Emission Mossbauer study of the electronic phases in La0.7Ca0.3MnO3

A well characterized homogeneous ceramic sample of La-0.7Ca0.3Mn(Co-57)O-3 shows two ferromagnetic phases below T-c in contrast to the 20% Ca compound where only one is observed. One of the phases exhibits stronger exchange interactions with more rapid electron transfer between Mn3+/Mn4+. At lower temperatures, there is a tendency for a single phase to exist, with well ordered spins. In both 20% and 30% Ca materials, the long-range ferromagnetic order breaks down above T/T-c = 0.7 and small spin clusters with superparamagnetic-like behavior an formed. Above T-c, the spin clusters persist giving predominantly a single phase (as seen by the Mossbauer probe Fe-57 with a Larmor period of similar to 10(-8) sec). Under the influence of an external magnetic field, the small spin clusters coalesce to give larger clusters with better alignment of spins exhibiting negative magnetoresistivity by percolation. Our work raises the question whether superparamagnetic behavior is a prerequisite for observing negative magnetoresistivity.