Experimental manifestations of the Nb^{4+}-O^{-} polaronic excitons in KTa_{0.988}Nb_{0.012}O_{3}

TL;DR

This study detects and characterizes Nb^{4+}-O^{-} polaronic excitons in KTa_{0.988}Nb_{0.012}O_{3} using photoinduced EPR and optical absorption, revealing their spectral features, dynamics, and temperature dependence.

Contribution

It provides the first experimental evidence and detailed analysis of Nb^{4+}-O^{-} polaronic excitons in this perovskite, linking EPR signals with optical absorption.

Findings

Detection of Nb^{4+}-O^{-} excitons via EPR at low temperatures.

Identification of spectral parameters for the excitons, including g-values and D.

Correlation between EPR signals and optical absorption features.

Abstract

The formation of the photo-polaronic excitons in ABO_{3} perovskite type oxides has been detected experimentally by means of the photoinduced electron paramagnetic resonance studies of KTa_{0.998}Nb_{0.012}O_{3} crystals. The corresponding microwave X-band spectrum at T < 10 K consists of a narrow, nearly isotropic signal located at g ~ 2 and a strongly anisotropic component. The first signal, which has a rich structure due to hyperfine interactions with the lattice nuclei, is attributed to the single trapped charge carriers: the electrons and/or the holes. The anisotropic spectrum is caused by the axial centers oriented along the C_{4} pseudo-cubic principal crystalline axes. The spectrum angular dependence can be described well by an axial center with S = 1, g_{\parallel) = 0.82, g_{\perp} = 0.52 and D = 0.44 cm^{-1}. The anisotropic spectrum is attributed to the Nb^{4+}-O^{-} polaronic excitons. The temperature dependence of the anisotropic component is characterized by two activation energies: the internal dynamics activation E_{a1} = 3.7\pm0.5 meV, which makes the EPR spectrum unobservable above 10 K, and the destruction energy E_{a2} = 52\pm4 meV. By comparing the anisotropic photo-EPR spectrum and the photoinduced optical absorption temperature dependencies, we found that the Nb^{4+}-O^{-} polaronic excitons also manifested themselves via the ~0.7 eV wide absorption band arising under UV light excitation in the weakly concentrated KTaO_{3}:Nb crystals.