Alexander E. Karkin

Structural stability of a golden semiconducting orthorhombic polymorph of Ti2O3 under high pressures and high temperatures

An orthorhombic polymorph of titanium oxide (Ti(2)O(3)) has been synthesized at high pressure-high temperature (HP-HT) conditions. It has been refined in the Pnma space group and the Th(2)S(3) structural type with the unit cell parameters as follows: a = 7.8248(6) Å, b = 2.8507(4) Å, c = 8.0967(3) Å, V = 180.61(1) Å(3) and Z = 4. The samples of Pnma-Ti(2)O(3) were of a golden colour, in contrast to the conventional black corundum-structured Ti(2)O(3). The structural stability of this polymorph has been examined by simultaneous Raman and x-ray diffraction studies under high pressure over 70 GPa and high temperature over 2200 K. No phase transformations or chemical reactions have been established. The electrical resistivity of Th(2)S(3)-structured Ti(2)O(3) samples showed a semiconducting behaviour and, at ambient conditions, was equal to 0.20-0.46 Ω cm. Conventional near-infrared absorption spectroscopy established the absence of energy gaps above 0.25 eV.

Significant enhancement of thermoelectric properties and metallization of Al-doped Mg2Si under pressure

We report results of investigations of electronic transport properties and lattice dynamics of Al-doped magnesium silicide (Mg2Si) thermoelectrics at ambient and high pressures to and beyond 15 GPa. High-quality samples of Mg2Si doped with 1 at. % of Al were prepared by spark plasma sintering technique. The samples were extensively examined at ambient pressure conditions by X-ray diffraction studies, Raman spectroscopy, electrical resistivity, magnetoresistance, Hall effect, thermoelectric power (Seebeck effect), and thermal conductivity. A Kondo-like feature in the electrical resistivity curves at low temperatures indicates a possible magnetism in the samples. The absolute values of the thermopower and electrical resistivity, and Raman spectra intensity of Mg2Si:Al dramatically diminished upon room-temperature compression. The calculated thermoelectric power factor of Mg2Si:Al raised with pressure to 2–3 GPa peaking in the maximum the values as high as about 8 × 10−3 W/(K2m) and then gradually decreased ...

A Hard Oxide Semiconductor with A Direct and Narrow Bandgap and Switchable p–n Electrical Conduction

An oxide semiconductor (perovskite-type Mn2 O3 ) is reported which has a narrow and direct bandgap of 0.45 eV and a high Vickers hardness of 15 GPa. All the known materials with similar electronic band structures (e.g., InSb, PbTe, PbSe, PbS, and InAs) play crucial roles in the semiconductor industry. The perovskite-type Mn2 O3 described is much stronger than the above semiconductors and may find useful applications in different semiconductor devices, e.g., in IR detectors.

Ferro-and antiferromagnetic ordering in LaMnO3+δ

A neutron diffraction study of the crystalline structure and magnetic state of LaMnO3+δ samples with different deviations from oxygen stoichiometry has been made at 4.2 K. It is shown that annealing at reduced oxygen pressure is accompanied by transformation of the magnetic structure from ferromagnetic, with magnetic moments parallel to the b axis, to antiferromagnetic, with the wave vector k=0 and the moments along the a axis (space group Pnma). A comparison of experimental with expected Mn ion moments suggests that magnetic order does not extend throughout the sample volume. Part of the Mn ions form magnetic clusters ∼20 Å in size.

Superconductivity in iron silicideLu2Fe3Si5probed by radiation-induced disordering

Resistivity r(T), Hall coefficient RH(T), superconducting temperature Tc, and the slope of the upper critical field -dHc2/dT were studied in poly- and single-crystalline samples of the Fe-based superconductor Lu2Fe3Si5 irradiated by fast neutrons. Atomic disordering induced by the neutron irradiation leads to a fast suppression of Tc similarly to the case of doping of Lu2Fe3Si5 with magnetic (Dy) and non-magnetic (Sc, Y) impurities. The same effect was observed in a novel FeAs-based superconductor La(O-F)FeAs after irradiation. Such behavior is accounted for by strong pair breaking that is traceable to scattering at non-magnetic impurities or radiation defects in unconventional superconductors. In such superconductors the sign of the order parameter changes between the different Fermi sheets (s+- model). Some relations that are specified for the properties of the normal and superconducting states in high-temperature superconductors are also observed in Lu2Fe3Si5. The first is the relationship -dHc2/dT ~ Tc, instead of the one expected for dirty superconductors -dHc2/dT ~ r0. The second is a correlation between the low-temperature linear coefficient a in the resistivity r = r0 + a1T, which appears presumably due to the scattering at magnetic fluctuations, and Tc; this correlation being an evidence of a tight relation between the superconductivity and magnetism. The data point to an unconventional (non-fononic) mechanism of superconductivity in Lu2Fe3Si5, and, probably, in some other Fe-based compounds, which can be fruitfully studied via the radiation-induced disordering.

