Metastable behavior of Urbach tail states in BaTiO3 across phase transition

TL;DR

This study investigates the temperature-dependent optical properties of BaTiO3 across its phase transition, revealing metastable Urbach tail states and electronic heterogeneity that couple with phonon modes, affecting dielectric relaxation.

Contribution

It provides new insights into the electronic disorder and metastability of Urbach tail states in BaTiO3 during phase transition, using optical spectroscopy.

Findings

Presence of two Urbach focus values near transition temperature indicating heterogeneity.

Metastability of Urbach energy EU observed as a time-dependent function near transition.

Coupling of electronic disorder with soft phonon modes linked to terahertz dielectric relaxation.

Abstract

The temperature dependent diffuse reflectance spectroscopy measurements were carried out on the polycrystalline samples of BaTiO3 across the tetragonal to cubic structural phase transition temperature. The values of various optical parameters such as band gap (Eg), Urbach energy (EU) and Urbach focus (E0) are estimated in the range of 300 K to 470K. It is observed that near structural phase transition temperatures there exists two value of E0, suggesting presence of electronic heterogeneity over wide temperature range. Further near transition temperature EU shows metastability i.e. value of EU at temperature T is not constant but is a function of time (t). Interestingly it is observed that the ratio of EU(t=0)/ EU(t = tm), is almost remains constant at 295 K (pure tetragonal phase) and at 450 K (pure cubic phase), whereas this ratio shows decreasing behavior close to structural phase transition temperature, which confirms the presence of electronic metastibility in the pure BaTiO3. The observed metastibility can be fitted with the stretch exponents relaxation behavior, suggesting the presence of dynamic heterogeneous electronic disorder present in the sample across the transition. Further it appears that these metastable Urbach tail states (electronic disorder) may couple with the soft phonon modes and responsible for the observed terahertz dielectric relaxation (Phys. Rev. Lett. 101, 167402 (2008)). Further; present studies suggest that the optical studies appear to be more sensitive to probe the disorder/heterogeneity present in the sample.