Photosensitive poly(amic acid)/organoclay nanocomposites

Lien-Chung Hsu, Ulin Wang, Jinn Shing King, Jyh Long Jeng

Research output: Contribution to journalArticle

34 Citations (Scopus)

Abstract

A project was carried out aimed at reducing the coefficient of thermal expansion (CTE) of photosensitive polyimide formulations (photoresists) through the incorporation of small amounts of an organoclay. The organoclay was formed by a cation exchange reaction between a NA+-montmorillonite clay and an ammonium salt of dodecylamine. Two polyimide precursors, a poly(amic ester) (PAE) and a poly(amic acid) (PAA), were used in this study. The PAE was prepared by direct polymerization of 2,2′-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane and bis(n-butyl)ester of pyromellitic acid in the presence of phenylphosphonic dichloride as an activator. The polymer had an inherent viscosity of 0.23 dL/g. The PAA copolymer was prepared by polymerization of pyromellitic dianhydride, oxydiphthalic anhydride and oxydianiline. The polymer had an inherent viscosity of 1.00 dL/g. Two photosensitive resin/clay formulations were prepared from these two PI precursors using 2,3,4-tris(1-oxo-2-diazonaphthoquinone-5-sulfonyloxy)-benzophenone as the photosensitizer and 3 wt% organoclay. The films obtained from the PAA formulation were transparent and tough, while the films prepared from the PAE formulation were opaque and brittle. Both X-ray diffraction and transmission electron microscope analyses showed that, although the organoclay was not dispersed well in the PAE matrix, it was dispersed in the PAA matrix on a nanometer scale. The clay particles remained well dispersed after the PAA film was thermally imidized. The CTE of the polyimide film obtained was 23% lower than that of a similar film that did not contain the organoclay. The temperature at which the polyimide underwent a 5% weight loss when subjected to TGA in nitrogen was also increased by 13%. The photosensitive PAA/clay nanocomposite showed a sensitivity of 301 mJ/cm2 and a contrast of 1.66 when a 0.2 wt% tetramethylammonium hydroxide developer was used. A line/space pattern with a resolution of 10 μm was obtained from this formulation.

Original languageEnglish
Pages (from-to)5533-5540
Number of pages8
Journalpolymer
Volume44
Issue number19
DOIs
Publication statusPublished - 2003 Aug 21

Fingerprint

Organoclay
Nanocomposites
Polyimides
Clay
Acids
Thermal expansion
Esters
Polymers
Polymerization
Viscosity
Bentonite
Photosensitizing Agents
Photosensitizers
Anhydrides
Photoresists
Clay minerals
Ammonium Compounds
Cations
Ion exchange
Electron microscopes

All Science Journal Classification (ASJC) codes

  • Organic Chemistry
  • Polymers and Plastics

Cite this

Hsu, Lien-Chung ; Wang, Ulin ; King, Jinn Shing ; Jeng, Jyh Long. / Photosensitive poly(amic acid)/organoclay nanocomposites. In: polymer. 2003 ; Vol. 44, No. 19. pp. 5533-5540.
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abstract = "A project was carried out aimed at reducing the coefficient of thermal expansion (CTE) of photosensitive polyimide formulations (photoresists) through the incorporation of small amounts of an organoclay. The organoclay was formed by a cation exchange reaction between a NA+-montmorillonite clay and an ammonium salt of dodecylamine. Two polyimide precursors, a poly(amic ester) (PAE) and a poly(amic acid) (PAA), were used in this study. The PAE was prepared by direct polymerization of 2,2′-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane and bis(n-butyl)ester of pyromellitic acid in the presence of phenylphosphonic dichloride as an activator. The polymer had an inherent viscosity of 0.23 dL/g. The PAA copolymer was prepared by polymerization of pyromellitic dianhydride, oxydiphthalic anhydride and oxydianiline. The polymer had an inherent viscosity of 1.00 dL/g. Two photosensitive resin/clay formulations were prepared from these two PI precursors using 2,3,4-tris(1-oxo-2-diazonaphthoquinone-5-sulfonyloxy)-benzophenone as the photosensitizer and 3 wt{\%} organoclay. The films obtained from the PAA formulation were transparent and tough, while the films prepared from the PAE formulation were opaque and brittle. Both X-ray diffraction and transmission electron microscope analyses showed that, although the organoclay was not dispersed well in the PAE matrix, it was dispersed in the PAA matrix on a nanometer scale. The clay particles remained well dispersed after the PAA film was thermally imidized. The CTE of the polyimide film obtained was 23{\%} lower than that of a similar film that did not contain the organoclay. The temperature at which the polyimide underwent a 5{\%} weight loss when subjected to TGA in nitrogen was also increased by 13{\%}. The photosensitive PAA/clay nanocomposite showed a sensitivity of 301 mJ/cm2 and a contrast of 1.66 when a 0.2 wt{\%} tetramethylammonium hydroxide developer was used. A line/space pattern with a resolution of 10 μm was obtained from this formulation.",
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Photosensitive poly(amic acid)/organoclay nanocomposites. / Hsu, Lien-Chung; Wang, Ulin; King, Jinn Shing; Jeng, Jyh Long.

