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Lanthanides ($Ln$) are notoriously difficult to intercalate into graphite. We investigated the possibility of using Na to catalyze the formation of $Ln$-intercalated graphite and successfully synthesized $Ln$C$_6$ ($Ln$ = Sm, Eu, and Yb) significantly rapidly in high yields. The synthesis process involves the formation of the reaction intermediate NaC$_x$, through the mixing of Na and C, which subsequently reacts with $Ln$ upon heating to form $Ln$C$_6$. Well-sintered $Ln$C$_6$ pellets with low residual Na concentrations ($Ln$:Na = 98:2) were fabricated by the two-step method. The pellets enabled the evaluation of $Ln$C$_6$ by powder X-ray diffraction and electrical resistivity measurements. This study highlights the versatility of the Na-catalyzed method and lays the foundation for the rapid mass production of $Ln$C$_6$, with potential applications in superconducting and rechargeable battery materials., Comment: 16 pages, 7 figures

In this study, we conducted experiments on CaC6 for elucidating the Na-catalyzed formation mechanism and achieving rapid mass synthesis of graphite intercalation compounds (GICs). Rapidly synthesized CaC6 was characterized by analysis of its crystal structure and physical properties. We found that the formation of the reaction intermediate Na-GIC (NaCx, x = 64) requires a larger amount of Na than is intercalated between the graphite interlayers. The requirement for excess Na may provide insights into the mechanism of Na-catalyzed GIC formation. A Na-to-C molar mixing ratio of 1.5-2.0:6 was suitable for the efficient formation of CaC6 under heat treatment at 250{\deg}C for 2 h, and the catalytic Na remaining in the sample was demonstrably reduced to a Na:Ca ratio of approximately 3:97. The upper critical field Hc2 was enhanced approximately three times compared to those of previous reports. Based on X-ray diffraction and experimental parameter analysis, we concluded that the enhancement of Hc2 was attributed to the disordered stacking sequence in CaC6, possibly because of the rapid and low-temperature formation. Physical properties derived from specific heat measurements were comparable to those of high-quality CaC6, which is slowly synthesized using the molten Li-Ca alloy method. This study provides new avenues for future research and exploration in the rapid mass synthesis of GICs as practical materials, for applications such as battery electrodes and superconducting wires., Comment: 17 pages, 6 figures, 1 table

We investigated the temperature evolution of crystal structure of orthorhombic CoZr3, which is a superconductor with a transition temperature of 4.3 K, by synchrotron and laboratory (CuK{\alpha}) X-ray diffraction. Uniaxial negative thermal expansion along the c-axis, which is similar to that observed in tetragonal CoZr2, has been observed at a wide temperature range of T = 90-800 K in CoZr3, while a-and b-axis exhibit positive thermal expansion., Comment: 9 pages, 3 figures, supplemental materials

Enriching the material variation often contributes to the progress of materials science. We have discovered for the first time antiperovskite arsenide SrPd$_{3}$As and revealed a hidden structural and superconducting phase in Sr(Pd$_{1-x}$Pt$_{x}$)$_{3}$As. The Pd-rich samples (0 $\leq$ x $\leq$ 0.2) had the same non-centrosymmetric (NCS) tetragonal structure (a space group of $I41md$) as SrPd$_{3}$P. For the samples with 0.3 $\leq$ x $\leq$ 0.7, a centrosymmetric (CS) tetragonal structure ($P4/nmm$) identical to that of SrPt$_{3}$P was found to appear, accompanied by superconductivity at a transition temperature ($T_\mathrm{c}$) up to 3.7 K. In the samples synthesized with Pt-rich nominal compositions (0.8 $\leq$ x $\leq$ 1.0), Sr$_{2}$(Pd,Pt)$_{8-y}$As$_{1+y}$ with an intergrowth structure (CS-orthorhombic with Cmcm) was crystallized. The phase diagram obtained for Sr(Pd,Pt)$_{3}$As was analogous to that of (Ca,Sr)Pd$_{3}$P in that superconductivity ($T_\mathrm{c}$ $\geq$ 2 K) occurred in the CS phases induced by substitutions to the NCS phases. This study indicates the potential for further material variation expansion and the importance of elemental substitutions to reveal hidden phases in related antiperovskites., Comment: 18 pages, 5 figures, 1 table

