JP2005122134A - Photosensitive composition and pattern-forming method using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive composition for use in manufacturing steps of a semiconductor such as an IC, for manufacture of a circuit board of a liquid crystal, a thermal head or the like, or for other photofabrication steps, the photosensitive composition having a wide margin of exposure and little dependence on pattern density, and to provide a rpattern-forming using the composition. <P>SOLUTION: The photosensitive composition contains a compound which generates a specified acid having a plurality of sulfonic acid groups by irradiation with active rays or radiation. The pattern-forming method is carried out by using the composition. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a photosensitive composition whose properties change upon reaction with irradiation of actinic rays or radiation. More specifically, the present invention relates to a resist composition used in a semiconductor manufacturing process such as an IC, a circuit board such as a liquid crystal or a thermal head, and other photofabrication processes.

  The chemically amplified resist composition generates an acid in the exposed area by irradiation with radiation such as far ultraviolet light, and the acid-catalyzed reaction changes the solubility of the active radiation irradiated area and non-irradiated area in the developer. And a pattern forming material for forming a pattern on the substrate.

  When a KrF excimer laser is used as an exposure light source, a resin having a basic skeleton of poly (hydroxystyrene) having a small absorption mainly in the 248 nm region is used as a main component. A pattern is formed, which 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.
For this reason, an ArF excimer laser resist containing a resin having an alicyclic hydrocarbon structure has been developed.

Various compounds have also been found for acid generators, which are the main constituents of chemically amplified resists. Patent Document 1 (Japanese Patent Laid-Open No. 9-309874) discloses a divalent arylsulfonic acid sulfonium salt or iodonium salt. A positive photosensitive composition is described.
However, performance such as an exposure margin whose performance changes due to a slight change in exposure amount, or a density dependency where performance changes due to the density of patterns such as dense patterns and isolated patterns has not been sufficient, and improvement has been demanded.

  Further, since the resin having an alicyclic hydrocarbon structure becomes extremely hydrophobic as a harmful effect of the alicyclic hydrocarbon structure, tetramethylammonium hydroxide (hereinafter, TMAH), which has been widely used as a resist developer, has been widely used. Phenomena such as difficulty in development with an aqueous solution and peeling of the resist from the substrate during development are observed.

For example, in Patent Document 2 (Japanese Patent Laid-Open No. 9-73173) and Patent Document 3 (Japanese Patent Laid-Open No. 10-161313), an alkali-soluble group protected with a structure containing an alicyclic group, and the alkali-soluble group is an acid. Describes a resist material using an acid-sensitive compound containing a structural unit that is eliminated by the above-described method and becomes alkali-soluble. These materials are excellent designs that provide hydrophilic / hydrophobic contrast because the structure containing hydrophobic alicyclic groups is eliminated. However, the developability with aqueous TMAH solution and the peeling of the resist from the substrate during development are important. Was still not enough. For this reason, various studies have been made on the introduction of a hydrophilic group into a resin having an alicyclic hydrocarbon moiety introduced therein.
In Patent Document 4 (Japanese Patent No. 2776273) and Patent Document 5 (Japanese Patent Laid-Open No. 11-109632), a resin containing a polar group-containing alicyclic functional group and an acid-decomposable group is used as a radiation-sensitive material. Has been described.
Further, Patent Documents 6 to 10 (Japanese Patent Laid-Open Nos. 9-90637, 10-2007069, 10-274852, 2001-188351, Japanese Patent 3042618).
No.) describes a photoresist composition containing a polymer obtained by copolymerizing a (meth) acrylate derivative having a lactone structure with another polymerizable compound.

  Patent Documents 11 to 14 (JP 2001-109154, JP 2000-137327, JP 2002-296783, JP 2001-215704) describe the lactone monomer and the polar group-containing alicyclic functional group. A positive photoresist composition containing a copolymer resin of a monomer having a hydroxyadamantane structure as a group is described.

  As described above, various means as described above for improving the hydrophobicity of the resin have been studied. However, the above techniques still have insufficient points, and improvement is desired. In particular, when a fine pattern having a line width of 100 nm or less is formed, the pattern does not depend on the mask coverage ratio (exposed portion / non-exposed portion area ratio) and the pattern pitch, that is, regardless of the presence / absence of pattern density. It is required that the film is not easily affected by variations in the forming conditions (exposure amount and focus) (that is, the process window is wide). However, the composition as described above still has room for improvement with respect to the process window.

  In addition, the resist for ArF excimer laser containing a resin having an alicyclic hydrocarbon structure causes the resist pattern to collapse when a fine pattern with a line width of 100 nm or less is formed, and subsequent substrate processing by dry etching cannot be performed. There was a problem. This problem becomes more prominent as the processing line width becomes finer, and a resist capable of forming a fine pattern without falling is demanded.

  Further, it is necessary to form a fine pattern with a line width of 100 nm or less, and it is difficult to ensure a defocus latitude (DOF) (DOF), particularly when forming an isolated pattern. There is a need for resist compositions having wider DOF performance.

  When forming a resist pattern from a resist composition, it is generally used by dissolving the composition in an appropriate solvent, but the accuracy and resolution of the resulting resist pattern are used when forming the resist pattern. It depends greatly on the type and combination of solvents used. Furthermore, when the composition is applied as a solution on a substrate (especially by spin coating), there is a problem that the surface of the applied resist film is not always sufficiently uniform and the film thickness uniformity is insufficient. .

  Conventionally, various solutions such as ethers, glycol ethers, glycol ether acetates, cellosolve esters, aromatic hydrocarbons, ketones, esters, etc. are used as solutions of chemically amplified radiation sensitive compositions. There are a wide variety of types used, and the characteristics of the resist pattern are closely related to the composition used.

  For example, Patent Document 15 (Japanese Patent Application Laid-Open No. 10-254139) includes (A) an alkali-insoluble or hardly alkali-soluble acid-cleavable group-containing resin having an alicyclic skeleton in the main chain and / or side chain, Resins that become alkali-soluble when the acid-cleavable group is cleaved, (B) a radiation-sensitive acid generator that generates an acid upon irradiation with radiation, and (C) a cyclic ketone or propylene glycol monoalkyl ether acetate and 2-hydroxy Radiation-sensitive resin composition characterized by containing a solvent comprising a mixture of at least one selected from the group of alkyl propionates and linear ketones, transparency to radiation, dry etching resistance, film thickness uniformity In addition, it is described that a radiation-sensitive resin composition excellent in substrate adhesion, sensitivity, resolution, developability and the like can be provided.

Patent Document 16 (Japanese Patent Laid-Open No. 2000-241964) includes cyclohexanone, isobutyl methyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, cyclopentanone, 2-methylcyclopentanone, and 3-methylcyclopenta. Non-, 2-methylcyclohexanone, 3-methylcyclohexanone, and photoresist compositions containing ketone solvents such as 2,4-dimethylpentanone show fluidization, even in an atmosphere where a high concentration of amine exists Further, it is described that an excellent fine photoresist pattern can be obtained without adding a separate step for amine removal, and the cost can be reduced.

  However, the scope of application of the contents disclosed in these documents is not necessarily wide, and from the viewpoint of the overall performance as a resist, an appropriate resin according to the composition such as a resin, a photoacid generator, and an additive used. In reality, it is extremely difficult to find a solvent or a combination thereof, and furthermore, resist pattern collapse prevention when forming a fine pattern having a line width of 100 nm or less, and an allowable defocus range for an isolated line pattern ( There was still a need for improvement in terms of defocus latitude.

JP-A-9-309874 JP-A-9-73173 JP-A-10-161313 Japanese Patent No. 2776273 JP-A-11-109632 JP-A-9-90637 JP-A-10-207069 JP-A-10-274852 JP 2001-188351 A Japanese Patent No. 3042618 Japanese Patent Laid-Open No. 2001-109154 JP 2000-137327 A Japanese Patent Laid-Open No. 2002-296783 JP 2001-215704 A Japanese Patent Laid-Open No. 10-254139 JP 2000-241964 A

Accordingly, an object of the present invention is to provide an excellent photosensitive composition having a wide exposure margin and small dependence on density.
Furthermore, even in the formation of a fine pattern of 110 nm or less, a positive resist composition with little pattern collapse and a wide defocus latitude (DOF) in forming an isolated line pattern, or a wide process window in forming isolated lines and dense patterns. It is an object of the present invention to provide a positive resist composition that can be secured, and a pattern forming method using them.

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

  (1) As a photosensitive composition having a wide exposure margin and low density dependency, (A) containing a compound capable of generating a sulfonic acid represented by the following general formula (I) by irradiation with actinic rays or radiation. A photosensitive composition is provided.

In general formula (I),
A ₁ represents an n-valent linking group.
A ₂ represents a single bond or a divalent aliphatic group. The n A _{2 s} may be the same or different.
However, at least one of the group represented by A ₁ and the group represented by A ₂ has a fluorine atom.
n represents an integer of 2 to 4.

  (2) In addition to having the performance of the photosensitive composition described in (1) above, there is little occurrence of pattern collapse even in the formation of fine patterns of 110 nm or less, and defocus latitude (DOF) in forming isolated line patterns. In addition, as a positive photosensitive composition having a wide range, (Ba) a resin having a monocyclic or polycyclic alicyclic hydrocarbon structure and having increased solubility in an alkaline developer by the action of an acid, and (Ha) at least one A positive photosensitive composition as described in (1) above, which contains a solvent containing a cyclic ketone.

  (3) As a positive photosensitive composition that has the performance of the photosensitive composition as described in (1) above and is capable of ensuring a wide process window in forming isolated lines and dense patterns, (Baa) Having at least one repeating unit selected from the repeating unit represented by the general formula (1), the repeating unit represented by the general formula (2) and the repeating unit represented by the general formula (3), The positive photosensitive composition as described in (1) is provided, which contains a resin whose solubility in an alkaline developer is increased by action.

In general formula (1),
R represents a hydrogen atom or a methyl group.
A represents a single bond or a linking group.
ALG represents a group represented by any one of the following general formulas (pI) to (pV).

In the 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.
Z represents an atomic group necessary for forming an alicyclic hydrocarbon group together with a carbon atom.
R _{12 to} R ₁₆ each independently represents a linear or branched alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group. However, at least one of R _{12 to} R ₁₄ and any one of R ₁₅ and R ₁₆ represents an alicyclic hydrocarbon group.
R _{17 to} R ₂₁ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or an alicyclic hydrocarbon group. However, at least one of R _{17 to} R ₂₁ represents an alicyclic hydrocarbon group. Further, either R ₁₉ or R ₂₁ represents a linear or branched alkyl group or alicyclic hydrocarbon group having 1 to 4 carbon atoms.
R _{22 to} R ₂₅ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or an alicyclic hydrocarbon group. However, at least one of R _{22 to} R ₂₅ represents an alicyclic hydrocarbon group. R ₂₃ and R ₂₄ may be bonded to each other to form a ring.

In general formula (2),
R _1a represents a hydrogen atom or a methyl group.
W ₁ represents a single bond, an alkylene group, an ether group, a thioether group, a carbonyl group, or a group of two or more groups selected from the group consisting of an ester group.
Lc represents a lactone residue represented by any one of the following general formulas (IV), (V-1) to (V-6) and (VI).

