An unusual temperature dependence in the oxidation of oxycarbide layers on uranium

An anomalous temperature dependence has been observed for the oxidation kinetics of outermost oxycarbide layers on polycrystalline uranium metal. Normally, oxidation or corrosion reactions are expected to proceed more rapidly as the temperature is elevated. Thus, it came as a surprise when we observed that the removal of the outermost atomic layers of carbon from uranium oxycarbide by O₂ reproducibly proceeds at a much faster rate at 25°C than at 280°C.     

Low temperature one-step synthesis of cobalt nanowires encapsulated in carbon

The one-step method of carbon nanotubes filled with continuous cobalt nanowires (CoF-CNT) synthesis is presented. Co/ZSM-5 (8 wt% Co) was used as catalyst for CoF-CNT production by methane decomposition at the temperature of 400 °C and 800 °C at atmospheric pressure in a conventional gas-flow system. The average diameter of the CoF-CNT is about 25 and 40 nm for products obtained at 400 °C and at 800 °C, respectively. The average size of coherently scattering domains along the normal to graphite layers L _c , the interlayer spacing d ₀₀₂, the graphitization degree of carbon, and the relative intensities of the G and D bands in Raman spectroscopy were determined to characterize the quality of carbon. It was proved that cobalt-filled carbon nanotubes can be produced by a simple method. The results of XRD, FE-SEM, and TEM show that CoF-CNT can be obtained even at 400 °C by catalytic decomposition of methane. On the basis of XRD, TEM, Raman spectroscopy was found that at a temperature of 800 °C, a better quality of carbon was produced.     

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.     

Study of the features of BaF<Subscript>2</Subscript> heteroepitaxy on CaF<Subscript>2</Subscript>/Si(100) layers obtained in the high-temperature growth mode

The surface morphology of BaF₂ epitaxial films grown by MBE (molecular beam epitaxy) in various modes on the surface of CaF₂/Si(100) is investigated by AFM. The CaF₂ layers on Si(100) are obtained in the high-temperature growth mode (Т _S = 750°C). It is shown that the epitaxy of BaF2 at a temperature of 600°C at the initial stage of growth leads to the formation of defects such as perforations in the epitaxial film, while epitaxy at a temperature of 750°C provides a defect-free film with a surface morphology suitable for the subsequent growth of semiconductors of IV–VI type and solid solutions based on them.     

Raman characterization before and after rapid thermal annealing of CeO2 thin films grown by rf sputtering on (111) Si

We investigated by Raman spectroscopy (RS) the crystalline quality of CeO₂ thin films radio frequency magnetron sputtered on n‐type (111) Si substrates from CeO₂ target. The deposition temperature was in the range of 200–800 °C. We also realized structural investigations on CeO₂ layers after Rapid Thermal Annealing (RTA) performed in the range of 750–1000 °C for 30 s under nitrogen atmosphere. So this study displays that a high‐growth temperature and a high post‐growth‐RTA temperature improves the crystalline structure of the film. In fact, the best crystalline quality, which is close to the CeO₂ target taken as a reference, is obtained for a CeO₂ layer deposited at 800 °C and post‐annealed at 1000 °C for 30 s. Copyright © 2008 John Wiley & Sons, Ltd.     

On the stability of thin epitaxial NiSi2 layers on Si (111)

By repeated deposition of several Å of Ni below 100 °C and subsequent annealing to typically 350 °C, thin continuous NiSi₂-layers have been grown epitaxially on Si (111). Thicknesses exceeding ∼- 70 Å require a different procedure due to the increasing importance of lateral growth, spoiling the layer quality. We show that MBE at substrate temperatures above 500 °C is not a viable technique to increase the thickness of the ultrathin layers. The reason is found to lie in the insufficient stability of the NiSi₂ templates, disintegrating into islands at temperatures above 500 °C. Perfectly smooth layers up to 1000 Å have, however, been grown by a new method in which alternate layers of Ni and Si (typically 1 Å and 4 Å respectively) are deposited onto the initial template at substrate temperatures between 350 °C and 380 °C.     

