I just want to warn you that PDMS as such exhibits very low tensile strength as compared to organic rubbers. In macroscopic silicone rubbers the tensile properties are made accaeptable by adding silica aerogel (aerosil, Cab-O-Sl andt he like). So if you want remove a thin PDSM layer from a substrate without tearing it apart you sould try one of the following:
1. hydrophization of the glass surface to reduce the adhesion
2. using a lower polarity surace (e.g. teflon or the like)
3. adding some active silica nanofiller to the layer to increase the strength of your coating.
The intactness of the layer during peeling is determined by the ratio of adhesion stregtht and tensile strength.
If you spin PVA on the wafer first, you can release the PDMS in warm water and float the layer onto another substrate or supporting structure. Good luck.
Bond a supporting thick circular ring to the film while it is on the surface and then peel of the ring. It will avoid the collapsing of the PDMS film and will ease the handling of the PDMS film.