In general formula (IV),
R _a1 , R _b1 , R _c1 , R _d1 and R _e1 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
m and n each independently represents an integer of 0 to 3, and m + n is 2 or more and 6 or less.

In general formulas (V-1) to (V-6),
R _{1b to} R _5b each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, or COOR _6b . Here, R _6b represents an alkyl group. Two of R _{1b to} R _5b may be bonded to form a ring.

In general formula (3),
R ₃₀ represents a hydrogen atom or a methyl group.
R _{31 to} R ₃₃ each independently represents a hydrogen atom, a hydroxyl group or an alkyl group, provided that at least one represents a hydroxyl group.

  (4) The resin of the component (Baa) is selected from the repeating unit represented by the general formula (1), the repeating unit represented by the general formula (2), and the repeating unit represented by the general formula (3). The positive photosensitive composition as described in (3), which has at least one type of repeating unit.

  (5) The resin of the component (Baa) has a repeating unit represented by the general formula (1), a repeating unit represented by the general formula (2), and a repeating unit represented by the general formula (3). The positive photosensitive composition as described in (4).

(6) In the general formula (I), A ₂ is an aliphatic group having a structure represented by the following general formula (II): (1) to (5) Sex composition.

In general formula (II):
Rf ₁ and Rf ₂ each independently represents a hydrogen atom, a halogen atom, an alkyl group or a cycloalkyl group. However, at least one of Rf ₁ and Rf ₂ is a fluorine atom or a fluoroalkyl group.

  (7) The component (A) is one kind selected from a sulfonium salt compound, an iodonium salt compound, and an ester compound of a sulfonic acid represented by the above general formula (I) (1) to (6) ) The photosensitive composition in any one of.

  (8) Further described in any one of (1) and (3) to (7), wherein the structure further comprises a mixed solvent in which a solvent containing a hydroxyl group and a solvent not containing a hydroxyl group are mixed. Photosensitive composition.

  (9) A pattern forming method comprising forming a film from the photosensitive composition according to any one of (1) to (8), and exposing and developing the film.

Furthermore, the following structures are mentioned as a preferable embodiment of this invention.
(10) In the sulfonic acid represented by the general formula (I), each of a plurality of —SO ₃ H in the sulfonic acid represented by the general formula (I) is directly bonded to at least one of a fluorine atom and a fluoroalkyl group. The photosensitive composition according to any one of (1) to (8) above, which is a sulfonic acid directly bonded to a carbon atom.

  (11) The above (1) to (8) and (10), further comprising (A ′) a compound capable of generating a sulfonic acid having one sulfonic acid group upon irradiation with an actinic ray or radiation. The photosensitive composition in any one of.

  (12) The photosensitive composition as described in (11) above, wherein the compound as the component (A ′) is a sulfonium salt of monovalent perfluoroalkanesulfonic acid.

(13) (A) A compound that generates the sulfonic acid represented by the general formula (I) by irradiation with actinic rays or radiation, and (B) a resin that increases the solubility in an alkali developer by the action of the acid. A positive photosensitive composition characterized by the above.

  (14) The positive photosensitive composition as described in (13) above, wherein the resin as the component (B) has a fluorine atom.

  (15) The positive photosensitive composition as described in (14) above, wherein the resin as the component (B) has a hexafluoroisopropanol structure.

  (16) The positive photosensitive composition as described in (13) above, wherein the resin as the component (B) has a hydroxystyrene structural unit.

  (17) The positive resist composition as described in (13) above, wherein the resin as the component (B) has a monocyclic or polycyclic alicyclic hydrocarbon structure.

  (18) The positive photosensitive composition as described in (17) above, wherein the resin as the component (B) further has a repeating unit having a lactone structure.

  (19) The above (2) to (5), further comprising (C) a dissolution inhibiting compound having a molecular weight of 3000 or less, which decomposes by the action of an acid and increases the solubility in an alkaline developer. (10) The positive photosensitive composition in any one of (15).

(20) (A) a compound capable of generating a sulfonic acid represented by the above general formula (I) by irradiation with actinic rays or radiation,
(D) A positive type comprising a dissolution inhibiting compound having a molecular weight of 3000 or less, which is decomposed by the action of an acid in an alkali developer and (C) is decomposed by the action of an acid to increase the solubility in the alkali developer. Photosensitive composition.

(21) (A) a compound capable of generating a sulfonic acid represented by the above general formula (I) by irradiation with actinic rays or radiation,
A negative photosensitive composition 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.

  (22) (1) to (8) and (10) to (21), further comprising (F) a basic compound and / or (G) fluorine and / or a silicon-based surfactant The photosensitive composition in any one.

  (23) (F) a compound in which the basic compound has a structure selected from an imidazole structure, a diazabicyclo structure, an onium hydroxide structure, an onium carboxylate structure, a trialkylamine structure, an aniline structure and a pyridine structure, a hydroxyl group and / or an ether The photosensitive composition according to (22), which is an alkylamine derivative having a bond or an aniline derivative having a hydroxyl group and / or an ether bond.

  (24) A pattern forming method comprising forming a film from the photosensitive composition according to any one of (10) to (23), and exposing and developing the film.

According to the present invention, an excellent photosensitive composition and a pattern forming method using the same can be provided.
According to the present invention, it is possible to provide an excellent photosensitive composition having a wide exposure margin and low density dependency and a pattern forming method using the same.
According to the present invention, there is provided a positive resist composition that causes little pattern collapse even when forming a fine pattern of 110 nm or less and has a wide defocus latitude (DOF) in forming an isolated line pattern, and a pattern forming method using the same. be able to.
According to the present invention, it is possible to provide a positive resist composition capable of ensuring a wide process window in forming isolated lines and dense patterns, and a pattern forming method using the same.

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 decomposed by the action of the compound (A) that generates acid upon irradiation with actinic rays or radiation and the action of the acid in an alkaline developer. Containing a resin (B) having increased solubility, and further containing a dissolution inhibiting compound (C) having a molecular weight of 3000 or less, which is further decomposed by the action of an acid to increase the solubility in an alkali developer, if necessary. Alternatively, a compound (A) that generates an acid upon irradiation with actinic rays or radiation, a resin (D) that is soluble in an alkaline developer, and a decomposition due to the action of the acid to increase the solubility in the alkaline developer. A dissolution inhibiting compound (C).

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

  [1] Compound (also referred to as “compound (A)”) that generates a sulfonic acid represented by the general formula (I) upon irradiation with actinic rays or radiation

In general formula (I),
A ₁ represents an n-valent linking group.
A ₂ represents a single bond or a divalent aliphatic group. The n A _{2 s} may be the same or different. However, at least one of the group represented by A ₁ and the group represented by A ₂ has a fluorine atom.
n represents an integer of 2 to 4.

As the linking group as A ₁ , for example, an alkylene group, a cycloalkylene group, an arylene group, an alkenylene group, a single bond, an ether bond, an ester bond, an amide bond, a sulfide bond, a urea bond, a carbonyl group, a carbon atom, or these A linking group in which a plurality are linked may be mentioned.

The alkylene group as A ₁ may have a substituent, and preferably has 1 to 8 carbon atoms, for example, methylene group, ethylene group, propylene group, butylene group, hexylene group, octylene group and the like. it can.
The cycloalkylene group as A ₁ may have a substituent, and preferably has 3 to 8 carbon atoms, such as a cyclopentylene group and a cyclohexylene group.

The alkenylene group as A ₁ may have a substituent, and preferably has 2 to 6 carbon atoms, for example, ethenylene group, propenylene group, butenylene group and the like.

The arylene group as A ₁ may have a substituent, and preferably has 6 to 15 carbon atoms, such as a phenylene group, a tolylene group, and a naphthylene group.

  Examples of the substituent that these groups may have include, for example, those having active hydrogen such as a cycloalkyl group, an aryl group, an amino group, an amide group, a ureido group, a urethane group, a hydroxyl group, and a carboxyl group, Halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), alkoxy group (for example, methoxy group, ethoxy group, propoxy group, butoxy group, etc.), thioether group, acyl group (acetyl group, propanoyl group, benzoyl group, etc.) An acyloxy group (acetoxy group, propanoyloxy group, benzoyloxy group etc.), alkoxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group etc.), cyano group, nitro group and the like. Further, the arylene group may further include an alkyl group (methyl group, ethyl group, propyl group, butyl group, etc.).

The divalent aliphatic group as A ₂ is preferably an alkylene group or cycloalkylene group having 1 to 8 carbon atoms, more preferably an alkylene group or cycloalkylene group substituted with a fluorine atom or a fluoroalkyl group. .

The alkylene group as A ₂ may have a substituent, and preferably has 1 to 8 carbon atoms, such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and an octylene group. it can.
The cycloalkylene group as A ₂ may have a substituent, and preferably has 3 to 8 carbon atoms, such as a cyclopentylene group and a cyclohexylene group.
The fluoroalkyl group (alkyl group in which at least one hydrogen atom is substituted with a fluorine atom) that the alkylene group and cycloalkylene group as A ₂ preferably have may have a substituent, preferably carbon. 1 to 8, more preferably 1 to 3 carbon atoms, for example, monofluoromethyl group, difluoromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group, 2,2 , 3,3,3-pentafluoropropyl group, heptafluoropropyl group, 2,2,3,3,4,4,4-heptafluorobutyl group, nonafluorobutyl group, perfluorohexyl group, etc. it can. Examples of the further substituent of the fluoroalkyl group include a hydroxyl group, an alkoxy group (preferably having 1 to 5 carbon atoms), a halogen atom, a cyano group, and the like.

A ₂ is preferably an aliphatic group containing a structure of the following formula (II).

In general formula (II):
Rf ₁ and Rf ₂ each independently represents a hydrogen atom, a halogen atom, an alkyl group or a cycloalkyl group. However, at least one of Rf ₁ and Rf ₂ is a fluorine atom or a fluoroalkyl group.

The alkyl group as Rf ₁ and Rf ₂ may have a substituent, preferably an alkyl group having 1 to 8 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, Preferred examples include n-butyl group and sec-butyl group. Preferred examples of the substituent which the alkyl group as Rf ₁ and Rf ₂ may have include a halogen atom.
The cycloalkyl group as Rf ₁ and Rf ₂ may have a substituent, and is preferably a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof include a cyclopentyl group and a cyclohexyl group. it can.
The fluoroalkyl group as Rf ₁ and Rf ₂ is a group in which a fluorine atom is substituted on the above alkyl group or cycloalkyl group, and examples thereof include the groups mentioned as the above fluoroalkyl group.

  In the general formula (I), n represents an integer of 2 to 4, preferably 2 or 3, and more preferably 2.

  In addition, it is preferable that the structure of general formula (II) is couple | bonded with the adjacent position (sulfur atom of a sulfonic acid atomic group) of a sulfonic acid.

  Furthermore, as the sulfonic acid represented by the general formula (I), a sulfonic acid represented by the following general formula (III) is more preferable.

A ₁ and n are synonymous with A ₁ and n in formula (I).
A ₃ represents a single bond, an ether bond, a sulfide bond, an alkylene group, a cycloalkylene group or an arylene group, and more preferably a single bond or an ether bond. The n A _{3 s} may be the same or different.
a represents an integer of 1 to 4.
b represents an integer of 0 to 4.

