JPH1152568A - Radiation sensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a negative resist type radiation sensitive resin compsn. excellent in heat and chemical resistances, adhesion to a substrate and transparency in a visible light region as well as excellent in sensitivity, developability and the rate of a residual film. SOLUTION: This radiation sensitive resin compsn. consists of (A) a copolymer contg. polymerized units of an unsatd. carboxylic acid and polymerized units of a compd. represented by formula I [where R<1> -R<3> are each individually an H atom or 1-5C an alkyl group, R<4> is 1-5C an alkyl group and (m) and (n) are individually to each other integers of 1-5] or further contg. polymerized units of other radical polymerizable compd. copolymerizable with the unsatd. carboxylic acid and the compd. of the formula I according to need, (B) a polymerizable compd. having an ethylenically unsatd. double bond and (C) a photopolymn. initiator.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a radiation-sensitive resin composition. More specifically, thin film transistors (TFTs) for semiconductor integrated circuits and liquid crystal displays (LCDs)
The present invention relates to a radiation-sensitive resin composition suitable as a negative resist for forming a mask for producing circuits and circuits, and 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. That is, when manufacturing an IC, a resist capable of obtaining a high resolution of submicron or less may be required. On the other hand, a resolution of the order of several μm to several tens of μm is obtained, and particularly, a large diameter resist is required. There is a strong demand for a high-sensitivity resist exhibiting a high yield even when the throughput is increased by using a silicon wafer.

[0003] For example, in the etching process of a silicon wafer in the manufacture of an IC, for example, a large amount of batch processing is often performed by a wet etching method, and thus a resist pattern formed is in close contact with a substrate. It is required to have chemical resistance and chemical resistance which is not affected by an etching solution. Further, when an ion implantation step or the like is added, heat resistance that can withstand high-temperature heating is required. Conventionally, novolak resin and 1,1
A radiation-sensitive resin composition as a positive resist containing a 2-quinonediazide compound is known, and is widely used in the production of integrated circuits. However, this type of radiation-sensitive resin composition is excellent in resolution and dry etching resistance required in the case of the reactive ion etching (RIE) method, but has chemical resistance enough to withstand the above-mentioned wet etching. 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 used 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. Such an AM-LCD TFT circuit may be formed using a radiation-sensitive resin composition (resist) and use a resist capable of obtaining a resolution of about several microns. It is necessary to use a larger substrate as compared to the manufacture of semiconductors such as the above, and the resist used in such a case has excellent sensitivity, adhesion to the substrate and heat resistance as in the case of mass production of semiconductors. Is required.

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, and the like which are conventionally formed using a thermosetting resin are used. Attempts to form a permanent film with a radiation-sensitive resin composition have been actively made. In order to form a permanent film such as an interlayer insulating film or a protective film of such a liquid crystal display, a heat-sensitive, chemical-resistant, radiation-sensitive resin composition having excellent transparency is required. Conventional radiation-sensitive resin compositions containing a novolak resin and a quinonediazide compound are not sufficiently satisfactory in terms of chemical resistance, adhesion to a substrate, heat resistance, and the like.

Accordingly, it is possible to manufacture a micron-order semiconductor integrated circuit, a large-sized AM-LCD screen, and the like with high productivity, and furthermore, a chemical resistant material suitable as a material for forming a permanent film such as an interlayer insulating film and a protective film. There is a demand for a radiation-sensitive resin composition having excellent properties, sensitivity, adhesion to a substrate, heat resistance and transparency.

[0007]

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

[0008]

Means for Solving the Problems The radiation-sensitive resin composition according to the present invention comprises (A) (a-1) a polymerized unit of an unsaturated carboxylic acid, (a-2) a polymer represented by the following formula [I]:

[0009]

Embedded image

Wherein R ^{1 to} R ³ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ⁴ is a group having 1 carbon atom.
And m and n are each independently 1 to 5
It is an integer of 5. ) And, if necessary, (a-3) a polymerization unit of the unsaturated carboxylic acid and another radically polymerizable compound copolymerizable with the compound of the formula [I]. It is characterized by comprising a polymer (hereinafter, also referred to as “copolymer [A]”), [B] a polymerizable compound having an ethylenically unsaturated double bond, and [C] a photopolymerization initiator.

