Intrinsic defect structures of polycrystalline CaKFe4As4 superconductors.

We investigated the defect structures of polycrystalline CaKFe4As4 (CaK1144) superconductors by scanning transmission electron microscopy (STEM). The STEM studies revealed the presence of a one-layer CaFe2As2 (∼1 nm size) defect along the ab-plane, as observed in single crystalline CaK1144. Step-like CaFe2As2 defects are also observed. These nanoscale defects generate fine-sized stacking faults, a lattice mismatch, and stress field defects in the matrix of CaK1144 owing to the different sizes. Correlation of the defects in polycrystalline and single crystalline samples suggests that the defects type and their density depend on the synthesis conditions. A self-field critical current density (Jc) of 15.2 kA cm-2 was obtained at 5 K, and the curves were sustained above 30 K with a considerable Jc value of 1.4 kA cm-2. We investigated the relationship between the observed intrinsic defects and the behavior of the field dependence of Jc. The intrinsically intergrown planar defects, even in polycrystalline samples, are expected to be advantageous for various high-field applications of bulk CaK1144 superconductors.

Synthesis, Electronic Structure, and Physical Properties of Layered Oxypnictides Sr2ScCrAsO3 and Ba3Sc2Cr2As2O5.

New CrAs-based layered mixed-anion compounds Sr2ScCrAsO3 (SrScO-21113) and Ba3Sc2Cr2As2O5 (BaScO-32225) were synthesized, and their electronic structures and physical properties were investigated. The structures of these compounds comprise stacking of the anti-fluorite CrAs layer and perovskite-like SrScO or BaScO layers. The lattice constants of these compounds are relatively longer than those of the related compounds, such as BaCr2As2, owing to the insertion of a large perovskite blocking layer of SrScO/BaScO. While there are variations in the crystal structure of this system, such as 21113 and 32225, their chemical stability calculated by the first-principles calculations indicated that SrScO-21113 is energetically favorable compared to SrScO-32225. The formation energies of BaScO-32225 and BaScO-21113 are close to each other; in the experiment, while there was an indication of BaScO-21113 formation, only BaScO-32225 was formed as a single phase because of the low chemical stability of BaScO-21113. The partial density of states indicates that the majority of states are obtained from the 3d4-electrons of the Cr element hybridized modestly with p electrons at the Fermi energy. The magnetic properties of these compounds were paramagnetic, and they were different from related compounds, such as BaCr2As2, probably because of their long a-axis lengths. The temperature dependences of the electrical resistivities of both samples were in good agreement with the electronic band structure calculations. The variety of structures in the series of compounds with a CrAs layer results in different physical properties, and further development of new compounds may bring novel functionalities, such as superconductivity.

Experimental and Computational Determination of Optimal Boron Content in Layered Superconductor Sc20C8-xBxC20.

It is generally difficult to quantify the amount of light elements in materials because of their low X-ray-scattering power, as this means that they cannot be easily estimated via X-ray analyses. Meanwhile, the recently reported layered superconductor, Sc20C8-xBxC20, requires a small amount of boron, which is a light element, for its structural stability. In this context, here, we quantitatively evaluate the optimal x value using both experimental and computational approaches. Using the high-pressure synthesis approach, which can maintain the starting composition even after sintering, we obtain the Sc20(C,B)8C20 phase by the reaction of the previously reported Sc15C19 and B (Sc15ByC19). Our experiments demonstrate that an increase in y values promotes the phase formation of the Sc20(C,B)8C20 structure; however, there appears to be an upper limit to the nominal y value to form this phase. The maximum critical temperature (Tc = 7.6 K) is found to correspond with the actual x value of x ≈ 5 under the assumption that the sample with the same Tc as the reported value (7.7 K) possesses the optimal x amount. Moreover, we construct the energy convex hull diagram by calculating the formation enthalpy based on first principles. Our computational results indicate that the composition of Sc20C4B4C20 (x = 4) is the most thermodynamically stable, which is reasonably consistent with the experimentally obtained value.

New-Structure-Type Fe-Based Superconductors: CaAFe4As4 (A = K, Rb, Cs) and SrAFe4As4 (A = Rb, Cs).

Fe-based superconductors have attracted research interest because of their rich structural variety, which is due to their layered crystal structures. Here we report the new-structure-type Fe-based superconductors CaAFe4As4 (A = K, Rb, Cs) and SrAFe4As4 (A = Rb, Cs), which can be regarded as hybrid phases between AeFe2As2 (Ae = Ca, Sr) and AFe2As2. Unlike solid solutions such as (Ba(1-x)K(x))Fe2As2 and (Sr(1-x)Na(x))Fe2As2, Ae and A do not occupy crystallographically equivalent sites because of the large differences between their ionic radii. Rather, the Ae and A layers are inserted alternately between the Fe2As2 layers in the c-axis direction in AeAFe4As4 (AeA1144). The ordering of the Ae and A layers causes a change in the space group from I4/mmm to P4/mmm, which is clearly apparent in powder X-ray diffraction patterns. AeA1144 is the first known structure of this type among not only Fe-based superconductors but also other materials. AeA1144 is formed as a line compound, and therefore, each AeA1144 has its own superconducting transition temperature of approximately 31-36 K.

Large enhancement of superconducting transition temperature of SrBi3 induced by Na substitution for Sr.

The Matthias rule, which is an empirical correlation between the superconducting transition temperature (Tc) and the average number of valence electrons per atom (n) in alloys and intermetallic compounds, has been used in the past as a guiding principle to search for new superconductors with higher Tc. The intermetallic compound SrBi3 (AuCu3 structure) exhibits a Tc of 5.6 K. An ab-initio electronic band structure calculation for SrBi3 predicted that Tc increases on decreasing the Fermi energy, i.e., on decreasing n, because of a steep increase in the density of states. In this study, we demonstrated that high-pressure (~ 3 GPa) and low-temperature ( < 350 °C) synthesis conditions enables the substitution of Na for about 40 at.% of Sr. With a consequent decrease in n, the Tc of (Sr,Na)Bi3 increases to 9.0 K. A new high-Tc peak is observed in the oscillatory dependence of Tc on n in compounds with the AuCu3 structure. We have shown that the oscillatory dependence of Tc is in good agreement with the band structure calculation. Our experiments reaffirm the importance of controlling the number of electrons in intermetallic compounds.

Spectroscopic observation of bipolaronic point defects in Ba(1-x)KxBiO3.

An infrared-absorption band centered at 0.85 eV, which is below the big optical absorption at the charge-density-wave (CDW) gap energy of 1.85 eV, has been observed for semiconducting single crystalline Ba(1-x)KxBiO3. With substituting K for Ba, the spectral weight of the new band increases with x, while that of the CDW-gap excitation decreases. Since the impurity state with the K substitution is known to be nonmagnetic at low temperatures, Bi3+ the state with 6s2 electrons surrounded by the six Bi5+ ions forms a small bipolaron by losing a pair of electrons in the Rice-Sneddon model. The new band is assigned to a transition from the lower-Peierls band to a state of the bipolaronic point defect.