WO2007046442A1 - Novel compound, acid generator, chemical amplification type photoresist composition, resist layer laminate and method of forming resist pattern - Google Patents

Abstract

A compound that exhibits high absorption in the long wavelength region of 365 nm or greater and exhibits high sensitivity in the long wavelength region of 365 nm or greater, excelling in solubility in organic solvents; an acid generator consisting of the compound; a chemical amplification type photoresist composition containing the acid generator; and making use of the chemical amplification type photoresist composition, a resist layer laminate and method of forming a resist pattern. The compound is any of those represented by the general formula (B1). In the formula (B1), at least one of R1, R2 and R3 is any of groups of the formula (B1a). In the formula (B1a), Y is a group of aromatic ring devoid of two hydrogen atoms, the aromatic ring optionally having a substituent; Z is a group of aromatic ring devoid of one hydrogen atom, the aromatic ring optionally having a substituent; and the aromatic ring of at least one of Y and Z has at least one alkoxy.

Description

 Novel compound, acid generator, chemically amplified photoresist composition, resist layer stack, and resist pattern forming method

 Technical field

 [0001] The present invention relates to a novel compound, an acid generator, a chemically amplified photoresist composition, a resist layer laminate, and a resist pattern forming method.

 This application claims priority based on Japanese Patent Application No. 2005-303926 filed in Japan on October 19, 2005 and Japanese Patent Application No. 2005-304123 filed in Japan on October 19, 2005. The contents thereof are incorporated herein.

 Background art

 [0002] Currently, it is the mainstream of precision microfabrication technology! / Photophoto application is the application of a photosensitive resin composition such as photoresist to the surface of a workpiece to form a coating film, which is a photolithography technology. This is a generic term for technologies for manufacturing various precision parts such as semiconductor packages by patterning the coating film by using the mask as a mask and performing chemical etching, electrolytic etching, and elect mouth forming mainly consisting of Z or electrical plating. .

 In recent years, with the downsizing of electronic equipment, high-density mounting technology for semiconductor packages has progressed. Based on the multi-pin thin film mounting of the knocker, the smaller size of the knocker, the 2D mounting technology using the flip chip method, and the 3D mounting technology. The mounting density has been improved. In such high-density mounting technology, as connection terminals, for example, protruding electrodes (mounting terminals) such as bumps protruding on the package, or metal posts that connect the rewiring extending from the peripheral terminals on the wafer and the mounting terminals. Are placed on the board with high accuracy.

The connection terminals are formed by, for example, forming a resist layer made of a photoresist on a support, exposing through a predetermined mask pattern, developing, and selectively removing (peeling off) portions where connection terminals are to be formed. After the resist pattern is formed, a conductor such as copper is buried in the removed portion (non-resist portion) by plating, and the surrounding resist pattern is removed. Currently, in the formation of connection terminals, the resist pattern is mainly formed using a photopolymerizable photosensitive resin composition as described in Patent Documents 1 to 3, for example, as a photoresist. It is performed using light in a long wavelength region, for example, light in the ultraviolet region such as g-line (436 nm), h-line (405 nm), i-line (365 nm).

[0003] On the other hand, as one of the high-resolution resist materials that can reproduce resist patterns with fine dimensions, a base resin that changes in alkali solubility due to the action of acid and acid is generated by irradiation (exposure) A chemically amplified photoresist containing a compound (acid generator) is known.

 The feature of chemically amplified photoresist is that the acid generator absorbs the irradiated radiation to generate an acid, and the acid generated from the acid generator causes an acid-catalyzed reaction to the base resin in the photoresist. , Changing its alkali solubility. Chemically amplified photoresists are classified into positive types that are alkali-insoluble when exposed to radiation and negative types that are alkali-insoluble when alkali-soluble.

 Acid generators used in chemically amplified photoresists include sulfo-acid salt acid generators, onium salt-based acid generators such as iodine salt-based acid generators, oxime sulfonate-based acid generators, Various proposals such as imidosulfonate acid generators have been made. Among these, onium salt-based acid generators use photons with wavelengths shorter than those of i-line, such as KrF excimer laser (248 nm) and ArF excimer laser (193 nm). It is currently most commonly used because of its high sensitivity in lithography.

 Patent Document 1: Japanese Patent Laid-Open No. 10-207057

 Patent Document 2: JP 2000-39709 A

 Patent Document 3: Japanese Patent Laid-Open No. 2000-66386

 Disclosure of the invention

 Problems to be solved by the invention

[0004] However, the form salt acid generator hardly absorbs in a long wavelength region of 365 nm or more. Therefore, in photo-applications in the long wavelength region of 365 nm or more, the present situation is that chemically amplified photoresists using an acid salt-based acid generator have low sensitivity and cannot be practically used. In addition, as the cation of the acid salt-based acid generator, a highly hydrophobic cation such as trisulfolsulfum is generally used, but an onium having a strong cation. The salt-based acid generator also has a problem of low solubility in an organic solvent (resist solvent) used for dissolving various components of the resist. Such low solubility in a resist solvent reduces the temporal stability of the resist, and accordingly causes a bad pattern pattern.

 For this reason, the present situation is that chemically amplified photoresists using an acid salt-based acid generator as an acid generator cannot be used practically for photo applications in the long wavelength region of 365 nm or more.

 The present invention has been made in view of the above circumstances, and exhibits high absorption in a long wavelength region of 365 nm or more and excellent solubility in an organic solvent having high sensitivity in a long wavelength region of 365 nm or more. It is an object to provide a compound, an acid generator comprising the compound, a chemically amplified photoresist composition containing the acid generator, a resist layer laminate using the chemically amplified photoresist composition, and a method for forming a resist pattern. And

 The present invention also includes a sulfo salt salt acid generator as an acid generator and high sensitivity in a long wavelength region of 365 nm or more, a chemically amplified photoresist composition, and the chemically amplified photoresist composition. It is another object of the present invention to provide a resist layer laminate and a resist pattern forming method using the above.

 Means for solving the problem

As a result of intensive studies, the present inventors have found that the above problems can be solved by a compound having a specific structure, and have completed the present invention.

 That is, the first aspect of the present invention is a compound represented by the following general formula (B1).

[0006] [Chemical 1]

[In formula (Bl), R \ R ² and R ³ are each independently a group represented by the following general formula (Bla), an alkyl group, or a group obtained by removing one hydrogen atom from an aromatic ring. In addition, the aromatic ring may have a substituent, and at least one of R ² and R ³ is a group represented by the following general formula (Bla); ]

[0007] [Chemical 2]

O

—— γ—— c—— Z ( ^Bla )

[In the formula (Bla), Y is a group obtained by removing two hydrogen atoms from an aromatic ring, and the aromatic ring may have a substituent; Z is a group obtained by removing one hydrogen atom from the aromatic ring. The aromatic ring may have a substituent; the aromatic ring in at least one of Y and Z has at least one alkoxy group. ]

[0008] The second aspect of the present invention is the acid generator having the compound power of the first aspect.

 A third aspect of the present invention is a chemically amplified photoresist composition comprising (a) a resin whose alkali solubility is changed by an acid, and (b) a compound which generates an acid upon irradiation. The (b) compound capable of generating an acid upon irradiation contains the acid generator according to the second aspect, which is a chemically amplified photoresist composition.

 A fourth aspect of the present invention is a resist layer laminate characterized in that a resist layer comprising the chemically amplified photoresist composition of the third aspect is laminated on a support. is there.

 A fifth aspect of the present invention includes a laminating step of laminating a resist layer having a chemically amplified photoresist composition on a support to obtain a resist layer laminate of the fourth aspect, and the resist layer A resist pattern forming method comprising: an exposure step of selectively irradiating a laminate with radiation; and a development step of developing after the exposure step to obtain a resist pattern.

