KR100897292B1 - Stimuli-sensitive composition and compound - Google Patents

Abstract

It provides a positive photosensitive composition excellent in sensitivity and resolution.

(A) a specific acid generator which generates an acid by irradiation of actinic light or radiation,

(B) A positive photosensitive composition having a monocyclic or polycyclic alicyclic hydrocarbon structure and containing a resin which is decomposed by the action of an acid and has increased solubility in an alkali developer.

Description

Potato-polar compositions and compounds {STIMULI-SENSITIVE COMPOSITION AND COMPOUND}

 The present invention relates to 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 recording head, a flat plate printing plate, an acid curing composition, a radical curing composition, and other light manufacturing processes, and the potato polarity. It relates to a compound used in the composition. In more detail, it is related with the photosensitive composition preferable when the ultraviolet ray etc. which are 250 nm or less are used as an exposure light source, and the compound used for this photosensitive composition.

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

When the KrF excimer laser is used as an exposure light source, a resin mainly composed of poly (hydroxystyrene), which has a small absorption in the 248 nm region, is used as a main component, thereby forming a highly sensitive, high resolution, and desirable pattern. The system is better than the conventional naphthoquinone diazide / novolak resin system.

However, when another short wavelength light source such as an ArF excimer laser (193 nm) is used as the exposure light source, since the compound having an aromatic group exhibits a large absorption in the 193 nm region essentially, the chemical amplification system is sufficient. Was not.

In addition, as a polymer having a low absorption in the 193 nm wavelength region, the use of poly (meth) acrylate is described in J. Vac. Sci. Although described in Technol., B9, 3357 (1991)., This polymer has a problem that the resistance to dry etching generally performed in the semiconductor manufacturing process is lower than that of the conventional phenol resin having an aromatic group.

In addition, Japanese Patent No. 2964990 and Japanese Patent No. 2965016 describe sulfonium salts having a 2-oxoalkyl group as an acid generator. However, the sulfonium salts described in these have high transparency to light of 220 nm or less, but have little absorption especially for light of 193 nm, and therefore do not generate a sufficient amount of acid even when added in large quantities. Sensitivity becomes low. Further, Japanese Patent Application Laid-Open No. 2000-292917 discloses a resist composition using a mixture of a triarylsulfonium salt and a phenacylsulfonium salt as an acid generator, but the triarylsulfonium salt and the phenacylsulfonium salt have an aromatic ring structure. In particular, since the absorption of the light having a large amount of 193 nm is too large, and the resist having a large amount added thereto does not reach the bottom of the resist film, the resist becomes a profile called taper.

Accordingly, an object of the present invention is a general formula (I) having an excellent absorption property with respect to light of 250 nm or less, especially light of 248 nm, 193 nm, 157 nm, and an electron beam, as an acid generator. Or it uses to provide the photosensitive composition of high sensitivity and high resolution by using the compound represented by (II).

This invention is the photosensitive composition of the following structure, and the said objective of this invention is achieved by this.

(1) (A) Potato-polar composition characterized by containing the compound represented by the following general formula (I) or (II) which generate | occur | produces an acid or a radical by the stimulus from the exterior.

In general formula (I) and (II),

R ₁ to R ₃ may be the same or different and represent an alkyl group, an alkenyl group, an aryl group or an alkoxy group which may have a hydrogen atom or a substituent.

R <_4> and R <_5> may be same or different and represents the alkyl group, the aryl group, or the alkoxy group which may have a hydrogen atom, a cyano group, or a substituent.

Y <_1> and Y <_2> represent the aromatic group containing an alkyl group, an aryl group, an aralkyl group, or a hetero atom which may be same or different and may have a substituent.

n represents the integer of 1-4. When n is two or more, two or more R <_1> and R <_2> may be same or different.

Two or more of R ₁ to R ₃ , R ₄ , R ₅ , Y _1, and Y ₂ may be bonded to form a ring structure.

In addition, at any one of R <_1> -R <_3> , R <_4> , R <_5> , Y <_1> and Y <_2> , it may couple through a coupling group and may have two or more structures of general formula (I) or (II).

X ⁻ represents a non-nucleophilic anion.

(2) (A) Photosensitive composition containing compound represented by following General formula (I) or (II) which generate | occur | produces an acid by irradiation of actinic light or a radiation.

In general formula (I) and (II),

R ₁ to R ₃ may be the same or different and represent an alkyl group, an alkenyl group, an aryl group or an alkoxy group which may have a hydrogen atom or a substituent.

R <_4> and R <_5> may be same or different and represents the alkyl group, the aryl group, or the alkoxy group which may have a hydrogen atom, a cyano group, or a substituent.

Y ₁ and Y ₂ represent an aromatic group containing an alkyl group, an aryl group, an aralkyl group or a hetero atom which may be the same or different and may have a substituent.

n represents the integer of 1-4. When n is two or more, two or more R <_1> and R <_2> may be same or different.

Two or more of R ₁ to R ₃ , R ₄ , R ₅ , Y _1, and Y ₂ may be bonded to form a ring structure.

In addition, at any one of R <_1> -R <_3> , R <_4> , R <_5> , Y <_1> and Y <_2> , it may couple through a coupling group and may have two or more structures of general formula (I) or (II).

X ⁻ represents a non-nucleophilic anion.

(3) (A) a compound represented by the following general formula (I) or (II) which generates an acid by irradiation with actinic rays or radiation; and

(B) A positive photosensitive composition characterized by containing a resin which is decomposed by the action of an acid and the solubility in the alkali developer is increased.

In general formula (I) and (II),

R ₁ to R ₃ may be the same or different and represent an alkyl group, an alkenyl group, an aryl group or an alkoxy group which may have a hydrogen atom or a substituent.

R <_4> and R <_5> may be same or different and represents the alkyl group, the aryl group, or the alkoxy group which may have a hydrogen atom, a cyano group, or a substituent.

Y <_1> and Y <_2> represent the aromatic group containing an alkyl group, an aryl group, an aralkyl group, or a hetero atom which may be same or different and may have a substituent.

n represents the integer of 1-4. When n is two or more, two or more R <_1> and R <_2> may be same or different.

Two or more of R ₁ to R ₃ , R ₄ , R ₅ , Y _1, and Y ₂ may be bonded to form a ring structure.

In addition, at any one of R <_1> -R <_3> , R <_4> , R <_5> , Y <_1> and Y <_2> , it may couple through a coupling group and may have two or more structures of general formula (I) or (II).

X ⁻ represents a non-nucleophilic anion.

(4) The positive photosensitive composition as described in (3), wherein the resin of the component (B) has a monocyclic or polycyclic alicyclic hydrocarbon structure.

(5) (A) the compound represented by the following general formula (I) or (II) which generate | occur | produces an acid by irradiation of actinic light or radiation;

(C) acid crosslinking agents; And

(D) A negative photosensitive composition, containing an alkyl soluble resin.

In general formula (I) and (II),

R ₁ to R ₃ may be the same or different and represent an alkyl group, an alkenyl group, an aryl group or an alkoxy group which may have a hydrogen atom or a substituent.

R <_4> and R <_5> may be same or different and represents the alkyl group, the aryl group, or the alkoxy group which may have a hydrogen atom, a cyano group, or a substituent.

Y <_1> and Y <_2> represent the aromatic group containing an alkyl group, an aryl group, an aralkyl group, or a hetero atom which may be same or different and may have a substituent.

n represents the integer of 1-4. When n is two or more, two or more R <_1> and R <_2> may be same or different.

Two or more of R ₁ to R ₃ , R ₄ , R ₅ , Y _1, and Y ₂ may be bonded to form a ring structure.

Moreover, you may couple | bond with a coupling group in any one of R <_1> -R <_3> , R <_4> , R <_5> , Y <_1> and Y <_2> , and may have two or more structures of general formula (I) or (II).

X ⁻ represents a non-nucleophilic anion.

(6) The photosensitive composition according to any one of (1) to (5), further comprising a basic compound and a fluorine and / or silicone surfactant.

(7) The compound according to (6), wherein the basic compound has at least a compound having a structure selected from imidazole structure, diazabicyclo structure, onium hydroxide structure, onium carboxylate structure, trialkylamine structure and aniline structure It contains 1 type, The photosensitive composition characterized by the above-mentioned.

(8) The soluble base material having a molecular weight of 3000 or less in any one of (1) to (4) and (6) to (7), which further has a group which is decomposed by the action of an acid to increase the solubility in the alkali developer. A photosensitive composition comprising a low molecular weight compound.

(9) A compound characterized by the following general formula (I) or (II).

In general formula (I) and (II),

R ₁ to R ₃ may be the same or different and represent an alkyl group, an alkenyl group, an aryl group or an alkoxy group which may have a hydrogen atom or a substituent.

R <_4> and R <_5> may be same or different and represents the alkyl group, the aryl group, or the alkoxy group which may have a hydrogen atom, a cyano group, or a substituent.

Y <_1> and Y <_2> represent the aromatic group containing an alkyl group, an aryl group, an aralkyl group, or a hetero atom which may be same or different and may have a substituent.

n represents the integer of 1-4. When n is two or more, two or more R <_1> and R <_2> may be same or different.

Two or more of R ₁ to R ₃ , R ₄ , R ₅ , Y _1, and Y ₂ may be bonded to form a ring structure.

Moreover, you may couple | bond with a coupling group in any one of R <_1> -R <_3> , R <_4> , R <_5> , Y <_1> and Y <_2> , and may have two or more structures of general formula (I) or (II).

X ⁻ represents a non-nucleophilic anion.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

The present invention relates to a potato polar composition containing a compound represented by the above general formula (I) or (II) which generates an acid or a radical by stimulation from the outside, more preferably by irradiation with actinic radiation or radiation A photosensitive composition containing a compound represented by the general formula (I) or (II) for generating an acid and a compound represented by the general formula (I) or (II) for generating an acid by irradiation with actinic light or radiation It is about.

As a photosensitive composition which concerns on this invention, a positive photosensitive composition and a negative photosensitive composition can be illustrated, Preferably a positive photoresist composition and a negative photoresist composition can be illustrated.

The positive photosensitive composition which concerns on this invention is decomposed | disassembled by the action of the compound represented by the said general formula (I) or (II) which generate | occur | produces an acid by irradiation of (A) actinic light or a radiation, and (B) acid, It contains a resin which increases the solubility in the alkali developer, and if necessary, further contains a dissolution inhibiting compound having a molecular weight of 3,000 or less, which is decomposed by the action of an acid to increase the solubility in the alkali developer, or (A) active light Or molecular weight 3000, in which the solubility in an alkali developer is increased by decomposition by the action of the compound represented by the general formula (I) or (II), (D) an alkali-soluble resin and an acid that generates an acid by irradiation with radiation. It contains the following dissolution inhibiting compound.

The negative photosensitive composition which concerns on this invention is a compound represented by said general formula (I) or (II) which generate | occur | produces an acid by irradiation of (A) actinic light or a radiation, (D) alkali-soluble resin, and (C) acid It contains an acid crosslinking agent which crosslinks with this alkali-soluble resin by the effect | action of.

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

Compounds that generate acids or radicals by stimulation from the outside are active acids such as infrared rays, visible light, ultraviolet light, and far ultraviolet light, charged particle beams such as X-rays and electron beams, and external stimuli such as heat and ultrasonic waves. Or a compound that generates radicals, and more preferably a compound that generates an acid by irradiation with actinic light or radiation.                     

In General Formulas (I) and (II), R ₁ to R ₃ may be the same or different and represent an alkyl group, an alkenyl group, an aryl group or an alkoxy group which may have a hydrogen atom or a substituent. R <_4> and R <_5> may be same or different and represents the alkyl group, the aryl group, or the alkoxy group which may have a hydrogen atom, a cyano group, or a substituent. Y <_1> and Y <_2> represent the aromatic group containing an alkyl group, an aryl group, an aralkyl group, or a hetero atom which may be same or different and may have a substituent. n represents the integer of 1-4. When n is two or more, two or more R <_1> and R <_2> may be same or different. Two or more of R ₁ to R ₃ , R ₄ , R ₅ , Y _1, and Y ₂ may be bonded to form a ring structure. In addition, at any one of R <_1> -R <_3> , R <_4> , R <_5> , Y <_1> and Y <_2> , it may couple through a coupling group and may have two or more structures of general formula (I) or (II). X ⁻ represents a non-nucleophilic anion.

The alkyl group of R ₁ to R ₅ , Y ₁ and Y ₂ is preferably an alkyl group having 1 to 10 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, n-butyl group, sec-butyl group, t-butyl group, Linear, branched, and cyclic alkyl groups, such as a pentyl group, a cyclopentyl group, a hexyl group, and a cyclohexyl group, can be illustrated. The alkyl group may have an oxygen atom, a sulfur atom, a carbonyl group, or the like in the alkyl chain.

The aryl groups of R ₁ to R ₅ , Y _1, and Y ₂ are preferably aryl groups having 6 to 14 carbon atoms, and examples thereof include a phenyl group, a tolyl group, a naphthyl group, and the like.

The alkenyl group of R ₁ to R ₃ is preferably an alkenyl group having 2 to 6 carbon atoms, for example, a vinyl group, propenyl group, allyl group, butenyl group, pentenyl group, hexenyl group, cyclopentenyl group, cyclohexenyl group , 3-oxocyclopentenyl group, 3-oxocyclohexenyl group, etc. can be illustrated.

The alkoxy group of R ₁ to R ₅ is preferably an alkoxy group having 1 to 8 carbon atoms, for example, a methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, butoxy group, pentoxy group, allyloxy group or octo. Oxy group etc. can be illustrated.

Aralkyl groups of Y ₁ and Y ₂ are preferably aralkyl groups having 7 to 12 carbon atoms, and examples thereof include benzyl groups, phenethyl groups, cumyl groups, and the like.

The aromatic group containing a hetero atom represents, for example, a group having a hetero atom, for example, a nitrogen atom, an oxygen atom, a sulfur atom, or the like in an aromatic group such as an aryl group having 4 to 14 carbon atoms.

As an aromatic group containing the hetero atom of Y <_1> and Y <_2> , heterocyclic aromatic hydrocarbon groups, such as furan, thiophene, a pyrrole, a pyridine, an indole, are illustrated, for example.

