A study of 13C hyperfine structure in the EPR of nickel-nitrogen-containing centres in diamond and correlation with their optical properties

Abstract

Electron paramagnetic resonance (EPR) and optical spectroscopy have been used to determine the structure and electronic state of nickel-nitrogen centres in natural diamonds and in synthetic diamonds enriched in 13C. The latter were grown in an Fe-Ni-C solvent/catalyst system at 1750 K, under stabilizing pressure, by the temperature gradient method and afterwards treated at high temperature and pressure. The parameters and directions of the 13C hyperfine structure (HFS) tensors for the NE1 centre were found to confirm the previously proposed model for this defect, with a nickel ion at the centre of a double semivacancy as the basic structural unit. In this unit the nickel atom has six atoms in its coordination shell. The NE1 centre has C2h symmetry, and the two equivalent nitrogen atoms in the coordination shell lie in the symmetry plane. New data on the HFS of 14N and 13C for the NE5 centre, also with C2h symmetry, indicated the same structural unit, but the two equivalent nitrogen atoms (and two equivalent carbon atoms) lie out of the symmetry plane and are related to one another by reflection in it. A new paramagnetic centre was found, labelled NE8, also with C2h symmetry, with four equivalent nitrogen atoms in the coordination shell all lying out of the symmetry plane. This centre is responsible for the 793.6 nm vibronic system in absorption and luminescence spectra. The new data have allowed a reinterpretation of the HFS tensors for the NE2 centre, which has C1 symmetry, suggesting that it has the same structure as NE1 but with one additional nitrogen atom in the coordination shell. The electronic states of these nickel-containing centres are discussed using the approach of Ludwig and Woodbury to transition metal ions in covalent crystals.