JP5416889B2 - Resist polymer, resist composition, and method for producing substrate on which pattern is formed - Google Patents

Description

  The present invention relates to a resist polymer, a resist composition containing the same, and a method for producing a substrate on which a pattern is formed, and more particularly to a resist composition suitable for fine processing using excimer laser and electron beam lithography.

  In recent years, in the field of microfabrication in the manufacture of semiconductor elements and liquid crystal elements, miniaturization has rapidly progressed due to advances in lithography technology. As a method for miniaturization, generally, the irradiation light has a shorter wavelength, and specifically, from conventional ultraviolet rays typified by g-line (wavelength: 438 nm) and i-line (wavelength: 365 nm). The irradiation light is changing to a shorter wavelength DUV (Deep Ultra Violet).

  At present, KrF excimer laser (wavelength: 248 nm) lithography technology has been introduced to the market, and ArF excimer laser (wavelength: 193 nm) lithography technology and EUV excimer laser (wavelength: 13 nm) lithography technology for further shortening the wavelength have been studied. ing. Recently, these immersion lithography techniques have also been studied. Also, as a different type of lithography technology, electron beam lithography technology has been energetically studied.

  As a high-resolution resist using such short-wavelength irradiation light or electron beam, a “chemically amplified resist” containing a photoacid generator has been proposed, and improvement and development of this chemically amplified resist are currently underway. It has been.

  For example, as a chemically amplified resist resin used in ArF excimer laser lithography, an acrylic resin that is transparent with respect to light having a wavelength of 193 nm has attracted attention. As such an acrylic resin, for example, a polymer of (meth) acrylic acid ester having an adamantane skeleton in the ester portion and a polymer of (meth) acrylic acid ester having a lactone skeleton in the ester portion is disclosed in Patent Document 1, Patent Document 2, and the like. Is disclosed.

  However, when these acrylic resins are used as a resist composition, the depth of focus may not be sufficient, which may lead to a decrease in yield in the actual resist pattern manufacturing process.

  Further, a development defect called a defect may occur during the development process using an alkali developer for producing a resist pattern. Then, due to this defect, the resist pattern may be missing, causing circuit disconnection, defects, and the like, which may lead to a decrease in yield in the semiconductor manufacturing process.

  Furthermore, there is a concern that the dry etching resistance is insufficient due to the thin film thickness of the resist.

  On the other hand, Patent Document 3, Patent Document 4, Patent Document 5 and the like disclose polymers having an aromatic ring or a heteroaromatic ring.

However, although these resins are excellent in dry etching resistance, especially in the case of ArF excimer laser (wavelength: 193 nm) lithography, the light transmittance of the polymer at the exposure wavelength is often insufficient, which adversely affects sensitivity and resolution. there is a possibility.
JP 10-319595 A JP-A-10-274852 JP 2005-114968 A JP 2004-163877 A JP 2006-276458 A

  The present invention is a dry etching that has high sensitivity, high resolution, high light transmittance, few defects during development, and can resist resist film thinning when used as a resist composition in DUV excimer laser lithography and the like. An object of the present invention is to provide a resist monomer having resistance, a resist polymer, a resist composition containing the resist polymer, and a method for producing a substrate on which a pattern using the resist composition is formed.

  The present invention relates to a resist polymer containing a structural unit (A) having a naphthalene skeleton represented by the following formula (1-1), and relates to a resist composition containing the resist polymer. The present invention relates to a method for producing a substrate on which a pattern using the resist composition is formed.

(In Formula (1-1), R ¹⁰ represents a hydrogen atom or a methyl group. Y represents —C (═O) —OH, —CH ₂ —C (═O) —OH, —OH, —C ( ═O) —OR ¹³ , —CH ₂ —C (═O) —OR ¹³ , or —OR ¹³ , wherein R ¹³ represents a linear, branched, or cyclic hydrocarbon group having 1 to 20 carbon atoms. The hydrocarbon group may have a hetero atom, L ¹ represents —CH ₂ —R ¹⁴ —CH ₂ —O—, wherein R ¹⁴ represents a single bond or a straight chain having 1 to 20 carbon atoms. Represents a hydrocarbon group of a chain, and this hydrocarbon group may have a hetero atom between the chains, X ¹ is a linear or branched alkyl group having 1 to 6 carbon atoms, a hydroxyl group, a carboxyl group, Esterified with an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and an alcohol having 1 to 6 carbon atoms Carboxyl represents a group or an amino group,. A linear or branched alkyl group having 1 to 6 carbon atoms wherein X ¹ is a hydroxyl group as a substituent, a carboxyl group, an acyl group having 1 to 6 carbon atoms, 1 to 6 carbon atoms And at least one group selected from the group consisting of a carboxyl group esterified with an alcohol having 1 to 6 carbon atoms, a cyano group, and an amino group, and h11 represents an integer of 0 to 4. (In addition, when h11 is 2 or more, it includes that X ¹ has a plurality of different groups.)

  The present invention also relates to a polymerizable monomer having a naphthalene skeleton represented by the following formula (1-4).

(In formula (1-4), R ¹⁰ represents a hydrogen atom or a methyl group. Y represents —C (═O) —OH, —CH ₂ —C (═O) —OH, —OH, —C ( ═O) —OR ¹³ , —CH ₂ —C (═O) —OR ¹³ , or —OR ¹³ , wherein R ¹³ represents a linear, branched, or cyclic hydrocarbon group having 1 to 20 carbon atoms. The hydrocarbon group may have a hetero atom, L ¹ represents —CH ₂ —R ¹⁴ —CH ₂ —O—, wherein R ¹⁴ represents a single bond or a straight chain having 1 to 20 carbon atoms. Represents a hydrocarbon group of a chain, and this hydrocarbon group may have a hetero atom between the chains, X ¹ is a linear or branched alkyl group having 1 to 6 carbon atoms, a hydroxyl group, a carboxyl group, Esterified with an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and an alcohol having 1 to 6 carbon atoms Carboxyl represents a group or an amino group,. A linear or branched alkyl group having 1 to 6 carbon atoms wherein X ¹ is a hydroxyl group as a substituent, a carboxyl group, an acyl group having 1 to 6 carbon atoms, 1 to 6 carbon atoms And at least one group selected from the group consisting of a carboxyl group esterified with an alcohol having 1 to 6 carbon atoms, a cyano group, and an amino group, and h11 represents an integer of 0 to 4. (In addition, when h11 is 2 or more, it includes that X ¹ has a plurality of different groups.)

  When the polymerizable monomer of the present invention is copolymerized with a polymerizable monomer such as (meth) acrylic acid or (meth) acrylic acid ester, a copolymer having good composition and a uniform composition can be obtained. it can.

  The resist composition containing the resist polymer of the present invention has high sensitivity, high resolution, wide depth of focus, high light transmittance with respect to excimer laser light, few defects during development, and thinning of the resist film. It has a high dry etching resistance and can be copolymerized with other monomers.

  In addition, when the resist polymer of the present invention is used as a resist composition for immersion, a resist pattern can be formed with high resolution. Therefore, the resist polymer and resist composition of the present invention can be suitably used for DUV excimer laser lithography, these immersion lithography and electron beam lithography, particularly ArF excimer laser lithography and this immersion lithography.

  Furthermore, a substrate on which a highly accurate fine pattern is formed can be manufactured by the manufacturing method of the present invention.

  The resist polymer of the present invention will be described.

  The resist polymer of the present invention contains a structural unit (A) having a naphthalene skeleton represented by the following formula (1-1).

