TWI589988B - Resist composition, method for producing resist pattern, method for producing thick film resist pattern, and method for producing connecting terminal - Google Patents

Description

Photoresist composition, method for forming photoresist pattern, method for manufacturing thick film photoresist pattern, and method for manufacturing connection terminal

The present invention relates to a photoresist composition, a method for forming a photoresist pattern, a method for producing a thick film photoresist pattern, and a method for producing a connection terminal.

In the lithography technique, for example, a photoresist film formed of a photoresist material is formed on a substrate, and the photoresist film is irradiated with light such as light or electron lines through a mask forming a specific pattern. The selective exposure, the development treatment, and the like are carried out, and the step of forming a photoresist pattern having a specific pattern on the photoresist film is performed.

The photoresist having a change in the exposed portion is a positive resistive material having a property of being dissolved in a developing solution, and a resistive material having a characteristic in which the exposed portion is not dissolved in the developing solution is referred to as a negative type.

In recent years, in the manufacture of semiconductor elements or liquid crystal display elements, the pattern has been rapidly refined with the progress of the lithography etching technology.

The method of miniaturization is generally carried out in such a manner that the source of the exposure light is shortened (high energy). Specifically, conventionally, ultraviolet rays typified by g-line and i-line have been used, and mass production of semiconductor devices has been started using KrF excimer lasers or ArF excimer lasers. Further, studies have been started on electron beams, EUV (extreme ultraviolet rays) or X-rays which are shorter wavelengths (high energy) than these excimer lasers.

In recent years, photofabrication has become the mainstream of precision microfabrication technology. Photosensitive etching means that a photosensitive resin composition is applied onto the surface of a workpiece to form a coating film, and the coating film is patterned by photolithography, and patterning is performed by patterning. The latter coating film is a general term for a technique of manufacturing various precision members such as a semiconductor device by chemical etching, electrolytic etching, or electroforming, or electroforming.

In addition, in recent years, with the miniaturization of electronic equipment, semiconductor devices have been subjected to high-density mounting technology, and it has been demanded to implement the mounting of a plurality of pin films, to miniaturize the size of devices, and to bridge wafers. Based on the two-dimensional mounting technology and the three-dimensional mounting technology, the method of increasing the density of the mounting is carried out. In these high-density mounting technologies, the terminals are connected with high precision, for example, bumps (mounting terminals) protruding from bumps on the device, or by peripheral devices on the wafer. A metal post or the like connected to the rewiring of the terminal and the mounting terminal is disposed on the substrate.

In the above photofabrication, the photoresist is used, and the photoresist used in the photosensitive etching process is known to contain, for example, an acid. A photoresist composition of a green agent (for example, refer to Patent Documents 1 and 2).

The photoresist used in the above-mentioned photosensitive etching process is generally a photoresist for using a thick film. The photoresist for thick film is used, for example, for forming a bump or a metal post in a plating step. For example, a thick film photoresist layer having a film thickness of about 20 μm is formed on the support, and exposure and development are performed through a specific mask pattern, and portions forming bumps or metal pillars are selectively removed (peeled). To form a photoresist pattern. Then, the removed portion (non-photosensitive portion) is buried in a conductor such as copper by plating or the like, and then a bump or a metal pillar can be formed by removing the photoresist pattern around it.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] JP-A-9-176112

[Patent Document 2] Japanese Patent Publication No. 11-52562

In the future, as semiconductor devices become denser, it is necessary to increase the density of the bump electrodes or the metal pillars. Therefore, in the case where the photoresist composition is used as a photoresist for a thick film, in order to achieve a higher density of the bump electrode or the metal pillar, it is necessary to seek a thick film having higher sensitivity and high masking faith. A photoresist composition is used.

However, in the use of the previous acid generator or the ability to produce acid In the case of a unit, there is still room for improvement in terms of sensitivity.

The present invention has an object of providing a photoresist composition containing an acid generator suitable for a photoresist composition, a method for forming a photoresist pattern, a method for producing a thick film photoresist pattern, a method for producing a connection terminal, and the like.

A first aspect of the present invention is a photoresist composition which is a resin component (A) containing a change in solubility of a developer via an action of an acid, and an acid generator component which generates an acid via exposure ( B), the acid generator component (B) is an acid generator (B1) containing a compound represented by the following formula (b1-1), [wherein, R ¹ and R ² are an alkyl group having 1 to 10 carbon atoms which may have a substituent, and R ³ and R ⁴ are an alkyl group having 2 to 10 carbon atoms which may have a substituent, and R ³ and R ⁴ , It may form a ring together with the sulfur atom to which it is bonded, and X ^- is a pair of anions].

A second aspect of the present invention is a method for forming a photoresist pattern, comprising the steps of forming a photoresist film using the photoresist composition of the first aspect, exposing the photoresist film, and The step of developing the aforementioned photoresist film to form a photoresist pattern.

A third aspect of the present invention is a method of fabricating a thick film photoresist pattern, comprising: a lamination step of laminating a thick film photoresist layer containing the photoresist composition of the first aspect; Selectively irradiating the thick film photoresist layer with active light or radiation to expose the thick film photoresist layer in the exposure step, and obtaining a thick film photoresist pattern Development step.

A fourth aspect of the present invention provides a method of manufacturing a connection terminal, comprising: forming a non-resistive portion in a thick film photoresist pattern obtained by using the method for manufacturing a thick film photoresist pattern; The step of connecting the terminals formed by the conductors.

The present invention provides a photoresist composition containing an acid generator suitable for a photoresist composition, a method for forming a photoresist pattern, a method for producing a thick film photoresist pattern, and a method for producing a connection terminal.

[Formation of the Invention]

In the present specification and the scope of the present patent application, "aliphatic" means a concept of relativity to aromatics, and is defined as a group or a compound having no aromaticity.

The "alkyl group" is a group containing a linear, branched or cyclic monovalent saturated hydrocarbon group, unless otherwise specified.

The "alkylene group" is a group containing a linear, branched or cyclic divalent saturated hydrocarbon group, unless otherwise specified. The alkyl group in the alkoxy group is also the same content.

The "halogenated alkyl group" means a group in which a part or all of a hydrogen atom of an alkyl group is substituted by a halogen atom, for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

The "fluorinated alkyl group" or "fluorinated alkyl group" means a group in which a part or all of a hydrogen atom of an alkyl group or an alkyl group is substituted by a fluorine atom.

The "structural unit" means a monomer unit constituting a polymer compound (resin, polymer, copolymer).

The "structural unit derived from acrylate" means the structural unit composed of the cleavage of the ethylenic double bond of the acrylate.

"Acrylate" means a compound in which a hydrogen atom at the carboxyl terminal of acrylic acid (CH ₂ =CH-COOH) is substituted with an organic group.

In the acrylate, a hydrogen atom bonded to a carbon atom at the α-position may be substituted with a substituent. The substituent (R ^α ) of the hydrogen atom to which the carbon atom of the α-position is bonded is an atom or a group other than a hydrogen atom, for example, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms. Hydroxyalkyl and the like. Further, the carbon atom at the α position of the acrylate is not particularly limited, and means a carbon atom to which a carbonyl group is bonded.

Hereinafter, the acrylate in which the hydrogen atom to which the carbon atom bonded to the α-position is substituted by a substituent is also referred to as an α-substituted acrylate. Further, the inclusion of an acrylate and an α-substituted acrylate is also referred to as "(α-substituted) acrylate".

The "structural unit derived from a hydroxystyrene or a hydroxystyrene derivative" means a structural unit composed of a vinyl double bond of a hydroxystyrene or a hydroxystyrene derivative which is cleaved.

The "hydroxystyrene derivative" means a concept in which a hydrogen atom containing an α-position of a hydroxystyrene is substituted with another substituent such as an alkyl group or a halogenated alkyl group, and derivatives thereof. The derivatives, for example, a hydrogen atom in which the hydrogen atom at the α position may be substituted by a substituent, and a hydrogen atom in the hydroxyl group of the hydroxystyrene may be substituted with an organic group, and a hydrogen atom at the α position may be substituted with a hydroxybenzene group. On the benzene ring of ethylene, a substituent other than a hydroxyl group is bonded, and the like. Further, the α-position (the carbon atom in the α-position) means, unless otherwise specified, the meaning of the carbon atom to which the benzene ring is bonded.

The substituent of the hydrogen atom at the α-position of the substituted hydroxystyrene is, for example, the same as the substituent of the α-substituted acrylate.

The "structural unit derived from a vinyl benzoic acid or a vinyl benzoic acid derivative" means a structural unit composed of a vinyl double bond of a vinyl benzoic acid or a vinyl benzoic acid derivative which is cleaved.

The "vinyl benzoic acid derivative" means a group containing a hydrogen atom of the alpha position of vinyl benzoic acid substituted with another substituent such as an alkyl group or a halogenated alkyl group, and the concept of these derivatives. The derivatives, for example, a hydrogen atom of a vinyl benzoic acid in which the hydrogen atom at the alpha position may be substituted by an organic group, and a hydrogen atom at the alpha position may be substituted with a substituent. On the benzene ring of benzoic acid, a substituent other than a hydroxyl group or a carboxyl group is bonded. Further, the α-position (the carbon atom in the α-position) means, unless otherwise specified, the meaning of the carbon atom to which the benzene ring is bonded.

"Styrene" means a concept in which a hydrogen atom containing an α-position of styrene and styrene is substituted with another substituent such as an alkyl group or a halogenated alkyl group.

The "structural unit derived from styrene" and "structural unit derived from a styrene derivative" mean a structural unit composed of a vinyl double bond of styrene or a styrene derivative which is cleaved.

The alkyl group which is a substituent of the above α position is preferably a linear or branched alkyl group, and specifically, for example, an alkyl group having 1 to 5 carbon atoms (methyl, ethyl, propyl, isopropyl) Base, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl) and the like.

In addition, the halogenated alkyl group which is a substituent of the α-position is, for example, a group in which a part or all of a hydrogen atom of the above-mentioned "alkyl group as a substituent at the α-position" is substituted by a halogen atom. The halogen atom is, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or the like, and particularly preferably a fluorine atom.

In addition, the hydroxyalkyl group which is a substituent of the α-position is, for example, a group in which a part or all of a hydrogen atom of the above-mentioned "alkyl group as a substituent at the α-position" is substituted with a hydroxyl group. In the hydroxyalkyl group, the number of hydroxyl groups is preferably from 1 to 5, and most preferably from 1.

In the case where "the substituent may be substituted", the case where the hydrogen atom (-H) is substituted with a monovalent group is substituted, and the methyl group (-CH ₂ -) is substituted with a divalent group. By.

"Exposure" is the concept of including all radiation exposure.

The photoresist composition of the present invention is characterized in that it contains a resin component (A) which changes the solubility of a developer by an action of an acid, and an acid generator component (B) which generates an acid by exposure, and is characterized by The acid generator component (B) is an acid generator (B1) containing a compound represented by the following formula (b1-1).

[wherein, R ¹ and R ² are an alkyl group having 1 to 10 carbon atoms which may have a substituent, and R ³ and R ⁴ are an alkyl group having 2 to 10 carbon atoms which may have a substituent, and R ³ and R ⁴ , It may form a ring together with the sulfur atom to which it is bonded, and X ^- is a pair of anions].

The photoresist composition of the present invention is a photoresist composition which generates an acid by exposure and which changes the solubility of the developer by the action of an acid, and contains a change in the solubility of the developer via the action of an acid. Resin component (A) (hereinafter also referred to as "(A) component").

When the resist film is formed using the photoresist composition, and the resist film is selectively exposed, an acid is generated in the exposed portion, and the solubility of the component (A) to the developer is changed by the action of the acid. At the same time, in the unexposed portion, the solubility of the developer (A) does not change, and the difference in solubility between the exposed portion and the unexposed portion is caused to the developer. Therefore, when the photoresist film is developed, when the photoresist composition is positive, the exposed portion is dissolved and removed to form a positive photoresist pattern, and when the photoresist composition is negative, The exposed portion is dissolved and removed to form a negative photoresist pattern.

In the present specification, the photoresist composition in which the exposed portion is dissolved and removed to form a positive photoresist pattern is referred to as a positive photoresist composition, and the unexposed portion is dissolved and removed. The photoresist composition forming the negative photoresist pattern is referred to as a negative photoresist composition.

The photoresist composition of the present invention may be a positive photoresist composition or a negative photoresist composition.

Further, the photoresist composition of the present invention may be a process for forming a photoresist pattern or a process for using an alkali developer, and a developer containing an organic solvent (organic developer) may be used for the development process. The solvent development process can also be used.

The photoresist composition of the present invention is an acid generating ability capable of generating an acid by exposure, which may be obtained by exposing an acid to the component (A), and adding an additive component which is not added simultaneously with the component (A). The acid produced by exposure can also be used.

Specifically, the photoresist composition of the present invention may be (1) an acid generator component (B) (hereinafter, also referred to as "(B) component") containing an acid generated by exposure; 2) (A) The component may be a component which generates an acid by exposure; (3) The component (A) is a component which generates an acid by exposure, and may further contain (B) component.

In other words, in the case of the above (2) and (3), the component (A) is a "substrate component which generates an acid by exposure and which changes the solubility of the developer through the action of an acid". (A) The component is a substrate component which generates an acid by exposure and changes the solubility of the developer by the action of an acid, and the component (A1) described later generates an acid by exposure, and A polymer compound which changes the solubility of the developer by the action of an acid is preferred. These polymer compounds can be used to have an acid generated by exposure. Structural unit of resin. A well-known component can be used for the structural unit which generates an acid by exposure.

The photoresist composition of the present invention is particularly preferable in the case of the above (1).

<Resin component (A)>

The resin component (A) which changes the solubility of the alkali by the action of an acid is not particularly limited, and any resin which changes the solubility of the alkali by the action of an acid can be used. Among them, a resin containing at least one selected from the group consisting of novolac resin (Anv1), polyhydroxystyrene resin (Aphs1), and acrylic resin (Aac1) is preferred.

The resin component (A) is an acid-decomposable group which changes its polarity by the action of an acid.

The "acid-decomposable group" is an acid-decomposable group which causes cracking of at least a part of the structure of the acid-decomposable group by the action of an acid.

The acid-decomposable group which increases the polarity by the action of an acid, for example, is decomposed by the action of an acid to form a group of a polar group or the like.

A polar group such as a carboxyl group, a hydroxyl group, an amine group, a sulfo group (-SO ₃ H) or the like. Among these, a polar group containing -OH in the structure (hereinafter also referred to as "polar group containing OH") is preferred, and a carboxyl group or a hydroxyl group is preferred, and a carboxyl group is particularly preferred.

The acid-decomposable group is more specifically, for example, a group in which the aforementioned polar group is protected by an acid-cleavable group (for example, a group in which a hydrogen atom of a polar group containing OH is protected by an acid-cleavable group).

Here, the "acid dissociable group" means an acid dissociable group which (i) causes a bond between atoms of the acid dissociable group and the acid dissociable group to cause cracking via an action of an acid, or (ii) after a part of the bond is cracked by the action of an acid, and then a bond between the acid dissociable group and the atom adjacent to the acid dissociable group is generated by a decarbonation reaction to generate a cracking basis. The meaning of the two.

The acid dissociable group constituting the acid-decomposable group must be a group having a polarity lower than that of the polar group formed by dissociation of the acid dissociable group, and thus the acid dissociable group is dissociated by the action of an acid. Further, a polar group having a polarity higher than that of the acid dissociable group is generated, and the polarity can be increased. As a result, the polarity of the entire component (A1) can be increased. When the polarity is increased, the solubility of the developer may be relatively changed. When the developer is an alkali developer, the solubility may be increased. When the developer is an organic developer, the dissolution may be lowered. Sex.

The acid dissociable group is not particularly limited, and a component which has been proposed as an acid dissociable group of a base resin for chemically amplified photoresist has been used.

In the above-mentioned polar group, an acid dissociable group which protects a carboxyl group or a hydroxyl group, for example, an acid dissociable group represented by the following formula (a1-r-1) (hereinafter also referred to as "acetal type acid dissociable group") )Wait.

[wherein, Ra' ¹ and Ra' ² are a hydrogen atom or an alkyl group, Ra' ³ is a hydrocarbon group, and Ra' ³ may be bonded to any of Ra' ¹ and Ra' ² to form a ring].

In the formula (a1-r-1), among Ra' ¹ and Ra' ² , at least one of them is preferably a hydrogen atom, and both of them are preferably a hydrogen atom.

In the case where Ra' ¹ or Ra' ² is an alkyl group, for example, in the description of the above-mentioned α-substituted acrylate, the alkyl group exemplified by the substituent bonded to the carbon atom of the α-position is the same content, etc. It is preferably an alkyl group having 1 to 5 carbon atoms. Specifically, for example, a linear or branched group of a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group or the like. A chain alkyl group or the like is preferably a methyl group or an ethyl group, and a methyl group is particularly preferred.

