Topotactic synthesis of a new BiS2-based superconductor Bi2(O,F)S2

A new BiS2-based superconductor Bi2(O,F)S2 was discovered. This is a layered compound consisting of alternate stacking structure of rock-salt-type BiS2 superconducting layer and fluorite-type Bi(O,F) blocking layer. Bi2(O,F)S2 was obtained as the main phase by topotactic fluorination of undoped Bi2OS2 using XeF2, which is the first topotactic synthesis of an electron-doped superconductor via reductive fluorination. With increasing F-content, a- and c-axis length increased and decreased, respectively, and Tc increased up to 5.1 K.Comment: 9 pages, 4 figure

New iron-based arsenide oxides (Fe2As2)(Sr4M2O6)(M = Sc, Cr)

We have discovered new layered oxyarsenides (Fe2As2)(Sr4M2O6) (M = Sc, Cr: M-22426). These materials are isostructural with (Fe2P2)(Sr4Sc2O6), which was found in our previous study. The new compounds are tetragonal with a space group of P4/nmm and consist of the anti-fluorite type FeAs layer and perovskite-type blocking layer. The lattice constants are a = 4.050 A, c = 15.809 A for M = Sc and a = 3.918 A, c = 15.683 A for M = Cr. These compounds have long interlayer Fe-Fe distances corresponding to the c-axis length, the 15.8 A in Sc-22426 is the longest in the iron-based oxypnictide systems. Chemical flexibility of the perovskite block in this system was probed by chromium containing (Fe2As2)(Sr4Cr2O6). Different trends were found in bond angle and bond length of the new oxypnictides compared to the reported systems, such as REFePnO. Absence of superconductivity in these compounds is considered to be due to insufficient carrier concentration as in the case of undoped REFeAsO.Comment: 7 pages, 5 figures, 1 tabl

Strongly connected ex-situ MgB2 polycrystalline bulks fabricated by solid-state self-sintering

We have investigated the microstructure, normal-state electrical connectivity, and critical current density of ex-situ MgB2 polycrystalline bulks prepared by systematically varying the sintering conditions under low pressure. Samples heated at a high temperature of ~900{\deg}C for a long period showed an increased packing factor, a larger intergrain contact area, and a significantly enhanced electrical connectivity, all of which indicate solid-state self-sintering of MgB2. Sintered ex-situ MgB2 bulks from a laboratory-made ball-milled powder exhibited a greatly enhanced connectivity of 28%, which is the highest connectivity of pressureless ex-situ MgB2 bulks, wires, and tapes. Surprisingly, grain growth did not occur during long-duration (~100 h) sintering in the sintered ex-situ MgB2 bulks. This is in marked contrast to in-situ processed MgB2 samples for which significant grain growth occurred during heat treatment at ~900{\deg}C, producing grains that are several tens of times larger than the initial boron grains. Consequently, the critical current density as a function of the external magnetic field at 20 K progressively improved with sintering due to the relatively small grain size and good intergrain connectivity. We thus conclude that solid-state self-sintering is an effective approach for producing strongly connected, dense ex-situ MgB2 polycrystals without grain growth.Comment: 21 pages, 9 figures, to be published in Supercond. Sci. Techno

Superconductivity Above 40 K Observed in a New Iron Arsenide Oxide (Fe2As2)(Ca4(Mg,Ti)3Oy)

A new layered iron arsenide oxide (Fe2As2)(Ca4(Mg,Ti)3Oy) was discovered. Its crystal structure is tetragonal with a space group of I4/mmm consisted of the anti-fluorite type FeAs layer and blocking layer of triple perovskite cells and is identical with (Fe2As2)(Sr4(Sc,Ti)3O8) discovered in our previous study. The lattice constants of (Fe2As2)(Ca4(Mg,Ti)3Oy) are a = 3.877 A and c = 33.37 A. This compound exhibited bulk superconductivity up to 43 K in susceptibility measurement without intentional carrier doping. A resistivity drop was observed at ~47 K and zero resistance was achieved at 42 K. These values correspond to the second highest Tc among the layered iron-based superconductors after REFeAsO system

New Series of Nickel-Based Pnictide Oxide Superconductors (Ni2Pn2)(Sr4Sc2O6) (Pn = P, As)

We have discovered new nickel-based pnictide oxide superconductors, (Ni2Pn2)(Sr4Sc2O6) (Pn = P, As). These compounds have a tetragonal unit cell with a space group of P4/nmm and they consist of alternate stacking of anti-fluorite Ni2Pn2 layers and K2NiF4-type Sr4Sc2O6 blocking layers. Lattice parameters were a = 4.044 A and c = 15.23 A for (Ni2P2)(Sr4Sc2O6) and a = 4.078 A and c = 15.41 A for (Ni2As2)(Sr4Sc2O6), indicating their thicker blocking layers than that of LaNiPO (c ~ 8.1 A). Both (Ni2P2)(Sr4Sc2O6) and (Ni2As2)(Sr4Sc2O6) exhibited superconductivity with zero resistivity at 3.3 K and 2.7 K, respectively. The perfect diamagnetism observed in both compounds guaranteed their bulk superconductivity.Comment: 4 pages, 3 figures, 1 tabl

