KR100987614B1 - Positive resist composition, method of forming resist pattern, polymeric compound, and compound - Google Patents

Abstract

Compounds represented by the following general formula (I); And a polymer compound having a structural unit (a0) represented by the following General Formula (a0-1).

[Formula 1]

[In formula, R <^1> is a hydrogen atom, a lower alkyl group, or a halogenated lower alkyl group, A is a C2 or more bivalent hydrocarbon group which may have a substituent, B is a C1 or more bivalent hydrocarbon group which may have a substituent, R ² is an acid dissociable, dissolution inhibiting group]

Description

Positive resist composition, resist pattern formation method, high molecular compound and compound {POSITIVE RESIST COMPOSITION, METHOD OF FORMING RESIST PATTERN, POLYMERIC COMPOUND, AND COMPOUND}

The present invention relates to a positive resist composition containing a novel polymer compound, a resist pattern forming method using the positive resist composition, the polymer compound, a compound useful as a monomer for the polymer compound, a method of producing the compound, and a method of producing the same. A compound useful as an intermediate in the present invention.

This application claims priority based on Japanese Patent Application No. 2007-205500 for which it applied to Japan on August 7, 2007, and Japanese Patent Application No. 2008-003339 which was filed in Japan on January 10, 2008, Here it is.

In the lithography technique, for example, a resist film made of a resist material is formed on a substrate, and the resist film is selectively exposed to radiation such as light or electron beam through a mask having a predetermined pattern formed thereon, and then developed. By performing the above step, a step of forming a resist pattern having a predetermined shape in the resist film is performed.

The resist material in which the exposed portion is changed to the characteristic of dissolving in the developer is positive type, and the resist material in which the exposed portion is changed to the characteristic of not dissolving in the developer is called negative type.

In recent years, in manufacture of a semiconductor element and a liquid crystal display element, refinement | miniaturization of a pattern is progressing rapidly with the advance of the lithography technique.

As a miniaturization method, shortening of the exposure light source is generally performed. Specifically, ultraviolet rays typified by g-line and i-line have conventionally been used, but mass production of semiconductor devices using KrF excimer lasers and ArF excimer lasers is now disclosed. In addition, studies have been conducted on F ₂ excimer lasers, electron beams, EUV (extreme ultraviolet rays), X-rays, and the like, which are shorter than those excimer lasers.

The resist material is required for lithographic characteristics such as sensitivity to these exposure light sources and resolution capable of reproducing a pattern of fine dimensions.

As a resist material that satisfies these requirements, a chemically amplified resist composition containing a base component whose solubility in an alkaline developer is changed by the action of an acid and an acid generator which generates an acid by exposure is used.

For example, as a positive chemically amplified resist composition, one containing a resin component (base resin) in which solubility in an alkaline developer is increased by the action of an acid and an acid generator component are generally used. Such a resist film formed by using a resist composition, when selective exposure is performed at the time of forming a resist pattern, an acid is generated from an acid generator in the exposed portion, and the solubility of the resin component in the alkaline developer by the action of the acid. This increases, so that the exposed portion becomes soluble to the alkaline developer.

Currently, as a base resin of a resist used in ArF excimer laser lithography, etc., since transparency is excellent in the vicinity of 193 nm, resin (acrylic resin) etc. which have a structural unit derived from (meth) acrylic acid ester in a principal chain are common. (See Patent Document 1, for example).

Here, "(meth) acrylic acid" means one or both of acrylic acid which the hydrogen atom couple | bonded with the (alpha) position, and methacrylic acid which the methyl group couple | bonded with the (alpha) position. "(Meth) acrylic acid ester" means one or both of the acrylic acid ester which the hydrogen atom couple | bonded with the (alpha) position, and the methacrylic acid ester which the methyl group couple | bonded with the (alpha) position. "(Meth) acrylate" means one or both of the acrylate which the hydrogen atom couple | bonded with the (alpha) position, and the methacrylate which the methyl group couple | bonded with the (alpha) position.

Patent Document 1: Japanese Unexamined Patent Publication No. 2003-241385

In the future, while new advances in lithography technology and expansion of applications are anticipated, there is an increasing demand for new materials that can be used for lithography applications.

This invention is made | formed in view of the said situation, The novel high molecular compound which can be used as a base component of a positive resist composition, the compound useful as a monomer for this polymer compound, its manufacturing method, the compound useful as an intermediate in the said manufacturing method, said It is an object to provide a positive resist composition containing a high molecular compound, and a resist pattern forming method using the positive resist composition.

In order to achieve the above object, the present invention adopts the following configuration.

That is, the 1st aspect of this invention is a positive type resist containing the base component (A) which the solubility to alkaline developing solution increases by the action of an acid, and the acid generator component (B) which generate | occur | produces an acid by exposure. As a composition,

The said base component (A) contains the high molecular compound (A1) which has a structural unit (a0) represented by the following general formula (a0-1), It is a positive resist composition characterized by the above-mentioned.

[Formula 1]

[Wherein, R ¹ is a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group, A is a C 2 or more divalent hydrocarbon group which may have a substituent, and B is a C 1 or more divalent hydrocarbon group which may have a substituent Hydrocarbon group, and R ² is an acid dissociable, dissolution inhibiting group]

According to a second aspect of the present invention, there is provided a process of forming a resist film on a support using the positive resist composition of the first aspect, a process of exposing the resist film, and an alkali development of the resist film to form a resist pattern. It is a resist pattern formation method containing.

3rd aspect of this invention is a high molecular compound (henceforth a high molecular compound (A1)) which has a structural unit (a0) represented by the following general formula (a0-1).

[Formula 2]

[In formula, R <^1> is a hydrogen atom, a lower alkyl group, or a halogenated lower alkyl group, A is a C2 or more bivalent hydrocarbon group which may have a substituent, B is a C1 or more bivalent hydrocarbon group which may have a substituent, R ² is an acid dissociable, dissolution inhibiting group]

A 4th aspect of this invention is a compound represented by the following general formula (I) (henceforth a compound (I)).

(3)

[In formula, R <^1> is a hydrogen atom, a lower alkyl group, or a halogenated lower alkyl group, A is a C2 or more bivalent hydrocarbon group which may have a substituent, B is a C1 or more bivalent hydrocarbon group which may have a substituent, R ² is an acid dissociable, dissolution inhibiting group]

5th aspect of this invention is a process of making the compound represented by the following general formula (I-3) react with the compound represented by the following general formula (I-1), and the compound represented by the following general formula (I-2), And

A process of reacting a compound represented by the following General Formula (I-3) with a compound represented by the following General Formula (I-4) to obtain a compound represented by the following General Formula (I); It is a manufacturing method (henceforth a 1st manufacturing method) of the compound represented by I).

[Formula 4]

[In formula, R <^1> is a hydrogen atom, a lower alkyl group, or a halogenated lower alkyl group, A is a C2 or more bivalent hydrocarbon group which may have a substituent, B is a C1 or more bivalent hydrocarbon group which may have a substituent, R ² is an acid dissociable, dissolution inhibiting group, X ¹⁰ and X ¹² are each independently a hydroxyl group or a halogen atom, one of X ¹⁰ and X ¹² is a hydroxyl group, the other is a halogen atom, and X ¹¹ is a halogen atom ]

A sixth aspect of the present invention includes a step of reacting a compound represented by the following general formula (I-5) with a compound represented by the following general formula (I-2) to obtain a compound represented by the following general formula (I). It is a manufacturing method (henceforth a 2nd manufacturing method) of the compound represented by following General formula (I) characterized by the above-mentioned.

[Chemical Formula 5]

[Wherein, R ¹ is a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group, A is a C 2 or more divalent hydrocarbon group which may have a substituent, B is a C 1 or more divalent hydrocarbon group which may have a substituent, R ² is an acid dissociable, dissolution inhibiting group, and X ¹¹ is a halogen atom]

7th aspect of this invention is a compound represented by the following general formula (II) (henceforth a compound (II)).

[Formula 6]

[Wherein A 'is a C2 or more divalent hydrocarbon group which may have a substituent, B' is a C1 or more divalent hydrocarbon group which may have a substituent, and R ^{2 '} is an acid dissociable, dissolution inhibiting group]

In this specification and a claim, unless otherwise indicated, a "alkyl group" shall contain a linear, branched chain, and cyclic monovalent saturated hydrocarbon group. In addition, "alkylene group" shall contain a straight chain, a branched chain, and a cyclic divalent saturated hydrocarbon group unless there is particular notice.

A "lower alkyl group" is a C1-C5 alkyl group.

The "halogenated alkyl group" is a group in which part or all of the hydrogen atoms of the alkyl group are substituted with halogen atoms, and examples of the halogen atoms include fluorine atom, chlorine atom, bromine atom and iodine atom.

A "structural unit" means the monomeric unit (monomer unit) which comprises a high molecular compound (polymer, a copolymer).

"Exposure" is taken as the concept including the whole radiation irradiation.

According to the present invention, a novel high molecular compound that can be used as a base component of a positive resist composition, a compound useful as a monomer for the polymer compound, a method for producing the compound, a compound useful as an intermediate in the production method, and a positive containing the polymer compound A resist pattern formation method and the resist pattern formation method using the positive resist composition can be provided.

<Compound (Ⅰ) >>

First, the compound (I) of the 4th aspect of this invention is demonstrated.

Compound (I) is represented by the said General formula (I).

In formula (I), R <^1> is a hydrogen atom, a lower alkyl group, or a halogenated lower alkyl group.

The lower alkyl group of R ¹ is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert- Butyl group, pentyl group, isopentyl group, neopentyl group and the like.

The halogenated lower alkyl group of R ¹ is a group in which part or all of the hydrogen atoms of the lower alkyl group are substituted with halogen atoms. As this halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, A fluorine atom is especially preferable.

As R ¹ , a hydrogen atom, a lower alkyl group or a fluorinated lower alkyl group is preferable, and from an industrial availability, it is most preferable that it is a hydrogen atom or a methyl group.

A is a C2 or more bivalent hydrocarbon group which may have a substituent. A hydrocarbon group "has a substituent" means that part or all of the hydrogen atoms in the hydrocarbon group are substituted with groups or atoms other than hydrogen atoms.

The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

Here, the term "aliphatic" in the claims and the specification is defined as meaning relative to aromatics, meaning groups, compounds and the like having no aromaticity. An aliphatic hydrocarbon group means the hydrocarbon group which does not have aromaticity.

The aliphatic hydrocarbon group in A may be saturated or unsaturated, and is preferably saturated.

As an aliphatic hydrocarbon group, a linear or branched aliphatic hydrocarbon group, the aliphatic hydrocarbon group containing a ring in a structure, etc. are mentioned more specifically.

The linear or branched aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 2 to 8, still more preferably 2 to 5, and most preferably 2.

As the linear aliphatic hydrocarbon group, a linear alkylene group is preferable, and specifically, an ethylene group [-(CH ₂ ) _2- ], trimethylene group [-(CH ₂ ) _3- ], tetramethylene group [ -(CH ₂ ) _4- ], pentamethylene group [-(CH ₂ ) _5- ], and the like.

As the branched chain aliphatic hydrocarbon group, a branched chain alkylene group is preferable, and specifically, -CH (CH ₃ )-, -CH (CH ₂ CH ₃ )-, -C (CH ₃ ) _2- , -C Alkylmethylene groups such as (CH ₃ ) (CH ₂ CH ₃ ) —, —C (CH ₃ ) (CH ₂ CH ₂ CH ₃ ) —, and —C (CH ₂ CH ₃ ) ₂ —; -CH (CH ₃ ) CH _2- , -CH (CH ₃ ) CH (CH ₃ )-, -C (CH ₃ ) ₂ CH _2- , -CH (CH ₂ CH ₃ ) CH _2- , -CH (CH Alkyl ethylene groups such as ₂ CH ₃ ) CH _2- ; _{-CH (CH 3) CH 2 CH} 2 -, -CH 2 CH (CH 3) CH 2 - alkyl trimethylene group and the like; _{-CH (CH 3) CH 2 CH} 2 CH 2 - and the like can be mentioned alkyl groups such as alkyl groups, such as tetramethylene _{-, -CH 2 CH (CH 3} ) CH 2 CH 2. As an alkyl group in an alkylalkylene group, a C1-C5 linear alkyl group is preferable.

The chain aliphatic hydrocarbon group may or may not have a substituent. Examples of the substituent include a fluorine atom, a fluorinated lower alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, an oxygen atom (= O), and the like.

Examples of the aliphatic hydrocarbon group containing a ring include a cyclic aliphatic hydrocarbon group (a group obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring), and the cyclic aliphatic hydrocarbon group bonded to the terminal of the aforementioned chain aliphatic hydrocarbon group or a chain aliphatic group. The group etc. which are interposed in the middle of a hydrocarbon group are mentioned.

It is preferable that carbon number is 3-20, and, as for a cyclic aliphatic hydrocarbon group, it is more preferable that it is 3-12.

The cyclic aliphatic hydrocarbon group may be a polycyclic group or a monocyclic group. As the monocyclic group, a group in which two hydrogen atoms are removed from a monocycloalkane having 3 to 6 carbon atoms is preferable, and cyclopentane, cyclohexane and the like can be exemplified as the monocycloalkane.

As the polycyclic group, a group in which two hydrogen atoms are removed from a polycycloalkane having 7 to 12 carbon atoms is preferable, and specifically, as the polycycloalkane, adamantane, norbornane, isobornane, tricyclodecane, tetra Cyclododecane etc. are mentioned.

The cyclic aliphatic hydrocarbon group may or may not have a substituent. As a substituent, a C1-C5 lower alkyl group, a fluorine atom, a C1-C5 fluorinated lower alkyl group substituted by the fluorine atom, an oxygen atom (= O), etc. are mentioned.

As A, a linear aliphatic hydrocarbon group is preferable, a linear alkylene group is more preferable, a C2-C5 linear alkylene group is still more preferable, and an ethylene group is the most preferable.

B is a C1 or more bivalent hydrocarbon group which may have a substituent.

As a hydrocarbon group in B, the methylene group which may have a C2 or more bivalent hydrocarbon group and substituent which are the same as what was illustrated by said A is mentioned. As a substituent which the methylene group may have, the thing similar to the substituent illustrated as the substituent which the said linear aliphatic hydrocarbon group may have is mentioned.

As B, a linear or branched aliphatic hydrocarbon group is preferable, and a methylene group or an alkylmethylene group is particularly preferable.

The alkyl group in the alkylmethylene group is preferably a linear alkyl group having 1 to 5 carbon atoms, a linear alkyl group having 1 to 3 carbon atoms is preferred, and a methyl group is most preferred.

R ² is an acid dissociable, dissolution inhibiting group. When the acid dissociable, dissolution inhibiting group is blended into a positive type resist composition with an acid generator component using a high molecular compound obtained using the compound (I), It has an acid dissociation property which dissociates by, and before dissociation, it has alkali dissolution inhibiting property which makes the whole said high molecular compound hard-soluble with an alkaline developing solution.

As an acid dissociable, dissolution inhibiting group of R <^2> , what has been proposed as an acid dissociable, dissolution inhibiting group of the base resin for chemically amplified resist can be used. Generally, the group which forms a cyclic or chain | strand-type tertiary alkyl ester with the carboxyl group in (meth) acrylic acid etc .; Acetal acid dissociable, dissolution inhibiting groups, such as an alkoxyalkyl group, are widely known. In addition, "(meth) acrylic acid ester" means the one or both of the acrylate ester which the hydrogen atom couple | bonded with the (alpha) position, and the methacrylic acid ester which the methyl group couple | bonded with the (alpha) position.

Here, the "tertiary alkyl ester" means ester by being substituted with a chain or cyclic alkyl group by the hydrogen atom of a carboxyl group, and of the terminal of the carbonyloxy group (-C (O) -O-) The structure which the tertiary carbon atom of the said chain | strand or cyclic alkyl group couple | bonded with the oxygen atom is shown. In this tertiary alkyl ester, when an acid acts, the bond is cleaved between the oxygen atom and the tertiary carbon atom.

In addition, the chain or cyclic alkyl group may have a substituent.

Hereinafter, group which becomes acid dissociation by making a carboxy group and tertiary alkyl ester are called "tertiary alkyl ester type acid dissociable, dissolution inhibiting group" for convenience.

Examples of the tertiary alkyl ester type acid dissociable, dissolution inhibiting group include an aliphatic branched chain acid dissociable, dissolution inhibiting group and an acid dissociable, dissolution inhibiting group containing an aliphatic cyclic group.

The "aliphatic branched chain" means having a branched chain structure having no aromaticity.

Although the structure of an "aliphatic branched-type acid dissociable, dissolution inhibiting group" is not limited to the group (hydrocarbon group) which consists of carbon and hydrogen, It is preferable that it is a hydrocarbon group. Moreover, although the hydrocarbon group may be either saturated or unsaturated, it is preferable that it is normally saturated.

As an aliphatic branched-type acid dissociable, dissolution inhibiting group, group represented by -C (R ⁷¹ ) (R ⁷² ) (R ⁷³ ) is mentioned, for example. In formula, R <^71> -R <^73> is a C1-C5 linear alkyl group each independently. The group represented by -C (R ⁷¹ ) (R ⁷² ) (R ⁷³ ) preferably has 4 to 8 carbon atoms, and specific examples thereof include tert-butyl group, tert-pentyl group and tert-heptyl group. .

An "aliphatic cyclic group" represents a monocyclic group or a polycyclic group having no aromaticity.

The aliphatic cyclic group may or may not have a substituent. As a substituent, a C1-C5 lower alkyl group, a fluorine atom, a C1-C5 fluorinated lower alkyl group substituted by the fluorine atom, an oxygen atom (= O), etc. are mentioned.

Although the structure of the basic ring of an aliphatic cyclic group except a substituent is not limited to being a group (carbon group) which consists of carbon and hydrogen, It is preferable that it is a hydrocarbon group. The hydrocarbon group may be either saturated or unsaturated, but is usually saturated.

