JP4484681B2 - Photosensitive composition and pattern forming method using the photosensitive composition - Google Patents

Description

  The present invention relates to a photosensitive composition whose properties change upon irradiation with actinic rays or radiation, a compound used in the photosensitive composition, and a pattern forming method using the photosensitive composition. More specifically, 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, a further photofabrication process, a lithographic printing plate, an acid curable composition, and the photosensitivity. The present invention relates to a compound used in the composition and a pattern forming method using the photosensitive composition.

  The chemically amplified resist composition generates an acid in the exposed area by irradiation with actinic rays or radiation such as far ultraviolet light, and a reaction solution using the acid as a catalyst to develop a developing solution for the irradiated and non-irradiated areas of the active light or radiation It is a pattern forming material that changes the solubility in the substrate and forms a pattern on the substrate.

  When a KrF excimer laser is used as the exposure light source, the main component is a resin having a basic skeleton of poly (hydroxystyrene), which has a small absorption in the 248 nm region, and has a high sensitivity, high resolution, and good pattern. This is a better system than the conventional naphthoquinone diazide / novolak resin system.

  On the other hand, when a further short wavelength light source, for example, an ArF excimer laser (193 nm) is used as an exposure light source, the compound having an aromatic group exhibits a large absorption in the 193 nm region. It wasn't.

  Therefore, an ArF excimer laser resist containing a resin having a highly transparent alicyclic hydrocarbon structure has been developed. However, the alicyclic structure is generally low in polarity, and the deprotection reactivity in the resin is greatly reduced compared to that in poly (hydroxystyrene). For this reason, an acid having a high acidity is required for image formation. 11-501909), Patent Document 4 (Japanese Patent Laid-Open No. 6-242606), Patent Document 5 (Japanese Patent Laid-Open No. 11-160861, Patent Document 6 (US Patent Publication No. 2004 / 0087690A1)) Organic sulfonic acids are used.

JP 2002-131897 A JP 2003-149812 A Japanese National Patent Publication No. 11-501909 JP-A-6-242606 Japanese Patent Laid-Open No. 11-160861 US 2004/0087690 A1

  However, there are still many unsatisfactory points, and it is desired to improve exposure latitude, PEB temperature dependency, pattern profile improvement, sensitivity in EUV light exposure, and dissolution contrast.

An object of the present invention is to provide a photosensitive composition having improved exposure latitude, PEB temperature dependency, pattern profile, and improved sensitivity and dissolution contrast in EUV light exposure, a compound used in the photosensitive composition, and It is providing the pattern formation method using this photosensitive composition.

  The present invention is as follows.

(1) Contains a sulfonium salt compound or iodonium salt compound of an organic acid represented by the general formula (I), which generates an organic acid represented by the following general formula (I) by irradiation with actinic rays or radiation. And a photosensitive composition.

In general formula (I),
A represents a divalent linking group.
X represents —CO ₂ — or —SO ₃ —.
Rf represents a monovalent organic group having a fluorine atom.

(2) In addition, (B) decomposing by the action of an acid, the photosensitive composition according to the above (1), characterized by containing a resin capable of increasing the solubility in an alkali developer.
(3) The photosensitive composition as described in (2) above, wherein the resin that decomposes by the action of an acid and has increased solubility in an alkaline developer has a hydroxystyrene structural unit.
(4) The resin according to (2) above, wherein the resin that decomposes by the action of an acid and has increased solubility in an alkali developer has a repeating unit having a monocyclic or polycyclic hydrocarbon structure. Photosensitive composition.
(5) The above (1) further comprising (D) 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. ) Photosensitive composition.
(6) The photosensitive composition as described in (4) above, wherein the resin contains a repeating unit represented by the following general formula (AI).
In general formula (AI), Rb ₀ represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms.
Represents.
Ab is an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, a single bond, an ether group, an ester group, a carbonyl group, a carboxyl group, or a divalent group obtained by combining these. To express.
V represents a group represented by any one of the general formulas (LC1-1) to (LC1-16).
Rb ₂ represents a substituent. n ₂ represents an integer of 0-4. When n ₂ is an integer of 2 or more, a plurality of Rb ₂ may be the same or different, and a plurality of Rb ₂ may be bonded to form a ring.
(7) The compound (A) that generates an organic acid represented by the general formula (I) upon irradiation with actinic rays or radiation is a compound represented by the following general formula (A1) or (A2) The photosensitive composition according to any one of (1) to (6) above.
In general formulas (A1) and (A2),
R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represents an organic group.
R ₂₀₄ and R ₂₀₅ each independently represents an aryl group, an alkyl group or a cycloalkyl group.
X ⁻ represents a sulfonate anion from which a hydrogen atom of the organic acid —SO ₃ H moiety represented by the general formula (I) is removed.
(8) Further, in addition to the compound (A) that generates an organic acid represented by the general formula (I) by irradiation with actinic rays or radiation, a compound that decomposes by irradiation with actinic rays or radiation to generate an acid is contained. The photosensitive composition as described in any one of (1) to (7) above.
(9) A pattern forming method comprising a step of forming a resist film from the photosensitive composition according to any one of (1) to (8), and exposing and developing the resist film.
(10) The pattern forming method as described in (9) above, wherein the exposure is performed through an immersion liquid.
(11) An organic acid, a salt thereof or a halide thereof represented by the following general formula (I):

In general formula (I),
A represents a divalent linking group.
X represents —CO ₂ — or —SO ₃ —.
Rf represents a cycloalkyl group having a fluorine atom.
(12) An organic acid sulfonium salt compound represented by the following general formula (I) or an organic acid iodonium salt compound represented by the general formula (I):
In general formula (I),
A represents a divalent linking group.
X represents —CO ₂ — or —SO ₃ —.
Rf represents a monovalent organic group having a fluorine atom.

(13) The positive photosensitive composition as described in (2) above, wherein the resin which is decomposed by the action of an acid and has increased solubility in an alkaline developer contains a repeating unit having an alcoholic hydroxyl group. object.

(14) repeating unit having an alcoholic hydroxyl group, monohydroxy adamantane structure, characterized in that it is a repeating unit containing at least one selected from dihydroxy adamantane structure or trihydroxy adamantane structure according to (13) Positive photosensitive composition.

(15) The resin that decomposes by the action of an acid and increases the solubility in an alkaline developer is a resin having a repeating unit of at least one methacrylate and a repeating unit of at least one acrylic ester. The positive photosensitive composition as described in (2) above, wherein

(16) The positive type as described in (2) above, wherein the resin which is decomposed by the action of an acid and has increased solubility in an alkaline developer has a fluorine atom in at least one of a main chain or a side chain Photosensitive composition.

(17) a main chain or a resin having at least one fluorine atom in the side chain, positive photosensitive composition according to the above (16) characterized by having a Hekisafuroro-2-propanol structure.

(18) (C) The above-mentioned (2) to (8) and (13) comprising 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. )-(17) The positive photosensitive composition in any one.

(19) The above (2) to (8) and (13), comprising (F) a basic compound and (G) at least one compound selected from fluorine and / or silicon surfactants -The positive photosensitive composition in any one of (18) .

(20) Repeating resin selected from 2-alkyl-2-adamantyl (meth) acrylate or dialkyl (1-adamantyl) methyl (meth) acrylate, which is decomposed by the action of an acid and has increased solubility in an alkaline developer Any one of the above (2), (18) and (19) characterized by having at least one type of unit, at least one type of repeating unit having a lactone structure, and at least one type of repeating unit having 1 to 3 hydroxyl groups. The positive photosensitive composition as described.

(21) The above-mentioned (2) to (8) and (1), wherein the resin that is decomposed by the action of an acid and has increased solubility in an alkaline developer has a repeating unit having a carboxy group.
The positive photosensitive composition according to any one of 3) to (20) .

(22) Repetitive resin selected from 2-alkyl-2-adamantyl (meth) acrylate or dialkyl (1-adamantyl) methyl (meth) acrylate, which is decomposed by the action of an acid and has increased solubility in an alkaline developer The positive photosensitive composition as described in any one of (2), (18), (19) and (21) above, which has at least one unit and at least one repeating unit having a hydroxystyrene structure. .

  INDUSTRIAL APPLICABILITY According to the present invention, a photosensitive composition having a small PEB temperature dependency, a large exposure latitude, a good pattern profile, and improved sensitivity and dissolution contrast in EUV light exposure, and a pattern forming method using the same And a compound useful for the photosensitive composition can be provided.

