Mild Hydrothermal Crystallization of Heavy Rare-Earth Chromite RECrO3 (RE = Er, Tm, Yb, Lu) Perovskites and Magnetic Properties.

Abstract

Crystallization of perovskite structure chromites (ACrO3) in aqueous conditions is difficult owing to the amphoteric nature of the Cr3+ in the alkaline-mediated reaction conditions. This is especially true for the small metal cations at the A-site with large distortion angle of CrO6 octahedral and small Goldschmidt tolerance factors. Here, we performed a progressive dehydration crystallization strategy to synthesize four RECrO3 with the smallest radii of rare earth elements (Er, Tm, Yb, Lu) in mild hydrothermal conditions. Profile refinement of the high-resolution powder X-ray diffraction results indicated slightly longer unit cell parameters of a and c in our samples with a higher distorted angle of CrO6 octahedral units along ⟨010⟩ direction. All of the samples show rounded rectangle plate morphology with uniform distribution of particle sizes. These four RECrO3 crystals can only form in a very narrow mineralization temperature range, i.e., 260-280 °C and 4.45-6.24 M of KOH. HRTEM results indicated that the normal crystallographic direction is ⟨001⟩, and the lattice of steps at the edge of elliptic rounded crystal is consistent with the bulk, which demonstrated single crystalline nature of the as-obtained crystals. Room-temperature Raman and FT-IR spectra reveal a continuous symmetry mode shift-dependent on the radii of A-site rare-earth cations. Temperature-dependent magnetization curves of RECrO3 show typical antiferromagnetism to paramagnetism transition with Néel temperature of 93, 90, 86, and 83 K for ErCrO3, TmCrO3, YbCrO3, and LuCrO3, respectively. Samples of YbCrO3 and LuCrO3 show clear magnetization reversal and exchange bias phenomena below their Néel points. This paper indicates that the coupling of magnetic exchange in perovskite structure oxides could be tailorable in mild hydrothermal condition, towards the exploration of new magnetic and other physical properties.