It is preferable that an aliphatic cyclic group is a polycyclic group.

As the aliphatic cyclic group, for example, polycycloalkane such as monocycloalkane, bicycloalkane, tricycloalkane, tetracycloalkane, which may or may not be substituted with a lower alkyl group, a fluorine atom or a fluorinated alkyl group, may be used. The group etc. which removed more than one hydrogen atom are mentioned. More specifically, it is one or more from monocycloalkane, such as cyclopentane and cyclohexane, and polycycloalkane, such as adamantane, norbornane, isobornane, dicyclodecane, tricyclodecane, and tetracyclododecane. The group etc. which removed the hydrogen atom are mentioned.

Examples of the acid dissociable, dissolution inhibiting group containing an aliphatic cyclic group include (iii) a group having a tertiary carbon atom on the ring skeleton of a monovalent aliphatic cyclic group; And (ii) a group having a monovalent aliphatic cyclic group and a branched alkylene having a tertiary carbon atom bonded thereto.

(Iii) Specific examples of the group having a tertiary carbon atom on the ring skeleton of the monovalent aliphatic cyclic group include, for example, groups represented by the following general formulas (1-1) to (1-9); Can be mentioned.

(Ii) As a specific example of group which has an aliphatic cyclic group and the branched chain alkylene which has the tertiary carbon atom couple | bonded with this, For example, following General formula (2-1)-(2-6) The group represented by) is mentioned.

[Formula 7]

[Wherein, R ¹⁴ is a lower alkyl group and g is an integer of 0 to 8]

[Formula 8]

[Wherein, R ¹⁵ and R ¹⁶ are each independently an alkyl group]

As an alkyl group of R <^14> -R < ¹⁶ >, a lower alkyl group is preferable and a linear or branched alkyl group is preferable. Specific examples include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group and neopentyl group. Among these, a methyl group, an ethyl group, or n-butyl group is preferable, and a methyl group or ethyl group is more preferable.

The integer of 0-3 is preferable, as for g, the integer of 1-3 is more preferable, and 1 or 2 is further more preferable.

The "acetal acid dissociable, dissolution inhibiting group" is generally substituted with a hydrogen atom at the terminal of an alkali-soluble group such as a carboxyl group or a hydroxyl group and bonded to an oxygen atom. When an acid is generated by exposure, the acid acts to break the bond between the acetal-type acid dissociable, dissolution inhibiting group and the oxygen atom bonded to the acetal-type acid dissociable, dissolution inhibiting group.

As an acetal type acid dissociable, dissolution inhibiting group, group represented by the following general formula (p1) is mentioned, for example.

[Formula 9]

[Wherein, R ^{1 ′} and R ^{2 ′} each independently represent a hydrogen atom or a lower alkyl group, n represents an integer of 0 to 3, and Y represents a lower alkyl group or an aliphatic cyclic group]

In said formula, it is preferable that n is an integer of 0-2, 0 or 1 is more preferable, and 0 is the most preferable.

Examples of the lower alkyl group of R ^{1 '} and R ^{2' include} the same as those of the lower alkyl group of R, a methyl group or an ethyl group is preferred, and a methyl group is most preferred.

In the present invention, at least one of R ^{1 ′} and R ^{2 ′} is preferably a hydrogen atom. That is, it is preferable that acid dissociable, dissolution inhibiting group (p1) is group represented by the following general formula (p1-1).

[Formula 10]

[Wherein, R ^{1 ′} , n, Y are the same as described above]

As a lower alkyl group of Y, the same thing as the lower alkyl group of said R is mentioned.

As the aliphatic cyclic group of Y, any of monocyclic or polycyclic aliphatic cyclic groups that have been proposed in the conventional ArF resist or the like can be appropriately selected and used, and examples thereof can be the same as those described above for the "aliphatic cyclic group".

Moreover, as an acetal type acid dissociable, dissolution inhibiting group, the air represented by the following general formula (p2) is mentioned.

[Formula 11]

[Wherein, R ¹⁷ and R ¹⁸ are each independently a linear or branched alkyl group or a hydrogen atom, and R ¹⁹ Is a linear, branched or cyclic alkyl group. Or R ¹⁷ And R ¹⁹ are each independently a linear or branched alkylene group, and the terminal of R ^{17 and} the terminal of R ¹⁹ may be bonded to each other to form a ring.]

R ¹⁷ , R ¹⁸ WHEREIN: Carbon number of an alkyl group becomes like this. Preferably it is 1-15, any of a linear type and a branched chain type may be sufficient, an ethyl group and a methyl group are preferable, and a methyl group is the most preferable.

It is preferable that especially one of R <^17> , R <^18> is a hydrogen atom, and the other is a methyl group.

R ¹⁹ Is a linear, branched or cyclic alkyl group, and carbon number is preferably 1 to 15, and may be any of linear, branched or cyclic.

R ¹⁹ When is linear or branched, it is preferable that it is C1-C5, an ethyl group and a methyl group are more preferable, and ethyl group is the most preferable especially.

R ¹⁹ When a cyclic | annular form is cyclic, it is preferable that it is C4-C15, It is more preferable that it is C4-C12, and C5-C10 is the most preferable. Specifically, the group which removed one or more hydrogen atoms from polycycloalkane, such as monocycloalkane, bicycloalkane, tricycloalkane, and tetracycloalkane, which may or may not be substituted with a fluorine atom or a fluorinated alkyl group, may be used. It can be illustrated. Specific examples thereof include a monocycloalkane such as cyclopentane and cyclohexane, a group obtained by removing one or more hydrogen atoms from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane and tetracyclododecane And the like. Especially, the group remove | excluding one or more hydrogen atoms from adamantane is preferable.

In the above formula, R ¹⁷ And R ¹⁹ Are independently a linear or branched alkylene group (preferably an alkylene group having 1 to 5 carbon atoms), and the terminal of R ^{19 and} the terminal of R ¹⁷ may be bonded to each other.

In this case, R ¹⁷ And R ¹⁹ With, R ¹⁹ Is an oxygen atom bonded to the oxygen atom and R ¹⁷ A cyclic group is formed by this bonded carbon atom. As this cyclic group, a 4-7 membered ring is preferable and a 4-6 membered ring is more preferable. Specific examples of the cyclic group include tetrahydropyranyl group, tetrahydrofuranyl group and the like.

As a specific example of an acetal type acid dissociable, dissolution inhibiting group, group represented by following formula (3-1)-(3-12) etc. are mentioned, for example.

[Formula 12]

[Wherein, R ¹³ is a hydrogen atom or a methyl group, g is the same as above]

In the present invention, R ² is preferably a tertiary alkyl ester type acid dissociable, dissolution inhibiting group, and group II having a tertiary carbon atom on the ring skeleton of the (i) monovalent aliphatic cyclic group described above More preferably, the group represented by general formula (1-1) is especially preferable.

As compound (I), the compound represented by the following general formula (I ') or (II') is preferable, and the compound represented with the following general formula (I ') is especially preferable.

[Formula 13]

[In formula, R <^1> , R <^14> is the same as the above, R <^10> is a hydrogen atom or a methyl group, a is an integer of 2-10, n is an integer of 0-3.]

The integer of 2-5 is preferable, and 2 is a most preferable.

Although compound (I) is not specifically limited, It can manufacture by the 1st manufacturing method or 2nd manufacturing method mentioned later.

The compound (I) of this invention mentioned above is a novel thing conventionally unknown.

Compound (I) can be used suitably for manufacture of the high molecular compound which can be used as a base component of a positive resist composition. That is, compound (I) is a compound which has a polymerizability, and can be used as a monomer of a high molecular compound (polymer, a copolymer).

By using compound (I) as a monomer, the high molecular compound (A1) of this invention containing the structural unit (a0) represented by the said general formula (a0-1) can be manufactured.

<< first manufacturing method >>

Next, a 1st manufacturing method (manufacturing method of the 5th aspect of this invention) is demonstrated.

A 1st manufacturing method is a compound represented by the said General formula (I-1) (henceforth a compound (I-1)), and a compound represented by the said General formula (I-2) (henceforth a compound (I-2) ) To react to obtain a compound represented by the general formula (I-3) (hereinafter referred to as compound (I-3)) (hereinafter referred to as first step), and compound (I-3) And the process (henceforth a 2nd process) which reacts with the compound represented by the following general formula (I-4) (henceforth a compound (I-4)), and obtains compound (I).

Equation (Ⅰ-1) ~ (Ⅰ -4) R 1, A, B, R 2 is in, respectively, is the same as ^{R 1, A, B, R} 2 in the formula (Ⅰ).

X ¹⁰ and X ¹² are each independently a hydroxyl group or a halogen atom, one of X ¹⁰ and X ¹² is a hydroxyl group, the other is a halogen atom, and X ¹¹ is a halogen atom. Examples of the halogen atom include bromine atom, chlorine atom, iodine atom and fluorine atom.

The halogen atom of X ¹⁰ or X ¹² is preferably a chlorine atom or a bromine atom because of excellent reactivity.

As X ¹¹ , since it is excellent in reactivity, a bromine atom or a chlorine atom is preferable, and a bromine atom is particularly preferable.

`` First step ''

Compound (I-1) and compound (I-2) can be reacted by a well-known method. For example, the method of making compound (I-1) and compound (I-2) contact in presence of a base in a reaction solvent is mentioned. The method can be performed, for example, by adding compound (I-2) to a solution in which compound (I-1) is dissolved in a reaction solvent in the presence of a base.

As a compound (I-1) and a compound (I-2), a commercially available thing may be used and you may synthesize | combine.

Compound (I-1) is a dihydric alcohol when X ¹⁰ is a hydroxyl group, and halogenated alcohol when X ¹⁰ is a halogen atom. The compound (I-1) is not particularly limited as long as it is a dihydric alcohol or a halogenated alcohol. Specific examples of the dihydric alcohol include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, and the like. Specific examples of the halogenated alcohols include 2-bromo-1-ethanol, 3-chloro-1-propanol, 4-chloro-1-butanol, 5-chloro-1-pentanol, and the like.

Examples of the compound (I-2) include 2-methyl-2-adamantyloxycarbonylmethyl chloride, 2-ethyl-2-adamantyloxycarbonylmethyl chloride, and 1-methyl-1-cyclohexyloxycarbonyl Methyl chloride, 1-ethyl-1-cyclohexyloxycarbonylmethyl chloride, 1-methyl-1-cyclopentyloxycarbonylmethyl chloride, 1-ethyl-1-cyclopentyloxycarbonylmethylchloride, and the like. Can be.

As a reaction solvent, what is necessary is just to be able to melt | dissolve compound (I-1) and compound (I-2) which are raw materials, and specifically, tetrahydrofuran (THF), acetone, dimethylformamide (DMF), and dimethylacetic acid. Amide, dimethyl sulfoxide (DMSO), acetonitrile, etc. are mentioned.

Examples of the base include, for example, sodium hydride, inorganic bases such as K ₂ CO _3; Organic bases such as triethylamine, 4-dimethylaminopyridine (DMAP), pyridine and the like.

In the first step, sodium hydride is particularly preferably used.

About 1-100 mol double amount is preferable with respect to compound (I-1), and, as for the addition amount of compound (I-2), 1-50 mol double amount is more preferable.

0-50 degreeC is preferable, as for reaction temperature, 5-40 degreeC is more preferable, and reaction at room temperature is the most preferable.

Although reaction time changes also with reactivity, reaction temperature, etc. of a compound (I-1) and a compound (I-2), 1 to 24 hours are preferable normally, and 3 to 12 hours are more preferable.

After completion | finish of reaction, a reaction liquid may be used for the next process as it is, and you may isolate and refine | compound compound (I-3) in a reaction liquid. A conventionally well-known method can be used for isolation | separation and purification, For example, concentration, solvent extraction, crystallization, recrystallization, chromatography, etc. can be used individually or in combination of 2 or more types.

`` 2nd process ''

Although it does not specifically limit as a method of making compound (I-3) and compound (I-4) react, For example, in the presence of a base in the solution in which the compound (I-3) obtained by the 1st process was dissolved, And the method of adding compound (I-4).

As a solution in which compound (I-3) is dissolved, the reaction solution obtained in the first step may be used as it is, or a solution in which compound (I-3) isolated and purified from the reaction solution is dissolved in a reaction solvent is used. do.

What is necessary is just to be able to melt | dissolve compound (I-3) which is a raw material as a reaction solvent, For example, the thing similar to the reaction solvent illustrated by the 1st process is mentioned.

As a base, the thing similar to the base illustrated by the 1st process is mentioned. Especially in a 2nd process, triethylamine is used preferably.

As the compound (I-4), in the case of using a dihydric alcohol as the compound (I-1), a compound in which X ¹² is a halogen atom is used, and in the case of using a halogenated alcohol as the compound (I-1), X ^The compound whose ¹² is a hydroxyl group is used.

About 1-2 mol double quantity is preferable with respect to compound (I-3), and, as for the addition amount of compound (I-4), 1-1.5 mol double is more preferable.

0-50 degreeC is preferable, as for reaction temperature, 5-40 degreeC is more preferable, and reaction at room temperature is the most preferable.

Although reaction time changes also with reactivity, reaction temperature, etc. of compound (I-3) and (I-4), 1 to 24 hours are preferable normally, and 3 to 12 hours are more preferable.

After completion of the reaction, the compound (I) in the reaction solution may be isolated and purified. A conventionally well-known method can be used for isolation | separation and purification, For example, concentration, solvent extraction, crystallization, recrystallization, chromatography, etc. can be used individually or in combination of 2 or more types.

The structure of the compound obtained in the above process is ¹ H-nuclear magnetic resonance (NMR) spectroscopy, ¹³ C-NMR spectroscopy, ¹⁹ F-NMR spectroscopy, infrared absorption (IR) spectroscopy, mass spectrometry (MS), It can confirm by general organic analysis methods, such as an element analysis method and X-ray crystal diffraction method.

<< second manufacturing method >>

Next, a 2nd manufacturing method (manufacturing method of 6th aspect of this invention) is demonstrated.

The second production method is a step of reacting a compound represented by the general formula (I-5) (hereinafter referred to as compound (I-5)) with compound (I-2) to obtain compound (I) 1st process).

Equation ^{(Ⅰ-5), R 1} , A, B, R 2 in (Ⅰ-2), it is respectively the same as ^{R 1, A, B, R} 2 in the formula (Ⅰ).

X ¹¹ is a halogen atom. Examples of the halogen atom include bromine atom, chlorine atom, iodine atom and fluorine atom.

As X ¹¹ , since it is excellent in reactivity, a bromine atom or a chlorine atom is preferable, and a bromine atom is particularly preferable.

"1st process"

Compound (I-5) and compound (I-2) can be reacted by a well-known method. For example, the method of making compound (I-5) and compound (I-2) contact in presence of a base in a reaction solvent is mentioned. The method can be performed, for example, by adding compound (I-2) to a solution in which compound (I-5) is dissolved in a reaction solvent in the presence of a base.

As a compound (I-5) and a compound (I-2), a commercially available thing may be used and you may synthesize | combine. For example, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, etc. are mentioned as a specific example of a compound (I-5). Can be.

As a reaction solvent, what is necessary is just to be able to melt | dissolve compound (I-5) and compound (I-2) which are raw materials, and specifically, tetrahydrofuran (THF), acetone, dimethylformamide (DMF), and dimethylacetate Amide, dimethyl sulfoxide (DMSO), acetonitrile, etc. are mentioned.

Examples of the base include, for example, sodium hydride, inorganic bases such as _{K 2 CO 3, Cs 2 CO} 3; Organic bases such as triethylamine, 4-dimethylaminopyridine (DMAP), pyridine and the like. In the 1 'process, sodium hydride is especially used preferably.

About 1-2 mol double quantity is preferable with respect to compound (I-5), and, as for the addition amount of compound (I-2), 1-1.5 mol double is more preferable.

0-50 degreeC is preferable, as for reaction temperature, 5-40 degreeC is more preferable, and reaction at room temperature is the most preferable.

Although reaction time changes also with reactivity, reaction temperature, etc. of a compound (I-5) and a compound (I-2), 1 to 24 hours are preferable normally, and 3 to 12 hours are more preferable.

After completion of the reaction, the compound (I) in the reaction solution may be isolated and purified. A conventionally well-known method can be used for isolation | separation and purification, For example, concentration, solvent extraction, crystallization, recrystallization, chromatography, etc. can be used individually or in combination of 2 or more types.

The structure of the compound obtained by the said process is ¹ H-NMR spectral method, ¹³ C-NMR spectral method, ¹⁹ F-NMR spectral method, infrared absorption (IR) spectrum method, mass spectrometry (MS) method, elemental analysis method, X-ray It can confirm by general organic analysis methods, such as a crystal diffraction method.

<Compound (II) >>

Next, the compound (II) of the seventh aspect of the present invention will be described.

Compound (II) is represented by the said General formula (II).

X <^10> , A ', B', and R <^2>' in formula (II) are the same as X <^10> , A, B and R <^{2> in} said general formula (I), respectively.

Compound (II) can be manufactured similarly to the said compound (I-3). That is, it can manufacture by the process similar to the 1st process in the said 1st manufacturing method.

Compound (II) can be used as compound (I-3) in the above-mentioned first manufacturing method.

<< polymeric compound (A1) >>

Next, the high molecular compound (A1) of 3rd aspect of this invention is demonstrated.

A high molecular compound (A1) has a structural unit (a0) represented by the said general formula (a0-1).

^{R 1, A, B, R} 2 in the general formula (a0-1), it is respectively the same as ^{R 1, A, B, R} 2 in the formula (Ⅰ).

Especially as a structural unit (a0-1), the structural unit represented with the following general formula (a0-1-1) is preferable.