In the formula (a1-r-1), the hydrocarbon group of Ra' ³ is, for example, a linear, branched or cyclic alkyl group. The linear alkyl group preferably has a carbon number of 1 to 5, preferably 1 to 4, more preferably 1 or 2. Specifically, for example, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group or the like. Among these, a methyl group, an ethyl group or an n-butyl group is preferred, and a methyl group or an ethyl group is more preferred.

The branched alkyl group is preferably a carbon number of 3 to 10, more preferably 3 to 5. Specifically, for example, isopropyl, isobutyl, tert-butyl, isopentyl, neopentyl or the like is preferably isopropyl.

The cyclic alkyl group is preferably 3 to 20 carbon atoms, and 4 to 12 carbon atoms. good. Specifically, for example, it is removed by a monocyclic alkane such as cyclopentane or cyclohexane, or a polycyclic alkane such as adamantane, norbornane, isodecane, tricyclodecane or tetracyclododecane. The base obtained by more than one hydrogen atom, and the like. A part of the carbon atom constituting the ring of the cyclic alkyl group may be substituted by an etheric oxygen atom (-O-).

Ra' ³ , in the case of bonding with any of Ra' ¹ and Ra' ² , the ring base is preferably a 4 to 7 ring, and a 4 to 6 ring is preferred. Specific examples of the cyclic group include, for example, a tetrahydropyranyl group, a tetrahydrofuranyl group and the like.

In the above-mentioned polar group, an acid dissociable group which protects a carboxyl group, for example, an acid dissociable group represented by the following general formula (a1-r-2) (an acid represented by the following formula (a1-r-2)) Among the dissociable groups, those which are composed of an alkyl group are hereinafter referred to as "triester alkyl ester type acid dissociable group".

[wherein, Ra' ⁴ to Ra' ⁶ are each represented by a hydrocarbon group, and Ra' ⁵ and Ra' ⁶ may be bonded to each other to form a ring].

The hydrocarbon group of Ra' ⁴ ~Ra' ⁶ is, for example, the same as the aforementioned Ra' ³ .

Ra' ⁴ is preferably an alkyl group having 1 to 5 carbon atoms. Ra' ⁵ and Ra' ⁶ are bonded to each other to form a ring, and may be, for example, a group represented by the following formula (a1-r2-1). On the other hand, in the case where Ra' ⁴ to Ra' ^{6 are} not bonded to each other and are independent hydrocarbon groups, for example, a group represented by the following formula (a1 - r2-2) can be used.

[In the formula, Ra ^'10 is alkyl of 1 to 10, Ra' ¹¹ with the Ra ^'10 together form a carbon atom bonded to the group of the aliphatic cyclic group, Ra' ¹² ~ Ra ^'14 each independently represents Hydrocarbyl group].

In the formula (a1-r2-1), the alkyl group in the alkyl group having 1 to 10 carbon atoms of Ra' ¹⁰ is a linear or branched alkane of Ra' ³ in the formula (a1-r-1). The base listed is preferred. In the formula (a1-r2-1), Ra 'in the aliphatic cyclic group consisting of ^11, the formula (a1-r-1) Ra ' of the ^cycloalkyl group preferably enumerated.

In the formula (a1-r2-2), Ra' ¹² and Ra' ¹⁴ are each independently an alkyl group having 1 to 10 carbon atoms, and the alkyl group is represented by Ra' ³ in the formula (a1-r-1). The group of the linear or branched alkyl group is preferably a group, and a linear alkyl group having 1 to 5 carbon atoms is more preferred, and a methyl group or an ethyl group is particularly preferred.

In the formula (a1-r2-2), Ra' ¹³ is preferably a linear, branched or cyclic alkyl group exemplified by the hydrocarbon group of Ra' ³ in the formula (a1-r-1). Among these groups, the group exemplified by the cyclic alkyl group of Ra' ³ is more preferable.

Specific examples of the above formula (a1-r2-1) are as follows, for example. Hereinafter, "*" indicates a key button.

Specific examples of the above formula (a1 - r2-2) are as follows, for example.

Further, among the above-mentioned polar groups, an acid-dissociable group which protects a hydroxyl group, for example, an acid-dissociable group represented by the following formula (a1-r-3) (hereinafter, conveniently referred to as "tri-terminated alkoxycarbonyl group" Acid dissociable group").

[wherein, Ra' ⁷ ~ Ra' ⁹ represents an alkyl group, respectively].

In the formula (a1-r-3), the Ra' ⁷ ~Ra' ⁹ group is preferably an alkyl group having 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms.

Further, the total carbon number of each alkyl group is preferably from 3 to 7, preferably from 3 to 5, and most preferably from 3 to 4.

[Acrylic Resin (Aac1)]

As the acrylic resin (Aac1), a resin containing a structural unit represented by the following general formulae (a1-1) to (a1-2) can be used.

[In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms. Va ¹ is a divalent hydrocarbon group which may have an ether bond, a urethane bond, or a guanamine bond, n _a1 is independently 0 to 2, and Ra ¹ is the above formula (a1-r-1) An acid dissociable group represented by ~(a1-r-2). Wa ¹ is a hydrocarbon group of n _a2 +1 valence, n _a2 is 1-3, and Ra ² is an acid dissociable group represented by the above formula (a1-r-1) or (a1-r-3).

In the above formula (a1-1), the alkyl group having 1 to 5 carbon atoms may be linear or branched, and specifically, for example, methyl, ethyl, propyl, isopropyl, n - butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, and the like. The halogenated alkyl group having 1 to 5 carbon atoms is a group in which a part or all of a hydrogen atom in the alkyl group having 1 to 5 carbon atoms is substituted by a halogen atom. The halogen atom is, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or the like, and particularly preferably a fluorine atom.

R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a fluorinated alkane having 1 to 5 carbon atoms. The base is preferred, and in terms of industrial ease, it is preferred to use a hydrogen atom or a methyl group.

The hydrocarbon group having a valence of two of Va ¹ may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group is intended to be a hydrocarbon group having no aromaticity. The aliphatic hydrocarbon group which is a divalent hydrocarbon group in Va ¹ may be saturated or unsaturated, and is usually saturated.

The aliphatic hydrocarbon group is more specifically, for example, a linear or branched aliphatic hydrocarbon group or a hydrocarbon group having a ring in the structure.

Further, Va ^{1 is,} for example, a bond of a divalent hydrocarbon group bonded via an ether bond, a urethane bond, or a guanamine bond.

The linear or branched aliphatic hydrocarbon group is preferably a carbon number of 1 to 10, preferably 1 to 6, more preferably 1 to 4, and most preferably 1 to 3.

a linear aliphatic hydrocarbon group, preferably a linear alkyl group, specifically, for example, methyl [-CH ₂ -], ethyl (-(CH ₂ ) ₂ -), or The group [-(CH ₂ ) ₃ -], tetramethyl [-(CH ₂ ) ₄ -], pentamethyl [-(CH ₂ ) ₅ -], and the like.

a branched aliphatic hydrocarbon group, preferably a branched alkyl group, specifically, for example, -CH(CH ₃ )-, -CH(CH ₂ CH ₃ )-, -C(CH ₃ ) ₂ -, -C(CH ₃ )(CH ₂ CH ₃ )-, -C(CH ₃ )(CH ₂ CH ₂ CH ₃ )-, -C(CH ₂ CH ₃ ) ₂ - or the like alkyl-methyl group; CH(CH ₃ )CH ₂ -, -CH(CH ₃ )CH(CH ₃ )-, -C(CH ₃ ) ₂ CH ₂ -, -CH(CH ₂ CH ₃ )CH ₂ -, -C(CH ₂ CH _{3) 2} -CH ₂ -, etc. extending ethyl _{group; -CH (CH 3) CH 2} CH 2 -, - CH 2 CH (CH 3) CH 2 - , etc. extending trimethyl alkyl; -CH (CH ₃ ) An alkyl group such as CH ₂ CH ₂ CH ₂ -, -CH ₂ CH(CH ₃ )CH ₂ CH ₂ - or the like is extended to an alkyl group such as a tetramethyl group. The alkyl group in the alkylalkyl group is preferably a linear alkyl group having 1 to 5 carbon atoms.

The above structure contains a ring-shaped aliphatic hydrocarbon group, for example, an alicyclic hydrocarbon group (a group obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring), and an alicyclic hydrocarbon group bonded to a linear or branched aliphatic hydrocarbon group. The terminal group and the alicyclic hydrocarbon group are in the middle of a linear or branched aliphatic hydrocarbon group. The linear or branched aliphatic hydrocarbon group is the same as described above.

The alicyclic hydrocarbon group is preferably a carbon number of from 3 to 20, more preferably from 3 to 12.

The alicyclic hydrocarbon group may be a polycyclic ring or a monocyclic ring. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a monocyclic alkane. The monocyclic alkane is preferably a carbon number of 3 to 6, and specifically, for example, cyclopentane or cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a polycyclic alkane, preferably having a carbon number of from 7 to 12, specifically, for example, adamantane , norbornane, isodecane, tricyclodecane, tetracyclododecane, and the like.

The aromatic hydrocarbon group is a hydrocarbon group having an aromatic ring.

In the above Va ¹ , the aromatic hydrocarbon group as the divalent hydrocarbon group is preferably 3 to 30, more preferably 5 to 30, more preferably 5 to 20, and most preferably 6 to 15. 6~10 is the best. Among them, the carbon number is not including the carbon number in the substituent.

An aromatic ring possessed by an aromatic hydrocarbon group, specifically, for example, benzene, An aromatic hydrocarbon ring such as biphenyl, anthracene, naphthalene, anthracene or phenanthrene; an aromatic heterocyclic ring constituting a part of a carbon atom of the aromatic hydrocarbon ring substituted by a hetero atom; The hetero atom in the aromatic hetero ring is, for example, an oxygen atom, a sulfur atom, a nitrogen atom or the like.

The aromatic hydrocarbon group is specifically, for example, a group obtained by removing two hydrogen atoms from the aromatic hydrocarbon ring (aryl group); and 1 in the group (aryl group) obtained by removing one hydrogen atom from the aromatic hydrocarbon ring. a group in which a hydrogen atom is substituted by an alkyl group (for example, an arylalkyl group such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group or a 2-naphthylethyl group) a group obtained by removing one hydrogen atom from an aryl group; a group obtained by removing two hydrogen atoms from an aromatic compound containing two or more aromatic rings (for example, biphenyl, anthracene, etc.); The carbon number of the alkylene group (alkyl chain in the arylalkyl group) is preferably from 1 to 4, more preferably from 1 to 2, particularly preferably from 1 to 1.

In the above formula (a1-2), the hydrocarbon group having a n _a2 +1 valence in Wa ¹ may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group means a hydrocarbon group which does not have an aromaticity, and may be either saturated or unsaturated, and is usually saturated. The above aliphatic hydrocarbon group, for example, a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group having a ring in the structure, or a linear or branched aliphatic hydrocarbon group and a cyclic hydrocarbon group containing a ring in the structure Specifically, for example, the base and the like of the above formula (a1-1) are the same as those exemplified for Va ¹ of the above formula (a1-1).

The aforementioned n _a2 +1 price is preferably 2 to 4, and more preferably 2 or 3.

In the above formula (a1-2), in particular, the following formula (a1-2-01) The structural unit represented is preferred.

In the formula (a1-2-01), Ra ² is an acid dissociable group represented by the above formula (a1-r-1) or (a1-r-3). n _a2 is an integer of 1 to 3, preferably 1 or 2, more preferably 1 or more. c is an integer of 0 to 3, preferably 0 or 1, and more preferably 1. R is the same as the foregoing.

The following is a specific example of the above formula (a1-1). In the following formulae, R ^α is a hydrogen atom, a methyl group or a trifluoromethyl group.

The following is a specific example of the above formula (a1-2).

Further, the acrylic resin (Aac1) is a copolymer having a structural unit derived from a polymerizable compound having an ether bond, which is a structural unit represented by the above formulas (a1-1) to (a1-2). The resulting resin is preferred.

The polymerizable compound having an ether bond may, for example, be a radically polymerizable compound having an ether bond or an ester-bonded (meth)acrylic acid derivative, and, for example, 2-methoxyethyl (A) Acrylate, 2-ethoxyethyl (meth) acrylate, methoxy triethylene glycol (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethyl card An alcoholic (meth) acrylate, a phenoxy polyethylene glycol (meth) acrylate, a methoxy polypropylene glycol (meth) acrylate, a tetrahydro fluorenyl (meth) acrylate, or the like. Further, the above polymerizable compound having an ether bond is preferably 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate or methoxy triethylene ethane. Alcohol (meth) acrylate. These polymerizable compounds may be used singly or in combination of two or more kinds.

Also, in the acrylic resin (Aac1), moderate control For the purpose of chemical and chemical properties, other polymerizable compounds may be contained as structural units. The polymerizable compound may, for example, be a known radically polymerizable compound or an anionically polymerizable compound. Further, the polymerizable compounds are, for example, monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; 2-methylpropenyloxyethyl succinic acid; , 2-methylpropenyloxyethyl maleic acid, 2-methylpropenyloxyethyl phthalic acid, 2-methylpropenyl oxyethyl hexahydrophthalic acid, etc., and an ester-bonded group Acrylic acid derivatives; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate and other alkyl (meth) acrylates; 2-hydroxyethyl (A (meth) hydroxyalkyl (meth) acrylate such as acrylate or 2-hydroxypropyl (meth) acrylate; phenyl (meth) acrylate, benzyl (meth) acrylate, etc. (methyl) Aromatic acrylates; dicarboxylic acid diesters such as diethyl maleate and dibutyl fumarate; styrene, α-methylstyrene, chlorostyrene, chloromethylstyrene, vinyl toluene a vinyl-containing aromatic compound such as hydroxystyrene, α-methylhydroxystyrene or α-ethylhydroxystyrene; a vinyl-containing aliphatic group such as vinyl acetate a conjugated diene such as butadiene or isobutylene; a polymerizable compound containing a nitrile group such as acrylonitrile or methacrylonitrile; a chlorine-containing polymerizable compound such as vinyl chloride or dichloroethylene; and acrylamide a polymerizable compound containing a guanamine bond such as methacrylamide or the like;

(Structural unit (a4))

The acrylic resin (Aac1) may, if necessary, have a structural unit (a4) containing a non-acid dissociable cyclic group. (Aac1) component has structural unit (a4) In this case, the dry etching resistance of the formed photoresist pattern can be improved.

The "non-acid dissociable cyclic group" in the structural unit (a4) means that when an acid is generated from the component (B) by exposure, even if it is subjected to the action of the acid, dissociation does not occur, and remains in the A ring group in a structural unit.

The structural unit (a4) is preferably, for example, a structural unit derived from an acrylate having a non-acid dissociable aliphatic cyclic group. The ring group can be, for example, the same as those exemplified in the case of the above-mentioned acrylic resin (Aac1), and it is possible to use a conventionally known majority component which is used as a resin component of the photoresist composition.

In particular, when at least one selected from the group consisting of a tricyclic fluorenyl group, an adamantyl group, a tetracyclododecyl group, an isodecyl group, and a fluorenyl group is industrially preferable, it is preferable. These polycyclic groups may have a linear or branched alkyl group having 1 to 5 carbon atoms as a substituent.

Specifically, the acrylic resin (Aac1) may have a structure of the following general formulae (a4-1) to (a4-7).

[wherein R ^α is the same as described above].

The structural unit (a4) contained in the resin component (A1) may be 1 It is also possible to use two or more species.

When the resin component (A1) contains the structural unit (a4), the ratio of the structural unit (a4) is preferably from 1 to 30 mol%, preferably from 10 to 20, based on the total of the structural units constituting the component (A1). Molar% is better.

Among the above resin components (A), an acrylic resin (Aac1) is preferably used. Among the acrylic resins (Aac1), the structural unit represented by the above formula (a1-1), the structural unit derived from (meth)acrylic acid, and the alkyl (meth)acrylate The derived structural unit is preferably a copolymer obtained from a structural unit derived from an aryl (meth) acrylate.

These copolymers are preferably copolymers represented by the following formula (a8).

In the above formula (a8), Ra ³⁰ represents a hydrogen atom or a methyl group, and Ra ³¹ represents a linear or branched alkyl group having 2 to 4 carbon atoms, and Xa and its bonded carbon atoms together form a carbon number of 5 to 20 The hydrocarbon ring, Ra ³² represents a linear or branched alkyl group having 1 to 6 carbon atoms or an alkoxyalkyl group having 1 to 6 carbon atoms, and Ra ³³ represents an aryl group having 6 to 12 carbon atoms.

The above Xa, together with the carbon atom to which it is bonded, forms an aliphatic cyclic group having 5 to 20 carbon atoms. Specific examples of the aliphatic cyclic group include a group obtained by removing one or more hydrogen atoms from a polycyclic alkane such as a monocyclic alkane, a bicycloalkane, a tricycloalkane or a tetracycloalkane. Specifically, for example, a monocyclic alkane such as cyclopentane, cyclohexane, cycloheptane or cyclooctane, or adamantane, norbornane, isodecane, tricyclodecane or tetracyclododecane A group obtained by removing one or more hydrogen atoms from a polycyclic alkane. In particular, a group obtained by removing one or more hydrogen atoms from cyclohexane or adamantane (which may have a substituent) is preferred.

