JP4823640B2 - NOVEL ACID GENERATOR, CHEMICALLY AMPLIFIED PHOTORESIST COMPOSITION, RESIST LAYER LAMINATE, AND RESIST PATTERN FORMING METHOD - Google Patents

Description

  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.

Photofabrication, which is currently the mainstream of precision microfabrication technology, is the application of a photosensitive resin composition such as photoresist to the surface of a workpiece to form a coating film, which is then patterned by photolithography technology. Is a general term for technologies for manufacturing various precision parts such as semiconductor packages by performing chemical forming, electrolytic etching and / or electroforming mainly composed of electroplating using as a mask.
In recent years, with the downsizing of electronic equipment, high-density packaging technology for semiconductor packages has progressed. Based on multi-pin thin film packaging of packages, miniaturization of package size, flip-chip two-dimensional packaging technology, and three-dimensional packaging technology. The packaging density is improved. In such a high-density mounting technique, as connection terminals, for example, protruding electrodes (mounting terminals) such as bumps protruding on the package, or metal posts that connect the rewirings extending from the peripheral terminals on the wafer and the mounting terminals. Are arranged with high accuracy on the substrate.
The connection terminal is 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) the part where the connection terminal is to be formed. After the resist pattern is formed, a conductor such as copper is embedded 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 as a photoresist, and a long wavelength of 365 nm or more for exposure. This is performed by using light in the ultraviolet region such as g-line (436 nm), h-line (405 nm), i-line (365 nm).

On the other hand, as one of the high-resolution resist materials that can reproduce resist patterns with fine dimensions, a base resin whose alkali solubility changes due to the action of acid and acid generation by irradiation (exposure) A chemically amplified photoresist containing a compound (acid generator) is known. The characteristic of chemically amplified photoresist is that the acid generator absorbs the irradiated radiation to generate 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 a positive type in which an alkali-insoluble one becomes alkali-soluble by irradiation and a negative type in which an alkali-soluble one becomes alkali-insoluble.
Examples of acid generators used in chemically amplified photoresists include onium salt acid generators such as sulfonium salt acid generators and iodonium salt acid generators, oxime sulfonate acid generators, and imide sulfonates. Various proposals have been made, such as acid generators. Among these, onium salt-based acid generators have high sensitivity in photolithography using radiation in the shorter wavelength region than i-line, such as KrF excimer laser (248 nm) and ArF excimer laser (193 nm). Because of its superiority, it is currently most commonly used.
JP-A-10-207057 JP 2000-39709 A JP 2000-66386 A

However, the onium salt acid generator hardly absorbs in the long wavelength region of 365 nm or more. Therefore, in photofabrication in a long wavelength region of 365 nm or longer, a chemically amplified photoresist using an onium salt-based acid generator has low sensitivity and cannot be practically used.
In addition, as the cation of the onium salt acid generator, a highly hydrophobic cation such as triphenylsulfonium is generally used, and the onium salt acid generator having such a cation has various components of the resist. There is also a problem that the solubility in an organic solvent (resist solvent) used for dissolution is low. Such low solubility in the resist solvent lowers the temporal stability of the resist, and accordingly causes deterioration of the resist pattern shape.
For this reason, in the photofabrication in the long wavelength region of 365 nm or more, the present situation is that a chemically amplified photoresist using an onium salt acid generator as an acid generator cannot be used.
The present invention has been made in view of the above circumstances, and shows a high absorption in a long wavelength region of 365 nm or more, a high sensitivity in a long wavelength region of 365 nm or more, and an excellent solubility in an organic solvent. And 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 resist pattern forming method. .

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 an acid generator comprising a compound represented by the following general formula (B1).

［式（Ｂ１）中、Ｒ^１、Ｒ^２、Ｒ^３は、それぞれ独立に、下記一般式（Ｂ１ａ）で表される基、炭素数１〜１２のアルキル基、または炭素数６〜１８の芳香環から１つの水素原子を除いた基であって、該芳香環は炭素数１〜１２のアルコキシ基、炭素数１〜１２のアルキル基および水酸基から選ばれる置換基を有していてもよく、かつＲ^１、Ｒ^２、Ｒ^３のうちの１つが下記一般式（Ｂ１ａ）で表される基であり；Ｘ⁻はアニオンである。］

[In formula (B1), R ¹ , R ² and R ³ are each independently a group represented by the following general formula (B1a), an alkyl group having 1 to 12 carbon atoms , or an aromatic group having 6 to 18 carbon atoms. A group obtained by removing one hydrogen atom from a ring, and the aromatic ring may have a substituent selected from an alkoxy group having 1 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms, and a hydroxyl group ; and one of ^{R 1,} R 2, ^{R 3} is a group represented by the following general formula (B1a); X ^- represents an anion. ]

［式（Ｂ１ａ）中、Ｙは炭素数６〜１８の芳香環から２つの水素原子を除いた基であって、該芳香環は炭素数１〜１２のアルコキシ基、炭素数１〜１２のアルキル基および水酸基から選ばれる置換基を有し；Ｚは炭素数６〜１８の芳香環から１つの水素原子を除いた基であって、該芳香環は炭素数１〜１２のアルコキシ基、炭素数１〜１２のアルキル基および水酸基から選ばれる置換基を有し；ＹおよびＺのうち少なくとも一方における芳香環が、少なくとも１つの炭素数１〜１２のアルコキシ基を有する。］

