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Register a new userSuperconductivity Above 40 K Observed in a New Iron Arsenide Oxide (Fe2As2)(Ca4(Mg,Ti)3Oy)
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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.
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A new layered iron arsenide oxide (Fe2As2)(Ca5(Mg,Ti)4Oy) and its structural derivative were found in the Fe-As-Ca-Mg-Ti-O system. The crystal structure of (Fe2As2)(Ca5(Mg,Ti)4Oy) is identical to that of (Fe2As2)(Ca5(Sc,Ti)4Oy), which was reported in our previous study. The lattice constants of this compound are a = 3.86(4) A and c = 41.05(2) A. In addition, another phase with a thicker blocking layer was found. The structure of the compound and its derivative was tentatively assigned through STEM observation as (Fe2As2)(Ca8(Mg,Ti)6Oy) with sextuple perovskite-type sheets divided by a rock salt layer. The interlayer Fe-Fe distance of this compound is ~30 A. The compound and its derivative exhibited bulk superconductivity, as found from magnetization and resistivity measurements.
We synthesized new layered iron arsenide oxides (Fe2As2)(Sr4(Sc,Ti)3O8),(Fe2As2)(Ba4Sc3O7.5), and (Fe2As2)(Ba3Sc2O5). The crystal structures of these compounds are tetragonal with a space group of I4/mmm. The structure of (Fe2As2)(Sr4(Sc,Ti)3O8) and (Fe2As2)(Ba4Sc3O7.5) consists of the alternate stacking of antifluorite Fe2As2 layers and triple perovskite-type oxide layers. The interlayer distance between the Fe planes of (Fe2As2)(Ba4Sc3O7.5) is ~18.7 A. Moreover, the a-axis of (Fe2As2)(Ba3Sc2O5) is the longest among the layered iron pnictides, indicating the structural flexibility of the layered iron pnictide containing perovskite-type layers. The bulk sample of (Fe2As2)(Sr4(Sc0.6Ti0.4)3O8) exhibited diamagnetism up to 28 K in susceptibility measurements.
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.
$^{75}$As and $^{45}$Sc NMR measurements unravel the electronic state for Fe-based superconductors with perovskite-type blocking layers Ca$_4$(Mg,Ti)$_3$Fe$_2$As$_2$O$_{8-y}$ ($T_c^{onset}=47$ K) and Ca$_5$(Sc,Ti)$_4$Fe$_2$As$_2$O$_{11-y}$ ($T_c^{onset}=41$ K). In Ca$_5$(Sc,Ti)$_4$Fe$_2$As$_2$O$_{11-y}$, the nuclear spin relaxation rate $1/T_1$ shows pseudogap behavior below $sim80$ K, suggesting that the electronic state is similar to that of LaFeAs(O,F) system with moderate electron doping. The presence of the pseudogap behavior gives an interpretation that the hole-like band (so-called $gamma$ pocket) is located just below the Fermi level from the analogy to LaFeAs(O,F) system and the disappearance of the $gamma$ pocket yields the suppression of the low-energy spin fluctuations. On the other hand, in Ca$_4$(Mg,Ti)$_3$Fe$_2$As$_2$O$_{8-y}$ satisfying the structural optimal condition for higher $T_c$ among the perovskite systems, the extrinsic contribution, which presumably originates in the Ti moment, is observed in $1/T_1T$; however, the moderate temperature dependence of $1/T_1T$ appears by its suppression under high magnetic field. In both systems, the high $T_c$ of $sim40$ K is realized in the absence of the strong development of the low-energy spin fluctuations. The present results reveal that the structural optimization does not induce the strong development of the low-energy spin fluctuations. If we consider that superconductivity is mediated by spin fluctuations, the structural optimization is conjectured to provide a benefit to the development of the high-energy spin fluctuations irrespective to the low-energy part.
EuFe2As2 is a member of the ternary iron arsenide family. Similar to BaFe2As2 and SrFe2As2, EuFe2As2 exhibits a clear anomaly in resistivity near 200 K. It suggests that EuFe2As2 is another promising parent compound in which superconductivity may be realized by appropriate doping. Here we report the discovery of superconductivity in Eu0.7Na0.3Fe2As2 by partial substitution of the europium site with sodium. ThCr2Si2 tetragonal structure, as expected for EuFe2As2, is formed as the main phase for the composition Eu0.7Na0.3Fe2As2. Resistivity measurement reveals a transition temperature as high as 34.7 K in this compound, which is higher than the Tc of Eu0.5K0.5Fe2As2.
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