JP4443898B2 - Photosensitive composition and pattern forming method using the same - Google Patents

Description

  The present invention relates to a photosensitive composition used in a semiconductor manufacturing process such as an IC, a circuit board such as a liquid crystal or a thermal head, and other photofabrication processes, and a pattern forming method using the same. .

The above-mentioned photosensitive composition is used as a pattern forming material for changing the solubility of actinic ray or radiation irradiated portion and non-irradiated portion with respect to a developer to form a pattern on a substrate.
In such a photosensitive composition, various acid generators that generate an acid upon irradiation with actinic rays or radiation have been proposed.

  Patent Documents 1 to 5 disclose resist compositions containing a compound that generates a specific sulfonic acid in order to improve various resist performances such as resolution and exposure margin.

However, there are still many inadequacies and various improvements are desired. For example, when using a wafer having a large diameter, it has been found that temperature variations in heating (PEB) using a hot plate after exposure affect the resulting pattern. It is desired to improve the PEB temperature dependency.
Furthermore, it is difficult to achieve both improvement in PEB temperature dependency and expansion of exposure latitude, and it is desired to improve PEB temperature dependency and exposure latitude at the same time.

JP 2002-131897 A JP 2002-214774 A JP 2003-140332 A European Patent Application No. 1270553 International Publication No. 02/42845 Pamphlet

Therefore, the object of the present invention is to make an ArF excimer laser light (
193 nm), and an exposure wavelength of F ₂ excimer laser light (157 nm). It is an object to provide a good photosensitive composition having a small PEB temperature dependency and a large exposure latitude, and a pattern forming method using the same.

  The present invention has the following configuration, whereby the above object of the present invention is achieved.

(1) (A) A compound that generates a sulfonic acid represented by the general formula (X) and represented by any one of the general formulas (Xa), (Xb), and (Xg) upon irradiation with actinic rays or radiation. And (B) a resin containing a repeating unit represented by the following general formula (AI) and a repeating unit having two or more hydroxyl groups, decomposed by the action of an acid, and increased in solubility in an alkali developer A photosensitive composition.

In formula (X), R _{1a to} R _13a are each independently a hydrogen atom, an alkyl group, a cycloalkyl group,
Represents a halogen atom or a hydroxyl group.
A ₁ and A ₂ each independently represent a divalent linking group having a hetero atom or a single bond. However, when A ₁ and A ₂ are simultaneously a single bond, all of R _{1a to} R _13a do not simultaneously represent a fluorine atom, and all of R _{1a to} R _13a do not simultaneously represent a hydrogen atom.
m ₁ ~m ₅ represents each independently an integer from 0-12. p represents an integer of 0 to 4.
Rb is a group having at least one hydrogen atom.
n1 to n4 each independently represents an integer of 1 to 10.
Rc represents a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
In general formula (AI), R _b0 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms.
A _b is a single bond, an ether group, an ester group, a carbonyl group, an alkylene group, or these
Represents a divalent group in which
V represents a group represented by the following general formula (V-1).
In General Formula (V-1), R _{1b to} R _5b each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylsulfonylimino group, or an alkenyl group. Two of R _{1b to} R _5b may combine to form a ring.

(2) (A) a compound that generates a sulfonic acid represented by the general formula (X) and represented by the general formula (Xa-1) or (Xb-1) by irradiation with actinic rays or radiation; and (B) A photosensitive composition containing a resin containing a repeating unit having two or more hydroxyl groups, decomposed by the action of an acid, and increased in solubility in an alkaline developer .

Ax represents a linking group having 3 or more carbon atoms.
Ay represents a single bond or an oxygen atom.
Rg represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
n5 represents an integer of 1 to 4.
n6 represents an integer of 1 to 4.
n7 represents an integer of 1 to 4.

(3) The photosensitive composition as described in (1) or (2) above, further comprising a solvent containing a hydroxyl group and a solvent not containing a hydroxyl group.
(4) (A) a compound that generates a sulfonic acid represented by the general formula (X) and represented by the general formula (Xa) by irradiation with actinic rays or radiation, (D) soluble in an alkali developer A photosensitive composition comprising a resin, (E) an acid crosslinking agent that crosslinks with a resin soluble in the alkali developer by the action of an acid, a hydroxyl group-containing solvent, and a hydroxyl group-free solvent.
Rb represents an alkyl group or an aralkyl group having at least one hydrogen atom.
n1 represents an integer of 1 to 10.
(5) (A) A compound that generates a sulfonic acid represented by the general formula (X) and represented by the general formula (Xa-1) or (Xb-1) by irradiation with actinic rays or radiation, (D A) a resin soluble in an alkali developer, and (E) an acid crosslinking agent that crosslinks with the resin soluble in the alkali developer by the action of an acid, a solvent containing a hydroxyl group, and a solvent not containing a hydroxyl group. A photosensitive composition.
Ax in the formula (Xa-1) represents a linear or branched alkylene group having 3 or more carbon atoms.
Ax in Formula (Xb-1) represents a linking group having 3 or more carbon atoms.
Ay represents a single bond or an oxygen atom.
Rg represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
n5 represents an integer of 1 to 4.
n6 represents an integer of 1 to 4.
n7 represents an integer of 1 to 4.
(6) A compound that generates a sulfonic acid represented by the general formula (Xa-1) or (Xb-1) upon irradiation with an actinic ray or radiation.


Ax in the formula (Xa-1) represents a linear or branched alkylene group having 3 or more carbon atoms.
Ax in Formula (Xb-1) represents a linking group having 3 or more carbon atoms.
Ay in the general formula (Xa-1) represents an oxygen atom, and Ay in the general formula (Xb-1) represents a single bond or an oxygen atom.
Rg represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
n5 represents an integer of 1 to 4.
n6 and n7 each independently represents an integer of 1 to 10.

  Furthermore, the following structures are mentioned as a preferable aspect.

(7) The positive photosensitive composition according to any one of the above (1) to (3), wherein the repeating unit having two or more hydroxyl groups in (B) is a repeating unit containing a dihydroxyadamantane structure or a trihydroxyadamantane structure. object.

(8) The positive photosensitive composition as described in any one of (1) to (3) above, wherein (B) contains a repeating unit having a monocyclic or polycyclic hydrocarbon structure.
(9) The positive photosensitive composition according to any one of (1) to (3), wherein (B) is a resin containing a repeating unit having a lactone structure.
(10) Resin (B) is a resin containing a resin containing at least one repeating unit derived from at least one acrylic acid ester or acrylic acid repeating units derived from methacrylic acid ester or methacrylic acid above (1) -Positive photosensitive composition in any one of (3) .

(11) The positive photosensitive composition as described in any one of (1) to (3) above, wherein the resin (B) has a fluorine atom in the main chain or side chain.
(12) The positive photosensitive composition as described in any one of (1) to (3) above , wherein the resin (B) has a hexafluoroisopropanol structure.
(13) Further comprising (C) a dissolution inhibiting compound having a molecular weight of 3000 or less, which decomposes by the action of an acid and increases the solubility in an alkaline developer , The positive photosensitive composition in any one .

(14) The above (1) to (5), (7) to (13), further comprising (F) a basic compound and / or (G) fluorine and / or a silicon surfactant. The photosensitive composition in any one of.
(15) A pattern forming method comprising forming a film from the photosensitive composition according to any one of (1) to (5) and (7) to (14) , and exposing and developing the film. .

(16) The component (B) is at least one repeating unit selected from 2-alkyl-2-adamantyl (meth) acrylate or dialkyl (1-adamantyl) methyl (meth) acrylate, at least one repeating unit having a lactone structure, And at least one repeating unit having two or more hydroxyl groups. The photosensitive composition as described in any one of (1) to (3) above.

(17) The photosensitive composition as described in (16) above, wherein the component (B) further contains a repeating unit having a carboxyl group.

(18) The component (B) is at least one repeating unit selected from 2-alkyl-2-adamantyl (meth) acrylate or dialkyl (1-adamantyl) methyl (meth) acrylate, and at least one repeating unit having a hydroxystyrene structure. The photosensitive composition as described in any one of (1) to (3) above, which contains a seed.

  It is possible to provide a good photosensitive composition having a small PEB temperature dependency and a large exposure latitude at an exposure wavelength of 250 nm or less, and a pattern forming method using the same.

Hereinafter, the present invention will be described in detail.
In addition, in the description of group (atomic group) in this specification, the description which is not describing substitution and non-substitution includes what has a substituent with what does not have a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

[1] Compound (A) that generates a sulfonic acid represented by the general formula (X) upon irradiation with an actinic ray or radiation
The photosensitive composition of the present invention is a compound that generates a sulfonic acid represented by the general formula (X) (hereinafter referred to as (A)) as a compound that generates an acid upon irradiation with actinic rays or radiation (photoacid generator). Component or sulfonic acid generator).

In general formula (X), R < _1a > -R < _13a > respectively independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, or a hydroxyl group.
A ₁ and A ₂ each independently represent a divalent linking group having a hetero atom or a single bond. However, when A ₁ and A ₂ are simultaneously a single bond, all of R _{1a to} R _13a do not simultaneously represent a fluorine atom, and all of R _{1a to} R _13a do not simultaneously represent a hydrogen atom.
m ₁ ~m ₅ represents each independently an integer from 0-12. p represents an integer of 0 to 4.

  As the sulfonic acid represented by the general formula (X), a sulfonic acid represented by the following general formula (X ′) is preferable.

In general formula (X ′), R _{1a to} R _13a each represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, or a hydroxyl group.
A represents a divalent linking group having a hetero atom or a single bond. However, when A is a single bond, all of R _{1a to} R _13a do not simultaneously represent a fluorine atom, and all of R _{1a to} R _13a do not simultaneously represent a hydrogen atom.
m represents an integer of 0 to 12. n represents an integer of 0 to 12. q represents an integer of 1 to 3.

In the formula (X) or (X ′), the alkyl group represented by R _{1a to} R _13a may have a substituent, and preferably has 1 to 20 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, n -Butyl group, sec-butyl group, t-butyl group, hexyl group, octyl group, 2-ethylhexyl group, dodecyl group and the like can be mentioned.

The cycloalkyl group of R _{1a to} R _13a may be monocyclic or polycyclic and may have a substituent. The monocyclic type is preferably one having 3 to 8 carbon atoms, and preferred examples include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. The polycyclic type preferably has 6 to 20 carbon atoms. For example, an adamantyl group, norbornyl group, isobornyl group, camphanyl group, dicyclopentyl group, α-pyrenyl group, tricyclodecanyl group, tetracyclodecane group, and the like. A nyl group, an androstanyl group, etc. can be mentioned. However, the carbon atom in the monocyclic or polycyclic cycloalkyl group may be substituted with a heteroatom such as an oxygen atom.

Examples of the halogen atom for R _{1a to} R _13a include a fluorine atom, a chlorine atom, and an iodine atom.
As the substituent that the alkyl group and cycloalkyl group of R _{1a to} R _13a may have, a cycloalkyl group (preferably having 5 to 20 carbon atoms), a halogen atom (a fluorine atom, a chlorine atom, an iodine atom) are preferable. , Alkoxy groups (preferably having 1 to 4 carbon atoms), aryl groups (preferably having 6 to 10 carbon atoms), alkenyl groups (preferably having 2 to 6 carbon atoms), cyano groups, hydroxy groups, carboxy groups, alkoxycarbonyl groups (Preferably having 2 to 20 carbon atoms), a nitro group, and an acid-decomposable group (tertiary ester group, acetal ether group, acetal ester group, silyl ether group).
As for the cycloalkyl group, examples of the substituent further include an alkyl group (preferably having 1 to 5 carbon atoms).

Examples of the divalent linking group having a hetero atom in A ₁ , A ₂ or A include an oxygen atom, a sulfur atom, —CO—, —COO—, —CONR—, —SO ₂ NR—, —CONCCO—, —SO _{2 NRCO -, - SO 2 NRSO} 2 -, - OCONR- , and the like. Here, R represents a hydrogen atom or an alkyl group (preferably having 1 to 10 carbon atoms). The alkyl group of R may be substituted with a halogen atom, a hydroxyl group, or an alkoxy group (preferably having 1 to 4 carbon atoms). R may combine with any one or more of R _{1a to} R _13a to form a ring. Further, the ring may contain a linking group such as an oxygen atom, a nitrogen atom, a sulfur atom, and —CO—.

As the sulfonic acid represented by the general formula (X) or (X ′), one in which at least one of R _{1a to} R _13a represents a halogen atom is preferable, and more preferably at least one of R _{1a to} R _13a is fluorine. What represents an atom is preferable, It is especially preferable that one or both of R _{< 12a>} and R _<13a> are fluorine atoms.

Among these, CF ₃ (CF ₂ ) _k [A (CF ₂ ) _{k ′} ] _q SO ₃ H, CF ₃ (CF ₂ ) _k (CH ₂ ) _{k ′} SO ₃ H, CH ₃ (CH _{2) k (CF 2) k} 'SO 3 H { here, k is an integer of 0 to 12. k ′ represents an integer of 1 to 12. A and q are as defined above} or a sulfonic acid represented by the following formula.

In the formula (X ″), R _2a , R _10a , R _11a , R _13a , ml and A ₁ are the same as those in the formula (X).
m1 is preferably an integer of 0 to 3, more preferably 0 or 1, A ₁ is a single bond, an oxygen atom, -CONR- or -COO- are preferred.

  Further, the sulfonic acid represented by the general formula (X) is most preferably a sulfonic acid represented by the following general formulas (Xa) to (Xh).

Rb is a group having at least one hydrogen atom. Preferably a hydrogen atom, an alkyl group (preferably 1 to 20 carbon atoms), a cycloalkyl group (preferably 5 to 20 carbon atoms), an aryl group (preferably 6 to 10 carbon atoms), an aralkyl group (preferably 7 carbon atoms). -15) represents a hydroxyl group and has at least one hydrogen atom.
Examples of the alkyl group and cycloalkyl group in Rb include the alkyl groups and cycloalkyl groups mentioned in R _{1a to} R _13a .
Examples of the aryl group in Rb include a phenyl group and a naphthyl group.

Examples of the aralkyl group in Rb include a benzyl group, a phenethyl group, a naphthylmethyl group, and a naphthylethyl group.
Rf is a fluorine atom or a group having a fluorine atom, and the group having a fluorine atom as Rf is preferably 1 to 5 carbon atoms, preferably 1 to 11 fluorine atoms, more preferably 1 to 9, and still more preferably. Is 3-7. Rf is preferably a fluorine atom or a fluoroalkyl group (preferably having 1 to 4 carbon atoms), more preferably a fluorine atom, trifluoromethyl, pentafluoroethyl or heptafluoropropyl.
Rh represents a hydrogen atom or an alkyl group (preferably having 1 to 10 carbon atoms).

n1-n4 represents the integer of 1-10. Preferably it is an integer of 2-4.
Rc, Rd and Re may be the same or different, and are each a hydrogen atom, a halogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably having 5 to 20 carbon atoms), an aryl group ( Preferably it represents C6-C10 and an aralkyl group (preferably C7-C15).
Examples of the alkyl group, cycloalkyl group, aryl group, and aralkyl group in Rc, Rd, and Re include the alkyl group, cycloalkyl group, aryl group, and aralkyl group mentioned in Rb.

The alkyl group, cycloalkyl group, aryl group and aralkyl group in Rb, Rc, Rd and Re may be substituted, and may have a linking group such as an oxygen atom or a sulfur atom in the alkyl chain. .
Preferred substituents that Rb, Rc, Rd and Re may have include a cycloalkyl group (preferably having 5 to 20 carbon atoms), an alkoxy group (preferably having 1 to 4 carbon atoms), a halogen atom (fluorine atom). , Chlorine atom, iodine atom), aryl group (preferably having 6 to 10 carbon atoms), alkenyl group (preferably having 2 to 6 carbon atoms), cyano group, hydroxy group, carboxy group, alkoxycarbonyl group (preferably having 2 carbon atoms) -15), nitro groups, acid-decomposable groups (tertiary ester groups, acetal ether groups, acetal ester groups, silyl ether groups, etc.) and the like.
As for the cyclic structure such as a cyclo ring and an aryl ring in these groups, examples of the substituent further include an alkyl group (preferably having a carbon number of 1 to 5).

  Among the sulfonic acids represented by the general formulas (Xa) to (Xg), the sulfonic acid represented by the general formula (Xa) or (Xb) is preferable, and the following general formula (Xa-1) or (Xb- The sulfonic acid represented by 1), and most preferably the sulfonic acid represented by the following general formula (Xb-2).

