KR101064548B1 - Stimulus-sensitive composition and pattern formation method using the stimulus-sensitive composition - Google Patents

Abstract

Potential polar composition with low PEB temperature dependence, improved contact hole resolution and profile, and pattern formation method using the same, and low PEB temperature dependence in the exposure wavelength of 200 nm or less, especially F ₂ laser light (157 nm). In order to provide a resolving power, an improved potato polar composition having a profile and a pattern forming method using the same, and also a composition thereof, a new compound (A) which generates an acid or a radical by stimulation from the outside is provided.

Potato-polar composition containing the compound (A) of the specific structure which generate | occur | produces an acid or a radical by stimulation from the outside, the pattern formation method using the same, and the compound (A) of a specific structure.

Description

Pattern formation method using a potato polar composition and a potato polar composition {STIMULUS-SENSITIVE COMPOSITION AND PATTERN FORMATION METHOD USING THE STIMULUS-SENSITIVE COMPOSITION}

Disclosure of Invention The present invention provides a potato polar composition for use in a semiconductor manufacturing process such as an IC, a circuit board such as a liquid crystal, a thermal head, other photo publication processes, a flat printing plate, an acid curable composition, a radical curable composition, and the like. It relates to a pattern forming method using the compound and the compound used in the potato polar composition.

The cationic polar composition is a composition which generates an acid or a radical by stimulation from the outside and changes the physical properties of the site to which the stimulus is imparted by the reaction. More preferably, the irradiating portion and the non-irradiating portion of actinic radiation, radiation or heat It is a pattern formation material which changes solubility to a developing solution and forms a pattern on a board | substrate.

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

For example, Patent Document 1 (Japanese Patent Laid-Open No. 2000-292917) describes a resist composition using a mixture of a triarylsulfonium salt and a phenacylsulfonium salt, and Patent Document 2 (Japanese Patent Laid-Open No. 2001-294570) discloses a ring composition. A resist composition containing a phenacylsulfonium salt having a structure is described, and Patent Document 3 (Japanese Patent Laid-Open No. 2003-114522) describes a resist composition containing a phenacylsulfonium salt having a chain structure.

However, in the conventional resist composition, when it is used for a wafer with a large diameter, it is known that the variation in temperature in heating (PEB) by a hot plate or the like after the exposure affects the obtained pattern, and such PEB temperature dependence is known. There is a demand for improvement.

In addition, in the conventional resist composition, new improvements are required for the resolution and profile of contact holes.

[Patent Document 1] Japanese Patent Application Laid-Open No. 2000-292917

[Patent Document 2] Japanese Patent Application Laid-Open No. 2001-294570

[Patent Document 3] Japanese Patent Publication No. 2003-114522

Accordingly, an object of the present invention is a potato-polar composition having a low PEB temperature dependency, an improved contact hole resolution, and a profile at an exposure wavelength of 200 nm or less, especially an ArF excimer laser light (193 nm) or an F ₂ excimer laser light (157 nm). In order to provide the pattern formation method using the potato polar composition, and the said potato polar composition, it is providing the new compound which generate | occur | produces an acid or a radical by stimulation from the outside.

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

(1) A potato polar composition comprising a compound represented by the following general formula (I) which generates an acid or a radical by stimulation from the outside.

In general formula (I),

Ar represents an aryl group.

R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group. R ₁ and R ₂ may be bonded to each other to form a ring.

Y ₁ and Y ₂ each independently represent an alkyl group, a cycloalkyl group, or an aryl group. Y ₁ and Y ₂ may be bonded to each other to form a ring.

n represents the integer of 1-3.

X <^-> represents a non-nucleophilic anion.

(2) A compound represented by the following general formula (I).

In general formula (I),

Ar represents an aryl group.

R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group. R ₁ and R ₂ may be bonded to each other to form a ring.

Y ₁ and Y ₂ each independently represent an alkyl group, a cycloalkyl group, or an aryl group. Y ₁ and Y ₂ may be bonded to each other to form a ring.

n represents the integer of 1-3.

X <^-> represents a non-nucleophilic anion.

(3) A pattern forming method comprising the step of forming a resist film by using the potato polar composition as described in (1) and exposing and developing the resist film.

Hereinafter, preferred embodiment of this invention is further illustrated.

(4) (A) the compound represented by the said general formula (I) which generate | occur | produces an acid by irradiation of actinic light or a radiation, and

(B) A positive type potato polar composition comprising a resin that is decomposed by the action of an acid and has increased solubility in an alkaline developer.

(5) The positive cationic polar composition according to the above (4), wherein the resin which is decomposed by the action of (B) acid and the solubility in the alkaline developing solution increases has a fluorine atom in the main chain or in the side chain.                     

(6) The positive potato polar composition according to the above (5), wherein the resin which is decomposed by the action of (B) acid and the solubility in the alkaline developer is increased has a hexafluoroisopropanol structure.

(7) The positive cationic polar composition according to (4), wherein the resin which is decomposed by the action of (B) acid to increase the solubility in the alkaline developer has a hydroxystyrene structural unit.

(8) The positive cationic polar composition according to the above (4), wherein the resin which is decomposed by the action of (B) acid to increase the solubility in the alkaline developer has a monocyclic or polycyclic alicyclic hydrocarbon structure.

(9) The positive cationic polar composition according to the above (8), wherein the resin which is decomposed by the action of (B) acid to increase the solubility in the alkaline developer further has a repeating unit having a lactone structure.

(10) In addition, in any one of said (4)-(9) characterized by containing the dissolution inhibiting compound of molecular weight 3000 or less which is decomposed by the action of (C) acid and the solubility in alkaline developing solution is increased. The positive cationic polar composition described.

(11) (A) the compound represented by the said general formula (I) which generate | occur | produces an acid by irradiation of actinic light or a radiation,

(D) resins soluble in alkaline developer and

(C) A positive sensory composition comprising a dissolution inhibiting compound having a molecular weight of 3000 or less, which is decomposed by the action of an acid to increase the solubility in an alkaline developer.

(12) (A) the compound represented by the said general formula (I) which generate | occur | produces an acid by irradiation of actinic light or a radiation,

(D) resins soluble in alkaline developer and

(E) The negative potato polar composition containing the acid crosslinking agent which bridge | crosslinks with soluble resin in the said alkaline developing solution by action of an acid.

(13) Moreover, the potato polar composition as described in any one of (1), (4)-(12) containing (F) basic compound and / or (G) fluorine and / or silicone type surfactant.

(14) A compound having a structure in which the (F) basic compound has a structure selected from an imidazole structure, a diazabicyclo structure, an onium hydroxide structure, an onium carboxylate structure, a trialkylamine structure, an aniline structure and a pyridine structure, a hydroxyl group and And / or an alkylamine derivative having an ether bond or an aniline derivative having a hydroxyl group and / or an ether bond.

Hereinafter, the present invention will be described in detail.

In addition, in description of group (atom group) in this specification, the description which is not based on substitution and unsubstitution includes what has a substituent as well as not having 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 potato polar composition of this invention contains the compound (henceforth a "compound (A)") represented by the said General formula (I) which generate | occur | produces an acid or a radical by the stimulus from the exterior.

As a potato polar composition of this invention, Preferably, a photosensitive or thermosensitive composition is mentioned, More specifically, a positive or negative photosensitive or thermosensitive composition is mentioned.

The positive photosensitive or thermosensitive composition of the present invention, more preferably the positive resist composition, is decomposed by the action of the compound (A) and acid generating an acid by irradiation of actinic light or radiation and solubility in an alkaline developer. Contains a dissolution inhibiting compound (C) having a molecular weight of 3,000 or less, which contains a resin (B) which increases, and decomposes by the action of an acid, if necessary, and increases in solubility in an alkaline developer, or actinic radiation or radiation The dissolution inhibiting compound (C) having a molecular weight of 3000 or less, which is decomposed by the action of the compound (A) which generates an acid by irradiation of the resin, the resin (D) and acid which are soluble in an alkaline developer, and the solubility in an alkaline developer is increased. It contains.

The negative photosensitive or thermosensitive composition of the present invention, more preferably, the negative resist composition is composed of a compound (A) that generates an acid by irradiation of actinic light or radiation, a resin (D) soluble in an alkaline developer, and an acid. An acid crosslinking agent (E) which crosslinks with the soluble resin is contained in the alkaline developer by the action.