R ¹⁰ in formula (1-1) represents a hydrogen atom or a methyl group.

^{L 1} in the formula (1-1), ^{L 1} _{represents -CH} ² -R 14 -CH ² -O-. R ¹⁴ represents a single bond or a straight chain hydrocarbon group having 1 to 20 carbon atoms, and this hydrocarbon group may have a hetero atom between the chains.

  Although it does not restrict | limit especially as a hetero atom, For example, a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, etc. are mentioned.

The L ^1, is not particularly limited, for example, the following formulas (2-1) to (2-29) can be mentioned. Note that the present invention is not limited to these examples.

L ¹ in formula (1-1) represents the above-described formulas (2-1) to (2-7), (2-13), and (2-16) from the viewpoint of the glass transition temperature and transmittance of the polymer. , (2-19), (2-20), (2-22), (2-23), (2-25), and a structure represented by (2-26) are preferable.

Y in Formula (1-1) represents —C (═O) —OH, —CH ₂ —C (═O) —OH, —OH, —C (═O) —OR ¹³ , —CH ₂ —C. (═O) —OR ¹³ or —OR ¹³ , wherein R ¹³ represents a linear, branched, or cyclic hydrocarbon group having 1 to 20 carbon atoms, and this hydrocarbon group has a hetero atom. May be. Examples of the hetero atom include those described above.

From the viewpoint of 193 nm transmittance, sensitivity, and rectangularity, Y is preferably —CH ₂ —C (═O) —OH, —C (═O) —OR ¹³ , —OH, —OR ¹³ , —OR ¹³ , — OH is particularly preferred.

The R ^13, is not particularly limited, for example, the following formula (3-1) to (3-30) can be mentioned. Note that the present invention is not limited to these examples.

  Among these, the formulas (3-21) to (3-24) are preferable in terms of transmittance. In terms of sensitivity, the formulas (3-1), (3-2), the formulas (3-13), (3-14), and the formulas (3-25) to (3-30) are preferable.

X ¹ is preferably a linear or branched alkyl group having 1 to 6 carbon atoms having a hydroxy group or a hydroxy group or a cyano group as a substituent from the viewpoint of reducing defects in the resist composition and improving pattern rectangularity.

  h11 is preferably 0 from the viewpoint of resolution.

The structural unit (A) having a naphthalene skeleton represented by the formula (1-1) may be one type or two or more types.
The structural unit (A) having a naphthalene skeleton represented by the formula (1-1) is preferably the following formulas (1-2) and (1-3) from the viewpoint of transparency to 193 nm excimer laser light. .

In formulas (1-2) and (1-3), R ¹⁰ , L ¹ , and Y have the same meanings as formula (1-1), respectively.

  The structural unit (A) having a naphthalene skeleton represented by formulas (1-2) and (1-3) can be used alone or in combination of two or more as necessary.

  The content of the structural unit (A) having a naphthalene skeleton represented by the formulas (1-2) and (1-3) is not particularly limited, but from the viewpoint of dry etching resistance and refractive index, In a structural unit, 2 mol% or more is preferable and 4 mol% or more is more preferable. Further, in terms of sensitivity and resolution, 20 mol% or less is preferable, 15 mol% or less is more preferable, and 10 mol% or less is more preferable.

  The polymer containing the structural unit (A) having a naphthalene skeleton represented by the formula (1-1) gives the structural unit (A) having a naphthalene skeleton, and is represented by the following formula (1-4) It can be produced by polymerizing a composition containing a polymerizable monomer (hereinafter also referred to as monomer (a)).

In formula (1-4), R ¹⁰ , Y, L ¹ , X ¹ , and h11 are synonymous with formula (1-1).

  Moreover, the polymer containing the structural unit (A) having a naphthalene skeleton represented by the formulas (1-2) and (1-3) gives the structural unit (A) having a naphthalene skeleton. -5), It can manufacture by superposing | polymerizing the composition containing the monomer (a) represented by (1-6).

In formulas (1-5) and (1-6), R ¹⁰ , L ¹ , and Y have the same meaning as in formula (1-1).

  The monomer (a) represented by the formula (1-4) is not particularly limited, and examples thereof include monomers represented by the following formulas (8-1) to (8-117). In formulas (8-1) to (8-117), R represents a hydrogen atom or a methyl group.

  Among these, from the viewpoint of transmittance, (8-1), formula (8-3), formula (8-5) to (8-8), formula (8-10) to (8-16), formula (8) -18) to (8-25), monomers represented by formulas (8-27) to (8-36), formulas (8-38) to (8-117), and geometric isomers thereof and Optical isomers are preferable, and the above formula (8-1), formula (8-3), formula (8-15) (8-16), formula (8-18), formula (8-20) to (8-) 22), Formula (8-24) (8-25), Formula (8-35) (8-36), Formula (8-38), Formula (8-40) to Formula (8-43), Formula ( 8-45) to (8-47), Formula (8-50), Formula (8-56) to (8-60), Formula (8-62) to (8-67), Formula (8-72) To (8-77), formulas (8-87) to (8-96), formulas (8-98) to (8- 05), formula (8-113) (8-114) monomer represented by the formula (8-117) is more preferred.

  When the resist polymer of the present invention contains a structural unit (A) having a naphthalene skeleton represented by the formula (1-1), when used as a resist composition for immersion exposure, an immersion liquid is particularly used. In the case of pure water, the effect of reducing the defect of the resist composition is also achieved.

In the resist polymer containing the structural unit (A), when the structural unit (A) has an acid leaving group (when Y is an acid leaving group), the acid leaving group is By desorption, it becomes soluble in alkali, and a resist pattern can be formed. In the case where the structural unit (A) does not have an acid leaving group (when Y is —CH ₂ —C (═O) —OH, —C (═O) —OH or —OH). Since the structural unit (A) itself has an acidic group, the resist polymer containing the structural unit (A) becomes soluble in alkali and enables formation of a resist pattern.

  In the case where the structural unit (A) has an acid-eliminable group, it corresponds to the structural unit (C) described later. In the present invention, such a structural unit is a structural unit ( A).

  Further, when the structural unit (A) has a hydrophilic group, the resist pattern rectangularity tends to be good. In this case, the structural unit (A) corresponds to a structural unit (D) to be described later, but in the present invention, such a structural unit is regarded as the structural unit (A).

  The resist polymer of the present invention contains the structural unit (A) having a naphthalene skeleton represented by the formula (1-1), and if necessary, the structural unit (B) having a lactone skeleton. Other structural units such as a structural unit (C) having an acid leaving group and a structural unit (D) having a hydrophilic group may be contained.

  The structural unit (B) having a lactone skeleton will be described.

  The structural unit (B) having a lactone skeleton is preferably used as a structural component of the resist polymer because it exerts the effect of developing the adhesion of the resist composition to the substrate.

  The content of the structural unit (B) is not particularly limited, but is preferably 30 mol% or more, more preferably 35 mol% or more, in the structural unit of the resist polymer, from the viewpoint of adhesion to the substrate. Further, in terms of resist sensitivity and resolution, it is preferably 60 mol% or less, more preferably 55 mol% or less, and even more preferably 50 mol% or less.

  Further, when the structural unit (B) has a group that is decomposed or eliminated by the action of an acid, it tends to have better sensitivity. In this case, the structural unit (B) corresponds to a structural unit (C) described later, but in the present invention, such a structural unit is regarded as the structural unit (B).

  Further, when the structural unit (B) has a hydrophilic group, the resist pattern rectangularity tends to be good. In this case, the structural unit (B) corresponds to a structural unit (D) to be described later, but in the present invention, such a structural unit is regarded as the structural unit (B).

