Radiation imagery chemistry: process – composition – or product th – Imaging affecting physical property of radiation sensitive... – Radiation sensitive composition or product or process of making
Patent
1999-01-29
2000-04-11
Baxter, Janet
Radiation imagery chemistry: process, composition, or product th
Imaging affecting physical property of radiation sensitive...
Radiation sensitive composition or product or process of making
4302831, 430325, G03F 7004
Patent
active
060486635
DESCRIPTION:
BRIEF SUMMARY
TECHNICAL FIELD
The present invention relates to a negative-working photoresist composition and the utilizations thereof, and specifically to a negative-working photoresist composition comprising a photosensitive polyamic acid and a method of forming a negative-type pattern and a method of producing a circuit substrate using the composition.
BACKGROUND OF THE INVENTION
Hitherto, a photoresist composition comprising a photosensitive polyimide or a polyamic acid which is a precursor thereof, such a photoresist composition, which has mainly been used practically, is one which is coated on a substrate, light-exposed by the irradiation of an actinic light via a definite photomask, whereby the solubility of the light-exposed portions to a developer is reduced. The unexposed portions are dissolved and removed with the developer to thereby form a desired negative-type pattern on the substrate.
Because in the photoresist composition using photosensitive polyimide or the precursor thereof, which leaves the light-exposed portions with an actinic light on a substrate, the pattern obtained is excellent in the heat resistance, various kinds of the photoresist compositions have hitherto been proposed. For example, a method of introducing a methacryloyl group into the polyimide precursor via an ester bond or an ionic bond (as described in JP-A-49-11541, JP-A-50-40922, JP-A-54-145794, JP-A-56-38038, etc.) (the term "JP-A" as used herein means an "unexamined published Japanese patent application"), a self-sensitizing-type polyimide having a benzophenone skeleton and having an alkyl group at the ortho-position to which a nitrogen atom is bonded (as described in JP-A-59-219330, JP-A-59-231533, etc.), etc., are proposed.
However, in the conventional negative-working photoresist composition comprising such a photosensitive polyimide or the precursor thereof, there are problems that the photoresist film is swelled with a developer at development and the light turns into at the light-exposure using a photomask to cause dissolution residues of the photoresist on the unexposed portions. Also, in the conventional negative-working photoresist composition, the shrinkage percentage of the film at hardening by heating is as large as about 50% and there is also a problem in the dimensional stability of the pattern obtained. Furthermore, because in the conventional photoresist composition, a developer containing an organic solvent is used, there is also a problem in the points of the working environment, the disposal of the waste solution, etc.
In addition, in the latter of the photoresist compositions described above, because the skeleton structure of the polymer is limited, the properties of the film finally obtained are subject to restriction and thus the polyimide cannot flexibly cope with various requirements.
Thus, the present inventors previously solved the above-described various problems in the negative-working photoresist composition comprising the conventional photosensitive polyamic acid by compounding the polyamic acid, which is a polyimide precursor, with a certain kind of a 1,4-dihydroxypyridine derivative forming a base having a pyridine skeleton by the irradiation of an actinic light as a photosensitive agent and clarified that a negative-working photoresist composition having a high sensitivity can be obtained as described in JP-A-6-75376.
However, in the negative-working photoresist composition, because the above-described 1,4-dihydroxypyridine derivative used as the photosensitive agent is insoluble in an aqueous alkali solution, an alcohol/water mixed solution of an alkali substance is used but in this case, depending on the component composition of the developer and the temperature of the development, the crystals of the above-described photosensitive agent sometimes deposit on the substrate during the development. When the crystals of the photosensitive agent deposit on the substrate, the development of a correct pattern is obstructed and also there is a possibility of lowering the resolving property by partiall
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patent: 5858518 (1999-01-01), Omote et al.
Fujii Hirofumi
Hayashi Shun-ichi
Ashton Rosemary
Baxter Janet
Nitto Denko Corporation
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