[In the formula (B1a), Y is a group obtained by removing two hydrogen atoms from an aromatic ring having 6 to 18 carbon atoms, and the aromatic ring is an alkoxy group having 1 to 12 carbon atoms and an alkyl group having 1 to 12 carbon atoms. have a substituent selected from the group and a hydroxyl group; Z is a group obtained by removing one hydrogen atom from an aromatic ring having 6 to 18 carbon atoms, aromatic ring the alkoxy group having 1 to 12 carbon atoms, carbon atoms have a substituent selected from 1-12 alkyl group and a hydroxyl group; an aromatic ring in at least one of Y and Z has at least one alkoxy group having 1 to 12 carbon atoms. ]

According to a second aspect of the present invention, there is provided 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 with radiation. The chemical amplification photoresist composition is characterized in that the compound that generates acid upon irradiation contains the acid generator of the first aspect.
A third aspect of the present invention is a resist layer laminate in which a resist layer made of the chemically amplified photoresist composition of the second aspect is laminated on a support.
According to a fourth aspect of the present invention, there is provided a laminating step of laminating a resist layer comprising a chemically amplified photoresist composition on a support to obtain the resist layer laminate of the third aspect, and selective to the resist layer laminate. A resist pattern forming method comprising: an exposure step of irradiating the substrate with radiation; and a development step of developing after the exposure step to obtain a resist pattern.

  According to the present invention, a compound having 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 generator comprising the compound, It is possible to provide a chemically amplified photoresist composition containing an acid generator, a resist layer laminate using the chemically amplified photoresist composition, and a resist pattern forming method.

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 ¹ , R ² and R ³ are each independently a group represented by the above general formula (B1a), 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 ¹ , R ² and R ³ needs to be a group represented by the general formula (B1a). By having the group represented by the formula (B1a), 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 (B1a), the aromatic ring in Y and Z is not particularly limited, and examples thereof include aromatic rings having 6 to 18 carbon atoms such as benzene and naphthalene.
In the present invention, the aromatic ring in at least one of Y and Z needs to have at least one alkoxy group as a substituent. In particular, it is preferable that both of the 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 aliphatic hydrocarbon group]. R is not particularly limited, but is preferably a linear or branched alkyl group, and more preferably a linear alkyl group. 1-12 are preferable and, as for carbon number of an aliphatic hydrocarbon group, 1-4 are more preferable. 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 effects 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.

The “alkyl group” of R ^{1 to} R ³ is not particularly limited, and examples thereof include linear, branched or cyclic alkyl groups having 1 to 12 carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an n-pentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, a nonyl group, and a decanyl group. .

The aromatic ring in the “group in which one hydrogen atom is removed from the aromatic ring” of R ^{1 to} R ³ is not particularly limited, and examples thereof include aromatic rings having 6 to 18 carbon atoms such as benzene, naphthalene, anthracene and the like. It is done. The aromatic ring in R ^{1 to} R ³ 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, the aromatic ring in R ^{1 to} R ³ “group obtained by removing one hydrogen atom from an aromatic ring” is a group obtained by removing one hydrogen atom from benzene or naphthalene, that is, a phenyl group or a naphthyl group. More preferably, it is a phenyl group.

In formula (B1), X ⁻ represents an anion. X ⁻ is not particularly limited, and may be any one proposed as an anion in a known acid generator conventionally used in a chemically amplified resist composition.
In the present invention, in particular, X ⁻ is preferably a fluorinated alkyl sulfonate ion in which at least one of the hydrogen atoms of the alkyl group is substituted with a fluorine atom, and in particular, all of the hydrogen atoms of the alkyl group are all A perfluoroalkylsulfonic acid ion substituted with a fluorine atom is preferred.
The number of carbon atoms of the alkyl group of the fluorinated alkyl sulfonate ion is not particularly limited, but is preferably 1 to 12 and more preferably 1 to 4 in terms of the bulk of the acid generated and the diffusion length of the acid.

In this invention, since it is excellent in the effect of this invention, ^{one of} R < ¹ > -R < ³ > is group represented by general formula (B1a), and two of R < ¹ > -R < ³ > are aromatic rings. A group excluding one hydrogen atom, particularly a phenyl group is preferred.

  Especially as a compound (B1), the compound represented with the following general formula (B2) is excellent in the effect of this invention, and preferable.

［式（Ｂ２）中、Ｒ^４、Ｒ^５は、それぞれ独立に、アルキル基、フェニル基またはナフチル基であり；Ｒ^６、Ｒ^７は、それぞれ独立に、アルコキシ基であり；Ｘ⁻はアニオンである。］

[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; and X ⁻ is an anion. is there. ]

In the formula (B2), examples of the alkyl group for R ⁴ and R ⁵ include the same alkyl groups as those described above for R ^{1 to} R ³ . The phenyl 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.
As the alkoxy group for R ⁶ and R ^7, the same alkoxy groups as those exemplified as the substituent for the aromatic ring in Y and Z can be mentioned. The alkoxy group of R ^{6 and} the alkoxy group of R ⁷ may be the same or different.
X ⁻ is the same as described above.