Superconductors comprising 5d transition metals of Ir and Pt have been widely explored because they have the potential of unique superconductivity caused by the strong spin-orbit interaction (SOI). We successfully synthesized BaIr2, the last Laves phase remaining unsynthesized in the MgCu2-type AM2 (A = Ca, Sr, Ba; M = Rh, Pd, Ir, Pt). BaIr2 was crystallized at 925 C under a pressure of 3.3 GPa via a solid-state reaction between Ba and Ir powders; it was found to have the longest a-lattice constant of 8.038(1) A among AM2. BaIr2 exhibited bulk superconductivity at a transition temperature (Tc) of 2.7 K. BaIr2 was found to have a type-II superconductor with an upper critical field of 67.7 kOe, which was above the Pauli paramagnetic limit (50 kOe). The electron-phonon coupling constant and normalized specific heat jump were measured to be 0.63 and 1.2, respectively, indicating that BaIr2 is a weak-coupling superconductor. The electronic-structure calculations for BaIr2 revealed that the Ir-5d states are dominant at the Fermi energy (EF) and the density of states at the EF is strongly affected by SOI as in the case of CaIr2 and SrIr2., Comment: 9 pages, 8 figures

We report the effects of low-temperature postannealing on the structural and superconducting properties of the recently discovered Ca-free double-layered cuprate, Sr$_2$SrCu$_2$O$_{4+y}$F$_{2-y}$. Although the as-synthesized sample prepared under high pressure has a tetragonal structure with a rock-salt-type blocking layer (the so-called $T$-phase), we found that the symmetry of the structure lowered to that of an orthorhombic system when annealed with CuF$_2$. The structural refinements reveal that such a topochemical reaction leads not only to the removal of excess O$^{2-}$ from the apical site but also to the intercalation of extra F$^-$ into the interstitial site. The orthorhombic phase exhibits bulk superconductivity at a critical temperature of 107 K, which is significantly higher than that of the $T$-phase ($\sim$50 K). Meanwhile, the $T$-phase turns into another structure possessing a fluorite-type blocking layer without apical fluorine (known as the $T^\prime$-phase) by annealing without CuF$_2$. Density functional theory calculations show that the $T^\prime$-phase is more stable than the $T$-phase. This is the first report on the formation of a $T^\prime$-type double-layered cuprate. Furthermore, the structural stability of the three phases of Sr$_2$SrCu$_2$O$_{4+y}$F$_{2-y}$ is discussed in terms of lattice matching between the blocking and conducting layers., Comment: 18 pages, 9 figures, 3 tables (including 3 pages, 3 figures for the Supporting Information)

Antiperovskites are a promising candidate structure for the exploration of new materials. We discovered an antiperovskite phosphide, LaPd$_{3}$P, following our recent synthesis of $A$Pd$_{3}$P ($A$ = Ca, Sr, Ba). While $A$Pd$_{3}$P and (Ca,Sr)Pd$_{3}$P were found to be tetragonal or orthorhombic systems, LaPd$_{3}$P is a new prototype cubic system ($a$ = 9.0317(1) A) with a noncentrosymmetric space group ($I-43m$). LaPd$_{3}$P exhibited superconductivity with a transition temperature ($T_\mathrm{c}$) of 0.28 K. The upper critical field, Debye temperature, and Sommerfeld constant ($\gamma$) were determined as 0.305(8) kOe, 267(1) K, 6.06(4) mJ mol-1 K-2 f.u.-1, respectively. We performed first-principles electronic band structure calculations for LaPd$_{3}$P and compared the theoretical and experimental results. The calculated Sommerfeld constant (2.24 mJ mol-1 K-2 f.u.-1) was much smaller than the experimental value of $\gamma$ because the Fermi energy ($E_\mathrm{F}$) was located slightly below the density of states (DOS) pseudogap. This difference was explained by the increase in the DOS at $E_\mathrm{F}$ due to the approximately 5 at.% La deficiency (hole doping) in the sample. The observed Tc value was much lower than that estimated using the Bardeen-Cooper-Schrieffer equation. To explain the discrepancy, we examined the possibility of an unconventional superconductivity in LaPd$_{3}$P arising from the lack of space inversion symmetry., Comment: 13 pages, 5 figures, 4 tables

