TWI607283B - Pattern forming method and method of manufacturing electronic device - Google Patents

Description

Pattern forming method, method of manufacturing electronic device

The present invention relates to a pattern forming method, a photosensitive ray-sensitive or radiation-sensitive resin composition and a photoresist film used therefor, and a method and an electronic device for manufacturing an electronic device using the same. More specifically, the present invention relates to a semiconductor substrate manufacturing process suitable for ICs and the like, a circuit substrate for manufacturing liquid crystals and thermal heads, and the like, and a pattern forming method of a lithography step of other photolithography processes, and a pattern forming method using the same. A sensitizing ray-sensitive or radiation-sensitive resin composition and a photoresist film, and a method and an electronic device for manufacturing an electronic device using the same. In particular, the present invention relates to a pattern forming method for exposure in an ArF exposure apparatus and an ArF liquid immersion type projection exposure apparatus using a far ultraviolet light having a wavelength of 300 nm or less as a light source, and a sensitizing ray property using the pattern forming method or A radiation sensitive resin composition, a photoresist film, and a method of manufacturing an electronic device and an electronic device.

Since the introduction of photoresists for KrF excimer lasers (248 nm), in order to compensate for the decrease in sensitivity caused by light absorption, a patterning method using chemical amplification has been adopted.

In recent years, a pattern forming method using a developing solution (organic-based developing liquid) containing an organic solvent has been continuously developed (Patent Document 1). For example, in the column of the example of Patent Document 1, the photoacid generator shown below is used:

Prior technical literature Patent literature

Patent Document 1 Japanese Patent Laid-Open Publication No. 2011-123469

On the other hand, the high functionality of various electronic devices has recently been demanded, and, in turn, further improvements in the characteristics of the photoresist patterns used in microfabrication are required. In particular, it is generally required to further improve the performance of pattern shape characteristics such as line width roughness (LWR), pattern shape, CDU (uniformity of pattern size), and MEEF (Mask Error Enhancement Factor).

The inventors of the present invention evaluated the above various characteristics by the pattern forming method described in Patent Document 1. As a result, although the conventional requirements have been met, the level required recently has not been satisfied, and further improvement is required.

The present invention has been made in view of the above circumstances in order to provide a pattern forming method capable of forming a pattern of a good shape.

Further, the present invention has an object of providing a sensitized ray-sensitive or radiation-sensitive resin composition, a photoresist film, an electronic device using the same, and a method for producing the same.

As a result of intensive studies on the problems of the prior art, the present inventors have found that the above problems can be solved by using a radiation sensitive resin composition containing a predetermined photoacid generator.

That is, it has been found that the above object can be attained by the following constitutions: (1) A pattern forming method comprising: (1) sensitizing ray or radiation sensitive by containing the following (A) and (B); The resin composition is a step of forming a film: (A) a resin which is increased in polarity by an action of an acid to reduce solubility in an organic solvent-containing developing solution, and (B) by irradiation with actinic rays or radiation. a compound represented by the formula (I) after the acid is produced; (2) a step of irradiating the film with actinic rays or radiation; and (3) a film irradiated with actinic rays or radiation using a developing solution containing an organic solvent. The steps to perform the imaging.

(2) The pattern forming method of (1), wherein R is a group having a cyclic structure.

(3) The pattern forming method according to (1) or (2), wherein W is a polycyclic aliphatic group.

(4) The pattern forming method according to any one of (1) to (3), wherein W is an adamantyl group.

(5) The pattern forming method according to any one of (1) to (4), wherein the content of the organic solvent in the developing solution containing the organic solvent is 90% by mass or more and 100% by mass based on the total amount of the developing liquid. %the following.

(6) The pattern forming method according to any one of (1) to (5), wherein the developing solution contains a ketone solvent, an ester solvent, an alcohol solvent, a guanamine solvent, and an ether solvent. At least one of the groups.

(7) The pattern forming method according to any one of (1) to (6), wherein the photosensitive ray-sensitive or radiation-sensitive resin composition further contains a hydrophobic resin (HR) different from the resin (A).

(8) The pattern forming method according to any one of (1) to (7), wherein the exposure of the step (2) is liquid immersion exposure.

(9) A sensitizing ray-sensitive or radiation-sensitive resin composition for use in the pattern forming method according to any one of (1) to (8).

(10) A photoresist film formed by a photosensitive ray-sensitive or radiation-sensitive resin composition as in (9).

(11) A method of producing an electronic device, comprising the pattern forming method according to any one of (1) to (8).

(12) An electronic device produced by the method of manufacturing an electronic device as (11).

According to the present invention, a pattern forming method capable of forming a pattern of a good shape can be provided.

Moreover, according to the present invention, it is possible to provide a sensitized ray-sensitive or radiation-sensitive resin composition, a photoresist film, and an electronic device using the same, and a method of manufacturing the same.

[Formation of the Invention]

Hereinafter, embodiments of the present invention will be described in detail.

In the labeling of the group (atomic group) of the present specification, a label which is not described as "substituted or unsubstituted" and a substituent which does not have a substituent include a substituent. For example, "alkyl" means not only an unsubstituted alkyl group (unsubstituted alkyl group) but also a substituted alkyl group (substituted alkyl group).

In the present specification, "actinic ray" or "radiation" means, for example, a ray spectrum of a mercury lamp, a far-ultraviolet light represented by an excimer laser, an extreme ultraviolet ray (EUV light), an X-ray, an electron beam (EB), or the like. Further, in the present invention, "light" means actinic rays or radiation.

The "exposure" in this manual, unless otherwise specified, refers not only to the exposure of far ultraviolet rays, extreme ultraviolet rays, X-rays, EUV light, etc. represented by mercury lamps or excimer lasers, but also to electron beams and ions. The depiction of a particle beam such as a beam is also included in the exposure.

In the present specification, the "(meth)acrylic monomer" means at least one of monomers having a structure of "CH ₂ =CH-CO-" or "CH ₂ =C(CH ₃ )-CO-". Similarly, "(meth)acrylate" and "(meth)acrylic" mean "at least one of acrylate and methacrylate" and "at least one of acrylic acid and methacrylic acid", respectively.

As a feature of the present invention, a group having a cyclic structure of a photoacid generator is further substituted with an organic group. By containing such an organic group, the molecular weight of the photoacid generator itself is increased, and the diffusibility in the film is lowered. Therefore, it is easy to form a latent image that has been subjected to an overexposure process. pattern. In particular, as an organic group, a group having a large structure (a group having a cyclic structure) has a large effect.

The pattern forming method of the present invention has the following steps (1) to (3): (1) a step of forming a film by containing a photosensitive ray-sensitive or radiation-sensitive resin composition of (A) and (B) described later. (2) a step of irradiating the film with actinic rays or radiation; and (3) a step of developing the film irradiated with actinic rays or radiation using a developing solution containing an organic solvent.

In the following, first, the components contained in the sensitizing ray-sensitive or radiation-sensitive resin composition (hereinafter, simply referred to as "composition") used in the step (1) will be described in detail. The procedure is detailed.

<Resin which increases the solubility of the developing solution containing an organic solvent by increasing the polarity by the action of an acid (hereinafter also referred to as a resin (A))

The resin (A) is a resin which increases the polarity by the action of an acid and reduces the solubility in an organic solvent. Such a resin (A) whose part or all of the hydrophilic group located in the molecule is protected by a protecting group which can be detached by contact with an acid, and when the resin (A) is contacted with an acid, the protective group is detached The solubility of the resin (A) in an organic solvent is reduced. The hydrophilic group protected by the protecting group is also referred to as "acid labile group" hereinafter. The hydrophilic group may, for example, be a hydroxyl group or a carboxyl group, and more preferably a carboxyl group.

The resin (A) can be produced by polymerizing a monomer having an acid labile group (hereinafter referred to as "monomer (a1)"). In the case of the polymerization, only one type of monomer (a1) may be used, or two or more types may be used in combination.

<monomer (a1)>

The monomer (a1) has an acid labile group. The acid-labile group in the case where the hydrophilic group is a carboxyl group is a group in which a hydrogen atom of a carboxyl group is substituted with an organic residue, and an atom of an organic residue bonded to an oxy group is a group of a tertiary carbon atom. Among such acid labile groups, a preferred acid labile group is represented by the following formula (1) (hereinafter referred to as "acid labile group (1)").

[In the formula (1), R ^a1 , R ^a2 and R ^a3 (hereinafter referred to as "R ^a1 to R ^a3 "; the same ^applies hereinafter) independently represent an aliphatic hydrocarbon group having 1 to 8 carbon atoms or a fat having 3 to 20 carbon atoms. a cycloalkyl group, or R ^a1 and R ^a2 are bonded to each other, and together with the carbon atoms to which they are bonded, form a ring having a carbon number of 3 to 20; when the aliphatic hydrocarbon group, the alicyclic hydrocarbon group or R ^a1 and R ^When a ring formed by bonding with each other has a methyl group, the methyl group may be substituted by an oxy group, -S- or a carbonyl group; * means a bond]

Examples of the aliphatic hydrocarbon group of R ^a1 to R ^a3 include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group or a hexyl group. The alicyclic hydrocarbon group of R ^a1 to R ^a3 may be either monocyclic or polycyclic, or may be any one which does not exhibit aromatic unsaturated or saturated.

The monocyclic alicyclic hydrocarbon group may, for example, be a cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, a cycloheptyl group or a cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group, a methylnorbornyl group, and the groups shown below:

The alicyclic hydrocarbon group of R ^a1 to R ^a3 is preferably a saturated hydrocarbon group, and the carbon number thereof is preferably in the range of 3 to 16.

In the ring formed by bonding R ^a1 and R ^{a2 to} each other, the group represented by -C(R ^a1 )(R ^a2 )(R ^a3 ) may be exemplified by the following:

The number of carbon atoms of the ring formed by bonding R ^a1 and R ^{a2 to} each other is preferably from 3 to 12.

Specific examples of the acid labile group (1) include a 1,1-dialkylalkoxycarbonyl group (in the formula (1), R ^a1 to R ^a3 are each a group belonging to an alkyl group, and one of the alkyl groups Preferred is a tertiary butoxycarbonyl group), a 2-alkyladamantan-2-yloxycarbonyl group (in the formula (1), R ^a1 and R ^a2 are bonded to each other, and together with the carbon atoms to which they are bonded An adamantyl ring is formed, and R ^a3 is a group of an alkyl group) and a 1-(adamantan-1-yl)-1-alkylalkoxycarbonyl group (in the formula (1), R ^a1 and R ^a2 are an alkyl group, R ^a3 is a group of an adamantyl group).

On the other hand, when the hydrophilic group is a hydroxyl group, the acid labile group is a hydrogen atom of a hydroxyl group substituted with an organic residue to form an acetal. The basis of the structure. Among such acid-labile groups, a preferred acid-labile group is, for example, represented by the following formula (2) (hereinafter, referred to as "acid-labile group (2)").

[In the formula (2), R ^b1 and R ^b2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, R ^b3 represents a hydrocarbon group having 1 to 20 carbon atoms, or R ^b2 and R ^b3 are bonded to each other, and The carbon atoms and the oxygen atoms bonded to each other together form a ring having a carbon number of 3 to 20; when the hydrocarbon group or the ring formed by the bonding of R ^b2 and R ^{b3 to} each other has a methyl group, the methyl group may be anoxy group. , -S- or carbonyl substitution; * indicates the bond]

Examples of the hydrocarbon group include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. At least one of R ^b1 to R ^b2 is preferably a hydrogen atom.

Specific examples of the acid labile group (2) include the following groups:

The monomer (a1) having an acid labile group is preferably a monomer having an acid labile group and a carbon-carbon double bond, and more preferably a (meth)acrylic monomer having an acid labile group.

In particular, the monomer (a1) is preferably a monomer having both an acid labile group (1) and/or an acid labile group (2) and a carbon-carbon double bond in the molecule, and more preferably an acid. A (meth)acrylic monomer which stabilizes the group (1).

a (meth)acrylic monomer having an acid labile group (1) Among them, the acid labile group (1) is preferably a group having an alicyclic hydrocarbon structure having 5 to 20 carbon atoms. Polymer (A) obtained by polymerizing a monomer (a1) having such a sterically bulky alicyclic hydrocarbon structure, when a resist pattern is produced using the composition of the present invention containing the resin (A), The photoresist pattern can be manufactured with better resolution. Here, the (meth)acrylonitrile group means an acryloyl group and/or a methacryloyl group.

Among the (meth)acrylic monomers having an acid labile group (1) having an alicyclic hydrocarbon structure, a monomer represented by the formula (a1-1) is preferred (hereinafter referred to as "monomer (a1-) 1)") and a monomer represented by the formula (a1-2) (hereinafter referred to as "monomer (a1-2)"). When the resin (A) is produced, these may be used alone or in combination of two or more. The resin (A) is preferably at least one selected from the group consisting of a repeating unit derived from a monomer represented by the formula (a1-1) and a repeating unit derived from a monomer represented by the formula (a1-2). Further, the resin (A) is preferably a repeating unit containing at least one kind of a repeating unit derived from the monomer represented by the formula (a1-1) and a monomer derived from the formula (a1-2). Further, in another embodiment, the resin (A) is preferably a repeating unit containing two or more kinds of monomers derived from the formula (a1-2). In the resin (A), the total amount of the repeating unit derived from the monomer represented by the formula (a1-1) and the repeating unit derived from the monomer represented by the formula (a1-2) is occupied by the total repeating unit. The ratio is preferably 40 mol% or more, more preferably 45 mol% or more, and still more preferably 50 mol% or more. In particular, the proportion of the repeating unit derived from the monomer represented by the formula (a1-2) in the total repeating unit is preferably 30 mol% or more, more preferably 35 mol% or more, and still more preferably 40. More than Mole. The content ratio of each repeating unit in the resin (A) can be determined by, for example, ¹³ C-NMR.

[In the formula (a1-1) and the formula (a1-2), L ^a1 and L ^a2 each independently represent an oxy group or a group represented by *-O-(CH ₂ ) _k1 -CO-O-; here, k1 An integer of 1 to 7, wherein * is a bond to a carbonyl group (-CO-); R ^a4 and R ^a5 each independently represent a hydrogen atom or a methyl group; and R ^a6 and R ^a7 independently represent a fat having 1 to 8 carbon atoms; a hydrocarbon group or an alicyclic hydrocarbon group having 3 to 10 carbon atoms; m1 represents an integer from 0 to 14, n1 represents an integer from 0 to 10; n1' represents an integer from 0 to 3]

Further, the label "-(CH ₃ ) _m1 " on the adamantane ring in the formula (a1-1) means a hydrogen atom bonded to a carbon atom constituting the adamantane ring (that is, a methyl group and/or a methine group). The hydrogen atom is substituted by a methyl group, and the number of the methyl groups is m1.

In the formula (a1-1) and the formula (a1-2), L ^a1 and L ^{a2 are} preferably an oxy group or *-O-(CH ₂ ) _f1 -CO-O- (however, f1 represents an integer of 1 to 4). The group shown is more preferably an oxy group. F1 is preferably 1. R ^a4 and R ^{a5 are} preferably a methyl group.

The aliphatic hydrocarbon group of R ^a6 or R ^a7 is preferably a group having 6 or less carbon atoms. The alicyclic hydrocarbon group of R ^a6 or R ^a7 preferably has a carbon number of 8 or less, more preferably 6 or less.

When R ^a6 or R ^a7 is an alicyclic hydrocarbon group, the alicyclic hydrocarbon group may be either monocyclic or polycyclic, and may be either saturated or unsaturated, and is preferably a saturated hydrocarbon group.

M1 is preferably an integer of 0 to 3, more preferably 0 or 1.

N1 is preferably an integer of 0 to 3, more preferably 0 or 1.

N1' is preferably 0 or 1.

Examples of the monomer (a1-1) include the following:

Among these, as the monomer (a1-1), it is preferably (meth) propyl 2-methyladamantane-2-ate, 2-ethyladamantan-2-(meth)acrylate and 2-isopropyladamantan-2-(meth)acrylate, more preferably A 2-methyladamantane-2-acrylate, 2-ethyladamantane-2-acrylate and 2-isopropyladamantan-2-carboxylate.

Examples of the monomer (a1-2) include the following. Among these, as the monomer (a1-2), 1-ethylcyclohexyl (meth)acrylate is preferred, and 1-ethylcyclohexyl methacrylate is more preferred.

Making a tree using monomer (a1-1) and/or monomer (a1-2) In the case of the fat (A), when the total structural unit of the obtained resin (A) is 100 mol%, the total content of the structural units derived from these monomers is preferably from 10 to 95 mol%. The range is preferably in the range of 15 to 90 mol%, and preferably in the range of 20 to 85 mol%. In order to make the total of the content of the structural unit derived from the monomer (a1-1) and/or the structural unit derived from the monomer (a1-2) in such a range, in the production of the resin (A), it is only necessary to adjust the monomer. The amount of (a1-1) and/or monomer (a1-2) relative to the total monomer amount may be used.

In the production of the resin (A), in addition to the (meth)acrylic monomer (In other words, the monomer (a1-1) and the monomer (a1-2)), other monomers having an acid labile group (1) and a carbon-carbon double bond in the molecule may be used.

