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Electron doped Ca10(Pt3As8)(Fe2As2)5 and Ca10(Pt4As8)(Fe2As2)5 - High Tc superconductors with skutterudite intermediary layers

It has been argued that the very high transition temperatures of the highest Tc cuprate superconductors are facilitated by enhanced CuO2 plane coupling through the (Bi,Tl,Hg)-O intermediary layers. Whether enhanced coupling through intermediary layers can also influence Tc in the iron arsenide superconductors has never been tested due the lack of appropriate systems for study. Here we report the crystal structures and properties of two iron arsenide superconductors, Ca10(Pt3As8)(Fe2As2)5 (the 10-3-8 phase) and Ca10(Pt4As8)(Fe2As2)5 (the 10-4-8 phase). Based on -Ca-(PtnAs8)-Ca-Fe2As2- layer stacking, the most important difference in the structures lies in the structural and electronic characters of the intermediary platinum arsenide layers. Electron doping through partial substitution of Pt for Fe in the Fe2As2 layers leads to Tc of 11 K in the 10-3-8 phase and 25 K in the 10-4-8 phase. Using the chemical concepts of Zintl ion electron counting and the stability of Pt in the 5d8 configuration we argue that the dramatic difference in Tc arises because the intermediary layer is semiconducting in the 10-3-8 phase but metallic in the 10-4-8 phase, leading to enhanced interlayer coupling in the 10-4-8 phase. The results suggest that metallic intermediary layers may offer a new road to higher Tc in iron arsenide superconductors.