  A preferred example of the compound (B1) of the present invention is a compound represented by the following formula (B3).

  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.

≪Acid generator≫
The acid generator of the second aspect of the present aspect (hereinafter sometimes referred to as the acid generator (b1)) is composed of the compound (B1) of the first aspect.
As an acid generator (b1), it may be comprised from 1 type of the said compound (B1) individually, and may be comprised from 2 or more types of mixtures of the compound (B1).

≪Chemically amplified photoresist composition≫
The chemically amplified photoresist composition according to 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 generated by radiation irradiation. The compound (hereinafter, also referred to as component (b)), wherein the component (b) contains the acid generator (b1) of the present invention, It may be negative or positive.

Hereinafter, an example of the negative type will be described.
(A) Component When the chemically amplified photoresist composition is a negative type, the component (a) is a resin whose alkali solubility is lowered by an acid, and is generally used as a base resin for a negative type chemically amplified photoresist. The resin is not particularly limited as long as it is a resin, and can be arbitrarily selected from conventionally known ones according to the light source used for exposure. For example, those having 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 one or more resins selected from (i) a novolak resin and (ro) a polymer having a hydroxystyrene structural unit. This is because it is easy to control the coating property and the development speed.

(I) A novolac resin (hereinafter referred to as component (a)) is obtained, for example, by addition condensation of an aromatic compound having a phenolic hydroxyl group (hereinafter simply referred to as “phenols”) and an aldehyde in the presence of an acid catalyst. It is done.
In this case, examples of phenols used include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p -Butylphenol, 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-phenylphenol, resorcinol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, phloroglicinol, hydroxydiphenyl, bisphenol A, gallic acid, gallic acid ester, α-naphthol, β-naphthol, etc. The
Examples of aldehydes include formaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, and acetaldehyde.
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 novolak resin has a mass average molecular weight of 3000 to 10000, preferably 6000 to 9000, and more preferably 7000 to 8000. When the mass average molecular weight is 3000 or more, the tendency of the film to decrease (become thin) 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.

(B) As a polymer having a hydroxystyrene structural unit (hereinafter referred to as (b) component), for example, hydroxystyrene such as p-hydroxystyrene, α-alkyl such as α-methylhydroxystyrene, α-ethylhydroxystyrene, etc. Examples thereof include radical polymers or ionic polymers composed only of hydroxystyrene structural units such as hydroxystyrene, and copolymers composed of the hydroxystyrene structural units and other structural units. The ratio of the hydroxystyrene structural unit in the polymer is preferably 1% by mass or more, more preferably 10 to 30% by mass. This is because when the ratio of the hydroxystyrene structural unit is 10% by mass or more, the developability and the resolution tend to be excellent.
The mass average molecular weight of the component (b) is preferably 5000 or less, more preferably 2000 or more and 4000 or less. This is because when the mass average molecular weight is 5000 or less, the resolution tends to be excellent.

  A monomer that forms a constituent unit other than the hydroxystyrene constituent unit is preferably a monomer in which the hydroxyl group of the hydroxystyrene constituent unit is substituted with another group or a monomer having an α, β-unsaturated double bond.

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.
Examples of the alkali dissolution inhibiting group that does not dissociate with an acid include a substituted or unsubstituted benzenesulfonyloxy group, a substituted or unsubstituted naphthalenesulfonyloxy group, a substituted or unsubstituted benzenecarbonyloxy group, and a substituted or unsubstituted naphthalenecarbonyloxy group. Specific examples of the substituted or unsubstituted benzenesulfonyloxy group include benzenesulfonyloxy group, chlorobenzenesulfonyloxy group, methylbenzenesulfonyloxy group, ethylbenzenesulfonyloxy group, propylbenzenesulfonyloxy group, methoxybenzenesulfonyl An oxy group, an ethoxybenzenesulfonyloxy group, a propoxybenzenesulfonyloxy group, an acetaminobenzenesulfonyloxy group, etc. may be substituted or unsubstituted naphthalene. Specific examples of the phonyloxy group include naphthalenesulfonyloxy group, chloronaphthalenesulfonyloxy group, methylnaphthalenesulfonyloxy group, ethylnaphthalenesulfonyloxy group, propylnaphthalenesulfonyloxy group, methoxynaphthalenesulfonyloxy group, ethoxynaphthalenesulfonyloxy group, propoxynaphthalene group A sulfonyloxy group, an acetaminonaphthalenesulfonyloxy group, and the like are preferable. Furthermore, examples of the substituted or unsubstituted benzenecarbonyloxy group and the substituted or unsubstituted naphthalenecarbonyloxy group include those in which the substituted or unsubstituted sulfonyloxy group is replaced with a carbonyloxy group. Among these, an acetaminobenzenesulfonyloxy group or an acetaminonaphthalenesulfonyloxy group is preferable.

