KR20080021511A - Method for producing polymer compound, polymer compound produced by the method, positive type photosensitive composition containing the polymer compound, and pattern forming method using the positive type photosensitive composition - Google Patents

Abstract

A method for preparing a polymer compound is provided to produce the polymer compound having higher sensitivity than the conventional polymer compound, and improved pattern collapse. A method for preparing a polymer compound includes a step of polymerizing a polymerizable compound having ethylenic double bonds using a polymerization initiator and a chain transfer agent represented by the following formula (1). A molar ratio(I/S) of the polymerization initiator(I) to the chain transfer agent(S) represented by the formula (1) added is 1.0 or less. In the formula (1), L represents a single bond or m+1-functional hydrocarbon group, each of R1 and R2 represents a bifunctional linker selected from the group consisting of an alkylene group, a cycloalkylene group, an oxyalkylene group, an arylene group, a bifunctional thiazoline ring, a bifunctional oxazoline ring, and a bifunctional imidazoline ring, or a bifunctional linker in which at least two thereof are linked with each other, each of R3 and R4 represents an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group, n represents 0 or 1, plural (n)s are identical to or different from one another, k represents 0 or 1, m represents an integer of 1-10, and R3 and R4 form a ring structure together with neighboring R1 or L.

Description

Manufacturing method of a high molecular compound, the high molecular compound manufactured by this manufacturing method, the positive photosensitive composition containing this high molecular compound, and the pattern formation method using this positive photosensitive composition TECHNICAL FOR PRODUCING POLYMER COMPOUND, POLYMER COMPOUND PRODUCED BY THE METHOD, POSITIVE TYPE PHOTOSENSITIVE COMPOSITION CONTAINING THE POLYMER COMPOUND, AND PATTERN FORMING METHOD USING THE POSITIVE TYPE PHOTOSENSITIVE COMPOSITION}

The present invention provides a method for producing a polymer compound for use in semiconductor manufacturing processes such as ICs, manufacturing of circuit boards such as liquid crystals, thermal heads, and other photofabrication processes, a polymer compound produced by the production method, and a polymer compound It relates to a positive photosensitive composition containing and a pattern forming method using the positive photosensitive composition. More specifically, a method for producing a polymer compound, a polymer compound produced by the production method, and the polymer compound, which are preferable when using an exposure light source such as far ultraviolet rays of 250 nm or less, preferably 220 nm or less, and an electron beam or the like It relates to a positive photosensitive composition containing and a pattern forming method using the positive photosensitive composition.

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

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

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

For this reason, resists for ArF excimer lasers containing resins having an alicyclic hydrocarbon structure have been developed. For example, Patent Literature 1 and Patent Literature 2 describe a composition containing a resin having a polycyclic acid decomposition repeating unit and a nonacid decomposition repeating unit. These resins are all chemically amplified resists having unstable protecting groups against acids decomposed by acid. However, it is difficult to obtain sufficient resist performance only with these protecting groups while further miniaturization of the resist pattern is required.

Then, as shown in patent documents 3-5, the resist polymer which introduce | transduced the crosslinking site | part which disintegrates by acid into resin containing the repeating unit which has an acid dissociable protecting group in the side chain is also examined.

This is because the crosslinking is cleaved by the acid catalyst to improve the dissolution contrast between the exposed and unexposed regions. However, the crosslinking reaction in the side chain of the polymer chain is carried out using a bifunctional monomer such as diacrylate for the polymerization of the polymer. Since the resulting polymer has a very large molecular weight distribution, solubility is poor and ultra-high molecular weight polymers are likely to be formed, so that a poorly soluble high molecular weight component that is difficult to dissolve in an alkaline developer even after decomposition with an acid exists. There was a problem that defects occurred when the fine pattern was formed by the dissolved residue.

Moreover, when using the crosslinked polymer which has an acid labile acetal frame | skeleton in a polymer side chain like patent document 3 as a resist polymer like patent document 3, although it is very sensitive with respect to an acid, there exists a tendency for the storage stability to be bad.

On the other hand, positive photosensitive resin which introduce | transduced an acid dissociative structure into the polymer main chain like patent document 6 and patent document 7 is proposed, for example. These proposals were proposals to solve the problem of the side chain crosslinked polymer, but the effect was not sufficient.

(Patent Document 1) Japanese Unexamined Patent Publication No. 2003-167347

(Patent Document 2) Japanese Unexamined Patent Publication No. 2003-223001

(Patent Document 3) Japanese Patent Application Laid-Open No. 2001-98034

(Patent Document 4) Japanese Patent Application Laid-Open No. 2000-214587

(Patent Document 5) Japanese Patent Application Laid-Open No. 2001-106737

(Patent Document 6) Japanese Patent Application Laid-Open No. 2006-91762

(Patent Document 7) WO2005 / 085301 A1 Brochure

SUMMARY OF THE INVENTION The present invention has been made in view of the above background, and an object thereof is a method for producing a polymer compound having a higher sensitivity than that of a conventional product used for forming a fine pattern such as semiconductor manufacturing and having improved pattern collapse, and a polymer produced by the production method. It is providing the compound, the positive photosensitive composition containing this high molecular compound, and the pattern formation method using this positive photosensitive composition.

The present invention is as follows.

(1) The chain transfer agent represented by General formula (1) in the manufacturing method of the high molecular compound which superposes | polymerizes the polymeric compound which has an ethylenic double bond using the chain transfer agent represented by following General formula (1), and a polymerization initiator. A method for producing a polymer compound, characterized in that the addition molar ratio (I / S) of (S) and the polymerization initiator (I) is 1.0 or less.

In general formula (1),

L represents a single bond or a m + 1 valent hydrocarbon group.

R ₁ and R ₂ are each independently a divalent linking group selected from the group consisting of an alkylene group, a cycloalkylene group, an oxyalkylene group, an arylene group, a divalent thiazolin ring, a divalent oxazoline ring and a divalent imidazoline ring Or the bivalent coupling group which at least 2 of these couple | bonded is shown.

R ₃ and R ₄ each independently represent an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group.

n represents 0 or 1. A plurality of n may be the same or different.

k represents 0 or 1.

m represents the integer of 1-10.

R ₃ and R ₄ may be bonded to adjacent R ₁ or L to form a ring structure.

(2) A polymer compound having a structural unit represented by the following General Formula (2), which is obtained by the production method described in (1).

In general formula (2),

L represents a single bond or a m + 1 valent hydrocarbon group.

R ₁ and R ₂ are each independently a divalent linking group selected from the group consisting of an alkylene group, a cycloalkylene group, an oxyalkylene group, an arylene group, a divalent thiazolin ring, a divalent oxazoline ring and a divalent imidazoline ring Or the bivalent coupling group which at least 2 of these couple | bonded is shown.

R ₃ and R ₄ each independently represent an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group.

n represents 0 or 1. A plurality of n may be the same or different.

k represents 0 or 1.

m represents the integer of 1-10.

R ₃ and R ₄ may be bonded to adjacent R ₁ or L to form a ring structure.

(3) The high molecular compound as described in (2) which has a structural unit which has an acid-decomposable group which decomposes at least by the action of an acid, and the solubility to alkaline developing solution increases.

(4) The polymer compound according to (2) or (3), wherein in the structural unit represented by the general formula (2), at least one of R ₃ and R ₄ is an alkyl group having 2 or more carbon atoms.

(5) The polymer according to (3) or (4), wherein the structural unit having an acid-decomposable group that is decomposed by the action of an acid and has increased solubility in an alkaline developer is represented by the following general formula (PA-A). compound.

In general formula (PA-A),

R represents a hydrogen atom, a halogen atom or an alkyl group. A plurality of Rs may be the same or different, respectively.

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

Rp ₁ represents any group represented by the following general formulas (pI) to (pV).

In general formula (pI)-(pV),

R ₁₁ represents an alkyl group.

Z represents an atomic group necessary to form a cycloalkyl group with a carbon atom.

R ₁₂ to R ₁₆ each independently represent an alkyl group or a cycloalkyl group.

R ₁₇ to R ₂₁ each independently represent a hydrogen atom, an alkyl group or a cycloalkyl group.

R ₂₂ to R ₂₅ each independently represent a hydrogen atom, an alkyl group, or a cycloalkyl group.

R ₂₃ and R ₂₄ may be bonded to each other to form a ring.

(6) In the general formulas (pI) to (pV), at least one of R ₁₁ , or R ₁₂ to R ₁₄ , or R ₁₆ , or at least one of R ₁₉ and R ₂₁ , or R ₂₂ and R ₂₅ At least 1 of is a methyl group, The high molecular compound as described in (5) characterized by the above-mentioned.

(7) At least, the high molecular compound in any one of (2)-(6) characterized by having a structural unit which has a lactone group.

(8) The molar number of the structural unit represented by General formula (2) with respect to the total number of moles of the structural unit contained in a high molecular compound is 2.5-10 mol%, In any one of (2)-(7) characterized by the above-mentioned. The high molecular compound described.

(9) At least, the positive photosensitive composition containing the high molecular compound in any one of (2)-(8), and the compound which generate | occur | produces an acid by irradiation of actinic light or a radiation.

(10) A pattern forming method comprising the step of forming a photosensitive film with the positive photosensitive composition as described in (9) and exposing and developing the photosensitive film.

INDUSTRIAL APPLICABILITY The present invention provides a method for producing a polymer compound, which is used for forming a fine pattern in semiconductor manufacturing and the like, and which has a higher sensitivity than a conventional product and has improved pattern collapse, a polymer compound produced by the production method, and a positive photosensitive property containing the polymer compound. A composition and a pattern formation method using this positive photosensitive composition can be provided.

Since the high molecular compound of this invention has the site | part cut off by an acidic catalyst in a polymer main chain, the dissolution contrast between an exposure area | region and an unexposed area | region can improve, and resist sensitivity can be made higher than a conventional product. In addition, since the polymer main chain is cut and the molecular size of the polymer is reduced, pattern collapse is improved by reduction of foreign matters after resolution and planarization of the resist pattern at the interface between the exposed and unexposed portions.

Moreover, the manufacturing method of this invention is a manufacturing method suitable for introduction of the acid dissociable structure introduce | transduced into a polymer main chain, and the high molecular compound (photosensitive resin and the same meaning as resin) manufactured by it can greatly raise the said effect.

