Sergei G. Buga

Structure and electrical properties of Sb2Te3 and Bi0.4Sb1.6Te3 metastable phases obtained by HPHT treatment

We have obtained the metastable phase of the thermoelectric alloy Bi0.4Sb1.6Te3 with electron type conductivity for the first time using the method of quenching under pressure after treatment at P=4.0 GPa and T=400–850 °C. We have consequently performed comparative studies with the similar phase of Sb2Te3. The polycrystalline X-ray diffraction patterns of these phases are similar to the known monoclinic structure α-As2Te3 (C2/m) with less monoclinic distortion, β ≈ 92°. We have measured the electrical resistivity and the Hall coefficient in the temperature range of T=77−450 K and we have evaluated the Hall mobility and density of charge carriers. The negative Hall coefficient indicates the dominant electron type of carriers at temperatures up to 380 K in the metastable phase of Sb2Te3 and up to 440 K in the metastable state of Bi0.4Sb1.6Te3. Above these temperatures, the p-type conductivity proper to the initial phases dominates.

Laser controlled magnetism in hydrogenated fullerene films

Room temperature ferromagnetic-like behavior in fullerene photopolymerized films treated with monatomic hydrogen is reported. The hydrogen treatment controllably varies the paramagnetic spin concentration and laser induced polymerization transforms the paramagnetic phase to a ferromagnetic-like one. Excess laser irradiation destroys magnetic ordering, presumably due to structural changes, which was continuously monitored by Raman spectroscopy. We suggest an interpretation of the data based on first-principles density-functional spin-unrestricted calculations which show that the excess spin from mono-atomic hydrogen is delocalized within the host fullerene and the laser-induced polymerization promotes spin exchange interaction and spin alignment in the polymerized phase.

Weak superconductivity in the surface layer of a bulk single-crystal boron-doped diamond

We have grown and investigated bulk single-crystal heavily boron-doped diamonds possessing superconductivity with . Only the surface layer with the thickness less than showed the degenerate semiconductor behavior with transition to the superconducting state, while the bulk of the crystal was a typical doped semiconductor. The morphology of the surface layer is dendritic polycrystalline with an average boron content of 2.5–2.9 at.%. The typical Josephson junction current-voltage characteristic was observed. The degenerate semiconductor-superconductor transition as in single-crystal high-temperature superconductors and the structural data analysis of the surface layer indicate the two-dimensional character of superconductivity, and the actual superconducting structure is a set of few-nanometer thick boron carbide layers embedded in a diamond structure.

Transport properties of nanocomposite thermoelectric materials based on Si and Ge

The modification of transport properties (thermal conductivity, electrical conductivity, and See-beck coefficient) of nanostructured thermoelectrics based on Ge and Si-Ge with inclusions of the second phase has been investigated experimentally. In the Ge-C60 nanocomposite, modifying inclusions are the fullerene C60 located along the germanium grain boundaries and 1- to 5-nm SiC nanocrystals in the Si-Ge-SiC nanocomposite. In particular, the presence of these inclusions in the nanocomposite leads to an increase of the Seebeck coefficient in the temperature range above 600 K and, in general, to an increase in the thermoelectric figure of merit ZT by a factor of 1.5–2 as compared to the corresponding characteristics of nanostructured thermoelectrics based on Si-Ge without modifying inclusions of the second phase.

Superhard superconductor composites obtained by sintering of diamond, c-BN and C60 powders with superconductors

Superhard superconducting samples with a critical temperature of TC = 10.5 - 12.6 K were obtained by high-pressure / high-temperature sintering of synthetic diamond powders coated with a niobium film and in 50% - 50% composition with superhard C60 fullerene. Superhard superconductors with TC = 9.3 K were obtained when diamond and molybdenum powders were sintered at a pressure of 7.7 GPa and a temperature of 2173 K. Superconducting samples with TC = 36.1 - 37.5 K have been obtained in the systems diamond-MgB2 and cubic boron nitride-MgB2.

Cluster structure and elastic properties of superhard and ultrahard fullerites

Velocities of the longitudinal and shear sound waves are measured in ultrahard fullerites created by static high-pressure-high-temperature treatment under P=13 GPa and T=1670–1870 K. The highest value of 26.0 km/s for the longitudinal waves is measured, that is about 40% more than in diamond. Bulk modulus of different ultrahard fullerites covers the range of about 600–1700 GPa. The highest hardness is about 30×103 kg/mm3. We ascribe these unique properties to formation of 20–30 atoms clusters by the walls of adjacent molecules under process of 3D-cross-linking. Most distinctly these clusters declare themselves in the cubic structure with the lattice parameter about 6 A and 32 atoms per unit cell.