  Ax is a linking group having 3 or more carbon atoms, preferably a linking group having 3 to 20 carbon atoms, more preferably a linking group having no aromatic ring having 3 to 15 carbon atoms, most preferably 3 to 15 carbon atoms. A linear, branched, or cyclic alkylene group. This alkylene group may be substituted, and may have a linking group such as an oxygen atom or a sulfur atom in the alkyl chain.

  As Ax, for example, arylene groups such as phenylene group and naphthylene group, aralkylene groups such as benzylene group and xylylene group, preferably propylene group, dimethylmethylene group, butylene group, isobutylene group, hexylene group, cyclohexylene group, adamantylene group And straight chain, branched, and cyclic alkylene groups. More preferably, it is a propylene group.

Ay represents a single bond or an oxygen atom, preferably an oxygen atom.
Rg represents an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group. Examples of the alkyl group, cycloalkyl group, aryl group and aralkyl group in Rg include the alkyl group, cycloalkyl group, aryl group and aralkyl group mentioned in Rb. These alkyl group, cycloalkyl group, aryl group and aralkyl group may be substituted, and may have a linking group such as an oxygen atom or a sulfur atom in the alkyl chain.
Preferred substituents include cycloalkyl groups (preferably having 5 to 20 carbon atoms), alkoxy groups (preferably having 1 to 4 carbon atoms), halogen atoms (fluorine atoms, chlorine atoms, iodine atoms), aryl groups (preferably carbon atoms). 6 to 10), alkenyl group (preferably 2 to 6 carbon atoms), cyano group, hydroxy group, carboxy group, alkoxycarbonyl group (preferably 2 to 15 carbon atoms), nitro group, acid-decomposable group (tertiary ester) Group, acetal ether group, acetal ester group, silyl ether group, etc.).
As for the cyclic structure such as a cyclo ring and an aryl ring in these groups, examples of the substituent further include an alkyl group (preferably having a carbon number of 1 to 5).

Rg is preferably a linear or branched alkyl group or cycloalkyl group having 6 to 20 carbon atoms, a linear or branched alkyl group or cycloalkyl group having two or more ether linking groups having 7 to 20 carbon atoms, An alkyl group substituted with a cycloalkyl group having 7 to 20 carbon atoms, for example, a hexyl group, an octyl group, a dodecyl group, a hexadecyl group, a cyclohexyl group, an adamantyl group, a norbornyl group, an isobornyl group, a camphanyl group, a diphenyl group Examples include cyclopentyl group, α-pyrenyl group, tricyclodecanyl group, tetracyclodecanyl group, methoxyethoxyethyl group, methoxyethoxyethoxyethyl group, adamantylmethyl group, adamantylethyl group, cyclohexylmethyl group, cyclohexylethyl group and the like. .
Here, the sum of the carbon numbers of Ax and Rg is preferably 4 to 40, more preferably the sum of the carbon numbers of Ax and Rg is 6 to 30, more preferably 8 to 25, and most preferably 10 to 10. 20. By adjusting the carbon number of Ax and Rg, the acid diffusion in the resist film can be controlled, and the resolution, profile, and exposure margin are improved.

n5 represents an integer of 1 to 4.
n6 and n7 are each independently an integer of 1 to 4, preferably an integer of 2 to 4, more preferably 2 or 3, and most preferably 2.

  Total carbon of the sulfonic acid represented by the general formula (X), (X ′), (X ″), (Xa) to (Xg), (Xa-1), (Xb-1) or (Xb-2) The number is preferably 4 to 40, more preferably 6 to 30 carbon atoms, still more preferably 8 to 25 carbon atoms, and most preferably 10 to 20 carbon atoms.

  The number of fluorine atoms contained in the sulfonic acid represented by the general formula (X) is preferably 20 or less, more preferably 15 or less, and most preferably 9 or less. Moreover, when the number of fluorine atoms contained in the sulfonic acid represented by the general formula (X) is less than the number of hydrogen atoms, the hydrophilicity of the acid generator is improved and development defects are reduced.

  It is contained in the sulfonic acid represented by the general formula (X), (X ′), (X ″), (Xa) to (Xg), (Xa-1), (Xb-1) or (Xb-2). The number of aromatic rings is preferably 1 or less, and further preferably does not contain an aromatic ring.

  Specific examples of the sulfonic acid represented by the general formula (X) are shown below.

  Specific examples of the sulfonic acid represented by the more preferred general formula (Xa-1) or (Xb-1) are shown below.

(A) The compound that generates the sulfonic acid represented by the general formula (X) upon irradiation with actinic rays or radiation is selected from a sulfonium salt compound or an iodonium salt compound of the sulfonic acid represented by the general formula (X). 1 type or 1 type chosen from the ester compound of the sulfonic acid represented by general formula (X) is preferable, More preferably, it is a compound represented by either of general formula (A1)-(5).

As a compound which generate | occur | produces the sulfonic acid represented by general formula (Xa-1) or (Xb-1) by irradiation of actinic light or a radiation, it represents with general formula (Xa-1) or (Xb-1), for example. Examples thereof include sulfonium salt compounds or iodonium salt compounds of sulfonic acids, and ester compounds of sulfonic acids represented by the general formula (Xa-1) or (Xb-1), preferably the following general formula (A1) or In the compound represented by (A2), X- is a sulfonate anion represented by the general formula (Xa-1) or (Xb-1), or represented by the following general formulas (A3) to (A5) X ₁ in the compound the general formula (Xa-1) or (Xb-1) represented -SO ₃ H hydrogen atoms of the acid is taken as to be able to include the compounds bound as the monovalent group that .

In the general formula (A1), R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represents an organic group.
X ^- represents a general formula -SO ₃ H sulfonate anion resulting from removal of the hydrogen atom of the sulfonic acid (X).
The carbon number of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is generally 1-30, preferably 1-20.
It is also possible to form the two members ring structure of R ₂₀₁ to R _203, an oxygen atom, a sulfur atom, an ester bond, or an amide bond or a carbonyl group.
The two of the group formed by bonding of the R ₂₀₁ to R _203, there can be mentioned an alkylene group (e.g., butylene, pentylene).
Specific examples of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ include corresponding groups in the compounds (A1a), (A1b) and (A1c) described later.

In addition, the compound which has two or more structures represented by general formula (A1) may be sufficient. For example, the general formula at least one of R ₂₀₁ to R ₂₀₃ of a compound represented by (A1) is at least one bond with structure of R ₂₀₁ to R ₂₀₃ of another compound represented by formula (A1) It may be a compound.
More preferred components (A1) include compounds (A1a), (A1b), and (A1c) described below.

Compound (A1a) is at least one of the aryl groups R ₂₀₁ to R ₂₀₃ in formula (A1), arylsulfonium compound, i.e., a compound having arylsulfonium as a cation.
In the arylsulfonium compound, all of R _{201 to} R ₂₀₃ may be an aryl group, or a part of R _{201 to} R ₂₀₃ may be an aryl group with the remaining being an alkyl group or a cycloalkyl group.
Examples of the arylsulfonium compounds include triarylsulfonium compounds, diarylalkylsulfonium compounds, aryldialkylsulfonium compounds, and compounds in which the alkyl group in these compounds is a cycloalkyl group.
The aryl group of the arylsulfonium compound is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. When the arylsulfonium compound has two or more aryl groups, the two or more aryl groups may be the same or different.
The alkyl group or cycloalkyl group that the arylsulfonium compound has as necessary is preferably a linear or branched alkyl group having 1 to 15 carbon atoms or a cycloalkyl group having 3 to 15 carbon atoms, such as a methyl group, Examples thereof include an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a cyclopropyl group, a cyclobutyl group, and a cyclohexyl group.

Aryl group R ₂₀₁ to R _203, an alkyl group, the cycloalkyl group substituent which may be possessed by, a cycloalkyl group (for example, 3 to 15 carbon atoms), an aryl group (for example, 6 to 14 carbon atoms), alkoxy Examples thereof include a group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, and a phenylthio group. Moreover, about cyclic structures, such as an aryl ring and a cyclo ring in each group, an alkyl group (for example, C1-C15) can be further mentioned as a substituent.

Preferred substituents are linear or branched alkyl groups having 1 to 12 carbon atoms, cycloalkyl groups having 3 to 12 carbon atoms, and linear, branched or cyclic alkoxy groups having 1 to 12 carbon atoms, most preferably carbon. These are an alkyl group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms. The substituent may be substituted with any one of the three R _{201 to} R ₂₀₃ , or may be substituted with all three. Moreover, about an aryl group, an alkyl group (for example, C1-C15) can be mentioned as a substituent further. The substituent is preferably substituted at the p-position of the aryl group.

Next, the compound (A1b) will be described.
Compound (A1b) is a compound in the case where R _{201 to} R ₂₀₃ in formula (A1) each independently represents an organic group containing no aromatic ring. Here, the aromatic ring includes an aromatic ring containing a hetero atom.
The organic group having no aromatic ring as R ₂₀₁ to R ₂₀₃ generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
R _{201 to} R ₂₀₃ are each independently preferably an alkyl group (particularly an alkoxycarbonylmethyl group as a substituted alkyl group), a cycloalkyl group, a linear, branched or cyclic group which may have a double bond in the chain. It is an oxoalkyl group, an allyl group or a vinyl group, more preferably a linear, branched or cyclic 2-oxoalkyl group, and most preferably a linear or branched 2-oxoalkyl group.
The alkyl group as R _{201 to} R ₂₀₃ may be either linear or branched, and is preferably a linear or branched alkyl group having 1 to 20 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, Butyl group, pentyl group).
The cycloalkyl group as R ₂₀₁ to R ₂₀₃ may preferably be mentioned a cycloalkyl group having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl, norbornyl).

The 2-oxoalkyl group as R _{201 to} R ₂₀₃ may be linear, branched or cyclic, and preferably includes a group having> C═O at the 2-position of the above alkyl group. it can.
The alkoxy group in the alkoxycarbonylmethyl group as the substituted alkyl group for R _{201 to} R ₂₀₃ is preferably an alkyl group having 1 to 5 carbon atoms (methyl group, ethyl group, propyl group, butyl group, pentyl group). Can do.
Each group as R ₂₀₁ to R ₂₀₃ is a halogen atom, an alkoxy group (for example, 1 to 5 carbon atoms), a hydroxyl group, a cyano group, may be substituted by nitro group.
Two members out of R _{201 to} R ₂₀₃ may combine to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. The two of the group formed by bonding of the R ₂₀₁ to R _203, there can be mentioned an alkylene group (e.g., butylene, pentylene).

  The compound (A1c) is a compound represented by the following general formula (A1c), and is a compound having an arylacylsulfonium salt structure.

_R213 represents an aryl group, which may have a substituent, and is preferably a phenyl group or a naphthyl group. Examples of the substituent which may be possessed by the aryl group R _213, e.g., an alkyl group, an alkoxy group, an acyl group, a nitro group, a hydroxyl group, an alkoxycarbonyl group and a carboxy group.
R ₂₁₄ and R ₂₁₅ represents a hydrogen atom, an alkyl group or a cycloalkyl group.
Y ₂₀₁ and Y ₂₀₂ each independently represents an alkyl group, a cycloalkyl group, an aryl group or a vinyl group.

R ₂₁₃ and R ₂₁₄ may combine to form a ring structure, R ₂₁₄ and R ₂₁₅ may combine to form a ring structure, and Y ₂₀₁ and Y ₂₀₂ each combine to form a ring structure. It may be formed. These ring structures may contain an oxygen atom, a sulfur atom, an ester bond, or an amide bond.
The alkyl group as Y ₂₀₁ and Y ₂₀₂ may have a substituent, may have an oxo group in the alkylene chain, and is a linear or branched alkyl group having 1 to 20 carbon atoms (for example, (Methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, t-butyl group) are preferred.
Examples of the alkyl group having a substituent include an alkoxycarbonylalkyl group and a carboxyalkyl group. As the alkyl group having an oxo group,
A 2-oxoalkyl group can be mentioned.

Examples of the 2-oxoalkyl group include a group having> C═O at the 2-position of the alkyl group.
The alkoxycarbonyl group in the alkoxycarbonylalkyl group is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms.

The cycloalkyl group as Y ₂₀₁ and Y ₂₀₂ is preferably a cycloalkyl group having 3 to 20 carbon atoms (for example, a cyclopropyl group, a cyclobutyl group, a cyclohexyl group), and has a substituent similarly to the above alkyl group. The alkylene chain may have an oxo group.

The aryl group as Y ₂₀₁ and Y ₂₀₂ is preferably a phenyl group or a naphthyl group, more preferably a phenyl group.

Examples of the group formed by combining Y ₂₀₁ and Y ₂₀₂ include a butylene group and a pentylene group.

Each group as R ₂₁₄ , R ₂₁₅ , Y ₂₀₁ and Y ₂₀₂ may have a substituent, and examples of the substituent include an aryl group (for example, 6 to 15 carbon atoms), an alkoxy group (for example, carbon Mathematical formulas 1 to 15), halogen atoms, hydroxyl groups, phenylthio groups and the like. Moreover, about cyclic structures, such as an aryl ring and a cyclo ring in each group, an alkyl group (for example, C1-C15) can be further mentioned as a substituent.

Y ₂₀₁ and Y ₂₀₂ are preferably an alkyl group or cycloalkyl group having 4 or more carbon atoms, more preferably an alkyl group or cycloalkyl group having 4 to 16, and more preferably 4 to 12.
Further, at least one of R ₂₁₄ or ₂₁₅ is preferably an alkyl group or a cycloalkyl group, and more preferably both R ₂₁₄ and R ₂₁₅ are an alkyl group or a cycloalkyl group.

In general formula (A2), _R204 and _R205 each independently represents an aryl group, an alkyl group, or a cycloalkyl group.
The aryl group for R ₂₀₄ and R ₂₀₅ is preferably a phenyl group or a naphthyl group, more preferably a phenyl group.
The alkyl group and cycloalkyl group as R ₂₀₄ and R _205, preferably a linear or branched alkyl group having 1 to 10 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, pentyl group), Examples thereof include a cycloalkyl group having 3 to 10 carbon atoms (cyclopentyl group, cyclohexyl group, norbornyl group).

In general formula (A3),
A represents an alkylene group, an alkenylene group or an arylene group.
X ₁ represents a monovalent group by removing the —SO ₃ H hydrogen atom of the sulfonic acid of the general formula (X).

In formula (A4),
R ₂₀₈ represents an alkyl group, a cycloalkyl group, or an aryl group.
R ₂₀₉ represents an alkyl group, a cycloalkyl group, a cyano group or an alkoxycarbonyl group, preferably a halogen-substituted alkyl group, a cycloalkyl group or a cyano group.

The alkyl group and cycloalkyl group as R ₂₀₉ may be an oxoalkyl group having an oxo group in the alkylene chain.

In formula (A5),
R ₂₁₀ and R ₂₁₁ represent a hydrogen atom, an alkyl group, a cycloalkyl group, a cyano group, a nitro group or an alkoxycarbonyl group, and preferably a halogen-substituted alkyl group, a cycloalkyl group, a nitro group or a cyano group.

_R212 represents a hydrogen atom, an alkyl group, a cycloalkyl group, a cyano group or an alkoxycarbonyl group.

  Each group in the general formulas (A2) to (A5) may have a substituent. Examples of the substituent include an aryl group (for example, 6 to 15 carbon atoms) and an alkoxy group (for example, 1 carbon atom). -15), halogen atoms, hydroxyl groups, phenylthio groups and the like. Moreover, about cyclic structures, such as an aryl ring and a cyclo ring in each group, an alkyl group (for example, C1-C15) can be further mentioned as a substituent.

  Preferably, it is a compound represented by general formula (A1), More preferably, it is a compound represented by general formula (A1a)-(A1c).

  Specific examples of the preferred component (A) are given below.

  More preferred components (A) are listed below.

  The compound of the component (A) can be synthesized by synthesizing a sulfonic acid derivative represented by the general formula (X) and then salt-exchange with onium halide or onium carboxylate or esterifying with a hydroxyl group-containing compound. The derivative of the sulfonic acid represented by the general formula (X) can be prepared by using, for example, a method described in Tetrahedron Vol. 50, No. 35, (1994), p10459, etc. It can be synthesized by radical coupling using a secondary phosphine compound, hydrosulfite salt or peroxosulfate, and reducing with zinc, tetraphenyldisilane, tributyltin hydride or the like, if necessary.

(A) The compound of a component can be used individually by 1 type or in combination of 2 or more types.
The content of the compound (A) in the photosensitive composition of the present invention is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, based on the solid content of the composition. Preferably it is 1-7 mass%.

