CN109557764B - Chemically amplified positive photosensitive resin composition, resist pattern, method for forming the same, and electronic device - Google Patents

Chemically amplified positive photosensitive resin composition, resist pattern, method for forming the same, and electronic device Download PDF

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CN109557764B
CN109557764B CN201811092392.3A CN201811092392A CN109557764B CN 109557764 B CN109557764 B CN 109557764B CN 201811092392 A CN201811092392 A CN 201811092392A CN 109557764 B CN109557764 B CN 109557764B
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group
resin composition
photosensitive resin
positive photosensitive
chemically amplified
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CN109557764A (en
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许智航
刘骐铭
施俊安
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Chi Mei Corp
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Chi Mei Corp
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists

Abstract

The invention provides a chemical amplification type positive photosensitive resin composition, a photoresist pattern, a forming method thereof and an electronic device, wherein the chemical amplification type positive photosensitive resin composition comprises the following components: polyhydroxystyrene resin (A) containing an acid dissociable protecting group; monounsaturated nitrile compound (B); photoacid generator (C); and a solvent (D) which can improve the problems of poor adhesion and taper angle by using the chemically amplified positive photosensitive resin composition.

Description

Chemically amplified positive photosensitive resin composition, resist pattern, method for forming the same, and electronic device
Technical Field
The present invention relates to a chemically amplified positive photosensitive resin composition, a resist pattern, a method of forming the same, and an electronic device, and more particularly, to a chemically amplified positive photosensitive resin composition capable of improving problems of adhesion and a taper angle, a resist pattern made of the same, a method of forming the same, and an electronic device including the same.
Background
Conventionally, in the field of manufacturing liquid crystal display devices using glass substrates, positive resist compositions containing a phenol resin as an alkali-soluble resin and a quinone diazide compound as a photosensitive component have been widely used as resist materials suitable for g, h, and i line exposure, low in cost, good in sensitivity and resolution, and capable of forming a resist pattern excellent in shape (patent documents 1 to 4).
At present, as a next-generation LCD, a technology of forming an integrated circuit portion such as a driver, a digital-to-analog converter (DAC), an image processing device, a video controller, and a RAM, and a display portion, that is, a high-function LCD called a "system LCD", on one glass substrate at the same time has been actively developed.
In this specification, for convenience, a substrate on which an 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 which replaces amorphous silicon and can be formed by a low-temperature process below 600 ℃ is low-temperature polysilicone, and compared with amorphous silicon, the low-temperature polysilicone has small resistance and high mobility. Accordingly, it is desirable for industry to develop photoresist compositions suitable for manufacturing system LCDs using low temperature polysilicones. Various types of photoresist materials used in conventional system LCDs are reported (patent documents 5 to 12).
In the case of manufacturing a TFT made of low-temperature polysilicon, after a polysilicon film is formed on a glass substrate by a low-temperature process, P (phosphorus), B (boron), or the like is implanted into the low-temperature polysilicon film, and it is necessary to implant a very high concentration of impurities in a so-called "implantation step".
The injection process is performed under a high vacuum condition in a state that a photoresist pattern is formed on a low temperature polysilicone glass substrate. However, in this process, the shape of the resist pattern on the substrate is changed by the heat generation effect of the impurity implantation, and some components in the resist pattern are vaporized during heating, so that the vacuum degree in the processing chamber is lowered.
A method for solving this problem is effective in that a heat treatment process called "post baking" is performed before the injection process. The "post baking" is performed under a temperature condition close to the heating temperature at the time of injection (for example, a high temperature of 200 ℃ or higher), and therefore the resist material needs to have a high heat resistance property that does not change the pattern shape during the heating treatment.
Therefore, in order to realize the production of the system LCD, it is necessary to provide a photoresist composition having excellent heat resistance.
Further, in the system LCD, for example, the pattern size with respect to the display portion is 2 to 10 μm, and the integrated circuit portion is formed in a fine size of 0.5 to 2.0 μm. Therefore, in addition to the capability (linearity) of simultaneously forming fine patterns and coarse patterns having good shapes, a photoresist composition used for manufacturing a system LCD is required to have higher resolution and good depth of focus (DOF) characteristics than those of a photoresist material used for manufacturing an LCD in the past.
However, in the field of manufacturing liquid crystal display devices, it is desirable to improve the problems of poor adhesion and taper angle because the adhesion and taper angle of a photoresist pattern formed from a positive photoresist composition used in conventional system LCDs are poor, which tends to cause serious productivity degradation.
[ patent literature ]
Patent document 1: japanese patent laid-open No. 2000-131835
Patent document 2: japanese patent laid-open No. 2001-075272
Patent document 3: japanese patent laid-open No. 2000-181055
Patent document 4: japanese patent laid-open No. 2000-112120
Patent document 5: japanese patent application laid-open No. 2004-23386
Patent document 6: japanese patent application laid-open No. 2004-191394
Patent document 7: japanese patent application laid-open No. 2004-145207
Patent document 8: japanese patent application laid-open No. 2004-144905
Patent document 9: japanese patent laid-open No. 2004-077999
Patent document 10: japanese patent laid-open No. 2004-045707
Patent document 11: japanese patent laid-open No. 2004-045618
Patent document 12: japanese patent laid-open publication No. 2003-233674
Disclosure of Invention
In view of the above, the present invention provides a chemically amplified positive photosensitive resin composition, which can improve the problems of poor adhesion and taper angle.
The present invention provides a chemically amplified positive photosensitive resin composition, comprising: an acid dissociable protective group-containing polyhydroxystyrene resin (A), a monounsaturated nitrile compound (B), a photoacid generator (C), and a solvent (D).
In one embodiment of the present invention, the monounsaturated nitrile compound (B) has 6 to 30 carbon atoms.
In one embodiment of the present invention, the monounsaturated nitrile compound (B) is selected from decenenitrile
(Deceneitrile), decendinitrile, undecylenic nitrile (Undecenitrile), dodecenenitrile
(Dodecenitrile), tridecenonitrile (Tridecenonitrile), tetradecenenitrile (Tetradecenenitrile), hexadecenenitrile (Hexadecenenitrile), hexadecenedinitrile, octadeceneitrile (octadienitrile), octadecenedinitrile and doconenitrile (Eruconitrile).
In one embodiment of the present invention, the chemically amplified positive photosensitive resin composition further comprises an alkaline compound (E).
In one embodiment of the present invention, the basic compound (E) includes a compound represented by the formula (E-1):
N(A) z (B) 3-z (E-1)
In the 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, a phenyl group having 6 to 20 carbon atoms, or an aralkyl group. 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.
In one embodiment of the present invention, the chemically amplified positive photosensitive resin composition further comprises a heterocyclic compound (F) having a nitrogen atom, which is selected from the group consisting of compounds represented by the following formulas (F-1) to (F-4):
In the formulae (F-1) to (F-4), G 1 G (G) 2 Each independently represents a hydrogen atom, an acyl group or an alkyl group; h 1 To H 9 Each independently represents 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. v, w, q and s each independently represent an integer of 0 to 3; p and r are each independentlyRepresents an integer of 0 to 2; and t and u each independently represent an integer of 0 to 4.
In one embodiment of the present invention, the monounsaturated nitrile compound (B) is used in an amount of 0.03 to 1.0 parts by weight, the photoacid generator (C) is used in an amount of 0.3 to 3 parts by weight, and the solvent (D) is used in an amount of 200 to 1200 parts by weight, based on 100 parts by weight of the total polyhydroxystyrene resin (a) containing an acid dissociable protecting group.
In one embodiment of the present invention, the basic compound (E) is used in an amount of 0.03 to 1.0 parts by weight based on 100 parts by weight of the total amount of the polyhydroxystyrene resin (A) containing an acid dissociable protecting group.
In one embodiment of the present invention, the heterocyclic compound (F) having a nitrogen atom is used in an amount of 0.01 to 0.5 parts by weight based on 100 parts by weight of the total amount of the polyhydroxystyrene resin (a) containing an acid dissociable protecting group.
The invention also provides a method for forming a photoresist pattern, comprising the following steps: and a step of coating the chemically amplified positive photosensitive resin composition on a substrate.