Specific examples of the monomer having an α, β-unsaturated double bond include styrene monomers such as styrene, chlorostyrene, chloromethylstyrene, vinyltoluene, α-methylstyrene, methyl acrylate, methyl methacrylate, Examples include acrylic acid monomers such as phenyl methacrylate and vinyl acetate monomers such as vinyl acetate and vinyl benzoate. Among them, styrene is preferable. Copolymers obtained from hydroxystyrene and styrene, such as poly (4-hydroxystyrene-styrene) copolymer and poly (4-hydroxystyrene-methylstyrene) copolymer, exhibit high resolution. High heat resistance is preferable.
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 (C) component) and (D) vinyl resin (hereinafter referred to as (D) component) can be mentioned.

(C) Ingredients:
The (c) component acrylic resin is not particularly limited as long as it is an alkali-soluble acrylic resin, but is particularly derived from a structural unit derived from a polymerizable compound having an ether bond and a polymerizable compound having a carboxyl group. It is preferable to contain the structural unit.
Examples of the polymerizable compound having an ether bond include 2-methoxyethyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethyl carbitol (meth) acrylate, phenoxy polyethylene glycol (meta ), (Meth) acrylic acid derivatives having an ether bond and an ester bond such as methoxypolypropylene glycol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, etc., preferably 2-methoxyethyl acrylate, Methoxytriethylene glycol acrylate. These compounds can be used alone or in combination of two or more.
Examples of the polymerizable compound 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, 2-methacryloyloxyethyl succinic acid, and 2-methacryloyloxyethyl. Examples include maleic acid, 2-methacryloyloxyethyl phthalic acid, 2-methacryloyloxyethyl hexahydrophthalic acid and other compounds having a carboxyl group and an ester bond, and acrylic acid and methacrylic acid are preferred. These compounds can be used alone or in combination of two or more.

(D) Ingredients:
The component (d) vinyl resin is poly (vinyl lower alkyl ether), and can be 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.

（上記一般式（Ｉ）において、Ｒ^６は炭素数１〜５の直鎖状もしくは分岐状のアルキル基を示す。）

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

  In the general formula (I), examples of the linear or branched alkyl group having 1 to 5 carbon atoms include, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i- A butyl group, n-pentyl group, i-pentyl group, etc. can be mentioned. 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 ether) is poly (vinyl methyl ether) and poly (vinyl ethyl ether).

  In addition, when (a) component consists of mixed resin containing (a) component and (b) component, the sum total of (a) component and (b) component shall be 100 mass parts, and (b) component is 50. It is good that it is -98 mass parts, Preferably it is 55-95 mass parts, (B) component is 50-2 mass parts, Preferably it is 45-5 mass parts.

(B) component In this invention, (b) component needs to contain the acid generator (b1) of the said this invention.
An acid generator (b1) may be used independently and may be used in combination of 2 or more type.
In the component (b), the ratio of the acid generator (b1) is preferably 50% by mass or more, more preferably 80 to 100% by mass, and most preferably 100% by mass for the effect of the present invention. is there.

In the present invention, the chemically amplified photoresist composition is a known acid generator (hereinafter referred to as acid generator (b2)) used in conventional chemically amplified resist compositions in addition to the acid generator (b1). May be included).
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 (b1). Specifically, 2,4-bis (trichloromethyl) -6- [2- (2-furyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (5- Methyl-2-furyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-ethyl-2-furyl) ethenyl] -s-triazine, 2,4-bis ( Trichloromethyl) -6- [2- (5-propyl-2-furyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,5-dimethoxyphenyl) ethenyl] -S-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,5-diethoxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2 -(3,5-dipropoxyv Nyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (3-methoxy-5-ethoxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (3-methoxy-5-propoxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-methylenedioxyphenyl) ethenyl] -S-triazine, 2,4-bis (trichloromethyl) -6- (3,4-methylenedioxyphenyl) -s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4methoxy ) Phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl- -(2-Bromo-4methoxy) styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4methoxy) styrylphenyl-s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2 -(2-furyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (5-methyl-2-furyl) ethenyl] -4,6-bis ( Trichloromethyl) -1,3,5-triazine, 2- [2- (3,5-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2 -(3,4-di Methoxyphenyl) ethenyl] -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 other halogen-containing triazine compounds and tris (2 Halogen-containing triazine compounds represented by the following general formulas such as (, 3-dibromopropyl) isocyanurate;

（式中、Ｒ^１〜Ｒ^３は、それぞれ同一であっても異なってもよく、ハロゲン化アルキル基を示す）

(Wherein R ^{1 to} R ³ may be the same or different and each represents a halogenated alkyl group)

α- (p-toluenesulfonyloxyimino) -phenylacetonitrile, α- (benzenesulfonyloxyimino) -2,4-dichlorophenylacetonitrile, α- (benzenesulfonyloxyimino) -2,6-dichlorophenylacetonitrile, α- (2 -Chlorobenzenesulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (ethylsulfonyloxyimino) -1-cyclopentenylacetonitrile, a compound represented by the following general formula;