A sixth aspect of the present invention includes (a) a resin whose alkali solubility is changed by an acid, (b) a compound that generates an acid upon irradiation, and (c) the following general formula (C1 ) A chemically amplified photoresist composition characterized in that the compound (b) that generates an acid upon irradiation with radiation contains a sulfonium salt-based acid generator (b-1). .

[0009] [Chemical 3]

[In the formula, R ¹ and R ² is an alkyl group having 1 to 4 carbon atoms, and an IT = R ^2. ]

[0010] Further, according to a seventh aspect of the present invention, there is provided a resist characterized in that a resist layer comprising the chemically amplified photoresist composition of the sixth aspect is laminated on a support. Layer stack.

 An eighth aspect of the present invention includes a laminating step of laminating a resist layer comprising a chemically amplified photoresist composition on a support to obtain a resist layer laminate of the seventh aspect, and the resist A resist pattern forming method comprising: an exposure step of selectively irradiating a layer stack with radiation; and a development step of obtaining a resist pattern by imaging after the exposure step.

 The invention's effect

 [0011] According to the present invention, a compound exhibiting high absorption in a long wavelength region of 365 nm or more, high sensitivity in a long wavelength region of 365 nm or more, and excellent solubility in an organic solvent, an acid comprising the compound It is possible to provide a generator, a chemically amplified photoresist composition containing the acid generator, a resist layer laminate using the chemically amplified photoresist composition, and a method for forming a resist pattern.

[0012] Further, according to the present invention, a chemically amplified photoresist composition containing a sulfo salt salt acid generator as an acid generator and having high sensitivity in a long wavelength region of 365 nm or more, A resist layer laminate using the chemically amplified photoresist composition and a method for forming a resist pattern can be provided. BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail.

 "Compound>>

 The compound of the first aspect of the present invention (hereinafter sometimes referred to as compound (B1)) is represented by the above general formula (B1).

In formula (B1),

R ² and R ³ each independently represent a group represented by the above general formula (Bla), an alkyl group, or a group obtained by removing one hydrogen atom from an aromatic ring. In the “group obtained by removing one hydrogen atom from an aromatic ring”, the aromatic ring may have a substituent.

In the present invention,

At least one of R ² and R ³ needs to be a group represented by the above general formula (Bla). By having the group represented by the formula (Bla), the compound (B1) exhibits sufficient absorption for use as an acid generator in a long wavelength region of 365 nm or longer.

In the formula (Bla), the aromatic ring in Y and Z is not particularly limited, and examples thereof include aromatic rings having a carbon number of S6-18, such as benzene and naphthalene.

 In the present invention, it is necessary to have at least one alkoxy group as an aromatic ring force substituent in at least one of Y and Z. In particular, it is preferred that both aromatic rings in Y and Z have an alkoxy group.

 The alkoxy group is represented by R—O— [R is a linear, branched or cyclic alkyl group]. R is not particularly limited, but is preferably a linear alkyl group, preferably a linear or branched alkyl group. The number of carbon atoms in the alkyl group is preferably 1-12, more preferably 1-4. Specific examples include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.

 The number of alkoxy groups bonded to the aromatic ring is not particularly limited, but for the effect of the present invention, 1 to 3 is preferable, and 1 is particularly preferable.

 The aromatic ring in Y and Z may have a substituent other than an alkoxy group. Examples of the substituent other than the alkoxy group include an alkyl group and a hydroxyl group. The alkyl group is not particularly limited, and examples thereof include a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms.

[0015]! ^ ~ Is not particularly limited as an "alkyl group", for example, a straight chain having 1 to 12 carbon atoms And a branched or cyclic alkyl group. Specifically, methyl group, ethyl group

, N-propyl group, isopropyl group, n-butyl group, isobutyl group, n-pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, nonyl group, and weak group.

 [0016]! The aromatic ring in the “group obtained by removing one hydrogen atom from an aromatic ring” is not particularly limited, and examples thereof include aromatic rings having 6 to 18 carbon atoms such as benzene, naphthalene, and anthracene. ! The aromatic ring in ^ to may have a substituent such as an alkoxy group, an alkyl group, or a hydroxyl group, like the aromatic rings in X and Y above.

 In the present invention, in particular! Aromatic ring strength in the “groups in which one hydrogen atom has been removed from an aromatic ring” in ^ ~. A group in which one hydrogen atom has been removed from benzene or naphthalene, that is, a phenyl group or a naphthyl group is more preferable. More preferably, it is a group.

 [0017] In the formula (B1), it is an anion. X— is not particularly limited, and is any one of those conventionally used in chemically amplified resist compositions and proposed as a key-on in known acid generators! Yo! /

 In the present invention, it is particularly preferred that X— is a fluorinated alkyl sulfonate ion in which at least one of the hydrogen atoms of the alkyl group is substituted with a fluorine atom. Preferably, all of these are perfluoroalkyl sulfonate ions substituted with fluorine atoms.

 The number of carbon atoms of the alkyl group of the fluorinated alkyl sulfonate ion is not particularly limited, but 1 to 12 is preferable and 1 to 4 is more preferable in terms of the bulk of the acid generated and the diffusion length of the acid.

[0018] In the present invention, the effect of the present invention is excellent. ^ ~ One of the general formulas

 It is a group represented by (Bla)! It is preferable that two of ^ ˜ are groups in which one hydrogen atom has been removed from an aromatic ring, particularly phenyl groups.

 [0019] As the compound (B1), a compound represented by the following general formula (B2) is particularly preferable because of excellent effects of the present invention.

[0020] [Chemical 4]

[In the formula (B2), R ⁴ and R ⁵ are each independently an alkyl group, a phenyl group or a naphthyl group; R ⁶ and R ⁷ are each independently an alkoxy group; Is on. [0021] In the formula (B2), as the alkyl group for R ⁴ and R ⁵ ,! Examples of the alkyl group in ^ ˜ are the same as those described above. The phenol group or naphthyl group of R ⁴ and R ⁵ may or may not have a substituent such as an alkoxy group, an alkyl group, or a hydroxyl group.

Examples of the alkoxy group for R ⁶ and R ⁷ are the same as the alkoxy groups mentioned as the substituents for the aromatic ring in Y and Z. The alkoxy group of R ^{6 and} the alkoxy group of R ⁷ may be the same or different.

 Same as above.

[0022] A preferred example of the compound (B1) of the present invention is a compound represented by the following formula () 3).

[0023] [Chemical 5]

The compound (B1) of the present invention is suitably used as an acid generator for a chemically amplified photoresist composition, particularly a chemically amplified photoresist composition for radiation having a wavelength of 365 nm or more. [0025] <Acid generator>

 The acid generator of the second aspect of the present embodiment (hereinafter sometimes referred to as the acid generator (bl)) is also the compound (B1) of the first aspect.

 The acid generator (bl) may be composed of one kind of the compound (B1) or a mixture of two or more kinds of the compound (B1).

<< Chemically Amplified Photoresist Composition >>

 The chemically amplified photoresist composition of the third aspect of the present invention comprises (a) a resin whose alkali solubility is changed by an acid (hereinafter sometimes referred to as (a) component), and (b) an acid upon irradiation. Wherein the component (b) contains the acid generator (bl) of the present invention. It can be negative or positive! /.

[0027] An example of the negative type will be described below.

 (a) Component

 When the chemically amplified photoresist composition is negative, component (a) is a resin whose alkali solubility is lowered by acid, and is generally used as a base resin for negative chemically amplified photoresists. If it is fat, it will not specifically limit, According to the light source used for exposure, it can select and use arbitrarily from a conventionally well-known thing. For example, those containing a novolac resin as a main component are generally widely used because of their good characteristics.

 Particularly preferable examples of the component (a) include those composed of (i) novolac resin, and (one) one or more kinds of resin that also have a polymer power having a hydroxystyrene constituent unit. This is because it is easy to control the coating property and the development speed.