The alkylene group, cycloalkylene group or arylene group as A _{3 is the same} as the alkylene group, cycloalkylene group or arylene group as A ₁ .

a preferably represents 1 or 2.
b preferably represents 0-2.

  As the sulfonic acid represented by the general formula (I), a sulfonic acid represented by the following general formulas (Ia) to (Ih) is even more preferable.

A ₄ represents an alkylene group, a cycloalkylene group, an arylene group, or a group in which a plurality of these are connected by at least one of a single bond, an ether bond, an ester bond, an amide bond, a sulfide bond, and a urea bond.
n1-n5 represents the integer of 1-8, Preferably it is an integer of 1-4.
Rf ₃ each independently represents a fluorine atom or a fluoroalkyl group.

The alkylene group, cycloalkylene group and arylene group as A _{4 are the same} as the alkylene group, cycloalkylene group and arylene group as A ₁ .
The fluoroalkyl group as Rf ₃ is the same as described above.

  Preferred specific examples of the sulfonic acid represented by the general formula (I) are shown below.

  The compound (A) that generates the sulfonic acid represented by the general formula (I) upon irradiation with actinic rays or radiation is selected from a sulfonium salt compound or an iodonium salt compound of the sulfonic acid represented by the general formula (I). One kind or one kind selected from sulfonic acid ester compounds represented by formula (I) is preferred, and compounds represented by the following formulas (A-1) to (A-5) are more preferred. .

In the general formula (A-1),
R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represents an organic group.
A ₁ and A ₂ have the same meanings as A ₁ and A _{2 in} formula (I).
n represents an integer of 2 to 4.
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).
Specific examples of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ include corresponding groups in the compounds (A-1a) to (A-1c) described later.
In addition, the compound which has two or more structures represented by general formula (A-1) may be sufficient. For example, at least one of R _{201 to} R ₂₀₃ of the compound represented by the general formula (A-1) is at least one of R _{201 to} R ₂₀₃ of another compound represented by the general formula (A-1). It may be a compound having a bonded structure.

  More preferred components (A-1) include compounds (A-1a), (A-1b) and (A-1c) described below.

Compound (A-1a) is at least one of the aryl groups R ₂₀₁ to R ₂₀₃ in the general formula (A-1), an 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 R ₂₀₁
Some of to R ₂₀₃ is an aryl group and the remainder may be 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, for example, a methyl group , Ethyl group, propyl group, n-butyl group, sec-butyl group, t-butyl group, cyclopropyl group, cyclobutyl group, cyclohexyl group and the like.
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 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 (A-1b) will be described.
The compound (A-1b) is a compound in the case where R _{201 to} R ₂₀₃ in the formula (A-1) each independently represents an organic group not containing an 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 and a cycloalkyl group (particularly, a linear, branched or cyclic oxoalkyl group which may have a double bond in the chain, an alkoxycarbonylmethyl group). Are allyl groups and vinyl groups, more preferably linear, branched or cyclic 2-oxoalkyl groups, and most preferably linear or branched 2-oxoalkyl groups.
The alkyl group as R ₂₀₁ to R ₂₀₃ may preferably be mentioned straight-chain or branched alkyl group having 1 to 20 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, pentyl group).
The cycloalkyl group as R ₂₀₁ to R ₂₀₃ is preferably, and a cyclic alkyl group having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl, norbornyl).

The 2-oxoalkyl group as R _{201 to} R ₂₀₃ may be linear, branched or cyclic, and is preferably a group having> C═O at the 2-position of the above alkyl group and cycloalkyl group Can be mentioned.
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, pentyloxy 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 (A-1c) is a compound represented by the following general formula (A-1c) and is a compound having an arylacylsulfonium salt structure.

In general formula (A-1c),
_R211 represents an aryl group, preferably a phenyl group or a naphthyl group. Alkyl groups as preferred substituents that have an aryl group as R _211, cycloalkyl group, alkoxy group, acyl group, a nitro group, a hydroxyl group, an alkoxycarbonyl group, a carboxy group.
R ₂₁₂ and R ₂₁₃ each independently represents a hydrogen atom, an alkyl group or a cycloalkyl group.
Y ₂₀₁ and Y ₂₀₂ are each independently an alkyl group (especially a 2-oxoalkyl group, an alkoxycarbonylalkyl group or a carboxyalkyl group is preferred), a cycloalkyl group (especially a 2-oxocycloalkyl group or an alkoxycarbonylcycloalkyl group). , A carboxycycloalkyl group is preferable), an aryl group, or a vinyl group.
R ₂₁₁ and R ₂₁₂ may combine to form a ring structure, R ₂₁₂ and R ₂₁₃ may combine to form a ring structure, and Y ₂₀₁ and Y ₂₀₂ each combine to form a ring structure. It may be formed. These ring structures may contain an oxygen atom, a sulfur atom, an ester bond, or an amide bond. _{Examples of} the group formed by combining R ₂₁₁ and R _212, the group formed by combining R ₂₁₂ and R _213, and the group formed by combining Y ₂₀₁ and Y ₂₀₂ include a butylene group and a pentylene group. Can do.
A ₁ and A ₂ have the same meanings as A ₁ and A _{2 in} formula (I).
n represents an integer of 2 to 4.

The alkyl group as R ₂₁₂ and R ₂₁₃ is preferably an alkyl group having 1 to 20 carbon atoms.
The cycloalkyl group as R ₂₁₂ and R ₂₁₃ is preferably a cycloalkyl group having 3 to 20 carbon atoms.

The alkyl group as Y ₂₀₁ and Y ₂₀₂ is preferably an alkyl group having 1 to 20 carbon atoms.
The cycloalkyl group as Y ₂₀₁ and Y ₂₀₂ is preferably a cycloalkyl group having 3 to 20 carbon atoms.
2-oxoalkyl group as Y ₂₀₁ and Y ₂₀₂ may be a group having> C = O at the 2-position of the alkyl group as Y ₂₀₁ and Y _202.
2-oxocycloalkyl group as Y ₂₀₁ and Y ₂₀₂ may be a group having> C = O at the 2-position of the cycloalkyl group as Y ₂₀₁ and Y _202.
The alkoxycarbonyl group in the alkoxycarbonylalkyl group and alkoxycarbonyl cycloalkyl alkyl group as Y ₂₀₁ and Y _202, preferably 2-20 alkoxycarbonyl group having a carbon.

Y ₂₀₁ and Y ₂₀₂ are preferably an alkyl group or cycloalkyl group having 4 or more carbon atoms, more preferably 4 to 16, and still more preferably 4 to 12 alkyl group or cycloalkyl group.
Further, at least one of R ₂₁₂ or R ₂₁₃ is preferably an alkyl group or a cycloalkyl group, more preferably both an alkyl group or a cycloalkyl group of R _212, R _213.

In general formula (A-2),
_R204 and _R205 each independently represents an aryl group, an alkyl group or a cycloalkyl group.
A ₁ and A ₂ have the same meanings as A ₁ and A _{2 in} formula (I).
n represents an integer of 2 to 4.
The aryl group as R ₂₀₄ and R ₂₀₅ are phenyl group and a naphthyl group are preferred, more preferably a phenyl group.
The alkyl group as _R204 and _R205 is preferably a linear or branched alkyl group having 1 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group).
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).
Examples of the substituent that the group as 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, carbon (Chemical formula 6-15), an alkoxy group (for example, C1-C15), a halogen atom, a hydroxyl group, a phenylthio group etc. can be mentioned.

In general formula (A-3),
A represents an alkylene group, an alkenylene group or an arylene group.
A ₁ and A ₂ have the same meanings as A ₁ and A _{2 in} formula (I).
n represents an integer of 2 to 4.

In General Formula (A-4), R ₂₀₆ represents an alkyl group, a cycloalkyl group, or an aryl group.
_R207 represents an alkyl group (especially an oxoalkyl group is preferred), a cycloalkyl group (especially an oxocycloalkyl group is preferred), a cyano group, an alkoxycarbonyl group, preferably a halogen-substituted alkyl group, a halogen-substituted cycloalkyl group, or It is a cyano group.
A ₁ and A ₂ have the same meanings as A ₁ and A _{2 in} formula (I).
n represents an integer of 2 to 4.

In General Formula (A-5), R ₂₀₈ and R ₂₀₉ represent a hydrogen atom, an alkyl group, a cycloalkyl group, a cyano group, a nitro group or an alkoxycarbonyl group, preferably a halogen-substituted alkyl group, a halogen-substituted cycloalkyl group, a nitro group Group or cyano group.
R ₂₁₀ represents a hydrogen atom, an alkyl group, a cycloalkyl group, a cyano group or an alkoxycarbonyl group.
A ₁ and A ₂ have the same meanings as A ₁ and A _{2 in} formula (I).

  Particularly preferred is a compound represented by formula (A-1).

  Although the specific example of a compound (A) is given to the following, it is not limited to these.

  The compound (A) can be synthesized by synthesizing a sulfonic acid derivative represented by the general formula (I) and then salt-exchange with onium halide or the like or esterifying with a hydroxyl group-containing compound. Examples of the sulfonic acid derivative represented by the general formula (I) include JP 2001-322975, J. Org. Chem., Vol. 56, No. 22, (1991), p6348, Synthesis., (1989), It can be synthesized by using the method described in p.

  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 generating an acid upon irradiation with an actinic ray or radiation may be further used in combination.

  The amount of the photoacid generator that can be used in combination is usually 100/0 to 20/80, preferably 100/0 to 40/60, and more preferably in molar ratio (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 may be used in combination and decomposed by irradiation with actinic rays or radiation, preferred compounds include compounds represented by the following general formulas (ZI), (ZII), and (ZIII). it can.

In the above 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).
X ⁻ represents a non-nucleophilic anion.

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

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

  Examples of the sulfonate anion include an 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, Methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, 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, etc. .

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

  Examples of the aliphatic moiety in the aliphatic carboxylate anion include the same alkyl group and cycloalkyl group as in the aliphatic sulfonate anion.

  Examples of the aryl 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 include aromatic The same halogen atom, alkyl group, cycloalkyl group, alkoxy group, alkylthio group and the like as in the sulfonate anion can be exemplified.

  Examples of the sulfonylimide anion include saccharin anion.

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

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

Examples of the non-nucleophilic anion of X ⁻ 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 particularly preferably a perfluoroaliphatic sulfonic acid anion having 4 to 8 carbon atoms, a benzenesulfonic acid anion having a fluorine atom, most preferably nonafluorobutanesulfonic acid anion, perfluorooctanesulfonic acid anion, penta Fluorobenzenesulfonate anion, 3,5-bis (trifluoromethyl) benzenesulfonate anion.

Specific examples of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ include corresponding groups in the compounds (Z1-1), (Z1-2) and (Z1-3) described later.

In addition, the compound which has two or more structures represented by general formula (ZI) may be sufficient. For example, 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 examples of the (ZI) component include compounds (Z1-1), (Z1-2), and (Z1-3) described below.