[1] (A) A compound represented by the above general formula (I), which generates an acid or a radical by stimulation from the outside

Compounds that generate acids or radicals by stimulation from the outside are acid or stimulation from the outside such as active light such as infrared light, visible light, ultraviolet light, far-ultraviolet light, X-rays, electron beams, radiation, heat, ultrasonic waves, etc. It is a compound that generates radicals.

In this invention, the compound represented by the said general formula (I) is used as a compound which generate | occur | produces an acid or a radical by the stimulus from the exterior.

In general formula (I),

Ar represents an aryl group.

R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group. R ₁ and R ₂ may be bonded to each other to form a ring.

Y ₁ and Y ₂ each independently represent an alkyl group, a cycloalkyl group, or an aryl group. Y ₁ and Y ₂ may be bonded to each other to form a ring.

n represents the integer of 1-3.

X <^-> represents a non-nucleophilic anion.

In general formula (I), the aryl group of Ar has a C6-C14 aryl group, for example, a phenyl group, a naphthyl group, an anthryl group, etc. are mentioned.

The aryl group of Ar includes the thing which does not have a substituent other than a hydroxyl group, and the thing which has a substituent other than a hydroxyl group. As a substituent which the aryl group of Ar may have other than a hydroxyl group, it is an alkyl group (preferably C1-C12 linear, branched alkyl group), a cycloalkyl group (preferably a C3-C12 cycloalkyl group), alkoxy Group (preferably C1-C12), acyl group (preferably C2-C12), aryl group (preferably C6-C14), acyloxy group (preferably C2-C12), alkoxycarbonyl group (Preferably C2-C12), nitro group, cyano group, halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom) etc. are mentioned. These substituents may further be substituted.

The alkyl group as R ₁ , R ₂ , Y ₁ and Y ₂ is preferably an alkyl group having 1 to 20 carbon atoms, for example, a methyl group, an ethyl group, a straight or branched propyl group, a straight or branched butyl group, a straight or branched pentyl group Etc. can be mentioned. The alkyl group as R ₁ , R ₂ , Y ₁ and Y ₂ may have an ether linking group.

The cycloalkyl group as R ₁ , R ₂ , Y ₁ and Y ₂ is preferably a cycloalkyl group having 3 to 20 carbon atoms, and examples thereof include cyclopentyl group, cyclohexyl group, norbornyl group, adamantyl group, and the like. have. The cycloalkyl group as R ₁ , R ₂ , Y ₁ and Y ₂ may have an ether linking group.

The aryl group as R ₁ , R ₂ , Y ₁ and Y ₂ is preferably an aryl group having 6 to 20 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, an anthryl group, and the like, and a phenyl group and a naphthyl group are more preferable. Do.

R ₁ and R ₂ may be bonded to each other to form a ring.

Y ₁ and Y ₂ may be bonded to each other to form a ring together with S ⁺ in General Formula (I).

As a group which R <_1> and R <_2> , Y <_1> and Y <_2> combine and form, it is a C2-C10 alkylene group, Preferably butylene group, a pentylene group, a hexylene group, Especially preferably, butylene group, A pentylene group is mentioned. In addition, the formed ring may contain a double bond and a hetero atom.

Each such R _1, R _2, Y ₁ and Y ₂ of the aryl group, an alkyl group, a cycloalkyl group, R ₁ and R _2, Y ₁ and Y cyclic structure ₂ is bonded to formation, it may not necessarily have a substituent, You may have a substituent. As the substituent, for example, a nitro group, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), hydroxyl group, amino group, cyano group, alkoxy group (preferably 1 to 20 carbon atoms), aryl group (preferably And C6-C20, an acyl group (preferably C2-C20), an alkoxycarbonyloxy group (preferably C2-C20), etc. are mentioned. About the aryl group and ring structure which each group has, an alkyl group (preferably C1-C20) and a cycloalkyl group (preferably C3-C20) are mentioned as a substituent.

Compound represented by the general formula _{(I), R 1, R 2, Y} 1 and Y ₂ at least one of, and preferably a group of the carbon number of _{2~20, R 1, R 2,} Y 1 and Y ₂ at least one of It is more preferable that the dog is a group having ₄ to 20 carbon atoms, and it is particularly preferable that Y ₁ and Y ₂ are a group having ₄ to 20 carbon atoms. The compound represented by general formula (I) has a hydroxyl group on the aryl group of Ar, and also has a C2-C20 group in at least 1 of R <_1> , R <_2> , Y <_1> and Y <_2> , and makes contact hole resist When used for, the profile is good, and the resolution is improved.

Examples of the non-nucleophilic anion as X ⁻ include a sulfonic acid anion, a carboxylic acid anion, a sulfonimide anion, a bis (alkylsulfonyl) imide anion, and a tris (alkylsulfonyl) methyl anion.

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

As a sulfonic acid anion, an alkyl sulfonic acid anion, a cycloalkyl sulfonic acid anion, an aryl sulfonic acid anion, a camphor sulfonic acid anion, etc. are mentioned, for example.

As a carboxylic acid anion, an alkyl carboxylic acid anion, a cycloalkyl carboxylic acid anion, an aryl carboxylic acid anion, an aralkyl carboxylic acid anion, etc. are mentioned, for example.

As the alkyl group in the alkyl sulfonic acid anion, preferably an alkyl group having 1 to 30 carbon atoms, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, pentyl group , Neopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, Nonadecyl, eicosyl, etc. are mentioned.

As a cycloalkyl group in a cycloalkyl sulfonic acid anion, Preferably it is a cycloalkyl group of 3-30 carbon atoms, for example, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a norbornyl group, a boronyl group, etc. Can be mentioned.

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

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

As such a substituent, a nitro group, a halogen atom (fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a carboxyl group, a hydroxyl group, an amino group, a cyano group, an alkoxy group (preferably C1-C5), an aryl group (Preferably C6-C14), alkoxycarbonyl group (preferably C2-C7), acyl group (preferably C2-C12), alkoxycarbonyloxy group (preferably C2-C7), etc. Can be mentioned. About the aryl group and ring structure which each group has, an alkyl group (preferably C1-C15) and a cycloalkyl group (preferably C3-C15) are mentioned as a substituent.

Examples of the alkyl group in the alkyl carboxylic acid anion include the same groups as the alkyl group in the alkyl sulfonic acid anion.

As a cycloalkyl group in a cycloalkyl carboxylic acid anion, the same thing as the cycloalkyl group in a cycloalkyl sulfonic acid anion is mentioned.

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

As an aralkyl group in an aralkyl carboxylic acid anion, Preferably, a C6-C12 aralkyl group, for example, a benzyl group, a phenethyl group, a naphthyl methyl group, a naphthyl ethyl group, etc. are mentioned.

The alkyl group, cycloalkyl group, aryl group and aralkyl group in the alkylcarboxylic acid anion, cycloalkylcarboxylic acid anion, arylcarboxylic acid anion and aralkylcarboxylic acid anion may have a substituent, and examples of the substituent include For example, the halogen atom, alkyl group, alkoxy group, alkylthio group, etc. which are the same as an aryl sulfonic acid anion are mentioned.

As a sulfonylimide anion, saccharin anion is mentioned, for example.

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

As another non-nucleophilic anion, phosphorus fluoride, a boron fluoride, antimony fluoride etc. are mentioned, for example.

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

Compound (A) of the present invention has a high photo acid generating ability with respect to light of 200 nm or less, especially ArF excimer laser light (193 nm) and F ₂ excimer laser light (157 nm), and the photosensitive composition using the same has a PEB temperature dependency. low.

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

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

Compound (A) is obtained by reacting a corresponding 2-halogen-substituted ketone and a sulfide compound in the presence of a non-catalyst or a silver catalyst, synthesizing a sulfonium skeleton, and salt-exchanging it with a corresponding anion. As another synthesis method, a sulfonium skeleton is synthesized by reacting a corresponding ketone derivative with trialkylsilylhalogenide under basic conditions and silylenol ether, and reacting it with sulfoxide to salt exchange with a corresponding anion. It is obtained by doing.

As for content in the potato polar composition of this invention of compound (A), 0.1-20 mass% is preferable based on solid content of a composition, More preferably, it is 1.0-15 mass%, More preferably, it is 3.0-10. Mass%.

(Combination acid generator)                     

In the present invention, in addition to the compound (A), a compound which decomposes upon irradiation with actinic light or radiation and generates an acid may be used in combination.