The monomer (a1) having an acid labile group (2) is preferably (meth) The acrylic monomer may, for example, be a monomer represented by the formula (a1-5) (hereinafter referred to as "monomer (a1-5)").

[In the formula (a1-5), R ³¹ represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom; and L ¹ to L ³ represent an oxy group, -S- or *-O- ( CH ₂ ) a group represented by _k1 -CO-O-; wherein k1 represents an integer from 1 to 7, * represents a bond to a carbonyl group (-CO-); Z ¹ is a single bond or a carbon number of 1 to 6 The alkyl group, the methyl group contained in the alkyl group may be an oxy group or a carbonyl group; s1 and s1' respectively represent an integer of 0 to 4]

In the formula (a1-5), R ^{31 is} preferably a hydrogen atom or a methyl group.

L ^{1 is} preferably an oxy group.

L ² and L ^{3 are} preferably either an oxy group and the other is -S-.

S1 is preferably 1.

S1' is preferably 0 to 2.

Z ^{1 is} preferably a single bond or -CH ₂ -CO-O-.

Specific examples of the monomer (a1-5) are as follows, for example:

When the resin (A) has a structural unit derived from the monomer (a1-5), the content thereof is preferably in the range of 10 to 95 mol% with respect to the total structural unit (100 mol%) of the resin (A). More preferably, it is in the range of 15 to 90 mol%, and preferably in the range of 20 to 85 mol%.

<acid stable monomer>

The resin (A) used as the composition is preferably a copolymer obtained by using a monomer (a1) and a monomer having no acid labile group (hereinafter referred to as "acid-stable monomer").

When the resin (A) is produced by using an acid-stable monomer together, The amount of the monomer (a1) is used as a reference to determine the amount of the acid-stable monomer. The ratio of the amount of the monomer (a1) to the amount of the acid-stable monomer is expressed by [monomer (a1)] / [acid-stable monomer], preferably 10 to 80 mol% / 90 to 20 mol%. More preferably, it is 20~60 mol%/80~40 mol%. Further, when a monomer having an adamantyl group (especially a monomer (a1-1)) is used as the monomer (a1), it is preferably a total amount (100 mol%) relative to the amount of the monomer (a1). The amount of the monomer having an adamantyl group is 15 mol% or more. Thereby, the dry etching resistance of the photoresist pattern derived from the photoresist composition containing the resin (A) tends to be better.

Examples of the acid-stable monomer include a hydroxyl group in the molecule or Lactone ring. It has an acid-stable monomer derived from a hydroxyl group (hereinafter referred to as "acid-stable monomer (a2)") and/or an acid-stable monomer containing a lactone ring (hereinafter referred to as "acid-stable monomer (a3)" The resin (A) of the structural unit is obtained by applying a photoresist composition containing the resin (A) to a substrate, a coating film formed on the substrate, or a composition layer and a substrate obtained from the coating film. It is easy to show excellent adhesion. In addition, such a composition can produce a photoresist pattern with good resolution.

<Acid Stabilized Monomer (a2)>

When the acid-stable monomer (a2) is used for the production of the resin (A), various preferred acid-stable monomers (a2) can be listed depending on the kind of the exposure source when the resist pattern is obtained from the composition containing the resin (A). ). That is, when the photoresist composition of the present invention is used for high-energy ray exposure of KrF excimer laser exposure (wavelength: 248 nm), electron beam or EUV light, it is preferred to use an acid-stable monomer having a phenolic hydroxyl group. (a2-0) [eg hydroxystyrene As the acid-stable monomer (a2), it is used for the production of the resin (A). When a short-wavelength ArF excimer laser exposure (wavelength: 193 nm) is used, it is preferred to use an acid-stable monomer represented by the following formula (a2-1) as an acid-stable monomer (a2) for the resin ( A) Manufacturing. Thus, the acid-stable monomer (a2) used for the production of the resin (A) can be selected according to the exposure source when the photoresist pattern is produced, respectively, but the acid-stable monomer (a2) can be based on the exposure source. The resin (A) is produced by using only one suitable monomer, and the resin (A) may be produced by using two or more suitable monomers depending on the type of the exposure source, or may be appropriately used depending on the type of the exposure source. The resin (A) is produced by using a monomer and two or more acid-stable monomers (a2).

As the acid-stable monomer (a2), the following formula (a2-0) can be mentioned. A styrene monomer such as p- or m-hydroxystyrene (hereinafter referred to as "acid-stable monomer (a2-0)"). Further, the formula (a2-0) is represented by a form in which the phenolic hydroxyl group is not protected by a suitable protecting group.

[In the formula (a2-0), R ^a30 represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom; and R ^a31 represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, and carbon. Alkoxy groups having 1 to 6 carbon atoms, fluorenyl groups having 2 to 4 carbon atoms, decyloxy groups having 2 to 4 carbon atoms, acrylonitrile groups or methacryl fluorenyl groups; ma representing an integer of 0 to 4; if ma is 2 In the above integer, a plurality of R ^a31 systems are independent of each other].

^Examples of the halogen atom of R ^a30 and the alkyl group having 1 to 6 carbon atoms which may have a halogen atom are the same as those exemplified in the description of R ^a32 of the above monomer (a1-4). ^Among these, R ^{a30 is} preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and still more preferably a methyl group.

The alkyl group of R ³¹ is preferably an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 or 2 carbon atoms, and particularly preferably a methyl group.

The alkoxy group of R ^a31 may be the same as those exemplified ⁱⁿ the description of R ^a33 of the above monomer (a1-4). Among these, R ^{a31 is} preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group or an ethoxy group, and still more preferably a methoxy group.

Preferably, ma is 0, 1 or 2, more preferably 0 or 1, more preferably 0.

When such a resin (A) having a structural unit derived from the acid-stable monomer (a2-0) is produced, a single phenolic hydroxyl group located in the acid-stable monomer (a2-0) may be used as a protective group. body. The protective group may, for example, be a protective group which is detached by an acid. The phenolic hydroxyl group protected by the protecting group desorbed by the acid can be deprotected by contact with an acid, and thus the structural unit derived from the acid-stable monomer (a2-0) can be easily formed.

However, since the resin (A) has a structural unit (a1) containing an acid labile group as described above, an acid-stable monomer which protects a phenolic hydroxyl group by using a protecting group which can be deprotected by a base (a2) is used. -0) When the polymerization is carried out and deprotected, it is preferably deprotected by contact with a base to prevent the acid labile group of the structural unit (a1) from being significantly impaired. The protective group which can be deprotected by a base is, for example, an ethenyl group. The base may, for example, be 4-dimethylaminopyridine or triethylamine.

Examples of the acid-stable monomer (a2-0) include the following monomer. Further, the following examples are shown in the form in which the phenolic hydroxyl group is not protected by a protecting group.

Among them, 4-hydroxystyrene or 4-hydroxy-α-methylstyrene is particularly preferred.

When the resin (A) is produced by using 4-hydroxystyrene or 4-hydroxy-α-methylstyrene, it is preferred to use a protecting group to protect the phenolic hydroxyl group located therein.

When the resin (A) has a structural unit derived from the acid-stable monomer (a2-0), the content is selected from the total structural unit (100% by mole) of the resin (A), and the content thereof is selected from 5 to 95% by mole. The range is preferably in the range of 10 to 80 mol%, and preferably in the range of 15 to 80 mol%.

The acid-stable monomer (a2-1) is a monomer represented by the following formula (a2-1).

[In the formula (a2-1), L ^a3 represents an oxy group or *-O-(CH ₂ ) _k2 -CO-O-; k2 represents an integer of 1 to 7; * represents a bond with -CO-; ^A14 represents a hydrogen atom or a methyl group; R ^a15 and R ^a16 each independently represent a hydrogen atom, a methyl group or a hydroxyl group; and o1 represents an integer of 0-10.

In the formula (a2-1), L ^a3 is preferably _{alkoxy, -O- (CH 2) f1 -CO} -O- ( where f1 is an integer of 1 to 4), more preferably group; R ^a14 more Preferably, it is a methyl group; R ^{a15 is} preferably a hydrogen atom; R ^{a16 is} preferably a hydrogen atom or a hydroxyl group; o1 is preferably an integer of 0 to 3, more preferably 0 or 1]

Examples of the acid-stable monomer (a2-1) include the following: among these, 3-hydroxyadamantane-1-(meth)acrylate and 3,5-dihydroxy(meth)acrylate are preferred. Adamantane-1-ester and 1-(3,5-dihydroxyadamantane-1-yloxycarbonyl)methyl (meth)acrylate, more preferably 3-hydroxyadamantane-1-(meth)acrylate And 3,5-dihydroxyadamantane-1-(meth)acrylate, preferably 3-hydroxyadamantane-1-acrylate and 3,5-dihydroxyadamantane-1-acrylate .

The resin (A) has a structure derived from an acid-stable monomer (a2-1) In the unit, the content is selected from the range of 3 to 40 mol%, more preferably 5 to 35 mol%, and more preferably 5 to the total structural unit (100 mol%) of the resin (A). ~30% of the range of moles, especially preferably 5 to 15% by mole.

<acid-stable monomer (a3)>

The lactone ring system of the acid-stable monomer (a3) may be a single ring such as a β-propiolactone ring, a γ-butyrolactone ring or a δ-valerolactone ring, or may be in a single ring. a condensed ring of an ester ring with other rings. Among these lactone rings, a condensed ring of a γ-butyrolactone ring and a γ-butyrolactone ring and another ring is preferred.

The acid-stable monomer (a3) is preferably represented by the following formula (a3-1), formula (a3-2) or formula (a3-3). In the production of the resin (A), only one of these may be used, or two or more of them may be used in combination. The resin (A) is preferably a repeating unit containing at least one monomer derived from the formula (a3-1). Further, the resin (A) is particularly preferably a repeating unit containing at least one monomer derived from the monomer represented by the formula (a3-1) and at least one repeating monomer derived from the monomer represented by the formula (a3-2). . In the following description, the acid-stable monomer (a3) represented by the formula (a3-1) is referred to as "acid-stable monomer (a3-1)", and the acid represented by the formula (a3-2) is stabilized. The monomer (a3) is referred to as "acid-stable monomer (a3-2)", and the acid-stable monomer (a3) represented by formula (a3-3) is referred to as "acid-stable monomer (a3-3)".

[In the formula (a3-1), the formula (a3-2), and the formula (a3-3), L ^a4 , L ^{a5 ,} and L ^a6 (hereinafter referred to as "L ^a4 to L ^a6 ") independently represent -O- or *-O-(CH ₂ ) _k3 -CO-O-; k3 represents an integer from 1 to 7; * represents a bond to -CO-; R ^a18 , R ^a19 and R ^a20 (hereinafter ^referred to as "R ^a18 ~ R ^a20 ") independently represents a hydrogen atom or a methyl group; R ^a21 represents an aliphatic hydrocarbon group having 1 to 4 carbon atoms; p1 is an integer of 0 to 5; and R ^a22 and R ^a23 each independently represent a carboxyl group, a cyano group or a carbon number of 1 ~4 of an aliphatic hydrocarbon group; q1 and r1 each independently represent an integer of 0 to 3; when p1, q1 or r1 is 2 or more, a plurality of R ^a21 , R ^a22 or R ^a23 may be identical or different from each other]

Formula (a3-1) ~ formula (A3-3) in the L ^a4 ~ L ^a6, include those described in L ^a3.

L ^a4 to L ^a6 are each independently preferably -O- or *-O-(CH ₂ ) _d1 -CO-O- (where d1 is an integer of 1 to 4), more preferably -O-.

R ^a18 to R ^{a21 are} preferably a methyl group.

R ^a22 and R ^a23 are each independently preferably a carboxyl group, a cyano group or a methyl group.

P1, q1 and r1 are each independently preferably an integer of 0 to 2, more preferably 0 or 1.

Examples of the acid-stable monomer (a3-1) include the following:

Examples of the acid-stable monomer (a3-2) having a condensed ring of a γ-butyrolactone ring and a norbornane ring include the following:

Examples of the acid-stable monomer (a3-3) having a condensed ring of a γ-butyrolactone ring and a cyclohexane ring include the following:

Among the acid-stable monomers (a3) having a lactone ring, more preferably (meth)acrylic acid (5-oxy-4-oxatricyclo[4.2.1.0 ^3,7 ]decane-2-ester, Tetrahydro-2-oxy-3-furoyl (meth)acrylate, 2-(5-oxy-4-oxatricyclo[4.2.1.0 ^3,7 ]decane-2-(meth)acrylate A methacrylate such as a oxy)-2-oxyethyl ester.

The resin (A) has a knot selected from the group consisting of monomers (a3-1). When the structural unit, the structural unit derived from the monomer (a3-2), and the structural unit derived from the group of the structural unit derived from the monomer (a3-3) [from the structural unit of the acid-stable monomer (a3)] With respect to the total structural unit (100% by mole) of the resin (A), the total content thereof is preferably from 5 to 60 mol%, more preferably from 5 to 50 mol%, and even more preferably from 10 to 40 mol. The range of the ear % is particularly preferably in the range of 15 to 40 mol%.

Further, the structural unit derived from the monomer (a3-1), the structural unit derived from the monomer (a3-2), and the monomer derived from the total structural unit (100 mol%) of the resin (A) The content of each of the structural units of a3-3) is preferably from 5 to 60 mol%, more preferably from 10 to 55 mol%, and even more preferably from 20 to 50 mol%.

<acid-stable monomer (a4)>

In addition, as the acid-stable monomer (a2) and the acid-stable monomer other than the acid-stable monomer (a3) (hereinafter referred to as "acid-stable monomer (a4)"), the formula (a4-1) can be mentioned. The maleic anhydride shown, the isaconic anhydride represented by the formula (a4-2), and the acid-stable monomer having a norbornene ring represented by the formula (a4-3) (hereinafter referred to as "acid-stable monomer" (a4-3)") and so on.

[In the formula (a4-3), R ^a25 and R ^a26 each independently represent a hydrogen atom, an aliphatic hydrocarbon group having a carbon number of 1 to 3, a cyano group, a carboxyl group or a -COOR ^a27 [wherein, R ^a27 represents carbon An aliphatic hydrocarbon group of 1 to 18 or an alicyclic hydrocarbon group having 3 to 18 carbon atoms, wherein the aliphatic hydrocarbon group and the methyl group contained in the alicyclic hydrocarbon group may be substituted with an oxy group or a carbonyl group; however, -COOR ^a27 is Except for the acid labile group (ie, the R ^a27 system does not contain a tertiary carbon atom and the -O-bond)], or R ^a25 and R ^a26 are bonded to each other to form -CO-O-CO-].

The aliphatic hydrocarbon group which may have a hydroxyl group in R ^a25 and R ^a26 of the monomer (a4-3) may, for example, be a methyl group, an ethyl group, a propyl group, a hydroxymethyl group or a 2-hydroxyethyl group.

The aliphatic hydrocarbon group of R ^a27 is preferably a carbon number of 1 to 8, more preferably a carbon number of 1 to 6. The alicyclic hydrocarbon group is preferably a carbon number of 4 to 18, more preferably a carbon number of 4 to 12. Examples of the R ^a27 include a methyl group, an ethyl group, a propyl group, a 2-oxy-oxypentan-3-yl group, and a 2-oxy-oxypentan-4-yl group.

Examples of the acid-stable monomer (a4-3) having a norbornene ring include 2-northene, 2-hydroxy-5-nordecene, 5-northene-2-carboxylic acid, and 5-nor Methyl terpene-2-carboxylate, 5-hydroxy-2-ene-2-carboxylic acid 2-hydroxy-1-ethyl ester, 5-northene-2-methanol, 5-northene-2,3-di Carboxylic anhydride, etc.

The resin (A) has a structural unit selected from the group consisting of maleic anhydride derived from the formula (a4-1), a structural unit derived from the isaconic anhydride represented by the formula (a4-2), and a single source. When the structural unit in the group of structural units of the body (a4-3) [derived from the structural unit of the acid-stable monomer (a4)], the total structural unit (100% by mole) relative to the resin (A) The total content is preferably in the range of 2 to 40 mol%, more preferably in the range of 3 to 30 mol%, and further preferably in the range of 5 to 20 mol%.

Further, examples of the acid-stable monomer (a4) include An acid-stable monomer of the sultone ring represented by the formula (a4-4) (hereinafter referred to as "acid-stable monomer (a4-4)") or the like.

[In the formula (a4-4), L ^a7 represents -O- or *-O-(CH ₂ ) _k2 -CO-O-, k2 represents an integer of 1 to 7; * represents a bond with -CO-; R ^a28 represents a hydrogen atom or a methyl group; W ¹ represents a residue containing a sultone ring which may have a substituent].

The sultone ring is exemplified below. The residue containing the sultone ring may, for example, be one in which a hydrogen atom in the sultone ring is substituted with a bond of L ^a7 .

The residue containing a sultone ring which may have a substituent means that the hydrogen atom other than the hydrogen atom substituted with the bond of L ^a7 is further substituted by a substituent; and examples of the substituent include a hydroxyl group. Cyano group, alkyl group having 1 to 6 carbon atoms, fluoroalkyl group having 1 to 6 carbon atoms, hydroxyalkyl group having 1 to 6 carbon atoms, alkoxy group having 1 to 6 carbon atoms, and alkoxy group having 1 to 7 carbon atoms A carbonyl group, a fluorenyl group having 1 to 7 carbon atoms, or a decyloxy group having 1 to 8 carbon atoms.

