CN113687573A

CN113687573A - Positive photosensitive resin composition, method for forming patterned resist film, and patterned resist film

Info

Publication number: CN113687573A
Application number: CN202110532928.4A
Authority: CN
Inventors: 松本直纯
Original assignee: Tokyo Ohka Kogyo Co Ltd
Current assignee: Tokyo Ohka Kogyo Co Ltd
Priority date: 2020-05-18
Filing date: 2021-05-17
Publication date: 2021-11-23
Also published as: TW202201130A; KR20210142544A; JP2021182041A

Abstract

The invention relates to a positive photosensitive resin composition, a method for forming a patterned resist film, and a patterned resist film. The invention provides a positive photosensitive resin composition having excellent depth of focus characteristics and excellent resolution, a method for forming a patterned resist film using the positive photosensitive resin composition, and a patterned resist film formed from the positive photosensitive resin composition. The solution of the present invention is to use a quinonediazide-containing compound (B) in which 2 kinds of quinonediazide-containing compounds having a specific structure are combined at a specific ratio in a positive photosensitive resin composition containing an alkali-soluble resin (A) and a quinonediazide-containing compound (B).

Description

Positive photosensitive resin composition, method for forming patterned resist film, and patterned resist film

Technical Field

The invention relates to a positive photosensitive resin composition, a method for forming a patterned resist film, and a patterned resist film.

Background

As a method for forming a wiring or a terminal on a substrate, a method is known in which a metal layer is etched using a resist pattern as a mask pattern, or plating is performed using a resist pattern as a mold pattern for plating.

As a method for forming a resist pattern when forming a wiring or a terminal on a substrate, the following method is generally used: a dry film formed of a negative photosensitive composition is used to form a photosensitive composition layer on a substrate, and the photosensitive composition layer is exposed and developed. However, when a negative photosensitive composition is used, there are the following problems: insufficient resolution; or sometimes it is difficult to peel the resist pattern from the substrate; and so on.

Therefore, as a method for solving the above problem, there is a method for forming a resist pattern using a positive photosensitive composition which has good resolution and is relatively easy to be peeled from a substrate.

As a positive photosensitive composition that can be used for forming a wiring, a terminal, or the like made of a metal, for example, a photosensitive composition containing an alkali-soluble Novolac resin such as a cresol Novolac resin, a photosensitizer, and a benzotriazole-based compound is known (see patent document 1).

Documents of the prior art

Patent document

Patent document 1: japanese patent application laid-open No. 2010-176012

Disclosure of Invention

Problems to be solved by the invention

However, it is difficult to achieve both excellent depth of focus (DOF) characteristics and excellent resolution (that is, to form a fine pattern with little development residue) in the positive photosensitive composition described in patent document 1. Therefore, it is desired to provide excellent depth of focus characteristics and excellent resolution to the positive photosensitive composition described in patent document 1.

In addition, the photosensitive composition is generally required to have high sensitivity. However, in general, when the sensitivity of the photosensitive composition is increased, the depth of focus characteristics and resolution are easily degraded. Therefore, in particular, it is desired that the photosensitive composition with high sensitivity has both excellent depth of focus characteristics and excellent resolution.

The present invention has been made in view of the above problems, and an object thereof is to provide a positive photosensitive resin composition having both excellent depth of focus characteristics and excellent resolution, a method for forming a patterned resist film using the positive photosensitive resin composition, and a patterned resist film formed from the positive photosensitive resin composition.

Means for solving the problems

The present inventors have found that the above problems can be solved by using a quinonediazide-containing compound (B) in which 2 kinds of quinonediazide-containing compounds having specific structures are combined at a specific ratio in a positive photosensitive resin composition containing an alkali-soluble resin (a) and a quinonediazide-containing compound (B), and have completed the present invention. Specifically, the present invention provides the following.

The invention of the 1 st mode is a positive photosensitive resin composition, which contains an alkali soluble resin (A) and containing quinone diazide group compound (B),

the quinonediazido group-containing compound (B) comprises a compound represented by the following formula (B1) and a compound represented by the following formula (B2),

(in the formula (B1), each D is independently a hydrogen atom or a 1, 2-diazidonaphthoquinone-5-sulfonyl group, and at least one of 4D is a 1, 2-diazidonaphthoquinone-5-sulfonyl group.)

(in the formula (B2), R^b1Each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R^b2Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms, each D independently represents a hydrogen atom or a 1, 2-diazidonaphthoquinone-5-sulfonyl group, and at least one of the 4D groups represents a 1, 2-diazidonaphthoquinone-5-sulfonyl group. )

When the mass of the compound represented by formula (B1) is M1 and the mass of the compound represented by formula (B2) is M2, M1/M2 is 1.2 or more and 5.0 or less.

The invention according to claim 2 is a method for forming a patterned resist film, including:

a step of forming a coating film by coating the positive photosensitive resin composition according to claim 1 on a substrate;

a step of exposing the coating film in a position-selective manner; and

and developing the exposed coating film with a developer.

The 3 rd aspect of the present invention is a patterned resist film formed from the positive photosensitive resin composition according to the 1 st aspect.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, a positive photosensitive resin composition having both excellent depth of focus characteristics and excellent resolution, a method for forming a patterned resist film using the positive photosensitive resin composition, and a patterned resist film formed from the positive photosensitive resin composition can be provided.

Detailed Description

Positive photosensitive resin composition

The positive photosensitive resin composition comprises an alkali-soluble resin (A) and a quinonediazido group-containing compound (B).

