Experimental TDPAC and Theoretical DFT Study of Structural, Electronic, and Hyperfine Properties in ($^{111}$In-->) $^{111}$Cd-Doped SnO$_2$ Semiconductor: Ab Initio Modeling of the Electron-Capture-Decay After-Effects Phenomenon

TL;DR

This study combines experimental TDPAC spectroscopy and first-principles DFT calculations to analyze the effects of Cd doping in SnO$_2$, revealing dynamic hyperfine interactions and electronic structure modifications due to electron-capture decay.

Contribution

It provides the first combined experimental and theoretical analysis of hyperfine interactions and electronic properties in Cd-doped SnO$_2$, elucidating decay-related effects.

Findings

Cd introduces a double acceptor level in SnO$_2$

Dynamic hyperfine interactions are caused by fluctuations between electronic configurations

First-principles calculations support the electron-capture after-effects scenario

Abstract

In this paper we investigate the effect of Cd doping at ultra-low concentrations in SnO$_2$ both experimentally, by measuring the temperature dependence of the electric quadrupole hyperfine interactions with time-differential perturbed angular correlation (TDPAC) spectroscopy using $^{111}$Cd as probe nuclei, and theoretically, by performing first-principles calculations based on the density functional theory. TDPAC spectra were successfully analyzed with a time-dependent on-off model for the perturbation factor. These results show combined dynamic plus static interactions whose electric-field gradients were associated in this model to different stable electronic configurations close to the Cd atoms. The dynamic regime is then originated in fast fluctuations between these different electronic configurations. First-principles calculations results show that the Cd impurity introduces a double acceptor level in the top of the valence band of the doped semiconductor and produces isotropic outward relaxations of the nearest oxygen neighbors. The variation of the calculated electric-field gradient tensor as a function of the charge state of the Cd impurity level shows an interesting behavior that explains the experimental results, giving strong support from first-principles to the electron-capture after-effects proposed scenario. The electron-capture decay of the parent $^{111}$In to $^{111}$Cd as well as the double acceptor character of the $^{111}$Cd impurity and the electric nature of the host are shown to contribute to the existence of these type of time-dependent hyperfine interactions.