As a ring structure which two or more of R <_1> -R <_3> , R <_4> , R <_5> , Y <_1> and Y <_2> combine and form, For example, R <_1> or R <_2> and the ring structure which R <_3> combines and forms, R ₁ or R ₂ , a ring structure formed by bonding of R ₄ or R ₅ , R ₃ , a ring structure formed by bonding of R ₄ or R ₅ , R ₁ , R ₂ , and R ₄ or R ₅ Ring structure formed by bonding, R ₁ , R ₂ , R ₃ , ring structure formed by R ₄ or R ₅ bonding, Y ₁ , and Y ₂ are bonded to general formula (I) or (II) The ring structure etc. which are formed with S <^+> in the inside can be illustrated.

When R <_1> or R <_2> and R <_3> combine and form ring structure, As group which R <_1> or R <_2> and R <_3> combine to form, Preferably, it is a C1-C10 alkylene group, for example, , Methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group and the like.

When R ₁ or R ₂ and R ₄ or R ₅ are bonded to form a ring structure, examples of the group formed by bonding of R ₁ or R ₂ to R ₄ or R ₅ include an alkylene group, a carbonyl group, and the like. It can be illustrated. As an alkylene group, Preferably, a C1-C10 alkylene group, for example, a methylene group, ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, etc. can be illustrated.

When R <_3> and R <_4> or R <_5> combine and form ring structure, As group which R <_3> and R <_4> or R <_5> combine and form, Preferably, it is a C1-C10 alkylene group, for example, , Methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group and the like.

As with R ₁ and, R _2, R ₄ or ring structure and R ₁ and, R ₂ and, R ₃ and, R ₄ or a ring structure of R ₅ it is formed by combining any of R ₅ is formed by combining, for example, carbon atoms The 5-15 bicyclic condensed ring structure can be illustrated, and it may have a hetero atom in a ring.

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

In this case, examples of the group formed by bonding of Y ₁ and Y ₂ include, for example, an alkylene group having 4 to 10 carbon atoms, preferably a butylene group, a pentylene group, a hexylene group, and particularly preferably a butylene group and a pentylene group. can do.

In addition, Y <_1> and Y <_2> may combine, and may contain the hetero atom in the ring formed with S <^+> in general formula (I) or (II).

Each of the alkyl group, alkenyl group, aryl group, aralkyl group, aromatic group, and cyclic structure may be, for example, a nitro group, a halogen atom, a carboxyl group, a hydroxyl group, an oxo group, an amino group, a cyano group, or an alkoxy group (preferably having 1 to 3 carbon atoms). 5) may be substituted. Moreover, about an aryl group and an aralkyl group, you may substitute by the alkyl group (preferably C1-C5).

Moreover, as a substituent of an alkyl group, a halogen atom, a hydroxyl group, and an alkoxy group are preferable.

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

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

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

As a carboxylic acid anion, an alkylcarboxylic acid anion, an arylcarboxylic acid anion, an aralkyl carboxylic acid anion, etc. are illustrated, 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, neo Pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group A real group, an ecosyl group, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a norbornyl group, a boronyl group, etc. can be illustrated.

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

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

As a substituent, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group etc. can be illustrated, for example.

As a halogen atom, a chlorine atom, a bromine atom, a fluorine atom, an iodine atom, etc. can be illustrated, for example.                     

As the alkyl group, for example, preferably an alkyl group having 1 to 15 carbon atoms, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, pentyl group, neopentyl group, hex Real group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group Etc. can be illustrated.

As an alkoxy group, Preferably, a C1-C5 alkoxy group, for example, a methoxy group, an ethoxy group, a propoxy group, butoxy group etc. can be illustrated.

As the alkylthio group, for example, preferably an alkylthio group having 1 to 15 carbon atoms, such as methylthio group, ethylthio group, propylthio group, isopropylthio group, n-butylthio group, isobutylthio group, sec -Butylthio group, pentylthio group, neopentylthio group, hexylthio group, heptylthio group, octylthio group, nonylthio group, decylthio group, undecylthio group, dodecylthio group, tridecylthio group, tetradecyl tea Ogi, pentadecylthio group, hexadecylthio group, heptadecylthio group, an octadecylthio group, a nonadecylthio group, an eicosylthio group etc. can be illustrated. In addition, the alkyl group, the alkoxy group, and the alkylthio group may be further substituted with a halogen atom (preferably a fluorine atom).

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

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

As the aralkyl group in the aralkyl carboxylic acid anion, preferably aralkyl groups having 6 to 12 carbon atoms, for example, benzyl group, phenethyl group, naphthylmethyl group, naphthylethyl group and the like can be exemplified.

The alkyl group, aryl group and aralkyl group in the alkyl carboxylic acid anion, the aryl carboxylic acid anion and the aralkyl carboxylic acid anion may have a substituent, and examples of the substituent include a halogen atom as in the aryl sulfonic acid anion. , Alkyl group, alkoxy group, alkylthio group and the like can be exemplified.

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 and the like can be exemplified. These alkyl groups may have a substituent and a halogen atom, an alkoxy group, an alkylthio group etc. can be illustrated as a substituent, for example.

As another non-nucleophilic anion, phosphorus fluoride, boron fluoride, antimony fluoride etc. can be illustrated, 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 in which an alkyl group is substituted with a fluorine atom An anion and a tris (alkylsulfonyl) methion anion in which the alkyl group is substituted with a fluorine atom are preferable, and particularly preferably a perfluoroalkanesulfonic anion having 1 to 8 carbon atoms, most preferably a nonafluorobutanesulfonic anion, and a perfluoro Rooctane sulfonic acid anion.

In general formula (I) or (II), it couple | bonds through a coupling group in any one of R <_1> -R <_3> , R <_4> , R <_5> , Y <_1> and Y <_2> , and general formula (I) or (II) You may have two or more structures.

The acid generator (A) of the present invention is characterized by having two kinds of bonds conjugated to a carbonyl group, thereby stabilizing an excited state and improving acid generating ability.

Further, when R ₁ or R ₂ and R ₄ or R ₅ combine to form a ring structure, or R ₃ and R ₄ or R ₅ combine to form a ring structure, the steric structure is a π * moiety of carbonyl. And C-S + σ start are fixed so as to be in parallel, and the acid generating ability is improved, which is more preferable.

In an acid generator (A), n = 1 or 2 is preferable, Especially preferably, n = 1.

It is preferable that two of R <_1> -R <_5> couple | bonds through an alkylene group, and forms the polycyclic cyclic structure containing a 5-7 membered ring or a 5-7 membered ring.

R ₄ and R ₅ are preferably a hydrogen atom or an alkyl group.

It is preferable that Y <_1> , Y <_2> couple | bonds through an alkylene group, and forms a 5-7 membered ring.

Although the preferable specific example of a compound represented by the said general formula (I) or (II) of this invention is shown below, this invention is not limited to this.

The compounds of the general formula (I) or (II) may be used alone or in combination of two or more thereof.

The compound represented by the general formula (I) or (II) is synthesized by reacting the corresponding unsaturated ketone compound with methylsilyl chloride or the like under basic conditions, and then reacting with sulfoxide to form a sulfonium salt, followed by salt exchange. can do.

In addition, the compound represented by general formula (I) or (II) is a halogenated α-position or an allyl position of a ketone of a corresponding unsaturated ketone compound by bromine or copper bromide, etc. After making it into a ketone, it can synthesize | combine it by making a sulfide compound react with this in presence of a noncatalyst or a silver catalyst, making it a sulfonium salt, and salt-exchanging.

As for content in the photosensitive composition of this invention of the compound of (A) component, 0.1-20 weight% is preferable based on solid content of a composition, More preferably, it is 0.5-10 weight%, More preferably, 1-7 Weight percent.

Acid-generating compounds which can be used in combination other than the component (A)

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

The amount of the acid generator that can be used in combination with the component (A) of the present invention is usually in the molar ratio (component (A) / other acid generator), and is usually 100/0 to 20/80, preferably 100/0 to 40/60, More preferably, it is 100 / 0-50 / 50.

When using together the acid valuation agent which has an aromatic ring structure especially, the usage-amount is 60 weight% or less of a total acid generator by weight ratio, More preferably, it is 50% or less.                     

As such acid generators that can be used together, acid is generated by irradiation of actinic rays or radiation used in photoinitiators of photocationic polymerization, photoinitiators of photoradical polymerization, photochromic agents of pigments, photochromic agents, or microresists. Known compounds and mixtures thereof can be appropriately selected and used.

For example, diazonium salt, phosphonium salt, sulfonium salt, iodonium salt, imide sulfonate, oxime sulfonate, diazo disulfone, disulfone, o-nitrobenzyl sulfonate can be illustrated.

Especially preferably, it is a sulfonium salt, and the sulfonium salt which has a triaryl sulfonium salt, a phenacyl sulfonium salt, and a 2-oxoalkyl group is the most preferable.

Moreover, the compound which introduce | transduced the group which generate | occur | produces an acid by these actinic rays or radiation, or a compound in the main chain or side chain of a polymer, for example, US Patent No. 3,849,137, German Patent No. 3914407, Japanese Patent Laid-Open No. 63- 26653, Japanese Patent Publication No. 55-164824, Japanese Patent Publication No. 69-69263, Japanese Patent Publication No. 63-146038, Japanese Patent Publication No. 63-163452, Japanese Patent Publication No. 62-153853, Japanese Patent The compound of Unexamined-Japanese-Patent No. 63-146029 etc. can be used.

In addition, a compound which generates an acid by light described in US Pat.

As a particularly preferable compound among compounds which decompose upon irradiation with actinic rays or radiation which may be used in combination, to generate an acid, compounds represented by the following general formulas (ZI), (ZII) and (ZIII) can be exemplified.

In the general formula (Z1), R ₂₀₁ , R _202, and R ₂₀₃ each independently represent an organic group.

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

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 illustrated.

Moreover, the compound which has two or more structures represented by general formula (Z1) may be sufficient. For example, the compound represented by formula (Z1), at least one of R ₂₀₁ ~R _203, the formula compound having the structure and at least one combination of (Z1) coming from another compound of R ₂₀₁ ~R ₂₀₃ represented by It may be.

As a more preferable (Z1) component, the compound (Z1-1), (Z1-2), and (Z1-3) demonstrated below can be illustrated.

Compound (Z1-1) is a compound in which each of R ₂₀₁ to R _{203 in} the general formula (Z1) is an aryl group, and a triarylsulfonium compound, that is, a triarylsulfonium as a cation.

As an aryl group of a triarylsulfonium cation, a phenyl group and a naphthyl group are preferable, More preferably, it is a phenyl group. The three aryl groups of the triarylsulfonium cation may be the same or different.

Each aryl group may have an alkyl group (for example, C1-C15), 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 linear, branched or cyclic alkyl group, a C1-C12 linear, branched or cyclic alkoxy group, Most preferably, they are a C1-C4 alkyl group and a C1-C4 alkoxy group. . The substituent may be substituted with any of three aryl groups, or may be substituted with all three. Moreover, it is preferable that the substituent is substituted by the p-position of an aryl group.

Next, compound (Z1-2) is demonstrated.

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

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

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

The alkyl group as R ₂₀₁ to R ₂₀₃ may be any of linear, branched or cyclic, preferably, a linear or branched alkyl group having 1 to 10 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, pentyl group), C3-C10 cyclic alkyl group (cyclopentyl group, cyclohexyl group, norbornyl group) can be illustrated.

The 2-oxoalkyl group as R ₂₀₁ to R ₂₀₃ may be any of straight chain, branched or cyclic, and preferably, a group having> C═O at the 2-position of the alkyl group can be exemplified.

As an alkoxy group in the alkoxycarbonylmethyl group as R <_201> -R <_203> , Preferably, the C1-C5 alkyl group (methyl group, ethyl group, propyl group, butyl group, pentyl group) can be illustrated.

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

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

A compound (Z1-3) is a compound represented by the following general formula (Z1-3), and is a compound which has a phenacylsulfonium salt structure.

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

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

Rx and Ry each independently represent an alkyl group, a 2-oxoalkyl group, an alkoxycarbonylmethyl group, an allyl group, or a vinyl group.

Two or more of R _1c to R _7c , and Rx and Ry 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, and an amide bond.

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

The alkyl group as R _1c to R _5c may be any of linear, branched or cyclic, for example, an alkyl group having 1 to 10 carbon atoms, preferably a linear and branched alkyl group having 1 to 5 carbon atoms (eg, a methyl group, an ethyl group, a straight chain or Branched propyl group, linear or branched butyl group, linear or branched pentyl group), and C3-C8 cyclic alkyl group (for example, cyclopentyl group, cyclohexyl group) can be illustrated.

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). The time period, a linear or branched propoxy group, a linear or branched butoxy group, a linear or branched pentoxy group, and a C3-C8 cyclic alkoxy group (for example, a cyclopentyloxy group, a cyclohexyloxy group) can be illustrated.

Preferably, any of R <_1c> -R <_5c> is a linear, branched, cyclic alkyl group, or a linear, branched, cyclic 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 particle | grains is suppressed at the time of storage.

About the alkyl group as R <_6c> and R <_7c> , the same thing as the alkyl group as R <_1c> -R <_5c> can be illustrated. As an aryl group, a C6-C14 aryl group (for example, a phenyl group) can be illustrated, for example.

The alkyl group as Rx and Ry can illustrate the same thing as the alkyl group as R <_1c> -R <_5c> .

2-oxoalkyl group can illustrate the group which has> C = O at 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 .

As a group which Rx and Ry combine and form, a butylene group, a pentylene group, etc. can be illustrated.

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

As an aryl group as R <_204> -R <_207>, a phenyl group and a naphthyl group are preferable, More preferably, it is a phenyl group.

The alkyl group as R ₂₀₄ to R ₂₀₇ may be any of linear, branched or cyclic, preferably, a linear or branched alkyl group having 1 to 10 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, pentyl group), C3-C10 cyclic alkyl group (cyclopentyl group, cyclohexyl group, norbornyl group) can be illustrated.

As a substituent which may have R <_204> -R <_207> , for example, an alkyl group (for example, C1-C15), an aryl group (for example, C6-C15), an alkoxy group (for example, C1-C15), a halogen atom, a hydroxyl group, phenyl thi Ogi etc. can be illustrated.

