TW201915607A - Chemically-amplified type positive photo sensitive resin composition, resist pattern and method of forming thereof, and electronic device - Google Patents

Abstract

A chemically-amplified type positive photo sensitive resin composition, resist pattern and method of forming thereof, and electronic device are provided. The chemically-amplified type positive photo sensitive resin composition includes a polyhydroxystyrene resin with acid-dissociated protecting group (A), a monounsaturated nitrile compound (B), a photoacid generator (C), and a solvent (D). The chemically-amplified type positive photo sensitive resin composition can improve the problem of poor adhesion and taper angle.

Description

Chemically amplified positive photosensitive resin composition, photoresist pattern, formation method thereof, and electronic device

The present invention relates to a chemically amplified positive photosensitive resin composition, a photoresist pattern, a method for forming the same, and an electronic device, and more particularly to a chemically amplified positive photosensitive resin composition capable of improving adhesion and poor taper angles. Type photosensitive resin composition, a photoresist pattern prepared from the chemically amplified positive photosensitive resin composition, a method for forming the same, and an electronic device including the photoresist pattern.

So far, in the field of manufacturing liquid crystal display elements using glass substrates, photoresist materials suitable for g, h, and i-line exposure, which are inexpensive, have good sensitivity and resolution, and can form photoresist patterns with excellent shapes, are mostly used. A phenolic resin is used as an alkali-soluble resin, and a positive-type photoresist composition containing a quinonediazide-based compound as a photosensitive component is used (Patent Documents 1 to 4).

Now, as the next-generation LCD, integrated circuit parts and display parts such as drivers, digital analog converters (DACs), image processing devices, video controllers, and RAMs are formed on a glass substrate. "System LCD" technology development of high-performance LCD is very popular.

In this specification, for convenience, a substrate on which a integrated circuit and a liquid crystal display portion are formed on one substrate is referred to as a system LCD.

In the system LCD, the material that can replace amorphous silicon and can be formed at a low temperature process below 600 ° C is low temperature polysilicon. Compared with amorphous silicon, low temperature polysilicon has lower resistance and higher mobility. Therefore, the industry expects to develop a photoresist composition suitable for manufacturing a system LCD using low-temperature polysilicon. There are various reports of photoresist materials used in current system LCDs (Patent Documents 5 to 12).

When manufacturing a TFT made of low-temperature polysilicon, a polysilicon film is formed on a glass substrate in a low-temperature process, and then P (phosphorus) or B (boron) is implanted on the low-temperature polysilicon film. Medium, it is necessary to implant a very high concentration of impurities.

This implantation step is performed under a condition of high vacuum in a state where a photoresist pattern is formed on a low-temperature polysilicon glass substrate. However, during this process, the shape of the photoresist pattern on the substrate is changed by the heating effect during the implantation of impurities, and some components in the photoresist pattern are vaporized during heating, which causes the vacuum in the processing chamber to decrease. The problem occurred.

The solution to this problem is to perform a heat treatment step called "post-baking" before the injection step, which is very effective. The "post-baking" here is performed under a temperature condition close to the heating temperature at the time of injection (for example, a high temperature of 200 ° C or higher), so the photoresist material must have high heat resistance that does not change the shape of the pattern during this heat treatment. characteristic.

Therefore, in order to realize the manufacture of the system LCD, it is necessary to make the photoresist composition used therein have good heat resistance.

In addition, in the system LCD, for example, the pattern size of the display portion is 2 to 10 μm, and the integrated circuit portion is formed with a fine size of 0.5 to 2.0 μm. Therefore, in addition to the photoresist composition used to manufacture system LCDs, the ability to form both fine patterns and rough patterns with good shapes (linearity) is required. It also requires a higher resolution than the photoresist materials used to manufacture LCDs in the past. , With a good fine pattern, the depth of focus (DOF) characteristics.

However, in the field of manufacturing liquid crystal display elements, the adhesion and taper angle of the photoresist pattern formed by the positive photoresist composition used in the conventional system LCD are not good, and it is easy to cause a serious decline in productivity, so improving the density The problem of poor adhesion and taper angle is expected by the industry.

[Patent Literature] Patent Literature 1: Japanese Patent Laid-Open No. 2000-131835 Patent Literature 2: Japanese Patent Laid-Open No. 2001-075272 Patent Literature 3: Japanese Patent Laid-Open No. 2000-181055 Patent Literature 4: Japanese Patent Laid-Open No. 2000-112120 Patent Document 5: Japanese Patent Application Laid-Open No. 2004-233846 Patent Document 6: Japanese Patent Application Laid-Open No. 2004-191394 Patent Literature 7: Japanese Patent Application Laid-Open No. 2004-145207 Patent Literature 8: Japanese Patent Application Laid-Open No. 2004-144905 Patent Document 9: Japanese Patent Application Laid-Open No. 2004-077999 Patent Document 10: Japanese Patent Application Laid-Open No. 2004-045707 Patent Literature 11: Japanese Patent Application Laid-Open No. 2004-045618 Patent Literature 12: Japanese Patent Application Laid-Open No. 2003-233174

In view of this, the present invention provides a chemically amplified positive photosensitive resin composition. The use of the chemically amplified positive photosensitive resin composition can improve the problems of poor adhesion and poor taper angles.

The present invention provides a chemically amplified positive photosensitive resin composition, comprising: a polyhydroxystyrene resin (A) containing an acid dissociative protective group, a monounsaturated nitrile compound (B), a photoacid generator (C), And solvent (D).

In one embodiment of the present invention, the number of carbon atoms of the monounsaturated nitrile compound (B) is 6-30.

In one embodiment of the present invention, the monounsaturated nitrile compound (B) is selected from the group consisting of decenenitrile, decenedinitrile, undecenitrile, dodecenitrile, and ten Trienecenonitrile, Tetradecenenitrile, Hexadecenenitrile, Hexadecenenitrile, Octadecenenitrile, Octadecenenitrile Dodecenenitrile (Eruconitrile) compounds.

In one embodiment of the present invention, the chemically amplified positive photosensitive resin composition further includes a basic compound (E).

In one embodiment of the present invention, the basic compound (E) includes a compound represented by formula (E-1): N (A) _z (B) _3-z formula (E-1) formula (E-1) ), A each independently represents an alkyl group having 4 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and a phenyl group or aralkyl group having 6 to 20 carbon atoms. B each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. z represents an integer from 1 to 3.

In one embodiment of the present invention, the chemically amplified positive photosensitive resin composition further includes a heterocyclic compound (F) having a nitrogen atom, and is selected from the group consisting of the following formulae (F-1) to (F-4). The group of compounds shown: Formula (F-1) Formula (F-2) Formula (F-3) Formula (F-4) In formulas (F-1) to (F-4), G ₁ and G ₂ each independently represent a hydrogen atom, a fluorenyl group, or an alkyl group; H ₁ to H ₉ each independently represent hydrogen Atom, hydroxy, carboxylic, sulfonic, alkyl, amine, halogen, or mercapto. v, w, q, and s each independently represent an integer from 0 to 3; p and r each independently represent an integer from 0 to 2; and t and u each independently represent an integer from 0 to 4.

In one embodiment of the present invention, the total amount of the polyhydroxystyrene resin (A) containing the acid dissociable protective group is 100 parts by weight, and the content of the monounsaturated nitrile compound (B) is 0.03 to 1.0 parts by weight. The content of the photoacid generator (C) is 0.3 to 3 parts by weight, and the content of the solvent (D) is 200 to 1200 parts by weight.

In one embodiment of the present invention, the total amount of the polyhydroxystyrene resin (A) based on the acid-dissociable protective group is 100 parts by weight, and the content of the basic compound (E) is 0.03 to 1.0 parts by weight. .

In one embodiment of the present invention, the total amount of the polyhydroxystyrene resin (A) based on the acid dissociable protective group is 100 parts by weight, and the content of the heterocyclic compound (F) having a nitrogen atom is 0.01 part by weight. To 0.5 parts by weight.

The present invention also provides a method for forming a photoresist pattern, comprising the step of applying the above-mentioned chemically amplified positive photosensitive resin composition on a substrate.

The present invention further provides a photoresist pattern formed by the method for forming a photoresist pattern described above.

The present invention also provides an electronic device including the above-mentioned photoresist pattern.

Based on the foregoing, the chemically amplified positive-type photosensitive resin composition of the present invention can improve adhesion by containing a polyhydroxystyrene resin (A) containing an acid dissociative protective group and a monounsaturated nitrile compound (B). And the problem of poor taper angle.

In order to make the above features and advantages of the present invention more comprehensible, embodiments are described below in detail, as follows.

< Chemically amplified positive photosensitive resin composition > The present invention provides a chemically amplified positive photosensitive resin composition, which includes a polyhydroxystyrene resin (A) containing an acid dissociative protective group, and a monounsaturated nitrile compound. (B), a photoacid generator (C), and a solvent (D). The chemically amplified positive photosensitive resin composition of the present invention may further include a basic compound (E) or a heterocyclic compound (F) having a nitrogen atom.

