KR100985743B1 - Photosensitive composition and pattern formation method using the same - Google Patents

Abstract

A photosensitive composition used for manufacturing semiconductor substrates such as ICs, liquid crystals, thermal heads, and the like, and other photo publication processes, and a pattern formation method using the photosensitive composition, including exposure latitude, exposure latitude stability, and EUV exposure. Provided are a photosensitive composition having improved sensitivity, dissolution contrast, and a pattern forming method using the photosensitive composition.

(A1) Photosensitive composition containing the compound which generate | occur | produces specific alkanesulfonic acid by irradiation of actinic light, or a radiation, and (A2) Compound which generate | occur | produce a specific acid by irradiation of actinic light, or radiation, and the pattern using the said photosensitive composition Formation method.

Description

Photosensitive composition and pattern formation method using the photosensitive composition {PHOTOSENSITIVE COMPOSITION AND PATTERN FORMATION METHOD USING THE SAME}

1 is a schematic diagram of a two-beam interference exposure experiment apparatus.

(Explanation of the sign)

1: laser

2: aperture

3: shutter

4,5,6: reflective mirror

7: condenser lens

8: Prism

9: immersion liquid

10: wafer with antireflection film and resist film

11: Wafer stage

The present invention relates to a photosensitive composition whose properties are changed by reacting with irradiation of actinic rays or radiation and a pattern forming method using the photosensitive composition. More specifically, a semiconductor manufacturing process such as an IC, a production of circuit boards such as liquid crystals, a thermal head, and other photo publishing processes, a flat panel, a photocurable composition used in an acid curable composition, and a pattern forming method using the photosensitive composition. It is about.

The chemically amplified resist composition generates an acid in an exposed portion by irradiation with actinic rays or radiation such as far ultraviolet light, and the solubility of the actinic or radiation irradiating portion and the non-irradiating portion in a developing solution by reaction using the acid as a catalyst. It is a pattern forming material which changes a shape and forms a pattern on a board | substrate.

When the KrF excimer laser is used as an exposure light source, a resin mainly composed of poly (hydroxystyrene) having a low absorption in the 248 nm region is used as a main component, thereby forming a high sensitivity, high resolution, and a good pattern. It is a good system compared with the naphthoquinone diazide / novolak resin system.

On the other hand, when another short wavelength light source, such as an ArF excimer laser (193 nm), is used as an exposure light source, the chemical amplification system was not sufficient because the compound having an aromatic group exhibited large absorption in the 193 nm region. .

For this reason, the resist for ArF excimer lasers containing resin which has alicyclic hydrocarbon structure was developed.

Various compounds have also been found for acid generators, which are the main constituents of chemically amplified resist compositions. For example, compounds that generate fluorine-substituted alkanesulfonic acid by irradiation with actinic light or radiation (see Patent Document 1, for example). In addition, perfluoroalkanesulfonic acid sulfonium salt (for example, refer patent document 2) is disclosed, and also patent document 3 (Unexamined-Japanese-Patent No. 2003-261529), patent document 4 (U.S. Patent 2003 / 0148211A) ), Patent Document 5 (U.S. Pat.No.5554664), Patent Document 6 (Japanese Patent Laid-Open No. 2002-341539), Patent Document 7 (Japanese Patent Laid-Open No. 2002-268223) and the like are bissulfonyl imide anions. Or a photosensitive composition containing a sulfonium salt and an iodonium salt having a trissulfonylmethide anion.

However, there are still many inadequate points, and it is desired to improve the exposure latitude, to reduce the change in the exposure latitude over time from exposure to post-heating, and to improve the sensitivity and dissolution contrast during EUV exposure. .

Patent Document 1: Japanese Patent Application Laid-Open No. 2002-268224

Patent Document 2: Japanese Patent Application Laid-Open No. 2000-275845

Patent Document 3: Japanese Unexamined Patent Publication No. 2003-261529

(Patent Document 4) US Patent No. 2003 / 0148211A

(Patent Document 5) US Patent No. 5554664

Patent Document 6: Japanese Patent Application Laid-Open No. 2002-341539

Patent Document 7: Japanese Patent Application Laid-Open No. 2002-268223

Accordingly, an object of the present invention is to improve the exposure latitude, to reduce the change in exposure latitude over time from exposure to post-heating, to improve sensitivity and dissolution contrast during EUV exposure, and the above It is providing the pattern formation method using the photosensitive composition.

The said subject was solved by the photosensitive composition of the following structure and the pattern formation method using the said photosensitive composition.

(1) (A1) A compound which generates fluorine-substituted alkanesulfonic acid having 2 or 3 carbon atoms by irradiation with actinic rays or radiation, and

(A2) Photosensitive composition containing the compound which generate | occur | produces the acid represented by either of following general formula (I)-(III) by irradiation of actinic light or a radiation.

In general formula (I)-(III),

Rb ₁ represents an electron withdrawing group.

Rb ₂ represents a hydrogen atom or an organic group.

m represents the integer of 0-5, n represents the integer of 0-5. However, m + n = 5.

Rb _{3 to} Rb ₅ each independently represent an organic group. Rb ₃ and Rb ₄ may be bonded to each other to form a ring.

(2) The photosensitive composition as described in (1) whose compound of (A1) component is a compound which produces pentafluoroethane sulfonic acid or perfluoro propane sulfonic acid by irradiation of actinic light or a radiation.

(3) At least one compound selected from sulfonium salt compounds of alkanesulfonic acids having 2 or 3 carbon atoms or iodineium compounds in which the compound of component (A1) is fluorine-substituted and ester compounds of alkanesulfonic acids having 2 or 3 carbon atoms which are fluorinated. The photosensitive composition as described in (1) characterized by the above-mentioned.

(4) The pattern formation method characterized by forming the photosensitive film with the photosensitive composition in any one of (1)-(3), and exposing and developing the said photosensitive film.

Hereinafter, preferable embodiment of this invention is given further.

(5) The positive photosensitive composition as described in any one of said (1)-(3) which further contains resin which decomposes | dissolves by the action of (B) acid, and the solubility in an alkali developing solution increases.

(6) The above-mentioned (1) to (3), further comprising an acid crosslinking agent which crosslinks with the soluble resin in the alkaline developer by the action of the soluble resin and (E) acid in the (D) alkali developer. The negative photosensitive composition as described in any one of them.

(7) The positive photosensitive composition as described in said (5) in which resin which decomposes | dissolves by the action of an acid, and the solubility in alkali developing solution increases has a hydroxystyrene structural unit.

(8) The positive photosensitive composition as described in the above (5), wherein the resin which is decomposed by the action of an acid and the solubility in the alkaline developer increases has a repeating unit having a monocyclic or polycyclic cyclic hydrocarbon structure.

(9) The positive photosensitive composition as described in the above (5), wherein the resin decomposed by the action of the acid and the solubility in the alkaline developer increases contains a repeating unit having an alcoholic hydroxyl group.

(10) Said repeating unit which has an alcoholic hydroxyl group is a repeating unit which has at least 1 sort (s) chosen from a monohydroxy adamantane structure, a dihydroxy adamantane structure, or a trihydroxy adamantane structure. The positive photosensitive composition as described in (9).

(11) The positive photosensitive composition as described in the above (5), wherein the resin which is decomposed by the action of an acid and the solubility in the alkaline developer is increased is a resin having a repeating unit having a lactone structure.

(12) Resin which is decomposed by the action of acid and the solubility in the alkaline developer increases is a resin having a repeating unit by at least one kind of methacrylic ester and a repeating unit by at least one kind of acrylic acid ester. The positive photosensitive composition as described in said (5) characterized by the above-mentioned.

(13) The positive photosensitive composition as described in the above item (5), wherein the resin which is decomposed by the action of an acid and the solubility in the alkaline developer increases has a fluorine atom on at least one of the main chain and the side chain.

(14) The positive photosensitive composition as described in the above (13), wherein the resin having a fluorine atom on at least one of the main chain and the side chain has a hexafluoro-2-propanol structure.

(15) Any one of the above (5) and (7) to (14), further comprising 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 an alkaline developer. The positive photosensitive composition as described in one.

(16) any one of the above (5) and (7) to (15), further comprising at least one compound selected from (F) basic compounds and (G) fluorine and / or silicon-based surfactants. The positive photosensitive composition as described in one.

(17) A resin which is decomposed by the action of an acid and whose solubility in an alkaline developer is increased is 2-alkyl-2-adamantyl (meth) acrylate or dialkyl (1-adamantyl) methyl (meth) acrylic. (5), (15), and at least one kind of repeating unit selected from the rate, at least one kind of repeating unit having a lactone structure, and at least one kind of repeating unit having one to three hydroxyl groups. The positive photosensitive composition as described in any one of (16).

(18) The positive of any one of (5) and (7) to (17) above, wherein the resin that is decomposed by the action of an acid and the solubility in the alkaline developer increases has a repeating unit having a carboxyl group. Type photosensitive composition.

(19) A resin which is decomposed by the action of an acid and whose solubility in an alkaline developer is increased is 2-alkyl-2-adamantyl (meth) acrylate or dialkyl (1-adamantyl) methyl (meth) acrylic. Any one of (5), (15), (16) and (18), characterized in that it has at least one of the repeating units selected from the rate and at least one of the repeating units having a hydroxystyrene structure. The positive photosensitive composition described.

Hereinafter, the present invention will be described in detail.

In addition, the description of group (atom group) in this specification WHEREIN: The description which is not described as substituted and unsubstituted 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.

The positive type photosensitive composition of the present invention, more preferably the positive type resist composition, can be used to irradiate a compound (A1), actinic light or radiation which generates fluorine-substituted alkanesulfonic acid having 2 or 3 carbon atoms by actinic light or radiation. It contains the compound (A2) which generate | occur | produces the acid represented by either of said general formula (I)-(III) by the action of an acid, and resin (B) which increases the solubility in alkaline developing solution, and is required. It also contains a dissolution inhibiting compound (C) having a molecular weight of 3000 or less, which is decomposed by the action of an acid and increases in solubility in an alkaline developer.

The negative photosensitive composition of the present invention, more preferably the negative resist composition, is irradiated with a compound (A1) that generates fluorine-substituted alkanesulfonic acid having 2 or 3 carbon atoms by actinic radiation or radiation, actinic radiation or radiation. Crosslinked with a compound (A2) for generating an acid represented by any one of the general formulas (I) to (III), a resin (D) soluble in an alkaline developer, and a resin soluble in the alkali developer by the action of an acid. Acid crosslinking agent (E) is contained.

[1] (A1) A compound which generates fluorine-substituted alkanesulfonic acid having 2 or 3 carbon atoms by irradiation with actinic light or radiation;

The photosensitive composition of this invention contains the compound (also called "compound (A1)") which produces the C2 or 3 alkanesulfonic acid fluorine-substituted by irradiation of actinic light or a radiation.

