JP3003064B2 - Radiation-sensitive resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a semiconductor integrated circuit and a thin film transistor (TFT) for a liquid crystal display (LCD).
The present invention relates to a radiation-sensitive resin composition which is suitable as a positive resist for forming a mask for producing circuits and circuits, 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, in the semiconductor industry, semiconductors have been manufactured by forming a pattern using a radiation-sensitive resin composition. However, with the miniaturization of patterns, high sensitivity and high sensitivity have been achieved. There is a need for a radiation resin composition.

In order to manufacture a fine pattern for forming a semiconductor, a resist capable of obtaining a high resolution of submicron or less is sometimes required.
There is a strong demand for a high-sensitivity resist capable of obtaining a resolution on the order of m to several tens of μm and exhibiting a high yield even if the throughput is increased using a substrate having a large diameter.

[0004] In order to manufacture such micron-order patterns with high productivity, various processes capable of high-volume processing or high-speed processing are often employed in each process, and these processing conditions cannot be tolerated. There is a need for a resist of good performance. For example, the etching process of an underlying substrate is often performed by a wet etching method capable of performing a large-scale batch processing. Therefore, a resist for forming a pattern needs to have adhesiveness to a substrate and chemical resistance not to be affected by an etchant. Is done. Further, when an ion implantation step or the like is added, heat resistance that can withstand high-temperature heating is required.

As such a resist, a radiation-sensitive composition as a positive resist containing a novolak resin and a quinonediazide compound has been conventionally known, and is widely 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 the reactive ion etching (RIE) method, but has chemical resistance capable of withstanding the above-mentioned wet etching, Furthermore, it cannot be said that it has sufficient characteristics with respect to 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 liquid crystal displays.
The active matrix type liquid crystal display (AM-LCD) incorporating the
It is regarded as a favorite of a next-generation display device replacing (CRT), and a larger display screen is desired.

The TFT circuit of such an AM-LCD is
A resist formed using a radiation-sensitive composition (resist) and capable of obtaining a resolution of about several microns may be used. It is necessary to use a substrate, and a resist used in such a case is required to have excellent sensitivity, adhesion to a substrate, heat resistance, and the like 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 are conventionally formed by using a thermosetting resin. Attempts to form a permanent film with a radiation-sensitive composition have been actively made.

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 novolak resin and a quinonediazide compound has not been sufficiently satisfactory in terms of chemical resistance, adhesion to a substrate, heat resistance, and the like.

As a result, a semiconductor integrated circuit on the order of microns, a large-sized AM-LCD screen, and the like can be manufactured with high productivity, and furthermore, a chemical resistant material suitable as a permanent film forming material such as an interlayer insulating film and a protective film. There is a demand for a radiation-sensitive composition having excellent properties, sensitivity, adhesion to a substrate, heat resistance, and transparency.

[0011]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and has excellent sensitivity, developability, excellent residual film ratio, heat resistance, chemical resistance, and substrate compatibility. An object of the present invention is to provide a positive resist type radiation-sensitive resin composition having excellent adhesion and transparency in a visible light region.

[0012]

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

[0013]

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(A-3) If necessary, the above (a-1) and (a-2)
And [B] a 1,2-quinonediazide compound.

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

[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 following general formula [I]. It is a copolymer with a contained radical polymerizable compound.

Examples of such unsaturated carboxylic acids (a-1) include unsaturated carboxylic acids having an ethylenically unsaturated double bond, and specific examples include methacrylic acid, acrylic acid, crotonic acid, o Monocarboxylic acids such as-, m-, p-vinylbenzoic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 1,4-cyclohexenedicarboxylic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, methyl And 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, itaconic acid and the like 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 or partially amidated unsaturated carboxylic acid as described above, that is, half of an 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 of the above compounds can 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]

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Examples of the epoxy group-containing radical 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 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-triglycidyloxymethylstyrene and the like.

Among these, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-
Vinylbenzyl glycidyl ether and the like are preferred. These compounds can be used in combination of two or more.

