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The thermodynamically stable long-range orbital order in bulk LaMnO3 becomesmetastable at nanoscale around a critical particle size d_C~20 nm. The orbitalorder-disorder transition switches from reversible to irreversible at d_C whilethe resistance in the orbital ordered state decays by 2-4% over a time scale of~3000s. At well below d_C, of course, a stable orbital disordered phaseemerges. The orthorhombic distortion of the underlying crystallographicstructure (space group Pbnm) decreases systematically with the decrease inparticle size and at far below d_C (e.g., at ~10 nm), the structure becomescubic (space group Pm-3m). Using the crystallographic and electrical resistancedata, a phase diagram has been constructed showing the evolution of differentorbital phases as a function of particle size across ~10 nm to bulk forstoichiometric LaMnO3.

Evolution of orbital phases with particle size in nanoscale stoichiometric LaMnO3