Hereinafter, each component of the chemically amplified positive photosensitive resin composition used in the present invention will be described in detail.

In this description, acrylic acid and / or methacrylic acid are represented by (meth) acrylic acid, and acrylate and / or methacrylic acid ester are represented by (meth) acrylic acid ester; similarly, (meth) Acrylofluorenyl refers to acrylfluorenyl and / or methacrylfluorenyl. Polyhydroxystyrene resin containing acid-dissociable protective group ( A )

In the polyhydroxystyrene resin (A) containing an acid-dissociable protective group, the so-called polyhydroxystyrene resin (before protection) includes a polymer made of hydroxystyrene (hydroxystyrene alone polymer) and its derivative. . Such polyhydroxystyrene is, for example, a single polymer of vinylphenol, a copolymer of vinylphenol, a comonomer that can be copolymerized therewith, and the like. Here, the comonomers are, for example, (meth) acrylic acid derivatives, (meth) acrylonitrile, styrene, α-methylstyrene, p-methylstyrene, o-methylstyrene, p- Styrene derivatives such as methoxystyrene and p-chlorostyrene. Among the polyhydroxystyrenes, a hydroxystyrene alone polymer and a hydroxystyrene-styrene copolymer are preferred.

In the polyhydroxystyrene resin (A) containing an acid-dissociable protective group, at least a part of the hydrogen atoms of the all-phenolic hydroxyl group are substituted with the acid-dissociable protective group, which shows poor alkali solubility or alkali insolubility. The acid-dissociable protective group may be dissociated from the phenolic hydroxyl group and become alkali-soluble.

The polyhydroxystyrene resin (A) containing an acid-dissociable protective group can be obtained by using a polyhydroxystyrene resin (a polyhydroxystyrene resin before protection) without an acid-dissociative protective group and an acid-dissociative protective group. The compound is obtained by reaction.

The term “hydroxystyrene” also includes derivatives thereof. The specific hydroxystyrene repeating unit is represented by the following formula (A-1): Formula (A-1) In formula (A-1), R ⁰ is a hydrogen atom or a lower alkyl group; k represents an integer of 1 to 3.

R ⁰ is a hydrogen atom or a lower alkyl group (for example, a linear or branched alkyl group having 1 to 5 carbon atoms, preferably a methyl group), and a hydrogen atom is preferred. The position of the hydroxyl group can be any of the ortho, meta, and para positions. From the viewpoint of easy availability and low price, the para position is preferred.

In the hydroxystyrene-styrene copolymer, styrene includes styrene in which the benzene ring is not substituted with an alkyl group, and compounds having a benzene ring substituted with a lower alkyl group having 1 to 5 carbon atoms. The number of the lower alkyl group of the substituent is 1-3.

The acid-dissociable protective group in the polyhydroxystyrene resin (A) containing an acid-dissociable protective group may be any one that can be dissociated by an acid generated by a photoacid generator (C) described later, for example: 1-ethyl Oxymethyl, 1-ethoxyethyl, 1-propoxymethyl, 1-propoxyethyl, 1-n-butoxymethyl, 1-isobutoxymethyl, 1- Alkoxyalkyl groups such as tributoxymethyl; alkoxycarbonylalkyl groups such as third butoxycarbonyl, third butoxycarbonmethyl, and third butoxycarbonylethyl; tetrahydrofuranyl; Hydropyranyl; linear or branched acetal; cyclic acetal; trimethylsilyl, triethylsilyl, triphenylsilyl, etc. Wait.

The weight-average molecular weight (Mw) of the polyhydroxystyrene resin before protection is preferably in the range of 1,000 to 200,000, more preferably 2,000 to 50,000, and most preferably 3,000 to 30,000.

When the chemically amplified positive photosensitive resin composition does not include a polyhydroxystyrene resin (A) containing an acid dissociative protective group, the taper angle of the photoresist pattern formed by the chemically amplified positive photosensitive resin composition Not good. Monounsaturated nitrile compound ( B )

The type of the monounsaturated nitrile compound (B) used in this case is not limited as long as it improves the adhesion and taper angle of the photoresist pattern formed by the chemically amplified positive photosensitive resin composition. : Acrylonitrile, Butenitrile, Butenedinitrile, Pentenitrile, Pentenitrile, Hexenenitrile, Hexenedinitrile, Heptenitrile, Heptene dinitrile, Octenonitrile, Octene dinitrile, Nonenenitrile, Nonene dinitrile, Decenenitrile, Decene dinitrile, Undecenitrile, Undecenitrile, Dodecenitrile, Tridecenonitrile, Tetradecenenitrile, Hexadecenenitrile, Hexadecenenitrile, Octacarbonitrile decenenitrile), octadeceneditrile, and eruconitrile (Eruconitrile).

The monounsaturated nitrile compound (B) can further be exemplified by 2-butenenitrile, 3-butenenitrile, 2-butenedinitrile, 2-pentenenitrile, 3-pentenenitrile, 4-pentenenitrile, 5-hexenenitrile, -hexenedinitrile, 6-heptenenitrile, 3-heptenenitrile, 6-octenenitrile, 3-octenedinitrile, 4-octenedinitrile, 2-nonenenitrile , 6-nonenenitrile, 9-decenenitrile, 10-undecenenitrile, 11-dodecenenitrile, 12-dodecenenitrile, 2-tridecenenitrile, 12-tridecene Acenenitrile, 7-tetradecenenitrile, 13-tetradecenenitrile, 3-hexadecenenitrile, 4-hexadecenenitrile, 15-hexadecenenitrile, 6-hexadecenediene Nitriles, 9-octadecenenitrile, 9-octadecadienitrile, 13-docosaenenitrile.

The carbon number of the monounsaturated nitrile compound (B) is preferably 6 to 30, and more preferably 10 to 22.

Preferred examples of the aforementioned monounsaturated nitrile compound (B) include 9-decenenitrile, 10-undecenenitrile, 11-dodecenenitrile, 12-dodecenenitrile, and 2-tridecene Nitrile, 12-tridecenenitrile, 7-tetradecenenitrile, 13-tetradecenenitrile, 3-hexadecenenitrile, 4-hexadecenenitrile, 15-hexadecenenitrile, 6-hexadecenedinitrile, 9-octadecenenitrile, 9-octadecenenitrile, 13-docosaenenitrile.

When the mono-unsaturated nitrile compound (B) is not contained in the chemically amplified positive photosensitive resin composition, the adhesion and taper angle of the photoresist pattern formed by the chemically amplified positive photosensitive resin composition are not good.

When the chemically amplified positive photosensitive resin composition contains a monounsaturated nitrile compound (B) and the number of carbon atoms of the monounsaturated nitrile compound (B) is 6 to 30, the chemically amplified positive photosensitive resin The adhesion and taper angle of the photoresist pattern formed by the resin composition are preferred.

Based on a total amount of the polyhydroxystyrene resin (A) containing the acid dissociable protective group, the content of the monounsaturated nitrile compound (B) is 0.03 to 1.0 parts by weight, preferably It is 0.04 parts by weight to 0.9 parts by weight, and more preferably 0.05 parts by weight to 0.8 parts by weight. Photoacid generator ( C )

The photoacid generator (C) is a compound that generates an acid by irradiation with actinic rays or radiation, and is not particularly limited as long as it is a compound that can generate an acid directly or indirectly by light. As the photoacid generator (C), the acid generators of the first to fifth aspects described below are preferred. Hereinafter, preferred ones of the photoacid generators (C) suitably used in the photosensitive resin composition will be described in the first to fifth aspects.

Examples of the first form of the photoacid generator (C) include compounds represented by the following formula (C-1): Formula (C-1) In formula (C-1), X ¹ represents a sulfur atom or an iodine atom having a valence of g, and g is 1 or 2. h represents the number of repeating units of the structure in parentheses. W ¹ is an organic group bonded to X ¹ , and represents an aryl group having 6 to 30 carbon atoms, a heterocyclic group having 4 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms, and a carbon atom. An alkenyl group of 2 to 30, or an alkynyl group of 2 to 30 carbon atoms, W ¹ may pass through an alkyl group, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group , Fluorenyloxy, arylthio, alkylthio, aryl, heterocyclic, aryloxy, alkanesulfinyl, arylenesulfonyl, alkanesulfonyl, arylsulfonyl, alkyleneoxy, At least one selected from the group consisting of amine, cyano, nitro, and halogen. The number of W ¹ is g + h (g-1) +1, and W ¹ may be the same as or different from each other. In addition, two or more W ¹ may be directly bonded to each other or via -O-, -S-, -SO-, -SO _2- , -NH-, -NW ^2- , -CO-, -COO-, -CONH-, an alkylene group having 1 to 3 carbon atoms, or a phenylene group is bonded to form a ring structure including X ¹ . W ² is an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms.

