Engineering Electro-Optic BaTiO₃ Nanocrystals via Efficient Doping

Electro-optic (EO) modulators provide electrical-to-optical signal conversion relevant to optical communications. Barium titanate (BaTiO₃) is a promising material system for EO modulation in light of its optical ultrafast nonlinearity, low optical loss, and high refractive index. To enhance further its spontaneous polarization, BaTiO₃ can be doped at the Ba and Ti sites; however, doping is often accompanied by ion migration, which diminishes EO performance. Here, donor–acceptor doping and its effect on EO efficiency are investigated, finding that La-doped BaTiO₃ achieves an EO coefficient of 42 pm V⁻¹ at 1 kHz, fully twice that of the pristine specimen; however, it is also observed that, with this single-element doping, the EO response falls off rapidly with frequency. From impedance spectroscopy, it is found that frequency-dependent EO is correlated with ion migration. Density functional theory calculations predict that the ion-migration barrier decreases with La³⁺ doping but can be recovered with further Mn²⁺ doping, a finding that prompts to prevent ion migration by incorporating Mn²⁺ into the Ti-site to compensate for the charge imbalance.