EMBODIMENT OF THE INVENTION Hereinafter, the best form for implementing this invention is demonstrated.

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

Chain transfer agent represented by general formula (1)

In the manufacturing method of the high molecular compound of this invention, the chain transfer agent represented by following General formula (1) is used.

In general formula (1),

L represents a single bond or a m + 1 valent hydrocarbon group.

R ₁ and R ₂ are each independently a divalent linking group selected from the group consisting of an alkylene group, a cycloalkylene group, an oxyalkylene group, an arylene group, a divalent thiazolin ring, a divalent oxazoline ring and a divalent imidazoline ring Or the bivalent coupling group which at least 2 of these couple | bonded is shown.

R ₃ and R ₄ each independently represent an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group.

n represents 0 or 1. A plurality of n may be the same or different.

k represents 0 or 1.

m represents the integer of 1-10.

R ₃ and R ₄ may be bonded to adjacent R ₁ or L to form a ring structure.

In the general formula (1), the m + monovalent hydrocarbon group of L is preferably a hydrocarbon group having 1 to 10 carbon atoms, and for example, an alkylene group, an alkenylene group, an alkynylene group, a cycloalkylene group, an arylene group, and these groups. Enumerate groups in which one to several more hydrogen atoms have been removed.

The hydrocarbon group of L may have a substituent.

Examples of the substituent which the hydrocarbon group of L may have include a thiol group, a hydroxyl group, a carboxy group, a C 1-6 acyl group, a C 1-6 alkoxy group, a carboxyl group esterified with a C 1-6 alcohol, and a C 1 -C 6 Carboxyl groups, cyano groups, amino groups, halogen atoms, nitrooxy groups, thiolalkylcarbonyloxy groups substituted with six thiols, and linear or branched alkyl groups having 1 to 6 carbon atoms substituted with these substituents, having 3 to 6 carbon atoms Cycloalkylene groups and the like.

The hydrocarbon group of L may have a hetero atom.

Examples of the hetero atom which the hydrocarbon group of L may have include sulfur atom, oxygen atom, nitrogen atom, and person atom. At this time, the number of bonds coming out of the heteroatom changes depending on the valence of the heteroatom.

Preferred examples of L include single bonds and the following hydrocarbon groups.

It is preferable that a hetero atom is contained in the following structures in the hydrocarbon group of L.

R ₁ and R ₂ are preferably an alkylene group, an oxyalkylene group, a cycloalkylene group, an arylene group, and more preferably an alkylene group having 1 to 10 carbon atoms, an oxyalkylene group having 1 to 10 carbon atoms, and 3 to 10 carbon atoms. A cycloalkylene group, a C1-C10 arylene group is mentioned, Especially preferably, a C6-C10 alkylene group, a C4-C10 oxyalkylene group, and a C6-C10 cycloalkylene group are mentioned.

R <_3> and R <_4> , Preferably they are a C1-C18 linear or branched alkyl group, a cycloalkyl group, an alkenyl group, and an aryl group, More preferably, they are a methyl group, an ethyl group, a propyl group, and an isobutyl group.

Examples of the ring structure formed by bonding of R ₁ or L adjacent to R ₃ or R ₄ include a cyclohexane ring structure and an adamantane ring structure.

m becomes like this. Preferably it is 1-3 which a thiol group becomes bifunctional-tetrafunctional.

Since the more acid-decomposition structure, the ratio of main chain cleavage increases, it is preferable that k has 1, ie, two or more acid-decomposition structures.

The chain transfer agent represented by General formula (1) can be synthesize | combined by the method as described in Unexamined-Japanese-Patent No. 2006-91762 or WO2005 / 085301 A1 pamphlet.

Hereinafter, although the specific example of the chain transfer agent represented by General formula (1) is shown, this invention is not limited to these.

Polymerization initiator

The polymerization initiator used in the method for preparing the polymer compound of the present invention is not particularly limited as long as it is generally used as a radical generator. For example, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2 -Methylbutylonitrile), 2,2'-azobisisobutyric acid dimethyl, 1,1'-azobis (cyclohexane-carbonitrile), 4,4'-azobis (4-cyano valeric acid) Azo compounds, such as these; Organic peroxides such as decanoyl peroxide, lauroyl peroxide, benzoyl peroxide, bis (3,5,5-trimethylhexanoyl) peroxide, succinic peroxide, t-butylperoxy-2-ethylhexanoate May be used alone or in combination.

Addition molar ratio of the chain transfer agent (S) and polymerization initiator (I) represented by General formula (1)

In the manufacturing method of the high molecular compound of this invention, the usage-amount of the chain transfer agent (S) and polymerization initiator (I) represented by General formula (1) is characterized by the addition molar ratio (I / S) being 1.0 or less. When the addition molar ratio (I / S) is larger than 1.0, the proportion of free radicals into which insoluble electrons derived from a polymerization initiator are introduced during the polymerization reaction increases, and the effect of lowering molecular weight due to main chain cleavage cannot be sufficiently caused.

In general, in the telomerization reaction using a chain transfer agent such as a mercapto compound, the reaction proceeds according to the following formula, so that the molar ratio of the first polymerization initiator and the chain transfer agent becomes very important for the unit introduced at the polymer terminal.

In the present invention, the ratio of the chain transfer agent (S) represented by the general formula (1) is greater than that of the polymerization initiator (I), whereby the main chain of the polymer compound is cleaved by the action of an acid, that is, the general formula (1). The structure by the displayed chain transfer agent can be introduced into the main chain of the high molecular compound at a high ratio. The polymer compound synthesized by the production method of the present invention has an addition molar ratio (I / S) of 1.0 or less, preferably 0.5 or less, more preferably 0.3 or less, and is represented by the general formula (1) introduced into the main chain of the obtained polymer compound. The ratio of the main chain cleavage structure by the displayed chain transfer agent is clearly increased compared to the high molecular compound in which the added molar ratio (I / S) is larger than 1.0. Therefore, when the polymer compound produced by the production method of the present invention is used as a resist composition, the effect of lowering the molecular weight due to main chain cleavage is more exhibited, so that the contrast of dissolution between the exposed and unexposed regions is improved. In addition, the resist sensitivity can be increased. In addition, since the polymer main chain is cleaved and the molecular size of the polymer compound decreases, the effect of improving the pattern collapse due to the reduction of foreign substances after development and the planarization of the resist pattern on the exposed and unexposed portions interfaces can be more remarkably exhibited.

The amount of the chain transfer agent represented by the general formula (1) is usually 0.1 to 50 mol%, preferably 1 to 30 mol%, particularly preferably based on the total number of moles of the polymerizable compound (monomer) having an ethylenic double bond. Is used in the range of 2.5 to 10 mol%. Although the content of the structure by the chain transfer agent represented by General formula (1) in a high molecular compound increases, so that the addition amount of the chain transfer agent represented by General formula (1) increases, since the molecular weight of the obtained high molecular compound becomes small, it is considered as a resist composition. When using the high molecular compound of this invention, the addition amount of the said range is preferable. In addition, the polymerization initiator may not be uniformly defined because it varies depending on the raw material monomer used in the polymerization reaction, the type and amount of the chain transfer agent, and the polymerization conditions such as the polymerization temperature or the polymerization solvent, but the addition molar ratio (I / S) In terms of satisfying the above, 0.1 to 100 mol% (0.001 to 1.0 in terms of the added molar ratio (I / S)) to 1 mol of the chain transfer agent, preferably 1 to 50 mol% (in terms of the added molar ratio (I / S)). 0.01 to 0.5), more preferably 10 to 30 mol% (0.1 to 0.3, expressed as an added molar ratio (I / S)).

A high molecular compound

Although it will not specifically limit if it is a polymeric compound (monomer) which has an ethylenic double bond reactively as a raw material monomer used when manufacturing the high molecular compound of this invention, A high molecular compound dissociates an acid dissociable protecting group by the action of an acid. It is preferable that it is a positive photosensitive resin which increases the solubility to alkaline developing solution, and for that purpose, it is preferable to have structural unit (A) which has a structure which dissociates by the action of an acid at least, and increases solubility to alkaline developing solution.

The structural unit (A) having a structure that is dissociated by the action of an acid to increase its solubility in an alkaline developer means a structure that has been generally used as a resist in the past. It can obtain by superposing | polymerizing the monomer which has a structure, or polymerizing the monomer which has an alkali-soluble structure, and protecting an alkali-soluble group by an acid dissociable group.

As a structural unit (A) which has a structure which dissociates by the action of an acid, and the solubility to an alkali developing solution increases, the structure which has a partial structure containing an alicyclic hydrocarbon represented by the following general formula (pI)-general formula (pV) It is preferable that it is at least 1 sort (s) chosen from the group of a unit and the structural unit represented by the following general formula (II-AB).

In general formula (pI)-(pV),

R ₁₁ represents an alkyl group.

Z represents an atomic group necessary to form a cycloalkyl group with a carbon atom.

R ₁₂ to R ₁₆ each independently represent an alkyl group or a cycloalkyl group.

R ₁₇ to R ₂₁ each independently represent a hydrogen atom, an alkyl group or a cycloalkyl group.

R ₂₂ to R ₂₅ each independently represent a hydrogen atom, an alkyl group, or a cycloalkyl group.

R ₂₃ and R ₂₄ may be bonded to each other to form a ring.

In general formula (II-AB),

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

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

It is preferable that the said general formula (II-AB) is the following general formula (II-AB1) or general formula (II-AB2).

In formulas (II-AB1) and (II-AB2),

R ₁₃ 'to R ₁₆ ' are each independently a hydrogen atom, a halogen atom, a cyano group, -COOH, -COOR ₅ , a group decomposed by the action of an acid, -C (= O) -X-A'-R ₁₇ ', An alkyl group or a cycloalkyl group. At least two of R ₁₃ ′ and R ₁₆ ′ may be bonded to each other to form a ring.

Here, R ₅ represents a group having an alkyl group, a cycloalkyl group or a lactone structure.

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

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

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

R ₆ represents an alkyl group or a cycloalkyl group.

n represents 0 or 1.

In general formula (pI)-(pV), as an alkyl group in R <_11> -R <_25> , a linear or branched alkyl group which has 1-4 carbon atoms is preferable.

