Electronic structure of shallow donor state associated with muonium in rutile TiO$_2$

The hyperfine structure of the interstitial muonium (Mu) center in rutile (TiO$_2$, weakly $n$-type) has been identified by means of muon spin rotation technique. The angle-resolved hyperfine parameter has a tetragonal anisotropy within the $ab$ plane and axial anisotropy along the $c$ axis, strongly suggesting that Mu simulates the known local structure of interstitial hydrogen (H) located at an off-center position within a channel along $c$ axis, and the electron wave function bound to Mu is highly delocalized (~1.5 nm along $c$ axis, ~0.8 nm for $a$ axis). The ionization energy of Mu ($\rightarrow μ^+ + e^-$) due to thermal activation is deduced to be 1.2(4) meV, as is directly inferred from the disappearance of Mu signal above ~8 K. These observations suggest that electronic level associated with Mu (as well as H) is situated near the bottom of the conduction band, serving as a shallow donor state in rutile.

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