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

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

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

Moreover, the compound which introduce | transduced the group or compound which generate | occur | produces an acid by the irradiation of these actinic rays or radiation, for example, US patent 3,849,137, German patent 3914407, Japanese patent publication 63-26653, Japanese Patent Publication No. 55-164824, Japanese Patent Publication No. 62-69263, Japanese Patent Publication No. 63-146038, Japanese Patent Publication No. 63-163452, Japanese Patent Publication No. 62-153853, The compound described in Unexamined-Japanese-Patent No. 63-146029 etc. can be used.

In addition, compounds which generate an acid by light described in US Pat. No. 3,779,778, European Patent No. 126,712 or the like can also be used.                     

As a preferable compound among the compounds which decompose by irradiation of actinic light or radiation which may be used together, and generate | occur | produces an acid, the compound represented by the following general formula (ZI), (ZII), (ZIII) is mentioned.

In the general formula (ZI), R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represent an organic group.

X <^-> represents a non-nucleophilic anion and the same thing as the non-nucleophilic anion of X <^-> in General formula (I) is mentioned.

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

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

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

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

Moreover, the compound which has two or more structures represented by general formula (ZI) may be sufficient. For example, at least one of R ₂₀₁ to R ₂₀₃ of the compound represented by the general formula (ZI) may be a compound having a structure in which at least one of R ₂₀₁ to R ₂₀₃ of another compound represented by the general formula (ZI) is bonded. good.

Moreover, as a preferable (ZI) component, the compound (Z1-1), (Z1-2), and (Z1-3) demonstrated below are mentioned.

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

Arylsulfonium compound, all of R ₂₀₁ ~R ₂₀₃ may be an aryl group, the R ₂₀₁ ~R ₂₀₃ A part may be an aryl group, and the rest may be an alkyl group or a cycloalkyl group.

Examples of the arylsulfonium compound include a triarylsulfonium compound, a diarylalkylsulfonium compound and an aryldialkylsulfonium compound, a diarylcycloalkylsulfonium compound, an aryldicycloalkylsulfonium compound, and an arylalkylcycloalkylsulfonate. A phosphium compound is mentioned.

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

The alkyl group which an arylsulfonium compound has as needed has a C1-C15 linear and branched alkyl group, For example, a methyl group, an ethyl group, a propyl group, n-butyl group, sec-butyl group, t-butyl And the like can be mentioned.

The cycloalkyl group which an arylsulfonium compound has as needed has a C3-C15 cycloalkyl group, and a cyclopropyl group, a cyclobutyl group, a cyclohexyl group, etc. are mentioned, for example.

The aryl group, alkyl group and cycloalkyl group of R ₂₀₁ to R ₂₀₃ are an alkyl group (for example, having 1 to 15 carbon atoms), a cycloalkyl group (for example, having 3 to 15 carbon atoms), an aryl group (for example, having 6 to 14 carbon atoms), You may have an alkoxy group (for example, C1-C15), a halogen atom, a hydroxyl group, and a phenylthio group as a substituent. Preferable substituents are a C1-C12 straight chain, a branched alkyl group, a C3-C12 cycloalkyl group, a C1-C12 alkoxy group, Most preferably, they are a C1-C4 alkyl group and a C1-C4 alkoxy group. . The substituent may be substituted with any one of three R ₂₀₁ to R ₂₀₃ , or may be substituted with all three. In the case where R ₂₀₁ to R ₂₀₃ are an aryl group, the substituent is preferably substituted at the p-position of the aryl group.

Next, the compound (Z1-2) will be described.

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

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

R ₂₀₁ to R ₂₀₃ are each independently, preferably an alkyl group, a cycloalkyl group, an allyl group, a vinyl group, more preferably a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylmethyl group, and most preferably 2 -Oxoalkyl group.

The alkyl group as R ₂₀₁ to R ₂₀₃ may be either linear or branched, and preferably a linear or branched alkyl group having 1 to 10 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and the like. Can be. The alkyl group as R ₂₀₁ to R ₂₀₃ is more preferably a 2-oxoalkyl group or an alkoxycarbonylmethyl group. The 2-oxoalkyl group may be either linear or branched, and preferably, a group having> C = 0 at the 2-position of the alkyl group. As an alkoxy group in the alkoxycarbonylmethyl group as R <_201> -R <_203> , Preferably, a C1-C5 alkoxy group is mentioned.

The cycloalkyl group as R ₂₀₁ to R ₂₀₃ is preferably a cycloalkyl group having 3 to 10 carbon atoms, and examples thereof include a cyclopentyl group, a cyclohexyl group, a norbornyl group, and the like. The cycloalkyl group as R ₂₀₁ to R ₂₀₃ is more preferably a 2-oxocycloalkyl group. 2-oxocycloalkyl group is group which has> C = 0 in the 2 position of the said cycloalkyl group.

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

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

Compound (Z1-3) is a compound represented by the following General Formula (Z1-3), and is a compound having a phenacylsulfonium salt structure.

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

R _6c and R _7c each independently represent a hydrogen atom, an alkyl group or a cycloalkyl group.

R _x and R _y each independently represent an alkyl group, a cycloalkyl group or a vinyl group.

Any two or more of R _1c to R _5c , and R _x and R _y may be bonded to each other to form a ring structure, and this ring structure may contain an oxygen atom, a sulfur atom, an ester bond, or an amide bond. good.

Z _C ^- represents a non-nucleophilic anion, and examples thereof include the same as the non-nucleophilic anion of X ⁻ in General Formula (I).

The alkyl group as R _1c to R _7c may be either linear or branched, for example, an alkyl group having 1 to 20 carbon atoms, preferably a straight and branched alkyl group having 1 to 12 carbon atoms, for example, a methyl group, an ethyl group, a straight chain or A branched propyl group, a linear or branched butyl group, a linear or branched pentyl group, etc. are mentioned.

The cycloalkyl group as R _1c to R _7c is preferably a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof include a cyclopentyl group and a cyclohexyl group.

The alkoxy group as R _1c to R _5c may be any of linear, branched or cyclic, for example, an alkoxy group having 1 to 10 carbon atoms, preferably a linear and branched alkoxy group having 1 to 5 carbon atoms (for example, a methoxy group and an ethoxy group). And linear or branched propoxy groups, linear or branched butoxy groups, linear or branched pentoxy groups, and cyclic alkoxy groups having 3 to 8 carbon atoms (eg, cyclopentyloxy groups, cyclohexyloxy groups).

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

Examples of the alkyl group as R _x and R _y include the same alkyl groups as R _1c to R _5c . The alkyl group as R _x and R _y is preferably a 2-oxoalkyl group or an alkoxycarboxymethyl group. 2-oxoalkyl group can illustrate the group which has> C = O in the 2nd position of the alkyl group as R < _1c > -R < _5c >. Examples of the alkoxy group in the alkoxycarbonylmethyl group include the same alkoxy groups as R _1c to R _5c .

_Examples of the cycloalkyl group as R _x and R _y include the same cycloalkyl groups as R _1c to R _5c . The cycloalkyl group as R _x and R _y is preferably a 2-oxocycloalkyl group. 2-oxocycloalkyl group can illustrate the group which has> C = O at the 2-position of the cycloalkyl group as R < _1c > -R < _5c >.

Examples of groups that R _x and R _y are combined to form and the like can be mentioned a butylene group, a pentylene group.

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

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

R _{204 207} ~R of the aryl group include a phenyl group, a naphthyl group, more preferably is a phenyl group.

The alkyl group as R ₂₀₄ to R ₂₀₇ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, and examples thereof include methyl group, ethyl group, propyl group, butyl group and pentyl group.

The cycloalkyl group as R ₂₀₄ to R ₂₀₇ is preferably a cycloalkyl group having 3 to 10 carbon atoms, and examples thereof include a cyclopentyl group, a cyclohexyl group, a norbornyl group, and the like.

R ₂₀₄ as ~R ₂₀₇ may have substituents, for example, an alkyl group (for example 1 to 15 carbon atoms), cycloalkyl groups (e.g. 3 to 15 carbon atoms), aryl groups (for example 6 to 15 carbon atoms), an alkoxy group (for example, carbon atoms 1-15), a halogen atom, a hydroxyl group, a phenylthio group, etc. are mentioned.

X <^-> represents a non-nucleophilic anion and can illustrate the same thing as the non-nucleophilic anion of X <^-> in General formula (I).