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

Preferred cycloalkyl groups are adamantyl, noadamantyl, decalinane, tricyclodecanyl, tetracyclododecanyl, norbornyl, cedrol, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl , Cyclodecanyl group, cyclododecanyl group and the like. More preferably, an adamantyl group, norbornyl group, a cyclohexyl group, a cyclopentyl group, a tetracyclo dodecanyl group, and a tricyclo decanyl group can be mentioned.

The alkyl group and cycloalkyl group may have a substituent.

Examples of the substituent for the alkyl group and the cycloalkyl group include an alkyl group (1 to 4 carbon atoms), a halogen atom, a hydroxy group, an alkoxy group (1 to 4 carbon atoms), a carboxyl group and an alkoxycarbonyl group (2 to 6 carbon atoms). Examples of the substituent which the alkyl group, alkoxy group, alkoxycarbonyl group and the like may further have include a hydroxy group, a halogen atom and an alkoxy group.

In formulas (pI) to (pV), at least one of R ₁₁ or R ₁₂ to R ₁₄ , or at least one of R ₁₆ , or R ₁₉ and R ₂₁ , or at least one of R ₂₂ and R ₂₅ . It is preferable that dog is a methyl group.

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

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

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

In general formula (PA-A),

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

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

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

The structural unit represented by general formula (pA-A) is preferably a structural unit with 2-alkyl-2-adanthyl (meth) acrylate and dialkyl (1-adanthyl) methyl (meth) acrylate.

Hereinafter, although the specific example of the structural unit represented by general formula (PA-A) is shown, this invention is not limited to this.

(Wherein Rx is H, CH ₃ , CF ₃ , CH ₂ 0H, Rxa, Rxb are each an alkyl group having 1 to 4 carbon atoms)

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

Examples of the alkyl group in R ₁₁ ′ and R ₁₂ ′ include linear or branched alkyl groups having 1 to 10 carbon atoms.

The atomic group for forming the Z 'alicyclic structure is an atomic group for forming a structural unit of the alicyclic hydrocarbon which may have a substituent in the resin, and among these, a crosslinked alicyclic type forming the structural unit of the crosslinked alicyclic hydrocarbon. Atom groups for forming the structure are preferred.

As a skeleton of the alicyclic hydrocarbon formed, the thing similar to the cycloalkyl group of R <_12> -R <_25> in general formula (pI)-(pVI) is mentioned.

The skeleton of the alicyclic hydrocarbon may have a substituent. As such a substituent, R <_13> -R <_16> in the said general formula (II-AB1) or (II-AB2) can be mentioned.

In the polymer compound according to the present invention, the group decomposed by the action of an acid has a structural unit having a partial structure containing an alicyclic hydrocarbon represented by general formulas (pI) to (pV), and general formula (II- It can be contained in at least 1 structural unit of the structural unit represented by AB), and the structural unit of the copolymerization component mentioned later.

Although one type may be used for an acid-decomposable structural unit, it is preferable to use together 2 or more types of acid-decomposable structural units from which the carbon number of an acid leaving group differs. As a result, the balance between resolution and exposure latitude becomes good.

Various substituents of R ₁₃ 'to R ₁₆ ' in the general formula (II-AB1) or the general formula (II-AB2) are atomic groups or crosslinks for forming the alicyclic structure in the general formula (II-AB). It may also be a substituent of the atomic group Z to form an alicyclic structure of the formula.

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

As the structural unit (A), a structural unit having a monocyclic alicyclic hydrocarbon group is preferable.

Moreover, it is preferable that the high molecular compound manufactured by the manufacturing method of this invention has a lactone group. Although any group can be used as long as it contains a lactone structure, Preferably it is a group containing a 5-7 member cyclic lactone structure, and is different in the form which forms a bicyclo structure and a spiro structure with a 5-7 member cyclic lactone structure. It is preferable that the ring structure is condensed. It is more preferable to have a structural unit which has group which has a lactone structure represented by either of following general formula (LC1-1)-(LC1-16). In addition, the group having a lactone structure may be directly bonded to the main chain. Preferred lactone structures are (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), (LC1-14), and the front edge is obtained by using a specific lactone structure. Roughness and development defects become good.

The lactone structure portion may or may not have a substituent (Rb ₂ ). Preferred substituents (Rb ₂ ) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, a carboxyl group, a halogen atom, a hydroxyl group, a cyano group, and an acid decomposition. Genitals and the like. n2 represents the integer of 0-4. when n2 is 2 or more, multiple presence (Rb ₂₎ is which may be the same or different to, or may form a ring by combining each other to present a plurality (Rb _2).

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

In general formula (AI),

Rb ₀ represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms. Preferred substituents which may have an alkyl group of Rb ₀ include hydroxy groups and halogen atoms. Examples of the halogen atom for Rb ₀ include fluorine, chlorine, bromine and iodine atoms. Rb ₀ is preferably a hydrogen atom or a methyl group.

Ab represents a divalent linking group, ether group, ester group, carbonyl group, or a divalent group combining these having a single bond, an alkylene group, a monocyclic or polycyclic alicyclic hydrocarbon structure. It is preferably a single bond, a linking group represented by -Ab ₁ -CO _2- . Ab ₁ represents a linear or branched alkylene group or a monocyclic or polycyclic cycloalkylene group, and is preferably a methylene group, an ethylene group, a cyclohexylene group, an ardanylene group or a norbornylene group.

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

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

As for content of the structural unit which has a lactone structure, 15-60 mol% is preferable with respect to the whole structural unit in a polymer, More preferably, it is 20-50 mol%, More preferably, it is 30-50 mol%.

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

Wherein R _x is H, CH ₃ , CH ₂ 0H or CF ₃

Wherein R _x is H, CH ₃ , CH ₂ 0H or CF ₃

Wherein R _x is H, CH ₃ , CH ₂ 0H or CF ₃

The following structural unit is mentioned as a structural unit which has especially preferable lactone group. By selecting the optimal lactone structure, the pattern profile and the roughness dependency become good.

Wherein R _x is H, CH ₃ , CH ₂ 0H, or CF ₃

Moreover, it is preferable that the high molecular compound manufactured by the manufacturing method of this invention has a structural unit which has an alicyclic hydrocarbon structure substituted by the polar group. This improves the substrate adhesion and the developer affinity. As an alicyclic hydrocarbon structure of the alicyclic hydrocarbon structure substituted by the polar group, an adanthyl group, a diadanthyl group, and a norbornane group are preferable. As a polar group, a hydroxyl group and a cyano group are preferable. As an alicyclic hydrocarbon structure substituted by the preferable polar group, the partial structure represented by the following general formula (VIIa)-(VIId) is preferable.

In general formula (VIIa)-(VIIc),

R _2c to R _4c each independently represent a hydrogen atom, a hydroxyl group or a cyano group. Provided that at least one of R _2c to R _4c represents a hydroxy group or a cyano group. Preferably, one or two of R _2c to R _4c are hydroxy groups and the rest are hydrogen atoms. In general formula (VIIa), More preferably, two of R <_2c> -R <_4c> are a hydroxyl group, and the remainder is a hydrogen atom.

Formula (VIIa) ~ as a structural unit having a group represented by (VIId) is the formula (II-AB1) or _{(II-AB) R 13 '} ~ R 16' , at least one is the general formula of the 2 (VIIa) Having a group represented by-(VIId) (for example, R ₅ of -COOR ₅ represents a group represented by general formulas (VIIa) to (VIId)), or a structure represented by the following general formulas (AIIa) to (AIId) The unit etc. can be enumerated.

In general formula (AIIa)-(AIId),

R ₁ c represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.

R ₂ c to R ₄ c each independently represent a hydrogen atom, a hydroxyl group or a cyano group. Provided that at least one of R ₂ c to R ₄ c represents a hydroxy group or a cyano group. R ₂ c ~ R ₄ c are the same as R ₂ c ~ c R ₄ in the formula (VIIa) ~ (VIIc).

As for content of the structural unit which has an alicyclic hydrocarbon structure substituted by a polar group, 5-40 mol% is preferable with respect to the whole structural unit in a polymer, More preferably, it is 5-30 mol%, More preferably, it is 10-25 mol% to be.

Although the specific example of the structural unit which has a structure represented by general formula (AIIa)-(AIIb) is enumerated below, this invention is not limited to these.

The high molecular compound manufactured by the manufacturing method of this invention may have a structural unit represented with the following general formula (VIII).

In general formula (VIII),

Z ₂ represents -O- or -N (R ₄₁ )-. R ₄₁ represents a hydrogen atom, a hydroxy group, an alkyl group or -OSO ₂ -R ₄₂ . R ₄₂ represents an alkyl group, a cycloalkyl group or a camphorzan group. The alkyl group of R ₄₁ and R ₄₂ may be substituted with a halogen atom (preferably a fluorine atom) or the like.

Although the following specific examples are listed as a structural unit represented by general formula (VIII), this invention is not limited to this.

It is preferable that the high molecular compound manufactured by the manufacturing method of this invention has a structural unit which has alkali-soluble group. Examples of the alkali-soluble group include a carboxyl group, a sulfonamido group, a sulfonylimido group, a bissulfonylimido group, and an aliphatic alcohol having a α-position substituted with an electron-withdrawing group (preferably represented by the following general formula (F1)). It is more preferable to have a structural unit which has a carboxyl group and a sulfonamido group.

In general formula (F1),

R ₅₀ to R ₅₅ each independently represent a hydrogen atom, a fluorine atom or an alkyl group. Provided that at least one of R ₅₀ to R ₅₅ represents an alkyl group in which a fluorine atom or at least one hydrogen atom is substituted with a fluorine atom. It is preferable that all of R ₅₀ to R ₅₅ are fluorine atoms.

Having a structural unit with an alkali soluble group increases the resolution in contact hole applications. Examples of the structural unit having an alkali-soluble group include a structural unit in which an alkali-soluble group is directly bonded to the main chain of the resin, such as acrylic acid or methacrylic acid, or a structural unit in which an alkali-soluble group is bonded to the main chain of the resin through a linking group. Moreover, all of the introduction is preferable at the terminal of a polymer chain using the polymerization initiator and chain transfer agent which have alkali-soluble group at the time of superposition | polymerization, and a linking group may have a monocyclic or polycyclic cyclic hydrocarbon structure. Especially preferably, it is a structural unit by acrylic acid and methacrylic acid.

