JPH07248629A - Radiation-sensitive resin composition - Google Patents

Abstract

PURPOSE:To provide a radiation-sensitive resin composition capable of forming a positive type resist film excellent in sensitivity, developing property, film remaining factor, heat resistance, chemical resistance, adhesion to a substrate, and transparency in the visible light region. CONSTITUTION:This radiation-sensitive resin composition is constituted of (A) a copolymer of (a-1) unsaturated carboxylic acid, an epoxy group-containing radical polymerization compound (a-2) expressed by the formula, and another radical polymerization compound capable of being copolymerized with (a-1), (a-2) when required and (B) a 1,2-quinonediazo compound, (in the formula, R<1>-R<3> are hydrogen atoms or alkyl groups having the number of carbon atom of 1-10, independently and (m) is an integer of 1-5).

Description

Detailed Description of the Invention

[0001]

The present invention relates to a semiconductor integrated circuit, a thin film transistor (TFT) for a liquid crystal display (LCD).
The present invention relates to a radiation-sensitive resin composition suitable as a positive resist for forming a circuit and a mask for manufacturing a circuit, and also as a material for forming a permanent film such as an interlayer insulating film and a protective film for a color filter.

[0002]

2. Description of the Related Art In recent years, semiconductors have been manufactured by forming a pattern using a radiation-sensitive resin composition in the field of semiconductor industry. However, with the miniaturization of the pattern, it is possible to obtain a high resolution and a high sensitivity. There is a need for radioactive resin compositions.

By the way, in order to manufacture a fine pattern for forming a semiconductor, a resist capable of obtaining a high resolution of submicron or less may be required.
There is a strong demand for a high-sensitivity resist that can obtain a resolution of the order of m to several tens of μm and that exhibits a high yield even when the throughput is increased by using a substrate having a large diameter.

In order to produce such a micron-order pattern with high productivity, various methods are usually adopted in each step, which are capable of mass processing or high-speed processing, and are resistant to such processing conditions. A high performance resist is needed. For example, the etching process of the underlying substrate is often performed by a wet etching method capable of large-scale batch processing. Therefore, the resist that forms the pattern needs to have adhesiveness with the substrate and chemical resistance that is not attacked by an etchant. To be done. Further, when an ion implantation process or the like is added, heat resistance capable of withstanding high temperature heating is required.

As such a resist, a radiation-sensitive composition as a positive resist containing a novolac resin and a quinonediazide compound has been conventionally known, and is often used in the production of integrated circuits. However, this type of radiation-sensitive composition is excellent in resolution and dry etching resistance required in the case of a reactive ion etching (RIE) system, but has chemical resistance that can withstand wet etching as described above, Further, it cannot be said that it has sufficient characteristics in terms of sensitivity, adhesion to a substrate, and heat resistance.

In the liquid crystal display (LCD) industry which has been rapidly developing in recent years, a thin film transistor (TFT) is provided for each pixel among the liquid crystal displays.
The active matrix type liquid crystal display (AM-LCD) incorporating the
It is regarded as a favorite of next-generation display devices to replace (cathode ray tube), and it is desired to increase the area of the display screen.

The TFT circuit of such an AM-LCD is
A resist formed by using a radiation-sensitive composition (resist) and capable of obtaining a resolution of about several microns may be used. However, in order to enlarge the screen area, a larger-sized resist is used as compared with the above-described semiconductor manufacturing. It is necessary to use a substrate, and the resist used in such a case is required to have excellent sensitivity, adhesion to the substrate, heat resistance, etc., as in the case of mass production of semiconductors.

Further, when manufacturing a liquid crystal display, in addition to the formation of the AM-LCD circuit as described above, an interlayer insulating film, a protective film for a color filter, etc., which is conventionally formed by using a thermosetting resin, is used. There have been many attempts to form a permanent film with a radiation-sensitive composition.

In order to form a permanent film such as an interlayer insulating film or a protective film of such a liquid crystal display, a radiation sensitive composition having excellent heat resistance, chemical resistance and transparency is required. A conventional radiation-sensitive composition containing such a novolac resin and a quinonediazide compound has not been sufficiently satisfactory in terms of chemical resistance, adhesion to a substrate, heat resistance and the like.

Therefore, micron-order semiconductor integrated circuits, large-sized AM-LCD screens, and the like can be manufactured with high productivity, and further, chemical resistance suitable as a material for forming a permanent film such as an interlayer insulating film and a protective film. It has been desired to develop a radiation-sensitive composition having excellent properties, sensitivity, adhesion to a substrate, heat resistance and transparency.

[0011]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned conventional techniques, and is excellent in sensitivity, developability, residual film rate, heat resistance, chemical resistance and substrate. It is an object of the present invention to provide a positive resist type radiation sensitive resin composition having excellent adhesion and transparency in the visible light region.

[0012]

A radiation-sensitive resin composition according to the present invention is represented by [A] (a-1) unsaturated carboxylic acid and (a-2) represented by the following general formula [I]. An epoxy group-containing radically polymerizable compound,

[0013]

[Chemical 2]

If necessary (a-3) above (a-1), (a-2)
It is characterized by comprising a copolymer with another radically polymerizable compound capable of copolymerizing with [B] 1,2-quinonediazide compound.

