Superconductivity in alkali metal intercalated iron selenides.

Alkali metal intercalated iron selenide superconductors A x Fe2-y Se2 (where A = K, Rb, Cs, Tl/K, and Tl/Rb) are characterized by several unique properties, which were not revealed in other superconducting materials. The compounds crystallize in overall simple layered structure with FeSe layers intercalated with alkali metal. The structure turned out to be pretty complex as the existing Fe-vacancies order below ~550 K, which further leads to an antiferromagnetic ordering with Néel temperature fairly above room temperature. At even lower temperatures a phase separation is observed. While one of these phases stays magnetic down to the lowest temperatures the second is becoming superconducting below ~30 K. All these effects give rise to complex relationships between the structure, magnetism and superconductivity. In particular the iron vacancy ordering, linked with a long-range magnetic order and a mesoscopic phase separation, is assumed to be an intrinsic property of the system. Since the discovery of superconductivity in those compounds in 2010 they were investigated very extensively. Results of the studies conducted using a variety of experimental techniques and performed during the last five years were published in hundreds of reports. The present paper reviews scientific work concerning methods of synthesis and crystal growth, structural and superconducting properties as well as pressure investigations.

Dispersive x-ray absorption studies at the Fe K-edge on the iron chalcogenide superconductor FeSe under pressure.

The local structure and the electronic properties of FeSe under hydrostatic pressure were studied by means of dispersive x-ray absorption measurements at the Fe K-edge. The pressure dependence of the x-ray absorption near edge structure features seems to follow the behavior of the superconducting transition temperature Tc. The local structure, that has an important impact on the superconducting properties, appears to fall into two regimes: the pressure dependence of the Fe-Fe bond distance shows a clear change in the compressibility at p ∼ 5 GPa; in contrast, the Fe-Se bond distance decreases continuously with increasing pressure with a lower compressibility than the Fe-Fe bond. The results suggest that the pressure dependent changes in Tc of FeSe are closely related to the changes in local structure.

Two-dimensional superfluid density in an alkali metal-organic solvent intercalated iron selenide superconductor Li(C5H5N)0.2Fe2Se2.

We report the low-temperature electronic and magnetic properties of the alkali metal-organic solvent intercalated iron selenide superconductor Li(C5H5N)0.2Fe2Se2 using muon-spin-spectroscopy measurements. The zero-field muon spin relaxation (µSR) results indicate that nearly half of the sample is magnetically ordered and spatially phase separated from the superconducting region. The transverse-field µSR results reveal that the superfluid density of Li(C5H5N)0.2Fe2Se2 is two dimensional in nature. The temperature dependence of the penetration depth λ(T) can be explained using a two-gap s-wave model. This implies that, despite the 2D nature of the superfluid density, the symmetry of the superconducting gap remains unaltered to the parent compound FeSe.

Synthesis of a new alkali metal-organic solvent intercalated iron selenide superconductor with Tc ≈ 45 K.

We report on a new iron selenide superconductor with a T(c) onset of 45 K and the nominal composition Li(x)(C(5)H(5)N)(y)Fe(2-z)Se(2), synthesized via intercalation of dissolved alkaline metal in anhydrous pyridine at room temperature. This superconductor exhibits a broad transition, reaching zero resistance at 10 K. Magnetization measurements reveal a superconducting shielding fraction of approximately 30%. Analogous phases intercalated with Na, K and Rb were also synthesized and characterized. The superconducting transition temperature of Li(x)(C(5)H(5)N)(y)Fe(2-z)Se(2) is clearly enhanced in comparison to those of the known superconductors FeSe(0.98) (T(c) ~ 8 K) and A(x)Fe(2-y)Se(2) (T(c) ~ 27-32 K) and is in close agreement with critical temperatures recently reported for Li(x)(NH(3))(y)Fe(2-z)Se(2). Post-annealing of intercalated material (Li(x)(C(5)H(5)N)(y)Fe(2-z)Se(2)) at elevated temperatures drastically enlarges the c-parameter of the unit cell (~44%) and increases the superconducting shielding fraction to nearly 100%. Our findings indicate a new synthesis route leading to possibly even higher critical temperatures for materials in this class: by intercalation of organic compounds between Fe-Se layers.

The synthesis, and crystal and magnetic structure of the iron selenide BaFe2Se3 with possible superconductivity at Tc = 11 K.

We report on the synthesis of single crystals of BaFe(2)Se(3) and study their crystal and magnetic structures by means of synchrotron single-crystal x-ray and neutron powder diffraction. The crystal structure has orthorhombic symmetry and consists of double chains of FeSe(4) edge connected tetrahedra intercalated with barium. Below 240 K, long range spin-block checkerboard antiferromagnetic order is developed. The magnetic structure is similar to one observed in A(0.8)Fe(1.6)Se(2) (A = K, Rb or Cs) superconductors. The crystals exhibit a transition to the diamagnetic state with an onset transition temperature of T(c) ∼ 11 K. Though we observe FeSe as an impurity phase (<0.8% mass fraction) it is not likely that the diamagnetism is attributable to the FeSe superconductor, which has T(c) ≈ 8.5 K.

Coexistence of magnetism and superconductivity in the iron-based compound Cs0.8(FeSe0.98)2.

We report on muon-spin rotation and relaxation (µSR), electrical resistivity, magnetization and differential scanning calorimetry measurements performed on a high-quality single crystal of Cs(0.8)(FeSe(0.98))(2). Whereas our transport and magnetization data confirm the bulk character of the superconducting state below T(c)=29.6(2) K, the µSR data indicate that the system is magnetic below T(N)=478.5(3) K, where a first-order transition occurs. The first-order character of the magnetic transition is confirmed by differential scanning calorimetry data. Taken all together, these data indicate in Cs(0.8)(FeSe(0.98))(2) a microscopic coexistence between the superconducting phase and a strong magnetic phase. The observed T(N) is the highest reported to date for a magnetic superconductor.

Synthesis and crystal growth of Cs(0.8)(FeSe(0.98))(2): a new iron-based superconductor with T(c) = 27 K.

We report on the synthesis of large single crystals of a new FeSe layer superconductor Cs(0.8)(FeSe(0.98))(2). X-ray powder diffraction, neutron powder diffraction and magnetization measurements have been used to compare the crystal structure and the magnetic properties of Cs(0.8)(FeSe(0.98))(2) with those of the recently discovered potassium intercalated system K(x)Fe(2)Se(2). The new compound, Cs(0.8)(FeSe(0.98))(2), shows a slightly lower superconducting transition temperature (T(c) = 27.4 K) in comparison to 29.5 in (K(0.8)(FeSe(0.98))(2)). The volume of the crystal unit cell increases by replacing K by Cs-the c parameter grows from 14.1353(13) to 15.2846(11) Å. For the alkali metal intercalated layered compounds known so far, (K(0.8)Fe(2)Se(2) and Cs(0.8)(FeSe(0.98))(2)), the T(c) dependence on the anion height (distance between Fe layers and Se layers) was found to be analogous to those reported for As-containing Fe superconductors and Fe(Se(1 - x)Ch(x)), where Ch = Te, S.