As a preferable compound among the compound which decomposes | disassembles by irradiation by actinic light or radiation which may be used together, and produces | generates an acid, the compound further represented by the following general formula (ZIV), (ZV), (ZVI) is mentioned.

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

R ₂₀₆ , R ₂₀₇ and R ₂₀₈ represent an alkyl group, a cycloalkyl group or an aryl group.

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

More preferably, it is a compound represented by general formula (ZI)-(ZIII) among compounds which decompose by irradiation of actinic light or radiation which may be used together, and generate an acid.

Among the compounds which decompose upon irradiation with actinic light or radiation which may be used in combination and generate an acid, examples of particularly preferable ones are given below.

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

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

Preferred groups as groups which can be decomposed to an acid are groups substituted with a group which desorbs a hydrogen atom of a -COOH or -OH group to an acid.

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

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

It is preferable that the alkali dissolution rate of these alkali-soluble resins is 170 Pa / sec or more as measured (23 degreeC) by 0.261N tetramethylammonium hydrooxide (TMAH). Especially preferably, it is 330 kPa / sec or more.

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

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

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

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

p-t-butoxystyrene / p-hydroxystyrene copolymer

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

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

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

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

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

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

p- (cumyloxycarbonylmethyloxy) styrene / p-hydroxystyrene copolymer

Cumyl methacrylate / methyl methacrylate copolymer

4-t-butoxycarbonylstyrene / dimethyl maleate copolymer

Benzyl methacrylate / tetrahydropyranyl methacrylate

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

p-t-butoxystyrene / p-hydroxystyrene / fumaronitrile copolymer

t-butoxystyrene / hydroxyethyl methacrylate copolymer                     

Styrene / N- (4-hydroxyphenyl) maleimide / N- (4-t-butoxycarbonyloxyphenyl) maleimide copolymer

p-hydroxystyrene / t-butyl methacrylate copolymer

Styrene / p-hydroxystyrene / t-butyl methacrylate copolymer

p-hydroxystyrene / t-butylacrylate copolymer

Styrene / p-hydroxystyrene / t-butylacrylate copolymer

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

t-butyl methacrylate / 1-adamantylmethyl methacrylate copolymer

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

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

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

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

The content rate of the group that can be decomposed into an acid has a number (B) of groups that can be decomposed into an acid in the resin and a number (S) of alkali-soluble groups that are not protected by a group that is desorbed into an 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 an ArF excimer laser beam to the positive cationic polar composition of the present invention, the resin of the component (B) has a monocyclic or polycyclic alicyclic hydrocarbon structure, decomposed by the action of an acid, and solubility in an alkaline developer. It is preferable that it is an increasing resin.

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

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

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

R ₁₇ to R ₂₁ each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group, provided that at least one of R ₁₇ to R ₂₁ represents an alicyclic hydrocarbon group. In addition, any of R <_19> , R <_21> represents a C1-C4 linear or branched alkyl group or alicyclic hydrocarbon group.

R ₂₂ to R ₂₅ each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group, provided that at least one of R ₂₂ to R ₂₅ represents an alicyclic hydrocarbon group. R ₂₃ and R ₂₄ may be bonded to each other to form a ring.)

In the formula (II-AB):                     

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

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

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

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

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

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

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.

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

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

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

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

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

Moreover, as a new substituent of the said alkyl group, a C1-C4 alkoxy group, halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), acyl group, acyloxy group, cyano group, hydroxyl group, carboxyl group, alkoxycarbonyl group, nitro And the like can be mentioned.

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

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

Substituents for these alicyclic hydrocarbon groups include alkyl groups, halogen atoms, hydroxyl groups, alkoxy groups, carboxyl groups and alkoxycarbonyl groups. As an alkyl group, lower alkyl groups, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group, are preferable, More preferably, the substituent selected from the group which consists of a methyl group, an ethyl group, a propyl group, and an isopropyl group is represented. As an alkoxy group, C1-C4, such as a methoxy group, an ethoxy group, a propoxy group, butoxy group, is mentioned. The alkyl group and the alkoxy group may further have a substituent. As a substituent which the alkyl group and the alkoxy group may further have, a hydroxyl group, a halogen atom, and an alkoxy group can be mentioned.

In the said resin, the structure represented by general formula (pI)-(pVI) can be used for protection of alkali-soluble group. As said alkali-soluble group, various groups known in the art can be enumerated.

Specifically, there are a carboxylic acid group, a sulfonic acid group, a phenol group, a thiol group, and the like, and preferably a carboxylic acid group and a sulfonic acid group.

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

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

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

A 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.

R _a represents any of the groups of the general formulas (pI) to (pVI).

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

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

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

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

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

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

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

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

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

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

Among the repeating units having the aforementioned alicyclic hydrocarbon, the repeating unit represented by General Formula (II-A) or (II-B) is more preferable.

In the alicyclic hydrocarbon-based acid-decomposable resin according to the present invention, the acid-decomposable group may be contained in the above-C (= O) -X-A'-R ₁₇ ', and Z' of the general formula (II-AB) It may be contained as a substituent.

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

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

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

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

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

As a ring which at least two of said R <_13>'-R<_16> bonds and forms, C5-C12 rings, such as cyclopentene, a cyclohexene, a cycloheptane, and a cyclooctane, are mentioned.

As an alkoxy group in said R <_17>', C1-C4 things, such as a methoxy group, an ethoxy group, a propoxy group, butoxy group, are mentioned.

As a new substituent in the said alkyl group, cyclic hydrocarbon group, and alkoxy group, a hydroxyl group, a halogen atom, a carboxyl group, an alkoxy group, an acyl group, a cyano group, an acyloxy group, an alkyl group, a cyclic hydrocarbon group, etc. are mentioned. Examples of the halogen atom include chlorine atom, bromine atom, fluorine atom and iodine atom. Examples of the alkoxy group include those having 1 to 4 carbon atoms, such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group, and examples of the acyl group include a formyl group and an acetyl group. Can be mentioned.

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

Examples of the divalent linking group for A 'include an alkylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a sulfonamide group, a urethane group, and a combination of two or more groups selected from the group consisting of urea groups. Can be.

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

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

Although the following can be illustrated as a specific example of the repeating unit represented by said general formula (II-A) or general formula (II-B), This invention is not limited to these specific examples.

It is preferable that alicyclic hydrocarbon type acid-decomposable resin of this invention has a lactone group, More preferably, lactone represented by either of the following general formula (Lc) or the following general formula (V-1)-(V-5) It has a repeating unit which has a group which has a structure, and the group which has a lactone structure may be directly bonded to the main chain.

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

In General Formulas (V-1) to (V-5), each of R _1b to R _5b independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylsulfonylimino group or an alkenyl group. . Two of R _1b to R _5b may be bonded to each other to form a ring.

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

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

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

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

A 'represents a single bond, an ether group, an ester group, a carbonyl group, an alkylene group, or the bivalent group which combined these.

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

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

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

In general formula (VII), R <_2c> -R <_4c> represents a hydrogen atom or a hydroxyl group each independently. Provided that at least one of R _2c to R _4c represents a hydroxyl group.

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

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

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

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

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

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

In the general formula (VIII), Z ₂ represents -O- or -N (R ₄₁ )-, wherein 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 camphorzan group. These alkyl groups, cycloalkyl groups, and camphor residues may have substituents such as halogen atoms.

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

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

Although such a repeating structural unit corresponds to the following monomer as 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 wear (selection of hydrophilic, alkali-soluble groups),

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

(6) dry etching resistance,

Fine adjustment of the back and the like 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 Can be mentioned.

In addition, as long as it is an addition-polymerizable unsaturated compound copolymerizable with the monomer corresponded to the said various repeating structural unit, 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.

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

(1) Containing repeating units having a partial structure containing alicyclic hydrocarbons represented by the above general formulas (pI) to (pVI) (side chain type)

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

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

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

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

In alicyclic hydrocarbon type acid-decomposable resin, 30-70 mol% is preferable for content of the repeating unit which has the partial structure containing alicyclic hydrocarbon represented by general formula (pI)-(pVI) with respect to 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 other copolymerization component can also be set suitably according to the performance of a predetermined | prescribed resist, it contains an alicyclic hydrocarbon represented generally by said general formula (pI)-(pVI). It is preferably at most 99 mol%, more preferably at most 90 mol%, even more preferably based on the total moles of the total number of repeating structural units having a partial structure and the repeating units represented by the general formula (II-AB). 80 mol% or less.