First, each component contained in the radiation-sensitive resin composition according to the present invention will be described below. In the present invention, the term "radiation" means ultraviolet rays, far ultraviolet rays,
X-ray, electron beam, molecular beam, γ-ray, synchrotron radiation,
It is used in the concept including proton beam lines.

[A] Copolymer The copolymer [A] used in the present invention comprises (a-1) an unsaturated carboxylic acid and (a-2) an epoxy group represented by the general formula [I] described below. It is a copolymer with a radical-containing polymerizable compound.

Examples of such unsaturated carboxylic acid (a-1) include unsaturated carboxylic acids having an ethylenically unsaturated double bond, and specific examples thereof include methacrylic acid, acrylic acid, crotonic acid, o. -, M-, p-Vinylbenzoic acid and other monocarboxylic acids, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 1,4-cyclohexene dicarboxylic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, methyl Examples thereof include dicarboxylic acids such as -5-norbornene-2,3-dicarboxylic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid and dimethyltetrahydrophthalic acid.

Of these, methacrylic acid, acrylic acid and itaconic acid are preferably used. Further, in the present invention, as the unsaturated carboxylic acid (a-1), if it has an unreacted carboxylic acid group, a partially esterified product or partially amidated product of the unsaturated carboxylic acid as described above, that is, a half of the unsaturated dicarboxylic acid. Esters or half amides can also be used.

As such a half ester or half amide of an unsaturated dicarboxylic acid, monomethyl itaconate, monobutyl itaconate and the like are preferably used. Further, as the unsaturated carboxylic acid (a-1), two or more kinds of the above compounds may be used in combination.

The epoxy group-containing radically polymerizable compound (a-2) used in the present invention is represented by the following general formula [I].

[0021]

[Chemical 3]

Examples of such an epoxy group-containing radically polymerizable compound (a-2) include, for example, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-
o-Vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-diglycidyloxymethylstyrene, 2,4-diglycidyloxymethylstyrene, 2 , 5-Diglycidyloxymethylstyrene, 2,6-diglycidyloxymethylstyrene, 2,3,4-triglycidyloxymethylstyrene, 2,3,5-triglycidyloxymethylstyrene, 2,3,6-tri Glycidyloxymethylstyrene, 3,4,5-triglycidyloxymethylstyrene, 2,
4,6-triglycidyl oxymethyl styrene etc. are mentioned.

Of these, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether and p-
Vinylbenzyl glycidyl ether and the like are preferable. These compounds may be used in combination of two or more kinds.

Further, the copolymer [A] used in the present invention.
Is a copolymer of the above unsaturated carboxylic acid (a-1), a compound having an epoxy group (a-2), and another radically polymerizable compound (a-3) copolymerizable therewith. It may be.

Specific examples of such radically polymerizable compound (a-3) include styrene, α-, o-, m-, p-methylstyrene, p-methoxystyrene, p-tertbutoxystyrene,
Styrenes such as chloromethylstyrene, butadiene,
Dienes such as 2,3-dimethylbutadiene and isoprene,
(Meth) acrylic acid-methyl, -ethyl, -n-propyl, -i-propyl, -n-butyl, -sec-butyl, -ter-
Butyl, -2-ethylhexyl, -lauryl, -dodecyl, -dicyclopentanyl, -isobornyl, -cyclohexyl, 2-methylcyclohexyl, -dicyclohexyl, -adamantyl, -allyl, -probagyl, -phenyl, -naphthyl,-. Anthracenyl, -cyclopentyl, -furyl, -tetrahydrofuryl, -pyranyl,
-Benzyl, -phenesyl, -cresyl, -1,1,1-trifluoroethyl, -perfluoroethyl, -perfluoro-n-propyl, -perfluoro-i-propyl, -triphenylmethyl, -adamantyl,- Such as (meth) acrylic acid alkyl ester such as cumyl, (meth) acrylic acid cycloalkyl, (meth) acrylic acid aryl ester, (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl, etc. (Meta)
(Meth) acrylic acid amides such as acrylic acid hydroxyalkyl ester, (meth) acrylic acid-amide, -N, N-dimethylamide, -N, N-propylamide, (meth) acrylic acid-anilide, (meth) acrylonitrile , Vinyl compounds such as acrolein, vinyl chloride, vinylidene chloride, N-vinylpyrrolidone and vinyl acetate, unsaturated dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconate, glycidyl (meth) acrylate, α-ethylglycidyl (Meth) acrylate, α-n-propylglycidyl (meth) acrylate,
α-n-butylglycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 3,4-epoxyheptyl (meth) acrylate, α-ethyl-6,7-epoxyheptyl (meth) acrylate, allylglycidyl The above general formula [I] such as ether and vinyl glycidyl ether
Examples thereof include glycidyl compounds that are not included in the composition.

Of these, styrene, glycidyl (meth) acrylate, p-tertbutoxystyrene, α-methylstyrene, dicyclopentanyl methacrylate, methyl methacrylate, 2-hydroxyethyl methacrylate, benzyl methacrylate, butadiene Etc. are preferably used. Moreover, you may use these in combination of 2 or more types.