Examples of the alkanesulfonic acid having 2 or 3 carbon atoms substituted with fluorine include, for example, 1,1,2,3,3,3-hexafluoropropanesulfonic acid, 1,1,1,3,3,3-hexafluoro-2. Propanesulfonic acid, 2,2,2-trifluoroethanesulfonic acid, perfluoroethanesulfonic acid, perfluoro-n-propanesulfonic acid, perfluoroisopropanesulfonic acid, and the like. More preferably, the α-position of sulfonic acid is sulfonic acid substituted with a fluorine atom, and more preferably perfluoroethanesulfonic acid, perfluoro-n-propanesulfonic acid, and perfluoroisopropanesulfonic acid. Especially preferred is perfluoro-n-propanesulfonic acid.

Examples of the compound that generates fluorine-substituted alkanesulfonic acid having 2 or 3 carbon atoms by irradiation with actinic rays or radiation include sulfonium salt compounds or iodonium salt compounds of fluorine-substituted alkanesulfonic acids having 2 or 3 carbon atoms, and fluorine-substituted carbon atoms 2 or 3 The ester compound of the alkanesulfonic acid of 3 is preferable, More preferably, it is a compound represented by either of the following general formula (A1a)-(A5a).

The compound represented by formula (A1a) or (A2a) is a compound wherein Xa ^- is an anion of alkanesulfonic acid having 2 or 3 carbon atoms substituted with fluorine, and the compound represented by formulas (A3a) to (A5a) is X _1a. Is a compound in which a hydrogen atom of —SO ₃ H of an alkanesulfonic acid having 2 or 3 carbon atoms substituted with fluorine is separated and bonded as a monovalent group.

In General Formula (A1a), R _201a , R _202a, and R _203a each independently represent an organic group.

Xa ^- represents a sulfonic acid anion in which the hydrogen atom of -SO ₃ H of a fluorine-substituted alkanesulfonic acid having 2 or 3 carbon atoms is depleted.

The carbon number of the organic group as R _201a , R _202a and R _203a is generally 1 to 30, preferably 1 to 20.

In addition, two of R _201a to R _{203a 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 _201a to R _203a include an alkylene group (for example, butylene group and pentylene group).

Specific examples of the organic group as R _201a , R _202a and R _203a include the corresponding groups in the compounds (A1aa), (A1ab), and (A1ac) described later.

Moreover, the compound which has two or more structures represented by general formula (A1a) may be sufficient. For example, at least one of R _201a to R _203a of the compound represented by General Formula (A1a) may be a compound having a structure in which at least one of R _201a to R _203a of another compound represented by General Formula (A1a) is bonded. good.

Moreover, as a preferable (A1a) component, the compound (A1aa), (A1ab), and (A1ac) demonstrated below are mentioned.

Compound (A1aa) is an arylsulfonium compound in which at least one of R _201a to R _203a in the general formula (A1a) is an aryl group, that is, a compound having arylsulfonium as a cation.

In the arylsulfonium compound, all of R _201a to R _203a may be an aryl group, a part of R _201a to R _203a may be an aryl group, and the rest may be an alkyl group or a cycloalkyl group.

As an arylsulfonium compound, the triarylsulfonium compound, the diarylalkylsulfonium compound, the aryldialkylsulfonium compound, and the compound whose alkyl group in these compounds is a cycloalkyl group are mentioned, for example.

As an aryl group of an arylsulfonium compound, the aryl group which consists of hydrocarbons, and the heteroaryl group containing hetero atoms, such as a nitrogen atom, a sulfur atom, and an oxygen atom, are mentioned. As an aryl group which consists of hydrocarbons, a phenyl group and a naphthyl group are preferable, More preferably, it is a phenyl group. As a heteroaryl group, a pyrrole group, an indole group, a carbazole group, a thiophene group, etc. are mentioned, Preferably it is an indole group. When an arylsulfonium compound has two or more aryl groups, two or more aryl groups may be same or different.

The alkyl group or cycloalkyl group which an arylsulfonium compound has as needed has a C1-C15 linear or branched alkyl group or a C3-C15 cycloalkyl group, For example, a methyl group, an ethyl group, a propyl group, n-butyl group , sec-butyl group, t-butyl group, cyclopropyl group, cyclobutyl group, cyclohexyl group and the like.

Examples of the substituent which the aryl group, alkyl group or cycloalkyl group of R _201a to R _203a may have include a cycloalkyl group (for example, having 3 to 15 carbon atoms), an aryl group (for example, having 6 to 14 carbon atoms) and an alkoxy group (for example C1-15), a halogen atom, a hydroxyl group, a phenylthio group, etc. are mentioned. Moreover, about cyclic structures, such as an aryl ring and a cyclo ring in each group, an alkyl group (for example, C1-C15) is mentioned further as a substituent.

As a preferable substituent, it is a C1-C12 linear or branched alkyl group, a C3-C12 cycloalkyl group, a C1-C12 linear, branched or cyclic alkoxy group, Especially preferably, it is a C1-C4 alkyl group and C1-C12 It is an alkoxy group of 4. The substituent may be substituted with any one of three R _201a to R _203a , or may be substituted with all three. Moreover, about an aryl group, an alkyl group (for example, C1-C15) is mentioned as a substituent further. Moreover, it is preferable that the substituent is substituted by the p-position of an aryl group.

Next, the compound (A1ab) will be described.

Compound (A1ab) is a compound in the case where R _201a to R _203a in General Formula (A1a) each independently represent an organic group containing no aromatic ring. Here, the aromatic ring also includes an aromatic ring containing a hetero atom.

The organic group containing no aromatic ring as R _201a to R _203a is generally 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.

R _201a to R _203a are each independently preferably an alkyl group (particularly an alkoxycarbonylmethyl group as a substituted alkyl group), a cycloalkyl group, a linear, branched, cyclic iodinealkyl group, allyl group, or vinyl group which may have a double bond in the chain. , More preferably a straight chain, branched, cyclic 2-iodinealkyl group, most preferably a straight chain, branched 2-iodinealkyl group.

The alkyl group as R _201a to R _203a may be either linear or branched, and preferably a linear or branched alkyl group having 1 to 20 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group and pentyl group).

The cycloalkyl group as R _201a to R _203a is preferably a cycloalkyl group having 3 to 10 carbon atoms (cyclopentyl group, cyclohexyl group, norbornyl group).

The 2-iodine alkyl group as R _201a to R _203a may be linear, branched or cyclic, or may have a double bond. Preferably, group which has> C = O at the 2nd position of said alkyl group is mentioned.

The alkoxy group in the alkoxycarbonylmethyl group as the substituted alkyl group of R _201a to R _203a is preferably an alkoxy group having 1 to 5 carbon atoms (methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy group). have.

Each group as R _201a to R _203a may be substituted with a halogen atom, an alkoxy group (for example, 1 to 5 carbon atoms), a hydroxyl group, a cyano group, a nitro group, or the like.

Compound (A1ac) is a compound represented by the following general formula (A1ac) and is a compound having an arylacylsulfonium salt structure.

In general formula (A1ac), R <_213> represents an aryl group, may have a substituent, Preferably it is a phenyl group or a naphthyl group. As a substituent which the aryl group of R <_213> may have, an alkyl group, an alkoxy group, an acyl group, a nitro group, a hydroxyl group, an alkoxycarbonyl group, and a carboxy group are mentioned, for example.

R ₂₁₄ and R ₂₁₅ each independently represent a hydrogen atom, an alkyl group or a cycloalkyl group.

Y ₂₀₁ and Y ₂₀₂ each independently represent an alkyl group, a cycloalkyl group, an aryl group or a vinyl group.

Xa ^- represents a sulfonic acid anion in which the hydrogen atom of -SO ₃ H of a fluorine-substituted alkanesulfonic acid having 2 or 3 carbon atoms is depleted.

R ₂₁₃ and R ₂₁₄ may be bonded to each other to form a ring structure, R ₂₁₄ and R ₂₁₅ may be bonded to each other to form a ring structure, and Y ₂₀₁ and Y ₂₀₂ may be bonded to each other to form a ring structure. These ring structures may contain an oxygen atom, a sulfur atom, an ester bond, and an amide bond. _Examples of the group formed by bonding of R ₂₁₃ and R ₂₁₄ , the group formed by bonding of R ₂₁₄ and R ₂₁₅ , respectively, and the group formed by bonding of Y ₂₀₁ and Y ₂₀₂ , respectively, include a butylene group and a pentylene group.

The alkyl group as R ₂₁₄ and R ₂₁₅ is preferably a linear or branched alkyl group having 1 to 20 carbon atoms (for example, methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, t-butyl group).

The cycloalkyl group as R ₂₁₄ and R _{215 is preferably} a cycloalkyl group having 3 to 20 carbon atoms (eg, cyclopropyl group, cyclobutyl group, cyclohexyl group).

The alkyl group as Y ₂₀₁ and Y ₂₀₂ may have a substituent, may have an iodine group in the alkylene chain, and a straight or branched alkyl group having 1 to 20 carbon atoms (for example, methyl group, ethyl group, propyl group, n-butyl group, sec-). Butyl group and t-butyl group) are preferable.

Especially as an alkyl group which has a substituent, an alkoxycarbonylalkyl group and a carboxyalkyl group are mentioned, As a alkyl group which has an iodine group, a 2-iodine alkyl group is mentioned.

2-iodine alkyl group is a group having> C = O at the 2-position of the alkyl group.

As for the alkoxycarbonyl group in an alkoxycarbonylalkyl group, a C2-C20 alkoxycarbonyl group is preferable.

The cycloalkyl group as Y ₂₀₁ and Y _{202 is preferably} a cycloalkyl group having 3 to 20 carbon atoms (for example, a cyclopropyl group, a cyclobutyl group, a cyclohexyl group), and may have a substituent in the same manner as the alkyl group, and iodine in the alkylene chain. You may have a flag.

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

Each group as R ₂₁₄ , R ₂₁₅ , Y ₂₀₁ and Y ₂₀₂ may have a substituent, and examples of the substituent include an aryl group (for example, having 6 to 15 carbon atoms), an alkoxy group (for example, having 1 to 15 carbon atoms) and alkoxy Carbonyl group (C2-C20), a carboxyl group, a halogen atom, a hydroxyl group, a phenylthio group, etc. are mentioned. Moreover, about cyclic structures, such as an aryl ring and a cyclo ring in each group, an alkyl group (for example, C1-C15) is mentioned as a substituent.

Y ₂₀₁ and Y ₂₀₂ are preferably alkyl groups having 4 or more carbon atoms or cycloalkyl groups, and more preferably 4-16, still more preferably 4-12 alkyl groups or cycloalkyl groups.

Moreover, it is preferable that at least 1 of R <_214> or R <_215> is an alkyl group or a cycloalkyl group, More preferably, both of R <_214> , R <_215> are an alkyl group or a cycloalkyl group.