[0028] (i) Novolak rosin (hereinafter referred to as (i) component and! /, U) includes, for example, aromatic compounds having a phenolic hydroxyl group (hereinafter simply referred to as “phenols”) and aldehydes. Can be obtained by addition-condensation in the presence of an acid catalyst.

In this case, the phenols used include, for example, phenol, o-cresol, m-cresol monole, p-creso mono nore, o-ethino leuenore, m-ethino leuenore, p-echi Rufenol, o-Butylphenol, m-Butinolenoenole, p-Butinolenoenore, 2, 3 xylenol, 2, 4 xylenol, 2, 5 xylenol, 2, 6 xylenol, 3, 4 xylenol, 3, 5 xylenol, 2, 3, 5 trimethylphenol, 3, 4, 5 —trimethylphenol, p-phenol Examples include lufenol, resorcinol, hydroquinone, hydroquinone monomethylol ether, pyrogallol, phloroglicinol, hydroxydiphenyl, bisphenol A, gallic acid, gallic acid ester, a naphthol, and β-naphthol.

 Examples of aldehydes include formaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, and acetoaldehyde.

 The catalyst for the addition condensation reaction is not particularly limited. For example, hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetic acid and the like are used as the acid catalyst.

 The novolac coconut resin preferably has a mass average molecular weight of 00000 to 10,000, preferably 6000 to 900, and more preferably 7000 to 8000. When the mass average molecular weight is 300,000 or more, the tendency of the film to decrease (thinner) after development can be sufficiently suppressed, and when the mass average molecular weight is 10,000 or less, residues can be prevented from remaining after development. preferable.

[0029] (Mouth) Polymers having a hydroxystyrene structural unit (hereinafter referred to as (mouth) component! /) Are, for example, hydroxystyrene such as ρ-hydroxystyrene, α-methylhydroxystyrene, _α -ethyl Examples thereof include a radical polymer or an ionic polymer in which only a hydroxystyrene structural unit such as a-alkylhydroxystyrene such as hydroxystyrene is effective, and a copolymer having the above hydroxystyrene structural unit and other structural units. Ratio of hydroxystyrene constituent unit in the polymer is preferably 1 mass _^0/0 or more, more preferably 10 to 30 wt%. This is because when the proportion of the hydroxystyrene structural unit is 10% by mass or more, the developability and resolution tend to be excellent.

 The mass average molecular weight of the (mouth) component is preferably 5000 or less, more preferably 20000 or more and 4000 or less. This is because if the mass average molecular weight is 5000 or less, the resolution tends to be excellent.

[0030] V is preferred as a monomer that forms a structural unit other than the hydroxystyrene structural unit. The monomer V is a monomer obtained by substituting the hydroxyl group of the hydroxystyrene structural unit with another group or an α, β unsaturated double bond. And the like. [0031] As another group that substitutes the hydroxyl group of the hydroxystyrene structural unit, an alkali dissolution inhibiting group that is not dissociated by an acid is used.

 Alkali dissolution inhibiting groups that are not dissociated by acid include substituted or unsubstituted benzenesulfoxy groups, substituted or unsubstituted naphthalenesulfoxy groups, substituted or unsubstituted benzenecarboxoxy groups, substituted or unsubstituted groups. Naphthalenecarboxoxy group, etc., and specific examples of the substituted or unsubstituted benzenesulfonyloxy group include benzenesulfoloxy group, black benzenesulfoloxy group, methylbenzenesulfoloxy group, Ethylbenzenesulfoloxy group, propylbenzenesulfuroxy group, methoxybenzenesulfuroxy group, ethoxybenzenesulfuroxy group, propoxybenzenesulfuroxy group, acetoaminobenzenesulfuroxy group, etc. Or unsubstituted naphthalene sulfo-loxy Specific examples of these include naphthalenesulfuroxy group, chloronaphthalenesulfuroxy group, methylnaphthalenesulfuroxy group, ethylnaphthalenesulfuroxy group, propylnaphthalenesulfuroxy group, methoxynaphthalenesulfuroxy group, ethoxynaphthalenesulfol group. -Luoxy group, propoxynaphthalene sulfo-loxy group, acetoamino naphthalene sulfo-loxy group and the like are preferable. Furthermore, examples of the substituted or unsubstituted benzencarboxoxy group and the substituted or unsubstituted naphthalenecarboxoxy group include those in which the substituted or unsubstituted sulfo-oxy group is replaced with a carbo-oxy group. Among them, acetaminobenzene sulfo-oxy group or anacetoamino naphthalene sulfo-oxy group is preferred.

[0032] Specific examples of monomers having ex and β unsaturated double bonds include styrene monomers such as styrene, chlorostyrene, chloromethyl styrene, butyltoluene, and monomethylol styrene, methyl acrylate, and methacrylic acid. Examples thereof include acrylic acid monomers such as methyl acid and methacrylic acid vinyl, and butyl acetate monomers such as vinyl acetate and benzoic acid butyl, among which styrene is preferable. The resulting copolymers, such as poly (4-hydroxystyrene styrene) copolymer and poly (4-hydroxystyrene-methylstyrene) copolymer, exhibit high resolution and heat resistance. It is also highly suitable. Furthermore, the component (a) can contain other resin components for the purpose of appropriately controlling physical and chemical properties. For example, (c) acrylic resin (hereinafter referred to as component (c)), (2) vinyl resin (hereinafter referred to as component (2)).

 [0033] Component C:

 The component (c) acrylic resin is not particularly limited as long as it is an alkali-soluble acrylic resin, and in particular, a structural unit derived from a polymerizable compound having an ether bond (st ructural unit). , And a constituent unit derived from a polymerizable compound having a carboxyl group.

 Examples of polymerizable compounds having an ether bond include 2-methoxyethyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethyl carbitol (meth) acrylate. Examples include (meth) acrylic acid derivatives having ether bonds and ester bonds such as acrylate, phenoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate. Preferred are 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate. These compounds can be used alone or in combination of two or more.

 Examples of polymerizable compounds having a carboxyl group include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; and 2-methacryloyloxychetyl succinate. Illustrative compounds such as acid, 2-methacryloyloxychetylmaleic acid, 2-methacryloyloxychetylphthalic acid, 2-methacryloyloxychetylhexahydrophthalic acid, and other compounds having an ester bond Acrylic acid and methacrylic acid are preferred. These compounds can be used alone or in combination of two or more.

[0034] Component (2):

 The component (2), butter resin, is poly (bule lower alkyl ether) and is obtained by polymerizing a single or a mixture of two or more vinyl lower alkyl ethers represented by the following general formula (I). (Co) polymer power

[0035] [Chemical 6]

(In the above general formula (I), R ⁶ represents a linear or branched alkyl group having 1 to 5 carbon atoms.)

 [0036] In the general formula (I), examples of the linear or branched alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, an n propyl group, an i propyl group, and an n butyl group. I-butyl group, n-pentyl group, i-pentyl group and the like. Of these alkyl groups, a methyl group, an ethyl group, and an i-butyl group are preferable, and a methyl group and an ethyl group are particularly preferable. In the present invention, particularly preferred poly (vinyl lower alkyl ethers) are poly (butymethyl ether) and poly (butyethyl ether).

 [0037] When the component (a) is made of a mixed resin containing the component (i) and the component (mouth), the sum of the component (i) and the component (port) is 100 parts by mass. ) Component is 50 to 98 parts by mass, preferably 55 to 95 parts by mass, and (mouth) component is 50 to 2 parts by mass, preferably 45 to 5 parts by mass.

 [0038] Component (b)

 In the present invention, the component (b) needs to contain the acid generator (bl) of the present invention. The acid generator (bl) may be used alone or in combination of two or more. Good. In the component (b), the ratio of the acid generator (bl) is preferably 50% by mass or more, more preferably 80 to L00% by mass, and most preferably 100% by mass for the effect of the present invention. %.