(in the formula (B2), R^b1Each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R^b2Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms, each D independently represents a hydrogen atom or a 1, 2-diazidonaphthoquinone-5-sulfonyl group, and at least one of the 4D groups represents a 1, 2-diazidonaphthoquinone-5-sulfonyl group. ).

In the quinonediazido group-containing compound (B), when the mass of the compound represented by formula (B1) is M1 and the mass of the compound represented by formula (B2) is M2, M1/M2 is 1.2 or more and 5.0 or less.

By including the compound represented by the formula (B1) and the compound represented by the formula (B2) in the above ratio in the positive photosensitive resin composition, the positive photosensitive resin composition has both excellent depth of focus characteristics and excellent resolution.

Hereinafter, essential or optional components contained in the positive photosensitive resin composition will be described.

< alkali soluble resin (A) >)

The alkali-soluble resin (a) is not particularly limited as long as it has an alkali-soluble group such as a carboxyl group or a phenolic hydroxyl group and can impart desired development characteristics to the positive photosensitive resin composition.

Preferred examples of the alkali-soluble resin (a) include:

novolac resin obtained by condensing phenols with aldehydes and/or ketones in the presence of an acidic catalyst;

hydroxystyrene resins such as homopolymers of hydroxystyrene, copolymers of hydroxystyrene and other styrene monomers, and copolymers of hydroxystyrene and acrylic acid or methacrylic acid or derivatives thereof;

and (meth) acrylic resins which are copolymers of (meth) acrylic acid and derivatives thereof.

Among these, the Novolac resin is preferable in that it has good heat resistance and can be synthesized or obtained relatively inexpensively. Hereinafter, the Novolac resin will be described.

As the Novolac resin, various Novolac resins conventionally blended in positive photosensitive resin compositions can be used. The Novolac resin is preferably a reaction product obtained by addition-condensing an aromatic compound having a phenolic hydroxyl group (hereinafter, simply referred to as "phenol") with an aldehyde under an acid catalyst.

Phenols

Examples of the phenols include phenol; cresols such as o-cresol, m-cresol and p-cresol; xylenols such as 2, 3-xylenol, 2, 4-xylenol, 2, 5-xylenol, 2, 6-xylenol, 3, 4-xylenol, and 3, 5-xylenol; ethylphenols such as o-ethylphenol, m-ethylphenol and p-ethylphenol; alkylphenols such as 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, o-butylphenol, m-butylphenol, p-butylphenol, and p-tert-butylphenol; trialkylphenols such as 2,3, 5-trimethylphenol and 3,4, 5-trimethylphenol; polyhydric phenols such as resorcinol, catechol, hydroquinone monomethyl ether, pyrogallol, and phloroglucinol; alkyl polyphenols such as alkylresorcinol, alkylcatechol, and alkylhydroquinone (all of alkyl groups have 1 to 4 carbon atoms); alpha-naphthol; beta-naphthol; hydroxybiphenyl; and bisphenol A and the like. These phenols may be used alone, or 2 or more of them may be used in combination.

Among these phenols, m-cresol and p-cresol are preferable, and m-cresol and p-cresol are more preferable in combination. In this case, various characteristics such as the sensitivity of the positive photosensitive resin composition and the heat resistance of the formed coating resin layer 17 can be adjusted by adjusting the blending ratio of the two. The mixing ratio of m-cresol and p-cresol is not particularly limited, and is preferably 3/7 or more and 8/2 or less in terms of a mass ratio of m-cresol/p-cresol. When the ratio of m-cresol is 3/7 or more, the sensitivity as a positive photosensitive resin composition can be improved, and when it is 8/2 or less, the heat resistance of a resist film formed using the photosensitive resin composition can be improved.

Aldehydes

Examples of the aldehydes include formaldehyde, paraformaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, and acetaldehyde. These aldehydes may be used alone, or 2 or more kinds thereof may be used in combination.

Acid catalyst

Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and phosphorous acid; organic acids such as formic acid, oxalic acid, acetic acid, diethyl sulfuric acid, and p-toluenesulfonic acid; and metal salts such as zinc acetate. These acid catalysts may be used alone, or 2 or more of them may be used in combination.

Molecular weight

From the viewpoints of developability, resolution, and the like of the positive photosensitive resin composition, the weight average molecular weight (Mw; hereinafter, also simply referred to as "weight average molecular weight") of the Novolac resin in terms of polystyrene is preferably 1000 or more, more preferably 2000 or more, further preferably 3000 or more, and further preferably 50000 or less, more preferably 40000 or less, further preferably 30000 or less, further more preferably 20000 or less.

The dispersity (weight average molecular weight Mw/number average molecular weight Mn) of the Novolac resin is preferably 1 or more and 20 or less, more preferably 2 or more and 17 or less, particularly preferably 3 or more and 15 or less, and further preferably 4 or more and 12 or less.

In the present specification, the weight average molecular weight Mw and the number average molecular weight Mn may be defined as relative values in terms of polystyrene in GPC (gel permeation chromatography) measurement.

When a plurality of types of Novolac resins are used, GPC (gel permeation chromatography) measurement may be performed in a state where these plurality of types of Novolac resins are combined, and the degree of dispersion may be determined from the obtained spectrum.

The Novolac resin may be a combination of at least 2 resins having different weight average molecular weights in terms of polystyrene. By using resins having different weight average molecular weights in combination, various excellent characteristics such as developability, resolution, film-forming property, and the like can be imparted to the positive photosensitive resin composition.

