KR101318086B1 - Resist Composition - Google Patents

Abstract

The present invention provides a resist composition which not only improves the solubility in the preparation of a resist and the resist film adhesion property at the time of development but also improves the resist stability and is also excellent in safety.

In addition, the present invention provides a resist composition comprising a resist composition and an organic solvent, the organic solvent (a1) C _{3 -6} alkanediols, (a2) an alkoxy mono- -C _{3 -6} alkanediols, (b1) C _{5 - 6} alkanediol mono acetate, (b2) a mono-alkoxy -C _3-6 alkane diol monoacetate, (c1) C _{5 -6} alkane diol diacetate and (c2) a mono-alkoxy the group consisting of -C _3-6 alkane diol diacetate It provides a resist composition which is at least one solvent selected from.

Resist composition

Description

Resist Composition

BRIEF DESCRIPTION OF THE DRAWINGS The schematic diagram which shows the state (evaluation: x) which the undercut generate | occur | produced in the contact part of a glass substrate and a resist pattern in the evaluation test of a cross-sectional shape.

<Explanation of symbols for the main parts of the drawings>

1: glass substrate

2: Resist pattern

3: undercut portion

[Document 1] Japanese Patent Application Laid-Open No. 3-1659

[Document 2] Japanese Unexamined Patent Publication No. 6-324483

The present invention relates to a resist composition which is sensitive to radiation such as ultraviolet rays, deep ultraviolet rays, X-rays, electron beams and the like and is excellent in safety at the time of use and has excellent properties such as coatability, residual film ratio at the time of development, And is excellent in adhesiveness at the time of development.

Microfabrication is required in the manufacture of integrated circuits, color filters, liquid crystal devices and the like, and resists have been conventionally used to satisfy this demand. Generally, there are a positive type and a negative type of resist, and either of them is usually dissolved in a solvent to form a resist composition in solution.

The resist composition is coated on a substrate such as a silicon substrate or a glass substrate by a known coating method such as spin coating, roller coating, slit coating, inkjet, or the like, followed by prebaking to form a resist film, and then a photosensitive wavelength region of the resist. After exposure and development by particle rays, such as an ultraviolet-ray, an ultraviolet-ray, X-ray, an electron beam, etc., dry etching is performed as needed, and a desired resist pattern is formed.

Various solvents are conventionally used as the solvent used in the resist composition, and are selected and used in consideration of solubility, coating property, sensitivity, developability, pattern characteristics to be formed, and the like. For example, ethylene glycol monoethyl ether acetate has been known as a solvent having excellent properties such as solubility, coatability, and resist formation properties. However, recently, a problem of safety to humans has been pointed out, and thus safety is high, and resin solubility and initiator are further increased. There is a need for a solvent having improved performance such as resist formation properties having excellent solubility.

As these solutions, propylene glycol monomethyl ether acetate and the like are disclosed as solvents instead of ethylene glycol monoethyl ether acetate (for example, Japanese Patent Application Laid-Open No. H3-1659). However, there existed a problem that the solvent which is considered to be high in safety compared with these ethylene glycol monoethyl ether acetate has inadequate characteristics, such as resist formation property and solubility. For example, in the case of propylene glycol monomethyl ether acetate, when the resist is applied onto a substrate, the amount of remaining solvent in the film decreases, thereby causing an abnormality in the film thickness distribution, or decreasing the line width uniformity and the adhesion of the resist film during development. .

Moreover, although the technique which improves resin solubility and initiator solubility using (beta) -type propylene glycol monomethyl ether acetate is disclosed, it is still inadequate in the point of resin solubility and initiator solubility (for example, Unexamined-Japanese-Patent No. 6). -324483).

An object of the present invention is to provide a resist composition that not only improves the solubility in producing a resist and the resist film adhesion during development, but also improves the stability of the resist and is excellent in safety.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching, the present inventors discovered that the said objective can be achieved by using a specific organic solvent, and came to this invention.