  The structural unit (B) having a lactone skeleton is not particularly limited, but is at least one selected from the group consisting of the following formulas (4-1) to (4-6) from the viewpoint of sensitivity or dry etching resistance. It is preferable.

In formula (4-1), R ⁴¹ represents a hydrogen atom or a methyl group, and R ⁴⁰¹ and R ⁴⁰² each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a hydroxy group, or a carboxy group. Or a carboxy group esterified with an alcohol having 1 to 6 carbon atoms, or R ⁴⁰¹ and R ⁴⁰² together form —O—, —S—, —NH—, or a chain length of 1 to 6 Methylene chain [— (CH ₂ ) _j — (j represents an integer of 1 to 6)].

i represents 0 or 1, X ⁵ represents a linear or branched alkyl group having 1 to 6 carbon atoms, a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, carbon A carboxy group esterified with an alcohol having a number of 1 to 6 or an amino group is represented. The linear or branched alkyl group having 1 to 6 carbon atoms is a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an alcohol having 1 to 6 carbon atoms as a substituent. It may have at least one group selected from the group consisting of esterified carboxy group, cyano group, and amino group.

n5 represents an integer of 0 to 4, and m represents 1 or 2. Incidentally, also includes having a plurality of different groups as X ⁵ in the case of n5 is 2 or more.

Wherein ^{(4-2), R 42} represents a hydrogen atom or a methyl ^group, each R ^{201, R 202} is independently hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, hydroxy group, carboxy group Or a carboxy group esterified with an alcohol having 1 to 6 carbon atoms.

Each of A ¹ and A ² independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a hydroxy group, a carboxy group, or a carboxy group esterified with an alcohol having 1 to 6 carbon atoms; Or A ¹ and A ² are taken together to form —O—, —S—, —NH— or a methylene chain having a chain length of 1 to 6 [— (CH ₂ ) _k — (k is an integer of 1 to 6) Represents)].

X ⁶ is an ester of a linear or branched alkyl group having 1 to 6 carbon atoms, a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an alcohol having 1 to 6 carbon atoms. Represents a carboxy group, a cyano group or an amino group. The linear or branched alkyl group having 1 to 6 carbon atoms is a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, a carboxy group esterified with an alcohol having 1 to 6 carbon atoms, or a cyano group. And at least one group selected from the group consisting of amino groups.

n6 represents an integer of 0 to 4. Incidentally, also includes having a plurality of different groups as X ⁶ in the case of n6 is 2 or more.

In formula (4-3), R ⁴³ represents a hydrogen atom or a methyl group, and R ²⁰³ and R ²⁰⁴ each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a hydroxy group, or a carboxy group. Or a carboxy group esterified with an alcohol having 1 to 6 carbon atoms.

Each of A ³ and A ⁴ independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a hydroxy group, a carboxy group, or a carboxy group esterified with an alcohol having 1 to 6 carbon atoms; Or A ³ and A ⁴ are taken together to form —O—, —S—, —NH—, or a methylene chain having a chain length of 1 to 6 [— (CH ₂ ) ₁ — (l is an integer of 1 to 6) Represents)].

X ⁷ is an ester of a linear or branched alkyl group having 1 to 6 carbon atoms, a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an alcohol having 1 to 6 carbon atoms. Represents a carboxy group, a cyano group, or an amino group. The linear or branched alkyl group having 1 to 6 carbon atoms is a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, a carboxy group esterified with an alcohol having 1 to 6 carbon atoms, or a cyano group. And at least one group selected from the group consisting of amino groups.

n7 represents an integer of 0 to 4. Incidentally, also includes having a plurality of different groups as X ⁷ in the case of n7 is 2 or more.

In formula (4-4), R ⁴⁴ represents a hydrogen atom or a methyl group, and R ²⁰⁵ , R ²⁰⁶ , and R ²⁰⁷ each independently represent a hydrogen atom or a methyl group. Y ¹¹ , Y ¹² and Y ¹³ each independently represent —CH ₂ — or —C (═O) —O—, and at least one of them represents —C (═O) —O—.

X ⁸ represents a linear or branched alkyl group having 1 to 6 carbon atoms, hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an ester with an alcohol having 1 to 6 carbon atoms Represents a carboxy group, a cyano group, or an amino group. The linear or branched alkyl group having 1 to 6 carbon atoms is a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, a carboxy group esterified with an alcohol having 1 to 6 carbon atoms, or a cyano group. And at least one group selected from the group consisting of amino groups.

n8 represents an integer of 0 to 4. Incidentally, also includes having a plurality of different groups as X ⁸ in the case of n8 is 2 or more.

In formula (4-5), R ⁹¹ , R ⁹² , R ⁹³ and R ⁹⁴ each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a hydroxy group, a carboxy group, or a carbon number of 1 Represents a carboxy group esterified with ˜6 alcohols, or R ⁹¹ and R ⁹² together represent —O—, —S—, —NH—, or a methylene chain having a chain length of 1 to 6 [ _{- (CH 2) t - (} t is an integer of 1 to 6) represents a], m1 represents 1 or 2. )

Wherein (4-6), R45 represents a hydrogen atom or a methyl ^group, each R ^{208, R 209} is independently hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, hydroxy group, carboxy group, Alternatively, it represents a carboxy group esterified with an alcohol having 1 to 6 carbon atoms.

R ²¹⁰ and R ²¹¹ each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms. Each of A ⁵ and A ⁶ independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a hydroxy group, a carboxy group, or a carboxy group esterified with an alcohol having 1 to 6 carbon atoms; Or A ⁵ and A ⁶ are combined together to form —O—, —S—, —NH—, or a methylene chain having a chain length of 1 to 6 [— (CH ₂ ) _k1 — (k1 is an integer of 1 to 6] Represents)]. Y ²¹ and Y ²² each independently represent —CH ₂ — or —C (═O) —, and at least one of them represents —C (═O) —.

X ⁹ is an ester of a linear or branched alkyl group having 1 to 6 carbon atoms, a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an alcohol having 1 to 6 carbon atoms. Represents a carboxy group, a cyano group, or an amino group. The linear or branched alkyl group having 1 to 6 carbon atoms is a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, a carboxy group esterified with an alcohol having 1 to 6 carbon atoms, or a cyano group. And at least one group selected from the group consisting of amino groups. n9 represents an integer of 0 to 4. Incidentally, also includes having a plurality of different groups as X ⁹ in the case of n9 is 2 or more.

  N5 in the formula (4-1) is preferably 0 from the viewpoint of high dry etching resistance.

  M in the formula (4-1) is preferably 1 in terms of sensitivity and resolution.

In terms of high dry etching resistance, A ¹ and A ^{2 in} formula (4-2) are preferably combined with each other to be —CH ₂ — and —CH ₂ CH ₂ — and dissolved in an organic solvent. From the standpoint of high properties, it is preferable to form —O— together.

R ²⁰¹ and R ^{202 in} formula (4-2) are each independently preferably a hydrogen atom, a methyl group, an ethyl group, or an isopropyl group from the viewpoint of high solubility in an organic solvent.

  N6 in the formula (4-2) is preferably 0 from the viewpoint of high dry etching resistance.

As A ³ and A ⁴ in the formula (4-3), from the viewpoint of high dry etching resistance, it is preferable that they together form —CH ₂ — or —CH ₂ CH ₂ —. From the viewpoint of high solubility, it is preferable that they are taken together as -O-.