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” is used in a concept including ultraviolet rays, far ultraviolet rays, X-rays, electron beams, molecular beams, γ-rays, synchrotron radiation, proton beam lines, and the like. [A] Copolymer The copolymer [A] used in the present invention comprises an unsaturated carboxylic acid, a compound represented by the following formula [I] and, if necessary, the above unsaturated carboxylic acid and the formula [I]. And a radical polymerizable compound copolymerizable with the compound of the formula (1).

As such an unsaturated carboxylic acid, an unsaturated carboxylic acid having an ethylenically unsaturated double bond is preferably used. Specifically, for example, monocarboxylic acids such as methacrylic acid, acrylic acid, crotonic acid, o-, 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-5-norbornene-2,3-dicarboxylic acid, 3,4,5,6-tetrahydrophthalic acid Acid 1,
Examples include dicarboxylic acids such as 2,3,6-tetrahydrophthalic acid and dimethyltetrahydrophthalic acid.

Of these, methacrylic acid, acrylic acid, itaconic acid and the like are preferably used. In addition, as the unsaturated carboxylic acid, in addition to the above, a partially esterified or partially amidated unsaturated carboxylic acid as described above, for example, a half ester or a half amide of an unsaturated dicarboxylic acid can also be used. As such a half ester or half amide of an unsaturated dicarboxylic acid, for example, monomethyl itaconate, monobutyl itaconate and the like are preferably used. As the unsaturated carboxylic acid, two or more of the above compounds can be used in combination. The radically polymerizable compound used in the present invention has the following formula [I]

[0014]

Embedded image

(Wherein, R ^{1 to} R ³ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ⁴ is an alkyl group having 1 to 5 carbon atoms, and m and n are Independently 1
Is an integer of up to 5. ). In the definition of R ^{1 to} R ³ , the alkyl group having 1 to 5 carbon atoms may be linear or branched, for example, a methyl group,
Ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group,
Examples include a pentyl group.

Specific examples of the compound represented by the above formula [I] include, for example, o-vinylbenzyl methyl ether,
m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinylbenzylethyl ether, m-vinylbenzylethylether, p-vinylbenzylethylether, o-vinylbenzylpropylether, m-vinylbenzylpropylether, p -Vinylbenzylpropyl ether, o-vinylbenzylisopropyl ether, m-vinylbenzylisopropylether, p-vinylbenzylisopropylether,
o-vinylbenzyl butyl ether, m-vinylbenzyl butyl ether, p-vinylbenzyl butyl ether, o-vinylbenzyl isobutyl ether, m-vinylbenzyl isobutyl ether, p-vinylbenzyl isobutyl ether, o-vinylbenzyl-tert-butyl ether, m- Vinylbenzyl-tert-butyl ether, p-vinylbenzyl-tertbutyl ether, α-methyl-o-vinylbenzyl methyl ether,
α-methyl-m-vinylbenzyl methyl ether, α-
Methyl-p-vinylbenzyl methyl ether, 2,3-
Dimethoxymethylstyrene, 2,4-dimethoxymethylstyrene, 2,5-dimethoxymethylstyrene, 2,6-
Dimethoxymethylstyrene, 2,3,4-trimethoxymethylstyrene, 2,3,5-trimethoxymethylstyrene, 2,3,6-trimethoxymethylstyrene, 3,4,5
-Trimethoxymethylstyrene, 2,4,6-trimethoxymethylstyrene and the like.

Of these, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinylbenzylethyl ether, m-vinylbenzylethylether, p-vinylbenzylethylether
Vinylbenzyl ethyl ether and the like are preferably used. These compounds can be used alone or in combination of two or more.

