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

TL;DR

This study reveals that muonium in rutile TiO$_2$ acts as a shallow donor, with a highly delocalized electron wave function and an ionization energy of about 1.2 meV, indicating its role in n-type conductivity.

Contribution

The paper provides the first detailed hyperfine structure analysis of muonium in rutile TiO$_2$, demonstrating its role as a shallow donor and elucidating its local electronic structure.

Findings

Muonium exhibits tetragonal and axial hyperfine anisotropy.

Electron wave function is highly delocalized (~1.5 nm along c).

Ionization energy is approximately 1.2 meV, indicating a shallow donor.

Abstract

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 ($\rightarrow \mu^+ + e^-$) 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.