[Formula 14]

Formula (a0-1-1) of ^{R 1, a, R 10,} R 14 , it is respectively the same as ^{R 1, a, R 10,} R 14 in the formula (Ⅰ ').

1 type may be sufficient as the structural unit (a0) contained in a high molecular compound (A1), and 2 or more types may be sufficient as it.

The high molecular compound (A1) may be a polymer composed only of the structural unit (a0), or may be a copolymer containing another structural unit.

In the high molecular compound (A1), the ratio of the structural unit (a0) is a total ratio between the structural unit (a0) and the structural unit (a1) described later (structural unit (a0) Ratio) is preferably in an amount of 10 to 80 mol%, more preferably in an amount of 20 to 70 mol%, and more preferably 25 to 50 mol%, based on the total constitutional units of the polymer compound (A1). The amount to be most preferred. By setting it as the lower limit or more, a pattern can be easily obtained when it is set as a resist composition, and it can balance with the other structural unit by setting it as the upper limit or less.

In particular, since lithographic characteristics such as resolution and line edge roughness of the positive resist composition containing the polymer compound (A1) are improved, the proportion of the structural unit (a0) constitutes the whole of the polymer compound (A1). It is preferable that it is 10 mol% or more with respect to a structural unit, and 20 mol% or more is more preferable.

When the high molecular compound (A1) of this invention is a copolymer containing structural units other than a structural unit (a0), it does not specifically limit as other structural units other than a structural unit (a0), and is a chemical amplification type so far Arbitrary structural units used for the base resin for resist may be used.

As a preferable structural unit, the structural unit guide | induced from acrylic acid esters, such as the following structural units (a1)-(a3), etc. are mentioned specifically ,.

Among these, it is preferable that a high molecular compound (A1) has a structural unit (a2) further in addition to a structural unit (a0).

In addition, the polymer compound (A1) preferably has a structural unit (a3) in addition to the structural unit (a0), or in addition to the structural unit (a0) and the structural unit (a2).

Here, in this specification and a claim, a "structural unit derived from an acrylate ester" means the structural unit in which the ethylenic double bond of an acrylate ester is cleaved and comprised.

"Acrylic acid ester" is taken as the concept including what the substituent (atoms other than a hydrogen atom or group) couple | bonded with the carbon atom of an alpha position in addition to the acrylate ester with which the hydrogen atom is couple | bonded with the carbon atom of the alpha position. As a substituent, a lower alkyl group, a halogenated lower alkyl group, etc. are mentioned. In addition, the alpha position (carbon atom of an alpha position) of the structural unit derived from an acrylate ester means the carbon atom to which the carbonyl group couple | bonded unless there is particular notice.

In acrylate ester, the lower alkyl group and halogenated lower alkyl group as a substituent of the (alpha) position are the same as the lower alkyl group and halogenated lower alkyl group of said R < ¹ >.

It is preferable that the thing couple | bonded with the (alpha) position of an acrylate ester is a hydrogen atom, a lower alkyl group, or a halogenated lower alkyl group, It is more preferable that it is a hydrogen atom, a lower alkyl group, or a fluorinated lower alkyl group, From an industrial availability, a hydrogen atom or a methyl group Is most preferred.

<Structural unit (a2)>

Structural unit (a2) is a structural unit derived from the acrylate ester containing a lactone containing cyclic group.

Here, a lactone containing cyclic group represents the cyclic group containing one ring (lactone ring) containing a -O-C (O)-structure. When a lactone ring is counted as a 1st ring and it is a lactone ring only, it is called a polycyclic group irrespective of its structure, when it has only a monocyclic group and when it has another ring structure.

When the high molecular compound (A1) is used for formation of a resist film, the lactone cyclic group of a structural unit (a2) is effective in improving adhesiveness with respect to the board | substrate of a resist film, or improving affinity with the developing solution containing water. .

As a structural unit (a2), it does not specifically limit but arbitrary things can be used.

Specifically, the lactone-containing monocyclic group includes a group in which one hydrogen atom is removed from γ-butyrolactone. Moreover, as a lactone containing polycyclic type group, the group remove | excluding one hydrogen atom from bicycloalkane, tricycloalkane, and tetracycloalkane which has a lactone ring is mentioned.

Specific examples of the structural unit (a2) include structural units represented by general formulas (a2-1) to (a2-5) shown below.

[Formula 15]

[Wherein R is a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group, R 'is a hydrogen atom, a lower alkyl group, a C1-C5 alkoxy group or -COOR' ', and R' 'is a hydrogen atom or carbon number Is a linear, branched or cyclic alkyl group of 1 to 15, m is an integer of 0 or 1, and A '' is an alkylene group or oxygen atom of 1 to 5 carbon atoms.]

R in General Formulas (a2-1) to (a2-5) is the same as R ¹ in the structural unit (a0).

The lower alkyl group of R 'is the same as the lower alkyl group of R ¹ .

When R '' is a linear or branched alkyl group, it is preferable that it is C1-C10, and it is more preferable that it is C1-C5.

When R '' is a cyclic alkyl group, it is preferable that it is C3-C15, It is more preferable that it is C4-C12, and C5-C10 is the most preferable. Specifically, the group which removed one or more hydrogen atoms from polycycloalkane, such as monocycloalkane, bicycloalkane, tricycloalkane and tetracycloalkane, which may or may not be substituted with a fluorine atom or a fluorinated alkyl group, may be used. It can be illustrated. Specifically, a group in which one or more hydrogen atoms are removed from monocycloalkanes such as cyclopentane and cyclohexane, and polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane Etc. can be mentioned.

As a C1-C5 alkylene group of A '', a methylene group, an ethylene group, n-propylene group, an isopropylene group, etc. are mentioned specifically ,.

In consideration of the fact that R 'is industrially available in general formulas (a2-1) to (a2-5), hydrogen atoms are preferable.

In the formula (a2-1), the bonding position of the oxygen atom (—O—) to the γ-butyrolactone ring is not particularly limited, but the α position or the β position is preferable.

Specific structural units of the general formulas (a2-1) to (a2-5) are shown below.

[Formula 16]

[Formula 17]

[Formula 18]

[Formula 19]

[Formula 20]

As the structural unit (a2), at least one member selected from the group consisting of structural units represented by the general formulas (a2-1) to (a2-5) is preferable, and general formulas (a2-1) to (a2-3) It is more preferable than at least 1 sort (s) chosen from the group which consists of structural units represented by the following. Among them, the chemical formulas (a2-1-1), (a2-1-2), (a2-1-3), (a2-1-4), (a2-2-1), and (a2-2-2) At least 1 sort (s) chosen from the group which consists of structural units represented by (a) -3- (1), (a2-3-1), (a2-3-2), (a2-3-9), and (a2-3-10) is preferable.

As the structural unit (a2), one type may be used alone, or two or more types may be used in combination.

5-60 mol% is preferable with respect to the total of all the structural units which comprise a polymeric compound (A1), and, as for the ratio of a structural unit (a2) in a high molecular compound (A1), 10-55 mol% is more preferable. , 20-55 mol% is more preferable. By setting it as the lower limit or more, the effect by containing a structural unit (a2) is fully acquired, and setting it as the upper limit or less can balance the other structural unit.

<Structural unit (a3)>

The structural unit (a3) is a structural unit derived from an acrylate ester containing a polar group-containing aliphatic hydrocarbon group.

When the high molecular compound (A1) has a structural unit (a3), the hydrophilicity of the high molecular compound (A1) increases, the affinity with the developing solution increases, alkali solubility in the exposed portion is improved, and contributes to improvement of resolution.

As a polar group, a hydroxyl group, a cyano group, a carboxy group, the hydroxyalkyl group in which one part of the hydrogen atoms of an alkyl group were substituted by the fluorine atom, etc. are mentioned, Especially a hydroxyl group is preferable.

As an aliphatic hydrocarbon group, a C1-C10 linear or branched hydrocarbon group (preferably alkylene group) and a polycyclic aliphatic hydrocarbon group (polycyclic group) are mentioned. As the polycyclic group, for example, a resin for a resist composition for an ArF excimer laser can be appropriately selected from among those proposed in a large number. It is preferable that carbon number of this polycyclic group is 7-30.

Especially, the structural unit derived from the acrylate ester containing the aliphatic polycyclic group containing the hydroxyalkyl group in which one part of the hydrogen atoms of a hydroxyl group, a cyano group, a carboxy group, or an alkyl group is substituted by a fluorine atom is more preferable. Examples of the polycyclic group include groups in which two or more hydrogen atoms have been removed from bicycloalkane, tricycloalkane, tetracycloalkane, and the like. Specifically, the group remove | excluding two or more hydrogen atoms from polycycloalkane, such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclo dodecane, etc. are mentioned. Among these polycyclic groups, a group in which two or more hydrogen atoms are removed from adamantane, a group in which two or more hydrogen atoms are removed from norbornane, and a group in which two or more hydrogen atoms are removed from tetracyclododecane are industrially preferable.

As a structural unit (a3), when the hydrocarbon group in a polar group containing aliphatic hydrocarbon group is a C1-C10 linear or branched hydrocarbon group, the structural unit derived from the hydroxyethyl ester of acrylic acid is preferable, and this hydrocarbon When group is a polycyclic group, the structural unit represented by following formula (a3-1), the structural unit represented by (a3-2), and the structural unit represented by (a3-3) are mentioned as a preferable thing.

[Formula 21]

(In formula, R is the same as the above, j is an integer of 1-3, k is an integer of 1-3, t 'is an integer of 1-3, l is an integer of 1-5, s is Is an integer of 1 to 3)

In formula (a3-1), j is preferably 1 or 2, and more preferably 1. When j is 2, it is preferable that the hydroxyl group is couple | bonded with the 3rd and 5th positions of an adamantyl group. When j is 1, it is preferable that the hydroxyl group is couple | bonded with the 3-position of an adamantyl group.

It is preferable that j is 1, and it is especially preferable that the hydroxyl group is couple | bonded with the 3-position of an adamantyl group.

In formula (a3-2), k is preferably 1. The cyano group is preferably bonded to the 5 or 6 position of the norbornyl group.

In formula (a3-3), t 'is preferably 1. l is preferably 1. s is preferably 1. It is preferable that these have the 2-norbornyl group or 3-norbornyl group couple | bonded with the terminal of the carboxy group of acrylic acid. The fluorinated alkyl alcohol is preferably bonded to the 5 or 6 position of the norbornyl group.

As the structural unit (a3), one type may be used alone, or two or more types may be used in combination.

5-50 mol% is preferable with respect to the whole structural unit which comprises a high molecular compound (A1), and, as for the ratio of a structural unit (a3), in a high molecular compound (A1), 5-40 mol% is more preferable, 5 35 mol% is more preferable. By setting it as the lower limit or more, the effect by containing a structural unit (a3) is fully acquired, and setting it as the upper limit or less can balance the other structural unit.

<Structural unit (a1)>

The polymer compound (A1) may have a structural unit (a1) derived from an acrylate ester containing an acid dissociable, dissolution inhibiting group that does not correspond to the structural unit (a0) within a range that does not impair the effects of the present invention. .

As an acid dissociable, dissolution inhibiting group in a structural unit (a1), the thing similar to what was illustrated as an acid dissociable, dissolution inhibiting group of said R <^2> is mentioned.

As a structural unit (a1), 1 or more types chosen from the group which consists of a structural unit represented by the following general formula (a1-0-1) and the following general formula (a1-0-2) are preferable.

[Formula 22]

[Wherein, R represents a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group; X ¹ represents an acid dissociable, dissolution inhibiting group]

[Formula 23]

[Wherein, R represents a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group; X ² represents an acid dissociable, dissolution inhibiting group; Y ² represents an alkylene group or an aliphatic cyclic group]

In general formula (a1-0-1), the lower alkyl group or halogenated lower alkyl group of R is the same as the lower alkyl group or halogenated lower alkyl group which may be bonded to the α position of the acrylate ester.

If X ¹ is an acid dissociable, dissolution inhibiting group, it will not be specifically limited, For example, the above-mentioned tertiary alkyl ester type acid dissociable, dissolution inhibiting group, acetal type acid dissociable, dissolution inhibiting group, etc. are mentioned, Alkyl ester type acid dissociable, dissolution inhibiting groups are preferred.

In general formula (a1-0-2), R is the same as the above.

X ² is the same as X ¹ in Formula (a1-0-1).

Y ² is preferably an alkylene group having 1 to 10 carbon atoms or a divalent aliphatic cyclic group, and the aliphatic cyclic group is the same as described above for the aliphatic cyclic group except that a group having two or more hydrogen atoms removed is used. Can be used.

When Y <^2> is a C1-C10 alkylene group, it is more preferable that it is C1-C6, It is especially preferable that it is C1-C4, It is most preferable that it is C1-C3.

When Y <^2> is a divalent aliphatic cyclic group, it is especially preferable that 2 or more hydrogen atoms were removed from cyclopentane, cyclohexane, norbornane, isobornane, adamantane, tricyclodecane, and tetracyclododecane. .

Specific examples of the structural unit (a1) include structural units represented by general formulas (a1-1) to (a1-4) shown below.

[Formula 24]

[In the formula, X 'represents a tertiary alkyl ester type acid dissociable, dissolution inhibiting group, and Y represents a C1-5 lower alkyl group or an aliphatic cyclic group; n represents an integer of 0 to 3; Y ² is the same as above; R is the same as above, and R ^{1 '} and R ^2' each independently represent a hydrogen atom or a lower alkyl group having 1 to 5 carbon atoms.]

In formula, X 'is the same as the tertiary alkyl ester type acid dissociable, dissolution inhibiting group illustrated in said X <^1> .

^{R 1 ', R 2',} n, Y roneun, each described above in the "acetal-type acid dissociable, dissolution inhibiting group" a general formula (p1) illustrated in the description of ^{R 1 ', R 2',} n, Y And the same thing as.

As Y <^2> , the same thing as Y <^2> in general formula (a1-0-2) mentioned above is mentioned.

Specific examples of the structural units represented by general formulas (a1-1) to (a1-4) are shown below.

[Formula 25]

[Formula 26]

[Formula 27]

[Formula 28]

[Formula 29]

[Formula 30]

[Formula 31]

[Formula 32]

[Formula 33]

[Formula 34]

[Formula 35]

Among the above, the structural unit represented by general formula (a1-1) is preferable, and specifically, (a1-1-1)-(a1-1-6) and (a1-1-35)-(a1-1-) It is more preferable to use at least 1 sort (s) chosen from the group which consists of 41).

In addition, as a structural unit (a1), especially represented by the following general formula (a1-1-01) which covers the structural unit of Formula (a1-1-1)-a formula (a1-1-4), and Formula (a1) The following general formula (a1-1-02) which covers the structural unit of -1-35)-(a1-1-41) is also preferable.

[Formula 36]

(Wherein R represents a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group, and R ¹¹ represents a lower alkyl group)

[Formula 37]

(Wherein R represents a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group, and R ¹² represents a lower alkyl group. H represents an integer of 1 to 3)

In general formula (a1-1-01), R is the same as above.

The lower alkyl group of R ¹¹ is the same as the lower alkyl group in R, and a methyl group or an ethyl group is preferable.

In general formula (a1-1-02), R is the same as above.

The lower alkyl group of R ¹² is the same as the lower alkyl group in R, preferably a methyl group or an ethyl group, and most preferably an ethyl group.

h is preferably 1 or 2, most preferably 2;

In the high molecular compound (A1), as the structural unit (a1), one type may be used alone, or two or more types may be used in combination.

As mentioned above, the ratio of a structural unit (a1) in a high molecular compound (A1) is a total ratio of a structural unit (a0) and a structural unit (a1) to all the structural units which comprise a high molecular compound (A1). The amount which becomes 10-80 mol% with respect to it is preferable, The amount which becomes 20-70 mol% is more preferable, The amount which becomes 25-50 mol% is the most preferable. By setting it as the lower limit or more, a pattern can be easily obtained when it is set as a resist composition, and it can balance with the other structural unit by setting it as the upper limit or less.

<Structural unit (a4)>

The high molecular compound (A1) may contain structural units (a4) other than the said structural unit (a0)-(a3) in the range which does not impair the effect of this invention.

The structural unit (a4) is not particularly limited as long as it is another structural unit which is not classified into the structural units (a0) to (a3) described above, and is not particularly limited for ArF excimer lasers and KrF excimer lasers (preferably for ArF excimer lasers). A large number of conventionally known ones can be used as used for resins for resists such as

As the structural unit (a4), for example, a structural unit derived from an acrylate ester containing an acid non-dissociable aliphatic polycyclic group is preferable. The polycyclic group can exemplify the same as those exemplified in the case of the structural unit (a1), for example, and a resist composition such as an ArF excimer laser or a KrF excimer laser (preferably an ArF excimer laser). As what is used for the resin component of the above, many conventionally known things can be used.

It is especially preferable at the point of at least 1 type chosen from tricyclo decanyl group, adamantyl group, tetracyclo dodecanyl group, isobornyl group, norbornyl group, and easy industrial acquisition. These polycyclic groups may have a C1-C5 linear or branched alkyl group as a substituent.

As a structural unit (a4), what is a structure of the following general formula (a4-1) (a4-5) can be illustrated specifically ,.

[Formula 38]

(Wherein R is the same as above)

When such a structural unit (a4) is contained in the high molecular compound (A1), the ratio of the structural unit (a4) in the high molecular compound (A1) is 1 to 1 based on the total of all the structural units constituting the high molecular compound (A1). 30 mol% is preferable and 10-20 mol% is more preferable.

In the present invention, the polymer compound (A1) is preferably a copolymer having the structural units (a0), (a2) and (a3). As this copolymer, the copolymer which consists of structural units (a0), (a2), and (a3), the copolymer which consists of structural units (a0), (a2), (a3), and (a4), and a structural unit (a0) and copolymers made of (a2), (a3) and (a1).

Especially as a high molecular compound (A1), the copolymer which has three types of structural units represented by following formula (A1-11) is preferable.

