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.

We have developed a new type electrical probing system based on an atomic force microscope. This method enables us to measure simultaneously the surface topography and surface potential of thin films containing the crystal grains. The obtained local potential changes give an insight into conduction through the grains and their boundaries.

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.

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.

To investigate the effect of alkyl chain length and adsorption time on the charge-transfer complex formation, ultraviolet-visible absorption and inelastic electron tunneling (IET) spectroscopy measurements were carried out for the tetramethylphenylenediamine (TMPD; donor molecule) adsorbed dodecyl-, pentadecyl- and octadecyl-tetracyanoquinodimethane (TCNQ) Langmuir-Blodgett (LB) films. In the optical absorption spectra, the main peak of LB films shows a red-shift depending on alkyl chain length and adsorption time. Furthermore, the dependence on alkyl chain length and adsorption time are also shown in the IET spectra. These results demonstrate that adsorption LB methods enable to control the adsorption ratio of functional molecules and the CT complex formation.

The doping effect of acceptor molecule tetracyanoquinodimethane (TCNQ) and donor molecule tetramethyltetraselenafulvalene (TMTSF) in an organic semiconductor was investigated by field effect measurements in merocyanine (MC) films. The electrical conductivity and carrier concentration of TCNQ-doped MC films were increased compared with those of undoped MC film. An efficient doping effect was observed at the doping concentration of approximately 9%. The electrical conductivity, on the other hand, was decreased by doping of the donor molecule TMTSF in MC film. However, no inversion of the conduction type was obtained. Furthermore, the transport mechanism of TCNQ-doped MC film and undoped film was elucidated from the temperature dependence of electrical parameters. These results demonstrate that TCNQ and TMTSF molecules act as acceptor and donor impurities in MC film, respectively, and the doping of these molecules is effective to control the electrical properties of organic semiconductors.

Thin films of PTFE (mean molecular weight of source material 8500) were deposited by ionization-assisted deposition (IAD) method at different ion acceleration voltages Va on substrates kept at room temperature. The molecular chains in the film were found to be oriented in parallel with the substrate, and the film has preferential crystal orientation to (100) plane. Although the ion acceleration did not give significant influence on the film orientation and chemical structure, IAD was effective to improve the surface smoothness. The Cu decoration test revealed that the pinhole density in the film is reduced and the insulating capability is improved by depositing the film at Va = 500 V. The result of dielectric loss measurement for Al/PTFE/Al capacitors was in consistency. However, excessive ion acceleration deteriorated the insulating property, probably due to the dielectric breakdown that occurred in the course of deposition.

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.

Semiconducting polymers, poly(1,4-phenylene) (PPP) and poly(4-diphenylaminostyrene) (PDAS), which are soluble to organic solvents, were synthesized and were deposited by means of electrospray deposition (ESD). The ESD generated spherical shells of diameters ranging from a few to several tens of microns. The shells consisted of coagulation of nanometric particles of the semiconducting polymers. Formation of the shells was largely influenced by the concentration of spray solution. It was also found that the formation of shells can be achieved with various types of soluble polymers.

STM/STS measurements have been carried out for TTF-TCNQ complex films evaporated on hydrogen-terminated silicon substrates, and the variation of tunneling spectra has been investigated on morphologically different crystal grains. Very thin semiconductive adsorbed layers were found to cover the as-deposited film surfaces. By removing the adsorbed layers, the intrinsic electronic structures of two different phases were revealed. A 'needle phase' which appears at the early stage of film growth has a semiconductive character and a 'granular phase' which grows later has a metallic character similar to bulk crystals. The electronic structure of the needle phase is considered to be affected by the substrate although the crystallographic structure is similar to the bulk crystal of TTF-TCNQ.

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.

We investigated the electrical properties of hole transport materials such as TPD, α-NPD and m-MTDATA using in-situ field effect measurement. TPD, α-NPD and m-MTDATA films showed p-type semiconducting properties, and their electrical parameters such as conductivity, carrier mobility and carrier concentration were obtained. We also examined the effect of the substrate temperature during vacuum deposition and the thermal treatment after deposition, on the electrical parameters of the films. Experimental results showed that conductivity and carrier mobility decreased as the substrate temperature increased over the glass transition temperature. These decreases in conductivity and carrier mobility as a result of thermal treatment appear to be strongly related to the degradation mechanism of organic electroluminescent devices.

Thin films of vinyl derivatives of naphthalene diimide were prepared by electron-assisted vapor deposition. Monomer materials of N, N'-bis(allyl)-naphthalene diimide (Allyl-NDI) and N,N'-bis(p-vinyl-benzyl)-naphthalene diimide (Sty-NDI) were newly synthesized for this purpose. Uniform films were obtained by vapor-depositing these materials, whereas spin-coating yielded nonuniform films. IR analysis suggested that Sty-NDI can be polymerized upon vapor deposition. An insoluble film of Sty-NDI was obtained by the electron-assisted vapor deposition. On the other hand, Allyl-NDI had lower reactivity for polymerization. It was concluded that Sty-NDI is a promising material for preparing thin films of vinyl polymer having naphthalene diimide units.

We have fabricated a static induction transistor structure by using copper phthalocyanine (CuPc) films. Its layer-structure is Au(drain)/CuPc/Al(gate)/CuPc/Au(source)/glass. The source-drain current is controlled by the Al gate bias-voltage when the drain voltage is positive but is almost independent of it when the drain voltage is negative. The current-voltage characteristics are governed by the space-charge-limited conduction which depends on shallow traps.

A self-assembled monolayer having a benzophenone unit as a photoreactive terminal group (BP-SAM) was prepared on an indium-tin oxide (ITO) electrode, on which a hole-transport layer of a phenoxazine-dioctylfluorene copolymer (H5) was spin-coated and irradiated with UV light. After washing the physisorbed H5 molecules, contact angle measurement and ellipsometry showed that the H5 molecules can be tethered to the ITO surface via the BP-SAM. Organic light-emitting diodes (OLEDs) were prepared in the structure of ITO/H5 hole transport layer/tris(8-hydroxyquinolato) aluminum/bathocuproin/LiF/Al electrode with and without the BP-SAM layer on the surface of ITO. The device with the BP-SAM showed higher current density and higher luminance due to the improvement of contact at the ITO/H5 interface by forming covalent bonds via the BP-SAM.