Nanowire Structural Evolution from Fe₃O₄ to ϵ‐Fe₂O₃

Abstract The ϵ‐Fe₂O₃ phase is commonly considered an intermediate phase during thermal treatment of maghemite (γ‐Fe₂O₃) to hematite (α‐Fe₂O₃). The routine method of synthesis for ϵ‐Fe₂O₃ crystals uses γ‐Fe₂O₃ as the source material and requires dispersion of γ‐Fe₂O₃ into silica, and the obtained ϵ‐Fe₂O₃ particle size is rather limited, typically under 200 nm. In this paper, by using a pulsed laser deposition method and Fe₃O₄ powder as a source material, the synthesis of not only one‐dimensional Fe₃O₄ nanowires but also high‐yield ϵ‐Fe₂O₃ nanowires is reported for the first time. A detailed transmission electron microscopy (TEM) study shows that the nanowires of pure magnetite grow along [111] and <211> directions, although some stacking faults and twins exist. However, magnetite nanowires growing along the <110> direction are found in every instance to accompany a new phase, ϵ‐Fe₂O₃, with some micrometer‐sized wires even fully transferring to ϵ‐Fe₂O₃ along the fixed structural orientation relationship, (001) ∥ (111), [010] ∥ <110>. Contrary to generally accepted ideas regarding epsilon phase formation, there is no indication of γ‐Fe₂O₃ formation during the synthesis process; the phase transition may be described as being from Fe₃O₄ to ϵ‐Fe₂O₃, then to α‐Fe₂O₃. The detailed structural evolution process has been revealed by using TEM. 120° rotation domain boundaries and antiphase boundaries are also frequently observed in the ϵ‐Fe₂O₃ nanowires. The observed ϵ‐Fe₂O₃ is fundamentally important for understanding the magnetic properties of the nanowires.