Examples of the fluoroalkyl group include difluoromethyl and trifluoromethyl. 1,1,1-difluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, perfluoroethyl, 1,1,2,2-tetrafluoropropyl, 1 1,2,2,3,3-hexafluoropropyl, perfluoroethylmethyl, 1-(trifluoromethyl)-1,2,2,2-tetrafluoroethyl, perfluoropropyl, 1,1,2,2-tetrafluorobutyl, 1,1,2,2,3,3-hexafluorobutyl, 1,1,2,2,3,3,4,4-octafluorobutyl , perfluorobutyl, 1,1-bis(trifluoro)methyl-2,2,2-trifluoroethyl, 2-(perfluoropropyl)ethyl, 1,1,2,2,3, 3,4,4-octafluoropentyl, perfluoropentyl, 1,1,2,2,3,3,4,4,5,5-decafluoropentyl, 1,1-bis(trifluoromethyl) Base)-2,2,3,3,3-pentafluoropropyl, 2-(perfluorobutyl)ethyl, 1,1,2,2,3,3,4,4,5,5-ten Fluoryl group, 1,1,2,2,3,3,4,4,5,5,6,6-dodecafluorohexyl, perfluoropentylmethyl and perfluorohexyl. Among them, the carbon number is preferably from 1 to 4, more preferably trifluoromethyl, perfluoroethyl and perfluoropropyl, and particularly preferably trifluoromethyl.

Examples of the hydroxyalkyl group include a methylol group and a 2-hydroxyethyl group.

Specific examples of the acid-stable monomer (a4-4) are shown below:

When the resin (A) has a structural unit derived from the acid-stable monomer (a4-4), it is based on the total structural unit (100% by mole) of the resin (A). The content is preferably from 2 to 40 mol%, more preferably from 3 to 35 mol%, and even more preferably from 5 to 30 mol%.

Preferred resin (A) is a polymerizable monomer (a1), an acid-stable monomer (a2) and/or a copolymer obtained by acid-stable monomer (a3). In the preferred copolymer, as the monomer (a1), at least one of the above-mentioned monomer (a1-1) and monomer (a1-2) is preferably used, and it is more preferred to use a monomer (a1-1). ). As the acid-stable monomer (a2), an acid-stable monomer (a2-1) is preferred; as the acid-stable monomer (a3), an acid-stable monomer (a3-1) and an acid-stable monomer (a3) are preferred. At least one of -2).

Resin (A) can use monomer (a1), and depending on the needs An acid-stable monomer in a group comprising an acid-stable monomer (a2), an acid-stable monomer (a3), and an acid-stable monomer (a4), and such a total relative to the resin (A) as described above After the structural unit is adjusted to an appropriate amount, it is produced by a known polymerization method (for example, a radical polymerization method).

The resin (A) is preferably in the form of the formula (II) The structural unit (hereinafter referred to as "structural unit (II)").

[In the formula (II), R ³ represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom; and the ring X1 represents a heterocyclic ring having 2 to 36 carbon atoms, and the hydrogen atom contained in the heterocyclic ring It may be substituted by a halogen atom, a hydroxyl group, a hydrocarbon group having 1 to 24 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a fluorenyl group having 2 to 4 carbon atoms or an anthracene group having 2 to 4 carbon atoms]

In the formula (II), examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group.

Examples of the alkyl group which may have a halogen atom include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluoro-second butyl group, and a perfluoro-tertiary butyl group. Base, perfluoropentyl, perfluorohexyl, and the like.

The hetero ring of the ring X1 may be an aromatic hetero ring or a non-aromatic one as long as it contains an atom of -CO- and a nitrogen atom as a constituent ring. Further, it may be either a single ring or a multiple ring.

Specific examples thereof include the following:

Examples of the hydrocarbon group include an alkyl group and an alicyclic hydrocarbon group. An aromatic hydrocarbon group or the like.

The alicyclic hydrocarbon group may be either a monocyclic ring or a polycyclic ring, and examples of the monocyclic alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, and a cycloheptyl group. A cycloalkyl group such as cyclooctyl. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group, a methylnorbornyl group, and the following groups.

Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, and an anthracenyl group. p-Methylphenyl, p-tert-butylphenyl, p-adamantylphenyl, tolyl, xylyl, cumyl, mesityl, biphenyl, phenanthryl, 2,6-di An aryl group such as an ethylphenyl group or a 2-methyl-6-ethylphenyl group.

Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a decyloxy group, and a dodecyloxy group.

Examples of the thiol group include an ethyl group, a propyl group, a butyl group, and the like.

Examples of the decyloxy group include an ethoxycarbonyl group, a propenyloxy group, a butoxy group, and an isobutyloxy group.

In the formula (II), R ^{3 is} preferably a hydrogen atom or a methyl group.

Ring X1 is preferably a heterocyclic ring of a 4 to 7 membered ring containing a nitrogen atom or a heterocyclic ring containing the 4 to 7 membered ring, more preferably a heterocyclic ring of a 4 to 6 membered ring containing a nitrogen atom or containing such a 4~ Heterocyclic ring of 6 members. Preferably, -CO- is disposed at a position bonded to a nitrogen atom, that is, ring X1 is a decylamine ring.

The structural unit (II) is preferably a structural unit derived from a compound represented by the following formula (IID):

[In the formula (IID), R ³¹ represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom; and R ³² represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, and a carbon number of 1; Alkoxy group of ~12, fluorenyl group having 2 to 4 carbon atoms or decyloxy group having 2 to 4 carbon atoms; n9 represents an integer of 0 to 8; when n9 is 2 or more, plural R ³² systems are the same or different ; n9 is preferably 0 or 1, more preferably 0]

As the structural unit (II), the following structural units can be cited:

In the above structural unit, the structural unit substituted with a hydrogen atom of R ³ may be exemplified as a specific example of the structural unit (II).

The weight average molecular weight of the resin (A) is preferably 2,500 or more, more preferably 3,000 or more, still more preferably 4,000 or more. The upper limit of the weight average molecular weight is preferably 50,000 or less, more preferably 30,000 or less, still more preferably 10,000 or less. In addition, the "weight average molecular weight" referred to herein is determined by gel permeation chromatography and is based on the conversion value based on standard polystyrene.

The resin (A) may be used alone or in combination of two or more.

The content of the resin (A) in the composition (the total amount when two or more kinds are used) is not particularly limited, and from the viewpoint of the effect of the present invention being more excellent, it is preferably 50 to 99 mass with respect to the total solid content in the composition. %, more preferably 70 to 97% by mass.

Further, the total solid content means the total mass of the components constituting the film to be described later, that is, other components excluding the solvent.

<Compound represented by the general formula (I) which generates an acid by irradiation with actinic rays or radiation>

The compound represented by the formula (I) is a photoacid generator which generates an acid by irradiation with actinic rays or radiation. By using this compound, the desired effect can be obtained.

Hereinafter, each group of the formula (I) will be described in detail.

In the formula (I), Z ⁺ represents a cation.

Examples of the cation include a phosphonium cation, a phosphonium cation, a phosphonium cation, an ammonium cation, a benzothiazolium cation, and a phosphonium cation. Among these, a phosphonium cation and a phosphonium cation are preferable, and an aryl phosphonium cation is more preferable.

The cation (Z ⁺ ) is preferably a phosphonium cation or a phosphonium cation, and more preferably an organic cation represented by any one of the following formulas (b2-1) to (b2-4) [hereinafter, according to the formula of each formula It is called "cation (b2-1)", "cation (b2-2)", "cation (b2-3)" and "cation (b2-4)"].

[In the formula (b2-1) to the formula (b2-4), R ^b4 , R ^b5 and R ^b6 each independently represent an aliphatic hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms or a carbon number; An aromatic hydrocarbon group of 6 to 18; the hydrogen atom contained in the aliphatic hydrocarbon group may be substituted by a hydroxyl group, an alkoxy group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the alicyclic hydrocarbon group is contained The hydrogen atom may be substituted by a halogen atom, a fluorenyl group having 2 to 4 carbon atoms or a glycidoxy group, and the aromatic hydrocarbon group may be a halogen atom, a hydroxyl group, an aliphatic hydrocarbon group having 1 to 18 carbon atoms, or a carbon number of 3 to 18. An alicyclic hydrocarbon group or an alkoxy group having 1 to 12 carbon atoms is substituted.

R ^b7 and R ^b8 each independently represent a hydroxyl group, an aliphatic hydrocarbon group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms.

M2 and n2 independently represent integers from 0 to 5.

R ^b9 and R ^b10 each independently represent an aliphatic hydrocarbon group having 1 to 18 carbon atoms or an alicyclic hydrocarbon group having 3 to 18 carbon atoms.

R ^b11 represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 18 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms or an aromatic hydrocarbon group having 6 to 18 carbon atoms.

R ^b9 to R ^b11 are each independently an aliphatic hydrocarbon group or an alicyclic hydrocarbon group. When these are aliphatic hydrocarbon groups, the carbon number is preferably from 1 to 12, and if it is an alicyclic hydrocarbon group, the carbon number is preferably 3~18, more preferably 4~12.

R ^b12 represents an aliphatic hydrocarbon group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms or an aromatic hydrocarbon group having 6 to 18 carbon atoms. The hydrogen atom contained in the aromatic hydrocarbon group may be an aliphatic hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms or an alkyl group having 1 to 12 carbon atoms. Replacement with a carbonyloxy group.

R ^b9 and R ^b10 may be bonded to each other with the sulfur atom to which they are bonded to form an alicyclic hydrocarbon ring of a 3-membered ring to a 12-membered ring (preferably a 3-membered ring to a 7-membered ring). The methyl group contained in the hydrocarbon ring may be substituted with an oxy group, a thioxy group or a carbonyl group.

R ^b13 , R ^b14 , R ^b15 , R ^b16 , R ^b17 and R ^b18 (hereinafter referred to as "R ^b13 ~ R ^b18 ") each independently represent a hydroxyl group, an aliphatic hydrocarbon group having 1 to 12 carbon atoms and a carbon number of 1 to 12 Alkoxy group.

L ^b11 represents -S- or -O-.

O2, p2, s2, and t2 each independently represent an integer from 0 to 5.

Q2 and r2 independently represent integers from 0 to 4.

U2 means 0 or 1.

When o2 is 2 or more, the plurality of R ^b13 may be the same or different from each other; when p2 is 2 or more, the plurality of R ^b14 may be the same or different from each other; when s2 is 2 or more, the plurality of R ^b17 may be the same or different from each other. When t2 is 2 or more, the plurality of R ^b18 may be the same or different from each other.

Examples of the alkoxy group include a methoxy group, an ethoxy group, and a propoxy group. Base, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, decyloxy and dodecyloxy.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the thiol group include an ethyl group, a propyl group, and a butyl group.

Examples of the alkylcarbonyloxy group include a methylcarbonyloxy group, an ethylcarbonyloxy group, a n-propylcarbonyloxy group, an isopropylcarbonyloxy group, a n-butylcarbonyloxy group, and a secondary butylcarbonyloxy group. Tertiary butylcarbonyloxy, pentylcarbonyloxy, hexylcarbonyloxy, octylcarbonyloxy, 2-ethylhexylcarbonyloxy and the like.

Preferred alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, dibutyl, tert-butyl, pentyl, hexyl, octyl and 2-ethylhexyl, especially The alkyl group of R ^b9 to R ^b12 is preferably a carbon number of 1 to 12.

Preferred alicyclic hydrocarbon groups are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclodecyl, 2-alkyladamantan-2-yl, 1-(adamantane-1- Base)-1-alkyl and isodecyl and the like. In particular, the alicyclic hydrocarbon group of R ^b9 to R ^b11 preferably has a carbon number of 3 to 18, more preferably a carbon number of 4 to 12.

Preferred aromatic hydrocarbon groups are preferably phenyl, 4-methylphenyl, 4-ethylphenyl, 4-tributylphenyl, 4-cyclohexylphenyl, 4-methoxyphenyl, in combination. Phenyl and naphthyl groups.

The aromatic hydrocarbon group is substituted by an alkyl group, and is typically an aralkyl group, and examples thereof include a benzyl group, a phenethyl group, a phenylpropyl group, a trityl group, a naphthylmethyl group, and a naphthylethyl group.

Examples of the ring formed by the sulfur atom bonded to R ^b9 and R ^b10 include a tetrahydrothiophene-1-anthracene ring (tetrahydrothiophene ring), a thioalkyl-1-anthracene ring, and 1,4-. Oxothiane 4-oxime ring and the like.

Examples of the ring formed by the combination of -CH-CO- bonded to R ^b11 and R ^b12 include an oxycycloheptane ring, an oxycyclohexane ring, an oxynorbornane ring, and an oxyadamantane ring. Wait.

Among them, a cation (b2-1) is preferred, and an organic cation represented by the following formula (b2-1-1) is more preferred (hereinafter referred to as "cation (b2-1-1)"], and further preferably triphenyl. a base cation (in the formula (b2-1-1), v2=w2=x2=0) or a tolyl sulfonium cation (in the formula (b2-1-1), v2=w2=x2=1, R ^b19 , R ^b20 and R ^b21 are both methyl).

In the formula ^{(b2-1-1), R b19 ~ R} b21 each independently represent a halogen atom (more preferably fluorine atom), a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, the carbon atoms of an alkoxy group having 1 to 12 carbons, or A number of 3 to 18 alicyclic hydrocarbon groups.

V2, w2, and x2 each independently represent an integer of 0 to 5 (preferably 0 or 1).

When v2 is 2 or more, the plurality of R ^b19 may be the same or different from each other; when w2 is 2 or more, the plurality of R ^b20 may be the same or different from each other; and when x2 is 2 or more, the plurality of R ^b21 may be the same or different from each other. .

Among them, R ^b19 , R ^b20 and R ^b21 are each independently preferably a halogen atom (more preferably a fluorine atom), a hydroxyl group, an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms.

Specific examples of the cation (b2-1-1) include the following:

Specific examples of the cation (b2-2) include the following:

Specific examples of the cation (b2-3) include the following:

Specific examples of the cation (b2-4) include the following:

Q ¹ and Q ² each independently represent a fluorine or an alkyl group substituted with at least one or more fluorines. The carbon number of the alkyl group is preferably from 1 to 10, more preferably from 1 to 4. Further, the alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group. Examples of the perfluoroalkyl group include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorodibutyl group, a perfluorotributyl group, and a perfluoropentane group. Base and perfluorohexyl group, etc.

Q ¹ and Q ^{2 are} preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, more preferably a fluorine atom or CF ₃ . In particular, Q ¹ and Q ^{2 are} preferably fluorine atoms.

L represents a divalent linking group. Examples of the divalent linking group include -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -O-, -S-, -SO-, -SO ₂ -, alkylene. (preferably having a carbon number of 1 to 6), a cycloalkyl group (preferably having a carbon number of 3 to 10), an alkenyl group (preferably having a carbon number of 2 to 6), or a combination of these Price link base, etc.

Among them, L is preferably a saturated hydrocarbon group having a divalent carbon number of 1 to 30, and when the divalent saturated hydrocarbon group has a methyl group, the methyl group may be substituted with an oxy group or a carbonyl group.

Examples of the divalent saturated hydrocarbon group include a linear alkanediyl group, a branched alkanediyl group, a monocyclic or polycyclic divalent alicyclic hydrocarbon group, and two or more of these groups may be combined. For example, a methyl group, an ethyl group, a propane-1,3-diyl group, a propionyl-1,2-diyl group, a butane-1,4-diyl group, a penta-1,5-diyl group, and a hex-1 are mentioned. ,6-diyl, hept-1,7-diyl, octane-1,8-diyl, indole-1,9-diyl, indol-1,10-diyl, undecane-1,11- Diyl, dodecane-1,12-diyl, tridecane-1,13-diyl, tetradecane-1,14-diyl, pentadecane-1,15-diyl, hexadecane a linear chain of -1,16-diyl, heptadecan-1,17-diyl, ethyl-1,1-diyl, propyl-1,1-diyl, propyl-2,2-diyl, etc. Alkanediyl; linear alkanediyl a side chain having an alkyl group (especially an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a secondary butyl group, a tertiary butyl group, etc.), for example, a di- 1,3-diyl, 2-methylpropan-1,3-diyl, 2-methylpropane-1,2-diyl, pent-1,4-diyl, 2-methylbuty-1, a branched alkanediyl group such as 4-diyl; cyclobutane-1,3-diyl, 1,3-cyclobutane-1,3-diyl, cyclohexane-1,4-diylfluorene ( a monocyclic divalent alicyclic hydrocarbon group of a cycloalkanediyl group such as a cyclohexyl group, a cyclooctane-1,5-diyl group or the like; a decane-1,4-diyl group, a decane-norbornane- A polycyclic divalent alicyclic hydrocarbon group such as a 2,5-diyl group, a 1,5-adamantane-1,5-diyl group, an adamantane-2,6-diyl group or the like.