R ²⁰³ and R ^{204 in} formula (4-3) are each independently preferably a hydrogen atom, a methyl group, an ethyl group, or an isopropyl group from the viewpoint of high solubility in an organic solvent.

  N7 in Formula (4-3) is preferably 0 from the viewpoint of high dry etching resistance.

R ²⁰⁵ , R ²⁰⁶ , and R ^{207 in} formula (4-4) are preferably a hydrogen atom from the viewpoint of high solubility in an organic solvent.

Y ¹¹ , Y ¹² and Y ¹³ in the formula (4-4) are ones that are —C (═O) —O—, and the remaining two are —CH— from the viewpoint of high adhesion to the substrate surface and the like. _2- is preferred.

  N8 in Formula (4-4) is preferably 0 from the viewpoint of high dry etching resistance.

In formula (4-5), R ⁹¹ , R ⁹² , R ⁹³ , and R ⁹⁴ are each preferably a hydrogen atom or a methyl group independently from the viewpoint of high solubility in an organic solvent.

  M1 in Formula (4-5) is preferably 1 from the viewpoint of sensitivity and resolution.

As A ⁵ and A ⁶ in the formula (4-6), from the viewpoint of high dry etching resistance, it is preferable that they together form —CH ₂ — or —CH ₂ CH ₂ —. From the viewpoint of high solubility, it is preferable that they are taken together as -O-.

R ²⁰⁸ and R ^{209 in} formula (4-6) are each independently preferably a hydrogen atom, a methyl group, an ethyl group, or an isopropyl group from the viewpoint of high solubility in an organic solvent.

R ²¹⁰ and R ^{211 in} Formula (4-6) are each independently preferably a hydrogen atom, a methyl group, an ethyl group, or an isopropyl group from the viewpoint of high solubility in an organic solvent.

In formula (4-6), Y ²¹ and Y ²² are each one of —C (═O) — and the remaining one of —CH ₂ — from the viewpoint of high adhesion to the substrate surface and the like. Is preferred.

  N9 in Formula (4-6) is preferably 0 from the viewpoint of high dry etching resistance.

  The structural unit (B) having a lactone skeleton can be used alone or in combination of two or more as necessary.

  The polymer having the structural unit (B) having a lactone skeleton can be produced by polymerizing a monomer containing the monomer (b) that gives the structural unit (B) having a lactone skeleton.

  The monomer (b) is not particularly limited, and examples thereof include monomers represented by the following formulas (10-1) to (10-29). In formulas (10-1) to (10-29), R represents a hydrogen atom or a methyl group.

  Among these, from the viewpoint of sensitivity, the monomers represented by the above formulas (10-1) to (10-3) and the above formula (10-5), and geometric isomers and optical isomers thereof are more preferable. From the point of dry etching resistance, the above formulas (10-7), (10-9), (10-10), (10-12), (10-14), (10-24) to (10-26) ) And (10-29), and geometrical isomers and optical isomers thereof are more preferable. From the viewpoint of solubility in a resist solvent, the above formula (10-8), Monomers represented by (10-13), (10-16) to (10-23), and (10-28), and geometric isomers and optical isomers thereof are more preferable.

  The structural unit (C) having an acid leaving group will be described.

  Here, the “acid-leaving group” refers to a group that decomposes or leaves by the action of an acid.

  The structural unit (C) having an acid-eliminable group is a component that is soluble in an alkali by an acid, and has an effect of enabling the formation of a resist pattern. Therefore, the structural unit (C) is preferably used as a structural component of a resist polymer. .

  The content of the structural unit (C) is not particularly limited, but is preferably 20 mol% or more, more preferably 25 mol% or more in the structural unit of the resist polymer from the viewpoint of sensitivity and resolution. Moreover, 60 mol% or less is preferable from the point of the adhesiveness to a substrate surface etc., 55 mol% or less is more preferable, and 50 mol% or less is more preferable.

  When the structural unit (C) has a lactone skeleton, the substrate adhesion tends to be good. In this case, the structural unit (C) also corresponds to the structural unit (B). However, in the present invention, such a structural unit is regarded as the structural unit (B).

  In addition, when the structural unit (C) has a hydrophilic group, it tends to have more excellent sensitivity. In this case, the structural unit (C) corresponds to a structural unit (D) to be described later, but in the present invention, such a structural unit is regarded as the structural unit (C).

  The structural unit (C) having an acid-eliminable group is not particularly limited, but has the following formulas (3-1-1) and (3-2-1) because the dry etching resistance required for the resist is high. ), (3-3-1), (3-4-1), (3-5-1), (3-6-1), (3-7-1) and (3-8-1) It is preferably at least one selected from the group consisting of

In formula (3-1-1), R ³¹ represents a hydrogen atom or a methyl group, R ¹ represents an alkyl group having 1 to 3 carbon atoms, and X ¹ represents a linear or branched alkyl group having 1 to 6 carbon atoms. N1 represents an integer of 0 to 4. Incidentally, also includes having a plurality of different groups as X ¹ in the case of n1 is 2 or more.

In formula (3-2-1), R ³² represents a hydrogen atom or a methyl group, R ² and R ³ each independently represents an alkyl group having 1 to 3 carbon atoms, and X ² represents 1 to 6 carbon atoms. N2 represents an integer of 0 to 4. Incidentally, also includes having a plurality of different groups as X ² in the case of n2 is 2 or more.

In formula (3-3-1), R ³³ represents a hydrogen atom or a methyl group, R ⁴ represents an alkyl group having 1 to 3 carbon atoms, and R ³³¹ , R ³³² , R ³³³ , and R ³³⁴ are each independently A hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, and V ¹ and V ² are each independently —O—, —S—, —NH—, or a methylene chain having a chain length of 1 to 6 [— ( CH ₂ ) _u1 — (u1 represents an integer of 1 to 6)], X ³ represents a linear or branched alkyl group having 1 to 6 carbon atoms, n3 represents an integer of 0 to 4, q Represents 0 or 1. Incidentally, also includes having a plurality of different group as X ³ in the case of n3 is 2 or more.

In formula (3-4-1), R ³⁴ represents a hydrogen atom or a methyl group, R ⁵ represents an alkyl group having 1 to 3 carbon atoms, and X ⁴ represents a linear or branched alkyl group having 1 to 6 carbon atoms. Represents a group, n4 represents an integer of 0 to 4, and r represents an integer of 0 to 2. Incidentally, also includes having a plurality of different groups as X ⁴ in the case of n4 is 2 or more.

In the formula (3-5-1), R ³⁵ represents a hydrogen atom or a methyl group, and R ³⁵¹ , R ³⁵² , R ³⁵³ , and R ³⁵⁴ are each independently a hydrogen atom, a linear or branched alkyl having 1 to 6 carbon atoms. V ³ and V ⁴ each independently represents —O—, —S—, —NH— or a methylene chain having a chain length of 1 to 6 [— (CH ₂ ) _u11 — (u11 represents an integer of 1 to 6; represents ^{represents)], X 51} represents a linear or branched alkyl group having 1 to 6 carbon atoms, n51 represents an integer of 0 to 4, q3 is 0 or 1.

R ³⁵⁵ , R ³⁵⁶ and R ³⁵⁷ each independently represent a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof, or a linear or branched alkyl group having 1 to 4 carbon atoms, and At least one of R ³⁵⁵ , R ³⁵⁶ , and R ³⁵⁷ is the alicyclic hydrocarbon group or a derivative thereof, or any two of R ³⁵⁵ , R ³⁵⁶ , and R ³⁵⁷ are bonded to each other, and each is bonded Together with the carbon atom forming a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof, and one of R ³⁵⁵ , R ³⁵⁶ , and R ³⁵⁷ that is not involved in the bond is A linear or branched alkyl group having 1 to 4 carbon atoms, a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, or a derivative thereof is represented. Incidentally, also includes having a plurality of different groups as X ⁵¹ in the case of n51 is 2 or more.

