Absorption Spectroscopy Analysis of Calcium-Phosphate Glasses Highly Doped with Monovalent Copper.

Abstract

CaO-P2 O5 glasses with high concentrations of monovalent copper ions were prepared by a simple melt-quench method through CuO and SnO co-doping. Spectroscopic characterization was carried out by optical absorption with the aim of analyzing the effects of Cu(+) ions on the optical band-gap energies, which were estimated on the basis of indirect-allowed transitions. The copper(I) content is estimated in the CuO/SnO-containing glasses after the assessment of the concentration dependence of Cu(2+) absorption in the visible region for CuO singly doped glasses. An exponential dependence of the change in optical band gaps (relative to the host) with Cu(+) concentration is inferred up to about 10 mol %. However, the entire range is divided into two distinct linear regions that are characterized by different rates of change with respect to concentration: 1) below 5 mol %, where the linear dependence presents a relatively high magnitude of the slope; and 2) from 5-10 mol %, where a lower magnitude of the slope is manifested. With increasing concentration, the mean Cu(+) -Cu(+) interionic distance decreases, thereby decreasing the sensitivity of monovalent copper for light absorption. The decrease in optical band-gap energies is ultimately shown to follow a linear dependence with the interionic distance, suggesting the potential of the approach to gauge the concentration of monovalent copper straightforwardly in amorphous hosts.