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Characteristics of transparent cured film patterns prepared from sol-gel-derived positive-type photosensitive oligomeric silsesquioxanes with random structure

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Abstract

In the previous study, prebaked films are prepared from positive-type photosensitive oligomeric silsesquioxanes with phenyl (>50 mol%) and methyl substituents containing a diazonaphthoquinone derivative. Subsequently, forward-tapered patterns with <10-µm resolution widths are created from the films through mask exposure and alkali development. However, transparent insulating films used in optical devices require chemical and heat resistance together with gently forward-tapered shapes to prevent disconnection of the upper-layer wirings. In the present work, both prebaked and developed films are subjected to bleaching exposure and subsequent post-baking to clarify the effects of these treatments on the film properties. The treatments are found to complete the condensation reactions to form films with high visible-range transparency and good chemical and heat (230 °C) resistance. Notably, flow, fusion, and wrinkling occur during post-baking, resulting in desirable gentle-shaped patterns. The minimum pattern widths decrease from 40 to 20 µm with increasing methyl group content. Infrared absorption spectroscopy and thermogravimetric analyses reveal that the decrease in width is due to the increased fraction of regular ladder structures generated by condensation reactions during post-baking. The increase in highly reactive methyl-substituted silanol groups results in lower molecular chain motion at lower temperatures, leading to an increase in this fraction.

Graphical Abstract

a Structural formulae of oligo- and poly-SQs (A)­–(C). b Process for transparent cured film pattern from positive-type photosensitive coatings. c Patterning performance of photosensitive oligo-SQs. d IR absorption spectra of bleach-cured films. e TG curves of bleached films

Highlights

  • Cured films and patterns were formed via a transparent curing treatment of developed films and patterns obtained from sol-gel-derived positive-type photosensitive oligomeric silsesquioxanes.

  • The films exhibited high visible-range transparency and good chemical and heat (230 °C) resistance, and all patterns had gently forward-tapered shapes.

  • The minimum pattern widths decreased from 40 to 20 μm with increasing methyl group content in the oligomeric silsesquioxanes.

  • The decrease in width was attributed to the lower molecular chain motion, which resulted from the increase in the fraction of regular ladder structures generated at low temperatures by condensation reactions during post-baking.

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Acknowledgements

We would like to thank the staff of Electronic and Imaging Materials Research Laboratories, Toray Industries, Inc., for cooperation in carrying out this research and Editage (www.editage.com) for English language editing.

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Authors and Affiliations

  1. Electronic and Imaging Materials Research Laboratories, Toray Industries, Inc., 3-1-1 Sonoyama, Otsu, Shiga, 520-0842, Japan

    Mitsuhito Suwa, Manami Fujii & Masao Kamogawa

  2. Department of Chemistry and Materials Engineering, Kansai University, 3-3-35 Yamate-cho, Suita, Osaka, 564-8680, Japan

    Hiromitsu Kozuka

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  1. Mitsuhito Suwa
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MS wrote the manuscript text and prepared figures and tables. All authors reviewed the manuscript.

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Correspondence to Mitsuhito Suwa.

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Suwa, M., Fujii, M., Kamogawa, M. et al. Characteristics of transparent cured film patterns prepared from sol-gel-derived positive-type photosensitive oligomeric silsesquioxanes with random structure. J Sol-Gel Sci Technol 108, 514–527 (2023). https://doi.org/10.1007/s10971-023-06199-3

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