Although this invention is invention which concerns on said (1)-(12), it describes including other matters. Hereinafter, the present invention will be described in detail.
In addition, in the description of a group (atomic group) in this specification, the description which does not describe substituted and unsubstituted 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).

The positive photosensitive composition of the present invention, more preferably the positive resist composition, is produced by the action of the compound (A) that generates an organic acid represented by the general formula (I) upon irradiation with actinic rays or radiation and an acid. Contains a resin (B) that decomposes and increases the solubility in an alkali developer, and if necessary, further decomposes by the action of an acid to increase the solubility in an alkali developer. Contains compound (C).

  The negative photosensitive composition of the present invention, more preferably the negative resist composition, comprises a compound (A) that generates an organic acid represented by the general formula (I) upon irradiation with actinic rays or radiation, and an alkaline developer. It contains a soluble resin (D) and an acid crosslinking agent (E) that crosslinks the resin soluble in the alkaline developer by the action of an acid.

[1] (A) Compound capable of generating organic acid represented by general formula (I) upon irradiation with actinic ray or radiation The photosensitive composition of the present invention has the following general formula (I) upon irradiation with actinic ray or radiation. The compound which generate | occur | produces the organic acid represented by these is contained.

In general formula (I),
A represents a divalent linking group.
X represents —CO ₂ — or —SO ₃ —.
Rf represents a monovalent organic group having a fluorine atom.

The divalent linking group as A is preferably a divalent organic group having 1 to 8 carbon atoms, and examples thereof include an alkylene group and a phenylene group, and those substituted with a fluorine atom from the viewpoint of sensitivity. preferable. The divalent linking group as A is more preferably an alkylene group, and preferably has 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms. The alkylene chain may have a linking group such as an oxygen atom or a sulfur atom. The alkylene group is preferably substituted with a fluorine atom, and in that case, an alkylene group in which 30 to 100% of the number of hydrogen atoms is substituted with a fluorine atom is particularly preferable, and the carbon atom bonded to the HO ₃ S-site is More preferably, it has a fluorine atom. Further, a perfluoroalkylene group is preferable, and a perfluoroethylene group, a perfluoropropylene group, and a perfluorobutylene group are particularly preferable.

  The monovalent organic group having a fluorine atom as Rf preferably has 4 to 30 carbon atoms, and the total number of fluorine atoms is preferably 1 to 8. Examples of the organic group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group.

The alkyl group as Rf may have a substituent, preferably a linear or branched alkyl group having 1 to 20 carbon atoms, and has an oxygen atom, a sulfur atom, or a nitrogen atom in the alkyl chain. May be. Specifically, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-dodecyl group, n-tetradecyl group, n-octadecyl group, etc. And a branched alkyl group such as isopropyl group, isopropyl group, isobutyl group, t-butyl group, neopentyl group, 2-ethylhexyl group.
Examples of the alkyl group having a substituent include groups in which a linear or branched alkyl group is substituted with a cycloalkyl group (for example, an adamantylmethyl group, an adamantylethyl group, a cyclohexylethyl group, a camphor residue, etc.). .

  The cycloalkyl group as Rf may have a substituent, preferably a cycloalkyl group having 3 to 20 carbon atoms, and may have an oxygen atom in the ring. Specific examples include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, an adamantyl group, and the like.

  The aryl group as Rf may have a substituent, and is preferably an aryl group having 6 to 14 carbon atoms, and examples thereof include a phenyl group and a naphthyl group.

  The aralkyl group as Rf is preferably an aralkyl group having 7 to 20 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, a naphthylmethyl group, and a naphthylethyl group.

  Examples of the alkenyl group as Rf include a group having a double bond at an arbitrary position of the alkyl group mentioned as Rx.

  Examples of the substituent that each of the above groups may have include, for example, a hydroxyl group, a nitro group, a cyano group, a carboxy group, a carbonyl group, a cycloalkyl group (preferably having 3 to 20 carbon atoms), and an aryl group (preferably having a carbon number). 6-14), an alkoxy group (preferably 1-20 carbon atoms), an acyl group (preferably 2-20 carbon atoms), an acyloxy group (preferably 2-20 carbon atoms), an alkoxycarbonyl group (preferably 2 carbon atoms). To 20), aminoacyl groups (preferably having 2 to 20 carbon atoms), and the like. As for the cyclic structure in the aryl group, cycloalkyl group and the like, examples of the substituent further include an alkyl group (preferably having a carbon number of 1 to 20). As for the aminoacyl group, examples of the substituent further include 1 or 2 alkyl groups (preferably having 1 to 20 carbon atoms).

The organic acid represented by the general formula (I), its salt (for example, onium salt, metal salt) and its halide are novel compounds.
The organic acid represented by the general formula (I) and a salt thereof (for example, an onium salt or a metal salt) can be synthesized by using a general sulfonic acid esterification reaction. For example, a method in which one sulfonyl halide part of a bissulfonyl halide compound is selectively reacted with an alcohol to form a sulfonic acid ester bond and then the other sulfonyl halide part is hydrolyzed, or a cyclic sulfonic acid anhydride is used. It can be obtained by a method of ring opening with alcohol.

  Hereinafter, although the preferable specific example of the organic acid represented by general formula (I) is given, this invention is not limited to this.

  As a compound that generates an organic acid represented by the general formula (I) upon irradiation with actinic rays or radiation (hereinafter also referred to as “compound (A)”), sulfonium of the organic acid represented by the general formula (I) Salt compounds and iodonium salt compounds of organic acids represented by general formula (I) are preferred, and compounds represented by the following general formulas (A1) to (A2) are more preferred.

In general formula (A1),
R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represents an organic group.
X ⁻ represents a sulfonate anion from which a hydrogen atom of the organic acid —SO ₃ H moiety represented by the general formula (I) is removed.

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 the R ₂₀₁ to R _203, 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).
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, and the rest may be an alkyl group or a cycloalkyl group.
Examples of the arylsulfonium compound include a triarylsulfonium compound, a diarylalkylsulfonium compound, a diarylcycloalkylsulfonium compound, an aryldialkylsulfonium compound, an aryldicycloalkylsulfonium compound, and an arylalkylcycloalkylsulfonium 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 that the arylsulfonium compound has as necessary is preferably a linear or branched alkyl group having 1 to 15 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an n-butyl group, sec- Examples thereof include a butyl group and a t-butyl group.
The cycloalkyl group that the arylsulfonium compound has as necessary is preferably a cycloalkyl group having 3 to 15 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, and a cyclohexyl group.
Aryl group, alkyl group of R ₂₀₁ to R _203, cycloalkyl group, 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 They are a C1-C4 alkyl group and a C1-C4 alkoxy group. The substituent may be substituted on any one of three R ₂₀₁ to R _203, or may be substituted on all three. When R _{201 to} R ₂₀₃ are an aryl group, the substituent is preferably substituted at the p-position of the aryl group.

Next, the compound (A1b) will be described.
The compound (A1b) is a compound in which R _{201 to} R ₂₀₃ in the general formula (A1) each independently represents an organic group having no aromatic ring. Here, the aromatic ring includes an aromatic ring having a hetero atom.
The aromatic ring-free organic group 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, a cycloalkyl group, an allyl group or a vinyl group, more preferably a linear or branched 2-oxoalkyl group, 2-oxocycloalkyl group, An alkoxycarbonylmethyl group, particularly preferably a linear or branched 2-oxoalkyl group.
The alkyl group as R ₂₀₁ to R ₂₀₃ may be linear, it may be either branched, preferably a straight-chain or branched alkyl group (e.g., methyl group having 1 to 20 carbon atoms, an ethyl group, a propyl Group, butyl group, pentyl group). The alkyl group as R ₂₀₁ to R ₂₀₃ is a straight-chain or branched 2-oxoalkyl group, an alkoxycarbonylmethyl group are preferred.
The cycloalkyl group as R ₂₀₁ to R ₂₀₃ is preferably, and a cycloalkyl group having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl, norbornyl). The cycloalkyl group as R ₂₀₁ to R ₂₀₃ is a 2-oxocycloalkyl group is more preferable.
The linear or branched 2-oxoalkyl group as R _{201 to} R ₂₀₃ may have a double bond in the chain, and preferably has> C═O at the 2-position of the alkyl group. The group can be mentioned.
The 2-oxocycloalkyl group as R _{201 to} R ₂₀₃ may have a double bond in the chain, and preferably includes a group having> C═O at the 2-position of the cycloalkyl group. be able to.
The alkoxy group in the alkoxycarbonylmethyl group as R ₂₀₁ to R _203, preferably may be mentioned alkoxy groups having 1 to 5 carbon atoms (a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group).
R _{201 to} R ₂₀₃ may be further substituted with a halogen atom, an alkoxy group (eg, having 1 to 5 carbon atoms), an alkoxycarbonyl group (eg, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group. .