（式中、Ｒ^４は、一価〜三価の有機基、Ｒ^５は置換、未置換の飽和炭化水素基、不飽和炭化水素基または芳香族性化合物基を示し、ｎは１〜３の自然数を示す。ここで芳香族性化合物基とは、芳香族化合物に特有な物理的・化学的性質を示す化合物の基を指し、例えばフェニル基、ナフチル基などの芳香族炭化水素基や、フリル基、チエニル基などの複素環基が挙げられる。これらは環上に適当な置換基、例えばハロゲン原子、アルキル基、アルコキシ基、ニトロ基などを１個以上有していてもよい。また、Ｒ^５は炭素数１〜４のアルキル基が特に好ましく、メチル基、エチル基、プロピル基、ブチル基が挙げられる。特にＲ^４が芳香族性化合物基、Ｒ^５が低級アルキル基の化合物が好ましい。上記一般式で表わされる酸発生剤としては、ｎ＝１の時、Ｒ^４がフェニル基、メチルフェニル基、メトキシフェニル基のいずれかであって、Ｒ^５がメチル基の化合物、具体的にはα−（メチルスルホニルオキシイミノ）−１−フェニルアセトニトリル、α−（メチルスルホニルオキシイミノ）−１−（ｐ−メチルフェニル）アセトニトリル、α−（メチルスルホニルオキシイミノ）−１−（ｐ−メトキシフェニル）アセトニトリルが挙げられる。ｎ＝２の時、上記一般式で表わされる酸発生剤としては、具体的には下記化学式で表される酸発生剤が挙げられる。）

(In the formula, R ⁴ represents a monovalent to trivalent organic group, R ⁵ represents a substituted, unsubstituted saturated hydrocarbon group, an unsaturated hydrocarbon group or an aromatic compound group; An aromatic compound group refers to a group of a compound exhibiting physical and chemical properties peculiar to an aromatic compound, such as an aromatic hydrocarbon group such as a phenyl group or a naphthyl group, or furyl. A heterocyclic group such as a group, thienyl group, etc. These may have one or more suitable substituents on the ring, for example, a halogen atom, an alkyl group, an alkoxy group, a nitro group, and the like. ⁵ is particularly preferably an alkyl group having 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, and a butyl group, particularly preferably a compound in which R ⁴ is an aromatic compound group and R ⁵ is a lower alkyl group. As an acid generator represented by the above general formula, When n = 1, R ⁴ is a phenyl group, methylphenyl group, be any of the methoxyphenyl group, the compound of R ⁵ is a methyl group, specifically alpha-(methylsulfonyl) -1- phenyl Acetonitrile, α- (methylsulfonyloxyimino) -1- (p-methylphenyl) acetonitrile, α- (methylsulfonyloxyimino) -1- (p-methoxyphenyl) acetonitrile, when n = 2, Specific examples of the acid generator represented by the general formula include acid generators represented by the following chemical formula.)

Bissulfonyldiazomethanes such as bis (p-toluenesulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (2,4-dimethylphenylsulfonyl) diazomethane; p-toluenesulfone Nitrobenzyl derivatives such as 2-nitrobenzyl acid, 2,6-dinitrobenzyl p-toluenesulfonate, nitrobenzyl tosylate, dinitrobenzyl tosylate, nitrobenzyl sulfonate, nitrobenzyl carbonate, dinitrobenzyl carbonate; pyrogallol trimesylate , Pyrgallol tritosylate, benzyl tosylate, benzyl sulfonate, N-methylsulfonyloxysuccinimide, N-trichloromethylsulfonyloxysk Sulfonic acid esters such as N-imide, N-phenylsulfonyloxymaleimide and N-methylsulfonyloxyphthalimide; trifluoromethanesulfonic acid esters such as N-hydroxyphthalimide and N-hydroxynaphthalimide; diphenyliodonium hexafluorophosphate, (4 -Methoxyphenyl) phenyliodonium trifluoromethanesulfonate, bis (p-tert-butylphenyl) iodonium trifluoromethanesulfonate, triphenylsulfonium hexafluorophosphate, (4-methoxyphenyl) diphenylsulfonium trifluoromethanesulfonate, (p-tert-butyl) Onium salts such as phenyl) diphenylsulfonium trifluoromethanesulfonate; Over DOO, benzoin tosylate such as α- methyl benzoin tosylate; other diphenyliodonium salts, triphenylsulfonium salts, phenyldiazonium salts, benzyl carbonate and the like.

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

  In the chemically amplified photoresist composition of the present invention, the content of the component (b) is preferably in the range of 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the component (a). Preferably, 1 to 5 parts by mass is 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. Moreover, the residual film rate of the resist layer after image development is high as it is 20 mass parts or less, and developability is excellent.