That is, the present invention provides a resist composition comprising a resist composition and an organic solvent, the organic solvent (a1) C _{3 -6} alkanediols, (a2) an alkoxy mono- -C _{3 -6} alkanediols, (b1) C _{5 -} It is done in ₆ alkanediol mono acetate, (b2) a mono-alkoxy -C _{3 -6} alkane diol monoacetate, (c1) C _{5 -6} alkane diol diacetate and (c2) an alkoxy mono- -C _{3 -6} alkane diol diacetate Provides a resist composition comprising at least one solvent selected from the group.

In the said resist composition, 2 or more types of organic solvent can be combined. As a preferable combination of the organic solvent,

_{(1) (a1) C 3} -6 alkanediols and (a2) an alkoxy mono- -C _{3 -6} and one or more diols selected from the group consisting of alkanediols, (b1 ') C _{3 -6} alkane diol monoacetate, (b2) a mono-alkoxy -C _{3 -6} alkane diol monoacetate, (c1 ') C _3-6 alkane diol diacetate and (c2) an alkoxy mono- -C _{3 -6} least one selected from the group consisting of an alkane diol diacetate Combination with acetates,

_{(2) (b1) C 5} -6 alkane diol monoacetate and (b2) a mono-alkoxy -C _{3 -6} alkanediol and monoacetate monomethyl acetates least one selected from the group consisting of, (c1 ') C _{3 -6} alkane diol diacetate and (c2) an alkoxy mono- -C _{3 -6} combination of the alkanediol di least one di-acetates selected from the group consisting of acetate,

(3) (b1 ') C 3 and _-6 alkane diol monoacetate and (b2) a mono-alkoxy -C _{3 -6} alkane diol monoacetate monomethyl acetates least one selected from the group consisting of, (c1) C _{5 -6} alkane diol diacetate and (c2) an alkoxy mono- -C _{3 -6} may be mentioned a combination of the alkanediol di-di-acetates least one selected from the group consisting of acetate.

The resist composition may further include one or more solvents selected from carboxylic acid alkyl esters and aliphatic ketones as organic solvents.

BEST MODE FOR CARRYING OUT THE INVENTION [

As the organic solvent in the present invention, (a1) C _{3 -6} alkanediols, (a2) an alkoxy mono- -C _{3 -6} alkanediols, (b1) C _{5 -6} alkane diol monoacetate, (b2) a mono-alkoxy -C _{3 -6} alkane diol monoacetate, (c1) a C _{5 -6} alkane diol diacetate and (c2) an alkoxy mono- -C _{3 -6} alkane diol diacetate one or more kinds of solvents selected from the group consisting of is used.

These organic solvents can be used individually, respectively, and can mix and use 2 or more types by arbitrary ratios. Moreover, it can mix and use with another organic solvent. Moreover, in each said organic solvent, as "alkoxy", a C1-C4 linear or branched alkoxy group, such as a methoxy, ethoxy, propoxy, butoxy group, is preferable.

The C _{3 -6} alkane diol (a1) As the number of carbon atoms of the alkyl chain is an alkane diol of 3 to 6 straight or branched chain and, for example, 1,2-propanediol, 1,3-propanediol, 2- Methyl-1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 3-methyl-1,3-butanediol, 3-ethyl-1,3-butanediol, 1,2 -Pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2,3-pentanediol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 3-methyl-1,5 -Pentanediol, 1,2-hexanediol, etc. are mentioned.

The mono alkoxy -C _{3 -6} alkane diols (a2) Examples of alkoxy groups are bonded one to the alkyl chain, and is the number of carbon atoms of the alkyl chain is an alkane diol of 3 to 6 straight or branched, for example 3-methoxy -1,2-propanediol, 3-ethoxy-1,2-propanediol, 3-propoxy-1,2-propanediol, 3-butoxy-1,2-propanediol, 2-methoxy- 1,3-propanediol, 2-ethoxy-1,3-propanediol, 2-propoxy-1,3-propanediol, 2-butoxy-1,3-propanediol, etc. are mentioned.

The C _{5 -6} alkanediol mono acetate (b1) as the carbon atoms in the alkyl chain and is an alkane diol monoacetate straight or branched 5 to 6, for example, 3-methyl-1,3-butanediol monoacetate, 3-ethyl-1,3-butanediol monoacetate, 1,2-pentanediol monoacetate, 1,4-pentanediol monoacetate, 1,5-pentanediol monoacetate, 2,3-pentanediol monoacetate, 2, 4-pentanediol monoacetate, 2-methyl-2,4-pentanediol monoacetate, 3-methyl-1,5-pentanediol monoacetate, 1,2-hexanediol monoacetate, etc. are mentioned.