The methyl group contained in the divalent saturated hydrocarbon group is substituted with an oxy group or a carbonyl group, and examples thereof include a group represented by any one of the following formulas (b1-1) to (b1-8). L ^{b1 is} preferably a group represented by any one of the formulae (b1-1) to (b1-4), more preferably a group represented by the formula (b1-1) or a formula (b1-2). base. Further, the formula (b1-1) to the formula (b1-8) are described in such a manner that the left and right sides thereof conform to the general formula (I), and the bond at the left side is bonded to C(Q ¹ )(Q ² ). The key on the right side is linked to W. Specific examples of the following formulas (b1-1) to (b1-8) are also the same.

[In the formula (b1-1) to the formula (b1-8), L ^b2 represents a single bond or a divalent saturated hydrocarbon group having 1 to 15 carbon atoms; and L ^b3 represents a single bond or a divalent saturated hydrocarbon group having 1 to 12 carbon atoms; L ^b4 represents a divalent saturated hydrocarbon group having 1 to 13 carbon atoms; the upper limit of the total carbon number of L ^b3 and L ^b4 is 20; L ^b5 represents a divalent saturated hydrocarbon group having 1 to 15 carbon atoms; and L ^b6 and L ^b7 are independent A divalent saturated hydrocarbon group having a carbon number of 1 to 15; wherein the upper limit of the total carbon number of L ^b6 and L ^b7 is 16; L ^b8 represents a divalent saturated hydrocarbon group having 1 to 14 carbon atoms; and L ^b9 and L ^b10 respectively represent carbon a divalent saturated hydrocarbon group of 1 to 11; the upper limit of the total carbon number of L ^b9 and L ^b10 is 12; L ^b11 represents a divalent saturated hydrocarbon group having a carbon number of 1 to 11; and L ^b12 represents a divalent carbon number of 1 to 11. a saturated hydrocarbon group; L ^b13 represents a divalent saturated hydrocarbon group having 1 to 11 carbon atoms; and L ^b14 represents a divalent saturated hydrocarbon group having 1 to 11 carbon atoms. Examples of the divalent group represented by the formula (b1-1) include the following:

The divalent group represented by the formula (b1-2) may, for example, be the following:

The divalent group represented by the formula (b1-3) may, for example, be the following:

The divalent group represented by the formula (b1-4) may, for example, be *-CH ₂ -O-CH ₂ -*.

Examples of the divalent group represented by the formula (b1-5) include the following:

Examples of the divalent group represented by the formula (b1-6) include the following:

Examples of the divalent group represented by the formula (b1-7) include the following:

Examples of the divalent group represented by the formula (b1-8) include the following:

The divalent saturated hydrocarbon group of L ^b1 may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, a carboxyl group, an aromatic hydrocarbon group having 6 to 18 carbon atoms, an aralkyl group having 7 to 21 carbon atoms, a fluorenyl group having 2 to 4 carbon atoms, and a glycidyloxy group. .

Examples of the aralkyl group include a benzyl group, a phenethyl group, a phenylpropyl group, a trityl group, a naphthylmethyl group, and a naphthylethyl group.

W represents a group having a cyclic structure (having a divalent cyclic structure) Base). Examples of the group having a cyclic structure include a group having a cyclic aliphatic group, an extended aryl group, and a heterocyclic structure.

The cyclic aliphatic group (alicyclic hydrocarbon group) as W may have The single ring structure may also have a multi-ring structure. As the cyclic aliphatic group having a monocyclic structure, a monocyclic cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group is preferable. As the cyclic aliphatic group (polycyclic aliphatic group) having a polycyclic structure, it is preferably a pendant decenyl group, a tricyclic fluorenyl group, a tetracyclic fluorenyl group, a tetracyclic decyl group, and an adamantane. A polycyclic cycloalkyl group such as a group. In particular, it is preferred to use an exo-adamantyl group as W.

Further, the methyl group contained in the cyclic aliphatic group may be substituted with an oxy group, a sulfonyl group (-SO ₂ -) or a carbonyl group. The group in which the methyl group contained in the cyclic aliphatic group is substituted with an oxy group, a sulfonyl group or a carbonyl group may, for example, be a cyclic ether group (one or two of the methyl groups contained in the alicyclic hydrocarbon group). An oxy-substituted group), a cyclic ketone group (one or two carbonyl-substituted groups of a methyl group contained in an alicyclic hydrocarbon group), and a sultone ring group (a thiol-containing hydrocarbon group) Two adjacent methyl groups in the group are substituted by an oxy group and a sulfonyl group, respectively, and a lactone ring group (the two adjacent methyl groups in the methyl group contained in the alicyclic hydrocarbon group are respectively oxygenated) a group substituted with a carbonyl group and the like.

In addition, examples of the cyclic aliphatic group include a group of two hydrogen atoms of a cycloalkane represented by the following formulas (KA-1) to (KA-7), which are monocyclic aliphatic hydrocarbon groups. Further, examples of the polycyclic aliphatic hydrocarbon group include a base of two hydrogen atoms from which a cycloalkane represented by the following formulas (KA-8) to (KA-22) is removed. In addition, specific examples of the group in which the methyl group constituting the alicyclic hydrocarbon group is substituted with an oxygen atom, a sulfonyl group or a carbonyl group may be a group represented by any one of the following formulas (Y1) to (Y15). Further, in the group represented by the equation (Y1) to the formula (Y15), * represents a bond to which L ^{b1 is} bonded. Further, the bond with the R bond is omitted in the following figure.

The aryl group as W is, for example, a phenylene group, a naphthyl group, a phenanthrene group, or a fluorene group.

The group having a heterocyclic structure as W may have aromaticity or may not have aromaticity. The hetero atom contained in the group is preferably a nitrogen atom or an oxygen atom. Specific examples of the heterocyclic ring structure include a lactone ring, a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, a pyridine ring, a piperidine ring, and A porphyrin ring or the like. Among them, a furan ring, a thiophene ring, a pyridine ring, a piperidine ring, and A porphyrin ring.

R represents an organic group. In this specification, "organic based" A functional group having at least one or more carbon atoms (for example, a linear aliphatic group, a cyclic aliphatic group, an aromatic group, or a combination thereof), and may contain a hetero atom (oxygen atom) Wait).

One of the preferred forms of R, which has a ring-shaped knot The basis of construction. Examples of the group having a cyclic structure include a cyclic aliphatic group, an aryl group, and a group having a heterocyclic structure.

The cyclic aliphatic group may have a single ring structure or a polycyclic structure. The cyclic aliphatic group having a monocyclic structure is preferably a monocyclic cycloalkyl group such as a cyclopentyl group, a cyclohexyl group or a cyclooctyl group. As the cyclic aliphatic group having a polycyclic structure, a polycyclic cycloalkyl group such as a thiol group, a tricyclic fluorenyl group, a tetracyclic fluorenyl group, a tetracyclododecyl group, and an adamantyl group is preferable.

The aryl group is, for example, a phenyl group, a naphthyl group, a phenanthryl group or a fluorenyl group.

The group having a heterocyclic structure may be aromatic or non-aromatic. The hetero atom contained in the group is preferably a nitrogen atom or an oxygen atom. Specific examples of the heterocyclic ring structure include a lactone ring, a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, a pyridine ring, a piperidine ring, and A porphyrin ring or the like. Among them, a furan ring, a thiophene ring, a pyridine ring, a piperidine ring, and A porphyrin ring.

The group having a cyclic structure represented by R may have a substituent. Examples of the substituent include an alkyl group (which may be a linear chain, a branched chain, or a cyclic chain). One is preferably a carbon number of 1 to 12), an aryl group (preferably having a carbon number of 6 to 14), a hydroxyl group, an alkoxy group, an ester group, a decylamino group, a urethane group, a urea group, or a sulfur group. Ether group, sulfonamide group and sulfonate group.

One of preferable embodiments of R is a hydroxyl group protected by a protective group (hereinafter, also referred to as "protected hydroxyl group" as the case may be).

The protecting group refers to a group which can be deprotected by the action of an acid. As long as the protecting group can be deprotected by the action of an acid, a protecting group known as a hydroxyl group in the field of organic synthesis can be used.

Here, a preferred example of the protective hydroxyl group is a group represented by the following formula (1A) and a group represented by the formula (2A). Among these, a group represented by the formula (2A) is more preferable.

[In the formula (1A), R ^a61 to R ^a63 each independently represent an alkyl group having 1 to 6 carbon atoms; * means a bond]

[In the formula (2A), R ^{a61 '} and R ^{a62 '} each independently represent a hydrogen atom or a hydrocarbon having 1 to 12 carbon atoms, and R ^a63' represents a hydrocarbon group having 1 to 20 carbon atoms, or R a ^{62 '} and R ^{A63' is} bonded to each other to form a divalent hydrocarbon group having 2 to 20 carbon atoms; the methyl group constituting the monovalent hydrocarbon group may be substituted by an oxygen atom or a sulfur atom, and the methyl group constituting the divalent hydrocarbon group may be substituted by an oxygen atom or a sulfur atom. ]

The alkyl group of R ^a61 to R ^a63 of the formula (1A) is included in the range of 1 to 6 carbon atoms, and it is preferred that all of R ^a61 to R ^a63 are methyl groups.

R ^{a61 '} to R ^a63' of the formula (2A) is a hydrogen atom or a hydrocarbon group, and the hydrocarbon group may be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and the aliphatic hydrocarbon group may be an alkyl group or an alicyclic hydrocarbon group. Further, R ^a62' and R ^a63' may be bonded to each other to form a divalent hydrocarbon group, and the divalent hydrocarbon group may contain a hetero atom. At least one of R ^{a61 '} and R ^{a62 '} is preferably a hydrogen atom.

One of the other preferable embodiments of R may be a group represented by -L _{10 -} R ₁₀ .

L ₁₀ represents a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and the methyl group constituting the divalent aliphatic saturated hydrocarbon group may be an oxygen atom, a carbonyl group or -NR ₁₁ - (R ₁₁ represents a hydrogen atom or a carbon number of 1~) 6 alkyl) substituted.

Examples of the group in which the methyl group constituting the aliphatic saturated hydrocarbon group of L ₁₀ is substituted with an oxygen atom or a carbonyl group may, for example, be *-CO-O-, *-CO-O-(CH ₂ )v- (v represents 0 to 4). Integer), *-CO-O-CH ₂ -, *-O-CO-, *-O-CH ₂ -CO-O-, *-O-CO-O-, *-O-CO-O- CH ₂ -, *-O-CO-CH ₂ -O-, *-O-CH ₂ -CO-O-CH ₂ -, *-O-CO-CH ₂ -O-CH ₂ - and *-O- CH ₂ -CH ₂ -O- or the like, wherein L _{10 is} preferably *-CO-O-(CH ₂ )v- (v represents an integer of 0 to 4). Further, in the specific example of L ₁₀ shown here, * represents a bond to a carbon atom of the ring W, that is, a bond to a carbon atom constituting a ring of the ring W.

R ₁₀ is a monovalent organic group containing an anthracene ring, an anthracene ring or a phenanthrene ring, and the organic group may have a substituent. More specifically, R ₁₀ is represented by the following formula (R ¹ -1) to formula (R ¹ -22). Further, the * system of each of the specific examples of R ¹ and the bond of L ₁₀ are provided.

One of the other preferred embodiments of R is a group represented by -O-CO-OL ₁₁ -Y ₁₁ .

L ₁₁ represents a single bond or an alkanediyl group (alkylene group) having 1 to 6 carbon atoms, and the methyl group constituting the alkanediyl group may be substituted with an oxygen atom or a carbonyl group.

The alkanediyl group in L ₁₁ may, for example, be a linear alkanediyl group or a branched alkanediyl group.

Specific examples thereof include a methyl group, an ethyl group, a propane-1,3-diyl group, a propionyl-1,2-diyl group, a butane-1,4-diyl group, a penta-1,5-diyl group, a linear alkanediyl group having a 1,6-diyl group or the like; a side chain having an alkyl group (particularly an alkyl group having 1 to 4 carbon atoms) on a linear alkanediyl group, for example, a di-1,3-1,3- Dibasic, 2-methylpropane-1,3-diyl, 2-methylpropan-1,2-diyl, 1-methylbutyl-1,4-diyl, 2-methylbuty-1, a branched alkanediyl group such as 4-diyl.

Among them, L _{11 is} preferably a single bond or a methyl group.

Y ₁₁ represents an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, and the methyl group constituting the alicyclic hydrocarbon group may be substituted with an oxygen atom, a sulfonyl group or a carbonyl group.

The alicyclic hydrocarbon group in Y ₁₁ may be either monocyclic or polycyclic. Further, it is not limited to an alicyclic hydrocarbon group having a carbon atom as a ring atom, and may be a group in which an alkyl group having 1 to 12 carbon atoms is bonded to a carbon atom of a ring atom.

The monocyclic alicyclic hydrocarbon group may, for example, be a cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, a cycloheptyl group or a cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group, a methylnorbornyl group, and the groups shown below.

The alicyclic hydrocarbon group optionally has a substituent. The "alicyclic hydrocarbon group having a substituent" means a group in which a hydrogen atom of the alicyclic hydrocarbon group is substituted with a substituent.

Examples of the substituent include a halogen atom (excluding a fluorine atom), a hydroxyl group, an alkoxy group having 1 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, an aralkyl group having 7 to 21 carbon atoms, and a carbon number. a thiol group of 2 to 4, a glycidoxy group or a group represented by -(CH ₂ ) _j2 -OCO-R _i1 (wherein, R _i1 represents an aliphatic hydrocarbon group having 1 to 16 carbon atoms, and a carbon number of 3 to 16 An alicyclic hydrocarbon group or an aromatic hydrocarbon group having 6 to 18 carbon atoms; j2 represents an integer of 0 to 4). The aromatic hydrocarbon group and the aralkyl group which are a substituent of the alicyclic hydrocarbon group may have, for example, an alkyl group having 1 to 8 carbon atoms, a halogen atom or a hydroxyl group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a decyloxy group, and a dodecyloxy group.

Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthracenyl group, a p-methylphenyl group, a p-tert-butylphenyl group, a p-adamantylphenyl group, a tolyl group, a xylyl group, and a cumyl group. An aryl group such as a trimethylphenyl group, a biphenylyl group, a phenanthryl group, a 2,6-diethylphenyl group or a 2-methyl-6-ethylphenyl group.

Examples of the aralkyl group include a benzyl group, a phenethyl group, a phenylpropyl group, a trityl group, a naphthylmethyl group, and a naphthylethyl group.

Examples of the thiol group include an ethyl group, a propyl group, and a butyl group.

The aliphatic hydrocarbon group may, for example, be an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group or an octyl group.

Examples of the methyl group-substituted methoxy group, the sulfonyl group (-SO ₂ -) or the carbonyl group constituting the alicyclic hydrocarbon group may, for example, be a cyclic ether structure (one of the methyl groups constituting the alicyclic hydrocarbon group or 2 groups substituted by an oxygen atom), a cyclic ketone group (one or two carbonyl-substituted groups constituting a methyl group of an alicyclic hydrocarbon group), a sultone ring group (constituting an alicyclic hydrocarbon group) The two adjacent methyl groups in the methyl group are substituted by an oxygen atom and a sulfonyl group, respectively, and the lactone ring group (the two adjacent methyl groups in the methyl group constituting the alicyclic hydrocarbon group are respectively oxygenated) Atom and a carbonyl substituted group) and the like.

The alicyclic hydrocarbon group of Y ₁₁ is preferably, for example, the following formula (Y1) to formula (Y29); * represents a bond with L ₁₁ .

Examples of the alicyclic hydrocarbon group having a substituent of Y ₁₁ include the following:

Y _{11 is} preferably an adamantyl group which may have a substituent, more preferably an adamantyl group, an oxyadamantyl group or a hydroxyadamantyl group.

The content of the compound represented by the above formula (I) in the composition is not particularly limited, but it is preferably from 3 to 30% by mass, more preferably from 3 to 30% by mass based on the total solid content in the composition, based on the viewpoint of the effect of the present invention being more excellent. It is 3 to 15% by mass.

Further, the total solid content means the total mass of the components constituting the film to be described later, that is, other components excluding the solvent.

In addition, the compound represented by the formula (I) may be used alone or in combination of two or more.

<Other ingredients>

The composition of the present invention may contain components other than the above-described resin (A) and the compound represented by the formula (I).

Hereinafter, any component will be described in detail.

<Compound (B2) which generates an acid by irradiation with actinic rays or radiation>

The composition of the present invention may contain a compound (B2) which is an acid generated by irradiation with actinic rays or radiation other than the compound represented by the above formula (I) (hereinafter also referred to as "acid generator" or "compound" (B2)").

As the compound (B2), a compound which generates an organic acid by irradiation with actinic rays or radiation is preferred.

The compound (B2) may be in the form of a low molecular compound or in a form incorporated into a part of the polymer. Further, the form of the low molecular compound and the form of being incorporated into a part of the polymer may be used in combination.

When the compound (B2) is in the form of a low molecular compound, the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, still more preferably 1,000 or less.

When the compound (B2) is incorporated in a form of a part of the polymer, it may be incorporated into a part of the acid-decomposable resin, or may be incorporated into a resin different from the acid-decomposable resin.