MBE-grown Si: Er light-emitting structures: Effect of epitaxial growth conditions on impurity concentration and photoluminescence

The technology and properties of light-emitting structures based on silicon layers doped by erbium during epitaxial MBE growth are studied. The epitaxial layer forming on substrates prepared from Czochralski-grown silicon becomes doped by oxygen and carbon impurities in the process. This permits simplification of the Si: Er layer doping by luminescence-activating impurities, thus eliminating the need to make a special capillary for introducing them into the growth chamber from the vapor phase. The photoluminescence spectra of all the structures studied at 78 K are dominated by an Er-containing center whose emission line peaks at 1.542 μm. The intensity of this line measured as a function of the substrate and erbium dopant source temperatures over the ranges 400–700°C and 740–800°C, respectively, exhibits maxima. The edge luminescence and the P line observed in the PL spectra are excited predominantly in the substrate. The erbium atom concentration in the epitaxial layers grown at a substrate temperature of 600°C was studied by Rutherford proton backscattering and exhibits an exponential dependence on the erbium source temperature with an activation energy of ～2.2 eV.     

Structural and optical properties of metastable SiGe/Si films with a low germanium concentration

The properties of metastable Si_{1 ? x} Ge _x /Si (10% < x < 16%) layers grown by molecular beam epitaxy on Si(100) substrates have been investigated using atomic force microscopy, X-ray diffraction, and low-temperature luminescence spectroscopy. It has been shown that ring-like aggregates are formed on the surface of layers grown at temperatures of 500–700°C. The size and shape of these aggregates suggest that their formation is associated with the diffusion instability arising due to the existence of a relationship between the surface diffusion, stresses, and the wetting potential during the growth of the epitaxial film. The existence of deviations from the homogeneous germanium distribution in the layer plane has been confirmed by a detailed analysis of the X-ray rocking curves and two-dimensional diffraction patterns. The structures with severe surface disturbances are characterized by an abnormal change in the decay times of the emission lines of bulk silicon, which indicate the presence of local electric and/or strain fields in subsurface regions. The perturbations of the flat crystallization front are suppressed as the growth temperature of layers decreases to 350°C. Despite the absence of a coating layer of silicon, the photoluminescence spectra of the layers themselves depend weakly on their thickness and growth temperature and remain sensitive only to the technological concentration of germanium. A slowly decaying luminescence associated presumably with the localization of excitons near the SiGe-Si interface has been observed in one of the samples grown at a temperature of 700°C and containing a dense array of ring-like aggregates.     

Surface morphology of ZnO buffer layer and its effects on the growth of GaN films on Si substrates by magnetron sputtering

ZnO thin films were first prepared on Si(111) substrates using a radio frequency magnetron sputtering system. Then the as-grown ZnO films were annealed in oxygen ambient at temperatures of 700, 800, 900, and 1000°C , respectively. The morphologies of ZnO films were studied by an atom force microscope (AFM). Subsequently, GaN epilayers about 500 nm thick were deposited on the ZnO buffer layers. The GaN/ZnO films were annealed in NH₃ ambient at 900°C. The microstructure, morphology and optical properties of GaN films were studied by x-ray diffraction (XRD), AFM, scanning electron microscopy (SEM) and photoluminescence (PL). The results are shown, their properties having been investigated particularly as a function of the ZnO layers. For better growth of the GaN films, the optimal annealing temperature of the ZnO buffer layers was 900°C.     

pH-Dependent shape changes of water-soluble CdS nanoparticles

Annealing of silicon-carbon nanoparticles was performed in argon at atmospheric pressure to enable formation of silicon carbide nanomaterials and/or carbon structures. Three precursor powders with increasing crystallinity and annealing temperatures from 1,900 to 2,600 °C were used to gain information about the effect of precursor properties (e.g. amorphous vs. nanocrystalline, carbon content) and annealing temperature on the produced materials. Three structures were found after annealing, i.e. silicon carbide crystals, carbon sheets and spherical carbon particles. The produced SiC crystals consisted of several polytypes. Low annealing temperature and increasing crystallinity of the precursor promoted the formation of the 3C-SiC polytype. Raman analysis indicated the presence of single-layer, undoped graphene in the sheets. The spherical carbon particles consisted of curved carbon layers growing from the amorphous Si–C core and forming a ‘nanoflower’ with a diameter below 60 nm. To our knowledge, the formation of this kind of structures has not been reported previously. The core was visible in transmission electron microscopy analysis at the annealing temperature of 1,900 °C, decreased in size with increasing temperature and disappeared above an annealing temperature of 2,200 °C. With increasing crystallinity of the precursor material, fewer layers (~5 with the most crystalline precursor) were detected in the carbon nanoflowers. The method presented opens up the possibility to produce new carbon nanostructures whose properties can be controlled by changing the properties of the precursor material or by adjusting an annealing temperature.     