In formula (3-6-1), R ³⁶ represents a hydrogen atom or a methyl group, and R ³⁶¹ , R ³⁶² , R ³⁶³ and R ³⁶⁴ are each independently a hydrogen atom, a linear or branched alkyl having 1 to 6 carbon atoms. V ⁵ and V ⁶ each independently represent —O—, —S—, —NH—, or a methylene chain having a chain length of 1 to 6 [— (CH ₂ ) _u12 — (u12 represents an integer of 1 to 6; represents ^{represents)], X 61} represents a linear or branched alkyl group having 1 to 6 carbon atoms, n61 represents an integer of 0 to 4, q4 is 0 or 1.

R ³⁶⁷ represents a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof, or a linear or branched alkyl group having 1 to 4 carbon atoms, and R ³⁶⁵ and R ³⁶⁶ are each independently hydrogen. Represents an atom or a linear or branched alkyl group having 1 to 4 carbon atoms, or two of R ³⁶⁵ and R ³⁶⁷ or R ³⁶⁶ and R ³⁶⁷ are bonded to each other, and together with the carbon atom to which each is bonded , A divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof, and the remaining one of R ³⁶⁵ and R ³⁶⁶ not participating in the bond represents a hydrogen atom. Incidentally, also includes having a plurality of different groups as X ⁶¹ in the case of n61 is 2 or more.

In the formula (3-7-1), R ³⁷ represents a hydrogen atom or a methyl group. R ³⁷³ represents a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof, or a linear or branched alkyl group having 1 to 4 carbon atoms, and R ³⁷¹ and R ³⁷² are each independently hydrogen. Represents an atom or a linear or branched alkyl group having 1 to 4 carbon atoms, or two of R ³⁷¹ and R ³⁷³ or R ³⁷² and R ³⁷³ are bonded to each other, and together with the carbon atom to which each is bonded , A divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof, and the remaining one of R ³⁷¹ and R ³⁷² not participating in the bond represents a hydrogen atom.

Wherein ^{(3-8-1), R 38} represents a hydrogen atom or a methyl group. R ³⁸¹ , R ³⁸² and R ³⁸³ each independently represent a linear or branched alkyl group having 1 to 4 carbon atoms. )

R ¹ in formula (3-1-1) is preferably a methyl group, an ethyl group, or an isopropyl group from the viewpoint of sensitivity and resolution.

  N1 in Formula (3-1-1) is preferably 0 from the viewpoint of high dry etching resistance.

In the formula (3-2-1), R ² and R ³ are preferably each independently a methyl group, an ethyl group, or an isopropyl group from the viewpoint of sensitivity and resolution.

  N2 in Formula (3-2-1) is preferably 0 from the viewpoint of high dry etching resistance.

R ⁴ in formula (3-3-1) is preferably a methyl group, an ethyl group, or an isopropyl group from the viewpoint of sensitivity and resolution.

V ¹ and V ² in the formula (3-3-1) are each preferably —CH ₂ — or —CH ₂ CH ₂ — independently from the viewpoint of high dry etching resistance.

R ³³¹ , R ³³² , R ³³³ , and R ³³⁴ in formula (3-3-1) are each independently a hydrogen atom, a methyl group, an ethyl group, or an isopropyl group from the viewpoint of high solubility in an organic solvent. It is preferable that

  N3 in Formula (3-3-1) is preferably 0 from the viewpoint of high dry etching resistance.

  Q in Formula (3-3-1) is preferably 1 from the viewpoint of high dry etching resistance, and preferably 0 from the viewpoint of good solubility in an organic solvent.

R ⁵ in formula (3-4-1) is preferably a methyl group, an ethyl group, or an isopropyl group from the viewpoint of sensitivity and resolution.

  N4 in the formula (3-4-1) is preferably 0 from the viewpoint of high dry etching resistance.

  R in the formula (3-4-1) is preferably 1 from the viewpoint of high dry etching resistance, and preferably 0 from the viewpoint of good solubility in an organic solvent.

V ³ and V ⁴ in the formula (3-5-1) are each preferably —CH ₂ — or —CH ₂ CH ₂ — independently from the viewpoint of high dry etching resistance.

R ³⁵¹ , R ³⁵² , R ³⁵³ , and R ³⁵⁴ in formula (3-5-1) are each independently a hydrogen atom, a methyl group, an ethyl group, or an isopropyl group from the viewpoint of high solubility in an organic solvent. It is preferable that

  N51 in Formula (3-5-1) is preferably 0 from the viewpoint of high dry etching resistance.

  Q3 in the formula (3-5-1) is preferably 1 from the viewpoint of high dry etching resistance, and preferably 0 from the viewpoint of good solubility in an organic solvent.

-C (R ³⁵⁵ ) (R ³⁵⁶ ) (R ³⁵⁷ ) in the formula (3-5-1) is represented by the following formulas (K-1) to (K-6) in that the line edge roughness is excellent. The structure represented is preferable, and the structure represented by the following formulas (K-7) to (K-17) is preferable in that the dry etching resistance is high.

V ⁵ and V ⁶ in the formula (3-6-1) are each preferably —CH ₂ — or —CH ₂ CH ₂ — independently from the viewpoint of high dry etching resistance.

R ³⁶¹ , R ³⁶² , R ³⁶³ , and R ³⁶⁴ in formula (3-6-1) are each independently a hydrogen atom, a methyl group, an ethyl group, or an isopropyl group from the viewpoint of high solubility in an organic solvent. It is preferable that

  N61 in Formula (3-6-1) is preferably 0 from the viewpoint of high dry etching resistance.

  Q4 in the formula (3-6-1) is preferably 1 from the viewpoint of high dry etching resistance, and preferably 0 from the viewpoint of good solubility in an organic solvent.

-C (R ³⁶⁵ ) (R ³⁶⁶ ) -O-R ³⁶⁷ in the formula (3-6-1) is superior in line edge roughness to the above formulas (J-1) to (J-24). In terms of high dry etching resistance, the structures represented by the formulas (J-25) to (J-52) are preferable.

-C (R ³⁷¹ ) (R ³⁷² ) -O-R ³⁷³ in the formula (3-7-1) is superior in line edge roughness to the above formulas (J-1) to (J-24). In terms of high dry etching resistance, the structures represented by the formulas (J-25) to (J-52) are preferable.

  The structural unit (C) having an acid leaving group can be used alone or in combination of two or more as necessary.

  The polymer having the structural unit (C) having an acid leaving group is produced by polymerizing a monomer containing the monomer (c) that gives the structural unit (C) having an acid leaving group. be able to.

  The monomer (c) is not particularly limited, and examples thereof include monomers represented by the following formulas (9-1) to (9-224). In formulas (9-1) to (9-224), R and R ′ each independently represents a hydrogen atom or a methyl group.

  Among these, from the points of sensitivity and resolution, the above formulas (9-1) to (9-3), the above formula (9-5), the above formula (9-16), the above formula (9-19), the above formula ( 9-20), the above formula (9-22), the above formula (9-23), the above formulas (9-25) to (9-28), the above formula (9-30), and the above formula (9-31). The monomers represented by the above formula (9-33), the above formula (9-34) and the above formulas (9-102) to (9-129), and their geometrical isomers and optical isomers. Preferably, the formula (9-1), the formula (9-2), the formula (9-16), the formula (9-20), the formula (9-23), the formula (9-28), Formula (9-31), Formula (9-34), Formula (9-109), Formula (9-111), Formula (9-114) to (9-117), Formula (9) -125 A monomer represented by the formula (9-128) and the formula (9-129) is particularly preferred.

