Pressure dependence of room-temperature structural properties of CaAl2Si2.

We investigated the pressure dependence of the crystal structure of CaAl2Si2 by means of ab initio calculations and room-temperature synchrotron x-ray powder diffraction. Ab initio calculations reproduce satisfactorily the experimentally observed pressure-dependent structural evolution up to 3 GPa where the title system remains in the trigonal [Formula: see text] phase. In the pressure range 3-8 GPa, pressure evolution of the calculated in-plane lattice parameters is steeper than the observed. Ab initio calculations predict a structural phase transition to a tetragonal phase ([Formula: see text] to I4/mmm) near 7.5 GPa for zero (or room) temperature. Temperature effects are included through calculation of vibrational properties (phonon spectra). These calculations confirm that both phases are either globally or locally stable (metastable) and allow for the construction of a P - T phase diagram for this system. However, our experiments show no sign of such a transition up to 12 GPa. Such a discrepancy can be explained if one considers the trigonal ([Formula: see text]) structure to be metastable above the critical pressure, but is separated from the predicted tetragonal (I4/mmm) structure by a relatively high energy barrier. The applied pressure alone may not be able to surpass the energy-barrier; rather a joint high-pressure and high-temperature (HPHT) treatment may lead to it. However, empirical verification of such a hypothetical transition may be hampered by the chemistry of CaAl2Si2 system which shows tendency to decompose peritectically into Ca2Al3Si4 and aluminum under HPHT treatment.

Quantum conductance-temperature phase diagram of granular superconductor K x Fe2-ySe2.

It is now well established that the microstructure of Fe-based chalcogenide K x Fe2-ySe2 consists of, at least, a minor (~15 percent), nano-sized, superconducting K s Fe2Se2 phase and a major (~85 percent) insulating antiferromagnetic K2Fe4Se5 matrix. Other intercalated A1-xFe2-ySe2 (A = Li, Na, Ba, Sr, Ca, Yb, Eu, ammonia, amide, pyridine, ethylenediamine etc.) manifest a similar microstructure. On subjecting each of these systems to a varying control parameter (e.g. heat treatment, concentration x,y, or pressure p), one obtains an exotic normal-state and superconducting phase diagram. With the objective of rationalizing the properties of such a diagram, we envisage a system consisting of nanosized superconducting granules which are embedded within an insulating continuum. Then, based on the standard granular superconductor model, an induced variation in size, distribution, separation and Fe-content of the superconducting granules can be expressed in terms of model parameters (e.g. tunneling conductance, g, Coulomb charging energy, E c , superconducting gap of single granule, Δ, and Josephson energy J = πΔg/2). We show, with illustration from experiments, that this granular scenario explains satisfactorily the evolution of normal-state and superconducting properties (best visualized on a [Formula: see text] phase diagram) of A x Fe2-ySe2 when any of x, y, p, or heat treatment is varied.

Linear magnetoresistivity in layered semimetallic CaAl2Si2.

According to an earlier Abrikosov model, a positive, nonsaturating, linear magnetoresistivity (LMR) is expected in clean, low-carrier-density metals when measured at very low temperatures and under very high magnetic fields. Recently, a vast class of materials were shown to exhibit extraordinary high LMR but at conditions that deviate sharply from the above-mentioned Abrikosov-type conditions. Such deviations are often considered within either classical Parish-Littlewood scenario of random-conductivity network or within a quantum scenario of small-effective mass or low carriers at tiny pockets neighboring the Fermi surface. This work reports on a manifestation of novel example of a robust, but moderate, LMR up to ∼100 K in the diamagnetic, layered, compensated, semimetallic CaAl2Si2. We carried out extensive and systematic characterization of baric and thermal evolution of LMR together with first-principles electronic structure calculations based on density functional theory. Our analyses revealed strong correlations among the main parameters of LMR and, in addition, a presence of various transition/crossover events based on which a P - T phase diagram was constructed. We discuss whether CaAl2Si2 can be classified as a quantum Abrikosov or classical Parish-Littlewood LMR system.

Manifestation of hopping conductivity and granularity within phase diagrams of LaO1-x F x BiS2, Sr1-x La x FBiS2 and related BiS2-based compounds.

Layered BiS [Formula: see text] -based series, such as LaO [Formula: see text] F [Formula: see text] BiS [Formula: see text] and Sr [Formula: see text] La [Formula: see text] FBiS [Formula: see text] , offer ideal examples for studying normal and superconducting phase diagram of a solid solution that evolves from a nonmagnetic band-insulator parent. We constructed typical [Formula: see text] phase diagrams of these systems based on events occurring in thermal evolution of their electrical resistivity, [Formula: see text]. Overall evolution of these diagrams can be rationalized in terms of (i) Mott-Efros-Shklovskii scenario which, within the semiconducting [Formula: see text] regime ([Formula: see text] metal-insulator transition), describes the doping influence on the thermally activated hopping conductivity. (ii) A granular metal (superconductor) scenario which, within [Formula: see text], describes the evolution of normal and superconducting properties in terms of conductance g, Coulomb charging energy E c and Josephson coupling J; their joint influence is usually captured within a [Formula: see text] phase diagram. Based on analysis of the granular character of [Formula: see text], we converted the [Formula: see text] diagrams into projected g - T diagrams which, being fundamental, allow a better understanding of evolution of various granular-related properties (in particular the hallmarks of normal-state [Formula: see text] feature and superconductor-insulator transition) and how such properties are influenced by x, pressure or heat treatment.