The copolymer [A] used in the present invention is obtained by copolymerizing each of the above compounds,
(a-1) An unsaturated carboxylic acid component, usually in an amount of 5 to 50% by weight, preferably 10 to 40% by weight, (a-2) an epoxy group-containing radically polymerizable compound component represented by the formula [I]. , Usually 5 to 95% by weight, preferably 30 to 80% by weight.

Further, (a-3) the other radically polymerizable compound is
It is contained as an optional component, but may be contained in an amount of less than 90% by weight in the copolymer [A]. Such a copolymer [A] has a carboxylic acid group and an epoxy group, is soluble in an alkaline aqueous solution, and can be crosslinked by heating.

Further, the copolymer [A] formed from each of the above components has an appropriate solubility in an alkaline aqueous solution, and the copolymer [A] has a developability. An excellent radiation-sensitive resin composition can be obtained, a film (pattern) can be formed with high sensitivity and an excellent development residual film rate, heat resistance, adhesion to a substrate, and visible light range. It is possible to form a coating (pattern) having excellent transparency.

When the content of the unsaturated carboxylic acid (a-1) component in the copolymer consisting of the above components is less than 5% by weight, the resulting coating film has a reduced solubility in an alkaline aqueous solution. In some cases, the developability may be lowered or the sensitivity may be lowered. On the other hand, when it exceeds 50% by weight, the resulting coating film may have too high solubility in an alkaline aqueous solution. Further, when the content of the epoxy group-containing radically polymerizable compound (a-2) component is less than 5% by weight, the resulting coating film may have insufficient crosslink density and poor heat resistance, while when it exceeds 95% by weight. In some cases, the resulting coating may have reduced solubility in an alkaline aqueous solution, resulting in poor developability and reduced sensitivity.

The copolymer [A] used in the present invention has a polystyrene-reduced weight average molecular weight (Mw) of usually 2 × 1.
0 ³ to 10 × 10 ^4, preferably 5 × 10 ^{3 to} 5 × 10 ^4.
Is desirable. From the copolymer [A] having such a molecular weight (Mw), a coating film having excellent pattern shape, developability, residual film rate, and heat resistance can be obtained.

The copolymer [A] has a molecular weight (M
When w) is less than 2 × 10 ³ , the resulting coating may have poor developability and residual film rate, and may be inferior in pattern shape and heat resistance. On the other hand, when it exceeds 10 × 10 ⁴ , the obtained film may be obtained. The resulting coating may have poor developability and sensitivity, or may be inferior in pattern shape.

The above-mentioned copolymer [A] used in the present invention comprises (a-1) an unsaturated carboxylic acid, (a-2) an epoxy group-containing radically polymerizable compound and, if necessary, Te (a
-3) It can be obtained by copolymerizing another polymerizable compound by a conventionally known polymerization method, but is preferably obtained by copolymerizing in a solvent in the presence of a catalyst (polymerization initiator).

Examples of the solvent used at this time include alcohols such as methanol, ethanol, propanol and butanol, cyclic ethers such as tetrahydrofuran and dioxane, cellosolve esters such as methyl cellosolve acetate and ethyl cellosolve acetate, ethylene glycol monomethyl ether. , Ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether and other glycol ethers, propylene glycol methyl ether acetate, propylene glycol propyl ether acetate and other propylene glycol alkyl ether acetates, benzene, toluene, xylene, etc. Aromatic hydrocarbon water S, methyl ethyl ketone, cyclohexanone, ketones such as 4-hydroxy-4-methyl-2-pentanone, ethyl 2-hydroxypropionate, 2-hydroxy-2-methylpropionic acid ethyl, 2-hydroxy-2-
Ethyl methyl propionate, Ethyl ethoxyacetate, Ethyl hydroxyate, Methyl 2-hydroxy-3-methylbutanoate, Methyl 3-methoxypropionate, Ethyl 3-methoxypropionate, Ethyl 3-ethoxypropionate, Methyl 3-ethoxypropionate , Esters such as ethyl acetate, butyl acetate, DMF (dimethylformamide), NM
An aprotic polar solvent such as P may be used.

These solvents are 10 in total of the polymerizable compound.
It is usually used in an amount of 20 to 1000 parts by weight with respect to 0 parts by weight. As the catalyst, those generally known as radical polymerization initiators can be widely used,
For example, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), etc. Azo compounds, organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, and 1,1'-bis (t-butylperoxy) cyclohexane, and hydrogen peroxide can be used. .

When a peroxide is used as the radical polymerization initiator, the peroxide may be used together with a reducing agent to prepare a redox type initiator. According to the above-mentioned copolymerization, the copolymer [A] is a polymerization (reaction solvent) liquid containing the copolymer [A] which is usually a reaction product in an amount of 1 to 85% by weight in solid content concentration. can get.