  Moreover, from the point which is excellent in line edge roughness, it represents with the monomer represented by said Formula (9-35)-(9-40), said Formula (9-52)-(9-62). Monomer, monomers represented by the above formulas (9-76) to (9-88), monomers represented by the above formulas (9-130) to (9-135), the above formula (9 -147) to (9-157), monomers represented by the above formulas (9-171) to (9-183), and their geometrical isomers and optical isomers. preferable.

  Moreover, from the point which is excellent in dry etching tolerance, it represents with the monomer represented by said Formula (9-41)-(9-51), said Formula (9-63)-(9-75). A monomer, a monomer represented by the above formulas (9-89) to (9-101), a monomer represented by the above formulas (9-136) to (9-146), the above formula (9 -158) to (9-170), monomers represented by the above formulas (9-184) to (9-196), and geometric isomers and optical isomers thereof. preferable.

  In addition, from the viewpoint of good pattern rectangularity, monomers represented by the above formulas (9-197) to (9-224), and geometric isomers and optical isomers thereof are more preferable.

The structural unit (D) having a hydrophilic group will be described.
Here, the “hydrophilic group” is at least one of —C (CF ₃ ) ₂ —OH, hydroxy group, cyano group, methoxy group, carboxy group, and amino group.

  The structural unit (D) having a hydrophilic group is preferably used as a structural unit of a resist polymer because it has an effect of reducing defects in the resist composition and improving pattern rectangularity.

  The content of the structural unit (D) is preferably 5 to 30 mol%, more preferably 10 to 25 mol%, in the structural unit of the resist polymer, from the viewpoint of pattern rectangularity.

  When the structural unit (D) has a group that decomposes or leaves by the action of an acid, it tends to have better sensitivity. In this case, the structural unit (D) corresponds to the structural unit (C), but in the present invention, such a structural unit is regarded as the structural unit (C).

  Moreover, when the structural unit (D) has a lactone skeleton, it tends to have more excellent sensitivity. In this case, the structural unit (D) corresponds to the structural unit (B), but in the present invention, such a structural unit is regarded as the structural unit (B).

  The structural unit (D) having a hydrophilic group is not particularly limited, but is selected from the group consisting of the following formulas (5-1) to (5-7) from the viewpoint of high dry etching resistance required for a resist. What is at least 1 type is preferable.

In formula (5-1), R ⁵¹ represents a hydrogen atom or a methyl group, R ⁵⁰¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and X ⁵¹ represents a straight or branched chain having 1 to 6 carbon atoms. Esterification with alkyl group, —C (CF ₃ ) ₂ —OH, hydroxy group, cyano group, carboxy group, C 1-6 acyl group, C 1-6 alkoxy group, C 1-6 alcohol Represents a carboxy group or an amino group.

The linear or branched alkyl group having 1 to 6 carbon atoms is substituted with —C (CF ₃ ) ₂ —OH, a hydroxy group, a cyano group, a carboxy group, an acyl group having 1 to 6 carbon atoms, It may have at least one group selected from the group consisting of a carboxy group esterified with 6 alcohols and an amino group. n51 represents an integer of 1 to 4. Incidentally, also includes having a plurality of different groups as X ₅₁ in the case of n51 is 2 or more.

In formula (5-2), R ⁵² represents a hydrogen atom or a methyl group, and X ⁵² represents a linear or branched alkyl group having 1 to 6 carbon atoms, —C (CF ₃ ) ₂ —OH, a hydroxy group, cyano. A group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group esterified with an alcohol having 1 to 6 carbon atoms, or an amino group. The linear or branched alkyl group having 1 to 6 carbon atoms is substituted with —C (CF ₃ ) ₂ —OH, a hydroxy group, a cyano group, a carboxy group, an acyl group having 1 to 6 carbon atoms, It may have at least one group selected from the group consisting of a carboxy group esterified with 6 alcohols and an amino group. n52 represents an integer of 1 to 4. Incidentally, also includes having a plurality of different groups as X ⁵² in the case of n52 is 2 or more.

In Formula (5-3), R ⁵³ represents a hydrogen atom or a methyl group, R ⁵⁰² represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ^{531 to} R ⁵³⁴ independently represent a hydrogen atom, a carbon atom, Represents a linear or branched alkyl group of 1 to 6, W ¹ and W ² are each independently —O—, —S—, —NH—, or a methylene chain having a chain length of 1 to 6 [— (CH ₂ ) _u2 -(U2 represents an integer of 1 to 6)].

X ⁵³ is a linear or branched alkyl group having 1 to 6 carbon atoms, —C (CF ₃ ) ₂ —OH, a hydroxy group, a cyano group, a carboxy group, an acyl group having 1 to 6 carbon atoms, or 1 to 6 carbon atoms. An alkoxy group, a carboxy group esterified with an alcohol having 1 to 6 carbon atoms or an amino group, and n53 represents an integer of 1 to 4. The linear or branched alkyl group having 1 to 6 carbon atoms is substituted with —C (CF ₃ ) ₂ —OH, a hydroxy group, a cyano group, a carboxy group, an acyl group having 1 to 6 carbon atoms, It may have at least one group selected from the group consisting of a carboxy group esterified with 6 alcohols and an amino group. q1 represents 0 or 1. Incidentally, also includes having a plurality of different groups as X ⁵³ in the case of n53 is 2 or more.

In formula (5-4), R ⁵⁴ represents a hydrogen atom or a methyl group, R ⁵⁰³ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and X ⁵⁴ is a linear or branched group having 1 to 6 carbon atoms. Esterification with alkyl group, —C (CF ₃ ) ₂ —OH, hydroxy group, cyano group, carboxy group, C 1-6 acyl group, C 1-6 alkoxy group, C 1-6 alcohol Represents a carboxy group or an amino group.

The linear or branched alkyl group having 1 to 6 carbon atoms is substituted with —C (CF ₃ ) ₂ —OH, a hydroxy group, a cyano group, a carboxy group, an acyl group having 1 to 6 carbon atoms, It may have at least one group selected from the group consisting of a carboxy group esterified with 6 alcohols and an amino group. n54 represents an integer of 1 to 4, and r1 represents an integer of 0 to 2. Incidentally, also includes having a plurality of different groups as X ⁵⁴ in the case of n54 is 2 or more.

Wherein ^{(5-5), R 55} represents a hydrogen atom or a methyl ^group, R ^{504, R 505} each independently represents an alkyl group having 1 to 3 carbon ^{atoms, X 55} represents a linear 1 to 6 carbon atoms Chain or branched alkyl group, —C (CF ₃ ) ₂ —OH, hydroxy group, cyano group, carboxy group, acyl group having 1 to 6 carbon atoms, alkoxy group having 1 to 6 carbon atoms, alcohol having 1 to 6 carbon atoms Represents a carboxy group esterified with or an amino group. As the linear or branched alkyl group substituent having 1 to 6 carbon atoms, —C (CF ₃ ) ₂ —OH, a hydroxy group, a cyano group, a carboxy group, an acyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms. It may have at least one group selected from the group consisting of a carboxyl group esterified with an alcohol and an amino group. n55 represents an integer of 1 to 4. Incidentally, also includes having a plurality of different groups as X ⁵⁵ in the case of n55 is 2 or more.