When the composition of this invention is for ArF exposure, it is preferable that resin does not have an aromatic group from the point of transparency to ArF light.

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, monomer species are added to a half vessel in a batch or during the reaction, and, if necessary, a reaction solvent such as tetrahydrofuran, 1,4-dioxane, diisopropyl ether, or the like. Ketones such as ethers, methyl ethyl ketone, methyl isobutyl ketone, ester solvents such as ethyl acetate, and the composition of the present invention, such as propylene glycol monomethyl ether acetate, described later, are dissolved in a solvent to dissolve, and then uniformized. In an inert gas atmosphere, such as argon and argon, it heats as needed, and superposition | polymerization is started using a commercial radical initiator (azo initiator, peroxide, etc.). 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 predetermined polymer by a method such as powder or solid recovery. The concentration of the reaction is 20% by mass or more, preferably 30% by mass or more, more preferably 40% by mass or more. Reaction temperature is 10-150 degreeC, Preferably it is 30-120 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 the resin having a silicon atom and decomposed by the action of an acid to increase the solubility in the alkaline developer, both resins having a silicon atom in at least one of the main chain and the 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.

When irradiating the F ₂ excimer laser beam to the positive cationic polar composition of the present invention, the resin of the component (B) has a structure in which a fluorine atom is substituted in the main chain and / or the side chain of the polymer skeleton, and also in the action of an acid. Resin (decomposed also as fluorine group-containing resin hereinafter) which is decomposed by an increase in solubility in an alkaline developing solution is preferable, and more preferably, a hydroxyl group or one-position is substituted with a fluorine atom or a fluoroalkyl group at one position; A resin containing a group in which a hydroxyl group substituted with a fluoroalkyl group is protected by an acid decomposer, and most preferably, a structure in which a hydroxy group of hexafluoro-2-propanol or a hydroxyl group of hexafluoro-2-propanol is protected by an acid decomposer. It is resin to do. By introducing a fluorine atom, transparency to ultraviolet light, especially F ₂ (157 nm) light can be improved.

As a fluorine-group containing resin in (B) acid-decomposable resin, resin which has at least one repeating unit represented by the following general formula (FA)-(FG) is mentioned preferably, for example.

In the above general formula,

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

R ₁₀₄ and R ₁₀₆ are each independently a hydrogen atom, a fluorine atom or an alkyl group, and at least one of R ₁₀₄ and R ₁₀₆ is an alkyl group substituted with a fluorine atom or a fluorine atom. 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, 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 or an acid.

b is 0, 1 or 2.

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

In said general formula (FA)-(FG), as an alkyl group, it is a C1-C12 alkyl group, specifically, a methyl group, an ethyl group, a propyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group and octyl group are mentioned preferably. The alkyl group is preferably a haloalkyl group, and more preferably a fluoroalkyl group. As a haloalkyl group, a chloromethyl group, a chloroethyl group, a chloro propyl group, a chlorobutyl group, a bromomethyl group, a bromoethyl group etc. are mentioned specifically as a haloalkyl group of C1-C12, for example. As a fluoroalkyl group, it is C4-C12, for example, Specifically, a perfluoro butyl group, a perfluorohexyl group, a perfluoro octyl group, a perfluoro octylethyl group, a perfluoro dodecyl group, etc. are preferable. It can be heard.

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

As an aryl group, it is a C6-C15 aryl group, specifically, a phenyl group, a tolyl group, a dimethylphenyl group, 2,4,6-trimethylphenyl group, a naphthyl group, anthryl group, 9,10- dimethoxyan A tril group etc. are mentioned preferably.

As an aralkyl group, a benzyl group, a phenethyl group, a naphthyl methyl group, etc. are mentioned specifically as an aralkyl group of C7-12, for example.

As an alkenyl group, a vinyl group, an allyl group, butenyl group, and a cyclohexenyl group are mentioned specifically as an alkenyl group of C2-C8, for example.

As an alkoxy group, it is a C1-C8 alkoxy group, Specifically, a methoxy group, an ethoxy group, n-propoxy group, iso-propoxy group, butoxy group, pentoxy group, allyloxy group, octoxy group, etc. These are mentioned preferably.

As an acyl group, For example, as a C1-C10 acyl group, a formyl group, an acetyl group, a propanoyl group, butanoyl group, pivaloyl group, an octanoyl group, a benzoyl group, etc. are mentioned specifically ,.

As an acyloxy group, a C2-C12 acyloxy group is preferable and an acetoxy group, a propionyloxy group, a benzoyloxy group etc. are mentioned, for example.

As an alkynyl group, a C2-C5 alkynyl group is preferable and an ethynyl group, a propynyl group, butynyl group etc. are mentioned, for example.

As the alkoxycarbonyl group, i-propoxycarbonyl group, t-butoxycarbonyl group, t-amyloxycarbonyl group, 1-methyl-1-cyclohexyloxycarbonyl group, etc., preferably secondary, more preferably tertiary alkoxycarbonyl group Can be.

As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, for example.

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

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

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

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

Moreover, these groups may have a substituent, and as a substituent, they have active hydrogen, such as an alkyl group, a cycloalkyl group, an aryl group, an amino group, an amide group, a ureide group, a urethane group, a hydroxyl group, and a carboxyl group, and a halogen atom (fluorine atom, Chlorine atom, bromine atom, iodine atom), alkoxy group (methoxy group, ethoxy group, propoxy group, butoxy group, etc.), thioether group, acyl group (acetyl group, propanoyl group, benzoyl group, etc.), acyloxy group (Acetoxy group, propanoyloxy group, benzoyloxy group, etc.), alkoxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, etc.), cyano group, nitro group, etc. are mentioned.

Although an alkyl group, a cycloalkyl group, and an aryl group can illustrate what was shown above, the alkyl group may be further substituted by the fluorine atom and the cycloalkyl group.

Examples of the group decomposed by the action of an acid and presenting alkali solubility included in the fluorine group-containing resin of the present invention include -OC (R ₃₆ ) (R ₃₇ ) (R ₃₈ ) and -OC (R ₃₆ ) (R ₃₇ ) (OR ₃₉ ), -O-COO-C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), -OC (R ₀₁ ) (R ₀₂ ) COO-C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), -COO-C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), -COO-C (R ₃₆ ) (R ₃₇ ) (OR ₃₉ ), and the like.

In addition, -C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ) means a group in which each group represented by R ₃₆ to R ₃₈ is bonded to a carbon atom by a single bond. Hereinafter, it is the same.

R ₃₆ to R ₃₉ represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group which may have a substituent, and R ₀₁ and R ₀₂ represent a hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group, an alkenyl group, or an aral. A kill group or an aryl group is represented.

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

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

The sum total of content of the repeating unit represented by general formula (FA)-(FG) is 10-80 mol% normally, Preferably it is 30-70 mol% with respect to the all the repeating units which comprise resin, More preferably, Is used in the range of 35 to 65 mol%.

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

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

It is preferable that such a fluorine-containing resin contains another repeating unit as a copolymerization component in addition to the repeating unit having the fluorine atom from the viewpoint of improving dry etching resistance, adjusting alkali solubility, improving substrate adhesion, and the like. Preferred as other repeat units are:

1) A repeating unit having an alicyclic hydrocarbon structure represented by general formulas (pI) to (pVI) and (II-AB). Specifically, the repeating units of 1 to 23 and the repeating units of [II-1] to [II-32]. Preferably, Rx in the specific examples 1 to 23 is CF ₃ .

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

3) The repeating units listed in the following general formula (XV) (XVI) (XVII) derived from a vinyl compound having maleic anhydride, a vinyl ether or a cyano group, specifically (C-1) to (C-15) Can be mentioned. The repeating unit other than these may or may not contain fluorine atoms.

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

R ₄₂ represents a hydrogen atom, a halogen atom, a cyano group or an alkyl group.

A ₅ is a single bond, a divalent alkylene group, an alkenylene group, a cycloalkylene group or an arylene group, or -O-CO-R _22- , -CO-OR _23- , -CO-N (R ₂₄ ) -R ₂₅ Indicates-.

R ₂₂ , R ₂₃ , R ₂₅ may be the same or different and may be a single bond or an ether group, an ester group, an amide group, a urethane group or a ureide group, a divalent alkylene group, an alkenylene group, a cycloalkylene group or An arylene group is shown.