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

Specific examples of such a radical 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;
-Methyl (meth) acrylate, -ethyl, -n-propyl, -i-propyl, -n-butyl, -sec-butyl, -ter-
Butyl, -2-ethylhexyl, -lauryl, -dodecyl, -dicyclopentanyl, -isobornyl, -cyclohexyl, -2-methylcyclohexyl, -dicyclohexyl, -adamantyl, -allyl, -provagyl, -phenyl, -naphthyl,- Anthracenyl, -cyclopentyl, -furyl, -tetrahydrofuryl, -pyranyl,
-Benzyl, -phenesyl, -cresyl, -1,1,1-trifluoroethyl, -perfluoroethyl, -perfluoro-n-propyl, -perfluoro-i-propyl, -triphenylmethyl, -adamantyl,- Alkyl (meth) acrylate such as cumyl, cycloalkyl (meth) acrylate, aryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate (Meta)
(Meth) acrylic acid amides such as hydroxyalkyl acrylate, (meth) acrylic acid-amide, -N, N-dimethylamide, -N, N-propylamide, (meth) acrylic acid-anilide, (meth) acrylonitrile , Acrolein, vinyl chloride, vinylidene chloride, N-vinylpyrrolidone, vinyl compounds such as 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, allyl glycidyl General formula [I] such as ether and vinyl glycidyl ether
Glycidyl compounds not contained therein.

Of these, styrene, glycidyl (meth) acrylate, p-tert butoxystyrene, α-methylstyrene, dicyclopentanyl methacrylate, methyl methacrylate, 2-hydroxyethyl methacrylate, benzyl methacrylate, butadiene And the like are preferably used. These may be used in combination of two or more.

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

(A-3) Other radically polymerizable compounds include:
Although it is contained as an optional component, it 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 aqueous alkali solution, and can be crosslinked by heating.

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

When the content of the unsaturated carboxylic acid (a-1) component is less than 5% by weight in the copolymer comprising the above components, the resulting coating film has reduced solubility in an aqueous alkali solution. When the content exceeds 50% by weight, the resulting coating may have too high a solubility in an aqueous alkali solution. If the content of the epoxy group-containing radically polymerizable compound (a-2) is less than 5% by weight, the resulting film may have insufficient crosslink density and poor heat resistance, whereas if it exceeds 95% by weight. In addition, the resulting coating film may have reduced solubility in an aqueous alkali solution, resulting in reduced developability and reduced sensitivity.

The copolymer [A] used in the present invention has a polystyrene equivalent weight average molecular weight (Mw) of usually 2 × 1.
0 ³ to 10 × 10 ^4, preferably 5 × 10 ^{3 to} 5 × 10 ⁴
It is desirable that From the copolymer [A] having such a molecular weight (Mw), a coating excellent in pattern shape, developability, residual film ratio, 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 is developing property, or residual film ratio decreases, and there may be poor pattern shape, heat resistance, whereas when it exceeds 10 × 10 ^4, to give The resulting film may have reduced developability and sensitivity and may have poor pattern shape.

The copolymer [A] used in the present invention as described above comprises (a-1) an unsaturated carboxylic acid, (a-2) a radical polymerizable compound containing an epoxy group, and Then (a
-3) It is 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 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, and ethylene glycol monomethyl ether. Glycol ethers such as ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol propyl ether acetate, benzene, toluene, xylene, etc. Aromatic hydrocarbons 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 , Ethyl acetate, esters such as butyl acetate, DMF (dimethylformamide), NM
And aprotic polar solvents such as P.

These solvents contain a total of 10 polymerizable compounds.
It is usually used in an amount of 20 to 1000 parts by weight relative to 0 parts by weight. Also, 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) and the like Azo compounds, benzoyl peroxide, lauroyl peroxide, t-butyl peroxypivalate, organic peroxides such as 1,1'-bis (t-butylperoxy) cyclohexane, hydrogen peroxide, and the like can be used. .

