Effect of Hydrothermal Treatment and Doping on the Microstructural Features of Sol-Gel Derived BaTiO₃ Nanoparticles

Barium Titanate (BaTiO₃) is one of the most promising lead-free ferroelectric materials for the development of piezoelectric nanocomposites for nanogenerators and sensors. The miniaturization of electronic devices is pushing researchers to produce nanometric-sized particles to be embedded into flexible polymeric matrices. Here, we present the sol-gel preparation of crystalline BaTiO₃ nanoparticles (NPs) obtained by reacting barium acetate (Ba(CH₃COO)₂) and titanium (IV) isopropoxide (Ti(OⁱPr)₄). The reaction was performed both at ambient conditions and by a hydrothermal process carried on at 200 °C for times ranging from 2 to 8 h. Doped BaTiO₃ nanoparticles were also produced by addition of Na, Ca, and Bi cations. The powders were annealed at 900 °C in order to improve NPs crystallinity and promote the cubic-to-tetragonal (c⟶t) phase transformation. The microstructural features of nanoparticles were investigated in dependence of both the hydrothermal reaction time and the presence of dopants. It is found that short hydrothermal treatment (2 h) can produce BaTiO₃ spherical and more homogeneous nanoparticles with respect to longer hydrothermal treatments (4 h, 6 h, 8 h). These particles (2 h) are characterized by decreased dimension (approx. 120 nm), narrower size distribution and higher tetragonality (1.007) in comparison with particles prepared at ambient pressure (1.003). In addition, the short hydrothermal treatment (2 h) produces particles with tetragonality comparable to the one obtained after the longest process (8 h). Finally, dopants were found to affect to different extents both the c⟶t phase transformation and the crystallite sizes.