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

In general formula (A1c):
_R213 represents an aryl group which may have a substituent, and is preferably a phenyl group or a naphthyl group.
Preferred substituents on the R _213, 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 each independently 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.
X ⁻ represents a sulfonate anion from which a hydrogen atom of the organic acid —SO ₃ H moiety represented by the general formula (I) is removed.
R ₂₁₃ and R ₂₁₄ may be bonded to form a ring structure, R ₂₁₄ and R ₂₁₅ may be bonded to form a ring structure, and Y ₂₀₁ and Y ₂₀₂ are bonded to each other. To form a ring structure. These ring structures may contain an oxygen atom, a sulfur atom, an ester bond, or an amide bond. Examples of the group R ₂₁₃ and R _214, R ₂₁₄ and R _215, Y ₂₀₁ and Y ₂₀₂ are formed by combined include a butylene group and a pentylene group.

The alkyl group as R ₂₁₄ , R ₂₁₅ , Y ₂₀₁ and Y ₂₀₂ is preferably a linear or branched alkyl group having 1 to 20 carbon atoms. The alkyl group as Y ₂₀₁ and Y ₂₀₂ is a 2-oxoalkyl group having> C═O at the 2-position of the alkyl group, an alkoxycarbonylalkyl group (preferably an alkoxy group having 2 to 20 carbon atoms), or a carboxyalkyl group. More preferred.
The cycloalkyl group as R ₂₁₄ , R ₂₁₅ , Y ₂₀₁ and Y ₂₀₂ is preferably a cycloalkyl group having 3 to 20 carbon atoms.
Y ₂₀₁ and Y ₂₀₂ are preferably an alkyl group having 4 or more carbon atoms, more preferably an alkyl group having 4 to 6, and further preferably 4 to 12.
In addition, at least one of R ₂₁₄ or R ₂₁₅ is preferably an alkyl group, and more preferably both R ₂₁₄ and R ₂₁₅ are alkyl groups.

In general formula (A2),
_R204 and _R205 each independently represents an aryl group, an alkyl group or a cycloalkyl group.
X ^- represents a general formula (I) an organic acid -SO ₃ sulfonate anion hydrogen atom H sites were taken indicated by.

The aryl group of R ₂₀₄ and R _205, a phenyl group, a naphthyl group, more preferably a phenyl group.
The alkyl group as _R204 and _R205 may be either linear or branched, and is preferably a linear or branched alkyl group having 1 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group). Group, butyl group, pentyl group).
The cycloalkyl group as R ₂₀₄ and R ₂₀₅ can preferably be mentioned a cycloalkyl group having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl, norbornyl).
_R204 and _R205 may have a substituent. Examples of the substituent that R ₂₀₄ and R ₂₀₅ 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), 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.

  The compound that generates the organic acid represented by the general formula (I) upon irradiation with actinic rays or radiation is preferably a compound represented by the general formula (A1), more preferably the general formula (A1a) to It is a compound represented by (A1c).

  Hereinafter, although the specific example of the compound which generate | occur | produces the organic acid represented by general formula (I) by irradiation of actinic light or a radiation is given, this invention is not limited to this.

  The sulfonium salt compound of the organic acid represented by the general formula (I) and the iodonium salt compound of the organic acid represented by the general formula (I) are novel compounds.

The compound (A) is synthesized from the compound represented by the general formula (I) or a lithium, sodium, potassium salt thereof, and hydroxide, bromide, chloride, etc. of iodonium or sulfonium, etc. It can be easily synthesized using the salt exchange method described in Japanese Patent Laid-Open No. 2003-246786.
The compound represented by the general formula (I) can be synthesized by using a general sulfonic acid esterification reaction. For example, a method in which one sulfonyl halide part of a bissulfonyl halide compound is reacted with an alcohol to form a sulfonic acid ester bond, and then the other sulfonyl halide part is hydrolyzed, or a cyclic sulfonic acid anhydride is represented by the general formula (I It can be obtained by a method of ring-opening with an alcohol containing a partial structure represented by

  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, and still more preferably based on the solid content of the composition. 1 to 7% by mass.

(Combination acid generator)
In the present invention, in addition to the compound (A), a compound capable of decomposing upon irradiation with actinic rays or radiation to generate an acid (acid generator) may be further used.

  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 (compound (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 ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represents an organic group.
The carbon number of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is generally 1-30, preferably 1-20.
Two of R _{201 to} R ₂₀₃ 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. 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).
Z ⁻ represents a non-nucleophilic anion.

Z ^- The non-nucleophilic anion as examples thereof include sulfonate anion, carboxylate anion, sulfonylimide anion, bis (alkylsulfonyl) imide anion, 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 aliphatic sulfonate anion, an aromatic sulfonate anion, and a camphor sulfonate anion.

  Examples of the carboxylate anion include an aliphatic carboxylate anion, an aromatic carboxylate anion, and an aralkylcarboxylate anion.

  The aliphatic moiety in the aliphatic sulfonate anion may be an alkyl group or a cycloalkyl group, preferably an alkyl group having 1 to 30 carbon atoms and a cycloalkyl group having 3 to 30 carbon atoms such as methyl. Group, ethyl 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 aromatic group in the aromatic 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 aliphatic sulfonate anion and aromatic sulfonate anion may have a substituent. Examples of the substituent of the alkyl group, cycloalkyl group, and aryl group in the aliphatic sulfonate anion and aromatic sulfonate anion include, for example, a nitro group, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), carboxyl group , Hydroxyl group, amino group, cyano group, alkoxy group (preferably having 1 to 5 carbon atoms), cycloalkyl group (preferably having 3 to 15 carbon atoms), aryl group (preferably having 6 to 14 carbon atoms), alkoxycarbonyl group ( Preferable examples include 2 to 7 carbon atoms, an acyl group (preferably 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably 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 aliphatic moiety in the aliphatic carboxylate anion include the same alkyl group and cycloalkyl group as in the aliphatic sulfonate anion.

  Examples of the aromatic group in the aromatic carboxylate anion include the same aryl group as in the aromatic sulfonate 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 aliphatic carboxylate anion, aromatic carboxylate anion and aralkylcarboxylate anion may have a substituent. Examples of the substituent of the alkyl group, cycloalkyl group, aryl group and aralkyl group in the aliphatic carboxylate anion, aromatic carboxylate anion and aralkylcarboxylate anion include, for example, the same halogen atom and alkyl as in the aromatic sulfonate anion Group, cycloalkyl group, alkoxy group, alkylthio group and the like.

  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. Examples of the substituent of these alkyl groups include a halogen atom, an alkyl group substituted with a halogen atom, an alkoxy group, and an alkylthio group, and an alkyl group substituted with a fluorine atom is preferable.

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

Examples of the non-nucleophilic anion of Z ⁻ include an aliphatic sulfonate anion in which the α-position of the sulfonic acid is substituted with a fluorine atom, an aromatic sulfonate anion substituted with a fluorine atom or a group having a fluorine atom, and an alkyl group. A bis (alkylsulfonyl) imide anion substituted with a fluorine atom and a tris (alkylsulfonyl) methide anion wherein an alkyl group is substituted with a fluorine atom are preferred. The non-nucleophilic anion is more preferably a perfluoroaliphatic sulfonic acid anion having 4 to 8 carbon atoms, a benzenesulfonic acid anion having a fluorine atom, still more preferably a nonafluorobutanesulfonic acid anion, a perfluorooctanesulfonic acid anion, It is a pentafluorobenzenesulfonic acid anion and 3,5-bis (trifluoromethyl) benzenesulfonic acid anion.

Examples of the organic group as R _201, R ₂₀₂ and R _203, for example, corresponding groups in the compounds (ZI-1), (ZI -2), can be exemplified corresponding groups in (ZI-3).

In addition, the compound which has two or more structures represented by general formula (ZI) may be sufficient. For example, the general formula at least one of R ₂₀₁ to R ₂₀₃ of a compound represented by (ZI) is, at least one bond with structure of R ₂₀₁ to R ₂₀₃ of another compound represented by formula (ZI) It may be a compound.