The Novolac resin is not particularly limited as a combination of resins having different weight average molecular weights, but a combination of a resin having a low weight average molecular weight of 1000 or more and 10000 or less and a resin having a high weight average molecular weight of 5000 or more and 50000 or less is preferable, a combination of a resin having a low weight average molecular weight of 2000 or more and 8000 or less and a resin having a high weight average molecular weight of 8000 or more and 40000 or less is more preferable, and a combination of a resin having a low weight average molecular weight of 3000 or more and 7000 or less and a resin having a high weight average molecular weight of 10000 or more and 20000 or less is further preferable.

When resins having different weight average molecular weights are used in combination as the Novolac resin, the content of each resin is not particularly limited, but the content of the resin on the low weight average molecular weight side in the total amount of the Novolac resin is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, and on the other hand, is preferably 50% by mass or less, more preferably 40% by mass or less.

When the positive photosensitive resin composition contains a Novolac resin as the alkali-soluble resin (a), the ratio of the mass of the Novolac resin to the mass of the alkali-soluble resin (a) is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, further more preferably 90% by mass or more, and particularly preferably 100% by mass.

The ratio of the mass of the alkali-soluble resin (a) to the total solid content of the positive photosensitive resin composition is not particularly limited as long as the positive photosensitive resin composition contains the desired amount of the quinonediazide group-containing compound (B).

The ratio of the mass of the alkali-soluble resin (a) to the total solid content of the positive photosensitive resin composition is preferably 40 mass% or more and 80 mass% or less, more preferably 45 mass% or more and 75 mass% or less, and still more preferably 50 mass% or more and 70 mass% or less.

< Compound (B) containing quinonediazido group >

The positive photosensitive resin composition contains a quinonediazido group-containing compound (B).

From the viewpoint of particularly good focal depth characteristics and the viewpoint of easy formation of a pattern having a rectangular cross-sectional shape with good cross-sectional shape, M1/M2 is preferably 1.3 or more and 4.0 or less, more preferably 1.5 or more and 2.5 or less, and still more preferably 1.7 or more and 2.2 or less.

In the formula (B2), R^b1Each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. The alkyl group having 1 to 6 carbon atoms may be linear or branched. Preferred examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a n-pentyl group, an isopentyl group, a neopentyl group, and a n-hexyl group.

As R^b1Preferably, a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

In the formula (B2), R^b2Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms.

An alkyl group having 1 to 6 carbon atoms and R as the radical^b1The same applies to the alkyl group of (1).

Specific examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, a n-propyloxy group, an isopropyloxy group, a n-butyloxy group, an isobutyloxy group, a sec-butyloxy group, a tert-butyloxy group, a n-pentyloxy group, an isopentyloxy group, a neopentyloxy group, and a n-hexyloxy group.

Specific examples of the cycloalkyl group having 3 to 6 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. Among these, cyclohexyl is preferable.

In the formulae (B1) and (B2), D represents a hydrogen atom or a 1, 2-diazidonaphthoquinone-5-sulfonyl group. The 1, 2-diazidonaphthoquinone-5-sulfonyl group as D can be introduced into the compound represented by the formula (B1) or the compound represented by the formula (B2) by condensing naphthoquinone-1, 2-diazido5-sulfonyl chloride with a phenolic hydroxyl group in a solvent such as dioxane in the presence of a base such as triethanolamine, a carbonate base, or a bicarbonate base.

In view of easily obtaining desired effects on the depth of focus characteristics and resolution, the ratio of the sum of M1 and M2 to the mass of the quinonediazide-containing compound (B) is preferably 20 mass% or more and 50 mass% or less, more preferably 23 mass% or more and 45 mass% or less, and still more preferably 25 mass% or more and 40 mass% or less.

The quinonediazide-containing compound (B) preferably contains a compound represented by formula (B3) and/or a compound represented by formula (B4) together with the compound represented by formula (B1) and the compound represented by formula (B2), and more preferably contains a compound represented by formula (B3) and a compound represented by formula (B4).

(in the formula (B3), R^b3Each independently represents an alkyl group having 1 to 5 carbon atoms, each D independently represents a hydrogen atom or a 1, 2-diazidonaphthoquinone-5-sulfonyl group, at least one of 2+ m D represents a 1, 2-diazidonaphthoquinone-5-sulfonyl group, and each of l and m independently represents 1 or 2. )

(in the formula (B4), each D is independently a hydrogen atom or a 1, 2-diazidonaphthoquinone-5-sulfonyl group, and at least one of 3D's is a 1, 2-diazidonaphthoquinone-5-sulfonyl group.)

By including the quinonediazide group-containing compound (B) with the compound represented by the formula (B3) and/or the compound represented by the formula (B4), a positive photosensitive resin composition having good sensitivity and capable of forming a pattern having a good rectangular cross-sectional shape can be easily obtained.

In the formula (B3), R^b3Each independently represents an alkyl group having 1 to 5 carbon atoms. The alkyl group having 1 to 5 carbon atoms may be linear or branched. Preferred examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, and a neopentyl group.

As R^b3Methyl and ethyl are preferred, and methyl is more preferred.

The average proportion (average esterification rate) of the 1, 2-diazidonaphthoquinone-5-sulfonyl group in the quinonediazide ester compound represented by formula (B3) in D is preferably 40% or more and 60% or less, and more preferably 50% or more and 55% or less, from the viewpoint of facilitating the solubility and sensitivity of the positive photosensitive resin composition in a developer to fall within an appropriate range.

The average proportion (average esterification rate) of the 1, 2-diazidonaphthoquinone-5-sulfonyl group in the quinonediazide ester compound represented by formula (B4) in D is preferably 65% or more and 85% or less, more preferably 70% or more and 75% or less, from the viewpoint of facilitating the solubility and sensitivity of the positive photosensitive resin composition in a developer to fall within an appropriate range.