Compound (Z1-1) is at least one of the aryl groups R ₂₀₁ to R ₂₀₃ in formula (ZI), arylsulfonium compound, i.e., a compound having arylsulfonium as a cation.

In the arylsulfonium compound, all of R _{201 to} R ₂₀₃ may be an aryl group, or a part of R _{201 to} R ₂₀₃ may be an aryl group with the remaining being an alkyl group or a cycloalkyl group.

  Examples of the arylsulfonium 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 that the arylsulfonium compound has as necessary is preferably a linear or branched alkyl group having 1 to 15 carbon atoms, such as methyl group, ethyl group, propyl group, n-butyl group, sec-butyl. Group, t-butyl group and the like.

The cycloalkyl group that the arylsulfonium compound has as necessary has 3 carbon atoms.
To 15 cycloalkyl groups are preferable, 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 carbon. It is a C1-C4 alkyl group and a C1-C4 alkoxy group. 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 (Z1-2) will be described.
Compound (Z1-2) is a compound in the case where R _{201 to} R ₂₀₃ in formula (ZI) each independently represents an organic group not containing an 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, most preferably a linear or branched 2-oxoalkyl group.

The alkyl group of R _{201 to} R ₂₀₃ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. . More preferred examples of the alkyl group include a 2-oxoalkyl group and an alkoxycarbonylmethyl group.

The cycloalkyl group of R _{201 to} R ₂₀₃ is preferably a cycloalkyl group having 3 to 10 carbon atoms, and examples thereof include a cyclopentyl group, a cyclohexyl group, and a norbornyl 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, pentyloxy 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 (Z1-3) is a compound represented by the following general formula (Z1-3), 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.
Rx and Ry each independently represents an alkyl group, a cycloalkyl group, an allyl group or a vinyl group.
Any two or more of R _{1c to} R _5c , 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, a sulfur atom, An ester bond or 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 as the non-nucleophilic anion of X ^{− in} formula (ZI).

The alkyl group as R _{1c to} R _7c may be either linear or branched, for example, an alkyl group having 1 to 20 carbon atoms, preferably a linear or branched alkyl group having 1 to 12 carbon atoms. (For example, a methyl group, an ethyl group, a linear or branched propyl group, a linear or branched butyl group, a linear or branched pentyl group).
The cycloalkyl group is preferably a cycloalkyl group having 3 to 8 carbon atoms (for example, a cyclopentyl group or a cyclohexyl group).

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

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

_Examples of the alkyl group and cycloalkyl group as R _x and R _y include the same alkyl groups and cycloalkyl groups as R _{1c to} R _{7c, and} include 2-oxoalkyl group, 2-oxocycloalkyl group. An alkoxycarbonylmethyl group is more preferable.

Examples of the 2-oxoalkyl group and 2-oxocycloalkyl group include a group having> C═O at the 2-position of the alkyl group or cycloalkyl group as R _{1c to} R _7c .

Examples of the alkoxy group in the alkoxycarbonylmethyl group include the same alkoxy groups as 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 as R ₂₀₄ to R ₂₀₇ is preferably a straight-chain or branched alkyl group having 1 to 10 carbon atoms, e.g., methyl group, ethyl group, propyl group, butyl group, a pentyl group it can.

The cycloalkyl group as R ₂₀₄ to R ₂₀₇ is preferably a cycloalkyl group having 3 to 10 carbon atoms, e.g., cyclopentyl, cyclohexyl group and a norbornyl group.

The R ₂₀₄ to R ₂₀₇ are substituents which may have, 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 (e.g., 6 carbon atoms 15), alkoxy groups (for example, having 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, phenylthio groups and the like.

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

  Examples of the compound that generates an acid upon irradiation with actinic rays or radiation that may be used in combination may further 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 or an aryl group.
A represents an alkylene group, an alkenylene group or an arylene group.

Among the compounds that generate an acid upon irradiation with actinic rays or radiation that may be used in combination, compounds represented by general formulas (ZI) to (ZIII) are more preferable.
In addition, as a compound that generates an acid 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 perfluoroaliphatic sulfonic acid is more preferable. It is a compound that generates an aromatic sulfonic acid that is substituted with a fluorine atom or a group containing a fluorine atom.

  Of the compounds that generate an acid upon irradiation with actinic rays or radiation that may be used in combination, examples of particularly preferable compounds are listed below.

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

A group preferable as a group that can be decomposed by an acid is a group in which a hydrogen atom of a —COOH group or —OH group is substituted with a group capable of leaving with an acid.
In the present invention, the acid-decomposable group is 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 preferred is 330 A / second or more (A is angstrom).

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

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

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

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

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

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

(Ba) Resin which has a monocyclic or polycyclic alicyclic hydrocarbon structure and has increased solubility in an alkaline developer by the action of an acid. When irradiating ArF excimer laser light to the positive photosensitive composition of the present invention The resin of component (B) is preferably a resin having a monocyclic or polycyclic alicyclic hydrocarbon structure and increasing the solubility in an alkali developer by the action of an acid.

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

Where
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.
Z represents an atomic group necessary for forming an alicyclic hydrocarbon group together with a carbon atom.
R _{12 to} R ₁₆ each independently represents a linear or branched alkyl group or alicyclic hydrocarbon group having 1 to 4 carbon atoms, provided that at least one of R _{12 to} R ₁₄ , or Either R ₁₅ or R ₁₆ represents an alicyclic hydrocarbon group.
R _{17 to} R ₂₁ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or an alicyclic hydrocarbon group, provided that at least one of R _{17 to} R ₂₁ Represents an alicyclic hydrocarbon group. Further, either R ₁₉ or R ₂₁ represents a linear or branched alkyl group or alicyclic hydrocarbon group having 1 to 4 carbon atoms.
R _{22 to} R ₂₅ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or an alicyclic hydrocarbon group, provided that at least one of R _{22 to} R ₂₅ Represents an alicyclic hydrocarbon group. R ₂₃ and R ₂₄ may be bonded to each other to form a ring.

In 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-A) or general formula (II-B).

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

  The -Y group;

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

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

  The alkyl group may further have a substituent. Examples of the substituent that the alkyl group may have include an alkoxy group having 1 to 4 carbon atoms, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), an acyl group, an acyloxy group, a cyano group, a hydroxyl group, A carboxy group, an alkoxycarbonyl group, a nitro group, etc. can be mentioned.

The alicyclic hydrocarbon group in R _{12 to} R _{25 or} the alicyclic hydrocarbon group formed by Z and a carbon atom may be monocyclic or polycyclic. Specific examples include groups having a monocyclo, bicyclo, tricyclo, tetracyclo structure or the like having 5 or more carbon atoms. The carbon number is preferably 6-30, and particularly preferably 7-25. These alicyclic hydrocarbon groups may have a substituent.

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

  The alicyclic hydrocarbon group may further have a substituent. Examples of the substituent for the alicyclic hydrocarbon group include an alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group, and an alkoxycarbonyl group. The alkyl group is preferably a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group, and more preferably selected from the group consisting of a methyl group, an ethyl group, a propyl group, and an isopropyl group. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. The alkyl group, alkoxy group, and alkoxycarbonyl group 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 (pVI) in the resin can be used for protecting alkali-soluble groups. Examples of the alkali-soluble group include various groups known in this technical field.

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

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

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

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

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

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

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

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

The alkyl group for R ₁₁ ′ and R ₁₂ ′ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, more preferably a linear or branched alkyl group having 1 to 6 carbon atoms. And more preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, or a t-butyl group.

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

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

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

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

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

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

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

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

The R ₁₃ '~R _16', the alkyl group in _{R 5, R 6, R 21} '~R 30', preferably a linear or branched alkyl group having 1 to 10 carbon atoms, more preferably carbon A linear or branched alkyl group of several to six, more preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, or a t-butyl group. is there.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

B ₂ represents a group represented by any one of general formula (Lc) and general formulas (V-1) to (V-5).

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

(Baa) having at least one repeating unit selected from the repeating unit represented by the following general formula (1), the repeating unit represented by the general formula (2), and the repeating unit represented by the general formula (3). A resin whose solubility in an alkaline developer is increased by the action of an acid. The alicyclic hydrocarbon-based acid-decomposable resin is a repeating unit represented by the following general formula (1) or a repeating unit represented by the following general formula (2): And a resin having at least one repeating unit selected from the repeating units represented by the general formula (3) and having increased solubility in an alkali developer by the action of an acid (hereinafter referred to as “alicyclic hydrocarbon-based acid decomposability”). Resin (Baa) ”) is preferable.
The alicyclic hydrocarbon-based acid-decomposable resin (Baa) includes a repeating unit represented by the general formula (1), a repeating unit represented by the general formula (2), and a repeating unit represented by the general formula (3). It is preferable to have at least one type of repeating unit selected from.
The alicyclic hydrocarbon-based acid-decomposable resin (Baa) includes a repeating unit represented by the general formula (1), a repeating unit represented by the general formula (2), and a repeating unit represented by the general formula (3). More preferably.
The positive photosensitive composition of the present invention can secure a wide process window in isolated lines and dense patterns by using an alicyclic hydrocarbon-based acid-decomposable resin (Baa).

In general formula (1),
R represents a hydrogen atom or a methyl group.
A represents a single bond or a linking group.
ALG represents a group represented by any one of the following general formulas (pI) to (pV).

In the 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.
Z represents an atomic group necessary for forming an alicyclic hydrocarbon group together with a carbon atom.
R _{12 to} R ₁₆ each independently represents a linear or branched alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group. However, at least one of R _{12 to} R ₁₄ and any one of R ₁₅ and R ₁₆ represents an alicyclic hydrocarbon group.
R _{17 to} R ₂₁ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or an alicyclic hydrocarbon group. However, at least one of R _{17 to} R ₂₁ represents an alicyclic hydrocarbon group. Further, either R ₁₉ or R ₂₁ represents a linear or branched alkyl group or alicyclic hydrocarbon group having 1 to 4 carbon atoms.
R _{22 to} R ₂₅ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or an alicyclic hydrocarbon group. However, at least one of R _{22 to} R ₂₅ represents an alicyclic hydrocarbon group. R ₂₃ and R ₂₄ may be bonded to each other to form a ring.

In general formula (2),
R _1a represents a hydrogen atom or a methyl group.
W ₁ represents a single bond, an alkylene group, an ether group, a thioether group, a carbonyl group, or a group of two or more groups selected from the group consisting of an ester group.
Lc represents a lactone residue represented by any one of the following general formulas (IV), (V-1) to (V-6) and (VI).

In general formula (IV),
R _a1 , R _b1 , R _c1 , R _d1 and R _e1 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
m and n each independently represents an integer of 0 to 3, and m + n is 2 or more and 6 or less.

In general formulas (V-1) to (V-6),
R _{1b to} R _5b each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, or COOR _6b . Here, R _6b represents an alkyl group. Two of R _{1b to} R _5b may be bonded to form a ring.

In general formula (3),
R ₃₀ represents a hydrogen atom or a methyl group.
R _{31 to} R ₃₃ each independently represents a hydrogen atom, a hydroxyl group or an alkyl group, provided that at least one represents a hydroxyl group.