The mono alkoxy -C _{3 -6} alkane diol monoacetate (b2) as if one alkoxy group is bonded to an alkyl chain, and an alkane diol mono-acetate of the carbon atoms in the alkyl chain with 3 to 6 is straight or branched, and, e.g. 3-methoxy-1,2-propanediol monoacetate, 3-ethoxy-1,2-propanediol monoacetate, 3-propoxy-1,2-propanediol monoacetate, 3-butoxy-1,2 Propanediol monoacetate, 2-methoxy-1,3-propanediol monoacetate, 2-ethoxy-1,3-propanediol monoacetate, 2-propoxy-1,3-propanediol monoacetate, 2- Butoxy-1,3-propanediol monoacetate, and the like.

The C _{5 -6} alkane diol diacetate (c1) as the carbon atoms in the alkyl chain is an alkane diol diacetate in 5 to 6 straight or branched chain and, for example, 3-methyl-1,3-butanediol diacetate, 3-ethyl-1,3-butanediol diacetate, 1,2-pentanediol diacetate, 1,4-pentanediol diacetate, 1,5-pentanediol diacetate, 2,3-pentanediol diacetate, 2 , 4-pentanediol diacetate, 2-methyl-2,4-pentanediol diacetate, 3-methyl-1,5-pentanediol diacetate, 1,2-hexanediol diacetate, and the like.

The mono alkoxy -C _{3 -6} alkane diol diacetate (c2) is as the one alkoxy group is bonded to an alkyl chain, and the carbon number of the alkyl chain alkanediol di-acetate of 3 to 6 straight or branched chain and, for example, 3-methoxy-1,2-propanediol diacetate, 3-ethoxy-1,2-propanediol diacetate, 3-propoxy-1,2-propanediol diacetate, 3-butoxy-1,2 Propanediol diacetate, 2-methoxy-1,3-propanediol diacetate, 2-ethoxy-1,3-propanediol diacetate, 2-propoxy-1,3-propanediol diacetate, 2- Butoxy-1,3-propanediol diacetate etc. are mentioned.

Especially preferred among these organic solvents are 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2-methyl-2,4-pentanediol C _3-6 alkanediols such as; Mono alkoxy -C _{3 -6} alkanediol (in particular, a mono C _1-4 alkoxy -C _3-6 alkanediols) such as 3-methoxy-1,2-propanediol; 1,5-diol diacetate, 2-methyl-2,4-pentanediol di-C _{5 -6} alkanediol, such as acetate, diacetate; 3-methoxy-l, 2 may be a mono-alkoxy -C _{3 -6} alkane diol diacetate (in particular, mono C ₁ -C _{3 -6 -4} alkoxy alkane diol diacetate), such as propanediol diacetate.

The solvent obtained a particularly excellent effect used alone, for example, 1,5-pentanediol diacetate, 2-methyl-2,4-pentanediol di-C _{5 -6} alkanediol, such as acetate, diacetate; 3-methoxy-l, 2 may be a mono-alkoxy -C _{3 -6} alkane diol diacetate (in particular, mono C ₁ -C _{3 -6 -4} alkoxy alkane diol diacetate), such as propanediol diacetate.

As a preferable combination in the case of using 2 or more types of organic solvents together,

_{(1) (a1) C 3} -6 alkanediols and (a2) an alkoxy mono- -C _{3 -6} and one or more diols selected from the group consisting of alkanediols, (b1 ') C _{3 -6} alkane diol monoacetate, (b2) a mono-alkoxy -C _{3 -6} alkane diol monoacetate, (c1 ') C _{3 -6} alkane diol diacetate and (c2) an alkoxy mono- -C _{3 -6} least one selected from the group consisting of an alkane diol diacetate Combination with acetates,

_{(2) (b1) C 5} -6 alkane diol monoacetate and (b2) a mono-alkoxy -C _{3 -6} alkanediol and monoacetate monomethyl acetates least one selected from the group consisting of, (c1 ') C _{3 -6} alkane diol diacetate and (c2) an alkoxy mono- -C _{3 -6} combination of the alkanediol di least one di-acetates selected from the group consisting of acetate,

(3) (b1 ') C 3 and _-6 alkane diol monoacetate and (b2) a mono-alkoxy -C _{3 -6} alkane diol monoacetate monomethyl acetates least one selected from the group consisting of, (c1) C _{5 -6} alkane diol diacetate and (c2) an alkoxy mono- -C _{3 -6} may be mentioned a combination of the alkanediol di-di-acetates least one selected from the group consisting of acetate.