  More preferable (ZI) components include compounds (ZI-1), (ZI-2), and (ZI-3) described below.

The compound (ZI-1) is at least one of the aryl groups R ₂₀₁ to R ₂₀₃ in formula (ZI), arylsulfonium compounds, namely, compounds containing an 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 compound include triarylsulfonium compounds, diarylalkylsulfonium compounds, aryldialkylsulfonium compounds, diarylcycloalkylsulfonium compounds, and aryldicycloalkylsulfonium compounds.

  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.

Aryl group, alkyl group of R ₂₀₁ to R _203, cycloalkyl group, 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, more 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. When R _{201 to} R ₂₀₃ are an aryl group, the substituent is preferably substituted at the p-position of the aryl group.

Next, the compound (ZI-2) will be described.
Compound (ZI-2) is a compound in which R _{201 to} R ₂₀₃ in formula (ZI) each independently represents an organic group having 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, 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, particularly preferably a linear or branched 2-oxoalkyl group.

The alkyl group and cycloalkyl group of R ₂₀₁ to R _203, 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), 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. More preferred examples of the cycloalkyl group include a 2-oxocycloalkyl 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 alkoxy group having 1 to 5 carbon atoms (methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy group).

R _{201 to} R ₂₀₃ may be further substituted with a halogen atom, an alkoxy group (for example, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group.

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

In general formula (ZI-3),
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 each independently represents a hydrogen atom, an alkyl group or a cycloalkyl group.
R _x and R _y 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 , R _6c and R _7c , 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 and a sulfur atom. , An ester bond and an amide bond may be included. Examples of the group formed by combining any two or more of R _{1c to} R _5c , R _6c and R _7c , and R _x and R _y include a butylene group and a pentylene group.

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

The alkyl group as R _1c to R _7c may be linear or branched may be any of, for example, alkyl group having 1 to 20 carbon atoms, preferably 1 to 12 linear or branched alkyl group having a carbon number ( Examples thereof include a methyl group, an ethyl group, a linear or branched propyl group, a linear or branched butyl group, and a linear or branched pentyl group. Examples of the cycloalkyl group include cyclohexane having 3 to 8 carbon atoms. An alkyl group (for example, a cyclopentyl group, a cyclohexyl group) can be mentioned.

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 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 2-15. 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 group and cycloalkyl group as in R _{1c to} R _7c , such as a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxy group. A carbonylmethyl group is more preferred.

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 _7c .

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

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 general formulas (ZII) and (ZIII),
R ₂₀₄ to R ₂₀₇ each independently represents an aryl group, an alkyl group or a cycloalkyl group.

Phenyl group and a naphthyl group are preferred as the aryl group of R ₂₀₄ to R _207, more preferably a phenyl group.

The alkyl group and cycloalkyl group in R ₂₀₄ to R _207, 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), carbon Examples thereof include cycloalkyl groups of several 3 to 10 (cyclopentyl group, cyclohexyl group, norbornyl group).

Aryl group, alkyl group of R ₂₀₄ to R _207, cycloalkyl groups may have a substituent. Aryl group, alkyl group of R ₂₀₄ to R _207, the cycloalkyl group substituent which may be possessed by, for example, 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, having 6 to 15 carbon atoms), an alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, and a phenylthio group.

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

  Examples of the compound capable of decomposing upon irradiation with actinic rays or radiation that may be used in combination include compounds represented by the following general formulas (ZIV), (ZV), and (ZVI).

In general formulas (ZIV) to (ZVI),
Ar ₃ and Ar ₄ each independently represents an aryl group.
R ₂₀₆ , R ₂₀₇ and R ₂₀₈ each independently represents an alkyl group, a cycloalkyl 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, particularly preferably a sulfonium salt of monovalent perfluoroalkanesulfonic acid.

  Of the compounds that decompose upon irradiation with actinic rays or radiation that may be used in combination, particularly preferred examples 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)”)
Resins that are decomposed by the acid used in the positive photosensitive composition of the present invention and have increased solubility in an alkali developer have acid main chain or side chain, or both main chain and side chain. It is a resin having a group (hereinafter also referred to as an “acid-decomposable group”) that can be decomposed by. 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 preferably 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 preferably, it 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. An alkali-soluble resin containing a repeating unit having a carboxyl group such as (meth) acrylic acid or norbornenecarboxylic acid.

  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. Alkyl-2-adamantyl (meth) acrylate and dialkyl (1-adamantyl) methyl (meth) acrylate are more preferred.

  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.

When the positive photosensitive composition of the present invention is irradiated with KrF excimer laser light, electron beam, X-ray, or high energy light (EUV, etc.) having a wavelength of 50 nm or less, the resin of component (B) is a hydroxystyrene repeating unit. It is preferable to have. More preferably, hydroxystyrene / hydroxystyrene copolymer protected with an acid-decomposable group and hydroxystyrene / (meth) acrylic acid tertiary alkyl ester are preferred.
Specific examples of the component (B) used in the present invention are shown below, but the present invention is not limited thereto.

  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 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.

  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 (pV) and repeating units represented by the following general formula (II-AB) A resin having one kind is preferred.

In general formulas (pI) to (pV),
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 is an atom necessary for forming a cycloalkyl group together with a carbon atom. Represents a group.
R _{12 to} R ₁₆ each independently represents a linear or branched alkyl group or cycloalkyl group having 1 to 4 carbon atoms. However, at least one of R _{12 to} R ₁₄ , or any of R ₁₅ and R ₁₆ represents a cycloalkyl 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 a cycloalkyl group. However, at least one of R _{17 to} R ₂₁ represents a cycloalkyl group. Further, either R ₁₉ or R ₂₁ represents a linear or branched alkyl group or cycloalkyl 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 a cycloalkyl group. However, at least one of R _{22 to} R ₂₅ represents a cycloalkyl group. R ₂₃ and R ₂₄ may be bonded to each other to form a ring.

In general 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-AB1) or general formula (II-AB2).

In general formulas (II-AB1) and (II-AB2),
R ₁₃ ′ to R ₁₆ ′ each independently represents a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, —COOH, —COOR ₅ , a group that decomposes by the action of an acid, —C (═O) —XA ′. -R ₁₇ ', an alkyl group or a cycloalkyl group. Further, at least two of R ₁₃ ′ to R ₁₆ ′ may be bonded to form a ring.
Wherein, R ₅ represents an alkyl group, a cycloalkyl group or a group having a lactone structure.
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.
R ₁₇ ′ represents —COOH, —COOR ₅ , —CN, a hydroxyl group, an alkoxy group, —CO—NH—R ₆ , —CO—NH—SO ₂ —R ₆ or a group having a lactone structure.
R ₆ represents an alkyl group or a cycloalkyl group.
n represents 0 or 1.

In the general formulas (pI) to (pV), the alkyl group in R _{12 to} R ₂₅ represents a linear or branched alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, or a propyl group. , N-butyl group, sec-butyl group, t-butyl group and the like.

The cycloalkyl group represented by R _{12 to} R ₂₅ or the cycloalkyl group formed by Z and the 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.

  Preferred cycloalkyl groups include adamantyl group, noradamantyl group, decalin residue, tricyclodecanyl group, tetracyclododecanyl group, norbornyl group, cedrol group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, A cyclodecanyl group and a cyclododecanyl group can be mentioned. More preferable examples include an adamantyl group, a norbornyl group, a cyclohexyl group, a cyclopentyl group, a tetracyclododecanyl group, and a tricyclodecanyl group.

  These alkyl groups and cycloalkyl groups may further have a substituent. As further substituents for alkyl groups and cycloalkyl groups, alkyl groups (1 to 4 carbon atoms), halogen atoms, hydroxyl groups, alkoxy groups (1 to 4 carbon atoms), carboxyl groups, alkoxycarbonyl groups (2 to 2 carbon atoms). 6). The above alkyl group, alkoxy group, alkoxycarbonyl group and the like may further have a substituent. 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 (pV) 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 structure in which a hydrogen atom of a carboxylic acid group, a sulfonic acid group, a phenol group, or a thiol group is substituted with a structure represented by the general formulas (pI) to (PV), preferably a carboxylic acid Group, the hydrogen atom of a sulfonic acid group is the structure substituted by the structure represented by general formula (pI)-(PV).

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

In the general formula (pA), 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 represents a single bond, 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. A single bond is preferable.
Rp1 represents any one of the general formulas (pI) to (pV).