The invention further provides a photoresist pattern formed by the method for forming the photoresist pattern.
The invention also provides an electronic device comprising the photoresist pattern.
Based on the above, the chemically amplified positive photosensitive resin composition of the present invention contains the polyhydroxystyrene resin (a) containing an acid dissociable protecting group and the monounsaturated nitrile compound (B), and thus the problems of poor adhesion and a poor taper angle can be improved.
In order to make the above features and advantages of the present invention more comprehensible, embodiments accompanied with figures are described in detail below.
Drawings
FIG. 1 is a schematic diagram of measuring the taper angle of a photoresist pattern.
[ description of the symbols ]
1: taper angle (theta)
2: photoresist pattern
3: substrate board
Detailed Description
< chemically amplified positive photosensitive resin composition >
The present invention provides a chemically amplified positive photosensitive resin composition, comprising: an acid dissociable protective group-containing polyhydroxystyrene resin (A), 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 contain a basic compound (E) or a heterocyclic compound (F) having a nitrogen atom.
The components of the chemically amplified positive photosensitive resin composition used in the present invention will be described in detail below.
It is to be noted that the following is the expression of acrylic acid and/or methacrylic acid in terms of (meth) acrylic acid, and acrylic acid ester and/or methacrylic acid ester in terms of (meth) acrylic acid ester; similarly, acryl and/or methacryl is represented by (meth) acryl.
Polyhydroxystyrene resin (A) containing an acid dissociable protecting group
Among the polyhydroxystyrene resins (a) containing an acid dissociable protecting group, polyhydroxystyrene resins (before protection) are those containing a polymer made of hydroxystyrene (hydroxystyrene alone polymer) and its derivatives. Such polyhydroxystyrenes are for example: a separate polymer of vinylphenol, a copolymer of vinylphenol and a copolymerizable monomer therewith, and the like. Here, the comonomer is, for example: and styrene derivatives such as (meth) acrylic acid derivatives, (meth) acrylonitrile, styrene, α -methylstyrene, p-methylstyrene, o-methylstyrene, p-methoxystyrene, and p-chlorostyrene. Among the polyhydroxystyrenes, hydroxystyrene alone polymer and hydroxystyrene-styrene copolymer are preferable.
In the polyhydroxystyrene resin (A) containing an acid dissociable protecting group, at least a part of hydrogen atoms of the total phenolic hydroxyl groups are substituted with the acid dissociable protecting group, and the resin (A) is not alkali-soluble or alkali-insoluble, and the acid dissociable protecting group dissociates from the phenolic hydroxyl groups to become alkali-soluble.
The polyhydroxystyrene resin (a) containing an acid dissociable protecting group can be obtained by reacting a polyhydroxystyrene resin (polyhydroxystyrene resin before protection) having no acid dissociable protecting group with a compound corresponding to the acid dissociable protecting group.
In addition, hydroxystyrene also includes derivatives thereof. A specific hydroxystyrene repeating unit is represented by the following formula (A-1):
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 straight or branched alkyl group having 1 to 5 carbon atoms, preferably a methyl group), preferably a hydrogen atom. The position of the hydroxyl group may be any of ortho-position, meta-position and para-position, and is preferably para-position, since it is easily available and inexpensive.
In the hydroxystyrene-styrene copolymer, styrene includes styrene in which a benzene ring is not substituted with an alkyl group and a compound in which a benzene ring is substituted with a lower alkyl group having 1 to 5 carbon atoms. The number of lower alkyl groups of the substituents is 1 to 3.
The acid dissociable protecting group in the polyhydroxystyrene resin (a) containing an acid dissociable protecting group may be any one that can be dissociated by an acid generated by a photoacid generator (C) described later, for example: alkoxyalkyl groups such as 1-ethoxymethyl, 1-ethoxyethyl, 1-propoxymethyl, 1-propoxyethyl, 1-n-butoxymethyl, 1-isobutoxymethyl and 1-t-butoxymethyl; an alkoxycarbonylalkyl group such as a t-butoxycarbonyl group, a t-butoxycarbonylmethyl group and a t-butoxycarbonylethyl group; a tetrahydrofuranyl group; tetrahydropyranyl; a linear or branched acetal group; cyclic acetal groups; trialkylsilyl groups such as trimethylsilyl, triethylsilyl and triphenylsilyl.
The weight average molecular weight (Mw) of the polyhydroxystyrene resin before the protection is preferably in the range of 1,000 ～ 200,000, more preferably 2,000 to 50,000, and most preferably 3,000 to 30,000.
When the polyhydroxystyrene resin (a) containing an acid dissociable protecting group is not contained in the chemically amplified positive photosensitive resin composition, the taper angle of the resist pattern formed by the chemically amplified positive photosensitive resin composition is not good.
Monounsaturated nitrile compound (B)
The monounsaturated nitrile compound (B) used in the present invention is not limited as long as it can improve the adhesion and taper angle of a resist pattern formed from the chemically amplified positive photosensitive resin composition, and its kind is, for example: acrylonitrile (Acrylonitrile), butenenitrile (Butenitrile), butenedinitrile, pentenenitrile
(Pentendinitriles), glutaronitriles, hexenenitriles (hexenelitriles), hexenedinitriles, heptenenitriles
(Heptenenitrile), heptenedinitrile, octenenitrile (Octenonitile), octenedinitrile, nonenenitrile
(Nonenitrile), nonenenitrile, decenonitrile (Decenitrile), decendinitrile, undecylenic nitrile (Undecenitrile), dodecenenitrile (Dodecinitrile), tridecenenitrile (Tridecinitrile), tetradecenenitrile (Tetradecinitrile), hexadecenenitrile (Hexadecinitrile), hexadecenedinitrile, octadecenenitrile (Octa Decenenitrile), octadecendinitrile (Eruconitrile).
The monounsaturated nitrile compound (B) can be further exemplified by: 2-butenenitrile, 3-butenenitrile, 2-butenedinitrile, 2-pentenenitrile, 3-pentenenitrile, 4-pentenenitrile, 5-hexenenitrile, -hexenedinitrile, 6-heptenedinitrile, 3-heptenedinitrile, 6-octenedinitrile, 3-octenedinitrile, 4-octenedinitrile, 2-nonenenitrile, 6-nonenenitrile, 9-decenenitrile, 10-undecenenitrile, 11-dodecenenitrile, 12-dodecenenitrile, 2-tridecenenitrile, 12-tridecenenitrile, 7-tetradecenenitrile, 13-tetradecenenitrile, 3-hexadecenenitrile, 4-hexadecenenitrile, 15-hexadecenenitrile, 6-hexadecenedinitrile, 9-octadecendinitrile, 13-docosenenitrile.
The number of carbon atoms of the monounsaturated nitrile compound (B) is preferably 6 to 30, more preferably 10 to 22.
Preferred examples of the monounsaturated nitrile compound (B) are 9-decenonitrile, 10-undecylenenitrile, 11-dodecenenitrile, 12-dodecenenitrile, 2-tridecenenitrile, 12-tridecenenitrile, 7-tetradecenenitrile, 13-tetradecenenitrile, 3-hexadecenenitrile, 4-hexadecenenitrile, 15-hexadecenenitrile, 6-hexadecenedinitrile, 9-octadecenenitrile, 9-octadecenodinitrile and 13-docosenenitrile.
When the monounsaturated nitrile compound (B) is not contained in the chemically amplified positive photosensitive resin composition, the adhesion and taper angle of the resist pattern formed by the chemically amplified positive photosensitive resin composition are poor.
When the monounsaturated nitrile compound (B) is contained in the chemically amplified positive photosensitive resin composition and the number of carbon atoms of the monounsaturated nitrile compound (B) is 6 to 30, the adhesion and taper angle of the resist pattern formed by the chemically amplified positive photosensitive resin composition are preferable.
The monounsaturated nitrile compound (B) is used in an amount of 0.03 to 1.0 parts by weight, preferably 0.04 to 0.9 parts by weight, more preferably 0.05 to 0.8 parts by weight, based on 100 parts by weight of the total amount of the polyhydroxystyrene resin (a) containing an acid dissociable protecting group.