Specific examples of other radically polymerizable compounds used in the present invention include glycidyl (meth) acrylate, glycidyl α-ethyl (meth) acrylate, α-n
Glycidyl propyl (meth) acrylate, glycidyl α-n-butyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 3,4-epoxyheptyl (meth) acrylate, α-ethyl-6,7 -Epoxyheptyl (meth) acrylate, allyl glycidyl ether, vinyl glycidyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3
-Vinylcyclohexene oxide 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-triglycidyloxymethyl Styrene, 2,3,5-triglycidyloxymethylstyrene, 2,3,6-triglycidyloxymethylstyrene, 3,4,5-triglycidyloxymethylstyrene,
Epoxy group-containing radically polymerizable compounds such as 2,4,6-triglycidyloxymethylstyrene; methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, (meth) acrylic acid -I-propyl, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, ter- (meth) acrylate
-Butyl, 2-ethylhexyl (meth) acrylate,
Lauryl (meth) acrylate, dodecyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, (meth) ) Dicyclohexyl acrylate, (meth)
Adamantyl acrylate, allyl (meth) acrylate,
Provagyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, anthracenyl (meth) acrylate, cyclopentyl (meth) acrylate, furyl (meth) acrylate, tetrahydrofuryl (meth) acrylate, Pyranyl (meth) acrylate, benzyl (meth) acrylate, phenesyl (meth) acrylate, cresyl (meth) acrylate, 1,1,1-trifluoroethyl (meth) acrylate, par (meth) acrylate Fluoroethyl, perfluoro-n-propyl (meth) acrylate, perfluoro-i (meth) acrylate
-Propyl, triphenylmethyl (meth) acrylate,
Cumyl (meth) acrylate, (meth) acrylic acid-2-
Hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl, (meth) acrylic acid-amide, (meth) acrylic acid-N, N-dimethylamide, (meth) acrylic acid-N, N-dipropylamide, ( (Meth) acrylic acid-
(Meth) acryloyl group-containing radically polymerizable compounds such as anilide and (meth) acrylonitrile; acrolein, vinyl chloride, vinylidene chloride, N-vinylpyrrolidone, vinyl acetate, styrene, α-methylstyrene, o-
Methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-methoxymethylstyrene, p-tert-butoxystyrene, chloromethylstyrene, butadiene, 2,3-dimethylbutadiene,
Vinyl group-containing radically polymerizable compounds such as isoprene;
And unsaturated dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconate.

Of these, styrene, α-methylstyrene, p-tertbutoxystyrene, dicyclopentanyl methacrylate, methyl methacrylate, 2-hydroxyethyl methacrylate, benzyl methacrylate, butadiene, isoprene and the like are preferably used. Can be By using these compounds as copolymer components, it is possible to control the alkali solubility, glass transition temperature, dielectric constant, etc. of the polymer, and as a result, the resist performance such as resolution and residual film ratio, and transparency In some cases, the performance as a permanent film such as heat resistance is improved. These other radically polymerizable compounds can be used alone or in combination of two or more.

The copolymer [A] used in the present invention can be obtained by copolymerizing the above compounds. The copolymer contains the polymerized unit (a-1) of the compound of the formula [I] in an amount of preferably 5 to 50% by weight, particularly preferably 10 to 40% by weight, of the polymerized unit (a-1) of the unsaturated carboxylic acid. 2)
It is preferably 5 to 90% by weight, particularly preferably 20 to 50% by weight.
It contains the polymerized unit (a-3) of another radically polymerizable compound in an amount of preferably 70% by weight or less, particularly preferably 20 to 60% by weight.

When the content of the polymerized unit (a-1) of the unsaturated carboxylic acid is less than 5% by weight, the resulting coating film has reduced solubility in a developing solution composed of an aqueous alkali solution and deteriorates developability. The sensitivity may decrease. On the other hand, if it exceeds 50% by weight, the obtained coating film has too high solubility in an aqueous alkali solution, and the residual film ratio of the obtained resist pattern may be deteriorated. Further, when the content of the polymerized unit (a-2) of the compound of the formula [I] is less than 5% by weight, the resulting coating film may have insufficient crosslink density, resulting in poor heat resistance and chemical resistance. If the content exceeds 90% by weight, the resulting coating film may have reduced solubility in an aqueous alkali solution to deteriorate the developability or lower the sensitivity. Further, when the content of the polymerized unit (a-3) of the other radical polymerizable compound exceeds 70% by weight, the solubility of the polymer in a developing solution composed of an alkaline aqueous solution is poor, and patterning becomes difficult. May be.

