Transitions of nitrogen optical centers induced by femtosecond laser pulses in treated natural diamond

Diamond is a unique optical material with ultra-hard lattice, which properties can be altered by optically active doping defects combined with carbon interstitials and vacancies. Direct laser writing by focused ultrashort laser pulses enables local modification of color centers in diamonds with excellent three-dimensional positioning accuracy, providing unique capabilities for quantum technologies, magnetometry, laser generation and photoluminescence (PL) micromarking. To shed light on currently unknown underlying atomistic transformations, we exposed electron-irradiated and annealed natural IaAB1-type diamond with an initially high content of various nitrogen-vacancy centers (NV, H3, N3 and H4) to millions of 0.2-ps, 525-nm laser pulses focused inside the sample. The modified areas were characterized by Fourier-transform infrared (FT-IR) and ultraviolet-visible transmission spectroscopy and confocal Raman/PL microspectroscopy with excitation wavelengths of 405 nm and 532 nm. We report on a local decrease in originally strong PL yield of NV, H3 and H4 centers with a monotonic dependence on both pulse energy and exposure time, as well as a rise of H1b and H1c lines in the FTIR spectra accompanied by a drop in the concentration of H1a center. The results indicate that laser-induced processes make possible both creation and destruction of NV, H3 and H4 centers influenced by their initial concentration and the parameters of laser modification, which can be useful for adjusting of laser writing regimes for PL micromark inscription and other local modification of diamond for photonics applications.