The role of self-trapped excitons in polaronic recombination processes in lithium niobate

Abstract

Transient absorption and photoluminescence are experimentally investigated in the polaronic reference system lithium niobate, LiNbO3 (LN), with the aim to refine the microscopic model of small polaron dynamics in materials with strong electron-phonon coupling. As a unique feature, our study is performed by using two different spectroscopic methods, in crystals with dopants enhancing photorefraction or damage resistance, and over a broad temperature range from 15-400 K. Although being self-consistent for particular experimental conditions, the hitherto used microscopic polaronic models reveal inconsistencies when applied to this larger data set. We show that comprehensive modeling is unlocked by the inclusion of an additional type of polaronic state with the following characteristics: (i) strongly temperature- and dopant-dependent relaxation times, (ii) an absorption feature in the blue-green spectral range, and (iii) a Kohlrausch-Williams-Watts decay shape with a temperature-dependent stretching factor beta(T) showing a behavior contrary to that of small, strong-coupling polarons. The hypothesis of self-trapped excitons (STEs, i.e. bound electron-hole pairs strongly coupled to Nb5+ and O2- within a niobium-oxygen octahedron) and their pinning on defects as the microscopic origin of these characteristics is supported by a spectroscopic linkage of photoluminescence at low (15 K) and elevated (300 K) temperatures and explains the long-lifetime components in transient absorption as due to pinned STEs.