[B] 1,2-Quinonediazide Compound As the 1,2-quinonediazide compound [B] used in the present invention, an ester-esterified product of a polyhydric phenol and 1,2-quinonediazidesulfonic acid is used. As the 1,2-quinonediazide compound [B], a compound in which all or part of the hydroxyl groups of polyhydric phenol are esterified with 1,2-quinonediazidesulfonic acid can be used. 20-100% of hydroxyl groups are 1,2-
Compounds esterified with quinonediazide sulfonic acid can be used. Examples of such a 1,2-quinonediazide compound [B] include, for example, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester and 2,3,4-trihydroxybenzophenone-
1,2-naphthoquinonediazide-5-sulfonic acid ester,
Trihydroxybenzophenones such as 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester and 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester An esterification product of 1,2-quinonediazide sulfonic acid, 2,
2 ', 4,4'-Tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2', 4,4'-Tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid Ester, 2,3,4,3'- Tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4,3'- Tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5- Sulfonate, 2,3,4,4'-tetrahydroxybenzophenone-
1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,
3,4,4'- Tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4,2'-tetrahydroxy-4'-methylbenzophenone-1,2-naphthoquinonediazide-4 -Sulfonic acid ester, 2,3,4,2'-tetrahydroxy-4'-methylbenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4,4'-tetrahydroxy-3 ' -Methoxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4,4'-
Esterification products of tetrahydroxybenzophenone such as tetrahydroxy-3'-methoxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester and 1,2-naphthoquinonediazidesulfonic acid, 2,3,4,2 ', 6 '-Pentahydroxybenzophenone-1,2-naphthoquinonediazide-4
-Sulfonic acid ester, 2,3,4,2 ', 6'-pentahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester and other pentahydroxybenzophenones
1,2-naphthoquinone diazidesulfonic acid esterification product, 2,4,6,3 ', 4'5'-hexahydroxybenzophenone-
1,2-naphthoquinonediazide-4-sulfonic acid ester,
2,4,6,3 ', 4'5'-Hexahydroxybenzophenone-1,2-
Naphthoquinonediazide-5-sulfonic acid ester, 3,4,5,
3 ', 4'5'-hexahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 3,4,5,3', 4 '
Esterification products of hexahydroxybenzophenone such as 5'-hexahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester and 1,2-naphthoquinonediazidesulfonic acid, bis (2,4'-dihydroxyphenyl) methane- 1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2,4'-dihydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonic acid ester and other bis (2,4'-dihydroxyphenyl) methane And 1,
An esterification product with 2-naphthoquinonediazide sulfonic acid,
Bis (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonic acid ester, etc. Phenyl)
Esterification product of methane and 1,2-naphthoquinonediazide sulfonic acid, tri (p-hydroxyphenyl) methane-1,2-
Tri (p-hydroxyphenyl) methane such as naphthoquinonediazide-4-sulfonic acid ester and tri (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonic acid ester and 1,2-naphthoquinonediazidesulfonic acid Esterification product of 1,1,1-tri (p-hydroxyphenyl) ethane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,1,1-tri (p-hydroxyphenyl) ethane-1,2 -1,1,1-tri (p-hydroxyphenyl) ethane such as naphthoquinonediazide-5-sulfonate and 1,
An esterification product with 2-naphthoquinonediazide sulfonic acid,
Bis (2,3,4-trihydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonate, bis (2,
3,4-trihydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonic acid ester and other bis (2,3,4-
Esterification product of (trihydroxyphenyl) methane and 1,2-naphthoquinonediazide sulfonic acid, 2,2-bis (2,3,4-
Trihydroxyphenyl) propane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2-bis (2,3,4-trihydroxyphenyl) propane-1,2-naphthoquinonediazide-5-sulfonic acid ester, etc. 2,2-bis (2,3,4-
Esterification product of trihydroxyphenyl) propane and 1,2-naphthoquinonediazide sulfonic acid, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinonediazide -4-sulfonic acid ester, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 1,1, 3-Tris (2,5-
Esterification product of dimethyl-4-hydroxyphenyl) -3-phenylpropane and 1,2-naphthoquinonediazidesulfonic acid, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methyl Ethyl] phenyl] ethylidene] bisphenol-1,2-
Naphthoquinonediazide-4-sulfonic acid ester, 4,4'-
[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-5-sulfonic acid ester and other 4,4 '-[1- [ 4- [1-
Esterification product of [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol and 1,2-naphthoquinonediazidesulfonic acid, bis (2,5-dimethyl-4-
Hydroxyphenyl) -2-hydroxyphenylmethane-
1,2-naphthoquinonediazide-4-sulfonic acid ester,
Bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2-naphthoquinonediazide-5-
Bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane such as sulfonate and 1,2-
Esterification products with naphthoquinone diazide sulfonic acid, 3,
3,3 ', 3'-Tetramethyl-1,1'-spiroindene-5,6,7,5',
6 ', 7'-hexanol-1,2-naphthoquinonediazide-4-sulfonic acid ester, 3,3,3', 3'-tetramethyl-1,1'-spiroindene-5,6,7,5 ' 3,6 ', 7'-Hexanol-1,2-naphthoquinonediazide-5-sulfonic acid ester such as 3,3,3',
3'-Tetramethyl-1,1'-spiroindene-5,6,7,5 ', 6', 7 '
-Esterification product of hexanol and 1,2-naphthoquinonediazide sulfonic acid, 2,2,4-trimethyl-7,2 ', 4'-trihydroxyflavan-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2 2,2,4-Trimethyl-7,2 ', 4'-trihydroxyflavan-1,2-naphthoquinonediazide-5-sulfonic acid ester and other 2,2,4-trimethyl-7,2', 4'-tri An esterification product of hydroxyflavan and 1,2-naphthoquinonediazide sulfonic acid can be mentioned.