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 directly or indirectly generate an acid by light. The photoacid generator (C) is preferably an acid generator of the first to fifth modes described below. Hereinafter, preferred photoacid generators (C) suitable for use in the photosensitive resin composition will be described in the first to fifth modes.
The first form of the photoacid generator (C) includes a compound represented by the following formula (C-1):
in the 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 brackets. W (W) 1 Is equal to X 1 The bonded organic group 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, an alkenyl group having 2 to 30 carbon atoms, or an alkynyl group having 2 to 30 carbon atoms, W 1 At least 1 substitution selected from the group consisting of alkyl, hydroxy, alkoxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, arylthiocarbonyl, acyloxy, arylthio, alkylthio, aryl, heterocycle, aryloxy, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, alkyleneoxy, amino, cyano, nitro, and halogen. W (W) 1 The number of (C) is g+h (g-1) +1, W 1 May be the same or different from each other, respectively. And more than 2W 1 Can be directly bonded to each other, or via-O-, -S-, -SO 2 -、-NH-、-NW 2 -, -CO-, -COO-; -CONH-; an alkylene group having 1 to 3 carbon atoms or phenylene bonding to form a polymer containing X 1 Is a ring structure of (a). W (W) 2 Is an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms.
X 2 The structure is represented by the following formula (C-1 a):
in the formula (C-1 a), X 4 Represents an alkylene group having 1 to 8 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a 2-valent hetero group having 8 to 20 carbon atoms, X 4 At least 1 substitution selected from the group consisting of 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, a nitro group, and a halogen. X is X 5 represents-O-, -S-, -SO-, -SO 2 -、-NH-、-NW 2 -, -CO-, -COO-; -CONH-; an alkylene group having 1 to 3 carbon atoms, or a phenylene group. h represents the number of repeating units of the structure in brackets. h+1X 4 H X 5 May be the same or different, respectively. W (W) 2 Is the same as defined above.
(X 3 ) - Examples of onium counter ions include fluoroalkyl fluorophosphoric acid anions represented by the following formula (C-1 b) and borate anions represented by the following formula (C-1C):
[(W 3 ) j PF 6-j ] - (C-1 b)
In the formula (C-1 b), W 3 More than 80% of hydrogen atoms are substituted by fluorine atoms. j represents the number of the two, and is an integer from 1 to 5. j W 3 May be the same or different, respectively.
In the formula (C-1C), W 4 ～W 7 Each independently represents a fluorine atom or a phenyl group, and a part or all of hydrogen atoms in the phenyl group may be substituted by at least 1 selected from the group consisting of a fluorine atom and a trifluoromethyl group.
Examples of onium ions in the compound represented by the formula (C-1) include triphenylsulfide, tri-p-tolylthio, 4- (phenylthio) phenyldiphenylsulfide, bis [4- (diphenylthio) phenyl ] sulfide, bis [4- { bis [4- (2-hydroxyethoxy) phenyl ] thio } phenyl ] sulfide, bis {4- [ bis (4-fluorophenyl) thio ] phenyl } sulfide, 4- (4-benzoyl-2-chlorophenyl) phenylbis (4-fluorophenyl) sulfide, 7-isopropyl-9-oxo-10-thia-9, 10-dihydro-anthracene-2-yldi-p-tolylthio, 7-isopropyl-9-oxo-10-thia-9, 10-dihydro anthracene-2-yldiphenylsulfide, 2- [ (diphenyl) thio ] thioxanthone, 4- [4- (4-tert-butylbenzoyl) phenylthio ] phenyl di-p-tolylthio, 4- (4-benzoylphenylthio) phenylthio, diphenyl sulfide, 4-acetyl-2-phenylthio, 4-methylphenyl-4- (4-methylbenzoyl) biphenyl, 4-phenylthio ] biphenyl, 4-acetyl-2-phenylthio-4- (4-methylbenzoyl) biphenyl-2-phenylthio) biphenyl, 4- (4-methylbenzoyl) thio) biphenyl-2-phenylthio-p-phenylthio [4- (4-Acetylphenylthio) phenyl ] diphenylthio, octadecyl methylphenylacetylthio, diphenyliodo, di-p-tolylidine, bis (4-dodecylphenyl) iodo, bis (4-methoxyphenyl) iodo, (4-octyloxyphenyl) phenyliodo, bis (4-dodecyloxy) phenyliodo, 4- (2-hydroxytetradecyloxy) phenylphenyliodo, 4-isopropylphenyl (p-tolyl) iodo, or 4-isobutylphenyl (p-tolyl) iodo, and the like.
Among the onium ions in the compound represented by the above formula (C-1), preferred onium ions include sulfide ions represented by the following formula (C-1 d):
in the formula (C-1 d), W 8 Each independently represents a group selected from the group consisting of a hydrogen atom, an alkyl group, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an alkylcarbonyloxy group, an alkoxycarbonyl group, a halogen atom, an optionally substituted aryl group, and an arylcarbonyl group. X is X 2 X in the formula (C-1) 2 The same meaning.
Specific examples of the sulfide ion represented by the above formula (C-1 d) include 4- (phenylthio) phenyldiphenylsulfide, 4- (4-benzoyl-2-chlorophenylthio) phenylbis (4-fluorophenyl) sulfide, 4- (4-benzoylphenylthio) phenyldiphenylsulfide, phenyl [4- (4-biphenylthio) phenyl ] 4-biphenylsulfide, phenyl [4- (4-biphenylthio) phenyl ] 3-biphenylsulfide, [4- (4-acetylphenylthio) phenyl ] diphenylsulfide, and diphenyl [4- (p-triphenylthio) phenyl ] diphenylsulfide.
W in the fluoroalkyl fluorophosphate anion represented by the above formula (C-1 b) 3 Represents an alkyl group substituted with a fluorine atom, preferably having 1 to 8 carbon atoms, more preferably having 1 to 4 carbon atoms. Specific examples of the alkyl group include a linear alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and an octyl group; branched alkyl groups such as isopropyl, isobutyl, secondary butyl, tertiary butyl and the like; further, the ratio of substitution of hydrogen atoms of the alkyl group with fluorine atoms is usually 80% or more, preferably 90% or more, more preferably 100% or more. When the substitution rate of fluorine atoms is less than 80%, the acid strength of the onium fluoroalkyl fluorophosphate represented by the above formula (C-1) is lowered.
Extra goodW of (2) 3 A linear or branched perfluoroalkyl group having 1 to 4 carbon atoms and a fluorine atom substitution rate of 100%, and examples thereof 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。W 3 The number j of (2) is an integer of 1 to 5, preferably 2 to 4, particularly preferably 2 or 3.
