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.

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.

Temperature and pressure evolution of the crystal structure of A(x)(Fe(1-y)Se)2 (A = Cs, Rb, K) studied by synchrotron powder diffraction.

Temperature-dependent synchrotron powder diffraction on Cs(0.83)(Fe(0.86)Se)(2) revealed first-order I4/m to I4/mmm structural transformation around 216 °C associated with a disorder of the Fe vacancies. Irreversibility observed during the transition is likely associated with a mobility of the intercalated alkali atoms. Pressure-dependent synchrotron powder diffraction on Cs(0.83)(Fe(1-y)Se)(2), Rb(0.85)(Fe(1-y)Se)(2), and K(0.8)(Fe(1-y)Se)(2) (y ~ 0.14) indicated that the I4/m superstructure reflections are present up to pressures of 120 kbar. This may indicate that the ordering of the Fe vacancies is present in both superconducting and nonsuperconductive states.

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.

High-pressure polymorphism of BaFe2Se3.

BaFe2Se3 is a potential superconductor material exhibiting transition at 11 K and ambient pressure. Here we extended the structural and performed electrical resistivity measurements on this compound up to 51 GPa and 20 GPa, respectively, in order to distinguish if the superconductivity in this sample is intrinsic to the BaFe2Se3 phase or if it is originating from minor FeSe impurities that show a similar superconductive transition temperature. The electrical resistance measurements as a function of pressure show that at 5 GPa the superconducting transition is observed at around 10 K, similar to the one previously observed for this sample at ambient pressure. This indicates that the superconductivity in this sample is most likely intrinsic to the BaFe2Se3 phase and not to FeSe with T c > 20 K at these pressures. Further increase in pressure suppressed the superconductive signal and the sample remained in an insulating state up to the maximum achieved pressure of 20 GPa. Single-crystal and powder x-ray diffraction measurements revealed two structural transformations in BaFe2Se3: a second order transition above 3.5 GPa from Pnma (CsAg2I3-type structure) to Cmcm (CsCu2Cl3-type structure) and a first order transformation at 16.6 GPa. Here, γ-BaFe2Se3 transforms into δ-BaFe2Se3 (Cmcm, CsCu2Cl3-type average structure) via a first order phase transition mechanism. This transition is characterized by a significant shortening of the b lattice parameter of γ-BaFe2Se3 (17%) and accompanied by an anisotropic expansion in the orthogonal ac plane at the transition point.

Local microscopic properties and annealing effect of Rb0.85Fe1.9Se2 single crystals.

Investigation of mesoscopically phase-separated Rb0.85Fe1.9Se2 single crystals has been performed and two iron sites: nonmagnetic and magnetic ones, were observed by Mössbauer spectroscopy. The softening of the nonmagnetic one, having clearly more soft dynamics, was found to be gained further by the annealing of the single crystals at phase separation temperature, T p, leading to the reduction of size of initially separated domains and their more homogenous distribution in the tetragonal matrix of the studied sample. The magnetic Fe sites of Rb0.85Fe1.9Se2 show strong magnetic texture, indicating the perpendicular to the ab-plane orientation of the iron magnetic moments. It was found that the annealing at T p causes a systematic decrease of the isomer shift of the doublet by 0.02(1) mm s-1.

Determination of hyperfine fields orientation in nuclear probe techniques.

One of the most popular nuclear probes, 57Fe is used for the investigation of orientations of hyperfine fields and also for the determination of other important properties. In particular, the orientation of iron magnetic moments can be unambiguously determined, including its signs. Experiments with polarized radiation are presented with regard to selected systems. Orientation of electric field gradient is used for acquiring information about the shape of the texture-free spectra. Applications on the analysis of iron-based superconductors are presented.

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.

Superconductivity in a new layered bismuth oxyselenide: LaO(0.5)F(0.5)BiSe2.

We report superconductivity at T(c) ≈ 2.6 K in a new layered bismuth oxyselenide LaO(0.5)F(0.5)BiSe2 with the ZrCuSiAs-type structure composed of alternating superconducting BiSe2 and blocking LaO layers. The superconducting properties of LaO(0.5)F(0.5)BiSe2 were investigated by means of dc magnetization, resistivity and muon-spin rotation experiments, revealing the appearance of bulk superconductivity with a rather large superconducting volume fraction of ≈ 70% at 1.8 K.