When the positive photosensitive resin composition contains the compound represented by the formula (B3) and/or the compound represented by the formula (B4) as the quinonediazide-containing compound (B), the ratio of the mass of the compound represented by the formula (B3) to the sum of the masses of the compounds represented by the formula (B4) is preferably 50 mass% or more, more preferably 70 mass% or more, further preferably 80 mass% or more, further more preferably 90 mass% or more, and particularly preferably 100 mass% with respect to the mass of the quinonediazide-containing compound (B) excluding the total mass of M1 and M2.

When the mass of the compound represented by formula (B3) is M3 and the mass of the compound represented by formula (B4) is M4, the range of M3/M4 is not particularly limited. From the viewpoint of good balance among various properties such as sensitivity, depth of focus property, and resolution of the positive photosensitive resin composition, M3/M4 is preferably 1.5 or more and 4.0 or less, more preferably 1.7 or more and 3.5 or less, and further preferably 2.0 or more and 3.0 or less.

The quinonediazide-containing compound (B) may contain a quinonediazide-containing compound other than the compound represented by formula (B1), the compound represented by formula (B2), the compound represented by formula (B3) and the compound represented by formula (B4). The other quinonediazide group-containing compound can be appropriately selected from compounds having quinonediazide groups which have been conventionally blended in various positive photosensitive resin compositions.

Preferable specific examples of the quinonediazide group-containing compound include a complete ester compound, a partial ester compound, an amide compound, a partial amide compound, and the like, of a quinonediazide group-containing sulfonic acid, wherein: polyhydroxy benzophenones such as 2,3, 4-trihydroxybenzophenone, 2,4,4 ' -trihydroxybenzophenone, 2,4, 6-trihydroxybenzophenone, 2,3, 4-trihydroxy-2 ' -methylbenzophenone, 2 ', 4,4 ' -tetrahydroxybenzophenone, 2,3 ', 4,4 ', 6-pentahydroxybenzophenone, 2 ', 3,4,4 ' -pentahydroxybenzophenone, 2 ', 3,4, 5-pentahydroxybenzophenone, 2,3 ', 4,4 ', 5 ', 6-hexahydroxybenzophenone, and 2,3,3 ', 4,4 ', 5 ' -hexahydroxybenzophenone; bis [ (poly) hydroxy-phenyl ] ethylidene } bisphenols such as bis (2, 4-dihydroxyphenyl) methane, bis (2,3, 4-trihydroxyphenyl) methane, 2- (4-hydroxyphenyl) -2- (4 '-hydroxyphenyl) propane, 2- (2, 4-dihydroxyphenyl) -2- (2', 4 '-dihydroxyphenyl) propane, 2- (2,3, 4-trihydroxyphenyl) -2- (2', 3 ', 4' -trihydroxyphenyl) propane, 4 '- {1- [4- [ 2- (4-hydroxyphenyl) -2-propyl ] phenyl ] ethylidene } bisphenol, and 3, 3' -dimethyl- {1- [4- [ 2- (3-methyl-4-hydroxyphenyl) -2-propyl ] phenyl ] ethylidene } bisphenol Phenyl ] alkanes; tris (4-hydroxyphenyl) methane, bis (4-hydroxy-3, 5-dimethylphenyl) -4-hydroxyphenyl methane, bis (4-hydroxy-2, 5-dimethylphenyl) -4-hydroxyphenyl methane, bis (4-hydroxy-3, 5-dimethylphenyl) -2-hydroxyphenyl methane, tris (hydroxyphenyl) methanes such as bis (4-hydroxy-2, 5-dimethylphenyl) -2-hydroxyphenyl methane, bis (4-hydroxy-2, 5-dimethylphenyl) -3, 4-dihydroxyphenyl methane, and bis (4-hydroxy-3, 5-dimethylphenyl) -3, 4-dihydroxyphenyl methane, or methyl-substituted products thereof; bis (3-cyclohexyl-4-hydroxyphenyl) -3-hydroxyphenyl methane, bis (3-cyclohexyl-4-hydroxyphenyl) -2-hydroxyphenyl methane, bis (3-cyclohexyl-4-hydroxyphenyl) -4-hydroxyphenyl methane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -2-hydroxyphenyl methane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -3-hydroxyphenyl methane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -4-hydroxyphenyl methane, bis (3-cyclohexyl-2-hydroxyphenyl) -3-hydroxyphenyl methane, bis (3-cyclohexyl-2-hydroxyphenyl) -2-hydroxyphenyl methane, bis (3-cyclohexyl-4-hydroxy-2-methylphenyl) -4-hydroxyphenyl methane, bis (3-cyclohexyl-2-hydroxyphenyl) -3-hydroxyphenyl methane, bis (3-cyclohexyl-4-hydroxy-2-hydroxyphenyl) methane, bis (2-cyclohexyl-4-hydroxy-2-hydroxyphenyl) methyl ether, bis (5-cyclohexyl-4-hydroxy-2-hydroxyphenyl) methyl ether, bis (3-hydroxy-2-hydroxyphenyl) methane, bis (3-hydroxy-phenyl) methane, bis (3-hydroxy-2-hydroxyphenyl) methane, bis (5-4-hydroxy-phenyl) methane, bis (5-hydroxy-4-hydroxy-phenyl) methane, bis (5-2-hydroxy-2-hydroxy-2-hydroxyphenyl) methane, bis (5-hydroxy-2-hydroxyphenyl) methane, bis (5-hydroxy-2-hydroxy-2-hydroxy-hydroxyphenyl) methane, bis (5-2-hydroxy-hydroxyphenyl) methane, bis (2-hydroxy-2-hydroxyphenyl) methane, bis (2-hydroxy-methyl-hydroxy-2-hydroxy-2-hydroxy-hydroxyphenyl methane, bis (2-hydroxy-methyl-hydroxy-methyl-2-hydroxy-2-hydroxy-methyl, bis (2-hydroxy-methyl-hydroxy-methyl-2-methyl, bis (2-methyl-2-methyl, bis (2-methyl-2-methyl, bis (2-methyl, bis (2-methyl, bis (5-cyclohexyl-4-hydroxy-3-methylphenyl) -4-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-3-methylphenyl) -3-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-3-methylphenyl) -2-hydroxyphenylmethane, bis (3-cyclohexyl-2-hydroxyphenyl) -4-hydroxyphenylmethane, bis (3-cyclohexyl-2-hydroxyphenyl) -2-hydroxyphenylmethane, bis (5-cyclohexyl-2-hydroxy-4-methylphenyl) -2-hydroxyphenylmethane, and bis (5-cyclohexyl-2-hydroxy-4-methylphenyl) -4-hydroxyphenylmethane Bis (cyclohexylhydroxyphenyl) (hydroxyphenyl) methanes such as alkanes and methyl-substituted compounds thereof; hydroxyl group-containing compounds such as phenol, p-methoxyphenol, dimethylphenol, hydroquinone, naphthol, catechol, pyrogallol monomethyl ether, pyrogallol-1, 3-dimethyl ether, and gallic acid; and pyrogallol-acetone resins and the like. These other quinonediazide group-containing compounds may be used alone or in combination of 2 or more.