When a peroxide is used as the radical polymerization initiator, the peroxide may be used together with a reducing agent to form a redox type initiator. According to the copolymerization as described above, the copolymer [A] is usually a polymerization (reaction solvent) liquid containing the copolymer [A], which is 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 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 a part of the hydroxyl groups of the polyhydric phenol is esterified with 1,2-quinonediazidesulfonic acid can be used. 20-100% of the hydroxyl groups are 1,2-
Compounds esterified with quinonediazidesulfonic acid can be used. Examples of such 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 Esterified with 1,2-quinonediazidesulfonic acid,
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-sulfonate, 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'-
Tetrahydroxy-3'-methoxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester and the like, esterified product of tetrahydroxybenzophenone and 1,2-naphthoquinonediazidesulfonic acid, 2,3,4,2 ', 6 '-Pentahydroxybenzophenone-1,2-naphthoquinonediazide-4
-Sulfonic acid esters, pentahydroxybenzophenones such as 2,3,4,2 ', 6'-pentahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester
Esterified product with 1,2-naphthoquinonediazidosulfonic acid, 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 '
Esterified product of hexahydroxybenzophenone such as 5'-hexahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester and 1,2-naphthoquinonediazidesulfonic acid, bis (2,4'-dihydroxyphenyl) methane- Bis (2,4'-dihydroxyphenyl) methane such as 1,2-naphthoquinonediazide-4-sulfonic acid ester and bis (2,4'-dihydroxyphenyl) methane And 1,
Esterified product with 2-naphthoquinonediazidesulfonic acid,
Bis (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonic acid ester Phenyl)
Esterified product of methane and 1,2-naphthoquinonediazidosulfonic 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 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 1,1
Esterified product with 2-naphthoquinonediazidesulfonic acid,
Bis (2,3,4-trihydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2,
Bis (2,3,4-) such as 3,4-trihydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonic acid ester
Esterified product of trihydroxyphenyl) methane and 1,2-naphthoquinonediazidosulfonic 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 2,2-bis (2,3,4-
Esterified product of trihydroxyphenyl) propane and 1,2-naphthoquinonediazidosulfonic acid, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinonediazide 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinonediazide-5-sulfonic acid ester 3-Tris (2,5-
Esterified product of dimethyl-4-hydroxyphenyl) -3-phenylpropane and 1,2-naphthoquinonediazidosulfonic acid, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methyl Ethyl] phenyl] ethylidene] bisphenol-1,2-
Naphthoquinonediazide-4-sulfonic acid ester, 4,4'-
4,4 '-[1- [4, such as [1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-5-sulfonate 4- [1-
Esterified product of [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol and 1,2-naphthoquinonediazidosulfonic 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 sulfonic acid ester and 1,2-
Esterified product with naphthoquinonediazidesulfonic 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 ' 3,3,3 ', such as, 6', 7'-hexanol-1,2-naphthoquinonediazide-5-sulfonic acid ester
3'-tetramethyl-1,1'-spiroindene-5,6,7,5 ', 6', 7 '
Esterified product of -hexanol and 1,2-naphthoquinonediazidesulfonic acid, 2,2,4-trimethyl-7,2 ', 4'-trihydroxyflavan-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2 2,2,4-trimethyl-7,2 ', 4'-triethyl, such as 2,2,4-trimethyl-7,2', 4'-trihydroxyflavan-1,2-naphthoquinonediazide-5-sulfonate Esterified products of hydroxyflavan and 1,2-naphthoquinonediazidosulfonic acid are exemplified.

Further, J.I. Kosar, “Light-Sensitive
Systems 339-352, (1965). John Willey & Sons (Ne
w York), “Photoresist” by WSDe Forse, 50, (1975) Mc
1,2-quinonediazide compounds described in Graw-Hill, Inc. (New York) and the like can also be mentioned.

Of these, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazido-4-sulfonic acid ester, 2,3,4-trihydroxybenzophenone-1,2-
Naphthoquinonediazide-5-sulfonic acid ester, 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-sulfonic acid ester, 1,1,1-tri (p-hydroxyphenyl) ethane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,1,1-tri (p-hydroxy Phenyl) ethane-1,2-naphthoquinonediazide-5-
Sulfonates and the like are preferably used.

These 1,2-quinonediazide compounds can be used in combination of two or more. The 1,2-quinonediazidesulfonic acid esters as described above include, for example, a halide of 1,2-quinonediazidesulfonic acid,
It is obtained by esterification with the corresponding polyhydric phenol (polyhydric hydroxy compound) in the presence of a base catalyst.

More specifically, for example,
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. Can be

In such an esterification reaction, it is desirable that the halide of 1,2-quinonediazidesulfonic 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 is excellent in sensitivity and developability, excellent in residual film ratio, and excellent in heat resistance, chemical resistance, adhesion to a substrate, and transparency in a visible light region. Pattern) can be formed.