[Formula 39]

[In formula, R <^1> , a, R <^10> , R <^14> is the same as the above, respectively.]

Formula (A1-11) of ^{R 1, a, R 10,} R 14 , it is respectively the same as ^{R 1, a, R 10,} R 14 in the formula (a0-1-1).

In addition, R is the same as R illustrated in the structural units (a2), (a3) and the like, and a plurality of Rs may be the same as or different from each other.

The high molecular compound (A1) is a compound (I) and a monomer which induces other structural units as necessary by, for example, known radical polymerization using a radical polymerization initiator such as azobisisobutyronitrile (AIBN) or the like. It can obtain by superposing | polymerizing.

In the polymer compound (A1), a chain transfer agent such as, for example, HS-CH ₂ -CH ₂ -CH ₂ -C (CF ₃ ) ₂ -OH is used in combination at the time of the polymerization so that -C at the terminal is used. (CF _{3) 2} -OH groups may be introduced. Thus, the copolymer into which the hydroxyalkyl group in which one part of the hydrogen atoms of the alkyl group was substituted by the fluorine atom was introduce | transduced is effective in reducing a developing defect and reducing LER (line edge roughness: uneven unevenness of a line side wall).

Although the mass mean molecular weight (Mw) (polystyrene conversion basis by gel permeation chromatography) of a high molecular compound (A1) is not specifically limited, 2000-50000 are preferable, 3000-30000 are more preferable, 5000-20000 This is particularly preferred. If it is smaller than the upper limit of this range, there is solubility in a resist solvent sufficient for use as a resist, and if it is larger than the lower limit of this range, dry etching resistance and resist pattern cross-sectional shape are favorable.

Moreover, 1.0-5.0 are preferable, as for dispersion degree (Mw / Mn), 1.0-3.0 are more preferable, and 1.2-2.5 are the most preferable. In addition, Mn represents a number average molecular weight.

The polymer compound (A1) of the present invention described above is novel.

For example, when the high molecular compound (A1) is blended into the positive resist composition together with the acid generator component (B) which generates an acid by irradiation with radiation, the acid generator component (by When an acid is generated from B), by the action of the acid, the bond between R ² in the structural unit (a0) and the oxygen atom bonded thereto is cleaved, and R ² is dissociated. As a result, the solubility of the high molecular compound (A1) in the alkaline developer is increased.

Therefore, a high molecular compound (A1) is useful as a base resin of the chemically amplified positive resist composition, and can be used suitably as a base component (A) of the positive resist composition of this invention below.

<< positive resist composition >>

Next, the positive resist composition of the first aspect of the present invention will be described.

The positive resist composition of the present invention is a base component (A) (hereinafter referred to as component (A)) in which solubility in an alkaline developer is increased by the action of an acid, and acid generation which generates an acid by irradiation with radiation. 1st component (B) (henceforth a component (B)) is contained. Here, a "base component" is an organic compound which has a film forming ability.

In such a positive resist composition, when radiation is irradiated (exposed), an acid is generated from the component (B), and the solubility of the component (A) in the alkaline developer is increased by the action of the acid. Therefore, in the formation of the resist pattern, selective exposure of the resist film obtained by using the positive resist composition increases the solubility of the resist film as an alkali developer of the exposed portion, while increasing the alkali developer of the unexposed portion. Since the solubility to is not changed, a resist pattern can be formed by performing alkali development.

&Lt; Component (A) >

(A) component contains the high molecular compound (A1) of this invention mentioned above.

In (A) component, a polymeric compound (A1) may be used individually by 1 type, and may be used in combination of 2 or more type.

50-100 mass% is preferable with respect to the gross mass of (A) component, as for the ratio of the high molecular compound (A1) in (A) component, 80-100 mass% is more preferable, and 100 mass% may be sufficient as it.

(A) component is a "base component which the solubility to alkaline developing solution increases by the action of an acid" other than the said high molecular compound (A1) in the range which does not impair the effect of this invention (Hereinafter, it is (A2) component. May be contained).

It does not specifically limit as such (A2) component, Many conventionally known as a base component for chemically amplified positive resist compositions (for example, for ArF excimer laser, for KrF excimer laser (preferably ArF excimer) What is necessary is just to select arbitrarily from base resins, such as laser). For example, as base resin for ArF excimer laser, what has the said structural unit (a1) as an essential structural unit, and further has the said structural units (a2)-(a4) arbitrarily is mentioned.

As the component (A2), one type may be used alone, or two or more types may be used in combination.

What is necessary is just to adjust content of (A) component in the resist composition of this invention according to the resist film thickness to be formed.

<(B) component>

It does not specifically limit as (B) component, What has been proposed as an acid generator for chemically amplified resist until now can be used. Examples of such acid generators include onium salt acid generators such as iodonium salts and sulfonium salts, oxime sulfonate acid generators, bisalkyl or bisarylsulfonyl diazomethanes, and poly (bissulfonyl) diazos. Many kinds of diazomethane-based acid generators such as methane, nitrobenzylsulfonate-based acid generators, iminosulfonate-based acid generators and disulfone-based acid generators are known.

As an onium salt type acid generator, the compound represented by following General formula (b-1) or (b-2) can be used, for example.

[Formula 40]

[Wherein, R ^{1 ″} to R ^{3 ″} and R ^{5 ″} to R ^{6 ″} each independently represent an aryl group or an alkyl group; Any two of R <^1> -R < ³ >> in a formula (b-1) may combine with each other, and may form a ring with the sulfur atom in a formula; R ^{4 ''} represents an alkyl group, a halogenated alkyl group, an aryl group, or an alkenyl group which may have a substituent; At least one of R ^{1 ''} to R ^{3 ''} represents an aryl group, and at least one of R ^{5 ''} to R ^{6 ''} represents an aryl group]

In formula (b-1), R <^1> -R < ³ >> respectively independently represents an aryl group or an alkyl group. Moreover, any two of R <^1> -R <^{3> in} Formula (b-1) may combine with each other, and may form a ring with the sulfur atom in a formula.

In addition, at least 1 represents an aryl group in R <^1> -R <^3> . ^{R 1 '' ~ R 3 '} ' of the two or more are preferable, and an aryl group, ^{R 1 '' ~ R 3 '} ' is an aryl group all of it is most preferred.

There is no restriction | limiting in particular as an aryl group of R <^1> -R <^3>" , For example, as a C6-C20 aryl group, one or all of the hydrogen atoms of this aryl group are an alkyl group, an alkoxy group, and a halogen atom Or a hydroxyl group or the like, or may not be substituted.

As an aryl group, a C6-C10 aryl group is preferable at the point which can be synthesize | combined at low cost. Specifically, a phenyl group and a naphthyl group are mentioned, for example.

As an alkyl group which the hydrogen atom of the said aryl group may be substituted, the C1-C5 alkyl group is preferable, and it is most preferable that they are a methyl group, an ethyl group, a propyl group, n-butyl group, and a tert- butyl group.

As an alkoxy group which the hydrogen atom of the said aryl group may substitute, the C1-C5 alkoxy group is preferable, and a methoxy group, an ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, tert-butok A timing is preferable and a methoxy group and an ethoxy group are the most preferable.

As a halogen atom in which the hydrogen atom of the said aryl group may be substituted, a fluorine atom is preferable.

There is no restriction | limiting in particular as an alkyl group of R <^1> -R <^3>" , For example, a C1-C10 linear, branched or cyclic alkyl group etc. are mentioned. It is preferable that it is C1-C5 from the point which is excellent in resolution. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, nonyl group, decanyl group, etc. are mentioned. A methyl group is mentioned at the point which is excellent in the resolution, and can be synthesize | combined at low cost.

When any two of R ^{1 ''} to R ^{3 ''} in formula (b-1) combine with each other to form a ring together with a sulfur atom in the formula, a sulfur atom is included to form a 3 to 10 membered ring. It is preferable that it is done, and it is especially preferable to form the 5-7 membered ring.

When any two of R <^1> -R <^{3> in} Formula (b-1) combine with each other and form a ring with the sulfur atom in a formula, it is preferable that the other one is an aryl group. Examples of the aryl group include the same aryl groups as R ^{1 ″} to R ^{3 ″} .

R ^{4 ''} represents an alkyl group, a halogenated alkyl group, an aryl group or an alkenyl group which may have a substituent.

The alkyl group for R ^{4 ″} may be either linear, branched or cyclic.

As said linear or branched alkyl group, it is preferable that it is C1-C10, It is more preferable that it is C1-C8, It is most preferable that it is C1-C4.

As said cyclic alkyl group, it is preferable that it is C4-C15, It is more preferable that it is C4-C10, It is most preferable that it is C6-C10.

As a halogenated alkyl group in R < ⁴ >>, the group in which one part or all part of the hydrogen atom of the said linear, branched or cyclic alkyl group was substituted by the halogen atom is mentioned. As this halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, A fluorine atom is preferable.

In a halogenated alkyl group, it is preferable that the ratio (halogenation rate (%)) of the number of halogen atoms with respect to the total number of the halogen atoms and hydrogen atoms contained in the said halogenated alkyl group is 10 to 100%, and it is 50 to 100% Preferably, 100% is the most preferable. The higher the halogenation rate is, the more preferable the acid strength becomes.

It is preferable that the aryl group in said R < ⁴ >> is a C6-C20 aryl group.

It is preferable that the alkenyl group in said R < ⁴ >> is a C2-C10 alkenyl group.

In said R <^4>"," it may have a substituent "means that one part or all part of the hydrogen atom in the said linear, branched or cyclic alkyl group, halogenated alkyl group, aryl group, or alkenyl group is a substituent ( Atom or group other than a hydrogen atom) may be substituted.

The number of substituents in R ^{4 ''} may be one or two or more.

Examples of the substituent include a group represented by a halogen atom, a hetero atom, an alkyl group, R ⁵ -O- [wherein R ⁵ is a monovalent aromatic organic group, a monovalent aliphatic hydrocarbon group or a hydroxyalkyl group], The group represented by R <^51> -OC (O)-[In formula, R <^51> is the monovalent aliphatic hydrocarbon group which may contain the hetero atom], etc. are mentioned.

As said halogen atom and an alkyl group, the thing similar to what was illustrated as a halogen atom and an alkyl group in a halogenated alkyl group in R <^4>' is mentioned.

An oxygen atom, a nitrogen atom, a sulfur atom etc. are mentioned as said hetero atom.

In the group represented by R ⁵ -O-, the monovalent aromatic organic group of R ⁵ is a phenyl group, a biphenyl group, a fluorenyl group, a naphthyl group, an anthryl group, or phenanthryl Aryl groups obtained by removing one hydrogen atom from a ring of an aromatic hydrocarbon such as a group; Heteroaryl group by which some carbon atoms which comprise the ring of these aryl groups were substituted by hetero atoms, such as an oxygen atom, a sulfur atom, and a nitrogen atom; Aryl alkyl groups, such as a benzyl group, a phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, and 2-naphthylethyl group, etc. are mentioned.

It is preferable that it is 1-4, as for carbon number of the alkyl chain in the said arylalkyl group, it is more preferable that it is 1-2, and it is especially preferable that it is one.

These aryl groups, heteroaryl groups, and arylalkyl groups may have substituents, such as a C1-C10 alkyl group, a halogenated alkyl group, an alkoxy group, a hydroxyl group, and a halogen atom. It is preferable that carbon number is 1-8, and, as for the alkyl group or halogenated alkyl group in this substituent, it is more preferable that it is 1-4. Moreover, it is preferable that this halogenated alkyl group is a fluorinated alkyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, an iodine atom and a bromine atom, and are preferably fluorine atoms.

As a monovalent aromatic organic group of R <^5> , an arylalkyl group is preferable, an arylmethyl group is more preferable, and a naphthylmethyl group is the most preferable.

Examples of the monovalent aliphatic hydrocarbon group for R ^{5 include} a linear, branched or cyclic monovalent saturated hydrocarbon group having 1 to 15 carbon atoms, or a linear or branched chain 1 having 2 to 5 carbon atoms. The aliphatic unsaturated hydrocarbon group can be mentioned.

Examples of the linear monovalent saturated hydrocarbon group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group and decanyl group.

Examples of the branched monovalent saturated hydrocarbon group include 1-methylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1 -Ethyl butyl group, 2-ethyl butyl group, 1-methyl pentyl group, 2-methyl pentyl group, 3-methyl pentyl group, 4-methyl pentyl group, etc. are mentioned.

The cyclic monovalent saturated hydrocarbon group may be any of a polycyclic group and a monocyclic group, for example, one hydrogen atom from polycycloalkane such as monocycloalkane, bicycloalkane, tricycloalkane and tetracycloalkane And the like from which the product was removed. More specifically, it is 1 from monocyclo alkanes, such as cyclopentane, cyclohexane, cycloheptane, cyclooctane, and polycyclo alkanes, such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclo dodecane. The group remove | excluding two hydrogen atoms is mentioned.

As a linear monovalent unsaturated hydrocarbon group, a vinyl group, a propenyl group (allyl group), butynyl group etc. are mentioned, for example.

As a branched monovalent unsaturated hydrocarbon group, a 1-methyl propenyl group, 2-methyl propenyl group, etc. are mentioned, for example.

2-4 are preferable and, as for carbon number of the monovalent aliphatic hydrocarbon group of R <^5> , 3 is especially preferable.

In the hydroxyalkyl group of R ⁵ , at least one hydrogen atom of a linear, branched or cyclic monovalent saturated hydrocarbon group is substituted with a hydroxyl group. It is preferable that one or two hydrogen atoms of the linear or branched monovalent saturated hydrocarbon group are substituted with hydroxyl groups. Specifically, a hydroxymethyl group, hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 2,3-dihydroxypropyl group, etc. are mentioned.

1-10 are preferable, as for carbon number of the monovalent hydroxyalkyl group of R <^5> , 1-8 are more preferable, 1-6 are especially preferable, and 1-3 are the most preferable.

In the group represented by the above-mentioned R ⁵¹ -OC (O)-, the monovalent aliphatic hydrocarbon group for R ⁵¹ includes the same ones as those exemplified for the monovalent aliphatic hydrocarbon group for R ⁵ , particularly preferably a cyclic alkyl group. Do. The cyclic alkyl group may have a substituent.

As this substituent, a C1-C5 lower alkyl group, a fluorine atom, a C1-C5 fluorinated lower alkyl group substituted by the fluorine atom, an oxygen atom (= O), etc. are mentioned.

The monovalent aliphatic hydrocarbon group may contain the hetero atom. For example, as a cyclic alkyl group containing a hetero atom, the group etc. represented by following formula (L1)-(L5), (S1)-(S4) are mentioned.

[Formula 41]

[Wherein Q '' is an alkylene group having 1 to 5 carbon atoms, -O-, -S-, -OR ⁹⁴ -or -SR ^95- , and R ⁹⁴ and R ⁹⁵ are each independently alkyl having 1 to 5 carbon atoms; Is a len group and m is an integer of 0 or 1;

In formula (b-2), R < ^{5 >>} and R <^6>" respectively independently represent an aryl group or an alkyl group. At least one of R ^{5 ''} and R ^{6 ''} represents an aryl group. It is preferable that both of R ^{5 ''} and R ^{6 ''} are aryl groups.

Examples of the aryl group for R ^{5 ″} and R ^{6 ″} include the same aryl groups as R ^{1 ″} to R ^{3 ″} .

Examples of the alkyl groups of R ^{5 ''} and R ^{6 '' include} the same alkyl groups as those of R ^{1 ''} to R ^{3 ''} .

Among them, R ^{5 ''} and R ^{6 ''} are most preferably both phenyl groups.

Examples of R ^{4 ″} in the formula (b-2) include the same ones as R ^{4 ″ in} the formula (b-1).

As a specific example of the onium salt type acid generator represented by Formula (b-1) and (b-2), the trifluoromethane sulfonate or nonafluoro butane sulfonate of diphenyl iodonium, bis (4-tert- Butylphenyl) trifluoromethanesulfonate or nonafluorobutanesulfonate of iodonium, trifluoromethanesulfonate of triphenylsulfonium, heptafluoropropanesulfonate or nonafluorobutanesulfonate thereof, tri ( Trifluoromethanesulfonate of 4-methylphenyl) sulfonium, heptafluoropropanesulfonate or nonafluorobutanesulfonate thereof, trifluoromethanesulfonate of dimethyl (4-hydroxynaphthyl) sulfonium, its Heptafluoropropanesulfonate or its nonafluorobutanesulfonate, trifluoromethanesulfonate of monophenyldimethylsulfonium, heptafluoropropanesulfonate or its nonafluoro Butane sulfonate; Trifluoromethanesulfonate of diphenylmonomethylsulfonium, heptafluoropropanesulfonate or nonafluorobutanesulfonate thereof, trifluoromethanesulfonate of (4-methylphenyl) diphenylsulfonium, heptafluoro Ropropansulfonate or its nonafluorobutanesulfonate, trifluoromethanesulfonate of (4-methoxyphenyl) diphenylsulfonium, heptafluoropropanesulfonate or its nonafluorobutanesulfonate, tri ( Trifluoromethanesulfonate of 4-tert-butyl) phenylsulfonium, heptafluoropropanesulfonate or nonafluorobutanesulfonate thereof, and diphenyl (1- (4-methoxy) naphthyl) sulfonium Trifluoromethanesulfonate, heptafluoropropanesulfonate or nonafluorobutanesulfonate thereof, trifluoromethanesulfonate of di (1-naphthyl) phenylsulfonium, heptafluoro Propanesulfonate or nonafluorobutanesulfonate thereof; Trifluoromethanesulfonate of 1-phenyltetrahydrothiophenium, heptafluoropropanesulfonate or nonafluorobutanesulfonate thereof; Trifluoromethanesulfonate of 1- (4-methylphenyl) tetrahydrothiophenium, heptafluoropropanesulfonate or nonafluorobutanesulfonate thereof; Trifluoromethanesulfonate of 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium, heptafluoropropanesulfonate or nonafluorobutanesulfonate thereof; Trifluoromethanesulfonate of 1- (4-methoxynaphthalen-1-yl) tetrahydrothiophenium, heptafluoropropanesulfonate or nonafluorobutanesulfonate thereof; Trifluoromethanesulfonate of 1- (4-ethoxynaphthalen-1-yl) tetrahydrothiophenium, heptafluoropropanesulfonate or nonafluorobutanesulfonate thereof; Trifluoromethanesulfonate of 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium, heptafluoropropanesulfonate or nonafluorobutanesulfonate thereof; Trifluoromethanesulfonate of 1-phenyltetrahydrothiopyranium, heptafluoropropanesulfonate or nonafluorobutanesulfonate thereof; Trifluoromethanesulfonate of 1- (4-hydroxyphenyl) tetrahydrothiopyranium, heptafluoropropanesulfonate or nonafluorobutanesulfonate thereof; Trifluoromethanesulfonate of 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiopyranium, heptafluoropropanesulfonate or nonafluorobutanesulfonate thereof; Trifluoromethanesulfonate of 1- (4-methylphenyl) tetrahydrothiopyranium, its heptafluoropropanesulfonate or its nonafluorobutanesulfonate, and the like.

