Defects and persistent luminescence in Eu-doped SrAl$_2$O$_4$

TL;DR

This study uses hybrid density-functional calculations to analyze defects and luminescence mechanisms in Eu-doped SrAl$_2$O$_4$, revealing new insights into carrier trapping and emission processes relevant for persistent phosphors.

Contribution

It provides a detailed defect analysis and clarifies the roles of specific defects and dopants in persistent luminescence, challenging previous assumptions.

Findings

Eu exists as Eu$^{2+}$ and Eu$^{3+}$ at Sr sites.

Dy is stable mainly as Dy$^{3+}$, with Dy$^{2+}$ generated under irradiation.

Strontium interstitials and Dy$_{ m Sr}$ act as electron traps.

Abstract

We investigate native point defects and rare-earth (co)dopants in SrAl$_2$O$_4$ using hybrid density-functional defect calculations. Europium (Eu) and dysprosium (Dy) are found to be mixed valence and energetically most favorable at the Sr lattice sites. However, unlike Eu where both Eu$^{2+}$ and Eu$^{3+}$ can be realized in synthesis, Dy is stable predominantly as Dy$^{3+}$, and the divalent Dy$^{2+}$ may only be photogenerated under irradiation. On the basis of an analysis of Eu-related band-defect (including charge-transfer) and interconfigurational $5d$-$4f$ optical transitions, we assign the characteristic broad blue (445 nm) and green (520 nm) emission bands in Eu$^{2+}$-doped SrAl$_2$O$_4$ to the $4f^65d^1$ $\rightarrow$ $4f^7$ transition in Eu$^{2+}$ incorporated at the Sr1 and Sr2 sites, respectively. Strontium interstitials (not oxygen vacancies, in contrast to what is commonly believed) and Dy$_{\rm Sr}$ can act as efficient electron traps for room-temperature persistent luminescence. This work calls for a re-assessment of certain assumptions regarding specific carrier trapping centers made in all mechanisms previously proposed for the persistent luminescence in Eu- and (Eu,Dy)-doped SrAl$_2$O$_4$. It also serves as a methodological template for the understanding and design of rare-earth doped phosphors.