In general formula (A2a),

R _204a and R _205a each independently represent an aryl group, an alkyl group or a cycloalkyl group.

Xa ^- represents a sulfonic acid anion in which the hydrogen atom of -SO ₃ H of a fluorine-substituted alkanesulfonic acid having 2 or 3 carbon atoms is depleted.

As an aryl group of R <_204a> and R <_205a> , a phenyl group and a naphthyl group are preferable, More preferably, it is a phenyl group.

As the alkyl group and the cycloalkyl group as R _204a and R _205a , a linear or branched alkyl group having 1 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group) and a cycloalkyl group having 3 to 10 carbon atoms (cyclo Pentyl group, cyclohexyl group, norbornyl group) is mentioned.

In general formula (A3a),

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

X _1a represents that the fluorine-substituted alkanesulfonic acid having 2 or 3 of the hydrogen atoms of the -SO ₃ H group off of the monovalent.

In general formula (A4a),

R _208a represents an alkyl group, a cycloalkyl group or an aryl group.

R _209a represents an alkyl group, a cycloalkyl group, a cyano group or an alkoxycarbonyl group, and is preferably a halogen-substituted alkyl group or a cycloalkyl group or a cyano group.

The alkyl group and the cycloalkyl group as R _209a may be an iodine alkyl group or an iodine cycloalkyl group having an iodine group in the alkylene chain.

X _1a represents that the fluorine-substituted alkanesulfonic acid having 2 or 3 of the hydrogen atoms of the -SO ₃ H group off of the monovalent.

In general formula (A5a),

R _210a and R _211a each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a cyano group, a nitro group or an alkoxycarbonyl group, preferably a halogen-substituted alkyl group or a cycloalkyl group, a nitro group or a cyano group.

R _212a represents a hydrogen atom, an alkyl group, a cycloalkyl group, a cyano group or an alkoxycarbonyl group.

X _1a represents that the fluorine-substituted alkanesulfonic acid having 2 or 3 of the hydrogen atoms of the -SO ₃ H group off of the monovalent.

Each group in said general formula (A3a)-(A5a) may have a substituent, As a substituent, an aryl group (for example, C6-C15), an alkoxy group (for example, C1-C15) And halogen atoms, hydroxyl groups, and phenylthio groups. Moreover, about cyclic structures, such as an aryl ring and a cyclo ring in each group, an alkyl group (for example, C1-C15) is mentioned as a substituent.

Preferably, it is a compound represented by general formula (A1a), More preferably, it is a compound represented by general formula (A1aa)-(A1ac).

Specific examples of the preferred compound (A1) are shown below.

As for content in the photosensitive composition (solid content) of a compound (A1), it is preferable to set it as 0.1-15 mass%, It is more preferable to set it as 0.5-10 mass%, It is especially preferable to set it as 1-7 mass%.

(A2) A compound which generates an acid represented by one of general formulas (I) to (III) by irradiation with actinic light or radiation

The photosensitive composition of this invention contains the compound (henceforth "a compound (A2)") which produces | generates the acid represented by either of following general formula (I)-(III) by irradiation of actinic light or a radiation.

In general formula (I)-(III),

Rb ₁ represents an electron withdrawing group.

Rb ₂ represents a hydrogen atom or an organic group.

m represents the integer of 0-5, n represents the integer of 0-5. However, m + n = 5.

Rb _{3 to} Rb ₅ each independently represent an organic group. Rb ₃ and Rb ₄ may be bonded to each other to form a ring.

In the formula (I), there may be mentioned as an electron-withdrawing group in Rb _1, preferably, a halogen atom, halogen-substituted alkyl group, a nitro group, a cyano group, an alkylsulfonyl group, a carboxyl group, an alkoxycarbonyl group, etc., more Preferably, they are a halogen atom, a halogen substituted alkyl group, More preferably, they are a fluorine atom and a fluoroalkyl group.

As the organic group in Rb ₂ , preferably, an alkyl group, an alkoxy group, a cycloalkyloxy group, an alkylthio group, a cycloalkylthio group, an aryl group, an aryloxy group, or an arylthio group thereof may be substituted. And a group connected with a linking group such as a plural-valent single bond, -O-, -C0 _2- , -S-, -SO _3- , -SO ₂ N (Rc ₁ )-, and preferably an alkyl group and an alkoxy group. , An alkylthio group, and an alkylsulfonyl group. As the preferred carbon number of the organic group of Rb _2, and 1 to 30 carbon atoms, more preferably 4-25 carbon atoms, more preferably from 8 to 20 carbon atoms. By adjusting the carbon number, it is possible to control the diffusibility of the generated acid in the film, thereby improving the resolution.

When m is two or more, some Rb < ₁ > may be same or different.

when n is 2 or more, a plurality of Rb ₂ may be the same or different.

As an acid represented by general formula (I), Preferably it is benzene sulfonic acid substituted by the fluorine atom and the C4-C25 organic group, More preferably, it is an acid represented by the following general formula (I ').

In general formula (I '), Rb ₂₁ represents an alkyl group, an alkoxy group, an alkylthio group, or an alkylsulfonyl group.

As the organic group, for Rb ₃ ~Rb ₅ in the general formula (II), (III), preferably, the 1 position is substituted with an alkyl group in the alkyl group, a fluorine atom or a fluoroalkyl group substituted with an alkyl group with a fluorine atom or a fluoroalkyl It is a phenyl group. By having a fluorine atom or a fluoroalkyl group, the acidity of the acid generated by light irradiation is improved and the sensitivity is improved. As Rb < ₃ > -Rb < ₅ >, More preferably, it is a C1-C8 perfluoroalkyl group, More preferably, it is a C1-C4 perfluoroalkyl group.

Examples of the group formed by bonding of Rb ₃ and Rb ₄ include an alkylene group and an arylene group. As a group Rb ₃ and Rb ₄ are combined to form, preferably an alkylene group having 2 to 4 carbon atoms in the perfluoroalkyl, more preferably a propylene group perfluoroalkyl. By combining Rb ₃ and Rb ₄ to form a ring, the acidity is improved and the sensitivity of the composition is improved as compared with not forming a ring.

The specific example of the acid represented by general formula (I) is shown below.

The specific example of the acid represented by general formula (II) is shown below.

The specific example of the acid represented by general formula (III) is shown below.

As a compound which produces | generates the acid represented by general formula (I)-(III) by irradiation of actinic light or a radiation, the sulfonium salt or iodonium salt of the acid represented by general formula (I)-(III) is preferable, More preferably, in said general formula (A1a) or (A2a), the compound whose Xa- is an anion from which the hydrogen atom fell from the acid represented by general formula (I)-(III) is mentioned.

The specific example of the compound which produces | generates the acid represented by general formula (I) by irradiation of actinic light or a radiation is shown below.

The specific example of the compound which produces | generates the acid represented by General formula (II) by irradiation of actinic light or a radiation is shown below.

The specific example of the compound which produces | generates the acid represented by general formula (III) by irradiation of actinic light or a radiation is shown below.

As for content in the photosensitive composition (solid content) of a compound (A2), it is preferable to set it as 0.1-15 mass%, It is more preferable to set it as 0.5-10 mass%, It is especially preferable to set it as 1-7 mass%.

In the present invention, the use ratio of the compound (A1) and the compound (A2) is preferably 90/10 to 10/90, more preferably 80/20 to 90, based on the mass ratio of the compound (A1) / compound (A2). 20/80.

(Combination acid generator)

In the present invention, in addition to the compound (A1) and the compound (A2), a compound (acid generator) which decomposes by irradiation of actinic light or radiation and generates an acid may be used in combination.

As such acid generators that can be used in combination, known photoacid generators which generate acids by irradiation with actinic rays or radiation used in photo cationic polymerization, photo radical polymerization photoinitiators, pigment photochromic agents, photochromic agents, or micro resists, etc. Compounds and mixtures thereof can be appropriately selected and used.

For example, a diazonium salt, a phosphonium salt, a sulfonium salt, an iodonium salt, an imide sulfonate, an oxime sulfonate, a diazo disulfone, a disulfone, o-nitrobenzyl sulfonate is mentioned.

(Z1) to (z41) shown below as an acid generator which can be used together are mentioned.

As a total use amount of the acid generator in the composition of this invention, 0.1-20 mass% is preferable with respect to solid content of a composition, More preferably, it is 0.5-10 mass%, More preferably, it is 1-7 mass%. By controlling the amount of acid generator added, resolution and line edge roughness are good while maintaining high sensitivity.

[2] A resin that is decomposed by the action of (B) acid and has increased solubility in alkaline developing solution (hereinafter also referred to as "(B) component")

The resin which is decomposed by the acid used in the positive photosensitive composition of the present invention and whose solubility in the alkaline developer is increased is a group that can be decomposed into an acid on the main chain or the side chain of the resin, or both the main chain and the side chain ( Hereinafter, it is resin which also calls "acid-decomposable group." Among these, resins having a group capable of decomposing into an acid in the side chain are more preferable.

Preferred groups that 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 preferably an acetal group or a tertiary ester group.

The mother resin in the case where groups which can be decomposed into these acids are bonded as side chains are alkali-soluble resins having -OH or -COOH groups in the side chains. For example, alkali-soluble resin mentioned later is mentioned.

The alkali dissolution rate of these alkali-soluble resins is preferably measured at 0.261 N tetramethylammonium hydrooxide (TMAH) (23 DEG C) and is 170 Pa / sec or more. Especially preferably, it is 330 ms / sec or more.

In this respect, particularly preferred alkali-soluble resins are o-, m-, p-poly (hydroxystyrene) and copolymers thereof, hydrogenated poly (hydroxystyrene), halogen or alkyl-substituted poly (hydroxystyrene), poly Alkali having a hydroxystyrene structural unit such as a part of (hydroxystyrene), O-alkylated or O-acylate, styrene-hydroxystyrene copolymer, α-methylstyrene-hydroxystyrene copolymer, hydrogenated novolak resin It is alkali-soluble resin containing repeating units which have carboxyl groups, such as soluble resin, (meth) acrylic acid, and norbornenecarboxylic acid.

As a repeating unit which has a preferable acid-decomposable group in this invention, t-butoxycarbonyloxy styrene, 1-alkoxyethoxy styrene, (meth) acrylic acid tertiary alkylester, etc. are mentioned, for example, 2- More preferred are alkyl-2-adamantyl (meth) acrylate and dialkyl (1-adamantyl) methyl (meth) acrylate.

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

When irradiating KrF excimer laser light, an electron beam, X-rays, and high energy light rays (EUV etc.) with a wavelength of 50 nm or less to the positive photosensitive composition of this invention, it is preferable that resin of (B) component has a hydroxystyrene repeating unit. desirable. More preferably, hydroxy styrene copolymer protected with hydroxy styrene / acid-decomposable group, hydroxy styrene / (meth) acrylic acid tertiary alkyl ester are preferable.

