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Journal Articles

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

Chemistry of Materials, 20(16), p.5320 - 5324, 2008/08

 Times Cited Count:2 Percentile:9.32(Chemistry, Physical)

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 $$lambda$$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 $$mu$$C/cm$$^{2}$$. 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.

Journal Articles

Refractive index change and color imaging of acid-chromic polymer films using EB-induced acid generation

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

Journal of Photopolymer Science and Technology, 19(1), p.105 - 110, 2006/00

 Times Cited Count:2 Percentile:6.52(Polymer Science)

The novel electron beam (EB)-induced color imaging system, consisting of polymer films with acid-responsive chromic molecules (chromic dyes) and EB-acid generators (EBAGs) was proposed. EB irradiation of the acid-chromic polymer films induced acid generation from EBAG, resulting in color formation of the acid-chromic molecules (protonated forms). Nanoscale color imaging on the acid- chromic polymer films was carried out using EB scanning direct drawing. Clear color imaging of 200 nm square and 100 nm line/space patterns could be observed with a dose of only 50 $$mu$$C cm$$^{-2}$$. Furthermore, the large EB-induced refractive index change of these films (0.013 at 632.8 nm) was observed in both TE and TM modes by an m-line method, which is sufficient to create an optical circuit.

Oral presentation

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

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

no journal, , 

The polymer films with acid-responsive chromic molecules Rhodamine B base and 4,4'-bis(dimethylamino)benzhydrol as an acid-chromic compound with electron beam-acid generators were well designed for the novel electron beam-induced color imaging system. Electron beam scanning direct drawing of the acid-chromic polymer films gave clear color imaging of 100-200 nm line/space patterns with a dose of only 10 $$mu$$C cm$$^{-2}$$.

Oral presentation

Electron beam-induced reaction of polymer films containing chromic dye molecules

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

no journal, , 

A color forming performance for fabricating nanoscale patterned polymer films has been examined using electron beam direct writing (EBDW) techniques. Upon EB irradiation the poly(methyl methacrylate) film consisting of 3 wt% bis(dimethylamino)benzhydrol and the equimolar sulfonium salt has an absorption band at 560 nm, which is assigned to protonated benzhydrol. The appearance of the new band at 560 nm with an isosbestic point in the spectral changes of indicates the quantitative transformation from colorless benzhydrol to the protonated form. The film is then exposed with a raster scanning by EBDW. Upon EB irradiation they also undergo chemical changes to provide optical differentiation between the exposed and unexposed regions. The blue-colored line/space patterns of 100 - 200 nm with a dose of 10 $$mu$$C/cm$$^{2}$$ are achieved.

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