As for content of the structural unit which has alkali-soluble group, 1-20 mol% is preferable with respect to all the structural units in a polymer, More preferably, it is 3-15 mol%, More preferably, it is 5-10 mol%.

Although the specific example of the structural unit which has alkali-soluble group is shown below, this invention is not limited to this.

(Wherein Rx is H, CH ₃ , CF ₃ , CH ₂ 0H)

The high molecular compound manufactured by the manufacturing method of this invention may further have a structural unit which has an alicyclic hydrocarbon structure and does not show acid decomposability. This can reduce the elution of the low molecular component from the resist film to the immersion liquid during immersion exposure. As such a structural unit, 1-adamantyl (meth) acrylate, tricyclo decanyl (meth) acrylate, cyclohexyl (meth) acrylate, etc. are mentioned, for example.

In addition to the repeating structural unit, the polymer compound prepared by the manufacturing method of the present invention may be used for the purpose of controlling dry etching resistance, standard developer aptitude, substrate adhesion, resist profile, and resolution, heat resistance, sensitivity, etc. which are general necessary characteristics of resist. It can have several repeating structural units.

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

Thereby, the performance required for an alicyclic hydrocarbon type acid-decomposable resin, especially

(1) solubility in coating solvents,

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

(3) alkali developability,

(4) membrane peeling (selection of hydrophilic, alkali-soluble group),

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

(6) dry etching resistance

Fine adjustment of such a thing becomes possible.

Examples of such monomers include compounds having one addition polymerizable unsaturated bond selected from acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, and the like. can do.

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

In the polymer compound prepared by the production method of the present invention, the molar ratio of each repeating structural unit is determined by the dry etching resistance of the resist, the standard developer aptitude, the substrate adhesion, the resist profile, and the resolution, heat resistance, and sensitivity, which are general necessary capabilities of the resist. It is appropriately set to adjust the degree and the like.

The following are mentioned as a preferable aspect of the high molecular compound manufactured by the manufacturing method of this invention.

(1) It contains the structural unit which has a partial structure containing the alicyclic hydrocarbon represented by said general formula (pI)-(pV) (side chain type).

The thing which has a (meth) acrylate structural unit which has a structure of (pI)-(pV) preferably.

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

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

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

In the polymer compound produced by the production method of the present invention, the content of the structural unit having an acid-decomposable group is preferably 10 to 60 mol%, more preferably 20 to 50 mol%, even more preferably in all the repeating structural units. 25-40 mol%.

In the high molecular compound manufactured by the manufacturing method of this invention, content of the structural unit which has a partial structure containing the alicyclic hydrocarbon represented by general formula (pI)-(pV) is 20-70 mol% among all the repeating structural units. It is preferable, More preferably, it is 20-50 mol%, More preferably, it is 25-40 mol%.

In the polymer compound produced by the production method of the present invention, the content of the structural unit represented by the general formula (II-AB) is preferably 10 to 60 mol% of the total repeating structural units, more preferably 15 to 55 Mol%, More preferably, it is 20-50 mol%.

Moreover, although content in resin of a repeating structural unit can also be suitably set according to the performance of a desired resist further based on the monomer of the said copolymerization component, In general, the alicyclic hydrocarbon represented by general formula (pI)-(pV) is used. It is preferably at most 99 mol%, more preferably at most 90 mol%, even more preferably based on the total moles of the total moles of the repeating structural unit having a partial structure and the structural unit represented by the general formula (II-AB). It is 80 mol% or less.

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

The high molecular compound manufactured by the manufacturing method of this invention has a structural unit represented by following General formula (2) by the chain transfer agent represented by the said General formula (1).

In general formula (2),

L represents a single bond or a m + 1 valent hydrocarbon group.

R ₁ and R ₂ are each independently a divalent linking group selected from the group consisting of an alkylene group, a cycloalkylene group, an oxyalkylene group, an arylene group, a divalent thiazolin ring, a divalent oxazoline ring and a divalent imidazoline ring Or the bivalent coupling group which at least 2 of these couple | bonded is shown.

R ₃ and R ₄ each independently represent an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group.

n represents 0 or 1. A plurality of n may be the same or different.

k represents 0 or 1.

m represents the integer of 1-10.

R ₃ and R ₄ may be bonded to adjacent R ₁ or L to form a ring structure.

L, R ₁ , R ₂ , R ₃ , R ₄ , n, k, and m in General Formula (2) represent L, R ₁ , R ₂ , R ₃ , R ₄ , in General Formula (1). same as n, k, m.

It is preferable that content of the structural unit represented by General formula (2) is 2.5-10 mol% with respect to the total mole number of the structural unit contained in a high molecular compound.

The polymer compound of the present invention is -S- (R ₂ ) _n -C (= O) -O- group and -L- (R ₁ ) _n − in the structural unit represented by the formula (2) by the action of an acid. The molecular weight decreases because the C (R ₃ ) (R ₄ ) -group is cleaved.

As a high molecular compound manufactured by the manufacturing method of this invention, Preferably, all of a structural unit consists of a (meth) acrylate type structural unit. In this case, all of the structural units are methacrylate-based structural units, all of the structural units may be any of an acrylate-based structural unit, a methacrylate-based structural unit / acrylate-based structural unit mixture, but acrylate-based It is preferable that a structural unit is 50 mol% or less of all the structural units.

As the polymer compound produced by the production method of the present invention, more preferably, 2.5 to 10 mol% of structural units represented by the general formula (2) and alicyclic hydrocarbons represented by the general formulas (pI) to (pV) are included. Copolymer having 20-50 mol% of the structural unit which has a partial structure, 20-50 mol% of the structural unit which has a lactone structure, 5-30 mol% of the structural unit which has an alicyclic hydrocarbon structure substituted by a polar group, or other structure It is a copolymer polymer which has a 0-20 mol% further unit.

As a particularly preferable high molecular compound, 20 to 50 mol% of structural units having an acid-decomposable group represented by 2.5 to 10 mol% of structural units represented by the general formula (2) and the following general formulas (ARA-1) to (ARA-5) 20-50 mol% of the structural unit which has a lactone group represented by the following general formula (ARL-1)-(ARL-6), and substituted by the polar group represented by the following general formula (ARH-1)-(ARH-3) Copolymers having 5 to 30 mol% of structural units having an alicyclic hydrocarbon structure, Furthermore, structural units having a carboxyl group or a structure represented by the general formula (F1), and structural units having an alicyclic hydrocarbon structure and not exhibiting acid decomposability. It is a copolymeric polymer which has -20 mol%.

In the formula, Rxy ₁ represents a hydrogen atom or a methyl group, Rxa ₁ and Rxb ₁ each independently represent a methyl group or an ethyl group.

The polymer compound produced by the production method of the present invention preferably has a structural unit in which at least one of R ₃ and R ₄ is an alkyl group having 2 or more carbon atoms in the structural unit represented by the general formula (2), and In the structural unit represented by Formula (2), at least one of R <_3> and R <_4> is a C2 or more alkyl group, the said specific example (1)-(25), or the said structural unit (ARA-1) In (ARA-5), more preferably at least one of Rxa ₁ and Rxb ₁ has a methyl group, and in the structural unit represented by the general formula (2), all of R ₃ and R ₄ are in and a structural unit having 2 or more alkyl group (especially an ethyl group), specific examples (1) to (25) or structural unit (ARA-1) to (ARA-5), in that all of Rxa ₁ and Rxb ₁ methyl It is more preferable to have a structural unit.

The high molecular compound manufactured by the manufacturing method of this invention can be synthesize | combined according to a conventional method (for example, radical polymerization). For example, as a general synthetic method, the monomer species, the chain transfer agent represented by General formula (1), and the polymerization initiator are melt | dissolved in a solvent, and are superposed | polymerized by superposition | polymerization by carrying out polymerization, and a monomer type in a heating solvent is represented by General formula (1). The dropping polymerization method etc. which add and add the solution of the chain transfer agent and a polymerization initiator which are added over 1 to 10 hours are mentioned, A drop polymerization method is preferable. Examples of the reaction solvent include ethers such as tetrahydrofuran, 1,4-dioxane and diisopropyl ether, ketones such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate, dimethylformamide and dimethyl acetyl. The solvent which melt | dissolves the composition of this invention, such as amide solvents, such as an amide, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and cyclohexanone mentioned later is mentioned. More preferably, it is preferable to superpose | polymerize using the same solvent as the solvent used for the resist composition of this invention. Thereby, generation | occurrence | production of the particle | grains at the time of storage can be suppressed.

It is preferable that a polymerization reaction is performed in inert gas atmosphere, such as nitrogen and argon.

After completion of the reaction, the desired high molecular compound is recovered by pouring into a solvent and recovering powder or solid. The concentration of the reaction is 5 to 50% by mass, preferably 10 to 30% by mass. Reaction temperature is 10-150 degreeC normally, Preferably it is 30-120 degreeC, More preferably, it is 60-100 degreeC.

The weight average molecular weight of the high molecular compound which concerns on this invention is polystyrene conversion value by GPC method, Preferably it is 1,000-200,000, More preferably, it is 3,000-20,000, Most preferably, it is 5,000-15,000. By setting a weight average molecular weight to 1,000-200,000, deterioration of heat resistance and dry etching resistance can be prevented, and developability deteriorates or a viscosity becomes high, and manufacturability can be prevented from deteriorating.

Dispersion degree (molecular weight distribution) of a high molecular compound is 1-5 normally, Preferably it is 1-3, More preferably, the thing of the range of 1-2 is used. The smaller the molecular weight distribution is, the better the resolution and the resist shape are, and the smoother the sidewall of the resist pattern is, the better the roughness is.

In the positive photosensitive composition of this invention, 60-99 mass% is preferable in the total solid of the compounding quantity in the whole composition of all the high molecular compounds which concerns on this invention, More preferably, it is 80-98 mass%.

In addition, in this invention, a polymeric compound may be used by 1 type, and may be used together plural.

The high molecular compound manufactured by the manufacturing method of this invention is used suitably for positive photosensitive compositions.

Hereinafter, components other than the high molecular compound of this invention used for a positive photosensitive composition are demonstrated.

Compounds that generate acids by irradiation with actinic light or radiation

The positive photosensitive composition of this invention contains the compound (henceforth a "photoacid generator") which generate | occur | produces an acid by irradiation of actinic light or a radiation.

