Temperature-dependent UV-Vis dielectric functions of BaTiO across ferroelectric-paraelectric phase transition.

Ferroelectric BaTiO with an electric-field-switchable spontaneous polarization has attracted wide attention in photovoltaic applications due to its efficient charge separation for photoexcitation. The evolution of its optical properties with rising temperature especially across the ferroelectric-paraelectric phase transition is critical to peer into the fundamental photoexcitation process. Herein, by combining spectroscopic ellipsometry measurements with first-principles calculations, we obtain the UV-Vis dielectric functions of perovskite BaTiO at temperatures varying from 300 to 873 K and provide the atomistic insights into the temperature-driven ferroelectric-paraelectric (tetragonal-cubic) structural evolution. The main adsorption peak in dielectric function of BaTiO is reduced by 20.6% in magnitude and redshifted as temperature increases. The Urbach tail shows an unconventional temperature-dependent behavior due to the microcrystalline disorder across the ferroelectric-paraelectric phase transition and the decreased surface roughness at around 405 K. From ab initio molecular dynamics simulations, the redshifted dielectric function of ferroelectric BaTiO coincidences with the reduction of the spontaneous polarization at elevated temperature. Moreover, a positive (negative) external electric field is applied which can modulate the dielectric function of ferroelectric BaTiO blueshift (redshift) with a larger (smaller) spontaneous polarization since it drives the ferroelectric further away from (closer to) the paraelectric structure. This work sheds light on the temperature-dependent optical properties of BaTiO and provides data support for advancing its ferroelectric photovoltaic applications.