X ² is a structure represented by the following formula (C-1a): Formula (C-1a) In formula (C-1a), X ⁴ represents an alkylene group having 1 to 8 carbon atoms, an arylene group having 6 to 20 carbon atoms, or an alkylene group having 8 to 20 carbon atoms. Divalent hetero group, X ⁴ can pass through an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, a hydroxyl group, a cyano group, and a nitro group And at least one selected from the group consisting of halogens. X ⁵ represents -O-, -S-, -SO-, -SO _2- , -NH-, -NW ^2- , -CO-, -COO-, -CONH-, carbon atoms having a number of 1 to 3 Alkyl, or phenylene. h represents the number of repeating units of the structure in parentheses. The h + 1 X ⁴ and h X ⁵ may be the same or different, respectively. W ² is the same as defined above.

(X ^{3) -} the onium ion (counter ion), may be exemplified by the following formula (C-1b) of FIG fluoroborate fluoroalkyl phosphate anions or the following formula (C-1c) shown in the anion _{^{: [(W 3) j PF}} 6-j] - in formula (C-1b) of formula (C-1b), W ³ represents more than 80% of the hydrogen atoms of the alkyl group substituted with a fluorine atom. j represents the number, and is an integer from 1 to 5. The j W ^3s may be the same or different. In formula (C-1c), in formula (C-1c), W ⁴ to W ⁷ each independently represent a fluorine atom or a phenyl group, and a part or all of the hydrogen atoms in the phenyl group may be formed through a fluorine atom and a trifluoromethyl group. At least one substitution selected from the group.

Examples of the onium ion in the compound represented by the formula (C-1) include triphenylphosphonium, tri-p-tolylphosphonium, 4- (phenylthio) phenyldiphenylphosphonium, and bis [4- ( Diphenylfluorenyl) phenyl] sulfide, bis [4- {bis [4- (2-hydroxyethoxy) phenyl] fluorenyl} phenyl] sulfide, bis {4- [bis (4- Fluorophenyl) fluorenyl] phenyl} sulfide, 4- (4-benzylidene-2-chlorophenylthio) phenylbis (4-fluorophenyl) fluorene, 7-isopropyl-9- Oxy-10-thia-9,10-dihydroanthracene-2-yldi-p-tolylfluorene, 7-isopropyl-9-oxy-10-thia-9,10-dihydroanthracene- 2-yldiphenylfluorene, 2-[(diphenyl) fluorenyl] thiaxanthone, 4- [4- (4-tert-butylbenzylfluorenyl) phenylthio] phenyldi-p- Tolylfluorene, 4- (4-benzylidenephenylthio) phenyldiphenylfluorene, diphenylphenethylfluorene, 4-hydroxyphenylmethylbenzylfluorene, 2-naphthylmethyl (1-ethoxycarbonyl) ethylfluorene, 4-hydroxyphenylmethylphenethylfluorene, phenyl [4- (4-biphenylthio) phenyl] 4-biphenylfluorene, phenyl [ 4- (4-biphenylthio) phenyl] 3-biphenylfluorene, [4- (4-ethylfluorenylphenylthio) phenyl] diphenylfluorene, stearylmethylphenethylfluorenylfluorene, Diphenylfluorene, di-p-tolylfluorene, bis (4-dodecylphenyl) fluorene, (4-methoxyphenyl) fluorene, (4-octyloxyphenyl) phenylfluorene, bis (4-dodecyl) phenylfluorene, 4- (2-hydroxytetradecyloxy) phenyl Phenylhydrazone, 4-isopropylphenyl (p-tolyl) fluorene, 4-isobutylphenyl (p-tolyl) fluorene, and the like.

Among the onium ions in the compound represented by the formula (C-1), preferred onium ions include a sulfonium ion represented by the following formula (C-1d): In formula (C-1d), in formula (C-1d), W ⁸ each independently represents a hydrogen atom, an alkyl group, a hydroxyl group, an alkoxy group, an alkoxy group, an alkoxy group, an alkoxycarbonyl group, a halogen atom, and may be substituted. Selected from the group consisting of aryl and arylcarbonyl. X ² has the same meaning as X ² in the formula (C-1).

Specific examples of the europium ion represented by the above formula (C-1d) include 4- (phenylthio) phenyldiphenylsulfonium and 4- (4-benzylfluorenyl-2-chlorophenylthio). ) Phenylbis (4-fluorophenyl) fluorene, 4- (4-benzylidenephenylthio) phenyldiphenylfluorene, phenyl [4- (4-biphenylthio) phenyl] 4 -Biphenylphosphonium, phenyl [4- (4-biphenylthio) phenyl] 3-biphenylphosphonium, [4- (4-ethylphenylphenyl) phenyl] diphenylphosphonium, diphenyl [4- (p-triphenylthio) phenyl] diphenylphosphonium.

In the fluoroalkyl fluorophosphate anion represented by the above formula (C-1b), W ³ represents an alkyl group substituted with a fluorine atom. The preferred number of carbon atoms is 1 to 8, and the more preferred number of carbon atoms is 1 to 4. Specific examples of the alkyl group include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, and octyl; isopropyl, isobutyl, secondary butyl, and tertiary butyl And other branched alkyl groups; even cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc., the proportion of hydrogen atoms of alkyl groups substituted with fluorine atoms is usually 80% or more, preferably 90% or more , More preferably 100%. When the substitution rate of the fluorine atom is less than 80%, the acid strength of the onium fluoroalkyl fluorophosphate represented by the formula (C-1) will decrease.

Particularly preferred W ³ is a linear or branched perfluoroalkyl group having 1 to 4 carbon atoms and a fluorine atom substitution rate of 100%. Specific examples include CF ₃ , CF ₃ CF ₂ , (CF ₃ ) ₂ CF, CF ₃ CF ₂ CF ₂ , CF ₃ CF ₂ CF ₂ CF ₂ , (CF ₃ ) ₂ CFCF ₂ , CF ₃ CF ₂ (CF ₃ ) CF, (CF ₃ ) ₃ C. The number j of W ^{3 is} an integer of 1 to 5, preferably 2 to 4, and particularly preferably 2 or 3.

Specific examples of the preferred fluoroalkylfluorophosphate anion include [(CF ₃ CF ₂ ) ₂ PF ₄ ] ^- , [(CF ₃ CF ₂ ) ₃ PF ₃ ] ^- , [((CF ₃ ) ₂ CF ) ₂ PF ₄ ] ^- , [((CF ₃ ) ₂ CF) ₃ PF ₃ ] ^- , [(CF ₃ CF ₂ CF ₂ ) ₂ PF ₄ ] ^- , [(CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ] ^- , [((CF ₃ ) ₂ CFCF ₂ ) ₂ PF ₄ ] ^- , [((CF ₃ ) ₂ CFCF ₂ ) ₃ PF ₃ ] ^- , [(CF ₃ CF ₂ CF ₂ CF ₂ ) ₂ PF ₄ ] ^- , Or [(CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ] ^- , among these, particularly preferred is [(CF ₃ CF ₂ ) ₃ PF ₃ ] ^- , [(CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ] ^- , [((CF ₃ ) ₂ CF) ₃ PF ₃ ] ^- , [((CF ₃ ) ₂ CF) ₂ PF ₄ ] ^- , [((CF ₃ ) ₂ CFCF ₂ ) ₃ PF ₃ ] ^- , or [ ((CF ₃ ) ₂ CFCF ₂ ) ₂ PF ₄ ] ^- .

As preferable specific examples of the borate anion represented by the above formula (C-1c), there may be mentioned (pentafluorophenyl) borate ([B (C ₆ F ₅ ) ₄ ] ^- ), [[Three Fluoromethyl) phenyl] borate ([B (C ₆ H ₄ CF ₃ ) ₄ ] ^- ), difluorobis (pentafluorophenyl) borate ([(C ₆ F ₅ ) ₂ BF ₂ ] ^- ) , Trifluoro (pentafluorophenyl) borate ([(C ₆ F ₅ ) BF ₃ ] ^- ), (difluorophenyl) borate ([B (C ₆ H ₃ F ₂ ) ₄ ] ^- ), etc. . Among these, particularly preferred is penta (pentafluorophenyl) borate ([B (C ₆ F ₅ ) ₄ ] ^- ).

