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Substitution Effects on FeSe Superconductor

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 Added by Yoshikazu Mizuguchi
 Publication date 2009
  fields Physics
and research's language is English




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We have investigated the effect of atomic substitutions in the FeSe system, which exhibits the simplest crystal structure among the iron-based superconductors. An enhancement of the superconducting transition temperature Tc was observed with the substitution of S or Te for Se; the Tc increased with S substitution by up to 20 %, and also increased with Te substitution up to 75 %. In contrast, Co or Ni substitutions for the Fe site significantly suppressed superconductivity. In this work we present a detailed description of the substitution technique employed to determine Tc in the FeSe system.



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We have synthesized AgSn1-xBixSe2 polycrystalline samples to investigate the effect of partial substitution of mixed-valence Sn by Bi3+ to the superconductivity of the valence-skip superconductor AgSnSe2. The Bi-substituted AgSn1-xBixSe2 were obtained up to x = 0.2, but an insulating phase Ag2SnBi2Se5 with a NaCl-type structure showed up above x = 0.3. The superconducting transition temperature increased from 4.5 K (x = 0) to 5.0 K (x = 0.1) by Bi substitution. The enhancement of superconductivity by the suppression of the valence-skip states of Sn suggests that the valence-skip states of Sn are not positively linked to the pairing mechanisms of superconductivity in the AgSnSe2 system.
A polycrystalline sample of FeSe, which adopts the tetragonal PbO-type structure (P4/nmm) at room temperature, has been prepared using solid state reaction. We have investigated pressure-induced structural changes in tetragonal FeSe at varying hydrostatic pressures up to 0.6 GPa in the orthorhombic (T = 50 K) and tetragonal (T = 190 K) phases using high resolution neutron powder diffraction. We report that the structure is quite compressible with a Bulk modulus around 31 GPa to 33 GPa and that the pressure response is anisotropic with a larger compressibility along the c-axis. Key bond angles of the SeFe4 pyramids and FeSe4 tetrahedra are also determined as a function of pressure.
Recent superconducting transition temperatures (Tc) over 100 K for monolayer FeSe on SrTiO3 have renewed interest in the bulk parent compound. In KCl:AlCl3 flux-transport-grown crystals of FeSe0.94Be0.06, FeSe0.97Be0.03 and, for comparison, FeSe, this work reports doping of FeSe using Be, among the smallest of possible dopants, corresponding to an effective chemical pressure. According to lattice parameter measurements, 6% Be doping shrank the tetragonal FeSe lattice equivalent to a physical pressure of 0.75 GPa. Using this flux-transport method of sample preparation, 6% of Be was the maximum amount of dopant achievable. At this maximal composition of FeSe0.94Be0.06, the lattice unit cell shrinks by 2.4%, Tc - measured in the bulk via specific heat - increases by almost 10%, the Tc vs pressure behavior shifts its peak Tconset downwards by ~1 GPa, the high temperature structural transition around TS = 89 K increases by 1.9 K (in contrast to other dopants in FeSe which uniformly depress TS), and the low temperature specific heat gamma increases by 10 % compared to pure FeSe. Also, upon doping by 6% Be the residual resistivity ratio, rho(300K)/rho(T->0), increases by almost a factor of four, while rho(300K)/rho(T=Tc+) increases by 50%.
A detailed magnetization study for the novel FeSe superconductor is carried out to investigate the behavior of the intrinsic magnetic susceptibility $chi$ in the normal state with temperature and under hydrostatic pressure. The temperature dependencies of $chi$ and its anisotropy $Delta chi=chi_{|}-chi_{bot}$ are measured for FeSe single crystals in the temperature range 4.2-300 K, and a substantial growth of susceptibility with temperature is revealed. The observed anisotropy $Delta chi$ is very large and comparable with the averaged susceptibility at low temperatures. For a polycrystalline sample of FeSe, a significant pressure effect on $chi$ is determined to be essentially dependent on temperature. Ab initio calculations of the pressure dependent electronic structure and magnetic susceptibility indicate that FeSe is close to magnetic instability with dominating enhanced spin paramagnetism. The calculated paramagnetic susceptibility exhibits a strong dependence on the unit cell volume and especially on the height $Z$ of chalcogen species from the Fe plane. The change of $Z$ under pressure determines a large positive pressure effect on $chi$ which is observed at low temperatures. It is shown that the literature experimental data on the strong and nonmonotonic pressure dependence of the superconducting transition temperature in FeSe correlate qualitatively with calculated behavior of the density of electronic states at the Fermi level.
The ab-plane resistivity of Ba(Fe1-xRux)2As2 (x = 0.00, 0.09, 0.16, 0.21, and 0.28) was studied under nearly hydrostatic pressures, up to 7.4 GPa, in order to explore the T-P phase diagram and to compare the combined effects of iso-electronic Ru substitution and pressure. The parent compound BaFe2As2 exhibits a structural/magnetic phase transition near 134 K. At ambient pressure, progressively increasing Ru concentration suppresses this phase transition to lower temperatures at the approximate rate of ~5 K/% Ru and is correlated with the emergence of superconductivity. By applying pressure to this system, a similar behavior is seen for each concentration: the structural/magnetic phase transition is further suppressed and superconductivity induced and ultimately, for larger x Ru and P, suppressed. A detailed comparison of the T-P phase diagrams for all Ru concentrations shows that 3 GPa of pressure is roughly equivalent to 10% Ru substitution. Furthermore, due to the sensitivity of Ba(Fe1-xRux)2As2 to pressure conditions, the melting of the liquid media, 4 : 6 light mineral oil : n-pentane and 1 : 1 iso-pentane : n-pentane, used in this study could be readily seen in the resistivity measurements. This feature was used to determine the freezing curves for these media and infer their room temperature, hydrostatic limits: 3.5 and 6.5 GPa, respectively.
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