In the present invention, the compound (B2) is preferably in the form of a low molecular compound.

The acid generator is used as a photoinitiator for photocation polymerization, a photoinitiator for photoradical polymerization, a photochromic dye for photoreceptors, a photochromic agent, or a micro-resistance. A well-known compound which produces an acid by irradiation with actinic rays or radiation and a mixture thereof.

For example, a diazonium salt, a phosphonium salt, a phosphonium salt, a phosphonium salt, a sulfonium sulfonimide, a sulfonium sulfonate, a diazodiazine, a diterpene, an o-nitrobenzene methanesulfonate can be cited.

Preferred compounds among the acid generators include compounds represented by the following formulae (ZI), (ZII), and (ZIII):

In the above formula (ZI), R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represent an organic group.

The carbon number of the organic groups of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is generally from 1 to 30, preferably from 1 to 20.

Further, two of R ₂₀₁ to R ₂₀₃ may be bonded to each other to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, a guanamine bond or a carbonyl group. Examples of the group which can be bonded by two of R ₂₀₁ to R ₂₀₃ include an alkylene group (for example, a butyl group and a pentyl group).

Z ^- represents a non-nucleophilic anion.

Examples of the non-nucleophilic anion belonging to Z ^- may, for example, be a sulfonic acid anion, a carboxylic acid anion, a sulfonimide anion, a bis(alkylsulfonyl) quinone anion, or a sulfonium alkyl anion. Wait.

The non-nucleophilic anion refers to an anion having a significantly lower ability to cause a nucleophilic reaction, and is an anion capable of inhibiting the catalyzed decomposition of the intramolecular nucleophilic reaction. Thereby, the diachronic stability of the sensitized ray-sensitive or radiation-sensitive resin composition is improved.

Examples of the sulfonic acid anion include an aliphatic sulfonate anion, an aromatic sulfonate anion, and a camphorsulfonate anion.

Examples of the carboxylic acid anion include an aliphatic carboxylic acid anion, an aromatic carboxylic acid anion, and an aralkyl carboxylate anion.

The aliphatic moiety in the aliphatic sulfonic acid anion and the aliphatic carboxylic acid anion may be an alkyl group or a cycloalkyl group, preferably an alkyl group having 1 to 30 carbon atoms and a cycloalkyl group having 3 to 30 carbon atoms.

The aromatic group in the aromatic sulfonic acid anion and the aromatic carboxylic acid anion is preferably an aryl group having 6 to 14 carbon atoms, and examples thereof include a phenyl group, a tolyl group, and a naphthyl group.

The alkyl group, the cycloalkyl group and the aryl group in the aliphatic sulfonic acid anion and the aromatic sulfonic acid anion may have a substituent.

As other non-nucleophilic anions, for example, phosphorus fluoride (such as PF ₆ ^- ), boron fluoride (such as BF ₄ ^- ), cesium fluoride or the like (such as SbF ₆ ^- ) can be cited.

As the non-nucleophilic anion of Z ^- , an aliphatic sulfonate anion having at least the α position of the sulfonic acid substituted by a fluorine atom, an aromatic sulfonic acid anion substituted by a fluorine atom or a group having a fluorine atom, an alkyl group a bis(alkylsulfonyl) quinone imine anion substituted with a fluorine atom, and a paraxanthene alkyl anion substituted with a fluorine atom. The non-nucleophilic anion is more preferably a perfluoroaliphatic sulfonate anion having 4 to 8 carbon atoms, an benzenesulfonic acid anion having a fluorine atom, more preferably a nonafluorobutanesulfonate anion or perfluorooctanesulfonic acid. Anion, pentafluorobenzenesulfonate anion, 3,5-bis(trifluoromethyl)benzenesulfonate anion.

Among the acid generators, as a particularly preferred example, the compounds exemplified in paragraph [0143] of US 2012/0207978 A1 can be cited.

The acid generator can be synthesized by a known method, and can be synthesized, for example, according to the method described in JP-A-2007-161707.

When two or more acid generators are used in combination, the total content of the composition of the acid generator is preferably from 0.1 to 30% by mass, more preferably from 0.5 to 25% by mass based on the total solid content of the composition. , preferably 3 to 20% by mass, and particularly preferably 3 to 15% by mass.

<(HR) hydrophobic resin>

The composition of the present invention may contain a hydrophobic resin (hereinafter also referred to as "hydrophobic resin (HR)") particularly when applied to liquid immersion exposure. Hydrophobic resin (HR) is free compared to resin (A) The resin can be relatively small, whereby the hydrophobic resin (HR) is locally present on the surface of the photoresist film. If the liquid immersion medium is water, the static/dynamic contact angle between the surface of the film and the water can be increased, thereby improving Liquid immersion liquid traceability.

As described above, the hydrophobic resin (HR) is locally present at the interface, except for the surfactant, which does not necessarily have a hydrophilic group in the molecule, and does not contribute to uniform mixing of the polar/nonpolar substance.

Hydrophobic resin (HR) contains fluorine atoms and/or ruthenium The child is better. The fluorine atom and/or the ruthenium atom in the hydrophobic resin (HR) may be contained in the main chain of the resin or may be contained in the side chain. Further, the hydrophobic resin (HR) preferably has a branched alkyl group or a long-chain alkyl group (preferably having a carbon number of 4 or more, more preferably a carbon number of 6 or more, particularly preferably a carbon number of 8 or more). .

The content of the hydrophobic resin (HR) in the composition can be appropriately adjusted In addition, the film receding contact angle formed by the composition is used in a preferred range to be described later, and is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass based on the total solid content of the composition. Further preferably, it is 0.1 to 10% by mass, and particularly preferably 0.2 to 8% by mass.

The hydrophobic resin (HR) may have a structural unit derived from a compound represented by the formula (a) (hereinafter referred to as "compound (a)"):

[In the formula (a), R ¹ represents a hydrogen atom or a methyl group; R ² represents an aliphatic hydrocarbon group having 1 to 18 carbon atoms which may have a substituent; and A ¹ represents an alkane having 1 to 6 carbon atoms which may have a substituent. a base or a group represented by the formula (a-g1);

(In the formula (a-g1), s represents 0 or 1; A ¹⁰ and A ¹² each independently represent an aliphatic hydrocarbon group having 1 to 5 carbon atoms which may have a substituent; and A ¹¹ represents a carbon number which may have a substituent 1~ An aliphatic hydrocarbon group or a single bond of 5; X ¹⁰ and X ¹¹ each independently represent an oxygen atom (in the present specification, the oxygen atom is represented by "-O-"), and a carbonyl group (the carbonyl group is referred to as "-CO" in the present specification. -" represents), a carbonyloxy group (in the present specification, the carbonyloxy group is represented by "-CO-O-") or an oxycarbonyl group (in the present specification, the oxycarbonyl group is represented by "-O-CO-") ; however, the total number of carbon atoms of A ¹⁰ , A ¹¹ , A ¹² , X ¹⁰ and X ¹¹ is 6 or less)]

A ¹ is an alkanediyl group having 1 to 6 carbon atoms or a group represented by the above formula (a-g1) (hereinafter referred to as "base (a-g1)").

The alkanediyl group of A ¹ may be linear or branched, and examples thereof include a methyl group, an ethyl group, a propylene group, a butyl group, a pentane group, and a hexyl group.

The hydrogen atom constituting the alkanediyl group may be substituted with a substituent. Examples of the substituent include a hydroxyl group and an alkoxy group having 1 to 6 carbon atoms.

Specific examples of the base (a-g1) are shown below. In the following specific examples, the left and right sides are described in the corresponding formula (a); in each of the two bonds indicated by *, the left side bond is bonded to the oxygen atom on the R ¹ side, and the right side The bond is bonded to the oxygen atom on the R ² side.

As the group having an oxygen atom (a-g1), there are mentioned:

Etc. (* indicates the bond).

As the group having a carbonyl group (a-g1), there are mentioned:

Etc. (* indicates the bond).

As the group having a carbonyloxy group (a-g1), there are mentioned:

Etc. (* indicates the bond).

As the group having an oxycarbonyl group (a-g1), there are mentioned:

Etc. (* indicates the bond).

Among them, A ^{1 is} preferably an alkanediyl group, more preferably an alkanediyl group having no substituent, and further preferably an alkanediyl group having 1 to 4 carbon atoms, particularly preferably an ethylidene group.

The aliphatic hydrocarbon group of R ² may have a carbon-carbon unsaturated bond, but is preferably an aliphatic saturated hydrocarbon group.

Examples of the aliphatic saturated hydrocarbon group include an alkyl group (the alkyl group may be a straight chain or a branched chain), an alicyclic hydrocarbon group, and an aliphatic hydrocarbon group in which an alkyl group and an alicyclic hydrocarbon group are combined.

Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group.

The alicyclic hydrocarbon group may be either monocyclic or polycyclic. The monocyclic alicyclic hydrocarbon group may, for example, be a cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, a cycloheptyl group or a cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group, a methylnorbornyl group, and the groups shown below.

The aliphatic hydrocarbon group of R ² may or may not have a substituent, and R ^{2 is} preferably an aliphatic hydrocarbon group having a substituent.

The substituent of R ² is preferably a halogen atom or a group represented by the formula (a-g3) (hereinafter referred to as "base (a-g3)").

-X ¹² -A ¹⁴ (a-g3)

(In the formula (a-g3), X ¹² represents an oxygen atom, a carbonyl group, a carbonyloxy group or an oxycarbonyl group; and A ¹⁴ represents an aliphatic hydrocarbon group having 3 to 17 carbon atoms which may have a halogen atom).

An aliphatic hydrocarbon group having a halogen atom, typically having An alkyl group of a halogen atom and an alicyclic hydrocarbon group having a halogen atom (preferably a cycloalkyl group having a halogen atom).

The alkyl group having a halogen atom means that the hydrogen atom constituting the alkyl group is substituted with a halogen atom. Similarly, an alicyclic hydrocarbon group having a halogen atom means that a hydrogen atom constituting the alicyclic hydrocarbon group is substituted with a halogen atom.

The halogen atom may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and is preferably a fluorine atom.

The aliphatic hydrocarbon group having a halogen atom of R ² is preferably a perfluoroalkyl group in which all of the hydrogen atoms constituting the alkyl group are substituted by a fluorine atom, and all of the hydrogen atoms constituting the cycloalkyl group are substituted by a fluorine atom. . Among them, a perfluoroalkyl group is preferred, a perfluoroalkyl group having a carbon number of 1 to 6 is more preferred, and a perfluoroalkyl group having a carbon number of 1 to 3 is preferred.

Examples of the perfluoroalkyl group include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, a perfluorohexyl group, a perfluoroheptyl group, and a perfluorooctyl group.

X ^{12 is} preferably a carbonyloxy group or an oxycarbonyl group.

The compound (a) in which R ² is an aliphatic hydrocarbon group having a fluorine atom and A ¹ is an ethylidene group includes a compound represented by the following formula (a1) to formula (a16):

The compound (a) wherein R ² is a perfluoroalkyl group or a perfluorocycloalkyl group corresponds to the formula (a3), the formula (a4), the formula (a7), the formula (a8), and the formula (a). A11) A compound represented by any one of the formula (a12), the formula (a15), and the formula (a16).

The aliphatic hydrocarbon group having a group represented by the formula (a-g3) may have one or a plurality of groups (a-g3), and the number of carbon atoms contained in the group (a-g3) may be an aliphatic hydrocarbon group. The total carbon number is preferably 15 or less, more preferably 12 or less. In order to satisfy this preferred total carbon number, a group having one group (a-g3) is preferred as the R ² system.

The aliphatic hydrocarbon group having a group (a-g3), that is, R ² having a group (a-g3) is preferably a group represented by the following formula (a-g2) (hereinafter referred to as "base (a-g2)").

-A ¹³ -X ¹² -A ¹⁴ (a-g2)

(In the formula (a-g2), A ¹³ represents an aliphatic hydrocarbon group having a carbon atom of 3 to 17; X ¹² represents a carbonyloxy group or an oxycarbonyl group; and A ¹⁴ represents a carbon number which may have a halogen atom of 3 to 17; An aliphatic hydrocarbon group; the total number of carbon atoms of A ¹³ , A ¹⁴ and X ¹² is 18 or less)

As a preferred one of the group (a-g2) (where the linkage of the * system and the carbonyl group), the following structure can be cited:

R ² is a compound (a) having an aliphatic hydrocarbon group represented by one formula (a-g3), that is, a compound (a) wherein R ² is a group represented by the formula (a-g2), specifically The person represented by the following formula (a') (hereinafter referred to as "compound (a')").

[In the formula (a'), A ¹³ represents an aliphatic hydrocarbon group having 3 to 17 carbon atoms which may have a halogen atom; X ¹² represents a carbonyloxy group or an oxycarbonyl group; and A ¹⁴ represents a carbon number of 3 to 17 which may have a halogen atom; An aliphatic hydrocarbon group; the total number of carbon atoms of A ¹³ and A ¹⁴ is 17 or less; A ¹ and R ¹ are synonymous with the above]

The compound (a') is a compound which is used as a raw material for the production of a hydrophobic resin (HR) contained in the composition.

In the compound (a'), both of A ¹³ and A ¹⁴ have a halogen atom, and it is preferred that only A ¹³ is an aliphatic hydrocarbon group having a halogen atom or only A ¹⁴ is an aliphatic hydrocarbon group having a halogen atom. More preferably, only A ¹³ is an aliphatic hydrocarbon group having a halogen atom, and among them, A ^{13 is more} preferably an alkanediyl group having a fluorine atom, and further preferably a perfluoroalkanediyl group. Further, the "perfluoroalkanediyl" means an alkanediyl group in which all hydrogen atoms are replaced by a fluorine atom.

The compound (a') in which R ² is a perfluoroalkanediyl group and A ¹ is an ethylidene group includes a compound represented by the following formula (a'1) to formula (a'10).

A ¹³ and A ¹⁴ are arbitrarily selected in the range of the total number of carbon atoms of 17 or less, and the carbon number of A ¹³ is preferably from 1 to 6, more preferably from 1 to 3. The carbon number of A ¹⁴ is preferably 4 to 15, more preferably 5 to 12. More preferably, A ¹⁴ is an alicyclic hydrocarbon group having 6 to 12 carbon atoms; and as the alicyclic hydrocarbon group, a cyclohexyl group and an adamantyl group are preferred.

<Acid Diffusion Control Agent>

The composition of the present invention preferably contains an acid diffusion controlling agent. The acid diffusion controlling agent functions as a quencher that traps an acid generated by an acid generator or the like. As the acid diffusion controlling agent, a basic compound; a low molecular compound containing a nitrogen atom and having a group which is desorbed by an action of an acid; and an alkali which is reduced or disappeared by irradiation with actinic rays or radiation can be used. a compound; a relative acid generator, a sulfonium salt which is relatively weakly acidic.

The basic compound is preferably a compound having a structure represented by the following formulas (A) to (E):

In the general formulae (A) and (E), R ²⁰⁰ , R ²⁰¹ and R ²⁰² may be the same or different and each represents a hydrogen atom, an alkyl group (preferably having a carbon number of 1 to 20), and a cycloalkyl group (preferably carbon). The number is 3 to 20) or the aryl group (carbon number is 6 to 20), and R ²⁰¹ and R ²⁰² may be bonded to each other to form a ring.

R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ may be the same or different and each represents an alkyl group having 1 to 20 carbon atoms.

In the above alkyl group, the alkyl group having a substituent is preferably an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms.

The alkyl group in these general formulae (A) and (E) is more preferably unsubstituted.

As preferred compounds, hydrazine, aminopyrrolidine, pyrazole, pyrazoline, and piperidin are mentioned. Amino group Porphyrin a porphyrin, a piperidine or the like; as a more preferable compound, a compound having an imidazole structure, a diazabicyclo structure, a ruthenium oxide structure, a ruthenium carboxylate structure, a trialkylamine structure, an aniline structure or a pyridine structure, and having a hydroxyl group And/or an alkylamine derivative of an ether bond, an aniline derivative having a hydroxyl group and/or an ether bond, or the like.

Specific examples of preferred compounds include the compounds listed in paragraph [0379] of US 2012/0219913 A1.

Further preferred examples of the basic compound include an amine compound having a phenoxy group, an ammonium salt compound having a phenoxy group, an amine compound having a sulfonate group, and an ammonium salt compound having a sulfonate group.

As the amine compound, a primary, secondary or tertiary amine compound can be used, and preferably an amine compound in which at least one alkyl group is bonded to a nitrogen atom. The amine compound is more preferably a tertiary amine compound. In the amine compound, as long as at least one alkyl group (preferably, carbon number 1 to 20) is bonded to a nitrogen atom, it may be a cycloalkyl group (preferably having a carbon number of 3 to 20) in addition to the alkyl group. The aryl group (preferably having a carbon number of 6 to 12) is bonded to the nitrogen atom. The amine compound preferably contains an oxygen atom in the alkyl chain to form an oxygen alkyl group. The number of the oxygen-extended alkyl groups is one or more in the molecule, preferably from 3 to 9, more preferably from 4 to 6. Among the oxygen alkyl groups, an oxygen extended ethyl group (-CH ₂ CH ₂ O-) or an oxygen extended propyl group (-CH(CH ₃ )CH ₂ O- or -CH ₂ CH ₂ CH ₂ O-) is preferred. More preferably, it is an oxygen-extended ethyl group.