Examples of the second form of the photoacid generator (C) include 2,4-bis (trichloromethyl) -6-piperyl-1,3,5-triazine and 2,4-bis (trichloro) (Methyl) -6- [2- (2-furanyl) vinyl] symmetric triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methyl-2-furanyl) Vinyl] symmetric triazine, 2,4-bis (trichloromethyl) -6- [2- (5-ethyl-2-furanyl) vinyl] symmetrical triazine, 2,4-bis (trichloro (Methyl) -6- [2- (5-propyl-2-furanyl) vinyl] symmetric triazine, 2,4-bis (trichloromethyl) -6- [2- (3,5-bis Methoxyphenyl) vinyl] symmetric triazine, 2,4-bis (trichloromethyl) -6- [2- (3,5-diethoxyphenyl) vinyl] symmetric triazine, 2 , 4-bis (trichloromethyl) -6- [2- (3,5-dipropoxyphenyl) vinyl] symmetric triazine, 2,4-bis (trichloromethyl) -6- [ 2- (3-methoxy-5-ethoxyphenyl) vinyl] symmetric triazine, 2,4-bis (trichloromethyl) -6- [2- (3-methoxy-5- Propoxyphenyl) vinyl] symmetric triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-methylenedioxyphenyl) vinyl] symmetric triazine, 2,4-bis (trichloromethyl) -6- (3,4-methylenedioxyphenyl) symmetric triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4 -Methoxy) phenylsymmetric triazine, 2,4-bis -Trichloromethyl-6- (2-bromo-4-methoxy) phenylsymmetric triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) benzene Vinylphenyl symmetric triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl symmetric triazine, 2- (4-methoxybenzene ) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -1, 3,5-triazine, 2- [2- (2-furanyl) vinyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (5 -Methyl-2-furanyl) vinyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (3,5-dimethoxyphenyl) ) Vinyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (3,4-dimethoxyphenyl) vinyl] -4,6 -Bis (trichloromethyl) -1,3,5-triazine, 2- (3,4-methylenedioxyphenyl) -4,6-bis (trichloromethyl) -1,3, 5-triazine, ginseng (1,3-dibromopropyl) -1,3,5-triazine, ginseng (2,3-dibromopropyl) -1,3,5-triazine, etc. A triazine compound and a halogen-containing triazine compound represented by the following formula (C-2) such as ginseng (2,3-dibromopropyl) trimeric isocyanate. Formula (C-2) In formula (C-2), W ⁹ to W ¹¹ are each independently represented as a haloalkyl group.

Further, as a third embodiment of the photoacid generator (C), α- (p-toluenesulfonyloxyimino) -phenylacetonitrile, α- (benzenesulfonyloxyimino) -2 , 4-Dichlorophenylacetonitrile, α- (benzenesulfonyloxyimino) -2,6-dichlorophenylacetonitrile, α- (2-chlorobenzenesulfonyloxyimino) -4- A methoxyphenylacetonitrile, α- (ethylsulfonyloxyimino) -1-chloropentenylacetonitrile, and a compound represented by the following formula (C-3) containing a sulfonic acid oxime group. Formula (C-3) In formula (C-3), W ¹² represents a monovalent, divalent, or trivalent organic group, and W ¹³ represents a substituted or unsubstituted saturated hydrocarbon group, an unsaturated hydrocarbon group, or an aromatic compound. Base, n represents the number of repeating units of the structure within the parentheses.

In the formula (C-3), the aromatic compound group represents a group of a compound that makes the aromatic compound exhibit unique physical and chemical properties, and examples thereof include aryl groups such as phenyl and naphthyl, or furanyl and thienyl And so on heteroaryl. These may have one or more appropriate substituents on the ring, such as a halogen atom, an alkyl group, an alkoxy group, a nitro group, and the like. Further, W ^{13 is} particularly preferably an alkyl group having 1 to 6 carbon atoms, and examples thereof include methyl, ethyl, propyl, and butyl. A compound in which W ¹² is an aromatic compound group and W ¹³ is an alkyl group having 1 to 4 carbon atoms is particularly preferred.

As the acid generator represented by the formula (C-3), when n = 1, compounds in which W ¹² is any of phenyl, methylphenyl, and methoxyphenyl, and W ¹³ is methyl Specific examples include α- (methanesulfonyloxyimino) -1-phenylacetonitrile, α- (methanesulfonyloxyimino) -1- (p-methylphenyl) acetonitrile, α- (methanesulfonyloxyimino) -1- (p-methoxyphenyl) acetonitrile, [2- (propanesulfonyloxyimino) -2,3-dihydroxythiophene-3- Subunit] (o-tolyl) acetonitrile and the like. When n = 2, examples of the acid generator represented by the formula (C-3) include acids represented by the following formulae (C-3-1) to (C-3-8) Generating agent: Formula (C-3-1) Formula (C-3-2) Formula (C-3-3) Formula (C-3-4) Formula (C-3-5) Formula (C-3-6) Formula (C-3-7) Formula (C-3-8)

Moreover, as a 4th aspect of a photoacid generator (C), the onium salt which has a naphthalene ring in a cationic part is mentioned. The "having a naphthalene ring" means having a structure derived from naphthalene, meaning a structure of at least two rings, and maintaining their aromaticity. The naphthalene ring may have substituents such as a linear or branched alkyl group having 1 to 6 carbon atoms, a hydroxyl group, a linear or branched alkoxy group having 1 to 6 carbon atoms, and the like. . The structure derived from the naphthalene ring can be a monovalent radical (free atomic valence is 1), or a divalent radical (free atomic valence is 2) or more. It is more preferably a monovalent radical (however, in this case, it is deducted from the above) (To calculate the free atomic valence of the bonded part of the substituent). The number of naphthalene rings is preferably 1 to 3.

As the cation part of such an onium salt having a naphthalene ring in the cation part, a structure represented by the following formula (C-4) is preferred: Formula (C-4) In formula (C-4), at least one of W ¹⁴ to W ¹⁶ represents a group represented by the following formula (C-4a), and the rest represents a straight chain having 1 to 6 carbon atoms. Alternatively, it may be a branched alkyl group, a phenyl group which may have a substituent, a hydroxyl group, or a linear or branched alkoxy group having 1 to 6 carbon atoms. Alternatively, one of W ¹⁴ to W ¹⁶ is a group represented by the following formula (C-4a), and the other two are each independently a linear or branched alkylene group having carbon number W ¹⁴ to W ¹⁶ , These ends can be bonded to form a ring. Formula (C-4a) In formula (C-4a), W ¹⁷ and W ¹⁸ each independently represent a hydroxyl group, a linear or branched alkoxy group having 1 to 6 carbon atoms, or a carbon number of A linear or branched alkyl group of 1 to 6, W ¹⁸ represents a single bond or a linear or branched alkylene group having 1 to 6 carbon atoms which may have a substituent. l and m each independently represent an integer from 0 to 2, and l + m is 3 or less. When there is a plurality of W ¹⁷ , they may be the same or different from each other. When plural W ¹⁸ are present, they may be the same as or different from each other.

The number of the groups represented by the above formula (C-4a) among the above W ¹⁴ to W ^{16 is} preferably one from the viewpoint of the stability of the compound, and the rest are linear or branched having 1 to 6 carbon atoms. Alkyl groups, these ends may be bonded to form a ring. In this case, the two alkylene groups may include a sulfur atom to form a 3- to 9-membered ring. The number of atoms (sulfur-containing atoms) constituting the ring is preferably 5 to 6.

Examples of the substituent which the above-mentioned alkylene group may have include an oxygen atom (in this case, a carbonyl group is formed together with a carbon atom constituting the alkylene group), a hydroxyl group, and the like.

Examples of the substituent which the phenyl group may have include a hydroxyl group, a linear or branched alkoxy group having 1 to 6 carbon atoms, and a linear or branched group having 1 to 6 carbon atoms. Alkyl, etc.

Those suitable as such cationic moieties include those represented by the following formulae (C-4b) and (C-4c), and a structure represented by the following formula (C-4c) is particularly preferred. Formula (C-4b) Formula (C-4c)

As such a cationic moiety, a sulfonium salt or a sulfonium salt may be used; a sulfonium salt is preferred from the viewpoint of acid production efficiency and the like.

Therefore, an anion part which is suitable as an anion part of an onium salt which has a naphthalene ring in a cationic part is desirable as an anion which can form a sulfonium salt.

As an anion part of such an acid generator, a part or all of hydrogen atoms are fluorinated fluoroalkylsulfonic acid ions or arylsulfonic acid ions.

The alkyl group in the fluoroalkylsulfonic acid ion may be linear, branched, or cyclic with 1 to 20 carbon atoms. Based on the volume of the generated acid and its diffusion distance, the number of carbon atoms is preferably 1 To 10. It is particularly preferable to have a branched or ring shape because the diffusion distance is short. In addition, from the viewpoint of inexpensive synthesis, methyl, ethyl, propyl, butyl, and octyl are preferred.

The aryl group in the arylsulfonic acid ion is an aryl group having 6 to 20 carbon atoms, and examples thereof include a phenyl group and a naphthyl group which may be substituted with an alkyl group or a halogen atom. In particular, an aryl group having 6 to 10 carbon atoms is preferred because it can be synthesized inexpensively. Specific preferred examples include phenyl, tosyl, ethylphenyl, naphthyl, and methylnaphthyl.