Furthermore, J. "Light-Sensitive" by Kosar
Systems ”339-352, (1965). John Willey & Sons (Ne
w York), "Photoresist" 50, (1975) Mc by WS De Forse
Other examples include 1,2-quinonediazide compounds described in Graw-Hill, Inc. (New York).

Of these, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester and 2,3,4-trihydroxybenzophenone-1,2-
Naphthoquinonediazide-5-sulfonate, 2,3,4,
4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide
-5-sulfonic acid ester, 1,1,3-tris (2,5-dimethyl-
4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1 , 2-Naphthoquinonediazide-5-sulfonic acid ester, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1
-Methylethyl] phenyl] ethylidene] bisphenol-
1,2-naphthoquinonediazide-4-sulfonic acid ester,
4,4 '-[1- [4- [1- [4-Hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,2,4 -Trimethyl-7,2 ', 4'-trihydroxyflavan-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2,4-trimethyl-7,2', 4'-trihydroxyflavan-1, 2-naphthoquinonediazide-5-sulfonate, 1,1,1-tri (p-hydroxyphenyl) ethane-1,2-naphthoquinonediazide-4-sulfonate, 1,1,1-tri (p-hydroxy) Phenyl) ethane-1,2-naphthoquinonediazide-5-
Sulfonic acid esters and the like are preferably used.

Also, these 1,2-quinonediazide compounds can be used in combination of two or more kinds. Examples of 1,2-quinonediazide sulfonic acid esters as described above include halides of 1,2-quinonediazide sulfonic acid,
Obtained by esterification with the corresponding polyhydric phenol (polyhydric hydroxy compound) in the presence of a base catalyst.

More specifically, for example, the above 2,
3,4-Trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester is obtained by condensing 2,3,4-trihydroxybenzophenone and 1,2-quinonediazide-5-sulfonic acid chloride. To be

In such an esterification reaction, it is desirable that the halide of 1,2-quinonediazide sulfonic acid is usually used in an amount of 1.0 to 1.2 mol per 1 mol of the hydroxyl group of the hydroxy compound. .

Radiation-sensitive resin composition The radiation-sensitive resin composition according to the present invention comprises the above-mentioned copolymer [A] and 1,2-quinonediazide compound [B]. A] to 100 parts by weight of 1,2-
It is desirable to contain the quinonediazide compound [B] in an amount of 5 to 100 parts by weight, preferably 10 to 50 parts by weight.

Such a radiation-sensitive composition has excellent sensitivity and developability and a high residual film ratio, and also has excellent heat resistance, chemical resistance, adhesion to a substrate and transparency in the visible light region ( Pattern) can be formed.

When the amount of the 1,2-quinonediazide compound [B] in the radiation-sensitive resin composition is less than 5 parts by weight based on 100 parts by weight of the copolymer [A], the composition is formed from the composition. The coating film formed may have difficulty in patterning due to a small difference in solubility between exposed and unexposed areas.
If the amount exceeds 1 part by weight, the 1,2-quinonediazide compound may not be sufficiently decomposed by irradiation with radiation for a short time, and the sensitivity may decrease.

Such a radiation-sensitive resin composition of the present invention is used as a positive resist for preparing a semiconductor integrated circuit, a liquid crystal display (LCD) thin film transistor (TFT) circuit, a mask for manufacturing a circuit, and further, It is also suitable as a material for forming a permanent film such as an interlayer insulating film and a protective film for a color filter.

The radiation-sensitive resin composition according to the present invention may contain components other than the above components, if necessary, within the range not impairing the object of the present invention. Other Components The radiation-sensitive resin composition according to the present invention may contain a sensitizer for the 1,2-quinonediazide compound [B] in order to further improve the sensitivity.

Examples of such a sensitizer include 2H-
Pyrido- (3,2-b) -1,4-oxazin-3 (4H) -ones, 10H-
Examples thereof include pyrido- (3,2-b) -1,4-benzothiazines, urazoles, hydantoins, barbituric acids, glycine anhydrides, 1-hydroxybenzotriazoles, alloxans, maleimides and the like. You may use these in combination.

The radiation-sensitive resin composition according to the present invention contains such a sensitizer as a 1,2-quinonediazide compound [B] 1
It may be contained in an amount of usually 100 parts by weight or less, preferably 4 to 60 parts by weight, based on 00 parts by weight.