The ammonium salt compound may be a primary, secondary, tertiary or quaternary ammonium salt compound, preferably an ammonium salt compound in which at least one alkyl group is bonded to a nitrogen atom. The ammonium salt compound may be a cycloalkyl group (preferably having a carbon number of 3 to 20) in addition to the alkyl group as long as at least one alkyl group (preferably having 1 to 20 carbon atoms) is bonded to the nitrogen atom. Or an aryl group (preferably having a carbon number of 6 to 12) bonded to a nitrogen atom. The ammonium salt compound preferably contains an oxygen atom in the alkyl chain to form an oxygen alkyl group. The number of the oxygen-extended alkyl groups is one or more in the molecule, preferably from 3 to 9, more preferably from 4 to 6. Among the oxygen alkyl groups, an oxygen extended ethyl group (-CH ₂ CH ₂ O-) or an oxygen extended propyl group (-CH(CH ₃ )CH ₂ O- or -CH ₂ CH ₂ CH ₂ O-) is preferred. More preferably, it is an oxygen-extended ethyl group.

As an anion of the ammonium salt compound, a halogen atom can be cited A sulfonate, a borate, a phosphate or the like, among which a halogen atom or a sulfonate is preferred.

In addition, the following compounds are also preferred as basic compounds:

As a basic compound, in addition to the above compounds, Paragraphs [0180] to [0225] of JP-A-2011-22560, paragraphs [0218] to [0219] of JP-A-2012-137735, and paragraphs [0416] to [International Publication Handbook WO2011/158687A1] 0438] The compound or the like described.

These basic compounds may be used alone or in combination of two or more.

The composition of the present invention may or may not contain a basic compound. When it is contained, the content of the basic compound is generally 0.001 to 10% by mass, preferably 0.01 to 5 by mass based on the solid content of the composition. %.

The ratio of use of the acid generator to the basic compound in the composition is preferably an acid generator/basic compound (mole ratio) = 2.5 to 300. That is, the molar ratio is preferably 2.5 or more based on the sensitivity and the resolution, and is preferably 300 in the case where the resolution is lowered due to the suppression of the retardation pattern caused by the passage of time after the exposure to the heat treatment. the following. The acid generator/basic compound (mole ratio) is preferably from 5.0 to 200, more preferably from 7.0 to 150.

Containing a nitrogen atom and having a basis for detachment by the action of an acid Among the low molecular compounds, as a group which is desorbed by the action of an acid, an acetal group, a carbonate group, a urethane group, a tertiary ester group, a tertiary hydroxyl group, a half amine acetal group is preferred. Particularly preferred is a urethane group or a hemiamine acetal group.

The molecular weight of the compound (C) having a group which is desorbed by the action of an acid is preferably from 100 to 1,000, more preferably from 100 to 700, particularly preferably from 100 to 500.

The compound (C) is preferably an amine derivative having a group on the nitrogen atom which is desorbed by the action of an acid.

The compound (C) may have a urethane group having a protective group on a nitrogen atom. The protective group constituting the urethane group can be represented by the following formula (d-1):

In the formula (d-1), Rb each independently represents a hydrogen atom, an alkyl group (preferably having a carbon number of 1 to 10), a cycloalkyl group (preferably having a carbon number of 3 to 30), and an aryl group (preferably a carbon). The number is 3 to 30), the aralkyl group (preferably, the carbon number is 1 to 10), or the alkoxyalkyl group (preferably, the carbon number is 1 to 10). Rb may be bonded to each other to form a ring.

The alkyl group, cycloalkyl group, aryl group or aralkyl group represented by Rb may be a hydroxyl group, a cyano group, an amine group, a pyrrolidinyl group or a piperidinyl group. a functional group of a phenyl group, an oxy group or the like; an alkoxy group; a halogen atom substitution. The same is true for the alkoxyalkyl group represented by Rb.

Rb is preferably a linear or branched alkyl group, a cycloalkyl group or an aryl group. More preferably, it is a linear or branched alkyl group or a cycloalkyl group.

Examples of the ring formed by linking two Rbs to each other include an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic hydrocarbon group, or a derivative thereof.

The specific structure of the group represented by the formula (d-1) is as disclosed in the paragraph [0466] of US 2012/0135348 A1, but is not limited thereto.

The compound (C) is particularly preferably those having a structure represented by the following formula (6).

In the formula (6), Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. When l is 2, the two Ra groups may be the same or different, and the two Ra groups may be bonded to each other to form a hetero ring together with the nitrogen atom in the formula. The heterocyclic ring may contain a hetero atom other than the nitrogen atom in the formula.

The Rb system is synonymous with Rb in the formula (d-1), and preferred examples are also the same.

l represents an integer from 0 to 2, and m represents an integer from 1 to 3, which satisfies l+m=3.

In the formula (6), the alkyl group, the cycloalkyl group, the aryl group and the aralkyl group which are Ra may be substituted with the same group as the above-mentioned group, and the group is an alkyl group, a cycloalkyl group or a aryl group which may be a genus Rb. a group substituted with a aryl group.

As the alkyl group, the cycloalkyl group, the aryl group, and the aralkyl group of Ra (this Specific examples of the alkyl group, the cycloalkyl group, the aryl group, and the aralkyl group may be substituted by the above group include the same groups as those of the above specific examples for Rb.

Specific examples of the particularly preferable compound (C) include The compounds disclosed in paragraph [0475] of US 2012/0135348 A1, except this.

The compound represented by the formula (6) can be synthesized based on, for example, JP-A-2007-298569, JP-A-2009-199021, and the like.

In the present invention, the low molecular compound (C) having a group which is desorbed by the action of an acid on the nitrogen atom may be used singly or in combination of two or more kinds.

The content of the compound (C) in the composition of the present invention is preferably 0.001 to 20% by mass, more preferably 0.001 to 10% by mass, even more preferably 0.01 to 5 by mass based on the total solid content of the composition. %.

Decreasing alkalinity by irradiation with actinic rays or radiation The disappearing basic compound is a compound having a proton-receptive functional group and decomposed by irradiation with actinic rays or radiation to reduce or disappear proton acceptor properties or to be converted into acidic by proton acceptability. Hereinafter, it is also referred to as a compound (PA).

The term "proton acceptor functional group" refers to a group capable of electrostatically interacting with a proton or a functional group having an electron, that is, a functional group having a macrocyclic structure such as a cyclic polyether, or containing a non-participating π. A functional group of a nitrogen atom of a conjugated lone pair. A nitrogen atom having a lone pair of electrons not participating in π conjugate means, for example, a nitrogen atom having a partial structure represented by the following formula:

Preferred structural examples of the proton acceptor functional group include, for example, a crown ether, an azacrown ether, a mono- to tertiary amine, a pyridine, an imidazole, and a pyridyl group. Structure, etc.

Compound (PA) can be produced by actinic ray or radiation A compound that decomposes by irradiation to reduce or disappear proton acceptor properties or convert from proton acceptor to acid. Here, the reduction or disappearance of proton acceptor or the conversion from proton acceptor to acid refers to a change in proton acceptor caused by the addition of a proton to a proton acceptor functional group, specifically, When a compound having a proton-receptive functional group (PA) forms a proton-added proton with a proton, the equilibrium constant of the chemical equilibrium is reduced.

Proton acceptability can be confirmed by performing pH measurement.

In the present invention, the acid dissociation constant pKa of the compound produced by decomposition of the compound (PA) by irradiation with actinic rays or radiation preferably satisfies pKa<-1, more preferably -13<pKa<-1, and is preferably -13<pKa<-3.

In the present invention, the acid dissociation constant pKa is an acid dissociation constant pKa in an aqueous solution, and is, for example, a chemical note (II) (Revision 4, 1993, edited by the Chemical Society of Japan, Maruzen Co., Ltd.). The lower the value, the greater the acid strength. The acid dissociation constant pKa in the aqueous solution can be actually measured by measuring the acid dissociation constant at 25 ° C using an infinitely diluted aqueous solution, and the substituent constant based on Harmant can also be obtained by calculation using the following software 1 And the value of the database of well-known literature values. The pKa values described in the present specification all indicate values obtained by calculation using the package software.

Package Software 1: Advanced Chemistry Development (ACD/Labs) Software V8.14 for Solaris (1994-2007 ACD/Labs).

The compound (PA) can produce, for example, a compound represented by the following formula (PA-1) which is a proton-added product which is produced by decomposition by irradiation with actinic rays or radiation. The compound represented by the formula (PA-1) is one having an acidic group at the same time as the proton acceptor functional group, whereby the proton acceptor is reduced, disappeared, or converted from a proton acceptor to a compound (PA). Acidic compound.

QA-(X) _n -BR (PA-1)

In the formula (PA-1), Q represents -SO ₃ H, -CO ₂ H, or -W ₁ NHW ₂ R _f . Here, R _f represents an alkyl group, a cycloalkyl group or an aryl group, and W ₁ and W ₂ each independently represent -SO ₂ - or -CO-.

A represents a single bond or a divalent linking group.

X represents -SO ₂ - or -CO-.

n represents 0 or 1.

B represents a single bond, an oxygen atom, or -N(R _x )R _y -. Here, R _x represents a hydrogen atom or a monovalent organic group, and R _y represents a single bond or a divalent organic group. R _x may be bonded to R _y to form a ring, or may be bonded to R to form a ring.

R represents a one-valent organic group having a proton acceptor functional group.

The general formula (PA-1) will be described in more detail.

The divalent linking group of A is preferably a divalent linking group having 2 to 12 carbon atoms, and examples thereof include an alkylene group and a phenylene group. More preferably, it is an alkyl group having at least one fluorine atom, preferably a carbon number of 2 to 6, more preferably a carbon number of 2 to 4. The alkyl chain may have a linking group such as an oxygen atom or a sulfur atom. The alkylene group is particularly preferably an alkylene group in which 30 to 100% of the number of hydrogen atoms is substituted by a fluorine atom, and more preferably a carbon atom bonded to the Q site has a fluorine atom. Further, it is preferably a perfluoroalkylene group, more preferably a perfluoroextended ethyl group, a perfluoroextended propyl group or a perfluorobutylene group.

The one-valent organic group of R _{x is} preferably a carbon number of 1 to 30, and examples thereof include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group. These groups may further have a substituent.

The alkyl group of R _x may have a substituent, and is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, and the alkyl chain may have an oxygen atom, a sulfur atom or a nitrogen atom.

The divalent organic group of R _y is preferably an alkylene group.

Examples of the ring structure in which R _x and R _y are bonded to each other include a 5 to 10 member ring containing a nitrogen atom, and particularly preferably a 6 member ring.

The proton acceptor functional group of R, such as the above, may be enumerated Aza crown ether, mono-, tertiary amine, pyridine or imidazole, etc. having a nitrogen-containing heterocyclic aromatic structure or the like.

The organic group having such a structure preferably has 4 to 30 carbon atoms, and examples thereof include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group.

Alkyl, cycloalkyl, aryl, aralkyl, alkyl, alkenyl, cycloalkyl, aryl, aralkyl, alkenyl groups of R having a proton-receptor functional group or an ammonium group The alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group are the same as R _x .

When B is -N(R _x )R _y -, it is preferred that R and R _x are bonded to each other to form a ring. By forming a ring structure, stability is improved, and the storage stability of the composition using the same is improved. The number of carbon atoms forming the ring is preferably 4 to 20, and may be monocyclic or polycyclic, or may contain an oxygen atom, a sulfur atom or a nitrogen atom in the ring.

Examples of the single ring structure include a 4-membered ring containing a nitrogen atom, a 5-membered ring, a 6-membered ring, a 7-membered ring, and an 8-membered ring. The polycyclic structure includes a combination of two or more single ring structures.

As to the Q represents -X ₁ NHX ₂ R _f is R _f, may be preferably a carbon number of an alkyl group having 1 to 6 fluorine atoms, more preferably a perfluoroalkyl group having a carbon number of 1 to 6. Further, as X ₁ and X ₂ , at least one of them is preferably -SO ₂ -, and more preferably both X ₁ and X ₂ are -SO ₂ -.

From the viewpoint of the hydrophilicity of the acid group, Q is particularly preferably -SO ₃ H or -CO ₂ H.

Among the compounds represented by the formula (PA-1), a compound having a Q moiety as a sulfonic acid can be synthesized by a general sulfonylation reaction. For example, a method in which another sulfonyl halide is partially hydrolyzed by reacting one of the sulfonyl halides of the bisulphantyl halide compound with an amine compound to form a sulfonamide bond, or The cyclic sulfonic anhydride is reacted with an amine compound to cause ring opening.

The compound (PA) is preferably an ionic compound. The proton acceptor functional group may be contained in either the anion site or the cation site, and is preferably contained in the anion site.

The compound (PA) is preferably a compound represented by the following formula (4) to (6): R _f -X ₂ -N ^- -X ₁ -A-(X) _n -BR [C] ⁺ (4)

R-SO ₃ ^- [C] ⁺ (5)

R-CO ₂ ^- [C] ⁺ (6)

In the general formulae (4) to (6), A, X, n, B, R, Rf, X ₁ and X ₂ are synonymous with each of the formula (PA-1).

C ⁺ represents a pair of cations.

As the counter cation, a phosphonium cation is preferred. Wherein the sulfonium cations include metal above general formula (ZI) in the _{^{S + (R 201) (R}} 202) (R 203) while described, it is of the general formula (ZII) of _{^{I + (R 204) (R}} 205 The cation cation described is a preferred example.

Hereinafter, specific examples of the compound (PA) include compounds exemplified in paragraph [0280] of US2011/0269072A1.

Further, in the present invention, a compound (PA) other than the compound which can produce the compound represented by the formula (PA-1) can be appropriately selected. For example, an ionic compound, that is, a compound having a proton acceptor moiety in a cationic moiety, may be employed. More specifically, a compound represented by the following formula (7):

In the formula, A represents a sulfur atom or an iodine atom.

m represents 1 or 2, and n represents 1 or 2. However, when A is a sulfur atom, m+n=3; when A is an iodine atom, m+n=2.

R represents an aryl group.

R _N represents an aryl group substituted with a proton acceptor functional group.

X ^- represents a pair of anions.

Specific examples of X ^- may be the same as those of the acid generator.

Specific examples of the aryl group of R and R _N include a phenyl group.

Specific examples of the proton acceptor functional group possessed by R _N are the same as the proton acceptor functional group described in the above formula (PA-1).

Specific examples of the ionic compound having a proton acceptor moiety at the cation site include a compound exemplified in paragraph [0291] of US2011/0269072A1.

In addition, such a compound can be synthesized by referring to the methods described in, for example, JP-A-2007-230913 and JP-A-2009-122623.

The compound (PA) may be used alone or in combination of two or more. The content of the compound (PA) is preferably from 0.1 to 10% by mass, more preferably from 1 to 8% by mass based on the total solid content of the composition.

In the composition of the present invention, an onium salt having a relatively weak acid relative to the acid generator can be used as the acid diffusion controlling agent.

When an acid generator is used in combination, and a phosphonium salt which produces an acid which is relatively weakly acidic with respect to an acid produced by the acid generator, if the acid generated by the acid generator is irradiated by actinic rays or radiation, When the phosphonium salt of the weak acid anion of the reaction collides, a weak acid is released by salt exchange to form a phosphonium salt having a strong acid anion. In this process, since the strong acid is exchanged for a weak acid having a low catalytic activity, the acid is apparently inactivated to control the acid diffusion.

The onium salt which is a relatively weak acid relative to the acid generator is preferably a compound represented by the following formula (d1-1) to (d1-3):

In the formula, R ⁵¹ is a hydrocarbon group which may have a substituent, Z ^2c is a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent (only a carbon system adjacent to S is not substituted with a fluorine atom), and R ⁵² is an organic group. Y ³ is a linear, branched or cyclic alkyl or aryl group, Rf is a hydrocarbon group containing a fluorine atom, and M ^{+ is} independently a ruthenium or osmium cation.

Preferred examples of the phosphonium cation or the phosphonium cation represented by M ⁺ include a phosphonium cation represented by the above S ⁺ (R ₂₀₁ ) (R ₂₀₂ ) (R ₂₀₃ ), and I ⁺ (R ₂₀₄ ) (R ₂₀₅ ). Represents a cation.

Preferred examples of the anion site of the compound represented by the formula (d1-1) include the structures listed in paragraph [0198] of JP-A-2012-242799.

Preferred examples of the anion site of the compound represented by the formula (d1-2) include the structures listed in paragraph [0201] of JP-A-2012-242799.

Preferred examples of the anion site of the compound represented by the formula (d1-3) include the structures listed in paragraphs [0209] to [0210] of JP-A-2012-242799.

The ruthenium salt of the relative acid generator relative to the weak acid may be a compound having a cation moiety and an anion site in the same molecule, and the cation site and the anion site are linked by a covalent bond.

The compound represented by any one of the following formulae (C-1) to (C-3) is preferably the compound:

In the general formulae (C-1) to (C-3), R ₁ , R ₂ and R ₃ represent a substituent having 1 or more carbon atoms.