(Combination acid generator)
In the present invention, in addition to the component (A), a compound that decomposes upon irradiation with actinic rays or radiation to generate an acid may be used in combination.

  The amount of the photoacid generator that can be used in combination is usually 100/0 to 20/80, preferably 100/0 to 40/60, and more preferably in molar ratio (component (A) / other acid generator). 100/0 to 50/50.

  As such photoacid generators that can be used in combination, they are used in photocationic photoinitiators, photoinitiators of radical photopolymerization, photodecolorants of dyes, photochromic agents, or microresists. Known compounds that generate acids upon irradiation with actinic rays or radiation and mixtures thereof can be appropriately selected and used.

  Examples thereof include diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imide sulfonates, oxime sulfonates, diazodisulfones, disulfones, and o-nitrobenzyl sulfonates.

  Further, a group that generates an acid upon irradiation with these actinic rays or radiation, or a compound in which a compound is introduced into the main chain or side chain of the polymer, for example, US Pat. No. 3,849,137, German Patent No. 3914407. JP, 63-26653, JP, 55-164824, JP, 62-69263, JP, 63-146038, JP, 63-163452, JP, 62-153853, The compounds described in JP-A 63-146029 can be used.

  Furthermore, compounds capable of generating an acid by light described in US Pat. No. 3,779,778, European Patent 126,712 and the like can also be used.

  Among the compounds that can be used in combination and decompose upon irradiation with actinic rays or radiation to generate an acid, compounds represented by the following general formulas (ZI), (ZII), and (ZIII) are mentioned. it can.

In the general formula (ZI), R ₃₀₁ , R ₃₀₂ and R ₃₀₃ each independently represents an organic group.
The organic group as R ₃₀₁ , R ₃₀₂ and R ₃₀₃ generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
Two of R ₃₀₁ , R ₃₀₂ and R ₃₀₃ may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond or a carbonyl group.
Examples of the group formed by combining two of R ₃₀₁ , R _302, and R ₃₀₃ include an alkylene group (eg, butylene group, pentylene group).
Z ⁻ represents a non-nucleophilic anion.

Examples of the non-nucleophilic anion as Z ⁻ include a sulfonate anion, a carboxylate anion, a sulfonylimide anion, a bis (alkylsulfonyl) imide anion, and a tris (alkylsulfonyl) methyl anion.

  A non-nucleophilic anion is an anion that has an extremely low ability to cause a nucleophilic reaction, and is an anion that can suppress degradation over time due to an intramolecular nucleophilic reaction. This improves the temporal stability of the resist.

  Examples of the sulfonate anion include an alkyl sulfonate anion, an aryl sulfonate anion, and a camphor sulfonate anion.

  Examples of the carboxylate anion include an alkylcarboxylate anion, an arylcarboxylate anion, and an aralkylcarboxylate anion.

  The alkyl moiety in the alkyl sulfonate anion may be an alkyl group or a cycloalkyl group, and preferably an alkyl group having 1 to 30 carbon atoms and a cycloalkyl group having 3 to 30 carbon atoms, such as a methyl group or an ethyl group. Group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group Tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group and the like.

  The aryl group in the aryl sulfonate anion is preferably an aryl group having 6 to 14 carbon atoms, such as a phenyl group, a tolyl group, and a naphthyl group.

  The alkyl group, cycloalkyl group, and aryl group in the alkyl sulfonate anion and aryl sulfonate anion may have a substituent.

  Examples of such substituents include nitro groups, halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, iodine atoms), carboxyl groups, hydroxyl groups, amino groups, cyano groups, and alkoxy groups (preferably having 1 to 5 carbon atoms). ), A cycloalkyl group (preferably 3 to 15 carbon atoms), an aryl group (preferably 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably 2 to 7 carbon atoms), an acyl group (preferably 2 to 12 carbon atoms). ), An alkoxycarbonyloxy group (preferably having 2 to 7 carbon atoms), and the like. About the aryl group and ring structure which each group has, an alkyl group (preferably C1-C15) can further be mentioned as a substituent.

  Examples of the alkyl moiety in the alkylcarboxylate anion include those similar to the alkyl group and cycloalkyl group in the alkylsulfonate anion.

  Examples of the aryl group in the arylcarboxylate anion include the same aryl groups as in the arylsulfonate anion.

  The aralkyl group in the aralkyl carboxylate anion is preferably an aralkyl group having 6 to 12 carbon atoms, such as a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, and a naphthylmethyl group.

  The alkyl group, cycloalkyl group, aryl group and aralkyl group in the alkylcarboxylate anion, arylcarboxylate anion and aralkylcarboxylate anion may have a substituent. Examples of the substituent include an arylsulfonate anion. And the same halogen atom, alkyl group, cycloalkyl group, alkoxy group, alkylthio group and the like as in.

  Examples of the sulfonylimide anion include saccharin anion.

  The alkyl group in the bis (alkylsulfonyl) imide anion and tris (alkylsulfonyl) methyl anion is preferably an alkyl group having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, An isobutyl group, a sec-butyl group, a pentyl group, a neopentyl group, and the like can be given. These alkyl groups may have a substituent, and examples of the substituent include a halogen atom, an alkyl group substituted with a halogen atom, an alkoxy group, an alkylthio group, and the like, which are substituted with a fluorine atom. Alkyl groups are preferred.

  Examples of other non-nucleophilic anions include fluorinated phosphorus, fluorinated boron, and fluorinated antimony.

Examples of the non-nucleophilic anion of Z ⁻ include an alkanesulfonic acid anion in which the α-position of the sulfonic acid is substituted with a fluorine atom, an arylsulfonic acid anion substituted with a fluorine atom or a group having a fluorine atom, and an alkyl group having a fluorine atom And a tris (alkylsulfonyl) methide anion in which the alkyl group is substituted with a fluorine atom. The non-nucleophilic anion is particularly preferably a perfluoroalkanesulfonic acid anion having 4 to 8 carbon atoms, a benzenesulfonic acid anion having a fluorine atom, most preferably nonafluorobutanesulfonic acid anion, perfluorooctanesulfonic acid anion, penta Fluorobenzenesulfonate anion, 3,5-bis (trifluoromethyl) benzenesulfonate anion.

Specific examples of the organic group as R ₃₀₁ , R ₃₀₂ and R ₃₀₃ include corresponding groups in the compounds (Z1-1), (Z1-2) and (Z1-3) described later.

In addition, the compound which has two or more structures represented by general formula (ZI) may be sufficient. For example, at least one of R ₃₀₁ , R ₃₀₂ and R ₃₀₃ of the compound represented by the general formula (ZI) is at least one of R ₃₀₁ , R ₃₀₂ and R ₃₀₃ of the other compound represented by the general formula (ZI). A compound having a structure bonded to one may be used.

  More preferable examples of the (ZI) component include compounds (Z1-1), (Z1-2), and (Z1-3) described below.

The compound (Z1-1) is an arylsulfonium compound in which at least one of R ₃₀₁ , R ₃₀₂ and R _{303 in} the general formula (ZI) is an aryl group, that is, a compound having arylsulfonium as a cation.

In the arylsulfonium compound, all of R ₃₀₁ , R ₃₀₂ and R ₃₀₃ may be an aryl group, or a part of R _{201 to} R ₂₀₃ may be an aryl group and the rest may be an alkyl group or a cycloalkyl group.

  Examples of the arylsulfonium compound include a triarylsulfonium compound, a diarylalkylsulfonium compound, and an aryldialkylsulfonium compound.

  The aryl group of the arylsulfonium compound is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. When the arylsulfonium compound has two or more aryl groups, the two or more aryl groups may be the same or different.

  The alkyl group or cycloalkyl group that the arylsulfonium compound has as necessary is preferably a linear or branched alkyl group having 1 to 15 carbon atoms and a cycloalkyl group having 3 to 15 carbon atoms, such as a methyl group, Examples thereof include an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a cyclopropyl group, a cyclobutyl group, and a cyclohexyl group.

The aryl group, alkyl group, and cycloalkyl group of R _{301 to} R ₃₀₃ are an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms), an aryl group (for example, 6 to 14 carbon atoms). , An alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, or a phenylthio group may be substituted. Preferred substituents are linear or branched alkyl groups having 1 to 12 carbon atoms, cycloalkyl groups having 3 to 12 carbon atoms, and linear, branched or cyclic alkoxy groups having 1 to 12 carbon atoms, most preferably carbon. These are an alkyl group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms. The substituent may be substituted with any one of three R _{301 to} R ₃₀₃ , or may be substituted with all three. Further, when R _{301 to} R ₃₀₃ are an aryl group, the substituent is preferably substituted at the p-position of the aryl group.

Next, the compound (Z1-2) will be described.
Compound (Z1-2) is a compound in the case where R _{301 to} R ₃₀₃ in formula (ZI) each independently represents an organic group containing no aromatic ring. Here, the aromatic ring includes an aromatic ring containing a hetero atom.

The organic group not containing an aromatic ring as R _{301 to} R ₃₀₃ generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.

R _{301 to} R ₃₀₃ are each independently preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, more preferably a linear or branched 2-oxoalkyl group, 2-oxocycloalkyl group, alkoxy group. A carbonylmethyl group, most preferably a linear or branched 2-oxoalkyl group.

The alkyl group and cycloalkyl group represented by R _{301 to} R ₃₀₃ are preferably a linear or branched alkyl group having 1 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group), carbon Examples thereof include cycloalkyl groups of several 3 to 10 (cyclopentyl group, cyclohexyl group, norbornyl group). More preferred examples of the alkyl group include a 2-oxoalkyl group and an alkoxycarbonylmethyl group.

The 2-oxoalkyl group may be either linear or branched, and a group having> C = O at the 2-position of the above alkyl group is preferable.
The 2-oxocycloalkyl group is preferably a group having> C═O at the 2-position of the cycloalkyl group.

  The alkoxy group in the alkoxycarbonylmethyl group is preferably an alkyl group having 1 to 5 carbon atoms (methyl group, ethyl group, propyl group, butyl group, pentyl group).

R _{301 to} R ₃₀₃ may be further substituted with a halogen atom, an alkoxy group (eg, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group.

Two of R _{301 to} R ₃₀₃ may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. Examples of the group formed by combining two of R _{301 to} R ₃₀₃ include an alkylene group (eg, butylene group, pentylene group).

  The compound (Z1-3) is a compound represented by the following general formula (Z1-3), and is a compound having a phenacylsulfonium salt structure.

R _1c to R _5c each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group or a halogen atom.
R _6c and R _7c represent a hydrogen atom, an alkyl group, or a cycloalkyl group.
Rx and Ry each independently represents an alkyl group, a cycloalkyl group, an allyl group or a vinyl group.

Any two or more of R _{1c to} R _5c , and R _x and R _y may be bonded to each other to form a ring structure, and this ring structure includes an oxygen atom, a sulfur atom, an ester bond, and an amide bond. May be included.

Zc ⁻ represents a non-nucleophilic anion, and examples thereof include the same as the non-nucleophilic anion of Z ^{− in} formula (ZI).

The alkyl group as R _{1c to} R _{5c may} be either linear or branched, for example, an alkyl group having 1 to 20 carbon atoms, preferably a linear or branched alkyl group having 1 to 12 carbon atoms ( For example, methyl group, ethyl group, linear or branched propyl group, linear or branched butyl group, linear or branched pentyl group)
Examples of the cycloalkyl group include a cyclic alkyl group having 3 to 8 carbon atoms (for example, a cyclopentyl group and a cyclohexyl group).

The alkoxy group as R _{1c to} R _{5c may} be linear, branched or cyclic, for example, an alkoxy group having 1 to 10 carbon atoms, preferably a linear or branched alkoxy group having 1 to 5 carbon atoms. (For example, methoxy group, ethoxy group, linear or branched propoxy group, linear or branched butoxy group, linear or branched pentoxy group), C3-C8 cyclic alkoxy group (for example, cyclopentyloxy group, cyclohexyloxy group) ).

Preferably, any one of R _{1c to} R _5c is a linear or branched alkyl group, a cycloalkyl group, or a linear, branched or cyclic alkoxy group, and more preferably the sum of the carbon number of R _1c to R _5c is 2 to 2. 15. Thereby, solvent solubility improves more and generation | occurrence | production of a particle is suppressed at the time of a preservation | save.

_Examples of the alkyl group and cycloalkyl group as R _x and R _y include the same alkyl groups and cycloalkyl groups as R _{1c to} R _{5c, such} as a 2-oxoalkyl group and a 2-oxocycloalkyl group. An alkoxycarbonylmethyl group is more preferable.

Examples of the 2-oxoalkyl group and 2-oxocycloalkyl group include a group having> C═O at the 2-position of the alkyl group or cycloalkyl group as R _{1c to} R _5c .

Examples of the alkoxy group in the alkoxycarbonylmethyl group include the same alkoxy groups as R _{1c to} R _5c .

Examples of the group formed by combining R _x and R _y include a butylene group and a pentylene group.

R _x and R _y are preferably an alkyl group or cycloalkyl group having 4 or more carbon atoms, more preferably 6 or more, and still more preferably 8 or more alkyl groups or cycloalkyl groups.

In the general formulas (ZII) and (ZIII), R _{304 to} R ₃₀₇ each independently represents an aryl group, an alkyl group, or a cycloalkyl group.

The aryl group of R _{304 to} R ₃₀₇ is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group.

The alkyl group and cycloalkyl group as R _{304 to} R ₃₀₇ are preferably a linear or branched alkyl group having 1 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group), carbon A cyclic alkyl group (cyclopentyl group, cyclohexyl group, norbornyl group) of several 3 to 10 can be exemplified.

Examples of the substituent that R _{304 to} R ₃₀₇ may have include, for example, an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms), and an aryl group (for example, 6 to 6 carbon atoms). 15), alkoxy groups (for example, having 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, phenylthio groups and the like.

Z ⁻ represents a non-nucleophilic anion, and examples thereof include the same as the non-nucleophilic anion of Z ^{− in} formula (ZI).

  Among the compounds that can be used in combination and decomposed by irradiation with actinic rays or radiation, preferred compounds further include compounds represented by the following general formulas (ZIV), (ZV), and (ZVI). be able to.

In general formulas (ZIV) to (ZVI), Ar ₃ and Ar ₄ each independently represents an aryl group.

R ₃₀₆ , R ₃₀₇ and R ₃₀₈ represent an alkyl group or an aryl group.
A represents an alkylene group, an alkenylene group or an arylene group.

Of the compounds that may be used in combination and decompose upon irradiation with actinic rays or radiation to generate an acid, compounds represented by general formulas (ZI) to (ZIII) are more preferable.
Further, as a compound that decomposes upon irradiation with actinic rays or radiation that may be used in combination, a compound that generates a sulfonic acid having one sulfonic acid group is preferable, and a monovalent perfluoroalkanesulfone is more preferable. A compound that generates an acid, or a compound that generates an aromatic sulfonic acid substituted with a fluorine atom or a group containing a fluorine atom.

  Examples of particularly preferable compounds among the compounds that are decomposed by irradiation with actinic rays or radiation that may be used in combination are listed below.

[2] (B) Resin that decomposes by the action of an acid and increases the solubility in an alkaline developer (hereinafter also referred to as “component (B)”)
As a resin that is decomposed by the acid used in the positive photosensitive composition of the present invention and has increased solubility in an alkaline developer, the main chain or side chain of the resin, or both the main chain and side chain, It is a resin having a group that can be decomposed by an acid (hereinafter also referred to as “acid-decomposable group”). Among these, a resin having a group capable of decomposing with an acid in the side chain is more preferable.

A group preferable as a group that can be decomposed by an acid is a group in which a hydrogen atom of a —COOH group or —OH group is substituted with a group capable of leaving with an acid.
In the present invention, the acid-decomposable group is an acetal group or a tertiary ester group.

  The base resin in the case where these acid-decomposable groups are bonded as side chains is an alkali-soluble resin having —OH or —COOH groups in the side chains. For example, the alkali-soluble resin mentioned later can be mentioned.

  The alkali dissolution rate of these alkali-soluble resins is preferably 170 A / second or more as measured with 0.261 N tetramethylammonium hydroxide (TMAH) (23 ° C.). Particularly preferred is 330 A / second or more (A is angstrom).

  From this point of view, particularly preferred alkali-soluble resins are o-, m-, p-poly (hydroxystyrene) and copolymers thereof, hydrogenated poly (hydroxystyrene), halogen or alkyl-substituted poly (hydroxystyrene). Hydroxystyrene structural units such as a part of poly (hydroxystyrene), O-alkylated or O-acylated product, styrene-hydroxystyrene copolymer, α-methylstyrene-hydroxystyrene copolymer, hydrogenated novolak resin, etc. It is an alkali-soluble resin.