[0039] In the present invention, the chemically amplified photoresist composition includes, in addition to the acid generator (bl), a known acid generator (hereinafter referred to as an acid generator (hereinafter referred to as "acid generator")) used in conventional chemically amplified resist compositions. b2) t may be contained).

The acid generator (b2) is not particularly limited as long as it is a compound that generates an acid directly or indirectly by light and is not included in the acid generator (bl). Specifically, 2, 4 —bis (trichloromethyl) 6— [2— (2 furyl) etul] — s triazine, 2, 4 bis (trichloromethyl) —6— [2— (5-methyl-2) Frills) etul] —s triadine, 2 , 4 -Bis (trichloromethyl) 6- [2- (5-ethyl 2-furyl) ether] s Triazine, 2, 4 Bis (trichloromethyl) -6- [2- (5-propyl-2-furyl) ether

1—s triazine, 2, 4-bis (trichloromethyl) 6— [2— (3,5-dimethoxyphenol) ether] — ₅ —triazine, 2,4 bis (trichloromethyl) 6— [ 2— (3, 5 jetoxy) ether] — s triazine, 2, 4 bis (trichloromethyl) 6— [2— (3,

5 dipropoxyphenyl)-s triazine, 2, 4 bis (trichloromethyl) 6- [2— (3-methoxy-5-ethoxyphenyl) ---] trisazine, 2, 4 bis (trichloromethyl) 6— [2— (3-Methoxy-5-propoxyphenyl) ester] — s— Triazine, 2, 4 Bis (trichloromethyl) 6— [2— (3, 4-Methylenedioxyphenyl) Tales] — ₅ — Triazine, 2, 4 Bis (trichloromethyl) 6— (3, 4-Methylenedioxyphenyl) 1 s Triazine, 2, 4 Bis 1 Trichloromethyl 1 6— (3-Bromo 4 methoxy) ) Phenyl-1-striazine, 2,4 bis-trichloromethyl-6- (2 bromo 4-methoxy) Phenyl-1-s triazine, 2, 4 bis-trichloromethyl-1-6- (2 bromo-4 methoxy) styrylphenol s Triazine, 2,4 Bis-trichloromethyl 1-6— (3-Bromo-4-methoxy) styrylphenol s triazine, 2 -— (4-methoxyphenol) 1,4,6-bis (trichloromethyl) 1, 3,5 triazine, 2 -— (4— Methoxynaphthyl) 4, 6 Bis (trichloromethyl) —1, 3, 5 Triazine, 2— [2— (2 Furyl) ether] — 4, 6— Bis (trichloromethyl) 1, 3, 5 Triazine, 2— [2 -— (5-Methyl-2-furyl) ether] —4, 6 Bis (trichloromethyl) -1, 3, 5 Triazine, 2-— [2— (3, 5 Dimethoxyphenyl) ether] — 4 , 6 Bis (trichloromethyl) 1, 3, 5 Triazine, 2— [

2— (3,4 Dimethoxyphenol)] 4,6 bis (trichloromethyl) 1, 3, 5 —triazine, 2— (3,4, methylenedioxyphenyl) 1,4,6 bis (Trichloromethyl) 1, 3, 5 Triazine, Tris (1, 3 Dibromopropyl) 1, 3, 5 Triazine, Tris (2, 3 Dibromopropyl) — 1, 3, 5 Triazine and other halogen-containing triazine compounds and Tris ( 2, 3 dibromopropyl) isocyanurate and other halogen-containing triazine compounds represented by the following general formula (i);

[Chemical 7]

(In the formula (i), the scales ¹ to! ^ Represent the same or different halogenated alkyl groups)

 [0041] α- (ρ-Toluenesulfo-ruximino) -phenylacetonitrile, α- (Benzenesulfonyloximino) — 2,4-dichlorophenylacetonitrile, α— (Benzenesulfonyloxymino) 1 2 , 6-Dichlorophenylacetonitrile, α- (2-Chronobenzenesulfo-ruximino) -4-methoxyphenylacetonitrile, α- (Ethylsulfo-ruximino) —1-cyclopente-rucetonitrile, represented by the following general formula (ii) A compound;

 [0042] [Chemical 8]

(In the formula (ii), R ⁴ represents a monovalent to trivalent organic group, R ⁵ represents a substituted or unsubstituted saturated hydrocarbon group, an unsaturated hydrocarbon group or an aromatic compound group, and n is 1 It indicates a natural number of ~ 3. Here, the aromatic compound group refers to a group of a compound exhibiting physical 'chemical properties peculiar to an aromatic compound, for example, an aromatic hydrocarbon such as a phenyl group or a naphthyl group. Groups, and heterocyclic groups such as a furyl group and a chenyl group, which have one or more suitable substituents on the ring, such as a neurogen atom, an alkyl group, an alkoxy group, and a nitro group. Even Good. R ⁵ includes a methyl group, an ethyl group, a propyl group, and a butyl group, in which an alkyl group having 1 to 4 carbon atoms is particularly preferred. Particularly preferred are compounds wherein R ⁴ is an aromatic compound group and R ⁵ is a lower alkyl group. The acid generator represented by the above general formula is a compound in which when n = l, R ⁴ is any of a phenyl group, a methyl phenol group, and a methoxy phenol group, and R ⁵ is a methyl group. In particular, _a (methylsulfo-ruximino) 1-fluoroacetonitrile, _a- (methylsulfo-ruximino) — 1— (p-methylphenyl) aceto-tolyl, (X— (methylsulfo-ruximino) — 1— (p-methoxyphenyl) acetonitrile When _n = 2, the acid generator represented by the general formula is specifically an acid generator represented by the following chemical formula (iii). )

[Chemical 9]

• Gii) [0044] Bis (p-toluenesulfol) diazomethane, bis (1,1 dimethylethylsulfol) diazomethane, bis (cyclohexylsulfol) diazomethane, bis (2,4 dimethylphenylsulfol) diazomethane, etc. P-Toluenesulfonic acid 2 Nitrobenzyl, p Toluenesulfonic acid 2, 6 Dinitrobenzyl, Nitrobenzinoretosylate, Di-Trobenzinoretosylate, Nitrobenzinoresnolefonate, Nitrobenze -Trobenzyl derivatives such as lucarbonate and dinitrobenzyl carbonate; pyrogallo monoretrimesylate, pyrgarol tritosylate, benzyl tosylate, benzyl sulfonate, N-methylsulfo-luoxysuccinimide, N-trichloromethyl sulfone -Luoxy succinimide Sulfonic acid esters such as N-phenylsulfo-loxymaleimide and N-methylsulfo-loxyphthalimide; Trifluoromethane sulfonic acid esters such as N-hydroxyphthalimide and N-hydroxynaphthalimide; Safluorophosphate, (4-methoxyphenyl) phenol trifluoromethanesulfonate, bis (p-tert butylphenol) iodine-trifluoromethanesulfonate, trisulfolsulfonate OH salts such as muhexafluorophosphate, (4-methoxyphenyl) diphenylsulfo-trifluoromethanesulfonate, (p-tert-butylphenol) diphenylsulfo-mutrifluoromethanesulfonate Benzoins such as benzoin tosylate and a methylbenzoin tosylate Intosylates; other diphenol-donium salts, trisulfol-sulfur salts, ferrodiazo-um salts, benzyl carbonates and the like.

 [0045] As the acid generator (b2), these compounds may be used alone or in combination of two or more.

 [0046] In the chemically amplified photoresist yarn composition of the present invention, the content of the component (b) is preferably in the range of 0.1 to 20 parts by mass with respect to 100 parts by mass of the component (a). -10 mass parts is more preferable, and 1-5 mass parts is still more preferable. When the content of the component (b) is 0.1 parts by mass or more, high sensitivity can be obtained and sufficient image formation can be performed. On the other hand, if the amount is 20 parts by mass or less, the resist film has a high residual film ratio after image formation and excellent developability.

