In this study, we succeeded in synthesizing new antiperovskite phosphides MPd 3 P (M = Ca, Sr, Ba) and discovered the appearance of a superconducting phase (0.17 ≤ x ≤ 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 (Aba2) occurred in CaPd 3 P near room temperature. The phase transition temperature decreased as Ca 2+ was replaced with a largersized 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 (I4 1 md) remained stable for 0.6 ≤ x ≤ 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 1x Sr x )Pd 3 P, this material may offer a unique opportunity to study the relationship between inversion symmetry and superconductivity.
Calcium is a vital constituent in multilayered cuprate superconductors with critical temperatures (Tc) above 100 K, because it plays a key role in separating CuO2 planes. Here, we demonstrate the synthesis of calcium-free double-layered cuprates: Sr2SrCu2O4(X,O)2(X = F, Cl, and Br) and M(Sr,Ba)2SrCu2Oy(M = Hg/Re, Tl, and B/C), where strontium exists between the CuO2 planes. Oxyfluoride and mercury-based materials show a Tc of 107 K and 110 K, respectively, which are high compared to existing calcium-free cuprates. These findings indicate Tc greater than 100 K can be realized by replacing both barium and calcium, which have been indispensable in conventional multilayered cuprates, with strontium. Furthermore, the non-toxicity of Sr2SrCu2O4F2 and (B,C)Sr2SrCu2Oy simplifies the synthesis process and ensures their safety in potential applications. We also perform a comparison of the characteristic structural parameters between the calcium-free and calcium-containing cuprates considering the number of CuO2 planes.
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