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

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

[2] (B) A resin that is decomposed by the action of an acid and has increased solubility in an alkali developer (referred to as an "acid decomposable resin")

As a resin which is decomposed by an acid used in the positive photosensitive composition of the present invention and the solubility in an alkali developer is increased, a group which can be decomposed by an acid in both the main chain or the side chain of the resin, or both the main chain and the side chain (hereinafter, , An "acid-decomposable group"). Among these, resin which has a group which can decompose | dissolve into an acid in a side chain is more preferable.                     

As a group which can be decomposed | dissolved into an acid, preferable group is group which substituted the hydrogen atom of -COOH group and -OH group with an acid-decomposable group.

As the acid-decomposable group, preferably, silyl ether group, cumyl ester group, acetal group, tetrahydropyranyl ether group, enol ether group, enol ester group, tertiary alkyl ether group, tertiary alkyl ester group, agent Tertiary alkyl carbonate groups; More preferably, they are tertiary alkyl ester group, tertiary alkyl carbonate group, cumyl ester group, acetal group, and tetrahydropyranyl ether group.

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

The alkali dissolution rate of these alkali-soluble resins is preferably 170 Pa / sec or higher as measured by 0.261 N tetramethylammonium hydroxide (TMAH) (23 ° C). Especially preferably, it is 330 microseconds / sec or more (it is Angstrom).

In view of this, particularly preferred alkali-soluble resins are o-, m-, p-poly (hydroxystyrene) and these copolymers, hydrogenated poly (hydroxystyrene), halogen or alkyl-substituted poly (hydroxystyrene), A hydroxystyrene structural unit such as a part of poly (hydroxystyrene), O-alkylated or O-acylate, styrene-hydroxystyrene copolymer, α-methylstyrene-hydroxystyrene copolymer, hydrogenated novolac resin Alkali-soluble resin.

Component (B) used in the present invention is decomposed to an acid in an alkali-soluble resin, as disclosed in European Patent No. 254853, Japanese Patent Application Laid-Open No. 2-25850, Japanese Patent No. 3-223860, Japanese Patent No. 4-251259 and the like. The alkali-soluble resin monomer which reacted the precursor of the group which can be made, or the group which can decompose | disassemble into an acid can be obtained by copolymerizing with various monomers.

Although the specific example of component (B) 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% hydrogen additive) copolymer,

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

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

p- (t-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,

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

When irradiating ArF excimer laser light to the positive photosensitive composition which concerns on this invention, resin of (B) component has monocyclic or polycyclic alicyclic hydrocarbon structure, decomposes by the action of an acid, and the solubility to an alkaline developing solution is carried out. It is preferable that it is an increasing resin.

As a resin having a monocyclic or monocyclic alicyclic hydrocarbon structure, which is decomposed by the action of an acid and has increased solubility in an alkali developing solution (hereinafter referred to as &quot; alicyclic hydrocarbon-based acid decomposable resin &quot;), the following general formulas (pI) to It is preferable that it is resin containing at least 1 sort (s) chosen from the group of the repeating unit which has a partial structure containing an alicyclic hydrocarbon represented by general formula (pVI), and the 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, and Z is used to form an alicyclic hydrocarbon group together with a carbon atom) Mark the atomic group required for.

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

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

R ₂₂ to R ₂₅ each independently represent a linear or branched alkyl group or an alicyclic hydrocarbon group having 1 to 4 carbon atoms, 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 formula (II-AB),

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

Z '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 ' each independently represent a hydrogen atom, a halogen atom, a cyano group, -COOH, -COOR _5- , a group decomposed by the action of an acid, -C (= O) -X-A ' -R ₁₇ have a ', or a substituent optionally represents an alkyl or cyclic hydrocarbon group.

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

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

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

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

R ₁₇ 'are, -COOH, represents -COOR _5, -CN, a hydroxyl group, which may have a substituent, an alkoxy group, a group _{-CO-NH-R 6, -CO} -NH-SO 2 -R 6 or a -Y .

R ₆ represents an alkyl group or a cyclic hydrocarbon group which may have a substituent.

-Y group;

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

In general formula (pI)-(pVI), as an alkyl group in R <_12> -R <_25> , the linear or branched alkyl group which has 1-4 carbon atoms which may be either substituted or unsubstituted is represented. As this alkyl group, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group etc. are illustrated, for example.

Further, other substituents of the alkyl group include an alkoxy group having 1 to 4 carbon atoms, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), acyl group, acyloxy group, cyano group, hydroxyl group, carboxyl group, alkoxycarbonyl group, Nitro group etc. can be illustrated.

The alicyclic hydrocarbon group in R ₁₁ to R ₂₅ or the alicyclic hydrocarbon group formed by Z and a carbon atom may be monocyclic or polycyclic. Specifically, the group which has a C5 or more monocyclo, bicyclo, tricyclo, tetracyclo structure, etc. can be illustrated. 6-30 are preferable and, as for the carbon number, 7-25 are especially preferable. These alicyclic hydrocarbon groups may have a substituent.

Below, the structural example of an alicyclic part is shown in an alicyclic hydrocarbon group.

In the present invention, preferred examples of the alicyclic moiety include an adamantyl group, noadamantyl group, decarin moiety, tricyclodecanyl group, tetracyclododecanyl group, norbornyl group, cedrol group, cyclohexyl group and cycloheptyl group , A cyclooctyl group, a cyclodecanyl group, and a cyclododecanyl group can be illustrated. More preferably, they are an adamantyl group, a decalin residue, a norbornyl group, a cedrol group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecanyl group, and a cyclododecanyl group.

As a substituent of these alicyclic hydrocarbon groups, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, an alkoxyl group, a carboxyl group, and an alkoxycarbonyl group are illustrated. As an alkyl group, lower alkyl groups, such as a methyl group, an ethyl group, a propyl group, 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 a substituent of a substituted alkyl group, a hydroxyl group, a halogen atom, and an alkoxyl group can be illustrated. As said alkoxyl group, 1-4 things, such as a methoxy group, an ethoxy group, a propoxy group, butoxy group, can be illustrated.

The structure represented by general formula (pI)-(pVI) in the said resin can be used for protection of an alkali-soluble group. Examples of the alkali-soluble group include various groups known in the art.

As the specific example, a carboxylic acid group, a sulfonic acid group, a phenol group, and a thiol group are mentioned, A carboxylic acid group and a sulfonic acid group are preferable.

As an alkali-soluble group protected by the structure represented by general formula (pI)-(pVI) in the said resin, Preferably, the group represented by the following general formula (pVII)-(pXI) is illustrated.

Wherein R ₁₁ to R ₂₅ and Z are the same as defined above, respectively.

In the said resin, it is preferable that it is a repeating unit represented with the following general formula (pA) as a repeating unit which has the alkali-soluble group protected by the structure represented by general formula (pI)-(pVI).

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.

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

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

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 which may have a substituent.

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

As a halogen atom in said R <_11>', R <_12>', a chlorine atom, a bromine atom, a fluorine atom, an iodine atom, etc. can be illustrated.

Wherein _{R 11 ', R 12',} R 21 the alkyl group in the '~R _30', C1-10 linear or branched alkyl group and more preferably 1 to 6 carbon atoms of straight or branched 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 substituent in the said alkyl group, a hydroxyl group, a halogen atom, a carboxyl group, an alkoxy group, an acyl group, a cyano group, an acyloxy group, etc. can be illustrated. Examples of the halogen atom include chlorine, bromine, fluorine and iodine atoms. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as methoxy, ethoxy, propoxy and butoxy groups. As a real group, a formyl group, an acetyl group, etc. can be illustrated, and an acetoxy group etc. can be illustrated as an acyloxy group.

The atomic group for forming the alicyclic structure of Z 'is an atomic group for forming a repeating unit of an alicyclic hydrocarbon which may have a substituent in the resin, and a bridged alicyclic structure for forming a repeating unit of an alicyclic hydrocarbon which has been bridged therein. Atom groups for forming are preferred.

Examples of the skeleton of the alicyclic hydrocarbon formed include the above structural examples (1) to (R ₁₁ to R ₂₅ in general formulas (pI) to (pVI) and Z 'alicyclic moieties in general formula (II-AB). 51) is illustrated.

As a preferable bridge | crosslinked alicyclic hydrocarbon, as for the structure, (5), (6), (7), (9), (10), (13), (14), (15), (23) in the said structural example. , 28, 36, 37, 42, 47 are illustrated.

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

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

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

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

In formula, R <_{0> is} tertiary alkyl groups, such as t-butyl group and t-amyl group, isoboroyl group, 1-ethoxyethyl group, 1-butoxyethyl group, 1-isobutoxyethyl group, 1-cyclohexyloxyethyl group, etc. Alkoxymethyl groups, such as 1-alkoxyethyl group, 1-methoxymethyl group or 1-ethoxymethyl group, 3-oxoalkyl group, tetrahydropyranyl group, tetrahydrofuranyl group, trialkylsilyl ester group, 3-oxocyclohexyl ester group , 2-methyl-2-adamantyl group, mevalonic lactone residue, etc. can be illustrated. X ₁ is the same as X.

As a halogen atom in said R <_13> -R <_16>', a chlorine atom, a bromine atom, a fluorine atom, an iodine atom, etc. can be illustrated.

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 and 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, methyl group, isomentyl group, neomentyl group, tetracyclododecanyl group, etc. Can be illustrated.

Examples of the ring formed by bonding at least two of R ₁₃ 'to R ₁₆ ' to each other include a C 5-12 ring such as cyclopentene, cyclohexene, cycloheptane and cyclooctane.

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

As another substituent in the said alkyl group, a cyclic hydrocarbon group, and an alkoxy group, a hydroxyl group, a halogen atom, a carboxyl group, an alkoxy group, an acyl group, a cyano group, an acyloxy group, an alkyl group, a cyclic hydrocarbon group, etc. can be illustrated. As a halogen atom, a chlorine atom, a bromine atom, a fluorine atom, an iodine atom, etc. can be illustrated. As an alkoxy group, C1-C4 things, such as a methoxy group, an ethoxy group, a propoxy group, butoxy group, can be illustrated, A formyl group, an acetyl group, etc. can be illustrated as an acyl group, As an acyloxy group, The timing can be illustrated.

In addition, an alkyl group and a cyclic hydrocarbon group are illustrated by the above.

As the divalent linking group for A ', an alkylene group, a substituted alkylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a sulfonamide group, a urethane group, or a urea group is selected alone or in combination of two or more. Combinations of groups are illustrated.

As an alkylene group and substituted alkylene group in said A ', group represented by a following formula can be illustrated.

-[C (R _a ) (R _b )] _r-

In formula, R _<a> , R <_b> represents a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, and an alkoxy group, and both may be same or different. As an alkyl group, lower alkyl groups, such as a methyl group, an ethyl group, a propyl group, isopropyl group, and a butyl group, are preferable, More preferably, they are selected from a methyl group, an ethyl group, a propyl group, and an isopropyl group. As a substituent of a substituted alkyl group, a hydroxyl group, a halogen atom, and an alkoxy group can be illustrated. As an alkoxy group, C1-C4 things, such as a methoxy group, an ethoxy group, a propoxy group, butoxy group, can be illustrated. As a halogen atom, a chlorine atom, a bromine atom, a fluorine atom, an iodine atom, etc. can be illustrated. r represents the integer of 1-10.

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

Various substituents of R ₁₃ ′ to R ₁₆ ′ in General Formula (II-A) or General Formula (II-B) are atomic groups for forming an alicyclic structure in General Formula (II-AB). To substituents of the atomic group Z to form a bridged alicyclic structure.

Although the following are 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.

The alicyclic hydrocarbon-based acid decomposable resin of the present invention preferably contains a repeating unit having a group having a lactone structure represented by any one of the following general formulas (Lc) or the following general formulas (V-1) to (V-5). Do.

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

In General Formulas (V-1) to (V-5), R _1b to R _5b are each independently an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group or an alkylsulfonyl, which may have a hydrogen atom or a substituent. An imino group or an alkenyl group is represented. Two of R _1b to R _5b may be bonded to each other to form a ring.

Alkyl group of Ra <_1> -Re <_1> in general formula (Lc), Alkyl group, alkoxy group, alkoxycarbonyl group, alkylsulfonyl group of R <_1b> -R < _5b in general formula (V-1)-(V-5) As an alkyl group in a furnace group, a linear and branched alkyl group may be illustrated and may have a substituent.

As a linear or branched alkyl group, a C1-C12 linear or branched alkyl group is preferable, More preferably, it is a C1-C10 linear or branched alkyl group, More preferably, a methyl group, an ethyl group, and a propyl group , Isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group and decyl group.

As a cycloalkyl group in R <_1b> -R <_5b> , C3-C8 things, such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group, are preferable.

As an alkenyl group in R <_1b> -R <_5b> , C2-C6 things, such as a vinyl group, a propenyl group, butenyl group, and a hexenyl group, are preferable.

Moreover, as a ring formed by combining two of R <_1b> -R <_5b> , 3-8 membered rings, such as a cyclo propane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, and a cyclooctane ring, are illustrated.

In addition, R _1b to R _5b in General Formulas (VI) to (V-5) may be bonded to any one of the carbon atoms constituting the cyclic skeleton.

As a preferable substituent which the alkyl group of Ra <_1> -Re <_{1> and} the alkyl group of R <_1b> -R < _6b , a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylsulfonyl imino group, and an alkenyl group may hold, a C1-C4 alkoxy group, Halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), acyl group of 2 to 5 carbon atoms, acyloxy group of 2 to 5 carbon atoms, cyano group, hydroxyl group, carboxyl group, alkoxycarbonyl group of 2 to 5 carbon atoms, nitro group Etc. can be illustrated.

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' represents the formula (Lc) or the general formula (V-1) ~ R ₅ is of the formula (V-5) to (e.g., -COOR ₅ having a group represented by (Lc) Or a group represented by general formulas (V-1) to (V-5)), or a repeating unit represented by the following general formula (AI).

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

As a halogen atom of R <_b0> , a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom can be illustrated. 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 a group represented by any one of General Formulas (Lc) or General Formulas (V-1) to (V-5). In A ', the thing of the following formula is illustrated as this combined bivalent group, for example.

