Chemistry of electron doped Ln_2-xCe_xCuO₄ superconductors

The electron doped Ln_2-xCe_xCuO₄ (Ln=lanthanide) oxides have intergrowth structures consisting of superconductively active CuO₂ sheets alternating with inactive (Ln, Ce)₂O₂ fluorite layers along the c-axis. Stabilization of such intergrowth structures requires bond length matching across the intergrowth interface. The bond length matching criterion causes a monotonic decrease in the Ce solubility limit from x=0.24 to x=0.15 as the size of Ln³⁺ decreased from Ln=La_0.5Nd_0.5 to Ln=Gd. Annealing in N₂ atm of Ln_2-xCe_xCuO₄ at temperatures above 900°C creates oxygen vacancies and the number of vacancies decreases with increasing Ce content. The value of x at which a semiconductor to superconductor transition occurs in Ln_2-xCe_xCuO₄ increases with decreasing size of Ln³⁺ due to an increasing Madelung energy caused by a decreasing Cu-O bond length. © 1993 The Minerals, Metals & Materials Society.