Moreover, the onium salt in which the anion part of these onium salt was substituted by methanesulfonate, n-propanesulfonate, n-butanesulfonate, n-octanesulfonate can also be used.

In addition, in the said general formula (b-1) or (b-2), the onium salt type acid generator which substituted the anion part by the anion part represented by the following general formula (b-3) or (b-4) can also be used. (The cation part is the same as (b-1) or (b-2).).

[Formula 42]

[Wherein, X '' represents an alkylene group having 2 to 6 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom; Y '' and Z '' each independently represent an alkyl group having 1 to 10 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom]

X '' is a linear or branched alkylene group in which at least one hydrogen atom is substituted with a fluorine atom, and the alkylene group has 2 to 6 carbon atoms, preferably 3 to 5 carbon atoms, and most preferably 3 carbon atoms. to be.

Y '' and Z '' are each independently a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and the alkyl group has 1 to 10 carbon atoms, preferably 1 to 7 carbon atoms. Preferably it is C1-C3.

The carbon number of the alkylene group of X '' or the carbon number of the alkyl group of Y '' and Z '' is preferably smaller, for the reason that the solubility in the resist solvent is also good within the range of the carbon number.

In addition, in the alkylene group of X '' or the alkyl group of Y '', Z '', the more the number of hydrogen atoms substituted with fluorine atoms, the stronger the strength of the acid, and the higher energy light or electron beam of 200 nm or less. It is preferable because the transparency to the resin is improved. The proportion of the fluorine atom in the alkylene group or the alkyl group, that is, the fluorination rate, is preferably 70 to 100%, more preferably 90 to 100%, and most preferably, perfluoroalkyl in which all hydrogen atoms are substituted with fluorine atoms. Ethylene group or perfluoroalkyl group.

Moreover, the sulfonium salt which has the cation part represented by following General formula (b-5) or (b-6) can also be used as an onium salt type acid generator.

[Formula 43]

[Wherein, R ⁴¹ to R ⁴⁶ are each independently an alkyl group, an acetyl group, an alkoxy group, a carboxyl group, a hydroxyl group or a hydroxyalkyl group; n ₁ to n ₅ Are each independently an integer of 0 to 3, n ₆ is an integer of 0 to 2]

In R ⁴¹ to R ⁴⁶ , the alkyl group is preferably an alkyl group having 1 to 5 carbon atoms, more preferably a linear or branched alkyl group, and methyl group, ethyl group, propyl group, isopropyl group, and n-butyl. It is especially preferable that it is a group or a tert- butyl group.

The alkoxy group is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a linear or branched alkoxy group, particularly preferably a methoxy group and an ethoxy group.

The hydroxyalkyl group is preferably a group in which one or a plurality of hydrogen atoms in the alkyl group is substituted with a hydroxy group, and examples thereof include a hydroxymethyl group, a hydroxyethyl group, and a hydroxypropyl group.

Symbols n ₁ to n ₆ assigned to R ⁴¹ to R ^46; When it is an integer of 2 or more, some R <^41> -R <^46> may be the same respectively and may differ.

n ₁ Silver is preferably 0 to 2, more preferably 0 or 1, and even more preferably 0.

n ₂ and n ₃ are preferably each independently 0 or 1, and more preferably 0.

n ₄ becomes like this. Preferably it is 0-2, More preferably, it is 0 or 1.

n ₅ becomes like this. Preferably it is 0 or 1, More preferably, it is zero.

n ₆ becomes like this. Preferably it is 0 or 1, More preferably, it is 1.

The anion part of the sulfonium salt which has a cation part represented by Formula (b-5) or (b-6) is not specifically limited, It may be the same as the anion part of the onium salt type acid generator currently proposed. The anionic portion is, for example, the formula (b-1) or (b-2) an onium salt-based no moiety of the acid generator _{^{(R 4 '' SO 3 -}} ) represents a fluorinated alkyl sulfonic acid ion and the like; The anion part etc. which are represented by the said general formula (b-3) or (b-4) are mentioned.

In this specification, an oxime sulfonate-type acid generator is a compound which has at least 1 group represented by following General formula (B-1), and has a characteristic which generate | occur | produces an acid by irradiation of a radiation. Since these oxime sulfonate-type acid generators are used abundantly for chemical amplification resist compositions, they can be selected arbitrarily and used.

[Formula 44]

(In Formula (B-1), R ³¹ and R ³² each independently represent an organic group.)

The organic group of R <^31> , R <^32> is group containing a carbon atom, and atoms other than a carbon atom (for example, a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a halogen atom (fluorine atom, a chlorine atom, etc.), etc.) You may have

As an organic group of R <^31> , a linear, branched or cyclic alkyl group or an aryl group is preferable. These alkyl groups and aryl groups may have a substituent. There is no restriction | limiting in particular as this substituent, For example, a fluorine atom, a C1-C6 linear, branched or cyclic alkyl group etc. are mentioned. Here, "having a substituent" means that one part or all part of the hydrogen atom of an alkyl group or an aryl group is substituted by the substituent.

As an alkyl group, C1-C20 is preferable, C1-C10 is more preferable, C1-C8 is further more preferable, C1-C6 is especially preferable, C1-C4 is the most preferable. As the alkyl group, a partially or completely halogenated alkyl group (hereinafter sometimes referred to as a halogenated alkyl group) is preferable. In addition, the partially halogenated alkyl group means the alkyl group in which a part of hydrogen atoms were substituted by the halogen atom, and the fully halogenated alkyl group means the alkyl group in which all the hydrogen atoms were substituted by the halogen atom. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, A fluorine atom is especially preferable. That is, the halogenated alkyl group is preferably a fluorinated alkyl group.

The aryl group preferably has 4 to 20 carbon atoms, more preferably 4 to 10 carbon atoms, and most preferably 6 to 10 carbon atoms. As the aryl group, a partially or fully halogenated aryl group is particularly preferable. Moreover, the partially halogenated aryl group means the aryl group in which a part of hydrogen atoms were substituted by the halogen atom, and the fully halogenated aryl group means the aryl group in which all the hydrogen atoms were substituted by the halogen atom.

Especially as R <^31> , a C1-C4 alkyl group or C1-C4 fluorinated alkyl group which does not have a substituent is preferable.

As an organic group of R <^32> , a linear, branched or cyclic alkyl group, an aryl group, or a cyano group is preferable. As an alkyl group and an aryl group of R <^32> , the thing similar to the alkyl group and aryl group which were illustrated by said R <^31> is mentioned.

Especially as R <^32> , a cyano group, a C1-C8 alkyl group which does not have a substituent, or a C1-C8 fluorinated alkyl group is preferable.

As an oxime sulfonate-type acid generator, the compound represented by the following general formula (B-2) or (B-3) more preferable is mentioned.

[Formula 45]

[In Formula (B-2), R ³³ is a cyano group, an alkyl group having no substituent, or a halogenated alkyl group. R ³⁴ Is an aryl group. R ³⁵ Is an alkyl group or a halogenated alkyl group having no substituent]

[Formula 46]

[In Formula (B-3), R ³⁶ is a cyano group, an alkyl group having no substituent, or a halogenated alkyl group. R ³⁷ is a divalent or trivalent aromatic hydrocarbon group. R ³⁸ is an alkyl group or halogenated alkyl group having no substituent. p '' is 2 or 3]

In the general formula (B-2), the alkyl group or halogenated alkyl group having no substituent of R ³³ is preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and most preferably 1 to 6 carbon atoms. Do.

As R ³³ , a halogenated alkyl group is preferable, and a fluorinated alkyl group is more preferable.

R ³³ It is preferable that 50% or more of the hydrogen atoms of an alkyl group are fluorinated, It is more preferable that the fluorinated alkyl group in is 70% or more, and it is especially preferable that it is 90% or more.

As an aryl group for R ³⁴ , one hydrogen atom is formed from a ring of an aromatic hydrocarbon such as a phenyl group, a biphenyl group, a fluorenyl group, a naphthyl group, an anthryl group, and a phenanthryl group. And a heteroaryl group in which a part of the removed group and the carbon atoms constituting the ring of these groups are substituted with a hetero atom such as an oxygen atom, a sulfur atom, or a nitrogen atom. Among these, a fluorenyl group is preferable.

The aryl group of R ³⁴ may have substituents, such as a C1-C10 alkyl group, a halogenated alkyl group, and an alkoxy group. It is preferable that carbon number is 1-8, and, as for the alkyl group or halogenated alkyl group in this substituent, C1-C4 is more preferable. Moreover, it is preferable that this halogenated alkyl group is a fluorinated alkyl group.

The alkyl group or halogenated alkyl group not having a substituent of R ³⁵ preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and most preferably 1 to 6 carbon atoms.

As R ³⁵ , a halogenated alkyl group is preferable, and a fluorinated alkyl group is more preferable.

R ³⁵ In the fluorinated alkyl group in the group, the hydrogen atom of the alkyl group is preferably 50% or more fluorinated, more preferably 70% or more fluorinated, and particularly preferably 90% or more fluorinated because the generated acid has a high strength. Do. Most preferably, it is a fully fluorinated alkyl group in which the hydrogen atom is 100% fluorine substituted.

In said general formula (B-3), the alkyl group or halogenated alkyl group which does not have a substituent of R <^36> is the same as the alkyl group or halogenated alkyl group which does not have a substituent of said R <^33> .

As a bivalent or trivalent aromatic hydrocarbon group of R <^37> , the group remove | excluding one or two hydrogen atoms from the said aryl group of R <^34> is mentioned.

As an alkyl group or halogenated alkyl group which does not have a substituent of R <^38> , the same thing as the alkyl group or halogenated alkyl group which does not have a substituent of said R <^35> is mentioned.

p '' is preferably 2.

Specific examples of the oxime sulfonate acid generator include α- (p-toluenesulfonyloxyimino) -benzyl cyanide, α- (p-chlorobenzenesulfonyloxyimino) -benzyl cyanide, and α- ( 4-nitrobenzenesulfonyloxyimino) -benzyl cyanide, α- (4-nitro-2-trifluoromethylbenzenesulfonyloxyimino) -benzyl cyanide, α- (benzenesulfonyloxyimino) -4- Chlorobenzyl cyanide, α- (benzenesulfonyloxyimino) -2,4-dichlorobenzyl cyanide, α- (benzenesulfonyloxyimino) -2,6-dichlorobenzylcyanide, α- (benzenesulfonyloxyi Mino) -4-methoxybenzylcyanide, α- (2-chlorobenzenesulfonyloxyimino) -4-methoxybenzylcyanide, α- (benzenesulfonyloxyimino) -thien-2-ylacetonitrile, α- (4-dodecylbenzenesulfonyloxyimino) -benzyl cyanide, α-[(p-toluenesulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α-[(dodecylbenzenesulfonyloxyi Mino) -4-methoxyphenyl] acetonitrile , α- (tosyloxyimino) -4-thienyl cyanide, α- (methylsulfonyloxyimino) -1-cyclopentenylacetonitrile, α- (methylsulfonyloxyimino) -1-cyclohexenylaceto Nitrile, α- (methylsulfonyloxyimino) -1-cycloheptenylacetonitrile, α- (methylsulfonyloxyimino) -1-cyclooctenylacetonitrile, α- (trifluoromethylsulfonyloxyimino) -1-cyclopentenyl acetonitrile, α- (trifluoromethylsulfonyloxyimino) -cyclohexylacetonitrile, α- (ethylsulfonyloxyimino) -ethylacetonitrile, α- (propylsulfonyloxyimino) -Propyl acetonitrile, α- (cyclohexylsulfonyloxyimino) -cyclopentylacetonitrile, α- (cyclohexylsulfonyloxyimino) -cyclohexylacetonitrile, α- (cyclohexylsulfonyloxyimino) -1- Cyclopentenylacetonitrile, α- (ethylsulfonyloxyimino) -1-cyclopentenylacetonitrile, α- Sopropyl sulfonyloxyimino) -1-cyclopentenylacetonitrile, α- (n-butylsulfonyloxyimino) -1-cyclopentenylacetonitrile, α- (ethylsulfonyloxyimino) -1-cyclohex Senylacetonitrile, α- (isopropylsulfonyloxyimino) -1-cyclohexenylacetonitrile, α- (n-butylsulfonyloxyimino) -1-cyclohexenylacetonitrile, α- (methylsulfonyloxyi Mino) -phenylacetonitrile, α- (methylsulfonyloxyimino) -p-methoxyphenylacetonitrile, α- (trifluoromethylsulfonyloxyimino) -phenylacetonitrile, α- (trifluoromethylsul Ponyloxyimino) -p-methoxyphenylacetonitrile, α- (ethylsulfonyloxyimino) -p-methoxyphenylacetonitrile, α- (propylsulfonyloxyimino) -p-methylphenylacetonitrile, α- ( Methylsulfonyloxyimino) -p-bromophenyl acetonitrile etc. are mentioned.

Moreover, the oxime sulfonate-type acid generator disclosed by Unexamined-Japanese-Patent No. 9-208554 (Paragraph [18]-[Formula 19] of paragraph [0012]-[0014], WO2004 / 074242A2 (65- The oxime sulfonate acid generator disclosed in Examples 1 to 40) on page 85 can also be preferably used.

Moreover, the following can be illustrated as a preferable thing.

[Formula 47]

As a specific example of bisalkyl or bisaryl sulfonyl diazomethanes in a diazomethane-type acid generator, bis (isopropylsulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (2,4-dimethylphenylsulfonyl) diazomethane, etc. are mentioned.

Moreover, the diazomethane type acid generator disclosed in Unexamined-Japanese-Patent No. 11-035551, Unexamined-Japanese-Patent No. 11-035552, and Unexamined-Japanese-Patent No. 11-035573 can also be used preferably.

Moreover, as poly (bissulfonyl) diazomethanes, 1, 3-bis (phenylsulfonyl diazommethylsulfonyl) propane, 1 which is disclosed by Unexamined-Japanese-Patent No. 11-322707, 1, for example, , 4-bis (phenylsulfonyldiazomethylsulfonyl) butane, 1,6-bis (phenylsulfonyldiazomethylsulfonyl) hexane, 1,10-bis (phenylsulfonyldiazomethylsulfonyl) decane , 1,2-bis (cyclohexylsulfonyldiazomethylsulfonyl) ethane, 1,3-bis (cyclohexylsulfonyldiazomethylsulfonyl) propane, 1,6-bis (cyclohexylsulfonyldiazomethyl Sulfonyl) hexane, 1, 10-bis (cyclohexylsulfonyl diazommethylsulfonyl) decane, etc. are mentioned.

As the component (B), these acid generators may be used alone, or may be used in combination of two or more thereof.

In this invention, it is preferable to use onium salt type acid generator which makes the fluorinated alkyl sulfonate ion which may have a substituent as an (B) component anion.

0.5-30 mass parts is preferable with respect to 100 mass parts of (A) component, and, as for content of (B) component in the positive resist composition of this invention, 1-10 mass parts is more preferable. Pattern formation is fully performed by setting it as the said range. Moreover, since a uniform solution is obtained and storage stability becomes favorable, it is preferable.

<Optional ingredient>

In the positive resist composition of the present invention, a nitrogen-containing organic compound (D) (hereinafter referred to as component (D)) is further added as an optional component in order to improve resist pattern shape, post-exposure stability over time, and the like. It can be compounded.

Since many kinds of this (D) component are already proposed, what is necessary is just to use arbitrarily from a well-known thing, Especially, an aliphatic amine, especially a secondary aliphatic amine and tertiary aliphatic amine is preferable. Herein, the aliphatic amine is an amine having one or more aliphatic groups, and the aliphatic group preferably has 1 to 20 carbon atoms.

Examples of the aliphatic amines include amines (alkylamines or alkylalcoholamines) or cyclic amines in which at least one hydrogen atom of ammonia NH ₃ is substituted with an alkyl group having 20 or less carbon atoms or a hydroxyalkyl group. .

Specific examples of alkyl amines and alkyl alcohol amines include monoalkyl amines such as n-hexyl amine, n-heptyl amine, n-octyl amine, n-nonyl amine, and n-decyl amine; Dialkylamines such as diethylamine, di-n-propylamine, di-n-heptylamine, di-n-octylamine and dicyclohexylamine; Trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-hexylamine, tri-n-pentylamine, tri-n-heptylamine, tri-n-octylamine, tri trialkylamines such as -n-nonylamine, tri-n-decanylamine and tri-n-dodecylamine; Alkyl alcohol amines such as diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, di-n-octanolamine, tri-n-octanolamine, stearyl diethanolamine, and lauryl diethanolamine. have. Among them, trialkylamines and alkylalcoholamines having 5 to 10 carbon atoms are preferable, and tri-n-pentylamine, diethanolamine and stearyl diethanolamine are particularly preferable.