  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 above structural formulas, Rx represents H, CH ₃ , CF ₃ or CH ₂ OH, and Rxa and Rxb each independently represents an alkyl group having 1 to 4 carbon atoms.

In the general formula (II-AB), examples of the halogen atom represented by R ₁₁ ′ and R ₁₂ ′ include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom.

As the alkyl group for R ₁₁ ′ and R ₁₂ ′, a linear or branched alkyl group having 1 to 10 carbon atoms is preferable, for example, methyl group, ethyl group, n-propyl group, isopropyl group, linear group Or a branched butyl group, pentyl group, hexyl group, heptyl group, etc. are mentioned.

  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.

As the skeleton of alicyclic hydrocarbon formed are the same as those of the cycloalkyl group in R ₁₂ to R ₂₅ in formulas (pI) ~ (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-AB1) or (II-AB2).

  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 (pV). It can be contained in at least one kind of repeating unit among the repeating unit having, the repeating unit represented by 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-AB1) or the general formula (II-AB2) are atomic groups for forming an alicyclic structure in the general formula (II-AB). It can also be a substituent of the atomic group Z for forming a bridged alicyclic structure.

  Specific examples of the repeating unit represented by the general formula (II-AB1) or (II-AB2) include the following specific examples, 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 repeating unit having a lactone group. As the lactone group, any group having a lactone structure can be used, but a group having a 5- to 7-membered ring lactone structure is preferred, and a bicyclo structure or spiro is added to the 5- to 7-membered ring lactone structure. Those in which other ring structures are condensed to form a structure are preferred. The alicyclic hydrocarbon-based acid-decomposable resin of the present invention preferably has a repeating unit having a group having a lactone structure represented by any of the following general formulas (LC1-1) to (LC1-16). . Further, a group having a lactone structure may be directly bonded to the main chain. Preferred lactone structures are (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), (LC1-14), and a specific lactone structure is used. This improves line edge roughness and development defects.

  The lactone structure moiety may or may not have a substituent (Rb2). As preferred substituents (Rb2), an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, a carboxyl group, Examples thereof include a halogen atom, a hydroxyl group, a cyano group, and an acid-decomposable group. n2 represents an integer of 0 to 4. When n2 is an integer of 2 or more, a plurality of Rb2s may be the same or different, and a plurality of Rb2s may be bonded to form a ring.

As the repeating unit having a group having a lactone structure represented by any one of the general formulas (LC1-1) to (LC1-16), R _{13 in the} general formula (II-AB1) or (II-AB2) is used. A group having a group represented by general formula (LC1-1) to (LC1-16) in at least one of 'to R ₁₆ ' (for example, R _{5 of} -COOR ₅ is represented by formulas (LC1-1) to ( And a repeating unit represented by the following general formula (AI).

In general formula (AI), Rb ₀ represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms.
Examples of the alkyl group for Rb ₀ include a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, and a t-butyl group. The alkyl group for Rb ₀ may have a substituent. Preferable substituents that the alkyl group of Rb ₀ may have include, for example, a hydroxyl group and a halogen atom.

Examples of the halogen atom for Rb ₀ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Rb0 is preferably a hydrogen atom or a methyl group.

Ab is an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, a single bond, an ether group, an ester group, a carbonyl group, a carboxyl group, or a divalent group obtained by combining these. To express. Preferably, it is a linking group represented by a single bond or -Ab ₁ -CO _2- .
Ab ₁ is a linear, branched alkylene group, monocyclic or polycyclic cycloalkylene group, preferably a methylene group, an ethylene group, a cyclohexyl residue, an adamantyl residue, or a norbornyl residue.

  V represents a group represented by any one of the general formulas (LC1-1) to (LC1-16).

The repeating unit having a lactone structure usually has an optical isomer, but any optical isomer may be used. One optical isomer may be used alone, or a plurality of optical isomers may be mixed and used. When one kind of optical isomer is mainly used, the optical purity (ee) thereof is preferably 90 or more, more preferably 95 or more.
Specific examples of the repeating unit having a group having a lactone structure are given below, but the present invention is not limited thereto.

The alicyclic hydrocarbon-based acid-decomposable resin of the present invention preferably has a repeating unit having an alicyclic hydrocarbon structure substituted with a polar group. This improves the substrate adhesion and developer compatibility. The polar group is preferably a hydroxyl group or a cyano group.
Examples of the alicyclic hydrocarbon structure substituted with a polar group include structures represented by the following general formula (VIIa) or (VIIb).

In the general formula _{(VIIa), R 2 c~R 4} c each independently represents a hydrogen atom, a hydroxyl group or a cyano group. However, at least one of R ₂ c to R ₄ c represents a hydroxyl group or a cyano group. Preferably, one or two of R ₂ c to R ₄ c are a hydroxyl group and the remaining is a hydrogen atom, more preferably _two of R ₂ c to R ₄ c are a hydroxyl group and the remaining is a hydrogen atom. It is.

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

The repeating unit having a group represented by the general formula (VIIa) or (VIIb) includes at least one of R ₁₃ ′ to R ₁₆ ′ in the general formula (II-AB1) or (II-AB2). Having the group represented by the above general formula (VIIa) or (VIIb) (for example, R _{5 in} —COOR ₅ represents a group represented by the general formula (VIIa) or (VIIb)), or the following general group Mention may be made of the repeating units of the formula (AIIa) or (AIIb).

In the general formulas (AIIa) and (AIIb), R ₁ c represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.
R ₂ c to R ₄ c have the same meanings as in R ₂ c to R ₄ c in formula (VIIa).

  Specific examples of the repeating unit having an alicyclic hydrocarbon structure substituted with a polar group represented by the general formula (AIIa) or (AIIb) will be given below, but the present invention is not limited thereto.

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

In 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 the present invention is not limited thereto.

  The alicyclic hydrocarbon-based acid-decomposable resin of the present invention preferably has a repeating unit having an alkali-soluble group, and more preferably has a repeating unit having a carboxyl group. By having this, the resolution in contact hole applications increases. The repeating unit having a carboxyl group includes a repeating unit in which a carboxyl group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid or methacrylic acid, or a carboxyl group in the main chain of the resin through a linking group. Any of the bonded repeating units is preferable, and the linking group may have a monocyclic or polycyclic hydrocarbon structure. Most preferred are acrylic acid and methacrylic acid.

  The alicyclic hydrocarbon-based acid-decomposable resin of the present invention may have a repeating unit having 1 to 3 groups represented by the following general formula (F1). This improves line edge roughness performance.

In general formula (F1), R _{50 to} R ₅₅ each independently represents a hydrogen atom, a fluorine atom or an alkyl group. However, at least one of R _{50 to} R ₅₅ represents a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom.
Rx represents a hydrogen atom or an organic group (preferably an acid-decomposable protecting group, an alkyl group, a cycloalkyl group, an acyl group, or an alkoxycarbonyl group).

The alkyl group of R _{50 to} R ₅₅ may be substituted with a halogen atom such as a fluorine atom, a cyano group, etc., preferably an alkyl group having 1 to 3 carbon atoms, such as a methyl group or a trifluoromethyl group. be able to.
R _{50 to} R ₅₅ are preferably all fluorine atoms.

  Examples of the organic group represented by Rx include an acid-decomposable protective group and an optionally substituted alkyl group, cycloalkyl group, acyl group, alkylcarbonyl group, alkoxycarbonyl group, alkoxycarbonylmethyl group, alkoxymethyl group. , 1-alkoxyethyl group is preferable.

  Preferred examples of the repeating unit having a group represented by the general formula (F1) include a repeating unit represented by the following general formula (F2).

In General Formula (F2), Rx represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. Preferable substituents that the alkyl group of Rx may have include a hydroxyl group and a halogen atom.
Fa represents a single bond or a linear or branched alkylene group, preferably a single bond.
Fb represents a monocyclic or polycyclic hydrocarbon group.
Fc represents a single bond or a linear or branched alkylene group, preferably a single bond or a methylene group.
F ₁ represents a group represented by the general formula (F1).
P ₁ represents a 1 to 3.

  The cyclic hydrocarbon group in Fb is preferably a cyclopentyl group, a cyclohexyl group, or a norbornyl group.

  Specific examples of the repeating unit having the structure of the general formula (F1) are shown below.