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

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

The content rate of the group which can be decomposed into an acid has the number (B) of the group which can be decomposed into an acid in the resin and the number (S) of alkali-soluble groups not protected by the group which is desorbed to the acid, and B / (B + S). 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 ArF excimer laser light to the positive photosensitive composition of this invention, resin of (B) component has monocyclic or polycyclic alicyclic hydrocarbon structure, it decomposes by the action of an acid, and the solubility to alkaline developing solution is carried out. 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 which has at least 1 sort (s) chosen from the group of the repeating unit which has a partial structure containing alicyclic hydrocarbon represented by general formula (pV), and the repeating unit represented by the following general formula (II-AB).

In general formula (pI)-(pV),

R ₁₁ represents a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group or sec-butyl group, and Z represents an atomic group necessary for forming a cycloalkyl group together with carbon atoms.

R <_12> -R <_16> represents a C1-C4 linear or branched alkyl group or a cycloalkyl group each independently. Provided that at least one of R ₁₂ to R ₁₄ or any one of R ₁₅ and R ₁₆ represents a cycloalkyl group.

R ₁₇ to R ₂₁ each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a cycloalkyl group. Provided that at least one of R ₁₇ to R ₂₁ represents a cycloal group. In addition, any one of R <_19> , R <_21> represents a C1-C4 linear or branched alkyl group or a cycloalkyl 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 a cycloalkyl group. Provided that at least one of R ₂₂ to R ₂₅ represents a cycloalkyl group. R ₂₃ and R ₂₄ may be bonded to each other to form a ring.

In general formula (II-AB),

R11 'and R12' each independently represent a hydrogen atom, a cyano group, a halogen atom or an alkyl group.

Z 'contains two bonded carbon atoms (C-C) and represents an atomic group for forming an alicyclic structure.

In addition, the general formula (II-AB) is more preferably the following general formula (II-AB1) or general formula (II-AB2).

In general formula (II-AB1), (II-AB2),

R ₁₃ 'to R ₁₆ ' are each independently a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, -COOH, -COOR ₅ , a group decomposed by the action of an acid, -C (= O) -X-A'- R ₁₇ ′, an alkyl group or a cycloalkyl group.

Here, R <_5> represents the group which has an alkyl group, a cycloalkyl group, or a lactone structure.

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

A 'represents a single bond or a bivalent coupling group.

R ₁₇ ′ represents a group having a —COOH, —COOR ₅ , —CN, a hydroxyl group, an alkoxy group, —CO—NH—R ₆ , —CO—NH—SO ₂ —R _6, or a lactone structure.

R ₆ represents an alkyl group or a cycloalkyl group.

In addition, at least two of R ₁₃ ′ to R ₁₆ ′ may combine to form a ring.

n represents O or 1;

In the general formulas (pI) to (pV), the alkyl group in R ₁₂ to R ₂₅ represents a straight or branched alkyl group having 1 to 4 carbon atoms, for example, methyl group, ethyl group, propyl group, n-butyl Group, sec-butyl group, t-butyl group, etc. are mentioned.

The cycloalkyl group in R ₁₂ to R ₂₅ or the cycloalkyl group formed by Z and a carbon atom may be monocyclic or polycyclic. Specifically, group which has a C5 or more monocyclo, bicyclo, tricyclo, tetracyclo structure, etc. are mentioned. 6-30 are preferable and, as for the carbon number, 7-25 are especially preferable. These cycloalkyl groups may have a substituent.

As a preferable cycloalkyl group, an adamantyl group, a noadamantyl group, a decalin residue, a tricyclo decanyl group, a tetracyclo dodecanyl group, a norbornyl group, a cedrol group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooxyl A methyl group, a cyclodecanyl group, and a cyclododecanyl group are mentioned. More preferably, an adamantyl group, norbornyl group, cyclohexyl group, cyclopentyl group, tetracyclo dodecanyl group, and tricyclo decanyl group are mentioned.

These alkyl groups and cycloalkyl groups may further have a substituent. As another substituent of an alkyl group and a cycloalkyl group, an alkyl group (C1-C4), a halogen atom, a hydroxyl group, an alkoxy group (C1-C4), a carboxyl group, an alkoxycarbonyl group (C2-C6) is mentioned. Said alkyl group, alkoxy group, alkoxycarbonyl group, etc. may further have a substituent. Examples of the substituent which an alkyl group, an alkoxy group, an alkoxycarbonyl group, or the like may also have include a hydroxyl group, a halogen atom and an alkoxy group.

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

Specifically, the structure in which the hydrogen atom of a carboxylic acid group, a sulfonic acid group, a phenol group, and a thiol group was substituted by the structure represented by general formula (pI)-(pV), etc. are mentioned, Preferably a carboxylic acid group and a sulfonic acid are mentioned. It is a structure where the hydrogen atom of group was substituted by the structure represented by general formula (pI)-(pV).

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

In general formula (pA), R represents a hydrogen atom, a halogen atom, or a linear or branched alkyl group having 1 to 4 carbon atoms. A plurality of Rs may be the same or different, respectively.

A represents a single bond or a combination of two or more groups selected from the group consisting of a single bond, an alkylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a sulfonamide group, a urethane group, or a urea group. Preferably it is a single bond.

Rp ₁ represents any one of the general formulas (pI) to (pV).

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

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

In each of the above structural formulas, Rx represents H, CH ₃ , CF ₃ or CH ₂ 0H, and Rxa and Rxb each independently represent an alkyl group having 1 to 4 carbon atoms.

Examples of the halogen atoms of R ₁₁ ′ and R ₁₂ ′ in General Formula (II-AB) include chlorine, bromine, fluorine and iodine atoms.

As an alkyl group in R <_11>'and R <_12>', a C1-C10 linear or branched alkyl group is preferable, For example, a methyl group, an ethyl group, n-propyl group, isopropyl group, linear or branched form is preferable. , Butyl group, pentyl group, hexyl group, heptyl group and the like.

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 pedestrian alicyclic group forming a repeating unit of an aliphatic alicyclic hydrocarbon. Atom groups for forming the formula structure are preferred.

As a skeleton of the alicyclic hydrocarbon formed, the thing similar to the cycloalkyl group of R <_12> -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-AB1) or (II-AB2) is mentioned.

In the alicyclic hydrocarbon-based acid-decomposable resin according to the present invention, the group decomposed by the action of an acid includes a repeating unit having a partial structure containing an alicyclic hydrocarbon represented by the above general formulas (pI) to (pV), It can have as a repeating unit represented by general formula (II-AB), and at least 1 repeating unit of the repeating unit of a late copolymerization component.

The various substituents of R ₁₃ ′ to R ₁₆ ′ in the general formula (II-AB1) or the general formula (II-AB2) may be from an atomic group to form an alicyclic structure in the general formula (II-AB). It may also be a substituent of the atomic group Z to form a bridged alicyclic structure.

Although the following specific example is given as a repeating unit represented by said general formula (II-AB1) or general formula (II-AB2), this invention is not limited to these specific examples.

It is preferable that the alicyclic hydrocarbon type acid-decomposable resin of this invention has a repeating unit which has a lactone group. As the lactone group, any group can be used as long as it has a lactone structure, but is preferably a group having a 5- to 7-membered ring lactone structure, and other rings in the form of forming a bicyclo structure and a spiro structure in the 5- to 7-membered ring lactone structure. It is preferable that the structure is substituted. It is more preferable that the alicyclic hydrocarbon-based acid decomposable resin of the present invention has a repeating unit having a group having a lactone structure represented by any one of the following general formulas (LC1-1) to (LC1-16). In addition, the group having a lactone structure may be directly bonded to the main chain. Preferred lactone structures are (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13) and (LC1-14), and the line edges are formed by using a specific lactone structure. Roughness and development defects become good.

The lactone structure portion may or may not have a substituent (Rb ₂ ). Preferred substituents (Rb ₂ ) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, a carboxyl group, a halogen atom, a hydroxyl group, a cyano group, Acid-decomposable group etc. are mentioned. n ₂ represents an integer of 0 to 4. n ₂ is 2 or more, when a plurality presence Rb _2, which may be the same or different to, and in combination the plurality of Rb ₂ there between may form a ring.

Examples of the repeating unit having a group having a lactone structure represented by any one of General Formulas (LC1-1) to (LC1-16) include R ₁₃ ′ to R ₁₆ ′ in General Formula (II-AB1) or (II-AB2). At least one of which has a group represented by formulas (LC1-1) to (LC1-16) (for example, R ₅ of -COOR ₅ is represented by formulas (LC1-1) to (LC1-16) Group, or a repeating unit represented by the following general formula (AI), etc. are mentioned.

In general formula (AI), Rb ₀ represents a hydrogen atom, a halogen atom, or a C1-C4 alkyl group.

As an alkyl group of Rb ₀ , a methyl group, an ethyl group, a propyl group, n-butyl group, sec-butyl group, t-butyl group etc. are mentioned, for example. The alkyl group of Rb ₀ may have a substituent. An alkyl group of Rb ₀ may have good as the preferred substituents, for example, there may be mentioned a hydroxyl group, a halogen atom.

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

Ab represents a divalent linking group having an alkylene group, a monocyclic or polycyclic alicyclic hydrocarbon structure, a single bond, an ether group, an ester group, a carbonyl group, a carboxyl group, or a divalent group combining these. Preferably, they are a single bond or a linking group represented by -Ab ₁ -CO _2- .

Ab ₁ is a linear, branched alkylene group, monocyclic or polycyclic cycloalkylene group, and preferably a methylene group, an ethylene group, a cyclohexyl residue, an adamantyl residue and a norbornyl residue.

V represents a group represented by any one of General Formulas (LC1-1) to (LC1-16).

The repeating unit having a lactone structure usually has an optical isomer, but any optical isomer may be used. Moreover, 1 type of optical isomers may be used individually, or several optical isomers may be mixed and used. When mainly using one type of optical isomer, the optical purity (ee) of it is preferable that it is 90 or more, More preferably, it is 95 or more.

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

Wherein Rx is H, CH ₃ , CH ₂ OH, or CF ₃

Wherein Rx is H, CH ₃ , CH ₂ OH, or CF ₃

Wherein Rx is H, CH ₃ , CH ₂ OH, or CF ₃

It is preferable that the alicyclic hydrocarbon type acid-decomposable resin of this invention has a repeating unit which has an alicyclic hydrocarbon structure substituted by the polar group. This improves substrate adhesion and developer affinity. As a polar group, a hydroxyl group and a cyano group are preferable.

As an alicyclic hydrocarbon structure substituted by the polar group, the structure represented by the following general formula (VIIa) or (VIIb) is mentioned, for example.