As specific examples of preferred fluoroalkyl fluorophosphoric acid anions, [ (CF) may be mentioned 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 ] - Of 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 a preferred specific example of the borate anion represented by the above formula (C-1C), tetrakis (pentafluorophenyl) borate ([ B (C) 6 F 5 ) 4 ] - ) Tetrakis [ (trifluoromethyl) phenyl ]]Borate ([ B (C) 6 H 4 CF 3 ) 4 ] - ) Difluoro bis (pentafluorophenyl) borate ([ (C) 6 F 5 ) 2 BF 2 ] - ) Trifluoro (pentafluorophenyl) borate ([ (C) 6 F 5 )BF 3 ] - ) Tetrakis (difluorophenyl) borate ([ B (C) 6 H 3 F 2 ) 4 ] - ) Etc. Of these, particularly preferred is tetrakis (pentafluorophenyl) borate ([ B (C) 6 F 5 ) 4 ] - )。
Examples of the second form of the photoacid generator (C) include 2, 4-bis (trichloromethyl) -6-piperonyl-1, 3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (2-furyl) vinyl ] symmetrical triazine, 2, 4-bis (trichloromethyl) -6- [2- (5-methyl-2-furyl) vinyl ] symmetrical triazine, 2, 4-bis (trichloromethyl) -6- [2- (5-ethyl-2-furyl) vinyl ] symmetrical triazine, 2, 4-bis (trichloromethyl) -6- [2- (5-propyl-2-furyl) vinyl ] symmetrical triazine, 2, 4-bis (trichloromethyl) -6- [2- (3, 5-dimethoxyphenyl) vinyl ] symmetrical triazine, 2, 4-bis (trichloromethyl) -6- [2- (3, 5-diethoxyphenyl) vinyl ] symmetrical triazine, 2, 4-bis (trichloromethyl) -6- [2- (3, 5-dipropoxyphenyl) vinyl ] symmetrical triazine, 2, 4-bis (trichloromethyl) -6- [2- (3, 5-dimethoxyphenyl) vinyl ] symmetrical triazine, and 2, 4-bis (trichloromethyl) -6- [2- (3, 5-dimethoxyphenyl) vinyl ] symmetrical triazine 2, 4-bis (trichloromethyl) -6- [2- (3-methoxy-5-propoxyphenyl) vinyl ] symmetrical triazine, 2, 4-bis (trichloromethyl) -6- [2- (3, 4-methylenedioxyphenyl) vinyl ] symmetrical triazine, 2, 4-bis (trichloromethyl) -6- (3, 4-methylenedioxyphenyl) symmetrical triazine, 2, 4-bis-trichloromethyl-6- (3-bromo-4-methoxy) phenyl symmetrical triazine, 2, 4-bis-trichloromethyl-6- (2-bromo-4-methoxy) styrylphenyl symmetrical triazine, 2, 4-bis-trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl symmetrical triazine, 2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) room-round-door-plate
Halogen-containing triazine compounds represented by the following formula (2-bromopropyl) and the like, such as 1,3, 5-triazine, 2- (4-methoxynaphthyl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine, 2- [2- (2-furyl) vinyl ] -4, 6-bis (trichloromethyl) -1,3, 5-triazine, 2- [2- (5-methyl-2-furyl) vinyl ] -4, 6-bis (trichloromethyl) -1,3, 5-triazine, 2- [2- (3, 5-dimethoxyphenyl) vinyl ] -4, 6-bis (trichloromethyl) -1,3, 5-triazine, 2- (3, 4-methylenedioxyphenyl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine, tris (1, 3-dibromopropyl) -1,3, 5-triazine, tris (2, 3-dibromopropyl) -1,3, 5-triazine, and the like, and tris (2, 3-bromopropyl) triazine compounds.
In the formula (C-2), W 9 ～W 11 Each independently represents a haloalkyl group.
Further, examples of the tertiary form of the photoacid generator (C) include α - (p-toluenesulfonyloxy imino) -phenylacetonitrile, α - (benzenesulfonyloxy imino) -2, 4-dichlorophenylacetonitrile, α - (benzenesulfonyloxy imino) -2, 6-dichlorophenylacetonitrile, α - (2-chlorobenzyloxy imino) -4-methoxyphenylacetonitrile, α - (ethylsulfonyloxy imino) -1-chloropentenylacetonitrile, and a compound represented by the following formula (C-3) containing a sulfonic acid oxime group.
In the formula (C-3), W 12 Represents a 1-valent, 2-valent or 3-valent organic group, W 13 Represents a substituted or unsubstituted saturated hydrocarbon group, unsaturated hydrocarbon group, or aromatic compound group, and n represents the number of repeating units of the structure in brackets.
In the above formula (C-3), the aromatic compound group means that the aromatic compound exhibits unique physical and chemical propertiesExamples of the radical of the compound include aryl radicals such as phenyl and naphthyl, and heteroaryl radicals such as furyl and thienyl. These may have 1 or more suitable substituents on the ring, for example, halogen atom, alkyl group, alkoxy group, nitro group, etc. Also, W 13 Particularly preferred is an alkyl group having 1 to 6 carbon atoms, and examples thereof include methyl, ethyl, propyl and butyl. Especially W 12 Is an aromatic compound group, W 13 The compound is preferably an alkyl group having 1 to 4 carbon atoms.
As the acid generator represented by the above formula (C-3), when n=1, W is exemplified 12 Is any one of phenyl, methylphenyl and methoxyphenyl, W 13 Specific examples of the methyl group include α - (methylsulfonyloxyimino) -1-phenylacetonitrile, α - (methylsulfonyloxyimino) -1- (p-methylphenyl) acetonitrile, α - (methylsulfonyloxyimino) -1- (p-methoxyphenyl) acetonitrile, and [2- (propylsulfonyloxyimino) -2, 3-dihydroxythiophen-3-ylidene ](o-tolyl) acetonitrile, and the like. When n=2, specific examples of the acid generator represented by the above formula (C-3) include acid generators represented by the following formulas (C-3-1) to (C-3-8):
in addition, as a fourth form of the photoacid generator (C), an onium salt having a naphthalene ring in a cation portion is exemplified. The term "having naphthalene ring" means having a naphthalene-derived structure, meaning a structure of at least 2 rings, and can maintain their aromaticity. The naphthalene ring may have a substituent 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, or the like. The structure derived from the naphthalene ring may be a 1-valent group (free valence is 1), or may be a 2-valent group (free valence is 2) or more, and is preferably a 1-valent group (in this case, the free valence is calculated by subtracting the bond with the substituent). The number of naphthalene rings is preferably 1 to 3.
As the cation moiety of such an onium salt having a naphthalene ring, a structure represented by the following formula (C-4) is preferable:
in the formula (C-4), W 14 ～W 16 At least 1 of them represents a group represented by the following formula (C-4 a), and the others represent a linear or branched alkyl group having 1 to 6 carbon atoms, 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, W 14 ～W 16 One of them is a group represented by the following formula (C-4 a), and the other two are each independently a C atom number W 14 ～W 16 Straight-chain or branched alkylene groups, the terminal ends of which may be bonded to form a ring.
In the formula (C-4 a), W 17 、W 18 Independently represent a hydroxyl group, a linear or branched alkoxy group having 1 to 6 carbon atoms, or a linear or branched alkyl group having 1 to 6 carbon atoms, 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 independently represent an integer of 0 to 2, and l+m is 3 or less. When W is 17 Where plural are present, they may be the same or different from each other. When W is 18 Where plural are present, they may be the same or different from each other.
The above W 14 ～W 16 In the case where the number of groups represented by the above formula (C-4 a) is preferably 1 from the viewpoint of stability of the compound, the remainder is a linear or branched alkylene group having 1 to 6 carbon atoms, and these terminals may be bonded to form a ring. In this case, the 2 alkylene groups may contain a sulfur atom to form a 3-to 9-membered ring. The number of atoms constituting the ring (sulfur-containing atoms) is preferably5～6。
Examples of the substituent that the 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 that the phenyl group may have include a hydroxyl group, a linear or branched alkoxy group having 1 to 6 carbon atoms, a linear or branched alkyl group having 1 to 6 carbon atoms, and the like.
As those cation moieties, those represented by the following formulas (C-4 b) and (C-4C) are preferable, and those represented by the following formula (C-4C) are particularly preferable.
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As such cationic moieties, there may be iodine salts or sulfur salts; the sulfur salt is preferable from the viewpoint of acid production efficiency and the like.
Thus, anions capable of forming a sulfur salt are preferable for the anion portion of the onium salt having a naphthalene ring as the cation portion.
The anionic portion of such an acid generator is a fluoroalkylsulfonic acid ion or an arylsulfonic acid ion in which a part or all of hydrogen atoms are fluorinated.
The alkyl group in the fluoroalkyl sulfonic acid ion may be linear, branched or cyclic having 1 to 20 carbon atoms, and is preferably 1 to 10 carbon atoms based on the volume size of the acid to be generated and the diffusion distance thereof. Particularly branched or annular ones are preferable because of a short diffusion distance. Further, from the viewpoint of inexpensive synthesis, methyl, ethyl, propyl, butyl, octyl, and the like are preferable.
The aryl group in the arylsulfonic acid ion is an aryl group having 6 to 20 carbon atoms, and examples thereof include phenyl and naphthyl groups which may be substituted with an alkyl group or a halogen atom. In particular, an aryl group having 6 to 10 carbon atoms is preferable from the viewpoint of being synthesized at low cost. Specific examples of preferred examples include phenyl, tosyl, ethylphenyl, naphthyl, methylnaphthyl, and the like.