Such photoacid generators include known compounds that generate acids by irradiation with actinic rays or radiation used in photoinitiators of photocationic polymerization, photoinitiators of photoradical polymerization, photochromic agents of pigments, photochromic agents, or microresists, and the like. A mixture of can be selected and used suitably.

For example, diazonium salt, phosphonium salt, sulfonium salt, iodonium salt, imidosulfonate, oxime sulfonate, diazo disulfone, disulfone, o-nitobenzyl sulfonate can be mentioned.

Further, compounds in which an acid or a group which generates an acid by irradiation of these actinic rays or radiations are introduced into the main chain or side chain of the polymer, such as US Patent No. 3,849,137, German Patent No. 3914407, and Japanese Patent Publication No. 63-26653. Japanese Patent Publication No. 55-164824, Japanese Patent Publication No. 62-69263, Japanese Patent Publication No. 63-146038, Japanese Patent Publication No. 63-163452, Japanese Patent Publication No. 62-153853, Japanese Patent Publication No. The compound described in 63-146029 etc. can be used.

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

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

In general formula (ZI),

R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represent an organic group.

X ⁻ represents a non-nucleophilic anion, preferably a sulfonic acid anion, a carboxylic acid anion, a bis (alkylsulfonyl) amide anion, a tris (alkylsulfonyl) methed anion, BF ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ And the like, and are preferably organic anions having carbon atoms.

Preferred organic anions include organic anions represented by the following general formulas (AN1) to (AN4).

In general formula (AN1) and (AN2),

Rc ₁ represents an organic group.

Examples of the organic groups in the general formulas (AN1) to (AN2) and Rc ₁ include those having 1 to 30 carbon atoms, preferably an alkyl group which may be substituted, a cycloalkyl group, an aryl group, or a plurality of these are a single bond, And groups linked with a linking group such as —O—, —CO ₂ —, —S—, —SO ₃ —, or —SO ₂ N (Rd ₁ ) —. Rd ₁ may represent a hydrogen atom or an alkyl group, and may form a ring structure with the alkyl group, cycloalkyl group, and aryl group bonded thereto.

More preferred as the organic group of Rc ₁ is a phenyl group substituted with an alkyl group in the alkyl group, a fluorine atom or a fluoroalkyl group substituted with an alkyl group is the 1-position a fluorine atom or a fluoroalkyl group. By having a fluorine atom or a fluoroalkyl group, the acidity of the acid generated by light irradiation is increased and the sensitivity is improved. When Rc ₁ has five or more carbon atoms, at least one carbon atom preferably has all hydrogen atoms instead of being substituted with fluorine atoms, and more preferably has more hydrogen atoms than fluorine atoms. By not having a perfluoroalkyl group having 5 or more carbon atoms, ecological toxicity is reduced.

As a particularly preferable form of Rc ₁ , the groups represented by the following general formulas can be listed.

In the above general formula,

Rc ₆ is substituted with up to 4 carbon atoms, more preferably 2 to 4, more preferably 2 to 3 perfluoroalkylene groups, 1 to 4 fluorine atoms and / or 1 to 3 fluoroalkyl groups A phenylene group is shown.

Ax represents a single bond or a divalent linking group (preferably -O-, -CO _2- , -S-, -SO _3- , -SO ₂ N (Rd ₁ )-). Rd ₁ may represent a hydrogen atom or an alkyl group, and may combine with Rc ₇ to form a ring structure.

Rc ₇ represents a hydrogen atom, a fluorine atom, a linear or branched, monocyclic or polycyclic cycloalkyl group or an aryl group which may be substituted. It is preferable that the alkyl group, cycloalkyl group, and aryl group which may be substituted do not have a fluorine atom as a substituent.

In the general formulas (AN3) and (AN4),

Rc ₃ , Rc ₄ and Rc ₅ each independently represent an organic group.

Rc ₃ and Rc ₄ may be bonded to each other to form a ring.

As Rc _3, Rc ₄ and Rc ₅ organic groups of in formula (AN3) and (AN4), and preferably may be exemplified the same preferred organic groups in Rc _1.

In the case where Rc ₃ and Rc ₄ are bonded to form a ring, examples of the group formed by bonding of Rc ₃ and Rc ₄ include an alkylene group and an arylene group. Preferably it is a C2-C4 perfluoroalkylene group. By combining Rc ₃ and Rc ₄ to form a ring, the acidity of the acid generated by light irradiation is increased, and the sensitivity is improved, which is preferable.

Carbon number of the organic group as R <_201> , R <_202> and R <_{203> in the} said general formula (ZI) is generally 1-30, Preferably it is 1-20.

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 (eg, butylene group, pentylene group).

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

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

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

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

Arylsulfonium compound may be a group all of R ₂₀₁ R ₂₀₃ ~ aryl, R ₂₀₁ ~ R ₂₀₃ is a part of the aryl group, the remaining group may be a cycloalkyl group.

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

As an aryl group of an arylsulfonium compound, heteroaryl groups, such as an aryl group, such as a phenyl group and a naphthyl group, an indole residue, and a pyrrole residue, are preferable, More preferably, they are a phenyl group and an indole residue. When an arylsulfonium compound has two or more aryl groups, two or more aryl groups may be same or different.

The alkyl group possessed by the arylsulfonium compound as needed is preferably a linear or branched alkyl group having 1 to 15 carbon atoms, and for example, methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, t-butyl group and the like. Can be enumerated.

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

The aryl group, alkyl group and cycloalkyl group of R ₂₀₁ to R ₂₀₃ are an alkyl group (e.g., 1 to 15 carbon atoms), a cycloalkyl group (e.g., 3 to 15 carbon atoms), an aryl group (e.g., 6 to 14 carbon atoms), alkoxy You may have a group (for example, C1-C15), a halogen atom, a hydroxyl group, and a phenylthio group as a substituent. Preferred substituents are a linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a linear, branched or cyclic alkoxy group having 1 to 12 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. And a C1-4 alkoxy group. The substituent may be substituted on any one of three R ₂₀₁ to R ₂₀₃ , and may be substituted on all three. In the case where R ₂₀₁ to R ₂₀₃ are an aryl group, the substituent is preferably substituted at the p-position of the aryl group.

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

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

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

R ₂₀₁ to R ₂₀₃ are each independently preferably an alkyl group, a cycloalkyl group, an allyl group, a vinyl group, more preferably a linear, branched, cyclic 2-oxoalkyl group, an alkoxycarbonyl methyl group, and particularly preferably It is a chain and branched 2-oxoalkyl group.

The alkyl group as R ₂₀₁ to R ₂₀₃ may be either linear or branched, and preferably includes a linear or branched alkyl group having 1 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group and a pentyl group). can do. As for the alkyl group as R <_201> -R <_203> , it is more preferable that they are a linear or branched 2-oxoalkyl group and the alkoxy methyl group.

The cycloalkyl group as R ₂₀₁ to R ₂₀₃ is preferably a C3-C10 cycloalkyl group (cyclopentyl group, cyclohexyl group, norbornyl group).

The 2-oxoalkyl group as R ₂₀₁ to R ₂₀₃ may be any of linear, branched or cyclic, and preferably groups having> C═O at the 2-position of the alkyl group and cycloalkyl group can be listed.

The alkoxy group in the alkoxycarbonyl methyl group as R ₂₀₁ to R ₂₀₃ is preferably an alkoxy group having 1 to 5 carbon atoms (methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy group).

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

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

In general formula (ZI-3),

R ₁ c to R ₅ c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group or a halogen atom.

R ₆ c and R ₇ c each independently represent a hydrogen atom, an alkyl group or a cycloalkyl group.

Rx and Ry each independently represent an alkyl group, a cycloalkyl group, an allyl group or a vinyl group.

R ₁ R ₇ c ~ c of any two or more, and Rx and Ry may be bonded to form a ring structure by bonding each of the ring structure may contain an oxygen atom, a sulfur atom, an ester bond or an amide bond. Any two or more of R ₁ c to R ₇ c, and a group formed by bonding Rx and Ry may include a butylene group, a pentylene group, and the like.

X <^-> represents a non-nucleophilic anion and is the same as X <^-> in general formula (ZI).

The alkyl group as R ₁ c to R ₇ c may be either linear or branched, for example, an alkyl group having 1 to 20 carbon atoms, preferably a linear and branched alkyl group having 1 to 12 carbon atoms (eg, a methyl group, an ethyl group, Linear or branched propyl groups, linear or branched butyl groups, and linear or branched pentyl groups).

The cycloalkyl group as R ₁ c to R ₇ c is preferably a cycloalkyl group having 3 to 8 carbon atoms (eg, a cyclopentyl group and a cyclohexyl group).

The alkoxy group as R ₁ c to R ₅ c 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 (e.g., Methoxy group, ethoxy group, linear or branched propoxy group, linear or branched butoxy group, linear or branched pentoxy group, cyclic alkoxy group having 3 to 8 carbon atoms (e.g. cyclopentyloxy group, cyclohex) Siloxy group) can be enumerated.

Preferably, any one of R ₁ c to R ₅ c is a linear or branched alkyl group, a cycloalkyl group, or a linear, branched or cyclic alkoxy group, and more preferably of R ₁ c to R ₅ c The sum is 2-15. Thereby, the solubility to a solvent improves and particle generation at the time of storage is suppressed.

Alkyl groups as Rx and Ry may be the same as the alkyl groups as R _1c to R _7c . The alkyl group as Rx and Ry is more preferably a linear or branched 2-oxoalkyl group or an alkoxymethyl group.

Cycloalkyl groups as Rx and Ry may be the same as the cycloalkyl groups as R _1c to R _7c . It is more preferable that the cycloalkyl group as Rx and Ry is a cyclic 2-oxoalkyl group.

The linear, branched, cyclic 2-oxoalkyl group can enumerate the group which has> C = O at the 2-position of the alkyl group and cycloalkyl group as R < _1c > -R < _7c >.

Examples of the alkoxy group in the alkoxycarbonyl methyl group include the same alkoxy groups as R _1c to R _5c .

Rx and Ry are preferably alkyl groups having 4 or more carbon atoms, more preferably 6 or more, more preferably 8 or more alkyl groups.

In said general formula (ZII), (ZIII),

R ₂₀₄ to R ₂₀₇ each independently represent an aryl group, an alkyl group or a cycloalkyl group.