In formula (VIIa), R ₂ c to R ₄ c each independently represent a hydrogen atom, a hydroxyl group or a cyano group. Provided that R ₂ c to R ₄ c At least one represents a hydroxyl group or a cyano group. Preferably, one or two of R ₂ c to R ₄ c are hydroxyl groups, and the rest are hydrogen atoms, more preferably R ₂ c to R ₄ c. Two of them are hydroxyl groups and the other are hydrogen atoms.

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

As the repeating unit having a group represented by the general formula (VIIa) or (VIIb), the general formula (II-AB1) or (II-AB2) of the R ₁₃ '~R _16' at least one is the above-mentioned general formula (VIIa) Or having a group represented by (VIIb) (for example, R ₅ of -COOR ₅ represents a group represented by General Formula (VIIa) or (VIIb)), or represented by the following General Formula (AIIa) or (AIIb) Loss repeat units.

In General Formulas (AIIa) and (AIIb), R ₁ c represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

R ₂ c~R ₄ c are the same as R ₂ c~R ₄ c in the general formula (VIIa).

Although the specific example of the repeating unit which has an alicyclic hydrocarbon structure substituted by the polar group represented by general formula (AIIa) or (AIIb) is shown below, this invention is not limited to these.

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

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

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

It is preferable to have a repeating unit which has an alkali-soluble group, and, as for the alicyclic hydrocarbon type acid-decomposable resin of this invention, it is more preferable to have a repeating unit which has a carboxyl group. Having this increases the resolution in contact hole applications. As a repeating unit which has a carboxyl group, any of the repeating unit in which the carboxyl group is couple | bonded directly with the main chain of resin, such as the repeating unit by acrylic acid or methacrylic acid, or the repeating unit in which the carboxyl group is couple | bonded with the main chain of resin via a coupling group is preferable. In addition, the linking group may have a monocyclic or polycyclic cyclic hydrocarbon structure. Most preferably acrylic acid and methacrylic acid.

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

In general formula (F1), R <_50> -R <_55> represents a hydrogen atom, a fluorine atom, or an alkyl group each independently. Provided that at least one of R ₅₀ to R ₅₅ represents an alkyl group in which a fluorine atom or at least one hydrogen atom is substituted with a fluorine atom.

Rx represents a hydrogen atom or an organic group (preferably an acid-decomposable protecting group, an alkyl group, a cycloalkyl group, an acyl group, an alkoxycarbonyl group).

The alkyl group of R ₅₀ to R ₅₅ may be substituted with a halogen atom such as a fluorine atom, a cyano group, or the like, and preferably an alkyl group having 1 to 3 carbon atoms, for example, a methyl group or a trifluoromethyl group.

It is preferable that all of R ₅₀ to R ₅₅ are fluorine atoms.

As an organic group which Rx represents, the alkyl group, cycloalkyl group, acyl group, alkylcarbonyl group, alkoxycarbonyl group, alkoxycarbonylmethyl group, alkoxymethyl group, and 1-alkoxyethyl group which may have an acid-decomposable protecting group and a substituent are preferable.

As a repeating unit which has group represented by general formula (F1), Preferably, the repeating unit represented by the following general formula (F2) is mentioned.

In general formula (F2), Rx represents a hydrogen atom, a halogen atom, or a C1-C4 alkyl group. As a preferable substituent which the alkyl group of Rx may have, a hydroxyl group and a halogen atom are mentioned.

Fa represents a single bond, a straight chain or a branched alkylene group, and is preferably a single bond.

Fb represents a monocyclic or polycyclic cyclic hydrocarbon group.

Fc represents a single bond, a straight chain or a branched alkylene group, and is preferably a single bond or a methylene group.

F1 represents a group represented by the general formula (F1).

P1 represents 1-3.

As a cyclic hydrocarbon group in Fb, a cyclopentyl group, a cyclohexyl group, and norbornyl group is preferable.

Hereinafter, the specific example of the repeating unit which has a structure of general formula (F1) is shown.

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 properties of the resist, in addition to the above-described repeating structural unit. It can have a repeating structural unit.

Although the repeating structural unit corresponding to the following monomer is mentioned as such a repeating structural unit, It is not limited to these.

Thereby, the performance especially calculated | required by alicyclic hydrocarbon type acid-decomposable resin,

(1) solubility in coating solvents,

(2) film forming property (glass transition point),

(3) alkali developability,

(4) film loss (select hydrophilic, alkali-soluble group),

(5) adhesion to the substrate of the unexposed portion,

(6) dry etching resistance

Fine adjustment of such a thing becomes possible.

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. Etc. can be mentioned.

In addition, as long as it is an addition polymerizable unsaturated compound copolymerizable with the monomer corresponding 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, and the resolution, heat resistance, sensitivity, etc. It is set appropriately.

The following are mentioned as a preferable aspect of alicyclic hydrocarbon type acid-decomposable resin of this invention.

(1) It contains the repeating unit which has a partial structure containing the alicyclic hydrocarbon represented by said general formula (pI)-(pV) (side chain type). The thing which has a repeating unit by the (meth) acrylate which has a structure of (pI)-(pV) preferably.

(2) Having a repeating unit represented by general formula (II-AB) (backbone type).

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

(3) Having a repeating unit represented by general formula (II-AB), a maleic anhydride derivative structure, and a (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 all the repeating structural units, More preferably, it is 20-50 mol%, More preferably, 25-40 mol% to be.

In alicyclic hydrocarbon type acid-decomposable resin, content of the repeating unit which has a partial structure containing alicyclic hydrocarbon represented by general formula (pI)-(pV) is 25-70 mol% in all the repeating structural units, More Preferably it is 35-65 mol%, More preferably, it is 40-60 mol%.

In alicyclic hydrocarbon type acid-decomposable resin, 10-60 mol% is preferable in all the repeating structural units, and, as for content of the repeating unit represented by general formula (II-AB), 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 another copolymerization component can also be set suitably according to the performance of a desired resist, In general, the alicyclic hydrocarbon represented by said general formula (pI)-(pV) is mentioned. 99 mol% or less is preferable with respect to the total number of moles which the repeating structural unit which has a partial structure containing the sum total, and the repeating unit represented by the said general formula (II-AB), 90 mol% or less, More preferably, 80 It is less than mol%.

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.

As alicyclic hydrocarbon type acid-decomposable resin used for this invention, Preferably, all the repeating units are comprised from the (meth) acrylate repeating unit. In this case, all of the repeating units may be methacrylate, and all of the repeating units may be any of acrylate and methacrylate / acrylate mixture, but it is preferable that the acrylate repeating units are 50 mol% or less of all the repeating units. Do.

More preferably, 25 to 50% of repeating units having a partial structure containing an alicyclic hydrocarbon represented by general formulas (pI) to (pV), 25 to 50% of repeating units having the lactone structure, and the polar group It is a ternary copolymer polymer which has a 5-30% repeating unit which has a substituted alicyclic hydrocarbon structure, or a 4-membered copolymer polymer which has a 5-20% repeating unit which has a carboxyl group or a structure represented by general formula (F1).

Alicyclic hydrocarbon type acid-decomposable resin used for this invention can be synthesize | combined according to a conventional method (for example, radical polymerization). For example, as a general synthesis method, the batch polymerization method which melt | dissolves a monomer species and an initiator in a solvent, and superposes | polymerizes by heating, and the dropping polymerization method which adds the solution of a monomer species and an initiator dropwise to the heating solvent for 1 to 10 hours, etc. are mentioned. The dropping polymerization method is preferable. Examples of the reaction solvent include ethers such as tetrahydrofuran, 1,4-dioxane and diisopropyl ether, ketones such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate, dimethylformamide and dimethyl. Amide solvents, such as acetamide, and the solvent which melt | dissolves the composition of this invention, such as propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and cyclohexanone mentioned later, are mentioned. More preferably, it is preferable to superpose | polymerize using the same solvent as the solvent used for the photosensitive composition of this invention. As a result, generation of particles during storage can be suppressed.

It is preferable that a polymerization reaction is performed in inert gas atmosphere, such as nitrogen and argon. As a polymerization initiator, superposition | polymerization is started using a commercial radical initiator (azo initiator, peroxide, etc.). As a radical initiator, an azo initiator is preferable, and the azo initiator which has an ester group, a cyano group, and a carboxyl group is preferable. Preferred initiators include azobisisobutylonitrile, azobisdimethylvaleronitrile, dimethyl 2,2'-azobis (2-methylpropionate) and the like. If desired, an initiator is added or added in portions, and after completion of the reaction, it is added to a solvent to recover a desired polymer by a method such as powder or solid recovery. The concentration of the reaction is 5 to 50% by mass, preferably 10 to 30% by mass. Reaction temperature is 10 degreeC-150 degreeC normally, Preferably it is 30 degreeC-120 degreeC, More preferably, it is 50-100 degreeC.

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 solubility in alkaline developing solution, 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 is mentioned, for example.

As the resin having a silicon atom, a resin having a trialkylsilyl structure, a monocyclic or polycyclic cyclic siloxane structure is preferable, and a resin having a repeating unit having a structure represented by the following general formulas (SS-1) to (SS-4). More preferably, resin having a (meth) acrylic acid ester repeating unit, a vinyl repeating unit, or an allyl repeating unit having a structure represented by General Formulas (SS-1) to (SS-4) is more preferable.

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

The resin having a silicon atom preferably has a repeating unit having two or more other silicon atoms, more preferably a repeating unit having 1 to 4 silicon atoms (Sa) and 5 to 10 silicon atoms (Sb). It is resin which has both of the repeating unit which has, More preferably, it is represented by at least 1 sort (s) of repeating unit which has a structure represented by general formula (SS-1) (SS-3), and general formula (SS-4). It is resin which has a repeating unit which has a structure.

When irradiating F ₂ excimer laser light to the positive 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 decompose | dissolves by action of an acid. Resin (hereinafter also referred to as fluorine group-containing resin) which increases the solubility in alkaline developing solution is preferable, More preferably, hydroxyl group or 1-position is substituted with fluorine atom or fluoroalkyl group at 1-position is fluorine atom or fluorine A resin containing a group in which a hydroxyl group substituted with a roalkyl group is protected with an acid-decomposable group, and most preferably a hexafluoro-2-propanol structure or a structure in which a hydroxyl group of hexafluoro-2-propanol is protected with an acid-decomposable group. Resin. By introducing a fluorine atom, transparency to ultraviolet light, especially F ₂ (157 nm) light can be improved.

As the fluorine group-containing resin in the (B) acid-decomposable resin, for example, a resin having at least one repeating unit represented by the following general formulas (FA) to (FG) is preferable.

In the above general formula, R ₁₀₀ ~R ₁₀₃ represents each a hydrogen atom, a fluorine atom, an alkyl group or an aryl group.

R ₁₀₄ and R ₁₀₆ are each a hydrogen atom, a fluorine atom or an alkyl group, and at least one of R ₁₀₄ and R ₁₀₆ is a fluorine atom or a fluoroalkyl group. R ₁₀₄ and R ₁₀₆ are preferably both trifluoromethyl groups.

