KR101011711B1 - Photosensitive composition - Google Patents

Abstract

(Tasks) in the exposure wavelength of 250nm or less, particularly ArF excimer laser light (193nm), F ₂ excimer laser light (157nm), to provide a photosensitive composition excellent PEB temperature dependency is small.

(Solution) (A) a compound which generates an acid by irradiation of actinic rays or radiation having a carboxyl group, and (B) is decomposed by the action of an acid having at least one of an acid decomposable acetal group and a tertiary ester group. The photosensitive composition containing resin in which the solubility in alkaline developing solution increases.

Description

Photosensitive composition {PHOTOSENSITIVE COMPOSITION}

BACKGROUND OF THE INVENTION Field of the Invention The present invention relates to photosensitive compositions used in semiconductor manufacturing processes such as ICs, production of circuit boards such as liquid crystals, thermal heads, and other optical processing steps.

The said photosensitive composition is used as a pattern formation material which changes the solubility to the developing solution of an irradiation part and a non-irradiation part of actinic light or a radiation, and forms a pattern on a board | substrate.

In such a photosensitive composition, various acid generators which generate an acid by irradiation of actinic light or radiation have been proposed.

Patent document 1 (WO02 / 1296) describes a chemically amplified resist composition using a resin having a protecting group and a sulfonium salt having a water-soluble substituent.

However, there are still many insufficient points, and various improvements are required. For example, when using a wafer having a large aperture, it has been confirmed that a temperature difference in heating (PEB) by a hot plate or the like after exposure affects the obtained pattern, and improves such PEB temperature dependency with a good profile. Is required.

(Patent Document 1) International Patent Publication No. 02/1296

It is therefore an object of the present invention is to provide a photosensitive composition excellent low PEB temperature dependence in the exposure wavelength of 250nm or less, particularly ArF excimer laser light (193nm), F ₂ excimer laser light (157nm).

This invention has the following structures, and the said objective of this invention is achieved by this.

(1) A compound which generates an acid by irradiation of actinic light or radiation which has (A) carboxyl group, and
(B) contains a resin which is decomposed by the action of at least one of an acid decomposable acetal group and a tertiary ester group with an acid having a lactone structure or a structure represented by the following formula, thereby increasing the solubility in an alkaline developer; The photosensitive composition made into.

(2) The photosensitive composition as described in the item (1), wherein the compound (A) is a sulfonium salt compound.

(3) The photosensitive composition as described in the above (1) or (2), wherein the resin (B) is a resin having a monocyclic or polycyclic alicyclic hydrocarbon structure.

(4) The photosensitive composition as described in any one of said (1)-(3) whose resin (B) is resin which has a fluorine atom in a principal chain or a side chain.

Hereinafter, preferred embodiment of this invention is further enumerated.

(5) The positive photosensitive composition as described in the item (4), wherein the resin which is decomposed by the action of the acid (B) and the solubility in the alkaline developer is increased has a hexafluoroisopropanol structure.

(6) The positive photosensitive composition as described in the item (1) or (2), wherein the resin which is decomposed by the action of the acid (B) to increase the solubility in the alkaline developer has a hydroxystyrene structural unit. .

(7) The positive photosensitive composition as described in the item (3), wherein the resin which is decomposed by the action of the acid (B) and the solubility in the alkaline developer increases further has a repeating unit containing a lactone structure. .

(8) Positive type photosensitive property of said (1) or (2) whose resin which decomposes by action of (B) acid and the solubility in alkali developing solution increases is resin containing a silicon atom. Composition.

(9) The positive of any one of the above (1) to (8), which contains a dissolution inhibiting compound having a molecular weight of 3000 or less, which is decomposed by the action of (C) acid to increase the solubility in the alkaline developer. Type photosensitive composition.

(10) The photosensitive composition as described in any one of said (1)-(9) containing (F) basic compound and / or (G) fluorine and / or silicon type surfactant.

(11) The above-mentioned (10), wherein the (F) basic compound is selected from an imidazole structure, diazabicyclo structure, onium hydroxide structure, onium carboxylate structure, trialkylamine structure, aniline structure and pyridine structure A compound having a structure, an alkyl amine derivative having a hydroxyl group and / or an ether bond or an aniline derivative having a hydroxyl group and / or an ether bond.

Hereinafter, the present invention will be described in detail.

In addition, in description of group (atom group) in this specification, the description which is not describing substitution and unsubstitution includes what has a substituent with the thing which does not have a substituent. For example, an "alkyl group" includes not only the alkyl group (unsubstituted alkyl group) which does not have a substituent but the alkyl group (substituted alkyl group) which has a substituent.

As a photosensitive composition of this invention, a positive photosensitive composition, Preferably a positive resist composition is mentioned.

A positive resist composition contains the compound (A) which generate | occur | produces an acid by irradiation of actinic light or a radiation, and resin (B) which decomposes by action of an acid, and the solubility in alkaline developing solution increases, as needed. It further contains a dissolution inhibiting compound (C) having a molecular weight of 3000 or less, which is decomposed by the action of an acid and the solubility in the alkaline developer is increased.

Hereinafter, the present invention will be described in detail.

[1] (A) A compound which generates an acid by irradiation of actinic light or radiation having a carboxyl group

Compound (A) which generates an acid by irradiation of actinic light or radiation having a carboxyl group to be used in the present invention includes infrared light, visible light, ultraviolet light and far ultraviolet light (preferably 250 nm) used for exposure for pattern formation. Below, more preferably, ultraviolet light having a wavelength of 220 nm or less, specifically, KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (157 nm), EUV (13 nm), X-ray, electron beam, etc. It is a compound which generates an acid by actinic light or radiation.

As the compound (A) used in the present invention, for example, a sulfonium salt compound, an iodonium salt compound, a bis (sulfonyl) diazomethane compound, an imidosulfonate compound, an oxime sulfonate compound, having one or more carboxyl groups, Nitrobenzylsulfonate compounds are listed. Especially preferably, it is a sulfonium salt.

When compound (A) consists of an anion part and a cation part, it is preferable that a cation part has a carboxyl group.

1-3 are preferable and, as for the number of the carboxyl groups per molecule which a compound (A) has, 1 or 2 is more preferable.

A compound (A) can be used individually by 1 type or in combination of 2 or more types.

As for content of the compound (A) in the composition of this invention, 0.1-20 mass% is preferable on the basis of solid content of a composition, More preferably, it is 0.5-15 mass%, More preferably, it is 1.0-10 mass%.

As a compound (A), the compound which has group containing a carboxyl group in arbitrary substitution positions among the compounds represented by the following general formula (ZI)-(ZVI) is preferable. More preferably, it is a compound represented by following General formula (I), More preferably, it is a compound which has a group containing a carboxyl group in arbitrary substitution positions of following compound (Z1-1)-(Z1-3).

In said general formula (ZI), R <_201> , R <_202> and R <_203> represent an organic group each independently.

X <^-> represents a non-nucleophilic anion, and can mention a sulfonic acid anion, a carboxylic acid anion, a sulfonylimide anion, a bis (alkylsulfonyl) imide anion, a tris (alkylsulfonyl) methyl anion, etc.

A non-nucleophilic anion is an anion which is remarkably low in ability to generate a nucleophilic reaction, and is an anion which can suppress the degradation over time by the intramolecular nucleophilic reaction. This improves the stability over time of the resist.

Examples of the sulfonic acid anion include alkylsulfonic acid anion, arylsulfonic acid anion, camphorsulfonic acid anion and the like.

Examples of the carboxylic acid anion include alkyl carboxylic acid anions, arylcarboxylic acid anions, aralkyl carboxylic acid anions, and the like.

As the alkyl group in the alkyl sulfonic acid anion, preferably an alkyl group having 1 to 30 carbon atoms, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, pentyl group, neo Pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group The actual group, the eicosyl group, the cyclopropyl group, the cyclopentyl group, the cyclohexyl group, the adamantyl group, the norbornyl group, the boronyl group, etc. can be mentioned.

As an aryl group in an aryl sulfonic acid anion, Preferably, a C6-C14 aryl group, for example, a phenyl group, a tolyl group, a naphthyl group, etc. can be mentioned.

The alkyl group and aryl group in the said alkyl sulfonic acid anion and aryl sulfonic acid anion may have a substituent. Examples of the substituent include a nitro group, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), carboxyl group, hydroxyl group, amino group, cyano group, alkoxy group (preferably 1 to 5 carbon atoms), aryl group (preferably And C6-14), an alkoxycarbonyl group (preferably C2-C7), an acyl group (preferably C2-C12), an alkoxycarbonyloxy group (preferably C2-C7), etc. can be mentioned. have. Moreover, about an aryl group, the aryl site | part, and ring structure which a substituent has, an alkyl group (preferably C1-C12) can be enumerated as a substituent.

As an alkyl group in an alkylcarboxylic acid anion, the thing similar to the alkyl group in an alkyl sulfonic acid anion can be mentioned.

As an aryl group in an arylcarboxylic acid anion, the same thing as the aryl group in an aryl sulfonic acid anion can be mentioned.

As the aralkyl group in the aralkyl carboxylic acid anion, preferably aralkyl groups having 6 to 12 carbon atoms, such as benzyl group, phenethyl group, naphthylmethyl group, naphthylethyl group, naphthylmethyl group, etc. may be mentioned.                     

The alkyl group, aryl group and aralkyl group in the alkyl carboxylic acid anion, the arylcarboxylic acid anion and the aralkyl carboxylic acid anion may have a substituent, and examples of the substituent include the same halogen atoms as in the aryl sulfonic acid anion. , An alkyl group, an alkoxy group, an alkylthio group, and the like.

Examples of the sulfonylimide anion include saccharin anion.

The alkyl group in the bis (alkylsulfonyl) imide anion and the tris (alkylsulfonyl) methyl anion is preferably an alkyl group having 1 to 5 carbon atoms, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl Groups, isobutyl group, sec-butyl group, pentyl group, neopentyl group and the like. These alkyl groups may have a substituent, As a substituent, a halogen atom, the alkyl group substituted by the halogen atom, an alkoxy group, an alkylthio group, etc. can be mentioned, The alkyl group substituted by the fluorine atom is preferable.

As other non-nucleophilic anions, phosphorus fluoride, boron fluoride, antimony fluoride, etc. can be mentioned, for example.

Examples of the non-nucleophilic anion of X ⁻ include an alkanesulfonic anion in which the α position of the sulfonic acid is substituted with a fluorine atom, an aryl sulfonic acid anion substituted with a fluorine atom or a group having a fluorine atom, and a bis (alkylsulfonyl) imide anion in which the alkyl group is substituted with a fluorine atom The tris (alkylsulfonyl) methed anion in which the alkyl group is substituted with a fluorine atom is preferable. As the non-nucleophilic anion, particularly preferably a perfluoroalkanesulfonic anion having 4 to 8 carbon atoms, a benzenesulfonate anion having a fluorine atom, most preferably a nonafluorobutanesulfonic acid anion, a perfluorooctane sulfonic acid anion and a pentafluoro Benzene sulfonic acid anion and 3,5-bis (trifluoromethyl) benzene sulfonic acid anion.

Carbon number of the organic group as R <_201> , R <_202> and R <_203> is 1-30 normally, Preferably it is 1-20.

In addition, two of R ₂₀₁ to R _{203 may be} bonded to each other to form a ring structure, and the ring may include an oxygen atom, a sulfur atom, an ester bond, an amide bond, and a carbonyl group.