  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. It can have various repeating structural units 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 (pV) (side chain type)
Those having a repeating unit of (meth) acrylate preferably having a structure of (pI) to (pV).
(2) Having a repeating unit represented by the general formula (II-AB) (main chain type)
However, in (2), for example, the following can be further mentioned.
(3) Those having a repeating unit represented by formula (II-AB), a maleic anhydride derivative structure 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 (pV) is 25 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 an alicyclic hydrocarbon represented by (pV) 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 alicyclic hydrocarbon-based acid-decomposable resin used in the present invention is preferably one in which all of the repeating units are composed of (meth) acrylate repeating units. In this case, all of the repeating units may be methacrylate, all of the repeating units may be acrylate, or a mixture of methacrylate / acrylate, but the acrylate repeating unit is preferably 50 mol% or less of the entire repeating unit.

  More preferably, the repeating unit having a partial structure containing an alicyclic hydrocarbon represented by the general formulas (pI) to (pV) is 25 to 50%, the repeating unit having the lactone structure is 25 to 50%, and the polarity is A ternary copolymer having 5 to 30% of repeating units having an alicyclic hydrocarbon structure substituted with a group, or a repeating unit having a structure represented by a carboxyl group or general formula (F1) It is a quaternary copolymer having 20%.

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, a monomer polymerization method in which a monomer species and an initiator are dissolved in a solvent and the polymerization is performed by heating, and a solution of the monomer species and the initiator is dropped into the heating solvent over 1 to 10 hours. The dropping polymerization method is added, and the dropping polymerization method is preferable. Examples of the reaction solvent include ethers such as tetrahydrofuran, 1,4-dioxane and diisopropyl ether, ketones such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate, amide solvents such as dimethylformamide and dimethylacetamide, Furthermore, the solvent which melt | dissolves the composition of this invention like the below-mentioned propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and cyclohexanone is mentioned. More preferably, the polymerization is performed using the same solvent as the solvent used in the photosensitive composition of the present invention. Thereby, generation | occurrence | production of the particle at the time of a preservation | save can be suppressed.
The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon. As a polymerization initiator, a commercially available radical initiator (azo initiator, peroxide, etc.) is used to initiate the polymerization. As the radical initiator, an azo initiator is preferable, and an azo initiator having an ester group, a cyano group, or a carboxyl group is preferable. Preferred examples of the initiator include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2′-azobis (2-methylpropionate) and the like. 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 5 to 50% by mass, preferably 10 to 30% by mass. The reaction temperature is usually 10 ° C to 150 ° C, preferably 30 ° C to 120 ° C, more preferably 50 to 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, a resin 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 having a trialkylsilyl structure or a monocyclic or polycyclic siloxane structure is preferable, and a resin having a structure represented by the following general formulas (SS-1) to (SS-4) is used. The resin which has the structure represented by general formula (SS-1)-(SS-4) is more preferable, and the resin which has a (meth) acrylate type repeating unit which has a structure represented by general formula (SS-1)-(SS-4), or an allyl type repeating unit is more. preferable.

  In general formulas (SS-1) to (SS-4), Rs represents an alkyl group having 1 to 5 carbon atoms, preferably a methyl group or an ethyl group.

The resin having a silicon atom preferably has a repeating unit having two or more different types of silicon atoms, more preferably (Sa) a repeating unit having 1 to 4 silicon atoms and (Sb) 5 to 10 silicon atoms. A resin having both of the repeating units, and more preferably, at least one repeating unit having a structure represented by formulas (SS-1) to (SS-3) and formula (SS-4). It is resin which has a repeating unit which has the structure represented by these.

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 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 independently represents a hydrogen atom, a fluorine atom, an alkyl group or an aryl group.
R ₁₀₄ and R ₁₀₆ are each independently 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, a cycloalkyl 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 A linking group having a plurality of R ₂₄ is a hydrogen atom or an alkyl group.
R ₁₀₇ and R ₁₀₈ are each independently 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, a cycloalkyl group, or a group that decomposes under the action of an acid.
a is 0 or 1.
b is 0, 1 or 2;
R ₁₀₀ and R ₁₀₁ in the general formulas (FA) and (FC) may form a ring via an alkylene group (having 1 to 5 carbon atoms) which may be substituted with fluorine.
However, 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.

  The weight average molecular weight of the resin of component (B) is preferably 2,000 to 200,000 as a polystyrene conversion value by GPC method. By making the weight average molecular weight 2,000 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. And since a viscosity becomes low, film forming property can be improved. The molecular weight is more preferably 5,000 to 50,000, and still more preferably 7,000 to 30,000. By adjusting the molecular weight, it is possible to achieve both heat resistance, resolution, development defects, and the like of the composition. The dispersity (Mw / Mn) of the component (B) resin is preferably 1.0 to 3.0, more preferably 1.2 to 2.5, and even more preferably 1.2 to 1.6. It is. The line edge roughness performance can be improved by adjusting the degree of dispersion to an appropriate range.

  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, more preferably 50 to 50% in the total solid content. It is 99 mass%, More preferably, it is 80-96 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 the present invention is 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 kg / sec or more as measured with 0.261N tetramethylammonium hydroxide (TMAH) (23 ° C.). Particularly preferably, it is 200 Å / second 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, 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) Acid crosslinking agent that crosslinks with the alkali-soluble resin by the action of 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 the formula, L ^{1 to} L ⁸ may be the same or different and each represents a hydrogen atom, a hydroxymethyl group, a methoxymethyl group, an ethoxymethyl group, or an alkyl group having 1 to 6 carbon atoms.
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>
[6] (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.

  Preferable structures include structures represented by the following formulas (A) to (E).

Here, R ²⁵⁰ , R ²⁵¹ and R ²⁵² are each independently a hydrogen atom, an alkyl having 1 to 20 carbons, a cycloalkyl group having 3 to 20 carbons or an aryl group having 6 to 20 carbons, 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, an aminocycloalkyl group having 3 to 20 carbon atoms, and 1 to 1 carbon atoms. A 20 hydroxyalkyl group or a C 3-20 hydroxycycloalkyl group is preferred.
These may contain an oxygen atom, a sulfur atom, or a nitrogen atom in the alkyl chain.

In the formula, R ²⁵³ , R ²⁵⁴ , R ²⁵⁵ and R ²⁵⁶ each independently represent 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 preferred compounds include compounds having an imidazole structure, diazabicyclo structure, onium hydroxide structure, onium carboxylate structure, trialkylamine structure, aniline structure or pyridine structure, alkylamine derivatives having a hydroxyl group and / or an ether bond, hydroxyl groups 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. Examples of the compound having a diazabicyclo structure include 1,4-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4,3,0] non-5-ene, and 1,8-diazabicyclo [5,4,0. ] Undec-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.

[7] (G) Fluorine and / or Silicone Surfactant The photosensitive composition of the present invention further comprises a fluorine and / or silicon surfactant (fluorine surfactant and silicon surfactant, fluorine It is preferable that one or two or more surfactants containing both atoms and silicon atoms are contained.

  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 F-top EF301, EF303 (manufactured by Shin-Akita Kasei Co., Ltd.), Florard FC430, 431 (manufactured by Sumitomo 3M Co., Ltd.), MegaFuck F171, F173, F176, F189, 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 a silicon-based 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. It 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 001 to 1% by mass, based on the total amount of the photosensitive composition (excluding the solvent). .

[8] (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 containing two or more solvents having different functional groups. As a mixed solvent having different functional groups, a mixed solvent in which a solvent having a hydroxyl group and a solvent having no hydroxyl group are mixed, or a mixed solvent in which a solvent having an ester structure and a solvent having a ketone structure are mixed is used. Is preferred. Thereby, the generation of particles during storage of the resist solution can be reduced.

  Examples of the solvent having 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. Propylene glycol monomethyl ether and ethyl lactate are particularly preferred.

Examples of the solvent having no hydroxyl group include propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, butyl acetate, N-methylpyrrolidone, N, N-dimethylacetamide, dimethyl sulfoxide. Of these, propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, and butyl acetate are more preferable, and propylene glycol monomethyl ether acetate, ethyl ethoxypropio Nate, 2-heptanone and cyclohexanone are particularly preferred.

  The mixing ratio (mass) of the solvent having a hydroxyl group and the solvent having no hydroxyl group is from 1/99 to 99/1, preferably from 10/90 to 90/10, more preferably from 20/80 to 60/40. . A mixed solvent containing 50% by mass or more of a solvent having no hydroxyl group is particularly preferable from the viewpoint of coating uniformity.