The radiation-sensitive resin composition according to the present invention also comprises
In order to improve heat resistance and adhesion to the substrate, a compound having at least two epoxy groups in the molecule may be contained. As such an epoxy group-containing compound,
For example, Epicoat 1001, 1002, 100
3, 1004, 1007, 1009, 101
0, 828 (trade name; manufactured by Yuka Shell Epoxy Co., Ltd.)
Bisphenol A type epoxy resin such as Epicoat 8
07 (trade name; Yuka Shell Epoxy Co., Ltd.) and other bisphenol F type epoxy resins, Epicoat 152, 154 (trade name; Yuka Shell Epoxy Co., Ltd.), EP
PN201, 202 (trade name; manufactured by Nippon Kayaku Co., Ltd.) and other phenol novolac type epoxy resins, EOCN1
02, 103S, 104S, 1020, 1025,
1027 (trade name; manufactured by Nippon Kayaku Co., Ltd.), Epikote 1
Cresol novolac type epoxy resin such as 80S75 (trade name; manufactured by Yuka Shell Epoxy Co., Ltd.), CY-17
5, the same 177, the same 179, Aldalite CY-182,
192, 184 (trade name; Ciba-Geigy Co., Ltd.)
Manufactured), ERL-4234, 4299, 4221, 420
6 (trade name; manufactured by U.C.C. company), Shodyne 509
(Trade name: Showa Denko KK), Epicron 200, 400 (trade name: Dainippon Ink & Co., Ltd.), Epicoat 871, 872 (trade name; Yuka Shell Epoxy Co., Ltd.)
, ED-5661, ED-5661 (trade name; manufactured by Celanese Coating Co., Ltd.), and other cycloaliphatic epoxy resins, Epolite 100MF (Kyoeisha Oil and Fat Chemical Co., Ltd.)
Manufactured by Nippon Oil & Fats Co., Ltd., and the like, and aliphatic polyglycidyl ethers.

Among these, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, and aliphatic polyglycidyl ether are preferably used.

The molecular weight of the above epoxy group-containing compound is not particularly limited, and may be a high molecular weight, or may be a low molecular weight such as glycidyl ether of bisphenol A (or F). Good.

The epoxy group-containing compound as an optional component is optionally used in an amount of 5 to 50 parts by weight with respect to 100 parts by weight of the copolymer [A]. In the present invention,
A surfactant may be added to improve the coating property of the radiation-sensitive resin composition, for example, to prevent striation (coating streaks) and to improve the developability of the coating film. As the surfactant, for example, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether and other polyoxyethylene alkyl ethers, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, and the like. Nonionic surfactants such as oxyethylene aryl ethers, polyoxyethylene dilaurate, polyoxyethylene dialkyl esters such as polyoxyethylene distearate, Ftop EF301, 303, 352 (manufactured by Shin-Akita Kasei Co., Ltd.) ), Megafac F171, F172, F
173 (manufactured by Dainippon Ink and Chemicals, Inc.), Florard FC-430, FC-431 (Sumitomo 3M Limited)
Made), Asahi Guard AG710, Surflon S-38
2, the same SC-101, the same SC-102, the same SC-10
3, the same SC-104, the same SC-105, the same SC-106
(Asahi Glass Co., Ltd.) and other commercially available fluorosurfactants, organosiloxane polymer KP341
(Manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid-based copolymer Polyflow No. 57, 95 (manufactured by Kyoeisha Yushi-Kagaku Kogyo Co., Ltd.) and the like.

Two or more of these may be used. Such a surfactant has a total amount of the radiation-sensitive resin composition of 1
When the amount is 00 parts by weight, it may be contained in an amount of 2 parts by weight or less, preferably 1 part by weight or less.

The radiation-sensitive resin composition according to the present invention may contain an adhesion aid in order to improve the adhesion to the substrate. Examples of such an adhesion aid include a functional silane coupling agent and the like.

Further, the radiation-sensitive resin composition according to the present invention may contain an antistatic agent, a storage stabilizer, an antifoaming agent and the like, if necessary. The radiation-sensitive resin composition according to the present invention can be easily prepared by uniformly mixing the above components.

Such a radiation-sensitive resin composition is usually dissolved in an appropriate solvent and used in a solution state. For example, the copolymer [A] is dissolved in a solvent and 1,2-
The radiation-sensitive resin composition in a solution state can be prepared by mixing the quinonediazide compound [B] and, if necessary, optional components in a predetermined ratio immediately before use.

As the solvent, the same solvent as the polymerization solvent used when producing the copolymer [A] can be used. Furthermore, N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzylethylether, dihexylether, acetonylacetone , Isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ
Solvents such as butyrolactone, ethylene carbonate, propylene carbonate and phenyl cellosolve acetate can also be used.

Among these solvents, glycol ethers such as ethylene glycol monoethyl ether and ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate are used because of their solubility, reactivity with each component, and ease of forming a coating film. , Esters such as ethyl 2-hydroxypropionate, and diethylene glycols such as diethylene glycol monomethyl ether are preferably used.

In the present invention, the radiation-sensitive resin composition is applied to the object to be coated as a solution dissolved in a solvent so that the solid content concentration is preferably 20 to 40% by weight. Further, the radiation-sensitive resin composition solution prepared as described above,
It can also be used after being filtered using a Millipore filter having a pore size of about 0.2 μm.

