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The other possible explanation of the spectral features observed in the F-implanted and annealed region relates to the formation of F-related complexes containing F interstitials or other stable nonvacancy-related defect structures. The latter ones would exhibit an intrinsic PL emission under the implantation conditions, which could possibly explain the origin of the observed FB1 band. Notably, it is well known that Si-related complexes in diamond are intrinsically luminescent at room-temperature, the emission peak lying around 1-1.5eV above the absorption edge of diamond. The PL wavelength of F-related complexes in diamond has been reported as lying in the red spectral range, close to that of the FB1 band. According to our previous results, the spectral range and intensity of F-related emission are strongly dependent on the energy value of the implanted F ions. We are currently working on the identification and characterization of possible stable F-related complexes in diamond and their photoluminescence emission, and will report on this in detail in a subsequent publication.

On the other hand, upon the introduction of F in the diamond lattice it is well known that a stable FB1 emission is observed upon annealing at high-temperature in vacuum. It can be achieved by annealing F-implanted samples at 76 and/or high pressures. Until now, only hexagonal-close-packed (hcp) CVD samples with a 50 ppm F-doping concentration in the N-rich diamond layer, and subsequently annealed at 0.7 GPa for 24 hours, have been reported as exhibiting luminescence properties comparable to those of the band-edge states of bulk CVD diamond. Recently, however, Zhisui, et al. 101 reported on the preparation of cubic-BN underlayer grown by RIBE followed by in situ F ion implantation at room temperature. Annealing the system at 720oC for various periods of time resulted in the formation of low-temperature luminescent diamond. Spectroscopic investigations revealed that the emission of the layer was related to the crystalline band-edge states of diamond. In particular, the temperature-dependent PL spectral analysis revealed the presence of defects with an emission band centred at 624nm at low temperature, as well as of other defects with emission bands in the near IR spectral range at high temperature. Interestingly, the authors observed that the relative intensity of the first defect decreases with increasing annealing temperature, while the relative intensity of the second defect increases. Finally, the emission intensity of the latter defect, associated with low-temperature band-edge states, drops at high temperature, resulting in a characteristic step-like reduction of the PL intensity. These results suggested that the annealing-induced transformation of the hcp-BN layer was accomplished by means of a conversion from cubic-BN to hcp-diamond, and that the co-existence of hcp-CVD diamond and cubic-BN has the potential to be a new class of diamond-BN heterostructures.


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