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Tuning the valence and concentration of europium and luminescence centers in GaN through co-doping and defect association

Defect physics of europium (Eu) doped GaN is investigated using first-principles hybrid density-functional defect calculations. This includes the interaction between the rare-earth dopant and native point defects (Ga and N vacancies) and other impurities (O, Si, C, H, and Mg) unintentionally present or intentionally incorporated into the host material. While the trivalent Eu$^{3+}$ ion is often found to be predominant when Eu is incorporated at the Ga site in wurtzite GaN, the divalent Eu$^{2+}$ is also stable and found to be predominant in a small range of Fermi-level values in the band-gap region. The Eu$^{2+}$/Eu$^{3+}$ ratio can be tuned by tuning the position of Fermi level and through defect association. We find co-doping with oxygen can facilitate the incorporation of Eu into the lattice. The unassociated Eu$_{\rm Ga}$ is an electrically and optically active defect center and its behavior is profoundly impacted by local defect--defect interaction. Defect complexes such as Eu$_{\rm Ga}$-O$_{\rm N}$, Eu$_{\rm Ga}$-Si$_{\rm Ga}$, Eu$_{\rm Ga}$-H$_i$, Eu$_{\rm Ga}$-Mg$_{\rm Ga}$, and Eu$_{\rm Ga}$-O$_{\rm N}$-Mg$_{\rm Ga}$ can efficiently act as deep carrier traps and mediate energy transfer from the host into the Eu$^{3+}$ $4f$-electron core which then leads to sharp red intra-$f$ luminescence. Eu-related defects can also give rise to defect-to-band luminescence. The unassociated Eu$_{\rm Ga}$, for example, is identified as a possible source of the broad blue emission observed in n-type, Eu$^{2+}$-containing GaN. This work calls for a re-assessment of certain assumptions regarding specific defect configurations previously made for Eu-doped GaN and further investigation into the origin of the photoluminescence hysteresis observed in (Eu,Mg)-doped samples.