In Formula (5-6), R ⁵⁶ represents a hydrogen atom or a methyl group, R ⁵⁰⁶ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ^{535 to} R ⁵³⁶ independently represent a hydrogen atom or a carbon number. 1 to 6 linear or branched alkyl groups, W ³ represents —O—, —S—, —NH— or a methylene chain having a chain length of 1 to 6 [— (CH ₂ ) _u3 — (u3 represents 1 to 6 Represents an integer of

X ⁵⁶ is a linear or branched alkyl group having 1 to 6 carbon atoms, —C (CF ₃ ) ₂ —OH, a hydroxy group, a cyano group, a carboxy group, an acyl group having 1 to 6 carbon atoms, or 1 to 6 carbon atoms. An alkoxy group, a carboxy group esterified with an alcohol having 1 to 6 carbon atoms, or an amino group. The linear or branched alkyl group having 1 to 6 carbon atoms is substituted with —C (CF ₃ ) ₂ —OH, a hydroxy group, a cyano group, a carboxy group, an acyl group having 1 to 6 carbon atoms, It may have at least one group selected from the group consisting of a carboxy group and an amino group esterified with 6 alcohols. n56 represents an integer of 1 to 4, and q2 represents 0 or 1. Incidentally, also includes having a plurality of different groups as X ⁵⁶ in the case of n56 is 2 or more.

In formula (5-7), R ⁵⁷ represents a hydrogen atom or a methyl group, R ⁵⁷¹ represents a linear or branched alkyl group having 1 to 6 carbon atoms, a bridged cyclic hydrocarbon group having 4 to 16 carbon atoms, or Represents a linear or branched alkyl group having 1 to 6 carbon atoms having a bridged cyclic hydrocarbon group having 4 to 16 carbon atoms, and R ⁵⁷² represents a linear or branched alkyl group having 1 to 6 carbon atoms, Alternatively, R ⁵⁷¹ and R ⁵⁷² may be combined to form a bridged cyclic hydrocarbon group having 4 to 16 carbon atoms together with the carbon atom to which each is bonded.

  Here, the alkyl group may have a hydroxy group, a carboxy group, an acyl group having 2 to 6 carbon atoms, or a carboxy group esterified with an alcohol having 1 to 6 carbon atoms. The pre-bridged cyclic hydrocarbon group may have a linear or branched alkyl group having 1 to 6 carbon atoms, and the alkyl group is a hydroxy group, a carboxy group, or an acyl group having 2 to 6 carbon atoms. Or a carboxy group esterified with an alcohol having 1 to 6 carbon atoms.

X ⁵⁷ represents a linear or branched alkyl group having 1 to 6 carbon _{atoms, -C (CF 3) 2 -OH} , hydroxy group, a cyano group, a carboxy group, an acyl group having 1 to 6 carbon atoms, 1 to 6 carbon atoms An alkoxy group, a carboxy group esterified with an alcohol having 1 to 6 carbon atoms, or an amino group. The linear or branched alkyl group having 1 to 6 carbon atoms is substituted with —C (CF ₃ ) ₂ —OH, a hydroxy group, a cyano group, a carboxy group, an acyl group having 1 to 6 carbon atoms, It may have at least one group selected from the group consisting of a carboxy group esterified with 6 alcohols and an amino group.

R ⁵⁰¹ in formula (5-1) is preferably a methyl group, an ethyl group or an isopropyl group from the viewpoint of sensitivity and resolution, and is preferably a hydrogen atom from the viewpoint of good solubility in an organic solvent. preferable.

  N51 in Formula (5-1) is preferably 1 from the viewpoint of high dry etching resistance.

X ⁵¹ in formula (5-1) is preferably —C (CF ₃ ) ₂ —OH, a hydroxy group, a cyano group, or a methoxy group from the viewpoint of good pattern shape.

  N52 in Formula (5-2) is preferably 1 from the viewpoint of high dry etching resistance.

X ⁵² in formula (5-2) is preferably —C (CF ₃ ) ₂ —OH, a hydroxy group, a cyano group, or a methoxy group from the viewpoint of good pattern shape.

R ⁵⁰² in formula (5-3) is preferably a methyl group, an ethyl group or an isopropyl group from the viewpoint of sensitivity and resolution, and is preferably a hydrogen atom from the viewpoint of good solubility in an organic solvent. preferable.

W ¹ and W ^{2 in} Formula (5-3) are preferably —CH ₂ — and —CH ₂ CH ₂ — from the viewpoint of high dry etching resistance.

R ⁵³¹ , R ⁵³² , R ⁵³³ , and R ⁵³⁴ in formula (5-3) are each independently a hydrogen atom, a methyl group, an ethyl group, or an isopropyl group from the viewpoint of high solubility in an organic solvent. Preferably there is.

  N53 in Formula (5-3) is preferably 1 from the viewpoint of high dry etching resistance.

X ⁵³ in formula (5-3) is preferably —C (CF ₃ ) ₂ —OH, a hydroxy group, a cyano group, or a methoxy group from the viewpoint of good pattern shape.

  Q1 in the formula (5-3) is preferably 1 from the viewpoint of high dry etching resistance, and preferably 0 from the viewpoint of good solubility in an organic solvent.

R ⁵⁰³ in formula (5-4) is preferably a methyl group, an ethyl group, or an isopropyl group from the viewpoint of sensitivity and resolution, and is preferably a hydrogen atom from the viewpoint of good solubility in an organic solvent. preferable.

  N54 in Formula (5-4) is preferably 1 from the viewpoint of high dry etching resistance.

X ⁵⁴ in formula (5-4) is preferably —C (CF ₃ ) ₂ —OH, a hydroxy group, a cyano group, or a methoxy group from the viewpoint of good pattern shape.

  R1 in formula (5-4) is preferably 1 from the viewpoint of high dry etching resistance, and preferably 0 from the viewpoint of good solubility in an organic solvent.

In formula (5-5), R ⁵⁰⁴ and R ⁵⁰⁵ are preferably each independently a methyl group, an ethyl group, or an isopropyl group from the viewpoint of sensitivity and resolution.

  N55 in Formula (5-5) is preferably 1 from the viewpoint of high dry etching resistance.

X ⁵⁵ in formula (5-5) is preferably —C (CF ₃ ) ₂ —OH, a hydroxy group, a cyano group, or a methoxy group from the viewpoint of good pattern shape.

R ⁵⁰⁶ in formula (5-6) is preferably a methyl group, an ethyl group, or an isopropyl group from the viewpoint of sensitivity and resolution, and is preferably a hydrogen atom from the viewpoint of good solubility in an organic solvent. preferable.

W ³ in formula (5-6) is preferably —CH ₂ — or —CH ₂ CH ₂ — from the viewpoint of high dry etching resistance.

R ⁵³⁵ and R5 ^{36 in} formula (5-6) are preferably a hydrogen atom, a methyl group, an ethyl group, or an isopropyl group from the viewpoint of high solubility in an organic solvent.

  N56 in Formula (5-6) is preferably 1 from the viewpoint of high dry etching resistance.

X ⁵⁶ in formula (5-6) is preferably —C (CF ₃ ) ₂ —OH, a hydroxy group, a cyano group, or a methoxy group from the viewpoint of good pattern shape.

  Q2 in Formula (5-6) is preferably 1 from the viewpoint of high dry etching resistance, and preferably 0 from the viewpoint of good solubility in an organic solvent.