The copolymer [A] used in the present invention has a weight average molecular weight in terms of polystyrene (hereinafter referred to as “Mw”) of usually 2 × 10 ³ to 1 × 10 ⁵ , preferably 5 ×.
Desirably, it is 10 ^{3 to} 5 × 10 ⁴ . Mw is 2 × 1
If it is less than 0 ³ , the resulting film may have poor developability, residual film ratio, and the like, and may be inferior in pattern shape and heat resistance. On the other hand, if it exceeds 1 × 10 ⁵ , sensitivity will decrease. And the pattern shape may be inferior.

The above-mentioned copolymer [A] used in the present invention comprises an unsaturated carboxylic acid, a compound represented by the above-mentioned formula [I], and optionally other radical polymerizable compounds. It is obtained by copolymerization by a polymerization method. Preferably, the polymerization is carried out in a solvent in the presence of a catalyst (polymerization initiator).

Specific examples of the solvent used for the copolymerization 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 ethers such as glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, and propylene glycol monomethyl ether; propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene Glico Propylene glycol alkyl ether acetates such as propyl ether acetate; aromatic hydrocarbons such as benzene, toluene, and xylene; ketone, cyclohexanone, 2-
Ketones such as heptanone and 4-hydroxy-4-methyl-2-pentanone; ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate;
Ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, Esters such as methyl 3-ethoxypropionate, ethyl acetate and butyl acetate; aprotic polar solvents such as dimethylformamide and N-methyl-2-pyrrolidone.

These solvents are generally used in an amount of 20 to 1.0% based on 100 parts by weight of the total of the unsaturated carboxylic acid, the compound of the formula [I] and the other radically polymerizable compounds.
It is used in an amount of 00 parts by weight. As the catalyst, those generally known as a radical polymerization initiator can be used. For example, 2,2′-azobisisobutyronitrile, [2,2′-azobis (2,4- ADVN], 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), [dimethyl 2,2′-azobis (2-methylpropionate): V-601 Azo compounds such as benzoyl peroxide, lauroyl peroxide, t-butyl peroxypivalate, organic peroxides such as 1,1′-bis (t-butylperoxy) cyclohexane, and hydrogen peroxide. be able to. When a peroxide is used as the radical polymerization initiator, the peroxide may be used together with a reducing agent to form a redox polymerization initiator. Further, in the above copolymerization, a molecular weight regulator such as α-methylstyrene dimer may be added.

The copolymer [A] has a carboxyl group derived from an unsaturated carboxylic acid and a benzyl group derived from the compound represented by the above formula [I]. Having. Also, the copolymer [A]
Has a suitable solubility in an aqueous alkali solution, and provides a radiation-sensitive resin composition excellent in high sensitivity, high residual film ratio, developability, and the like. Further, the resist pattern obtained by using the copolymer [A] is excellent in various properties such as heat resistance, adhesion to a substrate, transparency in a visible light region, and chemical resistance.

[B] Polymerizable compound having an ethylenically unsaturated double bond The polymerizable compound having an ethylenically unsaturated double bond used in the present invention includes one or more (meth) acryloyloxy groups. Compounds having the same are preferred. Examples of the compound having one (meth) acryloyloxy group include, for example, Aronix M-101 and M-101.
111, M-114 (manufactured by Toa Gosei Chemical Industry Co., Ltd.),
KAYARAD TC-110S, TC-120S
(Manufactured by Nippon Kayaku Co., Ltd.), V-158 and V-2311 (manufactured by Osaka Organic Chemical Industry Co., Ltd.) (commercially available). Compounds containing two (meth) acryloyloxy groups include, for example, Aronix M-210,
-240, M-6200 (Toa Gosei Chemical Industry Co., Ltd.)
KAYARAD-DDDA, HX-220, R-604 (Nippon Kayaku Co., Ltd.), V260, V31
2. V335HP (manufactured by Osaka Organic Chemical Industry Co., Ltd.) (commercially available).

