La2CuO4+δ: Synthesis under high oxygen pressure and study of phase relations and energetics

Abstract

High oxygen pressures have been achieved in a piston-cylinder apparatus using a double capsule assembly consisting of a sealed outer Au capsule, containing an oxygen source (KMnO4), and an inner, open Pt capsule containing the sample. Using this technique, La2CuO4 was annealed at 800 °C, 5–25 kbar for 2–4 h. Transposed temperature drop calorimetry at 704 °C was used to determine the enthalpy of oxidation, and weight loss measurements characterized the oxygen nonstoichiometry, δ, in La2CuO4+δ, in the high-pressure, oxygen-annealed samples. For samples analyzed at room temperature, x-ray diffraction measurements show that beyond δ ≍ 0.10–0.13, additional oxygen is accommodated in a perovskite-like LaCuO3−α phase. An analysis of the thermochemical measurements indicates that the nature of holes in La2CuO4+δ could change in the range of δ ≍ 0.03–0.06.16,17 It is further suggested that the observed change in the thermochemical behavior in the range of δ ≍ 0.03–0.06 could be the driving influence behind the spinodal decomposition of La2CuO4+δ at low temperatures (Dabrowski et al.10).