Radiation imagery chemistry: process – composition – or product th – Diazo reproduction – process – composition – or product – Composition or product which contains radiation sensitive...
Reexamination Certificate
2002-08-08
2004-10-19
Chu, John S. (Department: 1752)
Radiation imagery chemistry: process, composition, or product th
Diazo reproduction, process, composition, or product
Composition or product which contains radiation sensitive...
C430S191000, C430S192000, C430S193000, C430S326000
Reexamination Certificate
active
06806019
ABSTRACT:
TECHNICAL FIELD
This invention relates to a pattern forming method by i-line light exposure and a radiation sensitive resin composition used therefor which is suitable for a manufacturing of semiconductor devise, flat panel display (FPD), etc.
BACKGROUND ART
In the wide field of manufacturing semiconductor integrated circuits such as LSI, producing a display surface of FPD, manufacturing a circuit substrate for thermal head etc., and like use, photolithography technique has so far been employed for forming microelements or conducting fine processing. In the photolithography technique, a positive or negative-working radiation sensitive resin composition is used for forming a resist pattern. Of these radiation sensitive resin compositions, those compositions comprising an alkali-soluble resin and a photosensitizer of quinonediazide compound are popularly used as the positive-working radiation sensitive resin compositions. As such compositions, there are described compositions having different formulations as, for example, ‘novolak resin/quinonediazide compound’ in many documents such as Japanese Examined Patent Publication No. documents such as Japanese Examined Patent Publication No. S54-23570 (U.S. Pat. No. 3,666,473), Japanese Examined Patent Publication No. S56-30850 (U.S. Pat. No. 4,115,128), Japanese Unexamined Patent Publication Nos. S55-73045 and S61-205933, etc.
These compositions comprising a novolak resin and a quinonediazide compound have so far been studied and developed with respect to both novolak resins and radiation sensitive materials. In respect of novolak resins, there have been developed novel resins. In addition, radiation sensitive resin compositions having excellent properties have also been obtained by improving physical properties of conventionally known resins. For example, there are disclosed techniques providing a radiation sensitive resin composition having excellent properties by using a novolak resin with a particular molecular weight distribution in Japanese Unexamined Patent Publication Nos. S60-140235 and H01-105243 and by using a novolak resin from which low-molecular-weight components of the resin has been removed by fractionation in Japanese Unexamined Patent Publication Nos. S60-97347, S60-189739 and Japanese Patent Publication No.2590342.
On the other hand, degree of integration in semiconductor elements have been increased year by year and, in the manufacture of semiconductor elements or the like, processing of patterns with a line width of less than sub-micron order has become required. However, conventionally known radiation sensitive resin compositions can not satisfy enough these requirements in the prior art described above. Furthermore upon manufacturing a display surface of liquid crystal display (LCD) etc., the exposure by using exposure apparatus with g-line or g+h-line radiation source has been being conducted so far, however it has begun to examine a manufacturing process using i-line radiation source for forming a fine element and the radiation sensitive resin composition having high resolution suitable for i-line light exposure.
In order to realize the high resolving ability of a radiation sensitive resin composition for i-line light exposure, a technique to apply 1,2-naphthoquinone-2-diazide-5-sulfonic acid ester of 1,1,1-tris(4-hydroxy-3,5-dimethylphenyl)butane as a photosensitizer (Japanese Unexamined Patent Publication No. H06-332167), a technique to apply novolak resin derived from the particular phenolic compounds and photosensitizer (Japanese Unexamined Patent Publication Nos. H05-88364, H10-20503, and 2000-137324), a technique to apply photosensitive components containing naphthoquinonediazide sulfonic acid ester of trihydroxybenzophenone and trihydroxybenzophenone at the particular ratio (Japanese Unexamined Patent Publication No. H08-82926), a technique to apply an admixture of 1,2-naphthoquinone-2-diazide-5-sulfonic acid ester of 2,3,4-trihydroxybenzophenone with the particular esterification ratio and 1,2-naphthoquinone-2-diazide-5-sulfonic acid ester of 2,3,4,4′-tetrahydroxybenzophenone as a photosensitizer (Japanese Unexamined Patent Publication No. H02-109051), a technique to apply a photosensitizer restricting the amount of tetra ester component of 1,2-naphthoquinone-2-diazide-5 and/or 4-sulfonic acid ester of particular polyhydroxy compounds (Japanese Unexamined Patent Publication No. H09-15853), a technique to apply an admixture as a photosensitizer of 1,2-naphthoquinone-2-diazide-5-sulfonic acid ester and 1,2-naphthoquinone-2-diazide-4-sulfonic acid ester of 2,3,4,4′-tetrahydroxybezophenone at the particular mixing ratio have been being proposed. However in the prior art so far proposed, there are problems in view point of resolution and pattern form where the tailing occurred and it is desired to provide a radiation sensitive resin composition having high resolution and good pattern shape which can be applied for i-line light source exposure and the patter forming method using it.
Under the circumstances described above, an object of the present invention is to provide a radiation sensitive resin composition for i-line light exposure having high resolution and being able to form a good pattern without tailing etc. and a pattern forming method using it.
DISCLOSURE OF THE INVENTION
As a result of eager study and examination, the present inventors found that in pattern forming method using i-line light exposure source a radiation sensitive resin composition comprising an alkali-soluble resin and a quinonediazide group-containing photosensitizer wherein the alkali-soluble resin is a mixture of a novolak resin and one or more resins selected from (i) polyacrylate, (ii) polymethacrylate, (iii) a polystyrene derivative, and (iv) a copolymer consisting of two or more monomer units selected from acrylate, methacrylate and a styrene derivative can attain the above object and reached to the present invention.
It means the present invention relates to a pattern forming method which is characterized in that in pattern forming method using i-line light exposure source a radiation sensitive resin composition comprises an alkali-soluble resin and a quinonediazide group-containing photosensitizer wherein the alkali-soluble resin is a mixture of a novolak resin and one or more resins selected from (i) polyacrylate, (ii) polymethacrylate, (iii) a polystyrene derivative, and (iv) a copolymer consisting of two or more monomer units selected from acrylate, methacrylate and styrene derivatives.
Further the present invention relates to a radiation sensitive resin composition for i-line light exposure which is characterized in that a radiation sensitive resin composition comprises an alkali-soluble resin and a quinonediazide group-containing photosensitizer wherein the alkali-soluble resin is a mixture of a novolak resin and one or more resins selected from (i) polyacrylate, (ii) polymethacrylate, (iii) a polystyrene derivative, and (iv) a copolymer consisting of two or more monomer units selected from acrylate, methacrylate and styrene derivatives.
Hereinafter, the present invention will be described below further in more detail.
In the pattern forming method of the present invention i-line is used for light exposure source and as a radiation sensitive resin composition an alkali-soluble resin and a quinonediazide group-containing photosensitizer wherein the alkali-soluble resin is a mixture of a novolak resin and one or more resins selected from (i) polyacrylate, (ii) polymethacrylate, (iii) a polystyrene derivative, and (iv) a copolymer consisting of two or more monomer units selected from acrylate, methacrylate and styrene derivatives is used. The light exposure amount upon exposing i-line using the radiation sensitive resin composition of the present invention can be varied depending on the constitution of the radiation sensitive resin composition, however optimal exposure amount forming a pattern without tailing and being practically applied is 50 to 500 mJ/cm
2
. When applied for FPD it preferably applied
Chu John S.
Clariant Finance (BVI) Limited
Jain Sangya
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