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

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

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

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

The content of the other repeating units such as the repeating units represented by General Formulas (XV) to (XVII) is generally 0 to 70 mol%, preferably 10 to 60 mol%, and more, relative to all the repeating units constituting the resin. Preferably it is used in 20-50 mol%.

(B) The fluorine group-containing resin as the acid-decomposable resin may contain an acid-decomposable group in any repeating unit.

As for content of the repeating unit which has an acid-decomposable group, 10-70 mol% is preferable with respect to all the repeating units, More preferably, it is 20-60 mol%, More preferably, it is 30-60 mol%.

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

The weight average molecular weight of resin of (B) component which concerns on this invention is a polystyrene conversion value by GPC method, Preferably it is 1,000-200,000. By setting the weight average molecular weight to 1,000 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 very low, film forming property can be improved. .

In the positive cationic polar 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 solid, more preferably from 50 to 99.97 mass%. to be.

[3] A dissolution inhibiting compound having a molecular weight of 3000 or less (hereinafter, also 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, so 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. As acid-decomposable group and alicyclic structure, the thing similar to what was demonstrated by the part of the said alicyclic hydrocarbon type acid-decomposable resin is mentioned.

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

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

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

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

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

The alkali dissolution rate of the alkali-soluble resin is preferably 20 Pas / sec or more as measured by 0.261 N tetramethylammonium hydrooxide (TMAH) (23 占 폚). 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-tetrahydropyranilide, O- (t-butoxycarbonyl) methylate, etc.) or O-acylates (e.g., 5-30 mol% o-acetylated group, O- (t-butoxy) carbonylate, etc.), styrene-anhydride Maleic acid copolymer, styrene-hydroxy styrene copolymer, α-methylstyrene-hydroxy styrene copolymer, carboxyl group-containing methacryl type Although resin, its derivative (s), and polyvinyl alcohol derivative (s) can be 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 using a predetermined monomer as a main component.

Moreover, the weight average molecular weight of alkali-soluble resin is 2,000 or more, Preferably it is 5,000-200,000, More preferably, it is 5,000-100,000.

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

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

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

[5] An acid crosslinking agent which crosslinks with 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 potato polar composition of this invention.

As a crosslinking agent, as long as it is a compound which bridge | crosslinks soluble resin to an alkaline developing solution by the action of an acid, any can be used, but 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 listed below.

(Wherein, L ₁ ~L ₈ are, same or different, represents an alkyl group of a hydrogen atom, a hydroxymethyl group, methoxymethyl group, ethoxymethyl group or a 1 to 6 carbon atoms.)

The crosslinking agent is usually used in an amount of from 3 to 70 mass%, preferably from 5 to 50 mass%, in the solid content of the potato polar composition.

<Other ingredients>

[6] (F) basic compounds                     

It is preferable that the potato polar composition of this invention contains (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 group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, wherein R ²⁵⁰ and R ²⁵¹ are You may combine with each other and form a ring. The alkyl group, cycloalkyl group, and aryl group may have a substituent. As an alkyl group which has a substituent, a C1-C20 aminoalkyl group and a C1-C20 hydroxyalkyl group are mentioned, for example. As a cycloalkyl group which has a substituent, a C3-C20 aminocycloalkyl group and a C3-C20 hydroxycycloalkyl group are mentioned, for example.

Moreover, you may contain an oxygen atom, a sulfur atom, and a nitrogen atom in these alkyl chains and a cycloalkyl chain.

(Wherein, R ²⁵³ ~R ²⁵⁶ represents an alkyl group or a cycloalkyl group of 3 to 20 carbon atoms having 1 to 20 carbon atoms, each independently).

Preferred compounds include substituted or unsubstituted guanidine, substituted or unsubstituted aminopyrrolidine, substituted or unsubstituted pyrazole, substituted or unsubstituted pyrazoline, substituted or unsubstituted piperazine, substituted or unsubstituted Aminomorpholine, substituted or unsubstituted aminoalkylmorpholine, substituted or unsubstituted piperidine, and more preferred compounds include imidazole structure, diazabicyclo structure, onium hydroxide structure and oniumcarboxyl And a compound having a late structure, a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, an aniline derivative having a hydroxyl group and / or an ether bond, and the like.

Examples of the compound having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole, and the like. Examples of the compound having a diazabicyclo structure include 1,4-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-oxoalkyl group, specifically triphenylsulfonium hydroxide and tris (t -Butylphenyl) sulfonium hydroxide, bis (t-butylphenyl) iodonium hydroxide, phenacylthiophenium hydroxide, 2-oxopropylthiophenium hydroxide, etc. are mentioned. As a compound which has an onium carboxylate structure, the anion part of the compound which has an onium hydroxide structure consists of carboxylates, For example, acetate, adamantane-1-carboxylate, perfluoroalkyl carboxylate, etc. Can be mentioned. Examples of the compound having a trialkylamine structure include tri (n-butyl) amine, tri (n-octyl) amine, and the like. 2, 6- diisopropyl aniline, N, N- dimethylaniline, etc. are mentioned as an aniline compound. 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 can be used alone or in combination of two or more. The usage-amount of a basic compound is 0.001-10 mass% normally based on solid content of a potato polar composition, Preferably it is 0.01-5 mass%. 0.001 mass% or more is preferable at the point which acquires sufficient addition effect, 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 silicone surfactants

The potato polar composition of the present invention may also contain any one or two or more of fluorine-based and / or silicon-based surfactants (fluorine-based and silicon-based surfactants, surfactants containing both fluorine and silicon atoms). desirable.

Since the potato polar 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 give a resist pattern with little adhesion and development defect with good sensitivity and resolution. It becomes possible.

As these fluorine and / or silicone 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. 62-170950 Japanese Patent Laid-Open No. 63-34540, Japanese Patent Laid-Open No. 7-230165, Japanese Patent Laid-Open No. 8-62834, Japanese Patent Laid-Open No. 9-54432, Japanese Patent Laid-Open No. 9-5988 Japanese Patent Publication No. 2002-277862, US Patent No. 557520, East 5360692, East 5529881, East 5296330, East 5436098, East 5576143, East 5294511, East East The surfactant described in the 5824451 specification can be mentioned, 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 Niaki Kitasei Co., Ltd.), Prorad FC430, 431 (made by Sumitomo 3M Co., Ltd.), Megapack F171, F173, F176, F189, R08 (product of Dainippon Ink & Chemicals Co., Ltd.), Supron S-382, SC101, 102, 103, 104, 105, 106 (product of Asahi Glass Co., Ltd.), Troisol S-366 (Troy And fluorine-based surfactants such as Chemical Co., Ltd.) or silicone-based surfactants. Moreover, polysiloxane polymer KP-341 (made by Shin-Etsu Kagaku Kogyo Co., Ltd.) can also be used as a silicone type surfactant.

Moreover, as a surfactant, the fluoro aliphatic derived from the fluoro aliphatic compound manufactured by the telomerization method (also called telomer method) or the oligomerization method (also called oligomer method) other than the well-known thing shown above is mentioned. Surfactants using polymers having groups 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. It may be present or 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, Also, poly (oxyethylene, oxypropylene, and oxyethylene Or a unit having an alkylene having a different chain length in a chain length such as a block 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, as a commercially available surfactant, Megapack F178, F-470, F-473, F-475, F-476, and F-472 (made by Dainippon Ink & Chemicals Co., Ltd.) can be mentioned. Further, copolymers of acrylate (or methacrylate) having a C ₆ F ₁₃ group and (poly (oxyalkylene)) acrylate (or methacrylate), acrylate (or methacryl having a C ₆ F ₁₃ group) Copolymer of (rate) and (poly (oxyethylene)) acrylate (or methacrylate) and (poly (oxypropylene)) acrylate (or methacrylate), an acrylate (or methacryl) having a C ₈ F ₁₇ group Copolymer of (rate) and (poly (oxyalkylene)) acrylate (or methacrylate), acrylate (or methacrylate) and (poly (oxyethylene)) acrylate (or meta) having C ₈ F ₁₇ groups Acrylate) and the copolymer of (poly (oxypropylene)) acrylate (or methacrylate), etc. are mentioned.

The amount of fluorine and / or silicone-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 potato polar composition (excluding the solvent).

[8] organic solvents (H)

The potato polar composition of the present invention is used by dissolving the above components in a predetermined organic solvent.

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

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

Examples of the solvent containing a hydroxyl group include ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethyl lactate, and the like. Among them, propylene glycol monomethyl ether and ethyl lactate are particularly preferable.

