Particle size dependence of magnetization and phase transition near TN in multiferroic BiFeO3

Abstract

We report results of a comprehensive study of the phase transition at TN (∼643K) as a function of particle size in multiferroic BiFeO3 system. We employed electrical, thermal, and temperature dependent x-ray diffraction studies in order to characterize the transition in a host of samples. We also carried out detailed magnetic measurements over a temperature regime of 2–300K under a magnetic field of 100–10000Oe both on bulk and nanocrystalline systems. While in the bulk system a sharp endothermic peak at TN together with a broad feature, ranging over nearly ∼100K (ΔT), could be observed in calorimetry, the nanoscale systems exhibit only the broad feature. The characteristic dielectric anomaly, expected at TN, is found to occur both at TO and TN across ΔT in the bulk sample. The Maxwell-Wagner component due to interfaces between heterogenous regions with different conductivities is also present. The magnetic properties, measured at lower temperature, corroborate our observations in calorimetry. The metastability increases in the nanoscale BiFeO3 with divergence between zero-field cooled and field cooled magnetizations below ∼100K and faster magnetic relaxation. Interestingly, in nanoscale BiFeO3 one also observes finite coercivity at lower temperature, which points out that suitable design of particle size and shape may induce ferromagnetism. The inhomogeneous distribution of Bi∕Fe ions and/or oxygen nonstoichiometry seems to be giving rise to broad features in thermal, magnetic as well as electrical responses.