Phase transitions in cerium at high pressures (up to 15 GPa) and high temperatures

Phase transitions in cerium have been studied by the electrical resistance method in the 15-GPa pressure range at high temperatures. At pressures above 10 GPa, cerium represents a mixture of stable and metastable phases, the composition of this mixture being dependent on the trajectory in the P-T plane that leads to a given point. Transformations in both stable and metastable components of the mixture proceeding rather independently display a complicated picture of phase transitions. It was assumed that only the α (fcc) and α′ (α-U) phases are stable at pressures above the well-known γ-α transition, the other phases being metastable. The proposed bow-shaped equilibrium phase diagram includes an extremely wide hysteresis region, where stable and metastable phases can coexist. The fcc α phase alone survives upon heating above 50°C at 15 GPa.     

Synthesis and investigation of titanium diselenide intercalated with ferrocene and cobaltocene

Single crystals and polycrystals of titanium diselenide TiSe₂ intercalated with ferrocene Fe(η⁵-C₅H₅)₂ and cobaltocene Co(η⁵-C₅H₅)₂ are synthesized. The magnetic susceptibility and electrical resistivity of the intercalation compounds are measured. The results obtained demonstrate that the intercalation brings about the formation of an impurity band with a temperature-dependent width.     

Thermo-and galvanomagnetic properties of lead chalcogenides at high pressures up to 20 GPa

The Nernst-Ettingshausen (NE) effect in the initial NaCl and high-pressure GeS phases was studied at a high pressure P for n-PdTe, p-PbSe, and p-PbS to estimate the mobility µ and the charge-carrier scattering parameter r. It was found that the transverse and longitudinal NE effects in PbTe and PbSe increase with pressure, indicating the transition to the gapless state near P≈3 GPa. The sign of the transverse NE effect changes because of the change in the electron scattering mechanism in the GeS phase. The experimentally observed weakening of the NE and magnetoresistance effects at high P gives evidence for the indirect energy gap E_g in the high pressure phases with GeS structure.     

Magnetoresistance and thermopower of tellurium at high pressures up to 30 GPa

Measurements are reported of the transverse magnetoresistance MR and of the thermopower S, carried out at high pressures P on Te single crystals in synthetic-diamond chambers. The MR is found to increase with decreasing gas width under a pressure up to 4 GPa as one approaches the semiconductor-metal phase-transition point, to fall off subsequently in the high-pressure metallic phase. The behavior of S(P) correlates with the pressure dependences of the measured MR. A negative MR at T=77 K was found within a narrow interval P=1.5–2 GPa, where the valence band of Te is assumed to undergo rearrangement. Above the point of the phase transition to the β-Po structure, MR is established to increase with pressure for P>12 GPa. The MR data are used to estimate the hole mobility μ for various Te phases. A comparison is made of the mobilities in Te, Se, and high-pressure phases of mercury chalcogenides, which are their structural and electronic analogs, for pressures of up to 30 GPa.     

Magnetic susceptibility of titanium diselenide intercalated with copper

The temperature dependence of the magnetic susceptibility of Cu _x TiSe₂ polycrystalline samples has been measured. The electron density of states near the Fermi level N(E _F) in the Pauli model of paramagnetism has been calculated and discussed. The concentration dependences of the density of states N(E _F) and the unit cell parameter in the direction perpendicular to the layers in Cu _x TiSe₂ correlate with the concentration of centers V-Ti-Cu and Cu-Ti-V (V is the vacancy).     

Thermoelectric study of the phase transitions in cerium at ultrahigh pressures from 0 to 20 GPa

The pressure dependences of the thermoelectric power S of Ce samples were measured at pressures P from 0 to 20 GPa in a synthetic diamond cell. The dependence of S on P was found to be nonmonotonic both in the region of transitions from the fcc (γ) phase to the modified fcc (α) phase followed by the transition to the body-centered monoclinic (α″) and the tetragonal (ε) phases at pressures of about 1, 5–6, and 12–15 GPa, respectively, and in the stability region of these phases. The thermoelectric power sign was found to be positive for all high-pressure Ce phases. The found S(P) dependence was compared with the published computational data on the electronic structure of the cerium phases. Cerium was taken as an example to demonstrate the advantage of the thermoelectric studies over other methods of investigation of phase transitions.     

Phase transitions in PbTe under quasi-hydrostatic pressure up to 50 GPa

PbTe has been investigated using synchrotron X-ray diffraction (XRD) in a diamond anvil cell under quasi-hydrostatic pressures up to 50 GPa. Upon compression to 6.6 GPa, the initial NaCl phase transforms to an intermediate phase, which is confirmed to be an orthorhombic structure with a space group Pnma. At 18.4 GPa, the intermediate Pnma phase undergoes a phase transition to the CsCl structure. The systemic analysis of the crystal structures between the NaCl and intermediate phases indicates that the structure of the Pnma phase could be derived from the distortion of the NaCl structure. The bulk modulus of the CsCl phase is B₀=52(2) GPa with V₀=60.8(4) ų and B′₀=4.0 (fixed), slightly larger than the NaCl phase (B₀=44(1) GPa) and the intermediate phase (B₀=49(3) GPa).     

