The simultaneous diffusion of Si and the dopants B, P, and As has been studied by the use of a multilayer structure of isotopically enriched Si. This structure, consisting of 5 pairs of 120 nm thick natural Si and 28 Si enriched layers, enables the observation of 30 Si self-diffusion from the natural layers into the 28 Si enriched layers, as well as dopant diffusion from an implanted source in an amorphous Si cap layer, via Secondary Ion Mass Spectrometry (SIMS). The dopant diffusion created regions of the multilayer structure that were extrinsic at the diffusion temperatures. In these regions, the Fermi level shift due to the extrinsic condition altered the concentration and charge state of the native defects involved in the diffusion process, which affected the dopant and selfdiffusion.The simultaneously recorded diffusion profiles enabled the modeling of the coupled dopant and self-diffusion. From the modeling of the simultaneous diffusion, the dopant diffusion mechanisms, the native defect charge states, and the self-and dopant diffusion coefficients can be determined. This information is necessary to enhance the physical modeling of dopant diffusion in Si. It is of particular interest to the modeling of pushing me to achieve. I am grateful to Ana for her unwavering love and support, for giving me the time during this busy year to write this thesis, but also for knowing when I need a break.