Studies of electronic structure by x-ray Raman and emission spectroscopy: applications to MgB2 superconductors and high pressure physics

X-ray Raman scattering and x-ray emission spectroscopies were used to study the electronic properties and phase transitions in several condensed matter systems. The experimental work, carried out at the European Synchrotron Radiation Facility, was complemented by theoretical calculations of the x-ray spectra and of the electronic structure. The electronic structure of MgB2 at the Fermi level is dominated by the boron σ and π bands. The high density of states provided by these bands is the key feature of the electronic structure contributing to the high critical temperature of superconductivity in MgB2. The electronic structure of MgB2 can be modified by atomic substitutions, which introduce extra electrons or holes into the bands. X ray Raman scattering was used to probe the interesting σ and π band hole states in pure and aluminum substituted MgB2. A method for determining the final state density of electron states from experimental x-ray Raman scattering spectra was examined and applied to the experimental data on both pure MgB2 and on Mg(0.83)Al(0.17)B2. The extracted final state density of electron states for the pure and aluminum substituted samples revealed clear substitution induced changes in the σ and π bands. The experimental work was supported by theoretical calculations of the electronic structure and x-ray Raman spectra. X-ray emission at the metal Kβ line was applied to the studies of pressure and temperature induced spin state transitions in transition metal oxides. The experimental studies were complemented by cluster multiplet calculations of the electronic structure and emission spectra. In LaCoO3 evidence for the appearance of an intermediate spin state was found and the presence of a pressure induced spin transition was confirmed. Pressure induced changes in the electronic structure of transition metal monoxides were studied experimentally and were analyzed using the cluster multiplet approach. The effects of hybridization, bandwidth and crystal field splitting in stabilizing the high pressure spin state were discussed. Emission spectroscopy at the Kβ line was also applied to FeCO3 and a pressure induced iron spin state transition was discovered.

Structure and optical properties of Cd-substituted ZnO (Zn1-xCdxO) nanostructures synthesized by the high-pressure solution route

We report the synthesis of Cd-substituted ZnO nanostructures (Zn1-xCdxO with x up to approximate to 0.09) by the high-pressure solution growth method. The synthesized nanostructures comprise nanocrystals that are both particles (similar to 10-15 nm) and rods which grow along the [002] direction as established by transmission electron microscope (TEM) and x-ray diffraction (XRD) analysis. Rietveld analysis of the XRD data shows a monotonic increase of the unit cell volume with the increase of Cd concentration. The optical absorption, as well as the photoluminescence (PL), shows a red shift on Cd substitution. The line width of the PL spectrum is related to the strain inhomogeneity and it peaks in the region where the CdO phase separates from the Zn1-xCdxO nanostructures. The time-resolved photoemission showed a long-lived (similar to 10 ns) component. We propose that the PL behaviour of the Zn1-xCdxO is dominated by strain in the sample with the red shift of the PL linked to the expansion of the unit cell volume on Cd substitution.

High-pressure NMR investigations of the protonic conductor (NH4)4Fe(CN)6.1.5H2O

The effect of high hydrostatic pressure up to 1.5 GPa on ionic motion in (NH4)4Fe(CN)6.1.5H2O has been studied by wide-line 1H NMR experiments performed in the temperature range from room temperature to 77 K. The experiments at room temperature have shown a large increase in the second moment at 0.45 GPa as a result of a pressure-induced phase transition. The temperature dependence study up to 0.425 GPa has shown a gradual increase in the values of activation energy and attempt frequency with increase in pressure. The activation volume for motion at 300 K has been estimated to be 6% of molar volume. Vacancy-assisted ionic jumps are concluded to be the mode of charge transport. Second moments estimated at 77 K show evidence for tunnelling reorientation of at least one of the two NH4+ groups in the compound.

High-pressure studies on Ge-Te glasses. Evidence for a critical composition in IV-VI chalcogenide glassy systems

The electrical resistivity of bulk GexTe100-x glasses has been measured as a function of temperature and pressure. Under high pressure, all the glasses were found to undergo sharp discontinuous transitions from glassy semiconductors to crystalline metal. Several of the observed properties such as the transition pressure, conductivity activation energy and pre-exponential factor, exhibit anomalous trends at a composition x = 20. These results suggest that the x = 20 composition in the Ge-Te system should possess salient structural features. A model based on the unusual stability of structural units is proposed for explaining the anomaly at 20 at.% Ge concentration.