(a1), (a2), (b1), (b2), (c1) and (c2) are the same as above. The (b1 ') C _{3 -6} alkanediol in addition to mono-acetate, the solvent contained in (b1), 1,2- propanediol monoacetate, 1,3-propanediol monoacetate, 2-methyl- diol monoacetate, include 1,2-butanediol monoacetate, 1,3-butanediol monoacetate, 1,4-butanediol monoacetate, etc. C _{3 -4} alkane diol monoacetate. In addition, (c1 ') C _{3 -6} alkanediol di addition to acetate, the solvent contained in (c1), 1,2- propanediol diacetate, 1,3-propanediol diacetate, and 2-methyl-1,3 such as propanediol diacetate, 1,2-butanediol diacetate, 1,3-butanediol diacetate, 1,4-butanediol diacetate include C _{3 -4} alkane diol diacetate.

More specifically, two or more kinds of mixed solvents, for example, 1,2-propanediol and 1,2-propanediol diacetate, 1,3-propanediol and 1,3-propanediol diacetate, 1,3- Butanediol and 1,3-butanediol diacetate, 1,4-butanediol and 1,4-butanediol diacetate, 1,5-pentanediol monoacetate and 1,5-pentanediol diacetate, 2-methyl-2,4- Pentanediol, 2-methyl-2,4-pentanediol diacetate, 3-methoxy-1,2-propanediol, 3-methoxy-1,2-propanediol diacetate, and the like can be given as preferred mixed solvents. . In particular, it is preferable to combine the diols and monoacetates which the alkyl chain part has in common, the diols and diacetates which the alkyl chain part has in common, and the monoacetates and diacetates which the alkyl chain part has in common, respectively.

C _{3 -4} alkanediol mono acetate or C _{3 -4} alkane diol diacetate is used not used alone, in the former case, if the flow or diol and di-acetates, and the latter is combined with the diol acetates flow or in mono It is desirable to.

As mentioned above, when mixing and using 2 types of organic solvent, the ratio of both is suitably selected according to the kind and objective of a solvent. For example, in the case of using a mixture of diols and acetates (monoacetates and / or diacetates) as in the case of (1) above, the ratio of both is the former / the latter (weight ratio) = 10/90 To 99/1, preferably 40/60 to 95/5, more preferably 50/50 to 90/10, particularly preferably about 60/40 to 90/10. In the case of using a mixture of monoacetates and diacetates as in the case of (2) or (3) above, the former / the latter (weight ratio) = 1/99 to 99/1, preferably 10/90 To 90/10, more preferably 20/80 to 80/20, particularly preferably about 30/70 to 70/30.

Another organic solvent (d) can be added (combined) to the organic solvent in this invention, unless the effect of this invention is impaired. As another organic solvent (d) which can be added, carboxylic acid alkyl ester, aliphatic ketone, etc. are mentioned, for example. In the carboxylic acid esters, for example, such as lactic acid esters, acetic acid esters, propionic acid esters, alkoxy acid esters, hydroxyl groups, alkoxy groups (e.g., C _{1 -4} alkoxy group, etc.), etc. that may have an aliphatic carboxylic acid alkyl ester with a carbon number of about 1 to 4 substituents which, and the like (for example, C _{1 -6} alkyl esters, etc.).