L ₁ represents a divalent linking group or a single bond linking a cationic moiety to an anionic moiety.

-X ^- represents an anion moiety selected from the group consisting of -COO ^- , -SO ₃ ^- , -SO ₂ ^- , and -N ^- -R ₄ . R ₄ represents a carbonyl group at a linking site with an adjacent N atom: -C(=O)-, sulfonyl group: -S(=O) ₂ -, sulfinyl group: -S(=O)- Valency substituent.

R ₁ , R ₂ , R ₃ , R ₄ and L ₁ may be bonded to each other to form a ring structure. Further, in (C-3), two of R ₁ to R ₃ may be combined to form a double bond with the N atom.

Examples of the substituent having 1 or more carbon atoms of R ₁ to R ₃ include an alkyl group, a cycloalkyl group, an aryl group, an alkyloxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, and a ring. An alkylaminocarbonyl group, an arylaminocarbonyl group, or the like. Preferred are an alkyl group, a cycloalkyl group, and an aryl group.

The L _{1 which} is a divalent linking group may, for example, be a linear or branched alkyl group, a cycloalkyl group, an extended aryl group, a carbonyl group, an ether bond, an ester bond, a guanamine bond, a urethane bond, or a urea bond. And a combination of two or more of these. L _{1 is more} preferably an alkyl group, an aryl group, an ether bond, an ester bond, or a combination of two or more of these.

Preferred examples of the compound represented by the formula (C-1) include paragraphs [0037] to [0039] of JP-A-2013-6827 and paragraphs [0027] of JP-A-2013-8020. ]~[0029] The compounds listed.

Preferred examples of the compound represented by the formula (C-2) include the compounds listed in paragraphs [0012] to [0013] of JP-A-2012-189977.

Preferred examples of the compound represented by the formula (C-3) include the compounds listed in paragraphs [0029] to [0031] of JP-A-2012-252124.

The content of the relative acid generator relative to the bismuth salt of the weak acid is preferably from 0.5 to 10.0% by mass, more preferably from 0.5 to 8.0% by mass, even more preferably from 1.0 to 8.0% by mass, based on the solid content of the composition. .

<Solvent (hereinafter referred to as "solvent (D)")>

The composition may also contain a solvent (D). The solvent (D) can be further coated in the production of the photoresist pattern described later in accordance with the type and amount of the resin (A) and the type and amount of the compound represented by the formula (I), based on the coating of the composition of the present invention. The optimum one is appropriately selected from the viewpoint of good coatability on the substrate.

Examples of the solvent (D) include glycol ether esters such as ethyl stilbene acetate, methyl stilbene acetate, and propylene glycol monomethyl ether acetate (PGMEA); propylene glycol monomethyl ether (PGME) And other glycol ethers; esters of ethyl lactate, butyl acetate, amyl acetate and ethyl propionate; ketones such as acetone, methyl isobutyl ketone, 2-heptanone and cycloheptanone a cyclic ester such as γ-butyrolactone or a carbonate such as propylene carbonate. Solvent (D) can only One type may be used, or two or more types may be used in combination. Preferred examples of the solvent include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 2-heptanone, cyclohexanone, and γ-butyrolactone. More preferably, it is a solvent containing at least one of 2-heptanone and γ-butyrolactone, and more preferably a mixed solvent of two or more types containing 2-heptanone and γ-butyrolactone.

Specifically, it is preferably selected from two mixed solvents of PGMEA/ethyl lactate, PGMEA/PGME, PGMEA/cyclohexanone, and selected from PGMEA/ethyl lactate/γ-butyrolactone, PGMEA/cyclohexanone/ Γ-butyrolactone, PGMEA/2-heptanone/propylene carbonate, PGME/cyclohexanone/propylene carbonate, three mixed solvents of PGMEA/PGME/γ-butyrolactone, PGMEA/PGME/cyclohexanone/ Four kinds of mixed solvents of γ-butyrolactone.

<Other ingredients>

The composition may contain constituent components other than the above-mentioned components (for example, the resin (A), the acid generator (B), the solvent (D), and the basic compound (E), etc.), and the constituent component is referred to as "ingredient". (F)". The component (F) is not particularly limited, and examples thereof include additives known in the field of photoresist, such as a sensitizer, a dissolution inhibitor, a surfactant, a stabilizer, and a dye.

<pattern forming method>

Next, the pattern forming method of the present invention will be described.

The pattern forming method (negative pattern forming method) of the present invention has at least the following steps: (1) a step of forming a film (photoresist film) comprising the composition of the present invention (film forming step); (2) irradiating the film with light a step of ray or radiation (exposure step); and (3) A step of developing a film irradiated with actinic rays or radiation using an organic solvent-containing developing solution (organic solvent developing step).

The exposure (irradiation of actinic rays or radiation) of the above step (2) may be liquid immersion exposure.

The pattern forming method of the present invention preferably comprises (4) a heating step after (2) the exposing step.

The pattern forming method of the present invention may further comprise (5) a step of performing development using an alkali developing solution. By including the step (5), it is expected that a photoresist pattern having a finer optical pattern is formed by one exposure as described in Japanese Laid-Open Patent Publication No. 2008-292975.

The pattern forming method of the present invention may comprise a plurality of (2) exposure steps.

The pattern forming method of the present invention may comprise a plurality of (4) heating steps.

The photoresist film of the present invention is formed from the above-described composition of the present invention, and more specifically, a film formed by coating a composition on a substrate. In the pattern forming method of the present invention, the step of forming a film composed of a composition on a substrate, the step of exposing the film, and the developing step can be carried out by a well-known method.

After film formation, it is also preferred to include a pre-heating step (PB; Prebake) before the exposure step.

Further, after the exposure step and before the development step, it is preferable to include a post exposure heating step (PEB; Post Exposure Bake).

The heating temperature is preferably such that PB and PEB are carried out at 70 to 130 ° C, more preferably at 80 to 120 ° C.

The heating time is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and preferably 30 to 90 seconds.

Heating can be generally exposed. The means of the developing machine can be carried out by using a heating plate or the like.

The sensitivity or pattern profile can be improved by baking to promote the reaction of the exposed portion.

The wavelength of the light source used in the exposure apparatus of the present invention is not limited, and examples thereof include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-ray, electron beam, etc., preferably 250 nm or less, more preferably 220 nm or less. Particularly preferred is far-ultraviolet light with a wavelength of 1 to 200 nm, specifically KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (157 nm), X-ray, EUV ( 13 nm), electron beam, etc., preferably KrF excimer laser, ArF excimer laser, EUV or electron beam, more preferably ArF excimer laser.

Furthermore, the immersion exposure can be applied to the exposure step of the present invention. method.

The liquid immersion exposure method is a technique for improving the resolution by a technique in which a projection lens and a sample are filled with a high refractive index liquid (hereinafter also referred to as "liquid immersion liquid") for exposure.

In the "liquid immersion effect", if λ ₀ is the wavelength of the exposure light in the air, n is the refractive index of the liquid immersion liquid to the air, and θ is the convergence half angle of the light, and is set to NA ₀ = sin θ. When immersed, the resolution force and depth of focus (DOF) can be expressed by the following formula. Here, k ₁ and k _{2 are} coefficients related to the process.

(resolving power) = k ₁ . (λ ₀ /n)/NA ₀

(DOF) = ± k ₂ . (λ ₀ /n)/NA ₀ ²

That is, the effect of the liquid immersion is equivalent to the wavelength at which the wavelength is 1/n. In other words, in the case of a projection optical system of the same NA, the depth of focus can be made n times by liquid immersion. This is effective for all pattern shapes, and can be combined with super-resolution techniques such as phase shift method and deformed illumination method in the current research.

When performing immersion exposure, after (1) forming a film on the substrate Before the step of performing the exposure, and/or (2) the step of exposing the film through the liquid immersion liquid, the step of heating the surface of the film with the aqueous solution may be performed before the step of heating the film.

The liquid immersion liquid preferably has a temperature coefficient of refractive index as small as possible The liquid is transparent to the exposure wavelength and the distortion of the optical image projected onto the film is only minimal; especially when the exposure source is an ArF excimer laser (wavelength 193 nm), in addition to the above, based on It is preferable to use water from the viewpoints of ease of handling, ease of handling, and the like.

If water is used, a table that can add water in a small proportion An additive (liquid) having reduced surface tension and increased interfacial activity. The additive preferably does not dissolve the photoresist layer on the wafer and can neglect the effects on the lower optical coating of the lens element.

As such an additive, for example, an aliphatic alcohol having a refractive index substantially equal to that of water is preferable, and specific examples thereof include methanol, ethanol, and isopropyl alcohol. By adding an alcohol having a refractive index substantially equal to that of water, it is possible to obtain an advantage in that the concentration of the alcohol in the water is evaporated to change the concentration of the liquid, and the refractive index change of the entire liquid can be minimized.

On the other hand, when a substance that is opaque to 193 nm light or an impurity whose refractive index is significantly different from water is mixed, it causes projection to The distortion of the optical image on the photoresist, therefore, the water used is preferably distilled water. Pure water which is further filtered by ion exchange filter paper or the like can also be used.

The electric resistance of the water used as the liquid immersion liquid is preferably 18.3 MQcm or more, and the TOC (organic matter concentration) is preferably 20 ppb or less, and preferably subjected to degassing treatment.

Moreover, by increasing the refractive index of the liquid immersion liquid, the lithography performance can be improved. From this point of view, additives for increasing the refractive index can also be added to water, or heavy water (D ₂ O) can be used instead of water.

The photoresist film formed by using the composition of the present invention is retreated The contact angle is preferably 70° or more at a temperature of 23±3° C. and a humidity of 45±5%, and is suitable for exposure with a liquid immersion medium, more preferably 75° or more, and still preferably 75 to 85°.

When the receding contact angle is too small, it is not suitable for exposure with a liquid immersion medium, and the effect of reducing water mark (watermark) defects is not sufficiently exerted.

If the resin (A) is substantially free of fluorine atoms and germanium atoms, By making the composition of the present invention contain a hydrophobic resin (HR), the receding contact angle of the surface of the photoresist film can be increased.

From the viewpoint of raising the receding contact angle, the ClogP value of the hydrophobic resin (HR) is preferably 1.5 or more. Further, from the viewpoint of enhancing the receding contact angle, the mass content of the CH ₃ partial structure of the side chain portion in the hydrophobic resin (HR) in the hydrophobic resin (HR) is preferably 12.0% or more.

In the immersion exposure step, due to the need to follow the exposure head The high-speed scanning on the wafer continues to form the exposure pattern, and the liquid immersion liquid moves on the wafer. Therefore, it is important that the contact angle between the liquid immersion liquid and the photoresist film in a dynamic state, and thus the photoresist It is required that the droplets do not remain and can follow the performance of the high speed scanning of the exposure head.

The substrate for forming a film in the present invention is not particularly limited, and an inorganic substrate such as ruthenium, SiN, SiO ₂ or SiN, a coated inorganic substrate such as SOG, or the like, a semiconductor manufacturing step such as IC, a liquid crystal, a thermal head, or the like can be used. The substrate used in the manufacturing steps of the circuit board, and even the other lithography steps of the photosensitive etching process. Further, an organic anti-reflection film may be formed between the film and the substrate as needed.

The pattern forming method of the present invention further has the use of a base When the developing solution is subjected to the development step, as the alkali developing solution, for example, an inorganic base such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate or aqueous ammonia can be used. a primary amine such as propylamine, a secondary amine such as diethylamine or di-n-butylamine; a tertiary amine such as triethylamine or methyldiethylamine; an alcohol amine such as dimethylethanolamine or triethanolamine. An alkaline aqueous solution of a quaternary ammonium salt such as tetramethylammonium hydroxide or tetraethylammonium hydroxide or a cyclic amine such as pyrrole or piperidine.

Furthermore, it is also possible to add an appropriate amount of alcohol to the above alkaline aqueous solution. Classes, surfactants are used.

The alkali concentration of the alkali developing solution is generally 0.1 to 20% by mass.

The pH of the alkali imaging solution is generally from 10.0 to 15.0.

In particular, it is preferably a 2.38% by mass aqueous solution of tetramethylammonium hydroxide.

The rinsing liquid in the rinsing treatment performed after the alkali imaging In other words, pure water may be used, and an appropriate amount of surfactant may be added for use.

Further, after the development processing or the rinsing treatment, the treatment of removing the developing liquid or the rinsing liquid attached to the pattern by the supercritical fluid may be performed.

Contained as a pattern forming method of the present invention The developing solution in the step of developing the developing solution of the organic solvent (hereinafter also referred to as an organic developing solution) may be a ketone solvent, an ester solvent, an alcohol solvent, a guanamine solvent, or an ether system. A polar solvent such as a solvent or a hydrocarbon solvent.

Examples of the ketone solvent include 1-octanone and 2-octanone. 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutanone, cyclohexanone, methyl Cyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetone acetonide, acetyl ketone, ionone, diacetone alcohol, acetamethanol, acetophenone, methyl naphthalene Ketone, isophorone, propylene carbonate, and the like.

Examples of the ester solvent include methyl acetate and acetic acid. Butyl ester, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, two Ethylene glycol monoethyl ether acetate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, Butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, and the like.

Examples of the alcohol-based solvent include methanol, ethanol, and positive Alcohols such as propanol, isopropanol, n-butanol, secondary butanol, tertiary butanol, isobutanol, n-hexanol, n-heptanol, n-octanol, n-nonanol, etc.; ethylene glycol, two Glycol solvent such as ethylene glycol or triethylene glycol; ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol single A glycol ether solvent such as diethyl ether or methoxymethylbutanol.

Examples of the ether solvent include, in addition to the above glycol ether solvent, Alkane, tetrahydrofuran, and the like.

As the amide-based solvent, for example, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, trimethylamine hexamethylphosphate, or the like can be used. 1,3-Dimethyl-2-tetrahydroimidazolidone or the like.

The hydrocarbon-based solvent may, for example, be an aromatic hydrocarbon solvent such as toluene or xylene; or an aliphatic hydrocarbon solvent such as pentane, hexane, octane or decane.

The above solvents may be mixed in plural kinds, or may be other than the above Solvent or water is used in combination. However, in order to fully exert the effects of the present invention, it is preferred that the water content of the entire developing liquid is less than 10% by mass, and more preferably substantially no moisture.

In other words, the amount of the organic solvent to the organic-based developing liquid is preferably 90% by mass or more and 100% by mass or less based on the total amount of the developing liquid, and is preferably 95% by mass or more and 100% by mass or less.

In particular, the organic-based developing liquid preferably contains a developing liquid of at least one organic solvent selected from the group consisting of a ketone solvent, an ester solvent, an alcohol solvent, a guanamine solvent, and an ether solvent.

The vapor pressure of the organic-based developing liquid is preferably 5 kPa or less, more preferably 3 kPa or less, and particularly preferably 2 kPa or less at 20 °C. The vapor pressure of the organic imaging solution is less than 5 kPa, and the developing solution is on the substrate or Evaporation in the image cup is suppressed, which improves the temperature uniformity in the wafer surface, resulting in better dimensional uniformity in the wafer surface.

As a specific example having a vapor pressure of 5 kPa or less, Examples thereof include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 2-heptanone (methyl amyl ketone), 4-heptanone, 2-hexanone, diisobutyl ketone, and a ring. a ketone solvent such as ketone, methylcyclohexanone, phenylacetone or methyl isobutyl ketone; butyl acetate, amyl acetate, isoamyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol Ethyl acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl acetate Ester solvent of -3-methoxybutyl ester, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, etc.; n-propanol, isopropanol, n-butanol, secondary butanol , an alcohol solvent such as tertiary butanol, isobutanol, n-hexanol, n-heptanol, n-octanol or n-nonanol; a glycol solvent such as ethylene glycol, diethylene glycol or triethylene glycol; Glycol ether solvent such as diol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether or methoxy methyl butanol An ether solvent such as tetrahydrofuran; N-methyl-2-pyrrolidone, N , an amine-based solvent such as N-dimethylacetamide or N,N-dimethylformamide; an aromatic hydrocarbon solvent such as toluene or xylene; or an aliphatic hydrocarbon such as octane or decane. Solvent.

As a vapor pressure of 2 kPa or less with a particularly good range Specific examples thereof include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, 2-hexanone, diisobutylketone, cyclohexanone, and methylcyclohexanone. a ketone solvent such as phenylacetone; butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether Acid ester, diethylene glycol monoethyl ether acetate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl lactate, An ester solvent such as butyl lactate or propyl lactate; an alcohol solvent such as n-butanol, secondary butanol, tertiary butanol, isobutanol, n-hexanol, n-heptanol, n-octanol or n-nonanol. a glycol solvent such as ethylene glycol, diethylene glycol or triethylene glycol; ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, a glycol ether solvent such as triethylene glycol monoethyl ether or methoxymethylbutanol; N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethyl A guanamine solvent of carbamide, an aromatic hydrocarbon solvent such as xylene, or an aliphatic hydrocarbon solvent such as octane or decane.

Add appropriate amount of interfacial activity to the visible requirements of organic imaging solutions Agent.