  Preferred examples of the repeating unit having an acid-decomposable group in the present invention include t-butoxycarbonyloxystyrene, 1-alkoxyethoxystyrene, (meth) acrylic acid tertiary alkyl ester and the like.

  Component (B) used in the present invention is decomposed with an acid into an alkali-soluble resin, as disclosed in European Patent No. 254853, JP-A-2-25850, JP-A-3-223860, JP-A-4-251259 and the like. It is possible to obtain an alkali-soluble resin monomer having a group capable of being decomposed or reacting with an acid-decomposable group by copolymerization with various monomers.

Although the specific example of (B) component used for this invention is shown below, it is not limited to these.
pt-butoxystyrene / p-hydroxystyrene copolymer,
p- (t-butoxycarbonyloxy) styrene / p-hydroxystyrene copolymer,
p- (t-butoxycarbonylmethyloxy) styrene / p-hydroxystyrene copolymer,
4- (t-butoxycarbonylmethyloxy) -3-methylstyrene / 4-hydroxy-3-methylstyrene copolymer,
p- (t-butoxycarbonylmethyloxy) styrene / p-hydroxystyrene (10% hydrogenated) copolymer,
m- (t-butoxycarbonylmethyloxy) styrene / m-hydroxystyrene copolymer,
o- (t-butoxycarbonylmethyloxy) styrene / o-hydroxystyrene copolymer,
p- (cumyloxycarbonylmethyloxy) styrene / p-hydroxystyrene copolymer,
Cumyl methacrylate / methyl methacrylate copolymer,
4-t-butoxycarbonylstyrene / dimethyl maleate copolymer,
Benzyl methacrylate / tetrahydropyranyl methacrylate,
p- (t-butoxycarbonylmethyloxy) styrene / p-hydroxystyrene / styrene copolymer,
pt-butoxystyrene / p-hydroxystyrene / fumaronitrile copolymer,
t-butoxystyrene / hydroxyethyl methacrylate copolymer,
Styrene / N- (4-hydroxyphenyl) maleimide / N- (4-t-butoxycarbonyloxyphenyl) maleimide copolymer,
p-hydroxystyrene / t-butyl methacrylate copolymer,
Styrene / p-hydroxystyrene / t-butyl methacrylate copolymer,
p-hydroxystyrene / t-butyl acrylate copolymer,
Styrene / p-hydroxystyrene / t-butyl acrylate copolymer,
p- (t-butoxycarbonylmethyloxy) styrene / p-hydroxystyrene / N-methylmaleimide copolymer,
t-butyl methacrylate / 1-adamantyl methyl methacrylate copolymer, p-hydroxystyrene / t-butyl acrylate / p-acetoxystyrene copolymer,
p-hydroxystyrene / t-butyl acrylate / p- (t-butoxycarbonyloxy) styrene copolymer,
p-hydroxystyrene / t-butyl acrylate / p- (t-butoxycarbonylmethyloxy) styrene copolymer,

  In the above specific example, tBu represents a t-butyl group.

  The content of the group that can be decomposed by an acid is determined by the number of groups (B) that can be decomposed by an acid in the resin and the number of alkali-soluble groups that are not protected by a group capable of leaving by an acid (S). B + S). The content of the group capable of decomposing with an acid is preferably 0.01 to 0.7, more preferably 0.05 to 0.50, and still more preferably 0.05 to 0.40.

  When the positive photosensitive composition of the present invention is irradiated with ArF excimer laser light, the resin of component (B) has a monocyclic or polycyclic alicyclic hydrocarbon structure and is decomposed by the action of an acid. A resin that increases the solubility in an alkali developer is preferable. In this case, the resin preferably has no aromatic group from the viewpoint of transparency to ArF light.

  As a resin that has a monocyclic or polycyclic alicyclic hydrocarbon structure, decomposes by the action of an acid, and increases its solubility in an alkaline developer (hereinafter also referred to as “alicyclic hydrocarbon-based acid-decomposable resin”) , At least selected from the group consisting of repeating units having a partial structure containing an alicyclic hydrocarbon represented by the following general formula (pI) to general formula (pVI) and repeating units represented by the following general formula (II-AB) It is preferable that it is resin containing 1 type.

(Wherein R ₁₁ represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a sec-butyl group, and Z represents an alicyclic hydrocarbon group together with a carbon atom. Represents the atomic group necessary to form.
R _{12 to} R ₁₆ each independently represents a linear or branched alkyl group or alicyclic hydrocarbon group having 1 to 4 carbon atoms, provided that at least one of R _{12 to} R ₁₄ , or Either R ₁₅ or R ₁₆ represents an alicyclic hydrocarbon group.
R _{17 to} R ₂₁ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or an alicyclic hydrocarbon group, provided that at least one of R _{17 to} R ₂₁ Represents an alicyclic hydrocarbon group. Further, either R ₁₉ or R ₂₁ represents a linear or branched alkyl group or alicyclic hydrocarbon group having 1 to 4 carbon atoms.
R _{22 to} R ₂₅ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or an alicyclic hydrocarbon group, provided that at least one of R _{22 to} R ₂₅ Represents an alicyclic hydrocarbon group. R ₂₃ and R ₂₄ may be bonded to each other to form a ring. )

In formula (II-AB):
R ₁₁ ′ and R ₁₂ ′ each independently represents a hydrogen atom, a cyano group, a halogen atom or an alkyl group.
Z ′ represents an atomic group for forming an alicyclic structure containing two bonded carbon atoms (C—C).

  The general formula (II-AB) is more preferably the following general formula (II-A) or general formula (II-B).

In formulas (II-A) and (II-B):
R ₁₃ ′ to R ₁₆ ′ each independently represents a hydrogen atom, a halogen atom, a cyano group, —COOH, —COOR ₅ , a group that decomposes by the action of an acid, —C (═O) —XA′—R. ₁₇ ′ represents an alkyl group or a cyclic hydrocarbon group.
Wherein, R ₅ represents an alkyl group, cyclic hydrocarbon group, or -Y group shown below.
X represents an oxygen atom, a sulfur atom, -NH -, - NHSO ₂ - or an -NHSO ₂ NH-.
A ′ represents a single bond or a divalent linking group.
Further, at least two of R ₁₃ ′ to R ₁₆ ′ may be bonded to form a ring. n represents 0 or 1.
R ₁₇ ′ represents —COOH, —COOR ₅ , —CN, a hydroxyl group, an alkoxy group, —CO—NH—R ₆ , —CO—NH—SO ₂ —R ₆ or the following —Y group.
R ₆ represents an alkyl group or a cyclic hydrocarbon group.

  The -Y group;

(In the —Y group, R ₂₁ ′ to R ₃₀ ′ each independently represents a hydrogen atom or an alkyl group. A and b represent 1 or 2.)

In the general formulas (pI) to (pVI), the alkyl group in R _{12 to} R ₂₅ represents a linear or branched alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a t-butyl group.

  In addition, examples of the substituent that each alkyl group and alkoxy group may have include an alkoxy group having 1 to 4 carbon atoms, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), an acyl group, and an acyloxy group. Group, cyano group, hydroxyl group, carboxy group, alkoxycarbonyl group, nitro group and the like.

The alicyclic hydrocarbon group in R _{11 to} R _{25 or} the alicyclic hydrocarbon group formed by Z and a carbon atom may be monocyclic or polycyclic. Specific examples include groups having a monocyclo, bicyclo, tricyclo, tetracyclo structure or the like having 5 or more carbon atoms. The carbon number is preferably 6-30, and particularly preferably 7-25. These alicyclic hydrocarbon groups may have a substituent.

  Preferred examples of the alicyclic hydrocarbon group include an adamantyl group, a noradamantyl group, a decalin residue, a tricyclodecanyl group, a tetracyclododecanyl group, a norbornyl group, a cedrol group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Group, cyclodecanyl group, and cyclododecanyl group. More preferred are an adamantyl group, a decalin residue, a norbornyl group, a cedrol group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecanyl group, and a cyclododecanyl group.

  Examples of the substituent for these alicyclic hydrocarbon groups include an alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group, and an alkoxycarbonyl group. The alkyl group is preferably a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group, and more preferably selected from the group consisting of a methyl group, an ethyl group, a propyl group, and an isopropyl group. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Examples of the substituent that the alkyl group, alkoxy group, alkoxycarbonyl group and the like may further have include a hydroxyl group, a halogen atom, and an alkoxy group.

  The structures represented by the general formulas (pI) to (pVI) in the resin can be used for protecting alkali-soluble groups. Examples of the alkali-soluble group include various groups known in this technical field.

  Specific examples include a carboxylic acid group, a sulfonic acid group, a phenol group, and a thiol group, and a carboxylic acid group and a sulfonic acid group are preferable.

  As the alkali-soluble group protected by the structure represented by the general formulas (pI) to (pVI) in the above resin, the hydrogen atom of the carboxyl group is preferably substituted with the structure represented by the general formula (pI) to (pVI). Structure.

  As the repeating unit having an alkali-soluble group protected by the structure represented by the general formulas (pI) to (pVI), a repeating unit represented by the following general formula (pA) is preferable.

Here, R represents a hydrogen atom, a halogen atom, or a linear or branched alkyl group having 1 to 4 carbon atoms. A plurality of R may be the same or different.
A is a single bond, a group selected from the group consisting of an alkylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a sulfonamide group, a urethane group, or a urea group, or a combination of two or more groups. Represents.
Ra represents any group of the above formulas (pI) to (pVI).

  The repeating unit represented by the general formula (pA) is most preferably a repeating unit of 2-alkyl-2-adamantyl (meth) acrylate and dialkyl (1-adamantyl) methyl (meth) acrylate.

  Specific examples of the repeating unit represented by the general formula (pA) are shown below.

In the general formula (II-AB), R ₁₁ ′ and R ₁₂ ′ each independently represent a hydrogen atom, a cyano group, a halogen atom, or an alkyl group.
Z ′ represents an atomic group for forming an alicyclic structure containing two bonded carbon atoms (C—C).

Examples of the halogen atom in R ₁₁ ′ and R ₁₂ ′ include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom.

As the alkyl group in R ₁₁ ′, R ₁₂ ′, and R ₂₁ ′ to R ₃₀ ′, a linear or branched alkyl group having 1 to 10 carbon atoms is preferable, and more preferably 1 to 6 carbon atoms. It is a linear or branched alkyl group, more preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, or a t-butyl group.

Examples of the further substituent in the above alkyl group include a hydroxyl group, a halogen atom, a carboxyl group, an alkoxy group, an acyl group, a cyano group, and an acyloxy group. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Examples of the acyl group include a formyl group and an acetyl group, and examples of the acyloxy group include an acetoxy group.

  The atomic group for forming the alicyclic structure of Z ′ is an atomic group that forms a repeating unit of an alicyclic hydrocarbon which may have a substituent in a resin, and among them, a bridged type alicyclic group. An atomic group for forming a bridged alicyclic structure forming a cyclic hydrocarbon repeating unit is preferred.

Examples of the skeleton of the alicyclic hydrocarbon formed include the same alicyclic hydrocarbon groups as R _{11 to} R _{25 in} the general formulas (pI) to (pVI).

The alicyclic hydrocarbon skeleton may have a substituent. Examples of such a substituent include R ₁₃ ′ to R ₁₆ ′ in the general formula (II-A) or (II-B).

  Among the repeating units having the bridged alicyclic hydrocarbon, the repeating unit represented by the general formula (II-A) or (II-B) is more preferable.

In the alicyclic hydrocarbon-based acid-decomposable resin according to the present invention, the acid-decomposable group may be contained in the aforementioned —C (═O) —XA′—R ₁₇ ′, or may be represented by the general formula (II- AB) may be included as a substituent for Z ′.

The structure of the acid-decomposable group is represented by —C (═O) —X ₁ —R ₀ .
In the formula, R ₀ is a tertiary alkyl group such as t-butyl group or t-amyl group, isobornyl group, 1-ethoxyethyl group, 1-butoxyethyl group, 1-isobutoxyethyl group, 1-cyclohexyloxy. 1-alkoxyethyl group such as ethyl group, 1-methoxymethyl group, alkoxymethyl group such as 1-ethoxymethyl group, 3-oxoalkyl group, tetrahydropyranyl group, tetrahydrofuranyl group, trialkylsilyl ester group, 3- An oxocyclohexyl ester group, a 2-methyl-2-adamantyl group, a mevalonic lactone residue and the like can be mentioned. X ₁ has the same meaning as X above.

Examples of the halogen atom in R ₁₃ ′ to R ₁₆ ′ include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom.

The alkyl group in R ₅ , R ₆ and R ₁₃ ′ to R ₁₆ ′ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, more preferably a linear chain having 1 to 6 carbon atoms. Or a branched alkyl group, more preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, or a t-butyl group.

Examples of the cyclic hydrocarbon group in R ₅ , R ₆ and R ₁₃ ′ to R ₁₆ ′ include a cyclic alkyl group and a bridged hydrocarbon group, such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, 2- List methyl-2-adamantyl group, norbornyl group, boronyl group, isobornyl group, tricyclodecanyl group, dicyclopentenyl group, nobornane epoxy group, menthyl group, isomenthyl group, neomenthyl group, tetracyclododecanyl group, etc. Can do.

Examples of the ring formed by combining at least two of R ₁₃ ′ to R ₁₆ ′ include rings having 5 to 12 carbon atoms such as cyclopentene, cyclohexene, cycloheptane, and cyclooctane.

Examples of the alkoxy group for R ₁₇ ′ include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.

  Examples of further substituents in the alkyl group, cyclic hydrocarbon group, and alkoxy group include a hydroxyl group, a halogen atom, a carboxyl group, an alkoxy group, an acyl group, a cyano group, an acyloxy group, an alkyl group, and a cyclic hydrocarbon group. Can do. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group. Examples of the acyl group include a formyl group and an acetyl group. Examples thereof include an acetoxy group.

  Examples of the alkyl group and cyclic hydrocarbon group include those listed above.

  The divalent linking group for A ′ is one or two selected from the group consisting of an alkylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a sulfonamide group, a urethane group, and a urea group. Combinations of the above groups can be mentioned.

  In the alicyclic hydrocarbon-based acid-decomposable resin according to the present invention, the group decomposed by the action of an acid has a partial structure containing the alicyclic hydrocarbon represented by the general formula (pI) to the general formula (pVI). It can be contained in at least one type of repeating unit among the repeating unit having, the repeating unit represented by the general formula (II-AB), and the repeating unit of the copolymerization component described later.

Various substituents of R ₁₃ ′ to R ₁₆ ′ in the general formula (II-A) or the general formula (II-B) are atomic groups for forming an alicyclic structure in the general formula (II-AB). Or it becomes a substituent of atomic group Z for forming a bridged alicyclic structure.

  Specific examples of the repeating unit represented by the general formula (II-A) or the general formula (II-B) include the following, but the present invention is not limited to these specific examples.

  The alicyclic hydrocarbon-based acid-decomposable resin of the present invention preferably has a lactone group, and more preferably any of the following general formulas (Lc) and general formulas (V-1) to (V-5) below. It has a repeating unit having a group having a lactone structure represented, and the group having a lactone structure may be directly bonded to the main chain.

In the general formula (Lc), Ra _1, Rb _1, Rc _1, Rd ₁ and Re ₁ each independently represent a hydrogen atom or an alkyl group. m and n each independently represents an integer of 0 to 3, and m + n is 2 or more and 6 or less.

In the general formulas (V-1) to (V-5), R _{1b to} R _5b each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylsulfonylimino group, or an alkenyl group. Represents. Two of R _{1b to} R _5b may combine to form a ring.

R _{1 to} Re ₁ alkyl groups in general formula (Lc) and R _{1b to} R _5b alkyl groups, alkoxy groups, alkoxycarbonyl groups, alkyl groups in general formulas (V-1) to (V-5) Examples of the alkyl group in the sulfonylimino group include linear and branched alkyl groups, which may have a substituent.

As the repeating unit having a group having a lactone structure represented by general formula (Lc) or any one of general formulas (V-1) to (V-5), the above general formula (II-A) or (II- B) wherein at least one of R ₁₃ ′ to R ₁₆ ′ has a group represented by general formula (Lc) or general formula (V-1) to (V-5) (for example, R in —COOR ₅ ) ₅ represents a group represented by general formula (Lc) or general formulas (V-1) to (V-5)), or a repeating unit represented by the following general formula (AI).

