I like to silanize my masters with a tridecafluoro-silane. I use vapor deposition either in a desiccator or in a custom deposition chamber that I had some summer students build.
An easy option would be soak your silicon wafer in 1~5% Pluronic F127 (available at sigma and cheap) for 30min to 1hr. After soaking either wash wafer w/ water or directly blow dry it. This will coat a thin layer (visible) of surfactant on your mold and that will help with PDMS releasing. You can simply rinse your mold with water thoroughly to remove the Pluronic coating afterward
I use Trimethylchlorosilane (TMCS) to salinize the surface of Silicon model in sealed container for 15-30 min. You can hard bake the Silicone mold for about 10 min at 105 oC and cool it down before applying the TMCS to enhance the formation of molecular layer of TMCS. Be sure to use the chemicals in a chemical hood.
You can coat your wafers with a thin layer of sigmacote to prevent adhesion of PDMS.
In terms of PDMS residue left behind, make sure that the PDMS is totally hard before peeling. If you want to have a 'soft' PDMS, bake the system at 65C for at least 3 h. The totally hard PDMS should not leave any residue on top of the wafer.