Further, the aliphatic cyclic group of the above Xa may have a substituent on the ring skeleton, and the substituent may be, for example, a polar group such as a hydroxyl group, a carboxyl group, a cyano group or an oxygen atom (=O), or a carbon number of 1~. a linear or branched lower alkyl group of 4 or the like. The polar group is particularly preferably an oxygen atom (=O).

Further, in the copolymer represented by the above formula (a8), s, t, u, and v each represent a molar ratio of the structural unit, s is 8 to 45 mol%, and t is 10 to 65 mol%. u is 3 to 25 mol%, and v is 6 to 25 mol%.

[Novolak resin (Anv1)]

As the novolak resin (Anv1), a resin containing a structural unit represented by the following formula (anv1) can be used.

[In the formula, Ra ¹¹ is an acid dissociable group, and Ra ¹² and Ra ¹³ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms].

In the above formula (anv1), Ra ¹¹ represents an acid-dissociable group, and Ra ¹² and Ra ¹³ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Ra ¹¹ , a group represented by the above formula (a1-r-1) or (a1-r-3), a linear or branched chain having 1 to 6 carbon atoms, or a cyclic alkyl group or tetrahydropyridyl A decyl group, a tetrahydrofuranyl group or a trialkyldecyl group is preferred.

The alkyl group having 1 to 6 carbon atoms is, for example, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms. a linear or branched alkyl group, for example, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, etc. , a cyclic alkyl group, for example, a cyclopentyl group, a cyclohexyl group or the like.

[Polyhydroxystyrene resin (Aphs1)]

As the polyhydroxystyrene resin (Aphs1), a resin containing a structural unit represented by the following formula (aphs1) can be used.

[In the formula, Ra ¹⁸ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Ra ¹⁹ is an acid dissociable group].

In the above formula (aphs1), Ra ¹⁸ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Ra ¹⁹ represents an acid dissociable dissolution inhibiting group.

In the above formula (aphs1), Ra ^{19 is,} for example, the same group as Ra ¹¹ in the above formula (anv1).

The alkyl group having 1 to 6 carbon atoms is, for example, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms. a linear or branched alkyl group, for example, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, etc. , a cyclic alkyl group, for example, a cyclopentyl group, a cyclohexyl group or the like.

Further, the polyhydroxystyrene resin (Aphs1) may contain other polymerizable compounds as structural units in order to appropriately control physical and chemical properties. The polymerizable compound may, for example, be a known radically polymerizable compound or an anionically polymerizable compound. Further, the polymerizable compounds are, for example, monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; 2-methylpropenyloxyethyl succinic acid; , 2-methylpropenyloxyethyl maleic acid, 2-methylpropenyloxyethyl phthalic acid, 2-methylpropenyl oxyethyl hexahydrophthalic acid, etc., and an ester-bonded group Acrylic acid derivatives; methyl (meth)acrylic acid (meth)acrylic acid alkyl esters such as ester, ethyl (meth) acrylate, butyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (methyl) Hydroxyalkyl (meth) acrylate such as acrylate; aryl (meth) acrylate such as phenyl (meth) acrylate or benzyl (meth) acrylate; diethyl maleate, rich Dicarboxylic acid diesters such as dibutyl phthalate; styrene, α-methylstyrene, chlorostyrene, chloromethylstyrene, vinyltoluene, hydroxystyrene, α-methylhydroxystyrene, A vinyl-containing aromatic compound such as α-ethylhydroxystyrene; a vinyl-containing aliphatic compound such as vinyl acetate; a conjugated diene such as butadiene or isobutylene; acrylonitrile or methacrylonitrile; a polymerizable compound containing a nitrile group; a chlorine-containing polymerizable compound such as vinyl chloride or dichloroethylene; a polymerizable compound containing a guanamine bond such as acrylamide or methacrylamide; or the like.

The resin component (A) can be used by combining a novolac resin (Anv1) and a polyhydroxystyrene resin (Aphs1) with an acrylic resin (Aac1). In this case, the acrylic resin occupies the total of the resins. The ratio is preferably 5 to 100% by mass, preferably 50 to 100% by mass, more preferably 100% by mass.

The polystyrene-converted mass average molecular weight of the resin component (A) is preferably from 5,000 to 300,000, more preferably from 7,000 to 200,000, most preferably from 10,000 to 200,000. In the case of the mass average molecular weight, the thick film photoresist layer can be maintained at a sufficient strength without deteriorating the peeling property from the support, and the expansion of the outer surface can be prevented or cracked during plating. .

Further, the resin component (A) is preferably a resin having a degree of dispersion of 1.05 or more. Where the degree of dispersion is the mass average molecular weight divided by the number average molecule The amount obtained. In such a range of dispersion, it is possible to obtain the desired stress resistance against plating, or to avoid the problem that the metal layer obtained by the plating treatment is likely to expand.

The content of the resin component (A) is not particularly limited. For example, when used as a resin for a thick film, it is preferably 5 to 60% by mass based on the total mass of the photoresist composition of the present invention. 20 to 60% by mass, more preferably 30 to 50% by mass.

In the present invention, the resin component (A) may contain the following structural units (a2), (a3), and (a5).

(Structural unit (a2))

The resin component (A) may contain a structural unit (a2) containing a cyclic group containing a lactone.

The lactone ring group of the structural unit (a2) is effective in the viewpoint of improving the adhesion of the photoresist film to the substrate in the case where the resin component (A) is used to form the photoresist film.

The "per lactone-containing cyclic group" means a ring-form group containing a ring containing -O-C(=O)- (lactone) in the ring-shaped lattice. The lactone ring is counted in the form of a ring. The case where only the lactone ring is called a monocyclic group, and the case of other ring structures, regardless of its structure, is called a polycyclic group. The cyclic group containing a lactone may be a monocyclic group or a polycyclic group.

The cyclic group containing a lactone in the structural unit (a2) is not particularly limited, and any component may be used. Specifically, for example, the following formula The group represented by (a2-r-1)~(a2-r-7). Hereinafter, "*" indicates a key button.

[wherein, Ra' ^{21 is} each independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, -COOR", -OC(=O)R", a hydroxyalkyl group or a cyano group; "A hydrogen atom or an alkyl group; A" is an alkyl, oxygen or sulfur atom having 1 to 5 carbon atoms which may contain an oxygen atom or a sulfur atom, n' is an integer of 0 to 2, and m' is 0 or 1. ].

In the above formula (a2-r-1) to (a2-r-7), A" is an alkylene group having 1 to 5 carbon atoms which may contain an oxygen atom (-O-) or a sulfur atom (-S-). An oxygen atom or a sulfur atom. The alkyl group having a carbon number of 1 to 5 in A" is preferably a linear or branched alkyl group, for example, a methyl group, an ethyl group, and an n-propylene group. Base, isopropyl, etc. The alkylene group is in the case of containing an oxygen atom or a sulfur atom, and specifically, for example, a terminal of the alkylene group or a group having a -O- or -S- group, such as -O-CH ₂ -, -CH ₂ -O-CH ₂ -, -S-CH ₂ -, -CH ₂ -S-CH ₂ -, and the like. A", preferably an alkyl group having a carbon number of 1 to 5 or -O-, preferably a alkyl group having 1 to 5 carbon atoms, preferably a methyl group, and an alkyl group in Ra' ²¹ , An alkoxy group, a halogen atom, a halogenated alkyl group, -COOR", -OC(=O)R", a hydroxyalkyl group, respectively, and a two-valent ring group in V ₀ ^a1 in the above formula (a0) The alkyl group, the alkoxy group, the halogenated alkyl group, the -COOR", the -OC(=O)R", and the hydroxyalkyl group which may be substituted by the substituent are the same.

Specific examples of the group represented by the general formula (a2-r-1) to (a2-r-7) will be listed below.

The structural unit (a2) is not particularly limited as long as it has a cyclic group containing a lactone, and may be, for example, the following The structural unit represented by the formula (a2-1).

Wherein R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms; Ya ²¹ is a single bond or a divalent linking group, and La ²¹ is -O-, -COO- , -CON(R')-, -OCO-, -CONHCO- or -CONHCS-, R' represents a hydrogen atom or a methyl group. However, when La ²¹ is -O-, Ya ^{21 is} not -CO-. Ra ²¹ is a lactone-containing ring group, a carbonate-containing ring group, or a -SO ₂ -containing ring group.

The linking group of the two valences of Ya ²¹ is not particularly limited, and a divalent hydrocarbon group having a substituent, a divalent linking group containing a hetero atom, or the like is preferably exemplified.

(a divalent hydrocarbon group which may have a substituent)

The hydrocarbon group which is a divalent linking group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

The aliphatic hydrocarbon group is intended to be a hydrocarbon group having no aromaticity. The aliphatic hydrocarbon group may be either saturated or unsaturated, and is usually saturated.

The aliphatic hydrocarbon group, for example, a linear or branched aliphatic hydrocarbon group or a structure, or a ring-containing aliphatic hydrocarbon group or the like, specifically, for example, exemplified by Va ¹ in the above formula (a1-1) Base.

The linear or branched aliphatic hydrocarbon group may have a substituent or may have no substituent. The substituent is, for example, a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms which may be substituted by a fluorine atom, a carbonyl group or the like.

The aliphatic hydrocarbon group having a ring in the above structure, for example, a cyclic aliphatic hydrocarbon group which may have a substituent containing a hetero atom in the ring structure (a group obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring), the aforementioned cyclic aliphatic group The hydrocarbon group is bonded to a terminal group of a linear or branched aliphatic hydrocarbon group, and the above-mentioned cyclic aliphatic hydrocarbon group is a group in the middle of a linear or branched aliphatic hydrocarbon group. The linear or branched aliphatic hydrocarbon group is the same as described above.

The cyclic aliphatic hydrocarbon group is preferably a carbon number of 3 to 20, more preferably 3 to 12.

The cyclic aliphatic hydrocarbon group is specifically, for example, a group exemplified by Va ¹ in the above formula (a1-1).

The cyclic aliphatic hydrocarbon group may have a substituent or may have no substituent. The substituent is, for example, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group or the like.

The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group or a tert-butyl group.

The alkoxy group as the above substituent is an alkoxy group having 1 to 5 carbon atoms. Preferably, a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group and a tert-butoxy group are preferred, and a methoxy group and an ethoxy group are preferred.

The halogen atom as the substituent, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or the like, is preferably a fluorine atom.

The halogenated alkyl group as the above substituent is, for example, a group in which a part or all of a hydrogen atom in the above alkyl group is substituted by the aforementioned halogen atom.

The cyclic aliphatic hydrocarbon group, a part of the carbon atom constituting the ring structure thereof may be substituted by a substituent containing a hetero atom. The substituent containing the hetero atom is preferably -O-, -C(=O)-O-, -S-, -S(=O) ₂ -, -S(=O) ₂ -O-.

Specific examples of the aromatic hydrocarbon group of the divalent hydrocarbon group include, for example, the group exemplified by Va ¹ in the above formula (a1-1).

In the aromatic hydrocarbon group, a hydrogen atom of the aromatic hydrocarbon group may be substituted with a substituent. The hydrogen atom to which the aromatic ring in the aromatic hydrocarbon group is bonded may be substituted by a substituent. The substituent is, for example, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group or the like.

The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group or a tert-butyl group.

The alkoxy group, the halogen atom and the halogenated alkyl group as the substituent are exemplified by a substituent which substitutes for the hydrogen atom of the cyclic aliphatic hydrocarbon group.

(a divalent linking group containing a hetero atom)

The hetero atom in the divalent linking group containing a hetero atom is an atom other than a carbon atom and a hydrogen atom, such as an oxygen atom, a nitrogen atom, a sulfur atom, or a halogen atom. Son and so on.

Ya ²¹ is a divalent linking group containing a hetero atom, and a preferred one of the linking groups, for example, -O-, -C(=O)-O-, -C(=O)-, -OC (=O)-O-, -C(=O)-NH-, -NH-, -NH-C(=NH)-(H can be substituted by a substituent such as an alkyl group or a fluorenyl group), -S- _{, -S (= O) 2 -} , - S (= O) 2 -O-, the formula ^{-Y 21 -OY 22 -, - Y} 21 -O -, - Y 21 -C (= O) -O- , -[Y ²¹ -C(=O)-O] _m' -Y ²² - or -Y ²¹ -OC(=O)-Y ²² - the group represented by the formula [wherein, Y ²¹ and Y ²² are each independently A divalent hydrocarbon group which may have a substituent, O is an oxygen atom, m' is an integer of 0 to 3, and the like.

When the divalent linking group containing the hetero atom is -C(=O)-NH-, -NH-, -NH-C(=NH)-, the H may be substituted by an alkyl group, a thiol group or the like. Replace. The substituent (alkyl group, mercapto group, etc.) is preferably one having a carbon number of from 1 to 10, more preferably from 1 to 8, and particularly preferably from 1 to 5.

Formula -Y ²¹ -OY ²² -, -Y ²¹ -O-, -Y ²¹ -C(=O)-O-, -[Y ²¹ -C(=O)-O] _m' -Y ²² -or- In Y ²¹ -OC(=O)-Y ²² -, Y ²¹ and Y ²² are each a divalent hydrocarbon group which may have a substituent. The divalent hydrocarbon group is the same as the "two-valent hydrocarbon group which may have a substituent" as exemplified in the description of the above-mentioned two-valent linking group.

Y ^{21 is} preferably a linear aliphatic hydrocarbon group, preferably a linear alkyl group, and preferably a linear alkyl group having 1 to 5 carbon atoms. Ethyl is especially good.

Y ^{22 is} preferably a linear or branched aliphatic hydrocarbon group, and more preferably a methyl group, an ethyl group or an alkyl group. The alkyl group in the alkyl group is preferably a linear alkyl group having 1 to 5 carbon atoms, preferably a linear alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group.

In the formula represented by the formula -[Y ²¹ -C(=O)-O] _m' -Y ²² -, m' is an integer of 0 to 3, preferably an integer of 0 to 2, preferably 0 or 1 Better, with 1 being especially good. That is, the group represented by the formula -[Y ²¹ -C(=O)-O] _m' -Y ²² - is particularly preferably a group represented by the formula -Y ²¹ -C(=O)-OY ²² -. Among them, the group represented by the formula -(CH ₂ ) _a' -C(=O)-O-(CH ₂ ) _b' - is preferred. In the formula, a' is an integer of 1 to 10, preferably an integer of 1 to 8, preferably an integer of 1 to 5, more preferably 1 or 2, and most preferably 1. b' is an integer from 1 to 10, preferably from 1 to 8 integers, preferably from 1 to 5, more preferably from 1 or 2, and most preferably from 1.

In the present invention, Ya ^{21 is} a single bond, or an ester bond [-C(=O)-O-], an ether bond (-O-), a linear or branched alkyl group or the like. The combination is better.

The following is a specific example of a structural unit having a group represented by the above formula (a2-r-1) in the structural unit represented by the above formula (a2-1). In the following formulae, R ^α represents a hydrogen atom, a methyl group or a trifluoromethyl group.

(A) The structural unit (a2) of the component may be one type or two or more types.

(A) The proportion of the component in the case of the structural unit (a2) is preferably from 5 to 70 mol%, preferably from 10 to 65 mol%, relative to the total structural unit constituting the component (A). It is better to use 20~60 mol%.

When the ratio of the structural unit (a2) is at least the lower limit value, the effect which can be achieved by the structural unit (a2) can be sufficiently obtained. When the ratio is equal to or less than the upper limit value, the balance with other structural units can be obtained, and various micro-structures can be obtained. The shadow etching characteristics and pattern shape are better.

(Structural unit (a3))

The resin component (A) may also have a structural unit (a3). The structural unit (a3) is a structural unit containing a polar group-containing aliphatic hydrocarbon group (excluding the above structural units (a1) and (a2)).

When the resin component (A) has a structural unit (a3), the hydrophilicity of the component (A) can be improved, and the resolution can be improved.

The polar group is, for example, a hydroxy group such as a hydroxyl group, a cyano group, a carboxyl group or a part of a hydrogen atom in which an alkyl group is substituted by a fluorine atom, and particularly preferably a hydroxyl group.

The aliphatic hydrocarbon group is, for example, a linear or branched hydrocarbon group having 1 to 10 carbon atoms (preferably an alkylene group), or a cyclic aliphatic hydrocarbon group (cyclo) or the like. The ring group may be a monocyclic group or a polycyclic group. For example, it may be used in a resin for a photoresist composition for an ArF excimer laser, and is appropriately selected from the contents of most proposals. . The ring type is preferably a polycyclic type base, and more preferably a carbon number of 7 to 30.