New elaboration technique, structure and physical properties of infinite-layer Sr1−xLnxCuO2(Ln = Nd, Pr)

Abstract The infinite-layer compounds of the (Sr, Ln)CuO 2 family have been prepared by a new synthesis method from the low-pressure phase of SrCuO 2 and NdCuO 2 as starting materials. The crystal structure, microstructure and superconductivity of these samples have been studied with use of neutron powder diffraction, optical micrographs, energy-dispersive X-ray analysis. magnetic-susceptibility and electrical-resistivity measurements. The ratio of the lattice constants a/c as an empirical parameter for the existence of superconductivity in the electron-doped infinite-layer compounds is discussed.

Pressure cycling of InN to 20 GPa: In situ transport properties and amorphization

Indium nitride was grown on Al2O3 substrate and characterized by x-ray diffraction, Raman, electrical resistivity, Hall, and magnetoresistance studies. Thermoelectric and electrical properties of free-standing films were measured in situ under high pressure (HP) cycling to 20 GPa, across a phase transformation to a rock-salt-structured lattice. HP-cycling-induced amorphization was established. The thermopower (Seebeck effect) data evidence that both crystalline and amorphous InN kept n-type conductivity to 20 GPa. Pressure effect on the carrier concentration and effective mass is analyzed. Two features that can be related to structural transitions in amorphous InN were found near 11 and 17 GPa.

Localization effects in disordered high-Tc superconductors

Abstract Investigations of the effects of disorder in HTSC induced by fast neutron irradiation at T=80K show that localized effects are essential even at small disorder in states with high enough Tc. Localization leads to a decrease in Tc and full suppression of superconductivity within the range of strong localization.

Electronic transport properties of MFe2As2 (M = Ca, Eu, Sr) at ambient and high pressures up to 20 GPa

We experimentally investigated the electronic transport properties of four iron pnictide crystals, namely, EuFe2As2, SrFe2As2, and CaFe2As2 parent compounds, and superconducting CaFe1.94Co0.06As2 at ambient and high pressures up to 20 GPa. At ambient pressure we examined the electrical resistivity, Hall and magnetoresistance effects of the samples in a temperature range from 1.5 to 380 K in high magnetic fields up to 13.6 T. In this work we carried out the first simultaneous investigations of the in-plane and out-of-plane Hall coefficients, and found new peculiarities of the low-temperature magnetic and structural transitions that occur in these materials. In addition, the Hall coefficient data suggested that the parent compounds are semimetals with a multi-band conductivity that includes hole-type and electron-type bands. We measured the pressure dependence of the thermoelectric power (the Seebeck effect) of these samples up to 20 GPa, i.e. across the known phase transition from the tetragonal to the collapsed tetragonal lattice. The high-pressure behavior of the thermopower of EuFe2As2 and CaFe2As2 showing the p-n sign inversions was consistent with the semimetal model described above. By means of thermopower, we found in single-crystalline CaFe2As2 direct evidence of the band structure crossover related to the formation of As–As bonds along the c-axis on the tetragonal → collapsed tetragonal phase transition near 2 GPa. We showed that this feature is distinctly observable only in high-quality samples, and already for re-pressurization cycles this crossover was strongly smeared because of the moderate deterioration of the sample. We also demonstrated by means of thermopower that the band structure crossover that should accompany the tetragonal → collapsed tetragonal phase transition in EuFe2As2 near 8 GPa is hardly visible even in high-quality single crystals. This behavior may be related to a gradual valence change of the Eu ions under pressure that leads to an injection of free electrons and the steady shift of the conduction to n-type.

Relation between structural distortions and Tc in high-Tc superconductors

Abstract Structural distortions in high-T c 1-2-3 compounds under low temperature fast neutron irradiation are studied with neutron powder diffraction and compared with oxygen deficient samples. The results show the absence of essential charge transfer between the chains and planes for radiation-induced disorder and point to random defects to be responsible for the behavior of physical properties of high-T c superconductors.