Thermodynamic and kinetic behavior of an argon plasma jet. Decomposition of nitric oxide between 1300 - 1750 degrees K in an argon plasma

In the first part of the study, an RF coupled, atmospheric pressure, laminar plasma jet of argon was investigated for thermodynamic equilibrium and some rate processes.

Improved values of transition probabilities for 17 lines of argon I were developed from known values for 7 lines. The effect of inhomogeneity of the source was pointed out.

The temperatures, T, and the electron densities, n_e , were determined spectroscopically from the population densities of the higher excited states assuming the Saha-Boltzmann relationship to be valid for these states. The axial velocities, v_z, were measured by tracing the paths of particles of boron nitride using a three-dimentional mapping technique. The above quantities varied in the following ranges: 10¹² ˂ n_e ˂ 10¹⁵ particles/cm³, 3500 ˂ T ˂ 11000 °K, and 200 ˂ v_z ˂ 1200 cm/sec.

The absence of excitation equilibrium for the lower excitation population including the ground state under certain conditions of T and n_e was established and the departure from equilibrium was examined quantitatively. The ground state was shown to be highly underpopulated for the decaying plasma.

Rates of recombination between electrons and ions were obtained by solving the steady-state equation of continuity for electrons. The observed rates were consistent with a dissociative-molecular ion mechanism with a steady-state assumption for the molecular ions.

In the second part of the study, decomposition of NO was studied in the plasma at lower temperatures. The mole fractions of NO denoted by x_NO were determined gas-chromatographically and varied between 0.0012 ˂ x_NO ˂ 0.0055. The temperatures were measured pyrometrically and varied between 1300 ˂ T ˂ 1750°K. The observed rates of decomposition were orders of magnitude greater than those obtained by the previous workers under purely thermal reaction conditions. The overall activation energy was about 9 kcal/g mol which was considerably lower than the value under thermal conditions. The effect of excess nitrogen was to reduce the rate of decomposition of NO and to increase the order of the reaction with respect to NO from 1.33 to 1.85. The observed rates were consistent with a chain mechanism in which atomic nitrogen and oxygen act as chain carriers. The increased rates of decomposition and the reduced activation energy in the presence of the plasma could be explained on the basis of the observed large amount of atomic nitrogen which was probably formed as the result of reactions between excited atoms and ions of argon and the molecular nitrogen.

Defect and disorder reduction by annealing in hydrogenated tetrahedral amorphous carbon

Hydrogenated tetrahedral amorphous carbon (ta-C:H) is a form of diamond-like carbon with a high sp3 content (>60%), grown here using a plasma beam source. Information on the behaviour of hydrogen upon annealing is obtained from effusion measurements, which show that hydrogen does not effuse significantly at temperatures less than 500 °C in films grown using methane and 700 °C in films grown using acetylene. Raman measurements show no significant structural changes at temperatures up to 300 °C. At higher temperatures, corresponding to the onset of effusion, the Raman spectra show a clustering of the sp2 phase. The density of states of ta-C:H is directly measured using scanning tunnelling spectroscopy. The measured gradients of the conduction and valence band tails increase up to 300 °C, confirming the occurrence of band tail sharpening. Examination of the photoluminescence background in the Raman spectra shows an increase in photoluminescence intensity with decreasing defect density, providing evidence that paramagnetic defects are the dominant non-radiative recombination centres in ta-C:H.

