ABSTRACTSeveral recent experiments assessing the role of impurities (C, O), dopants (P, B) and clustering on defect evolution in ion implanted Si are reviewed. Deep level transient spectroscopy measurements were used to analyze the defect structure in a wide range of ion implantation fluences (1×10⁸–5×10¹³ cm⁻²) and annealing temperatures (100–800 °C). By using substrates with a different impurity content and comparing ion implanted and electron irradiated Si samples, many interesting features of defect evolution in Si have been elucidated. It is found that only a small percentage, 4–16 % depending on ion mass, of the Frenkel pairs generated by the beam escape direct recombination and is stored into an equal number of room temperature stable vacancy- (V-) and interstitial-type (I-) defect complexes. Identical defect structures and annealing behavior have been measured in ion implanted (1.2 MeV Si, 1×10⁸–1×10¹⁰/cm²) and electron irradiated (9.2 MeV to fluences between 1 and 3×10¹⁵/cm²) samples in spite of the fact that denser collision cascades are produced by the ions. The O and C content of the substrate plays a major role in determining the point defect migration, the room temperature stable defect structures and their annealing behavior. Annealing at temperatures up to 300 °C produces a concomitant reduction of the I- and V-type defect complexes concentration, demonstrating that defect annihilation occurs preferentially in the bulk. At temperatures above 300 °C, when all V-type complexes have been annealed out, ion implanted samples present a residual I-type damage, storing 2–3 I per implanted ion. This unbalance is not observed in electron irradiated samples and it is a direct consequence of the extra implanted ion. The simple point defect structures produced at low ion fluence (1×10⁸–1×10¹¹ /cm²) anneal at ∼ 550 °C. At higher fluences (∼ 10¹²–10¹³/cm²) and for annealing temperatures above 500 °C the deep level spectrum is dominated by two signatures at Ev+0.33 eV and at Ev+0.52 eV that we have associated to Si interstitial clusters. Impurities (C, O and B) play a role in determining nucleation kinetics of these defects, but they are not their main constituents. The dissolution temperature of these clusters indicates that they might store the interstitials that drive transient enhanced diffusion phenomena occurring in the absence of extended defects. Finally, at higher implantation fluence, a signature of extended defects is observed and associated to the presence of {311} defects detected by transmission electron microscopy analyses.