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We discuss the particle size driven tunability of the coexistence offerromagnetism and ferroelectricity in Pr0.67Ca0.33MnO3(PCMO) with the help ofx ray diffraction, magnetization, impedance spectroscopy, and remanentpolarization measurements. The remanent polarization measurements using thepositive up negative down method clearly prove the existence offerroelectricity in PCMO with phase separation between Zener polaron(ZP)ordered P21nm and disordered Pbnm structures. We also find that theferroelectric response is enhanced in nanocrystalline samples so long as ZPordering is not destroyed while the long-range antiferromagnetic ordering atlow temperature in bulk system is replaced by ferromagnetic correlations innanoparticles. The conclusion that by reducing the crystallite size it might bepossible to make ferromagnetism and ferroelectricity coexist near roomtemperature should be generally applicable to all ZP ordered manganites.

Direct experimental evidence of multiferroicity in a nanocrystalline Zener polaron ordered manganite