More specifically, the lactic acid alkyl ester as methyl lactate, ethyl lactate, such as C _{1 -6} alkyl esters such as the acetate, acetic acid alkyl ester as propyl acetate, n- butyl acetate, C _{1 -6} alkyl esters such as amyl acetate, n- etc., as the acid alkyl ester propionic acid methyl propionate, ethyl propionate, propyl propionate, the propionic acid ester such as C _{1 -6} alkyl, such as butyl, alkoxy propionic acid alkyl ester, methyl methoxy propionate, ethyl ethoxy propionate, ethyl methoxy propionate, a C _{1 -4} alkoxy, such as ethoxy-propionic acid methyl-propionic acid and the like can be mentioned C _{1 -6} alkyl esters. Examples of the aliphatic ketone include aliphatic ketones having about 3 to 10 carbon atoms such as 2-butanone, 2-pentanone, 2-hexanone and 2-heptanone.

Moreover, as another organic solvent (d) which can be added, Glycol ether, such as monopropylene glycol alkyl ether and dipropylene glycol alkyl ether, in addition to the above; Glycol ether acetates such as monopropylene glycol alkyl ether acetate (propylene glycol methyl ether acetate and the like).

The amount of the other organic solvent (d) can be appropriately selected within the range of not impairing the solubility of the resin or other properties as the resist solvent, but is usually 80% by weight or less, preferably 70% by weight, based on the total amount of the organic solvent in the resist composition. Or less, more preferably 50% by weight or less, particularly preferably 10% by weight or less, and may be substantially 0% by weight.

The resist component in the resist composition of the present invention may be either conventionally known or known positive or negative resist. Representative examples of the resist that can be used in the present invention include, for example, a quinonediazide-based photosensitive agent and an alkali-soluble resin in a positive type, a chemically amplified resist, and the like, for example, polycinnamic acid. Containing a high molecular compound having a photosensitive group such as vinyl, containing an aromatic azide compound or containing an azide compound containing a cyclized rubber and a bisazide compound, containing a diazo resin, addition polymerization Photopolymerizable compositions containing a unsaturated unsaturated compound, a chemically amplified negative resist containing an alkali-soluble resin, a crosslinking agent, and an acid generator, and the like.

In the present invention, those containing a quinonediazide photosensitive agent and an alkali-soluble resin are preferable as a resist material to be used. The positive resist containing a quinonediazide type photosensitive agent and alkali-soluble resin is known conventionally, but what kind of thing is good in this invention, It does not specifically limit.

Examples of the quinonediazide-based photosensitizers used in positive resists containing these quinonediazide-based photosensitizers and alkali-soluble resins include 1,2-benzoquinonediazide-4-sulfonic acid and 1,2-naphthoquinone. Diazide-4-sulfonic acid, 1,2-naphthoquinone diazide-5-sulfonic acid, esters or amides of these sulfonic acids, and the like. The ester or amide compound of sulfonic acid can be obtained by condensation reaction of the corresponding quinonediazide sulfonic acid or quinonediazidesulfonyl chloride with a compound having a hydroxyl group or a compound having an amino group.

Examples of the compound having a hydroxyl group include dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phenol, naphthol, p-methoxyphenol, bisphenol A, pyrocatechol, pyrogallol, pyrogallol methyl ether, gallic acid, α, α ', α' '-tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene, tris (hydroxyphenyl) methane, and the like, and further include amino groups such as aniline and p-amino Diphenylamine etc. are mentioned. These quinone diazide-based photosensitizers can be used alone or as a mixture of two or more thereof.

On the other hand, as alkali-soluble resin, the copolymer of novolak resin, polyvinyl phenol, polyvinyl alcohol, acrylic acid, or methacrylic acid, etc. are mentioned, for example.

Examples of the novolak resins include phenol, o-cresol, m-cresol, p-cresol, xylenol, trimethylphenol, t-butylphenol, ethylphenol, 2-naphthol, 1,3-dihydroxynaphthalene, and the like. And polycondensation products of one or two or more of the phenols with aldehydes such as formaldehyde and paraformaldehyde. Alkali-soluble resins, such as these novolak resins, can be used in combination of 2 or more type as needed, Furthermore, another resin can be added for the improvement of film formation property, etc .. As the quinonediazidesulfonic acid ester, polycondensates of phenols, aldehydes or ketones and esters of quinonediazidesulfonic acid can be used.