Among the above-mentioned fluoroalkyl sulfonic acid ions or aryl sulfonic acid ions, the fluorination ratio when part or all of the hydrogen atoms are fluorinated is preferably 10 to 100%, more preferably 50 to 100%, and particularly, the fluorine atoms are substituted for all of the hydrogen atoms, and the strength of the acid is preferably enhanced. Specific examples of such compounds include trifluoromethanesulfonate, perfluorobutanesulfonate, perfluorooctanesulfonate, and perfluorobenzenesulfonate.
Of these, preferable anionic moieties are those represented by the following formula (C-4 d):
W 20 SO 3 - (C-4 d)
In the formula (C-4 d), W 20 The groups represented by the following formulas (C-4 e), (C-4 f) and (C-4 g).
-C x F 2x+1 (C-4 e)
In the formula (C-4 e), x represents an integer of 1 to 4. In the formula (C-4 f), 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 alkoxy group having 1 to 6 carbon atoms, and y represents an integer of 1 to 3. Of these, trifluoromethanesulfonate and perfluorobutanesulfonate are preferable from the viewpoint of safety.
As the anion moiety, those having nitrogen represented by the following formulas (C-4 h) and (C-4 i) may be used.
In the formula (C-4 h) and the formula (C-4 i), X a Represents a linear or branched alkylene group having at least 1 hydrogen atom substituted with a fluorine atom, and the number of carbon atoms of the alkylene group is 2 to 6, preferably 3 to 5, and most preferably 3. Also, Y a 、Z a Each independently represents a linear or branched alkyl group having at least 1 hydrogen atom substituted with a fluorine atom, and the number of carbon atoms of the alkyl group is 1 to 10, preferably 1 to 7, more preferably 1 to 3.
X a Or the number of carbon atoms of the alkylene group of Y a 、Z a The smaller the number of carbon atoms of the alkyl group, the better the solubility in the organic solvent, and thus, is preferable.
Also, X a Alkylene or Y of (2) a 、Z a The more the number of hydrogen atoms substituted with fluorine atoms, the stronger the acid strength, and thus is preferred. The ratio 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%, most preferably a perfluoroalkylene group or perfluoroalkyl group in which all hydrogen atoms are substituted with fluorine atoms.
As onium salts having naphthalene ring in such cation moiety, compounds represented by the following formulas (C-4 j) and (C-4 k) are suitable:
further, as the fifth form of the photoacid generator (C), there may be mentioned bissulfonyldiazomethane such as bis (p-toluenesulfonyl) diazomethane, bis (1, 1-dimethylethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, and bis (2, 4-dimethylphenylsulfonyl) diazomethane; nitrobenzyl derivatives such as 2-nitrobenzyl p-toluenesulfonate, 2, 6-dinitrobenzyl p-toluenesulfonate, nitrobenzyl toluene sulfonate, dinitrobenzyl toluene sulfonate, nitrobenzyl carbonate and dinitrobenzyl carbonate; sulfonic acid esters such as trimellitic acid ester, phenylmethyl tosylate, phenylmethyl sulfonate, N-methanesulfonyloxy succinimide, N-trichloromethylsulfonyloxy succinimide, N-phenylsulfonyloxy maleimide, and N-methanesulfonyloxy phthalimide; triflates such as N-hydroxyphthalimide and N-hydroxynaphthalimide; onium salts such as diphenyliodohexafluorophosphate, (4-methoxyphenyl) phenyliodotrifluoromethanesulfonate, bis (p-tert-butylphenyl) iodotrifluoromethanesulfonate, triphenylthiohexafluorophosphate, (4-methoxyphenyl) diphenylthiotrifluoromethanesulfonate, and (p-tert-butylphenyl) diphenylthiotrifluoromethanesulfonate; benzoin tosylate such as benzoin tosylate and α -methyl benzoin tosylate; other diphenyliodonium salts, triphenylsulfonium salts, phenyldiazonium salts, benzyl carbonate, and the like.
The photoacid generator (C) may be used alone or in combination of 2 or more. The photoacid generator (C) is used in an amount of 0.3 to 3 parts by weight, preferably 0.4 to 2.8 parts by weight, more preferably 0.5 to 2.5 parts by weight, based on 100 parts by weight of the total polyhydroxystyrene resin (a) containing an acid dissociable protecting group.
Solvent (D)
The solvent (D) is not particularly limited as long as it is used in the chemically amplified positive photosensitive resin composition. For example, an ester solvent, a non-ester solvent, and the like.
Examples of the ester solvents include propylene glycol monoalkyl ether acetate [ e.g., propylene Glycol Monomethyl Ether Acetate (PGMEA), ethyl 3-ethoxypropionate, and lactate (e.g., ethyl lactate).
Examples of the non-ester solvents include ketones, polyvalent alcohols, derivatives thereof, cyclic ethers, and the like.
Examples of the ketones include acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, and 2-heptanone. Examples of the polyvalent alcohols and derivatives thereof include ethylene glycol, propylene glycol, diethylene glycol, and monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, dimethyl ether, diethylene glycol dimethyl ether, and monophenyl ether thereof. Examples of cyclic ethers include dioxane.
The solvent may be used alone or in combination of two or more.
The chemically amplified positive photosensitive resin composition of the present invention preferably contains at least one selected from propylene glycol monoalkyl ether acetate and 2-heptanone in order to improve storage stability and to ensure stable film coating properties.
The solvent (D) is used in an amount of 200 to 1200 parts by weight, preferably 200 to 1100 parts by weight, more preferably 250 to 1000 parts by weight, based on 100 parts by weight of the total polyhydroxystyrene resin (a) containing an acid dissociable protecting group.
Basic compound (E)
The basic compound (E) is not particularly limited as long as it has compatibility with the chemically amplified positive photosensitive resin composition, and there are compounds described in JP-A-9-006001, for example.
The basic compound (E) preferably includes a compound represented by the formula (E-1):
N(A) z (B) 3-z (E-1)
In the 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, a phenyl group having 6 to 20 carbon atoms, or an aralkyl group;
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 compound represented by the formula (E-1) is preferably a compound in which z is 2 or 3 and the groups represented by X are each the same.
When the carbon number of the alkyl group as the group A is less than 4, it is difficult to improve the stability of the resist with time. The carbon number is further 5 or more, particularly 8 or more. The upper limit is not particularly limited, but is preferably 20 or less, more preferably 15 or less, from the viewpoint of confirming the effect of stabilization with time or commercially available products. When the alkali strength exceeds 20, the alkali strength is lowered, and the effect of storage stability is lowered.
The alkyl group may be linear or branched. Specifically, for example, n-decyl, n-octyl, n-pentyl and the like are preferable.
Among cycloalkyl groups as group A, cycloalkyl groups having 4 to 8 carbon atoms are commercially available, and have excellent effect of improving stability with time, and are suitable. Cyclohexyl having 6 carbon atoms is more preferable.
As the aralkyl group of the group A, a group represented by the formula (E-1 a):
Q-P type (E-1 a)
In the formula (E-1 a), Q represents an alkylene group; p represents an aromatic hydrocarbon group.
As the group P, phenyl, naphthyl and the like are exemplified, with phenyl being preferred. As the alkylene group of the group Q, it is sufficient that the carbon number is 1 or more, and preferably 1 to 3.
As the aralkyl group of the group A, for example, benzyl, phenylethyl and the like are preferable.
The alkyl group as the group B may be a straight chain or branched one. Particularly, methyl and ethyl are preferable.
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 the group B, the group B is preferably an alkyl group.
Specifically, examples of the compound represented by the formula (E-1) include tri-N-decylamine, methyldi-N-octylamine, tri-N-pentylamine, N-dicyclohexylmethylamine, and tribenzylamine.
The basic compound (E) may be used alone or in combination of two or more. The basic compound (E) is used in an amount of 0.03 to 1.0 parts by weight, preferably 0.04 to 0.8 parts by weight, more preferably 0.05 to 0.5 parts by weight, based on 100 parts by weight of the total polyhydroxystyrene resin (A) containing an acid dissociable protecting group.