NMR study of ammonium halides under high pressure

Wide-line c.w. proton resonance investigations have been carried out on the ammonium halides, namely, ammonium chloride, ammonium bromide and ammonium iodide in the temperature range between 77 and 300 K and in the pressure range between 1 bar and 14 kbar. It has been found that the narrow iodide spectrum at 77 K broadens under the application of hydrostatic pressure. The barrier height for the ammonium ion motion in ammonium iodide under pressure has been estimated by carrying out a temperature variation study. The rotational potential for the motion of ammonium ion in ammonium iodide at 1 bar and 14 kbar has been calculated using earlier theoretical models and compared with values calculated for ammonium chloride and bromide. The barrier height in the case of ammonium iodide under pressure is found to be of the same order of magnitude as the value obtained in the case of ammonium bromide at atmospheric pressure indicating that the high pressure phase of ammonium iodide is likely to have the same structure as the low temperature ordered CsCl phase found in the case of the chloride and the bromide. The increase in the potential barrier height in the case of ammonium iodide under pressure indicates that the reorientational motion executed by the ammonium ions is inhibited by the application of pressure. This is also confirmed by the broadening of the spectral line at 77 K under the application of pressure.

A bibliographical review of the high pressure studies of ferroelectric phase transitions

A brief review of the various high pressure studies on the phase transitions in ferroelectric crystals carried out over the past two decades is presented. The theoretical framework in which high pressure studies have to be viewed is given. The pressure data of ferroelectric crystals are organized in the form of tables. High pressure spectroscopic and structural studies are included. The review contains a bibliography of over two hundred references.

A High Pressure Study of the Phase Diagram and the Critical Exponent β of Binary Liquid Systems

The pressure dependence of critical parameters xc, Tc, and β have been analysed in four systems namely cyclohexane + acetic anhydride, n-heptane + acetic anhydride, methanol + n-heptane, and carbon disulphide + acetonitrile. The separation temperature was found to increase linearly with pressure the value of dTc/dP being 28 mK, 11 mK, 22 mK, and 25 mK respectively. These are in fair agreement with earlier measurements available for two systems. For the methanol + n-heptane system dTc/dP is apparently not consistent with the value predicted from the specific heat and thermal expansion data.Die Druckabhängigkeit der kritischen Parameter xc, Tc und β ist in den vier Systemen Cyclohexan + Essigsäureanhydrid, n-Heptan + Essigsäureanhydrid, Methanol + n-Heptan und Schwefelkohlenstoff + Acetonitril analysiert worden. Es wurde gefunden, daß die kritische Temperatur linear mit dem Druck ansteigt. Die Werte für dTc/dP betragen 28 mK, 11 mK, 22 mK und 25 mK. Sie sind in guter überein-stimmung mit früheren Messungen an zweien dieser Systeme. Für Methanol + n-Heptan stimmt der Wert für dT/dP offensichtlich nicht mit Werten, die mit Hilfe von Daten für die spezifische Wärme und die thermische Ausdehnung vorhergesagt wurden, überein.

Effect of High Pressure on the Electrical Conductivity of TlInX2 (X = Se, Te) Layered Semiconductors

The dc electrical conductivity of TlInX2 (X = Se, Te) single crystals, parallel and perpendicular to the (001) c-axis is studied under high quasi-hydrostatic pressure up to 7.0 GPa, at room temperature. Conductivity measurements parallel to the c-axis are carried out at high pressures and down to liquid nitrogen temperatures. These materials show continuous metallization under pressure. Both compounds have almost the same pressure coefficient of the electrical activation energy parallel to the c-axis, d(ΔE∥)/dP = −2.9 × 10−10 eV/Pa, which results from the narrowing of the band gap under pressure. The results are discussed in the light of the band structure of these compounds.