The aryl group of R ₂₀₄ ~ R ₂₀₇ may be a phenyl group, a naphthyl group, more preferably is a phenyl group.

The alkyl group as R ₂₀₄ to R ₂₀₇ may be either linear or branched, and preferably a linear or branched alkyl group having 1 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl, pentyl) Can be enumerated.

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

R ₂₀₄ to R ₂₀₇ may have a substituent. Substituents which R ₂₀₄ to R ₂₀₇ may have include, for example, an alkyl group (e.g., 1 to 15 carbon atoms), a cycloalkyl group (e.g., 3 to 15 carbon atoms), an aryl group (e.g., 6 to 15 carbon atoms), alkoxy Group (for example, C1-C15), a halogen atom, a hydroxyl group, a phenylthio group, etc. can be mentioned.

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

As a preferable compound among the compound which generate | occur | produces an acid by irradiation of actinic light or a radiation, the compound represented by the following general formula (ZIV), (ZV), (ZVI) can be enumerated further.

In general formulas (ZIV) to (ZVI),

Ar ₃ And Ar ₄ each independently represent an aryl group.

R ₂₀₈ represents an alkyl group, a cycloalkyl group or an aryl group.

R ₂₀₉ And R ₂₁₀ each independently represent an alkyl group, a cycloalkyl group, an aryl group or an electron withdrawing group. R ₂₀₉ is preferably an aryl group. R ₂₁₀ is preferably an electron withdrawing group, more preferably a cyano group or a fluoroalkyl group.

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

Among the compounds which generate an acid by irradiation with actinic light or radiation, more preferably, they are compounds represented by the general formulas (ZI) to (ZIII), still more preferably compounds represented by (ZI), and particularly preferably It is a compound represented by (ZI-1)-(ZI-3).

Moreover, the compound which generate | occur | produces the acid represented by the following general formula (AC1)-(AC3) by irradiation of actinic light or a radiation is preferable.

That is, as a form of a particularly preferable photoacid generator, in the structure represented by the general formula (ZI), compounds in which X ⁻ is an anion selected from the general formulas (AN1), (AN3) and (AN4) can be enumerated. have.

Examples of particularly preferable compounds among those compounds that decompose upon irradiation with actinic light or radiation to generate an acid are listed below.

Photoacid generators can be used individually by 1 type or in combination of 2 or more types. When using in combination of 2 or more types, it is preferable to combine the compound which generate | occur | produces 2 or more types of organic acids in which all the atomic numbers except 2 hydrogen atoms differ.

As for content in the composition of a photo-acid generator, 0.1-20 mass% is preferable based on the total solid of a positive photosensitive composition, More preferably, it is 0.5-10 mass%, More preferably, it is 1-7 mass%.

Resins without groups decomposed by the action of acids

The positive photosensitive composition of this invention may contain resin which does not have group which decomposes by the effect | action of an acid.

In the image forming process in which the positive photosensitive composition of the present invention is usually used, there is no degradability due to the action of an acid or extremely small, so that the image forming by the acid decomposition is substantially used. It does not have a contributing group. As such resin, resin which has alkali-soluble group, resin which has group which decomposes by the action of alkali, and improves the solubility to alkaline developing solution is mentioned.

As the resin having no group decomposed by the action of an acid, a resin having at least one structural unit derived from a (meth) acrylic acid derivative and / or an alicyclic olefin derivative is preferable.

Alkali-soluble groups contained in the resin having no group decomposed by the action of an acid include a carboxyl group, a phenolic hydroxy group, an aliphatic hydroxyl group in which one or two positions are substituted with an electron withdrawing group, and an amino group substituted with an electron withdrawing group (e.g. Amido groups, sulfonimido groups, bissulfonyl imido groups), methylene groups substituted with electron-withdrawing groups, or methine groups (e.g., at least two substituted methylene groups and methine groups selected from ketone groups and ester groups) are preferable. .

Lactone group and acid anhydride group are preferable as a group which is contained by resin which does not have a group decomposed by the effect | action of an acid, and the solubility in alkaline developing solution increases by the action of an acid, More preferably, it is a lactone group.

As a resin which does not have a group decomposed by the action of an acid, you may have a structural unit which has a functional group other than the above. As a structural unit which has another functional group, a suitable functional group can be introduce | transduced in consideration of dry etching tolerance, hydrophilicity, interaction, etc. Other structural units include a structural unit having a polar functional group such as a hydroxyl group, a cyano group, a carbonyl group, an ester group, a structural unit having a monocyclic or polycyclic cyclic hydrocarbon structure, a silicon atom, a halogen atom, a fluoroalkyl group, Or a structural unit having a plurality of these functional groups.

Specific examples of the resin having no group decomposed by the action of a preferred acid are shown below.

The addition amount of resin which does not have a group decomposed by the action of an acid is 0-30 mass% with respect to a high molecular compound, Preferably it is 0-20 mass%, More preferably, it is 0-15 mass%.

Dissolution control compound having a molecular weight of 3000 or less having at least one selected from an alkali soluble group, a hydrophilic group and an acid-decomposable group

To the positive photosensitive composition of the present invention, a dissolution control compound having a molecular weight of 3000 or less (hereinafter, also referred to as a "dissolution control compound") having at least one selected from an alkali-soluble group, a hydrophilic group, and an acid-decomposable group may be added.

As the dissolution control compound, a compound having an alkali-soluble group such as a carboxyl group, a sulfonylimido group, a hydroxy group in which the α position is substituted with a fluoroalkyl group, a hydroxyl group, a lactone group, a cyano group, an amido group, a pyrrolidone group, a sulfonamido group, etc. Preferred are compounds having a hydrophilic group or a compound containing a group which is decomposed by the action of an acid to release an alkali-soluble group or a hydrophilic group. As a group which decomposes by the action of an acid to release an alkali-soluble group or a hydrophilic group, a group in which a carboxyl group or a hydroxy group is protected with an acid-decomposable group is preferable. It is preferable to use the compound which does not contain an aromatic ring, or to use the compound which has an aromatic ring in the addition amount of 20 weight% or less with respect to solid content of a composition, in order not to reduce permeability of 220 nm or less as a dissolution control compound.

As a preferable dissolution control compound, the carboxylic acid compound which has alicyclic hydrocarbon structure, such as adamantane (di) carboxylic acid, norbornane carboxylic acid, and a cholic acid, or the compound which protected this carboxylic acid with the acid-decomposable group, Polyols, such as sugars, or the compound which protected the hydroxyl group with the acid-decomposable group are preferable.

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

The addition amount of the dissolution control compound is preferably 3 to 40% by mass, more preferably 5 to 20% by mass, with respect to the solid content of the positive photosensitive composition.

Although the specific example of a dissolution control compound is shown below, this invention is not limited to these.

Basic compound

It is preferable that the positive photosensitive composition of this invention contains a basic compound in order to reduce the performance change with time-lapse from exposure to heating, or to control the diffusibility in the film | membrane of the acid produced by exposure.

Examples of the basic compound include nitrogen-containing basic compounds and onium salt compounds. As a structure of a preferable nitrogen containing basic compound, the compound which has a partial structure represented by the following general formula (A)-(E) can be mentioned.

In general formula (A),

R ²⁵⁰ , R ²⁵¹ and R ²⁵² are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, wherein R ²⁵⁰ and R ²⁵¹ combine with each other to form a ring Also good. These may have a substituent, and as an alkyl group and a cycloalkyl group which have a substituent, a C1-C20 amino alkyl group or a C3-C20 amino cycloalkyl group, a C1-C20 hydroxyalkyl group, or a C3-C20 hydroxy Cycloalkyl groups are preferred. These may contain an oxygen atom, a sulfur atom, and a nitrogen atom in the alkyl chain.

In general formula (E),

R ²⁵³ , R ²⁵⁴ , R ²⁵⁵ and R ²⁵⁶ each independently represent a C 1-6 alkyl group or a C 3-6 cycloalkyl group.

Examples of preferred compounds include guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine and piperidine, and may have a substituent. More preferred compounds include imidazole structures, diazabicyclo structures, onium hydroxide structures, oniumcarboxylate structures, trialkylamine structures, compounds having aniline structures or pyridine structures, alkyl amines having hydroxy groups and / or ether bonds. Derivatives, aniline derivatives having hydroxy groups and / or ether bonds, and the like.

Examples of the compound having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole and the like. Compounds having a diazabicyclo structure include 1,4-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4,3,0] nona-5-ene, 1,8-dia Xabicyclo [5,4,0] undec-7-ene and the like are listed. Examples of the compound having an onium hydroxide structure include triarylsulfonium hydroxide, phenacylsulfonium hydroxide, sulfonium hydroxide having a 2-oxoalkyl group, specifically triphenylsulfonium hydroxide and tris (t-butylphenyl) sulfonium hydroxide, bis (t-butylphenyl) iodonium hydroxide, phenacylthiophenium hydroxide, 2-oxopropylthiophenium hydroxide, etc. are mentioned. As the compound having an onium carboxylate structure, the anion portion of the compound having an onium hydroxide structure is a carboxylate, and examples thereof include acetate, adamantane-1-carboxylate, and perfluoroalkyl carboxylate. Listed. Examples of the compound having a trialkylamine structure include tri (n-butyl) amine, tri (n-octyl) amine, and the like. 2, 6- diisopropyl aniline, N, N- dimethylaniline, etc. are mentioned as an aniline compound. Alkylamine derivatives having a hydroxyl group and / or ether bonds include ethanolamine, diethanolamine, triethanolamine, tris (methoxyethoxyethyl) amine, and the like. Examples of aniline derivatives having a hydroxy group and / or ether bond include N, N-bis (hydroxyethyl) aniline and the like.

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

Fluorine and / or Silicon Based Surfactants

The positive photosensitive composition of the present invention preferably further contains any one or two or more of fluorine- and / or silicon-based surfactants (fluorine-based and silicon-based surfactants, surfactants containing both fluorine and silicon atoms). Do.

Since the positive photosensitive composition of the present invention contains a fluorine and / or silicon-based surfactant, it is possible to give a resist pattern having good sensitivity and resolution when using an exposure light source of 250 nm or less, especially 220 nm or less, and having low adhesion and low development defects. Lose.