In a mixed solvent in which a solvent having an ester structure and a solvent having a ketone structure are mixed, examples of the solvent having a ketone structure include cyclohexanone and 2-heptanone, with cyclohexanone being preferred. Examples of the solvent having an ester structure include propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, γ-butyrolactone, and butyl acetate, with propylene glycol monomethyl ether acetate being preferred.
The mixing ratio (mass) of the solvent having an ester structure and the solvent having a ketone structure is 1/99 to 99/1, preferably 10/90 to 90/10, and more preferably 20/80 to 60/40. . A mixed solvent containing 50% by mass or more of a solvent having an ester structure is particularly preferable from the viewpoint of coating uniformity.

<Other additives>
If necessary, the photosensitive composition of the present invention further contains a dye, a plasticizer, a surfactant other than the component (G), a photosensitizer, a compound that promotes solubility in a developer, and the like. be able to.

  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 phenol compounds having a molecular weight of 1000 or less can be obtained by referring to methods described in, for example, JP-A-4-1222938, JP-A-2-28531, U.S. Pat. No. 4,916,210 and European Patent 219294. Can be easily 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.

(Pattern formation method)
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.
Exposure (immersion exposure) may be performed by filling a liquid having a higher refractive index than air between the photosensitive film and the lens during irradiation with actinic rays or radiation. Thereby, resolution can be improved.

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) An electron beam 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.

Synthesis Example 1 (Synthesis of Compound (A-1))
Under a nitrogen stream, a mixture of 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonyldifluoride 7.0 g (22.1 mmol) and THF 50 mL was ice-cooled, and 4-fluorophenol was added thereto. A mixed solution of 2.48 g (22.1 mmol), triethylamine 2.24 g (22.1 mmol) and THF 50 mL was added dropwise over 60 minutes. After completion of dropping, the mixture was stirred at room temperature for 5 hours. Ethyl acetate is added and the organic layer is washed successively with water, a saturated aqueous ammonium chloride solution and water, the organic layer is dried over sodium sulfate, the solvent is removed, brown, oily, represented by the general formula (I) of the following structure An organic acid halide was obtained.

  Methanol 100mL and 1N-NaOH50mL were added to this, and it stirred at room temperature for 1 hour. Ethyl acetate was added, the organic phase was washed with 50 mL of water, and the solvent was removed to obtain a brown, oily compound having the following structure.

The above compound was dissolved in 150 mL of methanol, 6.07 g (6.77 mmol) of triphenylsulfonium bromide was added, and the mixture was stirred at room temperature for 3 hours. Chloroform 200 mL was added, the organic layer was washed with water, the solvent was removed, and the target compound (12.0 g) was obtained as a colorless oil.
¹ H-NMR (500 MHz, CDCl3) δ 7.08 (m, 2H), 7.27 (m, 2H), 2.510 (bs, 1H), 7.67-7.78 (m, 15H)
¹⁹ F-NMR (500 MHz, CDCl3) δ -107.12 (m, 2F), -113.18 (m, 1F), -114.00 (m, 2F), -118.34 (m 2F)

  Other acid generators were synthesized in the same manner.

<Resin (B)>
The structure, molecular weight, and dispersity of the resin (B) used in the examples are shown.

Examples 1-17 and Comparative Examples 1-5
<Resist preparation>
The components shown in Table 1 below were dissolved in a solvent to prepare a solution having a solid concentration of 10% 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 Table 1.

  Hereinafter, abbreviations in the table are shown.

[Acid generator]
TPSB: Triphenylsulfonium pentafluorobenzenesulfonate TPSPB: Triphenylsulfonium perfluorobutanesulfonate TPSPFBSI: Triphenylsulfonium bis (perfluorobutanesulfonyl) imide TPSPP: Triphenylsulfonium 1, 1, 2, 2, 3, 3-hexafluoro -3-phenoxysulfonylpropane sulfonate (the following structure)

[Basic compounds]
TPI: 2,4,5-triphenylimidazole TPSA: triphenylsulfonium acetate HEP: N-hydroxyethylpiperidine DIA: 2,6-diisopropylaniline DCMA: dicyclohexylmethylamine TPA: tripentylamine HAP: hydroxyantipyrine TBAH: tetrabutyl Ammonium hydroxide TMEA: Tris (methoxyethoxyethyl) amine PEA: N-phenyldiethanolamine

[Surfactant]
W-1: MegaFuck 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 monomethyl ether acetate A2: 2-heptanone A3: Cyclohexanone A4: γ-butyrolactone B1: Propylene glycol monomethyl ether B2: Ethyl lactate

<Resist evaluation>
An antireflection film DUV-42 manufactured by Brewer Science Co., Ltd. was uniformly applied to 600 Å on a silicon substrate subjected to hexamethyldisilazane treatment with a spin coater, dried on a hot plate at 100 ° C. for 90 seconds, 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 0.20 μm resist film.
The resist film was exposed with an ArF excimer laser stepper (NA = 0.75 manufactured by ASML) 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.

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.

PEB temperature dependence:
The exposure amount that reproduces the line-and-space 1/1 with a mask size of 80 nm when post-heated at 120 ° C. for 90 seconds is the optimum exposure amount, and after performing exposure at the optimum 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.

Pattern profile:
The profile at the optimum exposure dose was observed with a scanning microscope (SEM).

  From Table 1, it is clear that the photosensitive composition of the present invention has good exposure latitude, PEB temperature dependency, and pattern profile.

[Immersion exposure evaluation]
<Resist preparation>
The components of Examples 1 to 17 shown in Table 1 were dissolved in a solvent to prepare a solution having a solid content concentration of 8% by mass, and this was filtered through a 0.1 μm polyethylene filter to prepare a positive resist solution. The prepared positive resist solution was evaluated by the following method.
<Resolution evaluation>
An organic antireflection film ARC29A (Nissan Chemical Co., Ltd.) was applied on a silicon wafer and baked at 205 ° C. for 60 seconds to form a 78 nm antireflection film. The prepared resist composition was applied thereon and baked at 120 ° C. for 60 seconds to form a 150 nm resist film. The wafer thus obtained was subjected to two-beam interference exposure (wet exposure) using pure water as the immersion liquid. In the two-beam interference exposure (wet), as shown in FIG. 1, a laser 1, an aperture 2, a shutter 3, three reflecting mirrors 4, 5, 6 and a condenser lens 7 are used, and a prism 8, liquid The wafer 10 having an antireflection film and a resist film was exposed through an immersion liquid (pure water) 9. The wavelength of the laser 1 was 193 nm, and the prism 8 forming a 65 nm line and space pattern was used. Immediately after the exposure, the resist pattern obtained by heating at 120 ° C. for 60 seconds, developing with an aqueous tetramethylammonium hydroxide solution (2.38%) for 60 seconds, rinsing with pure water, and spin drying is applied to the scanning pattern. When observed using a microscope (S-9260, manufactured by Hitachi), a 65 nm line and space pattern was resolved.
The compositions of Examples 1 to 17 had good image forming ability even in the exposure method through the immersion liquid.

Examples 18-23 and Comparative Examples 6-9
(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 the upper resist layer The components shown in Table 2 below are dissolved in a solvent to prepare a solution having a solid content of 11% by mass, and the solution is precisely filtered through a membrane filter having a diameter of 0.1 μm to prepare an upper resist composition. did.
The upper resist composition was applied onto the lower resist layer in the same manner as the lower layer, heated at 130 ° C. for 90 seconds to form an upper resist layer having a thickness of 0.20 μm, and evaluation was performed as follows.

  Resins (SI-1) to (SI-5) in Table 2 are as follows.

(3) Resist evaluation The wafer thus obtained was exposed with an ArF excimer laser stepper (NAML = 0.75 manufactured by ASML) through a mask, and immediately after exposure, 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.

Exposure latitude:
The exposure amount that reproduces a 130-nm line-and-space mask pattern is set as the optimal exposure amount, and when the exposure amount is changed, an exposure amount width that allows a pattern size of 130 nm ± 10% is obtained. 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.

PEB temperature dependence:
The exposure amount that reproduces the line-and-space 1/1 with a mask size of 130 nm when post-heated at 120 ° C. for 90 seconds is 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.

Pattern profile:
The profile at the optimum exposure dose was observed with a scanning microscope (SEM).
The evaluation results are shown in Table 2.

  From the results in Table 2, it can be seen that the photosensitive composition of the present invention has good exposure latitude, PEB temperature dependency, and pattern profile even when used as a two-layer resist.