When the chemically amplified positive photosensitive resin composition further contains the basic compound (E), the taper angle of the resist pattern formed by the chemically amplified positive photosensitive resin composition can be further improved.
Heterocyclic Compound having Nitrogen atom (F)
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 formulas (F-1) to (F-4):
In the formulae (F-1) to (F-4), G 1 G (G) 2 Each independently represents a hydrogen atom, an acyl group or an alkyl group; h 1 To H 9 Each independently represents 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; w, v, q and s each independently represent an integer of 0 to 3; p and r each independently represent 0 toAn integer of 2; and t and u each independently represent an integer of 0 to 4.
In the formulae (F-1) to (F-4), G 1 And G 2 Each independently represents a hydrogen atom, an acyl group or an alkyl group. Specifically, G 1 And G 2 Preferably, an acyl group having 2 to 4 carbon atoms or an alkyl group having 1 to 3 carbon atoms is used. The acyl group having 2 to 4 carbon atoms may include, but is not limited to, acetyl (acetyl group), propionyl (propionyl group) or butyryl (butyryl group). The alkyl group having 1 to 3 carbon atoms may include, but is not limited to, methyl, ethyl, isopropyl (i-propyl group) or n-propyl (n-propyl group).
H as described above 1 To H 9 Each independently represents 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 When alkyl, H 1 To H 9 Preferably, it may be an alkyl group having 1 to 3 carbon atoms (e.g., methyl, ethyl, isopropyl or n-propyl); when H is 1 To H 9 In the case of halogen atoms, the H 1 To H 9 Preferably, it may be a chlorine atom, a bromine atom or an iodine atom. When H is 1 To H 9 In the case of an amine group, the hydrogen atom to which the amine group is bonded may be substituted with 1 or 2 alkyl groups having 1 to 3 carbon atoms (for example, methyl, ethyl, isopropyl or n-propyl). In addition, H 1 To H 9 An alkyl group having 1 to 3 carbon atoms and an amino group (for example, aminomethyl group, aminoethyl group, aminoisopropyl group or aminon-propyl group) is also possible.
When w, v, p, q, r and s are greater than or equal to 2, a plurality of H 1 、H 2 、H 4 、H 5 、H 6 H and H 7 Each of which may be the same or different.
The heterocyclic compound (F) having nitrogen atom may include, but is not limited to, 6-methyl-8-hydroxyquinine (6-methyl-8-hydroxyquinine), 6-ethyl-8-hydroxyquinine (6-methyl-8-hydroxyquinine), 5-methyl-8-hydroxyquinine (5-methyl-8-hydroxyquinine), 8-hydroxyquinine (8-hydroxyquinine), 8-acetoxyquinine (8-acetyloxy quinoline), 4-hydroxyppteridine (4-hydroxy pteridine), 2,4-dihydroxypteridine (2, 4-dihydroxypteridine) 4-hydroxypteridine-2-sulfonic acid (4-hydroxypteridine-2-sulfonic acid), 2-ethyl-4-hydroxypteridine (2-methyl-4-hydroxypteridine), 2-methyl-4-hydroxypteridine (2-methyl-4-hydroxy pteridine), 2-Amino-6, 7-dimethyl-4-hydroxypteridine (2-Amino-6, 7-dimethyl-4-hydroxy pteridine), 1,10-phenanthroline (1, 10-phenanthrene), 5,6-dimethyl-1,10-phenanthroline (5, 6-dimethyl-1, 10-phenanthrene), 3,8-dimethyl-1, 10-phenanthrene (3, 8-dimethyl-1, 10-phenanthrene), and combinations thereof, 3,8-dihydroxy-1,10-phenanthroline (3, 8-dihydroxy-1, 10-phenanthroline), 5-carboxy-1,10-phenanthroline (5-carboxy-1, 10-phenanthroline), 5,6-dihydroxy-1,10-phenanthroline (5, 6-dihydroxy-1, 10-phenanthroline), 1,10-phenanthroline-5-sulfonic acid (1, 10-phenanthroline-5-sulfonic acid), 4' -dimethyl-2,2' -bipyridine (4, 4' -dimethyl-2,2' -bipyridine), 2' -bipyridine (2, 2' -bipyridine), 2' -bipyridine-5-carboxylic acid (2, 2' -bipyridine-5-carbolic acid), 5' -dichloro-2,2' -bipyridine (5, 5' -bipyridine-5-sulfonic acid), 3, 2' -bipyridine (3, 3' -bipyridine) or a combination of any of these (3, 2, 3' -bipyridine-3, 2' -bipyridine). The heterocyclic compound (F) having a nitrogen atom may be used singly or in combination of plural kinds.
Preferably, the heterocyclic compound (F) having a nitrogen atom may be 8-hydroxyquinine, 8-acetoxyquinine, 4-hydroxyppteridine, 2, 4-dihydroxypteridine, 1, 10-phenanthroline, 5, 6-dimethyl-1, 10-phenanthroline, 2 '-bipyridine, 2' -bipyridine-5-carboxylic acid, or a combination of the above compounds.
The heterocyclic compound having a nitrogen atom (F) may be used in an amount of 0.01 to 0.5 parts by weight, preferably 0.01 to 0.4 parts by weight, and more preferably 0.02 to 0.3 parts by weight, based on 100 parts by weight of the total amount of the polyhydroxystyrene resin (a) having an acid dissociable protecting group.
When the chemically amplified positive photosensitive resin composition of the present invention contains the heterocyclic compound (F) having a nitrogen atom, the resist pattern produced from the chemically amplified positive photosensitive resin composition has better adhesion.
Additive (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 impaired, and the additive (G) may be used alone or in combination of two or more thereof, depending on the actual need. The details of the additive (G) are described below.
The chemically amplified positive photosensitive resin composition may further contain a polyethylene resin as an additive (G) for improving the plasticity. Specific examples of the polyethylene resin include polyvinyl chloride, polystyrene, polyhydroxystyrene, polyvinyl acetate, polyvinyl benzoic acid, polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl phenol, and copolymers thereof. Polyethylene resins are preferably polyethylene methyl ether, based on a low glass transition point.
In addition, the chemically amplified positive photosensitive resin composition may further contain an adhesion promoter as an additive (G) for improving adhesion between a template formed using the photosensitive resin composition and a metal substrate.
The chemically amplified positive photosensitive resin composition may further contain a surfactant as an additive (G) for improving coatability, defoaming property, leveling property, and the like. Specific examples of the surfactant include commercially available fluorine-based surfactants such as BM-1000, BM-1100 (both manufactured by BM Chue Co., ltd.), MEGAFACE F D, MEGAFACE F PA, MEGAFACE F173, MEGAFACE F183 (both manufactured by DIC Co., ltd.), FLUORAD FC-135, FLUORAD FC-170C, FLUORAD FC-430, FLUORAD FC-431 (both manufactured by Sumitomo 3M Co., ltd.), SURFLON S-112, SURFLON S-113, SURFLON S-131, SURFLON S-141, SURFLON S-145 (both manufactured by Asahi Nitro Corp.), SH-28PA, SH-190, SH-193, SZ-6032, SF-8428 (both manufactured by Toray Silicone Co., ltd.), but are not limited thereto.
In addition, the chemically amplified positive photosensitive resin composition may further contain an acid, an acid anhydride, or a high boiling point solvent as an additive (G) for fine adjustment of solubility in a developer.
Specific examples of the acid and the acid anhydride include monocarboxylic acids such as acetic acid, propionic acid, n-butyric acid, isobutyric acid, n-valeric acid, isovaleric acid, benzoic acid, cinnamic acid, and the like; hydroxy monocarboxylic acids such as lactic acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 2-hydroxy cinnamic acid, 3-hydroxy cinnamic acid, 4-hydroxy cinnamic acid, 5-hydroxy isophthalic acid, and syringic acid; polycarboxylic acids such as 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-cyclohexanedicarboxylic acid, butanetetracarboxylic acid, trimellitic acid, pyromellitic acid, cyclopentanetetracarboxylic acid, butanetetracarboxylic acid, and 1,2,5, 8-naphthalene tetracarboxylic acid; anhydride such as itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, propane tricarboxylic anhydride, maleic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, humic anhydride, 1,2,3, 4-butanetetracarboxylic anhydride, cyclopentane tetracarboxylic dianhydride, phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol ditrimellitic anhydride, glycerol trimellitic anhydride, and the like; etc.