In: polymer, Vol. 44, No. 19, 21.08.2003, p. 5533-5540.

Research output: Contribution to journalArticle

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AU - Hsu, Lien-Chung

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N2 - A project was carried out aimed at reducing the coefficient of thermal expansion (CTE) of photosensitive polyimide formulations (photoresists) through the incorporation of small amounts of an organoclay. The organoclay was formed by a cation exchange reaction between a NA+-montmorillonite clay and an ammonium salt of dodecylamine. Two polyimide precursors, a poly(amic ester) (PAE) and a poly(amic acid) (PAA), were used in this study. The PAE was prepared by direct polymerization of 2,2′-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane and bis(n-butyl)ester of pyromellitic acid in the presence of phenylphosphonic dichloride as an activator. The polymer had an inherent viscosity of 0.23 dL/g. The PAA copolymer was prepared by polymerization of pyromellitic dianhydride, oxydiphthalic anhydride and oxydianiline. The polymer had an inherent viscosity of 1.00 dL/g. Two photosensitive resin/clay formulations were prepared from these two PI precursors using 2,3,4-tris(1-oxo-2-diazonaphthoquinone-5-sulfonyloxy)-benzophenone as the photosensitizer and 3 wt% organoclay. The films obtained from the PAA formulation were transparent and tough, while the films prepared from the PAE formulation were opaque and brittle. Both X-ray diffraction and transmission electron microscope analyses showed that, although the organoclay was not dispersed well in the PAE matrix, it was dispersed in the PAA matrix on a nanometer scale. The clay particles remained well dispersed after the PAA film was thermally imidized. The CTE of the polyimide film obtained was 23% lower than that of a similar film that did not contain the organoclay. The temperature at which the polyimide underwent a 5% weight loss when subjected to TGA in nitrogen was also increased by 13%. The photosensitive PAA/clay nanocomposite showed a sensitivity of 301 mJ/cm2 and a contrast of 1.66 when a 0.2 wt% tetramethylammonium hydroxide developer was used. A line/space pattern with a resolution of 10 μm was obtained from this formulation.

AB - A project was carried out aimed at reducing the coefficient of thermal expansion (CTE) of photosensitive polyimide formulations (photoresists) through the incorporation of small amounts of an organoclay. The organoclay was formed by a cation exchange reaction between a NA+-montmorillonite clay and an ammonium salt of dodecylamine. Two polyimide precursors, a poly(amic ester) (PAE) and a poly(amic acid) (PAA), were used in this study. The PAE was prepared by direct polymerization of 2,2′-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane and bis(n-butyl)ester of pyromellitic acid in the presence of phenylphosphonic dichloride as an activator. The polymer had an inherent viscosity of 0.23 dL/g. The PAA copolymer was prepared by polymerization of pyromellitic dianhydride, oxydiphthalic anhydride and oxydianiline. The polymer had an inherent viscosity of 1.00 dL/g. Two photosensitive resin/clay formulations were prepared from these two PI precursors using 2,3,4-tris(1-oxo-2-diazonaphthoquinone-5-sulfonyloxy)-benzophenone as the photosensitizer and 3 wt% organoclay. The films obtained from the PAA formulation were transparent and tough, while the films prepared from the PAE formulation were opaque and brittle. Both X-ray diffraction and transmission electron microscope analyses showed that, although the organoclay was not dispersed well in the PAE matrix, it was dispersed in the PAA matrix on a nanometer scale. The clay particles remained well dispersed after the PAA film was thermally imidized. The CTE of the polyimide film obtained was 23% lower than that of a similar film that did not contain the organoclay. The temperature at which the polyimide underwent a 5% weight loss when subjected to TGA in nitrogen was also increased by 13%. The photosensitive PAA/clay nanocomposite showed a sensitivity of 301 mJ/cm2 and a contrast of 1.66 when a 0.2 wt% tetramethylammonium hydroxide developer was used. A line/space pattern with a resolution of 10 μm was obtained from this formulation.

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