High Pressure NMR Study of Ammonium Thiocyanate

Wide-line proton NMR spectra of ammonium thiocyanate have been recorded at 77 K as a function of external hydrostatic pressure. Contrary to expectations the line-width and the second moment decrease with the increase of pressure. This, however, is in accordance with the anomalous behaviour observed in other magnetic resonance studies of this compound and can be understood in terms of the change of electron density around the nitrogen atom of the SCN- group.

Plasma diagnostics of the high pressure oxygen-sputtering process

The characteristics of the high pressure oxygen-sputtering plasma in the pressure range 0.8–2.4 mbar have been studied using the Langmuir probe technique. The variation in plasma parameters such as positive ion density, electron density, mean electron energy and floating potential with pressure and temperature has been investigated. It has been observed that the positive ion density increases at high substrate temperatures whereas the negative ion density decreases. The study of the variation in mean electron energy and floating potential also indicated the possibility that the number of negative ions is less when the substrates are at elevated temperatures. Since the negative ions are supposed to cause re-sputtering and make the films off-stoichiometric, the reduction in the negative ion density as observed at elevated substrate temperatures is better suited for depositing stoichiometric YBa2Cu3O7−δ superconducting thin films.

High-pressure studies on the critical composition in Ge—As—Te glasses

High-pressure resistivity measurements have been performed on G37.5AsxTe92.5-x (x = 20, 40, 45, 50 and 55) and Ge10AsxTe90-x (x = 15, 20, 35, 40, 45 and 50) glasses. The glasses show reversible metallization behaviour under pressure. The pressure derivative of the logarithm of the resistivity of the glasses is a minimum at glass compositions corresponding to the average coordination number [r] = 2.60. This behaviour is interpreted on the basis of the existence of a critical composition in glasses with a layered structure.

High pressure studies on AgI-Ag2O-MoO3 glasses

he effect of pressure on the conductivity of AgI-Ag2 O-MoO3 glasses has been reexamined. A conductivity maximum is observed around 0.7 GPa. No variation of the sample temperature is noted under pressure. The results are found to agree well with the cluster-tissue model.

High pressure study of Fe3O4 through the verwey transition

The thermopower (TEP) and electrical resistance of stoichiometric Fe3O4 crystals have been measured up to pressures of 6 GPa over the temperature range of 80-160 K. The resistance decreases markedly with increasing pressure below the Verwey transition temperature TV and TV decreases linearly with increasing pressure. The magnitude of the TEP as well as the discontinuity at TV decrease with increasing pressure. The thermopower of Fe3O4 shows an interesting upswing at low temperatures (lt;100 K) which is affected significantly by pressure.

High-pressure synchrotron X-ray diffraction study of the pyrochlores: Ho2Ti2O7, Y2Ti2O7 and Tb2Ti2O7

Synchrotron-based X-ray diffraction was used to study the phase diagrams and determine the compressibilities of the pyrochlore rare-earth titanates Ho2Ti2O7, Y2Ti2O7 and Tb2Ti2O7 to 50GPa. The bulk moduli of the cubic phase of these materials were calculated to be 213 +/- 2, 204 +/- 3 and 199 +/- 1GPa, respectively. The onset of a structural phase change from cubic to monoclinic was observed near 37, 42 and 39GPa, respectively. The bulk modulus for the high pressure monoclinic phase of Y2Ti2O7 has been determined to be 185 +/- 3GPa.

High pressure electrical measurements on Ge-Te-Se glasses

Electrical resistivity measurements have been carried out on bulk Ge-Te-Se glasses in a Bridgman anvil System. The resistivity of the Ge-Te-Se samples is found to decrease continuously with increasing pressure, with the metallization occurring around 8 GPa. Ge20TexSe80-x glasses (10 less than or equal to x less than or equal to 50) with the mean co-ordination number Z(av) = 2.4 exhibit a plateau in resistivity up to about 4 GPa pressure, followed by a continuous decrease to metallic values. On the other hand, Ge10TexSe90-x glasses (10 less than or equal to x less than or equal to 40) having Z(av) = 2.2, exhibit a smaller plateau (only up to 1 GPa), followed by a decrease in resistivity with pressure. This subtle difference in the high pressure resistivity of Ge-Te-Se glasses with Z(av) < 2.4 and Z(av) greater than or equal to 2.4 can be associated with the changes in the local structure of the chalcogenide glasses with composition.