When the chemically amplified photoresist composition is a negative type, a crosslinking agent is further included in addition to the components (a) and (b) described above.
There is no restriction | limiting in particular as a crosslinking agent used for this invention, It can select from the crosslinking agent currently used for arbitrary well-known chemically amplified negative photoresist compositions suitably, and can use it. For example, melamine resin, urea resin, guanamine resin, glycoluril-formaldehyde resin, succinylamide-formaldehyde resin, ethyleneurea-formaldehyde resin, etc. are used, but in particular alkoxymethylation such as alkoxymethylated melamine resin and alkoxymethylated urea resin An amino resin or the like can be preferably used.
The alkoxymethylated amino resin is obtained by, for example, condensing a condensate obtained by reacting melamine or urea with formalin in a boiling aqueous solution with a lower alcohol such as methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, or isopropyl alcohol. And then the reaction solution is cooled and precipitated.
Specific examples of the alkoxymethylated amino resin include methoxymethylated melamine resin, ethoxymethylated melamine resin, propoxymethylated melamine resin, butoxymethylated melamine resin, methoxymethylated urea resin, ethoxymethylated urea resin, and propoxymethyl. And urea-oxygenated resin, butoxymethylated urea resin, and the like.
The said alkoxymethylated amino resin can be used individually or in combination of 2 or more types.
In particular, an alkoxymethylated melamine resin is preferable because it can form a stable resist pattern with a small dimensional change of the resist pattern with respect to a change in radiation dose. Among these, methoxymethylated melamine resin, ethoxymethylated melamine resin, propoxymethylated melamine resin and butoxymethylated melamine resin are preferable.

  It is preferable to contain the said crosslinking agent in 1-30 mass parts with respect to 100 mass parts of (a) component. When the crosslinking agent is 1 part by mass or more, the resulting film has high plating resistance, chemical resistance, and adhesion, and the formed resist pattern shape is good. Further, if it is 30 parts by mass or less, it is difficult for development failure to occur during development.

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. The organic solvent is not particularly limited as long as it can dissolve each component to be used to form a uniform solution. Conventionally, any one or more of the known solvents for chemically amplified resists may be used. It can be appropriately selected and used.
Specific examples of organic solvents include ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, and 2-heptanone; ethylene glycol, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, diester Polyhydric alcohols such as propylene glycol or dipropylene glycol monoacetate monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether and derivatives thereof; cyclic ethers such as dioxane; and methyl lactate, lactic acid Ethyl, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate It can be mentioned esters such as ethyl ethoxypropionate. These may be used alone or in combination of two or more.
Among these, from the viewpoint of the solubility of the acid generator (b1) of the present invention, polyhydric alcohols and derivatives thereof are preferable, and propylene glycol monomethyl ether is more preferable.

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 a connection terminal or the like, a chemically amplified photoresist composition is used to obtain a thick resist layer having a thickness of, for example, 5 μm or more by using, for example, a spin coating method. The amount in which the solid content concentration in the product 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 the production of connection terminals, and when it is 65% by mass or less, the composition has good fluidity and is easy to handle. In addition, a uniform resist film is easily obtained by spin coating.

  The chemically amplified photoresist composition of the present invention has, as long as the essential properties are not impaired, further miscible additives, for example, additional resins, plasticizers and adhesives for improving the performance of the resist film. Conventional additives such as auxiliaries, stabilizers, colorants, surfactants and the like can be added and contained.

Next, a positive type example is shown.
In the case of the positive type, a crosslinking agent is unnecessary. The component (b) and the organic solvent are the same as in 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 that is generally used as a base resin for a positive chemically amplified photoresist, and is arbitrarily selected from conventionally known ones depending on the light source used for exposure. Can be used. For example, an acrylic resin as a main component, and at least a part of the hydroxyl group is substituted with an alkali dissolution inhibiting group dissociated by an acid, or a polymer having a hydroxyl styrene constituent unit as a main component, the hydroxyl group Those in which at least a part is substituted with an alkali dissolution inhibiting group dissociated by an acid are preferable.
As the particularly preferred component (a), it is composed of one or more resins selected from (b) a polymer having a hydroxystyrene structural unit, (c) an acrylic resin, as in the negative type described above, and at least one of its hydroxyl groups. An example in which part is substituted with an alkali dissolution inhibiting group dissociated by an acid can be exemplified. This is because it is easy to control the coating property and the development speed.

  Examples of the alkali dissolution inhibiting group dissociated by the action of an acid include tertiary alkyloxy groups such as tert-butyloxy group and tert-amyloxy group; cyclic acetaloxy groups such as tetrahydropyranyloxy group and tetrahydrofuranyloxy group; ethoxyethyl Chain acetaloxy groups such as oxy group and methoxypropyloxy group; cycloalkyloxy groups such as cyclohexyloxy group and cyclopentyloxy group; 1-alkyl-cyclo such as 1-methylcyclohexyloxy group and 1-ethylcycloalkyloxy group Preferred examples include at least one selected from alkyloxy groups; 1-alkyl-polycycloalkyloxy groups such as 1-methyladamantyloxy group and 1-ethyladamantyloxy group.

Furthermore, the component (a) can contain other resin components for the purpose of appropriately controlling physical and chemical properties. For example, (i) novolak resin and (d) vinyl resin similar to the negative type described above can be mentioned.
In the above negative type example, the same component can be used as the component (b), the organic solvent, and other components except the crosslinking agent and the component (a).