Among the above fluoroalkylsulfonic acid ions or arylsulfonic acid ions, the fluorination rate when part or all of the hydrogen atoms are fluorinated is preferably 10 to 100%, more preferably 50 to 100%, and especially substituted with fluorine atoms. All hydrogen atoms are preferred because the strength of the acid is increased. Those belonging to this category include trifluoromethanesulfonate, perfluorobutanesulfonate, perfluorooctanesulfonate, and perfluorobenzenesulfonate.

Among these, as a preferable anion part, the following formula (C-4d) can be mentioned: W ²⁰ SO ₃ ^- Formula (C-4d) In formula (C-4d), W ²⁰ is the following formula (C-4e), (C-4f), and (C-4g). -C _x F _{2x + 1} (C-4e) Formula (C-4f) Formula (C-4g) In formula (C-4e), x represents an integer of 1 to 4. In the formula (C-4f), W ²¹ represents a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 6 carbon atoms, or a linear or branched chain having 1 to 6 carbon atoms. Alkoxy, y represents an integer of 1 to 3. Among these, trifluoromethanesulfonate and perfluorobutanesulfonate are preferred from the viewpoint of safety.

In addition, as the anion part, a nitrogen-containing one represented by the following formula (C-4h) or (C-4i) may be used. Formula (C-4h) Formula (C-4i) In formula (C-4h) and formula (C-4i), X ^a represents a linear or branched alkylene group having at least one hydrogen atom substituted with a fluorine atom. The number of carbon atoms is 2 to 6, preferably 3 to 5, and most preferably 3 carbon atoms. In addition, Y ^a and Z ^a each independently represent a linear or branched alkyl group in which at least one hydrogen atom is replaced by a fluorine atom, and the number of carbon atoms in the alkyl group is 1 to 10, preferably 1 to 7, and more It is preferably 1 ~ 3.

X ^a number of carbon atoms of the alkylene group, or Y ^a, Z ^a group of the smaller number of carbon atoms is more excellent solubility in an organic solvent, and therefore preferred.

And, X ^a or an alkylene group of Y ^a, Z ^a in the alkyl group, the number of substituted hydrogen atoms in the more fluorine atoms, the stronger acid strength, and therefore preferred. The proportion of fluorine atoms in the alkylene group or alkyl group, that is, the fluorination rate is preferably 70 to 100%, more preferably 90 to 100%, and most preferably perfluoroalkylene in which all hydrogen atoms are replaced by fluorine atoms. Or perfluoroalkyl.

Those which are suitable as such an onium salt having a naphthalene ring in the cationic moiety include compounds represented by the following formulae (C-4j) and (C-4k): Formula (C-4j) Formula (C-4k)

Furthermore, as a fifth embodiment of the photoacid generator (C), bis (p-toluenesulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, Bis (cyclohexylsulfonyl) diazomethane, bis (2,4-dimethylphenylsulfonyl) diazomethane and other bissulfonyldiazomethanes; p-toluenesulfonic acid 2-nitrobenzyl Esters, 2,6-dinitrobenzyl p-toluenesulfonate, nitrobenzyl tosylate, dinitrobenzyl tosylate, nitrobenzyl sulfonate, nitrobenzyl carbonate , Nitrobenzyl derivatives such as dinitrobenzyl carbonate, pyrogallol trifluoromethanesulfonate, pyrogallol tritoluenesulfonate, benzyltoluenesulfonate, benzylsulfonate , N-methanesulfonyloxysuccinimide, N-trichloromethylsulfonyloxysuccinimide, N-phenylsulfonyloxymaleimide, N-methanesulfonyloxyimine Sulfonates such as xylylenediamine; trifluoromethanesulfonates such as N-hydroxyphthalimide and N-hydroxynaphthalene imine; diphenylsulfonium hexafluorophosphate, (4 -Methoxyphenyl) phenylsulfonium triflate, bis (p-tert-butylphenyl) sulfonium triflate, tris Onium salts such as sulfonium hexafluorophosphate, (4-methoxyphenyl) diphenylsulfonium trifluoromethanesulfonate, (p-tributylphenyl) diphenylsulfonium trifluoromethanesulfonate ; Benzoin tosylate such as benzoin tosylate, α-methyl benzoin tosylate; other diphenylphosphonium salts, triphenylphosphonium salts, phenyldiazonium salts, benzyl carbonate, etc. .

The photoacid generator (C) may be used alone or in combination of two or more kinds. In addition, the total amount of the polyhydroxystyrene resin (A) based on the acid-dissociable protective group is 100 parts by weight, and the content of the photoacid generator (C) is 0.3 to 3 parts by weight, preferably 0.4 weight. Parts to 2.8 parts by weight, more preferably 0.5 parts to 2.5 parts by weight. Solvent ( D )

The solvent (D) is not particularly limited as long as it is used by the chemically amplified positive photosensitive resin composition, and it can be used. Examples thereof include an ester-based solvent and a non-ester-based solvent.

Examples of the ester-based solvent include propylene glycol monoalkyl ether acetate [for example, propylene glycol monomethyl ether acetate (PGMEA), etc.], ethyl 3-ethoxypropionate, and lactate (for example, ethyl lactate).

Non-ester solvents include ketones, polyvalent alcohols and their derivatives, and cyclic ethers.

Ketones include acetone, methyl ethyl ketone, cyclohexanone, methyl isopentanone, and 2-heptanone. Polyvalent alcohols and their derivatives include ethylene glycol, propylene glycol, diethylene glycol, or monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, dimethyl ether, and diethylene glycol dimethyl ether. Ether or monophenyl ether. Cyclic ethers include dioxane and the like.

The solvent may be used singly or in combination of two or more.

In the chemically amplified positive photosensitive resin composition of the present invention, in order to improve the storage stability and ensure the stability of the coating film, the organic solvent contains at least one selected from the group consisting of propylene glycol monoalkyl ether acetate and 2-heptanone. good.

The total amount of the polyhydroxystyrene resin (A) based on the acid-dissociable protective group is 100 parts by weight, and the content of the solvent (D) is 200 to 1200 parts by weight, preferably 200 to 1100 parts by weight , More preferably 250 parts by weight to 1000 parts by weight. Basic compounds ( E )

The basic compound (E) is not particularly limited as long as it is compatible with the chemically amplified positive-type photosensitive resin composition, and includes, for example, compounds described in Japanese Patent Application Laid-Open No. 9-006001.

The basic compound (E) preferably includes a compound represented by the formula (E-1): N (A) _z (B) _3-z Formula (E-1) In the formula (E-1), each of A is independent Represents an alkyl group having 4 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and a phenyl or aralkyl group having 6 to 20 carbon atoms; B each independently represents a hydrogen atom or 1 to 3 carbon atoms Alkyl; z represents an integer of 1 to 3.

The compound represented by formula (E-1) is preferably a compound in which z is 2 or 3, and the groups represented by X are each the same.

As the alkyl group of the group A, if the carbon number is less than 4, it is difficult to improve the stability of the photoresist over time. The carbon number is further 5 or more, and more preferably 8 or more. The upper limit value is not particularly limited, and it is more preferably 20 or less, and more preferably 15 or less, from the viewpoint of confirming the effect of stabilization over time or commercially obtained. In addition, when it exceeds 20, the alkali strength decreases, and the effect of storage stability decreases.

The alkyl group may be linear or branched. Specifically, for example, n-decyl, n-octyl, and n-pentyl are preferred.

Among the cycloalkyl groups as the group A, especially cycloalkyl groups having 4 to 8 carbon atoms can be obtained commercially, and the effect of improving stability over time is superior, which is more suitable. A cyclohexyl group having 6 carbon atoms is more preferred.

As the aralkyl group of the group A, a group represented by the formula (E-1a) can be listed: -QP Formula (E-1a) In the formula (E-1a), Q represents an alkylene group; P represents an aromatic group. Group of hydrocarbon groups.

Examples of the group P include a phenyl group and a naphthyl group, and a phenyl group is preferred. As the alkylene group of the group Q, the carbon number may be 1 or more, and preferably 1 to 3.

As the aralkyl group of the group A, for example, benzyl, phenylethyl and the like are preferred.

As the alkyl group of the group B, it may be a straight chain or a branched chain. Especially preferred are methyl and ethyl.

The compound represented by the formula (E-1) is preferably a tertiary amine compound. That is, when the compound represented by the formula (E-1) has a group B, the group B is preferably an alkyl group.

Specific examples of the compound represented by the formula (E-1) include tri-n-decylamine, methyl-di-n-octylamine, tri-n-pentylamine, N, N-dicyclohexylmethylamine, and tribenzylamine. Wait.