Specific examples of the high boiling point solvent include N-methylformamide, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzyl ether, dihexyl ether, acetylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, gamma-butyrolactone, ethylene carbonate, propylene carbonate, phenylsirtuin acetate, and the like.
The chemically amplified positive photosensitive resin composition may further contain a sensitizer as an additive (G) for improving sensitivity.
< method for producing chemically amplified positive photosensitive resin composition >
The method for producing the chemically amplified positive photosensitive resin composition is not particularly limited, and the above-mentioned components may be mixed and stirred in a usual manner. Examples of the apparatus that can be used for mixing and stirring the above-mentioned components include a dissolver, a homogenizer, a three-roll mill, and the like. After the above components are uniformly mixed, the resulting mixture may be further filtered by 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, and the method for forming a photoresist pattern of the present invention will be described below.
First, the chemically amplified positive photosensitive resin composition of the present invention is applied to a substrate by a rotator or the like to form a coating film.
The substrate is preferably a glass substrate provided with a silicon film. In general, amorphous silicon is used for forming a silicon film, and in the field of system LCDs, low-temperature polysilicon is preferable. Further, a large substrate of 300mm×400mm or more, particularly 550mm×650mm or more may be used.
Then, the substrate on which the coating film is formed is subjected to a heat treatment (prebaking) at, for example, 90 to 140 ℃ to remove the residual solvent, thereby forming a photoresist coating film. The method of heat treatment (pre-baking) is preferably a Proximity baking (Proximity bak) heating method having a gap between the heating plate and the substrate.
Then, the resist film is selectively exposed using a mask that depicts both a mask pattern for an integrated circuit and a mask 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). The exposure process used in the exposure is an exposure process under a low NA condition having an NA of 0.3 or less, preferably 0.2 or less, and more preferably 0.15 or less. By adopting the exposure process under the low NA condition, the exposure area of one time can be enlarged, and the productivity can be improved.
Subsequently, the selectively exposed resist film is subjected to a heat treatment (post-exposure baking). The post-exposure baking method comprises the following steps: proximity baking (Proximity baking) with a gap between the heating plate and the substrate, direct baking (Direct baking) without a gap, and the like. Among them, in order to obtain a diffusion effect of post-exposure baking without causing warpage of the substrate, a method of performing direct baking after performing adjacent baking is preferable. Here, the heating temperature is 90 to 150℃and more preferably 100 to 140 ℃.
Then, the resist film after the post-exposure baking is developed with a developer, for example, an aqueous alkali solution of 1 to 10 mass% tetramethyl ammonium hydroxide, and the exposed portion is dissolved and removed, and a resist pattern for an integrated circuit and a resist pattern for a liquid crystal display portion are formed on the substrate.
Then, the developer remaining on the surface of the resist pattern is washed with a rinse solution such as pure water, whereby the resist pattern can be formed.
In the step of performing the selective exposure, it is preferable to use a mask which is used to form a resist pattern having a thickness of 2.0 μm or less and a mask which is used to form a resist pattern having a thickness of more than 2.0 μm as the mask.
The chemically amplified positive photosensitive resin composition of the present invention has excellent linearity, so that a resist pattern that faithfully reproduces a coarse pattern and a fine pattern of a mask pattern can be obtained. Therefore, a resist pattern for an integrated circuit having a pattern size of 2.0 μm or less and a resist pattern for a liquid crystal display portion having a pattern size exceeding 2.0 μm can be formed simultaneously on a substrate.
< example >
Synthesis example of polyhydroxystyrene resin (A) containing acid dissociable protecting group
Synthesis examples A-1 to A-6 and comparative Synthesis example A' -1 of polyhydroxystyrene resin (A) having an acid dissociable protecting group are described below:
synthesis example A-1
After 120 parts by weight of polyhydroxystyrene resin having a weight average molecular weight of 13,000 was dissolved in 680 parts by weight of N, N-dimethylacetamide, 42.3 parts by weight of 1-chloro-ethoxyethane was added to a four-necked flask, and the above mixed solution was slowly stirred until complete dissolution. Then, 78.8 parts by weight of triethylamine was added dropwise through an addition funnel at a rate of about 30 minutes, and the reaction was carried out for 3 hours. After the completion of the reaction, pure water was added in an amount of 20 times the total amount of the above mixed solution to precipitate a polyhydroxystyrene resin containing 1-ethoxyethyl group as an acid dissociable protecting group, and the precipitate was washed with pure water, dehydrated and dried to obtain a polyhydroxystyrene resin (A-1) containing 1-ethoxyethyl group as an acid dissociable protecting group, the substitution rate of the hydrogen atoms of the phenolic hydroxyl groups of which was 39 mol%.
Synthesis examples A-2 to A-3
Synthesis examples A-2 to A-3 were prepared in the same procedure as in Synthesis example A-1, and they were different in that: the weight average molecular weight of the polyhydroxystyrene resin used and the substitution rate of the hydrogen atoms of the phenolic hydroxyl groups thereof were changed (as shown in Table 1).
Synthesis example A-4
120 parts by weight of polyhydroxystyrene resin having a weight average molecular weight of 13,000 was added to 680 parts by weight of N, N-dimethylacetamide to dissolve, and then 85 parts by weight of di-t-butyl dicarbonate was added to a four-necked flask, and the above mixed solution was slowly stirred until complete dissolution. Then, 59 parts by weight of triethylamine was added dropwise through an addition funnel at a rate of about 15 minutes, and the reaction was carried out for 3 hours. After the completion of the reaction, pure water was added in an amount of 20 times the total amount of the above mixed solution to precipitate a polyhydroxystyrene resin containing a t-butoxycarbonyl group as an acid dissociable protecting group, and the precipitate was washed with pure water, dehydrated and dried to obtain a polyhydroxystyrene resin (A-4) containing a t-butoxycarbonyl group as an acid dissociable protecting group, the substitution rate of the hydrogen atom of the phenolic hydroxyl group of which was 39 mol%.
Synthesis examples A-5 to A-6
Synthesis examples A-5 to A-6 were prepared in the same procedure as in Synthesis example A-1, and they were different in that: the weight average molecular weight of the polyhydroxystyrene resin used and the substitution rate of the hydrogen atoms of the phenolic hydroxyl groups thereof were changed (as shown in Table 1).
Comparative Synthesis example A' -1
In a three-necked flask having a volume of 1000 ml and equipped with a cooling tube, 120 parts by weight of 4-hydroxystyrene was added to 480 parts by weight of tetrahydrofuran to dissolve, and then the above-mentioned mixed solution was slowly stirred until dissolved. Next, 2' -azobis-2-isopropyl butyronitrile (AIBN) was charged into a three-necked flask to conduct polymerization, and the reaction temperature was maintained at 75℃throughout the polymerization. After the completion of the polymerization, the polymerization product was taken out from the four-necked flask and the solvent was removed to obtain a polyhydroxystyrene resin (A' -1) having no acid dissociable protecting group and having a weight average molecular weight of 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 the polyhydroxystyrene resin (A-1) having an acid dissociable protective group obtained in Synthesis example A-1, 0.03 part by weight of 9-decenonitrile (abbreviated as B-1), and 2.5 parts by weight of a photoacid generator (C-1) were added to 350 parts by weight of propylene glycol monomethyl ether acetate (abbreviated as D-1), and the mixture was dissolved and mixed with a shaker, whereby a chemically amplified positive photosensitive resin composition was prepared, which was evaluated in the following measurement and evaluation methods, and the obtained results are shown in Table 2.
Examples 2 to 13
Examples 2 to 13 were conducted by the same method as that for producing the chemically amplified positive photosensitive resin composition of example 1, except that the types and amounts of the raw materials in the chemically amplified positive photosensitive resin compositions were changed in examples 2 to 13, and the formulations and the following evaluation results were shown in tables 2 or 3.