In general formula (AI), R _b0 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms.

Examples of the halogen atom for R _b0 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. R _b0 is preferably a hydrogen atom.

A _b represents a single bond, an ether group, an ester group, a carbonyl group, an alkylene group, or a divalent group obtained by combining these.

  V represents a group represented by any one of the general formula (Lc) and the general formulas (V-1) to (V-5).

  Specific examples of the repeating unit having a group having a lactone structure are shown below, but the present invention is not limited thereto.

  The alicyclic hydrocarbon-based acid-decomposable resin of the present invention preferably contains a repeating unit having a group represented by the following general formula (VII).

In general formula (VII), R ₂ c to R ₄ c each independently represents a hydrogen atom or a hydroxyl group. However, at least one of R ₂ c to R ₄ c represents a hydroxyl group.

  The group represented by the general formula (VII) is preferably a dihydroxy form or a monohydroxy form, and more preferably a dihydroxy form.

As the repeating unit having a group represented by the general formula (VII), at least one of R ₁₃ ′ to R ₁₆ ′ in the general formula (II-A) or (II-B) is the above general formula (VII ) (For example, R _{5 in} —COOR ₅ represents a group represented by the general formula (VII)), or a repeating unit represented by the following general formula (AII). it can.

In general formula (AII), R ₁ c represents a hydrogen atom or a methyl group.
R ₂ c to R ₄ c each independently represents a hydrogen atom or a hydroxyl group. However, at least one of R ₂ c to R ₄ c represents a hydroxyl group. _{Two of} R ₂ c to R ₄ c are preferably hydroxyl groups.

  Although the specific example of the repeating unit which has a structure represented by general formula (AII) below is given, it is not limited to these.

  The alicyclic hydrocarbon-based acid-decomposable resin of the present invention may contain a repeating unit represented by the following general formula (VIII).

In the general formula (VIII), Z ₂ represents —O— or —N (R ₄₁ ) —. R ₄₁ represents a hydrogen atom, a hydroxyl group, an alkyl group, or —OSO ₂ —R ₄₂ . R ₄₂ represents an alkyl group, a cycloalkyl group or a camphor residue. The alkyl group of R ₄₁ and R ₄₂ may be substituted with a halogen atom (preferably a fluorine atom) or the like.

  Examples of the repeating unit represented by the general formula (VIII) include the following specific examples, but are not limited thereto.

  In addition to the above repeating structural units, the alicyclic hydrocarbon-based acid-decomposable resin of the present invention has a dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and resolving power that is a general necessary characteristic of a resist. Various repeating structural units can be contained for the purpose of adjusting heat resistance, sensitivity, and the like.

  Examples of such a repeating structural unit include, but are not limited to, repeating structural units corresponding to the following monomers.

Thereby, performance required for the alicyclic hydrocarbon-based acid-decomposable resin, in particular,
(1) Solubility in coating solvent,
(2) Film formability (glass transition point),
(3) Alkali developability,
(4) Membrane slip (hydrophobic, alkali-soluble group selection),
(5) Adhesion of unexposed part to substrate,
(6) Dry etching resistance,
Etc. can be finely adjusted.

  As such a monomer, for example, a compound having one addition polymerizable unsaturated bond selected from acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, etc. Etc.

  In addition, any addition-polymerizable unsaturated compound that can be copolymerized with monomers corresponding to the above various repeating structural units may be copolymerized.

  In alicyclic hydrocarbon-based acid-decomposable resins, the molar ratio of each repeating structural unit is the resist's dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and resolution that is a general required performance of resists. In order to adjust heat resistance, sensitivity, etc., it is set appropriately.

Preferred embodiments of the alicyclic hydrocarbon-based acid-decomposable resin of the present invention include the following.
(1) Containing a repeating unit having a partial structure containing an alicyclic hydrocarbon represented by the general formulas (pI) to (pVI) (side chain type)
(2) Containing repeating units represented by general formula (II-AB) (main chain type)
However, in (2), for example, the following can be further mentioned.
(3) A repeating unit represented by the general formula (II-AB), a maleic anhydride derivative and a (meth) acrylate structure (hybrid type)
In the alicyclic hydrocarbon-based acid-decomposable resin, the content of the repeating unit having an acid-decomposable group is preferably 10 to 60 mol%, more preferably 20 to 50 mol%, still more preferably 25 in all repeating structural units. -40 mol%.

  In the alicyclic hydrocarbon-based acid-decomposable resin, the content of the repeating unit having a partial structure containing the alicyclic hydrocarbon represented by the general formulas (pI) to (pVI) is 30 to 70 in all the repeating structural units. The mol% is preferable, more preferably 35 to 65 mol%, and still more preferably 40 to 60 mol%.

  In the alicyclic hydrocarbon-based acid-decomposable resin, the content of the repeating unit represented by the general formula (II-AB) is preferably 10 to 60 mol%, more preferably 15 to 55 mol% in all repeating structural units. More preferably, it is 20-50 mol%.

  In addition, the content of the repeating structural unit based on the monomer of the further copolymer component in the resin can also be appropriately set according to the performance of the desired resist. 99 mol% with respect to the total number of moles of the repeating structural unit having a partial structure containing the alicyclic hydrocarbon represented by (pVI) and the repeating unit represented by the above general formula (II-AB) The following is preferable, More preferably, it is 90 mol% or less, More preferably, it is 80 mol% or less.

When the composition of the present invention is for ArF exposure, the resin preferably has no aromatic group from the viewpoint of transparency to ArF light.

  The acid-decomposable resin used in the present invention preferably contains a repeating unit having two or more hydroxyl groups.

The repeating unit having two or more hydroxyl groups is not particularly limited, but a repeating unit containing a structure in which two or more hydroxyl groups are substituted on a monocyclic or polycyclic hydrocarbon group having 5 to 30 carbon atoms is preferable. Preferably, it is a repetition containing a structure in which two or more hydroxyl groups are substituted on a polycyclic hydrocarbon group.
Examples of the cyclic hydrocarbon group substituted with a hydroxyl group include monocyclic cyclic hydrocarbon groups such as cyclopentane and cyclohexane, and polycyclic cyclic hydrocarbon groups having a bicyclo, tricyclo or tetracyclo structure such as norbornane and adamantane.
Any two or more hydroxyl groups may be substituted with each other, but those substituted at the position of 1,2- or 1,3-diol structure are preferred.
Examples of the repeating unit having two or more hydroxyl groups include a repeating unit in which at least two of R ₂ c to R ₄ c are hydroxyl groups in the repeating unit represented by the general formula (AII). .

  In particular, as the repeating unit having two or more hydroxyl groups, a repeating unit containing the structure of the formula (IA) is preferable.

  Rx represents a hydroxyl group, a hydrogen atom, an alkyl group, an alkoxy group or an alkoxycarbonyl group.

  As the repeating unit containing the structure of the formula (IA), a repeating unit represented by the formula (IB) is preferable.

Rx represents a hydroxyl group, a hydrogen atom, an alkyl group, an alkoxy group or an alkoxycarbonyl group.
Ry represents a hydrogen atom, an alkyl group, a fluorine atom or a fluoroalkyl group.

The alkyl group as Rx and Ry may have a substituent, and preferably has 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, for example, a methyl group or an ethyl group.
The alkoxy group as Rx may have a substituent, and preferably has 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, such as a methoxy group and an ethoxy group.
The alkoxycarbonyl group as Rx may have a substituent, and preferably has 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms, such as a methoxycarbonyl group and an ethoxycarbonyl group.
The fluoroalkyl group as Ry may have a substituent, preferably having 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, such as a trifluoromethyl group or a perfluoroethyl group. it can.
Examples of the substituent include a hydroxyl group, a cyano group, a halogen atom, a carboxyl group, and an alkoxy group (preferably having 1 to 5 carbon atoms).

  Rx is preferably a hydroxyl group.

  Although a specific example is given below, it is not limited to these.

The acid-decomposable resin is preferably a resin containing at least one repeating unit derived from methacrylic acid ester or methacrylic acid and at least one repeating unit derived from acrylic acid ester or acrylic acid.
These repeating units may be any repeating unit as long as they are a repeating unit contained in an acid-decomposable resin, the above-mentioned repeating unit having an acid-decomposable group, a repeating unit having two or more hydroxyl groups, It may be a repeating unit having a lactone structure, a repeating unit having a cyclic hydrocarbon structure, or another repeating unit.
The ratio (molar ratio) of the acrylic acid ester or the repeating unit derived from acrylic acid to the repeating unit derived from the acrylic acid ester and methacrylic acid ester or methacrylic acid is usually 10/90 to 90/10, preferably 20/80 to 80/20, more preferably 30/70 to 70/30, most preferably 40/60 to 60/40.

The alicyclic hydrocarbon-based acid-decomposable resin used in the present invention can be synthesized according to a conventional method (for example, radical polymerization). For example, as a general synthesis method, monomer species are charged into a reaction vessel in a batch or in the course of reaction, and if necessary, a reaction solvent such as ethers such as tetrahydrofuran, 1,4-dioxane, diisopropyl ether, methyl ethyl ketone, A ketone such as methyl isobutyl ketone, an ester solvent such as ethyl acetate, and the composition of the present invention such as propylene glycol monomethyl ether acetate described below are dissolved in a solvent that dissolves uniformly and then nitrogen, argon, etc. Polymerization is started using a commercially available radical initiator (azo initiator, peroxide, etc.) as necessary under an inert gas atmosphere. If desired, an initiator is added or added in portions, and after completion of the reaction, it is put into a solvent and a desired polymer is recovered by a method such as powder or solid recovery. The concentration of the reaction is 20% by mass or more, preferably 30% by mass or more, and more preferably 40% by mass or more. The reaction temperature is 10 ° C to 150 ° C, preferably 30 ° C to 120 ° C, more preferably 50-100 ° C.

  When the composition of the present invention is used for the upper resist of the multilayer resist, the resin as the component (B) preferably has a silicon atom.

  As the resin having a silicon atom and decomposing by the action of an acid to increase the solubility in an alkaline developer, any of resins having a silicon atom in at least one of a main chain and a side chain can be used. Examples of the resin having a siloxane structure in the side chain of the resin include, for example, an olefin monomer having a silicon atom in the side chain, maleic anhydride and a (meth) acrylic acid monomer having an acid-decomposable group in the side chain. Mention may be made of copolymers.

  As the resin having a silicon atom, a resin containing a trialkylsilyl structure or a monocyclic or polycyclic siloxane structure is preferable, and a resin containing a repeat having a structure represented by SS-1 to SS-4 below. More preferably, (meth) acrylate repeating units having a structure represented by SS-1 to SS-4, or vinyl or allyl repeating units having a structure represented by SS-1 to SS-4 is there.

  As the resin having a silicon atom, a resin containing a trialkylsilyl structure or a monocyclic or polycyclic siloxane structure is preferable, and a resin containing a repeat having a structure represented by SS-1 to SS-4 below. More preferably, (meth) acrylate repeating units having a structure represented by SS-1 to SS-4, or vinyl or allyl repeating units having a structure represented by SS-1 to SS-4 is there.

When irradiating the positive photosensitive composition of the present invention with F ₂ excimer laser light, the resin of component (B) has a structure in which fluorine atoms are substituted on the main chain and / or side chains of the polymer skeleton, In addition, a resin that decomposes by the action of an acid and increases the solubility in an alkali developer (hereinafter also referred to as a fluorine group-containing resin) is preferable, and more preferably, a hydroxyl group substituted with a fluorine atom or a fluoroalkyl group at the 1-position or the 1-position Is a resin containing a group in which a hydroxyl group substituted with a fluorine atom or a fluoroalkyl group is protected with an acid-decomposable group, and most preferably the hexafluoro-2-propanol structure or the hydroxyl group of hexafluoro-2-propanol is protected with an acid-decomposable group The resin containing the structure. By introducing fluorine atoms, it is possible to improve transparency to far ultraviolet light, particularly F ₂ (157 nm) light.

  (B) Preferred examples of the fluorine group-containing resin in the acid-decomposable resin include resins having at least one repeating unit represented by the following general formulas (FA) to (FG).

In the general formula,
R _{100 to} R ₁₀₃ each represent a hydrogen atom, a fluorine atom, an alkyl group or an aryl group.
R ₁₀₄ and R ₁₀₆ are each a hydrogen atom, a fluorine atom or an alkyl group, and at least one of R ₁₀₄ and R ₁₀₆ is a fluorine atom or a fluoroalkyl group. R ₁₀₄ and R ₁₀₆ are preferably both trifluoromethyl groups.
R ₁₀₅ is a hydrogen atom, an alkyl group, an acyl group, an alkoxycarbonyl group or a group that decomposes under the action of an acid.
A ₁ is a single bond, a divalent linking group, for example, a linear, branched, cyclic alkylene group, alkenylene group, arylene group, —OCO—, —COO—, or —CON (R ₂₄ ) —, and of these It is a linking group containing a plurality. R ₂₄ is a hydrogen atom or an alkyl group.
R ₁₀₇ and R ₁₀₈ are each a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group or a group that decomposes under the action of an acid.
R ₁₀₉ is a hydrogen atom, an alkyl group, or a group that decomposes under the action of an acid.
b is 0, 1 or 2;

  The repeating units represented by the general formulas (FA) to (FG) contain at least one, preferably three or more fluorine atoms per one repeating unit.

  In the general formulas (FA) to (FG), the alkyl group is, for example, an alkyl group having 1 to 8 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, an n-butyl group, Preferred examples include sec-butyl group, hexyl group, 2-ethylhexyl group, and octyl group.

  The cycloalkyl group may be monocyclic or polycyclic. The monocyclic type has 3 to 8 carbon atoms, and preferred examples include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. The polycyclic type has 6 to 20 carbon atoms, and includes, for example, an adamantyl group, norbornyl group, isobornyl group, camphanyl group, dicyclopentyl group, α-pinel group, tricyclodecanyl group, tetocyclododecyl group, An androstanyl group etc. can be mentioned preferably. However, the carbon atom in the monocyclic or polycyclic cycloalkyl group may be substituted with a heteroatom such as an oxygen atom.

  Examples of the fluoroalkyl group include those having 1 to 12 carbon atoms, specifically, a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluorohexyl group, and a perfluorooctyl group. A perfluorooctylethyl group, a perfluorododecyl group and the like can be preferably exemplified.

  As the aryl group, for example, an aryl group having 6 to 15 carbon atoms, specifically, phenyl group, tolyl group, dimethylphenyl group, 2,4,6-trimethylphenyl group, naphthyl group, anthryl group, Preferable examples include 9,10-dimethoxyanthryl group.

  As the aralkyl group, for example, an aralkyl group having 7 to 12 carbon atoms, specifically, a benzyl group, a phenethyl group, a naphthylmethyl group, and the like can be preferably exemplified.

  As an alkenyl group, it is a C2-C8 alkenyl group, for example, Specifically, a vinyl group, an allyl group, a butenyl group, and a cyclohexenyl group can be mentioned preferably.

  Examples of the alkoxy group include an alkoxy group having 1 to 8 carbon atoms, and specifically include a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, a butoxy group, a pentoxy group, an allyloxy group, and an octoxy group. Preferred examples include groups.

  As the acyl group, for example, an acyl group having 1 to 10 carbon atoms, specifically, a formyl group, an acetyl group, a propanoyl group, a butanoyl group, a pivaloyl group, an octanoyl group, a benzoyl group and the like can be preferably exemplified. it can.

  The acyloxy group is preferably an acyloxy group having 2 to 12 carbon atoms, and examples thereof include an acetoxy group, a propionyloxy group, and a benzoyloxy group.

  The alkynyl group is preferably an alkynyl group having 2 to 5 carbon atoms, and examples thereof include an ethynyl group, a propynyl group, and a butynyl group.

  Examples of the alkoxycarbonyl group include i-propoxycarbonyl group, t-butoxycarbonyl group, t-amyloxycarbonyl group, 1-methyl-1-cyclohexyloxycarbonyl group and the like, preferably secondary, more preferably tertiary alkoxycarbonyl. Groups.

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

  Examples of the alkylene group preferably include those having 1 to 8 carbon atoms such as a methylene group, ethylene group, propylene group, butylene group, hexylene group and octylene group which may have a substituent.

  The alkenylene group is preferably an alkenylene group having 2 to 6 carbon atoms such as an optionally substituted ethenylene group, propenylene group, butenylene group.

  Preferred examples of the cycloalkylene group include those having 5 to 8 carbon atoms such as a cyclopentylene group and a cyclohexylene group which may have a substituent.