First, general formula (1) will be described.
The alicyclic hydrocarbon-based acid-decomposable resin (Baa) is a resin (acid-decomposable resin) whose solubility in an alkaline developer is increased by the action of an acid, and is decomposed by the action of an acid to be a carboxyl group that is an alkali-soluble group. It is preferable to have a repeating unit represented by the general formula (1) that yields

  In the general formula (1), R represents a hydrogen atom or a methyl group, A represents a single bond or a linking group, and ALG represents a group represented by the above general formula (pI) to general formula (pV).

The linking group of A is selected from the group consisting of an alkylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a sulfonamide group, a urethane group, or a urea group, or a combination of two or more groups Represents. Examples of the alkylene group in A include groups represented by the following formulas.
− [C (R _b ) (R _c )] _r −
In the formula, R _b and R _c represent a hydrogen atom, an alkyl group, a halogen atom, a hydroxyl group and an alkoxy group, and both may be the same or different. The alkyl group is preferably a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group, and more preferably selected from a methyl group, an ethyl group, a propyl group, and an isopropyl group. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. r represents an integer of 1 to 10. The alkyl group and alkoxy group may have a substituent. Examples of the substituent that the alkyl group and alkoxy group may have include a hydroxyl group, a halogen atom, and an alkoxy group (preferably having 1 to 4 carbon atoms).

In the general formulas (pI) to (pV), the alkyl group in R _{12 to} R ₂₅ may be either substituted or unsubstituted, and a linear or branched alkyl group having 1 to 4 carbon atoms Represents. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a t-butyl group.
Further, the further substituent of the alkyl group includes an alkoxy group having 1 to 4 carbon atoms, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an acyl group, an acyloxy group, a cyano group, a hydroxyl group, A carboxy group, an alkoxycarbonyl group, a nitro group, etc. can be mentioned.

The alicyclic hydrocarbon group in R _{12 to} R _{25 or} the alicyclic hydrocarbon group formed by Z and a carbon atom may be monocyclic or polycyclic. Specific examples include groups having a monocyclo, bicyclo, tricyclo, tetracyclo structure or the like having 5 or more carbon atoms. The carbon number is preferably 6-30, and particularly preferably 7-25. These alicyclic hydrocarbon groups may have a substituent.
Below, the structural example of an alicyclic part is shown among alicyclic hydrocarbon groups.

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

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

  In addition, from the point that profile stability (SEM resistance) when observing the obtained profile with a scanning electron microscope is good, in the general formula (1), A is a single bond, and ALG is represented as follows. The repeating unit which is a group is particularly preferred.

R ₂₆ and R ₂₇ each independently represents a linear or branched alkyl group having 1 to 4 carbon atoms.

  Specific examples of the monomer corresponding to the repeating unit represented by the general formula (1) are shown below.

Next, general formula (2) will be described.
R _1a represents a hydrogen atom or a methyl group. W ₁ represents a single bond, an alkylene group, an ether group, a thioether group, a carbonyl group, or a group of two or more groups selected from the group consisting of an ester group. Lc is a lactone residue represented by any one of the general formulas (IV), (V-1) to (V-6), and (VI).

Examples of the alkylene group for W ₁ include groups represented by the following formulae.
− [C (Rf) (Rg)] r ₁ −
In the above formula, Rf and Rg represent a hydrogen atom, an alkyl group, a halogen atom, a hydroxyl group or an alkoxy group, and both may be the same or different. The alkyl group is preferably a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group, and more preferably selected from a methyl group, an ethyl group, a propyl group, and an isopropyl group.
Examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.
Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. r ₁ is an integer of 1 to 10.
The alkyl group and alkoxy group may have a substituent. Examples of the substituent that the alkyl group and alkoxy group may have include a hydroxyl group, a halogen atom, and an alkoxy group.

Examples of the alkyl group having 1 to 4 carbon atoms of R _{a1 to} R _e1 in the general formula (IV) include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, t- A butyl group etc. can be mentioned.

Examples of the alkyl group as R _{1b to} R _5b in formulas (V-1) to (V-6) include linear and branched alkyl groups, which may have a substituent. The alkyl group as R _{1b to} R _5b is preferably a linear or branched alkyl group having 1 to 12 carbon atoms, more preferably a linear or branched alkyl group having 1 to 10 carbon atoms, More preferably, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group It is.
R _6b in COOR _6b as R _{1b to} R _{5b in the} general formulas (V-1) to (V-6) is preferably a linear or branched alkyl group having 1 to 12 carbon atoms, and more preferably. Is a linear or branched alkyl group having 1 to 10 carbon atoms, more preferably methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl. Group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group and decyl group.

As a cycloalkyl group in R _<1b > -R < _5b >, C3-C8 things, such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, are preferable.
As an alkenyl group in R _<1b > -R < _5b >, C2-C6 things, such as a vinyl group, a propenyl group, a butenyl group, a hexenyl group, are preferable.
Examples of the ring formed by combining two of R _{1b to} R _5b include a 3- to 8-membered ring such as a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, and a cyclooctane ring. .
In addition, R _<1b > -R < _5b > in general formula (V-1)-(V-6) may be connected with any of the carbon atoms which comprise the cyclic skeleton.

  Moreover, as a preferable substituent which the said alkyl group, a cycloalkyl group, and an alkenyl group may have, a C1-C4 alkoxy group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), Examples thereof include an acyl group having 2 to 5 carbon atoms, an acyloxy group having 2 to 5 carbon atoms, a cyano group, a hydroxyl group, a carboxy group, an alkoxycarbonyl group having 2 to 5 carbon atoms, and a nitro group.

Specific examples of the repeating unit having a group having a lactone structure represented by the general formula (IV), (V-1) to (V-6) or (VI) are shown below, but the present invention is limited thereto. Is not to be done.
First, although the specific example of the repeating unit of General formula (2) which has a lactone structure represented by general formula (IV) is shown below, it is not limited to these.

  Next, specific examples of the repeating unit of the general formula (2) having a lactone structure represented by the general formulas (V-1) to (V-6) are shown below, but are not limited thereto.

  Specific examples of the repeating unit of the general formula (2) having a lactone structure represented by the general formula (VI) are shown below.

Next, the repeating unit represented by the general formula (3) will be described.
In general formula (3), R ₃₀ represents a hydrogen atom or a methyl group.
R _{31 to} R ₃₃ each independently represents a hydrogen atom, a hydroxyl group or an alkyl group, provided that at least one represents a hydroxyl group.

The alkyl group of R _{31 to} R ₃₃ is preferably an alkyl group having 1 to 5 carbon atoms, such as a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group. , T-butyl group and the like.
In the repeating unit represented by the general formula (3), one or two of R _{31 to} R ₃₃ are preferably a hydroxyl group, and two are particularly preferably a hydroxyl group.

  Although the specific example of the repeating unit represented by General formula (3) below is given, it is not limited to these.

  In addition to the above repeating structural units, the alicyclic hydrocarbon-based acid-decomposable resin (Baa) has a dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and resolving power that is a general required property of resist. It can have various repeating structural units for the purpose of adjusting heat resistance, sensitivity and the like.

Examples of such repeating structural units include, but are not limited to, repeating structural units corresponding to the following monomers.
As a result, the performance required for the resin, especially
(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 the alicyclic hydrocarbon-based acid-decomposable resin (Baa), the content molar ratio of each repeating structural unit is the resistance to dry etching resistance of the resist, standard developer suitability, substrate adhesion, resist profile, and general resist characteristics. It is appropriately set in order to adjust the necessary performance such as resolving power, heat resistance and sensitivity.

In the alicyclic hydrocarbon-based acid-decomposable resin (Baa), the content of the repeating unit represented by the general formula (1) is preferably 0 to 60 mol%, more preferably 20 to 55 mol in all repeating structural units. %, More preferably 25 to 50 mol%.
The content of the repeating unit of the general formula (2) is preferably 0 to 70 mol%, more preferably 20 to 65 mol%, still more preferably 25 to 60 mol% in all repeating structural units.
The content of the repeating unit of the general formula (3) is preferably 0 to 50 mol%, more preferably 15 to 45 mol%, still more preferably 20 to 40 mol% in all repeating structural units.

Further, the content of the repeating structural unit based on the monomer of the further copolymer component in the resin can be appropriately set according to the performance of the desired resist, but the general formulas (1) to (3) 50 mol% or less is preferable with respect to the total number of moles, more preferably 40 mol% or less, still more preferably 30 mol% or less.
When the composition of the present invention is for ArF exposure, the alicyclic hydrocarbon-based acid-decomposable resin (Baa) preferably has no aromatic group from the viewpoint of transparency to ArF light.

The alicyclic hydrocarbon-based acid-decomposable resin (Baa) can be synthesized according to a conventional method (for example, radical polymerization). For example, as a general synthesis method, monomer species are charged into a reaction vessel in a batch or in the course of reaction, and this is added to a reaction solvent, for example, cyclic ethers such as tetrahydrofuran and 1,4-dioxane, methyl ethyl ketone, methyl isobutyl. Ketones, ketones such as cyclohexanone, and the composition of the present invention such as propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether, which will be described later, are uniformly dissolved in a solvent, and then inert gas such as nitrogen or argon. Polymerization is started using a commercially available radical initiator (azo initiator, peroxide, etc.) as necessary under an atmosphere. If desired, an initiator is added or added in portions, and after completion of the reaction, it is put into a solvent and a desired polymer is recovered by a method such as powder or solid recovery. The concentration of the reaction is 10% by mass or more, preferably 15% by mass or more, and more preferably 20% by mass or more. The reaction temperature is 10 ° C to 150 ° C, preferably 30 ° C to 130 ° C, more preferably 50 ° C to 110 ° C.
The repeating structural units represented by the above specific examples may be used singly or in combination.
In the present invention, the alicyclic hydrocarbon-based acid-decomposable resin (Baa) may be used singly or in combination.

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

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

When the positive photosensitive composition of the present invention is irradiated with F ₂ excimer laser light, the resin of component (B) has fluorine atoms and is decomposed by the action of an acid to increase the solubility in an alkali developer. Resin (hereinafter also referred to as fluorine group-containing resin), more preferably a hydroxyl group substituted at the 1-position with a fluorine atom or a fluoroalkyl group or a hydroxyl group substituted at the 1-position with a fluorine atom or a fluoroalkyl group is acid-decomposed. A resin having a group protected by a group, and most preferably a resin having a hexafluoro-2-propanol structure or a structure in which the hydroxyl group of hexafluoro-2-propanol is protected by an acid-decomposable group. By introducing fluorine atoms, it is possible to improve transparency to far ultraviolet light, particularly F ₂ (157 nm) light.

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

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

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

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

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

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

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

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

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

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

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

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

As the alkynyl group, an alkynyl group having 2 to 5 carbon atoms is preferable, for example, an ethynyl group,
A propynyl group, a butynyl group, etc. can be mentioned.