Compounds containing three or more (meth) acryloyloxy groups include, for example, trimethylolpropane triacrylate, pentaerythritol triacrylate, trisacryloyloxyethyl phosphate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, And pentaerythritol hexaacrylate. Specific examples thereof include Aronix M-309, M-400, and M-4.
05, M-450, M-7100, M-803
0, M-8060 (manufactured by Toa Gosei Chemical Industry Co., Ltd.), K
AYARAD Same DPHA, TMPTA, Same DPCA-
20, -30, -60, and -120 (manufactured by Nippon Kayaku Co., Ltd.), V-295, -300, -360, -GPT, -3PA, -400 (Osaka Organic Chemicals) And commercial products such as PPZ (manufactured by Idemitsu Petrochemical Co., Ltd.).

Of these, Aronix M-400,
Trifunctional or higher polyfunctional (meth) acrylates such as KAYARAD DPHA are preferably used. The polymerizable compound [B] having an ethylenically unsaturated double bond as described above may be used in combination of two or more.

[C] Photopolymerization Initiator As the photopolymerization initiator used in the present invention, a photoradical polymerization initiator, a photocationic polymerization initiator, a photoamine generator and the like can be used. Examples of the photoradical polymerization initiator include α-diketones such as benzyl and diacetyl; acyloins such as benzoin; acyloin ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether; thioxanthon, 2,4- Thioxanthones such as diethylthioxanthone and thioxanthone-4-sulfonic acid;
Benzophenones such as benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone; Michler's ketones; acetophenone, 2- (4-toluenesulfonyloxy) -2-phenylacetophenone, p -Dimethylaminoacetophenone, α, α'-dimethoxyacetoxybenzophenone, 2,2'-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl [4- (methylthio) phenyl] -2-morpholino-1-propanone , 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-
Acetophenones such as on; anthraquinone, 1,4
Quinones such as naphthoquinone; halogen compounds such as phenacyl chloride, trihalomethylphenylsulfone, and tris (trihalomethyl) -s-triazine; acylphosphine oxides; and peroxides such as di-t-butyl peroxide. Can be

Examples of such a photo-radical polymerization initiator include IRGACURE-184, 261 and 500, and
651, 907 (manufactured by Ciba-Geigy), Daroc
ur-1173, 1116, 2959, 166
4, 4043 (Merck Japan), KAYACU
RE-DETX, MBP, DMBI, E
PA, OA (manufactured by Nippon Kayaku Co., Ltd.), VICURE-1
0, 55 (STAUFFER Co. LTD),
TRIGONALP1 (AKZO Co. LTD),
SANDORAY 1000 (SANDOZ Co.L
TD), DEAP (APJOHN Co. LTD)
Made), QUANTACURE-PDO, same ITX, same
EPD (WARD BLEKINSOP Co. LTD)
Available as commercial products.

Examples of the cationic photopolymerization initiator include diazonium salts, triphenylsulfonium salts, metallocene compounds, diaryliodonium salts, nitrobenzylsulfonates, α-sulfonyloxyketones, diphenyldisulfones, and imidylsulfonates. And the like. Such cationic photopolymerization initiators are ADEKA ULTRASET PP-33, OPTMER SP-15.
0, 170 (manufactured by Asahi Denka Kogyo KK) (diazonium salt), OPTOMER SP-150, 170 (manufactured by Asahi Denka Kogyo KK) (sulfonium salt), IRGACURE
261 (manufactured by Ciba-Geigy) (a metallocene compound).

Examples of the photoamine generator include nitrobenzylcarbamimates and iminosulfonates. The photopolymerization initiator as described above is appropriately selected and used depending on exposure conditions (for example, under an oxygen atmosphere or under an oxygen-free atmosphere). Further, these photopolymerization initiators can be used in combination of two or more kinds.

Radiation-Sensitive Resin Composition The radiation-sensitive resin composition according to the present invention comprises the above-mentioned components [A], [B] and [C], but 100 parts by weight of the copolymer [A]. 10 to 200 parts by weight of a polymerizable compound [B] having an ethylenically unsaturated double bond,
Preferably, the photopolymerization initiator [C] is used in an amount of 0.1 to 100 parts by weight, preferably 0.5 to 50 parts by weight in an amount of 50 to 150 parts by weight.
It is desirable to contain it in an amount of part by weight. The radiation-sensitive resin composition according to the present invention comprising such components is as follows:
A film (pattern) having excellent sensitivity, developability, residual film ratio, heat resistance, chemical resistance, adhesion to a substrate, and transparency in a visible light region can be formed.