In the recently discovered antiperovskite phosphide (Ca,Sr)Pd$_3$P, centrosymmetric (CS) and non-centrosymmetric (NCS) superconducting phases appear depending on the Sr concentration, and their transition temperatures ($T_\mathrm{c}$) differ by as much as one order of magnitude. In this study, we investigated the superconducting properties and electronic band structures of CS orthorhombic (CSo) (Ca$_{0.6}$Sr$_{0.4}$)Pd$_3$P ($T_\mathrm{c}$ = 3.5 K) and NCS tetragonal (NCSt) (Ca$_{0.25}$Sr$_{0.75}$)Pd$_3$P ($T_\mathrm{c}$ = 0.32 K) samples with a focus on explaining their large $T_\mathrm{c}$ difference. Specific heat measurements indicated that CSo (Ca$_{0.6}$Sr$_{0.4}$)Pd$_3$P was an s-wave superconductor in a moderate-coupling regime with a 2$\Delta$$_0$/k$_B$$T_\mathrm{c}$ value of 4.0. Low-lying phonons leading to the strong coupling in the structurally analogous SrPt$_3$P were unlikely to be present in CSo (Ca$_{0.6}$Sr$_{0.4}$)Pd$_3$P. Given that CSo (Ca$_{0.6}$Sr$_{0.4}$)Pd$_3$P and NCSt (Ca$_{0.25}$Sr$_{0.75}$)Pd$_3$P exhibited similar Debye temperatures ($\Theta$$_D$) of approximately 200 K, the large $T_\mathrm{c}$ difference could not be attributed to $\Theta$$_D$.$T_\mathrm{c}$ of each phase was accurately reproduced based on the Bardeen-Cooper-Schrieffer (BCS) theory using experimental data and the density of states of the Fermi level $N$(0) calculated from their band structures. We concluded that the considerable suppression of $T_\mathrm{c}$ in NCSt (Ca$_{0.25}$Sr$_{0.75}$)Pd$_3$P can be primarily attributed to the decrease in $N$(0) associated with the structural phase transition without considering the lack of inversion symmetry., Comment: 14 pages, 8 figures

It is generally difficult to quantify the amounts 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, Sc$_{20}$C$_{8-x}$B$_x$C$_{20}$, 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 the experimental and computational approaches. Using the high-pressure synthesis approach that can maintain the starting composition even after sintering, we obtain the Sc$_{20}$(C,B)$_{8}$C$_{20}$ phase by the reaction of the previously reported Sc$_{15}$C$_{19}$ and B (Sc$_{15}$B$_y$C$_{19}$). Our experiments demonstrate that an increase in $y$ values promotes the phase formation of the Sc$_{20}$(C,B)$_{8}$C$_{20}$ structure; however, there appears to be an upper limit to the nominal $y$ value to form this phase. The maximum $T_\mathrm{c}$ $(=7.6\text{ K})$ is found to correspond with the actual $x$ value of $x \sim 5$ under the assumption that the sample with the same $T_\mathrm{c}$ as the reported value $(=7.7\text{ K})$ 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 Sc$_{20}$C$_4$B$_4$C$_{20}$ $(x=4)$ is the most thermodynamically stable, which is reasonably consistent with the experimentally obtained value., Comment: 10 pages, 1 table, 7 figures

In this study, we succeeded in synthesizing new antiperovskite phosphides $M$Pd$_3$P ($M$ = Ca, Sr, Ba) and discovered the appearance of a superconducting phase (0.17 $\leq$ $x$ $\leq$ 0.55) in a solid solution (Ca$_{1-x}$Sr$_x$)Pd$_3$P. Three perovskite-related crystal structures were identified in (Ca$_{1-x}$Sr$_x$)Pd$_3$P and a phase diagram was built on the basis of experimental results. The first phase transition from centrosymmetric ($Pnma$) to non-centrosymmetric orthorhombic ($Aba$2) occurred in CaPd$_3$P near room temperature. The phase transition temperature decreased as Ca$^{2+}$ was replaced with a larger-sized isovalent Sr$^{2+}$. Bulk superconductivity at a critical temperature ($T$$_c$) of approximately 3.5 K was observed in a range of $x$ = 0.17 - 0.55; this was associated with the centrosymmetric orthorhombic phase. Thereafter, a non-centrosymmetric tetragonal phase ($I$41$md$) remained stable for 0.6 $\leq$ $x$ $\leq$ 1.0, and superconductivity was significantly suppressed as samples with $x$ = 0.75 and 1.0 showed ($T$$_c$) values as low as 0.32 K and 57 mK, respectively. For further substitution with a larger-sized isovalent Ba$^{2+}$, namely (Sr$_{1-y}$Ba$_y$)Pd$_3$P, the tetragonal phase continued throughout the composition range. BaPd$_3$P no longer showed superconductivity down to 20 mK. Since the inversion symmetry of structure and superconductivity can be precisely controlled in (Ca$_{1-x}$Sr$_x$)Pd$_3$P, this material may offer a unique opportunity to study the relationship between inversion symmetry and superconductivity., Comment: 7 pages, 8 figures, 3 tables

We report the XRD and Raman scattering measurements in combination with DFT calculations that reveal the formation of beryllium polyhydride Be4H8(H2)2 by laser heating Be/H2 mixture to above 1700 K at pressures between 5 GPa and 8 GPa. The Be4H8(H2)2 crystallizes in a P6_3/mmc structure and consists of corner-sharing BeH4 tetrahedrons and H2 molecules that are in an interstitial site. The Be4H8(H2)2 is stable at least to 14 GPa on compression and stable down to 4 GPa at room temperature. Our ab-initio calculations suggest that the Be4H8(H2)2 is a meta-stable phase of Be-H system.

