Effect of tetragonal to cubic phase transition on the upconversion luminescence properties of A/B site erbium-doped perovskite BaTiO3

Abstract

With the increasing number of applications for upconversion materials, a more detailed understanding of the intrinsic mechanisms of their optical processes is required. Thus far, various lanthanide-doped host materials or nanoparticle systems have been investigated as representative upconversion systems owing to their major advantage as optical probes. As for the energetics of upconversion and the associated upconversion pathways, the role of the host material is very important because it provides a unique microscopic environment; for example, a unique local lattice structure in the case of crystalline samples. In general, the upconversion luminescence intensity decreases as a function of temperature owing to thermally accelerated multiphonon relaxation. Here, we report that the temperature dependence of the upconversion luminescence efficiency is affected differently in an Er³⁺-doped perovskite material, barium titanate (BaTiO₃, BT), than in a general system. We show that Er³⁺ doped at the A (Ba²⁺) and B (Ti⁴⁺) sites of tetragonal phase BT, referred to as A-BT and B-BT, respectively, show different upconversion behaviors. The slope of the plot of the upconversion emission intensity as a function of temperature changed significantly in case of B-BT, but not for A-BT. This anomalous behavior of Er³⁺-doped BT is attributed to the phase transition (at ∼120 °C) of BT from tetragonal to cubic phase. Essentially, the temperature-dependent upconversion luminescence trend depends on the doping sites of Er³⁺, i.e., at A or B sites in BT, which is explained by the difference in the symmetry of the crystalline structure with different crystal phase surrounding the Er³⁺ ions.