Ge-on-Si structures with three different dopants (P, As and B) and those without intentional doping were grown, annealed and characterized by several different material characterization methods. All samples have a smooth surface (roughness < 1.5 nm), and the Ge films are almost entirely relaxed. B doped Ge films have threading dislocations above 1 × 10 cm, while P and As doping can reduce the threading dislocation density to be less than 10 cm without annealing. The interdiffusion of Si and Ge of different films have been investigated experimentally and theoretically. A quantitative model of Si-Ge interdiffusion under extrinsic conditions across the full x range was established including the dislocationmediated diffusion. The Kirkendall effect has been observed. The results are of technical significance for the structure, doping, and process design of Ge-on-Si based devices, especially for photonic applications.