The use ratio of the quinonediazide-based photosensitive agent and the alkali-soluble resin is different depending on the photosensitive agent and the alkali-soluble resin specifically used, and in general, the weight ratio is preferably in the range of 1: 1 to 1:20. It is not limited to this.

A chemically amplified resist is also a positive resist which can be preferably used in the present invention. The chemically amplified resist generates an acid by irradiation with radiation, and forms a pattern by changing the solubility of the developer in the irradiation portion by chemical change caused by the catalysis of the acid, for example, by radiation. And an acid sensitive group-containing resin which decomposes in the presence of an acid to generate an acid and generates an alkali-soluble group such as a phenolic hydroxyl group or carboxyl group.

As an acid generating compound which generate | occur | produces an acid by the said irradiation, bissulfonyl diazomethanes, such as bis (isopropylsulfonyl) diazomethane, bissulfonyl methane, such as methylsulfonyl p-toluenesulfonyl methane Sulfonylcarbonyldiazomethanes such as cyclohexylsulfonyl cyclohexylcarbonyldiazomethane, sulfonylcarbonylalkanes such as 2-methyl-2- (4-methylphenylsulfonyl) propiophenone, 2-nitro Nitrobenzylsulfonates such as benzyl p-toluenesulfonate, alkyl or arylsulfonates such as pyrogallol trismethanesulfonate, benzoinsulfonates such as benzointosylate, N- (trifluoromethylsulfonyl N-sulfonyloxyimides such as oxy) phthalimide, pyrrolidones such as (4-fluoro-benzenesulfonyloxy) -3,4,6-trimethyl-2-pyridone, 2,2,2 -Trifluoro-1-trifluoromethyl-1- (3-vinylphenyl) -ethyl 4- Sulfonic acid esters such as chlorobenzenesulfonate, onium salts such as triphenylsulfonium methanesulfonate, and the like, and these compounds may be used alone or in combination of two or more thereof.

The acid-sensitive group-containing resin that decomposes in the presence of an acid to produce an alkali-soluble group such as a phenolic hydroxyl group or a carboxyl group is composed of an alkali-soluble resin portion having an acid-sensitive group and an alkali-soluble group that decompose in the presence of an acid. Examples of the acid-sensitive group include silyl groups such as substituted methyl groups such as benzyl groups, 1-substituted ethyl groups such as 1-methoxyethyl group and 1-benzyloxyethyl group, 1-branched alkyl groups such as t-butyl group, and trimethylsilyl group, and trimethylger Cyclic acid decomposers, such as an alkylcarbonyl group, such as the germanyl group, such as a mill, and t-butoxycarbonyl group, an acyl group, such as an acetyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, a tetrahydrothiopyranyl group, and a tetrahydrothiofuranyl group, etc. Can be mentioned. Preferred among these acid-decomposable groups are benzyl group, t-butyl group, t-butoxycarbonyl group, tetrahydropyranyl group, tetrahydrofuranyl group, tetrahydrothiopyranyl group, tetrahydrothiofuranyl group and the like.

As alkali-soluble resin which has alkali-soluble group, such as a phenolic hydroxyl group or a carboxyl group, For example, hydroxy styrene, hydroxy- (alpha) -methylstyrene, hydroxymethyl styrene, hydroxy adamantyl (meth) acrylate, carboxyadamant Polymers from vinyl monomers such as methyl (meth) acrylate, vinylbenzoic acid, carboxymethylstyrene, carboxymethoxystyrene, acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, citraconic acid, mesaconic acid, cinnamic acid Or polycondensation resins such as copolymers, copolymers of one or more of these monomers with other monomers, and novolak resins.

As the chemically amplified resist, in addition to the above, a compound which decomposes in the presence of an alkali-soluble resin, an acid generator and an acid to lower the solubility control effect of the alkali-soluble resin or promotes the solubility of the alkali-soluble resin may be contained. It is known and these can be used.

These resist components can be melt | dissolved in the said organic solvent, and it can be set as the resist composition of this invention. Although the ratio of a resist component can be suitably set according to the kind of resist and the kind of solvent used, it is 50-50 weight part normally with respect to 100 weight part of resist solid components, Preferably it is 70-2000 weight part, More preferably, 100 to 1000 parts by weight of an organic solvent is used. In particular, when 100 to 500 parts by weight of the organic solvent is used, the solubility of the alkali-soluble resin is often exhibited.