As a solvent which does not contain 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 is particularly preferred, and propylene glycol monomethyl ether acetate, ethyl ethoxy propionate and 2-heptanone are most preferred.

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

<Other additives>

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

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

The preferable addition amount of these dissolution promoting compounds is 2-50 mass% with respect to resin of (B) component or resin of (D) component, More preferably, it is 5-30 mass%. 50 mass% or less is preferable at the point of 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 can be easily synthesized by those skilled in the art by referring to methods described in, for example, Japanese Patent Application Laid-Open No. Hei 4-122938, Japanese Patent Application Laid-Open No. Hei 2-28531, US Patent No. 4916210, and European Patent No. 219294. Can be.

Specific examples of the alicyclic or aliphatic compound having a carboxyl group include carboxylic acid derivatives having a steroid structure such as cholic acid, dioxycholic acid and tricholic acid, adamantanecarboxylic acid derivatives, adamantanedicarboxylic acid, and cyclohexanecarboxyl. Acid, cyclohexanedicarboxylic acid, etc. are mentioned, but it is not limited to these.

In this invention, you may add surfactant other than the said (G) fluorine type and / or silicone type surfactant. 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.

<< How to use >>

The potato polar composition of this invention is melt | dissolved in the predetermined organic solvent, Preferably the said mixed solvent, and apply | coats on a predetermined | prescribed support body as follows, and is used.

For example, the potato polar composition is applied onto a substrate (for example, silicon / silicon dioxide coating) used for the manufacture of the precision integrated circuit device by a suitable coating method such as a spinner or a coater to form a resist film.

Subsequently, actinic light and a radiation are irradiated to a resist film through a predetermined mask, and it bakes and develops. In this way, a good pattern can be obtained. Examples of the active light include infrared light, visible light, ultraviolet light, far-ultraviolet light, X-rays, and electron beams, but are preferably ultraviolet light having a wavelength of 250 nm or less, more preferably 220 nm or less, specifically KrF 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, with ArF excimer laser and F ₂ excimer laser being most preferred. Moreover, in this invention, X-ray and an electron beam shall also be included in actinic ray.

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 of Compound (A)

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

54.7 g of copper (II) bromide was mixed with 100 ml of ethyl acetate, 20 g of p-hydroxyacetophenone was dissolved in 100 ml of chloroform, and the mixture was refluxed for 3 hours. The reaction solution was filtered, and the filtrate was concentrated to give a crude product. Purification by column chromatography gave 18 g of p-bromoacetylphenol.                     

10 g of p-bromoacetyl phenol was dissolved in 150 ml of acetonitrile, and 8.2 g of tetrahydrothiophene was added thereto and reacted at 60 ° C for 1 hour. The reaction solution was allowed to cool and 150 ml of ethyl acetate was added thereto. The precipitated powder was filtered and dried to obtain 12 g of 4-hydroxyphenacyltetrahydrothiophenium bromide.

11.9 g of the bromide was dissolved in methanol, and 13.9 g of potassium nonafluorobutane sulfonate was dissolved in a water / acetonitrile mixed solvent and added thereto. The reaction solution was concentrated, dissolved in chloroform and washed with water. 13.2g of compound (I-1) was obtained when the chloroform layer was concentrated.

30OMHz ¹ H-NMR (CDCl3)

δ2.1-2.4 (m.4H), δ3.4-3.6 (m.4H), δ5.2 (s.2H), δ6.95 (d.2H), δ7.9 (d.2H), δ10 .8 (bs. 1 H)

Synthesis Example 2 (Synthesis of Compound (I-4))

7.6 g of p-bromoacetyl phenol and 19.6 g of dodecyl sulfide were dissolved in 200 ml of acetonitrile, and 8.3 g of tetrafluoroboric acid was added thereto to reflux for 10 hours. The reaction solution was allowed to cool and filtered. The filtrate was concentrated, and the obtained powder was washed with diisopropyl ether and dried to obtain 19.5 g of 4-hydroxyphenacyl dididodecylsulfonium tetrafluoroborate.

19.4 g of the obtained tetrafluoroborate salt was dissolved in 100 ml of chloroform, and 17.9 g of potassium nonafluorobutane sulfonate was dissolved and added to this solution in a water / acetonitrile mixed solvent, followed by stirring at room temperature for 1 hour. The reaction solution was extracted with chloroform, and the chloroform phase was washed three times with an aqueous ammonium chloride solution followed by distilled water. The chloroform phase was filtered with a filter of 0.1 mu m, and the filtrate was concentrated to give a crude product. Purification by column chromatography gave 13 g of compound (I-4).

300 MHz ¹ H-NMR (CDCl3)

δ 0.9 (t. 6H), δ 1.2-1.4 (m. 32H), δ 1.4-1.6 (m. 4H), δ 1.8-2.0 (m. 4H), δ 3.4-3.6 (m. 4H), δ5.3 (s. 2H), δ6.85 (d. 2H), δ7.9 (d. 2H)

<Synthesis example of resin (B)>

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

2-ethyl-2-adamantyl methacrylate and bromolactone methacrylate were added at a ratio of 55/45, dissolved in methyl ethyl ketone / tetrahydrofuran = 5/5, and a solution having a solid content concentration of 20% 100 ML was prepared. 2 mol% of Wako Pure Chemical Industries Ltd. V-65 was added to this solution, and it was dripped at 10 ml of methyl ethyl ketone heated at 60 degreeC over 4 hours in nitrogen atmosphere. After completion of the dropwise addition, the reaction solution was heated for 4 hours, 1 mol% of V-65 was further added, and stirred for 4 hours. After the completion of the reaction, the reaction solution was cooled to room temperature, and crystallized in 3 L of a mixed solvent of distilled water / ISO propyl alcohol = 1/1 to recover Resin (1), which was a precipitated white powder.

The polymer composition ratio determined from C ¹³ NMR was 46/54. In addition, the mass mean molecular weight of the standard polystyrene conversion calculated | required by GPC measurement was 10700.

Resin (2)-(12) and (26)-(31) were synthesize | combined similarly to the said synthesis example 1.                     

Synthesis Example 2 Synthesis of Resin (13) (Main Chain Type)

Norbornene carboxylic acid tbutyl ester, norbornene carboxylic acid butyrolactone ester, maleic anhydride (molar ratio 40/10/50), and THF (reaction temperature 60 mass%) are put into a separate flask, and the nitrogen stream is 60 Heated to ° C. When the reaction temperature was stabilized, 2 mol% of a Wako Pure Chemical Industries radical initiator V-601 was added to initiate the reaction. It heated for 12 hours. The obtained reaction mixture was diluted twice with tetrahydrofuran and then poured into a mixed solution of hexane / isopropyl alcohol = 1/1 to precipitate a white powder. The precipitated powder was filtered out and dried to obtain Resin (13) as a target.

As a result of testing the molecular weight analysis by GPC of obtained resin (13), it was 8300 (mass average) in polystyrene conversion. Moreover, it confirmed that the molar ratio of the norbornene carboxylic acid tbutyl ester / norbornene carboxylic acid butyrolactone ester / maleic anhydride repeating unit of resin (1) was 42/8/50 from NMR spectrum.

Resins (14) to (19) were synthesized in the same manner as in Synthesis example 2.

Synthesis Example 3 Synthesis of Resin 20 (Hybrid Type)

Norbornene, maleic anhydride, tbutyl acrylate and 2-methylcyclohexyl-2-propyl acrylate are added to the reaction vessel at a molar ratio of 35/35/20/10, dissolved in tetrahydrofuran and a solution having a solid content of 60%. Prepared. This was heated at 65 degreeC under nitrogen stream. When the reaction temperature was stabilized, 1 mol% of a Wako Pure Chemical Industries radical initiator V-601 was added to initiate the reaction. After heating for 8 hours, the reaction mixture was diluted twice with tetrahydrofuran, and then charged into a 5-fold volume of hexane of the reaction mixture to precipitate a white powder. The precipitated powder was collected by filtration, dissolved in methyl ethyl ketone, reprecipitated in a 5-fold volume of hexane / t-butyl methyl ether = 1/1 mixed solvent, and the precipitated white powder was collected by filtration and dried. Resin (20) which was a target object was obtained.

As a result of testing the molecular weight analysis by GPC of obtained resin (20), it was 12100 (mass average) in polystyrene conversion. The composition of the resin (1) from the NMR spectrum was 32/39/19/10 in a molar ratio of norbornene / maleic anhydride / tbutyl acrylate / 2-methylcyclohexyl-2-propyl acrylate of the present invention.

