Pressure-induced effects on the spectroscopic properties of Nd3+ in MgO:LiNbO3 single crystal. A crystal field approach

Abstract

The effects of pressure on the Nd3+-doped MgO:LiNbO3 single crystal have been studied by luminescence spectroscopy at low temperature and high pressures from ambient conditions up to 33GPa. Specifically, the pressure-induced evolution of the emission spectra, corresponding to the 4F3/2→4I9/2,4I11/2 transitions, and the excitation spectra, corresponding to the 4I9/2→4F5/2+2H9/2, and 4I9/2→4F7/2+4S3/2 transitions, show a gradual red-shift that follows a linear pressure dependence and a decrease in the intensity of the spectra with increasing pressure. The initial effect of increasing pressure on the MgO:LiNbO3 crystal is the modification of the relative amount of the several centers in the sample. At pressures around 20GPa the characteristic multicenter Nd3+ structure eventually disappears indicating that all the centers have very similar environments near this pressure. At higher pressures, observed changes seem to have a different origin. The evolution of Nd3+ luminescence is studied in the frame of crystal-field theory in order to evaluate its capability of monitoring the pressure-induced structural changes. Crystal-field analysis, under approximated C3v symmetry, shows a smooth increase of the overall crystal-field strength on the luminescent ion, which can be related to the volume reduction as pressure increases. Crystal-field parameters also show a general monotonic behavior with pressure that indicates a structural modification of the local structure that, maintaining the trigonal symmetry around the impurity ion, evolves towards a lower axial character. No evidences of a phase transition have been observed in the studied pressure range.