In addition, various conventionally known additives, such as surfactant and a sensitizer, can be mix | blended with these resist compositions suitably. In the case of water solubility, water may be added and used.

Although the resist composition of this invention can be used for various uses, such as manufacture of a semiconductor device or manufacture of a liquid crystal display element, it is preferable to use as a photoresist composition for semiconductor manufacture or a liquid crystal display element manufacture. Formation of the resist pattern using the resist composition of this invention is performed as follows, for example.

First, the resist composition of the present invention is prepared by dissolving a resist material in the solvent. The resist composition of the present invention thus prepared is free of insoluble matters by filter filtration as necessary, and is spin coated, roll coated, reverse roll coated. The film thickness after prebaking is apply | coated on board | substrates, such as silicone and glass, for example by 0.01-1000 micrometers by the conventionally well-known coating method, such as casting | flow_spread coating and doctor coating.

The resist composition applied to the substrate is, for example, prebaked on a hot plate to remove the solvent and to form a resist film. The preliminary baking temperature varies depending on the type of solvent or resist used, and is usually performed at a temperature of about 30 to 200 ° C, preferably about 50 to 150 ° C.

Although exposure is performed after a resist film is formed, since a photosensitive area | region differs with each resist to be used, exposure is performed using the exposure source according to the photosensitive band of a resist. Exposure uses a well-known irradiation apparatus, such as a high pressure mercury lamp, a metal halide lamp, an ultrahigh pressure mercury lamp, a KrF excimer laser, an ArF excimer laser, an F2 laser, a soft X-ray irradiation apparatus, an electron beam drawing apparatus, and a mask as needed. Irradiation of a predetermined pattern is performed by ultraviolet rays, far ultraviolet rays, X-rays, electron beams, or the like. After exposure, after baking is performed as needed, in order to improve developability, resolution, pattern shape, etc., image development is performed. After the development, dry etching using a gas plasma or the like is performed to remove the antireflection film or the like, if necessary, and a resist pattern is formed.

The development of the resist is usually performed using a developer using a difference in solubility in a solvent in an exposed area and an unexposed area or a solubility in an alkaline solution. Examples of the alkaline developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate and sodium silicate, amines such as ammonia, ethylamine, diethylamine, triethylamine, diethylethanolamine, triethanolamine and benzylamine, Aqueous solutions or aqueous solutions in which amides such as formamide, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide and quaternary ammonium salts such as choline, and cyclic amines such as pyrrole and piperazine are dissolved.

<Examples>

Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited thereto.

<Examples 1 to 6, Comparative Examples 1 to 3>

2 g of esterification reaction product of 1 mol of 2,4,4,4'-tetrahydroxybenzophenone and 3 mol of naphthoquinone-1,2-diazide-5-sulfonyl chloride, and 8 g of cresol novolak resin Was dissolved in 40 g of a solvent (numbers by weight) having the composition shown in Table 1 below to prepare a coating liquid for a positive photoresist composition. The evaluation test of following (1)-(4) was done about the coating liquid obtained in this way. The results are shown in Table 1.

(1) Presence or absence of precipitate

The prepared coating liquid was filtered with a 0.2 μm membrane filter and left at 40 ° C. to check for the presence or absence of precipitates in the coating liquid at the time of 2 months.

(2) Sensitivity change

The presence or absence of a change in sensitivity of the photoresist composition after 3 months was examined. That is, when the coating liquid immediately after manufacture was apply | coated to a base material and dried, the minimum exposure amount (sensitivity) when applying and drying the coating liquid which passed 3 months after manufacture was compared, and it showed that there was no change at all. The thing with which the sensitivity fell was called "x".

(3) Cross-sectional shape

The prepared coating liquid was slit coated on a glass substrate and dried on a hot plate at 90 DEG C for 90 seconds to form a resist film having a film thickness of 1.3 mu m and exposed to light through a predetermined mask using a stepper, The plate was heated on a plate at 110 占 폚 for 90 seconds, then developed with a 2.38% by weight aqueous solution of tetramethylammonium hydroxide (TMAH), washed with water for 30 seconds, and dried.

