We present experimental results of impurity and self-diffusion in an isotopically controlled silicon heterostructure extrinsically doped with phosphorus. As a consequence of extrinsic doping, the concentration of singly negatively charged native defects is enhanced and the role of these native defect charge states in the simultaneous phosphorus and Si self-diffusion can be determined. Multilayers of isotopically controlled 28Si and natural silicon enable simultaneous analysis of 30Si self-diffusion into the 28Si enriched layers and phosphorus diffusion throughout the multilayer structure. An amorphous 260 nm thick Si cap layer was deposited on top of the Si isotope heterostructure. The phosphorus ions were implanted to a depth such that all the radiation damage resided inside this amorphous cap layer, preventing the generation of excess native defects and enabling the determination of the Si self-diffusion coefficient and the phosphorus diffusivity under equilibrium conditions. These samples were annealed at temperatures between 950 and 1100°C to study the diffusion. Detailed analysis of the diffusion process was performed on the basis of a P diffusion model which involves neutral and positively charged mobile P species and neutral and singly negatively charged self-interstitial.