Phase transitions of lanthanide monophosphides with NaCl-type structure at high pressures

Lanthanide monophosphides LnP (Ln = La, Ce, Pr, Nd, Sm, Gd, Tb, Tm and Yb) with a NaCl-type structure have systematically been prepared at high temperatures. Using synchrotron radiation, X-ray diffractions of LnP have been studied up to 61 GPa at room temperature. The NaCl---CsCl transition for CeP is found at around 25 GPa. First-order phase transitions of LnP (Ln = La, Pr and Nd) with the crystallographic change occur at around 24, 26 and 30 GPa, respectively. The structure of the high pressure phases of these phosphides is a body center tetragonal structure (Ln: 0, 0, 0; P: 1/2, 1/2, 1/2; space group P4/mmm), which can be seen as the distorted CsCl-type structure. The Pr---P distance in the high pressure form of PrP is 2.789 Å. This almost agrees with the sum of covalent radii of Pr and P. The Pr---P bond has the covalent character at very high pressures. Similar results are also obtained for LaP and NdP. The pressure-induced phase transitions of SmP, GdP, TbP, TmP and YbP occur at around 35, 40, 38, 53 and 51 GPa, respectively. The structure of the high pressure phase is unknown. The phase transitions of LnP with many f-electrons are not due to the mechanism of the ordinary NaCl---CsCl transition. The transition pressures of LnP increase with decreasing the lattice constants in the NaCl-type structure, which decrease with increasing atomic number of the lanthanide atoms.     

Structural phase transitions in Si and Ge under pressures up to 50 GPa

The crystal structures of Si and Ge were studied by energy dispersive X-ray diffraction at room temperature and pressures up to 50 GPa. Si transforms to a primitive hexagonal (Si-V) structure around 16 GPa, to an intermediate phase Si-VI between 35 and 40 GPa, and to hcp (Si-VII) around 40 GPa. In contrast, Ge remains in the β-tin structure up to at least 51 GPa. The pseudopotential method reproduces these differences in the high-pressure behavior of Si and Ge.     

Superconductivity of tin selenide at pressures up to 70 GPa

We report the discovery of superconductivity in SnSe with T _c around 4.5 K at pressures exceeding 58 GPa. It is conjectured that the high-pressure superconducting modification has the CsCl structure. Fiz. Tverd. Tela (St. Petersburg) 39, 236 (February 1997)     

Phase transitions in uranium dioxide at high pressures and temperatures

The melting curve is plotted for uranium dioxide with fluorite structure in a pressure range from ?2.5 to +100 GPa. This curve has a peak at the point 3348 K, 6 GPa, and has a negative derivative at high pressures. The pressure corresponding to a polymorphic transition of uranium dioxide (37 GPa) at a temperature of 1015 K is determined. The slope of the equilibrium curve of the polymorphic transition in UO₂ in the temperature range 300–1000 K is ? 56 K/GPa.     

Structure of liquid iron at pressures up to 58 GPa

We report structural data on liquid iron at pressures up to 58 GPa measured by x-ray scattering in a laser heated diamond anvil cell. The determined structure factor preserves essentially the same shape along the melting curve. Our data demonstrate that liquid iron at high pressures is a close-packed hard-sphere liquid. The results place important constraints on the thermodynamic and transport properties of liquid iron and the melting curve of iron.     

Electrical and magnetic properties of titanium diselenide intercalated with cobalt

This paper discusses experimental studies of the temperature dependence of the magnetic susceptibility, electrical conductivity, and Seebeck coefficient of the compounds Co_xTiSe₂ (0.1⩽x⩽0.5), along with the structural behavior exhibited by these compounds. For Co_0.5TiSe₂, the observed temperature dependence of the magnetic susceptibility is characteristic of an antiferromagnet with a Néel temperature of 510 K. The data obtained on the structural characteristics and physical properties of the intercalated phases are interpreted using a model that assumes the formation of bands of localized states near the Fermi level. Fiz. Tverd. Tela (St. Petersburg) 39, 1618–1621 (Sepember 1997)     

Structure and physical properties of titanium diselenide intercalated with nickel

The structure, electrical resistivity, thermopower, and magnetic susceptibility of titanium diselenide intercalated with nickel (N_xTiSe₂) are studied systematically in the nickel concentration range x=0–0.5. In accordance with a model proposed earlier, strong hybridization of the Ni3d/Ti3d states is observed, giving rise to suppression of the magnetic moment because of delocalization of the nickel d electrons. It is shown that the strain caused by the Ni3d/Ti3d hybridization does not change the local coordination of a titanium atom.     

Conductivity of double-walled carbon nanotubes at pressures of up to 30 GPa

Results from experimental studies of the electrical resistance of double-walled carbon nanotubes (DWNTs) in conducting diamond high-Pressure chambers at pressures of up to 30 GPa and room temperature are presented. The effect pressure has on the structure of the outer and inner tubes is analyzed. Ranges of pressure are found in which the electrical resistance of DWNTs changes considerably.     

Magnetoresistance of HgSeS crystals at hydrostatic pressures of up to 1 GPa

Magnetoresistance (MR) of HgSe_1−x S_x crystals has been studied in the temperature range 4.2–300 K and in magnetic fields up to 12 T under hydrostatic pressures P exceeding the threshold P _t for the structural phase transition. Shubnikov-de Haas quantum oscillations in longitudinal and transverse MR were observed to occur in the original samples at T=4.2 K. For P>P _t, HgSeS crystals transferred to metastable states, which presumably incorporate the high-and low-pressure phases, and in which the oscillations vanished. At the same time the monotonic behavior of MR with magnetic field B, as well as the temperature dependences of resistivity ρ retained the shape characteristic of the original phases. The observed weakening of the dependences of ρ on B and T is attributed to an increase of the temperature independent contribution to ρ caused by phase inclusions and structural defects in the metastable states. It is the corresponding decrease of electron mobility that suppresses the oscillations. Fiz. Tverd. Tela (St. Petersburg) 39, 1717–1722 (October 1997)