[0047] When the chemically amplified photoresist composition is negative, a crosslinking agent is further included in addition to the above-mentioned components (a) and (b). The cross-linking agent used in the present invention can be appropriately selected from cross-linking agents used in any known chemically amplified negative photoresist composition without particular limitation. For example, melamine resin, urea resin, guanamine resin, glycoluryl-formaldehyde resin, succinamide-formaldehyde resin, ethylene urea formaldehyde resin, etc. Alkoxymethyl-aminoamino resin such as fluorinated urea resin can be suitably used.

 For example, the alkoxymethyl-aminoamino resin is obtained by converting a condensate obtained by reacting melamine or urea with formalin in a boiling aqueous solution to a lower alcohol such as methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, or isopropyl alcohol. It can be produced by etherifying with a kind and then cooling and precipitating the reaction liquid with.

 Specific examples of the alkoxymethyl-aminoamino resin include methoxymethylated melamine resin, ethoxymethylated melamine resin, propoxymethylated melamine resin, butoxymethylated melamine resin, methoxymethylethylamine resin, Examples thereof include ethoxymethyl iurea resin, propoxymethylated urea resin, butoxymethyl iurea resin.

 The alkoxymethylamino amino coffin can be used alone or in combination of two or more.

 In particular, alkoxymethylated melamine rosin is preferable because it can form a stable resist pattern with a small amount of dimensional change of the resist pattern with respect to a change in radiation dose. Of these, methoxymethylated melamine, ethoxymethylated melamine, propoxymethyl melamine and butoxymethylated melamine are preferred.

 [0048] The crosslinking agent is preferably contained in the range of 1 to 30 parts by mass with respect to 100 parts by mass of the component (a). When the cross-linking agent is 1 part by mass or more, the resist pattern shape formed with high adhesion resistance, chemical resistance and adhesion of the obtained film is good. If the amount is 30 parts by mass or less, development defects are unlikely to occur during development.

[0049] In the chemically amplified photoresist composition of the present invention, an organic solvent (resist solvent) can be blended in order to dissolve the above components. Any organic solvent can be used as long as it can dissolve each component used to form a uniform solution. Conventionally, one or two of the known solvents for chemically amplified resists can be used. Select and use as appropriate. Togashi.

 Specific examples of organic solvents include ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, and 2-heptanone; ethylene glycol, ethylene glycol mono-monoacetate, diethylene glycol, diethylene glycol mono-monoacetate. Polyhydric alcohols such as propylene glycol, propylene glycol monoacetate, dipropylene glycol or dipropylene glycol monoacetate monomethyl ether, monoethyl etherate, monopropyl ether, monobutyl ether or monophenyl ether and their derivatives; Cyclic ethers such as dioxane; and methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methoxypropiate Methyl phosphate, can be mentioned esters such as ethoxypropionate Echiru. These may be used alone or in admixture of two or more.

 Among these, from the viewpoint of solubility of the acid generator (bl) of the present invention, propylene glycol monomethyl ether, which is preferred for polyhydric alcohols and derivatives thereof, is more preferred.

[0050] The organic solvent is usually used in an amount such that the solid content concentration in the chemically amplified photoresist composition is in the range of 1 to 65% by mass.

 In particular, when a chemically amplified photoresist composition is used for manufacturing connection terminals, etc., for example, a spin-coating method is used to obtain a thick resist layer having a thickness of, for example, 5 m or more. An amount such that the solid content concentration in the photoresist composition is in the range of 30 to 65% by mass is preferable. When the solid content concentration is 30% by mass or more, it is easy to obtain a thick film suitable for manufacturing connection terminals. When the solid content concentration is 65% by mass or less, the composition has good fluidity and is easy to handle. Furthermore, it is easy to obtain a uniform resist film by spin coating.

 [0051] In the chemically amplified photoresist composition of the present invention, an additive having a miscibility, for example, an additional resin for improving the performance of the resist film, as long as it does not impair the essential characteristics. Conventional materials such as plasticizers, adhesion assistants, stabilizers, colorants, and surfactants can be added and contained.

[0052] Next, a positive type example is shown. In the case of the positive type, a crosslinking agent is unnecessary. Further, the component (b) and the organic solvent are the same as in the case of the negative type, but the component (a) is a resin whose alkali solubility is increased by an acid. The component (a) is not particularly limited as long as it is a resin generally used as a base resin for a positive chemically amplified photoresist, and it is not limited to those conventionally known depending on the light source used for exposure. It can be arbitrarily selected and used. For example, acryl resin is the main component, and at least part of its hydroxyl group is substituted with an alkali dissolution inhibiting group dissociated by an acid, or a polymer having a hydroxyl styrene structural unit as a main component. A group in which at least a part of the group is replaced with an alkali dissolution inhibiting group dissociated by an acid is preferable.

 As the particularly preferred component (a), it is composed of a polymer having a (mouth) hydroxystyrene structural unit similar to the negative type described above, and (c) one or more types of resin selected from acrylic resin, and the hydroxyl group Examples thereof include those substituted at least with an alkali dissolution inhibiting group dissociated by an acid S and an acid. This is because it is easy to control coating properties and development speed.

 [0053] Alkali dissolution inhibiting groups dissociated by the action of an acid include tertiary alkyloxy groups such as tert-ptyloxy group and tert-amyloxy group; cyclic acetaloxy groups such as tetrahydrobiraloxy group and tetrahydrofuranyloxy group ; Chain acetaloxy group such as ethoxyethyloxy group, methoxypropyloxy group; cycloalkyloxy group such as cyclohexyloxy group, cyclopentyloxy group; 1-methylcyclohexyloxy group, 1 ethyl; 1-alkyl cycloalkyloxy group such as cycloalkyloxy group; 1-alkyl-polycycloalkyloxy group such as 1-methyladamantyloxy group and 1-ethyladamantyloxy group At least one of the above is preferred.

 [0054] Furthermore, the component (a) can contain other rosin components for the purpose of appropriately controlling physical and chemical properties. For example, (i) novolak resin and (2) vinyl resin similar to the negative type described above can be mentioned.

In the negative type examples described above, the crosslinking agent and the component (a) are excluded. The component (b), the organic solvent, and other components can be the same. [0055] The chemically amplified photoresist composition of the present invention can be used to form a resist layer on a support.

 In particular, the chemically amplified photoresist composition of the present invention has a high sensitivity to radiation of 365 nm or more, and a resist solution having a high solid content concentration in which the acid generator (bl) is highly soluble in an organic solvent (resist solvent). Therefore, a thick resist layer having a film thickness of 5 m or more can be easily formed. Therefore, as described later, it is suitably used for manufacturing connection terminals.

[0056] <Regist layer laminate of fourth aspect>

 The resist layer laminate of the present invention is obtained by laminating a resist layer made of the chemically amplified photoresist composition on a support.

 The support is not particularly limited, and a conventionally known one can be used. For example, a substrate for an electronic component or a substrate on which a predetermined wiring pattern is formed can be exemplified. .

 Examples of the substrate include a metal substrate such as silicon, silicon nitride, titanium, tantalum, noradium, titanium tungsten, copper, chromium, iron, and aluminum, and a glass substrate. As a material for the wiring pattern, for example, copper, solder, chromium, aluminum, nickel, gold, or the like is used.

 In particular, when copper is used for at least a part of the surface of the support, such as a substrate or a wiring pattern, at least a part of the surface on the resist layer side, conventionally, the portion of the support that is in contact with copper is used. The power of the chemically amplified photoresist is obstructed by copper, and there is a problem of substrate dependency such as development failure such as soldering at that part. (B) The acid generator (bl) of the present invention is used as a component. By using it, the substrate dependency is reduced. Therefore, a resist pattern having an excellent shape can be formed.