Among them, a structural unit derived from a hydroxyl group, a cyano group, a carboxyl group, or an aliphatic polycyclic group-containing acrylate having a hydroxyalkyl group in which a part of hydrogen atoms in the alkyl group is substituted by a fluorine atom is preferred. The polycyclic group may be, for example, a group obtained by removing two or more hydrogen atoms from a bicycloalkane, a tricycloalkane or a tetracycloalkane. Specifically, for example, a group obtained by removing two or more hydrogen atoms from a polycyclic alkane such as adamantane, norbornane, isodecane, tricyclodecane or tetracyclododecane is used. Among these polycyclic groups, a group obtained by removing two or more hydrogen atoms from adamantane, a group obtained by removing two or more hydrogen atoms from norbornane, and two or more groups removed from tetracyclododecane The base derived from the hydrogen atom is industrially more preferable.

The structural unit (a3) is not particularly limited as long as it contains a polar group-containing aliphatic hydrocarbon group, and any component can be used.

In the structural unit (a3), a hydrogen atom bonded by a carbon atom having an α-position may be a structural unit derived from a acrylate substituted by a substituent, and contains The structural unit of the polar group-containing aliphatic hydrocarbon group is preferred.

The structural unit (a3) is preferably a structural unit derived from a hydroxyethyl acrylate when the hydrocarbon group having a polar group-containing aliphatic hydrocarbon group is a linear or branched hydrocarbon group having 1 to 10 carbon atoms. When the hydrocarbon group is a polycyclic group, the structural unit represented by the following formula (a3-1), the structural unit represented by the formula (a3-2), and the structural unit represented by the formula (a3-3) are preferred. Illustrative.

[wherein, R is the same as the above, j is an integer from 1 to 3, k is an integer from 1 to 3, t' is an integer from 1 to 3, l is an integer from 1 to 5, and s is from 1 to 3. Integer].

In the formula (a3-1), j is preferably 1 or 2, and more preferably 1 is used. In the case where j is 2, it is preferred that the hydroxyl group is bonded to the 3 and 5 positions of the adamantyl group. In the case where j is 1, it is preferred that the hydroxy group is bonded to the adamantyl group.

j is preferably 1 or more, particularly preferably a 3-hydroxyl group bonded to an adamantyl group.

In the formula (a3-2), k is preferably 1. Cyano group bonded to hail The base of 5 or 6 is better.

In the formula (a3-3), t' is preferably 1. l is better than 1. s is better than 1. Among them, those in which a terminal of a carboxyl group of acrylic acid is bonded to a 2-norbornyl group or a 3-norinyl group are preferred. The fluorinated alkanol is preferably bonded to the 5 or 6 position of the thiol group.

The structural unit (a3) contained in the resin component (A) may be one type or two or more types.

The proportion of the resin component (A) having the structural unit (a3) is preferably from 1 to 50 mol%, and from 5 to 40 mol%, based on the total of the total structural units constituting the resin component (A). Preferably, it is preferably 5 to 25 mol%.

When the ratio of the structural unit (a3) is at least the lower limit value, the effect obtained by the structural unit (a3) can be sufficiently obtained, and when it is equal to or less than the upper limit value, the balance with other structural units can be easily obtained.

(Structural unit (a5))

The resin component (A) may further contain a structural unit (a5) containing a ring group of -SO ₂ -.

The "cyclic group containing -SO ₂ -" which the resin component (A) may have means a ring group containing a ring containing -SO ₂ - in the ring skeleton, specifically, -SO ₂ - The sulfur atom (S) in the ring is a ring group obtained by forming a part of the ring skeleton of the ring group. Counting the ring containing -SO ₂ - in the ring skeleton as a ring, only the case of the ring is called a monocyclic group, and in the case of other ring structures, regardless of its structure, it is called a multi-ring. Formula. The cyclic group containing -SO ₂ - may be a monocyclic group or a polycyclic group.

Containing -SO ₂ - group of cyclic, in particular in the ring skeleton containing -O-SO ₂ - group of cyclic, i.e. containing -O-SO ₂ - is formed in one part of -OS- ring skeleton The cyclosyl group of the sultone ring is preferred. The ring group containing -SO ₂ -, more specifically, for example, a group represented by the following formula (a5-r-1) to (a5-r-4).

[wherein, Ra' ^{51 is} each independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, -COOR", -OC(=O)R", a hydroxyalkyl group or a cyano group; "A hydrogen atom or an alkyl group; A" is an alkyl group having 1 to 5 carbon atoms which may contain an oxygen atom or a sulfur atom, an oxygen atom or a sulfur atom, and n' is an integer of 0 to 2].

In the above formula (a5-r-1) to (a5-r-4), A" is the same as A' in the above formula (a2-r-1) to (a2-r-7). An alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a -COOR", -OC(=O)R", a hydroxyalkyl group in Ra' ⁵¹ , and the above formula (a2-r-1) to (a2) Ra' ²¹ in -r-7) is the same.

Specific examples of the groups represented by the general formulae (a5-r-1) to (a5-r-4) will be listed below. In the formula, "Ac" means an ethyl group.

In the structural unit (a5), as long as it is a unit having a cyclic group containing -SO ₂ -, the structure of the other moiety is not particularly limited. For example, Ra ²¹ in the above formula (a2-1) is The structural unit of the group represented by any one of the above formulae (a5-r-1) to (a5-r-4).

The ring group containing -SO ₂ -, in the above, is preferably a group represented by the above formula (a5-r-1), and is used by the aforementioned chemical formula (r-sl-1-1), At least one selected from the group consisting of: r-sl-1-18), (r-sl-3-1), and (r-sl-4-1) is preferred. The group represented by the aforementioned chemical formula (r-sl-1-1) is optimal.

(A) The structural unit (a5) of the component may be one type or two or more types.

(A) In the case where the component has a structural unit (a5), the ratio of the structural unit (a5) is preferably 5 to 70 mol%, and 5 to 60, based on the total of the total structural units constituting the component (A). Molar% is preferred, preferably 10 to 55 mol%.

When the ratio of the structural unit (a5) is at least the lower limit value, the effect that the structural unit (a2) can be obtained can be sufficiently obtained, and when it is equal to or less than the upper limit value, the balance with other structural units can be obtained, and various micro-structures can be obtained. The shadow etching characteristics and pattern shape are better.

<alkali soluble resin (C)>

The photoresist composition of the present invention preferably contains an alkali-soluble resin (C) for the purpose of improving crack resistance and the like. In the case of the alkali-soluble resin, a resin solution having a resin concentration of 20% by mass (solvent: propylene glycol monomethyl ether acetate) is used, and a resin film having a thickness of 1 μm is formed on the substrate, and immersed in a 2.38 mass% TMAH aqueous solution 1 In the minute, it can dissolve 0.01μm or more. The alkali-soluble resin (C) is preferably a resin selected from the group consisting of novolac resin (Cnv1), polyhydroxystyrene resin (Cphs1), and acrylic resin (Cac1).

[Novolak resin (Cnv1)]

The novolak resin (Cnv1) is obtained by, for example, condensing an aromatic compound having a phenolic hydroxyl group (hereinafter also referred to as "phenol") with an aldehyde under an acid catalyst.

The above phenols, for example, phenol, o-cresol, m-cresol, p-cresol, o-acetol, m-ethylphenol, p-ethylphenol, o-butanol, m-butanol, p- Butanol, 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, gallicol, Chloromonoethanolamine, hydroxydiphenyl, bisphenol A, gallic acid, gallic acid ester, α-naphthol, β-naphthol, and the like.

The above aldehydes, for example, formaldehyde, furfural, benzaldehyde, nitrobenzene Aldehyde, acetaldehyde, etc.

The catalyst for the addition condensation reaction is not particularly limited. For example, an acid catalyst may be hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetic acid or the like.

Further, when o-cresol is used, the hydrogen atom of the hydroxyl group in the resin is substituted with another substituent, or when a high bulk density aldehyde is used, the softness of the novolak resin can be further increased.

The mass average molecular weight of the novolak resin (Cnv1) is preferably from 1,000 to 50,000.

[Polyhydroxystyrene resin (Cphs1)]

A hydroxystyrene compound constituting a polyhydroxystyrene resin (Cphs1), for example, p-hydroxystyrene, α-methylhydroxystyrene, α-ethylhydroxystyrene or the like.

Further, the polyhydroxystyrene resin (Cphs1) is preferably one which forms a copolymer with a styrene resin. The styrene-based compound constituting the styrene resin is, for example, styrene, chlorostyrene, chloromethylstyrene, vinyltoluene or α-methylstyrene.

The polyhydroxystyrene resin (Cphs1) preferably has a mass average molecular weight of from 1,000 to 50,000.

[Acrylic Resin (Cac1)]

Acrylic resin (Cac1) derived from a structural unit derived from a polymerizable compound having an ether bond and a polymerizable compound having a carboxyl group The structural unit is better.

The above polymerizable compound having an ether bond, for example, 2-methoxyethyl (meth) acrylate, methoxy triethylene glycol (meth) acrylate, 3-methoxy butyl (methyl) Acrylate, ethyl carbitol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, tetrahydrofurfuryl (methyl) An example of a (meth)acrylic acid derivative having an ether bond or an ester bond such as an acrylate. The above polymerizable compound having an ether bond is preferably 2-methoxyethyl acrylate or methoxy triethylene glycol acrylate. These polymerizable compounds may be used singly or in combination of two or more kinds.

The polymerizable compound having a carboxyl group may, for example, be a monocarboxylic acid such as acrylic acid, methacrylic acid or crotonic acid; a dicarboxylic acid such as maleic acid, fumaric acid or itaconic acid; 2-methylpropenyloxyethyl amber a carboxyl group such as an acid, 2-methylpropenyloxyethyl maleic acid, 2-methylpropenyloxyethyl phthalic acid, 2-methylpropenyl oxyethyl hexahydrophthalic acid, and an ester-bonded group Compound; et al. The above polymerizable compound having a carboxyl group is preferably acrylic acid or methacrylic acid. These polymerizable compounds may be used singly or in combination of two or more kinds.

The acrylic resin (Cac1) preferably has a mass average molecular weight of 50,000 to 800,000.

The content of the alkali-soluble resin (C) is preferably 5 to 200 parts by mass, more preferably 10 to 180 parts by mass, per 100 parts by mass of the resin component (A). When the content of the alkali-soluble resin (C) is 5 parts by mass or more based on 100 parts by mass of the resin component (A), crack resistance can be improved. When it is 200 parts by mass or less, it tends to prevent film from being reduced during development.

Further, in the case of using the alkali-soluble resin (C), it is preferred to use a novolak resin (Cnv1) and a polyhydroxystyrene resin (Cphs1) in combination with the above acrylic resin (Aac1). In this case, the proportion of the acrylic resin is preferably from 5 to 80% by mass, more preferably from 10 to 70% by mass, even more preferably from 10 to 40% by mass, based on the total of the resins. Further, the ratio of the novolac resin is preferably from 5 to 80% by mass, more preferably from 20 to 70% by mass, even more preferably from 45 to 65% by mass. Further, the ratio of the polyhydroxystyrene resin is preferably 5 to 60% by mass, more preferably 5 to 35% by mass, and most preferably 5 to 30% by mass. At these ratios, the acid generator can be uniformly dispersed within the thick film photoresist layer.

<acid generator component; (B) component>

The photoresist composition of the present invention contains an acid generator component (B) (hereinafter, also referred to as a component (B)) which generates an acid by exposure. Further, the acid generator component (B) is an acid generator (B1) containing a compound represented by the following formula (b1-1).

[wherein, R ¹ and R ² are an alkyl group having 1 to 10 carbon atoms which may have a substituent, and R ³ and R ⁴ are an alkyl group having 2 to 10 carbon atoms which may have a substituent, and R ³ and R ⁴ , It may form a ring together with the sulfur atom to which it is bonded, and X ^- is a pair of anions].

In the formula (b1-1), R ¹ and R ² are an alkyl group having 1 to 10 carbon atoms which may have a substituent. In R ¹ and R ² , an alkyl group having 1 to 10 carbon atoms may be, for example, a linear alkyl group having 1 to 5 carbon atoms. Specifically, for example, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group or the like. Among these, a methyl group, an ethyl group or an n-butyl group is preferred, and an n-butyl group is preferred.

In the formula (b1-1), the alkyl group having 1 to 10 carbon atoms in R ¹ and R ² may be a branched or cyclic alkyl group.

The branched alkyl group preferably has a carbon number of 3 to 10 and preferably 3 to 8. Specifically, for example, isopropyl, isobutyl, tert-butyl, isopentyl, neopentyl or the like is preferably isopropyl.

The cyclic alkyl group preferably has a carbon number of 3 to 10 and preferably 4 to 10. Specifically, for example, one monocyclic alkane such as cyclopentane or cyclohexane or one polycyclic alkane such as adamantane, norbornane, isodecane, tricyclodecane or tetracyclododecane is removed. The base obtained by the above hydrogen atom and the like. A part of the carbon atom constituting the ring of the cyclic alkyl group may be substituted by an etheric oxygen atom (-O-).

In the formula (b1-1), R ¹ and R ² may have a substituent such as an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group or the like.

The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group or a tert-butyl group.

The alkoxy group as the above substituent is preferably an alkoxy group having 1 to 5 carbon atoms, and a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, and an n-butoxy group. The base and tert-butoxy group are preferred, and the methoxy group and the ethoxy group are preferred.

The halogen atom as the substituent, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or the like, is preferably a fluorine atom.

The halogenated alkyl group as the above substituent is, for example, a group in which a part or all of a hydrogen atom in the above alkyl group is substituted by the aforementioned halogen atom.

In the cyclic aliphatic hydrocarbon group, a part of the carbon atom constituting the ring structure thereof may be substituted with a substituent containing a hetero atom. The substituent containing the hetero atom is preferably -O-, -C(=O)-O-, -S-, -S(=O) ₂ -, -S(=O) ₂ -O-.

In the present invention, R ¹ and R ^{2 have} a carbon number of 1 to 8, preferably a carbon number of 1 to 5, and most preferably an alkyl group having 3 to 5 carbon atoms. Further, a branched or chain alkyl group is preferred, and a chain alkyl group is preferred. Further, an unsubstituted alkyl group is preferred.

In the formula (b1-1), R ³ and R ⁴ are a C 2-10 alkyl group which may have a substituent, and R ³ and R ⁴ may form a ring together with the sulfur atom to which they are bonded.

In R ³ and R ⁴ , an alkyl group having 2 to 10 carbon atoms which may have a substituent, for example, a linear alkyl group having 2 to 5 carbon atoms. A linear alkyl group having 2 to 5 carbon atoms, for example, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group or the like. Among these, a methyl group, an ethyl group or an n-butyl group is preferred, and an n-butyl group is preferred.

R ³ and R ⁴ are an alkyl group having 1 to 10 carbon atoms, which may have a branched or cyclic alkyl group. In R ³ and R ⁴ , the description of the branched or cyclic alkyl group having 1 to 10 carbon atoms is the same as that described in the above R ¹ and R ² .

R ³ and R ⁴ may have a substituent, and the substituents which R ³ and R ⁴ may have are the same as those described for R ¹ and R ² described above.

In the present invention, in the formula (b1-1), R ³ and R ⁴ are a carbon number of 2 to 8, preferably a carbon number of 2 to 6, and most preferably an alkyl group having 3 to 5 carbon atoms. Further, a branched or chain alkyl group is preferred, and a chain alkyl group is preferred. Further, an unsubstituted alkyl group is preferred.

In the above formula (b1-1), X ^- is a counter anion.

X ^- anion of, e.g., sulfonic acid anion, a carboxylate anion, acyl imide anion, a methyl metal anion, carbanion, anionic borate anion, halogen anion, a phosphate anion, an anion antimonate, arsenate anion anion.

For example, an anion represented by the following formula (b-an1) or an anion represented by the following formulae (b-1) to (b-3) may be used.

[wherein, R ¹¹ to R ¹⁴ are each independently a fluorine atom, an alkyl group which may have a substituent, or an aryl group].

In the above formula (b-an1), the alkyl group in R ¹¹ to R ¹⁴ is preferably an alkyl group having 1 to 20 carbon atoms, for example, the same as Ra' ³ of the above formula (a1-r-1). Chain or cyclic alkyl groups, etc.

The aryl group in R ¹¹ to R ¹⁴ is preferably a phenyl group or a naphthyl group.

When R ¹¹ to R ¹⁴ are an alkyl group or an aryl group, they may have a substituent such as a halogen atom, an alkyl halide group, an alkyl group, an alkoxy group, an alkylthio group, a hydroxyl group, a carbonyl group or the like. Examples of the substituents may be, for example, a group represented by the formula (a2-r-1) to (a2-r-7). Further, the alkylthio group is, for example, a carbon number of 1 to 4. Among them, a halogen atom, an alkyl halide, an alkyl group, an alkoxy group or an alkylthio group is preferred.

In the above formula (b-an1), R ¹¹ to R ^{14 are} preferably a fluorine atom, a fluorinated alkyl group or a group represented by the following formula (b-an1').

[wherein, R' ¹¹ to R' ¹⁵ are each independently a hydrogen atom, a fluorine atom, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group or an alkylthio group].

In the above formula (b-an1'), the alkyl group having 1 to 4 carbon atoms is specifically, for example, a methyl group, an ethyl group, an n-propyl group or an n-butyl group. Among these, a methyl group, an ethyl group or an n-butyl group is preferred, and a methyl group or an ethyl group is more preferred.