R ₁₀₅ is a group decomposed by the action of a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an alkoxycarbonyl group or an acid.

A ₁ represents 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 coupling group containing. 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, 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 cycloalkyl group and an acid.

a is 0 or 1;

b is 0, 1 or 2.

In addition, R <_100> and R <_101> in general formula (FA) and (FC) may form the ring through the alkylene group (C1-C5) which may be substituted by fluorine.

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

The weight average molecular weight of the resin of the component (B) is preferably 2,000 to 200,000 as a polystyrene conversion value by the GPC method. By setting the weight average molecular weight to 2,000 or more, heat resistance and dry etching resistance can be improved, and by setting the weight average molecular weight to 200,000 or less, developability can be improved, and since the viscosity is lowered, film forming property can be improved. . As a more preferable molecular weight, it is 5,000-50,000, More preferably, it is 7,000-30,000. By adjusting the molecular weight, heat resistance, resolution, development defects, and the like of the composition can be made compatible. 1.0-3.0 are preferable, as for dispersion degree (Mw / Mn) of resin of (B) component, More preferably, it is 1.2-2.5, More preferably, it is 1.2-1.6. By adjusting the dispersion degree to an appropriate range, the line edge roughness performance can be improved.

In the positive photosensitive composition of the present invention, the blending amount in the whole composition of the resin of the component (B) according to the present invention is preferably from 40 to 99.99 mass% in the total solids, more preferably from 50 to 99 mass% Preferably it is 80-96 mass%.

[3] A dissolution inhibiting compound having a molecular weight of 3000 or less (hereinafter referred to as "(C) component" 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 the solubility in an alkaline developer is increased, the permeability of 220 nm or less is not reduced, and therefore, it is described in Proceeding of SPIE, 2724,355 (1996). Preferred are alicyclic or aliphatic compounds containing acid-decomposable groups, such as cholic acid derivatives containing acid-decomposable groups. Examples of the acid-decomposable group and the alicyclic structure include those described for the alicyclic hydrocarbon-based acid-decomposable resin.

When exposing the photosensitive composition of this invention with a KrF excimer laser or irradiating with an electron beam, it is preferable to contain the structure which substituted the phenolic hydroxyl group of the phenolic compound by the acid-decomposable group. 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, this invention is not limited to these.

[4] (D) Resin which is 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 measured at 0.261 N tetramethylammonium hydroxide (TMAH) (23 DEG C) and 20 Pa / sec or more. Especially preferably, it is 200 microseconds / sec or more.

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, hydrogenation, for example Polyhydroxystyrene, halogen or alkyl-substituted polyhydroxystyrene, hydroxystyrene-N-substituted maleimide copolymers, o / p- and m / p-hydroxystyrene copolymers, some of the hydroxyl groups of polyhydroxystyrene O-alkylates (e.g., 5-30 mole% O-methylate, O- (1-methoxy) ethylate, O- (1-ethoxy) ethylate, O-2-tetrahydropyranylide , 0- (t-butoxycarbonyl) methylate, etc.) or O-acylates (for example, 5-30 mole% o-acetylate, O- (t-butoxy) carbonylate, etc.), styrene Maleic anhydride copolymer, styrene-hydroxystyrene copolymer, α-methylstyrene-hydroxystyrene copolymer, carboxyl group-containing metac Although a reel-type resin, its derivative (s), and a polyvinyl alcohol derivative are mentioned, It is not limited to these.

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

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

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, a weight average molecular weight is defined by the polystyrene conversion value of gel permeation chromatography.

These (D) alkali-soluble resins in this invention may be melt | dissolved 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 precursor 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 a crosslinking agent, although any compound can be used as long as it is a compound which bridge | crosslinks soluble resin to alkaline developing solution by the effect | action of an acid, the following (1)-(3) is preferable.

(1) The hydroxymethyl body, alkoxy methyl body, and acyloxy methyl body of a phenol derivative.

(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 shown below.

In formula, L <^1> -L <^8> may be same or different and shows a hydrogen atom, a hydroxymethyl group, a methoxymethyl group, an ethoxymethyl group, or a C1-C6 alkyl group.

A crosslinking agent is used in the addition amount of 3-70 mass% normally, Preferably it is 5-50 mass% in solid content of the photosensitive composition.

<Other ingredients>

[6] (F) basic compounds

It is preferable that the photosensitive composition of this invention contains the (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) is mentioned.

R ²⁵⁰ , R ²⁵¹ and R ²⁵² each independently represent a hydrogen atom, an alkyl having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, wherein R ²⁵⁰ and R ²⁵¹ are each other You may combine and form a ring. These may have a substituent and as an alkyl group and cycloalkyl group which have a substituent, a C1-C20 aminoalkyl group or a C3-C20 aminocycloalkyl group, a C1-C20 hydroxyalkyl group, or a C3-C20 hydroxycyclo Alkyl groups are preferred.

In addition, they 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 or a cycloalkyl group having 3 to 6 carbon atoms.

Preferred compounds include guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine and piperidine, and may have a substituent. As a more preferable compound, a compound having an imidazole structure, a diazabicyclo structure, an onium hydroxide structure, an onium carboxylate structure, a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine having a hydroxyl group and / or an ether bond And aniline derivatives having derivatives, hydroxyl groups and / or ether bonds.

Examples of the compound having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole, and the like. Examples of the compound having a diazabicyclo structure include 1,4-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4,3,0] nona-5-ene and 1,8-diazabi Cyclo [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-iodine alkyl group, specifically triphenylsulfonium hydroxide and tris (t -Butylphenyl) sulfonium hydroxide, bis (t-butylphenyl) iodonium hydroxide, phenacylthiophenium hydroxide, 2-iodine propylthiophenium 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, an acetate, adamantane-1-carboxylate, a perfluoroalkyl carboxylate, etc. Can be mentioned. 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. are 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. As an aniline derivative which has a hydroxyl group and / or an ether bond, N, N-bis (hydroxyethyl) aniline etc. are mentioned.

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. In order to acquire sufficient addition effect, 0.001 mass% or more is preferable, and 10 mass% or less is preferable at the point of a sensitivity or developability of a non-exposed part.

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

The photosensitive composition of the present invention further contains any one or two or more of a fluorine-based 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). desirable.

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, it is possible to impart a resist pattern with good sensitivity and resolution and less adhesion and development defects. Done.

As these fluorine and / or silicon type surfactant, For example, Unexamined-Japanese-Patent No. 62-36663, Unexamined-Japanese-Patent No. 61-226746, Unexamined-Japanese-Patent No. 61-226745, and Unexamined-Japanese-Patent No. 62- Japanese Patent Application Laid-Open No. 170950, Japanese Patent Application Laid-Open No. 63-34540, Japanese Patent Application Laid-Open No. 7-230165, Japanese Patent Application Laid-Open No. 8-62834, Japanese Patent Application Laid-Open No. 9-54432, Japanese Patent Publication No. 9- Japanese Patent Application Laid-Open No. 5988, Japanese Patent Application Laid-Open No. 2002-277862, US Patent No. 557520, US Pat. No. 5,606,923, US Pat. No.5529881, US Pat. No. 5296330, US 5436098, US Pat. The surfactant described in the specification of 5,451,451 is mentioned, and 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-Akita Kasei Co., Ltd.), Florade FC430, 431 (made by Sumitomo 3M Co., Ltd.), Megapack F171, F173, F176, F189, R08 (made by Dainippon Ink & Chemicals Co., Ltd.), saffron S-382, SC101, 102, 103, 104, 105, 106 (made by Asahi Glass Co., Ltd.), Troisol S-366 (Troy Fluorine-type surfactant, such as Chemical Co., Ltd. product, or a silicon type surfactant can be mentioned. Moreover, polysiloxane polymer KP-341 (made by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon type surfactant.

Moreover, as surfactant, it has a fluoro aliphatic group introduce | transduced from the fluoro aliphatic compound manufactured by the teromerization method (also called teromer method) or the oligomerization method (also called oligomer method) besides the well-known thing shown above. Surfactants using polymers can be used. A fluoro aliphatic compound can be synthesize | combined by the method of Unexamined-Japanese-Patent No. 2002-90991.

As the polymer having a fluoroaliphatic group, a copolymer of a monomer having a fluoroaliphatic group with (poly (oxyalkylene)) acrylate and / or (poly (oxyalkylene)) methacrylate is preferable and is irregularly distributed. Even if it exists, it may be block copolymerized. Moreover, as a poly (oxyalkylene) group, a poly (oxyethylene) group, a poly (oxypropylene) group, a poly (oxybutylene) group, etc. are mentioned, Furthermore, the block of poly (oxyethylene, oxypropylene, and oxyethylene) is mentioned. Or a unit having an alkylene of a different length in the chain such as a linker) or a poly (block linker of oxyethylene and oxypropylene). The copolymer of a monomer having a fluoro aliphatic group and a (poly (oxyalkylene)) acrylate (or methacrylate) is not only a binary copolymer but also a monomer having two or more other fluoro aliphatic groups, or another 2 It may be a ternary or higher copolymer obtained by simultaneously copolymerizing paper-like (poly (oxyalkylene)) acrylate (or methacrylate).

For example, megapack F178, F-470, F-473, F-475, F-476, F-472 (made by Dainippon Ink & Chemicals Kakuku Kogyo Co., Ltd.) is mentioned as a commercial surfactant. 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).

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] (H) organic solvents

In the resist composition of the present invention, each component is dissolved in a predetermined organic solvent and used.

As an organic solvent which can be used, for example, ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, (gamma)-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, 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 containing two or more solvents having different functional groups. As a mixed solvent which has another functional group, it is preferable to use the mixed solvent which mixed the solvent which has a hydroxyl group in the structure, the solvent which does not have a hydroxyl group, or the mixed solvent which mixed the solvent which has an ester structure, and the solvent which has a ketone structure. . Thereby, particle generation at the time of resist storage can be reduced.

Examples of the solvent having a hydroxyl group include ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethyl lactate, and the like. Glycol monomethyl ether and ethyl lactate are more preferable.

As a solvent which does not have a hydroxyl group, For example, propylene glycol monomethyl ether acetate, ethyl ethoxy propionate, 2-heptanone, (gamma)-butyrolactone, cyclohexanone, butyl acetate, N-methylpyrrolidone, N , N-dimethylacetamide, dimethyl sulfoxide, and the like, among them, propylene glycol monomethyl ether acetate, ethyl ethoxy propionate, 2-heptanone, γ-butyrolactone, cyclohexanone, butyl acetate More preferably, propylene glycol monomethyl ether acetate, ethyl ethoxy propionate, 2-heptanone, and cyclohexanone are especially preferable.