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

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

<Fluorine-containing resin>                     

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

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

Examples 1 to 25 and Comparative Example 1

<Resist preparation>

The components shown in the following Tables 3-5 were melt | dissolved in the solvent, the solution of 12 mass% of solid content concentration was prepared, This was filtered by 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 result was shown to Tables 3-5.                     

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

[Acid generator]

PAG-A;

         PAG-A

[Basic compound]

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

TPI; 2,4,5-triphenylimidazole

TPSA; Triphenylsulfonium acetate

HEP; N-hydroxyethylpiperidine

DIA; 2,6-diisopropylaniline

DCMA; Dicyclohexylmethylamine

TPA; Tripentylamine

TOA; Tri-n-octylamine

HAP; Hydroxyantipyrine

TBAH; Tetrabutylammonium hydroxide                     

TMEA; Tris (methoxyethoxyethyl) amine

PEA; N-phenyldiethanolamine

[Surfactants]

W-1; Mega pack F176 (product made by Dainippon Ink & Chemicals Co., Ltd.) (fluorine system)

W-2; Megapack R08 (products of Dainippon Ink & Chemicals Kakuku Kogyo Co., Ltd.) (fluorine and silicon)

W-3; Polysiloxane Polymer KP-341 (manufactured by Shin-Etsu Kagaku Kogyo Co., Ltd.)

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

[solvent]

A1; Propylene Glycol Methyl Ether Acetate

A2; 2-heptanone

A3; Ethyl ethoxy propionate

A4; γ-butyrolactone

A5; Cyclohexanone

B1; Propylene Glycol Methyl Ether

B2; Ethyl lactate

[Dissolution inhibiting agent]

LCB; Litocholic acid t-butyl

Resist Evaluation

[PEB temperature dependence]

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

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

The exposure amount which reproduces the isolated contact hole pattern of mask size 180 nm at 130 nm, and exposes the isolated contact hole pattern of mask size 180 nm, and reproduces the exposure amount which reproduces in 130 nm of isolated contact hole of mask size 180 nm at post-heating temperature of 120 degreeC Next, after exposing at the optimum exposure dose, the post-heating was performed at two temperatures of + 2 ° C and -2 ° C (122 ° C and 118 ° C) with respect to the post-heating temperature, respectively. length-measuring and was determined their diameter L ₁ and L _2. PEB temperature dependence was defined as the change of the diameter per 1 degreeC of PEB temperature change, and it computed by the following formula.

PEB temperature dependence (nm / ℃) = | L ₁ -L ₂ | / 4

[Resolution and Profile of Contact Holes]

The limit resolution in the exposure amount which reproduces the isolated contact hole of mask size 180 nm in 130 nm was made into the resolution. In addition, the profile of the contact hole pattern of 130 nm was observed by cross-sectional SEM.                     

From Tables 3 to 5, it is clear that the positive resist compositions of Examples 1 to 25 had low PEB temperature dependence and improved resolution and profile of contact holes.

Examples 26-28 and Comparative Example 2

(1) Formation of lower layer resist layer

FHi-028DD resist (resin for Fujifilm Orin i line) was apply | coated to a 6-inch silicon wafer using the spin coater Mark8 by Tokyo Electron, and baked for 90 degreeC and 90 second, and the uniform film of 0.55 micrometer in thickness was obtained.

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 6 was melt | dissolved in the solvent, the solution of 11 mass% of solid content concentration was prepared, and it filtered fine with a menblelen filter of 0.1 micrometer of diameter, and prepared the upper layer resist composition.

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

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

(3) resist evaluation

The wafer thus obtained was exposed with an ArF excimer laser (wavelength 193 nm, ArF stepper manufactured by ISI of NA = 0.6).

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

The resist pattern of the silicon wafer thus obtained was observed by SEM and evaluated in the same manner as in Example 1. Table 6 shows the results of the evaluation. From Table 6, it is clear that the positive resist compositions of Examples 26 to 28 had low PEB temperature dependency, and improved resolution and profile of contact holes.

Examples 29-48 and Comparative Example 3                     

<Resist preparation>

The components shown in the following Tables 7-8 were dissolved in a solvent, and this was filtered through a 0.1 micrometer polytetrafluoroethylene filter to prepare a positive resist solution.

Resist Evaluation

[PEB temperature dependence]

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

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

The results are shown in Tables 7-8.                     

From Tables 7-8, it is clear that the positive resist compositions of Examples 29-48 have low PEB temperature dependency.

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

Moreover, the potato polar composition of this invention is considered to have the same effect also about EUV light.

Advantageous Effects of Invention The present invention can provide a potato polar composition having low PEB temperature dependency and improved contact hole resolution and profile.

Claims (5)

Repetition having a partial structure containing a compound represented by the following general formula (I) which generates an acid or a radical by stimulation from the outside, and an alicyclic hydrocarbon represented by the following general formula (pI) to general formula (pVI) A potato polar composition comprising a unit and a resin having at least one selected from the group of repeating units represented by the following general formula (II-AB).

In general formula (I), Ar represents an aryl group. R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group. R ₁ and R ₂ may be bonded to each other to form a ring. Y ₁ and Y ₂ each independently represent an alkyl group, a cycloalkyl group, or an aryl group. Y ₁ and Y ₂ may be bonded to each other to form a ring. n represents the integer of 1-3. X <^-> represents a non-nucleophilic anion.

In general formula (pI)-general formula (pVI), 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 an alicyclic hydrocarbon group together with a carbon atom. R ₁₂ to R ₁₆ each independently represent a linear or branched alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group, provided that at least one of R ₁₂ to R ₁₄ or any one of R ₁₅ and R ₁₆ is alicyclic; Hydrocarbon group is represented. R ₁₇ to R ₂₁ each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group, provided that at least one of R ₁₇ to R ₂₁ represents an alicyclic hydrocarbon group. In addition, any of R <_19> , R <_21> represents a C1-C4 linear or branched alkyl group or alicyclic hydrocarbon group. R ₂₂ to R ₂₅ each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group, provided that at least one of R ₂₂ to R ₂₅ represents an alicyclic hydrocarbon group. In addition, R ₂₃ and R ₂₄ may be bonded to each other to form a ring.

In general formula (II-AB), R ₁₁ ′ and R ₁₂ ′ each independently represent a hydrogen atom, a cyano group, a halogen atom, or an alkyl group. Z 'contains the two bonded carbon atoms (C-C) and represents an atomic group for forming an alicyclic structure which may have a substituent. Containing a compound represented by the following general formula (I) which generates an acid or a radical by stimulation from the outside, and at least one of repeating units represented by the following general formulas (FA) to (FG) Potato-polar composition characterized in that.

In general formula (I), Ar represents an aryl group. R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group. R ₁ and R ₂ may be bonded to each other to form a ring. Y ₁ and Y ₂ each independently represent an alkyl group, a cycloalkyl group, or an aryl group. Y ₁ and Y ₂ may be bonded to each other to form a ring. n represents the integer of 1-3. X <^-> represents a non-nucleophilic anion.

In general formula (FA)-(FG), R ₁₀₀ to R ₁₀₃ each independently represent a hydrogen atom, a fluorine atom, an alkyl group or an aryl group. R ₁₀₄ and R ₁₀₆ are each independently a hydrogen atom, a fluorine atom or an alkyl group, and at least one of R ₁₀₄ and R ₁₀₆ is an alkyl group substituted with a fluorine atom or a fluorine atom. R ₁₀₅ is a group decomposed by the action of a hydrogen atom, an alkyl group, an acyl group, an alkoxycarbonyl group or an acid. A ₁ is a single bond or a divalent linking 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 or an acid. a is 0 or 1; b is 0, 1 or 2. However, the repeating unit represented by general formula (FA)-(FG) contains at least 1 fluorine atom per one repeating unit. A pattern forming method comprising the step of forming a resist film by using the potato polar composition according to claim 1 or 2, and exposing and developing the resist film. The potato polar composition according to claim 1, wherein the resin further has a repeating unit having a lactone group. The potato polar composition according to claim 1, wherein the resin further has a repeating unit having a group represented by the following general formula (VII).

In general formula (VII), R <_2c> -R <_4c> represents a hydrogen atom or a hydroxyl group each independently. Provided that at least one of R _2c to R _4c represents a hydroxyl group.