Examples of the group formed by bonding of two of R ₂₀₁ to R ₂₀₃ include an alkylene group (for example, butylene group and pentylene group).

As a specific example of the organic group as R <_201> , R <_202> and R <_203> , the corresponding group in compound (Z1-1), (Z1-2), and (Z1-3) mentioned later can be mentioned.

Moreover, the compound which has two or more structures represented by general formula (ZI) may be sufficient. For example, even if one or more of R <_201> -R <_203> of the compound represented by general formula (ZI) is a compound which has a structure couple | bonded with one or more of R <_201> -R <_203> of another compound represented by general formula (ZI) good.

In General Formulas (ZII) and (ZIII), R ₂₀₄ to R ₂₀₇ each independently represent an aryl group or an alkyl group.

R ₂₀₄ ~R group of aryl _207, may have a substituent, a phenyl group, and naphthyl groups are preferred, and more preferably a phenyl group.

The alkyl group as R ₂₀₄ to R ₂₀₇ may be any of linear, branched or cyclic, or may have a substituent. As a preferable alkyl group, a C1-C10 linear or branched alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group), a C3-C10 cyclic alkyl group (cyclopentyl group, cyclohexyl group, norbornyl group) Can be enumerated.

As a substituent which R <_204> -R <_207> may have, an aryl group (for example, C6-C15), an alkoxy group (for example, C1-C15), a halogen atom, a hydroxyl group, a phenylthio group, etc. can be mentioned, for example. In addition, about an aryl group, an alkyl group (for example, C1-C15) can further be enumerated as a substituent.

X <^-> in general formula (ZII) represents a non-nucleophilic anion, and can mention the same thing as the non-nucleophilic anion of X <^-> in general formula (ZI).

In General Formulas (ZIV) to (ZVI), Ar ₃ and Ar ₄ each independently represent an aryl group.

R ₂₀₆ represents an alkyl group or an aryl group.

R ₂₀₇ and R ₂₀₈ each independently represent an alkyl group, an aryl group, a cyano group, or a haloalkyl group.

A represents an alkylene group, an alkenylene group or an arylene group.

The aryl group as Ar <_3> , Ar <_4> , R <_206> , R <_207> and R <_208> may have a substituent, The thing similar to the aryl group as R <_204> -R <_207> is enumerated.

The alkyl group as R ₂₀₆ , R ₂₀₇ and R ₂₀₈ may have a substituent, and the same as the alkyl group as R ₂₀₄ to R ₂₀₇ are listed.

The haloalkyl group as R ₂₀₇ and R ₂₀₈ may include those in which the halogen atom is substituted with the alkyl group.

The alkylene group as A may have a substituent, Preferably, C1-C8 things, such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, an octylene group, a cyclopentylene group, and a cyclohexylene group Listed.

The alkenylene group may have a substituent, Preferably, C2-C6 things, such as an ethenylene group, a propenylene group, butenylene group, are mentioned.

The arylene group may have a substituent, Preferably, C6-C15 things, such as a phenylene group, a tolylene group, a naphthylene group, are mentioned.

As a substituent, R ₂₀₄ ~R ₂₀₇ may have the same that are listed as substituents.

As compound (A), More preferably, it is a compound represented with the following general formula.

R ₁ , R ₂ and R ₃ each independently represent an alkyl group, an aryl group or an aralkyl group. _{Two of} R ₁ , R ₂ and R ₃ may combine to form a ring.

A ₁ , A ₂ and A ₃ represent a single bond or a divalent linking group.

1, m, and n represent the integer of 0-3 each independently. However, l + m + n is 1 or more.

X ⁻ represents an anion.

In General Formula (I), for example, -R _1- (A ₁ -COOH) ₁ means that one-(A ₁ -COOH) group is substituted with a monovalent group as R ₁ .

R ₁ , R ₂ and R ₃ are each independently, preferably an aryl group, an oxoalkyl group or an arylcarbonylmethyl group, and more preferably a phenyl group.

Preferred substituents which may be an alkyl group, an aryl group or an aralkyl group as R ₁ , R ₂ and R ₃ include hydroxyl, alkyl, alkoxy, alkoxycarbonyl, nitro, cyano, acyl, acyloxy or halogen atoms. do.

A ₁ , A ₂ and A ₃ are preferably an arylene group, an alkylene group which may have a hetero atom in the chain, or a plural number thereof single bond, ester bond, ether bond, sulfide bond, sulfoxide bond, amide It is a group connected by a bond, a urea bond.

The alkyl group as R ₁ , R ₂ and R ₃ may have a substituent, may be any of linear, branched or cyclic, and may have an oxo group in the alkylene chain. For example, an alkyl group having 1 to 20 carbon atoms, preferably a straight and branched alkyl group having 1 to 12 carbon atoms (eg, a methyl group, an ethyl group, a straight or branched propyl group, a straight chain or a branched butyl group, a straight chain or a branched pentyl group), and 3 carbon atoms The cyclic alkyl group (for example, cyclopentyl group, cyclohexyl group) of -8 can be mentioned.

The aryl group may have a substituent, a C6-C4 aryl group is preferable, for example, a phenyl group, a naphthyl group, an anthryl group, etc. can be mentioned, A phenyl group and a naphthyl group are more preferable.

As the aralkyl group, preferably aralkyl groups having 6 to 12 carbon atoms, such as benzyl group, phenethyl group, naphthylmethyl group, naphthylethyl group, naphthylmethyl group and the like can be mentioned.

As a preferable substituent which each group as R <_1> , R <_2> and R <_3> may have, a hydroxyl group, an alkyl group (preferably C1-C20), an alkoxy group (preferably C1-C20), the alkoxycarbonyl group (preferably 2 to 20 carbon atoms, nitro group, cyano group, acyl group (preferably 2 to 12 carbon atoms), acyloxy group (preferably 2 to 12 carbon atoms) or halogen atom (fluorine atom, chlorine atom, bromine atom, iodine Atoms) are listed.

A ₁ , A ₂ and A ₃ are preferably an arylene group, an alkylene group which may have a hetero atom in the chain, or a plurality of these single bonds, ester bonds, ether bonds, sulfide bonds, sulfoxide bonds, Amide bond, urea bond.

As an alkylene group, C1-C8 things, such as the methylene group, ethylene group, propylene group, butylene group, hexylene group, octylene group, cyclopentylene group, and cyclohexylene group which may preferably have a substituent are mentioned.

As an arylene group, C6-C15 things, such as the phenylene group, tolylene group, and naphthylene group which may preferably have a substituent, are mentioned.

Preferably carbon number of the coupling group as A <_1> , A <_2> and A <_3> is 1-10.

The sum of l + m + n is 1-3, and 1 or 2 is preferable.

The anion as X ⁻ may, for example, enumerate non-nucleophilic anions as X ⁻ in the general formulas (ZI) and (ZII).

Preferred combinations of R ₁ , R ₂ and R ₃ in General Formula (I) are listed below.

a) R <_1> -R <_3> is all an aryl group.

b) One or two of R ₁ to R ₃ are an aryl group, and the other is an alkyl group.

c) R ₁ is a 2-aryl-2-oxoalkyl group, and R ₂ and R ₃ are an alkyl group or an aryl group.

d) R ₁ is a 2- (linear, branched, cyclic or polycyclic cyclic) alkyl-2-oxoalkyl group, and R ₂ and R ₃ are an alkyl group or an aryl group.

e) R ₁ is a 2-oxo (monocyclic or polycyclic) cyclic alkyl group, and R ₂ and R ₃ are an alkyl group or an aryl group.

In a) to e), two of R ₁ to R ₃ may combine to form a ring.

As especially preferable compound (A), Especially preferably, the following compound (Z1-1), (Z1-2), and (Z1-3) can mention the compound which has a carboxyl group in arbitrary substitution positions.

Compound (Z1-1) is an arylsulfonium compound in which at least one of R ₂₀₁ to R ₂₀₃ of the general formula (ZI) is an aryl group, that is, a compound having arylsulfonium as a cation.

Arylsulfonium compound, R ₂₀₁ may all ~R ₂₀₃ is an aryl group may be, a part of R ₂₀₁ ~R ₂₀₃ is an aryl group, an alkyl group may be a remainder.

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

As an aryl group of an arylsulfonium compound, a phenyl group and a naphthyl group are preferable, More preferably, it is a phenyl group. When an arylsulfonium compound has two or more aryl groups, two or more aryl groups may be same or different.

The alkyl group possessed by the arylsulfonium compound as needed is preferably a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms, for example, methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, t-butyl The group, cyclopropyl group, cyclobutyl group, cyclohexyl group, etc. can be mentioned.

The aryl group and alkyl group of R ₂₀₁ to R ₂₀₃ are an alkyl group (for example, having 1 to 15 carbon atoms), an aryl group (for example, having 6 to 14 carbon atoms), an alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, and a phenylthio group. You may have as. As a preferable substituent, it is a C1-C12 linear, branched or cyclic alkyl group, a C1-C12 linear, branched or cyclic alkoxy group, Most preferably, they are a C1-C4 alkyl group and a C1-C4 alkoxy group. The substituent may be substituted with any of three R ₂₀₁ to R ₂₀₃ , and may be substituted with all three.

In the case where R ₂₀₁ to R ₂₀₃ are an aryl group, the substituent is preferably substituted at the p position of the aryl group.

The compound (Z1-2) is a compound in the case where R ₂₀₁ to R ₂₀₃ in Formula (ZI) each independently represent an organic group containing no aromatic ring. Here, an aromatic ring also includes the aromatic ring containing a hetero atom.

The organic group which does not contain an aromatic ring as R ₂₀₁ to R ₂₀₃ is generally 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.

R ₂₀₁ to R ₂₀₃ are each independently, preferably an alkyl group, a 2-oxoalkyl group, an alkoxy carbonylmethyl group, an allyl group, a vinyl group, and more preferably a straight chain, branched, cyclic 2-oxoalkyl group, or alkoxycarbonyl Methyl groups, most preferably straight chain, branched 2-oxoalkyl groups.

The alkyl group as R ₂₀₁ to R ₂₀₃ may be any of linear, branched or cyclic, preferably, a linear or branched alkyl group having 1 to 10 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, pentyl group), And cyclic alkyl groups having 3 to 10 carbon atoms (cyclopentyl group, cyclohexyl group, norbornyl group).

The 2-oxoalkyl group as R ₂₀₁ to R ₂₀₃ may be any of linear, branched or cyclic ones, preferably groups having> C = O at the 2-position of the alkyl group described above.

As the alkoxy group in the alkoxycarbonylmethyl group as R ₂₀₁ to R ₂₀₃ , preferably an alkyl group having 1 to 5 carbon atoms (methyl group, ethyl group, propyl group, butyl group, pentyl group) can be mentioned.

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

Two of R ₂₀₁ to R _{203 may be} bonded to each other to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. Examples of the group formed by bonding of two of R ₂₀₁ to R ₂₀₃ to form an alkylene group (for example, butylene group and pentylene group) can be given.

Compound (Z1-3) is a compound represented by the following general formula (Z1-3).

Ar represents an aryl group.

R _1c to R _5c each independently represent a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom.

R _6c and R _7c represent a hydrogen atom or an alkyl group.

Ar and R _6c may be bonded to each other to form a ring.

R _x and R _y each independently represent an alkyl group, a 2-oxoalkyl group, an alkoxycarbonylmethyl group, an allyl group, or a vinyl group.

Any two or more of R _lc to R _5c , and R _x and R _y may be bonded to each other to form a ring structure, and the ring structure may include an oxygen atom, a sulfur atom, an ester bond, or an amide bond. good.