Examples of the quinonediazido group-containing sulfonic acid that can be used as another quinonediazido group-containing compound include, but are not particularly limited to, naphthoquinone-1, 2-diazido-5-sulfonic acid, naphthoquinone-1, 2-diazido-4-sulfonic acid, and other diazidonaphthoquinone sulfonic acids; anthraquinone diazido sulfonic acid, etc., preferably diazido naphthoquinone sulfonic acid. The above ester compound containing a quinonediazido sulfonic acid, preferably a naphthoquinonediazide sulfonic acid, is well dissolved in a solvent which is generally used when a positive photosensitive resin composition is used in the form of a solution, and has good compatibility with the alkali-soluble resin (a).

The content of the quinonediazido group-containing compound (B) is preferably in the following range from the viewpoint of the sensitivity of the positive photosensitive resin composition. The lower limit is preferably 5 parts by mass or more, and more preferably 10 parts by mass or more, per 100 parts by mass of the alkali-soluble resin (a). The upper limit is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, and still more preferably 30 parts by mass or less, per 100 parts by mass of the alkali-soluble resin (a).

< sensitizer (C) >)

The positive photosensitive resin composition may contain a sensitizer (C). The sensitizer (C) is a compound having a phenolic hydroxyl group with a molecular weight of 1000 or less.

By combining the positive photosensitive resin composition containing the alkali-soluble resin (a), the quinonediazide group-containing compound (B), and the sensitizer (C), it is easy to simultaneously realize a good cross-sectional shape and high sensitivity of the patterned resist film.

Preferred examples of the compound that can be used as the sensitizer (C) include various phenolic hydroxyl group-containing compounds described for the quinonediazido group-containing compound (B).