Superconductivity of niobium nitride single crystals after implantation of carbon and nitrogen

Single crystals of δ-NbN_0.85 with a superconducting transition temperature T_c of 14.3 K were implanted with nitrogen and carbon ions at room temperature and subsequently annealed at high temperatures. Implantation was also performed at high substrate temperatures. After implantation at about 920°C maximum T_c-values of 16.5 and 17.8 K were obtained with N- and C-ions respectively. Disorder observed after room temperature implantation consisted of displaced Nb-atoms which could not be completely annealed in an isochromous annealing process up to 1000°C. For annealing temperatures above 1100°C nitrogen diffusion out of the implanted layers resulted in a reduction of T_c.     

Spherical shape BaO-ZnO-B<Subscript>2</Subscript>O<Subscript>3</Subscript>-SiO<Subscript>2</Subscript> glass powders prepared by spray pyrolysis

Fine-sized BaO-ZnO-B₂O₃-SiO₂ (BZBS) glass powders were directly prepared by high temperature spray pyrolysis. The hollow glass powders prepared at low preparation temperature of 1000 °C had a low density of 2.65 g/cm³. However, the densities of the BZBS powders obtained at preparation temperatures of 1200 and 1400 °C were each 3.92 and 4.13 g/cm³. The mean size of the BZBS glass powders prepared by spray pyrolysis at preparation temperature of 1400 °C was 0.98 μm. The glass transition temperature (T_g) of the prepared BZBS glass powders was 518.9 °C. The dielectric layers formed from the prepared BZBS glass powders with a dense structure had a clean surface and a dense inner structure without voids at the firing temperature of 580 °C. The transparencies of the dielectric layers formed from the prepared BZBS glass powders were higher than 90% within the visible range. PACS 42.70.Ce; 85.60.Pg; 71.55.Jv     

Raman studies on nanocomposite silicon carbonitride thin film deposited by r.f. magnetron sputtering at different substrate temperatures

Raman studies of nanocomposite SiCN thin film by sputtering showed that with increase of substrate temperature from room temperature to 500 °C, a transition from mostly sp² graphitic phase to sp³ carbon took place, which was observed from the variation of I_D/I_G ratio and the peak shifts. This process resulted in the growth of C₃N₄ and Si₃N₄ crystallites in the amorphous matrix, which led to increase in hardness (H) and modulus (E) obtained through nanoindentation. However, at a higher temperature of 600 °C, again an increase of sp² C concentration in the film was observed but the H and E values showed a decrease due to increased growth of the graphitic carbon phase. The whole process got reflected in a modified four‐stage Ferrari–Robertson model of Raman spectroscopy. Copyright © 2010 John Wiley & Sons, Ltd.     

Relationship between the structural and catalytic properties of mechanosynthesized lithiated manganese oxides

The relationship between the structural and catalytic properties of lithiated spinel manganese oxides was investigated by means of X-ray diffraction, Infrared and Xanes spectroscopies, thermogravimetric analysis, and by evaluating two catalytic oxidation tests, namely the carbon black combustion and the toluene conversion. Li-Mn-O catalysts were prepared from stoichiometric (Li₂O + MnO₂) mixtures, either by the classical high temperature ceramic method or by mechanochemistry. For both catalytic tests, some spectacular temperature reductions were measured as a function of grinding. A remarkable decrease of 210 °C (from 650 °C to 440 °C) in the carbon black combustion temperature was obtained when using mechanosynthesized Li-Mn-O spinel prepared from a mixture of Li₂O and MnO₂ ground for 3 hours, whereas a 100 % toluene conversion rate was achieved for a temperature lower than 200 °C for the 5 hours milled ceramic LiMn₂O₄ while the as-made ceramic was inactive. The enhancement of the performances (i.e. decrease in carbon black combustion temperature Tc and decrease in toluene conversion temperature T_95%) is due both to an increase in grain boundaries and in specific BET surface area and to the nano-crystallite size nature of the material. Besides, the spinel stoichiometry (both in oxygen or in cations) reflected by the lattice parameter variation plays a significant role in the catalytic reaction mechanism.     