Zc <^-> represents a non-nucleophilic anion and can mention the same thing as the non-nucleophilic anion of X <^-> in general formula (ZI).

Ar is preferably a phenyl group or a naphthyl group, and particularly preferably a group represented by the following general formula.

The alkyl group as R _1c to R _5c may be any of linear, branched or cyclic, for example, an alkyl group having 1 to 20 carbon atoms, preferably a straight and branched alkyl group having 1 to 12 carbon atoms (eg, a methyl group, an ethyl group, a straight chain or a branch). A propyl group, a linear or branched butyl group, a linear or branched pentyl group), and a C3-C8 cyclic alkyl group (for example, a cyclopentyl group, a cyclohexyl group) can be mentioned.

The alkoxy group as R _1c to R _5c may be any of linear, branched or cyclic, for example, an alkoxy group having 1 to 10 carbon atoms, preferably a linear and branched alkoxy group having 1 to 5 carbon atoms (eg, a methoxy group, an ethoxy group). The time period, a linear or branched propoxy group, a linear or branched butoxy group, a linear or branched pentoxy group, and a C3-C8 cyclic alkoxy group (for example, a cyclopentyloxy group, a cyclohexyloxy group) can be mentioned.

Preferably, any one of R <_1c> -R <_5c> is a linear, branched, cyclic alkyl group, or a linear, branched, cyclic alkoxy group, More preferably, the sum of R <_1c> -R <_5c> carbon number is 2-15. Thereby, solvent solubility improves more and generation | occurrence | production of particle | grains is suppressed at the time of storage.

As a naphthyl group also bring substituents as Ar, the substituents represented by the R _lc ~R _5c is preferred.

The alkyl group as R _x and R _y can enumerate the same as the alkyl group as R _1c to R _5c .

2-oxoalkyl group can enumerate the group which has> C = O at the 2nd position of the alkyl group as R < _1c > -R < _5c >.

About the alkoxy group in the alkoxycarbonylmethyl group, the same thing as the alkoxy group as R <_1c> -R <_5c> can be mentioned.

Examples of the group formed by bonding of R _x and R _y include a butylene group, a pentylene group, and the like.

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

Although the preferable specific example of a compound (A) is shown below, this invention is not limited to these.

(Combination acid generator)

In this invention, you may use together the compound (A photo-acid generator) which decomposes | disassembles by irradiation of other actinic light or a radiation, and produces an acid with a compound (A).

The amount of photoacid generator that can be used in combination is usually in a molar ratio (compound (A) / other photoacid generator), usually 100/0 to 1/99, preferably 100/0 to 5/95, and more preferably 100/0 to 20/100.

Other photoacid generators used in combination are known to generate an acid by irradiation with actinic rays or radiation used in photoinitiators of photocationic polymerization, photoinitiators of photoradical polymerization, photochromic agents of pigments, photochromic agents, or micro resists. The compound and mixtures thereof may be appropriately selected and used.

For example, a diazonium salt, a phosphonium salt, a sulfonium salt, an iodonium salt, an imido sulfonate, an oxime sulfonate, a diazo disulfone, a disulfone, o-nitrobenzyl sulfonate can be mentioned.                     

In addition, a compound in which an acid is generated by irradiation of actinic light or radiation, or a compound in which a compound is introduced into the main chain or side chain of the polymer, for example, US Patent No. 3,849,137, German Patent No. 3914407, and Japanese Patent Application Publication No. 63-26653. Japanese Patent Publication No. 55-164824, Japanese Patent Publication No. 62-69263, Japanese Patent Publication No. 63-146038, Japanese Patent Publication No. 63-163452, Japanese Patent Publication No. 62-153853, Japanese Patent Publication The compound described in sub-63-l46029 etc. can be used.

In addition, a compound which generates an acid by light described in US Pat. No. 3,779,778, EP 126,712 or the like can also be used.

As other photoacid generators which may be used in combination, Preferably, the compounds represented by the above general formulas (ZI) to (ZVI) having no carboxyl group, and more preferably the compounds (Z1 to 1) to (not having a carboxyl group) Z1-3).

Examples of particularly preferable ones as other photoacid generators that may be used in combination are listed below.

[Resin which is decomposed by the action of 2 (B) acid to increase solubility in alkaline developing solution (hereinafter also referred to as "component B")

As a resin which is decomposed by an acid used in the positive photosensitive composition of the present invention and the solubility in an alkaline developer is increased, a group which can be decomposed into an acid in both the main chain or the side chain, or both the main chain and the side chain (hereinafter, " Acid decomposable group "). Among these, resins having a group capable of decomposing into an acid in the side chain are more preferable.

Preferred groups which can be decomposed into acids are -COOH groups and groups substituted with groups that desorb hydrogen atoms of -OH groups to acids.                     

In the present invention, the acid-decomposable group is an acetal group or a tertiary ester group.

As a mother resin in the case where the group which can decompose | disassemble into these acids couple | bonds as a side chain, it is alkali-soluble resin which has -OH or -COOH group in a side chain. For example, alkali-soluble resin mentioned later can be enumerated.

It is preferable that the alkali dissolution rate of these alkali-soluble resins is 170A / sec or more as measured (23 degreeC) by 0.261N tetramethylammonium hydroxide (TMAH). Especially preferably, it is 330 A / sec 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), Part of a poly (hydroxystyrene), having an hydroxystyrene structural unit such as O-alkylated or O-acylate, styrene-hydroxystyrene copolymer, α-methylstyrene-hydroxystyrene copolymer, hydrogenated novolak resin Alkali-soluble resin.

As a repeating unit which has a preferable acid-decomposable group in this invention, t-butoxycarbonyloxy styrene, 1-alkoxy ethoxy styrene, (meth) acrylic acid tertiary alkylester, etc. can be mentioned, for example.

The component (B) used in the present invention can be decomposed into an acid in an alkali-soluble resin, which is disclosed in European Patent No. 254853, Japanese Patent Laid-Open No. 2-25850, No. 3-223860, No. 4-251259 and the like. It can be obtained by reacting a precursor of an existing group or copolymerizing a combined alkali-soluble resin monomer of a group that can be decomposed into an acid with various monomers.

Although the specific example of (B) component used for this invention is shown below, it is not limited to these.

p-t-butoxystyrene / p-hydroxystyrene copolymer

p- (t-butoxycarbonyloxy) styrene / p-hydroxystyrene copolymer

p- (t-butoxycarbonylmethyloxy) styrene / p-hydroxystyrene copolymer

4- (t-butoxycarbonylmethyloxy) -3-methylstyrene / 4-hydroxy-3-methylstyrene copolymer

p- (t-butoxycarbonylmethyloxy) styrene / p-hydroxystyrene (10% hydrogenated) copolymer

m- (t-butoxycarbonylmethyloxy) styrene / m-hydroxystyrene copolymer

o- (t-butoxycarbonylmethyloxy) styrene / o-hydroxystyrene copolymer

p- (cumyloxycarbonylmethyloxy) styrene / p-hydroxystyrene copolymer

Cumyl methacrylate / methyl methacrylate copolymer

4-t-butoxycarbonylstyrene / dimethyl maleate copolymer

Benzyl methacrylate / tetrahydropyranyl methacrylate

p- (t-butoxycarbonylmethyloxy) styrene / p-hydroxystyrene / styrene copolymer

p-t-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-butylacrylate copolymer

Styrene / p-hydroxystyrene / t-butylacrylate copolymer

p- (t-butoxycarbonylmethyloxy) styrene / p-hydroxystyrene / N-methylmaleimide copolymer

t-butyl methacrylate / 1-adamantylmethyl methacrylate copolymer

p-hydroxystyrene / t-butylacrylate / p-acetoxystyrene copolymer

p-hydroxystyrene / t-butylacrylate / p- (t-butoxycarbonyloxy) styrene copolymer

p-hydroxystyrene / t-butylacrylate / p- (t-butoxycarbonylmethyloxy) styrene copolymer

TBu in the said embodiment represents a t-butyl group.

The content rate of the group that can be decomposed into acid is the number of groups (B) which can be decomposed into acid in the resin and the number (S) of alkali-soluble groups not protected by the group that is desorbed to the acid, B / (B + S Is represented by). The content rate is preferably 0.01 to 0.7, more preferably 0.05 to 0.50, still more preferably 0.05 to 0.40.

When irradiating an ArF excimer laser beam to the positive photosensitive composition of the present invention, the resin of the component (B) has a monocyclic or polycyclic alicyclic hydrocarbon structure, decomposed by the action of an acid, and solubility in an alkaline developer. It is preferable that it is an increasing resin.

As a resin having a monocyclic or polycyclic alicyclic hydrocarbon structure, decomposed by the action of an acid, and having increased solubility in an alkaline developer (hereinafter also referred to as an "alicyclic hydrocarbon-based acid-decomposable resin"), the following general formulas (pI) to It is preferable that it is resin containing at least 1 sort (s) chosen from the group of the repeating unit which has a partial structure containing alicyclic hydrogen represented by general formula (pVI), and the repeating unit represented by the following general formula (II-AB). Do.

(Wherein R ₁₁ represents a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group or sec-butyl group, Z represents an atomic group necessary for forming an alicyclic hydrocarbon group together with carbon atoms) Indicates.

R ₁₂ to R ₁₆ each independently represent a linear or branched alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group, provided that at least one of R ₁₂ to R ₁₄ or any one of R ₁₅ and R ₁₆ is alicyclic; Hydrocarbon group is represented.

R ₁₇ to R ₂₁ each independently represent 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. In addition, any one of R <_19> , R <_21> represents a C1-C4 linear or branched alkyl group or alicyclic hydrocarbon group.

R ₂₂ to R ₂₅ each independently represent 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 the formula (II-AB):

R ₁₁ ′ and R ₁₂ ′ each independently represent a hydrogen atom, a cyano group, a halogen atom, or an alkyl group which may have a substituent.

Z 'is an atomic group for forming an alicyclic structure which may contain two carbon atoms (C-C) bonded and may have a substituent.

Moreover, it is more preferable that the said general formula (II-AB) is the following general formula (II-A) or general formula (II-B).

In formulas (II-A) and (II-B):

R ₁₃ 'to R ₁₆ ' each independently represent a hydrogen atom, a halogen atom, a cyano group, -COOH, -COOR ₅ , a group decomposed by the action of an acid, -C (= O) -X-A'-R ₁₇ 'or the alkyl group or cyclic hydrocarbon group which may have a substituent is shown.

Here, R <_5> represents the alkyl group which may have a substituent, a cyclic hydrocarbon group, or the following -Y group.

X represents an oxygen atom, a sulfur atom, -NH-, -NHSO ₂ or -NHSO ₂ NH.

A 'represents a single bond or a divalent linking group.

In addition, two or more of R ₁₃ ′ to R ₁₆ ′ may combine to form a ring. n represents 0 or 1.

R ₁₇ ′ represents —COOH, —COOR ₅ , —CN, a hydroxyl group, an alkoxy group which may have a substituent, —CO—NH—R ₆ , —CO—NH—SO ₂ —R _6, or the following —Y groups.

R <_6> represents the alkyl group or cyclic hydrocarbon group which may have a substituent.

-Y group;

(In the -Y group, R ₂₁ 'to R ₃₀ ' each independently represent a hydrogen atom or an alkyl group which may have a substituent. A and b represent 1 or 2.)