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

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

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

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

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

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

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

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

Examples of the group that is decomposed by the action of an acid contained in the fluorine group-containing resin of the present invention include —O—C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), —O—C (R ₃₆ ) (R _{37) (OR 39), -} O-COO-C (R 36) (R 37) (R 38), - O-C (R 01) (R 02) COO-C (R 36) (R 37) ( R ₃₈ ), —COO—C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), —COO—C (R ₃₆ ) (R ₃₇ ) (OR ₃₉ ) and the like.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

[3] (C) Dissolution-inhibiting compound having a molecular weight of 3000 or less (hereinafter also referred to as “(C) component” or “dissolution-inhibiting compound”) that is decomposed by the action of an acid to increase the solubility in an alkaline developer.
(C) As a dissolution-inhibiting compound having a molecular weight of 3000 or less that decomposes by the action of an acid and increases its solubility in an alkaline developer, the transmittance of 220 nm or less is not lowered, so Proceeding of SPIE, 2724,355 (1996) An alicyclic or aliphatic compound having an acid-decomposable group, such as a cholic acid derivative containing an acid-decomposable group described in 1) is preferred. 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 has the structure which substituted the phenolic hydroxyl group of the phenolic compound by the acid decomposition group is preferable. As a phenol compound, what contains 1-9 phenol frame | skeleton is preferable, More preferably, it contains 2-6 pieces.

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

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

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

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

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

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

  The novolak resin is obtained by subjecting a predetermined monomer as a main component to addition condensation with aldehydes 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 formula, L < ¹ > -L < ⁸ > may be same or different and shows a hydrogen atom, a hydroxymethyl group, a methoxymethyl group, an ethoxymethyl group, or a C1-C6 alkyl group.)
The crosslinking agent is generally used in an amount of 3 to 70% by mass, preferably 5 to 50% by mass, in the solid content of the photosensitive composition.

<Other ingredients>
[5] (F) Basic compound The photosensitive composition of the present invention preferably contains (F) a basic compound in order to reduce a change in performance over time from exposure to heating.

  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 group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, And R ²⁵⁰ and R ²⁵¹ may combine with each other to form a ring. These may have a substituent. Examples of the alkyl group and cycloalkyl group having a substituent include an aminoalkyl group having 1 to 20 carbon atoms, an aminocycloalkyl group having 3 to 20 carbon atoms, and 1 carbon atom. A -20 hydroxyalkyl group or a C3-C20 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 20 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms.

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

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

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

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

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

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

  Examples of commercially available surfactants that can be used include 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. Fluoroaliphatic compounds are disclosed in JP-A-2002.
It can be synthesized by the method described in Japanese Patent No. -90991.

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

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

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

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

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

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

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

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

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

(Ha) Solvent containing at least one cyclic ketone When the positive photosensitive composition contains an alicyclic hydrocarbon-based acid-decomposable resin, a solvent containing at least one cyclic ketone is used as the organic solvent. It is preferable to do.
The positive photosensitive composition of the present invention makes it difficult to cause pattern collapse by using an alicyclic hydrocarbon-based acid-decomposable resin and a cyclic ketone, and can increase the allowable range of defocus for an isolated line pattern. .
Examples of the cyclic ketone include a total carbon number of 5 such as cyclopentanone, 3-methyl-2-cyclopentanone, cyclohexanone, 2-methylcyclohexanone, 2,6-dimethylcyclohexanone, cycloheptanone, cyclooctanone, isophorone and the like. -8 compounds and the like can be mentioned. Cyclohexanone and cycloheptanone are preferable.

The cyclic ketone can be used alone or as a mixed solvent with other solvents. Examples of the solvent to be mixed (combined solvent) include propylene glycol monoalkyl ether carboxylate, alkyl lactate, propylene glycol monoalkyl ether, alkyl alkoxypropionate, and linear ketone.
Specific examples of the propylene glycol monoalkyl ether carboxylate include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, and propylene glycol monoethyl ether acetate.
Examples of the alkyl lactate include methyl lactate and ethyl lactate.
Examples of the propylene glycol monoalkyl ether include propylene glycol monomethyl ether and propylene glycol monoethyl ether.
Examples of the alkyl alkoxypropionate include methyl methoxypropionate, ethyl methoxypropionate, methyl ethoxypropionate, and ethyl ethoxypropionate.
Examples of the linear ketone include methyl ethyl ketone, 2-heptanone, 3-heptanone, and 4-heptanone.

Preferred examples of the combined solvent include propylene glycol monoalkyl ether carboxylate, alkyl lactate, and propylene glycol monoalkyl ether.
By mixing the cyclic ketone and the combined solvent, substrate adhesion, developability, DOF, and the like are improved.
The ratio (mass ratio) between the cyclic ketone and the combined solvent is preferably 30/70 to 95/5, more preferably 35/65 to 90/10, and still more preferably 40/60 to 80/20.

Further, from the viewpoint of improving the film thickness uniformity and development defect performance, it is preferable to mix a high boiling point solvent having a boiling point of 200 ° C. or higher, such as ethylene carbonate, propylene carbonate, γ-butyrolactone.
The amount of these high-boiling solvents added is from 0.1 to 15% by mass, preferably from 0.5 to 10% by mass, and more preferably from 1 to 5% by mass in the total solvent.

  Using such a cyclic ketone alone or a mixed solvent with another solvent, the photosensitive composition having a solid content concentration of usually 3 to 25% by mass, preferably 5 to 22% by mass, more preferably 7 to 20% by mass. Prepare the product.

<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 easily obtained by those skilled in the art with reference to the methods described in, for example, JP-A-4-122938, JP-A-2-28531, U.S. Pat. No. 4,916,210, European Patent 219294, and the like. Can be synthesized.

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

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

  These surfactants may be added alone or in some combination.

≪How to use≫
The photosensitive composition of the present invention is used by dissolving each component 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, baked (heated), and developed. Thereby, a good pattern can be obtained.

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

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

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

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

  EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, the content of this invention is not limited by this.

<Compound (A)>
Synthesis Example 1 (Synthesis of Compound (I-1))
Diiodoperfluorobutane 8.44 g (18.6 mmol), hydrosulfite sodium 8.50 g (48.8 mmol), sodium hydrogen carbonate 4.60 g (55 mmol), acetonitrile 25 mL and water 15 mL were added and stirred at room temperature for 1 hour. . The reaction solution was filtered, and the filtrate was ice-cooled to precipitate a white solid. This was collected by filtration and dried to obtain 6.8 g (98%) of sodium perfluorobutane-1,5-disulfinate.
Triphenylsulfonium iodide (15.77 g, 40.4 mmol), silver acetate (7.07 g, 42.4 mmol), acetonitrile (400 mL) and water (200 mL) were added, and the mixture was stirred at room temperature for 1 hour. The reaction solution was filtered to obtain a triphenylsulfonium acetate solution.
7.2 g (19.2 mmol) of sodium perfluorobutane-1,5-disulfinate, 80 mL of hydrogen peroxide (30%) and 8 mL of acetic acid were added and stirred at 60 ° C. for 4 hours. After confirming the completion of the reaction by ¹⁹ F-NMR, 30 mL of 1N NaOH was added to neutralize, and the above triphenylsulfonium acetate solution was added to this solution and stirred at room temperature for 3 hours. Chloroform 500 mL was added, and the organic layer was washed successively with water, a saturated aqueous sodium sulfite solution, water, a saturated aqueous ammonium chloride solution, and water. The organic layer was filtered through a 0.1 μm filter, and the solvent was removed by an evaporator to obtain a colorless transparent oil. This was left to stand at −10 ° C. for 6 hours for crystallization, filtered and dried to obtain the target compound (I-1) (7.5 g, 44%).
¹ H-NMR (300 MHz, CDCl ₃ ) δ 7.27-7.55 (m, 9H), 7.70-7.69 (m, 6H)
¹⁹ F-NMR (300 MHz, CDCl ₃ ) δ-114 (t, 4F), −120 (t, 4F)

  Other acid generators were synthesized in the same manner.

<Resin (B)>
Synthesis Example 1 (Synthesis of resin (1) (side chain type))
2-ethyl-2-adamantyl methacrylate and butyrolactone methacrylate were charged at a ratio of 55/45 and dissolved in methyl ethyl ketone / tetrahydrofuran = 5/5 to prepare 100 mL of a 20% solid content solution. To this solution, 2 mol% of V-65 manufactured by Wako Pure Chemical Industries, Ltd. was added dropwise to 10 mL of methyl ethyl ketone heated to 60 ° C. over 4 hours under a nitrogen atmosphere. After completion of the dropwise addition, the reaction solution was heated for 4 hours, 1 mol% of V-65 was added again, and the mixture was stirred for 4 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and the resin (1) which was a white powder crystallized and precipitated in 3 L of a mixed solvent of distilled water / ISO propyl alcohol = 1/1 was recovered.
The polymer composition ratio determined from C ¹³ NMR was 46/54. Moreover, the standard polystyrene conversion mass mean molecular weight calculated | required by GPC measurement was 10700.
Resins (2) to (12) and (26) to (31) were synthesized in the same manner as in Synthesis Example 1.

Synthesis Example 2 (Synthesis of resin (13) (main chain type))
Norbornenecarboxylic acid tbutyl ester, norbornenecarboxylic acid butyrolactone ester, maleic anhydride (molar ratio 40/10/50) and THF (reaction temperature 60 mass%) were charged into a separable flask and heated at 60 ° C. in a nitrogen stream. When the reaction temperature was stabilized, 2 mol% of a radical initiator V-601 manufactured by Wako Pure Chemical Industries, Ltd. was added to initiate the reaction. Heated for 12 hours. The resulting reaction mixture was diluted twice with tetrahydrofuran and then poured into a mixed solution of hexane / isopropyl alcohol = 1/1 to precipitate a white powder. The precipitated powder was filtered out and dried to obtain the desired resin (13).

When the molecular weight analysis by GPC of the obtained resin (13) was tried, it was 8300 (mass average) in terms of polystyrene. Further, from the NMR spectrum, it was confirmed that the molar ratio of the norbornenecarboxylic acid tbutyl ester / norbornenecarboxylic acid butyrolactone ester / maleic anhydride repeating unit of the resin (1) was 42/8/50.
Resins (14) to (19) were synthesized in the same manner as in Synthesis Example 2.

Synthesis Example 3 (Synthesis of Resin (20) (Hybrid Type))
Norbornene, maleic anhydride, t-butyl acrylate and 2-methylcyclohexyl-2-propyl acrylate were charged into a reaction vessel at a molar ratio of 35/35/20/10 and dissolved in tetrahydrofuran to prepare a solution having a solid content of 60%. . This was heated at 65 ° C. under a nitrogen stream. When the reaction temperature was stabilized, 1 mol% of radical initiator V-601 manufactured by Wako Pure Chemical Industries, Ltd. was added to initiate the reaction. After heating for 8 hours, the reaction mixture was diluted 2 times with tetrahydrofuran and then poured into hexane having a volume 5 times that of the reaction mixture to precipitate a white powder. The precipitated powder was filtered out, dissolved in methyl ethyl ketone, reprecipitated in a 5-fold volume of hexane / t-butyl methyl ether = 1/1 mixed solvent, and the precipitated white powder was collected by filtration, dried and dried. Resin (20) which is a thing was obtained.

When the molecular weight analysis by GPC of the obtained resin (20) was tried, it was 12100 (mass average) in terms of polystyrene. From the NMR spectrum, the composition of the resin (1) was norbornene / maleic anhydride / tbutyl acrylate / 2-methylcyclohexyl-2-propyl acrylate according to the present invention in a molar ratio of 32/39/19/10.
Resins (21) to (25) were synthesized in the same manner as in Synthesis Example 3.

