Nanoscale Vacancy-Mediated Aggregation, Dissociation, and Splitting of Nitrogen Centers in Natural Diamond Excited by Visible-Range Femtosecond Laser Pulses

Natural IaA+B diamonds were exposed in their bulk by multiple 0.3 ps, 515 nm laser pulses focused by a 0.25 NA micro-objective, producing in the prefocal region (depth of 20–50 μm) a bulk array of photoluminescent nanostructured microtracks at variable laser exposures and pulse energies. These micromarks were characterized at room (25°) and liquid nitrogen cooling (−120 °C) temperatures through stationary 3D scanning confocal photoluminescence (PL) microspectroscopy at 405 and 532 nm excitation wavelengths. The acquired PL spectra exhibit a linearly increasing pulse-energy-dependent yield in the range of 575 to 750 nm (NV(0), NV(−) centers) at the expense of the simultaneous reductions in the blue–green (450–570 nm; N3a, H4, and H3 centers) and near-IR (741 nm; V(0) center) PL yield. A detailed analysis indicates a low-energy rise in PL intensity for B2-related N3a, H4, and H3 centers, while at higher, above-threshold pulse energies it decreases for the H4, H3, and N3a centers, converting into NV centers, with the laser exposure effect demonstrating the same trend. The intrinsic and (especially) photo-generated vacancies were considered to drive their attachment as separate species to nitrogen centers at lower vacancy concentrations, while at high vacancy concentrations the concerted splitting of highly aggregated nitrogen centers by the surrounding vacancies could take place in favor of resulting NV centers.