In general formula (pI)-(pVI), as an alkyl group in R <_12> -R <_25> , the linear or branched alkyl group which has 1-4 carbon atoms which may be either substituted or unsubstituted is represented. Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and t-butyl group.

Further, other substituents of the alkyl group include an alkoxy group having 1 to 4 carbon atoms, a halogen atom (fluorine atom, chlorine atom, bromine atom or iodine atom), acyl group, acyloxy group, cyano group, hydroxyl group, carboxyl group, alkoxycarbonyl group, And nitro groups.

As an alicyclic hydrocarbon group in R <_11> -R <_25> or the alicyclic hydrocarbon group which Z and a carbon atom form, monocyclic or polycyclic may be sufficient. Specifically, the group which has a C5 or more monocyclo, bicyclo, tricyclo, tetracyclo structure, etc. can be mentioned. 6-30 are preferable and, as for the carbon number, 7-25 are especially preferable. These alicyclic hydrocarbon groups may have a substituent.

Preferable examples of the alicyclic hydrocarbon group include an adamantyl group, noadamantyl group, decalinane group, tricyclodecanyl group, tetracyclododecanyl group, norbornyl group, cedrol group, cyclohexyl group, cycloheptyl group and cycloocta A methyl group, a cyclodecanyl group, and a cyclododecanyl group can be mentioned. More preferably, they are an adamantyl group, a decalin residue group, a norbornyl group, a cedrol group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecanyl group, and a cyclododecanyl group.

As a substituent of these alicyclic hydrocarbon groups, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group, and an alkoxycarbonyl group are mentioned. The alkyl group is preferably a lower alkyl group such as methyl group, ethyl group, propyl group, isopropyl group or butyl group, and more preferably a substituent selected from the group consisting of methyl group, ethyl group, propyl group and isopropyl group. As a substituent of a substituted alkyl group, a hydroxyl group, a halogen atom, and an alkoxy group can be mentioned. As said alkoxy group, C1-C4 things, such as a methoxy group, an ethoxy group, a propoxy group, butoxy group, can be mentioned.

The structures represented by general formulas (pI) to (pVI) in the resin can be used for protecting the alkali-soluble group. As the alkali-soluble group, various groups known in the art are listed.

Specifically, a carboxylic acid group, a sulfonic acid group, a phenol group, a thiol group, etc. are mentioned, Preferably, they are a carboxylic acid group and a sulfonic acid group.

As an alkali-soluble group protected by the structure represented by general formula (pI)-(pVI) in the said resin, Preferably the structure where the hydrogen atom of the carboxyl group was substituted by the structure represented by general formula (pI)-(pVI) is Listed.

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

Here, R represents a hydrogen atom, a halogen atom or a substituted or unsubstituted linear or branched alkyl group having 1 to 4 carbon atoms. A plurality of Rs may be the same or different, respectively.

A is a single bond, an alkylene group, a substituted alkylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amido group, a sulfonamido group, a urethane group, or a combination of two or more groups selected from the group consisting of urea groups Indicates.

Ra represents a group in any one of the formulas (pI) to (pVI).

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

Hereinafter, the specific example of the repeating unit represented by general formula (pA) is shown.                     

(Wherein R _x is H, CH ₃ or CF ₃ )

In General Formula (II-B), R ₁₁ ′ and R ₁₂ ′ each independently represent a hydrogen atom, a cyano group, a halogen atom or an alkyl group which may have a substituent.

Z 'is an atomic group for forming an alicyclic structure which may contain two carbon atoms (C-C) bonded and may have a substituent.

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

Wherein _{R 11 ', R 12',} R 21 the alkyl group in the '~R _30', C1-10 linear or branched alkyl group and more preferably a carbon number of 1 to 6 linear or branched It is an alkyl group, More preferably, they are a methyl group, an ethyl group, a propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, and t-butyl group.

As another substituent in the said alkyl group, a hydroxyl group, a halogen atom, a carboxyl group, an alkoxy group, an acyl group, a cyano group, an acyloxy group, etc. can be mentioned. Examples of the halogen atom include chlorine, bromine, fluorine and iodine atoms. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as methoxy, ethoxy, propoxy or butoxy groups. As a formyl group, an acetyl group, etc. can be mentioned, An acetoxy group etc. can be mentioned as an acyloxy group.

The atomic group for forming the alicyclic structure of Z 'is an atomic group for forming a repeating unit of an alicyclic hydrocarbon which may have a substituent in the resin, and among them, a Confucian formula for forming a repeating unit of an aliphatic alicyclic hydrocarbon. Atom groups for forming the alicyclic structure are preferable.

As a skeleton of the alicyclic hydrocarbon formed, the thing similar to the alicyclic hydrocarbon group of R <_11> -R <_25> in general formula (pI)-(pVI) is mentioned.

The skeleton of the alicyclic hydrocarbon may have a substituent. As such a substituent, R <_13> -R <_16>'in the said general formula (II-A) or (II-B) can be mentioned.

Also in the repeating unit which has the said alicyclic hydrocarbon, the repeating unit represented by the said 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 included in the above-C (= O) -X-A'-R ₁₇ ', and a substituent of Z' of the general formula (II-AB). It may be included as.

As a structure of an acid-decomposable group, it represents with -C (= O) -X <_1> -R <_0> .

In formula, as R <_0> , tertiary alkyl groups, such as a t-butyl group and a t-amyl group, isoboroyl group, 1-ethoxyethyl group, 1-butoxyethyl group, 1-isobutoxyethyl group, 1-cyclohexyloxy Alkoxymethyl groups, such as 1-alkoxyethyl group, 1-methoxymethyl group, and 1-ethoxymethyl group, such as an ethyl group, 3-oxoalkyl group, tetrahydropyranyl group, tetrahydrofuranyl group, trialkylsilyl ester group, and 3-oxocyclohexyl Ester groups, 2-methyl-2-adamantyl groups, melononic lactone residues, and the like. X ₁ is the same as X described above.

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

As said alkyl group in said R <_5> , R <_6> , R <_13> -R <_16>', a C1-C10 linear or branched alkyl group is preferable, More preferably, it is a C1-C6 linear or branched alkyl group. More preferably, they are a methyl group, an ethyl group, a propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, and t-butyl group.

As said cyclic hydrocarbon group in said R <_5> , R <_6> , R <_13> -R <_16>', it is a cyclic alkyl group, a piercing hydrocarbon, for example, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, 2-methyl- 2-adamantyl group, norbornyl group, boronyl group, isobornyl group, tricyclodecanyl group, dicyclopentenyl group, norbornane epoxy group, menthyl group, isomentyl group, neomentyl group, tetracyclododecanyl group, etc. Can be enumerated.

Examples of the ring formed by bonding two or more of R ₁₃ 'to R ₁₆ ' to each other include a ring having 5 to 12 carbon atoms such as cyclopentene, cyclohexene, cycloheptane and cyclooctane.

As an alkoxy group in said R < ₁₇ '>, C1-C4 things, such as a methoxy group, an ethoxy group, a propoxy group, butoxy group, can be mentioned.

As another substituent in the said alkyl group, cyclic hydrocarbon group, and alkoxy group, a hydroxyl group, a halogen atom, a carboxyl group, an alkoxy group, an acyl group, a cyano group, an acyloxy group, an alkyl group, a cyclic hydrocarbon group, etc. can be mentioned. Examples of the halogen atom include chlorine atom, bromine atom, fluorine atom and iodine atom. As an alkoxy group, C1-C4 things, such as a methoxy group, an ethoxy group, a propoxy group, butoxy group, can be mentioned, As an acyl group, a formyl group, an acetyl group, etc. can be mentioned, As an acyloxy group, an acetoxy group is mentioned. And the like.                     

In addition, alkyl groups and cyclic hydrocarbon groups include those listed above.

As the divalent linking group for A ′, an alkylene group, a substituted alkylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amido group, a sulfonamido group, a urethane group, or a single or two or more groups selected from the group consisting of urea groups Combinations are listed.

In the alicyclic hydrocarbon-based acid-decomposable resin according to the present invention, the group decomposed by the action of an acid is a repeating unit having a partial structure containing an alicyclic hydrocarbon represented by the above general formulas (pI) to (pVI), and general formula It may be contained in at least 1 type of repeating unit of the repeating unit represented by (II-AB) and the repeating unit of the copolymerization component described later.

The various substituents of R ₁₃ ′ to R ₁₆ ′ in General Formula (II-A) or General Formula (II-B) may be from an atomic group to form an alicyclic structure in General Formula (II-AB). It consists of a substituent of the atomic group Z to form an organic alicyclic structure.

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

It is preferable that the alicyclic hydrocarbon type acid-decomposable resin of this invention has a lactone group, More preferably, the lactone structure represented by either of following general formula (Lc) or following general formula (V-1)-(V-5) It may have a repeating unit including a group having a group, 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 which may have a substituent. m and n represent the integer of 0-3 each independently, and m + n is 2 or more and 6 or less.

In General Formulas (V-1) to (V-5), R _1b to R _5b are each independently a hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, or an alkylsulfonyl imide. A no group or an alkenyl group is represented. Two of R _1b to R _5b may be bonded to each other to form a ring.

An alkyl group of Ra _{1 to} Re ₁ in general formula (Lc) and an alkyl group, alkoxy group, alkoxycarbonyl group and alkylsulfonyl imino group of R _1b to R _5b in general formula (V-1) to (V-5). As an alkyl group in this, a linear and branched alkyl group may be mentioned and may have a substituent.

As a repeating unit containing the group which has a lactone structure represented by either general formula (Lc) or general formula (V-1)-(V-5), R in said general formula (II-A) or (II-B) ₁₃ at least one of '~R _16' is the general formula (Lc) or the general formula (V-1) ~ (V -5) having a group represented by (e.g., -COOR ₅ R ₅ represents the formula of (Lc ) Or a group represented by formulas (V-1) to (V-5)), or a repeating unit represented by the following formula (AI).

R <_b0> in general formula (A1) represents a hydrogen atom, a halogen atom, or a C1-C4 substituted or unsubstituted alkyl group. As a preferable substituent which the alkyl group of R <_b0> may have, what was illustrated previously as a preferable substituent which the alkyl group as R < _{1b in the} said General Formula (V-1)-(V-5) may have is mentioned.

_Examples of the halogen atom for R _b0 include fluorine, chlorine, bromine and iodine atoms. 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 the bivalent group which combined these.

B <_2> represents group represented by either general formula (Lc) or general formula (V-1)-(V-5).

Although the specific example of the repeating unit containing the group which has a lactone structure is listed below, this invention is not limited to these.

(Wherein R _x is H, CH ₃ or CF ₃ )

(Wherein R _x is H, CH ₃ or CF ₃ )

(Wherein R _x is H, CH ₃ or CF ₃ )

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 <_2c> -R <_4c> represents a hydrogen atom or a hydroxyl group each independently. Provided that at least one of R _2c to R _4c represents a hydroxyl group.

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

As a repeating unit which has group represented by general formula (VII), at least 1 of R <_13> -R <_16>'in said general formula (II-A) or (II-B) is represented with the said general formula (VII) The group which has a group (for example, R <_5> of -COOR <_5> represents group represented by general formula (VII)), the repeating unit represented with the following general formula (AII), etc. can be mentioned.

In General Formula (AII), R _1c represents a hydrogen atom or a methyl group.

R _2c to R _4c each independently represent a hydrogen atom or a hydroxyl group. Provided that at least one of R _2c to R _4c represents a hydroxyl group. It is preferable that two of R <_2c> -R <_4c> are hydroxyl groups.