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 solubility in an organic solvent (resist solvent) of the acid generator (b1) and a high solid content concentration. Therefore, a thick resist layer having a film thickness of 5 μm or more can be easily formed. Therefore, for example, as described later, it is suitably used for manufacturing connection terminals.

<< Resist 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. Examples thereof include a substrate for electronic parts and a substrate on which a predetermined wiring pattern is formed.
Examples of the substrate include substrates made of metal such as silicon, silicon nitride, titanium, tantalum, palladium, titanium tungsten, copper, chromium, iron, and aluminum, and glass substrates. 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 chemical of the portion in contact with copper There was a problem of substrate dependency that the function of the amplification type photoresist was hindered by copper, and development failure such as soaking occurred at that portion. However, the acid generator (b1) of the present invention was used as the component (b). As a result, the substrate dependency is reduced. Therefore, a resist pattern having an excellent shape can be formed.

  The chemical amplification type photoresist composition of the present invention can be prepared by, for example, mixing and stirring the above-mentioned components by a usual method, and using a disperser such as a dissolver, a homogenizer, or a three-roll mill, if necessary. You may let them. Moreover, after mixing, you may further filter using a mesh, a membrane filter, etc.

The resist layer laminate of the present invention can be produced, for example, as follows. 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 pre-baking conditions of the coating film of the composition of the present invention vary depending on the type of each component in the composition, the blending ratio, the coating film thickness, etc., but are usually 70 to 130 ° C., preferably 80 to 120 ° C. ~ About 60 minutes.

  The film 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 thickness of 5 μm or more, it can be suitably used for production of connection terminals. The thickness of the thick resist layer is preferably 20 μm or more, more preferably 30 μm or more, and even more preferably 55 μm or more as the lower limit. The upper limit is not particularly limited, but is preferably 1000 μm or less, more preferably 500 μm or less, more preferably 150 μm or less, further preferably 120 μm or less, and further preferably 75 μm or less.

<< Method for Forming Resist Pattern of Fifth Aspect >>
The resist pattern forming method of the present invention comprises: a laminating process for obtaining a resist layer laminate of the present invention by laminating a resist layer comprising the chemically amplified photoresist composition of the present invention on a support; and selecting the resist layer laminate In particular, the method includes an exposure step of irradiating radiation and a development step of developing after the exposure step to obtain a resist pattern.
The lamination step can be performed in the same manner as in the production of the resist layer laminate.
In the exposure step, 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 selectively applied to the obtained photoresist layer through a mask having a predetermined pattern. Irradiate (exposure). As these radiation sources, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, an argon gas laser, or the like can be used. Here, the 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, the film thickness of the coating film, etc., for example, an ultrahigh pressure mercury lamp (g-line (436 nm), h-line (405 nm), i-line (365 nm), etc.) In the case of use, it is 100 to 2000 mJ / cm ² .
Then, after exposure, heating and diffusion are promoted by using a known method to change the alkali solubility of the photoresist layer in the exposed portion.
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 can also be 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, but it is usually 1 to 30 minutes, and the development method is a liquid piling method, dipping method, paddle method, spray development method. Any of these may be used. After the development, washing with running water is performed for 30 to 90 seconds and dried using an air gun or an oven.

Then, a connection terminal such as a metal post or a bump is formed by embedding a conductor such as metal in the non-resist portion (the portion removed with the alkaline developer) of the resist pattern thus obtained, for example, by plating or the like. can do.
The plating method is not particularly limited, and various conventionally known methods can be employed. As the plating solution, solder plating or copper plating solution is particularly preferably used.
The remaining resist pattern is finally removed using a stripping solution or the like according to a conventional method.

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 longer, and can be exposed to resist using radiation having a wavelength of 365 nm or longer. A sufficient amount of acid is generated to form the pattern. Moreover, the solubility with respect to the organic solvent used for a resist is also high. Therefore, the acid generator (b1) comprising 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 (b1). The chemically amplified photoresist composition containing sulfur has high sensitivity.
Further, the chemically amplified photoresist composition of the present invention has low substrate dependency, and can form a resist pattern with excellent shape and accuracy regardless of the type of substrate used. That is, conventionally, for example, when using a support in which a metal such as copper or aluminum is used for at least a part of the support, a chemically amplified photoresist in a part in contact with the metal (in the case of a negative film) There was a problem of substrate dependency such that development failure (such as poor adhesion in the case of positive) occurred. However, the acid generator (b1) comprising the compound (B1) of the present invention was used as the component (b). By using it, the substrate dependency is reduced. The effect of reducing the substrate dependency is presumed because the compound (B1) of the present invention does not have a group that easily reacts with a metal such as copper, such as -CN.
Furthermore, since the compound (B1) of the present invention has a high solubility in an organic solvent, the chemical amplification 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 μm or more. It is suitable for forming a thick resist layer.
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 expected to have excellent temporal stability. Along with this, it is presumed that a decrease in sensitivity due to deterioration in performance over time and a deterioration in resist pattern shape can also be prevented.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited to these examples.