  Hereinafter, the structures and molecular weights of the resins (1) to (31) are shown.

Synthesis Example 4 (Synthesis of resin (RA21))
A mixture of norbornenecarboxylic acid t-Bu ester, norbornenecarboxylic acid, norbornenecarboxylic acid 2-hydroxyethyl ester and maleic anhydride was dissolved in tetrahydrofuran to prepare a solution having a solid content of 50% by mass. This was charged into a three-necked flask and heated at 60 ° C. under a nitrogen stream. When the reaction temperature was stabilized, 5 mol% of radical initiator V-60 manufactured by Wako Pure Chemical Industries, Ltd. was added to initiate the reaction. After heating for 6 hours, the reaction mixture was diluted twice with tetrahydrofuran, and then poured into hexane in an amount 5 times that of the reaction solution to precipitate a white powder. This was again dissolved in tetrahydrofuran and poured into 5 times the amount of hexane to precipitate a white powder. The precipitated powder was filtered out and dried to obtain a target resin (RA21) having the following repeating unit (formula (1) in JP-A No. 2000-241964).
When the molecular weight analysis (RI analysis) by GPC of the obtained resin (RA21) was tried, it was 7900 (weight average) in terms of polystyrene.

  Similarly, the following resins (RA1) to (RA20) were obtained.

Synthesis Example 5 ((Synthesis of Resin (RB1)))
2-Methyl-2-adamantyl methacrylate, β-hydroxy-γ-butyrolactone methacrylate, 3-hydroxy-1-adamantyl methacrylate were charged at a ratio of 50/25/25, and propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether = 70 / It melt | dissolved in 30 (mass ratio), and 450 g of solutions with a solid content concentration of 22 mass% were prepared. To this solution, 1.5 mol% of Wako Pure Chemical Industries, Ltd. polymerization initiator V-601 was added, and this was heated to 100 ° C. over 6 hours in a nitrogen atmosphere. Propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether = The solution was added dropwise to 50 g of a 70/30 (mass ratio) mixed solution. The reaction liquid was stirred for 2 hours after completion | finish of dripping. After completion of the reaction, the reaction solution was cooled to room temperature, crystallized in 5 L of a mixed solvent of hexane / ethyl acetate = 9/1 (mass ratio), the precipitated white powder was collected by filtration, and the target resin (RB1) Was recovered.
Polymer composition ratio determined from ¹³ C-NMR (2-methyl-2-adamantyl methacrylate / β-hydroxy-γ-butyrolactone methacrylate / 3-hydroxy-1-adamantyl methacrylate) and weight in terms of standard polystyrene determined by GPC measurement The average molecular weight and dispersity (Mw / Mn) were as follows.
Similarly, alicyclic hydrocarbon-based acid-decomposable resins (RB2) to (RB14) were synthesized.
Hereinafter, structures, weight average molecular weights, and dispersities of the alicyclic hydrocarbon-based acid-decomposable resins (RB1) to (RB14) are shown.

In addition, Resin A4 of Synthesis Example 10 of JP-A-10-274852, Resin H of Synthesis Example 8 of JP-A-2000-137327, and Resin (1) of Synthesis Example (1) of JP-A-2001-109154 were synthesized. Resins R1, R2 and R3.
The structure of the repeating unit of these resins is shown below. The weight average molecular weights were R1: 8000, R2: 14000, R3: 7200.

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

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

Examples 1 to 25 and Comparative Examples 1 and 2
<Resist preparation>
The components shown in Tables 3 to 5 below were dissolved in a solvent to prepare a solution having a solid content concentration of 12% by mass, and this was filtered through a 0.1 μm polytetrafluoroethylene filter or a polyethylene filter to prepare a positive resist solution. . The prepared positive resist solution was evaluated by the following method, and the results are shown in Tables 3 to 5.

  Hereinafter, the abbreviations in Tables 3 to 8 and Tables 10 to 13 are as follows. Resins and acid generators other than those listed below are those exemplified above. In each table, the ratio when a plurality of resins or solvents are used is a mass ratio.

[Acid generator]
The compound (A) and the combined acid generator of the present invention are those exemplified above.
However, PAG-A is the following compound.

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

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

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

[Dissolution inhibitor]
LCB; t-butyl lithocholic acid

<Resist evaluation>
An anti-reflective coating DUV-42 manufactured by Brewer Science Co., Ltd. was uniformly applied to 600 angstroms 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 0.30 μm resist film.
The resist film was exposed with an ArF excimer laser stepper (NA = 0.6 manufactured by ISI) through a mask, and immediately after the exposure, it was heated on a hot plate at 120 ° C. for 90 seconds. Further, the resist film was developed with an aqueous 2.38 mass% tetramethylammonium hydroxide solution at 23 ° C. for 60 seconds, rinsed with pure water for 30 seconds, and then dried to obtain a line pattern.

(Density dependency)
A line and space pattern (dense pattern: line and space 1/1) with a line width of 0.13 μm and an isolated line pattern (sparse pattern: line and space 1/5) are allowed to be 0.13 μm ± 10%, respectively. The overlapping range of the focal depth was obtained. The larger the value, the smaller the performance difference between the dense pattern and the sparse pattern, and the better the density dependency.

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

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

Examples 26-28 and Comparative Examples 3 and 4
(1) Formation of lower resist layer FHi-028DD resist (resist for i-line manufactured by Fuji Film Orin) was applied to a 6-inch silicon wafer using a spin coater Mark8 manufactured by Tokyo Electron, and baked at 90 ° C. for 90 seconds to form a film. A uniform film having a thickness of 0.55 μm was obtained.
This was further heated at 200 ° C. for 3 minutes to form a lower resist layer having a thickness of 0.40 μm.

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

  Resins (SI-1) to (SI-3) in Table 6 are as follows.

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

  In the same manner as in Examples 1 to 25, density dependency and exposure latitude were evaluated. The results are shown in Table 6.

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

Examples 29-48 and Comparative Examples 5 and 6
<Resist preparation>
The components shown in Tables 7 to 8 below were dissolved in a solvent to prepare a solution having a solid concentration of 5% by mass, and this was filtered through a 0.1 μm polyethylene filter to prepare a resist solution.
Each resist solution was applied to a silicon wafer subjected to hexamethyldisilazane treatment by a spin coater and dried by heating on a vacuum contact hot plate at 120 ° C. for 90 seconds to obtain a resist film having a thickness of 0.1 μm.
The obtained resist film was subjected to pattern exposure using an F ₂ excimer laser stepper (157 nm), and immediately after the exposure, it was heated on a hot plate at 120 ° C. for 90 seconds. The sample was developed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution for 60 seconds and rinsed with pure water to obtain a sample wafer. The density dependence and exposure latitude were evaluated for these.

(Density dependency)
Overlapping depth of focus allowing 80 nm ± 10% in line and space pattern (dense pattern: line and space 1/1) and isolated line pattern (sparse pattern: line and space 1/5) with a line width of 80 nm The range was determined. The larger the value, the smaller the performance difference between the dense pattern and the sparse pattern, and the better the density dependency.

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

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

Examples 49-60 and Comparative Examples 7 and 8
<Resist preparation>
The components shown in Table 10 below were dissolved in a solvent and filtered through a 0.1 μm polytetrafluoroethylene filter to prepare a positive resist solution having a solid content concentration of 14% by mass.
The prepared positive resist solution was evaluated by the following method, and the results are shown in Table 10.

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

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

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

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

(Density dependency)
A line and space pattern (dense pattern: line and space 1/1) with a line width of 0.13 μm and an isolated line pattern (sparse pattern: line and space 1/5) are allowed to be 0.13 μm ± 10%, respectively. The overlapping range of the focal depth was obtained. The larger the value, the smaller the performance difference between the dense pattern and the sparse pattern, and the better the density dependency.

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

  From the results in Table 10, it can be seen that the photosensitive composition of the present invention has a small dependence on density and is excellent in exposure latitude as a positive resist composition in KrF excimer laser exposure.

Examples 61-72 and Comparative Examples 9 and 10
<Resist preparation>
The components shown in Table 11 below were dissolved in a solvent, which was filtered through a 0.1 μm polytetrafluoroethylene filter to prepare a negative resist solution having a solid concentration of 14% by mass.
The prepared negative resist solution was evaluated in the same manner as in Examples 49 to 60, and the results are shown in Table 11.

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

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

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

Examples 73-84 and Comparative Examples 11 and 12
<Resist preparation>
The components shown in Table 12 were dissolved in a solvent, and this was filtered through a 0.1 μm polytetrafluoroethylene filter to prepare a positive resist solution having a solid content concentration of 12% by mass.
The prepared positive resist solution was evaluated by the following method, and the results are shown in Table 12.

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

(Density dependency)
The pattern size of the isolated contact hole (pitch 1000 nm) at the irradiation amount for resolving the 100 nm dense contact hole (pitch 300 nm) was measured, and the difference from 100 nm was calculated. The smaller the value, the smaller the performance difference between the dense pattern and the isolated pattern, and the better the density dependency.
(Exposure latitude)
The irradiation dose for resolving 100 nm dense contact holes (pitch 300 nm) is set as the optimum dose, and when the dose is changed, the dose width that allows the pattern size to be 100 nm ± 10% is obtained, and this value is set as the optimum dose. Divided by the amount and expressed as a percentage. The larger the value, the smaller the change in performance due to the change in exposure amount, and the better the exposure latitude.

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

Examples 85-96 and Comparative Examples 13 and 14
<Resist preparation>
The components shown in Table 13 were dissolved in a solvent, and this was filtered through a 0.1 μm polytetrafluoroethylene filter to prepare a negative resist solution having a solid concentration of 12% by mass.
The prepared negative resist solution was evaluated by the following method, and the results are shown in Table 13.

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

(Density dependency)
The pattern dimension of an isolated line (pitch 1000 nm) at an irradiation dose for resolving 100 nm dense line and space (pitch 200 nm) was measured, and the difference from 100 nm was calculated. The smaller the value, the smaller the performance difference between the dense pattern and the isolated pattern, and the better the density dependency.
(Exposure latitude)
The irradiation dose that resolves 100 nm dense line and space (pitch 200 nm) is the optimum irradiation dose, and when changing the irradiation dose, the dose width that allows the pattern size to be 100 nm ± 10% is obtained, and this value is optimal The percentage was displayed by dividing by the irradiation amount. The larger the value, the smaller the change in performance due to the change in exposure amount, and the better the exposure latitude.

  From the results shown in Table 13, it can be seen that the photosensitive composition of the present invention has low density dependency and excellent exposure latitude widely as a negative resist composition in electron beam irradiation.

Examples 97-118 and Comparative Examples 15-17
<Resist preparation>
The components shown in Tables 14 to 16 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 polyethylene filter to prepare a positive resist solution. The prepared positive resist solution was evaluated by the following method, and the results are shown in Tables 14-16. The ratio when using a plurality of components is a mass ratio.

  The symbols in Tables 14 to 16 are as follows.