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

As commercially available surfactants, for example, EFTOP EF301, EF303 (manufactured by Shin-Akita Kasei Co., Ltd.), FLUORAD FC430, 431 (manufactured by Sumitomo 3M Limited), MEGAFAC F171, F173, F176, F189, R08 (Dainippon Ink and Chemicals, Inc.), SURFLON S-382, SC101, 102, 103, 104, 105, 106 (manufactured by Asahi Glass Co., Ltd.), TROYSOL S-366 (manufactured by Troy Chemical Corp.) Surfactants or silicon-based surfactants may be enumerated. In addition, polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as the silicon-based surfactant.

In addition, the surfactant may be derived from a fluoroaliphatic compound prepared by a telomerization method (also referred to as a "telomer method") or an oligomerization method (also referred to as an "oligomer method") in addition to the known ones as described above. Surfactants using polymers having fluoroaliphatic groups 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 irregularly distributed. Even if it exists, it may be block copolymerized. Moreover, as a poly (oxyalkylene) group, a poly (oxyethylene) group, a poly (oxypropylene) group, a poly (oxybutylene) group, etc. are mentioned, and also a block of poly (oxyethylene, oxypropylene, and oxyethylene is mentioned. Units having different chain lengths of alkylene in the same chain length, such as a linking body) or poly (block linking body of oxyethylene and oxypropylene). The copolymer of a monomer having a fluoroaliphatic group and a (poly (oxyalkylene)) acrylate (or methacrylate) is not only a binary copolymer but also a monomer having two or more other fluoroaliphatic groups, or another two. It may be a ternary or higher copolymer obtained by simultaneously polymerizing species or more of (poly (oxyalkylene)) acrylate (or methacrylate).

For example, commercially available surfactants include MEGAFAC F178, F-470, F-473, F-475, F-476, and F-472 (manufactured by Dainippon Ink and Chemicals, Inc.). Further, copolymers of acrylate (or methacrylate) having a C ₆ F ₁₃ group and (poly (oxyalkylene)) acrylate (or methacrylate), acrylate (or methacrylate having a C ₆ F ₁₃ group) ) And a copolymer of (poly (oxyethylene)) acrylate (or methacrylate) and (poly (oxypropylene)) acrylate (or methacrylate), an acrylate (or methacrylate having a C ₈ F ₁₇ group) ) And (poly (oxyalkylene)) acrylates (or methacrylates), acrylates (or methacrylates) and (poly (oxyethylene)) acrylates (or methacrylates) having C ₈ F ₁₇ groups And copolymers of (poly (oxypropylene)) acrylate (or methacrylate) and the like.

The amount of the fluorine and / or silicon-based surfactant 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 positive photosensitive composition (excluding the solvent).

Organic solvent

In the positive photosensitive composition of the present invention, the above components are dissolved in a predetermined organic solvent and 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, pyruvic acid Ethyl, propyl pyruvate, N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, tetrahydrofuran and the like.

In the present invention, the organic solvent may be used alone or in combination, but it is preferable to use a mixed solvent containing two or more solvents having different functional groups. Thereby, the solubility of a raw material becomes high and generation | occurrence | production of particle | grains with time can be suppressed, and a favorable pattern profile is obtained. Preferred functional groups contained in the solvent include ester groups, lactone groups, hydroxyl groups, ketone groups, and carbonate groups. As a mixed solvent which has another functional group, the mixed solvent of the following (S1)-(S5) is preferable.

(S1) A mixed solvent in which a solvent containing a hydroxy group and a solvent not containing a hydroxy group are mixed,

(S2) a mixed solvent in which a solvent having an ester structure and a solvent having a ketone structure are mixed;

(S3) Mixed solvent in which a solvent having an ester structure and a solvent having a lactone structure are mixed

(S4) Mixed solvent which mixed the solvent which has a ester structure, the solvent which has a lactone structure, and the solvent containing a hydroxyl group,

(S5) A mixed solvent containing a solvent having an ester structure, a solvent having a carbonate structure, and a solvent having a hydroxy group.

Thereby, generation | occurrence | production of the particle | grains at the time of resist liquid storage can be reduced, and generation | occurrence | production of the defect at the time of application | coating can be suppressed.

Examples of the solvent containing a hydroxy 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 more preferable.

Examples of the solvent containing no hydroxy group include propylene glycol monomethyl ether acetate, ethyl ethoxy propionate, 2-heptanone, γ-butyrolactone, cyclohexanone, butyl acetate, N-methylpyrrolidone, and N. , N-dimethylacetoamide, dimethyl sulfoxide and the like, among them, propylene glycol monomethyl ether acetate, ethyl oxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, butyl acetate More preferably, propylene glycol monomethyl ether acetate, ethyl ethoxy propionate, 2-heptanone, and cyclohexanone are especially preferable.

Cyclohexanone, 2-heptanone, etc. are mentioned as a solvent which has a ketone structure, Preferably, it is cyclohexanone.

Examples of the solvent having an ester structure include propylene glycol monomethyl ether acetate, ethyl ethoxy propionate, butyl acetate and the like, and preferably propylene glycol monomethyl ether acetate.

Examples of the solvent having a lactone structure include γ-butyrolactone.

Examples of the solvent having a carbonate structure include polypropylene carbonate and ethylene carbonate, and preferably polypropylene carbonate.

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

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

The mixing ratio (mass) of the solvent having an ester structure and the solvent having a lactone structure is 70/30 to 99/1, preferably 80/20 to 99/1, and more preferably 90/10 to 99/1. The mixed solvent containing 70 mass% or more of the solvent which has an ester structure is especially preferable at the point of time stability.

When mixing the solvent which has an ester structure, the solvent which has a lactone structure, and the solvent containing a hydroxyl group, 30-80 mass% of the solvent which has an ester structure, 1-20 mass% of the solvent which has a lactone structure, and the solvent containing a hydroxy group It is preferable to contain 10-60 mass%.

When mixing the solvent which has an ester structure, the solvent which has a carbonate structure, and the solvent containing a hydroxyl group, 30-20 mass% of the solvent which has an ester structure, 1-20 mass% of the solvent which has a carbonate structure, and the solvent containing a hydroxyl group It is preferable to contain l0-60 mass%.

As a preferable form of these solvents, they are a solvent containing alkylene glycol monoalkyl ether carboxylate (preferably propylene glycol monomethyl ether acetate), More preferably, a solvent different from alkylene glycol monoalkyl ether carboxylate Is a mixed solvent, and the other solvent is at least one selected from a functional group selected from a hydroxy group, a ketone group, a lactone group, an ester group, an ether group, and a carbonate group, or a solvent having a plurality of functional groups among them. A particularly preferable mixed solvent is a mixed solvent of at least one selected from ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether, butyl acetate and cyclohexanone and propylene glycol monomethyl ether acetate.

The development defect performance can be improved by selecting an optimal solvent.

<Other additives>

If necessary, the positive photosensitive composition of the present invention may further contain a dye, a plasticizer, a surfactant other than the fluorine and / or silicon-based surfactant, a photosensitizer, a compound for promoting solubility in a developer, and the like.

The dissolution promoting compound for the developer usable in the present invention is a low molecular weight compound having a molecular weight of 1,000 or less having two or more phenolic OH groups or one or more carboxyl groups. 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 mass% with respect to a high molecular compound, More preferably, it is 5-30 mass%. 50 mass% or less is preferable at the point of suppression of a development residue and the prevention of pattern distortion at the time of image development.

Such phenol compounds having a molecular weight of 1000 or less are readily available to those skilled in the art by referring to methods described in, for example, Japanese Patent Application Laid-Open No. Hei 4-122938, Japanese Patent Application Laid-Open No. Hei 2-28531, US Pat. 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, adamantane carboxylic acid derivatives, adamantane dicarboxylic acid, and cyclo Hexane carboxylic acid, cyclohexane dicarboxylic acid, etc. are mentioned, but it is not limited to these.

In this invention, surfactant other than the said fluorine type and / or silicon type surfactant can also be added. Specifically, nonionics such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylene polyoxypropylene block copolymers, sorbitan aliphatic esters, and polyoxyethylene sorbitan aliphatic esters Surfactants may be enumerated.

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

(Pattern Forming Method)

The positive photosensitive composition of this invention is melt | dissolved in the predetermined organic solvent, Preferably the said mixed solvent, and filter-filtered, after apply | coating on a predetermined | prescribed support body as follows, are used. The filter used for filter filtration is preferably made of polytetrafluoroethylene, polyethylene, or nylon of 0.1 micron or less, more preferably 0.05 micron or less, and more preferably 0.03 micron or less.

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

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

At the time of irradiation of actinic light or a radiation, you may perform exposure (liquid immersion exposure) by filling the liquid (liquid immersion medium) with refractive index higher than air between the photosensitive film | membrane and a lens. Thereby, resolution can be improved. As the liquid immersion medium to be used, any liquid can be used as long as the liquid has a refractive index higher than that of air. In addition, in order to prevent a liquid immersion medium from directly contacting a photosensitive film when performing immersion exposure, you may further form an overcoat layer on the photosensitive film. As a result, elution of the composition from the photosensitive film to the liquid immersion medium is suppressed, and development defects are reduced.

Before forming a photosensitive film, you may apply an antireflection film on a board | substrate previously.

As the anti-reflection film, both an inorganic film type such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon, and porous silicon, and an organic film type made of a light absorber and a polymer material can be used. In addition, Brewer Science Inc. DUV-30 series, DUV-40 series, Shipley Co., Ltd. Commercially available organic antireflective films, such as AR-2, AR-3, and AR-5 of a product, can also be used.

Examples of the active light or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, X-ray, electron beam, etc., but are preferably ultraviolet light having a wavelength of 250 nm or less, more preferably 220 nm or less, specifically KrF. An excimer laser (248 nm), an ArF excimer laser (193 nm), an F ₂ excimer laser (157 nm), an X-ray, an electron beam, and the like, and an ArF excimer laser, an F ₂ excimer laser, an EUV (13 nm), and an electron beam are preferable.

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

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

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

The pH of the alkaline developer is usually 10.0-15.0.

Example

Next, although an Example is given and this invention is further demonstrated, this invention is not limited to these Examples. In addition, the weight average molecular weight (Mw) and dispersion degree (Mw / Mn) of the obtained high molecular compound were calculated | required from the measurement result of gel permeation chromatography (GPC).

