Dynamic annealing assisted near-surface structural and bond stabilization in high-temperature low-energy N2+ implanted diamond

Nitrogen-rich ultra-thin (1–2 nm thick) layers in diamond produced by high-temperature nitrogen ion (N2+) implantation at low N2+ energies studied by in situ x-ray photoelectron spectroscopy are reported. Nitrogen bonding at the subsurface region and its thermal stability, as well as structural defects in polycrystalline diamond (PCD) implanted with 200, 500, and 800 eV N2+ at room temperature (RT) and 600 °C at an ion dose of 4.5 × 1014 ions/cm2, are investigated. Implantation at RT leads to nitrogen bonding at interstitial and substitutional sites in the diamond lattice, which is associated with the C–N/C=N bond, lower intensity of the C≡N (nitrile-like) component associated with nitrogen bonding with carbon defects, and quaternary nitrogen. The relative composition of these chemical states varies with implantation energy, temperature, and post-implantation annealing temperature. Upon annealing the RT implanted layers above 500–600 °C, the interstitial nitrogen converts to substitutional nitrogen. This process competes with nitrogen desorption. The thermal stability of nitrogen increases with implantation energy. Implantation at 600 °C at 800 eV resulted in a significantly lower concentration of nitrile-like bonds and a lower density of structural defects compared to RT implantation at the same energy. These effects are associated with dynamic annealing, which becomes more significant at higher implantation energies. Upon high-temperature implantation, nitrogen mostly populates directly substitutional sites. Nitrogen implantation at low energy and high temperature may be a viable way to nitride diamond surfaces with reduced density of defects where nitrogen is selectively bonded to substitutional sites. Finally, a comparison between nitrogen implantation into PCD and Diamond (100) [Di(100)] surfaces is presented.