Light absorption in silicon quantum dots embedded in silica

The photon absorption in Si quantum dots (QDs) embedded in SiO2 has been systematically investigated by varying several parameters of the QD synthesis. Plasma-enhanced chemical vapor deposition (PECVD) or magnetron cosputtering (MS) have been used to deposit, upon quartz substrates, single layer, or multilayer structures of Si-rich- SiO2 (SRO) with different Si content (43-46 at. %). SRO samples have been annealed for 1 h in the 450-1250 °C range and characterized by optical absorption measurements, photoluminescence analysis, Rutherford backscattering spectrometry and x-ray Photoelectron Spectroscopy. After annealing up to 900 °C SRO films grown by MS show a higher absorption coefficient and a lower optical bandgap (∼2.0 eV) in comparison with that of PECVD samples, due to the lower density of Si-Si bonds and to the presence of nitrogen in PECVD materials. By increasing the Si content a reduction in the optical bandgap has been recorded, pointing out the role of Si-Si bonds density in the absorption process in small amorphous Si QDs. Both the photon absorption probability and energy threshold in amorphous Si QDs are higher than in bulk amorphous Si, evidencing a quantum confinement effect. For temperatures higher than 900 °C both the materials show an increase in the optical bandgap due to the amorphous-crystalline transition of the Si QDs. Fixed the SRO stoichiometry, no difference in the optical bandgap trend of multilayer or single layer structures is evidenced. These data can be profitably used to better implement Si QDs for future PV technologies. © 2009 American Institute of Physics.

Controlling electronic structures by irradiation in single-walled SiC nanotubes: a first-principles molecular dynamics study

Using first-principles molecular dynamics simulations, the displacement threshold energy and defect configurations are determined in SiC nanotubes. The simulation results reveal that a rich variety of defect structures (vacancies, Stone-Wales defects and antisite defects) are formed with threshold energies from 11 to 64 eV. The threshold energy shows an anisotropic behavior and exhibits a dramatic decrease with decreasing tube diameter. The electronic structure can be altered by the defects formed by irradiation, which suggests that the electron irradiation may be a way to use defect engineering to tailor electronic properties of SiC nanotubes.

Symmetry restrictions in the chirality dependence of physical properties of single-wall nanotubes

We investigate the chirality dependence of physical properties of nanotubes which are wrapped by the planar hexagonal lattice including graphite and boron nitride sheet, and reveal its symmetry origin. The observables under consideration are of scalar, vector, and tensor types. These exact chirality dependences obtained are useful to verify the experimental and numerical results and propose accurate empirical formulas. Some important features of physical quantities can also be extracted by considering the symmetry restrictions without complicated calculations.

立方氮化硼薄膜制备与性质研究新进展

立方氮化硼（c-BN）具有优异的物理和化学性质,在力学、光学和电子学等方面有着广泛的应用前景.自上世纪80年代开始,低压沉积c-BN薄膜的研究迅速发展,到90年代中期达到高潮,随后进展缓慢,c-BN薄膜研究转入低潮.近年来,c-BN薄膜研究在几方面取得了突破,如获得与衬底粘附良好、厚度超过1μm的c-BN厚膜;成功实现了c-BN单晶薄膜的异质外延生长;此外,在c-BN薄膜力学性质和过渡层微结构研究方面也取得了进展.本文主要评述最近几年c-BN薄膜研究在以上几方面取得的最新进展.

异质外延立方氮化硼薄膜的微结构研究

利用离子束辅助沉积技术在金刚石薄膜衬底上制备立方氮化硼薄膜,傅立叶变换红外谱的结果表明,在高度(001)织构金刚石薄膜衬底上沉积的立方氮化硼薄膜是纯的立方相,而在多晶金刚石薄膜衬底上制备的立方氮化硼薄膜中还含少量的六角氮化硼.高分辨透射电镜的分析表明,在金刚石晶粒上异质外延的c-BN直接成核于金刚石衬底,界面没有六角氮化硼过渡层;而在含有大量缺陷的晶粒边界,存在六角氮化硼的成核与生长.

Space-grown SI-GaAs and its application

A semi-insulating GaAs single crystal ingot was grown in a recoverable satellite, within a specially designed pyrolytic boron nitride crucible, in a power-travelling furnace under microgravity. The crystal was characterized systematically and was used in fabricating low noise field effect transistors and analogue switch integrated circuits by the direct ion-implantation technique. All key electrical properties of these transistors and integrated circuits have surpassed those made from conventional earth-grown gallium arsenide. This result shows that device-grade space-grown semiconducting single. crystal has surpassed the best. terrestrial counterparts. Studies on the correlation between SI-GaAs wafers and the electronic devices and integrated circuits indicate that the characteristics of a compound semiconductor single crystal depends fundamentally on its stoichiometry.