The discovery of nearly room-temperature superconductivity in superhydrides has motivated further materials research for conventional superconductors. To realize the moderately high critical temperature $(T_\mathrm{c})$ in materials containing light elements, we explored new superconducting phases in a scandium borocarbide system. Here, we report the observation of superconductivity in a new ternary Sc-B-C compound. The crystal structure, which was determined through a Rietveld analysis, belongs to tetragonal space group $P4/ncc$. By complementarily using the density functional theory calculations, a chemical formula of the compound was found to be expressed as Sc$_{20}$C$_{8-x}$B$_x$C$_{20}$($x=1\:\mathrm{or}\:2$). Interestingly, a small amount of B is essential to stabilize the present structure. Our experiments revealed the typical type-II superconductivity at $T_\mathrm{c}=7.7\:\mathrm{K}$. Additionally, we calculated the density of states within a first-principles approach and found that the contribution of the Sc-3d orbital was mainly responsible for the superconductivity., Comment: 13 pages, 3 tables, 8 figures

The search for non-centrosymmetric superconductors that may exhibit unusual physical properties and unconventional superconductivity has yielded the synthesis of a non-centrosymmetric phosphide Mg$_2$Rh$_3$P with an Al$_2$Mo$_3$C-type structure. Although stoichiometric Mg$_2$Rh$_3$P does not exhibit superconductivity at temperatures above 2 K, we found that an Mg deficiency of approximately 5 at.% in the Mg$_2$Rh$_3$P induced superconductivity at 3.9 K. Physical properties such as the lattice parameter a = 0.70881 nm, Sommerfeld constant $\gamma_n$ = 5.36 mJ mol$^{-1}$ K$^{-2}$, specific heat jump $\Delta$C$_{el}$/$\gamma_n$Tc = 0.72, electron-phonon coupling constant $\lambda$$_{e-p}$ = 0.58, upper critical field H$_{c2}$(0) = 24.3 kOe, and pressure effect dTc/dP = -0.34 K/GPa were measured for the superconducting Mg$_{2-\delta}$Rh$_3$P ($\delta$ $\sim$ 0.1). Band-structure calculations indicate that exotic fermions, which are not present in high-energy physics, exist in Mg$_2$Rh$_3$P. Since Mg, Rh, and P are the first elements used at each crystal site of Al$_2$Mo$_3$C-type compounds, the discovery of Mg$_2$Rh$_3$P may guide the search for new related materials., Comment: 12 pages, 9 figures. arXiv admin note: text overlap with arXiv:1603.03093 by other authors

We report synthesis, crystal structure and superconductivity in ThCr2Si2-type LaFe2As2 (La122). La122 was synthesized at 960{\deg}C for 1.5 h under a pressure of 3.4 GPa. An as-synthesized La122 (non-superconductor) had a collapsed tetragonal structure with a short c-axis length of 11.0144(4) {\AA} as observed in CaFe2As2 under pressure. The collapsed tetragonal transformed into an uncollapsed tetragonal by annealing the as-synthesized La122 at 500{\deg}C. The c-axis length remarkably extended to 11.7317(4) {\AA} and superconductivity emerged at 12.1 K in the uncollapsed tetragonal La122. A cylindrical hole-like Fermi-surface around the {\Gamma} point that plays an important role for an s+-wave paring in iron-based superconductors was missing in the uncollapsed tetragonal La122 due to heavily electron-doping. Superconductivity in La122 may be closely related to that induced in CaFe2As2 under pressure., Comment: 8 pages, 7 figures, 1 table

The crystal structure and electrical resistivity of YBa$_2$Cu$_4$O$_8$ (Y124) were studied under high pressure up to 18 GPa using diamond-anvil cells, respectively, in order to clarify its conduction mechanism. Y124 causes the first-order phase-transition into the orthorhombic Immm at pressure around 11 GPa. The high-pressure phase (HPP) also shows the superconductivity, while the manner of temperature dependence of electrical resistance and the pressure dependence of transition temperature, Tc, drastically change above 11 GPa. The CuO$_2$ plane persists in HPP but the CuO double chains collapse with the phase transition and transform into three-dimensional Cu-O network, resulting in the renewal of conduction system., Comment: 11 pages, 4 figures, to be published in JPSJ