Synthesis of superhard and ultrahard materials by 3d-polymerization of C60, C70 fullerenes under high pressure (15 GPa) and temperatures up to 1820 K

Solid fullerenes C60 and C70 have been treated at high pressure of 15 GPa and high temperatures of 520 - 1820 K for a time of exposure of 60 s and a quenching rate of 300 K s−1 using a toroid-type apparatus. X-ray diffraction and Raman spectra confirm the realization of 3D-polymerized phases in these solids at 15 GPa. The pressure/temperature maps of synthesis of metastable carbon phases on the basis of C60 and C70 have thus been extended to 15 GPa. The longitudinal and shear sound wave velocities were measured by acoustic microscopy techniques. A maximum sound wave velocity of (21±1)×105 m s−1 was observed in the sample synthesized from C60 at T = 1170 K. The elastic constants were calculated using experimental data. The acoustic microscopy images of experimental samples have been investigated.

Simulation of the interaction of bipartite bimetallic clusters with low-energy argon clusters

Molecular-dynamics simulation of the evolution of bipartite bimetallic clusters consisting of 390 atoms during bombardment by Arn (n = 1, 2, 13) clusters with initial energies from 1 eV to 1.4 keV is performed. Binary Cu–Au and Ni–Al clusters consisting of equal atomic fractions of corresponding elements were used as a target. As a result of simulation, the temperatures, changes in the potential energy, sputtering yields, and intensities of collision-stimulated displacement of atoms through the interface of monometallic parts of binary clusters, depending on the size and energy of incident particle, are obtained.

Structure and properties of metastable phases of m-Sb2Te3and m-Bi0.4Sb1.6Te3

The m-Sb2Te3 and m-Bi0.4Sb1.6Te3 metastable phases were found after high-pressure (4 GPa) and high-temperature (873 K) treatment of initial rhombohedral Sb2Te3 and Bi0.4Sb1.6Te3. These metastable phases crystallize in the same structure because they have almost identical diffraction pattern. The crystal structure of metastable phases, determined by the powder X-ray and electron diffraction methods, is monoclinic (C2/m). The cell dimensions of m-Sb2Te3 are: a=15.64(8) Å, b=4.282(8) Å, c=9.38(2) Å, β=89.70°(5). The reliability factors are: RBragg=0.12, RF=0.13, χ2=4.35. There are two different types of Sb atoms: with seven-coordinated by Te atoms for Sb1 and for Sb2 – eight-coordinated by Te atoms forming composite coordination polyhedra. A comparison with the structure of pressure-induced β-Sb2Te3-phase, observed in situ under high pressure, has been made. Pressure-induced β-Sb2Te3phase can be retained at ambient conditions as m-Sb2Te3. The annealing of m-Sb2Te3 and m-Bi0.4Sb1.6Te3 samples at 673 K during 2, 5 hours returns their structures to initial symmetry. This fact was supported by the exothermal peak found by differential scanning calorimetry. The ab initio study verified metallic character of quenched phases: the energy spectrum is consistent with the proposed monoclinic structure with short interlayer distances. The electrical resistivity and the Hall coefficient in the temperature range of T = 1.8−450 K have been measured. m-Sb2Te3 phase is superconductive at T < 2K.

Superhard Superconductive Composite Materials Obtained by High-Pressure-High-Temperature Sintering

Superhard superconducting materials are of considerable interest for the creation of high pressure devices for investigating electrical and superconducting properties of various materials. The superconducting composites consisting of superconductors and superhard materials that are in thermal and electrical contacts may satisfy very conflicting requirements imposed on superconducting materials for special research cryogenic technique, wear-resistive parts of superconductor devices, superconducting micro-electromechanical systems (MEMS), etc. The design of materials combining such properties as superconductivity, superhardness, and high strength is an interesting task for both scientific and applied reasons. Superconducting composites may be used for the production of large superconducting magnetic systems (Gurevich et al., 1987). The discovery of superconductivity in heavily boron-doped diamonds (Ekimov et al., 2004; Sidorov et al., 2005) has attracted much attention. Superconducting diamonds are the hardest known superconductors. The potential applications of superconducting diamonds are broad, ranging from anvils in research high-pressure apparatus to supecronducting MEMS. However, the highest value of the superconductivity onset temperature in borondoped diamonds was found just about 7 K in thin CVD-grown films (Takano et al., 2004) and at about 4 K in bulk diamonds grown at high-pressure and high-temperature (Ekimov et al., 2004; Sidorov et al., 2005). In these pioneering works bulk polycrystalline diamonds with micron grainsize have been synthesized from graphite and B4C composition (Ekimov et al., 2004) and graphite with 4 wt% amorphous boron (Sidorov et al., 2005). The synthesis have been carried out at 8-9 GPa pressure and 2500-2800 K temperature in both cases. Later Dubrovinskaya et al., 2006, carried out synthesis of graphite with B4C composition at much higher pressure value 20 GPa but the same temperature of 2700K and found the superconducting state transition at lower temperature 2.4 1.4 K in the obtained doped polycrystalline diamonds. Due to the sharpening of the temperature interval of the superconductivity transition in magnetic field they suggested that superconductivity could arise from filaments of zero-resistant material. An alternative method for the creation of composite diamond superconductors was suggested by one of the authors of the present