Negative ionic states of tin in the oxide superconductor Sr$_{3-x}$SnO revealed by Mössbauer spectroscopy

We report the temperature variation of the $^{119}$Sn-Mössbauer spectra of the antiperovskite (inverse perovskite) oxide superconductor Sr$_{3-x}$SnO. Both superconductive (Sr-deficient) and non-superconductive (nearly stoichiometric) samples exhibit major $γ$-ray absorption with isomer shift similar to that of Mg$_2$Sn. This fact shows that Sr$_{3-x}$SnO contains the metallic anion Sn$^{4-}$, which is rare especially among oxides. In both samples, we observed another $γ$-ray absorption with a larger isomer shift, indicating that there is another ionic state of Sn with a higher oxidation number. The temperature dependence of the absorption intensities reveals that the Sn ions exhibiting larger isomer shifts have a lower energy of the local vibration. The larger isomer shift and lower vibration energy are consistent with the values estimated from the first-principles calculations for hypothetical structures with various Sr-deficiency arrangements. Therefore, we conclude that the additional $γ$-ray absorptions originate from the Sn atoms neighboring the Sr deficiency.