Raman investigation of damage caused by deep ion implantation in diamond

Raman microscopy has been employed to investigate the nature of damage created when natural type-IIa diamond is irradiated with MeV alpha particles. Three features appear in the Raman spectrum due to damage, viz., (i) the first-order diamond Raman line is broadened and downshifted, (ii) broad features appear which are a measure of the vibrational density of states of ion-beam-amorphized diamond, and (iii) the damage causes the appearance of sharp defect-induced Raman peaks at 1490 and 1630 ${\mathrm{cm}}^{\mathrm{-}1}$. For damage below an amorphization threshold, a linear relationship exists between the full width at half maximum and frequency shift, which shows that these are Kramers-Kronig related. The annealing behavior of the sharp Raman feature at 1490 ${\mathrm{cm}}^{\mathrm{-}1}$ suggests that this peak is associated with vacancies with an activation energy for annealing of 4.06 eV, while the ${1630-\mathrm{c}\mathrm{m}}^{\mathrm{-}1}$ peak is due to an interstitial related defect with an activation energy of 1.2 eV. For sub-MeV ion irradiation, damage beyond the critical amorphization level usually leads to relaxation of the diamond structure to graphite upon thermal annealing. However, for MeV ion irradiation, it was found that annealing, even when the ion induced damage level is well above the amorphization threshold, could restore the original diamond structure. We attribute this result to the high internal pressure the damaged layer is subjected to which does not allow relaxation to graphitically bonded structures.