  The arylene group is preferably an arylene group having 6 to 15 carbon atoms such as an optionally substituted phenylene group, tolylene group or naphthylene group.

  These groups may have a substituent. Examples of the substituent include activities such as alkyl group, cycloalkyl group, aryl group, amino group, amide group, ureido group, urethane group, hydroxyl group, and carboxyl group. Those having hydrogen, halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom), alkoxy groups (methoxy group, ethoxy group, propoxy group, butoxy group, etc.), thioether group, acyl group (acetyl group, propanoyl group) Benzoyl group, etc.), acyloxy group (acetoxy group, propanoyloxy group, benzoyloxy group etc.), alkoxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group etc.), cyano group, nitro group, etc. .

  Here, examples of the alkyl group, cycloalkyl group, and aryl group include those described above, but the alkyl group may be further substituted with a fluorine atom or a cycloalkyl group.

Fluorine-containing are contained in the resin of the present invention, examples of the group in a disassembled alkali solubility by the action of an acid, for example, _{-O-C (R 36) (} R 37) (R 38), - O-C (R 36 ) (R ₃₇ ) (OR ₃₉ ), —O—COO—C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), —O—C (R ₀₁ ) (R ₀₂ ) COO—C (R ₃₆ ) (R _{37) (R 38), -} COO-C (R 36) (R 37) (R 38), - COO-C (R 36) (R 37) (OR 39) , and the like.

R _{36 to} R ₃₉ represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group, and R ₀₁ and R ₀₂ are a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group or an aryl group. Represents.

  Preferable specific examples include t-butyl group, t-amyl group, 1-alkyl-1-cyclohexyl group, 2-alkyl-2-adamantyl group, 2-adamantyl-2-propyl group, 2- (4-methylcyclohexyl). ) Ether group or ester group of tertiary alkyl group such as 2-propyl group, acetal group or acetal ester group such as 1-alkoxy-1-ethoxy group, tetrahydropyranyl group, t-alkyl carbonate group, t-alkyl A carbonylmethoxy group etc. are mentioned preferably.

  Specific examples of the repeating structural units represented by the general formulas (FA) to (FG) are shown below, but the present invention is not limited thereto.

  The total content of the repeating units represented by formulas (FA) to (FG) is generally 10 to 80 mol%, preferably 30 to 70 mol%, more preferably based on all repeating units constituting the resin. Is used in the range of 35 to 65 mol%.

  In addition to the above repeating structural units, the resin of the present invention (B) may be copolymerized with other polymerizable monomers for the purpose of further improving the performance of the resist of the present invention.

  Examples of copolymerizable monomers that can be used include those shown below. For example, an addition polymerizable unsaturated bond selected from acrylic acid esters, acrylamides, methacrylic acid esters, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, crotonic acid esters other than the above. A compound having one.

Such a fluorine-containing resin may contain other repeating units as a copolymerization component in addition to the repeating unit having fluorine atoms, from the viewpoint of improving dry etching resistance, adjusting alkali solubility, and improving substrate adhesion. preferable. Preferred as other repeating units are:
1) A repeating unit having an alicyclic hydrocarbon structure represented by the general formulas (pI) to (pVI) and (II-AB). Specifically, the repeating units 1 to 23 and the repeating units [II-1] to [II-32]. Of the above specific examples 1 to 23, Rx is preferably CF ₃ .

  2) A repeating unit having a lactone structure represented by the general formulas (Lc) and (V-1) to (V-5). Specifically, the repeating units (IV-1) to (IV-16) and the repeating units (Ib-1) to (Ib-11).

  3) The following general formula (XV) (XVI) (XVII) derived from a maleic anhydride, vinyl ether or a vinyl compound having a cyano group, specifically the repetitions listed in (C-1) to (C-15) Units are listed. These other repeating units may or may not contain a fluorine atom.

In the formula, R ₄₁ represents an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group. The alkyl group of R ₄₁ may be substituted with an aryl group.
R ₄₂ represents a hydrogen atom, a halogen atom, a cyano group or an alkyl group.
A ₅ is a single bond, a divalent alkylene group, an alkenylene group, a cycloalkylene group or an arylene group, or —O—CO—R ₂₂ —, —CO—O—R ₂₃ —, —CO—N (R ₂₄ ) —. R ₂₅ -is represented.
R ₂₂ , R ₂₃ and R ₂₅ may be the same or different and each may have a single bond, an ether group, an ester group, an amide group, a urethane group or a ureido group, a divalent alkylene group, an alkenylene group Represents a cycloalkylene group or an arylene group.
R ₂₄ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group.
n represents 0 or 1, and x, y, z represents an integer of 0 to 4.
Here, examples of each substituent include those similar to the substituents of the general formulas (FA) to (FG).

  Specific examples of the repeating structural units represented by the general formulas (XVI) to (XVII) are shown below, but the present invention is not limited thereto.

  The content of other repeating units such as the repeating units represented by the general formulas (XV) to (XVII) is generally 0 to 70 mol%, preferably 10 to 60 mol%, based on all repeating units constituting the resin. More preferably, it is used in the range of 20 to 50 mol%.

(B) The fluorine group-containing resin as the acid-decomposable resin may contain an acid-decomposable group in any repeating unit.
As for content of the repeating unit which has an acid-decomposable group, 10-70 mol% is preferable with respect to all the repeating units, More preferably, it is 20-60 mol%, More preferably, it is 30-60 mol%.

  The fluorine group-containing resin can be synthesized by radical polymerization in substantially the same manner as the alicyclic hydrocarbon-based acid-decomposable resin.

  The weight average molecular weight of the resin of the component (B) according to the present invention is preferably 1,000 to 200,000 as a polystyrene conversion value by the GPC method. By making the weight average molecular weight 1,000 or more, heat resistance and dry etching resistance can be improved, and by making the weight average molecular weight 200,000 or less, developability can be improved. In addition, since the viscosity is extremely low, the film forming property can be improved.

  In the positive photosensitive composition of the present invention, the blending amount of the resin of the component (B) according to the present invention in the entire composition is preferably 40 to 99.99% by mass in the total solid content, more preferably 50 to 50%. It is 99.97 mass%.

[3] (C) Dissolution-inhibiting compound having a molecular weight of 3000 or less (hereinafter also referred to as “(C) component” or “dissolution-inhibiting compound”) that is decomposed by the action of an acid to increase the solubility in an alkaline developer.
(C) As a dissolution-inhibiting compound having a molecular weight of 3000 or less that decomposes by the action of an acid and increases its solubility in an alkaline developer, the transmittance of 220 nm or less is not lowered, so Proceeding of SPIE, 2724,355 (1996) An alicyclic or aliphatic compound containing an acid-decomposable group is preferred, such as a cholic acid derivative containing an acid-decomposable group described in 1). Examples of the acid-decomposable group and alicyclic structure are the same as those described above for the alicyclic hydrocarbon-based acid-decomposable resin.

  When exposing the photosensitive composition of this invention with a KrF excimer laser, or irradiating with an electron beam, what contains the structure which substituted the phenolic hydroxyl group of the phenol compound by the acid-decomposable group is preferable. As a phenol compound, what contains 1-9 phenol frame | skeleton is preferable, More preferably, it contains 2-6 pieces.

  The molecular weight of the dissolution inhibiting compound in the present invention is 3000 or less, preferably 300 to 3000, and more preferably 500 to 2500.

  The addition amount of the dissolution inhibiting compound is preferably 3 to 50% by mass, more preferably 5 to 40% by mass, based on the solid content of the photosensitive composition.

  Specific examples of the dissolution inhibiting compound are shown below, but are not limited thereto.

[4] (D) Resin soluble in alkali developer (hereinafter also referred to as “component (D)” or “alkali-soluble resin”)
The alkali dissolution rate of the alkali-soluble resin is preferably 20 測定 / sec or more as measured with 0.261N tetramethylammonium hydroxide (TMAH) (23 ° C.). Particularly preferred is 200 Å / sec or more (Å is angstrom).

  Examples of the alkali-soluble resin used in the present invention include novolak resin, hydrogenated novolak resin, acetone-pyrogalol resin, o-polyhydroxystyrene, m-polyhydroxystyrene, p-polyhydroxystyrene, hydrogenated polyhydroxystyrene, and halogen. Alternatively, alkyl-substituted polyhydroxystyrene, hydroxystyrene-N-substituted maleimide copolymer, o / p- and m / p-hydroxystyrene copolymer, partially O-alkylated product of hydroxyl group of polyhydroxystyrene (for example, 5- 30 mol% O-methylated product, O- (1-methoxy) ethylated product, O- (1-ethoxy) ethylated product, O-2-tetrahydropyranylated product, O- (t-butoxycarbonyl) methylated product, etc.) Or O-acylated product (for example, 5 to 30 mol) O-acetylated product, O- (t-butoxy) carbonylated product, etc.), styrene-maleic anhydride copolymer, styrene-hydroxystyrene copolymer, α-methylstyrene-hydroxystyrene copolymer, carboxyl group-containing methacrylic acid Examples thereof include, but are not limited to, resins and derivatives thereof, and polyvinyl alcohol derivatives.

  Particularly preferred alkali-soluble resins are novolak resins and o-polyhydroxystyrene, m-polyhydroxystyrene, p-polyhydroxystyrene and copolymers thereof, alkyl-substituted polyhydroxystyrenes, partially O-alkylated polyhydroxystyrenes, Alternatively, O-acylated product, styrene-hydroxystyrene copolymer, and α-methylstyrene-hydroxystyrene copolymer.

  The novolak resin is obtained by subjecting a predetermined monomer as a main component to addition condensation with an aldehyde in the presence of an acidic catalyst.

  Moreover, the weight average molecular weight of alkali-soluble resin is 2000 or more normally, Preferably it is 5000-200000, More preferably, it is 5000-100000.

  Here, the weight average molecular weight is defined as a polystyrene equivalent value of gel permeation chromatography.

  These (D) alkali-soluble resins in the present invention may be used in combination of two or more.

  The usage-amount of alkali-soluble resin is 40-97 mass% with respect to solid content of the whole composition of a photosensitive composition, Preferably it is 60-90 mass%.

(5) (E) An acid crosslinking agent that crosslinks with the alkali-soluble resin by the action of an acid (hereinafter also referred to as “(E) component” or “crosslinking agent”).
A crosslinking agent is used in the negative photosensitive composition of the present invention.

Any crosslinking agent can be used as long as it is a compound that crosslinks a resin soluble in an alkaline developer by the action of an acid, but the following (1) to (3) are preferred.
(1) Hydroxymethyl, alkoxymethyl, and acyloxymethyl forms of phenol derivatives.
(2) A compound having an N-hydroxymethyl group, an N-alkoxymethyl group, or an N-acyloxymethyl group.
(3) A compound having an epoxy group.

  The alkoxymethyl group preferably has 6 or less carbon atoms, and the acyloxymethyl group preferably has 6 or less carbon atoms.

  Of these crosslinking agents, particularly preferred are listed below.

(In formula, L < ¹ > -L < ⁸ > may be same or different and shows a hydrogen atom, a hydroxymethyl group, a methoxymethyl group, an ethoxymethyl group, or a C1-C6 alkyl group.)
The crosslinking agent is generally used in an amount of 3 to 70% by mass, preferably 5 to 50% by mass, in the solid content of the photosensitive composition.

<Other ingredients>
[5] (F) Basic compound The photosensitive composition of the present invention preferably contains (F) a basic compound in order to reduce a change in performance over time from exposure to heating.
As the basic compound, a compound having a stronger basicity than phenol is preferable.

  As a preferable structure which a basic compound has, the structure shown by following formula (A)-(E) can be mentioned.

Here, R ²⁵⁰ , R ²⁵¹ and R ²⁵² are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, And R ²⁵⁰ and R ²⁵¹ may combine with each other to form a ring. These may have a substituent. Examples of the alkyl group and cycloalkyl group having a substituent include an aminoalkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and 1 to 1 carbon atoms. A 20 hydroxyalkyl group or a cycloalkyl group having 3 to 20 carbon atoms is preferred.
These may contain an oxygen atom, a sulfur atom, or a nitrogen atom in the alkyl chain.

(Wherein R ²⁵³ , R ²⁵⁴ , R ²⁵⁵ and R ²⁵⁶ each independently represents an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms).

  Preferable compounds include guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, and piperidine, and may have a substituent. More preferable compounds include compounds having an imidazole structure, a diazabicyclo structure, an onium hydroxide structure, an onium carboxylate structure, a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, a hydroxyl group and / or Or the aniline derivative which has an ether bond etc. can be mentioned.

  Examples of the compound having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole, and the like. The compound having a diazabicyclo structure is 1,4-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4,3,0] noner-5-ene, 1,8-diazabicyclo [5,4,0]. Undecar 7-ene. Examples of the compound having an onium hydroxide structure include triarylsulfonium hydroxide, phenacylsulfonium hydroxide, sulfonium hydroxide having a 2-oxoalkyl group, specifically triphenylsulfonium hydroxide, tris (t-butylphenyl) sulfonium. Examples thereof include hydroxide, bis (t-butylphenyl) iodonium hydroxide, phenacylthiophenium hydroxide, and 2-oxopropylthiophenium hydroxide. The compound having an onium carboxylate structure is a compound having an onium hydroxide structure in which the anion moiety is converted to a carboxylate, and examples thereof include acetate, adamantane-1-carboxylate, and perfluoroalkylcarboxylate. Examples of the compound having a trialkylamine structure include tri (n-butyl) amine and tri (n-octyl) amine. Examples of aniline compounds include 2,6-diisopropylaniline and N, N-dimethylaniline. Examples of the alkylamine derivative having a hydroxyl group and / or an ether bond include ethanolamine, diethanolamine, triethanolamine, and tris (methoxyethoxyethyl) amine. Examples of aniline derivatives having a hydroxyl group and / or an ether bond include N, N-bis (hydroxyethyl) aniline.

  These basic compounds are used alone or in combination of two or more. The usage-amount of a basic compound is 0.001-10 mass% normally on the basis of solid content of a photosensitive composition, Preferably it is 0.01-5 mass%. In order to obtain a sufficient addition effect, 0.001% by mass or more is preferable, and 10% by mass or less is preferable in terms of sensitivity and developability of the non-exposed area.

[6] (G) Fluorine-based and / or silicon-based surfactant The photosensitive composition of the present invention further includes a fluorine-based and / or silicon-based surfactant (fluorine-based surfactant and silicon-based surfactant, It is preferable to contain any one of surfactants containing both fluorine atoms and silicon atoms, or two or more thereof.

  When the photosensitive composition of the present invention contains fluorine and / or a silicon-based surfactant, adhesion and development defects can be obtained with good sensitivity and resolution when using an exposure light source of 250 nm or less, particularly 220 nm or less. A small resist pattern can be provided.

  Examples of these fluorine and / or silicon surfactants include, for example, JP-A No. 62-36663, JP-A No. 61-226746, JP-A No. 61-226745, JP-A No. 62-170950, JP 63-34540 A, JP 7-230165 A, JP 8-62834 A, JP 9-54432 A, JP 9-5988 A, JP 2002-277862 A, US Patent Nos. 5,405,720, 5,360,692, 5,529,881, 5,296,330, 5,436,098, 5,576,143, 5,294,511, 5,824,451 Surfactant can be mentioned, The following commercially available surfactant can also be used as it is.

  Examples of commercially available surfactants that can be used include EFTOP EF301 and EF303 (manufactured by Shin-Akita Kasei Co., Ltd.), Florard FC430 and 431 (manufactured by Sumitomo 3M Co., Ltd.), MegaFuck F171, F173, F176, F189, and R08. (Dainippon Ink Chemical Co., Ltd.), Surflon S-382, SC101, 102, 103, 104, 105, 106 (Asahi Glass Co., Ltd.), Troisol S-366 (Troy Chemical Co., Ltd.), etc. Fluorine type surfactant or silicon type surfactant can be mentioned. Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as the silicon surfactant.

  In addition to the known surfactants described above, the surfactant is derived from a fluoroaliphatic compound produced by a telomerization method (also called telomer method) or an oligomerization method (also called oligomer method). A surfactant using a polymer having a fluoroaliphatic group can be used. The fluoroaliphatic compound can be synthesized by the method described in JP-A-2002-90991.