The mixing ratio (mass) of the solvent having a hydroxyl group and the solvent not having a hydroxyl group is usually 1/99 to 99/1, preferably 10/90 to 90/10, and more preferably 20/80 to 60/40. A mixed solvent containing 50% by mass or more of a solvent having no hydroxyl group is preferable in terms of coating uniformity.

In the mixed solvent which mixed the solvent which has an ester structure, and the solvent which has a ketone structure, cyclohexanone, 2-heptanone, etc. are mentioned as a solvent which has a ketone structure, Preferably, it is cyclohexanone. As a solvent which has an ester structure, propylene glycol monomethyl ether acetate, ethyl ethoxy propionate, (gamma)-butyrolactone, butyl acetate, etc. are mentioned, Preferably it is propylene glycol monomethyl ether acetate.

The mixing ratio (mass) of the solvent having an ester structure and the solvent having a ketone structure is usually 1/99 to 99/1, preferably 10/90 to 90/10, and more preferably 20/80 to 60/40. A mixed solvent containing 50% by mass or more of a solvent having an ester structure is particularly preferable in terms of coating uniformity.

<Other additives>

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

The dissolution promoting compound for the developer which can be used 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. In the case of having a carboxyl group, an alicyclic or aliphatic compound is preferable.

The preferable addition amount of these dissolution accelerating 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 suppressing image development residue, and preventing pattern distortion at the time of image development.

Such phenol compounds having a molecular weight of 1000 or less are described in the art, for example, with reference to the methods described in JP-A 4-122938, JP-A 2-28531, US Pat. No. 4,162,10, European Patent No. 219294, and the like. Can be easily 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, nonionics such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylene polyoxypropylene block copolymers, sorbitan aliphatic esters, and polyoxyethylene sorbitan aliphatic esters Surfactant is mentioned.

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

(Pattern Forming Method)

The photosensitive composition of this invention is melt | dissolving said component in a predetermined organic solvent, Preferably the said mixed solvent, apply | coats and uses it on a predetermined | prescribed support body as follows.

For example, the photosensitive composition is applied and dried by a suitable coating method such as a spinner or a coater on a substrate (eg, silicon / silicon dioxide coating) used in the manufacture of precision integrated circuit devices to form a photosensitive film.

The photosensitive film is irradiated with actinic light or radiation through a predetermined mask, and preferably developed by baking (heating). Thereby, a favorable pattern can be obtained.

At the time of irradiation of actinic light or a radiation, you may perform exposure (liquid immersion exposure) by filling the liquid with refractive index higher than air between a photosensitive film | membrane and a lens. Thereby, resolution can be improved.

Examples of the active light or radiation include infrared light, visible light, ultraviolet light, far-ultraviolet light, X-rays, electron beams, and the like, but 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, and an ArF excimer laser, an F ₂ excimer laser, an EUV (13 nm), and an electron beam are preferable.

In the developing step, an alkaline developer is used as follows. As the alkaline 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 alkali 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 this.

Synthesis Example 1 (Synthesis of Compound (A1-1))

7.8 g of triphenylsulfonium iodine was dissolved in 100 ml of acetonitrile / 50 ml of water, and 3.5 g of silver acetate was added thereto. The mixture was stirred at room temperature for 30 minutes, and the precipitated silver iodide was removed by filtration. 5.0 g of pentafluoroethanesulfonic acid potassium was dissolved in water and added to the filtrate. This was extracted with chloroform, and the organic layer was washed sequentially with water, aqueous ammonium chloride solution and water. 8.6g of compounds (A1-1) were obtained when the organic layer was filtered and concentrated with a 0.1 micron tetrafluoroethylene filter.

Synthesis Example 2 (Synthesis of Compound (A2-1))

3.8 g of triphenylsulfonium iodine was dissolved in 100 ml of acetonitrile / 50 ml of water, and 1.8 g of silver acetate was added thereto. The mixture was stirred at room temperature for 30 minutes, and the precipitated silver iodide was removed by filtration. 3.0 g of potassium perfluoropropanesulfonic acid was dissolved in water / acetonitrile and added to the filtrate. The reaction solution was concentrated, and ethyl acetate was added thereto. This was washed sequentially with water, aqueous ammonium chloride solution and water, and the organic layer was filtered and concentrated with a 0.1 micron tetrafluoroethylene filter to obtain 3.5 g of compound (A2-1).

Other acid generators were synthesized in the same way.

<Resin (B)>

The structure, molecular weight, and dispersion degree of resin (B) used for the Example are shown.

Examples 1-20 and Comparative Examples 1-2

<Resist preparation>

The component shown in following Table 1 was melt | dissolved in the solvent, the solution of 10 mass% of solid content concentration was prepared, this was filtered with the 0.1 micrometer polytetrafluoroethylene filter or polyethylene filter, and the positive resist solution was prepared. The prepared positive resist solution was evaluated by the following method, and the results are also shown in Table 1.

(Table 1)

Hereinafter, the symbol in a table | surface is shown.

[Basic Compound]

TPI: 2,4,5-triphenylimidazole

TPSA: triphenylsulfonium acetate

HEP: N-hydroxyethylpiperidine

DIA: 2,6-diisopropylaniline

DCMA: dicyclohexylmethylamine

TPA: Tripentylamine

HAP: hydroxyantipyrine

TBAH: tetrabutylammonium hydroxide

TMEA: tris (methoxyethoxyethyl) amine

PEA: N-phenyldiethanolamine

〔Surfactants〕

W-1: Mega pack F176 (product made in Dainippon Ink & Chemicals Kakuku Kogyo Co., Ltd.) (fluorine system)

W-2: Mega pack R08 (made by Dainippon Ink & Chemicals KK) (fluorine and silicon system)

W-3: Polysiloxane polymer KP-341 (made by Shin-Etsukagaku Kogyo Co., Ltd.) (silicone system)

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

〔solvent〕

S1: propylene glycol methyl ether acetate

S2: 2-heptanone

S3: cyclohexanone

S4: γ-butylolactone

S5: Propylene Glycol Methyl Ether

S6: ethyl lactate

[Dissolution Blocking Compound]

LCB: Litocholic acid-t-butyl

Resist Evaluation

The anti-reflective film DUV-42 made by Brewer Science Co., Ltd. was uniformly coated on a silicon substrate subjected to hexamethyldisilazane treatment with a spin coater at 600 Hz, dried on a hot plate at 100 ° C. for 90 seconds, and then heated and dried at 190 ° C. for 240 seconds. Done. Thereafter, each positive resist solution was applied with a spin coater and dried at 120 ° C. for 90 seconds to form a resist film of 0.20 μm.

This resist film was exposed through a mask with an ArF excimer laser stepper (NA = 0.75 manufactured by ASML), and heated immediately on the hot plate at 120 ° C. for 90 seconds. Furthermore, it developed for 60 second at 23 degreeC with 2.38 mass% tetramethylammonium hydroxide aqueous solution, rinsed with pure water for 30 second, and dried, and obtained the line pattern.

Exposure Latitude:

The post-heating is performed immediately after the exposure, and the exposure dose for reproducing the mask pattern of the line-and-space with a line width of 80 nm is used as the optimum exposure dose. When the exposure dose is changed, the exposure dose width allowing the pattern size to allow 80 nm ± 10% is obtained. The exposure latitude was expressed as a percentage by dividing by the optimum exposure dose. Next, after exposure in an environment of ammonia concentration of 5 ppb for 1 hour from the exposure, heating was performed to calculate an exposure latitude after time.

The larger the value of the exposure latitude, the smaller the performance change caused by the change in the exposure dose, and the better the exposure latitude. Moreover, exposure latitude stability with or without time was computed according to the following formula. The smaller the value, the smaller the change in exposure latitude with time and the better the stability.

Exposure latitude stability = (exposure latitude (%) when post-heating immediately after exposure)-(exposure latitude (%) when post-heating after 1 hour of exposure)

From Table 1, it can be seen that the photosensitive composition of the present invention has a good exposure latitude, and a small change in the exposure latitude over time from exposure to post-heating.

[Immersion exposure evaluation]

<Resist preparation>

The components of Examples 1-20 shown in Table 1 were melt | dissolved in the solvent, the solution of 8 mass% of solid content concentration was prepared, This was filtered by the 0.1 micrometer polyethylene filter, and the positive resist solution was prepared. The prepared positive resist solution was evaluated by the following method.

<Resolution evaluation>

An organic antireflection film ARC29A (manufactured by Nissan Kagaku Co., Ltd.) was applied onto the silicon wafer, and baked at 205 ° C. for 60 seconds to form an antireflection film of 78 nm. The resist composition prepared thereon was apply | coated, and it baked at 120 degreeC for 60 second, and formed the 150 nm resist film. The wafer thus obtained was subjected to two-beam interference exposure using pure water as the liquid immersion liquid (wet exposure). In the two-beam interference exposure (wet), as shown in Fig. 1, the laser 1, the aperture 2, the shutter 3, the three reflection mirrors 4, 5, 6 and the condenser lens 7 The wafer 10 was exposed to a wafer 10 having an antireflection film and a resist film through the prism 8 and the immersion liquid (pure water) 9. The wavelength of the laser 1 was 193 nm, and the prism which forms the line-and-space pattern 8 of 65 nm was used. Immediately after exposure, the sample was heated at 120 ° C. for 60 seconds, developed for 60 seconds with an aqueous tetramethylammonium hydroxide solution (2.38%), rinsed with pure water, and spin-dried to a resist pattern obtained by scanning electron microscope (Hitachi Chemical Co., Ltd.). S-9260) observed the resolution of the line-and-space pattern of 65 nm.

The compositions of Examples 1 to 20 had good image forming ability also in the exposure method through the immersion liquid.

Examples 21-25 and Comparative Examples 3-4

(1) Formation of lower layer resist layer

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

This was further 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 following Table 2 was melt | dissolved in the 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 resist composition.

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

Table 2

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

(3) resist evaluation

The wafer thus obtained was exposed through a mask with an ArF excimer analyzer stepper (NA = 0.75 manufactured by ASML) and heated on a hot plate at 120 ° C. for 90 seconds immediately after the exposure. Furthermore, it developed in the 2.38 mass% tetramethylammonium hydroxide aqueous solution at 23 degreeC for 60 second, rinsed with pure water for 30 second, dried, and formed the line pattern, and it evaluated like Example 1.

The evaluation results are shown in Table 2.

The results in Table 2 show that even when the photosensitive composition of the present invention is used as a two-layer resist, the exposure latitude is good, and the change in the exposure latitude from time to exposure to post heating is small.

Examples 26-30 and Comparative Examples 5-6

<Resist preparation>

The component shown in following Table 3 was melt | dissolved in the solvent, this was filtered with the 0.1 micrometer polytetrafluoroethylene filter, the positive resist solution of 14 mass% of solid content concentration was prepared, and it evaluated as follows.

Table 3

The weight average molecular weight and dispersion degree of resin (R-1)-(R-5) used in Table 3 are shown in following Table 4.

