Experimental and theoretical investigations on high-pressure phase transition of Sr2Fe2O5

Sr₂Fe₂O₅ is a typical oxygen-deficient perovskite and adopts brownmillerite phase (Ibm2, Z = 4) at ambient conditions. Its high-pressure structural behavior has been investigated by both synchrotron radiation X-ray diffraction with diamond anvil cell technique and first principles calculations. Experimental results clearly show that the brownmillerite Sr₂Fe₂O₅ transforms into a tetragonal perovskite-type phase at 12.0 GPa and room temperature, and then into a Sr₂Mn₂O₅-type phase (Pbam, Z = 2) at 23.3 GPa after high-temperature annealing. The Sr₂Mn₂O₅-type phase is stable up to at least 60 GPa and it further undergoes a reversible transition to a lower symmetry phase at 79.1 GPa and ~2,000 K. The results from theoretical calculation not only confirm that the tetragonal phase of Sr₂Fe₂O₅ is isostructural with the high-temperature structure of Ba₂In₂O₅ (I4/mcm, Z = 4), but also predict a series of phase transitions from brownmillerite phase to Ba₂In₂O₅-type phase at 6.9 GPa, and then to Sr₂Mn₂O₅-type phase at 19.7 GPa, which coincides with present experiment results. Isothermal pressure–volume relationship of the Sr₂Mn₂O₅-type phase can be well described by the Birch–Murnaghan Equation of State with V ₀ = 111.6(10) ų, B ₀ = 122(9) GPa, B ₀ ^′  = 4(fixed) experimentally and V ₀ = 115.8(3) ų, B ₀ = 92(4) GPa, B ₀ ^′  = 4(fixed) theoretically. The transition mechanism from brownmillerite to Ba₂In₂O₅-type phase is the displacement of four-coordinated Fe³⁺ ions to higher coordinated positions upon compression. In addition, a semiconductor-to-metal crossover is predicted from brownmillerite to Ba₂In₂O₅-type or Sr₂Mn₂O₅-type phase.