The basic compound (E) may be used alone or as a mixture of two or more thereof. The total amount of the polyhydroxystyrene resin (A) based on the acid-dissociable protective group is 100 parts by weight, and the content of the basic compound (E) is 0.03 to 1.0 parts by weight, preferably 0.04 to 0.8 parts by weight. It is more preferably from 0.05 to 0.5 parts by weight.

When the chemically amplified positive photosensitive resin composition further contains a basic compound (E), the taper angle of the photoresist pattern formed by the chemically amplified positive photosensitive resin composition can be further improved. Heterocyclic compound (F) having a nitrogen atom

The chemically amplified positive photosensitive resin composition of the present invention may optionally contain a heterocyclic compound (F) having a nitrogen atom. The heterocyclic compound (F) having a nitrogen atom may include, but is not limited to, heterocyclic compounds of the following formula (F-1) to (F-4): Formula (F-1) Formula (F-2) Formula (F-3) Formula (F-4) In formulas (F-1) to (F-4), G ₁ and G ₂ each independently represent a hydrogen atom, a fluorenyl group, or an alkyl group; H ₁ to H ₉ each independently represent hydrogen Atom, hydroxyl, carboxylic acid group, sulfonic acid group, alkyl group, amine group, halogen atom or mercapto group; w, v, q and s each independently represent an integer of 0 to 3; p and r each independently represent 0 to 2 Integers; and t and u each independently represent an integer from 0 to 4.

In the formulae (F-1) to (F-4), G ₁ and G ₂ each independently represent a hydrogen atom, a fluorenyl group, or an alkyl group. Specifically, G ₁ and G ₂ may preferably be a fluorenyl group having 2 to 4 carbon atoms or an alkyl group having 1 to 3 carbon atoms. The fluorenyl group having a carbon number of 2 to 4 may include, but is not limited to, an acetyl group, a propionyl group, or a butyryl group. The alkyl group having 1 to 3 carbon atoms may include, but is not limited to, a methyl group, an ethyl group, an i-propyl group, or an n-propyl group.

The aforementioned H ₁ to H ₉ each independently represent a hydrogen atom, a hydroxyl group, a carboxylic acid group, a sulfonic acid group, an alkyl group, an amine group, a halogen atom, or a mercapto group. Specifically, when H ₁ to H ₉ are alkyl groups, H ₁ to H ₉ may preferably be an alkyl group having 1 to 3 carbon atoms (for example, methyl, ethyl, isopropyl, or n-propyl). When H ₁ to H ₉ are halogen atoms, the H ₁ to H ₉ may preferably be a chlorine atom, a bromine atom, or an iodine atom. When H ₁ to H ₉ is an amine group, the hydrogen atom bonded to the amine group may be 1 or 2 alkyl groups having 1 to 3 carbon atoms (for example, methyl, ethyl, isopropyl or n-propyl Group). In addition, H ₁ to H ₉ may be an alkyl group having a carbon number of 1 to 3 (for example, aminomethyl, aminoethyl, aminoisopropyl, or amino-n-propyl).

When the above of w, v, p, q, r and s is greater than or equal to 2, a plurality of _{H 1, H 2, H 4} , H 5, H 6 and H _7, respectively, may be the same or different groups.

The heterocyclic compound (F) having a nitrogen atom may include, but is not limited to, 6-methyl-8-hydroxyquinoline, 6-ethyl-8-hydroxyquinoline, 6-ethyl -8-hydroxyquinoline), 5-methyl-8-hydroxyquinoline, 8-hydroxyquinoline, 8-acetyloxy quinoline ), 4-hydroxypteridine, 4-hydroxypteridine, 2,4-dihydroxypteridine, 4-hydroxypteridine-2-sulfonic acid , 2-ethyl-4-hydroxypteridine, 2-methyl-4-hydroxypteridine, 2-amino-6,7 -2-Amino-6,7-dimethyl-4-hydroxy pteridine, 1,10-phenanthroline, 5,6-dimethyl -1,10-Phenanthroline (5,6-dimethyl-1,10-phenanthroline), 3,8-dimethyl-1,10-Phenanthroline (3,8-dimethyl-1,10- phenanthroline), 3,8-dihydroxy-1,10-phenanthroline, 5-carboxy-1,10-phenanthroline , 10-phenanthroline), 5,6-dihydroxy-1,10-o-phenanthroline (5,6-di hydroxy-1,10-phenanthroline), 1,10-phenanthroline-5-sulfonic acid, 4,4'-dimethyl-2,2'-linked Pyridine (4,4'-dimethyl-2,2'-bipyridyl), 2,2'-bipyridyl (2,2'-bipyridyl), 2,2'-bipyridine-5-carboxylic acid (2,2 ' -bipyridyl-5-carboxylic acid), 5,5'-dichloro-2,2'-bichloropyridine (5,5'-dichloro-2,2'-bipyridyl), 3,3'-dihydroxy-2, 2'-bipyridyl (3,3'-dihydroxy-2,2'-bipyridyl), 3,3'-dimercapto-2,2'-bipyridyl (3,3'-dimercapto-2,2'-bipyridyl ) Or any combination of the above. The aforementioned heterocyclic compound (F) having a nitrogen atom may be used singly or in combination.

Preferably, the heterocyclic compound (F) having a nitrogen atom may be 8-hydroxyquineline, 8-acetoxyquineline, 4-hydroxypteridine, 2,4-dihydroxypteridine, 1,10 -O-phenanthroline, 5,6-dimethyl-1,10-o-phenanthroline, 2,2'-bipyridine, 2,2'-bipyridine-5-carboxylic acid or a combination thereof.

Based on the total amount of the polyhydroxystyrene resin (A) containing the acid dissociable protective group being 100 parts by weight, the amount of the heterocyclic compound (F) having a nitrogen atom may be 0.01 to 0.5 parts by weight. Good may be 0.01 to 0.4 parts by weight, and more preferably 0.02 to 0.3 parts by weight.

When the chemically amplified positive photosensitive resin composition of the present invention contains a heterocyclic compound (F) having a nitrogen atom, the photoresist pattern prepared by the chemically amplified positive photosensitive resin composition has better adhesion. . Additives ( G )

The chemically amplified positive photosensitive resin composition may further contain an additive (G) as long as the effect of the present invention is not affected. The additive (G) may be used singly or in combination of a plurality of types, depending on actual needs. The specific content of the additive (G) is described below.

The chemically amplified positive-type photosensitive resin composition may further contain a polyethylene resin as an additive (G) in order to improve plasticity. Specific examples of the polyethylene resin include polyvinyl chloride, polystyrene, polyhydroxystyrene, polyvinyl acetate, polyvinylbenzoic acid, polyvinyl methyl ether, polyvinyl ether, polyvinyl alcohol, and polyvinylpyrrole. Pyridone, polyvinylphenol, and copolymers thereof. Polyethylene resin is preferably polyethylene methyl ether because of its low glass transition point.

In addition, the chemically amplified positive photosensitive resin composition may further include a bonding aid as an additive (G) in order to improve the adhesion between the template and the metal substrate formed using the photosensitive resin composition.

Furthermore, the chemically amplified positive photosensitive resin composition may further contain a surfactant as an additive (G) in order to improve coating properties, defoaming properties, leveling properties, and the like. Specific examples of the surfactant include BM-1000, BM-1100 (all manufactured by BM Chmie), MEGAFACE F142D, MEGAFACE F172, MEGAFACE F173, MEGAFACE F183 (all manufactured by DIC Corporation), FLUORAD FC-135 , FLUORAD FC-170C, FLUORAD FC-430, FLUORAD FC-431 (all made by Sumitomo 3M), SURFLON S-112, SURFLON S-113, SURFLON S-131, SURFLON S-141, SURFLON S-145 (all It is a commercially available fluorine-based surfactant such as manufactured by Asahi Glass Co., Ltd.), SH-28PA, SH-190, SH-193, SZ-6032, and SF-8428 (all manufactured by Toray Silicone), but is not limited thereto.

In addition, the chemically amplified positive-type photosensitive resin composition may further contain an acid, an acid anhydride, or a high-boiling point solvent as an additive (G) in order to finely adjust the solubility of the developer.

Specific examples of acids and anhydrides include monocarboxylic acids such as acetic acid, propionic acid, n-butyric acid, isobutyric acid, n-valeric acid, isovaleric acid, benzoic acid, and cinnamic acid; lactic acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 2-hydroxycinnamic acid, 3-hydroxycinnamic acid, 4-hydroxycinnamic acid, 5-hydroxyisophthalic acid, syringic acid, etc. Monocarboxylic acids; oxalic acid, succinic acid, glutaric acid, adipic acid, maleic acid, itaconic acid, hexahydrophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,2 -Cyclohexanedicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, butanetetracarboxylic acid, trimellitic acid, pyromellitic acid, cyclopentanetetracarboxylic acid, butanetetracarboxylic acid, Polycarboxylic acids such as 1,2,5,8-naphthalenetetracarboxylic acid; itaconic anhydride, succinic anhydride, citraconic anhydride, dodecene succinic anhydride, propanetricarboxylic anhydride, maleic anhydride, hexahydrophthalic anhydride , Methyltetrahydrophthalic anhydride, humic anhydride, 1,2,3,4-butanetetracarboxylic anhydride, cyclopentanetetracarboxylic dianhydride, phthalic anhydride, pyromellitic anhydride, trimylene Tricarboxylic anhydride, diphenyl Benzophenone tetracarboxylic acid anhydride, ethylene glycol bis trimellitic anhydride, glycerol, trimellitic anhydride reference anhydride; and the like.