The radiation-sensitive resin composition solution of the present invention thus prepared is excellent in long-term storage stability. Formation of coating film (pattern) A coating film can be formed by applying the radiation-sensitive resin composition according to the present invention to the surface of a substrate and removing the solvent by heating. The method of applying the radiation-sensitive resin composition onto the surface of the substrate is not particularly limited, and various methods such as a spray method, a roll coating method and a spin coating method can be adopted.

Next, this coating film is usually heated (prebaked). The heating condition is usually 70 to 90 ° C. for about 2 to 10 minutes, though it varies depending on the type of each component, the mixing ratio, and the like.

Next, the prebaked coating film is irradiated with ultraviolet rays or the like through a mask having a predetermined pattern, and then developed with a developing solution to remove unnecessary portions to form a predetermined pattern film. As the developer, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, inorganic alkalis such as aqueous ammonia, ethylamine, primary amines such as n-propylamine, diethylamine, diamine -Secondary amines such as n-propylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline Such as quaternary ammonium salts, pyrrole, piperidine, 1,8-diazabicyclo [5,4,0] -7-undecene, 1,5-diazabicyclo [4,3,
An aqueous solution of alkalis such as cyclic amines such as 0] -5-nonane can be used.

Further, in the above alkaline aqueous solution, methanol,
An aqueous solution containing a water-soluble organic solvent such as ethanol and a surfactant added in an appropriate amount can also be used as the developer. The developing time is usually 30 to 180 seconds, and the developing method may be any of a puddle method and a dipping method. After the development, washing with running water is carried out for 30 to 90 seconds, and by drying with compressed air or compressed nitrogen, unnecessary portions are removed and a pattern is formed. After this,
With a heating device such as a hot plate or an oven, at a predetermined temperature, for example, 150 to 250 ° C., for a predetermined time, for example, 5 to 30 minutes on a hot plate, or 30 in an oven.
A coating (pattern) can be obtained by performing heat treatment for 90 minutes.

[0065]

EXAMPLES The present invention will now be specifically described with reference to examples, but the present invention is not limited to these examples.

Synthesis of copolymer [A]

[0067]

Synthesis Example 1 A separable flask equipped with a stirrer, a cooling tube, a nitrogen introducing tube and a thermometer was charged with each compound shown in Table 1, purged with nitrogen for 30 minutes, and then the separable flask was immersed in an oil bath. Polymerization reaction was carried out for 3 hours while keeping the internal temperature at 70 ° C.

Thereafter, 3.0 g of 2,2'-azobis (2,4-dimethylvaleronitrile) was added, and the polymerization reaction was further performed for 3 hours to obtain a polymer solution containing the copolymer [A-1]. Obtained.
The solid content concentration of this polymer solution was 32.3% by weight.

Weight average molecular weight (Mw) of copolymer [A-1]
Was 4.11 × 10 ⁴ . The weight average molecular weight (Mw) of the obtained copolymer was measured by GPC (gel permeation chromatography) (HLC manufactured by Toyo Soda Co., Ltd.).
It is the polystyrene reduced molecular weight measured using -8020).

[0070]

[Synthesis Example 2] A polymer-containing polymer [A-2] was prepared in the same manner as in Synthesis Example 1 except that each component and solvent shown in Table 1 were charged in the amounts shown in Table 1. A combined solution was obtained. The results are shown in Table 1.

[0071]

[Synthesis Example 3] In the same manner as in Synthesis Example 1, except that the components and the solvent as shown in Table 1 were charged in the amounts shown in Table 1, a copolymer containing the copolymer [A-3] was prepared. A combined solution was obtained. The results are shown in Table 1.

[0072]

[Synthesis Example 4] A polymer-containing polymer [A-4] was prepared in the same manner as in Synthesis Example 1 except that each component and solvent shown in Table 1 were charged in the amounts shown in Table 1. A combined solution was obtained. The results are shown in Table 1.

[0073]

[Synthesis Example 5] Synthesis Example 1 was repeated in the same manner as in Synthesis Example 1 except that each component and solvent shown in Table 1 were charged in the amounts shown in Table 1 and the polymerization initiator was added in the amounts shown in Table 1. A polymer solution containing the copolymer [A-5] was obtained. The results are shown in Table 1.

[0074]

[Table 1]

The radiation-sensitive resin compositions obtained in the following examples were evaluated by forming patterns as described below. Evaluation of Radiation-Sensitive Resin Composition (i) Pattern Forming Method A solution of each radiation-sensitive resin composition (shown in Table 3) obtained in Examples was applied to a 6-inch silicon substrate by using a spinner. After that, prebaking was performed on a hot plate at 90 ° C. for 2 minutes to form a coating film having a film thickness of 2.0 μm.

The resulting coating film was used as NSR-175 manufactured by Nikon.
5i7A reduction projection exposure machine (NA = 0.50, λ = 365
nm) and the exposure time was changed, and then development was performed for 1 minute at 25 ° C. using an aqueous tetramethylammonium hydroxide solution having the concentration shown in Table 3.

Then, a pattern was formed on the silicon substrate by rinsing with water and drying. (ii) Sensitivity In the pattern created as described above, 2.00 μ
The exposure time ("optimum exposure time" or "sensitivity") required to obtain a pattern with a line line width of 2.00 μm of m line-and-line space (L / S) pattern was determined.