Co-co-doping effect for (Ca,RE)FeAs2 sintered bulk

Superconducting properties of Co-co-doped (Ca,RE)FeAs2 ((Ca,RE)112: RE = La, Pr) were investigated. Co-co-doping increased Tc of (Ca,Pr)112 while Mn-co-doping suppressed superconductivity of (Ca,RE)112. Co-co-doped (Ca,La)112 showed large diamagnetic screening and sharper superconducting transition than Co-free (Ca,La)112. Tczero observed in resistivity measurements increased from 14 K to 30 K by Co-co-doping, while Tconset was not increased. The critical current density (Jc) of Co-co-doped (Ca,La)112 were approximately 2.1 x 104 Acm-2 and 3.2 x 103 Acm-2 at 2 K and 25 K, respectively, near zero field. These relatively high Jcs and large diamagnetic screening observed in susceptibility measurement as for polycrystalline bulks suggest bulk superconductivity of Co-co-doped (Ca,RE)112 compounds

First Homologous Series of Iron Pnictide Oxide Superconductors (Fe2As2)(Can+1(Sc,Ti)nOy) [n = 3,4,5] with Extremely Thick Blocking Layers

We have discovered first homologous series of iron pnictide oxide superconductors (Fe2As2)(Can+1(Sc,Ti)nOy) [n = 3,4,5]. These compounds have extremely thick blocking layers up to quintuple perovskite oxide layers sandwiched by the Fe2As2 layers. These samples exhibited bulk superconductivity with relatively high Tc up to 42 K. The relationship between Tc and the iron-plane interlayer distance suggested that superconductivity due to the mono Fe2As2 layer is substantially 40 K-class.Comment: 11pages, 5figure

Effects of post-annealing and cobalt co-doping on superconducting properties of (Ca,Pr)Fe2As2 single crystals

In order to clarify the origin of anomalous superconductivity in (Ca,RE)Fe2As2 system, Pr doped and Pr,Co co-doped CaFe2As2 single crystals were grown by the FeAs flux method. These samples showed two-step superconducting transition with Tc1 = 25~42 K, and Tc2 < 16 K, suggesting that (Ca,RE)Fe2As2 system has two superconducting components. Post-annealing performed for these crystals in evacuated quartz ampoules at various temperatures revealed that post-annealing at ~400{\deg}C increased the c-axis length for all samples. This indicates that as-grown crystals have a certain level of strain, which is released by post-annealing at ~400{\deg}C. Superconducting properties also changed dramatically by post-annealing. After annealing at 400{\deg}C, some of the co-doped samples showed large superconducting volume fraction corresponding to the perfect diamagnetism below Tc2 and high Jc values of 104~105 Acm-2 at 2 K in low field, indicating the bulk superconductivity of (Ca,RE)Fe2As2 phase occurred below Tc2. On the contrary, the superconducting volume fraction above Tc2 was always very small, suggesting that 40 K-class superconductivity observed in this system is originating in the local superconductivity in the crystal

Second Homologous Series of Iron Pnictide Oxide Superconductors (Fe2As2)(Can+2(Al,Ti)nOy)[n = 2,3,4]

We have discovered a new homologous series of iron pnictide oxides (Fe2As2)(Can+2(Al,Ti)nOy)[n = 2,3,4]. These compounds have perovskite-like blocking layers between Fe2As2 layers. The structure of new compounds are tetragonal with space groups of P4/nmm for n = 2 and 4 and P4mm for n = 3, which are similar to those of (Fe2As2)(Can+1(Sc,Ti)nOy)[n = 3,4,5] found in our previous study. Compounds with n = 3 and 4 have new crystal structures with 3 and 4 sheets of perovskite layers, respectively, including a rock salt layer in each blocking layer. The a-axis lengths of the three compounds are approximately 3.8 A, which are close to those of FeSe and LiFeAs. (Fe2As2)(Ca6(Al,Ti)4Oy) exhibited bulk superconductivity in magnetization measurement with Tc(onset)~36 K and resistivity drop was observed at ~39 K. (Fe2As2)(Ca5(Al,Ti)3Oy) also showed large diamagnetism at low temperatures. These new compounds indicate considerable rooms are still remaining for new superconductors in layered iron pnictides.Comment: 10 pages, 5 figure

Pressure Effects on Superconducting Properties of the BiS2-Based Superconductor Bi2(O,F)S2

Pressure effects on a recently discovered BiS2-based superconductor Bi2(O,F)S2 (Tc = 5.1 K) were examined via two different methods; high pressure resistivity measurement and high pressure annealing. The effects of these two methods on the superconducting properties of Bi2(O,F)S2 were significantly different although in both methods hydrostatic pressure is applied to the sample by the cubic-anvil-type apparatus. In high pressure resistivity measurement, Tc linearly decreased at the rate of -1.2 K GPa-1. In contrast, the Tc of 5.1 K is maintained after high pressure annealing under 2 GPa and 470{\deg}C of optimally doped sample despite significant change of lattice parameters. In addition, superconductivity was observed in fluorine-free Bi2OS2 after high pressure annealing. These results suggest that high pressure annealing would cause a unique effect on physical properties of layered compounds.Comment: 8 pages, 6 figure