Pressure-dependent magnetization and magnetoresistivity studies on tetragonal FeS (mackinawite): revealing its intrinsic metallic character.

The transport and magnetic properties of the tetragonal Fe[Formula: see text]S were investigated using magnetoresistivity and magnetization within [Formula: see text] K, [Formula: see text] 70 kOe and [Formula: see text] 3.0 GPa. In addition, room-temperature x-ray diffraction and photoelectron spectroscopy were also applied. In contrast to previously reported nonmetallic character, Fe[Formula: see text]S is intrinsically metallic but due to a presence of a weak localization such metallic character is not exhibited below room temperature. An applied pressure reduces strongly this additional resistive contribution and as such enhances the temperature range of the metallic character which, for ∼3 GPa, is evident down to 75 K. The absence of superconductivity as well as the mechanism behind the weak localization will be discussed.

Resistivity studies on the layered semi-metallic CaAl2Si2: evaluating its temperature-, field- and pressure-dependence.

We studied the layered, hexagonal, semi-metal CaAl(2)Si(2) by magnetization, specific heat and resistivity measurements over a wide range of temperature, pressure and magnetic field. Both the Sommerfeld coefficient (γ = 1 mJ mol(-1) K(-2)) and the Debye temperature (θ(D) = 288 K) are in agreement with the values obtained from the band structure calculation. The resistivity shows a metallic character up to 200 K, followed by saturation and, afterwards, a weak decrease up to 840 K, at which it sharply rises reaching a local maximum at 847 ± 5 K. While the low-temperature thermal evolution was accounted for in terms of intrinsic and extrinsic effects, the additional high-temperature scattering was attributed, based on differential thermal analysis, to a first-order thermal event. No appreciable magnetoresistivity was observed at liquid helium temperatures even for fields up to 90 kOe, indicating an absence of coupling between the electronic and magnetic degrees of freedom. Finally, an externally applied pressure was found to induce a strong reduction in the resistivity following a second-order polynomial: this effect will be discussed in terms of the influence of pressure on the effective mobility and concentration of charge carriers.

On the ferromagnetic structure of the intermetallic borocarbide TbCo(2)B(2)C.

Based on magnetization, specific heat, magnetostriction and neutron-diffraction studies on single-crystal TbCo(2)B(2)C, it is found out that the paramagnetic properties, down to liquid nitrogen temperatures, are well described by a Curie-Weiss behavior of the Tb(3+) moments. Furthermore, below T(c) = 6.3 K, the Tb sublattice undergoes a ferromagnetic (FM) phase transition with the easy axis being along the (100) direction and, concomitantly, the unit cell undergoes a tetragonal-to-orthorhombic distortion. The manifestation of an FM state in TbCo(2)B(2)C is unique among all other isomorphous borocarbides, in particular TbNi(2)B(2)C (T(N) = 15 K, incommensurate modulated magnetic state) even though the Tb ions in both isomorphs have almost the same crystalline electric field properties. The difference among the magnetic modes of these Tb-based isomorphs is attributed to a difference in their exchange couplings which are in turn caused by a variation in their lattice parameters and in the position of their Fermi levels.

Magnetic structures of quaternary intermetallic borocarbides RCo(2)B(2)C (R = Dy, Ho, Er).

The magnetic structures of the title compounds have been studied by neutron diffraction. In contrast to the isomorphous RNi(2)B(2)C compounds, wherein a variety of exotic incommensurate modulated structures has been observed, the magnetic structure of ErCo(2)B(2)C is found to be a collinear antiferromagnet with [Formula: see text] while those of HoCo(2)B(2)C and DyCo(2)B(2)C are observed to be simple ferromagnets. For all studied compounds, the moments are found to be confined within the basal plane and their magnitudes are comparable to the values obtained from the low-temperature isothermal magnetization measurements. The absence of modulated magnetic structures in the RCo(2)B(2)C series (for ErCo(2)B(2)C, verified down to 50 mK) is attributed to the quenching of the Fermi surface nesting features.

Low-temperature magnetic and transport properties of single-crystal CeCoGe.

The low-temperature properties of single-crystal CeCoGe were investigated by specific heat C(T,H), magnetoresistivity ρ(T,H), and differential susceptibility measurements χ(T,H). The zero-field low-temperature specific heat evolves as C = γT+ßT(3) = 42T+23.5T(3) mJ mol(-1) K(-1). On comparing its γ = 42 mJ mol(-1) K(-1) with that of LaCoGe (12 mJ mol(-1) K(-2)) it is inferred that both 3d (Co) and 4f (Ce) orbitals contribute to the density of states at the Fermi level. Assuming that its phonic contribution to the specific heat is similar to LaCoGe (ß = 0.5 mJ mol(-1) K(-4)), then the extra cubic term in the specific heat (23T(3) mJ mol(-1) K(-1)) must be due to magnon excitation within the antiferromagnetically ordered state, T