Comparative examples 1 to 3
Comparative examples 1 to 3 were conducted by the same method as that for producing the chemically amplified positive photosensitive resin composition of example 1, except that the types and amounts of the raw materials in the chemically amplified positive photosensitive resin compositions were changed in comparative examples 1 to 3, and the formulations and the following evaluation results are shown in table 3.
The compounds corresponding to the numbers in tables 2 to 3 are shown below.
/>
TABLE 2
TABLE 3
Evaluation method
Adhesion to
The chemically amplified positive photosensitive resin compositions of examples and comparative examples were applied to an ITO substrate (100 mm. Times.100 mm) using a resist coater (device name: TR36000, manufactured by Tokyo applied Industrial Co., ltd.) and then pre-baked at 110℃for 90 seconds under heating conditions with a gap of about 1mm to form a resist film having a thickness of 1.5. Mu.m. Next, an i-line exposure apparatus (apparatus name: FX-702J, manufactured by Nikon Corp., NA=0.14) and L were used &Test pattern of S (line and space) photoresist at 100mJ/cm 2 Exposing the pre-baked coating film to ultraviolet light. After exposure, post-exposure bake (PEB) was performed by near heating at 110 ℃ for 90 seconds with a gap of 0.5 mm. Next, development treatment was performed for 41 seconds using a 23 ℃ 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) to remove the coating film of the exposed portion on the glass substrate. Finally, rinsing with pure water for 15 seconds, and recording the developed pattern on the glass substrateDevelopable line width on the plate. The evaluation criteria for the developable line width are shown below, wherein the smaller the developable line width, the better the adhesion at the time of development, and the specific evaluation criteria are as follows:
and (3) the following materials: developable line width is less than or equal to 5 mu m
O: 5 μm < developable linewidth < 10 μm-
Delta: 10 μm < developable linewidth < 20 μm-
X: developable linewidth >20 μm
Taper angle
Referring to fig. 1, fig. 1 is a schematic diagram of measuring a taper angle of a photoresist pattern. Post-baking the developed photoresist at 130 ℃ for 150 seconds, and observing the cross-sectional shape; the taper angle 1 is an angle (angle shown as θ in the figure) between the substrate 3 and the photoresist pattern 2, and its specific evaluation criteria are as follows:
And (3) the following materials: the angle of taper is 80 degrees or less and 90 degrees or less
O: the angle of the taper is less than or equal to 70 degrees and less than 80 degrees or 90 degrees and less than or equal to 100 degrees
Delta: the angle of the taper is less than or equal to 60 degrees and less than 70 degrees or 100 degrees and less than or equal to 110 degrees
X: the angle of the taper is less than 60 degrees or 110 degrees
Evaluation results
As is clear from tables 2 and 3, the taper angle of the chemically amplified positive photosensitive resin compositions (comparative examples 1 and 3) that did not include the polyhydroxystyrene resin (a) having an acid dissociable protecting group was evaluated to be inferior to the resist patterns obtained from the chemically amplified positive photosensitive resin compositions (examples 1 to 13) that included the polyhydroxystyrene resin (a) having an acid dissociable protecting group and the monounsaturated nitrile compound (B); and even when the composition contains the polyhydroxystyrene resin (A) having an acid dissociable protecting group, the composition does not contain the monounsaturated nitrile compound (B) having a specific structure, the adhesion and taper angle evaluation are not good (comparative example 2).
In addition, in the chemically amplified positive photosensitive resin composition, the adhesion and the taper angle were evaluated more favorably when the number of carbon atoms of the monounsaturated nitrile compound (B) was 6 to 30 (examples 1 to 11, 13) than when the number of carbon atoms of the monounsaturated nitrile compound (B) was 5 (example 12).
Further, when the chemically amplified positive photosensitive resin composition further comprises the basic compound (E) (examples 4 to 8, 11 and 13), the taper angle is evaluated more favorably.
Further, when the chemically amplified positive photosensitive resin composition further comprises a heterocyclic compound (F) having a nitrogen atom (examples 5 to 9, 11 and 13), the adhesion property is evaluated more preferably.
As described above, the chemically amplified positive photosensitive resin composition of the present invention contains the polyhydroxystyrene resin (a) containing an acid dissociable protecting group and the monounsaturated nitrile compound (B), and thus can improve the problems of poor adhesion and a poor taper angle.
On the other hand, in the chemically amplified positive photosensitive resin composition of the present invention, when the number of carbon atoms of the monounsaturated nitrile compound (B) is 6 to 30, the adhesion and the taper angle are more preferably evaluated.
On the other hand, when the alkali compound (E) is further contained in the chemically amplified positive photosensitive resin composition of the present invention, the taper angle is evaluated more favorably; further, when the chemically amplified positive photosensitive resin composition of the present invention further contains a heterocyclic compound (F) having a nitrogen atom, the adhesion property is evaluated more preferably.
Although the invention has been described with reference to the above embodiments, it should be understood that the invention is not limited thereto, but rather may be modified and practiced by those skilled in the art without departing from the spirit and scope of the present invention.

Claims (10)

1. A chemically amplified positive photosensitive resin composition, characterized by comprising:
polyhydroxystyrene resin (A) containing an acid dissociable protecting group;
monounsaturated nitrile compound (B);
photoacid generator (C); and
the solvent (D),
the monounsaturated nitrile compound (B) is at least one selected from the group consisting of decenonitrile, decendinitrile, undecylenic nitrile, dodecenenitrile, tridecenenitrile, tetradecylenic nitrile, hexadecylenic nitrile, hexadecenedinitrile, octadecenenitrile, octadecenedinitrile and docosenoic nitrile,
the monounsaturated nitrile compound (B) is used in an amount of 0.03 to 1.0 parts by weight based on 100 parts by weight of the total amount of the polyhydroxystyrene resin (a) containing an acid dissociable protecting group.
2. The chemically amplified positive photosensitive resin composition according to claim 1, further comprising an alkaline compound (E).
3. The chemically amplified positive photosensitive resin composition according to claim 2, wherein the basic compound (E) comprises a compound represented by formula (E-1):
N(A) z (B) 3-z (E-1)
In the 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, a phenyl group having 6 to 20 carbon atoms, or an aralkyl group;
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.
4. The chemically amplified positive photosensitive resin composition according to claim 1, further comprising:
a heterocyclic compound (F) having a nitrogen atom, selected from the group consisting of compounds represented by the following formulas (F-1) to (F-4):
in the formulae (F-1) to (F-4), G 1 G (G) 2 Each independently represents a hydrogen atom, an acyl group or an alkyl group; h 1 To H 9 Each independently represents 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; w, v, q and s each independently represent an integer of 0 to 3; p and r each independently represent an integer of 0 to 2; and t and u each independently represent an integer of 0 to 4.
5. The chemically amplified positive photosensitive resin composition according to claim 1, wherein the photoacid generator (C) is used in an amount of 0.3 to 3 parts by weight and the solvent (D) is used in an amount of 200 to 1200 parts by weight based on 100 parts by weight of the total amount of the polyhydroxystyrene resin (a) containing an acid dissociable protecting group.
6. The chemically amplified positive photosensitive resin composition according to claim 2, wherein the basic compound (E) is used in an amount of 0.03 to 1.0 parts by weight based on 100 parts by weight of the total usage of the polyhydroxystyrene resin (a) containing an acid dissociable protecting group.
7. The chemically amplified positive photosensitive resin composition according to claim 4, wherein the heterocyclic compound (F) having a nitrogen atom is used in an amount of 0.01 to 0.5 parts by weight based on 100 parts by weight of the total usage of the polyhydroxystyrene resin (a) having an acid dissociable protecting group.
8. A method for forming a photoresist pattern includes:
a step of applying the chemically amplified positive photosensitive resin composition according to any one of claims 1 to 7 on a substrate.
9. A photoresist pattern formed by the method for forming a photoresist pattern according to claim 8.
10. An electronic device comprising the photoresist pattern of claim 9.
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