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1.
Inorg Chem ; 56(14): 8590-8595, 2017 Jul 17.
Article in English | MEDLINE | ID: mdl-28657309

ABSTRACT

We have succeeded in crystallizing a new strontium digermanide (SrGe2-δ) with the ThSi2-type structure (tetragonal SrGe2), which is theoretically predicted to compete with the EuGe2-type one (trigonal SrGe2) under pressure. The tetragonal SrGe2 appeared as a metastable phase in samples at approximately 900 °C under a pressure of 2 GPa. X-ray diffraction studies show that the tetragonal SrGe2 is formed by the reaction between trigonal SrGe2 and excess Sr. The composition of the tetragonal SrGe2 was analyzed to be SrGe1.66(4). Lattice parameters for the tetragonal SrGe2 are determined to be a = 4.559(4) Å and c = 14.42(1) Å. The tetragonal SrGe2 shows metallic resistivity behavior and exhibits superconductivity with a critical temperature (Tc) of 7.3 K, which is the highest among compounds with the ThSi2-type structure. Superconducting properties of the tetragonal SrGe2, such as the upper critical field, and the effect of pressure on Tc, are presented and superconductivity is discussed on the basis of electronic band structure calculations.

2.
Nat Commun ; 6: 8990, 2015 Dec 01.
Article in English | MEDLINE | ID: mdl-26619829

ABSTRACT

How to enhance the superconducting critical temperature (Tc) has been a primary issue since the discovery of superconductivity. The highest Tc reported so far is 166 K in HgBa2Ca2Cu3O8+δ (Hg1223) at high pressure of 23 GPa, as determined with the reduction onset, but not zero, of resistivity. To clarify the possible condition of the real maximum Tc, it is worth revisiting the effects of pressure on Tc in the highest Tc family. Here we report a systematic study of the pressure dependence of Tc in HgBa2CaCu2O6+δ (Hg1212) and Hg1223 with the doping level from underdoped to overdoped. The Tc with zero resistivity is probed with a cubic-anvil-type apparatus that can produce hydrostatic pressures. Variation, not only increase but also decrease, of Tc in Hg1212 and Hg1223 with pressure strongly depends on the initial doping levels. In particular, we confirm a maximum Tc of 153 K at 22 GPa in slightly underdoped Hg1223.

3.
Sci Rep ; 5: 10089, 2015 May 12.
Article in English | MEDLINE | ID: mdl-25965162

ABSTRACT

The Matthias rule, which is an empirical correlation between the superconducting transition temperature (Tc) and the average number of valence electrons per atom (n) in alloys and intermetallic compounds, has been used in the past as a guiding principle to search for new superconductors with higher Tc. The intermetallic compound SrBi3 (AuCu3 structure) exhibits a Tc of 5.6 K. An ab-initio electronic band structure calculation for SrBi3 predicted that Tc increases on decreasing the Fermi energy, i.e., on decreasing n, because of a steep increase in the density of states. In this study, we demonstrated that high-pressure (~ 3 GPa) and low-temperature ( < 350 °C) synthesis conditions enables the substitution of Na for about 40 at.% of Sr. With a consequent decrease in n, the Tc of (Sr,Na)Bi3 increases to 9.0 K. A new high-Tc peak is observed in the oscillatory dependence of Tc on n in compounds with the AuCu3 structure. We have shown that the oscillatory dependence of Tc is in good agreement with the band structure calculation. Our experiments reaffirm the importance of controlling the number of electrons in intermetallic compounds.

4.
J Am Chem Soc ; 134(37): 15181-4, 2012 Sep 19.
Article in English | MEDLINE | ID: mdl-22934791

ABSTRACT

The effect of alloying the two perovskite-type iron-based superconductors (Ca(4)Al(2)O(6))(Fe(2)As(2)) and (Ca(4)Al(2)O(6))(Fe(2)P(2)) was examined. While the two stoichiometric compounds possess relatively high T(c)'s of 28 and 17 K, respectively, their solid solutions of the form (Ca(4)Al(2)O(6))(Fe(2)(As(1-x)P(x))(2)) do not show superconductivity over a wide range from x = 0.50 to 0.95. The resultant phase diagram is thus completely different from those of other typical iron-based superconductors such as BaFe(2)(As,P)(2) and LaFe(As,P)O, in which superconductivity shows up when P is substituted for As in the non-superconducting "parent" compounds. Notably, the solid solutions in the non-superconducting range exhibit resistivity anomalies at temperatures of 50-100 K. The behavior is reminiscent of the resistivity kink commonly observed in various non-superconducting parent compounds that signals the onset of antiferromagnetic/orthorhombic long-range order. The similarity suggests that the suppression of the superconductivity in the present case also has a magnetic and/or structural origin.

5.
Science ; 323(5921): 1585-90, 2009 Mar 20.
Article in English | MEDLINE | ID: mdl-19299615

ABSTRACT

The body-centered cubic A15-structured cesium fulleride Cs3C60 is not superconducting at ambient pressure and is free from disorder, unlike the well-studied face-centered cubic A3C60 alkali metal fulleride superconductors. We found that in Cs3C60, where the molecular valences are precisely assigned, the superconducting state at 38 kelvin emerges directly from a localized electron antiferromagnetic insulating state with the application of pressure. This transition maintains the threefold degeneracy of the active orbitals in both competing electronic states; it is thus a purely electronic transition to a superconducting state, with a dependence of the transition temperature on pressure-induced changes of anion packing density that is not explicable by Bardeen-Cooper-Schrieffer (BCS) theory.

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