 [0057] The chemically amplified photoresist composition of the present invention can be prepared, for example, by mixing and stirring the above-described components by a usual method, as necessary. A dissolver, a homogenizer, a three-neck roll mill (a triple roll mill) ) Or the like may be used for dispersion and mixing. Further, after mixing, it may be further filtered using a mesh, a membrane filter or the like.

[0058] The resist layer laminate of the present invention can be produced, for example, as follows. sand That is, a solution of the chemically amplified photoresist composition prepared as described above is applied onto a substrate, and the solvent is removed by heating to form a desired coating film (resist layer). As a coating method on the substrate to be processed, methods such as a spin coating method, a roll coating method, a screen printing method, and an applicator method can be employed.

 The prebeta conditions for the coating film of the composition of the present invention are different forces depending on the type of each component in the composition, the blending ratio, the coating film thickness, etc. Usually 70 to 130 ° C, preferably 80 to 120 ° C. 2-60 minutes.

[0059] The thickness of the resist layer is not particularly limited. In particular, in the present invention, when the resist layer is a thick film resist layer having a film thickness of 5 m or more, it can be suitably used for production of connection terminals. The lower limit of the thickness of the thick resist layer is more preferably 20 m / z m or more, more preferably 30 m or more, and even more preferably 55 m or more. Further, the upper limit is not particularly limited, but 1000 m or less force S is preferable, 500 m or less is more preferable, 150 / zm or less is more preferable, 120 m or less is more preferable, and 75 m or less is more preferable. Further preferred.

[0060] <Resist Pattern Forming Method of Fifth Aspect>

 The resist pattern forming method of the present invention comprises a laminating step of obtaining a resist layer laminate of the present invention by laminating a resist layer having a chemical amplification type photoresist composition force of the present invention on a support; It includes an exposure step of selectively irradiating radiation, and a development step of obtaining a resist pattern by forming an image after the exposure step.

 The lamination step can be performed in the same manner as in the production of the resist layer laminate.

 In the exposure process, for example, when using a negative type chemically amplified photoresist, radiation, for example, ultraviolet rays having a wavelength of 300 to 500 nm or visible light is selected through a mask having a predetermined pattern on the obtained photoresist layer. Irradiate (exposure). As these radiation sources, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal lamp, a ride lamp, an argon gas laser, or the like can be used. Here, radiation means ultraviolet rays, visible rays, far ultraviolet rays, X-rays, electron beams, and the like. The present invention is particularly suitable for an exposure process using radiation in a long wavelength region of 365 nm or more.

The amount of radiation irradiation varies depending on the type of each component in the composition, the blending amount, and the film thickness of the coating film.For example, ultra-high pressure mercury lamp (g-line (436nm), h-line (405nm), i-line (365nm) Including No) In the case of use, it is 100~2000mjZcm ^2.

 Then, after exposure, heating is performed using a known method to promote acid generation and diffusion, thereby changing the alkali solubility of the exposed photoresist layer.

 Next, a development process is performed. The development step can be performed, for example, by using a predetermined alkaline aqueous solution as a developer, and an unnecessary portion is dissolved and removed by the developer to obtain a predetermined resist pattern.

 As the developer, for example, an alkaline aqueous solution such as sodium hydroxide or potassium hydroxide can be used. Further, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the alkaline aqueous solution is used as a developer.

 The development time varies depending on the type of each component of the composition, the blending ratio, and the dry film thickness of the composition. Power is usually 1 to 30 minutes, and the development method is liquid deposition, dating, paddle, spray development, etc. Either of these is acceptable. After development, wash with running water for 30 to 90 seconds and dry using an air gun or oven.

[0061] Then, by burying a conductor such as metal in the non-resist portion (the portion removed with the alkali developer) of the resist pattern thus obtained, for example, by metal plating, connection of metal posts, bumps, etc. Terminals can be formed.

 Note that the treatment method is not particularly limited, and various methods known in the art can be employed. As the plating solution, solder plating and copper plating solution are particularly preferably used. The remaining resist pattern is finally removed using a stripping solution or the like according to a conventional method.

[0062] As described above, the compound (B1) of the present invention has sufficient absorption to function as an acid generator in a long wavelength region of 365 nm or more, and exposure using radiation having a wavelength of 365 nm or more. Also, a sufficient amount of acid is generated for forming a resist pattern. Also, the solubility in organic solvents used in resists is high. Therefore, the acid generator (bl) composed of the compound (B1) is suitably used for a chemically amplified photoresist composition, particularly a chemically amplified photoresist composition for radiation having a wavelength of 365 nm or more, and the acid generator (bl) The chemical amplification type photoresist composition containing the compound has high sensitivity. In addition, the chemically amplified photoresist composition of the present invention can form a resist pattern excellent in shape and accuracy regardless of the type of substrate used, which has low substrate dependency. In other words, conventionally, for example, when a support such as copper or aluminum is used for at least a part of the support, and such a support is used, it is in contact with the metal and becomes a part of the chemically amplified type photoresist. There was a problem of substrate dependency such as development failure (such as film loss in the case of negative, adhesion failure in the case of positive), but as a component (b) from the compound (B1) of the present invention. Substrate dependency is reduced by using the acid generator (bl). The effect of reducing the substrate dependency is presumed to be because the compound (B1) of the present invention has a group that easily reacts with a metal such as copper, such as CN.

 Furthermore, since the compound (B1) of the present invention has high solubility in an organic solvent, the chemically amplified photoresist composition of the present invention can increase the solid content concentration of the organic solvent solution of the resist, so that the film thickness is 5 Suitable for forming a thick resist layer of m or more.

 In addition, since the compound (B1) of the present invention has high solubility in an organic solvent, the chemically amplified photoresist composition of the present invention is also excellent in storage stability as a resist solution in a bottle. It is expected. Along with this, it is presumed that a decrease in sensitivity and a deterioration in resist pattern shape due to deterioration of performance over time can be prevented.

 [0063] << Chemically Amplified Photoresist Composition >>

 The chemically amplified photoresist composition according to the sixth aspect of the present invention comprises (a) a resin whose alkali solubility is changed by an acid (hereinafter sometimes referred to as (a) component), and (b) by irradiation with radiation. A compound that generates an acid (hereinafter also referred to as component (b)) and (c) a compound represented by the following general formula (C1) (hereinafter also referred to as component (c)), The component (b) includes a sulfonium salt-based acid generator (b-1), and may be negative or positive.

 [0064] An example in the case of the negative type will be described below.

 In this embodiment, the component (a) is the same as the component (a) in the first embodiment, and the description thereof is omitted.

 [0065] Component (b)

In the present invention, the component (b) is a sulfo-um salt-based acid generator (b-1) (hereinafter referred to as an acid generator). (b-1) may be contained).

 In the present invention, the acid generator (b-1) can be arbitrarily selected from the sulfo salt-based acid generators proposed for use in chemically amplified resist compositions. In the present invention, the “sulfo salt-based acid generator” is a compound having a sulfone ion as a force thione part and generating an acid upon irradiation with radiation. Examples of the sulfo-um ion include those represented by the following general formula (IX).

[0066] [Chemical 10]

IX;

In the general formula (IX), R ″ to R ″ each independently represents an aryl group or an alkyl group.

Of R ^U to R ^13, out of it is preferred instrument R ^U to R ¹³ at least Tsu is Ariru group, 2 or more, all it is more preferred instrument R "to R ¹³ is a Ariru group Most preferred is an aryl group.

As the aryl group of R ^{U to} R ¹³ , for example, a group represented by the general formula (Bla) described later, or an aryl group having 6 to 20 carbon atoms, which is substituted with an alkyl group, a halogen atom, or the like. Examples thereof include a fluorine group and a naphthyl group which may be omitted. The alkyl group which may be substituted on the aryl group is not particularly limited, and examples thereof include a linear or branched alkyl group having 1 to 5 carbon atoms. Examples of the halogen atom that may be substituted on the aryl group include a chlorine atom, a fluorine atom, an iodine atom, and a bromine atom.