In the above formula, R _ab , R _bb represent a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, or an alkoxy group, and both may be the same or different.

As an alkyl group, lower alkyl groups, such as a methyl group, an ethyl group, a propyl group, isopropyl group, and a butyl group, are preferable, More preferably, they are selected from a methyl group, an ethyl group, a propyl group, and an isopropyl group. As a substituent of a substituted alkyl group, a hydroxyl group, a halogen atom, and a C1-C4 alkoxyl group can be illustrated.

As an alkoxy group, C1-C4 things, such as a methoxy group, an ethoxy group, a propoxy group, butoxy group, can be illustrated. Examples of the halogen atom include chlorine atom, bromine atom, fluorine atom and iodine atom. r1 represents the integer of 1-10, Preferably the integer of 1-4 is represented. m represents an integer of 1 to 3, preferably 1 or 2.

Although the specific example of the repeating unit represented by general formula (AI ') is illustrated below, the content of this invention is not limited to these.

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 dihydroxyl or a monohydroxyl, more preferably a dihydroxyl.

As a repeating unit which has group represented by general formula (VII), at least 1 of R <_13>'-R<_16>' in general formula (II-A) or (II-B) is group represented by said general formula (VII) to (e. g. a represents an R ₅ of -COOR ₅ represented by formula (VII)), or to which there may be mentioned a repeating unit represented by the following formula (AII).

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.

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

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

In the general formula (VIII), Z ₂ represents -O- or -N (R ₄₁ )-. R ₄₁ represents a hydrogen atom, a hydroxyl group, an alkyl group, a haloalkyl group, or -OSO ₂ -R ₄₂ . R ₄₂ represents an alkyl group, haloalkyl group, cycloalkyl group, or camphor residue.

As said alkyl group in said R <_41> and R <_42> , a C1-C10 linear or branched alkyl group is preferable, More preferably, it is a C1-C6 linear or branched alkyl group, More preferably, a methyl group, Ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group.

Examples of the haloalkyl group for R ₄₁ and R ₄₂ include trifluoromethyl group, nonafluorobutyl group, pentadecafluorooctyl group, trichloromethyl group and the like. As a cycloalkyl group in said R <_42> , a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, etc. can be illustrated.

The alkyl group and haloalkyl group as R ₄₁ and R ₄₂ , the cycloalkyl group or camphor moiety as R ₄₂ may have a substituent. As such a substituent, a hydroxyl group, a carboxyl group, a cyano group, a halogen atom (for example, a chlorine atom, a bromine atom, a fluorine atom, an iodine atom), an alkoxy group (preferably C1-C4, for example, a methoxy group, an ethoxy group, Propoxy group, butoxy group, etc.), acyl group (preferably having 2 to 5 carbon atoms, such as formyl group, acetyl group, etc.), acyloxy group (preferably having 2 to 5 carbon atoms, such as acetoxy group), aryl Group (preferably C6-C14, a phenyl group) etc. can be illustrated.

Although the following [I'-1]-[I'-7] are illustrated as a specific example of the repeating unit represented by said general formula (VIII), this invention is not limited to these specific examples.

In addition to the repeating structural unit, the alicyclic hydrocarbon-based acid decomposable resin of the present invention may be used to control dry etching resistance, standard developer aptitude, substrate adhesion, resist profile, and resolution, heat resistance, and sensitivity, which are generally required characteristics of resist. It may contain repeating structural units.

As such a repeating structural unit, although the repeating structural unit corresponded to the following monomer can be illustrated, it is not limited to this.

Thereby, the performance required for the alicyclic hydrocarbon-based acid-decomposable resin, in particular,

(1) solubility in coating solvents,

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

(3) alkali developability,

(4) film loss (selection of hydrophilic, alkali-soluble groups),

(5) adhesion to the substrate of the non-exposed part,

(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, etc. It can be illustrated.

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

In cycloaliphatic hydrocarbon-based acid-decomposable resins, the molar ratio of each repeating structural unit is used to control dry etching resistance of resist, standard developer aptitude, substrate adhesion, resist profile, and resolution, heat resistance, sensitivity, etc. It is set appropriately.

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

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

(2) containing repeating units represented by the general formula (II-AB) (backbone type)

However, in (2), the following are further illustrated, 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 the partial structure containing alicyclic hydrocarbon represented by general formula (pI)-(pVI), in an alicyclic hydrocarbon type acid-decomposable resin, 30-70 mol% is preferable in all the repeating structural units, More preferably, it is 35-65 mol%, More preferably, it is 40-60 mol%.                     

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

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

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

Further, in the case of irradiating F ₂ excimer laser light in the positive photosensitive composition of the present invention, (B) resins, having a fluorine atom-substituted structures in the main chain and / or side chain of the polymer backbone, and the action of an acid of the component A resin (decomposed also as a fluorine group-containing resin) which is decomposed by decomposition to increase the solubility in an alkali developer is preferable, and at least a portion selected from a perfluoroalkylene group and a perfluoroarylene group is added to the main chain of the polymer skeleton. One site or a site selected from the group protecting the OH group of the perfluoroalkyl group, the perfluoroaryl group, the hexafluoro-2-propanol group, and the hexafluoro-2-propanol group is added to the side chain of the polymer skeleton. The fluorine-containing resin which has at least one is more preferable.

As the fluorine group-containing resin, for example, a resin having at least one repeating unit represented by the following General Formulas (IR) to (XR) can be preferably exemplified.

In general formula, R <_0> , R <_1> represents the hydrogen atom, the fluorine atom, and the alkyl group, perfluoroalkyl group, cycloalkyl group, or aryl group which may have a substituent.

R <_2> -R <_4> represents the alkyl group, the perfluoroalkyl group, the cycloalkyl group, or the aryl group which may have a substituent. In addition, R ₀ and R ₁ , R ₀ and R ₂ , R ₃ and R ₄ may be bonded to form a ring.

R ₅ represents a hydrogen atom, an alkyl group, a perfluoroalkyl group, a monocyclic or polycyclic cycloalkyl group, an acyl group, or an alkoxycarbonyl group which may have a substituent.

R <_6> , R <_7> , R <_8> may be same or different, and represents the alkyl group, perfluoroalkyl group, and alkoxy group which may have a hydrogen atom, a halogen atom, and a substituent.

R <_9> , R <_10> may be same or different and represents the alkyl group or haloalkyl group which may have a hydrogen atom, a halogen atom, a cyano group, and a substituent.

R ₁₁ and R ₁₂ may be the same or different and represent a hydrogen atom, a hydroxyl group, a halogen atom, a cyano group, an alkoxy group, an acyl group or an alkyl group, cycloalkyl group, alkenyl group, aralkyl group or aryl group which may have a substituent.

R <_13> , R <_14> may be same or different and represents the alkyl group or haloalkyl group which may have a hydrogen atom, a halogen atom, a cyano group, and a substituent.

R ₁₅ represents an alkyl group, a monocyclic or polycyclic cycloalkyl group, an alkenyl group, an aralkyl group or an aryl group having a fluorine atom.

R _16, R _17, R ₁₈ may be the same or different, and may be a hydrogen atom, a halogen atom, a cyano group, an optionally substituted displays good, an alkyl group, a perfluoroalkyl group, an alkoxy group, -CO-OR _15.

R ₁₉ , R ₂₀ and R ₂₁ may be the same or different and represent an alkyl group, a monocyclic or polycyclic cycloalkyl group, an alkenyl group, an aralkyl group, an aryl group or an alkoxy group having a hydrogen atom, a fluorine atom or a fluorine atom. Provided that at least one of R ₁₉ , R ₂₀ , and R ₂₁ is a group other than a hydrogen atom.

A ₁ and A ₂ are a divalent alkylene group, alkenylene group, cycloalkylene group or arylene group which may have a single bond or a substituent, or -O-CO-R _22- , -CO-OR ₂₃ -,- CO-N (R ₂₄ ) -R ₂₅ -is indicated.

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

R ₂₄ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group which may have a substituent.

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

As the fluorine group-containing resin, for example, a resin having at least one repeating unit represented by the following General Formulas (FA) to (FF) can also be preferably exemplified.

R ₁₀₁ and R ₁₀₂ represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a cyano group, and a trifluoromethyl group.

X represents a group decomposed by the action of a hydrogen atom or an acid.

R ₁₀₃ and R ₁₀₄ represent a hydrogen atom or an alkyl group, an aryl group, or an aralkyl group which may have a substituent, and the alkyl group and this aralkyl group each represent -O-, -S-, -CO _2- , -CO You may have-, -SO _2- , or -SO-. n represents the integer of 1-5.

R ₁₁₁ to R ₁₁₆ , R ₁₂₁ to R ₁₃₂ , R ₁₄₁ to R ₁₄₈ , and R ₁₅₁ to R ₁₅₆ each represent a hydrogen atom, a fluorine atom, or an alkyl group which may have a substituent, but at least one is a fluorine atom.

Examples of the group decomposed by the action of an acid at X include a group in which an OX group is acid decomposed to form an OH group, and an acetal group (eg, 1-alkoxyethyl group, tetrahydropyranyl group, t-butoxycarbonyl group), 3 A higher alkyl ether group (for example, t-butyl ether group) is illustrated.

The fluorine group-containing resin in the present invention may preferably have at least one repeating unit represented by the following general formulas (XIR) to (XIIIR).

In formula, R <_26> , R <_27> , R <_32> may be same or different, and represents the alkyl group or haloalkyl group which may have a hydrogen atom, a halogen atom, a cyano group, and a substituent.

R ₂₈ and R ₃₃ represent a group of -C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), -C (R ₃₆ ) (R ₃₇ ) (OR ₃₉ ), or of the following general formula (XIVR).

Wherein, R _29, R _30, R ₃₁ may be the same or different, and may be a hydrogen atom, a halogen atom, a cyano group, a substituent, shown by an alkyl group, perfluoroalkyl group, an alkoxy group, -CO-OR ₂₈ in.

R ₃₄ and R ₃₅ may be the same or different and represent an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group or an aryl group which may be the same or different and may have a hydrogen atom, a hydroxyl group, a halogen atom, a cyano group, an alkoxy group, an acyl group or a substituent. .

R <_36> , R <_37> , R <_38> and R <_39> may be same or different and represent an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group, or an aryl group which may have a substituent. Two of R ₃₆ , R ₃₇ , and R ₃₈ , or two of R ₃₆ , R ₃₇ , and R ₃₉ may combine to form a ring. In addition, the formed ring may contain an oxo group.

R ₄₀ represents an alkyl group cycloalkyl group, alkenyl group, alkynyl group, aralkyl group or aryl group which may have a substituent.

A _{3 to} A ₄ are a divalent alkylene group, alkenylene group, cycloalkylene group or arylene group which may have a single bond or a substituent, or -O-CO-R _22- , -CO-OR ₂₃ -,- CO-N (R ₂₄ ) -R ₂₅ -is indicated.

R ₂₂ to R ₂₅ are the same as described above. Z represents the atomic group which comprises a monocyclic or polycyclic alicyclic group with a carbon atom. n represents 0 or 1.

In the present invention, in order to control physical properties such as hydrophilicity, glass transition point, and transmittance to an exposure light source of the fluorine group-containing resin, or to control the polymerizability during polymer synthesis, the following general formulas (XVR) to At least one repeating unit derived from a vinyl compound containing maleic anhydride, vinyl ether or cyano group represented by (XVIIR) may be provided.

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

R ₄₂ represents a hydrogen atom, a halogen atom, a cyano group, or an alkyl group or haloalkyl group which may have a substituent.

A ₅ is a divalent alkylene group, alkenylene group, cycloalkylene group or arylene group which may have a single bond, a substituent, or -O-CO-R _22- , -CO-OR _23- , -CO-N ( R ₂₄ ) -R ₂₅ -is displayed.

R ₂₂ to R ₂₅ are the same as described above.

Moreover, as a more preferable fluorine-group containing resin in this invention, resin which has at least one repeating unit represented by the following general formula (IA) and (IIA), respectively, and the repeat represented by the following general formula (IIA) and (VIA) Resin which has at least one unit each can be illustrated.

These, resin which has at least one repeating unit represented by the following general formula (IA) and (IIA), respectively, and resin which has at least one each of the repeating unit represented by the following general formula (IIA) and (VIA) is further said general formula You may have a repeating unit represented by (IR)-(VR).

In General Formulas (IA) and (IIA), R _1a and R _6a may be the same or different and represent a hydrogen atom, a halogen atom, a cyano group, or an alkyl group which may have a substituent.

R _2a , R _3a , R _6a and R _7a may be the same or different, and may have a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group or a substituent, an alkyl group, a cycloalkyl group, an alkoxy group, an acyl group, an acyloxy group, An alkenyl group, an aryl group, or an aralkyl group is represented.

R _50a to R _55a may be the same or different and represent an alkyl group which may have a hydrogen atom, a fluorine atom or a substituent. However, at least one of R _50a to R _55a represents an alkyl group in which a fluorine atom or at least one hydrogen atom is substituted with a fluorine atom.

R _56a represents an alkyl group, a cycloalkyl group, an acyl group or an alkoxycarbonyl group which may have a hydrogen atom or a substituent, and is preferably a hydrogen atom.

R _4a represents a group of the following general formula (IVA) or (VA).

In general formula (IVA), R <_11a> , R <_12a> and R <_13a> may represent the same or different, and may represent an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, or an aryl group which may have a substituent.

In general formula (VA), R <_14a> and R <_15a> may be same or different, and represent the alkyl group which may have a hydrogen atom or a substituent. R _16a represents an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group which may have a substituent. Two of R _14a to R _16a may be bonded to each other to form a ring.

In general formula (VIA), R <_17a1> and R <_17a2> may be same or different and represent a hydrogen atom, a halogen atom, a cyano group, or the alkyl group which may have a substituent. R _18a represents -C (R _18a1 ) (R _18a2 ) (R _18a3 ) or -C (R _18a1 ) (R _18a2 ) (OR _18a4 ). R _18a1 to R _18a4 may be the same or different and represent an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group or an aryl group which may have a hydrogen atom or a substituent. R _18a1, R _18a2, R and the two are combined of two or R _18a1, R _18a2, R _18a4 from _18a3 may form a ring. Although A <_0> represents the bivalent coupling group which may have a single bond or a substituent, It is preferable that it is a single bond.