A new iron-based superconductor (Ca,Pr)FeAs2 was discovered. Plate-like crystals of the new phase were obtained and crystal structure was investigated by single-crystal X-ray diffraction analysis. The structure was identified as the monoclinic system with space group P21/m, and is composed of two Ca(Pr) planes, anti-fluorite Fe2As2 layers, and As2 zigzag chain layers. Plate-like crystals composed of the new phase showed superconductivity with Tc ~20 K in both magnetization and resistivity measurements., Comment: 5 pages, 1 table, 6 figures

The newly discovered BiS$_2$-based LaO$_{1-x}$F$_{x}$BiS$_2$ ($x$=0.5) becomes superconductive at $T_c$=2.5 K. Electrical resistivity and magnetization measurements are performed under pressure to determine the pressure dependence of the superconducting transition temperature $T_c$. We observe that $T_c$ abruptly increases from 2.5 K to 10.7 K at a pressure of 0.7 GPa. According to high-pressure X-ray diffraction measurements, a structural phase transition from a tetragonal phase ($P$4/$nmm$) to a monoclinic phase ($P$2$_1/m$) also occurs at around $\sim$ 1 GPa. We consider that a pressure-induced enhancement of superconductivity is caused by the structural phase transition.

We have successfully synthesized a new BiS2-based superconductor NdOBiS2 with F-doping. This compound is composed of superconducting BiS2 layers and blocking NdO layers, which indicates that the BiS2 layer is the one of the common superconducting layers like the CuO2 layer of cuprates or Fe-As layer of Fe-based superconductors. We can obtain NdO1-xFxBiS2 with bulk superconductivity by a solid-state reaction under ambient pressure. Therefore, NdO1-xFxBiS2 should be the suitable material to elucidate the mechanism of superconductivity in the BiS2-layer., Comment: 16 pages, 4 figures

Layered superconductors have provided some interesting fields in condensed matter physics owing to the low dimensionality of their electronic states. For example, the high-Tc (high transition temperature) cuprates and the Fe-based superconductors possess a layered crystal structure composed of a stacking of spacer (blocking) layers and conduction (superconducting) layers, CuO2 planes or Fe-Anion layers. The spacer layers provide carriers to the conduction layers and induce exotic superconductivity. Recently, we have reported superconductivity in the novel BiS2-based layered compound Bi4O4S3. It was found that superconductivity of Bi4O4S3 originates from the BiS2 layers. The crystal structure is composed of a stacking of BiS2 superconducting layers and the spacer layers, which resembles those of high-Tc cuprate and the Fe-based superconductors. Here we report a discovery of a new type of BiS2-based layered superconductor LaO1-xFxBiS2, with a Tc as high as 10.6 K., Comment: 23 pages, 5 figures, 1 table (table caption has been revised), to appear in J. Phys. Soc. Jpn

Exotic superconductivity has often been discovered in materials with a layered (two-dimensional) crystal structure. The low dimensionality can affect the electronic structure and can realize high transition temperatures (Tc) and/or unconventional superconductivity mechanisms. As standard examples, we now have two types of high-Tc superconductors. The first group is the Cu-oxide superconductors whose crystal structure is basically composed of a stacking of spacer (blocking) layers and superconducting CuO2 layers.1-4 The second group is the Fe-based superconductors which also possess a stacking structure of spacer layers and superconducting Fe2An2 (An = P, As, Se, Te) layers.5-13 In both systems, dramatic enhancements of Tc are achieved by optimizing the spacer layer structure, for instance, a variety of composing elements, spacer thickness, and carrier doping levels with respect to the superconducting layers. In this respect, to realize higher-Tc superconductivity, other than Cu-oxide and Fe-based superconductors, the discovery of a new prototype of layered superconductors needs to be achieved. Here we show superconductivity in a new bismuth-oxysulfide layered compound Bi4O4S3. Crystal structure analysis indicates that this superconductor has a layered structure composed of stacking of Bi4O4(SO4)1-x and Bi2S4 layers; the parent compound (x = 0) is Bi6O8S5. Band calculation suggests that Bi4O4S3 (x = 0.5) is metallic while Bi6O8S5 (x = 0) is a band insulator with Bi3+. Furthermore, the Fermi level for Bi4O4S3 is just on the peak position of the partial density of states of the Bi 6p orbital within the BiS2 layer. The BiS2 layer is a basic structure which provides another universality class for layered superconducting family, and this opens up a new field in the physics and chemistry of low-dimensional superconductors., Comment: 13 pages, 3 figures, 1 table