If the amount of the polymerizable compound [B] having an ethylenically unsaturated double bond is less than 10 parts by weight based on 100 parts by weight of the copolymer [A], the amount of the photopolymerization initiator [C] may be reduced. Depending on the type, the curing reaction may not proceed sufficiently. On the other hand, when it exceeds 200 parts by weight, the tackiness of the obtained coating film surface becomes too large, and the coating film obtained after curing may have a rough surface.

If the amount of the photopolymerization initiator [C] is less than 0.1 part by weight based on 100 parts by weight of the copolymer [A], the curing reaction may not proceed sufficiently.
If the amount exceeds 0 parts by weight, the photopolymerization initiator [C] may bleed (bleed) from the surface of the coating film formed from the radiation-sensitive resin composition, or the developability may be reduced. Such a radiation-sensitive resin composition of the present invention can be used as a negative resist for producing a semiconductor integrated circuit, a thin film transistor (TFT) circuit for a liquid crystal display (LCD), a mask for producing a circuit, and an interlayer insulating film. It is also suitable as a material for forming a permanent film such as a protective film for a color filter. The radiation-sensitive resin composition according to the present invention may contain components other than the 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 is used to improve the heat resistance of the radiation-sensitive resin composition and the adhesion to a substrate.
It may contain a compound having at least two epoxy groups in the molecule. Such epoxy group-containing compounds include, for example, Epicoat 1001, 1002, 1003, 1004, 1007, 1009, 1
010, 828 (trade name; Yuka Shell Epoxy Co., Ltd.)
Bisphenol A epoxy resin such as Epicoat 807 (trade name; manufactured by Yuka Shell Epoxy Co., Ltd.); Epicoat 15
2, 154 (trade name; Yuka Shell Epoxy Co., Ltd.)
Phenol novolak type epoxy resins such as EPPN201 and EPPN201 (product name; manufactured by Nippon Kayaku Co., Ltd.), EOCN102, 103S, 104S, 102
0, 1025, 1027 (trade name; Nippon Kayaku Co., Ltd.)
Cresol novolak type epoxy resins such as Epicoat 180S75 (trade name, manufactured by Yuka Shell Epoxy Co., Ltd.), CY-175, 177, 179, Araldite CY-182, 192, 184 (trade name; Ciba Geigy) ERL-4234, 4299, 42
21, 4206 (trade name; manufactured by UCC), Shodyne 509 (trade name, manufactured by Showa Denko KK), Epicron 2
00, 400 (trade name; manufactured by Dainippon Ink Co., Ltd.), Epicoat 871, 872 (trade name; manufactured by Yuka Shell Epoxy Co., Ltd.), ED-5661, and 5662 (trade name;
Cycloaliphatic epoxy resins such as Celanese Coatings Co., Ltd .; Epolite 100MF (Kyoeisha Yushi Kagaku Kogyo Co., Ltd.), Epiol TMP (Nippon Yushi Co., Ltd.)
And aliphatic polyglycidyl ethers.

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).
The epoxy group-containing compound as an optional component is preferably used in an amount of preferably 5 to 50 parts by weight based on 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 (after coating streaks) and to improve the developability of the coating film. . As a surfactant,
For example, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and polyoxyethylene oleyl ether; polyoxyethylene aryl ethers such as polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether; Nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; F-Top EF301;
03, 352 (manufactured by Shin-Akita Kasei), Megafac F171, F172, F173 (manufactured by Dainippon Ink and Chemicals, Inc.), Florard FC-430, FC-4
31 (manufactured by Sumitomo 3M Limited), Asahi Guard AG7
10, Surflon S-382, SC-101, SC
-102, SC-103, SC-104, SC-
105, SC-106 (manufactured by Asahi Glass Co., Ltd.), a fluorine-based surfactant commercially available, and an 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 KK) and the like. Two or more of these can be used together.