Examples of the alkyl group of R ^{U to} R ¹³ include a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms.

In the present invention, it is particularly preferable that the acid generator (b-1) contains a compound represented by the general formula (B1) (hereinafter sometimes referred to as the compound (B1)). . This further improves the sensitivity in a long wavelength region of 365 ηm or more. Note that the compound (Bl) is the same as the compound (Bl) in the first embodiment, and thus the description thereof is omitted.

[0069] The acid generator (b-1) may be used alone or in combination of two or more.

 In the component (b), the ratio of the acid generator (b-1) is preferably 50% by mass or more, more preferably 80 to L00% by mass, and most preferably 100 for the effect of the present invention. % By mass.

 [0070] In the present invention, the chemically amplified photoresist composition comprises an acid generator (b) as component (b).

 In addition to 1), it may contain a known acid generator (hereinafter sometimes referred to as acid generator (b-2)) used in conventional chemically amplified resist compositions. Here, since the acid generator (b-2) is the same as the acid generator (b2) in the first embodiment, description thereof is omitted.

 [0071] Component (c)

 Component (c) is a compound represented by the general formula (C1). By containing the strong component (c), the chemically amplified photoresist composition of the present invention contains the sulfo-acid salt generator (b-1) as the component (b)! /, However, it has high sensitivity to radiation in the long wavelength region of 365 nm or more.

In the formula (C1), R ¹ and R ² are alkyl groups having 1 to 4 carbon atoms, and I ^ = R ² . In the present invention, it is particularly preferred that R ¹ and R ² are an ethyl group or an n-butyl group because of the excellent effects of the present invention. 1 ^ = 1 ^ = 11-butyl group More preferred.

 [0072] In the chemically amplified photoresist yarn composition according to the present invention, the ratio of the component (c) to the component (b) is preferably within the range of 5 to 30% by mass, more preferably 10 to 25% by mass. Preferred 15 to 20% by mass is more preferred. When the content is 5% by mass or more, high sensitivity can be obtained and sufficient image formation can be performed. In addition, if it is 30% by mass or less, the sensitivity is not adversely affected.

[0073] When the chemically amplified photoresist composition is a negative type, in addition to the above-mentioned components (a), (b) and (c), a crosslinking agent is further contained. The cross-linking agent is the same as the cross-linking agent in the first aspect, and the description thereof is omitted. Similarly, the organic solvent is the same as the cross-linking agent in the first embodiment, and the description thereof is omitted.

Further, “positive type example”, “resist layer laminate”, and “resist pattern forming method” are also the same as described above, and thus description thereof is omitted.

 As described above, the chemically amplified photoresist composition of the present invention containing the sulfo-acid salt acid generator (b-1) and the component (c) has high sensitivity. This is because the component (c) has a function as a sensitizer of the sulfur salt-based acid generator (b-1). In addition, the chemically amplified photoresist composition of the present invention can form a resist pattern excellent in shape and accuracy regardless of the type of substrate used, which has low substrate dependency. In other words, conventionally, for example, when using a support in which a metal such as copper is used for at least a part of the support, the chemically amplified photoresist in the part in contact with the metal (in the case of negative) However, there is a problem of substrate dependency such as development failure (such as poor adhesion in the case of positive). However, as a component (b), sulfo-um salt-based acid generator (b-1) By using, substrate dependency is reduced. The effect of reducing the substrate dependency is presumed to be because the sulfo-acid salt generator (b-1) does not have a group that easily reacts with a metal such as copper, such as CN.

 In the present invention, the use of the compound (B 1) as the sulfo-salt salt acid generator (b-1) is particularly excellent in the above effects. This indicates that compound (B1) has sufficient absorption to function as an acid generator in the long wavelength region of 365 nm or more, and is sufficient to form a resist pattern even by exposure using radiation having a wavelength of 365 nm or more. This is because a large amount of acid is generated. In addition, since the compound (B1) has high solubility in the organic solvent used in the resist, the solid content concentration of the organic solvent solution of the resist can be increased. Therefore, the chemically amplified photoresist composition of the present invention can be used as a film. It is suitable for forming a thick resist layer with a thickness of 5 μm or more. In addition, since the compound (B1) has high solubility in an organic solvent, it is expected that the chemically amplified photoresist composition is excellent in bottle aging stability. Along with this, it is presumed that a decrease in sensitivity and a deterioration in resist pattern shape due to deterioration in performance over time can be prevented.

Example Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to these examples.

 [0076] [Synthesis Example 1] Synthesis of Kunovolak Resin>

 m-Talesol and p-Talesol were mixed at a mass ratio of 60:40, and formalin was added thereto, followed by condensation by a conventional method using a oxalic acid catalyst to obtain a cresol novolac coconut resin. A fractionation treatment was applied to this rosin, and the low molecular region was cut to obtain a novolac rosin having a mass average molecular weight of 8,000. This oil is called (A-1).

 [0077] [Example 1] <Preparation of chemically amplified photoresist composition>

 90 parts by mass of the resin (A-1) obtained in Example 1 of resin synthesis, 3 parts by mass of the acid generator (B-1) represented by the above formula (B3), and a crosslinking agent (hexamethoxymethylated) Melamine (manufactured by Sanwa Chemical Co., Ltd., trade name: -Carac Mw—100)) is mixed with propylene glycol monomethyl ether acetate to 10 parts by mass and filtered through a membrane filter with a pore size of 1 μm. As a result, a chemically amplified negative photoresist composition having a solid content of 50% by mass was obtained.

 [0078] [Comparative Example 1]

 Instead of 3 parts by mass of the acid generator (B-1), the same procedure as in Example 1 was carried out except that 3 parts by mass of triphenylsulfo-trifluoromethanesulfonate (acid generator (B-2)) was used. Thus, a chemically amplified negative photoresist composition was prepared.

[0079] <Evaluation>

 The solubility of the acid generator (B-1) obtained in Synthesis Example 1 and the acid generator (B-2) used in Comparative Example 1 was evaluated as follows. The results are shown in Table 1.

 <Solubility>

 The concentration of propylene glycol monomethyl ether acetate in each acid generator was adjusted by changing the concentration in increments of 1% by mass from 5% by mass to 1% by mass. After the adjustment, each solution was stirred to measure the concentration at which each acid generator was completely dissolved.

[0080] [Table 1] Acid generator (B—1) Acid generator (B—2) Solubility (mass ½) 3 1

[0081] The following evaluations were made on the chemically amplified negative resist compositions obtained in the above Examples and Comparative Examples.

First, apply a chemically amplified negative photoresist composition on a 5-inch copper sputtering wafer using a spinner to a thickness of about 30 m, and pre-beta on the hot plate at 110 ° C for 6 minutes. And a resist layer stack was formed. Next, using a stepper (Canon, Canon PLA-501F, ghi line multi, hard contact) through a pattern mask for resolution measurement, stepwise ultraviolet exposure is performed in the range of 100 to 10, OOOmjZcm ^2. went. After the exposure, PEB (post-exposure heating) was performed at 130 ° C for 4 minutes, and this was developed with a developer (2.38 mass% tetramethylammonium hydroxide aqueous solution) for 7 minutes. Thereafter, it was washed with running water and blown with nitrogen to obtain a resist pattern. The sensitivity, pattern shape, and remaining film rate were evaluated as follows. The results are shown in Table 2.

 Note that g-line (436 nm), h-line (405 nm), and i-line (365 nm) mixed light was used for the exposure in this evaluation, but the composition of the present invention has high sensitivity to i-line (365 nm), and i-line The same effect was obtained with single exposure (365 nm).

[0082] <Sensitivity>

 After the development, the exposure amount in which a contact resist line pattern having a line width of 40 m remained was measured. <Pattern shape>

 The shape of the formed resist pattern was observed using an optical microscope or an electron microscope, and judged according to the following evaluation criteria.