That is, preferable specific examples of the sensitizer (C) include 2,3, 4-trihydroxybenzophenone, 2,4,4 ' -trihydroxybenzophenone, 2,4, 6-trihydroxybenzophenone, 2,3, 4-trihydroxy-2 ' -methylbenzophenone, 2,3,4,4 ' -tetrahydroxybenzophenone, polyhydroxybenzophenones such as 2,2 ', 4,4 ' -tetrahydroxybenzophenone, 2,3 ', 4,4 ', 6-pentahydroxybenzophenone, 2 ', 3,4,4 ' -pentahydroxybenzophenone, 2 ', 3,4, 5-pentahydroxybenzophenone, 2,3 ', 4,4 ', 5 ', 6-hexahydroxybenzophenone and 2,3,3 ', 4,4 ', 5 ' -hexahydroxybenzophenone; bis [ (poly) hydroxyphenyl ] ethylidene } bisphenols such as bis (2, 4-dihydroxyphenyl) methane, bis (2,3, 4-trihydroxyphenyl) methane, 2- (4-hydroxyphenyl) -2- (4 '-hydroxyphenyl) propane, 2- (2, 4-dihydroxyphenyl) -2- (2', 4 '-dihydroxyphenyl) propane, 2- (2,3, 4-trihydroxyphenyl) -2- (2', 3 ', 4' -trihydroxyphenyl) propane, 4 '- {1- [4- [ 2- (4-hydroxyphenyl) -2-propyl ] phenyl ] ethylidene } bisphenol, and 3, 3' -dimethyl- {1- [4- [ 2- (3-methyl-4-hydroxyphenyl) -2-propyl ] phenyl ] ethylidene } bisphenol Alkyl alkanes; tris (4-hydroxyphenyl) methane, bis (4-hydroxy-3, 5-dimethylphenyl) -4-hydroxyphenyl methane, bis (4-hydroxy-2, 5-dimethylphenyl) -4-hydroxyphenyl methane, bis (4-hydroxy-3, 5-dimethylphenyl) -2-hydroxyphenyl methane, tris (hydroxyphenyl) methanes such as bis (4-hydroxy-2, 5-dimethylphenyl) -2-hydroxyphenyl methane, bis (4-hydroxy-2, 5-dimethylphenyl) -3, 4-dihydroxyphenyl methane, and bis (4-hydroxy-3, 5-dimethylphenyl) -3, 4-dihydroxyphenyl methane, or methyl-substituted products thereof; bis (3-cyclohexyl-4-hydroxyphenyl) -3-hydroxyphenyl methane, bis (3-cyclohexyl-4-hydroxyphenyl) -2-hydroxyphenyl methane, bis (3-cyclohexyl-4-hydroxyphenyl) -4-hydroxyphenyl methane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -2-hydroxyphenyl methane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -3-hydroxyphenyl methane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -4-hydroxyphenyl methane, bis (3-cyclohexyl-2-hydroxyphenyl) -3-hydroxyphenyl methane, bis (3-cyclohexyl-2-hydroxyphenyl) -2-hydroxyphenyl methane, bis (3-cyclohexyl-4-hydroxy-2-methylphenyl) -4-hydroxyphenyl methane, bis (3-cyclohexyl-2-hydroxyphenyl) -3-hydroxyphenyl methane, bis (3-cyclohexyl-4-hydroxy-2-hydroxyphenyl) methane, bis (2-cyclohexyl-4-hydroxy-2-hydroxyphenyl) methyl ether, bis (5-cyclohexyl-4-hydroxy-2-hydroxyphenyl) methyl ether, bis (3-hydroxy-2-hydroxyphenyl) methane, bis (3-hydroxy-phenyl) methane, bis (3-hydroxy-2-hydroxyphenyl) methane, bis (5-4-hydroxy-phenyl) methane, bis (5-hydroxy-4-hydroxy-phenyl) methane, bis (5-2-hydroxy-2-hydroxy-2-hydroxyphenyl) methane, bis (5-hydroxy-2-hydroxyphenyl) methane, bis (5-hydroxy-2-hydroxy-2-hydroxy-hydroxyphenyl) methane, bis (5-2-hydroxy-hydroxyphenyl) methane, bis (2-hydroxy-2-hydroxyphenyl) methane, bis (2-hydroxy-methyl-hydroxy-2-hydroxy-2-hydroxy-hydroxyphenyl methane, bis (2-hydroxy-methyl-hydroxy-methyl-2-hydroxy-2-hydroxy-methyl, bis (2-hydroxy-methyl-hydroxy-methyl-2-methyl, bis (2-methyl-2-methyl, bis (2-methyl-2-methyl, bis (2-methyl, bis (2-methyl, bis (5-cyclohexyl-4-hydroxy-3-methylphenyl) -4-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-3-methylphenyl) -3-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-3-methylphenyl) -2-hydroxyphenylmethane, bis (3-cyclohexyl-2-hydroxyphenyl) -4-hydroxyphenylmethane, bis (3-cyclohexyl-2-hydroxyphenyl) -2-hydroxyphenylmethane, bis (5-cyclohexyl-2-hydroxy-4-methylphenyl) -2-hydroxyphenylmethane, and bis (5-cyclohexyl-2-hydroxy-4-methylphenyl) -4-hydroxyphenylmethane Bis (cyclohexylhydroxyphenyl) (hydroxyphenyl) methanes such as alkanes and methyl-substituted compounds thereof; hydroxyl group-containing compounds such as phenol, p-methoxyphenol, dimethylphenol, hydroquinone, naphthol, catechol, pyrogallol monomethyl ether, pyrogallol-1, 3-dimethyl ether, and gallic acid.

The content of the sensitizer (C) is not particularly limited within a range not interfering with the object of the present invention. The content of the sensitizer (C) is preferably 10 parts by mass or more and 30 parts by mass or less, more preferably 13 parts by mass or more and 27 parts by mass or less, and further preferably 15 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the alkali-soluble resin (a), from the viewpoint of easily obtaining desired effects regarding the sectional shape and sensitivity of the resist film.

< other ingredients >

The positive photosensitive resin composition may contain various additives such as a colorant, an adhesion improver, a surfactant, and a plasticizer within a range not to impair the object of the present invention.

Adhesion improver

The adhesion improver may be appropriately selected from materials capable of improving adhesion between the patterned resist film and the surface on which the resist film is formed. For example, a hydroxyalkyl nitrogen-containing heterocyclic compound such as 2-hydroxyethylpyridine can be used as the adhesion improver.

Surfactants

The positive photosensitive resin composition may contain a surfactant in order to improve coatability, defoaming property, leveling property, and the like. As the surfactant, there can be used, for example, BM-1000, BM-1100 (manufactured by BM CHEMIE corporation, manufactured by BM ケミー Co., Ltd.), MEGAFACE (manufactured by メガファック Co., Ltd.), F142, 142D, MEGAFACE F172, MEGAFACE F173, MEGAFACE F183 (manufactured by Japan ink chemical industries, Ltd.), Fluorad (manufactured by フロラード Co., Ltd.), Fluorad FC-170C, Fluorad FC-430, Fluorad FC-431 (manufactured by Youklon 3M Co., Ltd.), Surflon (manufactured by サーフロン Co., Ltd.), S-112, commercially available silicon or fluorine surfactants such as Surflon S-113, Surflon S-131, Surflon S-141, Surflon S-145 (manufactured by Asahi glass Co., Ltd.), SH-28PA, SH-190, SH-193, SZ-6032, SF-8428 (manufactured by Toray Silicone Co., Ltd.), BYK-310, BYK-330 (manufactured by BYK-Chemie Japan Co., Ltd.).