Such a surfactant can be contained in an amount of 2 parts by weight or less, preferably 1 part by weight or less, when the total amount of the radiation-sensitive resin composition is 100 parts by weight.
Further, the radiation-sensitive resin composition according to the present invention may include an adhesion aid in order to improve adhesion to a substrate.
Examples of such an adhesion aid include a functional silane coupling agent. Further radiation-sensitive resin composition according to the present invention, if necessary, antistatic agent, storage stabilizer,
An antifoaming agent or the like may be contained. 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, a copolymer [A] is dissolved in a solvent, and a polymerizable compound [B] having an ethylenically unsaturated double bond, a photopolymerization initiator [C] and, if necessary, optional components are dissolved in this solution immediately before use. To form a radiation-sensitive resin composition in a solution state.

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

Among these solvents, glycol ethers such as ethylene glycol monoethyl ether, from the viewpoint of solubility, reactivity with each component, and ease of forming a coating film,
Ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate, esters such as ethyl 2-hydroxypropionate, and diethylene glycols such as diethylene glycol monomethyl ether are preferably used. The radiation-sensitive resin composition of the present invention,
The composition is applied to a substrate as a solution dissolved in a solvent such that the solid content concentration is preferably 20 to 40% by weight.

The solution of the radiation-sensitive resin composition prepared as described above can be used after being filtered using a millipore filter having a pore diameter of about 0.2 μm. The solution of the radiation-sensitive resin composition of the present invention prepared as described above has excellent 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. This coating is then usually heated (prebaked)
Is done. 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, the prebaked coating film is irradiated with ultraviolet rays or the like via a mask having a predetermined pattern, and then developed with a developer to remove unnecessary portions to form a predetermined pattern coating film.

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; Secondary amines such as diethylamine and di-n-propylamine; tertiary amines such as triethylamine and methyldiethylamine; alcoholamines such as dimethylethanolamine and triethanolamine; tetramethylammonium hydroxide and tetraethylammonium hydroxy And quaternary ammonium salts such as choline; pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5-nonane and the like. Of alkalis such as cyclic amines The solution can be used.

In addition, 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, running water washing is performed for 30 to 90 seconds, and an unnecessary portion is removed by air drying with compressed air or compressed nitrogen to form a pattern. After that, this pattern is heated by a heating device such as a hot plate or 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, and 3 minutes in an oven.
By performing the heat treatment for 0 to 90 minutes, a film (pattern) can be obtained.

[0048]

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] 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.
After purging with nitrogen for 0 minutes, the separable flask was immersed in an oil bath, and the polymerization reaction was performed for 5 hours while maintaining the internal temperature at 70 ° C.
A polymer solution containing the copolymer [A-1] was obtained. The solid concentration of this polymer solution was 38.3% by weight. The weight average molecular weight (Mw) of the copolymer [A-1] is 1.78.
× 10 4. The weight average molecular weight (Mw) of the obtained copolymer was determined by GPC (gel permeation chromatography) (HLC-8020 manufactured by Toyo Soda Co., Ltd.).
Is the molecular weight in terms of polystyrene measured using

Synthesis Examples 2 to 5 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. To [A-5] was obtained. Table 1 shows the results.

[0050]

[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 4-inch silicon substrate using a spinner. Thereafter, the film was prebaked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 2.0 μm. The obtained coating film was exposed with a PLA-501F mask liner (without a filter) manufactured by Canon Inc. with changing the exposure time, and then exposed to a developer having a concentration shown in Table 3 (aqueous tetramethylammonium hydroxide solution). Developed for 1 minute at ° C. Then, the pattern was formed by rinsing with water and drying. (Ii) Sensitivity In the pattern created as described above, the exposure time required to obtain a line and line space (L / S) pattern having a line width of 5.00 μm (“optimum exposure time”) Or "sensitivity").

(Iii) Resolution The size of the smallest space pattern resolved at the optimum exposure time was measured with a scanning electron microscope. (Iv) Developability The surface of the line portion after development and the undeveloped portion (scum) of the space portion were observed with a scanning electron microscope. (V) Pattern shape The cross-sectional shape of the resist pattern at the optimal exposure time was observed with a scanning electron microscope. Table 2 shows the evaluation of the cross-sectional shape.