In the above formula (b-an1'), an alkoxy group having 1 to 4 carbon atoms, specifically, a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, and an n-butoxy group. The base and tert-butoxy group are preferred, and the methoxy group and the ethoxy group are more preferred.

In the above formula (b-an1'), the alkylthio group having 1 to 4 carbon atoms is a methylthio group, an ethylthio group, an n-propylthio group, an iso-propylthio group, an n-butylthio group, a tert- The butylthio group is preferred, and the methylthio group and the ethylthio group are preferred.

Preferred specific examples of the anion moiety represented by the above formula (b-an1) are, for example, tetrakis(pentafluorophenyl)borate anion ([B(C ₆ F ₅ ) ₄ ] ^- ), tetra [(trifluoro Methyl)phenyl]borate anion ([B(C ₆ H ₄ CF ₃ ) ₄ ] ^- ), difluoro bis(pentafluorophenyl) borate anion ([(C ₆ F ₅ ) ₂ BF ₂ ] ^- ), trifluoro(pentafluorophenyl)borate anion ([(C ₆ F ₅ )BF ₃ ] ^- ), tetrakis(difluorophenyl) borate anion ([B(C ₆ H ₃ F ₂ ) ₄ ] ^- ) and so on. Among them, tetrakis(pentafluorophenyl)borate anion ([B(C ₆ F ₅ ) ₄ ] ^- ) is particularly preferred.

The anion of X ^- may be a halogen anion, a phosphate anion, a phthalic acid anion (SbF ₆ ^- ), or an arsenate anion (AsF ₆ ^- ). The halogen anion may be, for example, chlorine or bromine, a phosphate anion, for example, PF ₆ ^- or an anion represented by the following formula (b-an2).

[wherein, R ¹⁵ is a fluorinated alkyl group having 1 to 8 carbon atoms each independently. q is 1~6].

In the above formula (b-an2), specific examples of the fluorinated alkyl group having 1 to 8 carbon atoms include CF ₃ , CF ₃ CF ₂ , (CF ₃ ) ₂ CF, CF ₃ CF ₂ CF ₂ , and CF ₃ CF _{2 .} CF ₂ CF ₂ , (CF ₃ ) ₂ CFCF ₂ , CF ₃ CF ₂ (CF ₃ ) CF, C(CF ₃ ) ₃ and the like are exemplified.

In the above formula (b1-1), the anion of X ^- may be, for example, an anion represented by the following formulas (b-1) to (b-3).

[wherein R ¹⁰¹ and R ¹⁰⁴ to R ¹⁰⁸ are each a ring-form group which may have a substituent, a chain alkyl group which may have a substituent, or a chain-like alkenyl group which may have a substituent. R ¹⁰⁴ and R ¹⁰⁵ may be bonded to each other to form a ring. Any two of R ¹⁰⁶ to R ¹⁰⁷ may be bonded to each other to form a ring. R ¹⁰² is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. Y ¹⁰¹ is a single bond or a divalent linking group containing an oxygen atom. V ¹⁰¹ to V ¹⁰³ are each a single bond, an alkyl group, or a fluorinated alkyl group. L ¹⁰¹ ~ L ¹⁰² are each a single bond or an oxygen atom. L ¹⁰³ ~ L ¹⁰⁵ are independent single bonds, -CO- or -SO ₂ -].

In the formula (b-1), R ¹⁰¹ is a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain-like alkenyl group which may have a substituent.

(cyclic group which may have a substituent)

The cyclic group is preferably a cyclic hydrocarbon group, and the cyclic hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group.

The aromatic hydrocarbon group in R ¹⁰¹ is, for example, an aromatic hydrocarbon ring exemplified by a divalent aromatic hydrocarbon group in Va ¹ of the above formula (a1-1), or an aromatic compound containing two or more aromatic rings. The aryl group or the like obtained by one hydrogen atom is preferably a phenyl group or a naphthyl group.

The cyclic aliphatic hydrocarbon group in R ¹⁰¹ , for example, a group obtained by removing one hydrogen atom from a monocyclic alkane or a polycyclic alkane exemplified by a divalent aliphatic hydrocarbon group in Va ¹ of the above formula (a1-1) Etc., it is better to use adamantyl and sulfhydryl groups.

Further, the cyclic hydrocarbon group in R ¹⁰¹ may contain a hetero atom as in the case of a hetero ring, and specifically, for example, the above formula (a2-r-1) to (a2-r-7) a cyclic group of a lactone, a ring group containing -SO ₂ - represented by the above formula (a5-r-1) to (a5-r-4), and R ¹ in the above formula (b1-1) The heterocyclic groups and the like are exemplified.

The substituent in the cyclic hydrocarbon group of R ¹⁰¹ is, for example, an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a hydroxyl group, a carbonyl group, a nitro group or the like.

The alkyl group as a substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group or a tert-butyl group.

The alkylalkyl group as a substituent is preferably an alkoxy group having 1 to 5 carbon atoms, and a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, and a tert- group. The butoxy group is preferred, and the methoxy group and the ethoxy group are most preferred.

The halogen atom as a substituent, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or the like, is preferably a fluorine atom.

The halogenated alkyl group as a substituent, for example, an alkyl group having 1 to 5 carbon atoms, such as a hydrogen atom such as a methyl group, an ethyl group, a propyl group, an n-butyl group or a tert-butyl group. Some or all of the groups substituted by the aforementioned halogen atoms are exemplified.

(chain alkyl group which may have a substituent)

The chain alkyl group of R ¹⁰¹ may be either linear or branched.

The linear alkyl group preferably has a carbon number of from 1 to 20, preferably from 1 to 15, and most preferably from 1 to 10. Specifically, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, decyl, undecyl, dodecyl, tridecyl, Isotridecyl, tetradecyl, pentadecyl, hexadecyl, isohexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, twenty-one Alkyl, behenyl or the like.

The branched alkyl group preferably has a carbon number of 3 to 20, preferably 3 to 15, and preferably 3 to 10. Specifically, for example, 1-methylethyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1- Ethyl butyl, 2-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, and the like.

(chain-like alkenyl group which may have a substituent)

The chain alkenyl group of R ¹⁰¹ may be either a linear chain or a branched chain, preferably having a carbon number of 2 to 10, preferably 2 to 5, and more preferably 2 to 4. It is especially good for 3. A linear alkenyl group, for example, a vinyl group, a propenyl group, a butenyl group or the like. A branched alkenyl group is, for example, a 1-methylpropenyl group, a 2-methylpropenyl group or the like.

The chain-like alkenyl group is preferably a propylene group among the above.

The substituent in the chain alkyl group or alkenyl group of R ¹⁰¹ , for example, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amine group, a ring group in the above R ¹⁰¹ or the like.

Among them, R ¹⁰¹ is preferably a cyclic group which may have a substituent, and a cyclic hydrocarbon group which may have a substituent is preferred. More specifically, a group obtained by removing one or more hydrogen atoms from a polyphenylene alkene by a phenyl group, a naphthyl group, or the above formula (a2-r-1) to (a2-r-7) The cyclic group of the lactone, the ring group containing -SO ₂ - represented by the above formula (a5-r-1) to (a5-r-4), and the like are preferred.

In the formula (b-1), Y ¹⁰¹ is a single bond or a divalent linking group containing an oxygen atom.

Y ¹⁰¹ is a divalent linking group containing an oxygen atom, and Y ¹⁰¹ may contain an atom other than an oxygen atom. An atom other than an oxygen atom, such as a carbon atom, a hydrogen atom, a sulfur atom, a nitrogen atom or the like.

a divalent linking group containing an oxygen atom, for example, an oxygen atom (ether bond: -O-), an ester bond (-C(=O)-O-), an oxycarbonyl group (-OC(=O)- ), a non-hydrocarbon-based compound such as a guanamine bond (-C(=O)-NH-), a carbonyl group (-C(=O)-), or a carbonate bond (-OC(=O)-O-) a linking group of an oxygen atom; a combination of a non-hydrocarbon-based linking group containing an oxygen atom and an alkylene group; and the like. In this combination, the thiol group (-SO ₂ -) can be further linked. The combination is exemplified by, for example, a linking group represented by the following formulas (y-al-1) to (y-al-7).

[wherein, V' ¹⁰¹ is a single bond or an alkylene group having 1 to 5 carbon atoms, and V' ¹⁰² is a divalent saturated hydrocarbon group having 1 to 30 carbon atoms].

The divalent saturated hydrocarbon group in V' ¹⁰² is preferably an alkylene group having 1 to 30 carbon atoms.

The alkylene group in V' ¹⁰¹ and V' ¹⁰² may be a linear alkyl group or a branched alkyl group, and a linear alkyl group is preferred.

The alkylene group in V' ¹⁰¹ and V' ¹⁰² , specifically, for example, methyl [-CH ₂ -]; -CH(CH ₃ )-, -CH(CH ₂ CH ₃ )-, -C ( Alkyl extension of CH ₃ ) ₂ -, -C(CH ₃ )(CH ₂ CH ₃ )-, -C(CH ₃ )(CH ₂ CH ₂ CH ₃ )-, -C(CH ₂ CH ₃ ) ₂ -, etc. Methyl; exoethyl [-CH ₂ CH ₂ -]; -CH(CH ₃ )CH ₂ -, -CH(CH ₃ )CH(CH ₃ )-, -C(CH ₃ ) ₂ CH ₂ -, - The alkyl group of CH(CH ₂ CH ₃ )CH ₂ -etc. is an ethyl group; the trimethyl (n-propyl)[-CH ₂ CH ₂ CH ₂ -]; -CH(CH ₃ )CH ₂ CH ₂ -, -CH ₂ CH(CH ₃ )CH ₂ -etc. The alkyl group extends to a trimethyl group; tetramethyl [-CH ₂ CH ₂ CH ₂ CH ₂ -]; -CH(CH ₃ )CH ₂ CH ₂ CH ₂ -, The alkyl group of -CH ₂ CH(CH ₃ )CH ₂ CH ₂ - or the like is tetramethyl; the pentamethyl group [-CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -] or the like.

Further, in V' ¹⁰¹ or V' ¹⁰² , a methyl group of a part of the alkylene group may be substituted by a divalent aliphatic ring group having 5 to 10 carbon atoms. The aliphatic cyclic group is preferably a divalent group obtained by further removing one hydrogen atom from the cyclic aliphatic hydrocarbon group of Ra' ^{3 in} the above formula (a1-r-1), cyclohexyl group, 1, 5 - Ardenyl or 2,6-adamantyl is preferred.

Y ^{101 is} preferably a divalent linking group containing an ester bond or an ether bond, and a linking group represented by the above formula (y-al-1) to (y-al-5) is preferred.

In the formula (b-1), V ¹⁰¹ is a single bond, an alkylene group, or a fluorinated alkyl group. The alkyl group and the fluorinated alkyl group in V ¹⁰¹ are preferably a carbon number of 1 to 4. V ¹⁰¹ in the fluorinated alkylene, e.g., V ^101, the extension illustrated in the alkyl part or all of the hydrogen atoms are substituted by fluorine atom and the like. Among them, V ¹⁰¹ is a single bond, or a fluorinated alkyl group having 1 to 4 carbon atoms is preferred.

In the formula (b-1), R ¹⁰² is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. R ^{102 is} preferably a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms, and preferably a fluorine atom.

(b-1) Specific examples of the anion portion of the component, for example, when Y ¹⁰¹ is a single bond, for example, a fluorinated alkylsulfonate anion such as a trifluoromethanesulfonate anion or a perfluorobutanesulfonate anion In the case where Y ¹⁰¹ is a divalent linking group containing an oxygen atom, for example, an anion represented by any one of the following formulas (an-1) to (an-3) can be exemplified.

[wherein R" ¹⁰¹ is an aliphatic cyclic group which may have a substituent, a group represented by the above formula (r-hr-1) to (r-hr-6), or a chain which may have a substituent An alkyl group; R" ¹⁰² is an aliphatic cyclic group which may have a substituent, a lactone-containing ring group represented by the above formula (a2-r-1) to (a2-r-7), or The ring-form group containing -SO ₂ - represented by the above formula (a5-r-1) to (a5-r-4); R" ¹⁰³ is an aromatic ring group which may have a substituent, and may have An aliphatic cyclic group of a substituent, or a chain-like alkenyl group which may have a substituent; V" ¹⁰¹ is a fluorinated alkyl group; L" ¹⁰¹ is -C(=O)- or -SO ₂ -;v" For each of the independent integers of 0~3, q" is an integer of 1~20, and n" is 0 or 1].

An aliphatic cyclic group which may have a substituent of R" ¹⁰¹ , R" ¹⁰² and R" ¹⁰³ , preferably a group exemplified by the above-mentioned cyclic aliphatic hydrocarbon group in R ^{101. The} aforementioned substituent, for example, and a substitutable R The substituent of the cyclic aliphatic hydrocarbon group in ¹⁰¹ is the same.

The aromatic cyclic group which may have a substituent in R" ¹⁰³ is preferably the group exemplified as the aromatic hydrocarbon group in the cyclic hydrocarbon group in the above R ^{101. The} aforementioned substituent, for example, and the substitutable R ¹⁰¹ The substituent of the aromatic hydrocarbon group is the same.

a chain alkyl group which may have a substituent in R" ¹⁰¹ , preferably a group exemplified by the above-mentioned chain alkyl group in R ^101. A chain-like alkenyl group which may have a substituent in R" ¹⁰³ , The group exemplified by the chain-like alkenyl group in R ¹⁰¹ is preferred.

V" ¹⁰¹ , preferably a fluorinated alkyl group having 1 to 3 carbon atoms, particularly preferably -CF ₂ -, -CF ₂ CF ₂ -, -CHFCF ₂ -, -CF(CF ₃ )CF ₂ -, CH(CF ₃ )CF ₂ -.

The following is a specific example of the anion represented by the above formula (an-1). However, it is not limited to this range.

The following is a specific example of the anion represented by the above formula (an-2). However, it is not limited to this range.

The following is a specific example of the anion represented by the above formula (an-3). However, it is not limited to this range.

In the formula (b-2), R ¹⁰⁴ and R ¹⁰⁵ are each independently a ring group which may have a substituent, a chain alkyl group which may have a substituent, or a chain-like alkenyl group which may have a substituent, respectively It is the same as R ¹⁰¹ in the formula (b-1). Wherein R ¹⁰⁴ and R ¹⁰⁵ may be bonded to each other to form a ring.

R ¹⁰⁴ and R ^{105 are} preferably a chain alkyl group which may have a substituent, and a linear or branched alkyl group or a linear or branched fluorinated alkyl group is preferred.

The chain alkyl group preferably has 1 to 10 carbon atoms, preferably 1 to 7 carbon atoms, more preferably 1 to 3 carbon atoms. When the carbon number of the chain alkyl group of R ¹⁰⁴ or R ¹⁰⁵ is in the range of the above carbon number, the solubility in the resist solvent is also good, and the smaller the better. Further, in the chain alkyl group of R ¹⁰⁴ or R ¹⁰⁵ , the more the number of hydrogen atoms substituted by the fluorine atom, the stronger the strength of the acid, and the higher the energy or the electron beam of 200 nm or less, the transparency can be improved. Sex and other viewpoints are better. The proportion of the fluorine atom in the chain alkyl group, that is, the fluorination ratio is preferably from 70 to 100%, more preferably from 90 to 100%, and most preferably a perfluoroalkyl group in which all hydrogen atoms are replaced by fluorine atoms.

In the formula (b-2), V ¹⁰² and V ¹⁰³ are each independently a single bond, an alkylene group, or a fluorinated alkyl group, which are respectively the same as V ¹⁰¹ in the formula (b-1).

In the formula (b-2), L ¹⁰¹ to L ¹⁰² are each independently a single bond or an oxygen atom.

The following is a specific example of the anion represented by the above formula (b-2). However, it is not limited to this range.

In the formula (b-3), R ¹⁰⁶ to R ¹⁰⁸ are each independently a ring group which may have a substituent, a chain alkyl group which may have a substituent, or a chain-like alkenyl group which may have a substituent, respectively It is the same as R ¹⁰¹ in the formula (b-1).

L ¹⁰³ ~ L ¹⁰⁵ are each a separate single bond, -CO- or -SO ₂ -.

The following is a specific example of the anion represented by the above formula (b-3). However, it is not limited to this range.

The compound represented by the above formula (b1-1) is represented, for example, by the following general formulae (b2-1) to (b2-2), (b3-1) to (b3-2), and (b4-1). The compounds and the like are exemplified.

[wherein, R ¹ and R ² are an alkyl group having 1 to 10 carbon atoms which may have a substituent, and R ³ and R ⁴ are an alkyl group having 2 to 10 carbon atoms which may have a substituent, and R ³ and R ⁴ , It may form a ring together with the sulfur atom to which it is bonded, and X ^- is a pair of anions].

Description of R ¹ , R ² , R ³ , R ⁴ , and X ^{- in} the above general formulae (b2-1) to (b2-2), (b3-1) to (b3-2), and (b4-1) The same as the description in the above formula (b1-1).

