Polyimide thin films were prepared by vapor-deposition polymerization. Naphthalene carboxylic dianhydride (NTCDA) was coevaporated with either diamino naphthalene (DAN) or diamino benzophenone (DAB). Coevaporation of dianhydride and diamines yielded thin films of polyamic acids. A polyimide thin film was obtained by annealing the codeposited film of NTCDA-DAB. On the other hand, the codeposited film of NTCDA-DAN was not imidized by annealing. In both cases, chemical structures of the products were not largely influenced by the molar ratio of depositing monomers if sufficient amount of diamine molecules are supplied in the coevaporation process.

Fluoropolymer thin films were prepared by the ion-assisted vapor deposition polymerization (IAD) of 2-(perfluorohexyl)ethylacrylate (Rf-6). The adhesion strength of the film to substrates was estimated by sonicating the films in water and by immersing the films into dichloro-pentafluoro propane (HCFC225). The Rf-6 polymer films by IAD showed stronger adhesion to glass compared to a spin-coated Teflon AF film. The adhesion strength was improved with increasing ion energy Eion of IAD. The IAD films showed superior adhesion to PET surface compared to the glass substrate. The Rf-6 polymer film was effective as a single-layer antireflective coating. The refractive index of the film was 1.368 (λ = 546 nm), which increased slightly with increasing Eion. IAD can be a promising method to prepare fluoropolymer thin films due to the solvent-less process and the flexibility in controlling the film characteristics by the ion energy.

Thin films of a divinyl derivative of tetraphenyldiaminobiphenyl DvTPD were prepared by vapor deposition followed by annealing. After annealing at 200°C for 1 h, the film became practically insoluble to organic solvents due to polymerization. Electrical characteristics of the films were measured by current-voltage measurement, time-of-flight measurement, and dielectric measurement. It was found that the hole mobility of DvTPD decreases when the film is polymerized. As a consequence of the decrease of hole mobility, carrier balance in the emissive layer of an organic light emitting diode (OLED) was improved, leading to a higher quantum efficiency and a pure emission spectrum. The dielectric measurement also confirmed the high thermal stability of the polymerized film.

Thin film of polyurethane having metal complex was prepared by vapor deposition polymerization of bis (5,8-dihydroxyquinoline) zinc (ZnHq2) and 4, 4'-diphenylmethane diisocyanate monomers. The film was applied for the electron-transporting emissive layer of the organic light emitting diode. The deposition-polymerized film was found to give higher quantum efficiency of luminescence than the ZnHq2 monomer film.

Polyurea thin films containing azo-based nonlinear optical (NLO) chromophore were prepared by co-deposition of 4,4'-diphenylmethane diisocyanate and 2,4-diamino-4'-nitroazobenzene monomers using the ionization-assisted method. The co-deposited film reacted to form polyurea after annealing in the air. The dichroic optical absorption spectra indicated the preferential orientation of dipole moments in the as-deposited film. The substrate bias voltage influenced the optical anisotropy. Maker fringe measurement showed that the films have NLO activity without the poling process.

Polymeric thin films can be prepared by physical vapor deposition in several manners such as direct evaporation of the polymer, co-evaporation of two monomers followed by polyaddition or polycondensation reaction, or evaporation of single monomer followed by chain polymerization. The ionization-assisted deposition (IAD) was proposed as a new method of polymer deposition that has special features such as activation of polymerization reaction and aligning of the dipole orientation. These mechanisms were utilized for the formation of vinyl polymer and polyurea thin films aiming for such applications as organic light emitting diodes and piezoelectric devices.