1 to 100 eV. The thermal conductivity of the deposited films and the Kapitza resistance between the film and the diamond substrate were investigated. Results show that the average density, the average fraction of sp³ bonding and the thermal conductivity of the DLC films increase first, reaching a maximum around 20–40 eV before decreasing, while the Kapitza resistance decreases gradually with increased deposition energy. The analysis suggests that the thermal resistance of the interface layer is in the order of 10^?10 m²K/W, which is not ignorable when measuring the thermal conductivity of the deposited film especially when the thickness of the DLC film is not large enough. The fraction of sp³ bonding in the DLC film decreases gradually normal to the diamond surface. However, the thermal conductivity of the film in normal direction is not affected obviously by this kind of structural variation but depends linearly on the average fraction of sp³ bonding in the entire film. The dependence of the thermal conductivity on the fraction of sp³ bonding was analysed by the phonon theory.     

Effect of titanium incorporation on the structural, mechanical and biocompatible properties of DLC thin films prepared by reactive-biased target ion beam deposition method

Amorphous diamond like carbon (DLC) and titanium incorporated diamond like carbon (Ti-DLC) thin films were deposited by using reactive-biased target ion beam deposition method. The effects of Ti incorporation and target bias voltage on the microstructure and mechanical properties of the as-deposited films were investigated by means of X-ray photoelectron spectroscopy, Raman spectroscopy, transmission electron microscopy and nano-indentation. It was found that the Ti content in Ti-DLC films gets increased with increasing target bias voltage. At about 4.2 at.% of Ti, uniform sized well dispersed nanocrystals were seen in the DLC matrix. Using FFT analysis, a facility available in the TEM, it was found that the nanocrystals are in cubic TiC phase. Though at the core, the incorporated Ti atoms react with carbon to form cubic TiC; most of the surface exposed Ti atoms were found to react with the atmospheric oxygen to form weakly bonded Ti-O. The presence of TiC nanocrystals greatly modified the sp³/sp² hybridized bonding ratio and is reflected in mechanical hardness of Ti-DLC films. These films were then tested for their biocompatibility by an invitro cell culturing test. Morphological observation and the cell proliferation test have demonstrated that the human osteoblast cells well attach and proliferate on the surface of Ti incorporated DLC films, suggesting possible applications in bone related implant coatings.     

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.     

Diamond-like-carbon films produced by magnetically guided pulsed laser deposition

We have compared the quality of carbon films deposited with magnetically guided pulsed laser deposition (MGPLD) and conventional pulsed laser deposition (PLD). In MGPLD, a curved magnetic field is used to guide the plasma but not the neutral species to the substrate to deposit the films while, in conventional PLD, the film is deposited with a mixture of ions, neutral species and clusters. A KrF laser pulse (248 nm) was focused to intensities of 10 GW/cm² on a carbon source target and a magnetic field strength of 0.3 T was used to steer the plasma around a curved arc to the deposition substrate. Electron energy loss spectroscopy was used in order to measure the fraction of sp³ bonding in the films produced. It is shown that the sp³ fraction, and hence the diamond-like character of the films, increased when deposited only with the pure ion component by MGPLD compared with films produced by the conventional PLD technique. The dependence of film quality on the laser intensity is also discussed. Received: 7 December 2000 / Accepted: 20 August 2001 / Published online: 2 October 2001     

Characterization of heat-treated CN films fabricated by dual-facing-target sputtering for soft X-ray multilayer mirrors

The structural characterization of heat-treated CN films fabricated by dual-facing-target sputtering for soft X-ray multilayer mirrors was performed by means of X-ray diffraction (XRD), Raman spectroscopy (RS) and X-ray photoelectron spectroscopy (XPS). The XRD analyses indicate a graphization process in the CN films during thermal annealing. The Raman analyses imply that the primary bonding in the CN films is sp². In other words, the formation of the sp³ bonding in the CN films can be suppressed effectively by doping with N atoms, and thus the thickness expansion resulting from the changes in the density of CN films during annealing can be decreased considerably. This result is also clarified by the increased conductivity measured. The XPS results give the information of the existence of the strong covalent bonding between N and C atoms, which can slow down the tendency of the structural relaxation during annealing. These results suggest that CN films suitable for soft X-ray multilayers used at high-temperature environments can be obtained by reactive dual-facing-target sputtering. With the low-angle X-ray diffraction measurements, we do observe the enhanced thermal stability of CoN/CN multilayers. Received: 2 October 1998 / Accepted: 21 April 1999 / Published online: 23 September 1999     

Piezoelectric effect in graphene-like 2D supracrystals with a periodic perforation breaking the central symmetry

Components of the piezoelectric modulus tensor in graphene-like carbon 2D supracrystals with a periodic perforation breaking the centrosymmetry of the structure have been calculated. It has been shown that the piezoelectric moduli of the supracrystals with sp ² hybridization are one order of magnitude lower and those of the supracrystals with sp ³ hybridization are several time higher than in lithium niobate.