[0053]

[Table 2]

(Vi) Residual film ratio (film thickness after development / initial film thickness) × 100 was determined, and 90% or more was evaluated as ○, and less than 90% was evaluated as x. (Vii) Heat resistance The bulk pattern of about 100 mm × 100 mm formed on the silicon substrate as in the above (i) was heated at 250 ° C.
Was baked on a hot plate for 10 minutes, and the residual film ratio was determined from the film thickness before and after heating the pattern. 95% remaining film ratio
The above was evaluated as ○, and less than 95% was evaluated as ×. (Viii) Adhesion Using a 0.66 μm-thick silicon substrate with a thermal oxide film, a 10.00 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 a 40% ammonium fluoride aqueous solution and a 50% hydrogen fluoride aqueous solution, and the pattern is undercut by scanning electron. Observe with a microscope and 1.
未 満 indicates less than 50 μm, Δ indicates 1.50 to 2.50 μm, and X indicates more than 2.50 μm. (Ix) Transparency A bulk pattern of about 100 μm × 100 μm was formed as in (i) above, and the light transmittance at 400 to 800 nm after development and post-baking was measured. A minimum transmittance of 95% or more was rated as Δ, and a transmittance of less than 95% was rated as x.

Example 1 Preparation of Radiation-Sensitive Resin Composition Copolymer [A-1] (solid content) 10 obtained in Synthesis Example 1
0 parts by weight, and Aronix M-40 as the component [B]
0 (manufactured by Toa Gosei Chemical Industry Co., Ltd.) (polyfunctional acrylate) 100 parts by weight, and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1- as component [C] ON (Irgacure 369; C
30 parts by weight of IBA-GEIGY), dissolved in ethyl 2-hydroxypropionate so that the solid content concentration becomes 30% by weight, and then filtered through a 0.2 μm pore size millipore filter to obtain radiation-sensitive radiation. A solution of the conductive resin composition was prepared. A pattern was formed from the obtained radiation-sensitive resin composition and evaluated. Table 3 shows the results. In addition, a pattern was formed from the solution of the radiation-sensitive resin composition after storage at 5 ° C. for 3 months, and as a result of evaluation, a result equivalent to that of the radiation-sensitive resin composition immediately after preparation as described above was obtained. This radiation-sensitive resin composition was found to be excellent in storage stability.

Examples 2 to 20 A radiation-sensitive resin composition was 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] ··· Aronix M-400 (manufactured by Toa Gosei Chemical Industry Co., Ltd.) [B-2] ··· KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) [C-1] ··· 2 -Benzyl-2-dimethylamino-
1- (4-morpholinophenyl) -butan-1-one (Irgacure 369; manufactured by CIBA-GEIGY) [C-2]: 2- (4-toluenesulfonyloxy) -2-phenylacetophenone

COMPARATIVE EXAMPLE 1 In Example 1, O radiation was used instead of the radiation-sensitive resin composition.
FPR-800 (m / p cresol novolak, trihydroxybenzophenone-1,2-naphthoquinone-5
A composition containing a sulfonate; Tokyo Ohka Co., Ltd.
The pattern was formed in the same manner as in Example 1 except for the use of Table 3 shows the results. Comparative Example 2 In Example 1, O was used instead of the radiation-sensitive resin composition.
FPR-5000 (m / p cresol novolak, trihydroxybenzophenone-1,2-naphthoquinone-
A pattern was formed in the same manner as in Example 1 except that a composition containing 5-sulfonic acid ester (manufactured by Tokyo Ohka Co., Ltd.) was used. Table 3 shows the results.

[0058]

[Table 3]

[0059]

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.

Claims (1)

[Claims] (A) (a-1) a polymerized unit of an unsaturated carboxylic acid, (a-2) a compound represented by the following formula [I]: (Wherein, R ^{1 to} R ³ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ⁴ is an alkyl group having 1 to 5 carbon atoms, and m and n are each independently A polymerized unit of the compound represented by the formula (1), and, if necessary, (a-3) another radical polymerizable polymerizable with the unsaturated carboxylic acid and the compound of the formula [I]. A radiation-sensitive resin composition comprising: a copolymer containing a polymerized unit of a compound; [B] a polymerizable compound having an ethylenically unsaturated double bond; and [C] a photopolymerization initiator.