  As the polymer having a fluoroaliphatic group, a copolymer of a monomer having a fluoroaliphatic group and (poly (oxyalkylene)) acrylate and / or (poly (oxyalkylene)) methacrylate is preferable and distributed irregularly. Or may be block copolymerized. Examples of the poly (oxyalkylene) group include a poly (oxyethylene) group, a poly (oxypropylene) group, a poly (oxybutylene) group, and the like, and a poly (oxyethylene, oxypropylene, and oxyethylene group). A unit having different chain lengths in the same chain length, such as a block link) or poly (block link of oxyethylene and oxypropylene) may be used. Furthermore, a copolymer of a monomer having a fluoroaliphatic group and (poly (oxyalkylene)) acrylate (or methacrylate) is not only a binary copolymer but also a monomer having two or more different fluoroaliphatic groups, Further, it may be a ternary or higher copolymer obtained by simultaneously copolymerizing two or more different (poly (oxyalkylene)) acrylates (or methacrylates).

Examples of commercially available surfactants include Megafac F178, F-470, F-473, F-475, F-476, and F-472 (Dainippon Ink Chemical Co., Ltd.). Further, a copolymer of an acrylate (or methacrylate) having a C ₆ F ₁₃ group and (poly (oxyalkylene)) acrylate (or methacrylate), an acrylate (or methacrylate) having a C ₆ F ₁₃ group and (poly (oxy) (Ethylene)) acrylate (or methacrylate) and (poly (oxypropylene)) acrylate (or methacrylate) copolymer, acrylate (or methacrylate) and (poly (oxyalkylene)) acrylate having C ₈ F ₁₇ groups (or Copolymer of acrylate (or methacrylate), (poly (oxyethylene)) acrylate (or methacrylate), and (poly (oxypropylene)) acrylate (or methacrylate) having a C ₈ F ₁₇ group Coalesce, etc. Can.

  The amount of fluorine and / or silicon surfactant used is preferably 0.0001 to 2% by mass, more preferably 0.001 to 1% by mass, based on the total amount of the photosensitive composition (excluding the solvent). is there.

[7] (H) Organic solvent The photosensitive composition of the present invention is used by dissolving the above components in a predetermined organic solvent.

  Examples of the organic solvent that can be used include ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, γ-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, ethylene glycol monoethyl. Ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N, N -Dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, tetrahydrofuran, etc.

  In the present invention, the organic solvent may be used alone or in combination, but it is preferable to use a mixed solvent in which a solvent containing a hydroxyl group in the structure and a solvent not containing a hydroxyl group are mixed. . Thereby, the generation of particles during storage of the resist solution can be reduced.

  Examples of the solvent containing a hydroxyl group include ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethyl lactate, and the like. Particularly preferred are propylene glycol monomethyl ether and ethyl lactate.

  Examples of the solvent not containing a hydroxyl group include propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, butyl acetate, N-methylpyrrolidone, N, N-dimethylacetamide, dimethyl sulfoxide and the like. Among these, propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, and butyl acetate are particularly preferred, and propylene glycol monomethyl ether acetate, ethyl ethoxypropionate. 2-heptanone is most preferred.

  The mixing ratio (mass) of the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group is 1/99 to 99/1, preferably 10/90 to 90/10, more preferably 20/80 to 60/40. . A mixed solvent containing 50% by mass or more of a solvent not containing a hydroxyl group is particularly preferred from the viewpoint of coating uniformity.

[8] Other Additives The photosensitive composition of the present invention further has solubility in dyes, plasticizers, surfactants other than the above component (G), photosensitizers, and developers as necessary. A compound to be promoted and the like can be contained.

  The dissolution accelerating compound for the developer that can be used in the present invention is a low molecular weight compound having a molecular weight of 1,000 or less and having two or more phenolic OH groups or one or more carboxy groups. When it has a carboxy group, an alicyclic or aliphatic compound is preferable.

  A preferable addition amount of these dissolution promoting compounds is 2 to 50% by mass, and more preferably 5 to 30% by mass with respect to the resin of the component (B) or the resin of the component (D). 50 mass% or less is preferable at the point of development residue suppression and the pattern deformation prevention at the time of image development.

  Such phenolic compounds having a molecular weight of 1000 or less can be easily obtained by those skilled in the art with reference to the methods described in JP-A-4-122938, JP-A-2-28531, US Pat. Can be synthesized.

  Specific examples of alicyclic or aliphatic compounds having a carboxyl group include carboxylic acid derivatives having a steroid structure such as cholic acid, deoxycholic acid, lithocholic acid, adamantane carboxylic acid derivatives, adamantane dicarboxylic acid, cyclohexane carboxylic acid, cyclohexane Examples thereof include, but are not limited to, dicarboxylic acids.

  In the present invention, a surfactant other than the above (G) fluorine-based and / or silicon-based surfactant may be added. Specifically, nonionic interfaces such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylene / polyoxypropylene block copolymers, sorbitan aliphatic esters, polyoxyethylene sorbitan aliphatic esters, etc. Mention may be made of activators.

  These surfactants may be added alone or in some combination.

[9] Method of Use The photosensitive composition of the present invention is used by dissolving the above components in a predetermined organic solvent, preferably the mixed solvent, and applying the solution on a predetermined support as follows.

For example, the photosensitive composition is applied onto a substrate (eg, silicon / silicon dioxide coating) used for the manufacture of precision integrated circuit elements by an appropriate coating method such as a spinner or a coater, and dried to form a photosensitive film. Form.
The photosensitive film is irradiated with actinic rays or radiation through a predetermined mask, preferably baked (heated) and developed. Thereby, a good pattern can be obtained.

Examples of the actinic ray or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, X-ray, electron beam, etc., but preferably far ultraviolet light having a wavelength of 250 nm or less, more preferably 220 nm or less. Specifically, KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (157 nm), X-ray, electron beam, etc. ArF excimer laser, F ₂ excimer laser, EUV (13 nm) Is preferred.

  In the development step, an alkaline developer is used as follows. As an alkaline developer of the resist composition, inorganic hydroxides such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, primary amines such as ethylamine and n-propylamine, Secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide and the like Alkaline aqueous solutions such as quaternary ammonium salts, cyclic amines such as pyrrole and pihelidine can be used.

  Furthermore, alcohols and surfactants can be added in appropriate amounts to the alkaline developer.

The alkali concentration of the alkali developer is usually from 0.1 to 20% by mass.
The pH of the alkali developer is usually from 10.0 to 15.0.

EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, the content of this invention is not limited by this.
Examples 1-3, 5, 8, 10, 11, 13, 14, 17-36, 38, 39, 41-44, 46-56, 65, 67-75, 85 are reference examples.

(1) Synthesis Example of Component (A) [Synthesis of Compound (A-34)]
5-Iodooctafluoro-3-oxapentanesulfonyl fluoride 7.67 g (18 mmol), 1-dodecene 3.33 g (19.8 mmol), hydrosulfite sodium 3.84 g (22.1 mmol), sodium bicarbonate 2.65 g (31.5 mmol) , Acetonitrile (40 mL) and water (15 mL) were added, and the mixture was stirred at room temperature for 3 hr. 150 mL of ethyl acetate was added to the reaction solution, and the organic layer was washed with water and dried over magnesium sulfate. The solvent was removed to obtain a colorless transparent oil. To this, 7.0 mL (26.5 mmol) of tributyltin hydride, 1.16 g (7.06 mmol) of 2,2′-azobis (isobutyronitrile) and 50 mL of toluene were added, and the mixture was stirred at 70 ° C. for 3 hours under a nitrogen stream. The organic layer was washed successively with a saturated aqueous potassium fluoride solution and water, dried over sodium sulfate, and then the solvent was removed to obtain a colorless transparent oil. To this was added 3.0 g (75 mmol) of sodium hydroxide and 50 mL of ethanol, and the mixture was stirred at room temperature for 3 hours. A white solid was obtained by removing the solvent and extracting with ethyl acetate. This was dissolved in 50 ml of acetonitrile, a triphenylsulfonium acetate solution was added, and the mixture was stirred at room temperature for 2 hours. The solvent was removed by column chromatography (SiO _2, chloroform / methanol = 5/1) to afford compound as colorless transparent oil (A-34) (9.27 g , 12.7 mmol, 71%).

  The triphenylsulfonium acetate solution was added with 6.64 g (17 mmol) of triphenylsulfonium iodide, 3.00 g (18 mmol) of silver acetate, 150 mL of acetonitrile and 75 mL of water and stirred at room temperature for 1 hour, and the reaction solution was filtered. Prepared.

The results of NMR analysis were as follows.
¹ H-NMR (300 MHz, CDCl ₃ ) δ 0.876 (t, 3H), 1.243 (bs, 18H), 1.511 (q, 2H), 2.086 (m, 2H), 7.740 (m, 15H)
¹⁹ F-NMR (300 MHz, CDCl ₃ ) δ-118.8 (t, 2F), δ-118.2 (m, 2F), δ-89.0 (t, 2F), -82.9 (t, 2F)

[Synthesis of Compound (A-35)]
1- (adamantanylmethyloxy) propan-2-ene was synthesized in the same manner. (Yield 62%)
The results of NMR analysis were as follows.
¹ H-NMR (300 MHz, CDCl ₃ ) δ 1.499-2.181 (m, 19H), 2.934 (s, 2H), 3.397 (t, 2H), 7.714 (m, 15H)
¹⁹ F-NMR (300 MHz, CDCl ₃ ) δ-118.2 (m, 4F), δ-88.7 (t, 2F), -82.8 (t, 2F)

[Synthesis of Compound (A-38)]
Synthesized in a similar manner from 1- (2- (2- (2-methoxyethyloxy) ethyloxy) ethyloxy) propan-2-ene. (Yield 60%)
The results of NMR analysis were as follows.
¹ H-NMR (300 MHz, CDCl ₃ ) δ 1.824 (m, 2H), 2.173 (m, 2H), 3.369 (s, 3H), 3.469-3.661 (m, 14H), 7.720 (m, 15H)
¹⁹ F-NMR (300 MHz, CDCl ₃ ) δ-118.4 (t, 2F), δ-118.3 (m, 2F), δ-88.8 (t, 2F), -82.9 (t, 2F)

(2) Synthesis of resin [synthesis of resin (1)]
2-methyl-2-adamantyl methacrylate and butyrolactone methacrylate were charged at a ratio of 50/50 (molar ratio) and dissolved in methyl ethyl ketone / tetrahydrofuran = 5/5 (mass ratio) to prepare 100 mL of a solution having a solid content concentration of 20 mass%. . To this solution, 2 mol% of a polymerization initiator V-65 manufactured by Wako Pure Chemical Industries, Ltd. was added, and this was added dropwise to 10 mL of methyl ethyl ketone heated to 60 ° C. over 4 hours in a nitrogen atmosphere. After completion of the dropwise addition, the reaction solution was heated for 4 hours, 1 mol% of V-65 was added again, and the mixture was stirred for 4 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and the resin (1) which was a white powder crystallized and precipitated in 3 L of a mixed solvent of distilled water / ISO propyl alcohol = 1/1 (mass ratio) was recovered.
The polymer composition ratio (molar ratio) determined from C ¹³ NMR was 51/49. Moreover, the standard polystyrene conversion mass mean molecular weight calculated | required by GPC measurement was 9700.

  Resins (2) to (21) were synthesized in the same manner.

  Hereinafter, the structures and molecular weights of the resins (1) to (21) are shown.

<Fluorine group-containing resin>
Hereinafter, the structures of the fluorine group-containing resins (FII-1) to (FII-40) used in the examples are shown.

  Tables 1 and 2 below show the weight average molecular weights and the like of the fluorine group-containing resins (FII-1) to (FII-40).

Examples 1-21 and Comparative Examples 1 and 2
<Resist preparation>
The components shown in Tables 3 to 5 below were dissolved in a solvent to prepare a solution having a solid content concentration of 12% by mass, and this was filtered through a 0.1 μm polytetrafluoroethylene filter or a polyethylene filter to prepare a positive resist solution. . The prepared positive resist solution was evaluated by the following method, and the results are shown in Tables 3 to 5.

  Hereinafter, the abbreviations in each table are as follows. Resins and acid generators other than those listed below are those exemplified above. In each table, the ratio when a plurality of resins or solvents are used is a mass ratio.

[Acid generator]
The compound (A) and the combined acid generator of the present invention are those exemplified above.
TPSN: Triphenylsulfonium nonafluorobutane sulfonate TPSO: Triphenylsulfonium perfluorooctane sulfonate

[Basic compounds]
DBN; 1,5-diazabicyclo [4.3.0] non-5-ene TPI; 2,4,5-triphenylimidazole TPSA; triphenylsulfonium acetate HEP; N-hydroxyethylpiperidine DIA; 2,6-diisopropyl Aniline DCMA; dicyclohexylmethylamine TPA; tripentylamine TOA; tri-n-octylamine HAP; hydroxyantipyrine TBAH; tetrabutylammonium hydroxide TMEA; tris (methoxyethoxyethyl) amine PEA; N-phenyldiethanolamine

[Surfactant]
W-1; Megafac F176 (Dainippon Ink Chemical Co., Ltd.) (Fluorine)
W-2; Megafuck R08 (Dainippon Ink Chemical Co., Ltd.)
(Fluorine and silicon)
W-3: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Silicon)
W-4; Troisol S-366 (manufactured by Troy Chemical Co., Ltd.)

〔solvent〕
A1; propylene glycol methyl ether acetate A2; 2-heptanone A3; ethyl ethoxypropionate A4; γ-butyrolactone A5; cyclohexanone B1; propylene glycol methyl ether B2;

[Dissolution inhibitor]
LCB; t-butyl lithocholic acid

<Resist evaluation>
An anti-reflective coating DUV-42 manufactured by Brewer Science Co., Ltd. was uniformly applied on a silicon substrate subjected to hexamethyldisilazane treatment with a spin coater, dried at 100 ° C. for 90 seconds on a hot plate, and then at 190 ° C. Heat drying was performed for 240 seconds. Thereafter, each positive resist solution was applied by a spin coater and dried at 120 ° C. for 90 seconds to form a 0.30 μm resist film.
The resist film was exposed with an ArF excimer laser stepper (NA = 0.6 manufactured by ISI) through a mask, and immediately after the exposure, it was heated on a hot plate at 120 ° C. for 90 seconds. Further, the resist film was developed with an aqueous 2.38 mass% tetramethylammonium hydroxide solution at 23 ° C. for 60 seconds, rinsed with pure water for 30 seconds, and then dried to obtain a line pattern.

(PEB temperature dependence)
The exposure amount that reproduces the line-and-space 1/1 with a mask size of 130 nm when heated at 120 ° C. for 90 seconds is set as the optimal exposure amount, and after performing exposure at the optimal exposure amount, Post-heating was performed at two temperatures of + 2 ° C. and −2 ° C. (122 ° C., 118 ° C.), and the obtained line and space were measured to determine their line widths L ₁ and L ₂ . The PEB temperature dependency was defined as the fluctuation of the line width per PEB temperature change of 1 ° C., and was calculated by the following formula.
PEB temperature dependency (nm / ° C.) = | L ₁ −L ₂ | / 4
The smaller the value, the smaller the performance change with respect to the temperature change.

(Exposure latitude)
The exposure amount that reproduces a line-and-space mask pattern with a line width of 0.13 μm is set as the optimal exposure amount, and when the exposure amount is changed, an exposure amount width that allows a pattern size of 0.13 μm ± 10% is obtained. The value was divided by the optimum exposure and displayed as a percentage. The larger the value, the smaller the change in performance due to the change in exposure amount, and the better the exposure latitude.

  From the results of Tables 3 to 5, it is clear that the photosensitive composition of the present invention has small PEB temperature dependency and excellent exposure latitude in ArF exposure.

[Examples 22 to 26 and Comparative Examples 3 and 4]
(1) Formation of lower resist layer FHi-028DD resist (resist for i-line manufactured by Fuji Film Orin) was applied to a 6-inch silicon wafer using a spin coater Mark8 manufactured by Tokyo Electron, and baked at 90 ° C. for 90 seconds to form a film. A uniform film having a thickness of 0.55 μm was obtained.
This was further heated at 200 ° C. for 3 minutes to form a lower resist layer having a thickness of 0.40 μm.

(2) Formation of upper resist layer The components shown in Table 6 below are dissolved in a solvent to prepare a solution having a solid content of 11% by mass, and an upper resist composition is prepared by microfiltration with a membrane filter having a diameter of 0.1 μm. did.
The upper resist composition was similarly applied onto the lower resist layer and heated at 130 ° C. for 90 seconds to form an upper resist layer having a thickness of 0.20 μm.

  Resins (SI-1) to (SI-5) in Table 6 are as follows.

(3) Resist evaluation The wafer obtained in this manner was exposed to an ArF excimer stepper 9300 manufactured by ISI with a resolution mask and the exposure amount varied.
Subsequently, after heating at 120 ° C. for 90 seconds, the film was developed with a tetrahydroammonium hydroxide developer (2.38 mass%) for 60 seconds, rinsed with distilled water, and dried to obtain an upper layer pattern.