If 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 formed from the composition may be formed. In the coating film to be formed, the solubility difference between the exposed part and the unexposed part becomes small, so that patterning may become difficult.
If the amount is more than 1 part by weight, the 1,2-quinonediazide compound may not be sufficiently decomposed by short-time irradiation, and the sensitivity may decrease.

The radiation-sensitive resin composition of the present invention can be used as a positive resist for forming a semiconductor integrated circuit, a thin film transistor (TFT) circuit for a liquid crystal display (LCD), and a mask for manufacturing a circuit. 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 those described above, if necessary, as long as the object of the present invention is not impaired. Other Components The radiation-sensitive resin composition according to the present invention may include a sensitizer for the 1,2-quinonediazide compound [B] in order to further improve the sensitivity.

As such a sensitizer, for example, 2H-
Pyrido- (3,2-b) -1,4-oxazin-3 (4H) -ones, 10H-
Pyrido- (3,2-b) -1,4-benzothiazines, urazoles, hydantoins, barbituric acids, glycine anhydrides, 1-hydroxybenzotriazoles, alloxanes, maleimides and the like. These may be used in combination.

In the radiation-sensitive resin composition according to the present invention, such a sensitizer is used 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, per 100 parts by weight.

The radiation-sensitive resin composition according to the present invention comprises:
In order to improve heat resistance and adhesion to a substrate, a compound having at least two epoxy groups in a molecule may be included. As such an epoxy group-containing compound,
For example, Epicoat 1001, 1002, 100
3, 1004, 1007, 1009, 101
0, 828 (trade name; Yuka Shell Epoxy Co., Ltd.)
Bisphenol A epoxy resin, Epicoat 8
Bisphenol F type epoxy resin such as 07 (trade name; manufactured by Yuka Shell Epoxy Co., Ltd.), Epicoat 152 and 154 (trade name: manufactured by Yuka Shell Epoxy Co., Ltd.), EP
Phenol novolak type epoxy resin such as PN201, 202 (trade name; manufactured by Nippon Kayaku Co., Ltd.), EOCN1
02, 103S, 104S, 1020, 1025,
1027 (trade name; manufactured by Nippon Kayaku Co., Ltd.), Epikote 1
Cresol novolak type epoxy resin such as 80S75 (trade name; manufactured by Yuka Shell Epoxy Co., Ltd.), CY-17
5, 177, 179, Aldarite CY-182,
192, 184 (trade name; Ciba-Geigy Corporation)
ERL-4234, 4299, 4221, 420
6 (trade name; manufactured by UCC), Shodyne 509
(Trade name; manufactured by Showa Denko KK); Epicron 200, 400 (trade name; manufactured by Dainippon Ink Co., Ltd.); Epicoat 871, 872 (trade name: Yuka Shell Epoxy Co., Ltd.)
Cyclic epoxy resins such as ED-5661 and 5662 (trade names; manufactured by Celanese Coatings Co., Ltd.), Epolite 100MF (Kyoeisha Yushi Kagaku Kogyo Co., Ltd.)
Aliphatic polyglycidyl ethers such as EPOL TMP (manufactured by NOF Corporation).

Of these, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, aliphatic polyglycidyl ether and the like are preferably used.

The molecular weight of the epoxy group-containing compound as described above is not particularly limited, and may be a high molecular weight or 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 based on 100 parts by weight of the copolymer [A]. In the present invention,
Surfactants can also be added to improve the coatability of the radiation-sensitive resin composition, for example, to prevent striation (after coating streaks) and to improve the developability of the coating film. Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and polyoxyethylene oleyl ether, and polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether. Nonionic surfactants such as polyoxyethylene dialkyl esters such as oxyethylene aryl ethers, polyoxyethylene dilaurate, and polyoxyethylene distearate; ), Mega Fuck F171, F172, F
173 (manufactured by Dainippon Ink and Chemicals, Inc.), Florad FC-430, and FC-431 (Sumitomo 3M Limited)
Asahi Guard AG710, Surflon S-38
2, SC-101, SC-102, SC-10
3, SC-104, SC-105, SC-106
Fluorosurfactants and organosiloxane polymers KP341 commercially available under names such as (Asahi Glass Co., Ltd.)
(Manufactured by Shin-Etsu Chemical Co., Ltd.) and (meth) acrylic acid copolymer polyflow Nos. 57 and 95 (manufactured by Kyoeisha Yushi Kagaku Kogyo KK).

