A new method for fabricating high performance polymeric thin films by chemical vapor polymerization

A vacuum deposition method is presented in which copolymer films are grown from a vinylic monomer chosen for desirable properties and paraxylylene. The concentration of paraxylylene in the final copolymer can be negligibly small if proper deposition conditions, presented here for the first time, are employed. Films of paraxylylene with N-phenyl maleimide deposited at 40 °C, for example, showed thermal stability and FTIR spectra nearly identical with homopolymers of poly(N-phenyl maleimide). Different rate-limiting steps are proposed to explain film composition; paraxylylene is under surface reaction control, while the comonomer obeys mass flow control. This results in a deposition environment extremely rich in comonomer. Growth rates and compositions were consistent with predictions. The initiation reaction did not appear different from homopolymerization of paraxylylene. The general method presented here allows fabrication of vapor-deposited thin films with properties limited primarily by the comonomer employed.