 ○: The shape of the formed resist pattern is rectangular

 X: The shape of the formed resist pattern is an inverted trapezoid (the number in parentheses represents the contact angle between the pattern and the substrate)

 <Residual film rate>

Measure the film thickness of the formed resist pattern, and the film remains with respect to the film thickness before development! / ヽ The ratio was calculated as the remaining film ratio.

[0083] [Table 2]

[0084] [Synthesis Example 2] Synthesis of Kunovolak Resin>

 m-Talesol and p-Talesol were mixed at a mass ratio of 60:40, and formalin was added thereto, followed by condensation by a conventional method using a oxalic acid catalyst to obtain a cresol novolac resin. A fractionation treatment was applied to this rosin, and the low molecular region was cut to obtain a novolac rosin having a mass average molecular weight of 8,000. This oil is designated as (A-11).

[0085] [Example 2] <Preparation of chemically amplified photoresist composition>

90 parts by mass of the resin (A-11) obtained in Resin Synthesis Example 2, 3 parts by mass of the compound (B-11) represented by the above formula (B3), and a crosslinking agent (hexamethoxymethylated melamine (Sanwa Made by Chemical Co., Ltd., trade name: Niki-rak Mw—100)) 10 parts by mass and 9, 10-di (n-butoxy) anthracene 0.15 parts by mass in propylene glycol monomethyl ether acetate after, it filtered through a membrane filter having a pore size of 1 / xm, to give a chemically amplified negative photoresist composition with a solid content of 40 mass ^_0/0.

[0086] [Example 3] <Preparation of chemically amplified photoresist composition>

 A chemically amplified negative photoresist composition was obtained in the same manner as in Example 2 except that the blending amount of 9,10-di (n-butoxy) anthracene was changed to 0.3 parts by mass.

[0087] [Example 4] <Preparation of chemically amplified photoresist composition>

 A chemically amplified negative photoresist composition was obtained in the same manner as in Example 2 except that the blending amount of 9,10-di (n-butoxy) anthracene was changed to 0.5 parts by mass.

[0088] [Comparative Example 2]

 A chemically amplified negative photoresist composition was prepared in the same manner as in Example 2 except that 9,10-di (n-butoxy) anthracene was not added.

[0089] <Evaluation> [Sensitivity] The following evaluation was carried out on the obtained optically amplified negative photoresist composition. First, apply a chemically amplified negative photoresist composition on a 5-inch copper sputtering wafer using a spinner to a thickness of about 30 m, and pre-beta on the hot plate at 110 ° C for 6 minutes. And a resist layer stack was formed. Then, through a pattern mask for measurement of resolution, stepper (manufactured by Canon Inc., Canon PLA-501F, hard contact) using a 100 to 10, having conducted stepwise ultraviolet exposure in the range of OOOmiZcm ^2. After exposure, subjected to PEB (post exposure baking) for four minutes at 130 ° C, which, developer (2.38 mass _^0/0 tetramethylammonium - Umuhidorokishido solution) were developed for 7 minutes at. Thereafter, it was washed with running water and blown with nitrogen to obtain a resist pattern.

At this time, the exposure amount (miZcm ² ) at which a 40 μm contact line pattern was formed was determined as sensitivity. The results are shown in Table 3.

 Note that although g-line (436 nm), h-line (405 nm), and i-line (365 nm) mixed light was used for the exposure in this evaluation, the composition of the present invention is highly sensitive to i-line (365 nm). The same effect was obtained with single exposure (365 nm).

[0090] [Table 3]

 Industrial applicability

 [0091] The present invention relates to a compound that exhibits high absorption in a long wavelength region of 365 nm or more, excellent absorption in an organic solvent having high sensitivity in a long wavelength region of 365 nm or more, and an excellent solubility in an organic solvent. The present invention can be applied to an acid generator comprising the above, a chemically amplified photoresist composition containing the acid generator, a resist layer laminate using the chemically amplified photoresist composition, and a method for forming a resist pattern.

Claims

 The scope of the claims

 A compound represented by the following general formula (B1).

[In the formula (B1)

R ³ is each independently a group represented by the following general formula (Bla), an alkyl group, or a group obtained by removing one hydrogen atom from an aromatic ring, and the aromatic ring has a substituent. However, at least one of R ² and R ³ is a group represented by the following general formula (Bla); ]

 [Chemical 12]

0

 γ r »7 (TBla)

[In the formula (Bla), Y is a group obtained by removing two hydrogen atoms from an aromatic ring, and the aromatic ring may have a substituent; Z is a group obtained by removing one hydrogen atom from the aromatic ring. The aromatic ring may have a substituent; the aromatic ring in at least one of Y and Z has at least one alkoxy group. ]

 [2] The compound according to claim 1, wherein the X— is a fluorinated alkyl ion.

 [3] The compound according to claim 2, represented by the following formula (B3):

[Chemical 13]

[4] An acid generator comprising the compound according to any one of claims 1 to 3.

 [5] A chemically amplified photoresist composition comprising (a) a resin whose alkali solubility is changed by an acid, and (b) a compound which generates an acid upon irradiation.

 5. A chemically amplified photoresist composition, wherein the compound (b) that generates an acid upon irradiation contains the acid generator according to claim 4.

6. The chemically amplified photoresist composition according to claim 5, which is used for radiation having a wavelength of 365 nm or more.

 [7] A resist layer laminate in which a resist layer having the chemical amplification type photoresist composition according to claim 5 is laminated on a support.

8. The resist layer laminate according to claim 7, wherein the support is a support in which copper is used for at least a part of the surface on the resist layer side.

[9] A lamination process for obtaining a resist layer laminate according to claim 7 by laminating a resist layer having a chemically amplified photoresist composition on a support, and exposure for selectively irradiating the resist layer laminate And a development step of developing after the exposure step to obtain a resist pattern.

[10] containing (a) a resin whose alkali solubility is changed by an acid, (b) a compound that generates an acid upon irradiation, and (c) a compound represented by the following general formula (C1): The chemically amplified photoresist composition, wherein the compound (b) that generates an acid upon irradiation contains a sulfo salt salt acid generator (b-1).

[Chemical 14]

[Wherein R ¹ and R ² are alkyl groups having 1 to 4 carbon atoms, and R ¹ :! ^. 11. The chemically amplified photoresist composition according to claim 10, wherein the sulfonium salt acid generator (b-1) comprises a compound represented by the following general formula (B1).

 [Chemical 15]

[Formula (

Each independently represents a group represented by the following general formula (Bla), an alkyl group, or a group obtained by removing one hydrogen atom from an aromatic ring, and the aromatic ring may have a substituent. And at least one of R ² and R ³ is a group represented by the following general formula (Bla); ]

[Chemical 16]

[In the formula (Bla), Y is a group obtained by removing two hydrogen atoms from an aromatic ring, and the aromatic ring may have a substituent; Z is a group obtained by removing one hydrogen atom from the aromatic ring. The aromatic ring may have a substituent; the aromatic ring in at least one of Y and Z has at least one alkoxy group. ]

 12. The chemically amplified photoresist composition according to claim 11, wherein X— in the general formula (B1) is a fluorinated alkyl ion.

13. The compound according to claim 12, wherein the compound represented by the general formula (B1) is a compound represented by the following formula (B3). [Chemical 17]

[14] The chemically amplified photoresist composition according to any one of claims 10 to 13, which is used for radiation having a wavelength of 365 nm or more.

[15] A resist layer laminate, wherein a resist layer comprising the chemically amplified photoresist composition according to any one of claims 10 to 13 is laminated on a support.

16. The resist layer laminate according to claim 15, wherein the support is a support in which copper is used for at least a part of the surface on the resist layer side.

[17] A laminating process for obtaining a resist layer laminate according to claim 15 by laminating a resist layer having chemical amplification type photoresist composition on a support, and exposure for selectively irradiating the resist layer laminate And a development step of obtaining a resist pattern by developing after the exposure step.