Table 4

Resist Evaluation

The prepared positive resist solution was uniformly coated on a hexamethyldisilazane treated silicon substrate using a spin coater, and heated and dried on a hot plate at 120 ° C. for 90 seconds to form a 0.4 μm resist film.

This resist film was subjected to pattern exposure using a line-and-space mask using KrF excimer laser stepper (NA = 0.63), and heated on a hot plate at 110 ° C. for 90 seconds immediately after exposure. Furthermore, it developed at 23 degreeC for 60 second with 2.38 mass% tetramethylammonium hydroxide aqueous solution, rinsed with pure water for 30 second, and dried, and formed the line pattern.

Except for making the line width 130nm, similarly to Example 1, exposure latitude and exposure latitude stability were evaluated.

The evaluation results are shown in Table 3.

The results in Table 3 show that the photosensitive composition of the present invention has a good exposure latitude as a positive resist composition in KrF excimer laser exposure, and has a small change in the exposure latitude from time to exposure to post-heating. Can be.

Examples 31 to 35 and Comparative Examples 7 to 8

<Resist preparation>

The component shown in the said Table 3 was melt | dissolved in the solvent, it filtered with the 0.1 micrometer polytetrafluoroethylene filter, the positive resist solution of 11 mass% of solid content concentration was prepared, and it evaluated as follows.

Resist Evaluation

The prepared positive resist solution was uniformly coated on a hexamethyldisilazane-treated silicon substrate using a spin coater, and heated and dried on a hot plate at 120 ° C. for 60 seconds to form a 0.25 탆 resist film.

This resist film was pattern-irradiated with the electron beam drawing device (acceleration voltage 50 keV), and it heated immediately on 110 degreeC for 90 second on the hotplate after irradiation. Furthermore, it developed at 23 degreeC for 60 second using the tetramethylammonium hydroxide aqueous solution of 2.38 mass% of concentration, and rinsed with pure water for 30 second, and dried, and formed the line and space pattern.

The exposure latitude and exposure latitude stability were evaluated in the same manner as in Example 1 except that the line width was 120 nm.

The evaluation results are shown in Table 5 below.

Table 5

From Table 5, it can be seen that the photosensitive composition of the present invention exhibits good exposure latitude even as a positive resist composition in electron beam exposure, and shows a small change in exposure latitude from time to exposure and post-heating.

Examples 36-40 and Comparative Examples 9-10

The component shown in the said Table 3 was dissolved in a solvent, this was filtered with the 0.1 micrometer polytetrafluoroethylene filter, the positive resist solution of 8 mass% of solid content concentration was prepared, and it evaluated as follows.

Resist Evaluation

The prepared positive resist solution was uniformly coated on a hexamethyldisilazane-treated silicon substrate using a spin coater, and heated and dried on a hot plate at 120 ° C. for 60 seconds to form a resist film of 0.15 μm. Using the EUV light (wavelength 13 nm) for the obtained resist film, surface exposure was performed in 0.5 mJ increments in the range of 0-10.0 mJ, and it baked at 110 degreeC for 90 second. Then, the dissolution rate in each exposure amount was measured using 2.38% tetramethylammonium hydrooxide (TMAH) aqueous solution, and the sensitivity curve was obtained. In this sensitivity curve, the exposure dose when the dissolution rate of the resist was saturated was regarded as sensitivity, and the melt contrast (γ value) was calculated from the gradient of the linear portion of the sensitivity curve. The larger the γ value, the better the dissolution contrast.

The evaluation results are shown in Table 6 below.

Table 6

From the results in Table 6, it can be seen that the resist composition of the present invention has a higher sensitivity, a higher contrast, and is superior to the composition of the comparative example in the characteristic evaluation by irradiation of EUV light.

Examples 41 to 45 and Comparative Examples 11 to 12

The components shown in Table 7 were dissolved in a solvent, filtered through a 0.1 µm polytetrafluoroethylene filter to prepare a negative resist solution with a solid content concentration of 11% by mass, and evaluated as follows.

Table 7

Below, the structure, molecular weight, molecular weight distribution, and crosslinking agent of alkali-soluble resin in Table 7 are shown.

Resist Evaluation

The prepared negative resist solution was uniformly coated on a hexamethyldisilazane-treated silicon substrate using a spin coater, and heated and dried on a hot plate at 120 ° C. for 60 seconds to form a 0.25 탆 resist film.

This resist film was pattern-irradiated with the electron beam drawing device (acceleration voltage 50 keV), and it heated on the hotplate at 110 degreeC for 90 second immediately after irradiation. Furthermore, it developed for 60 second at 23 degreeC using the aqueous tetramethylammonium hydroxide solution of 2.38 mass% of concentration, and rinsed with pure water for 30 second, and dried, and formed the line and space pattern.

As in Example 31, the exposure latitude and the exposure latitude stability were evaluated.

The evaluation results are shown in Table 7.

Table 7 shows that the photosensitive composition of the present invention has a good exposure latitude even as a negative resist composition in electron beam exposure, and has a small change in exposure latitude from time to exposure to post-heating.

Examples 46-50 and Comparative Examples 13-14

<Resist preparation>

The component shown in the said Table 7 was melt | dissolved in the solvent, this was filtered with the 0.1 micrometer polytetrafluoroethylene filter, the negative resist solution of 8 mass% of solid content concentration was prepared, and it evaluated as follows.

Resist Evaluation

The prepared positive resist solution was uniformly coated on a hexamethyldisilazane treated silicon substrate using a spin coater, and heated and dried on a hot plate at 120 ° C. for 60 seconds to form a resist film of 0.15 μm. Surface exposure was performed using EUV light (wavelength 13 nm) for the obtained resist film, changing exposure amount by 0.5 mJ in the range of 0-10.0 mJ, and baking 110 degreeC and 90 second. Then, the dissolution rate in each exposure amount was measured using 2.38% tetramethylammonium hydrooxide (TMAH) aqueous solution, and the sensitivity curve was obtained. In this sensitivity curve, the exposure amount when the residual film ratio in the developing time of 60 seconds became 98% or more was regarded as sensitivity, and the melt contrast (γ value) was calculated from the gradient of the linear portion of the sensitivity curve. The larger the γ value, the better the dissolution contrast.

The evaluation results are shown in Table 8 below.

Table 8

The results of Table 8 show that the resist composition of the present invention has high sensitivity, high contrast, and excellent characteristics in the evaluation of characteristics by irradiation of EUV light.

INDUSTRIAL APPLICABILITY The present invention provides a photosensitive composition and a photosensitive composition in which the exposure latitude is improved, the change in exposure latitude from time to time after exposure is reduced, and the sensitivity and dissolution contrast during EUV exposure are improved. The pattern formation method used can be provided.

Claims (12)

(A1) a compound which generates pentafluoroethanesulfonic acid or perfluoropropanesulfonic acid by irradiation with actinic light or radiation; And (A2) Photosensitive composition containing the compound which generate | occur | produces the acid represented by either of following general formula (I)-(III) by irradiation of actinic light or a radiation.

[In general formula (I)-(III), Rb ₁ represents an electron withdrawing group. Rb ₂ represents a hydrogen atom or an organic group. m represents the integer of 0-5, n represents the integer of 0-5. However, m + n = 5. Rb _{3 to} Rb ₅ each independently represent an organic group. Rb ₃ and Rb ₄ may be bonded to each other to form a ring.] The method of claim 1, The compound of the component (A1) is at least one compound selected from a sulfonium salt compound or an iodonium salt compound of pentafluoroethanesulfonic acid or perfluoropropanesulfonic acid and an ester compound of pentafluoroethanesulfonic acid or perfluoropropanesulfonic acid Photosensitive composition, characterized in that. The method according to claim 1 or 2, The compound of the said (A1) component is a compound represented by the following general formula (A1a), The photosensitive composition characterized by the above-mentioned.

[In the general formula (A1a), R _201a , R _202a and R _203a each independently represent an organic group. Two of R _201a to R _203a may be bonded to each other to form a ring structure. Xa ^- represents a sulfonic acid anion in which the hydrogen atom of -SO ₃ H of pentafluoroethanesulfonic acid or perfluoropropanesulfonic acid is depleted.] The method of claim 3, wherein The compound of the said (A1) component is a compound in which two of R <_201a> -R <_203a> in the said General formula (A1a) couple | bonds, and forms the alkylene group. The photosensitive composition characterized by the above-mentioned. The method according to claim 1 or 2, (B) It further contains resin which decomposes | dissolves by the action of an acid, and the solubility in alkaline developing solution increases, and is positive type, The photosensitive composition characterized by the above-mentioned. The method of claim 5, Resin (B) which is decomposed by the action of the acid, and the solubility in the alkaline developer is increased, has a repeating unit having a monocyclic or polycyclic cyclic hydrocarbon structure. The photosensitive composition as claimed in claim 5, wherein the resin (B) decomposed by the action of the acid and having increased solubility in an alkaline developer is a resin having a repeating unit having a lactone structure. The method of claim 7, wherein The repeating unit having the lactone structure is a repeating unit represented by the following general formula (AI).

[In Formula (AI), Rb ₀ represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. Ab represents a divalent linking group having an alkylene group, a monocyclic or polycyclic alicyclic hydrocarbon structure, a single bond, an ether group, an ester group, a carbonyl group, a carboxyl group, or a divalent group combining these. V represents a group represented by any one of General Formulas (LC1-1) to (LC1-16).

In formula (LC1-1)-(LC1-16), Rb ₂ includes an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, a carboxyl group, a halogen atom, a hydroxyl group, a cyano group, or an acid-decomposable group. have. n ₂ represents an integer of 0 to 4. When n ₂ is 2 or more, a plurality of Rb _{2 's} may be the same or different, and a plurality of Rb _{2' s} may be bonded to each other to form a ring.] The photosensitive composition as claimed in claim 5, wherein the resin (B) decomposed by the action of the acid and having increased solubility in an alkaline developer is a resin having a repeating unit represented by the following general formula (AIIa).

[In general formula (AIIa), R ₁ c represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group. R ₂ c to R ₄ c each independently represent a hydrogen atom, a hydroxyl group or a cyano group. Provided that at least one of R ₂ c to R ₄ c represents a hydroxyl group or a cyano group.] The method of claim 5, Resin (B) which decomposes | dissolves by the action of the said acid, and the solubility in alkaline developing solution increases has a hydroxy styrene structural unit, The photosensitive composition characterized by the above-mentioned. The method according to claim 1 or 2, (D) The photosensitive composition which further contains an acid crosslinking agent which bridge | crosslinks with the soluble resin in the said alkaline developing solution by action of the resin which is soluble in an alkaline developing solution, and (E) acid. A pattern forming method comprising the step of forming a photosensitive film with the photosensitive composition according to claim 1 or 2, and exposing and developing the photosensitive film.

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