Identification of paramagnetic centers in irradiated Sn-doped silicon dioxide by first-principles.

Abstract

We present a first-principles investigation of Sn paramagnetic centers in Sn-doped vitreous silica based on calculations of the electron paramagnetic resonance (EPR) parameters. The present investigation provides evidence of an extended analogy between the family of Ge paramagnetic centers in Ge-doped silica and the family of Sn paramagnetic centers in Sn-doped silica for SnO2concentrations below phase separation. We infer, also keeping into account the larger spin-orbit coupling of Sn atoms with respect to Ge atoms, that a peculiar and highly distorted three-fold coordinated Sn center (i.e. the Sn forward-oriented configuration) should give rise to an orthorhombic EPR signal of which we suggest a fingerprint in the EPR spectra recorded by Chiodiniet al(2001Phys. Rev.B64073102). Given its structural analogy with theEα'and Ge(2) centers, we here name it as the 'Sn(2) center'. Moreover, we show that the single trapped electron at a SnO4tetrahedron constitutes a paramagnetic center responsible for the orthorhombic EPR signal reported in Chiodiniet al(1998Phys. Rev.B589615), confuting the early assignment to a distorted variant of the Sn-E' center. We hence relabel the latter orthorhombic EPR signal as the 'Sn(1) center' due to its analogy to the Ge(1) center in Ge-doped silica.