Electron-beam-induced color imaging of acid-chromic polymer films

Maekawa, Yasunari; Yuasa, Kanako*; Enomoto, Kazuyuki; Matsushita, Harumi*; Kato, Jun*; Yamashita, Takashi*; Ito, Kazuo*; Yoshida, Masaru

Polymer films with acid-responsive chromic dyes and acid generators have been designed for an electron beam (EB)-induced color imaging system. Arylsulfonic acid esters and triphenylsulfonium salts were used as an EB-sensitive acid generator; the acid (H) allows a chromic reaction with rhodamine B base (RB) and 4,4'-bis(dimethylamino)benzhydrol (BH) to be triggered. Upon EB irradiation, poly(methyl methacrylate) (PMMA) films consisting of RB or BH and acid generators exhibited a characteristic absorption band with max at 560 and at 612 nm, respectively, and an isosbestic point. These spectral changes clearly indicate that colorless chromic dyes in PMMA are transformed selectively to the colored form. The color imaging of these films was performed by electron beam direct writing (EBDW) with a 50 nm diameter beam to form 100 - 1000 nm line and space patterns and was evaluated by optical and confocal laser microscopy. EBDW on the acid chromic polymer films, especially for BH, yielded clear color imaging of 100 - 200 nm line and space patterns with a dose of only 10 C/cm. The confocal laser microscopy gave thinner lines than the laser wavelength (632.8 nm), probably because of the large change in refractive index of the patterned film induced by EB irradiation even with a low energy dose.