Although the specific example of the repeating unit which has a structure represented by general formula (AII) is listed below, this invention 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 )-. Here, R ₄₁ represents a hydrogen atom, a hydroxyl group, an alkyl group, a haloalkyl group or -OSO ₂ -R ₄₂ . R ₄₂ represents an alkyl group, haloalkyl group, cycloalkyl group or camphorzan group.

Although the following specific examples are listed as a repeating unit represented by the said general formula (VIII), It is not limited to these.

The alicyclic hydrocarbon-based acid-decomposable resin of the present invention may be used for various purposes such as dry etching resistance, standard developer aptitude, substrate adhesion, resist profile, and resolution, heat resistance, sensitivity, etc., which are general necessary characteristics of resist, in addition to the repeating structural unit. It may contain repeating structural units.

As such a repeating structural unit, although the repeating structural unit corresponded to the following monomer can be enumerated, It is not limited to these.

Thereby, the characteristic calculated | required by alicyclic hydrocarbon type acid-decomposable resin, especially the following can be fine-tuned.

(1) Solubility in coating solvents

(2) Film forming property (glass transition point)

(3) alkali developability

(4) Film reduction (selection of hydrophilic, alkali-soluble groups)

(5) Adhesion to the substrate of unexposed part

(6) dry etching resistance                     

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, and the like. And the like.

In addition, as long as it is an addition polymerizable unsaturated compound copolymerizable with the monomer corresponded to the said various repeating structural units, you may copolymerize.

In the alicyclic hydrocarbon-based acid-decomposable resin, the molar ratio of each repeating structural unit is used to control the dry etching resistance of the resist, the standard developer aptitude, the substrate adhesion, the resist profile, or the resolution, heat resistance, sensitivity, and the like, which are generally necessary capabilities of the resist. It is set appropriately.

As a preferable aspect of the alicyclic hydrocarbon type acid-decomposable resin of this invention, the following are mentioned.

(1) Containing repeating unit having partial structure containing alicyclic hydrocarbon represented by general formula (pI) to (pVI) (side chain type)

(2) Containing repeating unit represented by general formula (II-AB) (main chain type)

However, in (2), the following are further enumerated, for example.

(3) Having repeating unit represented by general formula (II-AB), maleic anhydride derivative and (meth) acrylate structure (hybrid type)

As for content of the repeating unit which has an acid-decomposable group in alicyclic hydrocarbon type acid-decomposable resin, 10-60 mol% is preferable in an appetizer repeating structural unit, More preferably, it is 20-50 mol%, More preferably, it is 25-40 Molar%.

As for content of the repeating unit which has a partial structure containing alicyclic hydrocarbon represented by general formula (pI)-(pVI), in alicyclic hydrocarbon type acid-decomposable resin, 30-70 mol% is preferable in all the repeating structural units, More preferably, it is 35-65 mol%, More preferably, it is 40-60 mol%.

10-60 mol% is preferable in all the repeating structural units, and, as for content of the repeating unit represented by general formula (ll-AB), in alicyclic hydrocarbon type acid-decomposable resin, 15-55 mol% is more preferable. Preferably it is 20-50 mol%.

Moreover, although content in resin of the repeating structural unit based on the monomer of the said other copolymerization component can also be set suitably according to the performance of a desired resist, In general, alicyclic type represented by said general formula (pI)-(pVI) 99 mol% or less is preferable with respect to the total mole number which added the repeating structural unit which has a partial structure containing a hydrocarbon, and the repeating unit represented with the said general formula (II-AB), More preferably, it is 90 mol% or less, More preferably Preferably it is 80 mol% or less.

When the composition of this invention is for ArF exposure, it is preferable that resin does not have an aromatic group from the point 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 (eg, radical polymerization). For example, as a general synthetic method, monomer species are placed in a reaction vessel in a batch or during the reaction, and if necessary, ethers such as tetrahydrofuran, 1,4-dioxane, diisopropyl ether, and methyl ethyl Ketones, ketones such as methyl isobutyl ketone, ester solvents such as ethyl acetate, or the composition of the present invention, such as propylene glycol monomethyl ether acetate, described below, are dissolved in a solvent for dissolution and homogenized, and then inert such as nitrogen or argon. Under a gas atmosphere, polymerization is initiated using a commercially available radical initiator (azo initiator, peroxide, etc.) as required. If desired, an initiator is added or added in portions, and after completion of the reaction, it is added to a solvent to recover a desired polymer 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, 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 to 100 ° C.

When using the composition of this invention for the upper layer resist of a multilayer resist, it is preferable that resin of (B) component has a silicon atom.

As resin which has a silicon atom, decomposes by the action of an acid, and increases the solubility in alkaline developing solution, all resin which has a silicon atom in at least one of a main chain and a side chain can be used. As resin which has a siloxane structure in the side chain of resin, the copolymer of the olefin type monomer which has a silicon atom in a side chain, maleic anhydride, and the (meth) acrylic acid type monomer which has an acid-decomposable group in a side chain can be mentioned, for example.

When irradiating F ₂ excimer laser light to the positive type photosensitive composition of this invention, resin of (B) component has the structure which substituted the fluorine atom in the main chain and / or side chain of a polymer skeleton, and also in the action of an acid. Resin (decomposed also referred to as " fluorine group-containing resin &quot;) which is decomposed to increase solubility in alkaline developing solution, more preferably hydroxyl group or one-position where one-position is substituted with a fluorine atom or a fluoroalkyl group Is a resin containing a group in which a hydroxyl group substituted with a fluorine atom or a fluoroalkyl group is protected by an acid-decomposable group, and most preferably, a hexafluoro-2-propanol structure or a hydroxyl group of hexafluoro-2-propanol is protected by an acid-decomposer. It is resin containing one structure. By introducing a fluorine atom, transparency to ultraviolet light, especially F ₂ (157 nm) light, can be improved.

As a fluorine-group containing resin in (B) acid-decomposable resin, resin which has one or more repeating units represented by the following general formula (FA)-(FG) can be enumerated, for example.

In the above general formula,

R ₁₀₀ to R ₁₀₃ each represent a hydrogen atom, a fluorine atom, an alkyl group, a fluoroalkyl group, or an aryl group.

R ₁₀₄ and R ₁₀₆ are each a hydrogen atom, a fluorine atom or a fluoroalkyl 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 group decomposed by the action of a hydrogen atom, an alkyl group, a fluoroalkyl group, an acyl group, an alkoxycarbonyl group or an acid.

A ₁ contains a single bond, a divalent linking group such as a straight chain, branched, cyclic alkylene group, alkenylene group, arylene group, -OCO-, -COO-, or -CON (R ₂₄ )-and a plurality thereof It is a coupler. R ₂₄ is a hydrogen atom or an alkyl group.

R ₁₀₇ and R ₁₀₈ are groups decomposed by the action of a hydrogen atom, a halogen atom, an alkyl group, a fluoroalkyl group, an alkoxy group, an alkoxycarbonyl group or an acid, respectively.

R ₁₀₉ is a group decomposed by the action of a hydrogen atom, an alkyl group, a fluoroalkyl group and an acid.

b is 0, 1 or 2.

The repeating unit represented by general formulas (FA) to (FG) contains one or more, preferably three or more fluorine atoms per one repeating unit.

In said general formula (FA)-(FG), as an alkyl group, it is a C1-C8 alkyl group, specifically, a methyl group, an ethyl group, a propyl group, n-butyl group, sec-butyl group, hexyl group, 2- Ethyl hexyl group and octyl group are mentioned preferably.                     

As a cycloalkyl group, monocyclic may be sufficient and polycyclic may be sufficient. As monocyclic type, it is C3-C8 thing, For example, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group can be mentioned preferably. As polycyclic type, it is C6-C20, For example, an adamantyl group, a norbornyl group, an isobornyl group, a camphoryl group, a dicyclopentyl group, the (alpha) -finel group, a tricyclo decanyl group, a tetracyclo dodecyl group, and A stanyl group etc. can be mentioned preferably. However, the carbon atom in the said monocyclic or polycyclic cycloalkyl group may be substituted by hetero atoms, such as an oxygen atom.

As the fluoroalkyl group, for example, one having 4 to 12 carbon atoms, specifically, a perfluorobutyl group, a perfluorohexyl group, a perfluorooctyl group, a perfluorooctylethyl group, a perfluorododecyl group, or the like is preferable. Can be enumerated.

As the haloalkyl group, for example, a haloalkyl group having 1 to 4 carbon atoms may specifically include chloromethyl group, chloroethyl group, chloropropyl group, chlorobutyl group, bromomethyl group, bromoethyl group and the like.

As an aryl group, it is a C6-C15 aryl group, specifically, a phenyl group, a tolyl group, a dimethylphenyl group, 2,4,6-trimethylphenyl group, a naphthyl group, anthryl group, 9,10- dimethoxy anthryl Group etc. can be mentioned preferably.

As an aralkyl group, for example, a benzyl group, a phenethyl group, a naphthyl methyl group, etc. can be mentioned preferably as an aralkyl group of 7 to 12 carbon atoms.

As an alkenyl group, a vinyl group, an allyl group, butenyl group, cyclohexenyl group can be mentioned specifically, as an alkenyl group of 2 to 8 carbon atoms, for example.                     

As the alkoxy group, for example, a methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, butoxy group, pentoxy group, allyloxy group, octoxy group, etc. It may be enumerated preferably.

As an acyl group, for example, a formyl group, an acetyl group, propanoyl group, butanoyl group, pivaloyl group, octanoyl group, benzoyl group, etc. can be mentioned preferably as an acyl group of 1-10 carbon atoms.

As an acyloxy group, a C2-C12 acyloxy group is preferable, For example, an acetoxy group, a propionyloxy group, a benzoyloxy group, etc. can be mentioned.

As an alkynyl group, a C2-C5 alkynyl group is preferable and an ethyl group, a propynyl group, butynyl group etc. can be mentioned, for example.

As the alkoxycarbonyl group, i-propoxycarbonyl group, t-butoxycarbonyl group, t-amyloxycarbonyl group, 1-methyl-1-cyclohexyloxycarbonyl group and the like, preferably secondary, more preferably tertiary alkoxycarbonyl groups do.

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

As an alkylene group, C1-C8 things, such as the methylene group, ethylene group, propylene group, butylene group, hexylene group, and octylene group which may preferably have a substituent are mentioned.

As an alkenylene group, C2-C6 things, such as the ethenylene group, the propenylene group, and the butenylene group which may preferably have a substituent are mentioned.                     

As a cycloalkylene group, C5-C8 things, such as the cyclopentylene group and cyclohexylene group which may preferably have a substituent, are mentioned.

As an arylene group, C6-C15 things, such as the phenylene group, tolylene group, and naphthylene group which may preferably have a substituent, are mentioned.

In addition, these groups may have a substituent, and the substituents include active hydrogens such as alkyl groups, cycloalkyl groups, aryl groups, amino groups, amido groups, ureido groups, urethane groups, hydroxyl groups, carboxyl groups, and halogen atoms (fluorine atoms, Chlorine atom, bromine atom, iodine atom), alkoxy group (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. are mentioned.

Here, although the alkyl group, the cycloalkyl group, and the aryl group are those shown above, the alkyl group may be further substituted with a fluorine atom and a cycloalkyl group.

