Structural and electron paramagnetic resonance (EPR) of Ba(1-x)SmxFeyTi(1-y)O3 (BSFT) with y=1% and x=0.25,0.50, 0.75% materials were prepared by sol-gel combustion method. The room temperature powder X-ray diffraction confirms the formation of single-phase perovskite (ABO3) structure with tetragonal symmetry (P4mm) for all the prepared samples. The EPR spectra of BSFT samples shows a broad signal and the giromagnetic constant values for Fe3+, Sm3+ are 1.999 and 1.998 respectively. The broadness of EPR spectra confirms the paramagnetic nature and strong dipolar-dipolar interactions of prepared BSFT ceramics. EPR spectra oxidation state as Fe3+ ion, along with the paramagnetic center of Ti3+ ion and surface defects, exhibited in the samples. The optical band gap values calculated from UV-spectra shows an increasing trend in bandgap values with decrease in crystallite size is due to Sm3+ ion co- doping concentrations in Ba(1-x)Fe0.01Ti0.99O3 (BFT).

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