As a cyclic amine, the heterocyclic compound which contains a nitrogen atom as a hetero atom is mentioned, for example. The heterocyclic compound may be monocyclic (aliphatic monocyclic amine) or polycyclic (aliphatic polycyclic amine).

Specific examples of the aliphatic monocyclic amines include piperidine and piperazine.

As the aliphatic polycyclic amine, one having 6 to 10 carbon atoms is preferable, and specifically 1,5-diazabicyclo [4.3.0] -5-nonene and 1,8-diazabicyclo [5.4.0] -7-undecene, hexamethylenetetramine, 1, 4- diazabicyclo [2.2.2] octane, etc. are mentioned.

Other aliphatic amines include tris (2-methoxymethoxyethyl) amine, tris {2- (2-methoxyethoxy) ethyl} amine, and tris {2- (2-methoxyethoxymethoxy) ethyl } Amine, tris {2- (1-methoxyethoxy) ethyl} amine, tris {2- (1-ethoxyethoxy) ethyl} amine, tris {2- (1-ethoxypropoxy) ethyl} amine And tris [2- {2- (2-hydroxyethoxy) ethoxy} ethylamine and the like.

These may be used independently and may be used in combination of 2 or more type.

(D) component is used in the range of 0.01-5.0 mass parts normally with respect to 100 mass parts of (A) component.

The positive resist composition of the present invention comprises, as an optional component, an organic carboxylic acid, an oxo acid of phosphorus and a derivative thereof as an optional component for the purpose of preventing degradation of sensitivity, improving the shape of a resist pattern, stability over time after exposure, and the like. At least 1 sort (s) of compound (E) (henceforth a component (E) component) chosen from group can be contained.

As organic carboxylic acid, acetic acid, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid, etc. are preferable, for example.

Phosphoric acid, phosphonic acid, phosphinic acid, etc. are mentioned as an oxo acid and its derivative (s) of phosphorus, Among these, phosphonic acid is especially preferable.

As a derivative of the oxo acid of phosphorus, the ester etc. which substituted the hydrogen atom of the said oxo acid with a hydrocarbon group are mentioned, for example, As a hydrocarbon group, a C1-C5 alkyl group, a C6-C15 aryl group, etc. are mentioned, for example. Can be mentioned.

Examples of the phosphoric acid derivative include phosphoric acid esters such as phosphoric acid di-n-butyl ester and phosphoric acid diphenyl ester.

Examples of the phosphonic acid derivatives include phosphonic acid dimethyl esters, phosphonic acid-di-n-butyl esters, phosphonic acid esters such as phenylphosphonic acid, phosphonic acid diphenyl esters, and phosphonic acid dibenzyl esters.

Examples of the derivatives of phosphinic acid include phosphinic acid esters such as phenylphosphinic acid.

As the component (E), one type may be used alone, or two or more types may be used in combination.

As (E) component, it is normally used in 0.01-5.0 mass part with respect to 100 mass parts of (A) component.

The positive type resist composition of the present invention may further contain miscible additives, for example, additional resins for improving the performance of resist films, surfactants for improving applicability, dissolution inhibitors, plasticizers, stabilizers, as desired. , Coloring agents, antihalation agents, dyes and the like can be appropriately added.

<Organic Solvent (S)>

The positive resist composition of the present invention can be produced by dissolving a material in an organic solvent (hereinafter sometimes referred to as component (S)).

As (S) component, what is necessary is just to melt | dissolve each component to be used and it can be set as a uniform solution, and conventionally select arbitrary 1 type (s) or 2 or more types from the well-known as a solvent of chemically amplified resist, Can be used.

For example, lactones, such as (gamma) -butyrolactone; Ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone, and 2-heptanone; Polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol and dipropylene glycol; Monomethyl ether, monoethyl ether of a compound having an ester bond, such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate, the polyhydric alcohol or the compound having the ester bond, Derivatives of polyhydric alcohols such as monoalkyl ethers such as monopropyl ether and monobutyl ether or compounds having ether bonds such as monophenyl ether [In these, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME) is preferable]; Cyclic ethers such as dioxane, esters such as methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate and ethyl ethoxypropionate; Anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phentol, butyl phenyl ether, ethyl benzene, diethyl benzene, pentyl benzene, isopropyl benzene, toluene, xylene, cymene, mesitylene Aromatic organic solvents, such as these, are mentioned.

These organic solvents may be used independently and may be used as 2 or more types of mixed solvents.

Especially, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), and EL are preferable.

A mixed solvent in which PGMEA and a polar solvent are mixed is also preferable. What is necessary is just to determine the compounding ratio (mass ratio) suitably in consideration of compatibility of PGMEA and a polar solvent, etc., Preferably it is 1: 9-9: 1, More preferably, it shall be in the range of 2: 8-8: 2. desirable.

More specifically, when mix | blending EL as a polar solvent, the mass ratio of PGMEA: EL becomes like this. Preferably it is 1: 9-9: 1, More preferably, it is 2: 8-8: 2. In addition, when mix | blending PGME as a polar solvent, the mass ratio of PGMEA: PGME becomes like this. Preferably it is 1: 9-9: 1, More preferably, it is 2: 8-8: 2, More preferably, it is 3: 7- 7: 3.

Moreover, as (S) component, the mixed solvent of at least 1 sort (s) chosen from PGMEA and EL and (gamma) -butyrolactone is also preferable. In this case, as a mixing ratio, the mass ratio of the former and the latter becomes like this. Preferably it is 70: 30-95: 5.

Although the usage-amount of (S) component is not specifically limited, Although it is a density | concentration which can be apply | coated to a board | substrate etc., it is set suitably according to the coating film thickness, Generally, solid content concentration of a resist composition is 2-20 mass%, Preferably it is 5-15. It is used so that it may be in the range of mass%.

The positive resist composition of the present invention is a novel one not known in the prior art.

In addition, according to the positive resist composition of the present invention, a resist pattern with reduced line edge roughness LER can be formed on a support with high resolution.

Here, LER means the roughness (roughness) of the resist pattern sidewall surface. Since LER causes deformation of the periphery of the hole in the hole pattern, variations in the line width in the line and space pattern, etc., there is a possibility that LER may adversely affect the formation of a fine semiconductor element, and the improvement is required. have.

Although the reason why the said effect is acquired is not certain, since the length of the side chain part of a structural unit (a0) is long, and the oxygen atom (-O-) which is an electron-withdrawing group is introduced in the side chain part, It is assumed that the acid dissociable, dissolution inhibiting group is likely to dissociate and the dissociation efficiency is improved.

<< resist pattern formation method >>

Next, the resist pattern formation method of the 2nd aspect of this invention is demonstrated.

The resist pattern forming method of the present invention includes forming a resist film on a support using the positive resist composition of the present invention, exposing the resist film, and developing the resist film to form a resist pattern. do.

The resist pattern formation method of this invention can be performed as follows, for example.

That is, first, the positive resist composition is coated on a support with a spinner or the like, and the prebaking (post-applied bake (PAB)) is applied for 40 to 120 seconds under a temperature condition of 80 to 150 ° C, preferably 60 to After 90 seconds and selectively exposing ArF excimer laser light through a desired mask pattern, for example, by an ArF exposure apparatus or the like, PEB (post-exposure heating) is applied under a temperature condition of 80 to 150 ° C. 120 seconds, Preferably it is 60 to 90 seconds. This is then developed using an alkaline developer, for example 0.1-10% by mass of tetramethylammonium hydroxide (TMAH) aqueous solution, preferably rinsed with pure water, and dried. In some cases, a bake treatment (post bake) may be performed after the developing treatment. In this way, a resist pattern faithful to the mask pattern can be obtained.

It does not specifically limit as a support body, A conventionally well-known thing can be used, For example, the board | substrate for electronic components, the thing in which the predetermined wiring pattern was formed, etc. can be illustrated. More specifically, a metal substrate such as a silicon wafer, copper, chromium, iron or aluminum, or a glass substrate can be given. As a material of a wiring pattern, copper, aluminum, nickel, gold, etc. can be used, for example.

As the support, an inorganic and / or organic film may be formed on the substrate described above. An inorganic antireflection film (inorganic BARC) is mentioned as an inorganic film. As an organic type film | membrane, an organic antireflection film (organic BARC) is mentioned.

The wavelength used for exposure is not specifically limited, ArF excimer laser, KrF excimer laser, F ₂ excimer laser, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron beam), X-ray, soft X-ray, etc. This can be done using radiation. The resist composition is effective for KrF excimer lasers, ArF excimer lasers, EB or EUV, in particular ArF excimer lasers.

Exposure of a resist film may be normal exposure (dry exposure) performed in inert gas, such as air and nitrogen, or liquid immersion exposure may be sufficient as it.

In liquid immersion exposure, as described above, at the time of exposure, a portion of the lens, which is conventionally filled with an inert gas such as air or nitrogen, and a resist film on the wafer, has a refractive index greater than that of air (immersion medium). Exposure is performed in the state filled with.

More specifically, the liquid immersion exposure fills the gap between the resist film obtained as described above and the lens at the lowermost position of the exposure apparatus with a solvent (immersion medium) having a refractive index larger than that of air, and the desired mask pattern in that state. It can carry out by exposing through (immersion exposure).

As the liquid immersion medium, a solvent having a refractive index larger than that of air and smaller than the refractive index of the resist film exposed by the immersion exposure is preferable. The refractive index of such a solvent is not particularly limited as long as it is within the above range.

As a solvent which has a refractive index larger than the refractive index of air and smaller than the refractive index of a resist film, water, a fluorine-type inert liquid, a silicone type solvent, a hydrocarbon type solvent, etc. are mentioned, for example.

Specific examples of the fluorine-based inert liquid include liquids containing fluorine-based compounds such as C ₃ HCl ₂ F ₅ , C ₄ F ₉ OCH ₃ , C ₄ F ₉ OC ₂ H ₅ , and C ₅ H ₃ F ₇ as main components. It is preferable that a boiling point is 70-180 degreeC, and it is more preferable that it is 80-160 degreeC. If the fluorine-based inert liquid has a boiling point in the above-mentioned range, it is preferable since the removal of the medium used for the liquid immersion can be performed by a simple method after the end of the exposure.

Especially as a fluorine-type inert liquid, the perfluoroalkyl compound in which all the hydrogen atoms of the alkyl group were substituted by the fluorine atom is preferable. Specific examples of the perfluoroalkyl compound include a perfluoroalkyl ether compound and a perfluoroalkylamine compound.

Specifically, as the perfluoroalkyl ether compound, perfluoro (2-butyl-tetrahydrofuran) (boiling point 102 ° C) may be mentioned, and as the perfluoroalkylamine compound, perfluoro Rotributylamine (boiling point 174 degreeC) is mentioned.

Example

Next, although an Example demonstrates this invention further in detail, this invention is not limited by these examples.

Example 1

4.8 g of sodium hydride (NaH) was added to a 1 L three-necked flask, and 300 g of tetrahydrofuran (THF) was added while maintaining at 0 ° C. in an ice bath. ) Was added and stirred for 10 minutes. Thereafter, 30 g of compound (2) was added while stirring, and reacted for 12 hours. After completion of the reaction, the reaction solution was suction filtered and THF was removed from the recovered filtrate by concentration under pressure. Thereafter, water and ethyl acetate were added to the concentrate, followed by extraction. The resulting ethyl acetate solution was concentrated under reduced pressure, purified by column chromatography (SiO ₂ , heptane: ethyl acetate = 8: 2) and fractionation The mixture was concentrated under reduced pressure and further dried under reduced pressure to obtain 12 g of Compound (3).

[Formula 48]

About the obtained compound (3), ¹ H-NMR was measured. The results are shown below.

 From the results above, it was confirmed that the compound (3) had a structure shown below.

[Formula 49]

[Example 2]

5 g of compound (3), 3.04 g of triethylamine (Et ₃ N) and 10 g of THF were added to a 300 ml three-necked flask, followed by stirring for 10 minutes. Then, 2.09 g of compound (4) and 10 g of THF were added, and reacted at room temperature for 12 hours. After completion of the reaction, the reaction solution was suction filtered, and THF was removed from the recovered filtrate by concentration under reduced pressure. Thereafter, water and ethyl acetate were added to the concentrate, followed by extraction. The obtained ethyl acetate solution was purified by column chromatography (SiO ₂ , heptane: ethyl acetate = 8: 2), the fraction was concentrated under reduced pressure and dried under reduced pressure to obtain 4.9 g of compound (5).

[Formula 50]

¹ H-NMR was measured for the obtained compound (5). The results are shown below.

From the results above, it was confirmed that the compound (5) had a structure shown below.

[Formula 51]

Example 3

Into a 1 L three-necked flask, 4 g of NaH was added, 100 g of THF was added while maintaining at 0 ° C in an ice bath, and 10 g of Compound (6) was added while stirring, followed by stirring for 10 minutes. Then, 22.07g of compound (2) was added stirring, and it was made to react for 12 hours. After completion of the reaction, the reaction solution was suction filtered, and THF was removed from the recovered filtrate by concentration under reduced pressure. Thereafter, water and ethyl acetate were added to the concentrate, followed by extraction. The obtained ethyl acetate solution was concentrated under reduced pressure, purified by column chromatography (SiO ₂ , heptane: ethyl acetate = 8: 2), the fraction was concentrated under reduced pressure, and dried under reduced pressure, to obtain 10 g of compound (5).

[Formula 52]

Example 4 (Synthesis of Polymer Compound (1))

1.18 g of Compound (6), 1.90 g of Compound (5) obtained in Example 2, and 0.67 g of Compound (7) were dissolved in 15.00 g of methyl ethyl ketone. 0.71 mmol of Wako Pure Chemicals V-601 (polymerization initiator) was added to this solution, and it was dissolved. This was dripped at 6.25 g of methyl ethyl ketone heated at 75 degreeC for 6 hours in nitrogen atmosphere. After completion of the dropwise addition, the reaction solution was heated and stirred for 1 hour, after which the reaction solution was cooled to room temperature. Thereafter, the reaction solution was added dropwise to a large amount of methanol / water mixed solution, and the operation of precipitating the reaction product was repeated three times. The reaction product thus obtained was dried under reduced pressure at room temperature to obtain a white powder.

[Formula 53]

Let obtained reaction product be a high molecular compound (1). The structural formula is shown below.

For this polymer compound (1), as a result of measuring carbon 13 nuclear magnetic resonance spectrum (600 MHz_ ¹³ C-NMR) at 600 MHz, the polymer composition (the ratio (molar ratio of each structural unit in the structural formula) is l. / m / n = 38.7 / 38.0 / 23.3. In addition, the mass mean molecular weight of standard polystyrene conversion calculated | required by GPC measurement was 23200, and dispersion degree was 2.31. From this result, it turned out that the obtained high molecular compound (1) is a copolymer of a compound (6), a compound (5), and a compound (7).

[Formula 54]

Comparative Example 1 (Synthesis of Polymer Compound (2))

4.99 g of the compound (6), 7.00 g of the following compound (8), and 1.26 g of the compound (7) were dissolved in 53.00 g of methyl ethyl ketone. 5.86 mmol of Wako Pure Chemicals V-601 (polymerization initiator) was added to this solution, and it was dissolved. This was dripped at 22.08 g of methyl ethyl ketone heated at 75 degreeC for 6 hours in nitrogen atmosphere. After completion of the dropwise addition, the reaction solution was heated and stirred for 1 hour, after which the reaction solution was cooled to room temperature. Thereafter, the reaction solution was added dropwise to a large amount of methanol / water mixed solution, and the operation of precipitating the reaction product was repeated three times. The reaction product thus obtained was dried under reduced pressure at room temperature to obtain a white powder.

(55)

Let obtained reaction product be a high molecular compound (2). The structural formula is shown below.

For this polymer compound (2), as a result of measuring the carbon 13 nuclear magnetic resonance spectrum (600 MHz_ ¹³ C-NMR) at 600 MHz, the polymer composition (a ratio (molar ratio) of each structural unit in the structural formula) was l. / m / n = 45.0 / 44.9 / 10.1. In addition, the mass mean molecular weight of standard polystyrene conversion calculated | required by GPC measurement was 8400, and dispersion degree was 1.96. From this result, it turned out that the obtained high molecular compound (2) is a copolymer of a compound (6), a compound (8), and a compound (7).

(56)

Example 5, Comparative Example 2

Each component shown in Table 1 was mixed and dissolved, and the positive resist composition was prepared.

In Table 1, the numerical value in [] shows a compounding quantity (mass part). In addition, the symbol in Table 1 represents the following, respectively.

(A) -1: high molecular compound (1).

(A) -2: high molecular compound (2).

(B) -1: Acid generator represented by following General formula (B) -1.

(D) -1: tri-n-pentylamine.

(S) -1: PGMEA.

(S) -2: PGME.

(57)

The acid generator (B) -1 dissolves 6.99 g of triphenylsulfonium bromide in 125 ml of pure water, and 5.50 g of lithium salt of 2-naphthylmethyloxytetrafluoroethanesulfonic acid is added to the solution, and the room temperature is After stirring for 19 hours, 125 g of dichloromethane was added and stirred, the organic phase was separated and taken out, and the organic phase was washed with pure water 40 ml, and then separated and the organic phase was taken out, and the extracted organic phase was concentrated. It is obtained by drying.

Using the obtained resist composition, a resist pattern was formed in the following procedure and the lithographic characteristics were evaluated.

[Resolution and sensitivity]

The organic type antireflection film composition "ARC29A" (brand name, Brewer Science Co., Ltd.) was apply | coated using a spinner on an 8-inch silicon wafer, It baked at 205 degreeC for 60 second on a hotplate, and dried, and it was an organic type of 77 nm film thickness. An antireflection film was formed. The resist composition obtained above was apply | coated using the spinner on this antireflection film, and it pre-baked (PAB) -processes on 110 degreeC and 60 second conditions on a hotplate, and dried, and the resist of a film thickness of 120 nm A film was formed.