Calculation of bulk modulus on carbon nitrides with chemical bond method

The bulk moduli of some superhard materials were calculated by using the chemical bond method. For simple crystals, such as diamonds, c-BN, SiC, Si, BP, and Ge, the calculated results agree with experimental and theoretical values. For crystals of complex structure, such as beta-BC2N crystal and various structural C3N4 crystals, the results indicate that their bulk moduli are large, but do not exceed that of diamond.

In situ synthesis of silica gel nanowire/Na+-montmorillonite nanocomposites by the sol-gel route

Silica-gel nanowire/Na+-montmorillonite (Na+-MMT) nanocomposites were prepared by the in situ sol-gel process of tetraethyl orthosilicate (TEOS) in the presence of Na+-MMT and ammonia as catalyst. Microstructure characterization of the nanocomposites was done by SEM, , EDX, XRD and FTIR. It was found that a lot of silica-gel nanowires grew along the edges of Na+-MMT. The combination between the nanowires and Na+-MMT was accomplished via polycondensation of the hydrolyzed TEOS and the edge-OH groups of Na+-MMT.

Well defined carbazole-based hole-transporting amorphous molecular materials

Monodisperse carbazole-based oligomers have been synthesized via C-N bonds formation by the modified Ullmann reaction. The full characterization of their structure is presented. These derivatives are highly thermally stable amorphous compounds with glass transition temperatures of 167-171 degrees C and thermal decomposition temperatures of ca. 400 degrees C. Amorphous films of the materials were fabricated and their hole-transporting properties were tested in a light emitting device with Alq(3) as an electroluminescent and electron-transporting material.

Synchrotron-laser pump-probe luminescence spectroscopy: Correlation of electronic defect states with x-ray absorption in wide-gap solids

Poolton, Nigel; Hamilton, B.; Evans, D.A., (2005) 'Synchrotron-laser pump-probe luminescence spectroscopy: Correlation of electronic defect states with x-ray absorption in wide-gap solids', Journal of Physics D: Applied Physics 38 pp.1478-1484 RAE2008

Observation of an optical phonon band in situ in TiO electrochemistry:A possible indicator of strongly trapped intermediates in the O evolution reaction

This Letter reports in situ Fourier transform infrared (FTIR) spectroscopic data on thermal TiO films fabricated by heating titanium plates in air at 475, 700 and 800 °C. The films were studied in the dark and under UV-irradiation in aqueous 0.1MNaClO in the presence and absence of 0.1 M Na(OOC) and at 10, 25 and 50 °C. The film fabricated at 800 °C showed a broad feature near 1580cm under UV-irradiation that was not observed in the dark, whilst the films fabricated at lower temperatures, 475 and 700 °C, showed no such feature. This feature appears to be associated with the accumulation of surface-mobile holes at the complex, porous film-electrolyte interface and the capacity of such holes to enhance the absorption cross-section of optical phonons characteristic of the rutile crystal form at and near the surface of the TiO/electrolyte interface. © 2001 Elsevier Science B.V.

Approximate solution of the autocatalytic hydrolysis of cellulose

Depolymerization of cellulose in homogeneous acidic medium is analyzed on the basis of autocatalytic model of hydrolysis with a positive feedback of acid production from the degraded biopolymer. The normalized number of scissions per cellulose chain, S(t)/nA degrees A = 1 - C(t)/C(0), follows a sigmoid behavior with reaction time t, and the cellulose concentration C(t) decreases exponentially with a linear and cubic time dependence, C(t) = C(0)exp[-at - bt (3)], where a and b are model parameters easier determined from data analysis.

Biodegradação de filmes de polipropileno (PP), poli(3-hidroxibutirato) (PHB) e blenda de PP/PHB por microrganismos das águas do Rio Atibaia

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)