[Resin synthesis example 1]
<Synthesis of novolac resin>
m-cresol and p-cresol were mixed at a mass ratio of 60:40, formalin was added thereto, and condensed by an ordinary method using an oxalic acid catalyst to obtain a cresol novolak resin. The resin was subjected to a fractionation treatment, and a low molecular region was cut to obtain a novolak resin having a mass average molecular weight of 8,000. This resin is referred to as (A-1).

[Example 1] <Preparation of chemically amplified photoresist composition>
90 parts by mass of the resin (A-1) obtained in Resin Synthesis Example 1, 3 parts by mass of the acid generator (B-1) represented by the above formula (B3), and a crosslinking agent (hexamethoxymethylated melamine (three Wako Chemical Co., Ltd., trade name: Nicalak Mw-100)) 10 parts by mass with propylene glycol monomethyl ether acetate to make a uniform solution, and then filtered through a membrane filter having a pore size of 1 μm to obtain a solid content concentration. A 50 mass% chemically amplified negative photoresist composition was obtained.

[Comparative Example 1]
A chemically amplified negative in the same manner as in Example 1 except that 3 parts by mass of triphenylsulfonium trifluoromethanesulfonate (acid generator (B-2)) was used instead of 3 parts by mass of the acid generator (B-1). A type photoresist composition was prepared.

<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 were evaluated as follows. The results are shown in Table 1.
<Solubility>
The concentration was changed in increments of 1% by mass from 5% by mass to 1% by mass to prepare a propylene glycol monomethyl ether acetate solution of each acid generator. After the adjustment, each solution was stirred to measure the concentration at which each acid generator was completely dissolved.

The following evaluation was performed on the chemically amplified negative resist compositions obtained in the above Examples and Comparative Examples.
First, a chemically amplified negative photoresist composition is applied onto a 5-inch copper sputtering wafer using a spinner so as to have a film thickness of about 30 μm, and prebaked on a hot plate at 110 ° C. for 6 minutes to form a resist. A layer stack was formed. Next, stepwise UV exposure is performed in the range of 100 to 10,000 mJ / cm ² using a stepper (Canon, PLA PLA-501F, ghi line multi, hard contact) through a pattern mask for resolution measurement. 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 by single exposure (365 nm).

<Sensitivity>
After the development, the exposure amount at which a contact resist line pattern having a line width of 40 μm 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 ×: The shape of the formed resist pattern is an inverted trapezoidal shape (the numbers in parentheses indicate the contact angle between the pattern and the substrate)
<Residual film ratio>
The film thickness of the formed resist pattern was measured, and the ratio of the remaining film to the film thickness before development was calculated as the remaining film ratio.

Claims (9)

The acid generator which consists of a compound represented by the following general formula (B1).

[In formula (B1), R ¹ , R ² and R ³ are each independently a group represented by the following general formula (B1a), an alkyl group having 1 to 12 carbon atoms , or an aromatic group having 6 to 18 carbon atoms. A group obtained by removing one hydrogen atom from a ring, and the aromatic ring may have a substituent selected from an alkoxy group having 1 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms, and a hydroxyl group ; and one of ^{R 1,} R 2, ^{R 3} is a group represented by the following general formula (B1a); X ^- represents an anion. ]

[In the formula (B1a), Y is a group obtained by removing two hydrogen atoms from an aromatic ring having 6 to 18 carbon atoms, and the aromatic ring is an alkoxy group having 1 to 12 carbon atoms and an alkyl group having 1 to 12 carbon atoms. have a substituent selected from the group and a hydroxyl group; Z is a group obtained by removing one hydrogen atom from an aromatic ring having 6 to 18 carbon atoms, aromatic ring the alkoxy group having 1 to 12 carbon atoms, carbon atoms have a substituent selected from 1-12 alkyl group and a hydroxyl group; an aromatic ring in at least one of Y and Z has at least one alkoxy group having 1 to 12 carbon atoms. ]   The acid generator according to claim 1, comprising a compound represented by the following general formula (B2).

[In formula (B2), R ⁴ , R ⁵ Are each independently an alkyl group having 1 to 12 carbon atoms, a phenyl group or a naphthyl group, and the phenyl group or naphthyl group is an alkoxy group having 1 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms and a hydroxyl group. Optionally having a substituent selected from: R ⁶ , R ⁷ Are each independently an alkoxy group having 1 to 12 carbon atoms; X ⁻ Is an anion. ] Wherein wherein X ^-, acid generator according to claim 1 or 2, wherein the fluorinated alkyl sulfonic acid ion. The acid generator according to claim 3, comprising a compound represented by the following formula (B3).

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 chemical amplification photoresist composition, wherein the compound (b) that generates acid upon irradiation contains the acid generator according to any one of claims 1 to 4.   The chemically amplified photoresist composition according to claim 5, which is used for radiation having a wavelength of 365 nm or more.   A resist layer laminate comprising a resist layer made of the chemically amplified photoresist composition according to claim 5 or 6 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.   A laminating step of laminating a resist layer made of a chemically amplified photoresist composition on a support to obtain a resist layer laminate according to claim 7 or 8, and an exposure step of selectively irradiating the resist layer laminate And a development step of developing after the exposure step to obtain a resist pattern.