The content of the surfactant is preferably 0.05 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the alkali-soluble resin (a).

< solvent >

In the positive photosensitive resin composition, the respective components are preferably dissolved in an appropriate solvent and used in the form of a solution. Examples of such solvents include: ethylene glycol alkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate; ketones such as acetone, methyl ethyl ketone, cyclohexanone, and methyl amyl ketone; aromatic hydrocarbons such as toluene and xylene; cyclic ethers such as dioxane; and esters such as methyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl oxoacetate, methyl 2-hydroxy-3-methylbutyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl formate, ethyl acetate, butyl acetate, methyl acetoacetate, and ethyl acetoacetate; and so on. These solvents may be used alone, or 2 or more kinds may be mixed and used.

The content of the solvent in the positive photosensitive resin composition can be appropriately adjusted in consideration of the viscosity and coatability of the positive photosensitive resin composition. Specifically, the solvent is used so that the solid content concentration of the positive photosensitive resin composition is preferably 5 mass% or more and 50 mass% or less, more preferably 10 mass% or more and 30 mass% or less.

< method for producing positive photosensitive resin composition >

The positive photosensitive resin composition can be prepared by: the above components are blended at a predetermined ratio, and then mixed and stirred by a usual method. Further, filtration may be performed using a mesh, a membrane filter, or the like as necessary.

Method for Forming patterned resist film

The patterned resist film may be formed by a method including the following steps:

a step of coating the positive photosensitive resin composition on a substrate to form a coating film;

a step of exposing the coating film in a position-selective manner; and

and developing the exposed coating film with a developer.

The application of the positive photosensitive resin composition to the substrate is performed using a spin coater, a roll coater, a spray coater, a slit coater, or the like. The coating device is not limited to these. Generally, the coating film is dried by a method such as heating. The drying method may be, for example, any of the following methods: (1) a method of drying the coating film at a temperature of 80 ℃ to 120 ℃ for 60 seconds to 120 seconds by a hot plate; (2) a method of leaving the coating film at room temperature for several hours to several days; (3) a method of removing the solvent by placing the coating film in a hot air heater or an infrared heater for several tens of minutes to several hours. The thickness of the coating film after drying is not particularly limited as necessary, but is preferably about 1.0 μm to 5.0 μm.

The kind of the substrate is not particularly limited. The positive photosensitive resin composition is excellent in sensitivity and therefore can be easily applied to a large-area substrate. Therefore, as a suitable substrate, a substrate for a display such as a liquid crystal display or an organic EL display can be mentioned. Examples of the substrate for these displays include a glass plate provided with a wiring such as a transparent conductive circuit, and if necessary, with a black matrix, a color filter, a polarizing plate, and the like.

Next, the coating film is exposed through a mask having a predetermined pattern corresponding to the pattern shape. The exposure is performed by irradiation with active energy rays such as ultraviolet rays and excimer laser light. Examples of the light source of the active energy ray include a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, and an excimer laser generator. The amount of energy radiation to be irradiated varies depending on the composition of the positive photosensitive resin composition, and may be, for example, 30 to 2000mJ/cm²Left and right.

Next, the exposed coating film is developed with a developer to form a patterned resist film. Examples of the developer include an aqueous solution of an organic base such as a tetramethylammonium hydroxide (TMAH) aqueous solution, and an aqueous solution of an inorganic base such as sodium hydroxide, potassium hydroxide, sodium metasilicate, or sodium phosphate.

After the development, the surface of the patterned resist film may be rinsed with water, an organic solvent that does not excessively dissolve the resist film, or the like. In addition, the patterned resist film may be baked as necessary.

Thereby, a patterned resist film formed of the positive photosensitive resin composition is formed. The resist film can be used as a protective film or an insulating film, and can also be used as a mask pattern for etching or a mold for plating.

Examples

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[ examples 1 to 4 and comparative examples 1 to 3 ]

In examples and comparative examples, as the alkali-soluble resin (a) ((a) component), cresol Novolac resin (weight average molecular weight 6000) having a mass of m-cresol/p-cresol of 36/64 was used.

In examples and comparative examples, the following B-I, B-II, B-III and B-IV were used as the quinonediazido group-containing compound (B) (component (B)). B-I belongs to the compounds represented by the aforementioned formula (B1). B-II belongs to the aforementioned compound represented by the formula (B2). B to III belong to the compounds represented by the aforementioned formula (B3). B to IV belong to the compounds represented by the aforementioned formula (B4). In addition, the average introduction rate of the quinonediazide group (which means how many moles of the substituent OD are substituted by the quinonediazide group on average) of each compound was 2.4 moles of B-I, 2.0 moles of B-II, 2.1 moles of B-III and 1.7 moles of B-IV.

100 parts by mass of an alkali-soluble resin (A), a quinonediazide group-containing compound (B) of the kind and amount shown in Table 1, 2-pyridylethanol as an adhesion enhancer in the amount shown in Table 1, and a surfactant BYK-310 (BYK-Chemie) in the amount shown in Table 1 were dissolved in propylene glycol monomethyl ether acetate so that the solid concentration became 24 mass%, to obtain positive photosensitive resin compositions of examples and comparative examples. Using the obtained positive photosensitive resin composition, the resolution, the cross-sectional shape, the sensitivity, and the depth of focus were evaluated in the following manner. The results of these evaluations are set forth in Table 1.