N′-1; N, N-dibutylaniline N′-2; N, N-dipropylaniline N′-3; N, N-dihydroxyethylaniline N′-4: 2,4,5-triphenylimidazole N '-5; 2,6-diisopropylaniline N'-6; hydroxyantipyrine

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.)

SL'-1: cyclopentanone SL'-2: cyclohexanone SL'-3: 2-methylcyclohexanone SL'-4; propylene glycol monomethyl ether acetate SL'-5: ethyl lactate SL'-6: propylene glycol monomethyl ether SL '-7: 2-heptanone SL'-8: γ-butyrolactone SL'-9: propylene carbonate

SI′-1; t-butyl lithocholic acid SI′-2; t-butyl adamantanecarboxylate

<Resist evaluation>
ARC29A manufactured by Brewer Science Co., Ltd. was uniformly applied to a silicon wafer with a spin coater at a thickness of 78 nm, and heat-dried at 205 ° C. for 60 seconds to form an antireflection film. Thereafter, each positive resist composition immediately after preparation was applied by a spin coater and dried (PB) for 90 seconds at a temperature shown in Tables 14 to 16 to form a 300 nm resist film.
This resist film is exposed with an ArF excimer laser stepper (PAS5500 / 1100 NA = 0.75 (2/3 annular illumination) manufactured by ASML) through a mask, and immediately after the exposure, at a temperature shown in Tables 14 to 90 for 90 seconds. Heated (PEB) on hot plate. 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 resist pattern.

[Density dependence and exposure latitude]
In the same manner as in Example 1, density dependency and exposure latitude were evaluated.

[Pattern collapse]
Development and pattern formation were carried out while changing the exposure amount for a trench repeating pattern (pitch 240 nm) having a line width of 110 nm, and the presence or absence of pattern collapse accompanying an increase in the exposure amount was observed with a scanning electron microscope (SEM). As the exposure amount increases, the line width becomes narrower, and pattern collapse eventually occurs. In this evaluation method, the line width (CDmin) immediately before the occurrence of pattern collapse due to the decrease in line width was used as an index of pattern collapse. That is, a smaller CDmin means that the pattern does not fall even if the line width becomes narrower, and the pattern is less likely to fall.

[Defocus latitude (DOF) when forming isolated line patterns]
The focal position was varied at an exposure amount for reproducing an isolated line pattern of 210 nm with a line width of 130 nm, and a focal fluctuation range (nm) satisfying a range of 130 nm ± 13 nm (± 10%) was obtained.

From the results of Tables 14 to 16, it can be seen that the resist composition of the present invention is excellent in density dependency and exposure latitude.
Further, from the results of Tables 14 to 16, the resist composition of the present invention is less susceptible to pattern collapse by using an alicyclic hydrocarbon-based acid-decomposable resin and a cyclic ketone, and the focus shift tolerance for an isolated line pattern. It is clear that it is large and excellent.

Examples 119 to 135 and Comparative Examples 18 to 19
<Resist preparation>
The components shown in Tables 17 to 18 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 polyethylene filter to prepare a positive resist solution. The prepared positive resist solution was evaluated by the following method, and the results are shown in Tables 17-18. The ratio when using a plurality of components is a mass ratio.

  The symbols in Tables 17-18 are as follows.

[Photoacid generator]
Corresponds to those exemplified above.

[Basic compounds]
N ″ -1: N, N-dibutylaniline N ″ -2: N, N-dipropylaniline N ″ -3: N, N-dihydroxyethylaniline N ″ -4: 2,4,5- Triphenylimidazole N ″ -5: 2,6-diisopropylaniline N ″ -6: hydroxyantipyrine

[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〕
SL ″ -1: Propylene glycol monomethyl ether acetate SL ″ -2: Propylene glycol monomethyl ether propionate SL ″ -3: Propylene glycol monomethyl ether SL ″ -4: 3-methoxybutanol SL ″ -5: Ethyl lactate SL ″ -6: Cyclohexanone SL ″ -7: 2-heptanone SL ″ -8: γ-butyrolactone SL ″ -9: Propylene carbonate

[Dissolution inhibitor compound]
SI ″ -1: t-butyl lithocholic acid SI ″ -2: t-butyl adamantanecarboxylate

<Resist evaluation>
ARC29A manufactured by Brewer Science Co., Ltd. was uniformly applied to a silicon wafer with a spin coater at 78 nm, and heat-dried at 205 ° C. for 60 seconds to form an antireflection film. Thereafter, each positive resist composition immediately after preparation was applied with a spin coater and dried (PB) for 60 seconds at a temperature described in Tables 17 to 18 to form a 270 nm resist film.
This resist film is exposed with an ArF excimer laser stepper (PAS5500 / 1100 NA = 0.75 (2/3 annular illumination) manufactured by ASML) through a mask, and immediately after the exposure, hot for 60 seconds at a temperature shown in Tables 16 to 17 Heated (PEB) on the plate. 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 resist pattern.

[Density dependence and exposure latitude]
In the same manner as in Example 1, density dependency and exposure latitude were evaluated.

[Process window evaluation method (dense pattern)]
For a line and space pattern with a mask size of 100 nm (pitch: 220 nm), the exposure amount reproduced at a size of 100 nm is the optimum exposure amount (E _dense ), and the condition is 100 nm ± 10 defocused under the condition of ± 0.3 μm with respect to the best focus. When the maximum exposure (E ₁ ) and the minimum exposure (E ₂ ) reproducing the line width in the range of% were defined, the process window was defined as follows.
| (E ₁ −E ₂ ) / E _dense | × 100 (%)

[Process window evaluation method (isolated pattern)]
For an isolated pattern with a mask size of 160 nm, the exposure amount reproduced at a size of 100 nm is the optimum exposure amount (Eiso), and the line width in the range of 100 nm ± 10% is obtained under the condition of ± 0.3 μm defocusing with respect to the best focus. The process window was defined as follows, assuming the maximum exposure (E ₁₁ ) and the minimum exposure (E ₁₂ ) to be reproduced.
| (E ₁₁ −E ₁₂ ) / E _iso | × 100 (%)

[Process window evaluation method (common)]
Based on the following equation, a common process window was calculated for the exposure range in which a dense pattern and an isolated pattern can be formed simultaneously under the condition of ± 0.3 μm defocusing with respect to the best focus.
｜ (E ₂₁ −E ₂₂ ) / E _dense ｜ × 100 (%)
Here, E ₂₁ is the smaller exposure amount of E ₁ and E ₁₁ , and E ₂₂ is the larger exposure amount of E ₂ and E ₁₂ .

From the results of Tables 17 to 18, it can be seen that the resist composition of the present invention is excellent in density dependency and exposure latitude.
From the results of Tables 17 to 18, the positive resist composition of the present invention can secure a wide process window in forming isolated lines and dense patterns by using an alicyclic hydrocarbon-based acid-decomposable resin (Baa). It turns out that it is possible.

Claims (9)

(A) A photosensitive composition comprising a compound capable of generating a sulfonic acid represented by the following general formula (I) upon irradiation with an actinic ray or radiation.

In general formula (I),
A ₁ represents an n-valent linking group.
A ₂ represents a single bond or a divalent aliphatic group. The n A _{2 s} may be the same or different.
However, at least one of the group represented by A ₁ and the group represented by A ₂ has a fluorine atom.
n represents an integer of 2 to 4. Further, (Ba) a resin having a monocyclic or polycyclic alicyclic hydrocarbon structure and having increased solubility in an alkali developer by the action of an acid, and (Ha) a solvent containing at least one cyclic ketone. The positive photosensitive composition according to claim 1. Furthermore, (Baa) at least one type of repeating unit selected from the repeating unit represented by the following general formula (1), the repeating unit represented by the general formula (2), and the repeating unit represented by the general formula (3) 2. The positive photosensitive composition according to claim 1, further comprising: a resin having a solubility in an alkali developer by the action of an acid.

In general formula (1),
R represents a hydrogen atom or a methyl group.
A represents a single bond or a linking group.
ALG represents a group represented by any one of the following general formulas (pI) to (pV).

In the 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.
Z represents an atomic group necessary for forming an alicyclic hydrocarbon group together with a carbon atom.
R _{12 to} R ₁₆ each independently represents a linear or branched alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group. However, at least one of R _{12 to} R ₁₄ and any one of R ₁₅ and R ₁₆ represents an alicyclic hydrocarbon group.
R _{17 to} R ₂₁ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or an alicyclic hydrocarbon group. However, at least one of R _{17 to} R ₂₁ represents an alicyclic hydrocarbon group. Further, either R ₁₉ or R ₂₁ represents a linear or branched alkyl group or alicyclic hydrocarbon group having 1 to 4 carbon atoms.
R _{22 to} R ₂₅ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or an alicyclic hydrocarbon group. However, at least one of R _{22 to} R ₂₅ represents an alicyclic hydrocarbon group. R ₂₃ and R ₂₄ may be bonded to each other to form a ring.

In general formula (2),
R _1a represents a hydrogen atom or a methyl group.
W ₁ represents a single bond, an alkylene group, an ether group, a thioether group, a carbonyl group, or a group of two or more groups selected from the group consisting of an ester group.
Lc represents a lactone residue represented by any one of the following general formulas (IV), (V-1) to (V-6) and (VI).

In general formula (IV),
R _a1 , R _b1 , R _c1 , R _d1 and R _e1 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
m and n each independently represents an integer of 0 to 3, and m + n is 2 or more and 6 or less.

In general formulas (V-1) to (V-6),
R _{1b to} R _5b each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, or COOR _6b . Here, R _6b represents an alkyl group. Two of R _{1b to} R _5b may be bonded to form a ring.

In general formula (3),
R ₃₀ represents a hydrogen atom or a methyl group.
R _{31 to} R ₃₃ each independently represents a hydrogen atom, a hydroxyl group or an alkyl group, provided that at least one represents a hydroxyl group.   The resin of the component (Baa) is at least one selected from the repeating unit represented by the general formula (1), the repeating unit represented by the general formula (2), and the repeating unit represented by the general formula (3). The positive photosensitive composition according to claim 3, wherein the positive photosensitive composition comprises:   The (Baa) component resin has a repeating unit represented by the general formula (1), a repeating unit represented by the general formula (2), and a repeating unit represented by the general formula (3). The positive photosensitive composition according to claim 4. In the general formula (I), A ₂ is The photosensitive composition according to claim 1, characterized in that an aliphatic group having a structure represented by the following general formula (II).

In general formula (II):
Rf ₁ and Rf ₂ each independently represents a hydrogen atom, a halogen atom, an alkyl group or a cycloalkyl group. However, at least one of Rf ₁ and Rf ₂ is a fluorine atom or a fluoroalkyl group.   The component (A) is one kind selected from a sulfonium salt compound, an iodonium salt compound, and an ester compound of a sulfonic acid represented by the above general formula (I). The photosensitive composition as described.   Furthermore, it contains the mixed solvent which mixed the solvent which contains a hydroxyl group in a structure, and the solvent which does not contain a hydroxyl group, The photosensitive composition in any one of Claim 1 and Claims 3-7 characterized by the above-mentioned. .   A pattern forming method comprising forming a film from the photosensitive composition according to claim 1, and exposing and developing the film.