Further, as specific examples of the high-boiling-point solvent, N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamidamine, N-methylpyrrolidone, dimethyl sulfene, benzyl ether, dihexyl ether, acetoacetone, isophorone, hexanoic acid, caprylic acid, 1-octanol , 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, vinyl carbonate, propylene carbonate, phenylcellulose Acetate, etc.

The chemically amplified positive photosensitive resin composition may further contain a sensitizer as an additive (G) in order to increase sensitivity. < Method for producing chemically amplified positive photosensitive resin composition >

The method for producing the chemically amplified positive-type photosensitive resin composition is not particularly limited, and the above-mentioned components can be obtained by mixing and stirring the components in a usual manner. Examples of a device that can be used when mixing and stirring the above-mentioned components include a dissolver, a homogenizer, and a three-roll mill. After the above components are uniformly mixed, the obtained mixture may be further filtered with a screen, a membrane filter, or the like. < Method of Forming Photoresist Pattern >

The present invention further provides a method for forming a photoresist pattern. The method for forming the photoresist pattern of the present invention is described below.

First, the chemically amplified positive photosensitive resin composition of the present invention is applied to a substrate with a spinner or the like to form a coating film.

The substrate is preferably a glass substrate provided with a silicon film. For the formation of silicon film, amorphous silicon is usually used. In the field of system LCD, low temperature polysilicon is preferred. In addition, a large substrate of 300 mm × 400 mm or more, especially a large substrate of 550 mm × 650 mm or more can be used.

Next, the substrate on which the coating film is formed is subjected to a heat treatment (pre-baking) at, for example, 90 to 140 ° C., and the remaining solvent is removed to form a photoresist film. The heat treatment (pre-baking) method is preferably a proximity baking (Proximity Bake) heating method with a gap between the heating plate and the substrate.

Next, the photoresist film is selectively exposed using a photomask that depicts both a photomask pattern for a integrated circuit and a photomask pattern for a liquid crystal display portion.

In order to form a fine pattern, the light source used here is preferably an i-line (365 nm). In addition, the exposure process used in this exposure is an exposure process with a NA of 0.3 or lower, preferably 0.2 or lower, and more preferably 0.15 or lower. By using the exposure process under low NA conditions, the exposure area can be enlarged at one time, and the production capacity can be improved.

Next, the photoresist film after selective exposure is heat-treated (post-exposure baking). Post-exposure bake methods include methods such as proximity baking with a gap between the heating plate and the substrate, and direct bake with no gap. Among them, in order to obtain the diffusion effect of post-exposure baking without causing warpage of the substrate, a method of performing direct baking after performing adjacent baking is preferred. Here, the heating temperature is 90 to 150 ° C, and more preferably 100 to 140 ° C.

Next, using a developing solution, for example, an alkali aqueous solution of 1 to 10% by mass of a tetramethylammonium hydroxide aqueous solution, the photoresist film after the above-mentioned baking is subjected to a development treatment to dissolve and remove the exposed portion, and at the same time form a bulk on the substrate. Photoresist pattern for circuit and photoresist pattern for liquid crystal display.

Next, the developing solution remaining on the surface of the photoresist pattern is washed with a washing liquid such as pure water to form a photoresist pattern.

In the step of performing the selective exposure described above, it is preferable to use a photomask that forms both a photoresist pattern-forming photomask pattern and a photoresist pattern-forming photomask pattern that exceeds 2.0 μm in size. Suitable for.

Since the chemically amplified positive photosensitive resin composition of the present invention is excellent in linearity, it is possible to obtain a photoresist pattern that faithfully reproduces a rough pattern and a fine pattern of a photomask pattern. Therefore, a photoresist pattern for an integrated circuit having a pattern size of 2.0 μm or less and a photoresist pattern for a liquid crystal display portion exceeding 2.0 μm can be simultaneously formed on a substrate. < Example > Synthesis example of polyhydroxystyrene resin ( A ) containing an acid dissociable protective group

The following describes Synthesis Examples A-1 to A-6 and Comparative Synthesis Example A'-1 of the polyhydroxystyrene resin (A) containing an acid-dissociable protective group:

Synthesis Example A-1 After 120 parts by weight of a polyhydroxystyrene resin having a weight average molecular weight of 13,000 was added to 680 parts by weight of N, N-dimethylacetamide, 42.3 parts by weight of 1-chloro-ethyl Ethoxyethane was added to a four-necked conical flask, and the mixed solution was slowly stirred until completely dissolved. Next, 78.8 parts by weight of triethylamine was added dropwise through the addition funnel at a rate of completion of the dropwise addition within about 30 minutes, and the reaction was performed for 3 hours. After the reaction is completed, 20 times the amount of pure water relative to the total amount of the mixed solution is added to precipitate a polyhydroxystyrene resin containing 1-ethoxyethyl group as an acid dissociative protective group, and the above-mentioned precipitates are separated. After washing with pure water, dehydration, and drying, a polyhydroxystyrene resin containing 1-ethoxyethyl group as an acid-dissociable protective group (A- 1).

Synthesis Examples A-2 to A-3 Synthesis Examples A-2 to A-3 were prepared in the same procedure as Synthesis Example A-1, except that the weight average of the polyhydroxystyrene resin used was changed Molecular weight and hydrogen atom substitution rate of its phenolic hydroxyl group (as shown in Table 1).

Synthesis Example A-4 After 120 parts by weight of a polyhydroxystyrene resin having a weight average molecular weight of 13,000 was added to 680 parts by weight of N, N-dimethylacetamide, 85 parts by weight of dicarbonate was added. Butyl ester was added to a four-necked conical flask, and the mixed solution was slowly stirred until completely dissolved. Next, 59 parts by weight of triethylamine was added dropwise through the addition funnel at a rate at which the addition was completed in about 15 minutes, and the reaction was performed for 3 hours. After the reaction, 20 times the amount of pure water was added to the total amount of the mixed solution to precipitate a polyhydroxystyrene resin containing a third butoxycarbonyl group as an acid-dissociable protective group. After washing with pure water, dehydration, and drying, a polyhydroxystyrene resin (A-4) containing a third butoxycarbonyl group as an acid-dissociable protective group with a hydrogen atom substitution rate of 39 mol% was obtained. .

Synthesis Examples A-5 to A-6 Synthesis Examples A-5 to A-6 were prepared in the same procedure as Synthesis Example A-1, except that the weight average of the polyhydroxystyrene resin used was changed Molecular weight and hydrogen atom substitution rate of its phenolic hydroxyl group (as shown in Table 1).

Comparative Synthesis Example A'-1 In a three-necked conical flask of 1,000 ml in volume equipped with a cooling tube, 120 parts by weight of 4-hydroxystyrene was added to 480 parts by weight of tetrahydrofuran to dissolve, and the mixed solution was slowly stirred until dissolved. . Next, 2,2'-azobis-2-isopropylbutyronitrile (AIBN) was added to a three-necked conical flask to perform a polymerization reaction, and the reaction temperature was maintained at 75 ° C throughout the polymerization process. After the polymerization was completed, the polymerization product was taken out of the four-necked conical flask and the solvent was removed to obtain a polyhydroxystyrene resin (A'-1) having no acid-dissociable protective group, and its weight average molecular weight was 13,000.

[Table 1] Examples of chemically amplified positive photosensitive resin composition

Examples 1 to 13 and Comparative Examples 1 to 3 of the chemically amplified positive photosensitive resin composition are described below:

Example 1 100 parts by weight of an acid-dissociable protective group-containing polyhydroxystyrene resin (A-1) obtained in the above Synthesis Example A-1 and 0.03 parts by weight of 9-decenenitrile (abbreviated as B-1) And 2.5 parts by weight of the photoacid generator (C-1) is added to 350 parts by weight of propylene glycol monomethyl ether acetate (referred to as D-1), and the mixture is dissolved and mixed with a shaking mixer to prepare and A chemically amplified positive photosensitive resin composition was obtained. The chemically amplified positive photosensitive resin composition was evaluated by each of the following measurement and evaluation methods, and the results are shown in Table 2.

Examples 2 to 13 Examples 2 to 13 use the same operation method as the method for manufacturing the chemically amplified positive-type photosensitive resin composition of Example 1, except that Examples 2 to 13 are Table 2 or Table 3 shows the types and amounts of raw materials in the chemically amplified positive photosensitive resin composition.