In the present invention, in the compound represented by the formula (b1-1), the group represented by -OR ¹ or -OR ² is bonded one by one to each ring of the naphthalene ring in the formula (b1-1). The winner is better in terms of making the sensitivity better.

In the present invention, the compound represented by the formula (b1-1) is preferably a compound represented by the above formula (b2-1) to (b2-2).

The following is a specific illustration of the compound represented by the formula (b1-1).

Acid generator (B1), either alone or in combination The above combination can also be used. The content of the acid generator (B1) is preferably 0.1 to 10% by mass, preferably 0.5 to 5% by mass, and 0.5 to 3% by mass based on the total mass of the photoresist composition of the present invention. For better.

As the acid generator (B), other acid generators other than the above may be used in combination.

The first aspect of other acid generators, for example, 2,4-bis(trichloromethyl)-6-flower base (Piperonyl)-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(2-furyl)ethenyl-s-three , 2,4-bis(trichloromethyl)-6-[2-(5-methyl-2-furyl)ethenyl-s-three , 2,4-bis(trichloromethyl)-6-[2-(5-ethyl-2-furyl)ethenyl-s-three 2,4-bis(trichloromethyl)-6-[2-(5-propyl-2-furyl)ethenyl-s-three , 2,4-bis(trichloromethyl)-6-[2-(3,5-dimethoxyphenyl)ethenyl-s-three , 2,4-bis(trichloromethyl)-6-[2-(3,5-diethoxyphenyl)ethenyl-s-three , 2,4-bis(trichloromethyl)-6-[2-(3,5-dipropoxyphenyl)ethenyl-s-three , 2,4-bis(trichloromethyl)-6-[2-(3-methoxy-5-ethoxyphenyl)ethene(ethenyl)]-s-three , 2,4-bis(trichloromethyl)-6-[2-(3-methoxy-5-propoxyphenyl)ethenyl]-s-three , 2,4-bis(trichloromethyl)-6-[2-(3,4-extended methyldioxyphenyl)ethenyl-eth-yl , 2,4-bis(trichloromethyl)-6-(3,4-extended methyldioxyphenyl)-s-three 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)phenyl-s-three 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)phenyl-s-three 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)styrylphenyl-s-three 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)styrylphenyl-s-three , 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-three , 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-three ,2-[2-(2-furyl)ethenyl]-4,6-bis(trichloromethyl)-1,3,5-three ,2-[2-(5-methyl-2-furyl)ethenyl]-4,6-bis(trichloromethyl)-1,3,5-three ,2-[2-(3,5-Dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-1,3,5-three ,2-[2-(3,4-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-1,3,5-three , 2-(3,4-Extended methyldioxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-three , tris(1,3-dibromopropyl)-1,3,5-three , tris(2,3-dibromopropyl)-1,3,5-three Halogen-containing three a halogen-containing compound represented by the following formula (b3), such as a compound and tris(2,3-dibromopropyl)isocyanurate; Compounds and the like are exemplified.

In the above formula (b3), Rb ⁹ , Rb ¹⁰ and Rb ¹¹ each independently represent a halogenated alkyl group.

Further, a second aspect of the other acid generator, for example, α-(p-toluenesulfonyloxyimino)-phenylacetonitrile, α-(phenylsulfonyloxyimino)- 2,4-Dichlorophenylacetonitrile, α-(phenylsulfonyloxyimino)-2,6-dichlorophenylacetonitrile, α-(2-chlorophenylsulfonyloxy) Amino)-4- Methoxyphenylacetonitrile, α-(ethylsulfonyloxyimino)-1-cyclopentenylacetonitrile, a compound represented by the following formula (b4) containing an oxime sulfonate group, etc. Illustrative.

In the above formula (b4), Rb ¹² represents a monovalent, divalent or trivalent organic group, Rb ¹³ represents a substituted or unsubstituted saturated hydrocarbon group, an unsaturated hydrocarbon group, or an aromatic compound group, and n represents a parenthesis. The number of repeating units of the structure.

In the above formula (b4), the aromatic compound group means a group of a compound having a specific physical or chemical property in an aromatic compound, for example, an aryl group such as a phenyl group or a naphthyl group, or a furyl group or a thienyl group. Examples of heteroaryl groups and the like. These may have one or more appropriate substituents on the ring, for example, a halogen atom, an alkyl group, an alkoxy group, a nitro group or the like. Further, Rb ¹³ is particularly preferably an alkyl group having 1 to 6 carbon atoms, and may, for example, be a methyl group, an ethyl group, a propyl group or a butyl group. In particular, a compound in which Rb ¹² is an aromatic compound group and Rb ¹³ is an alkyl group having 1 to 4 carbon atoms is preferred.

In the acid generator represented by the above formula (b4), when n=1, Rb ¹² may be any of a phenyl group, a methylphenyl group, and a methoxyphenyl group, and Rb ¹³ is a methyl group compound. For example, α-(methylsulfonyloxyimino)-1-phenylacetonitrile, α-(methylsulfonyloxyimino)-1-(p-methylphenyl) Acetonitrile, α-(methylsulfonyloxyimino)-1-(p-methoxyphenyl)acetonitrile, [2-(propylsulfonyloxyimino)-2,3 - Dihydroxythiophene-3-ylidene (o-tolyl)acetonitrile or the like. In the case of the acid generator represented by the above formula (b4), for example, an acid generator represented by the following formula is exemplified.

Further, in the third aspect of the other acid generator, for example, the cation portion has an anthracene salt of a naphthalene ring or the like. The term "having a naphthalene ring" means having a structure derived from naphthalene, and means a structure having at least two rings and maintaining the aromaticity of the particles. The naphthalene ring may, for example, be a linear or branched alkyl group having 1 to 6 carbon atoms, a hydroxyl group, a linear or branched alkoxy group having 1 to 6 carbon atoms, or the like, and may have a substituent. Knot produced by naphthalene ring The structure may be a monovalent group (the free atomic valence is 1 valence), and the 2 valent group (free valence is 2 valence) or more, and the 1 valent base is preferred (but, at this time, it is removed) The free atomic valence obtained from the moiety bonded to the above substituent). The number of naphthalene rings is preferably from 1 to 3.

The cation portion has a cation portion of a sulfonium salt of a naphthalene ring, and is preferably a structure represented by the following formula (b5).

In the above formula (b5), at least one of Rb ¹⁴ , Rb ¹⁵ and Rb ¹⁶ is a group represented by the following formula (b6), and the other is a linear or branched chain having 1 to 6 carbon atoms. An alkyl group, a phenyl group which may have a substituent, a hydroxyl group, or a linear or branched alkoxy group having 1 to 6 carbon atoms. Or at least one of Rb ¹⁴ , Rb ¹⁵ and Rb ¹⁶ is a group represented by the following formula (b6), and the other two are independent linear or branched carbon groups of 1 to 6 carbon atoms. The alkyl group may be bonded to form a ring at the end. In the following formulas, "*" indicates a bond key.

In the above formula (b6), Rb ¹⁷ and Rb ¹⁸ each independently represent a hydroxyl group, a linear or branched alkoxy group having 1 to 6 carbon atoms, or a linear or branched chain having 1 to 6 carbon atoms. The alkyl group, Rb ¹⁹ represents a single bond or a linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent. l and m each independently represent an integer of 0 to 2, and l+m is 3 or less. Wherein, Rb ¹⁷ has a plurality of cases, and the ones may be the same or different from each other. Further, Rb ¹⁸ has a plurality of cases, and the two may be the same or different from each other.

Among the above Rb ¹⁴ , Rb ¹⁵ and Rb ¹⁶ , the number of the groups represented by the above formula (b6) is preferably 1 in terms of the stability of the compound, etc., and the other may be a linear chain having 1 to 6 carbon atoms. Or a branched alkyl group, and the ends may be bonded to form a ring. In this case, the above two alkyl groups may constitute a 3 to 9 member ring containing a sulfur atom. The number of atoms (including sulfur atoms) constituting the ring is preferably 5-6.

Further, the above-mentioned alkylene group may have a substituent such as an oxygen atom (in this case, a carbonyl group formed together with a carbon atom constituting an alkylene group), a hydroxyl group or the like.

Further, the substituent which the phenyl group may have, for example, a hydroxyl group, a linear or branched alkoxy group having 1 to 6 carbon atoms, a linear or branched alkyl group having 1 to 6 carbon atoms, or the like.

Suitable as the cationic part of these, for example, the following The structure represented by the above formulas (b7) and (b8) is preferably a structure represented by the following formula (b8).

These cationic moieties may be either a phosphonium salt or a phosphonium salt, and a phosphonium salt is preferred from the viewpoint of acid production efficiency and the like.

Therefore, it is preferred to use a preferred component of the anion portion having a sulfonium salt of a naphthalene ring as the cation portion, and it is preferred to form an anion of the onium salt.

The anion portion of the acid generator, for example, a part or all of a hydrogen atom is fluorinated fluoroalkylsulfonate ion or arylsulfonate ion.

The alkyl group in the fluoroalkyl sulfonate ion may be a linear or branched or cyclic carbon number of 1 to 20, and the carbon density of the acid produced and its diffusion distance are carbon The number 1~10 is better. Particularly, in the case of a branched or a ring, the diffusion distance is shorter, and is preferable. Further, in view of economical synthesis and the like, a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group or the like is preferably exemplified.

The aryl group in the arylsulfonic acid ion, for example, an aryl group having 6 to 20 carbon atoms, and a phenyl group, a naphthyl group or the like which may be substituted or unsubstituted by an alkyl group or a halogen atom is exemplified. In particular, from the viewpoint of economical synthesis, an aryl group having 6 to 10 carbon atoms is preferred. Specific examples of preferred components may, for example, be a phenyl group, a tolylhydryl group, an ethylphenyl group, a naphthyl group or a methylnaphthyl group.

In the above-mentioned fluorine-based alkylsulfonic acid ion or arylsulfonic acid ion, the fluorination ratio in the case where part or all of the hydrogen atom is fluorinated is preferably from 10 to 100%, more preferably from 50 to 100%. It is particularly preferable that all of the hydrogen atoms are replaced by fluorine atoms, and the strength of the acid is stronger. The components are specifically, for example, trifluoromethanesulfonate, perfluorobutanesulfonate, perfluorooctanesulfonate, perfluorobenzenesulfonate or the like.

Among these, the preferred anion moiety is exemplified by the content represented by the following formula (b9).

In the above formula (b9), Rb ²⁰ is a group represented by the following formulas (b10) and (b11), or a group represented by the following formula (b12). In the following formulas, "*" indicates a bond key.

In the above formula (b10), x represents an integer of 1 to 4. Further, in the above formula (b11), Rb ²¹ represents a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 6 carbon atoms, or a linear or branched chain having 1 to 6 carbon atoms. Alkoxy, y represents an integer from 1 to 3. Among these, trifluoromethanesulfonate and perfluorobutanesulfonate are preferred from the viewpoint of safety.

Further, the anion portion is preferably a nitrogen-containing one represented by the following general formulae (b13) and (b14).

In the above formula (a13), Xb represents a linear or branched alkyl group in which at least one hydrogen atom is substituted by a fluorine atom, and the carbon number of the alkyl group is 2 to 6, more preferably 3 ~5, the best is carbon number 3. Further, in the above formula (a14), Yb and Zb each independently represent a linear or branched alkyl group in which at least one hydrogen atom is substituted by a fluorine atom, and the carbon number of the alkyl group is 1~ 10, more preferably 1~7, best 1~3.

The carbon number of the alkyl group of Xb or the smaller the carbon number of the alkyl group of Yb and Zb is preferable from the viewpoint of having good solubility in an organic solvent.

Further, in the alkyl group of Xb or the alkyl group of Yb or Zb, the more the number of hydrogen atoms substituted by the fluorine atom, the stronger the strength of the acid is. The ratio of the fluorine atom in the alkyl group or the alkyl group, that is, the fluorination rate, is preferably 70 to 100%, more preferably 90 to 100%, and most preferably the perfluoroalkylene group in which all hydrogen atoms are replaced by fluorine atoms. Base or perfluoroalkyl.

Preferred examples of the cation salt having a naphthalene ring in the cation portion are, for example, compounds represented by the following formulas (b15) and (b16).

Further, a fourth aspect of other acid generators, for example, bis(p-toluenesulfonyl)diazomethane, bis(1,1-dimethylethylsulfonyl)diazo Methane, bis(cyclohexylsulfonyl)diazomethane, bis(2,4-dimethylphenylsulfonyl)diazomethane, etc.; di-sulfonyldiazomethane; p-toluenesulfonic acid 2-nitrate Benzyl, p-toluenesulfonic acid 2,6-dinitrobenzyl, nitrobenzyl tosylate, nitrobenzyl tosylate, nitrobenzyl sulfonate, Nitrobenzyl derivative such as nitrobenzyl carbonate, dinitrobenzyl carbonate; Trisylate, gallicyl trimethylsulfonate, benzyl tosylate, benzyl Sulfonic acid ester, N-methylsulfonyloxy amber succinimide, N-trichloromethylsulfonyloxy amber succinimide, N-phenylsulfonyloxymaleimide, a sulfonate such as N-methylsulfonyloxyphthalic acid imide; a trifluoromethanesulfonate such as N-hydroxyphthalic imine or N-hydroxynaphthyl imine; Phenylphosphonium hexafluorophosphate, (4-methoxyphenyl)phenylphosphonium trifluoromethanesulfonate, bis(p-tert-butylphenyl)phosphonium trifluoromethanesulfonate, triphenyl Hexafluorophosphate, (4-methoxyphenyl)diphenylphosphonium trifluoromethanesulfonate, (p-ter Anthracene salts such as t-butylphenyl)diphenylsulfonium trifluoromethanesulfonate; benzoin tosylate, benzoin tosylate, etc. Esters; others such as diphenyl phosphonium salt, triphenyl phosphonium salt, phenyl diazonium salt, benzyl carbonate, and the like.

The other acid generator is preferably a compound represented by the above formula (b4), and preferably has a value of n of 2, and more preferably, Rb ¹² is a substituted or unsubstituted carbon of 1 to 8 of 2 valence. The alkyl group, or the substituted or unsubstituted aromatic group, preferably, Rb ¹³ is a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, or a substituted or unsubstituted aryl group, but is not limited thereto. this.

In the case of being used in combination with these other acid generators, the ratio of use thereof is not particularly limited as long as it does not hinder the effect of the present invention. In general, the other acid generator is 1 to 300 parts by mass based on 100 parts by mass of the acid generator including the cationic portion represented by the above formula (b5) and the anion portion represented by the above formula (b-an1). It is preferably 10 to 100 parts by mass.

The acid generator (B) may be used singly or in combination of two or more. The content of the acid generator (B) is preferably 0.1 to 10% by mass, and preferably 0.5 to 3% by mass based on the total mass of the photoresist composition of the present invention.

The photoresist composition of the present invention has a purpose of forming a thick film photoresist pattern on a support, and is preferably used as a thick film.

<arbitrary ingredients> [Basic compound component; (D) component]

The photoresist composition of the present invention may contain, in addition to the component (A), a basic compound component (hereinafter also referred to as "(D) component").

((D) component)

The component (D) is a compound which forms a relatively basic compound for the component (B) and has a function as an acid diffusion controlling agent, and is not particularly useful as long as it is not equivalent to the component (B). Qualified, it can be arbitrarily selected from known ingredients. Among them, aliphatic amines, particularly secondary aliphatic amines or tertiary aliphatic amines, are preferred.

The aliphatic amine refers to an amine having one or more aliphatic groups, and the aliphatic group preferably has a carbon number of from 1 to 12.

The aliphatic amine means an amine (alkylamine or alkanolamine) or a cyclic amine in which at least one hydrogen atom of ammonia NH ₃ is substituted with an alkyl group having 12 or less carbon atoms or a hydroxyalkyl group.

Specific examples of the alkylamine and the alkanolamine are, for example, a monoalkylamine such as n-hexylamine, n-heptylamine, n-octylamine, n-decylamine or n-decylamine; diethylamine amine, Dialkylamines such as bis-n-propylamine, di-n-heptylamine, di-n-octylamine, dicyclohexylamine; trimethylamine, triethylamine, tri-n-propyl Amine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-decylamine, three a trialkylamine such as -n-decylamine or tri-n-dodecylamine; diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, di-n-octanolamine, tri- An alkanolamine such as n-octanolamine or the like is exemplified. Among them, a trialkylamine having 5 to 10 carbon atoms is more preferable, and tri-n-pentylamine or tri-n-octylamine is particularly preferred.

The cyclic amine is exemplified, for example, by a heterocyclic compound containing a nitrogen atom as a hetero atom. The heterocyclic compound may be a monocyclic one (aliphatic monocyclic amine) or a polycyclic one (aliphatic polycyclic amine).

Aliphatic monocyclic amines, specifically, for example, piperidine, piperidine Wait.