Examples 24-29 and Comparative Examples 10-13
<Resist preparation>
The components shown in Table 3 below 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 14% by mass, and evaluated as follows. .

  The weight average molecular weights and dispersities of the resins (R-1) to (R-5) used in Table 3 are shown in Table 4 below.

<Resist evaluation>
The prepared positive resist solution is uniformly coated 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 0.4 μm resist. A film was formed.
This resist film was subjected to pattern exposure using a KrF excimer laser stepper (NA = 0.63) using a line and space mask, and immediately after 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 form a line pattern.

Exposure latitude:
The exposure amount that reproduces a 130-nm line-and-space mask pattern is set as the optimal exposure amount, and when the exposure amount is changed, an exposure amount width that allows a pattern size of 130 nm ± 10% is obtained. 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.

PEB temperature dependence:
The exposure amount that reproduces the line-and-space 1/1 with a mask size of 130 nm when post-heated at 120 ° C. for 90 seconds is 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.

Pattern profile:
The profile at the optimum exposure dose was observed with a scanning microscope (SEM).
The evaluation results are shown in Table 3.

From the results in Table 3, it can be seen that the photosensitive composition of the present invention has good exposure latitude, PEB temperature dependency, and pattern profile even as a positive resist composition in KrF excimer laser exposure.

Examples 30 to 35 and Comparative Examples 14 to 17
The components shown in Table 5 below 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 content concentration of 11% by mass.
For the prepared negative resist solution, the exposure latitude, PEB temperature dependency, and pattern profile were evaluated in the same manner as in Example 24.
The evaluation results are shown in Table 5.

The structure, molecular weight, molecular weight distribution, and crosslinking agent of the alkali-soluble resin in Table 5 are shown below.

  From Table 5, it can be seen that the photosensitive composition of the present invention has good exposure latitude, PEB temperature dependency, and pattern profile even as a negative resist composition in KrF excimer laser exposure.

Examples 36 to 41 and Comparative Examples 18 to 21
<Resist preparation>
The components shown in Table 3 above 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 11% by mass, and evaluated as follows. .

<Resist evaluation>
The prepared positive resist solution is uniformly coated 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 0.25 μm resist. A film was formed.
This resist film was irradiated with a pattern with an electron beam direct drawing device (acceleration voltage 50 keV), and immediately after irradiation, heated on a hot plate at 120 ° 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.

Exposure latitude:
The irradiation dose that reproduces a line-and-space with a line width of 130 nm is set as the optimum irradiation dose, and when the irradiation dose is changed, a dose width that allows a pattern size of 130 nm ± 10% is obtained, and this value is divided by the optimum irradiation dose. Percentages. The larger the value, the smaller the change in performance due to the change in dose, and the better the exposure latitude.

PEB temperature dependence:
The exposure amount that reproduces the line-and-space 1/1 with a mask size of 130 nm when post-heated at 120 ° C. for 90 seconds is 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.

Pattern profile:
The profile at the optimum exposure dose was observed with a scanning microscope (SEM).
The evaluation results are shown in Table 6 below.

  From Table 6, it can be seen that the photosensitive composition of the present invention has good exposure latitude, PEB temperature dependency, and pattern profile even as a positive resist composition in electron beam exposure.

Examples 42 to 47 and Comparative Examples 22 to 25
The components shown in Table 5 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 content concentration of 11% by mass.
For the prepared negative resist solution, the exposure latitude, PEB temperature dependency, and pattern profile were evaluated in the same manner as in Example 36.
The evaluation results are shown in Table 7 below.

  From Table 7, it can be seen that the photosensitive composition of the present invention has good exposure latitude, PEB temperature dependency, and pattern profile even as a negative resist composition in electron beam exposure.

Examples 48-53 and Comparative Examples 26-29
The components shown in Table 3 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 8% by mass, and evaluated as follows. .

<Resist evaluation>
The prepared positive resist solution is uniformly coated 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 0.15 μm resist. A film was formed. The obtained resist film was subjected to surface exposure using EUV light (wavelength 13 nm) while changing the exposure amount by 0.5 mJ in the range of 0 to 10.0 mJ, and further baked at 110 ° C. for 90 seconds. Then, using a 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution, the dissolution rate at each exposure amount was measured to obtain a sensitivity curve. In this sensitivity curve, the exposure amount when the dissolution rate of the resist is saturated was taken as sensitivity, and the dissolution contrast (γ value) was calculated from the gradient of the linear portion of the sensitivity curve. The larger the γ value, the better the dissolution contrast.
The evaluation results are shown in Table 8 below.

  From the results of Table 8, it can be seen that the resist composition of the present invention is superior in sensitivity and high contrast as compared with the composition of the comparative example in the property evaluation by irradiation with EUV light.

It is the schematic of a two-beam interference exposure experiment apparatus.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Laser 2 Aperture 3 Shutter 4, 5, 6 Reflection mirror 7 Condensing lens 8 Prism 9 Immersion liquid 10 Wafer having antireflection film and resist film 11 Wafer stage

Claims (12)

(A) containing a sulfonium salt compound or an iodonium salt compound of an organic acid represented by the general formula (I) that generates an organic acid represented by the following general formula (I) by irradiation with actinic rays or radiation. A photosensitive composition.
In general formula (I),
A represents a divalent linking group.
X represents —CO ₂ — or —SO ₃ —.
Rf represents a monovalent organic group having a fluorine atom.   2. The photosensitive composition according to claim 1, further comprising (B) a resin that decomposes by the action of an acid and increases the solubility in an alkali developer. 3.   The photosensitive composition according to claim 2, wherein the resin that decomposes by the action of an acid and has increased solubility in an alkaline developer has a hydroxystyrene structural unit.   3. The photosensitive composition according to claim 2, wherein the resin that decomposes by the action of an acid and has increased solubility in an alkali developer has a repeating unit having a monocyclic or polycyclic hydrocarbon structure. object.   Further, (D) a resin soluble in an alkali developer and (E) the alkali developer by the action of an acid.
The photosensitive composition according to claim 1, further comprising an acid cross-linking agent that cross-links with a soluble resin.   The photosensitive composition according to claim 4, wherein the resin that decomposes by the action of an acid and has increased solubility in an alkaline developer contains a repeating unit represented by the following general formula (AI): .

  In general formula (AI), Rb ₀ Represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms.
  Ab is an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, a single bond, an ether group, an ester group, a carbonyl group, a carboxyl group, or a divalent group obtained by combining these. To express.
  V represents a group represented by any one of the general formulas (LC1-1) to (LC1-16).

  Rb ₂ Represents a substituent. n ₂ Represents an integer of 0 to 4. n ₂ When R is an integer of 2 or more, there are a plurality of Rb ₂ May be the same or different, and a plurality of Rb ₂ They may combine to form a ring.   The compound (A) that generates an organic acid represented by the general formula (I) upon irradiation with actinic rays or radiation is a compound represented by the following general formula (A1) or (A2) Item 7. The photosensitive composition according to any one of Items 1 to 6.

  In general formulas (A1) and (A2),
  R ₂₀₁ , R ₂₀₂ And R ₂₀₃ Each independently represents an organic group.
  R ₂₀₄ And R ₂₀₅ Each independently represents an aryl group, an alkyl group or a cycloalkyl group.
  X ^- Is an organic acid -SO represented by the general formula (I) _Three It represents a sulfonate anion from which a hydrogen atom at the H site has been removed.   Furthermore, in addition to the compound (A) that generates an organic acid represented by the general formula (I) upon irradiation with actinic rays or radiation, it contains a compound that decomposes upon irradiation with actinic rays or radiation to generate an acid The photosensitive composition according to claim 1, wherein the photosensitive composition is characterized in that A pattern forming method comprising: forming a resist film from the photosensitive composition according to claim 1 ; and exposing and developing the resist film.   The pattern forming method according to claim 9, wherein the exposure is performed through an immersion liquid. An organic acid represented by the following general formula (I), a salt thereof or a halide thereof.
In general formula (I),
A represents a divalent linking group.
X represents —CO ₂ — or —SO ₃ —.
Rf represents a cycloalkyl group having a fluorine atom. A sulfonium salt compound of an organic acid represented by the following general formula (I) or an iodonium salt compound of an organic acid represented by the general formula (I):
In general formula (I),
A represents a divalent linking group.
X represents —CO ₂ — or —SO ₃ —.
Rf represents a monovalent organic group having a fluorine atom.