The surfactant is not particularly limited, and for example, an ionic or nonionic fluorine-based and/or lanthanoid surfactant can be used. For example, JP-A-62-36663, JP-A-61-226746, JP-A-61-226745, and JP-A-61-226745 Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 5,057, 520, the specification of the U.S. Patent No. 5, 560, 692, the specification of U.S. Patent No. 5, 560, 692, the specification of U.S. Patent No. 5, 296, 830, the specification of No. 5, 460, 998, the specification of No. 5, 576, 143, the description of the No. 5,294,411, and the surfactant described in the specification of No. 5,824,451. A nonionic surfactant is preferred. Ef The ionic surfactant is not particularly limited, and a fluorine-based surfactant or a quinone-based surfactant is more preferably used.

The amount of surfactant used relative to the total amount of imaging solution The amount is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, more preferably 0.01 to 0.5% by mass.

A developing solution containing an organic solvent may also contain a basic compound. Specific examples and preferred examples of the basic compound which can be contained in the developing solution used in the present invention are the same as those of the basic compound which can be contained in the above-mentioned composition.

As a developing method, for example, a substrate is immersed in a charge A method of immersing a liquid in a tank for a certain period of time (dipping method), and developing a developing solution on the surface of the substrate by a surface tension and standing still for a certain period of time (liquid coating method), spraying the surface of the substrate A liquid-like method (spraying method), a method of continuously discharging a developing liquid while scanning a developing liquid discharge nozzle at a constant speed on a substrate rotating at a constant speed (dynamic liquid method).

In the above various development methods, when the step of discharging the developing liquid to the photoresist film by the developing nozzle of the developing device is included, the discharge pressure of the developing liquid discharged (the flow rate per unit area of the developing developing liquid discharged) It is preferably 2 mL/sec/mm ² or less, more preferably 1.5 mL/sec/mm ² or less, still more preferably 1 mL/sec/mm ² or less. The lower limit of the flow rate is not particularly limited, and is preferably 0.2 mL/sec/mm ² or more when considering the yield.

By setting the discharge pressure of the discharged developing liquid to the above range, pattern defects derived from the photoresist residue after development can be remarkably reduced. Although the details of this mechanism have not been determined, it is believed that the reason may be that, by making the discharge pressure in the above range, the pressure of the developing liquid on the photoresist film is reduced, and the photoresist film can be suppressed. The photoresist pattern is inadvertently cut or collapsed.

Further, the discharge pressure (mL/sec/mm ² ) of the developing liquid is a value at the exit of the developing nozzle in the developing device.

As a method of adjusting the discharge pressure of the developing liquid, for example, a method of adjusting the discharge pressure by a pump or the like, or a method of adjusting the pressure by adjusting the supply from the pressurizing tank, or the like may be mentioned.

The pattern forming method of the present invention may further comprise using a base The aqueous solution is developed to form a photoresist pattern (5) (alkali development step). Thereby, a finer pattern can be formed.

In the present invention, the portion having a weak exposure intensity is removed by the organic solvent developing step (3), but the portion having a higher exposure intensity can be removed by further performing the alkali developing step. By performing multiple development processes of multiple developments in this manner, it is possible to form a pattern in which only the field in which the exposure intensity is centered is insoluble, and therefore, a pattern which is finer than usual can be formed (with Japanese Patent Laid-Open No. 2008-292975 [0077] The same mechanism).

The alkali imaging can be carried out before or after the development step (3) using an organic solvent-containing developing solution, and more preferably before the organic solvent developing step (3).

Further, after the development step using the developer containing the organic solvent, the step of simultaneously stopping the development while replacing the other solvent can be carried out.

After the development step using the developing solution containing the organic solvent, it is preferred to include a step of washing with a rinse liquid.

As a developing step using a developing solution containing an organic solvent The rinse liquid used in the subsequent rinsing step is not particularly limited as long as the resist pattern is not dissolved, and a general organic solvent-containing solution can be used. As the rinsing liquid, a rinsing liquid containing at least one organic solvent selected from the group consisting of a hydrocarbon solvent, a ketone solvent, an ester solvent, an alcohol solvent, a guanamine solvent, and an ether solvent is preferably used.

Specific examples of the hydrocarbon solvent, the ketone solvent, the ester solvent, the alcohol solvent, the guanamine solvent, and the ether solvent are the same as those described for the developer containing the organic solvent.

In the development step using a developing solution containing an organic solvent More preferably, the step of washing with a rinsing liquid containing at least one organic solvent selected from the group consisting of a ketone solvent, an ester solvent, an alcohol solvent, and a guanamine solvent is more preferably used. The step of washing the rinse liquid containing an alcohol solvent or an ester solvent is particularly preferably a step of washing with a rinse liquid containing a monohydric alcohol, and preferably washing with a rinse liquid containing a carbon number of 5 or more. The steps.

Here, as the monohydric alcohol used in the rinsing step, Listed as a linear, branched, or cyclic monohydric alcohol, specifically 1-butanol, 2-butanol, 3-methyl-1-butanol, tertiary butanol, 1-pentanol, 2 -pentanol, 1-hexanol, 4-methyl-2-pentanol, 1-heptanol, 1-octanol, 2-hexanol, cyclopentanol, 2-heptanol, 2-octanol, 3- Hexanol, 3-heptanol, 3-octanol, 4-octanol, etc., as a particularly preferred one having a carbon number of 5 or more, 1-hexanol, 2-hexanol, 4-methyl-2-pentyl Alcohol, 1-pentanol, 3-methyl-1-butanol, and the like.

Each component may be mixed in plural kinds, or may be used by mixing with an organic solvent other than the above.

The water content in the rinse liquid is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less. By setting the water content to 10% by mass or less, good development characteristics can be obtained.

The vapor pressure of the rinse liquid used after the development step using the developer containing the organic solvent is preferably 0.05 kPa or more and 5 kPa or less, more preferably 0.1 kPa or more and 5 kPa or less, and most preferably 0.12 at 20 ° C. kPa or more and 3 kPa or less. By setting the vapor pressure of the rinsing liquid to 0.05 kPa or more and 5 kPa or less, the temperature uniformity in the wafer surface is improved, and the swelling caused by the immersion of the rinsing liquid is suppressed, and the dimensional uniformity in the wafer surface is made. Better.

An appropriate amount of surfactant can also be added to the rinse solution for use.

In the rinsing step, a wafer subjected to development using a developing solution containing an organic solvent is used for cleaning using the above-described organic solvent-containing rinsing liquid. The method of the cleaning treatment is not particularly limited, and for example, a method of continuously discharging the rinsing liquid on a substrate rotating at a constant speed (rotary coating method), and immersing the substrate in a tank filled with the developing liquid for a certain period of time (dipping method) can be applied. a method of spraying a developing solution on a surface of a substrate (spraying method), etc., wherein it is preferably washed by a spin coating method, and after the cleaning, the substrate is rotated at a number of revolutions of 2000 rpm to 4000 rpm, and the rinsing liquid is self-cleaned. Removed on the substrate. Furthermore, it is preferred to include a heating step (Post Bake) after the rinsing step. The developing liquid and the rinsing liquid remaining between the patterns and the inside of the pattern are removed by baking. The heating step after the rinsing step is generally carried out at 40 to 160 ° C, preferably 70 to 95 ° C, and usually 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.

Furthermore, the invention also relates to a pattern comprising the above invention A method of manufacturing an electronic device forming a method, and an electronic device manufactured by the method.

The electronic device of the present invention is suitable for being mounted in an electric and electronic device (home appliances, OA. media related equipment, optical equipment, communication equipment, etc.).

[Examples]

The examples are shown below, but the invention is not limited by these.

<Preparation of composition (photoresist composition)>

A solution obtained by dissolving the components shown in the following Table 1 in the solvent shown in the above table was filtered through a polyethylene filter paper having a pore diameter of 0.03 μm to prepare a photoresist composition.

Hereinafter, the various components used in the above Table 1 are combined and shown.

With respect to each of the resins A1 to A9 described below, the composition ratio of the repeating unit was a molar ratio.

Further, in the B-14 and B-15 which will be described later, the organic group represented by R in the formula (I) is not contained.

N-4: 2,6-diisopropylaniline

W-1: MEGAFACE F176 (made by DIC)

W-2: MEGAFACE R08 (DIC system) (fluorine and antimony)

W-3: Polysiloxane Polymer KP-341 (Shin-Etsu Chemical Industry Co., Ltd.)

W-4: TROYSOL S-366 (made by TROY Chemical)

W-5: KH-20 (Asahi Kasei Co., Ltd.)

W-6: PolyFox ^TM PF-6320 (manufactured by OMNOVA solution inc.) (fluorine system)

[solvent]

SL-1: Propylene glycol monomethyl ether acetate

SL-2: Propylene glycol monomethyl ether propionate

SL-3: 2-heptanone

SL-4: ethyl lactate

SL-5: Propylene glycol monomethyl ether

SL-6: cyclohexanone

SL-7: γ-butyrolactone

SL-8: propylene carbonate

<Line and gap pattern evaluation> (Line and gap pattern forming method)

ARC29A (manufactured by Nissan Chemical Co., Ltd.) for forming an organic anti-reflection film was applied onto a tantalum wafer, and baked at 205 ° C for 60 seconds to form an anti-reflection film having a film thickness of 86 nm. The photoresist composition was applied thereon, and baked (PB) at 100 ° C for 60 seconds to form a photoresist film having a film thickness of 100 nm. For the obtained tantalum wafer, an ArF excimer laser immersion scanner (XT1700i, NA1.20, C-Quad, external mean square deviation 0.981, internal mean square deviation 0.895, XY deflection) manufactured by ASML was used, and the line width was 45 nm. The 1:1 line and 6% halftone mask of the gap pattern are exposed. Ultrapure water is used as the liquid immersion liquid system. Thereafter, the film was heated (PEB) at 105 ° C for 60 seconds, and then developed with a developing solution (butyl acetate) for 30 seconds, and then rinsed with pure water to be rinsed, and then the wafer was rotated at 4000 rpm. After rotating for 30 seconds, baking was performed at 90 ° C for 60 seconds, thereby obtaining a photoresist pattern having a pitch of 90 nm and a line width of 45 nm and a gap (1:1).

(Evaluation of mask error increase factor (MEEF))

With respect to the reticle used in each of the examples and the comparative examples, the line width of the reticle was changed under the distance between the fixed reticle (the sum of the line width and the gap width), and the above-described optimum exposure of each of the examples and the comparative examples. The amount (the amount of exposure of the above-described line and gap pattern was analyzed), and the pattern was formed by the method of each of the examples and the comparative examples, and the absolute value of the slope of the line width change of the obtained pattern was defined as MEEF. That is, the MEEF defined by the following formula is calculated. The closer this value is to 1, the better the performance of the photoresist itself.

Line width of the pattern (nm) = a × line width variation of the mask (nm) + b

(absolute value of a = MEEF, b = constant)

(Assessment of line width roughness (LWR))

The line pattern of the above-described size in each of the examples and the comparative examples was observed using a length-measuring scanning electron microscope (SEM-Hippon Seisakusho S-9380II), and the line width of 50 points was measured at equal intervals in the range of 2 μm in the longitudinal direction of the line pattern. And calculate the LWR from its standard deviation to calculate 3σ. The smaller the value, the better the performance.

(Assessment of pattern section shape)

The cross-sectional shape of the pattern obtained by the above method was observed by a scanning electron microscope, and the line width Lb at the bottom of the resist pattern and the line width La at the upper portion of the photoresist pattern were measured. The case where 0.9 ≦ (La/Lb) ≦ 1.1 is defined as "rectangular" and (La/Lb) > 1.1 is defined as "T-top shape", and the cross-sectional shape of the obtained pattern is observed by a scanning electron microscope. Those who obtained a rectangular pattern were rated as A, and those who obtained a T-top shape were rated as B. As the cross-sectional shape, a rectangular pattern is preferable.

<Contact hole pattern evaluation> (Contact hole pattern forming method)

ARC29A (manufactured by Nissan Chemical Co., Ltd.) for forming an organic anti-reflection film was applied onto a tantalum wafer, and baked at 205 ° C for 60 seconds to form an anti-reflection film having a film thickness of 86 nm. The photoresist composition was applied thereon, and baked (PB) at 100 ° C for 60 seconds to form a photoresist film having a film thickness of 100 nm. For the obtained tantalum wafer, an ArF excimer laser immersion scanner (XT1700i, NA1.20, C-Quad manufactured by ASML, external mean square deviation 0.900, internal mean square deviation 0.812, XY deflection) was used, and the hole portion was interposed. Pattern exposure was performed for a halftone mask of 45 nm and a square arrangement with a pitch of 90 nm between the holes. Ultrapure water is used as the liquid immersion liquid system. Thereafter, the film was heated (PEB) at 105 ° C for 60 seconds, and then developed with a developing solution (butyl acetate) for 30 seconds, and then rinsed with pure water to be rinsed, and then the wafer was rotated at 4000 rpm. After rotating for 30 seconds, baking was performed at 90 ° C for 60 seconds, thereby obtaining a contact hole pattern having a pore diameter of 45 nm.

(Evaluation of mask error increase factor (MEEF))

With respect to the reticle used in each of the examples and the comparative examples, the aperture of the reticle was changed under the distance between the fixed reticle (the sum of the aperture and the gap width), and the above-mentioned optimum exposure amount in the sensitivity evaluation was observed (analysis of the above) The exposure amount of the contact hole pattern is a change in the diameter of the hole pattern obtained at the time of pattern formation. Thereafter, the absolute value of the slope is MEEF. That is, the MEEF defined by the following formula is calculated. The closer this value is to 1, the better the performance of the photoresist itself.

Pattern aperture (nm) = a × aperture change of the mask (nm) + b

(absolute value of a = MEEF, b = constant)

(Assessment of Critical Dimensional Uniformity (CDU))

In each of the examples and the comparative examples, a hole pattern of the above-described size was observed using a length-measuring scanning electron microscope (SEM), and the diameter of 90 holes was measured, and the standard deviation was used to calculate 3σ to evaluate the CDU. . The smaller the value, the better the performance.

(pattern section shape)

The cross-sectional shape of the photoresist pattern was observed by a scanning electron microscope, and the aperture Lb at the bottom of the photoresist pattern and the aperture La at the upper portion of the photoresist pattern were measured, and the case of 0.9 ≦ (La/Lb) ≦ 1.1 was evaluated as "A (good)". If the situation is outside this range, it is rated as "B (bad)".

The summary of the above evaluation results is shown in Table 2 below.

As shown in the above table, in the pattern forming method of the present invention, it was confirmed that the formed pattern shape was excellent.

For example, it can be seen from the comparison between Example 5 and Example 17 that when a compound represented by any one of the formulae (C-1) to (C-3) is used as a basic compound, it is confirmed that it is more excellent. The effect.

Further, other examples in which Examples 6 and 18 using B-3 and B-10 having no cyclic structure as R and photoacid generator having no cyclic structure as R were used were confirmed. The LWR or CDU and the like of other embodiments are small, and a more excellent effect can be obtained.

On the other hand, in Comparative Examples 1 and 2 in which the compound specifically disclosed in Patent Document 1 (the compound having no organic group represented by R in the general formula (I)) was used, the pattern formed was compared with the example. Poor shape.

Claims (11)

A pattern forming method comprising: (1) having a cation moiety and an anion site in the same molecule by containing the following (A), (B) and a bismuth salt relative to (B) a relatively weak acid; The cation site and the anion site are a sensitizing ray-sensitive or radiation-sensitive resin composition of a compound linked by a covalent bond to form a film: (A) increasing the polarity by an action of an acid to reduce the organic solvent a resin for dissolving a developing solution, (B) a compound represented by the formula (I) which generates an acid by irradiation with actinic rays or radiation; and (2) a step of irradiating the film with actinic rays or radiation And (3) a step of developing the film irradiated with actinic rays or radiation using a developing solution containing an organic solvent; In the formula (I), Z ⁺ represents a cation; and Q ¹ and Q ² each independently represent a fluorine or an alkyl group substituted with at least one fluorine; L represents a divalent linking group; and W represents a group having a cyclic structure. ;R represents an organic group. The pattern forming method of claim 1, wherein R is a group having a cyclic structure. The pattern forming method of claim 1, wherein W is a polycyclic aliphatic group. The pattern forming method of claim 2, wherein W is a polycyclic aliphatic group. A pattern forming method according to claim 3, wherein W is an adamantyl group. A pattern forming method according to claim 4, wherein W is an adamantyl group. The pattern forming method of claim 1, wherein the content of the organic solvent in the organic solvent-containing developing solution is 90% by mass or more and 100% by mass or less based on the total amount of the developing liquid. The pattern forming method according to claim 1, wherein the developing solution contains at least one selected from the group consisting of a ketone solvent, an ester solvent, an alcohol solvent, a guanamine solvent, and an ether solvent. The pattern forming method according to any one of claims 1 to 8, wherein the photosensitive ray-sensitive or radiation-sensitive resin composition further contains a hydrophobic resin (HR) different from the resin (A). The pattern forming method of claim 1, wherein the exposure of the step (2) is liquid immersion exposure. A method of manufacturing an electronic device comprising the pattern forming method of claim 1.