The aliphatic polycyclic amine is preferably a carbon number of 6 to 10, specifically, for example, 1,5-diazabicyclo[4.3.0]-5-nonene, 1,8-diaza Heterobicyclo[5.4.0]-7-undecene, hexamethyltetramine, 1,4-diazabicyclo[2.2.2]octane, and the like.

Other aliphatic amines, for example, tris(2-methoxymethoxy B Amine, tris{2-(2-methoxyethoxy)ethyl}amine, tris{2-(2-methoxyethoxymethoxy)ethyl}amine, three {2-( 1-methoxyethoxy)ethyl}amine, tris{2-(1-ethoxyethoxy)ethyl}amine, tris{2-(1-ethoxypropoxy)ethyl} The amine, tris[2-{2-(2-hydroxyethoxy)ethoxy}ethyl]amine, triethanolamine triacetate, etc., are preferably triethanolamine triacetate.

Further, as the component (D2), an aromatic amine can also be used.

An aromatic amine, for example, aniline, pyridine, 4-dimethylaminopyridine, pyrrole, hydrazine, pyrazole, imidazole or derivatives thereof, diphenylamine, triphenylamine, tribenzylamine, 2,6-diisopropylaniline, N-tert-butoxycarbonylpyrrolidine, and the like.

(D) The components may be used singly or in combination of two or more.

The component (D) is usually used in an amount of 0.01 to 5.0 parts by mass based on 100 parts by mass of the resin solid content (total of the (A) component and the (C) component). In the above range, the shape of the resist pattern, the stability over time of storage, and the like can be improved.

<arbitrary ingredients> [(E) ingredients]

The photoresist composition of the present invention may contain an organic carboxylic acid and an oxyacid of phosphorus as an optional component for the purpose of preventing deterioration of sensitivity, or improving the shape of the photoresist pattern, stability over time of storage, and the like. At least one compound (E) (hereinafter also referred to as (E) component) selected from a group of derivatives.

Organic carboxylic acids, for example, acetic acid, malonic acid, citric acid, malic acid, Succinic acid, benzoic acid, salicylic acid and the like are preferred.

Phosphorus oxyacids, for example, phosphoric acid, phosphonic acid, phosphinic acid, etc., among which phosphonic acid is particularly preferred.

The derivative of the oxyacid of phosphorus, for example, an ester in which a hydrogen atom of the above-mentioned oxo acid is substituted with a hydrocarbon group, and the hydrocarbon group is, for example, an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 15 carbon atoms.

A derivative of phosphoric acid, for example, a phosphate such as di-n-butyl phosphate or diphenyl phosphate.

A derivative of a phosphonic acid, for example, a phosphonate such as dimethyl phosphonate, di-n-butyl phosphonate, phenyl phosphonate, diphenyl phosphonate or dibenzyl phosphonate.

A derivative of phosphinic acid, for example, phenyl phosphinate phenylphosphonate or the like.

The component (E) may be used singly or in combination of two or more.

The component (E) is usually used in an amount of 0.01 to 5.0 parts by mass based on 100 parts by mass of the resin solid content (total of the (A) component and the (C) component).

[Other additives]

In the photoresist composition of the present invention, an additive such as an additive resin, a dissolution inhibitor, a plasticizer, a stabilizer, a colorant, or an anti-additive containing an additive, for example, a property of improving the properties of the photoresist film can be appropriately added. Halo, dye, etc.

[(S) ingredients]

The photoresist composition of the present invention can dissolve the material in an organic solvent ( It can also be manufactured by means of the (S) component.

The component (S) may be any one of the components known as a solvent for chemically enhanced photoresist, as long as it can dissolve the components used and form a homogeneous solution. More than one kind is used.

For example, lactones such as γ-butyrolactone (GBL); acetone, methyl ethyl ketone (MEK), cyclohexanone, methyl-n-amyl ketone, methyl isoamyl ketone, 2-hexanone Ketones; polyols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol; ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoethyl a compound having an ester bond such as an acid ester, a monomethyl ether such as a polyhydric alcohol or a compound having an ester bond, a monoalkyl ether such as monoethyl ether, monopropyl ether or monobutyl ether, or monophenyl ether. a derivative of a polyol such as an ether-bonded compound [in which propylene glycol monomethyl ether acetate (PGMEA) or propylene glycol monomethyl ether (PGME) is preferred]; a cyclic ether such as dioxane , or methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxy propionate Esters; anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenyl ether, butyl phenyl ether, ethyl benzene, diethyl benzene benzene, pentyl benzene, isopropyl Benzobenzene, toluene, An aromatic organic solvent such as xylene, isopropyl toluene or mesitylene, or dimethyl hydrazine (DMSO).

Further, in the photoresist composition of the present invention, an organic solvent can be appropriately added for the purpose of adjusting the viscosity. Specific examples of the organic solvent include ketones such as methyl isoamyl ketone; ethylene glycol, ethylene glycol monoacetate, diethylene glycol, and Ethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, dipropylene glycol, and dipropylene glycol monoacetate monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, or monophenyl ether Alcohols and their derivatives; cyclic ethers such as dioxane; methyl ethyl acetate, ethyl acetate, ethyl pyruvate, ethyl ethoxyacetate, methyl 2-hydroxypropionate, 2- Ethyl hydroxypropionate, ethyl 2-hydroxy-2-methylpropanoate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3- An ester such as methoxybutyl acetate; an aromatic hydrocarbon such as toluene or xylene; and the like. These may be used alone or in combination of two or more.

These organic solvents may be used singly or in combination of two or more.

Among them, PGMEA and 3-methoxybutyl acetate are preferred.

The amount of the component (S) to be used is not particularly limited, and it can be applied to a concentration of a substrate or the like, and the thickness of the coating film can be appropriately set. In general, the solid concentration of the photoresist composition is set to be in the range of 1 to 65% by mass, preferably 2 to 65% by mass, but in the case of a photoresist composition for a thick film, a solid component is used. The concentration is preferably 30% by mass or more, more preferably 30% by mass to 65% by mass. When the solid concentration is less than 30% by mass, it is difficult to obtain a thick film of 5 μm or more, or more preferably 10 μm or more, which is suitable for the production of the connection terminal, and when it exceeds 65% by mass, the fluidity of the composition is remarkably deteriorated. In addition to the difficulty, it is not easy to obtain a uniform photoresist film in the spin coating method.

"other"

The photoresist composition of the present invention may further contain a polyethylene resin for the purpose of improving plasticity. The polyethylene resin preferably has a mass average molecular weight of 10,000 to 200,000 and preferably 50,000 to 100,000.

The polyethylene resin is a poly(vinyl lower alkyl ether) which can be obtained by polymerizing a vinyl lower alkyl ether represented by the following formula (Vi-1) alone or in a mixture of two or more kinds. Formed by a polymer or copolymer.

In the above formula (Vi-1), Rvi ¹ represents a linear or branched alkyl group having 1 to 6 carbon atoms.

These polyethylene resins are polymers obtained from vinyl compounds. The polyethylene resin, specifically, for example, polyvinyl chloride, polystyrene, polyhydroxystyrene, polyvinyl acetic acid, polyvinyl benzoic acid, polyvinyl methyl ether, polyvinyl ether, polyvinyl alcohol, poly Vinyl pyrrolidone, polyvinyl phenol, copolymers thereof, and the like. The polyethylene resin is preferably a polyvinyl methyl ether from the viewpoint of having a low glass shift point.

Further, the photoresist composition of the present invention may further contain an auxiliary agent for the purpose of improving adhesion to a substrate. The auxiliary agent to be used is preferably a functional decane coupling agent. Functional decane coupling agent, examples For example, a decane coupling agent having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group or an epoxy group is exemplified. Further, specific examples of the functional decane coupling agent include, for example, trimethoxydecyl benzoic acid, γ-methacryloxypropyltrimethoxydecane, vinyltriethoxydecane, vinyltrimethoxydecane, γ - γ-Glycidoxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, and the like. The content of the auxiliary agent is preferably 20 parts by mass or less based on 100 parts by mass of the total mass of the resin (A) and the alkali-soluble resin (C).

Further, in the photoresist composition of the present invention, a surfactant may be further contained for the purpose of improving coatability, defoaming property, smoothness, and the like. For surfactants, for example, BM-1000, BM-1100 (both manufactured by BM Chemical Co., Ltd.), Megfried F142D, Megfried F172, Megfried F173, and Megfried F183 (all are Japan Nippon Paint Chemical Industry Co., Ltd. System, Fluora FC-135, Fluora FC-170C, Fluora FC-430, Fluora FC-431 (all manufactured by Sumitomo 3M), Shaflon S-112, Shaflon S-113, sand Fluorine S-131, Shaflon S-141, Shaflon S-145 (all manufactured by Asahi Glass Co., Ltd.), SH-28PA, SH-190, SH-193, SZ-6032, SF-8428 (both are east) A commercially available fluorine-based surfactant or the like is exemplified, but is not limited thereto.

Further, in the photoresist composition of the present invention, an acid, an acid anhydride or a high boiling point solvent may be further contained for the purpose of finely adjusting the solubility of the alkali developing solution.

For example, acetic acid, propionic acid, n-butyric acid, and acid Monocarboxylic acids such as butyric acid, n-valeric acid, isovaleric acid, benzoic acid, cinnamic acid; lactic acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoin Acid, 2-hydroxycinnamic acid, 3-hydroxycinnamic acid, 4-hydroxycinnamic acid, 5-hydroxyisophthalic acid, syringic acid and other hydroxymonocarboxylic acids; oxalic acid, succinic acid, glutaric acid, adipic acid, horse Acid, itaconic acid, hexahydrophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,2-cyclohexanedicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid , polybutane carboxylic acid such as butane tetracarboxylic acid, trimellitic acid, pyromellitic acid, cyclopentane tetracarboxylic acid, butane tetracarboxylic acid, 1,2,5,8-naphthalenetetracarboxylic acid; itaconic anhydride , succinic anhydride, citraconic anhydride, dodecene succinic anhydride, tricarbonyl anhydride, maleic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, 5-bicycloheptene-2,3-dicarboxylate Anhydride (5-norbornene-2,3-dicarboxylic acid), 1,2,3,4-butanetetracarboxylic anhydride, cyclopentane tetracarboxylic dianhydride, phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, Benzophenone tetracarboxylic anhydride, trimellitate ethylene glycol dianhydride Three glycol trimellitate anhydride anhydride.

Further, examples of the high boiling point solvent are N-methylformamide, N,N-dimethylformamide, N-methylformamide, N-methylacetamide, N,N-dimethyl Acetamine, N-methylpyrrolidone, dimethyl hydrazine, benzyl ether, dihexyl ether, acetone acetone, isophorone, hexanoic acid, octanoic acid, 1-octanol, 1-nonanol, Benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, and the like.

The above-mentioned amount of the compound for the purpose of finely adjusting the solubility of the alkali developing solution can be used in combination. Coating method, etc. When the composition is uniformly mixed, the component is not particularly limited, and is generally 60% by mass or less, preferably 40% by mass or less based on the total mass of the obtained composition.

For the production of the photoresist composition of the present invention, for example, the above components may be mixed and stirred only by a usual method, and if necessary, a disperser such as a dissolver, a homomixer, or a 3-roll mill may be used. Disperse and mix. Further, after mixing, it can be filtered using a mesh type, a membrane filter or the like.

The photoresist composition of the present invention is a thick film resist layer suitable for forming a film thickness of from about 5 to about 200 μm, preferably from about 10 to about 120 μm, more preferably from about 10 to about 100 μm on the support.

The support is not particularly limited, and a conventionally known material such as a substrate for an electronic component or a specific wiring pattern formed thereon may be used. The substrate is, for example, a substrate made of a metal such as tantalum, tantalum nitride, titanium, tantalum, platinum, titanium tungsten, copper, chromium, iron or aluminum, or a glass substrate. In particular, the chemically-enhanced positive-type photoresist composition for thick films used in the present embodiment can form a good photoresist pattern on a copper substrate. As the material of the wiring pattern, for example, copper, solder, chromium, aluminum, nickel, gold, or the like can be used.

<<Formation method of photoresist pattern>>

The method for forming the photoresist pattern of the second aspect of the present invention can be carried out, for example, in the following manner.

First, the photoresist composition is applied to a branch using a spin coater or the like. The support is applied, for example, at a temperature of 80 to 150 ° C for 40 to 120 seconds, preferably 60 to 90 seconds by post-bake (PAB) treatment to form a photoresist film. Next, for example, an exposure device such as an ArF exposure device, an electron line drawing device, or an EUV exposure device is used to expose the photoresist film by masking a mask pattern (mask pattern) or not. After the selective exposure of the mask pattern and the direct illumination of the electron beam, for example, baking is performed for 40 to 120 seconds, preferably 60 to 90 seconds, at a temperature of 80 to 150 ° C (Post). Exposure Bake (PEB)) processing. After the photoresist film is subjected to development treatment using an organic developer, it is preferred to carry out a washing treatment and drying using a washing liquid containing an organic solvent.

After the development treatment or the washing treatment, the developer or the washing liquid attached to the pattern may be subjected to a removal treatment using a supercritical fluid.

Further, depending on the case, the residual organic solvent may be removed by a baking (post-baking) treatment after the development treatment, the washing treatment or the supercritical fluid treatment.

The support is not particularly limited, and a conventionally known material such as a substrate for an electronic component or a specific wiring pattern formed thereon may be used. More specifically, for example, a substrate made of a metal such as germanium wafer, copper, chromium, iron, or aluminum, or a glass substrate. As the material of the wiring pattern, for example, copper, aluminum, nickel, gold, or the like can be used.

Further, the support may be obtained by providing an inorganic or/or organic film on the substrate. An inorganic film, for example, an inorganic antireflection film (inorganic BARC) or the like is exemplified. Organic film, for example, an organic antireflection film (organic BARC) or an organic film such as a lower organic film in a multilayer photoresist method Show.

Wherein, the multilayer photoresist method means that at least one organic film (lower organic film) and at least one photoresist film (upper photoresist film) are disposed on the substrate, and the light formed on the upper photoresist film is formed. The pattern of the resist pattern is used as a mask to perform patterning of the underlying organic film, which can form a pattern of high aspect ratio. That is, according to the multilayer photoresist method, since the thickness of the lower organic film can be ensured, the photoresist film can be thinned, and a fine pattern having a high aspect ratio can be formed.

In the multilayer photoresist method, it is basically divided into a method of forming an upper photoresist film and a two-layer structure of a lower organic film (two-layer photoresist method), and a layer between the upper photoresist film and the lower organic film. A method of three-layer or more multilayer structure of an intermediate layer (metal thin film or the like) (three-layer photoresist method).

The wavelength used for the exposure is not particularly limited, and an ArF excimer laser, a KrF excimer laser, an F ₂ excimer laser, an EUV (very ultraviolet ray), a VUV (vacuum ultraviolet ray), an EB (electron) can be used. Radiation lines such as line), X-ray, and soft X-ray are performed. The photoresist composition is highly useful as a KrF excimer laser, ArF excimer laser, EB or EUV, and is particularly useful as an ArF excimer laser, EB or EUV.

The exposure method of the photoresist film may be general exposure (dry exposure) or liquid immersion exposure (Liquid Immersion Lithography) performed in an inert gas such as air or nitrogen.

The immersion exposure is such that a solvent having a refractive index higher than that of air is filled between the photoresist film and the lens at the lowest position of the exposure device. (Immersion medium), and an exposure method of exposure (immersion exposure) is performed in this state.

The immersion medium is preferably a solvent having a refractive index larger than that of air and having a refractive index smaller than that of the exposed photoresist film. The refractive index of the solvent is not particularly limited as long as it is within the above range.

A solvent having a refractive index larger than that of air and having a smaller refractive index than the resist film, for example, water, a fluorine-based inert liquid, an oxime-based solvent, a hydrocarbon-based solvent, or the like.

Specific examples of the fluorine-based inert liquid include, for example, a liquid such as C ₃ HCl ₂ F ₅ , C ₄ F ₉ OCH ₃ , C ₄ F ₉ OC ₂ H ₅ or C ₅ H ₃ F ₇ as a main component, Those with a boiling point of 70-180 ° C are preferred, and those with a boiling point of 80-160 ° C are preferred. When the fluorine-based inert liquid has a boiling point in the above range, it is preferred to remove the wetting medium in a simple manner after the completion of the exposure.

The fluorine-based inert liquid is particularly preferably a perfluoroalkyl compound in which all hydrogen atoms of the alkyl group are replaced by fluorine atoms. The perfluoroalkyl compound is specifically, for example, a perfluoroalkyl ether compound or a perfluoroalkylamine compound.

Further, specifically, the perfluoroalkyl ether compound may, for example, be perfluoro(2-butyl-tetrahydrofuran) (boiling point: 102 ° C), and the perfluoroalkylamine compound may, for example, be perfluorotributylamine (boiling point) 174 ° C).

Infiltration of the medium is more preferable in terms of cost, safety, environmental problems, and extensive use.

The organic solvent contained in the organic solvent used for development may be any one of the well-known organic solvents as long as it can dissolve the substrate component (A) (base component (A) before exposure). use. specific For example, a polar solvent such as a ketone solvent, an ester solvent, or a nitrile solvent can be used. The ester solvent is preferably butyl acetate. The ketone solvent is preferably methyl-n-pentyl-ketone (2-hexanone).