It is preferable that these fluorine-group containing resin is group in which R <_18a> in general formula (VIA) is represented with the following general formula (VIA-A) or general formula (VIA-B). Moreover, it is preferable that at least one of R <_1a> in General formula (IA), R <_5a> in General formula (IIA), and _R17a2 in General formula (VIA) of these fluorine-group containing resin (A) is a trifluoromethyl group. Do.

In General Formula (VIA-A), R _18a5 and R _18a6 may be the same or different and represent an alkyl group which may have a substituent. R _18a7 represents a cycloalkyl group which may have a substituent.

In General Formula (VIA-B), R _18a8 represents an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group or an aryl group which may have a substituent.

Moreover, resin which has at least one repeating unit represented by the said General formula (IA) and (IIA), respectively, and resin which has at least one each of the repeating unit represented by the said General formula (IIA) and (VIA) is further a following general formula You may have at least one repeating unit represented by (IIIA) or (VIIA).

In general formula (IIIA), R <_8a> represents a hydrogen atom, a halogen atom, a cyano group, or the alkyl group which may have a substituent. R _9a and R _10a may be the same or different, and may have a hydrogen atom, a halogen atom, a cyano group or a substituent, an alkyl group, a cycloalkyl group, an alkoxy group, an acyl group, an acyloxy group, an alkenyl group, an aryl group or an aralkyl Display the flag.

In General Formula (VIIA), R _19a and R _20a may be the same or different and represent a hydrogen atom, a halogen atom, a cyano group, or an alkyl group which may have a substituent. R _21a is, may have a hydrogen atom, a halogen atom, the substituent represents an alkyl group or -A ₁ -CN. A ₁ represents a single bond or a divalent linking group.

As said alkyl group, for example, a methyl group, an ethyl group, a propyl group, n-butyl group, a sec-butyl group, a hexyl group, 2-ethylhexyl group, an octyl group can be illustrated preferably, for example as a C1-C8 alkyl group. have.                     

As a cycloalkyl group, monocyclic may be sufficient and polycyclic may be sufficient. As monocyclic type, it is C3-C8 thing, For example, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group can be illustrated preferably. As polycyclic type, it is C6-C20, for example, an adamantyl group, a norbornyl group, an isobornyl group, a campanyl group, a dicyclopentyl group, a-pinel group, a tricyclo decanyl group, a tetracyclo dodecyl group, andandrostanyl group Etc. can be illustrated preferably. However, the carbon atom in the said monocyclic or polycyclic cycloalkyl group may be substituted by heteroatoms, such as an oxygen atom.

As the perfluoroalkyl group, for example, one having 4 to 12 carbon atoms, specifically, a perfluorobutyl group, a perfluorohexyl group, a perfluorooctyl group, a perfluorooctylethyl group, a perfluorododecyl group, or the like is preferable. It can be illustrated.

As a haloalkyl group, a chloromethyl group, a chloroethyl group, a chloropropyl group, a chlorobutyl group, a bromomethyl group, a bromoethyl group etc. can be illustrated specifically, for example as a haloalkyl group of 1-4 carbon atoms.

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

As the aralkyl group, for example, a benzyl group, a phenethyl group, a naphthyl methyl group, or the like can be preferably exemplified as an aralkyl group having 7 to 12 carbon atoms.

As an alkenyl group, a vinyl group, an allyl group, butenyl group, and a cyclohexenyl group can be illustrated specifically, for example as a C2-C8 alkenyl group.                     

As the alkoxy group, for example, a methoxy group, ethoxy group, n-propoxy group, iso-butoxy group, butoxy group, pentoxy group, allyloxy group, octoxy group, etc. are preferable. This can be illustrated.

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

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

As an alkynyl group, a C2-C5 alkynyl group is preferable, for example, an ethynyl group, a propynyl group, butynyl group, etc. can be illustrated.

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 Is illustrated.

As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. can be illustrated, 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 illustrated.

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

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

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

The divalent linking group may be a divalent, alkylene group, cycloalkylene group, alkenylene group or arylene group which may have a substituent or -O-CO-R _22a- , -CO-OR _23a -or -CO-N (R _24a ) -R _25a -is displayed. R _22a , R _23a and R _25a may be the same or different and may have 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 or a cycloalkylene group Or an arylene group. R _24a represents an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group which may have a hydrogen atom or a substituent.

Examples of the ring formed by bonding of R ₀ and R ₁ , R ₀ and R ₂ , R ₃ and R ₄ are, for example, a 5- to 7-membered ring, specifically, a pentane ring, a hexane ring, a furan ring, and a dioxo substituted with fluorine; A norl ring, a 1, 3- dioxolane ring, etc. are illustrated.

R 2 ~R ₃₆ of _38, or R ₃₆ and R ₃₉ ~R ₃₇ as the two are bonded to form a ring of, for example, a 3 to 8-membered ring, specifically a cyclopropane ring, a cyclopentyl bullet, cyclohexane ring, A furan ring, a pyran ring, etc. can be illustrated preferably.

Two of R _14a ~R _16a dog, R _18a1 as ring ~R formed by combining two or two of R _18a1, R _18a2, R _18a4 from _18a3, and 3 to 8-membered ring is preferred, for example, cyclopropane ring, a cycloalkyl Pentane ring, a cyclohexane ring, a tetramethylene oxide ring, a pentamethylene oxide ring, a hexamethylene oxide ring, a furan ring, a pyran ring, a dioxonol ring, a 1, 3- dioxolane ring, etc. can be illustrated.

Z represents an atomic group constituting a monocyclic or polycyclic alicyclic group, and the alicyclic group formed is monocyclic, having 3 to 8 carbon atoms, for example, cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclo An octyl group can be illustrated preferably. As polycyclic type, it is C6-C20, for example, an adamantyl group, a norbornyl group, an isobornyl group, a campanyl group, a dicyclopentyl group, a-pinel group, a tricyclo decanyl group, a tetracyclo dodecyl group, andandrostanyl group Etc. can be illustrated preferably.

Substituents substituted with these groups include those having active hydrogens such as alkyl groups, cycloalkyl groups, aryl groups, amino groups, amide groups, ureide groups, urethane groups, hydroxyl groups and carboxyl groups, and halogen atoms (fluorine atoms, chlorine atoms, bromine atoms). , 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.), a cyano group, a nitro group, etc. are illustrated.

Here, although the alkyl group, the cycloalkyl group, and the aryl group are illustrated above, the alkyl group may be further substituted with a fluorine atom and a 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. R <_36> -R <_39> is as above-mentioned, R <_01> , R <_02> represents a hydrogen atom, the alkyl group which may have a substituent shown above, a cycloalkyl group, an alkenyl group, an aralkyl group, or an aryl group.

As a preferable specific example, t-butyl group, t-amyl group, 1-alkyl-1-cyclohexyl group, 2-alkyl-2-adamantyl group, 2-adamantyl-2-propyl group, 2- (4- Acetal groups 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 illustrated.

The sum total of the content of the repeating unit represented by General Formula (IR)-(XR) is generally 10-80 mol%, Preferably it is 30-70 mol%, More preferably, 35-65 mol% in the whole polymer composition. It is used in the range of.

The content of the repeating units represented by the formulas (XIR) to (XIIIR) is generally 0 to 70 mol%, preferably 10 to 60 mol%, more preferably 20 to 50 mol% in the overall polymer composition. It is used in a range.

The content of the repeating units represented by the formulas (XVR) to (XVIIR) is generally 0 to 70 mol%, preferably 10 to 60 mol%, more preferably 20 to 50 mol% in the overall polymer composition. It is used in a range.                     

As the resin (B) of the present invention, it is more preferable to have at least one repeating unit represented by General Formulas (IR) to (IIIR) and at least one repeating unit represented by General Formulas (IVR) to (VIR).

In addition, as the resin (B) of the present invention, at least one repeating unit represented by the general formulas (IVR) to (VIR) and at least one repeating unit represented by the general formulas (VIIIR) to (XR) are described above. Likewise more preferred.

In addition, as the resin (B) of the present invention, at least one repeating unit represented by the general formulas (IVR) to (VIIR) and at least one repeating unit represented by the general formulas (XVR) to (XVIIR) are described above. Likewise more preferred.

Thereby, the permeability of 157 nm in resin can fully be improved, and the fall of dry etching resistance can be suppressed.

When (B) resin of this invention has at least one repeating unit represented by general formula (IR)-(IIIR), and at least one repeating unit represented by general formula (IVR)-(VIR), General formula ( The sum of the contents of the repeating units represented by IR) to (IIIR) is generally in the range of 0 to 70 mol%, preferably 10 to 60 mol%, more preferably 20 to 50 mol% in the overall polymer composition. Used.

The sum of the contents of the repeating units represented by the formulas (IVR) to (VIR) is generally 10 to 80 mol%, preferably 30 to 70 mol%, more preferably 35 to 65 mol in the total polymer composition. Used in the range of%.

When (B) resin of this invention has at least one repeating unit represented by general formula (IVR)-(VIR), and at least one repeating unit represented by general formula (VIIIR)-(XR), General formula ( The sum of the contents of the repeating units represented by IVR) to (VIR) is generally in the range of 10 to 80 mol%, preferably 30 to 70 mol%, more preferably 35 to 65 mol% in the overall polymer composition. Used.

The sum total of the content of the repeating unit represented by general formula (VIIIR)-(XR) is 0-70 mol%, Preferably it is 10-60 mol%, More preferably, 20-50 mol in the whole polymer composition. Used in the range of%.

When (B) resin of this invention has at least one repeating unit represented by general formula (IVR)-(VIIR), and at least one repeating unit represented by general formula (XVR)-(XVIIR), General formula ( The sum of the contents of the repeating units represented by IVR) to (VIIR) is generally in the range of 10 to 80 mol%, preferably 30 to 70 mol%, more preferably 35 to 65 mol% in the total polymer composition. Used.

The sum of the contents of the repeating units represented by formulas (XVR) to (XVIIR) is generally 0 to 70 mol%, preferably 10 to 60 mol%, more preferably 20 to 50 mol in the total polymer composition. Used in the range of%.

In the fluorine group-containing resin each having at least one repeating unit represented by General Formula (IA) and (IIA), the content of the repeating unit represented by General Formula (IA) is generally 5 to 80 mol%, preferably 10 75 mol%, More preferably, it is 20-70 mol%.

In the fluorine group-containing resin each having at least one repeating unit represented by the general formulas (IA) and (IIA), the content of the repeating unit represented by the general formula (IIA) is generally 5 to 80 mol%, preferably It is 10-70 mol%, More preferably, it is 20-65 mol%.

In the fluorine group-containing resin each having at least one repeating unit represented by General Formula (IIA) and (VIA), the content of the repeating unit represented by General Formula (IIA) is generally 5 to 80 mol%, preferably 10 70 mol%, More preferably, it is 20-65 mol%.

In the fluorine group-containing resin each having at least one repeating unit represented by General Formula (IIA) and (VIA), the content of the repeating unit represented by General Formula (VIA) is generally 5 to 80 mol%, preferably 10 70 mol%, More preferably, it is 20-65 mol%.

In these fluorine-group-containing resins, the content of the repeating unit represented by General Formula (IIIA) is generally 1 to 40 mol%, preferably 3 to 35 mol%, more preferably 5 to 30 mol%.

In these fluorine-group containing resins, the content of the repeating unit represented by General Formula (VIIA) is generally 1 to 40 mol%, preferably 3 to 35 mol%, more preferably 5 to 30 mol%.

(B) resin of this invention may copolymerize another polymerizable monomer in addition to the above-mentioned repeating structural unit, and also for the purpose of improving the performance of the positive photosensitive property of this invention.

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

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

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

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

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

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

Moreover, (F-40)-(F-45) mentioned above are mentioned as a specific example of the repeating unit represented by general formula (IIA).

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

Moreover, as a specific example of the repeating unit represented by general formula (VIA), (F-29)-(F-38) and (F-47)-(F-54) mentioned above are mentioned.                     

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

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

(B) acid-decomposable resin used for this invention can be synthesize | combined by a conventional method (for example, radical polymerization). For example, as a general synthesis method, monomer species are placed in a reaction vessel in a batch or during the reaction, and if necessary, ethers such as a reaction solvent, for example, tetrahydrofuran, 1,4-dioxane or diisopropyl ether, Ketones such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate, and propylene glycol monomethyl ether acetate, which will be described later. The polymerization is started using a commercially available radical initiator (azo-based initiator, peroxide, etc.) under an inert gas atmosphere if necessary. If desired, an initiator is added or dividedly added, and after completion of the reaction, it is put in a solvent to recover a desired polymer by a method such as powder or solid recovery.

The reaction concentration is 20% by weight or more, preferably 30% by weight or more, more preferably 40% by weight or more. The reaction temperature is 10 ° C to 150 ° C, preferably 30 ° C to 120 ° C, more preferably 50 to 100 ° C.

The repeating structural unit represented by the said specific example may be used individually by 1 type, and may be used in mixture of multiple numbers.

In addition, in this invention, (B) resin may be used by 1 type, and may be used in combination.

The weight average molecular weight of (B) resin which concerns on this invention is 1,000-200,000 as polystyrene conversion value by GPC method, More preferably, it is 3,000-20,000. If the weight average molecular weight is less than 1,000, it is not preferable because of deterioration of heat resistance and dry etching resistance, and if it exceeds 200,000, the developability deteriorates or the viscosity becomes very high. appear.

The molecular weight distribution is 1-10, Preferably it is 1-5, More preferably, the thing of the range of 1-4 is used. The smaller the molecular weight distribution is, the smoother the resolution, resist shape, and sidewall of the resist pattern are, and excellent in roughness.

In the positive photosensitive composition of this invention, 40-99.99 weight% is preferable in solid content of the whole composition, and, as for the compounding quantity of the whole composition which concerns on this invention, 50-99.97 weight% is more preferable.

[3] a dissolution inhibiting compound having a molecular weight of 3000 or less (hereinafter referred to as an "acid-decomposable dissolving compound"), which is decomposed by the action of an acid and solubility in an alkali developer is increased.