Structural and photoluminescence properties of heteroepitaxial silicon-on-sapphire layers

The growth of erbium-doped silicon layers on sapphire substrates through sublimation molecular-beam epitaxy is studied for the first time. Structural analysis data are given, and the luminescence properties of layers are discussed. Heteroepitaxial silicon-on-sapphire layers grown at a temperature T _s=600–700°C are found to be fairly perfect in structure. Photoluminescence spectra show a peak at a wavelength of 1.54 μm associated with intracenter transitions in the rare earth Er³⁺ ion. __________ Translated from Fizika Tverdogo Tela, Vol. 46, No. 1, 2004, pp. 15–17. Original Russian Text Copyright ? 2004 by Svetlov, Chalkov, Shengurov, Drozdov, Krasil’nik, Krasil’nikova, Stepikhova, Pavlov, Pavlova, Shilyaev, Khokhlov. Deceased.     

A (Ga,Mn)Sb magnetic semiconductor for spintronic applications

The structural, optical, and galvanomagnetic properties of (Ga, Mn)Sb layers grown by the laser sputtering of solid targets in H₂ flow are n studied. It is shown that at a growth temperature of 400°C, (Ga, Mn)Sb layers are single-crystal up to high Mn concentrations. The magnetic field dependence of the Hall resistance at measuring temperatures of 10–300 K contains a hysteresis loop; i. e., the layers are ferromagnetic semiconductors.     

Monitoring structural defects and crystallinity of carbon nanotubes in thin films

We report the influence of catalyst formulation and reaction temperature on the formation of carbon nanotube (CNT) thin films by the chemical vapour deposition (CVD) method. Thin films of CNTs were grown on Fe-Mo/Al₂O₃-coated silicon wafer by thermal decomposition of methane at different temperatures ranging from 800 to 1000°C. The electron microscopic investigations, SEM as well as HRTEM, of the as-grown CNT thin films revealed the growth of uniform multi-walled CNTs in abundance. The intensity ratio of D-band to G-band and FWHM of G-band through Raman measurements clearly indicated the dependency of structural defects and crystallinity of CNTs in thin films on the catalyst formulation and CVD growth temperature. The results suggest that thin films of multi-walled CNTs with negligible amount of defects in the nanotube structure and very high crystallinity can be obtained by thermal CVD process at 925°C.     

Temperature dependence of structural and optical properties of GeSbTe alloy thin films

Ge₂Sb₂Te₅ films sandwiched by ZnS–SiO₂ layers were studied by spectroscopic ellipsometry from room temperature up to 800°C. An irreversible modification of both materials is pointed out. ZnS cubic phase precipitation occurs after heating at 650°C, shown by grazing incidence X-ray diffraction. Chemical modification in phase change material is observed above 300°C, revealed by a typical behavior of a transparent layer.     

Phase transitions in the CN<Subscript>x</Subscript>-Co system induced by changes in the film growth temperature

The structures of amorphous CN_x-Co films grown at different temperatures (T _s = 200–365°C) are studied by X-ray diffraction. As the growth temperature increases above T _s = 200°C, a concentration phase transition is found to occur in the amorphous state; this transition is related to a change in the major portion of carbon or cobalt in the structure of the cluster films. At T _s = 365°C, a disorder-order phase transition, which is accompanied by the transition from the amorphous to crystalline state, occurs in the films.     

Low temperature synthesis of iron containing carbon nanoparticles in critical carbon dioxide

We develop a low temperature, organic solvent-free method of producing iron containing carbon (Fe@C) nanoparticles. We show that Fe@C nanoparticles are self-assembled by mixing ferrocene with sub-critical (25.0 °C), near-critical (31.0 °C) and super-critical (41.0 °C) carbon dioxide and irradiating the solutions with UV laser of 266-nm wavelength. The diameter of the iron particles varies from 1 to 100 nm, whereas that of Fe@C particles ranges from 200 nm to 1 μm. Bamboo-shaped structures are also formed by iron particles and carbon layers. There is no appreciable effect of the temperature on the quantity and diameter distributions of the particles produced. The Fe@C nanoparticles show soft ferromagnetic characteristics. Iron particles are crystallised, composed of bcc and fcc lattice structures, and the carbon shells are graphitised after irradiation of electron beams.