Preparation Example 1

Under a nitrogen stream, 4.7 g of cyclohexanone was placed in a three-necked flask, which was heated to 80 ° C. To this, 4.42 g of the monomer (A), 2.52 g of the monomer (B), 4.70 g of the monomer (C), 0.0821 g of a polymerization initiator (azobisisobutyronitrile (AIBN): manufactured by Wako Pure Chemical Industries, Ltd.), and a chain The solution which melt | dissolved 0.947 g of transfer agents (S1) in 41.9 g of cyclohexanone was dripped over 6 hours. After completion of the dropwise addition, the mixture was further reacted at 80 ° C for 2 hours. The reaction solution was allowed to cool and then added dropwise to 700 m of methanol over 20 minutes, and the precipitated powder was collected by filtration and dried to obtain 7.5 g of the target polymer compound (Manufacturing Example 1). The weight average molecular weight of the obtained high molecular compound was 8600 in terms of standard polystyrene, and the degree of dispersion (Mw / Mn) was 1.4.

Using the method of the same method to prepare a high molecular compound (Preparation Examples 2 to 21).

Comparative Production Example 1

Under a nitrogen stream, 4.7 g of cyclohexanone was placed in a three-necked flask, which was heated to 80 ° C. Monomer (A) 4.42g, Monomer (B) 2.52g, Monomer (C) 4.70g, Polymerization initiator (Azobisisobutyronitrile (AIBN): 0.246g from Wako Pure Chemical Industries, Ltd.), Chain transfer agent (S1) The solution which melt | dissolved 0.189g in 41.9g of cyclohexanone was dripped over 6 hours. After completion of the dropwise addition, the mixture was further reacted at 80 ° C for 2 hours. The reaction solution was allowed to cool, and then added dropwise to 700 m of methanol over 20 minutes, and the precipitated powder was collected by filtration and dried to obtain 8.0 g of the target polymer compound (Comparative Preparation Example 1). The weight average molecular weight of the obtained high molecular compound was 8900, and dispersion degree (Mw / Mn) was 1.5 in standard polystyrene conversion.

Using the same method to prepare a high molecular compound (Comparative Preparation Example 3).

Comparative Production Example 2

Under a nitrogen stream, 4.7 g of cyclohexanone was placed in a three-necked flask, which was heated to 80 ° C. 4.42 g of monomer (A), 2.52 g of monomer (B), 4.70 g of monomer (C), and 0.328 g of a polymerization initiator (azobisisobutyronitrile (AIBN): manufactured by Wako Pure Chemical Industries, Ltd.) The solution dissolved in 41.9 g of paddy was dripped over 6 hours. After completion of the dropwise addition, the mixture was further reacted at 80 ° C for 2 hours. After cooling the reaction solution, the reaction mixture was added dropwise to 700 m of methanol over 20 minutes, and the precipitated powder was collected by filtration and dried to obtain 8.0 g of the target polymer compound (Comparative Preparation Example 2). The weight average molecular weight of the obtained high molecular compound was 8600 in terms of standard polystyrene, and the degree of dispersion (Mw / Mn) was 1.6.

In Table 1 below, the amounts of the chain transfer agent (S) and the polymerization initiator (I) added to each of the polymer compounds of Production Examples 1 to 21 and Comparative Production Examples 1 to 3 (polymerizable compound having an ethylenic double bond used in the production) Mole% of each compound to the total number of moles of (monomer)), addition molar ratio (I / S), structural unit and composition ratio by monomer, weight average molecular weight (Mw), dispersion degree (Mw / Mn) of the obtained high molecular compound Indicates. The polymerization initiator "V-601" in Table 1 represents 2,2-azobisisobutyric acid dimethyl.

The structural unit and composition ratio by the monomer in Table 1 are as follows.

Examples 1-36 and Comparative Examples 1-3

<Preparation of Positive Resist Solution>

The components and surfactants shown in Table 2 (Troy Chemical's TROYSOL S-366: 0.01 g) were dissolved in a 6/4 (mass ratio) mixed solvent of propylene glycol methyl ether acetate / propylene glycol methyl ether to give a solid content of 8% by mass. A solution was prepared and this was filtered with a 0.03 m polyethylene filter to prepare a positive resist solution. The prepared positive resist solution was evaluated by the following method, and the result was also shown in Table 2.

Resist Evaluation

Brewer Science Inc. on a silicon substrate subjected to hexamethyldisilazane treatment with a spin coater. The antireflection film DUV-42 of the product was uniformly applied to 600 angstroms, dried on a hot plate at 100 ° C. for 90 seconds, and then heated and dried at 190 ° C. for 240 seconds. Then, each positive resist solution was apply | coated with a spin coater, and it dried for 60 second at 120 degreeC, and formed the 150 nm resist film.

This resist film was exposed through an mask with an ArF excimer laser stepper (ASML, NA = 0.75, 2/3 spherical shape), and immediately after exposure, it was heated on a hot plate at 120 ° C. for 60 seconds. Furthermore, it developed for 60 second at 23 degreeC in the 2.38 mass% tetramethylammonium hydroxide aqueous solution, rinsed with pure water for 30 second, and dried, and obtained the line pattern.

Sensitivity:

Sensitivity was shown by the minimum exposure amount which can form a line pattern.

Pattern collapse evaluation method:

When the exposure amount which reproduces the mask pattern of a 75 nm line / 90 nm space was made into the optimum exposure amount, when the line width of the line pattern formed by further increasing the exposure amount from the optimal exposure amount was narrowed, it was defined as the line width which does not collapse a pattern. The smaller the value, the finer the pattern is resolved without collapse, and the collapse of the pattern is less likely to occur, indicating the higher resolution.

The compound corresponding to the symbol of Table 2 is a compound shown below.

[Basic compound]

TPSA: triphenylsulfonium acetate

DIA: 2,6-diisopropyl aniline

TEA: Triethanolamine

DBA: N, N-dibutylaniline

PBI: 2-phenylbenzimidazole

TMEA: tris (methoxyethoxyethyl) amine

PEA: N-phenyldiethanolamine

From Table 2, it is clear that the positive resist solution containing the high molecular compound manufactured by the manufacturing method of this invention is highly sensitive, and pattern collapse is also favorable.

Claims (10)

In the manufacturing method of the high molecular compound which polymerizes the polymeric compound which has an ethylenic double bond using the chain transfer agent represented by following General formula (1), and a polymerization initiator, the chain transfer agent (S) represented by General formula (1) And the addition molar ratio (I / S) of the polymerization initiator (I) is 1.0 or less.

(In formula (1), L represents a single bond or a m + 1 valent hydrocarbon group. R ₁ and R ₂ are each independently a divalent linking group selected from the group consisting of an alkylene group, a cycloalkylene group, an oxyalkylene group, an arylene group, a divalent thiazolin ring, a divalent oxazoline ring and a divalent imidazoline ring Or the bivalent coupling group which two or more of these couple | bonded is shown. R ₃ and R ₄ each independently represent an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group. n represents 0 or 1. A plurality of n may be the same or different. k represents 0 or 1. m represents the integer of 1-10. R ₃ and R ₄ may be bonded to adjacent R ₁ or L to form a ring structure.) It is obtained by the manufacturing method of Claim 1, The high molecular compound which has a structural unit represented by following General formula (2).

(In formula (2), L represents a single bond or a m + 1 valent hydrocarbon group. R ₁ and R ₂ are each independently a divalent linking group selected from the group consisting of an alkylene group, a cycloalkylene group, an oxyalkylene group, an arylene group, a divalent thiazolin ring, a divalent oxazoline ring and a divalent imidazoline ring Or the bivalent coupling group which two or more of these couple | bonded is shown. R ₃ and R ₄ each independently represent an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group. n represents 0 or 1. A plurality of n may be the same or different. k represents 0 or 1. m represents the integer of 1-10. R ₃ and R ₄ may be bonded to adjacent R ₁ or L to form a ring structure.) The polymer compound according to claim 2, further comprising a structural unit having an acid-decomposable group that is decomposed at least by the action of an acid and has increased solubility in an alkaline developer. The polymer compound according to claim 2 or 3, wherein at least one of R ₃ and R ₄ in the structural unit represented by the general formula (2) is an alkyl group having 2 or more carbon atoms. 4. The polymer compound according to claim 3, wherein the structural unit having an acid-decomposable group which is decomposed by the action of an acid and whose solubility in an alkaline developer is increased is represented by the following general formula (PA-A).

(In general formula (PA-A), R represents a hydrogen atom, a halogen atom or an alkyl group. A plurality of Rs may be the same or different, respectively. A represents a single bond, an alkylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a sulfonamido group, a urethane group, or a combination of two or more groups selected from the group consisting of urea groups. Rp ₁ represents any group represented by the following general formulas (pI) to (pV).

In general formula (pI)-(pV), R ₁₁ represents an alkyl group. Z represents an atomic group necessary to form a cycloalkyl group with a carbon atom. R ₁₂ to R ₁₆ each independently represent an alkyl group or a cycloalkyl group. R ₁₇ to R ₂₁ each independently represent a hydrogen atom, an alkyl group or a cycloalkyl group. R ₂₂ to R ₂₅ each independently represent a hydrogen atom, an alkyl group, or a cycloalkyl group. R ₂₃ and R ₂₄ may be bonded to each other to form a ring.) The compound according to claim 5, wherein in formulas (pI) to (pV), one or more of R ₁₁ , or R ₁₂ to R ₁₄ , or R ₁₆ , or one or more of R ₁₉ and R ₂₁ , or R ₂₂ and At least one of R ₂₅ is a methyl group, characterized in that the polymer compound. The polymer compound according to any one of claims 2, 3, 5, or 6, which has at least a structural unit having a lactone group. The molar number of the structural unit represented by General formula (2) is 2.5 with respect to the total mole of the structural unit contained in a high molecular compound in any one of Claims 2, 3, 5, or 6. A high molecular compound, characterized in that ~ 10 mol%. Positive photosensitive property containing at least the high molecular compound as described in any one of Claims 2, 3, 5, or 6, and the compound which generate | occur | produces an acid by irradiation of actinic light or a radiation. Composition. A process for forming a photosensitive film with the positive photosensitive composition according to claim 9, and exposing and developing the photosensitive film.