Examples of the group which is decomposed by the action of an acid contained in the fluorine group-containing resin of the present invention and exhibits alkali solubility include -OC (R ₃₆ ) (R ₃₇ ) (R ₃₈ ) and -OC (R ₃₆ ) (R ₃₇ ). ) (OR ₃₉ ), -O-COO-C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), -OC (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 which may have a substituent, and R ₀₁ and R ₀₂ may represent a hydrogen atom or a substituent, an alkyl group, a cycloalkyl group or an alkenyl group. , Aralkyl group or aryl group.

As a preferable specific example, t-butyl group, t-amyl group, 1-alkyl-1-cyclohexyl group, 2-alkyl-2-adamantyl group, 2-adamantyl-2-propyl group, 2- (4- Acetal or acetal ester groups such as ether groups or ester groups of tertiary alkyl groups such as methylcyclohexyl) -2-propyl group, 1-alkoxy-1-ethoxy group and tetrahydropyranyl group, t-alkylcarbonate group, t -Alkylcarbonylmethoxy groups and the like are preferably listed.

Although the specific example of the repeating structural unit represented by general formula (FA)-(FG) is shown below, this invention is not limited to these.

The sum of the repeating unit contents represented by the general formulas (FA) to (FG) is generally 10 to 80 mol%, preferably 30 to 70 mol%, more preferably to all the repeating units constituting the resin. It is used in the range of 35-65 mol%.

The resin of the present invention (B) may further copolymerize another polymerizable monomer in order to improve the performance of the resist of the present invention in addition to the repeating structural units described above.

As a copolymerizable monomer which can be used, what is shown below is contained. For example, addition polymerization property selected from acrylic acid esters, acrylamides, methacrylic acid esters, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, crotonic acid esters and the like other than the above It is a compound which has one unsaturated bond.

It is preferable to contain another repeating unit in such a fluorine-containing resin as a copolymerization component other than the repeating unit which has the said fluorine atom from a viewpoint of dry etching resistance improvement, alkali solubility adjustment, board | substrate adhesiveness improvement, etc. Preferred as other repeat units are:

1) A repeating unit having an alicyclic hydrocarbon structure represented by general formulas (pI) to (pVI) and (II-AB). Specifically, the repeating units of 1 to 23 and the repeating units of [II-1] to [II-32]. Preferably, in said specific examples 1-23, R <_X> is CF <_3> .

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

3) The following general formula (XV) (XVI) (XVII) derived from a vinyl compound having maleic anhydride, a vinyl ether or a cyano group, specifically, repeating units listed as (C-1) to (C-15) Listed. The repeating unit other than these may not include a fluorine atom.

In the formula, R ₄₁ represents an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group.

R ₄₂ represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group or a haloalkyl 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-OR _23- , -CO-N (R ₂₄ ) -R ₂₅ Indicates.

R ₂₂ , R ₂₃ , R ₂₅ may be the same or different and may have a single bond or an ether group, an ester group, an amido group, a urethane group, or a ureido group. A divalent alkylene group, an alkenylene group, or a cycloalkylene group Or an arylene group.

R <_24> represents a hydrogen atom, the alkyl group which may have a substituent, a cycloalkyl group, an aralkyl group, or an aryl group.

n represents 0 or 1, and x, y, z represent the integer of 0-4.

Here, the example of each substituent is the same as the substituent of the said general formula (FA)-(FG).

Moreover, although the specific example of the repeating structural unit represented by general formula (XVI)-(XVII) is shown, this invention is not limited to these.

The content of other repeating units such as the repeating units represented by General Formulas (XV) to (XVII) is generally 0 to 70 mol%, preferably 10 to 60 mol%, more preferably based on the total repeating units constituting the resin. Preferably it is used in the range of 20-50 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 almost the same manner as the alicyclic hydrocarbon-based acid-decomposable resin.

The weight average molecular weight of resin of (B) component which concerns on this invention is a polystyrene conversion value by GPC method, Preferably it is 1,000-200,000. If the weight average molecular weight is less than 1,000, deterioration of heat resistance and dry etching resistance is observed, which is not preferable. If the weight average molecular weight exceeds 200,000, the developability is deteriorated or the sensitivity is extremely high. Produces undesired results.

In the photosensitive composition of this invention, 40-99.99 mass% is preferable in the total solid of the compounding quantity in the whole composition of resin of (B) component which concerns on this invention, More preferably, it is 50-99.97 mass%.

[3] a dissolution inhibiting compound having a molecular weight of 3000 or less (hereinafter also referred to as "component (C)" or "dissolution inhibiting compound"), which is decomposed by the action of (C) acid to increase the solubility in an alkaline developer.

As a dissolution inhibiting compound having a molecular weight of 3000 or less, which is decomposed by the action of (C) acid and increases in solubility in an alkaline developer, it is described in Proceeding of SPIE, 2724, 355 (1996) in order not to lower the permeability of 220 nm or less. Preferred are cycloaliphatic or aliphatic compounds containing acid-decomposable groups, such as cholic acid derivatives containing an acid-decomposable group. As an acid-decomposable group and an alicyclic structure, the thing similar to what was demonstrated in the part of the said alicyclic hydrocarbon type acid-decomposable resin is mentioned.

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

The molecular weight of the dissolution inhibiting compound in this invention is 3000 or less, Preferably it is 300-3000, More preferably, it is 500-2500.

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

Although the specific example of a dissolution inhibiting compound is shown below, it is not limited to these.

[4] (D) Resin soluble in alkali developer (hereinafter also referred to as "(D) component" or "alkali-soluble resin")

The alkali dissolution rate of the alkali-soluble resin is preferably 20 Pas / sec or more as measured by 0.261 N tetramethylammonium hydroxide (TMAH) (23 占 폚). Especially preferably, it is 200 microseconds / sec or more (small angstroms).

As alkali-soluble resin used for this invention, a novolak resin, a hydrogenated novolak resin, acetone pyrogallol resin, o-polyhydroxy styrene, m-polyhydroxy styrene, p-polyhydroxy styrene, hydrogenated polyhydroxy Styrene, halogen or alkyl substituted polyhydroxystyrenes, hydroxystyrene-N-substituted maleimide copolymers, o / p- and m / p-hydroxystyrene copolymers, some O-alkyl to hydroxyl groups of polyhydroxystyrene Cargoes (e.g., 5-30 mole% O-methylate, O- (1-methoxy) ethylate, O- (1-ethoxy) ethylate, O-2-tetrahydropyranylide, O- ( t-butoxycarbonyl) methylate, etc.) or O-acylates (e.g., 5-30 mol% o-acetylate, O- (t-butoxy) carbonylate, etc.), styrene-maleic anhydride copolymer , Styrene-hydroxy styrene copolymer, α-methyl styrene-hydroxy styrene copolymer, carboxyl group-containing methacryl type Resin and may be exemplified a derivative thereof, polyvinyl alcohol derivatives, but are not limited to these.

Particularly preferred alkali-soluble resins include novolak resins and o-polyhydroxystyrenes, m-polyhydroxystyrenes, p-polyhydroxystyrenes and copolymers thereof, alkyl substituted polyhydroxystyrenes, and polyhydroxystyrenes. O-alkylated or O-acylates, styrene-hydroxystyrene copolymers, α-methylstyrene-hydroxystyrene copolymers.

The said novolak resin has a predetermined monomer as a main component, and is obtained by 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 the polystyrene conversion value of gel permeation chromatography.                     

You may use these (D) alkali-soluble resin in this invention in combination of 2 or more types.

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

[5] an acid crosslinking agent which crosslinks with the alkali-soluble resin by the action of (E) acid (hereinafter also referred to as "E component" or "crosslinking agent")

The crosslinking agent is used for the negative photosensitive composition of this invention.

As the crosslinking agent, any compound can be used as long as it is a compound that crosslinks the soluble resin to the alkaline developer by the action of an acid, but the following (1) to (3) are preferable.

(1) hydroxymethyl, alkoxymethyl and acyloxymethyl compounds of phenol derivatives

(2) a compound having an N-hydroxymethyl group, an N-alkoxymethyl group, and an N-acyloxymethyl group

(3) a compound having an epoxy group

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

Among these crosslinking agents, particularly preferred ones are listed below.

(In the formula, L ¹ ~L ⁸ are, same or different, a hydrogen atom, a hydroxymethyl group, a methoxymethyl group, an ethoxycarbonyl group having 1 to 6 carbon atoms or an alkyl group.)

The crosslinking agent is used in the amount of 3 to 70% by mass, preferably 5 to 50% by mass, in the solid content of the photosensitive composition.

<Other ingredients>

[6] (F) basic compounds

It is preferable that the photosensitive composition of this invention contains a (F) basic compound in order to reduce the performance change by time-lapse from exposure to heating.

As a preferable structure, the structure represented by following formula (A)-(E) can be enumerated.

Herein, R ²⁵⁰ , R ²⁵¹ and R ²⁵² each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted carbon atom. An aryl group of a ring, wherein R ²⁵⁰ and R ²⁵¹ may combine with each other to form a ring.

In addition, these may contain an oxygen atom, a sulfur atom and a nitrogen atom in the alkyl chain.

(In the formula, R ²⁵³ , R ²⁵⁴ , R ²⁵⁵ and R ²⁵⁶ each independently represent an alkyl group having 1 to 6 carbon atoms).

As preferred compounds, substituted or unsubstituted guanidine, substituted or unsubstituted aminopyridine, substituted or unsubstituted pyrazole, substituted or unsubstituted pyrazoline, substituted or unsubstituted piperazine, substituted or unsubstituted aminomole Porin, substituted or unsubstituted aminoalkylmorpherine, substituted or unsubstituted piperidine, and more preferred compounds include imidazole structure, diazabicyclo structure, onium hydroxide structure, and oniumcarboxylate. And a compound having a structure, a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, an aniline derivative having a hydroxyl group and / or an ether bond, and the like.

Examples of the compound having an imidazole structure include imidazole, 2, 4, 5-triphenylimidazole, benzimidazole and the like. Examples of the compound having a diazabicyclo structure include 1,4-diaza bicyclo [2,2,2] octane, 1,5-diazabicyclo [4,3,0] nona-5-ene and 1,8-dia Xabicyclo [5,4,0] undec-7-ene and the like. Examples of the compound having an onium hydroxide structure include triarylsulfonium hydroxide, phenacylsulfonium hydroxide, and sulfonium hydroxide having a 2-oxoalkyl group, and specifically, triphenylsulfonium hydroxide and tris ( t-butylphenyl) sulfonium hydroxide, bis (t-butylphenyl) iodonium hydroxide, phenacylthiophenium hydroxide, 2-oxopropylthiophenium hydroxide, etc. are mentioned. As a compound which has an onium carboxylate structure, the anion part of the compound which has an onium hydroxide structure consists of carboxylates, For example, acetate, adamantane-1-carboxylate, perfluoroalkyl carboxylate, etc. Listed. Examples of the compound having a trialkylamine structure include tri (n-butyl) amine, tri (n-octyl) amine, and the like. As an aniline compound, 2, 6- diisopropyl aniline, N, N- dimethylaniline, etc. can be mentioned. Examples of the alkylamine derivative having a hydroxyl group and / or an ether bond include ethanolamine, diethanolamine, triethanolamine, tris (methoxyethoxyethyl) amine, and the like. Examples of aniline derivatives having a hydroxyl group and / or an ether bond include N, N-bis (hydroxyethyl) aniline and the like.

These basic compounds are used individually or in 2 or more types. The usage-amount of a basic compound is 0.001-10 mass% normally, Preferably it is 0.01-5 mass% based on solid content of the photosensitive composition. That is, 0.001 mass% or more is preferable at the point which fully acquires an addition effect, and 10 mass% or less is preferable at the point of a sensitivity and the developability of a non-exposed part.

