Formation of covalently attached polymer overlayers on Si(111) surfaces using ring-opening metathesis polymerization methods

We describe a method for growing uniform, covalently attached polymer onto crystalline Si(111) surfaces. H-Terminated Si was first chlorinated, and th e surface-bound chlorine was then replaced by a terminal olefin using a Gri gnard reaction. A ruthenium ring-opening metathesis polymerization catalyst was then crossed onto the terminal olefin, and the resulting surface was s ubsequently immersed into a solution of monomer to produce the desired surf ace-attached polymer. The method provides a direct linkage between the poly mer and the Si without the presence of an electrically defective oxide laye r. Growth of the polymeric layer could be controlled by varying the concent ration of monomer in solution, and polynorbornene films between 0.9 and 550 0 nm in thickness were produced through the use of 0.01-2.44 M solutions of norbornene.