  In the same manner as in Examples 1 to 21, the PEB temperature dependency and the exposure latitude were evaluated. The results are shown in Table 6.

  From the results in Table 6, it is clear that the photosensitive composition of the present invention has a low PEB temperature dependency and a wide range of exposure latitude even when used as a two-layer resist.

[Examples 27 to 46 and Comparative Examples 5 and 6]
<Resist preparation>
The components shown in Tables 7 to 8 below were dissolved in a solvent to prepare a solution having a solid concentration of 5% by mass, and this was filtered through a 0.1 μm polyethylene filter to prepare a resist solution.
Each resist solution was applied to a silicon wafer subjected to hexamethyldisilazane treatment by a spin coater and dried by heating on a vacuum contact hot plate at 120 ° C. for 90 seconds to obtain a resist film having a thickness of 0.1 μm.
The obtained resist film was subjected to pattern exposure using an F ₂ excimer laser stepper (157 nm), and immediately after the exposure, it was heated on a hot plate at 120 ° C. for 90 seconds. The sample was developed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution for 60 seconds and rinsed with pure water to obtain a sample wafer. About these, PEB temperature dependence and exposure latitude were evaluated.

(PEB temperature dependence)
The exposure amount that reproduces the line-and-space 1/1 with a mask size of 80 nm when heated at 120 ° C. for 90 seconds is set as the optimal exposure amount, and after performing exposure at the optimal exposure amount, Post-heating was performed at two temperatures of + 2 ° C. and −2 ° C. (122 ° C., 118 ° C.), and the obtained line and space were measured to determine their line widths L ₁ and L ₂ . The PEB temperature dependency was defined as the fluctuation of the line width per 1 ° C. PEB temperature change, and was calculated by the following formula.
PEB temperature dependency (nm / ℃) = | L 1 -L 2 | / 4
The smaller the value, the smaller the performance change with respect to the temperature change.

(Exposure latitude)
The exposure amount that reproduces a line-and-space mask pattern with a line width of 80 nm is set as the optimal exposure amount, and when the exposure amount is changed, an exposure amount width that allows the pattern size to be 80 nm ± 10% is obtained, and this value is the optimal exposure. Divided by the amount and expressed as a percentage. The larger the value, the smaller the change in performance due to the change in exposure amount, and the better the exposure latitude.
The results are shown in Tables 7-8.

From the results of Tables 7 to 8, it can be seen that the photosensitive composition of the present invention has small PEB temperature dependency and excellent exposure latitude in F ₂ excimer laser exposure.

[Examples 47 to 56 and Comparative Examples 7 and 8]
<Resist preparation>
The components shown in Table 10 below were dissolved in a solvent and filtered through a 0.1 μm polytetrafluoroethylene filter to prepare a positive resist solution having a solid content concentration of 14% by mass.
The prepared positive resist solution was evaluated by the following method, and the results are shown in Table 10.

Table 9 below shows the molar ratios and weight average molecular weights of the resins (R-2) to (R-24) in Table 10.

  PHS: Polyhydroxystyrene VP-8000 (manufactured by Nippon Soda Co., Ltd.)

The structures of dissolution inhibiting compounds (C-1) and (C-2) in Table 9 are as follows.

<Resist evaluation>
The prepared positive resist solution is uniformly applied on a silicon substrate subjected to hexamethyldisilazane treatment using a spin coater, and is heated and dried on a hot plate at 120 ° C. for 90 seconds to obtain a 0.6 μm resist. A film was formed.
The resist film was subjected to pattern exposure using a line and space mask using a KrF excimer laser stepper (NA = 0.63), and heated on a hot plate at 110 ° C. for 90 seconds immediately after the exposure. Further, the film was developed with an aqueous 2.38 mass% tetramethylammonium hydroxide solution at 23 ° C. for 60 seconds, rinsed with pure water for 30 seconds, dried, a line pattern was formed, and PEB temperature dependency and exposure latitude were evaluated. .

(PEB temperature dependence)
The exposure amount that reproduces a line-and-space 1/1 with a mask size of 130 nm when heated at 110 ° C. for 90 seconds is set as the optimal exposure amount, and then the exposure is performed with the optimal exposure amount. Post-heating was performed at two temperatures of + 2 ° C. and −2 ° C. (112 ° C., 108 ° C.), and the obtained line and space were measured to determine their line widths L ₁ and L ₂ . The PEB temperature dependency was defined as the fluctuation of the line width per 1 ° C. PEB temperature change, and was calculated by the following formula.
PEB temperature dependency (nm / ℃) = | L 1 -L 2 | / 4
The smaller the value, the smaller the performance change with respect to the temperature change.

(Exposure latitude)
The exposure amount that reproduces a line-and-space mask pattern with a line width of 0.13 μm is set as the optimal exposure amount, and when the exposure amount is changed, an exposure amount width that allows a pattern size of 0.13 μm ± 10% is obtained. The value was divided by the optimum exposure and displayed as a percentage. The larger the value, the smaller the change in performance due to the change in exposure amount, and the better the exposure latitude.

  From the results in Table 10, it can be seen that the photosensitive composition of the present invention has a small PEB temperature dependency and a wide range of exposure latitude as a positive resist composition in KrF excimer laser exposure.

[Examples 57 to 66 and Comparative Examples 9 and 10]
<Resist preparation>
The components shown in Table 11 below were dissolved in a solvent, which was filtered through a 0.1 μm polytetrafluoroethylene filter to prepare a negative resist solution having a solid concentration of 14% by mass.
The prepared negative resist solution was evaluated in the same manner as in Examples 47 to 56, and the results are shown in Table 11.

  The structure, molecular weight, and molecular weight distribution of the alkali-soluble resin in Table 11 are shown below.

  The structure of the crosslinking agent in Table 11 is shown below.

  From the results in Table 11, it can be seen that the photosensitive composition of the present invention has a small PEB temperature dependency and a wide range of exposure latitude as a negative resist composition in KrF excimer laser exposure.

[Examples 67 to 76 and Comparative Examples 11 and 12]
<Resist preparation>
The components shown in Table 12 were dissolved in a solvent, and this was filtered through a 0.1 μm polytetrafluoroethylene filter to prepare a positive resist solution having a solid content concentration of 12% by mass.
The prepared positive resist solution was evaluated by the following method, and the results are shown in Table 12.

<Resist evaluation>
The prepared positive resist solution is uniformly applied on a silicon substrate subjected to hexamethyldisilazane treatment using a spin coater, and is heated and dried on a hot plate at 120 ° C. for 60 seconds to obtain a 0.3 μm resist. A film was formed.
This resist film was irradiated with an electron beam projection lithography apparatus (acceleration voltage 100 keV) manufactured by Nikon Corporation, and immediately after the irradiation, it was heated on a hot plate at 110 ° C. for 90 seconds. Further, development was performed at 23 ° C. for 60 seconds using an aqueous tetramethylammonium hydroxide solution having a concentration of 2.38% by mass, rinsed with pure water for 30 seconds, and then dried to form a contact hole pattern.

(PEB temperature dependence)
When the post-heating at 110 ° C. is performed for 90 seconds, the irradiation dose that reproduces the dense line and space of 110 nm (pitch 200 nm) is set as the optimal exposure dose, and after performing exposure at the optimal exposure dose, Post-heating was performed at two temperatures of + 2 ° C. and −2 ° C. (112 ° C., 108 ° C.), and the obtained line and space were measured to determine their line widths L ₁ and L ₂ . The PEB temperature dependency was defined as the fluctuation of the line width per 1 ° C. PEB temperature change, and was calculated by the following formula.
PEB temperature dependency (nm / ℃) = | L 1 -L 2 | / 4
The smaller the value, the smaller the performance change with respect to the temperature change.

(Exposure latitude)
The irradiation dose for resolving 100 nm dense contact holes (pitch 300 nm) is set as the optimum dose, and when the dose is changed, the dose width that allows the pattern size to be 100 nm ± 10% is obtained, and this value is set as the optimum dose. Divided by the amount and expressed as a percentage. The larger the value, the smaller the change in performance due to the change in exposure amount, and the better the exposure latitude.

  From the results shown in Table 12, it can be seen that the photosensitive composition of the present invention has a low PEB temperature dependency and a wide range of exposure latitude as a positive resist composition in electron beam irradiation.

[Examples 77 to 86 and Comparative Examples 13 and 14]
<Resist preparation>
The components shown in Table 13 were dissolved in a solvent, and this was filtered through a 0.1 μm polytetrafluoroethylene filter to prepare a negative resist solution having a solid concentration of 12% by mass.
The prepared negative resist solution was evaluated by the following method, and the results are shown in Table 13.

<Resist evaluation>
The prepared negative resist solution is uniformly applied on a silicon substrate subjected to hexamethyldisilazane treatment using a spin coater, and is heated and dried on a hot plate at 120 ° C. for 60 seconds to obtain a 0.3 μm resist. A film was formed.
This resist film was irradiated with an electron beam projection lithography apparatus (acceleration voltage 100 keV) manufactured by Nikon Corporation, and immediately after the irradiation, it was heated on a hot plate at 110 ° C. for 90 seconds. Further, development was performed at 23 ° C. for 60 seconds using an aqueous tetramethylammonium hydroxide solution having a concentration of 2.38% by mass, rinsed with pure water for 30 seconds, and then dried to form a line and space pattern.

(PEB temperature dependence)
When the post-heating at 110 ° C. is performed for 90 seconds, the irradiation dose that reproduces the dense line and space of 110 nm (pitch 200 nm) is set as the optimal exposure dose, and after performing exposure at the optimal exposure dose, Post-heating was performed at two temperatures of + 2 ° C. and −2 ° C. (112 ° C., 108 ° C.), and the obtained line and space were measured to determine their line widths L ₁ and L ₂ . The PEB temperature dependency was defined as the fluctuation of the line width per 1 ° C. PEB temperature change, and was calculated by the following formula.
PEB temperature dependency (nm / ℃) = | L 1 -L 2 | / 4
The smaller the value, the smaller the performance change with respect to the temperature change.

(Exposure latitude)
The irradiation dose that resolves 100 nm dense line and space (pitch 200 nm) is the optimum irradiation dose, and when changing the irradiation dose, the dose width that allows the pattern size to be 100 nm ± 10% is obtained, and this value is optimal The percentage was displayed by dividing by the irradiation amount. The larger the value, the smaller the change in performance due to the change in exposure amount, and the better the exposure latitude.

  From the results shown in Table 13, it can be seen that the photosensitive composition of the present invention has a small PEB temperature dependency and a wide range of exposure latitude as a negative resist composition in electron beam irradiation.

Claims (7)

(A) a compound that generates a sulfonic acid represented by the general formula (X) and represented by any one of the general formulas (Xa), (Xb), and (Xg) by irradiation with actinic rays or radiation; B) Photosensitivity containing a resin containing a repeating unit represented by the following general formula (AI) and a repeating unit having two or more hydroxyl groups, and decomposed by the action of an acid to increase the solubility in an alkaline developer. Composition.
In formula (X), R _{1a to} R _13a are each independently a hydrogen atom, an alkyl group, a cycloalkyl group,
Represents a halogen atom or a hydroxyl group.
A ₁ and A ₂ each independently represent a divalent linking group having a hetero atom or a single bond. However, when A ₁ and A ₂ are simultaneously a single bond, all of R _{1a to} R _13a do not simultaneously represent a fluorine atom, and all of R _{1a to} R _13a do not simultaneously represent a hydrogen atom.
m ₁ ~m ₅ represents each independently an integer from 0-12. p represents an integer of 0 to 4.
Rb is a group having at least one hydrogen atom.
n1 to n4 each independently represents an integer of 1 to 10.
Rc represents a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
In general formula (AI), R _b0 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms.
A _b is a single bond, an ether group, an ester group, a carbonyl group, an alkylene group, or these
Represents a divalent group in which
V represents a group represented by the following general formula (V-1).
In General Formula (V-1), R _{1b to} R _5b each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylsulfonylimino group, or an alkenyl group. Two of R _{1b to} R _5b may combine to form a ring. (A) a compound that generates a sulfonic acid represented by the general formula (X) and represented by the general formula (Xa-1) or (Xb-1) by irradiation with actinic rays or radiation, and (B) a hydroxyl group A photosensitive composition containing a resin which contains a repeating unit having two or more, decomposes by the action of an acid, and increases the solubility in an alkaline developer.
In formula (X), R _{1a to} R _13a are each independently a hydrogen atom, an alkyl group, a cycloalkyl group,
Represents a halogen atom or a hydroxyl group.
A ₁ and A ₂ each independently represent a divalent linking group having a hetero atom or a single bond. However, when A ₁ and A ₂ are simultaneously a single bond , all of R _{1a to} R _13a may simultaneously represent a fluorine atom.
And all of R _{1a to} R _13a do not represent hydrogen atoms at the same time.
m ₁ ~m ₅ represents each independently an integer from 0-12. p represents an integer of 0 to 4.
Ax represents a linking group having 3 or more carbon atoms.
Ay represents a single bond or an oxygen atom.
Rg represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
n5 represents an integer of 1 to 4.
n6 represents an integer of 1 to 4.
n7 represents an integer of 1 to 4.   Furthermore, the photosensitive composition of Claim 1 or 2 containing the solvent containing a hydroxyl group and the solvent which does not contain a hydroxyl group. (A) a compound that generates a sulfonic acid represented by the general formula (X) and represented by the general formula (Xa) by irradiation with actinic rays or radiation, (D) a resin that is soluble in an alkali developer, ( E) A photosensitive composition comprising an acid crosslinking agent that crosslinks with a resin soluble in the alkali developer by the action of an acid, a solvent containing a hydroxyl group, and a solvent not containing a hydroxyl group.
In formula (X), R _{1a to} R _13a are each independently a hydrogen atom, an alkyl group, a cycloalkyl group,
Represents a halogen atom or a hydroxyl group.
A ₁ and A ₂ each independently represent a divalent linking group having a hetero atom or a single bond. However, when A ₁ and A ₂ are simultaneously a single bond, all of R _{1a to} R _13a do not simultaneously represent a fluorine atom, and all of R _{1a to} R _13a do not simultaneously represent a hydrogen atom.
m ₁ ~m ₅ represents each independently an integer from 0-12. p represents an integer of 0 to 4.
Rb represents an alkyl group or an aralkyl group having at least one hydrogen atom .
n1 represents an integer of 1 to 10. (A) a compound that generates a sulfonic acid represented by the general formula (X) and represented by the general formula (Xa-1) or (Xb-1) by irradiation with actinic rays or radiation, (D) alkali development A resin soluble in the liquid, and (E) an acid crosslinking agent that crosslinks with the resin soluble in the alkaline developer by the action of an acid, a solvent containing a hydroxyl group, and a solvent not containing a hydroxyl group. Photosensitive composition.
In formula (X), R _{1a to} R _13a are each independently a hydrogen atom, an alkyl group, a cycloalkyl group,
Represents a halogen atom or a hydroxyl group.
A ₁ and A ₂ each independently represent a divalent linking group having a hetero atom or a single bond. However, when A ₁ and A ₂ are simultaneously a single bond , all of R _{1a to} R _13a may simultaneously represent a fluorine atom.
And all of R _{1a to} R _13a do not represent hydrogen atoms at the same time.
m ₁ ~m ₅ represents each independently an integer from 0-12. p represents an integer of 0 to 4.
Ax in the formula (Xa-1) represents a linear or branched alkylene group having 3 or more carbon atoms.
Ax in Formula (Xb-1) represents a linking group having 3 or more carbon atoms.
Ay represents a single bond or an oxygen atom.
Rg represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
n5 represents an integer of 1 to 4.
n6 represents an integer of 1 to 4.
n7 represents an integer of 1 to 4.   A pattern forming method comprising forming a film from the photosensitive composition according to claim 1, and exposing and developing the film. The compound which generate | occur | produces the sulfonic acid represented by general formula (Xa-1) or (Xb-1) by irradiation of actinic light or a radiation.
Ax in the formula (Xa-1) represents a linear or branched alkylene group having 3 or more carbon atoms.
Ax in Formula (Xb-1) represents a linking group having 3 or more carbon atoms.
Ay in the general formula (Xa-1) represents an oxygen atom, and Ay in the general formula (Xb-1) represents a single bond or an oxygen atom.
Rg represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
n5 represents an integer of 1 to 4.
n6 and n7 each independently represents an integer of 1 to 10.