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

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

The addition amount of the acid-decomposable dissolution inhibiting compound is preferably 3 to 50% by weight, more preferably 5 to 40% by weight based on the solid content of the whole composition.

Although the specific example of an acid-decomposable dissolution inhibiting compound is shown below, it is not limited to these.

[4] (D) alkali-soluble resins

The alkali dissolution rate of the alkali-soluble resin is preferably measured at 0.261 N tetramethylammonium hydroxide (TMAH) (23 DEG C) and 20 Pa / sec or more. Especially preferably, it is 200 microseconds / sec or more (small angstroms).

As an alkali-soluble resin used for this invention, a novolak resin, a hydrogenated novolak resin, acetone- pyrogallol resin, o-polyhydroxy styrene, m-polyhydroxy styrene, p-polyhydroxy styrene, hydrogenated polyhydride, for example Oxystyrene, halogen or alkyl-substituted polyhydroxystyrene, hydroxystyrene-N-substituted maleimide copolymer, o / p- and m / p-hydroxystyrene copolymers, some O- to hydroxyl groups of polyhydroxystyrene Alkylates (e.g., 5-30 mole% O-methylate, O- (1-methoxy) ethylate, O- (1-ethoxy) ethylate, O-2-tetrahydropyranylide, O- (t-butoxycarbonyl) methylate, etc.) or O-acylates (e.g., 5-30 mol% o-acetylate, O- (t-butoxy) carbonylate, etc.), styrene-maleic anhydride Copolymer, styrene-hydroxystyrene copolymer, α-methylstyrene-hydroxystyrene copolymer, carboxyl group-containing methacrylic resin It may be exemplified a derivative thereof, polyvinyl alcohol derivatives, but is not limited thereto.

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.

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

In addition, the weight average molecular weight of alkali-soluble resin is 2000 or more, Preferably it is 5000-200000, More preferably, it is 5000-100000.                     

Here, the weight average molecular weight is measured as 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 use amount of alkali-soluble resin is 40 to 97 weight% with respect to solid content of the whole composition, Preferably it is 60 to 90 weight%.

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

A phenol derivative can be used for a crosslinking agent. Preferably, the molecular weight is 1200 or less, contains 3 to 5 benzene rings in the molecule, and further has two or more hydroxymethyl groups or alkoxymethyl groups in combination with the hydroxymethyl group and the alkoxymethyl group to at least one benzene ring. The phenol derivative which concentrates, or divides and combines can be illustrated.

By using such a phenol derivative, the effect of this invention can be made more remarkable.

As an alkoxy methyl group couple | bonded with a benzene ring, a C6 or less thing is preferable. Specifically, methoxymethyl group, ethoxymethyl group, n-propoxymethyl group, i-propoxymethyl group, n-butoxymethyl group, i-butoxymethyl group, sec-butoxymethyl group, t-butoxymethyl group are preferable. Moreover, the alkoxy substituted alkoxy group is preferable like 2-methoxyethoxy group and 2-methoxy-1-propyl group.

Among these phenol derivatives, particularly preferred ones are exemplified below.

(Wherein, L ¹ ~L ⁸ are, same or different, each represent a hydroxymethyl group, methoxy represents a methyl group or ethoxy group in.)

The phenol derivative having a hydroxymethyl group can be obtained by reacting a phenol compound (a compound in which L ^{1 to} L ⁸ is a hydrogen atom) having no hydroxymethyl group with formaldehyde under a base catalyst. At this time, in order to prevent resination or gelation, it is preferable to perform reaction temperature at 60 degrees C or less. Specifically, it can synthesize | combine by the method described in Unexamined-Japanese-Patent No. 6-282067, Unexamined-Japanese-Patent No. 7-64285, etc.

The phenol derivative having an alkoxymethyl group can be obtained by reacting a phenol derivative having a corresponding hydroxymethyl group with an alcohol under an acid catalyst. At this time, in order to prevent resination or gelation, it is preferable to perform reaction temperature at 100 degrees C or less. Specifically, it can synthesize | combine by the method described in European patent EP632003A1 etc.

The phenol derivative having a hydroxymethyl group or an alkoxymethyl group thus synthesized is preferable in view of stability at the time of storage, but the phenol derivative having an alkoxymethyl group is particularly preferred in view of stability at the time of storage.

Phenol derivatives having two or more hydroxymethyl groups or alkoxymethyl groups in combination and being concentrated in any one benzene ring or combined separately may be used alone or in combination of two or more thereof. good.

In addition to the phenol derivatives, the following compounds (i) and (ii) can be used as the crosslinking agent (E).

(i) a compound having an N-hydroxymethyl group, an N-alkoxymethyl group, or an N-acyloxymethyl group

(ii) epoxy compounds

In the present invention, as the crosslinking agent, a phenol derivative is preferable. Moreover, you may use the said crosslinking agent in combination of 2 or more type.                     

The ratio of the phenol derivative and the crosslinking agent of (i) or (ii) in the case of using the crosslinking agent together is 100/0 to 0/100, preferably 90/10 to 20/80, more preferably 90 / in molar ratio. 10 to 50/50.

(i) As a compound having an N-hydroxymethyl group, an N-alkoxymethyl group, or an N-acyloxymethyl group, European Patent Publication No. 0,133,216 (hereinafter referred to as "EP-A"), West German Patent No. 3,634,671, Monomers and oligomer-melamine-formaldehyde condensates and urea-formaldehyde condensates disclosed in US Pat. No. 3,711,264, benzoguanamine-formaldehyde condensates disclosed in the alkoxy substituted compounds disclosed in EP-A 0,212,482 and the like.

As a more preferred example, a melamine-formaldehyde derivative having, for example, at least two free N-hydroxymethyl groups, N-alkoxymethyl groups, or N-acyloxymethyl groups is exemplified, among which N-alkoxymethyl derivatives are particularly preferred.

(ii) As an epoxy compound, the epoxy compound of the monomer, dimer, oligomer, and polymer form containing one or more epoxy groups can be illustrated. For example, reaction products of bisphenol A and epichlorohydrin, reaction products of low molecular weight phenol-formaldehyde resin and epichlorohydrin, and the like are exemplified. In addition, the epoxy resin described in US Patent No. 4,026,705 and British Patent No. 1,539,192 can be illustrated.

The crosslinking agent is used in an added amount of 3 to 70% by weight, preferably 5 to 50% by weight of the total composition solids.

When the addition amount of a crosslinking agent is less than 3 weight%, a residual film ratio will fall, and when it exceeds 70 weight%, resolution will fall and it is not very preferable at the point of stability at the time of storage of a photosensitive composition.

<Other components used for the photosensitive composition of this invention>

[6] basic compounds

It is preferable that the photosensitive composition of this invention contains a basic compound further. Examples of the basic compound include nitrogen-containing basic compounds.

As the nitrogen-containing basic compound, an organic amine, a basic ammonium salt, a basic sulfonium salt, or the like may be used, so long as it does not deteriorate sublimation or resist performance.

Among these nitrogen-containing basic compounds, organic amines are preferred in terms of excellent image performance. For example, Japanese Patent Laid-Open No. 63-149640, Japanese Patent Laid-Open No. 5-249662, Japanese Patent Laid-Open No. 5-127369, Japanese Patent Laid-Open No. 5-289322, Japanese Patent Laid-Open No. 5-249683, Japanese Patent Laid-Open 5-289340, Japanese Patent Laid-Open No. 5-232706, Japanese Patent Laid-Open No. 5-257282, Japanese Patent Laid-Open No. 6-242605, Japanese Patent Laid-Open No. 6-242606, Japanese Patent Laid-Open No. 6-266100, Japanese Patent Laid-Open No. 6-266110, Japanese Patent Laid-Open No. 6-317902, Japanese Patent Laid-Open No. 7-120929, Japanese Patent Laid-Open No. 7-146558, Japanese Patent Laid-Open No. 7-319163, Japanese Patent Laid-Open No. 7 -508840, Japanese Patent Laid-Open No. 7-333844, Japanese Patent Laid-Open No. 7-219217, Japanese Patent Laid-Open No. 7-92678, Japanese Patent Laid-Open No. 7-28247, Japanese Patent Laid-Open No. 8-22120, Japan Japanese Patent Application Laid-Open No. Hei 8-110638, Japanese Patent Application Laid-Open No. Hei 8-123030, Japanese Patent Application Laid-Open No. 9-274312, Japanese Patent Application Laid-Open No. 9-166871, Japanese Patent Publication No. 9-292708, Japanese Patent Publication Basic compounds described in Japanese Patent Application Laid-Open No. 9-325496, Japanese Patent Application Laid-open No. Hei 7-508840, USP5525453, USP5629134, USP5667938 and the like can be used.

A basic compound can specifically illustrate the structure of following formula (A)-(E).

Here, R ²⁵⁰ , R ^251, and R ²⁵² may be the same or different, and represent a hydrogen atom, a C1-C20 alkyl group, a C1-C20 aminoalkyl group, a C1-C20 hydroxyalkyl group, or a C6-C20 substituent. Or an unsubstituted aryl group, wherein R ²⁵¹ and R ²⁵² may be bonded to each other to form a ring.

R ₂₅₃ , R ₂₅₄ , R ₂₅₅ and R ₂₅₆ may be the same or different and represent an alkyl group having 1 to 10 carbon atoms.

Further preferred compounds are nitrogen-containing compounds having two or more nitrogen atoms of different chemical environments in one molecule, or aliphatic tertiary amines.

Preferably, the nitrogen-containing basic compound is 1,5-diazabicyclo [4,3,0] -5-nonene, 1,8-diazabicyclo [5,4,0] -7-undecene, 1, 4-diazabicyclo [2,2,2] octane, 4-dimethylaminopyridine, 1-naphthylamine, piperidines, hexamethylenetetramine, imidazoles, hydroxypyridines, pyridines, anilines, Hydroxyalkylanilines, 4,4'-diaminodiphenylether, pyridinium p-toluenesulfonate, 2,4,6-trimethylpyridinium p-toluenesulfonate, tetramethylammonium p-toluenesulfonate, and Examples include tetrabutylammonium lactate, triethylamine, tributylamine, tripentylamine, tri-n-octylamine, tri-i-octylamine, tris (ethylhexyl) amine, tridecylamine, tridodecylamine, and the like. do.

Among them, 1,5-diazabicyclo [4,3,0] -5-nonene, 1,8-diazabicyclo [5,4,0] -7-undecene, 1,4-diazabicyclo [ 2,2,2] octane, 4-dimethylaminopyridine, 1-naphthylamine, piperidine, 4-hydroxypiperidine, 2,2,6,6-tetramethyl-4-hydroxypiperidine , Hexamethylenetetramine, imidazole, hydroxypyridines, pyridines, 4,4'-diaminodiphenyl ether, triethylamine, tributylamine, tripentylamine, tri-n-octylamine, tris ( Organic amines such as ethylhexyl) amine, tridodecylamine, N, N-di-hydroxyethylaniline, and N-hydroxyethyl-N-ethylaniline are preferred.

These basic compounds are used individually or in 2 or more types. The usage-amount of a basic compound is 0.001 to 10 weight% normally, based on solid content of the photosensitive composition, Preferably it is 0.01 to 5 weight%. If it is less than 0.001% by weight, the addition effect of the basic compound is not obtained. On the other hand, if it exceeds 10% by weight, the sensitivity is lowered and the developability of the non-exposed part tends to be deteriorated.

[7] fluorine and / or silicone surfactants

It is preferable that the photosensitive composition of this invention contains any 1 type, or 2 or more types of fluorine type and / or silicone type surfactant (surfactant containing both a fluorine type surfactant and a silicone type surfactant, a fluorine atom, and a silicon atom). .

When the photosensitive composition of the present invention contains the surfactant, it is possible to impart a resist pattern with low adhesion and development defects with good sensitivity and resolution when using an exposure light source of 250 nm or less, particularly 220 nm or less. .

As these surfactants, for example, Japanese Patent Laid-Open No. 62-36663, Japanese Patent Laid-Open No. 61-226746, Japanese Patent Laid-Open No. 61-226745, Japanese Patent Laid-Open No. 62-170950, Japanese Patent Laid-Open 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 Laid-Open Interfaces described in 2002-277862, US Pat. No. 5,540,2020, US 5360692, US 5529881, US 5296330, US 5436098, US 5576143, US 5294511, US 5824451. An active agent can be illustrated and the following commercially available surfactant can be used as it is.

Commercially available surfactants include, for example, Eftop EF301, EF303 (manufactured by New Akita Kasei), Florard FC430, FC431 (manufactured by Sumitomo 3M), Megafac F171, F173, F176, F189, R08 (manufactured by Dainippon Ink, Inc.). ), Fluorine surfactants or silicone surfactants such as Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.) and Tory Sol S-366 (manufactured by Troy Chemical Company). Moreover, polysiloxane polymer KP-341 (made by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicone surfactant.

As the surfactant, in addition to the known ones described above, fluorine derived from fluoroaliphatic compounds produced by the telomerization method (also called telomer method) or the oligomerization method (also called oligomer method) Surfactants using a polymer having a roaliphatic group can be used. A fluoroaliphatic 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 distributed irregularly. They 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 illustrated, and also a block of poly (oxyethylene, oxypropylene, and oxyethylene) is mentioned. The unit may be a unit having an alkylene group having a different chain length within the same chain length, such as a linking group) or a poly (block linking group of oxyethylene and oxypropylene). The copolymer of a monomer having a fluoroaliphatic group and a (poly (oxyalkylene)) acrylate (or methacrylate) is not only a diapolymer but also a monomer having two or more other fluoroaliphatic groups, It may be a ternary or higher copolymer obtained by copolymerizing species or more of (poly (oxyalkylene)) acrylate (or methacrylate) at the same time.

For example, as commercially available surfactants, Megafac F-178, F-470, F-473, F-475, F-476, and F-472 (manufactured by Dainippon Ink, Inc.) can be exemplified. Further, copolymers of acrylate (or methacrylate) having a C6F13 group and (poly (oxyalkylene)) acrylate (or methacrylate), acrylate (or methacrylate) having a C6F13 group and (poly (oxy Ethylene)) acrylate (or methacrylate) and copolymer of (poly (oxypropylene)) acrylate (or methacrylate), acrylate (or methacrylate) having C8F17 group and (poly (oxyalkylene) Copolymer of acrylate (or methacrylate), acrylate (or methacrylate) and (poly (oxyethylene)) acrylate (or methacrylate) and (poly (oxypropylene)) acrylate having a C8F17 group (Or the methacrylate) copolymer etc. can be illustrated.

