The relationship between the distribution of nitrogen impurity centres in diamond crystals and their internal structure and mechanism of growth

Fifty diamond crystals of different morphological types (octahedra, dodecahedroids, cubes and single tetrahexahedroid) with differing internal structures were examined using methods of cathodoluminescence (CL), anomalous birefringence and local infrared (IR) analysis. The main objective of the study was to examine the regularities of nitrogen impurity distribution in diamond with differing internal structures. Almost all the analyzed octahedra, as well as dodecahedroids with zonal structures and the blocky dodecahedroids, are characterized either by nearly isothermic growth conditions or by a decrease in formation temperature during the crystallization process. In contrast to zoned octahedra and dodecahedroids, dodecahedroids with zonal–sectorial and sectorial internal structures show a notably different distribution of nitrogen defects, with N_tot generally decreasing from crystal cores to marginal areas, and degree of nitrogen aggregation increasing in the same direction. From this, it would follow that in these crystals, the temperature of diamond formation of the outer crystal zones is approximately 40–50 °C higher than that of the inner zones. The same result (15 to 80 °C) was obtained for diamond crystals with cubic habit, which generally show a fibrous internal structure, reflecting normal mechanisms of growth. The anomalous distribution of nitrogen centres in diamond crystals that grew through the normal mechanism, with a high rate of growth and in an oversaturated medium, might point to non-equilibrium relationships between the concentrations of different nitrogen centres. It is likely that in crystals of this type, the rate of growth is higher than the rate of structural nitrogen aggregation. Thus, it appears that in these peculiar crystals of diamond we deal with non-equilibrium concentrations of nitrogen B centres and, consequently, with anomalous, non-actual diamond formation temperatures.