These may be used in combination of two or more. Such a surfactant is used when the total amount of the radiation-sensitive resin composition is 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.

Further, the radiation-sensitive resin composition according to the present invention may contain an adhesion aid for improving the adhesion to the substrate. Examples of such an adhesion aid include a functional silane coupling agent.

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 used in the form of a solution after being dissolved in an appropriate solvent. For example, 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 optional components as necessary at a predetermined ratio immediately before use.

As this solvent, the same solvent as the polymerization solvent used in producing the copolymer [A] can be used. Furthermore, N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzylethyl ether, dihexyl ether, 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 acetate such as ethyl cellosolve acetate are preferred in view of 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 a substrate as a solution dissolved in a solvent so that the solid content concentration is preferably 20 to 40% by weight. The radiation-sensitive resin composition solution prepared as described above,
After filtration using a Millipore filter having a pore size of about 0.2 μm, it can be used.

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

Next, this coating film is usually heated (prebaked). The heating conditions vary depending on the type and blending ratio of each component, but are usually at 70 to 90 ° C. for about 2 to 10 minutes.

Next, after irradiating the prebaked coating film with ultraviolet rays or the like via a mask having a predetermined pattern, the coating film is developed with a developing solution, and unnecessary portions are removed to form a coating film having a predetermined pattern. Examples of the developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia; primary amines such as ethylamine and n-propylamine; diethylamine; Secondary amines such as -n-propylamine, tertiary amines such as triethylamine and methyldiethylamine, alcoholamines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline Quaternary ammonium salts such as pyrrole, piperidine, 1,8-diazabicyclo [5,4,0] -7-undecene, 1,5-diazabicyclo [4,3,
An aqueous solution of an alkali such as a cyclic amine such as 0] -5-nonane can be used.

Also, methanol,
An aqueous solution to which an appropriate amount of a water-soluble organic solvent such as ethanol, a surfactant or the like has been added can also be used as the developer. The development time is usually from 30 to 180 seconds, and the development method may be any of a puddle method and a dipping method. After the development, washing with running water is performed for 30 to 90 seconds, and air drying with compressed air or compressed nitrogen removes unnecessary portions to form a pattern. Then this pattern,
By a heating device such as a hot plate or an oven, a predetermined temperature, for example, 150 to 250 ° C., for a predetermined time, for example, 5 to 30 minutes on the hot plate, and 30 minutes in the oven
A coating (pattern) can be obtained by performing the heat treatment for up to 90 minutes.

[0065]

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

Synthesis of copolymer [A]

[0067]

Synthesis Example 1 Each compound shown in Table 1 was charged into a separable flask equipped with a stirrer, a cooling pipe, a nitrogen introduction pipe, and a thermometer, and purged with nitrogen for 30 minutes. Then, the separable flask was immersed in an oil bath. The polymerization reaction was performed for 3 hours while maintaining the internal temperature at 70 ° C.

Thereafter, 3.0 g of 2,2′-azobis (2,4-dimethylvaleronitrile) was added, and a polymerization reaction was further carried out for 3 hours to obtain a polymer solution containing the copolymer [A-1]. Obtained.
The solid 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 determined by GPC (gel permeation chromatography) (HLC manufactured by Toyo Soda Co., Ltd.).
-8020).

[0070]

[Synthesis Example 2] A polymer containing copolymer [A-2] was prepared in the same manner as in Synthesis Example 1 except that the components and solvents shown in Table 1 were used in amounts shown in Table 1. A combined solution was obtained. Table 1 shows the results.

[0071]

Synthesis Example 3 The same procedure as in Synthesis Example 1 was repeated except that the components and the solvent shown in Table 1 were used in the amounts shown in Table 1, and the copolymer containing the copolymer [A-3] was used. A combined solution was obtained. Table 1 shows the results.

[0072]

[Synthesis Example 4] A copolymer containing copolymer [A-4] was prepared in the same manner as in Synthesis Example 1 except that the components and solvents as shown in Table 1 were used in amounts shown in Table 1. A combined solution was obtained. Table 1 shows the results.

[0073]

Synthesis Example 5 In the same manner as in Synthesis Example 1, except that the components and the solvent shown in Table 1 were charged in the amounts shown in Table 1, and the polymerization initiator was used in the amounts shown in Table 1, the synthesis initiator was used. A polymer solution containing the copolymer [A-5] was obtained. Table 1 shows the results.