[7] (G) Fluorine-based and / or silicon-based surfactants                     

The photosensitive composition of the present invention further contains any one or two or more of a fluorine- and / or silicon-based surfactant (a fluorine-based surfactant and a silicon-based surfactant, a surfactant containing both a fluorine atom and a silicon atom). It is preferable.

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

As these fluorine and / or silicon-based surfactants, for example, Japanese Patent Laid-Open No. 62-36663, Japanese Patent Laid-Open No. 61-226746, Japanese Patent Laid-Open No. 61-226745, and Japanese Patent Laid-Open No. 62-170950 Japanese Patent Laid-Open No. 63-34540, Japanese Patent Laid-Open No. 7-230165, Japanese Patent Laid-Open No. 8-62834, Japanese Patent Laid-Open No. 9-54432, Japanese Patent Laid-Open No. 9-5988 Japanese Unexamined Patent Publication No. 2002-277862, US Patent No. 557520, US 5360692, US 5529881, US 5296330, US 5436098, US 5576143, US 5294511, US 5824451 Surfactant as described in a patent specification can be enumerated, The following commercially available surfactant can also be used as it is.

As a commercially available surfactant which can be used, for example, F-Top EF301, EF303 (made by Shin-Akiga Chemical Co., Ltd.), Floroid FC430, 431 (made by Sumitomo 3M Co., Ltd.), Megapack F171, F173, F176, F189. , R08 (from Dainippon Ink & Chemicals, Kagaku Kogyo Co., Ltd.), Supron S-382, SC101, 102, 103, 104, 105, 106 (Asahi Glass Co., Ltd.), Troisol S-366 (Trochemical Co., Ltd.) Fluorine-based surfactants or silicon-based surfactants such as those produced by Shikisha. In addition, polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as the silicon-based surfactant.

As the surfactant, in addition to the known ones as described above, fluorine introduced from the fluoroaliphatic compound produced by the telomerization method (also called telomer method) or the oligomerization method (also called oligomer method) As the surfactant, a surfactant using a polymer having an aliphatic group can be used. A fluoro aliphatic compound can be synthesize | combined by the method as described in Unexamined-Japanese-Patent No. 2002-90991.

As the polymer having a fluoro aliphatic group, a copolymer of a monomer having a fluoro aliphatic group with (poly (oxyalkylene)) acrylate and / or (poly (oxyalkylene)) methacrylate is preferable and is distributed irregularly. It may be present or may be block copolymerized. Examples of the poly (oxyalkylene) group include poly (oxyethylene) groups, poly (oxypropylene) groups, poly (oxybutylene) groups and the like, and poly (oxyethylene, oxypropylene and oxyethylene The unit which has alkylene of different chain length in the same chain length, such as a block linker) and a poly (block linker of oxyethylene and oxypropylene) group, may be sufficient. In addition, the copolymer of the monomer which has a fluoro aliphatic group, and a (poly (oxyalkylene)) acrylate (or methacrylate) is not only a binary copolymer but a monomer which has another 2 or more types of fluoro aliphatic groups, A ternary or higher copolymer obtained by simultaneously copolymerizing two or more kinds of (poly (oxyalkylene)) acrylates (or methacrylates) may be used.

For example, as a commercially available surfactant, Megapack F178, F-470, F-473, F-475, F-476, and F-472 (made by Dainippon Ink & Chemicals Co., Ltd.) can be mentioned. Further, copolymers of acrylate (or methacrylate) having a C ₆ F ₁₃ group and (poly (oxyalkylene)) acrylate (or methacrylate), acrylate (or methacrylate having a C ₆ F ₁₃ group) ) And a copolymer of (poly (oxyethylene)) acrylate (or methacrylate) and (poly (oxypropylene)) acrylate (or methacrylate), an acrylate (or methacrylate having a C ₈ F ₁₇ group) ) And (poly (oxyalkylene)) acrylates (or methacrylates), acrylates (or methacrylates) and (poly (oxyethylene)) acrylates (or methacrylates) having C ₈ F ₁₇ groups And copolymers of (poly (oxypropylene)) acrylate (or methacrylate) and the like.

The amount of the fluorine and / or silicon-based 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).

[8] organic solvents (H)

The photosensitive composition of this invention uses the said component in the 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, ethyl pyruvate Methyl, ethyl pyruvate, propyl pyruvate, N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, tetrahydrofuran and the like.

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 and a solvent containing no hydroxyl group are mixed in the structure. Thereby, particle generation at the time of resist storage 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. Propylene glycol monomethyl ether and ethyl lactate are particularly preferred.

Examples of the solvent not containing a hydroxyl group include propylene glycol monomethyl ether acetate, ethyl ethoxy propionate, 2-heptanone, γ-butyrolactone, cyclohexanone, butyl acetate, N-methylpyrrolidone, and N. , N-dimethylacetamide, dimethyl sulfoxide and the like, among them, propylene glycol monomethyl ether acetate, ethyl ethoxy propionate, 2-heptanone, γ-butyrolactone, cyclohexanone, acetic acid Butyl is particularly preferred, with propylene glycol monomethyl ether acetate, ethyl ethoxy propionate and 2-heptanone being most preferred.

The mixing ratio (mass) of the solvent containing a hydroxyl group and the solvent containing no hydroxyl group is 1/99-99/1, Preferably it is 10/90-90/10, More preferably, it is 20/80-60/40. The mixed solvent which contains 50 mass% or more of solvents which does not contain a hydroxyl group is especially preferable at the point of coating uniformity.

<Other additives>

If necessary, the photosensitive composition of the present invention may contain a dye, a plasticizer, a surfactant other than the above-mentioned (G) component, a compound for promoting solubility in a photosensitizer and a developer, and the like.

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

The preferable addition amount of these dissolution promoting compounds is 2-50 mass% with respect to resin of (B) component or resin of (D) component, More preferably, it is 5-30 mass%. 50 mass% or less is preferable at the point of image distortion at the time of image development residue and image development.

Such phenolic compounds having a molecular weight of 1,000 or less can be easily used by those skilled in the art by referring to methods described in, for example, Japanese Patent Application Laid-Open No. Hei 4-122938, Japanese Patent Application Laid-Open No. 2-28531, US Patent No. 4916210, and European Patent No. Can be synthesized.

Specific examples of the alicyclic or aliphatic compound having a carboxyl group include carboxylic acid derivatives, adamantanecarboxylic acid derivatives, adamantanedicarboxylic acid, and cyclohexane having steroid structures such as cholic acid, deoxycholic acid, and lithocholic acid. Although carboxylic acid, cyclohexanedicarboxylic acid, etc. are mentioned, It is not limited to these.                     

In this invention, surfactant other than the said (G) fluorine type and / or silicon type surfactant can also be added. Specifically, nonionic interfaces such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylene polyoxypropylene block copolymers, sorbitan aliphatic esters, and polyoxyethylene sorbitan aliphatic esters Active agents may be enumerated.

These surfactants may be added alone, or may be added in some combination.

<< How to use >>

The photosensitive composition of this invention is used by dissolving the said component in the predetermined organic solvent, Preferably the said mixed solvent, and apply | coating on the following predetermined | prescribed support bodies.

For example, the photosensitive composition is applied onto a substrate (eg, silicon / silicon dioxide coating) by a suitable coating method such as a spinner, coater, etc. to be used in the manufacture of the precision integrated circuit device.

After application, actinic radiation and radiation are irradiated through a predetermined mask, followed by baking to develop. In this way, a good pattern can be obtained. Examples of the active light and the radiation include infrared light, visible light, ultraviolet light, far-ultraviolet light, X-rays, and electron beams, but are preferably ultraviolet light having a wavelength of 250 nm or less, more preferably 220 nm or less, specifically KrF. An excimer laser (248 nm), an ArF excimer laser (193 nm), an F ₂ excimer laser (157 nm), an X-ray, an electron beam, and the like. ArF excimer lasers and F ₂ excimer lasers are most preferred.

In the developing step, an alkaline developer is used as follows. As the alkali developer of the resist composition, inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate and aqueous ammonia, first amines such as ethylamine and n-propylamine, diethylamine and di-n- Second amines such as butylamine, third amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, fourth such as tetramethylammonium hydroxide and tetraethylammonium hydroxide Alkaline aqueous solutions, such as cyclic amines, such as a quaternary ammonium salt, a pyrrole, and piperidine, can be used.

Moreover, alcohol and surfactant can also be added and used for the said alkaline developing solution.

The alkali concentration of alkaline developing solution is 0.1-20 mass% normally.

The pH of alkaline developing solution is 10.0-15.0 normally.

(Example)

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

Synthesis Example of Compound (A)

Synthesis of Compound (I-1)

28.4 g of dibasic pentoxide was dissolved in 284 g of methanesulfonic acid, 40.5 g of diphenyl sulfoxide and 43.6 g of 4-phenyl benzoic acid were added thereto, and the mixture was reacted at 50 ° C for 12 hours. After cooling, the reaction solution was poured into 3 L of ice to remove the precipitated powder, and the aqueous phase was washed twice with 1 L of ethyl acetate. When an aqueous solution of 332 g of potassium iodide was added to the aqueous phase, an oily substance precipitated. The upper water was removed by supernatant separation, and the resulting oily substance was dissolved in 500 ml of acetone. When this was added to 4 L of ethyl acetate, powder precipitated. This was filtered off and dried to obtain 17.5 g of iodide of the cation of compound (I-1). 15.3 g of this iodide was dissolved in 250 ml of methanol, and 7.3 g of silver oxide was added thereto, followed by stirring for 3 hours. After the silver compound was removed by filtration, 10 ml of hydrochloric acid and 10.7 g of potassium nonafluorobutanesulfonate were added to the filtrate. Ethyl acetate was added to the reaction solution, the insolubles were removed by filtration, and the ethyl acetate solution was washed with water. When the organic phase was concentrated, 15.4 g of compound (I-1) was obtained.

Synthesis of Compound (I-2)

8.5 g of dibasic pentoxide was dissolved in 85 g of methanesulfonic acid, 13.8 g of p-tolyl sulfoxide and 1 lg of 2-methoxyphenylacetic acid were added thereto, and the mixture was reacted at 50 ° C for 5 hours. After allowing to cool, the reaction solution was poured into 500 ml of ice, and the aqueous phase was washed twice with 500 ml of ethyl acetate. An aqueous solution of 100 g of potassium iodide was added to the aqueous phase. This was extracted with chloroform, the crude product obtained by concentrating the organic phase was dissolved in acetone, and this was added to 2.5 L of ethyl acetate / hexane (1/1) to precipitate powder. This was filtered off and dried to obtain 7.5 g of iodide of the cation of compound (I-2). 5.0 g of this iodide was dissolved in 100 ml of acetonitrile / water (2/1), and 1.8 g of silver acetic acid was added thereto, followed by stirring for 30 minutes. After the silver compound was removed by filtration, a solution of 3.6 g of potassium nonafluorobutanesulfonic acid dissolved in 100 ml of acetonitrile / water (2/1) was added. The reaction solution was concentrated, ethyl acetate was added thereto to dissolve it, and the ethyl acetate solution was washed three times with water. 5.3g of compounds (I-2) were obtained when the organic phase was concentrated.

