A method of forming a doped semiconductor layer on a substrate is provided. A foundation layer having a crystal structure compatible with a thermodynamically favored crystal structure of the doped semiconductor layer is formed on the substrate and annealed, or surface annealed, to substantially crystallize the surface of the foundation layer. The doped semiconductor layer is formed on the foundation layer. Each layer may be formed by vapor deposition processes such as CVD. The foundation layer may be germanium and the doped semiconductor layer may be phosphorus doped germanium.