Subsequently, ArF excimer laser (193 nm) was made to mask pattern (6% halftone) by ArF exposure apparatus NSR-S302 (made by Nikon Corporation; NA (aperture number) = 0.60, 2/3 wheel illumination). It was selectively investigated through. Then, a post-exposure heating (PEB) treatment was performed under conditions of 100 ° C. and 60 seconds, further developed at 23 ° C. with a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution under conditions of 30 seconds, and then 30 The water was rinsed using pure water for a second time, and the water was shaken off and dried.

As a result, also in any example, the contact hole pattern of 130 nm in diameter and 260 nm in pitch was formed. The optimum exposure dose Eop (mJ / cm 2) at this time, that is, the sensitivity was determined. The results are shown in Table 2.

[Roundness]

The contact hole pattern of 130 nm in diameter and 260 nm in pitch formed above was observed over the air using the scanning electron microscope SEM, and the roundness of the hole pattern was evaluated on the following reference | standard. The results are shown in Table 2.

(Circle): Roundness is high.

(Triangle | delta): Low roundness.

As shown in said result, the roundness of the hole pattern of Example 5 was high and the sensitivity was also favorable.

Example 6 (Synthesis of Polymer Compound (3))

6.19 g (29.76 mmol) of the compound (6), 10.00 g (29.76 mmol) of the compound (5) and 3.51 g (14.88 mmol) of the compound (7) are added to 78.80 g of methyl ethyl ketone. Dissolved. 11.16 mmol of Wako Pure Chemicals V-601 (polymerization initiator) was added to this solution, and it was made to melt | dissolve. This was dripped at 32.83 g of methyl ethyl ketone heated at 75 degreeC for 6 hours in nitrogen atmosphere. After completion of the dropwise addition, the reaction solution was heated and stirred for 1 hour, after which the reaction solution was cooled to room temperature.

This polymerization liquid was concentrated to 30 mass% of solid content, it was dripped at 370 ml of n-heptane at room temperature, and the copolymer was deposited. Subsequently, 66 g of THF solution of this copolymer was prepared, and it was dripped at 370 ml of n-heptane, and the copolymer was deposited.

The copolymer is dispersed in a mixed solution of methanol / water = 60/40 (volume ratio) to clean the copolymer, and then dispersed in a mixed solution of methanol / water = 70/30 (volume ratio). After performing the operation | movement which washes a copolymer, it collect | recovered by filtration separation.

The copolymer thus obtained was dried at 40 ° C. for 3 days to obtain 13.0 g of white powder (yield 66%).

The obtained copolymer is made into the high molecular compound (3), and the structural formula is shown below. Carbon 13 nuclear magnetic resonance spectrum (600 MHz_ ¹³ C-NMR) of the polymer compound (3) was measured, and the polymer composition (the ratio (molar ratio) of each structural unit in the following structural formula) was l / m / n = 40.4 / 39.1 / 20.5. In addition, the mass mean molecular weight of the standard polystyrene conversion calculated | required by GPC measurement was 8,700, and dispersion degree was 2.18.

From this result, it was confirmed that the obtained high molecular compound (3) is a copolymer of the compound (6), the compound (5), and the compound (7).

(58)

Example 7 (Synthesis of Polymer Compound (4))

6.19 g (29.76 mmol) of the compound (6), 10.00 g (29.76 mmol) of the compound (5) and 3.51 g (14.88 mmol) of the compound (7) are added to 78.80 g of methyl ethyl ketone. Dissolved. 13.39 mmol of Wako Pure Chemicals V-601 (polymerization initiator) was added to this solution, and it was dissolved. This was dripped at 32.83 g of methyl ethyl ketone heated at 75 degreeC for 6 hours in nitrogen atmosphere. After completion of the dropwise addition, the reaction solution was heated and stirred for 1 hour, after which the reaction solution was cooled to room temperature.

This polymerization liquid was concentrated to 30 mass% of solid content, it was dripped at 370 ml of n-heptane at room temperature, and the copolymer was deposited. Subsequently, 66 g of THF solution of this copolymer was prepared, and it was dripped at 370 ml of n-heptane, and the copolymer was deposited.

The copolymer is dispersed in a mixed solution of methanol / water = 60/40 (volume ratio) to clean the copolymer, and then dispersed in a mixed solution of methanol / water = 70/30 (volume ratio). After performing the operation | movement which washes a copolymer, it collect | recovered by filtration separation.

Thus, the obtained copolymer was dried at 40 degreeC for 3 days, and 14.9 g of white powder was obtained (yield 76%).

The obtained copolymer is made into the high molecular compound (4), and the structural formula is shown below. The carbon 13 nuclear magnetic resonance spectra (600 MHz_ ¹³ C-NMR) of the polymer compound (4) were measured, and as a result, the polymer composition (a ratio (molar ratio) of each structural unit in the following structural formula) was l / m / n = 42.4 / 37.2 / 19.9. In addition, the mass mean molecular weight of standard polystyrene conversion calculated | required by GPC measurement was 6,400, and dispersion degree was 1.80.

From this result, it was confirmed that the obtained high molecular compound (4) is a copolymer of compound (6), compound (5), and compound (7).

[Chemical Formula 59]

Example 8 (Synthesis of Polymer Compound (5))

3.94 g (18.94 mmol) of the compound (6), 10.00 g (29.76 mmol) of the compound (5) and 4.47 g (18.94 mmol) of the compound (7) in 73.64 g of methyl ethyl ketone Dissolved. 12.17 mmol of Wako Pure Chemicals V-601 (polymerization initiator) was added to this solution, and it was dissolved. This was dripped at 30.68 g of methyl ethyl ketone heated at 75 degreeC for 6 hours in nitrogen atmosphere. After completion of the dropwise addition, the reaction solution was heated and stirred for 1 hour, after which the reaction solution was cooled to room temperature.

This polymerization liquid was concentrated to 30 mass% of solid content, it was dripped at 340 ml of n-heptane at room temperature, and the copolymer was deposited. Subsequently, 61 g of THF solution of this copolymer was prepared, and it was dripped at 340 ml of n-heptane, and the copolymer was deposited.

The copolymer is dispersed in a mixed solution of methanol / water = 60/40 (volume ratio) to clean the copolymer, and then dispersed in a mixed solution of methanol / water = 70/30 (volume ratio). After performing the operation | movement which washes a copolymer, it collect | recovered by filtration separation.

The copolymer thus obtained was dried at 40 ° C. for 3 days to obtain 13.8 g of white powder (yield 75%).

The obtained copolymer is made into the high molecular compound (5), and the structural formula is shown below. The carbon 13 nuclear magnetic resonance spectra (600 MHz_ ¹³ C-NMR) of the polymer compound (5) were measured, and as a result, the polymer composition (the ratio (molar ratio) of each structural unit in the following structural formula) was l / m / n = 30.5 / 39.0 / 30.5. In addition, the mass mean molecular weight of standard polystyrene conversion calculated | required by GPC measurement was 6,700, and dispersion degree was 1.99.

From this result, it was confirmed that the obtained high molecular compound (5) is a copolymer of compound (6), compound (5), and compound (7).

(60)

Example 9 (Synthesis of Polymer Compound (6))

4.99 g (23.99 mmol) of the compound (6), 7.00 g (20.83 mmol) of the compound (5), and 4.32 g (18.31 mmol) of the compound (7) in 65.24 g of methyl ethyl ketone Dissolved. 11.68 mmol of Wako Pure Chemicals V-601 (polymerization initiator) was added to this solution, and it was dissolved. This was dripped at 27.18 g of methyl ethyl ketone heated at 75 degreeC for 6 hours in nitrogen atmosphere. After completion of the dropwise addition, the reaction solution was heated and stirred for 1 hour, after which the reaction solution was cooled to room temperature.

This polymerization liquid was concentrated to 30 mass% of solid content, it was dripped at 320 ml of n-heptane at room temperature, and the copolymer was deposited. Subsequently, 54 g of THF solution of this copolymer was prepared, and it was dripped at 320 ml of n-heptane, and the copolymer was deposited.

The copolymer is dispersed in a mixed solution of methanol / water = 60/40 (volume ratio) to clean the copolymer, and then dispersed in a mixed solution of methanol / water = 70/30 (volume ratio). After performing the operation | movement which washes a copolymer, it collect | recovered by filtration separation.

The copolymer thus obtained was dried at 40 ° C. for 3 days to obtain 12.0 g of white powder (yield 74%).

The obtained copolymer is made into the high molecular compound (6), and the structural formula is shown below. The carbon 13 nuclear magnetic resonance spectra (600 MHz_ ¹³ C-NMR) of the polymer compound (6) were measured, and as a result, the polymer composition (a ratio (molar ratio) of each structural unit in the following structural formula) was l / m / n = 43.2 / 29.9 / 26.9. In addition, the mass mean molecular weight of standard polystyrene conversion calculated | required by GPC measurement was 7,500, and dispersion degree was 2.24.

From this result, it was confirmed that the obtained high molecular compound (6) is a copolymer of the compound (6), the compound (5), and the compound (7).

(61)

Example 10 (Synthesis of Polymer Compound (7))

6.30 g (30.30 mmol) of the compound (6), 7.00 g (20.83 mmol) of the compound (5) and 2.83 g (11.99 mmol) of the compound (7) are added to 64.52 g of methyl ethyl ketone. Dissolved. 11.68 mmol of Wako Pure Chemicals V-601 (polymerization initiator) was added to this solution, and it was dissolved. This was dripped at 26.88 g of methyl ethyl ketone heated at 75 degreeC for 6 hours in nitrogen atmosphere. After completion of the dropwise addition, the reaction solution was heated and stirred for 1 hour, after which the reaction solution was cooled to room temperature.

This polymerization liquid was concentrated to 30 mass% of solid content, it was dripped at 320 ml of n-heptane at room temperature, and the copolymer was deposited. Subsequently, 54 g of THF solution of this copolymer was prepared, and it was dripped at 320 ml of n-heptane, and the copolymer was deposited.

The copolymer is dispersed in a mixed solution of methanol / water = 60/40 (volume ratio) to clean the copolymer, and then dispersed in a mixed solution of methanol / water = 70/30 (volume ratio). After performing the operation | movement which washes a copolymer, it collect | recovered by filtration separation.

The copolymer thus obtained was dried at 40 ° C. for 3 days to obtain 12.0 g of white powder (yield 74%).

The obtained copolymer is used as a high molecular compound (7), and the structural formula thereof is shown below. The carbon 13 nuclear magnetic resonance spectra (600 MHz_ ¹³ C-NMR) of the polymer compound (7) were measured, and as a result, the polymer composition (the ratio (molar ratio) of each structural unit in the following structural formula) was l / m / n = 52.6 / 27.5 / 19.9. In addition, the mass mean molecular weight of standard polystyrene conversion calculated | required by GPC measurement was 5,300, and dispersion degree was 1.97.

From this result, it was confirmed that the obtained high molecular compound (7) is a copolymer of the compound (6), the compound (5), and the compound (7).

[Formula 62]

Example 11 (Synthesis of Polymer Compound (8))

2.94 g (13.26 mmol) of the following compound (9), 7.00 g (20.83 mmol) of the compound (5), and 3.13 g (13.26 mmol) of the compound (7) in 51.56 g of methyl ethyl ketone Dissolved. 8.76 mmol of Wako Pure Chemicals V-601 (polymerization initiator) was added to this solution, and it was dissolved. This was dripped at 21.48 g of methyl ethyl ketone heated at 75 degreeC for 6 hours in nitrogen atmosphere. After completion of the dropwise addition, the reaction solution was heated and stirred for 1 hour, after which the reaction solution was cooled to room temperature.

This polymerization liquid was concentrated to 30 mass% of solid content, it was dripped at 250 ml of n-heptane at room temperature, and the copolymer was deposited. Then, 44 g of THF solutions of this copolymer were prepared, and it was dripped at 250 ml of n-heptane, and the copolymer was deposited.

The copolymer is dispersed in a mixed solution of methanol / water = 60/40 (volume ratio) to clean the copolymer, and then dispersed in a mixed solution of methanol / water = 70/30 (volume ratio). After performing the operation | movement which washes a copolymer, it collect | recovered by filtration separation.

The copolymer thus obtained was dried at 40 ° C. for 3 days to obtain 9.3 g of white powder (yield 71%).

(63)

The obtained copolymer is made into the high molecular compound (8), and the structural formula is shown below. The carbon 13 nuclear magnetic resonance spectra (600 MHz_ ¹³ C-NMR) of the polymer compound (8) were measured, and as a result, the polymer composition (the ratio (molar ratio) of each structural unit in the following structural formula) was l / m / n = 31.5 / 38.3 / 30.2. In addition, the mass mean molecular weight of standard polystyrene conversion calculated | required by GPC measurement was 7,900, and dispersion degree was 2.13.

From this result, it was confirmed that the obtained high molecular compound (8) is a copolymer of the compound (9), the compound (5), and the compound (7).

&Lt; EMI ID =

Example 12 (Synthesis of Polymer Compound (9))

2.94 g (13.26 mmol) of the following compound (10), 7.00 g (20.83 mmol) of the compound (5) and 3.13 g (13.26 mmol) of the compound (7) were dissolved in 19.61 g of ethyl lactate. . To this solution, 3.3 mmol of Wako Pure Chemicals V-601 (polymerization initiator) was added and dissolved. This was dripped at 10.89 g of ethyl lactate heated at 80 degreeC for 6 hours in nitrogen atmosphere. After completion of the dropwise addition, the reaction solution was heated and stirred for 1 hour, after which the reaction solution was cooled to room temperature.

This polymer liquid was dripped at 250 ml of n-heptane at room temperature, and the copolymer was deposited. Then, 44 g of THF solutions of this copolymer were prepared, and it was dripped at 250 ml of n-heptane, and the copolymer was deposited.

The copolymer is dispersed in a mixed solution of methanol / water = 60/40 (volume ratio) to clean the copolymer, and then dispersed in a mixed solution of methanol / water = 70/30 (volume ratio). After performing the operation | movement which washes a copolymer, it collect | recovered by filtration separation.

The copolymer thus obtained was dried at 40 ° C. for 3 days to obtain 9.5 g of white powder (yield 73%).

(65)

The obtained copolymer is made into the high molecular compound (9), and the structural formula is shown below. The carbon 13 nuclear magnetic resonance spectra (600 MHz_ ¹³ C-NMR) of the polymer compound (9) were measured, and as a result, the polymer composition (a ratio (molar ratio) of each structural unit in the following structural formula) was l / m / n = 31.4 / 38.4 / 30.2. In addition, the mass mean molecular weight of standard polystyrene conversion calculated | required by GPC measurement was 7,800, and dispersion degree was 2.01.

From this result, it was confirmed that the obtained high molecular compound (9) is a copolymer of the compound (10), the compound (5), and the compound (7).

[Formula 66]

Example 13 (Synthesis of Polymer Compound (10))

6.30 g (30.30 mmol) of the compound (10), 7.00 g (20.83 mmol) of the compound (5) and 2.83 g (11.99 mmol) of the compound (7) are dissolved in 24.20 g of ethyl lactate. I was. To this solution, 4.5 mmol of Wako Pure Chemicals V-601 (polymerization initiator) was added and dissolved. This was dripped at 13.44 g of ethyl lactate heated at 80 degreeC under nitrogen atmosphere for 6 hours. After completion of the dropwise addition, the reaction solution was heated and stirred for 1 hour, after which the reaction solution was cooled to room temperature.

This polymer liquid was dripped at 320 ml of n-heptane at room temperature, and the copolymer was deposited. Subsequently, 54 g of THF solution of this copolymer was prepared, and it was dripped at 320 ml of n-heptane, and the copolymer was deposited.

The copolymer is dispersed in a mixed solution of methanol / water = 60/40 (volume ratio) to clean the copolymer, and then dispersed in a mixed solution of methanol / water = 70/30 (volume ratio). After performing the operation | movement which washes a copolymer, it collect | recovered by filtration separation.

The copolymer thus obtained was dried at 40 ° C. for 3 days to obtain 12.0 g of white powder (yield 74%).

The obtained copolymer is made into the high molecular compound (10), and the structural formula is shown below. The carbon 13 nuclear magnetic resonance spectra (600 MHz_ ¹³ C-NMR) of the polymer compound (10) were measured, and as a result, the polymer composition (a ratio (molar ratio) of each structural unit in the following structural formula) was l / m / n = 51.6 / 28.5 / 19.9. In addition, the mass mean molecular weight of standard polystyrene conversion calculated | required by GPC measurement was 7,300, and dispersion degree was 2.07. From this result, it was confirmed that the obtained high molecular compound (10) is a copolymer of the compound (10), the compound (5), and the compound (7).

(67)

Example 14 (Synthesis of Polymer Compound (11))

4.99 g (23.99 mmol) of the compound (10), 7.00 g (20.83 mmol) of the compound (5), and 4.32 g (18.31 mmol) of the compound (7) are dissolved in 24.47 g of ethyl lactate. I was. To this solution, 4.4 mmol of Wako Pure Chemicals V-601 (polymerization initiator) was added and dissolved. This was dripped at 13.59 g of ethyl lactate heated at 80 degreeC for 6 hours in nitrogen atmosphere. After completion of the dropwise addition, the reaction solution was heated and stirred for 1 hour, after which the reaction solution was cooled to room temperature.

This polymer liquid was dripped at 320 ml of n-heptane at room temperature, and the copolymer was deposited. Subsequently, 54 g of THF solution of this copolymer was prepared, and it was dripped at 320 ml of n-heptane, and the copolymer was deposited.

