Defect behavior during growth of heavily phosphorus-doped Czochralski silicon crystals. I. Experimental study

This report (I) aims to investigate defect behavior during the growth of heavily phosphorus (P)-doped Czochralski silicon (HP-Cz-Si) crystals. The defects and P chemical states in as-grown crystals with a resistivity of 0.6 mΩ cm and the wafers annealed at around 600 °C were evaluated by transmission electron microscopy and hard x-ray electron spectroscopy (HAXPES). Micro-dislocation loops (MDLs) were observed in the bottom portion of the crystal, and larger stacking faults (SFs), including complex dislocation clusters, were observed in the middle portion. HAXPES revealed two different P states, P1 and P2. P1 was attributed to a substitutional P (Ps). The P2 present in as-grown crystals was found to be electrically active, while the newly formed P2 after annealing was electrically inactive, indicating that they are in different states. HAXPES evaluation of HP-Cz-Si after electron irradiation showed similar behavior to P2 after annealing, suggesting that P-vacancy (V) clusters are formed when the crystals are held at temperatures below 600 °C during crystal growth. Combining the experimental results with our theoretical analysis in the report (II) based on density functional theory calculations, we identified the following defect formation mechanisms. Interstitial P (Pi) atoms introduced at the melting point become supersaturated during cooling to 600 °C, and MDLs are generated by the aggregation of Si self-interstitials (Is) released through a position exchange from Pi to Ps. In crystal portions with a long residence time below 600 °C, supersaturated Ps transforms into P–V clusters, and Is generated simultaneously are absorbed by the MDLs, which grow into SFs containing dislocation clusters.