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

[8] solvents, organic

The photosensitive composition of this invention melt | dissolves the said component in the predetermined organic solvent, and is used.

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

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, the generation | occurrence | production of the particle | grains at the time of the storage of the photosensitive composition can be reduced.

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

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

The mixing ratio (weight) of the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group is 1/99-99/1, Preferably it is 10/90-90/10, More preferably, it is 20/80-60/40. . The solvent which does not contain a hydroxyl group is especially preferable at the point of coating uniformity which the mixed solvent containing 50 weight% or more.

<Other additives>

The photosensitive composition of this invention can further contain a dye, a plasticizer, the said surfactant, the photosensitizer, the compound which accelerates the solubility to a developing solution, etc. as needed.                     

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

The preferable addition amount of these dissolution promoting compounds is 2-50 weight% with respect to (B) resin or (D) resin, More preferably, it is 5-30 weight%. At an added amount exceeding 50% by weight, the development residue deteriorates and new defects such as deformation of the pattern during development occur, which is not preferable.

Such phenolic compounds having a molecular weight of 1000 or less can be easily described by those skilled in the art, for example, with reference to the methods described in JP-A 4-122938, JP-A 2-28531, US Pat. No. 4,162,10, European Patent No. 219294, and the like. Can be synthesized.

Specific examples of the cycloaliphatic or aliphatic compound having a carboxyl group include carboxylic acid derivatives having a steroid structure such as cholic acid, deoxycholic acid, and lithocholic acid, adamantanecarboxylic acid derivatives, adamantanedicarboxylic acid, and cyclohexanecarboxes. Acid, cyclohexanedicarboxylic acid, etc. are illustrated, but it is not limited to these.

In this invention, surfactant other than the said fluorine type and / or silicone type surfactant can be added.

As a specific example, Polyoxyethylene alkyl ethers, such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether, polyoxyethylene Polyoxyethylene alkylallyl ethers such as nonylphenol ether, polyoxyethylene-polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan Sorbitan fatty acid esters such as trioleate and sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tri Oleate, polyoxyethylene sorbitan tristearate Nonionic surfactant, such as polyoxyethylene sorbitan fatty acid ester, such as these, can be illustrated.

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

<< How to use >>

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

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

After application, it is exposed through a predetermined mask, baked and developed. In this way, a good resist pattern can be obtained.

As exposure light here, Preferably it is 250 nm or less, More preferably, it is far ultraviolet of the wavelength of 220 nm or less. Specifically, KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (157 nm), EUV (13 nm), X-rays, electron beams, etc. are illustrated, but ArF excimer laser (193 nm) and F ₂ are illustrated. Excimer lasers (157 nm) are particularly preferred.

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

Furthermore, alcohols and surfactants can be added to the alkaline aqueous solution in an appropriate amount.

The alkali concentration of the alkali developing solution is usually 0.1 to 20% by weight, preferably 0.2 to 15% by weight, more preferably 0.5 to 10% by weight.

PH of alkali developing solution is 10-15 normally, Preferably it is 10.5-14.5, More preferably, it is 11-14.

(Example)

Hereinafter, although this invention is demonstrated concretely based on an Example, the scope of the present invention is not restrict | limited at all by an Example.

<Synthesis example of acid generator>                     

Synthesis Example (1): Synthesis of Compound (I-2)

10 g of mesityloxide was dissolved in 100 ml of N, N-dimethylformamide, and 50 ml of triethylamine was added thereto. 22.1 g of trimethylsilyl chloride was added to this solution, and the mixture was reacted at 100 ° C for 2 hours. After cooling, 300 ml of hexane was added, and washed twice with saturated aqueous sodium hydrogen carbonate solution and twice with distilled water. Concentration of the organic phase gave a crude product. When this was produced under reduced pressure distillation (78 ° C / 15 mmHg), silyl enol ether of mesityl oxide was obtained. 5 g of the obtained silyl enol ether and 3.1 g of tetramethylene sulfoxide were dissolved in 50 ml of chloroform, and the solution was cooled to -30 ° C. 9.9 g of anhydrous trifluoroacetic acid was dripped at this over 30 minutes. After 2 hours of reaction, 10 g of potassium nonafluorobutanesulfonate was added dissolved in acetonitrile / water. The mixture was washed with water and the chloroform phase was concentrated. The obtained crude product was washed with diisopropyl ether to obtain 4.2 g of compound (I-2).

300 MHz ¹ H-NMR (CDCl ₃ )

δ1.95 (s.3H), δ2.2 (s.3H), δ2.2 to 2.5 (m.4H), δ3.5 to 3.7 (m.4H), δ4.75 (s.2H), δ6 .2 (t.1H)

Synthesis Example (2): Synthesis of Compound (I-26)

20 g of 2-cyclohexen-1-one were dissolved in 300 ml of N, N-dimethylformamide, and 150 ml of triethylamine was added thereto. 45 g of trimethylsilyl chloride was added to this solution, and the mixture was reacted at 100 ° C for 2 hours. After cooling, 500 ml of hexane was added, and washed twice with saturated aqueous sodium hydrogen carbonate solution and twice with distilled water. Concentration of the organic phase gave a crude product. This was produced under reduced pressure distillation (86 ° C./15 mmHg) to give silylenol ether of 2-cyclohexen-1-one. 5 g of the obtained 2-cyclohexene-1one silylenol ether and 3.1 g of tetramethylene sulfoxide were dissolved in 100 ml of chloroform, and the solution was cooled to -30 ° C. 6.24 g of anhydrous trifluoroacetic acid was dripped at 30 minutes over this. After 2 hours of reaction, 10 g of potassium nonafluorobutanesulfonate was added dissolved in acetonitrile / water. The mixture was washed with water and the chloroform phase was concentrated. The crude product thus obtained was recrystallized from ethyl acetate / diisopropyl ether (40/60) to obtain 3.7 g of compound (I-26).

300 MHz ¹ H-NMR (CDCl ₃ )

δ2.1 to 2.3 (m.3H), δ2.5 to 2.8 (s.4H), δ3.05 (m.1H), δ3.45 (m.1H), δ3.8 (m.2H), δ3 .9 (m.1H), δ5.3 (m.1H), δ6.2 (dd.1H), δ7.25 (d.1H)

Synthesis Example (3): Synthesis of Compound (IA-32)

23.8 g of isophorone was dissolved in 100 ml of acetonitrile, and 20.9 g of triethylamine and 31.0 of sodium iodide were added thereto. 22.5 g of trimethylsilyl chloride was added slowly to this solution, and it was made to react at 60 degreeC for 2 hours. After allowing to cool, the reaction solution was poured into iced water, extracted with diisopropyl ether, and the organic phase was washed twice with saturated aqueous sodium hydrogen carbonate solution and twice with distilled water. Concentration of the organic phase gave a crude product. This was purified by distillation under reduced pressure (108 DEG C / 15 mmHg) to obtain enolsilyl ether from which hydrogen at the allyl position of isophorone was released. 15 g of the obtained enol silyl ether and 7.5 g of tetramethylene sulfoxide were dissolved in 100 ml of chloroform, and the solution was cooled at -30 ° C. 15.0 g of anhydrous trifluoroacetic acid was dripped at this over 30 minutes. After 2 hours of reaction, 24 g of potassium nonafluorobutanesulfonate was added dissolved in acetonitrile / water. The mixture was washed with water and the chloroform phase was concentrated. The obtained crude product was washed with diisopropyl ether to obtain a powder. This was recrystallized from ethyl acetate / diisopropyl ether, and 20g of compounds (IA-32) were obtained.

300 MHz ¹ H-NMR (CDCl ₃ )

δ1.2 (s.6H), δ1.75 (s.3H), δ2.3 (s.2H), δ2.4 (s.2H), δ2.3 to 2.6 (m.4H), δ3.4 3.8 (m.4H), δ4.2 (s.2H), δ6.2 (s.1H)

Other compounds were synthesized using the same method.

<Synthesis example of resin>

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

2-ethyl-2-adamantyl methacrylate and butyrolactone methacrylate were added at a ratio of 55/45, dissolved in methyl ethyl ketone / tetrahydrofuran = 5/5, and 100 ml of a solution having a solid content concentration of 20% was dissolved. It prepared. 2 mol% of V-65 by Wako Pure Chemical Industries Ltd. was added to this solution, and this was dripped at 10 ml of methyl ethyl ketone heated at 60 degreeC over 4 hours by nitrogen atmosphere. After completion of the dropwise addition, the reaction solution was heated for 4 hours, 1 mol% of V-65 was added again, and stirred for 4 hours. After the completion of the reaction, the reaction solution was cooled to room temperature, poured into 3 L of a mixed solvent of distilled water / isopropyl alcohol = 1/1 to crystallize, and the resin 1, which was a precipitated white powder, was recovered.

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

Resins (2) to (15) were synthesized in the same manner as in Synthesis Example (1).

The composition ratio and molecular weight of said resin (2)-(15) are shown below. (Repeat units 1, 2, 3, 4 are the numbers from left to right horizontally.)

Moreover, the structure of said resin (1)-(15) is shown below.

Synthesis Example (2): Synthesis of Resin (16) (Main Chain Type)

Norbornenecarboxylic acid t-butyl ester, norbornenecarboxylic acid butyrolactone ester, maleic anhydride (molar ratio 40/10/50) and THF (reaction concentration 60% by weight) are placed in a detachable flask and nitrogen stream Under heating at 60 ° C. After the reaction temperature was stabilized, 2 mol% of a radical initiator V-601 manufactured by Wako Pure Chemical Industries, Ltd. was added to initiate the reaction. Heated for 12 hours. The obtained reaction mixture was diluted twice with tetrahydrofuran and then poured into a mixed solution of hexane / ispropyl alcohol = 1/1 to precipitate white powder. The precipitated powder was collected by filtration and dried to obtain Resin (16) as a target product.

When molecular weight analysis was performed by GPC of the obtained resin (16), it was 8300 (weight average) in terms of polystyrene. Moreover, the NMR spectrum confirmed that the molar ratio of the norbornene carboxylic acid t-butyl ester / norbornene carboxylic acid butyrolactone ester / maleic anhydride repeating unit of resin (16) was 42/8/50.

Resins 17 to 27 were synthesized in the same manner as in Example (2).

The composition ratio and molecular weight of said resin (17)-(27) are shown below. (The alicyclic olefin units 1, 2, and 3 are the numbers from the left side horizontally.)                     

In addition, the structures of the resins 16 to 27 are shown below.

Synthesis Example (3): Synthesis of Resin (28) (Hybrid Type)

Norbornene, maleic anhydride, t-butyl acrylate and 2-methylcyclohexyl-2-propyl acrylate were added to the reaction vessel at a molar ratio of 35/35/20/10 and dissolved in tetrahydrofuran to give a solid content of 60%. The solution was prepared. It was heated at 65 ° C. under a nitrogen stream. When the reaction temperature was stabilized, 1 mol% of a radical initiator V-601 manufactured by Wako Pure Chemical Industries, Ltd. was added to start the reaction. After heating for 8 hours, the reaction mixture was diluted twice with tetrahydrofuran, and then charged into 5 times the volume of hexane of the reaction mixture to precipitate white powder. The precipitated powder was collected by filtration and dissolved in methyl ethyl ketone. The precipitated powder was reprecipitated in a 5-fold volume of hexane / t-butyl methyl ether = 1/1 mixed solvent, and the precipitated white powder was collected by filtration and dried to obtain the target product. Resin (28) was obtained.

When molecular weight analysis was performed by GPC of the obtained resin (28), it was 12100 (weight average) in terms of polystyrene. In the NMR spectrum, the composition of Resin (1) was 32/39/19/10 in molar ratio of norbornene / maleic anhydride / tbutyl acrylate / 2-methylcyclohexyl-2-propyl acrylate of the present invention.

Resins 29 to 41 were synthesized in the same manner as in Synthesis Example (3).

The composition ratio and molecular weight of the said resin (29)-(41) are shown below.                     

In addition, the structures of the resins 28 to 41 are shown below.

Synthesis Example (4): Synthesis of Resin (FII-1)

20 g of α-trifluoromethylacrylic acid t-butyl ester and 20 g of 3- (2-hydroxymethyl-2,2-bistrifluoromethylethyl) norbornene are dissolved in 40 g of THF and heated to 70 ° C. under a nitrogen stream. It was. 2.0 g of polymerization initiator V-65 (made by Wako Pure Chemical Industries, Ltd.) was added here, and it stirred for 6 hours. After standing to room temperature, 300 ml of hexane was added to the reaction solution to recover the precipitated resin. After dissolving the obtained resin in acetone, hexane was added again to remove the unreacted monomer and oligomer component, thereby obtaining a resin (FII-1) used in the present invention.

In the same manner as in Synthesis Example (4), resins (FII-1) to (FII-24) having the following structures were synthesized. Moreover, about the obtained resin, molecular weight measurement was performed by GPC, and the following result was obtained.

Synthesis Example (5): Synthesis of Resin (k-1)

VP-15000 (100 g) from Nippon Sodachi Co., Ltd. and propylene glycol monomethyl ether acetate (PGMEA) (400 g) were dissolved in a flask, distilled under reduced pressure, and azeotropic distillation of water and PGMEA were performed.

After confirming that the water contained was sufficiently small, ethyl vinyl ether (25.0 g) and p-toluenesulfonic acid (0.02 g) were added, and it stirred at room temperature for 1 hour. Triethylamine (0.03 g) was added to the reaction solution to stop the reaction. Water (400 ml) and ethyl acetate (800 ml) were added, the mixture was separated, washed with water, and then ethyl acetate, Water and azeotrope of PGMEA were removed by increment, and resin k-1 (30% PGMEA solution) having a substituent according to the present invention was obtained.

In the same manner as in Synthesis Example (5), resins (k-2) to (k-15) shown in Table 2 were synthesized.