Comparative Examples 1 to 3 Comparative Examples 1 to 3 use the same operation method as that of the chemically amplified positive-type photosensitive resin composition of Example 1 except that Comparative Examples 1 to 3 are As shown in Table 3, the type and amount of the raw materials in the chemically amplified positive photosensitive resin composition were changed, and the formula and the following evaluation results were changed.

The compounds corresponding to the numbers in Tables 2 to 3 are shown below.

[Table 2]

[table 3] Evaluation method

Adhesion Using a photoresist coating device (apparatus name: TR36000, manufactured by Tokyo Chemical Industry Co., Ltd.), the chemically amplified positive photosensitive resin composition of the examples and comparative examples was applied to an ITO substrate (100 mm × 100 mm), and then pre-baked under a heating condition of 110 ° C. for 90 seconds, with a gap of approximately 1 mm, to form a photoresist film with a thickness of 1.5 μm. Next, using an i-ray exposure device (device name: FX-702J, manufactured by Nikon Corporation, NA = 0.14) and a test chart mask of a photoresist pattern of L & S (line and space), a 100 mJ / cm ² UV light Pre-bake the coating film for exposure. After the exposure, at a temperature of 110 ° C. for 90 seconds, a close-bake (PEB) was performed with a proximity heating of a gap of 0.5 mm. Next, using a 23 ° C, 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution, a development process was performed for 41 seconds to remove the coating film on the exposed portion of the glass substrate. Finally, rinse with pure water for 15 seconds, and record the developable line width of the developed pattern on the glass substrate. The evaluation criteria for developable line width are shown below. The smaller the developable line width, the better the adhesion during development. The specific evaluation criteria are as follows: ◎: Developable line width ≦ 5 μm ○: 5 μm < Developable line width ≦ 10 μm △: 10 μm <Developable line width ≦ 20 μm X: Developable line width> 20 μm

Please refer to FIG. 1 for the taper angle. FIG. 1 is a schematic diagram of measuring the taper angle of the photoresist pattern. The developed photoresist is post-baked at 130 ° C for 150 seconds, and then the cross-sectional shape is observed; wherein the taper angle 1 is the angle between the substrate 3 and the photoresist pattern 2 (the angle shown by θ in the figure) The specific evaluation criteria are as follows: ◎: 80 ° ≦ | taper angle | ≦ 90 ° ○: 70 ° ≦ | taper angle | <80 ° or 90 ° <| taper angle | ≦ 100 ° △: 60 ° ≦ | taper angle | <70 degree or 100 degree <| taper angle | ≦ 110 degree X: | taper angle | <60 degree or | taper angle |> 110 degree evaluation result

As shown in Tables 2 and 3, the chemically amplified positive photosensitive resin composition containing the polyhydroxystyrene resin (A) containing the acid dissociable protective group and the monounsaturated nitrile compound (B) (Example 1) -13) Compared with the obtained photoresist pattern, the chemically amplified positive photosensitive resin composition (Comparative Examples 1, 3) that did not include the polyhydroxystyrene resin (A) containing an acid dissociative protective group, Poor taper angle evaluation; and even if it contains a polyhydroxystyrene resin (A) containing an acid dissociative protective group, it does not include a chemically amplified positive photosensitive resin composition containing a monounsaturated nitrile compound (B) having a specific structure. Object (Comparative Example 2), both the adhesion and the taper angle evaluation were not good.

In addition, when the number of carbon atoms of the monounsaturated nitrile compound (B) in the chemically amplified positive photosensitive resin composition is 6 to 30 (Examples 1 to 11, and 13), compared to monounsaturated nitriles When the number of carbon atoms of the compound (B) is 5 (Example 12), the adhesion and the taper angle are better evaluated.

In addition, when the chemically amplified positive photosensitive resin composition further includes a basic compound (E) (Examples 4-8, 11, 13), the evaluation performance of the taper angle is better.

In addition, when the chemically amplified positive photosensitive resin composition further includes a heterocyclic compound (F) having a nitrogen atom (Examples 5-9, 11, 13), the evaluation performance of its adhesion is better.

In summary, since the chemically amplified positive photosensitive resin composition of the present invention contains a polyhydroxystyrene resin (A) containing an acid dissociative protective group and a monounsaturated nitrile compound (B), the density can be improved. The problem of poor adhesion and taper angle.

On the other hand, if the number of carbon atoms of the monounsaturated nitrile compound (B) in the chemically amplified positive-type photosensitive resin composition of the present invention is 6 to 30, the adhesion and the taper angle are better evaluated.

On the other hand, if the chemically amplified positive-type photosensitive resin composition of the present invention further contains a basic compound (E), the evaluation of the taper angle is better; and if the chemically amplified positive-type photosensitive resin of the present invention In the case where the heterocyclic compound (F) having a nitrogen atom is further contained in the resin composition, the adhesion evaluation performance is better.

Although the present invention has been disclosed as above with the examples, it is not intended to limit the present invention. Any person with ordinary knowledge in the technical field can make some modifications and retouching without departing from the spirit and scope of the present invention. The protection scope of the present invention shall be determined by the scope of the attached patent application.

1‧‧‧taper angle (θ)

2‧‧‧Photoresist pattern

3‧‧‧ substrate

FIG. 1 is a schematic diagram of measuring a taper angle of a photoresist pattern.

Claims (12)

A chemically amplified positive photosensitive resin composition, comprising: a polyhydroxystyrene resin (A) containing an acid dissociative protective group; a monounsaturated nitrile compound (B); a photoacid generator (C); and a solvent ( D). The chemically amplified positive photosensitive resin composition according to item 1 of the scope of the patent application, wherein the number of carbon atoms of the monounsaturated nitrile compound (B) is 6 to 30. The chemically amplified positive photosensitive resin composition according to item 1 of the scope of the patent application, wherein the monounsaturated nitrile compound (B) is selected from the group consisting of decenenitrile, decenedinitrile, undecenenitrile, and ten Dicarbonenenitrile, tridecenenitrile, tetradecenenitrile, hexadecenenitrile, hexadecadienenitrile, octadecenenitrile, octadecenenitrile, and At least one of the groups of compounds. The chemically amplified positive-type photosensitive resin composition according to item 1 of the scope of patent application, which further includes a basic compound (E). The chemically amplified positive photosensitive resin composition according to item 4 of the scope of the patent application, wherein the basic compound (E) includes a compound represented by the formula (E-1): N (A) _z (B ) _3-z formula (E-1) In formula (E-1), A each independently represents an alkyl group having 4 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and 6 to 20 carbon atoms. Phenyl or aralkyl; B each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; z represents an integer of 1 to 3; The chemically amplified positive photosensitive resin composition according to item 1 of the scope of the patent application, further comprising: a heterocyclic compound (F) having a nitrogen atom, selected from the following formula (F-1) to formula (F- 4) The group of compounds shown: Formula (F-1) Formula (F-2) Formula (F-3) Formula (F-4) In formulas (F-1) to (F-4), G ₁ and G ₂ each independently represent a hydrogen atom, a fluorenyl group, or an alkyl group; H ₁ to H ₉ each independently represent hydrogen Atom, hydroxy, carboxylic, sulfonic, alkyl, amine, halogen, or mercapto; w, v, q, and s each independently represent an integer from 0 to 3; p and r each independently represent 0 to 2 An integer of 0; and t and u each independently represent an integer of 0 to 4. The chemically amplified positive photosensitive resin composition according to item 1 of the scope of the patent application, wherein the total amount of the polyhydroxystyrene resin (A) containing the acid-dissociable protective group is 100 parts by weight. The content of the monounsaturated nitrile compound (B) is 0.03 to 1.0 part by weight, the content of the photoacid generator (C) is 0.3 to 3 parts by weight, and the content of the solvent (D) is 200. Parts by weight to 1200 parts by weight. The chemically amplified positive-type photosensitive resin composition according to item 4 of the scope of the patent application, wherein the total amount of the polyhydroxystyrene resin (A) containing the acid-dissociable protective group is 100 parts by weight. The content of the basic compound (E) is 0.03 parts by weight to 1.0 part by weight. The chemically amplified positive photosensitive resin composition according to item 6 of the scope of the patent application, wherein the total amount of the polyhydroxystyrene resin (A) containing the acid-dissociable protective group is 100 parts by weight. The content of the heterocyclic compound (F) having a nitrogen atom is 0.01 to 0.5 parts by weight. A method for forming a photoresist pattern includes the step of coating a substrate with a chemically amplified positive photosensitive resin composition according to any one of claims 1 to 9 of a patent application scope on a substrate. A photoresist pattern is formed by the method for forming a photoresist pattern according to item 10 of the scope of patent application. An electronic device includes the photoresist pattern according to item 11 of the scope of patent application.