(Iii) Resolution The size of the smallest space pattern resolved at the optimum exposure time was measured with a scanning electron microscope.

(Iv) Residual film rate (film thickness after development / initial film thickness) × 100 was determined, and 90% or more was ◯ and 89% or less was x.

(V) Developability The presence or absence of the surface roughness of the line portion after development and the residual development (scum) in the space portion was observed with a scanning electron microscope.

(Vi) Pattern Shape The cross-sectional shape of the resist pattern at the optimum exposure time was observed with a scanning electron microscope.

Table 2 shows the evaluation of the cross-sectional shape.

[0083]

[Table 2]

(Vii) Heat resistance A silicon substrate on which a bulk pattern of about 100 μm × 100 μm was formed was irradiated with ultraviolet light having a light intensity of 5 mw at 365 nm for 60 seconds in the same manner as in (i) above. Then, it was heated on a hot plate in steps of 10 ° C. for 5 minutes each, and the temperature at which the bulk pattern was thermally deformed was observed.
160 ° C or higher is ◯, 130-150 ° C is Δ, and 1
The temperature of 20 ° C. or lower was marked with x.

(Viii) Adhesion: Using a silicon substrate with a thermal oxide film of 0.66 μm, a 5.00 μmL / S pattern was formed in the same manner as in (i) above, and heated on a hot plate at 150 ° C. for 5 minutes. .

The heated substrate is immersed for 6 minutes in a 25 ° C. etchant which is a 6: 1 (volume ratio) mixture of 40% ammonium fluoride aqueous solution and 50% hydrogen fluoride aqueous solution to undercut the pattern. Observing with a scanning electron microscope, ◯ is 1.00 μm or less, 1.01 to 1.30
μm was Δ, and 1.31 μm or more was X.

[0087]

Example 1 Preparation of Radiation Sensitive Resin Composition 100 parts by weight of the copolymer [A-1] (solid content) obtained in Synthesis Example 1 and 4,4 ′-[1 as the component [B] -[4- [1- [4-Hydroxyphenyl] -1-methylethyl] phenyl] ethylidene]
Condensate of bisphenol (1 mol) and 1,2-quinonediazide-5-sulfonic acid chloride (2.0 mol) ([B-1])
After mixing with 30 parts by weight and dissolving it in ethyl 2-hydroxypropionate so that the solid content concentration becomes 30% by weight, a solution of the radiation-sensitive resin composition is obtained by filtering with a Millipore filter having a pore size of 0.2 μm. Was prepared.

From the obtained radiation-sensitive resin composition,
A pattern was formed as in (i) and evaluated. The results are shown in Table 3. In addition, the solution of this radiation sensitive resin composition
After storage at 3 ° C for 3 months, a pattern was formed and evaluated. As a result, the same results as those of the radiation-sensitive resin composition immediately after preparation as described above were obtained, and the radiation-sensitive resin composition had a storage stability. It turned out to be excellent.

[0089]

Examples 2 to 15 Radiation-sensitive resin compositions were prepared in the same manner as in Example 1 except that the components shown in Table 1 were replaced. The results are shown in Table 3.

In Table 3, the abbreviations of the components indicate the following compounds. [B-1]… 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1
-Methylethyl] phenyl] ethylidene] Condensation product of bisphenol (1 mol) and 1,2-quinonediazide-5-sulfonic acid chloride (2.0 mol) [B-2]… 1,1,3-Tris (2 2,5-Dimethyl-4-hydroxyphenyl-3-phenyl) propane (1 mol) and 1,2-quinonediazide-5-sulfonic acid chloride (1.9 mol) condensate [B-3] , 4-trihydroxybenzophenone (1
Condensation product of 1,2-quinonediazide-5-sulfonic acid chloride (2.6 mol)

[0091]

[Table 3]

[0092]

Comparative Example 1 A composition of OFPR-800 (m / p cresol novolac and 1,2-naphthoquinone diazide-5-sulfonic acid ester in place of the radiation sensitive resin composition in Example 1; Tokyo Ohka A pattern was formed in the same manner as in Example 1 except that (trademark) was used. The results are shown in Table 3.

[0093]

Comparative Example 2 A composition of OFPR-5000 (m / p cresol novolac and 1,2-naphthoquinonediazide-5-sulfonic acid ester) in place of the radiation sensitive resin composition in Example 1; Tokyo Ohka (Manufactured by Co., Ltd.)
A pattern was formed in the same manner as in Example 1. The results are shown in Table 3.

[0094]

The radiation-sensitive resin composition according to the present invention is
It is possible to form a coating (pattern) which has excellent sensitivity and developability, an excellent residual film ratio, and excellent heat resistance, chemical resistance, adhesion to a substrate, and transparency.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location G03F 7/033 H01L 21/027

Claims (1)

[Claims] 1. An unsaturated carboxylic acid [A] (a-1) and (a-2)
An epoxy group-containing radically polymerizable compound represented by the following general formula [I]: If necessary, (a-3) a copolymer of the above-mentioned (a-1) and (a-2) with another radically polymerizable compound, and [B] 1,2-quinonediazide compound A radiation-sensitive resin composition comprising: