Structural Origin of Recovered Ferroelectricity in BaTiO3_3 Nanoparticles

Nanoscale BaTiO$_3$ particles (~10 nm) prepared by ball-milling a mixture of oleic acid and heptane have been reported to have an electric polarization several times larger than that for bulk BaTiO$_3$. In this work, detailed local, intermediate, and long-range structural studies are combined with spectroscopic measurements to develop a model structure of these materials. The X-ray spectroscopic measurements reveal large Ti off-centering as the key factor producing the large spontaneous polarization in the nanoparticles. Temperature-dependent lattice parameter changes reveal the sharpening of the structural phase transitions in these BaTiO$_3$ nanoparticles compared to the pure nanoparticle systems. Sharp crystalline-type peaks in the barium oleate Raman spectra suggest that this component in the composite core-shell matrix, a product of mechanochemical synthesis, stabilizes an enhanced polar structural phase of the BaTiO$_3$ core nanoparticles.Comment: 5 figures in main text. 1 table and 3 figures in supplementary documen