Crystal structure of BaFe2Se3 as a function of temperature and pressure: phase transition phenomena and high-order expansion of Landau potential.

BaFe2Se3 (Pnma, CsAg2I3-type structure), recently assumed to show superconductivity at ~11 K, exhibits a pressure-dependent structural transition to the CsCu2Cl3-type structure (Cmcm space group) around 60 kbar, as evidenced from pressure-dependent synchrotron powder diffraction data. Temperature-dependent synchrotron powder diffraction data indicate an evolution of the room-temperature BaFe2Se3 structure towards a high-symmetry CsCu2Cl3 form upon heating. Around 425 K BaFe2Se3 undergoes a reversible, first-order isostructural transition, which is supported by the differential scanning calorimetry data. The temperature-dependent structural changes occur in two stages, as determined by the alignment of the FeSe4 tetrahedra and corresponding adjustments of the positions of Ba atoms. On further heating, a second-order phase transformation into the Cmcm structure is observed at 660 K. A rather unusual combination of isostructural and second-order phase transformations is parameterized within phenomenological theory assuming high-order expansion of the Landau potential. A generic phase diagram mapping observed structures is proposed on the basis of the parameterization.

Intrinsic crystal phase separation in the antiferromagnetic superconductor Rb(y)Fe(2-x)Se2: a diffraction study.

The crystal and magnetic structures of the superconducting iron-based chalcogenides Rb(y)Fe(2-x)Se(2) have been studied by means of single-crystal synchrotron x-ray and high-resolution neutron powder diffraction in the temperature range 2-570 K. The ground state of the crystal is an intrinsically phase-separated state with two distinct-by-symmetry phases. The main phase has the iron vacancy ordered √5 × âˆš5 superstructure (I4/m space group) with AFM ordered Fe spins. The minority phase does not have √5 × âˆš5-type of ordering and has a smaller in-plane lattice constant a and larger tetragonal c-axis and can be well described by assuming the parent average vacancy disordered structure (I4/mmm space group) with the refined stoichiometry Rb(0.60(5))(Fe(1.10(5))Se)(2). The minority phase amounts to 8-10% mass fraction. The unit cell volume of the minority phase is 3.2% smaller than the one of the main phase at T = 2 K and has quite different temperature dependence. The minority phase merges with the main vacancy ordered phase on heating above the phase separation temperature T(P) = 475 K. The spatial dimensions of the phase domains strongly increase above T(P) from 1000 to >2500 Å due to the integration of the regions of the main phase that were separated by the second phase at low temperatures. Additional annealing of the crystals at a temperature T = 488 K, close to T(P), for a long time drastically reduces the amount of the minority phase.

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.

Room temperature antiferromagnetic order in superconducting X(y)Fe(2-x)Se2 (X = Rb, K): a neutron powder diffraction study.

Magnetic and crystal structures of superconducting X(y)Fe(2-x)Se2 (X = Rb and K with T(c) = 31.5 and 29.5 K) have been studied by neutron powder diffraction at room temperature. Both crystals show an ordered iron vacancy pattern and the crystal structure is well described by the I4/m space group with the lattice constants a = 8.799, c = 14.576 and a = 8.730, c = 14.115 Å and the refined stoichiometry x = 0.30(1), y = 0.83(2) and x = 0.34(1), y = 0.83(1) for Rb and K crystals, respectively. The structure contains one fully occupied iron position and one almost empty vacancy position. Assuming that the iron moment is ordered only on the fully occupied site we have sorted out all eight irreducible representations (irreps) for the propagation vector k = 0 and have found that irreps τ2 and τ7 fit the experimental data well with the moments along the c axis. The moment amplitudes amounted to 2.15(3) µ(B), 2.55(3) µ(B) for τ2 and 2.08(6) µ(B), 2.57(3) µ(B) for τ7 for Rb and K crystals, respectively. Irrep τ2 corresponds to the Shubnikov group I4/m' and gives a constant moment antiferromagnetic configuration, whereas τ7 does not have a Shubnikov counterpart and allows two different magnetic moments in the structure.

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.