Spectroscopic and microscopic characterizations of color lamellae in natural pink diamonds

Nineteen natural, untreated, type IaAB pink diamonds from various localities were studied. They display microscopic (∼1μm thick) pink lamellae along {111} in an otherwise colorless diamond. This coloration concentrated in lamellae is commonly referred to as “graining”. The diamonds were examined using high spatial resolution spectroscopic methods and transmission electron microscopy. TEM revealed that a pink lamella consists of a cluster of paired microtwins created under stress by plastic deformation. Raman line shift and broadening associated with the twinned pink lamellae indicate the presence of residual stress. Ultraviolet–visible absorption spectra from each of the samples showed a broad absorption band centered at ∼550nm, the source of the pink color. Cathodoluminescence spectra of the pink lamellae are different from those of the bulk, colorless diamond matrix. Within the lamellae only, the H3 center is observed along with a less intense N3 center. In some samples, instead of the N3 center a new center with a zero phonon line at 405.5nm is observed. This previously unreported 405.5nm center has phonon sidebands qualitatively identical to the N3 center, and may be an N3 center modified by a specific environment. These results suggest that lattice vacancies were created during twinning resulting from plastic deformation, and that impurity centers (such as those containing nitrogen) trap some of the diffusing vacancies. Since the pink lamellae are still under residual stress, new or modified defect centers are created, e.g. H3 and N3. The color center(s) responsible for the pink color (550nm absorption) was not identified, but likely is only present in diamonds that experienced plastic deformation. Reported annealing of plastically deformed brown diamonds, which results in a residual pink color, suggests that the pink color is stable under these high pressure, high temperature conditions. The reported observations that annealing plastically deformed brown diamonds results in a residual pink color and that the pink color does not anneal out under similar high pressure, high temperature conditions, suggests that the deformation inducing pink color occurs inside the Earth's mantle, whereas brown coloration might be induced during a more recent event such as the ascent of the diamond to the surface in a kimberlitic/lamproitic eruption.