< resolution >

A sample of the positive photosensitive resin composition was coated on an 8-inch Si wafer using a spin coater to form a coating film. The coating film was dried at 110 ℃ for 90 seconds with a Direct Hot Plate (DHP) to form a resist coating film having a thickness of 1.5 μm.

Next, exposure was performed using FPA-5510iv (product name, manufactured by Canon corporation, NA ═ 0.12) through a mask on which a mask pattern for realizing a hole (hole) pattern having a diameter of 1.5 μm was drawn or a mask on which a mask pattern for realizing a line-to-space (LS) pattern having a diameter of 1.3 μm was drawn, respectively.

The exposed resist film was brought into contact with a 2.38 mass% aqueous tetramethylammonium hydroxide (TMAH) solution at 23 ℃ for 65 seconds, and developed. The resist pattern obtained was washed with water for 30 seconds and spin-dried.

The obtained hole pattern and LS pattern were observed by SEM photograph, and the resolution was evaluated according to the following criteria.

O: the holes and LS having a predetermined size can be formed without generating development residue.

X: development residue is generated, or at least one of a hole having a predetermined size and LS is not formed.

< cross-sectional shape >

The cross-sectional shape of the 1.3 μm LS pattern obtained in the above-described resolution evaluation was observed by SEM photograph, and the cross-sectional shape was evaluated according to the following criteria.

Very good: rectangular shape

Good: a T-shaped top having a larger width near the surface of the resist pattern opposite to the substrate than near the center of the resist pattern in the height direction

X: without a head (Japanese: head き (section shape is nearly triangular pattern shape) and し)

< sensitivity >

By the above-described resolution evaluation, the exposure amount (optimum exposure amount) at which the LS pattern size became 1.30 μm was confirmed, and the sensitivity was evaluated according to the following criteria.

O: the exposure amount for LS pattern size of 1.3 μm is less than 40mJ/cm²。

X: the exposure dose for LS pattern size to be 1.3 μm was 40mJ/cm²The above.

< depth width of focus >

The LS pattern was formed by moving the focus up and down in the range of-20 μm to +20 μm for each 1 μm by the optimum exposure amount of each positive photosensitive resin composition identified by the above sensitivity evaluation, and the LS pattern was observed by SEM photograph.

From the observation results of the SEM photographs, a range of focus was obtained in which the cross-sectional shape of the LS pattern was excellent or good in the cross-sectional shape evaluation and the LS pattern size was in the range of 1.3 ± 0.13 μm, and the depth of focus (DOF) was evaluated.

[ Table 1]

1, 1: since it cannot be calculated.

As is clear from table 1, the positive photosensitive resin compositions of the examples, which combined B-I belonging to the compound represented by formula (B1) and B-II belonging to the compound represented by formula (B2), had good resolution and large depth of focus.

On the other hand, as is clear from comparative example 1, even when the positive photosensitive resin composition comprises B-I and B-II in combination, in the case where the ratio M1/M2 of the mass M1 of B-I to the mass M2 of B-II is less than 1.2, excellent resolution and excellent depth of focus characteristic cannot be simultaneously achieved.

In addition, as is clear from comparative examples 2 and 3, when B-I belonging to the compound represented by formula (B1) or B-II belonging to the compound represented by formula (B2) is absent from the positive photosensitive resin composition, the depth width of focus becomes narrow.

Claims

1. A positive photosensitive resin composition comprising an alkali-soluble resin (A) and a quinonediazido group-containing compound (B),

in the formula (B1), D's are each independently a hydrogen atom or a 1, 2-diazidonaphthoquinone-5-sulfonyl group, and at least one of 4D's is a 1, 2-diazidonaphthoquinone-5-sulfonyl group;

in the formula (B2), R^b1Each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R^b2Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms, each D independently represents a hydrogen atom, or a 1, 2-diazidonaphthoquinone-5-sulfonyl group, and at least one of the 4D is a 1, 2-diazidonaphthoquinone-5-sulfonyl group;

when the mass of the compound represented by the formula (B1) is M1 and the mass of the compound represented by the formula (B2) is M2, M1/M2 is 1.2 or more and 5.0 or less.

2. The positive photosensitive resin composition according to claim 1, wherein the quinonediazide group-containing compound (B) further comprises a compound represented by the following formula (B3) and/or a compound represented by the following formula (B4),

in the formula (B3), R^b3Each independently an alkyl group having 1 to 5 carbon atoms, each D independently is a hydrogen atom or a 1, 2-diazidonaphthoquinone-5-sulfonyl group, at least one of 2+ m D is a 1, 2-diazidonaphthoquinone-5-sulfonyl group, and each of l and m is 1 or 2;

in the formula (B4), D's are each independently a hydrogen atom or a 1, 2-diazidonaphthoquinone-5-sulfonyl group, and at least one of 3D's is a 1, 2-diazidonaphthoquinone-5-sulfonyl group.

3. The positive photosensitive resin composition according to claim 2, wherein the quinonediazide group-containing compound (B) comprises the compound represented by the formula (B3) and the compound represented by the formula (B4).

4. The positive photosensitive resin composition according to any one of claims 1 to 3, wherein a ratio of a sum of the M1 and the M2 to a mass of the quinonediazide group-containing compound (B) is 20 mass% or more and 50 mass% or less.

5. A method of forming a patterned resist film, comprising:

a step of forming a coating film by coating the positive photosensitive resin composition according to any one of claims 1 to 4 on a substrate;

exposing the coating film in a position-selective manner; and

and developing the exposed coating film with a developer.

6. A patterned resist film comprising the positive photosensitive resin composition according to any one of claims 1 to 4.