The ketone solvent is an organic solvent containing C-C(=O)-C in the structure. The ester solvent is an organic solvent containing C-C(=O)-O-C in the structure. The alcohol solvent is an organic solvent having an alcoholic hydroxyl group in the structure, and the "alcoholic hydroxyl group" means the hydroxyl group to which the carbon atom of the aliphatic hydrocarbon group is bonded. The guanamine-based solvent is an organic solvent containing a guanamine group in the structure. The ether solvent is an organic solvent containing C-O-C in the structure. Among the organic solvents, there are also organic solvents having a plurality of functional groups having the characteristics of the above respective solvents, and in this case, they correspond to any solvent type including a functional group contained in the organic solvent. For example, diethylene glycol monomethyl ether is equivalent to any of an alcohol solvent and an ether solvent in the above classification. Further, the hydrocarbon solvent refers to a hydrocarbon solvent which is formed of a hydrocarbon and does not have a substituent (a hydrogen atom or a hydrocarbon group or a group other than a hydrocarbon group).

In a specific example of each solvent, a ketone solvent, for example, 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-hexanone, 1-hexanone, 2-hexanone, Diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetyl ketone, acetone acetone, ionone, diacetone alcohol, Ethyl carbitol, acetophenone, methylnaphthyl ketone, isophorone, propyl carbonate, γ-butyrolactone, methyl-n-pentyl-ketone (2-hexanone), etc. .

Ester solvent, for example, methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, methoxy Ethyl acetate, ethyl ethoxyacetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, Ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monophenyl ether Acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4- Methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol Monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2- Methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl 3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, propylene glycol diacetate Methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, lactic acid propyl, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, Pyruvic propyl, butyl acetonate, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, propionate propyl, propionic acid isopropyl, methyl 2-hydroxypropionate , ethyl 2-hydroxypropionate, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, propyl-3- Methoxy propionate and the like.

A nitrile solvent such as acetonitrile, propionitrile, valeronitrile, butyronitrile or the like.

In the organic developer, a known additive may be added in accordance with necessity. This additive is exemplified, for example, as a surfactant. Surfactant, For example, in the same manner as described above, a nonionic surfactant is preferred, and a fluorine-based surfactant or a quinone-based surfactant is preferred.

The development treatment using an organic developer can be carried out by a known development method, for example, a method in which a support is immersed in a developer for a certain period of time (DIP method), and the developer is covered with a surface tension to cover the surface of the support, and a method of standing for a certain period of time (PUDDLE method), a method of spraying a developer on a surface of a support (SPRAY method), and a developer rotating at a constant speed, so that the developer coating nozzle is scanned at a constant speed, The method of applying the developer solution (Dynamic Dispense method) or the like.

After the above development treatment and before drying, the washing treatment may be carried out using a washing liquid containing an organic solvent. After washing, a good pattern can be formed.

The organic solvent to be used for the washing liquid is, for example, an organic solvent which is exemplified as the organic solvent used in the organic developing solution, and is not easily dissolved in the solvent of the resist pattern, and is appropriately selected and used. Usually, at least one type of solvent selected from a hydrocarbon solvent, a ketone solvent, an ester solvent, an alcohol solvent, a guanamine solvent, and an ether solvent is used. Among these, at least one selected from the group consisting of a hydrocarbon solvent, a ketone solvent, an ester solvent, an alcohol solvent, and a guanamine solvent is preferred, and at least one selected from the alcohol solvent and the ester solvent is selected. One type is more preferable, and an alcohol type solvent is particularly preferable.

The alcohol solvent used in the washing liquid is preferably a carbon number of 6 to 8 monohydric alcohol, and the monohydric alcohol may be linear, branched or cyclic. Specifically, for example, 1-hexanol, 1-heptanol, 1-octanol, 2-hexanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol 4-octanol, benzyl alcohol Wait. Among them, 1-hexanol, 2-heptanol and 2-hexanol are preferred, and 1-hexanol or 2-hexanol is preferred.

Any of these organic solvents may be used singly or in combination of two or more. Further, it may be used in combination with an organic solvent or water other than the above. In addition, when the development property is considered, the amount of water to be added to the washing liquid is preferably 30% by mass or less, more preferably 10% by mass or less, and most preferably 5% by mass or less, based on the total amount of the washing liquid. It is particularly preferable to be 3% by mass or less.

In the washing liquid, a known additive may be added in accordance with necessity. This additive is exemplified, for example, as a surfactant. The surfactant is preferably the same as described above, and a nonionic surfactant is preferred, and a fluorine-based surfactant or a quinone-based surfactant is preferred.

In the case where a surfactant is added, the amount thereof is usually 0.001 to 5% by mass based on the total amount of the washing liquid, preferably 0.005 to 2% by mass, and preferably 0.01 to 0.5% by mass.

The washing treatment (washing treatment) using the washing liquid can be carried out by a known washing method, for example, a method of coating the washing liquid on a support which is rotated at a constant speed (rotary coating method), The method in which the support is immersed in the washing liquid for a certain period of time (DIP method), the method of spraying the washing liquid onto the surface of the support (SPRAY method), or the like.

<Manufacturing method of thick film photoresist pattern>

The thick film photoresist pattern can be manufactured, for example, in the following manner. Applying a thick film with a solution of a positive photoresist composition to the support and removing the solution by heating The agent is formed to form a desired coating film (thick film photoresist layer). The method of applying to the support can be, for example, a spin coating method, a strip coating method, a roll coating method, a screen printing method, or an applicator method. The pre-baking conditions of the coating film containing the composition of the present embodiment vary depending on the type of each component in the composition, the addition ratio, the coating film thickness, etc., and are usually 70 to 150 ° C, preferably 80. ~140 ° C, more preferably about 2 to 60 minutes.

The thickness of the thick film photoresist layer is preferably from about 5 to about 200 μm, preferably from about 10 to about 120 μm, more preferably from about 10 to about 100 μm.

Subsequently, the resulting thick film photoresist layer is selectively irradiated (exposed) by a radiation containing electromagnetic waves or particle lines, such as ultraviolet rays or visible light having a wavelength of 300 to 500 nm, through a mask of a specific pattern.

As the light source of the radiation, for example, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, argon radiation, or the like can be used. Further, the radiation includes microwaves, infrared rays, visible rays, ultraviolet rays, X-rays, gamma rays, electron wires, yang wires, neutral wires, ion wires, and the like. The amount of radiation irradiation varies depending on the type of each component in the composition, the amount of addition, the film thickness of the coating film, and the like, and is, for example, in the case of using an ultrahigh pressure mercury lamp, 100 to 10,000 mJ/cm ² . Further, in the radiation, the purpose of generating an acid may include light for activating the acid generator.

Subsequently, after the exposure, heating can be carried out by a known method to promote the diffusion of the acid to change the alkali solubility of the thick film resist layer of the exposed portion. Secondly, for example, a specific alkaline aqueous solution can be used as a display The liquid solution is used, which will not be dissolved or removed to produce a specific thick film photoresist pattern.

As the developer, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium methyl citrate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propyl can be used. Amine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo ring An aqueous solution of a base such as [5,4,0]-7-undecene or 1,5-diazabicyclo[4,3,0]-5-nonane. Further, an aqueous solution obtained by adding an appropriate amount of an aqueous solution of the above-mentioned alkali such as a water-soluble organic solvent such as methanol or ethanol or a surfactant may be used as the developing solution.

The development time varies depending on the type of the components of the composition, the addition ratio, the thickness of the dried film of the composition, and the like, and is usually from 1 to 30 minutes, and the development method can be performed by immersion method, dip (DIPPING) method, or covering (PUDDLE). Any one of the method, the spray (SPRAY) development method, and the like. After development, it is washed with running water for 30 to 90 seconds, and dried by using an air gun or an oven.

<Method of manufacturing the connection terminal>

Then, in the non-resistance portion (the portion removed by the alkali developing solution) of the thick film resist pattern obtained in this manner, for example, a conductor such as a metal is buried by plating or the like. A connection terminal such as a metal post or a bump is formed. Further, the plating treatment method is not particularly limited, and various conventionally known methods can be employed. Plating solution, especially solder Plating, copper plating, gold plating, nickel plating solution, etc. can be used together.

The residual photoresist pattern can be removed by using a stripping solution or the like according to a specific method.

Since the photoresist composition of the present invention contains the acid generator component (B1), the pattern formation of the photoresist film using the photoresist composition can exhibit excellent lithographic etching characteristics such as sensitivity. Although this reason is not determined, it is presumed that it is an effect obtained by a structure in which a specific carbon number is bonded to a specific position of a naphthyl group by a sulfur atom.

Hereinafter, the present invention will be more specifically described by examples, but the present invention is not limited by the following examples.

[Synthesis Example of Compound (B)-1]

The following compound (B)-1 (1-(2,7-di-n-butoxynaphthyl)di-n-butylindole II (1,1,2,2,3,3,4,4) , 4-nonafluoro-n-butane oxime) quinone imine) was obtained by the following method.

Operation 1

Phosphorus pentoxide (1.7 g) and methanesulfonic acid (11.5 g) were added to the reaction vessel. Subsequently, 2,7-di-n-butoxynaphthalene (8.2 g) and di-n-butylarylene (6.3 g) were further added, and the mixture was stirred at room temperature for 16 hours. The temperature in the reaction vessel was maintained at 0 to 10 ° C, and a 20% aqueous NaOH solution (30 g) was added dropwise thereto, and dichloromethane (80 g) was added thereto, and the mixture was allowed to stand for stratification, and the aqueous layer was removed to obtain an organic layer. After the obtained organic layer was washed with deionized water (30 g), the mixture was allowed to stand for stratification, and the aqueous layer was removed to obtain a reaction solution of the condensation reaction product.

Operation 2

Deionized water (30 g) and bis(nonafluoro-n-butane oxime) quinone imide potassium salt (18.6 g) were added to another reaction vessel, and then the reaction solution obtained in the above operation 1 was added in its entirety. After stirring at room temperature for 20 minutes, the insoluble material was filtered. The obtained reaction solution was allowed to stand, layered, and the aqueous layer was removed to obtain an organic layer.

Operation 3

Dichloromethane was distilled off from the organic layer obtained in the organic layer 2, and methyl tert-butyl ether (hereinafter abbreviated as MTBE) (17 g) and hexane (34 g) were added at 50 ° C to give a concentrate. Crystallization gave Compound (B)-1 18.8 g.

The resulting white crystals, by the use of ¹ H-NMR and LC-MS analysis results by the following, it is confirmed that the general formula (I), the ^{R 1, R 2, R 3} , R 4 is n- butyl, X ^a compound which is a di(1,1,2,2,3,3,4,4,4-nonafluoro-n-butane oxime) quinone imine anion.

^{1 H-NMR (400MHz, DMSO} -d 6, internal standard substance: tetramethyl silane-): δ (ppm) 0.82 ( t, J = 7.3Hz, 6H), 0.97 (t, J = 7.3Hz, 3H), 1.00 (t, J = 7.3 Hz, 3H), 1.30 - 1.65 (m, 12H), 1.74-1.96 (m, 4H), 3.81-4.04 (m, 4H), 4.18 (t, J = 6.6 Hz, 2H) , 4.44 (t, J = 6.6 Hz, 2H), 7.24 (dd, J = 2.2 and 9.0 Hz, 1H), 7.50 (d, J = 2.2 Hz, 1H), 7.57 (d, J = 9.0 Hz, 1H) , 8.01 (d, J = 9.0 Hz, 1H), 8.36 (d, J = 9.0 Hz, 1H)

MS (LC/ESI(+)Spectrum): M ⁺ 417

MS (LC/ESI(-)Spectrum): M ^- 580

The following compounds (B)-7 and (B)-8 were obtained by the same method as the compound (B)-1.

[Production of positive photoresist composition for thick film]

A positive-type photoresist composition for thick films obtained by adding the respective components in the proportions shown in Table 1 (Examples 1 to 3 and Comparative Examples 1 to 6) was prepared.

Subsequently, it was uniformly dissolved, and filtered through a membrane filter having a pore size of 1 μm to obtain a positive-type photoresist composition for a thick film having a solid content concentration of 30 to 60% by mass.

In Table 1, each symbol has the following meaning, and the numerical value in [] is the addition amount (parts by mass).

. (A)-1; 12.5 parts by mass of the compound represented by the following formula (1) (l/m/n/o=45/35/10/10) (molecular weight: 200,000) and the following formula (2) (l /m/n/o/p=25/20/5/10/40) (molecular weight 50,000) compound 25 parts by mass of mixed resin

. (C)-1; novolac resin (molecular weight 20,000 of phenolic varnish resin obtained by addition condensation of m/p-cresol=6/4 with formaldehyde and acid catalyst) 52.5 parts by mass, polyhydroxybenzene The following formula (3) (l/m = 85/15) of the vinyl resin is 10 parts by mass.

. (B)-1~(B)-9; respectively represent the compound (B)-1~(B)-9.

. (4) A compound represented by the following formula (4).

. (E)-1; salicylic acid.

. (S)-1; a mixed solvent of PGMEA/3-methoxybutyl acetate (mass ratio 40/60).

(Formation of thick film photoresist pattern) (Examples 1 to 3, and Comparative Examples 1 to 6)

Each of the examples and the comparative examples of the thick film positive resist composition obtained in the above manner was applied onto a copper substrate of 8 inches using a spin coater to dry the applied photoresist composition. A thick film photoresist layer having a film thickness of about 50 μm is obtained. Next, the thick film photoresist layer was placed on a hot plate and prebaked at 140 ° C for 5 minutes.

After the prebaking, exposure was performed using an exposure apparatus NSR-i14E (manufactured by Nikon Corporation, NA: 0.54, σ: 0.59). Next, it was placed on a hot plate and exposed to light (PEB) at 85 ° C for 3 minutes. Subsequently, a 2.38% aqueous solution of tetramethylammonium hydroxide (TMAH) was dropped into the thick film photoresist layer, left at 23 ° C for 60 seconds, and this was repeated four times for development. Subsequently, it was washed with running water, and was blown with nitrogen to obtain a pattern of a thick film photoresist pattern having a line and space pattern of 100 μm and a large area (10000 μm ² ).

The minimum exposure amount until the photoresist film of the large-area pattern disappeared was measured as Eth (mJ/cm ² ). The results are shown in Table 2.

From the above results, it was confirmed that the positive-type photoresist compositions for thick films of Examples 1 to 3 were more excellent in sensitivity than the positive-type photoresist compositions for thick films of Comparative Examples 1 to 5.

Claims (9)

A photoresist composition comprising a resin component (A) which changes solubility in a developing solution by an action of an acid, and an acid generator component (B) which generates an acid by exposure, characterized in that the acid The generator component (B) is an acid generator (B1) containing a compound represented by the following formula (b1-1), [wherein, R ¹ and R ² are an alkyl group having 1 to 10 carbon atoms which may have a substituent, and R ³ and R ⁴ are a chain alkyl group having 2 to 10 carbon atoms which may have a substituent, and X ^- is a pair Anion]. The resist composition 1 of the requested item, wherein the X ^- is the following formula (b-2) represented by the anion, Wherein R ¹⁰⁴ and R ¹⁰⁵ are each independently a ring-form group which may have a substituent, a chain alkyl group which may have a substituent, or a chain-like alkenyl group which may have a substituent; R ¹⁰⁴ and R ¹⁰⁵ may mutually The bond forms a ring; V ¹⁰² and V ¹⁰³ are each independently a single bond, an alkyl group, or a fluorinated alkyl group; and L ¹⁰¹ to L ¹⁰² are each independently a single bond or an oxygen atom]. The photoresist composition according to claim 1 or 2, wherein the resin component (A) is a resin containing at least one selected from the group consisting of a novolak resin, a polyhydroxystyrene resin, and an acrylic resin. The photoresist composition according to claim 1 or 2, wherein the solid content concentration is 30% by mass or more. The photoresist composition according to claim 1 or 2, which is a resist composition for a thick film used for forming a thick film photoresist pattern on a support. A method for forming a photoresist pattern, comprising the steps of: forming a photoresist film on a support using the photoresist composition according to any one of claims 1 to 5, exposing the photoresist film, and The step of developing the aforementioned photoresist film to form a photoresist pattern. A method for fabricating a thick film photoresist pattern, comprising the step of laminating a thick film photoresist layer comprising the photoresist composition of claim 5 on a support, and combining the active light or radiation An exposure step of selectively irradiating the thick film photoresist layer to develop the exposed thick film photoresist layer in the exposure step to obtain a thick film photoresist pattern development step. The method for producing a thick film resist pattern according to claim 7, wherein the thick film resist layer has a film thickness of 10 μm or more. A method of manufacturing a connection terminal, characterized by comprising a thick film light obtained by using the method of manufacturing a thick film photoresist pattern of claim 7 or 8. In the resistive type non-resistive portion, a step of forming a connection terminal formed of a conductor is formed.