(Circle): Undercut does not generate | occur | produce in the contact part of a glass substrate and a resist pattern.

X: Undercut occurred at the contact portion between the glass substrate and the resist pattern (see Fig. 1).

(4) Coating condition

The coating solution prepared was slit-coated on a glass substrate, the film thickness of the thing dried at 90 ° C. for 90 seconds on a hot plate was measured, and it was "good" that the surface could be applied uniformly, and the surface could not be applied uniformly. "It was bad."

The abbreviations in the table are as follows.

1,3-MPGDA: 2-methyl-1,3-propanediol diacetate

HG: 2-methyl-2,4-pentanediol

HGDA: 2-methyl-2,4-pentanediol diacetate

GLMMA: 3-methoxy-1,2-propanediol monoacetate

GLMDA: 3-methoxy-1,2-propanediol diacetate

PGMEA: Propylene glycol methyl ether acetate

EL: Ethyl lactate

<Examples 7 to 8, Comparative Example 4>

Monohydroxyadamantyl acrylate and tetrahydrofuranyl methacrylate were copolymerized to obtain a weight average molecular weight of 8,000 of 70 mol% of monohydroxyadamantyl acrylate units and 30 mol% of tetrahydropyranyl methacrylate units. A copolymer was obtained. The solvent of the composition shown in following Table 2 was added so that solid component might be 25 weight% to obtained resin, and it heated at 50 degreeC for 10 minutes, and investigated the dissolution rate (soluble property) of resin. The results are shown in Table 2. Abbreviations in the table are the same as above.

○: becomes a homogeneous transparent solution

×: Granular insoluble resin remains on the container wall

Industrial availability

Since the resist composition of this invention is excellent in solvent solubility and excellent in safety or stability to a human body, it is useful as a photoresist composition for manufacture, such as a semiconductor device and a liquid crystal display element.

According to the present invention, the solubility in producing the resist is improved, the stability of the resist is greatly improved, and the drying rate is adjusted by maintaining the amount of residual solvent in the resist film at the time of applying the resist, and the film thickness uniformity and line width uniformity are maintained. The resist composition which improves the characteristics, such as the resist film adhesiveness at the time of image development, and is highly stable is provided.

Claims (5)

Contains a resist component and an organic solvent, The organic solvent is (a2) monoalkoxy-C _3-6 alkanediol, (b1) C _5-6 alkanediol monoacetate, (b2) monoalkoxy-C _3-6 alkanediol monoacetate, (c1) C _5- A resist composition comprising at least one solvent selected from the group consisting of ₆ alkanediol diacetate and (c2) monoalkoxy-C _3-6 alkanediol diacetate. The organic solvent of claim 1, wherein the organic solvent is (a2) monoalkoxy-C _3-6 alkanediol, (b1 ') C _3-6 alkanediol monoacetate, (b2) monoalkoxy-C _3-6 alkanediol monoacetate A resist composition comprising a combination of one or more acetates selected from the group consisting of (c1 ') C _3-6 alkanediol diacetate and (c2) monoalkoxy-C _3-6 alkanediol diacetate. The method of claim 1 wherein the organic solvent (b1) C _{5 -6} alkane diol monoacetate and (b2) a mono-alkoxy -C _3-6 alkane diol monoacetate monomethyl acetates least one selected from the group consisting of, (c1 ') C _{3 -6} alkane diol diacetate and (c2) an alkoxy mono- -C _{3 -6} resist composition comprising a combination of a di-acetates least one selected from the group consisting of an alkane diol diacetate. According to claim 1, wherein the organic solvent is (b1 ') C _{3 -6} alkane diol monoacetate and (b2) a mono-alkoxy -C _3-6 alkane diol monoacetate monomethyl acetates least one selected from the group consisting of, ( c1) _-6 C ₅ alkane diol diacetate and (c2) an alkoxy mono- -C _{3 -6} resist composition comprising a combination of a di-acetates least one selected from the group consisting of an alkane diol diacetate. The resist composition according to any one of claims 1 to 4, further comprising one or more solvents selected from carboxylic acid alkyl esters and aliphatic ketones as organic solvents.

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