[0074]

[Table 1]

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

The obtained coating film was coated on a Nikon NSR-175.
5i7A reduction projection exposure machine (NA = 0.50, λ = 365
After exposure was performed with the exposure time being changed according to (nm), development was performed at 25 ° C. for 1 minute using an aqueous solution of tetramethylammonium hydroxide having the concentration shown in Table 3.

Next, 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 μm
The exposure time ("optimum exposure time" or "sensitivity") required to obtain a line and line space (L / S) pattern having a line width of 2.00 μm was obtained.

(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 ratio (film thickness after development / initial film thickness) × 100 was obtained, and 90% or more was evaluated as Δ, and 89% or less was evaluated as ×.

(V) Developability The surface of the line portion after the development was roughened, and the presence or absence of the undeveloped portion (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 in the same manner as in (i) was irradiated with ultraviolet rays having a light intensity of 5 mw at 365 nm for 60 seconds. Thereafter, the resultant was heated on a hot plate in increments of 10 ° C. for 5 minutes, and the temperature at which the bulk pattern caused thermal deformation was observed.
160 ° C or higher is defined as Δ, and 130 to 150 ° C is defined as Δ,
20 ° C or less was evaluated as x.

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

The heated substrate was immersed in a 25 ° C. etchant, which is a 6: 1 (volume ratio) mixture of a 40% ammonium fluoride aqueous solution and a 50% hydrogen fluoride aqueous solution, for 6 minutes, and the pattern was undercut. Observation was performed with a scanning electron microscope.
μm was defined as Δ, and 1.31 μm or more was defined as 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]
Condensation product of bisphenol (1 mol) and 1,2-quinonediazide-5-sulfonic acid chloride (2.0 mol) ([B-1])
30 parts by weight, and dissolved in ethyl 2-hydroxypropionate so that the solid content concentration becomes 30% by weight. Then, the solution is filtered through a millipore filter having a pore diameter of 0.2 μm, and a solution of the radiation-sensitive resin composition is obtained. Was prepared.

From the obtained radiation-sensitive resin composition,
A pattern was formed as in (i) and evaluated. Table 3 shows the results. In addition, the solution of the radiation-sensitive resin
After storing at ℃ for 3 months, a pattern was formed and evaluated. As a result, a result equivalent to that of the radiation-sensitive resin composition immediately after preparation as described above was obtained. Was also found 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 used. Table 3 shows the results.

In Table 3, abbreviations of components indicate the following compounds. [B-1]… 4,4 '-[1- [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-2]… 1,1,3-tris (2 Condensation product of 1,5-dimethyl-4-hydroxyphenyl-3-phenyl) propane (1 mol) and 1,2-quinonediazide-5-sulfonic acid chloride (1.9 mol) [B-3]… 2,3 , 4-Trihydroxybenzophenone (1
Mol) and 1,2-quinonediazide-5-sulfonic acid chloride (2.6 mol)

[0091]

[Table 3]

[0092]

Comparative Example 1 In Example 1, OFPR-800 (m / p cresol novolak and 1,2-naphthoquinonediazide-5-sulfonic acid ester composition instead of the radiation-sensitive resin composition; Tokyo Ohka A pattern was formed in the same manner as in Example 1, except that (manufactured by Co.) was used. Table 3 shows the results.

[0093]

Comparative Example 2 In Example 1, a composition of OFPR-5000 (m / p cresol novolac and 1,2-naphthoquinonediazide-5-sulfonic acid ester) instead of the radiation-sensitive resin composition; Co., Ltd.)
A pattern was formed in the same manner as in Example 1. Table 3 shows the results.

[0094]

The radiation-sensitive resin composition according to the present invention comprises:
Excellent in sensitivity and developability, excellent in residual film ratio, and capable of forming a film (pattern) excellent in heat resistance, chemical resistance, adhesion to a substrate, and transparency.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-5-165214 (JP, A) JP-A-6-43643 (JP, A) JP-A-49-57055 (JP, A) JP-A-4- 198937 (JP, A) JP-A-59-67097 (JP, A) JP-A-60-102628 (JP, A) JP-A-60-129741 (JP, A) JP-A-58-207041 (JP, A) JP-A-1-293338 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03F 7/033 G03F 7/022 G03F 7/032

Claims (1)

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