Enhanced magnetoelectric coupling is observed in bismuth ferrite samples, co-doped with non-magnetic Ba and magnetic Gd ions replacing Bi and Fe, respectively. Distortion in Fe–O octahedra has a significant effect on the magnetic properties of the samples. Ferromagnetic signature is found to increase significantly in the co-doped samples with respect to the only-Gd-doped sample both at 80 and 300 K. The co-doped samples show enhanced electric polarization as well as the highest resistivity at room temperature, which might be due to the reduction in the leakage current and oxygen vacancy in the compositions. An interesting correlation between the antiferromagnetic Néel temperature (T
N) of bismuth ferrite and the temperature-dependent dielectric constant is observed in all samples. Bi0.9Ba0.1Fe0.95Gd0.05O3 ceramic possesses maximum coupling between electric dipole and magnetic dipole with an estimated magnetodielectric effect MD ([ε
r(H) − ε
r (0)]/ε
r (0)) ∼ 380 at an applied field of 6 kOe. Impedance spectroscopy in the frequency range 40–107 Hz and temperature within 30–300 °C suggests that grain relaxation is dominant in the samples. Electrical parameters (such as capacitance and resistance) of the grains are determined using the real and imaginary parts of impedance (Z′ and Z″) and the electrical modulus (M′ and M″) plot. The results of electrical conductivity indicate a correlated barrier hopping conduction mechanism in the samples.
We report the detailed experimental characteristics of LuMn0.5Fe0.5O3 synthesized by the wet chemical method and proclaim it as a new member of the multiferroic family. The compound stabilizes in P63cm crystal symmetry. It exhibits a spin re-orientation transition at TSR and an antiferromagnetic transition at TN. In addition, our magnetization vs. temperature data reveals an extra broad maximum close to room temperature; unseen in earlier studies. By invoking the compatible nature of the magnetic exchange path in P63cm symmetry, we have argued that the origin lies in the intraplane short-range spin ordering. Heat capacity is measured and analysed to elucidate the magnetic entropy. Though long-range antiferromagnetic ordering vanishes at TN ∼ 103 K, we find the experimental magnetic entropy calculated till 200 K is less by a significant amount from the value of theoretical spin randomization magnetic entropy; further supporting the existence of spin ordering beyond TN and even above 200 K. While the specific heat data and phonon modes of Raman spectra show a signature of spin-phonon coupling at TSR and TN both, dielectric anomaly indicating a magnetoelectric effect is seen only at TN. Piezoresponse force microscopy and ferroelectric hysteresis loop measurement confirm the room-temperature weak ferroelectricity with a saturation polarization value 0.007 μC/cm2 and low coercive field. Furthermore high-temperature dielectric characteristics reveal the ferroelectric transition at around 900 K and exhibit Maxwell-Wagner type relaxation. The present work serves as a bridge between h-RMnO3 and rare earth ferrite RFeO3. It assumes significance in the light of recent research developments in hexagonal RFeO3 (mainly h-LuFeO3) in the context of room-temperature multiferroicity and magnetoelectricity.
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