Posttreatment Effects on the Crystal Structure and Superconductivity of Ca-Free Double-Layered Cuprate Sr$_2$SrCu$_2$O$_{4+y}$F$_{2-y}$

Abstract

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.