The copolymer is dispersed in a mixed solution of methanol / water = 60/40 (volume ratio) to clean the copolymer, and then dispersed in a mixed solution of methanol / water = 70/30 (volume ratio). After performing the operation | movement which washes a copolymer, it collect | recovered by filtration separation.

The copolymer thus obtained was dried at 40 ° C. for 3 days to obtain 12.0 g of white powder (yield 74%).

The obtained copolymer is made into the high molecular compound (11), and the structural formula is shown below. The carbon 13 nuclear magnetic resonance spectra (600 MHz_ ¹³ C-NMR) of the polymer compound (11) were measured, and as a result, the polymer composition (the ratio (molar ratio) of each structural unit in the following structural formula) was l / m / n = 42.2 / 30.9 / 26.9. In addition, the mass mean molecular weight of standard polystyrene conversion calculated | required by GPC measurement was 7,600, and dispersion degree was 2.14. From this result, it was confirmed that the obtained high molecular compound (11) is a copolymer of the compound (10), the compound (5), and the compound (7).

(68)

Example 15 (Synthesis of Polymer Compound (12))

6.19 g (29.76 mmol) of the compound (10), 10.00 g (29.76 mmol) of the compound (5) and 3.51 g (14.88 mmol) of the compound (7) are dissolved in 29.55 g of ethyl lactate. I was. To this solution, 5.2 mmol of Wako Pure Chemicals V-601 (polymerization initiator) was added and dissolved. This was dripped at 16.42 g of ethyl lactate heated at 80 degreeC for 6 hours in nitrogen atmosphere. After completion of the dropwise addition, the reaction solution was heated and stirred for 1 hour, after which the reaction solution was cooled to room temperature.

This copolymer was dripped at 370 ml of n-heptane at room temperature, and the copolymer was deposited. Subsequently, 66 g of THF solution of this copolymer was prepared, and it was dripped at 370 ml of n-heptane, and the copolymer was deposited.

The copolymer is dispersed in a mixed solution of methanol / water = 60/40 (volume ratio) to clean the copolymer, and then dispersed in a mixed solution of methanol / water = 70/30 (volume ratio). After performing the operation | movement which washes a copolymer, it collect | recovered by filtration separation.

The copolymer thus obtained was dried at 40 ° C. for 3 days to obtain 14.8 g of white powder (yield 75%).

The obtained copolymer is made into the high molecular compound (12), and the structural formula is shown below. The carbon 13 nuclear magnetic resonance spectra (600 MHz_ ¹³ C-NMR) of the polymer compound (12) were measured, and as a result, the polymer composition (a ratio (molar ratio) of each structural unit in the following structural formula) was l / m / n = 40.4 / 40.1 / 19.5. In addition, the mass mean molecular weight of standard polystyrene conversion calculated | required by GPC measurement was 7,700, and dispersion degree was 2.11. From this result, it was confirmed that the obtained high molecular compound (12) is a copolymer of the compound (10), the compound (5), and the compound (7).

[Formula 69]

Example 16 (Synthesis of Polymer Compound (13))

2.94 g (13.26 mmol) of the following compound (11), 7.00 g (20.83 mmol) of the compound (5) and 3.13 g (13.26 mmol) of the compound (7) are dissolved in 19.61 g of ethyl lactate. I was. To this solution, 3.3 mmol of Wako Pure Chemicals V-601 (polymerization initiator) was added and dissolved. This was dripped at 10.89 g of ethyl lactate heated at 80 degreeC for 6 hours in nitrogen atmosphere. After completion of the dropwise addition, the reaction solution was heated and stirred for 1 hour, after which the reaction solution was cooled to room temperature.

This polymer liquid was dripped at 250 ml of n-heptane at room temperature, and the copolymer was deposited. Then, 44 g of THF solutions of this copolymer were prepared, and it was dripped at 250 ml of n-heptane, and the copolymer was deposited.

The copolymer is dispersed in a mixed solution of methanol / water = 60/40 (volume ratio) to clean the copolymer, and then dispersed in a mixed solution of methanol / water = 70/30 (volume ratio). After performing the operation | movement which washes a copolymer, it collect | recovered by filtration separation.

Thus, the obtained copolymer was dried at 40 degreeC for 3 days, and 9.1g white powder was obtained (yield 70%).

(70)

The obtained copolymer is made into the high molecular compound (13), and the structural formula is shown below. The carbon 13 nuclear magnetic resonance spectra (600 MHz_ ¹³ C-NMR) of the polymer compound (13) were measured, and as a result, the polymer composition (a ratio (molar ratio) of each structural unit in the following structural formula) was l / m / n = 31.0 / 39.4 / 29.6. In addition, the mass mean molecular weight of standard polystyrene conversion calculated | required by GPC measurement was 7,700, and dispersion degree was 2.06. From this result, it was confirmed that the obtained high molecular compound (13) is a copolymer of the compound (11), the compound (5), and the compound (7).

(71)

Example 17 (Synthesis of Polymer Compound (14))

6.30 g (30.30 mmol) of the compound (11), 7.00 g (20.83 mmol) of the compound (5) and 2.83 g (11.99 mmol) of the compound (7) are dissolved in 24.20 g of ethyl lactate. I was. To this solution, 4.5 mmol of Wako Pure Chemicals V-601 (polymerization initiator) was added and dissolved. This was dripped at 13.44 g of ethyl lactate heated at 80 degreeC under nitrogen atmosphere for 6 hours. After completion of the dropwise addition, the reaction solution was heated and stirred for 1 hour, after which the reaction solution was cooled to room temperature.

This polymer liquid was dripped at 320 ml of n-heptane at room temperature, and the copolymer was deposited. Subsequently, 54 g of THF solution of this copolymer was prepared, and it was dripped at 320 ml of n-heptane, and the copolymer was deposited.

The copolymer is dispersed in a mixed solution of methanol / water = 60/40 (volume ratio) to clean the copolymer, and then dispersed in a mixed solution of methanol / water = 70/30 (volume ratio). After performing the operation | movement which washes a copolymer, it collect | recovered by filtration separation.

The copolymer thus obtained was dried at 40 ° C. for 3 days to obtain 12.2 g of white powder (yield 76%).

The obtained copolymer is made into the high molecular compound (14), and the structural formula is shown below. The carbon 13 nuclear magnetic resonance spectra (600 MHz_ ¹³ C-NMR) of the polymer compound (14) were measured, and as a result, the polymer composition (the ratio (molar ratio) of each structural unit in the following structural formula) was l / m / n = 51.9 / 28.8 / 19.3. In addition, the mass mean molecular weight of standard polystyrene conversion calculated | required by GPC measurement was 7,300, and dispersion degree was 2.07. From this result, it was confirmed that the obtained high molecular compound (14) is a copolymer of the compound (11), the compound (5), and the compound (7).

(72)

Example 18 (Synthesis of Polymer Compound (15))

4.99 g (23.99 mmol) of the compound (11), 7.00 g (20.83 mmol) of the compound (5), and 4.32 g (18.31 mmol) of the compound (7) are dissolved in 24.47 g of ethyl lactate. I was. To this solution, 4.4 mmol of Wako Pure Chemicals V-601 (polymerization initiator) was added and dissolved. This was dripped at 13.59 g of ethyl lactate heated at 80 degreeC for 6 hours in nitrogen atmosphere. After completion of the dropwise addition, the reaction solution was heated and stirred for 1 hour, after which the reaction solution was cooled to room temperature.

This polymer liquid was dripped at 320 ml of n-heptane at room temperature, and the copolymer was deposited. Subsequently, 54 g of THF solution of this copolymer was prepared, and it was dripped at 320 ml of n-heptane, and the copolymer was deposited.

The copolymer is dispersed in a mixed solution of methanol / water = 60/40 (volume ratio) to clean the copolymer, and then dispersed in a mixed solution of methanol / water = 70/30 (volume ratio). After performing the operation | movement which washes a copolymer, it collect | recovered by filtration separation.

The copolymer thus obtained was dried at 40 ° C. for 3 days to obtain 11.6 g of white powder (yield 71%).

The obtained copolymer is made into the high molecular compound (15), and the structural formula is shown below. The carbon 13 nuclear magnetic resonance spectra (600 MHz_ ¹³ C-NMR) of the polymer compound (15) were measured, and as a result, the polymer composition (a ratio (molar ratio) of each structural unit in the following structural formula) was l / m / n = 42.8 / 30.4 / 26.8. In addition, the mass mean molecular weight of standard polystyrene conversion calculated | required by GPC measurement was 7,200, and dispersion degree was 2.18. From this result, it was confirmed that the obtained high molecular compound (15) is a copolymer of the compound (11), the compound (5), and the compound (7).

(73)

Example 19 (Synthesis of Polymer Compound (16))

6.19 g (29.76 mmol) of the compound (11), 10.00 g (29.76 mmol) of the compound (5), and 3.51 g (14.88 mmol) of the compound (7) are dissolved in 29.55 g of ethyl lactate. I was. To this solution, 5.2 mmol of Wako Pure Chemicals V-601 (polymerization initiator) was added and dissolved. This was dripped at 16.42 g of ethyl lactate heated at 80 degreeC for 6 hours in nitrogen atmosphere. After completion of the dropwise addition, the reaction solution was heated and stirred for 1 hour, after which the reaction solution was cooled to room temperature.

This copolymer was dripped at 370 ml of n-heptane at room temperature, and the copolymer was deposited. Subsequently, 66 g of THF solution of this copolymer was prepared, and it was dripped at 370 ml of n-heptane, and the copolymer was deposited.

The copolymer is dispersed in a mixed solution of methanol / water = 60/40 (volume ratio) to clean the copolymer, and then dispersed in a mixed solution of methanol / water = 70/30 (volume ratio). After performing the operation | movement which washes a copolymer, it collect | recovered by filtration separation.

The copolymer thus obtained was dried at 40 ° C. for 3 days to obtain 13.8 g of white powder (yield 70%).

The obtained copolymer is made into the high molecular compound (16), and the structural formula is shown below. The carbon 13 nuclear magnetic resonance spectra (600 MHz_ ¹³ C-NMR) of the polymer compound (16) were measured, and as a result, the polymer composition (a ratio (molar ratio) of each structural unit in the following structural formula) was l / m / n = 40.9 / 39.8 / 19.3. In addition, the mass mean molecular weight of standard polystyrene conversion calculated | required by GPC measurement was 7,700, and dispersion degree was 2.11. From this result, it was confirmed that the obtained high molecular compound (16) is a copolymer of the compound (11), the compound (5), and the compound (7).

&Lt; EMI ID =

[Examples 20-33]

Each component shown in Table 3 was mixed and dissolved, and the positive resist composition was prepared.

The numerical value shown in [] of Table 3 is a compounding quantity (mass part). In addition, the symbol of Table 3 shows the following.

(A) -3: high molecular compound (4).

(B) -1: The acid generator represented by the said general formula (B) -1.

(B) -2: Acid generator represented by following General formula (B) -2.

(B) -3: Acid generator represented by following General formula (B) -3.

(D) -1: tri-n-pentylamine.

(D) -2: diethanolamine

(D) -3: tris (2-methoxymethoxyethyl) amine.

(D) -4: tris {2- (2-methoxyethoxymethoxy) ethyl} amine

(S) -1: PGMEA.

(S) -2: PGME.

(75)

[Formula 76]

The resist pattern was formed in the following procedures using the obtained resist composition, and the lithographic characteristics were evaluated.

[Resolution and sensitivity]

The organic type antireflection film composition "ARC29A" (brand name, Brewer Science Co., Ltd.) was apply | coated using a spinner on an 8-inch silicon wafer, It baked at 205 degreeC for 60 second on a hotplate, and dried, and it was an organic type of 77 nm film thickness. An antireflection film was formed. The resist composition obtained above was apply | coated using the spinner on this antireflection film, respectively, and it performs 60 second prebaking (PAB) process at the temperature shown in Table 3, and forms a resist film with a film thickness of 120 nm. It was.

Subsequently, an ArF excimer laser (193 nm) was selectively selected through a mask pattern (6% halftone) by an ArF exposure apparatus NSR-S302 (manufactured by Nikon Corporation; NA (number of apertures) = 0.60, 2/3 annular illumination). Investigate. And post-exposure heating (PEB) treatment is performed on the conditions shown in Table 3 for 60 second, and it develops on the conditions for 30 second with 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution at 23 degreeC, The water was then rinsed with pure water for 30 seconds, and the water was shaken off and dried.

As a result, also in any example, the contact hole pattern of 140 nm in diameter and 280 nm in pitch was formed. Table 3 shows the optimum exposure dose Eop (mJ / cm 2), that is, the sensitivity at this time.

[Roundness]

The contact hole pattern of 140 nm in diameter and 280 nm in pitch formed above was observed over the air using a scanning electron microscope (SEM), and the roundness of the hole pattern was evaluated on the following reference | standard. The results are shown in Table 3.

(Double-circle): The roundness is very high (unevenness | corrugation was not observed in the peripheral part of the hole pattern observed from the air | atmosphere, and it was a very favorable shape).

(Circle): High roundness (An unevenness | corrugation was observed slightly in the circumference part of the hole pattern observed from the sky, but it was a shape with high roundness as a whole).

[Examples 34 to 36]

Each component shown in Table 4 was mixed and dissolved, and the positive resist composition was prepared.

The numerical value shown in [] of Table 4 is compounding quantity (mass part). In addition, the symbol of Table 4 shows the following.

(A) -4: high molecular compound (6).

(A) -5: high molecular compound (7).

(A) -6: high molecular compound (8).

(B) -3: Acid generator represented by the said General formula (B) -3.

(D) -5: stearyldiethanolamine.

(S) -1: PGMEA.

(S) -2: PGME.

The resist pattern was formed in the following procedures using the obtained resist composition, and the lithographic characteristics were evaluated.

[Resolution and sensitivity]

The organic type antireflection film composition "ARC29" (brand name, Brewer Science Co., Ltd.) was apply | coated using a spinner on an 8-inch silicon wafer, and it baked on 205 degreeC and 60 second on a hotplate, and dried, and it was an organic type of 89 nm film thickness. An antireflection film was formed. The resist composition obtained above is apply | coated using the spinner on this antireflection film, and it pre-bakes (PAB) -processes on 90 degreeC and 60 second conditions on a hotplate, and it is made to dry, and the resist of a film thickness of 120 nm A film was formed.

Next, on the said resist film, the coating liquid "TSRC-002" (brand name, Tokyo Chemical Industry Co., Ltd. product) for protective film formation is apply | coated using a spinner, and it heats at 90 degreeC for 60 second, and is a tower of a film thickness of 28 nm. A coat was formed.

Subsequently, with respect to the resist film on which the top coat was formed, the liquid immersion ArF exposure apparatus NSR-S609B (manufactured by Nikon Corporation; NA (number of openings) = 1.07, 2/3 ring zone illumination, reduced magnification 1/4 times, liquid immersion medium: water) ), The ArF excimer laser (193 nm) was selectively irradiated through a mask pattern (6% halftone).

Next, the top coat was removed using a protective film removal liquid "TS-Rememover-S" (trade name, manufactured by Tokyo Chemical Industry Co., Ltd.), and then subjected to PEB treatment at 90 ° C for 60 seconds, and further to 2.38 at 23 ° C. Alkali image development was carried out by mass% TMAH aqueous solution NMD-W (brand name, Tokyo Chemical Industry Co., Ltd. make) for 30 second conditions, and water rinsed using pure water for 25 second after that, water was shaken off, and it dried.

As a result, also in any example, the contact hole pattern of diameter 70nm and pitch 150nm was formed. Table 4 shows the optimum exposure dose Eop (mJ / cm 2), that is, the sensitivity at this time.

[Roundness]

The contact hole pattern of 70 nm in diameter and 150 nm in pitch formed above was observed over the air using a scanning electron microscope (SEM), and the roundness of the hole pattern was evaluated on the following reference | standard. The results are shown in Table 4.

(Double-circle): The roundness is very high (unevenness | corrugation was not observed in the peripheral part of the hole pattern observed from the air | atmosphere, and it was a very favorable shape).

(Circle): High roundness (An unevenness | corrugation was observed slightly in the circumference part of the hole pattern observed from the sky, but it was a shape with high roundness as a whole).

Claims (21)

delete delete delete delete delete delete delete delete delete A step of reacting a compound represented by the following General Formula (I-1) with a compound represented by the following General Formula (I-2) to obtain a compound represented by the following General Formula (I-3), and A process of reacting a compound represented by the following General Formula (I-3) with a compound represented by the following General Formula (I-4) to obtain a compound represented by the following General Formula (I); The manufacturing method of the compound represented by I). [Formula 4]

[In formula, R <^1> is a hydrogen atom, a lower alkyl group, or a halogenated lower alkyl group, A is a C2 or more bivalent hydrocarbon group which may have a substituent, B is a C1 or more bivalent hydrocarbon group which may have a substituent, R ² is an acid dissociable, dissolution inhibiting group, X ¹⁰ and X ¹² are each independently a hydroxyl group or a halogen atom, one of X ¹⁰ and X ¹² is a hydroxyl group, the other is a halogen atom, and X ¹¹ is a halogen atom] A process of reacting a compound represented by the following General Formula (I-5) with a compound represented by the following General Formula (I-2) to obtain a compound represented by the following General Formula (I); The manufacturing method of the compound represented by I). [Chemical Formula 5]

[Wherein, R ¹ is a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group, A is a C 2 or more divalent hydrocarbon group which may have a substituent, B is a C 1 or more divalent hydrocarbon group which may have a substituent, R ² is an acid dissociable, dissolution inhibiting group, and X ¹¹ is a halogen atom] The compound represented by the following general formula (II). [Formula 6]

[Wherein, A 'is a C 2 or more divalent hydrocarbon group which may have a substituent, B' is a C 1 or more divalent hydrocarbon group which may have a substituent, R ^{2 '} is an acid dissociable, dissolution inhibiting group, and X ¹⁰ is hydroxyl or halogen atom] delete delete delete delete delete delete delete delete delete