The composition ratio and molecular weight of said resin (k-1)-(k-15) are shown below.

<Alkali-soluble resin (D)>                     

Hereinafter, the structure, molecular weight, and molecular weight distribution of alkali-soluble resin (D) used in the Example are shown.

<Cross-linking system (C)>                     

Hereinafter, the structure of the crosslinking agent used in an Example is shown.

Examples 1-50 and Comparative Examples 1-3

<Registration Adjustment>

The raw material shown in following Tables 6-9 was melt | dissolved, the solution of 12 weight% of solid content concentration was adjusted, this was filtered with the 0.1 micrometer Teflon filter or the polyethylene filter, and the photosensitive composition was prepared. The prepared composition was evaluated by the following method, and the result is shown to the following Tables 10-13. In Comparative Examples 1, 2 and 3, the same components as in Examples 1, 16 and 28 were used except that sulfonium salts having no conjugated double bonds were used.

The symbol in a table | surface is as follows.

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

LCB; Litocholic acid t-butyl

W-1: Megafac F176 (product of Dainippon Ink Corporation) (fluorine system)

W-2: Megafac R08 (manufactured by Dainippon Ink, Inc.) (Fluorine and Silicon)

W-3: polysiloxane polymer KP-341 (product of Shin-Etsu Chemical Co., Ltd.) (silicone type)

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

The symbol for a solvent is as follows. In addition, the ratio in the case of using more than one in a table | surface is a weight ratio.

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

(1) Evaluation of sensitivity and resolution

On a hexamethyldisilazane-treated silicon substrate in a spin coater, Brewer Science's anti-reflection film ARC25 was uniformly applied to a thickness of 600 Angstroms, dried on a hot plate at 100 ° C. for 90 seconds, and then 240 ° C. at 190 ° C. for 240 seconds. Heated to dryness. Then, each photosensitive resin composition was apply | coated with a spin coater, and it dried at 120 degreeC for 90 second, and formed the resist film of 0.30 micrometer. This resist film was exposed through an mask with an ArF excimer laser stepper (NA = 0.6 manufactured by ISI), and heated on a hot plate at 120 캜 for 90 seconds immediately after the exposure. Furthermore, it developed for 60 second at 23 degreeC with 2.38 weight% tetramethylammonium hydroxide aqueous solution, and rinsed with pure water for 30 second, and dried, and formed the line pattern.

[Sensitivity] The sensitivity was expressed by an exposure amount which reproduces a mask pattern of 0.16 mu m.

RESOLUTION The resolution was expressed by the limit resolution at the exposure amount which reproduces the mask pattern of 0.16 micrometer.

It is clear from Tables 10-13 that the positive photosensitive compositions of Examples 1-50 are excellent in sensitivity and resolution.

Examples 51-62 and Comparative Example 4

The component shown in following Table 14 was melt | dissolved in the solvent shown in Table 14, and this was filtered with the 0.1 micrometer Teflon filter, and the positive photosensitive composition of 14 weight% of solid content concentration was prepared.

The prepared positive photosensitive composition was evaluated by the following method, and the result is shown in Table 15.                     

The structures of the dissolution inhibiting compounds (C-1) and (C-2) in Table 14 are as follows.

Resist Evaluation

The prepared positive photosensitive composition was uniformly coated on a hexamethyldisilazane-treated silicon substrate using a spin coater, and dried on a hot plate at 120 ° C. for 90 seconds to form a resist film of 0.5 μm.

The resist film was exposed to a pattern using a line-and-space mask using KrF excimer laser stepper (NA = 0.63), and heated on a hot plate at 110 ° C. for 90 seconds immediately after exposure. Further, the solution was developed in a 2.38% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 60 seconds, rinsed in pure water for 30 seconds, dried to form a line pattern, and the same sensitivity and resolution as in Example 1 were evaluated.

It is clear from Table 15 that the positive photosensitive compositions of Examples 51-62 are excellent in sensitivity and resolution.

Examples 63 to 74 and Comparative Example 5

<Photosensitive composition preparation>

The composition shown in following Table 16 was mixed, and it filtered with the 0.1 micrometer Teflon filter, and prepared the negative photosensitive composition of 12 weight% of solid content concentration.

The negative photosensitive composition thus prepared was evaluated in the same manner as in Example 51, and the results are shown in Table 17.

It is clear from Table 17 that the negative photosensitive compositions of Examples 63-74 are excellent in sensitivity and resolution.

Examples 75 to 86 and Comparative Example 6

<Resist preparation>

In the same manner as in Examples 51 to 62 and Comparative Example 4, the components shown in Table 14 were dissolved in the solvent shown in Table 14, and these were filtered through a 0.1 µm Teflon filter to prepare a positive photosensitive composition having a solid content concentration of 12% by weight. It was.

The prepared positive photosensitive composition was evaluated by the following method, and the result is shown in Table 18.

Resist Evaluation                     

The prepared positive photosensitive composition was uniformly coated on a hexamethyldisilazane-treated silicon substrate using a spin coater, heated and dried on a hot plate at 120 ° C. for 60 seconds to form a 0.3 μm resist film.

This resist film was irradiated with the Nikon electron beam projection lithography apparatus (acceleration voltage 100 keV), and it heated on the hotplate at 110 degreeC for 90 second immediately after irradiation.

Further, the solution was developed at 23 ° C. for 60 seconds using an aqueous solution of tetramethylammonium hydroxide having a concentration of 2.38% by weight, rinsed with pure water for 30 seconds, and then dried to form a line pattern. The same sensitivity, resolution, and profile as those in Example 1 were evaluated except that line and space was used.

It is clear from Table 18 that the positive photosensitive compositions of Examples 75-86 are excellent in sensitivity and resolution.

Examples 87-98 and Comparative Example 7

<Photosensitive composition preparation>

In the same manner as in Examples 63 to 74 and Comparative Example 5, the components shown in Table 16 were dissolved in a solvent and filtered through a 0.1 µm Teflon filter to prepare a negative photosensitive composition having a solid content concentration of 12% by weight.

The negative photosensitive composition thus prepared was evaluated in the same manner as in Example 75, and the results are shown in Table 19.

It is clear from Table 19 that the negative photosensitive compositions of Examples 87-98 are excellent in sensitivity and resolution.                     

Examples 99-122 and Comparative Example 8

<Photosensitive composition preparation>

The component shown in following Table 20 was melt | dissolved in the solvent shown in Table 20, and this was filtered through the 0.1 micrometer Teflon filter, and the positive photosensitive composition of 10 weight% of solid content concentration was prepared.

The prepared positive composition was evaluated by the following method, and the result is shown in Table 21.                     

Resist Evaluation

The prepared positive photosensitive composition was uniformly coated on a hexamethyldisilazane-treated silicon substrate using a spin coater, and dried on a vacuum tight hot plate at 120 ° C. for 90 seconds to form a resist film having a thickness of 0.1 μm. It was.

The obtained resist film was exposed using the 157 nm laser exposure and dissolution behavior analysis apparatus VUVES-4500 (manufactured by Lisotech Japan Co., Ltd.), and heated on a hot plate at 120 ° C. for 90 seconds immediately after exposure. It was developed in a 2.38% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 60 seconds, rinsed with pure water for 30 seconds, dried, and the exposure amount resolved by a large pattern was used as the sensitivity.                     

It is clear from Table 21 that the positive photosensitive compositions of Examples 99-122 are excellent in sensitivity.

In addition, the photosensitive composition of this invention is expected to exhibit the same effect not only in the exposure light described in the said Example but also in EUV (13 nm).

According to this invention, the photosensitive composition excellent in a sensitivity and a resolution can be provided.

Claims (18)

(A) Photosensitive composition characterized by having a compound represented by the following general formula (I) or (II) which generate | occur | produces an acid by irradiation of actinic light or a radiation.

(In formulas (I) and (II), R <_1> -R <_3> may be same or different and represents a hydrogen atom, the alkyl group which may have a substituent, the alkenyl group which may have a substituent, the aryl group which may have a substituent, or an alkoxy group. R ₄ and R ₅ may be the same or different and represent a hydrogen atom, a cyano group, an alkyl group which may have a substituent, or an aryl group or alkoxy group which may have a substituent. Y <_1> and Y <_2> represent the aromatic group containing an alkyl group, an aryl group, an aralkyl group, or a hetero atom which may be same or different and may have a substituent. n represents the integer of 1-4. When n is two or more, two or more R <_1> and R <_2> may be same or different. Two or more of R ₁ to R ₃ , R ₄ , R ₅ , Y _1, and Y ₂ may be bonded to form a ring structure. In addition, at any one of R <_1> -R <_3> , R <_4> , R <_5> , Y <_1> and Y <_2> , it may couple through a coupling group and may have two or more structures of general formula (I) or (II). X ⁻ represents a non-nucleophilic anion.) The photosensitive composition according to claim 1, further comprising a basic compound and a surfactant containing at least one of fluorine and silicon. The basic compound according to claim 2, wherein the basic compound contains at least one compound having a structure selected from imidazole structure, diazabicyclo structure, onium hydroxide structure, onium carboxylate structure, trialkylamine structure and aniline structure. Photosensitive composition characterized in that. The photosensitive composition according to any one of claims 1 to 3, further comprising a dissolving low molecular weight compound having a molecular weight of 3000 or less, which has a group which is decomposed by the action of an acid to increase the solubility in the alkali developer. . delete delete delete delete (A) A compound represented by the following general formula (I) or (II) which generates an acid by irradiation of actinic light or radiation, and (B) A positive photosensitive composition characterized by containing a resin which is decomposed by the action of an acid and the solubility in the alkali developer is increased.

(In formulas (I) and (II), R <_1> -R <_3> may be same or different and represents a hydrogen atom, the alkyl group which may have a substituent, the alkenyl group which may have a substituent, the aryl group which may have a substituent, or an alkoxy group. R ₄ and R ₅ may be the same or different and represent a hydrogen atom, a cyano group, an alkyl group which may have a substituent, or an aryl group or alkoxy group which may have a substituent. Y <_1> and Y <_2> represent the aromatic group containing an alkyl group, an aryl group, an aralkyl group, or a hetero atom which may be same or different and may have a substituent. n represents the integer of 1-4. When n is two or more, two or more R <_1> and R <_2> may be same or different. Two or more of R ₁ to R ₃ , R ₄ , R ₅ , Y _1, and Y ₂ may be bonded to form a ring structure. In addition, at any one of R <_1> -R <_3> , R <_4> , R <_5> , Y <_1> and Y <_2> , it may couple through a coupling group and may have two or more structures of general formula (I) or (II). X ⁻ represents a non-nucleophilic anion.) The positive photosensitive composition as claimed in claim 9, wherein the resin of component (B) has a monocyclic or polycyclic alicyclic hydrocarbon structure. 10. The positive photosensitive composition as claimed in claim 9, further comprising a basic compound and a surfactant containing at least one of fluorine and silicon. The compound according to claim 11, wherein the basic compound contains at least one compound having a structure selected from imidazole structure, diazabicyclo structure, onium hydroxide structure, onium carboxylate structure, trialkylamine structure and aniline structure. The positive photosensitive composition characterized by the above-mentioned. The positive photosensitive property according to any one of claims 9 to 12, further comprising a dissolution-lowering low molecular weight compound having a molecular weight of 3000 or less, which has a group which is decomposed by the action of an acid to increase the solubility in the alkali developer. Composition. (A) A compound represented by the following general formula (I) or (II) which generates an acid by irradiation of actinic light or radiation; (C) acid crosslinking agents; And (D) The negative photosensitive composition containing alkali-soluble resin.

(In formulas (I) and (II), R <_1> -R <_3> may be same or different and represents a hydrogen atom, the alkyl group which may have a substituent, the alkenyl group which may have a substituent, the aryl group which may have a substituent, or an alkoxy group. R ₄ and R ₅ may be the same or different and represent a hydrogen atom, a cyano group, an alkyl group which may have a substituent, or an aryl group or alkoxy group which may have a substituent. Y <_1> and Y <_2> represent the aromatic group containing an alkyl group, an aryl group, an aralkyl group, or a hetero atom which may be same or different and may have a substituent. n represents the integer of 1-4. When n is two or more, two or more R <_1> and R <_2> may be same or different. Two or more of R ₁ to R ₃ , R ₄ , R ₅ , Y _1, and Y ₂ may be bonded to form a ring structure. In addition, at any one of R <_1> -R <_3> , R <_4> , R <_5> , Y <_1> and Y <_2> , it may couple through a coupling group and may have two or more structures of general formula (I) or (II). X ⁻ represents a non-nucleophilic anion.) The negative photosensitive composition as claimed in claim 14, further comprising a basic compound and a surfactant containing at least one of fluorine and silicon. The compound according to claim 15, wherein the basic compound contains at least one compound having a structure selected from imidazole structure, diazabicyclo structure, onium hydroxide structure, onium carboxylate structure, trialkylamine structure and aniline structure. The negative photosensitive composition characterized by the above-mentioned. The negative photosensitive property of any one of Claims 14-16 which further contains the low molecular weight dissolving low molecular weight compound of 3000 or less which has group which decomposes by the action of an acid, and improves the solubility in an alkali developing solution. Composition. A compound represented by the following general formula (I) or (II).

(In formulas (I) and (II), R <_1> -R <_3> may be same or different and represents a hydrogen atom, the alkyl group which may have a substituent, the alkenyl group which may have a substituent, the aryl group which may have a substituent, or an alkoxy group. R ₄ and R ₅ may be the same or different and represent a hydrogen atom, a cyano group, an alkyl group which may have a substituent, or an aryl group or alkoxy group which may have a substituent. Y <_1> and Y <_2> represent the aromatic group containing an alkyl group, an aryl group, an aralkyl group, or a hetero atom which may be same or different and may have a substituent. n represents the integer of 1-4. When n is two or more, two or more R <_1> and R <_2> may be same or different. Two or more of R ₁ to R ₃ , R ₄ , R ₅ , Y _1, and Y ₂ may be bonded to form a ring structure. In addition, at any one of R <_1> -R <_3> , R <_4> , R <_5> , Y <_1> and Y <_2> , it may couple through a coupling group and may have two or more structures of general formula (I) or (II). X ⁻ represents a non-nucleophilic anion.)