<Synthesis of Resin (B)>

Synthesis Example 1 Synthesis of Resin (1) (Side Chain Type)

2-ethyl-2-adamantyl methacrylate and butyrolactone methacrylate were added at a ratio of 55/45, and dissolved in methyl ethyl ketone / tetrahydrofuran = 5/5 to obtain 100 mL of a solution having a solid concentration of 20%. It prepared. 2mo1% of V-65 by Wako Pure Chemical Industries Ltd. was added to this solution, and it was dripped at 10 mL of methyl ethyl ketone heated at 60 degreeC over 4 hours in nitrogen atmosphere. After completion of the dropwise addition, the reaction solution was heated for 4 hours, 1 mo1% of V-65 was further added, and stirred for 4 hours. The reaction liquid was cooled to room temperature after completion | finish of reaction, and resin (1) which was white powder crystallized and precipitated with 3 L of mixed solvents of distilled water / ISOpropyl alcohol = 1/1 was recovered.

The polymer composition ratio determined from C ¹³ NMR was 46/54. In addition, the mass mean molecular weight of the standard polystyrene conversion 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% by mass) are placed in a separate flask, and the mixture is kept under nitrogen stream. Heated at ° C. When the reaction temperature was stabilized, 2 mol% of a Wako Pure Chemical Industries radical initiator V-601 was added to initiate the reaction. After heating for 12 hours, the obtained reaction mixture was diluted twice with tetrahydrofuran, and then poured into a mixed solution of hexane / isopropyl alcohol = 1/1 to precipitate white powder. The precipitated powder was collected by filtration and dried to obtain Resin (13) as a target product.

When the molecular weight analysis by GPC of the obtained resin (13) was tested, it was 8300 (mass average) in polystyrene conversion. In addition, the NMR spectrum confirmed that the molar ratio of norbornenecarboxylic acid tbutyl ester / norbornenecarboxylic acid butyrolactone ester / maleic anhydride repeating unit of 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, tbutyl acrylate and 2-methylcyclohexyl-2-propyl acrylate are placed in a reaction vessel at a molar ratio of 35/35/20/10 and dissolved in tetrahydrofuran to give 60% solids. The solution was prepared. It was heated at 65 ° C. under a nitrogen stream. When the reaction temperature was stabilized, 1 mol% of a 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 twice with tetrahydrofuran, and then charged into a 5-fold volume of hexane of the reaction mixture to precipitate white powder. The precipitated powder was collected by filtration, 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 and dried to provide the desired product. Phosphorus resin (20) was obtained.

When the molecular weight analysis by GPC of the obtained resin (20) was experimented, it was 12100 (mass average) in polystyrene conversion. In addition, the composition of the resin (1) in the NMR spectrum was 32/39/19/10 in molar ratio of norbornene / maleic anhydride / tbutylacrylate / 2-methylcyclohexyl-2-propyl acrylate of the present invention.

In the same manner as in Synthesis example 3, resins (21) to (25) were synthesized.

Hereinafter, the structure and molecular weight of resin (1)-(31) are shown.

<Fluorine-containing resin>

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

In addition, the weight average molecular weight of fluorine group containing resin (FII-1) (FII-40), etc. are shown to following Tables 1-2.

[Examples 1 to 25 and Comparative Example 1]

<Resist preparation>

The component shown in the following Table 3 was melt | dissolved in the solvent, the solution of 12 mass% of solid content concentration was adjusted, and this was filtered through the 0.1 micrometer polytetrafluoroethylene filter or the polyethylene filter, and the positive resist solution was prepared. The prepared positive resist solution was evaluated by the following method, and the results are shown in Table 3.

Hereinafter, the symbol in each table is as follows. Resins and acid generators other than the following are exemplified above. In addition, the ratio at the time of using two or more resin or a solvent in each table is a mass ratio.

[Acid generator]                     

TPSN; Triphenylsulfonium nonafluorobutanesulfonate

[Basic compound]

DBN; 1,5-diazabicyclo [4.3.0] nona-5-ene

TPI; 2, 4, 5-triphenylimidazole

TPSA; Triphenylsulfonium acetate

HEP; N-hydroxyethylpiperidine

DIA; 2,6-diisopropylaniline

DCMA; Dicyclohexylmethylamine

TPA; Tripentylamine

TOA; Tri-n-octylamine

HAP; Hydroxyantipyrine

TBAH; Tetrabutylammonium hydroxide

TMEA; Tris (methoxyethoxyethyl) amine

PEA; N-phenyldiethanolamine

[Surfactants]

W-1; Mega pack F176 (Dainipon Ink & Chemicals, Kagaku Kogyo Co., Ltd.) (Fluorine)

W-2; Mega Pack R08 (Dai Nippon Ink Chemical Industries, Ltd.) (Fluorine and silicon)

W-3; Polysiloxane Polymer KR-341 (Shin-Etsu Kogyo Co., Ltd.) (Silicon)

W-4; Troisol S-366 (product of Troy Chemical Co., Ltd.)                     

[solvent]

A1; Propylene Glycol Methyl Ether Acetate

A2; 2-heptanone

A3; Ethyl ethoxy propionate

A4; γ-butyrolactone

A5; Cyclohexanone

B1; Propylene Glycol Methyl Ether

B2; Ethyl lactate

[Dissolution inhibiting agent]

LCB; Litocholic acid t-butyl

Resist Evaluation

[PEB temperature dependency]

First, the ARC-29A-8 manufactured by Blue Science Co., Ltd. was coated on a silicon wafer by using a spin coater at 78 nm, dried, and then the positive photosensitive composition obtained thereon was applied, dried at 120 ° C. for 90 seconds, and 200 nm positive. A resist film was prepared and exposed to it by an ArF excimer laser (wavelength 193 nm, ArF stepper manufactured by ISI of NA = 0.6), followed by heating at 120 ° C. for 90 seconds immediately after exposure to 2.38% by mass of tetramethylammonium hydroxide. It developed with the seed aqueous solution and washed with distilled water, and obtained the resist pattern profile.

The resist pattern of the silicon wafer thus obtained was observed by SEM, and the resist was evaluated as follows.                     

The exposure amount which reproduces the isolated contact hole pattern of mask size 180 nm at 130 nm, and exposes the isolated contact hole pattern of mask size 180 nm, and reproduces the exposure amount which reproduces with the isolated contact hole 130 nm of mask size 180 nm at post-heating temperature 120 degreeC Next, after exposing at the optimum exposure dose, the post-heating is performed at two temperatures of + 2 ° C and -2 ° C (122 ° C and 118 ° C) with respect to the post-heating temperature, and the obtained contact hole patterns are measured, respectively. Its length was obtained, and its diameters L ₁ and L ₂ were obtained. PEB temperature dependence was defined as the change of the diameter per 1 degreeC of PEB temperature change, and it computed by the following formula.

PEB temperature dependence (nm / ℃) = | L _1- L ₂ | / 4

[Examples 26 to 28 and Comparative Example 2]

(1) Formation of lower layer resist layer                     

FHi-028DD resist (i-ray resist from Fujifilm Orin) was applied to a 6-inch silicon wafer using spin coater Mark8 from Tokyo Electron, and baked at 90 ° C. for 90 seconds to obtain a uniform film having a thickness of 0.55 μm. .

This was heated at 200 ° C. for 3 minutes to form a lower layer resist layer having a film thickness of 0.40 μm.

(2) Formation of Upper Resist Layer

The component shown in the following Table 4 was dissolved in a solvent, the solution of 11 mass% of solid content concentration was prepared, and it filtered fine with the membrane filter of 0.1 micrometer of caliber, and prepared the upper layer resist composition.

The upper resist composition was applied to the lower resist layer in the same manner, and heated at 130 ° C. for 90 seconds to form an upper resist layer having a thickness of 0.20 μm.

(3) resist evaluation

The wafer thus obtained was loaded with a resolution mask on an ArF excimer stepper 9300 manufactured by ISI, and exposed with varying exposure dose.

Subsequently, after heating at 120 degreeC for 90 second, it developed for 60 second with tetrahydroammonium hydroxide developing solution (2.38 mass%), washed with distilled water, and dried, and obtained the upper layer pattern.

The resist pattern of the silicon wafer thus obtained was observed by SEM, and the resist was evaluated as follows.

The exposure amount which reproduces the isolated contact hole of mask size 180 nm at 130 nm is exposed, and the exposure amount which exposes the isolated contact hole pattern of mask size 180 nm is reproduced by the isolation contact hole 130 nm of mask size 180 nm at post-heating temperature of 120 degreeC. After the exposure amount and exposure at the optimum exposure amount, the post-heating is performed at two temperatures of + 2 ° C and -2 ° C (122 ° C and 118 ° C) with respect to the post-heating temperature, and the contact hole patterns obtained are respectively obtained. length-measuring, and was determined for its diameter L ₁ and L _2. PEB temperature dependence was defined as the change of the diameter per 1 degreeC of PEB temperature change, and it computed by the following formula.

PEB temperature dependence (nm / ℃) = | L _1- L ₂ | / 4

The results are shown in Table 4.

Resins (SI-1) to (SI-3) in Table 4 are as follows.

[Examples 29 to 48 and Comparative Example 3]

<Resist preparation>

The component shown in the following Table 5 was dissolved in a solvent, and this was filtered through the 0.1 micrometer polytetrafluoroethylene filter, and the positive resist solution was prepared.

Resist Evaluation

Each positive resist solution was applied to a silicon wafer subjected to hexamethyldisilazane treatment by a spin coater, and dried at 120 ° C. for 90 seconds using a vacuum tight hot plate to obtain a resist film having a film thickness of 100 nm.

The obtained resist film was exposed using the 157 nm laser exposure / dissolution behavior analyzer V UVES-4500 (manufactured by Listech Japan Co., Ltd.), and was heated on a hot plate at 120 ° C. for 90 seconds immediately after the exposure. It developed for 60 second with 2.38 mass% tetramethyl ammonium hydroxide aqueous solution, and washed with pure water, and obtained the sample wafer. About these, the exposure amount (sensitivity) D1 which a large pattern resolves was calculated | required. Moreover, the same operation was performed except having heated at 125 degreeC for 90 second immediately after exposure, and the exposure amount (sensitivity) D2 which a large pattern resolves was calculated | required. The sensitivity fluctuation rate by change of post-heating temperature (PEB temperature) was calculated | required by the following formula. The smaller the absolute value, the smaller the performance change by the post-heating temperature change.

The results are shown in Table 5.                     

In Tables 3 to 5, it is confirmed that the positive resist composition of the present invention has a small PEB temperature dependency and a good pattern profile.

In the above embodiment, as the actinic ray, but using ArF excimer laser light, F ₂ excimer laser light, the same result was obtained even when a KrF excimer laser light, exposure by the electron beam.

Moreover, it is thought that the photosensitive composition of this invention exhibits the same effect also about EUV light.

According to the present invention, it is possible to provide a photosensitive composition having a small PEB temperature dependency and having a good pattern profile.

Claims (4)

(A) a compound which generates an acid by irradiation of actinic rays or radiation having a carboxyl group, and (B) contains a resin which is decomposed by the action of at least one of an acid decomposable acetal group and a tertiary ester group with an acid having a lactone structure or a structure represented by the following formula, thereby increasing the solubility in an alkaline developer; The photosensitive composition made into.

The photosensitive composition as claimed in claim 1, wherein compound (A) is a sulfonium salt compound. The photosensitive composition according to claim 1 or 2, wherein the resin (B) is a resin having a monocyclic or polycyclic alicyclic hydrocarbon structure. The photosensitive composition as claimed in claim 1 or 2, wherein the resin (B) is a resin having a fluorine atom in the main chain or in the side chain.