^{R 571} and ^{R 572} in formula (5-7), from the viewpoint high dry etching ^resistance, and ^{R 571} and ^{R 572} are taken together, the number 4 to 16 carbon together with the carbon atom to which each is attached A structure forming a bridged cyclic hydrocarbon group is preferred. Further, heat resistance, from the viewpoint of excellent stability, so the R ⁵⁷¹ and R ⁵⁷² together form a ring is, each contained in a bridged cyclic hydrocarbon group formed together with the carbon atoms to which they are attached camphor ring , An adamantane ring, a norbornane ring, a pinane ring, a bicyclo [2.2.2] octane ring, a tetracyclododecane ring, a tricyclodecane ring, and a decahydronaphthalene ring.

X ⁵⁷ in formula (5-7) represents —CH ₂ —C (CF ₃ ) ₂ —OH, —CH ₂ —OH group, —CH ₂ —CN group, —CH ₂ from the viewpoint of good pattern shape. -O-CH ₃ group, _{- (CH} 2) is preferably 2 -O-CH ₃ group.

In the formulas (5-1) to (5-7), the position substituted with X ⁵¹ , X ⁵² , X ⁵³ , X ⁵⁴ , X ⁵⁵ , X ⁵⁶ and X ⁵⁷ is any position in the cyclic structure. May be.

  The structural unit (D) having a hydrophilic group can be used alone or in combination of two or more as necessary.

  The polymer having the structural unit (D) having a hydrophilic group can be produced by polymerizing a monomer containing the monomer (d) that gives the structural unit (D) having a hydrophilic group.

  The monomer (d) is not particularly limited, and examples thereof include monomers represented by the following formulas (13-1) to (13-79). In formulas (13-1) to (13-79), R represents a hydrogen atom or a methyl group.

  Among these, from the viewpoint of good solubility in a resist solvent, the above formulas (13-1) to (13-9), the above formulas (13-13) to (13-16), and the above formulas (13-21) to (13-24), the above formulas (13-30) to (13-34), the above formulas (13-37) to (13-43), the above formulas (13-56) to (13-59), the above formulas (13-62) to (13-63), the above formulas (13-66) to (13-69), the above formula (13-72), and the above formulas (13-76) to (13-79). Monomers, and geometric isomers thereof, and optical isomers thereof are more preferable.

  Further, from the viewpoint of high dry etching resistance, the above formulas (13-25) to (13-30), the above formulas (13-44) to (13-55), and the above formulas (13-60) to (13-61). ), Monomers represented by the above formulas (13-64) to (13-65), the above formula (13-71), the above formulas (13-73) to (13-75), and geometrical isomerism thereof. And their optical isomers are more preferred.

  The resist polymer of the present invention may contain a constituent unit (E) other than these constituent units as necessary in addition to the constituent units (B) to (D).

  As such a structural unit (E), for example, a structural unit (E1) having an alicyclic skeleton (nonpolar alicyclic skeleton) having no acid-eliminable group and hydrophilic group can be contained. . Here, the alicyclic skeleton is a skeleton having one or more cyclic saturated hydrocarbon groups. The structural unit (E1) can be used alone or in combination of two or more as necessary.

  The structural unit (E1) tends to exhibit an effect of expressing the dry etching resistance of the resist composition.

  The structural unit (E1) is not particularly limited, but structural units represented by the following formulas (11-1) to (11-4) are preferable from the viewpoint of high dry etching resistance required for the resist.

In formula (11-1), R ³⁰¹ represents a hydrogen atom or a methyl group, X ³⁰¹ represents a linear or branched alkyl group having 1 to 6 carbon atoms, and n301 represents an integer of 0 to 4. Note that in the case where n301 is 2 or more, X ³⁰¹ includes a plurality of different groups.

In formula (11-2), R ³⁰² represents a hydrogen atom or a methyl group, X ³⁰² represents a linear or branched alkyl group having 1 to 6 carbon atoms, and n302 represents an integer of 0 to 4. Incidentally, also includes having a plurality of different groups as ^{X 302} in the case of n302 is 2 or more.

In formula (11-3), R ³⁰³ represents a hydrogen atom or a methyl group, X ³⁰³ represents a linear or branched alkyl group having 1 to 6 carbon atoms, and n303 represents an integer of 0 to 4. Incidentally, also includes having a plurality of different groups as ^{X 303} in the case of n303 is 2 or more. Moreover, p represents the integer of 0-2.

In formula (11-4), R ³⁰⁴ represents a hydrogen atom or a methyl group, X ³⁰⁴ represents a linear or branched alkyl group having 1 to 6 carbon atoms, and n304 represents an integer of 0 to 4. Incidentally, also includes having a plurality of different groups as ^{X 304} in the case of n304 is 2 or more. Moreover, p1 represents the integer of 0-2. )

In the formulas (11-1) to (11-4), the position where X ³⁰¹ , X ³⁰² , X ³⁰³ and X ³⁰⁴ are bonded may be anywhere in the cyclic structure.

  N301 in Formula (11-1) is preferably 0 from the viewpoint of high dry etching resistance.

  N302 in Formula (11-2) is preferably 0 from the viewpoint of high dry etching resistance.

  N303 in Formula (11-3) is preferably 0 from the viewpoint of high dry etching resistance.

  P in Formula (11-3) is preferably 0 from the viewpoint of high solubility in an organic solvent, and is preferably 1 from the viewpoint of high dry etching resistance.

  N304 in Formula (11-4) is preferably 0 from the viewpoint of high dry etching resistance.

  P1 in formula (11-4) is preferably 0 from the viewpoint of high solubility in an organic solvent, and is preferably 1 from the viewpoint of high dry etching resistance.

  The polymer containing the structural unit (E1) having a nonpolar alicyclic skeleton can be produced by polymerizing a monomer containing the monomer (e1) having a nonpolar alicyclic skeleton.

  The monomer (e1) having a nonpolar alicyclic skeleton is not particularly limited, and examples thereof include cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, norbornyl (meth) acrylate, and (meth) acrylic acid. Adamantyl, tricyclodecanyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, and derivatives having a linear or branched alkyl group having 1 to 6 carbon atoms on the alicyclic skeleton of these compounds Is preferred.

  Specific examples include monomers represented by the following formulas (14-1) to (14-5). In formulas (14-1) to (14-5), R represents a hydrogen atom or a methyl group.

  The resist polymer may further contain a structural unit (E2) other than the above.

  The polymer containing the structural unit (E2) can be produced by polymerizing a monomer including the monomer (e2).

  The monomer (e2) is not particularly limited. For example, methyl (meth) acrylate, ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-propyl (meth) acrylate, (meth ) Isopropyl acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, methoxymethyl (meth) acrylate, n-propoxyethyl (meth) acrylate, iso-propoxyethyl (meth) acrylate, (meth) N-butoxyethyl acrylate, iso-butoxyethyl (meth) acrylate, tert-butoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, (meth) 2-hydroxy-n-propyl acrylate, 4-hydroxy (meth) acrylate n-butyl, 2-ethoxyethyl (meth) acrylate, 1-ethoxyethyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3, (meth) acrylic acid 3-tetrafluoro-n-propyl, (meth) acrylic acid 2,2,3,3,3-pentafluoro-n-propyl, methyl α- (tri) fluoromethylacrylate, α- (tri) fluoromethylacrylic Ethyl acetate, 2-ethylhexyl α- (tri) fluoromethyl acrylate, n-propyl α- (tri) fluoromethyl acrylate, iso-propyl α- (tri) fluoromethyl acrylate, α- (tri) fluoromethyl acrylic N-butyl acid, iso-butyl α- (tri) fluoromethyl acrylate, tert-butyl α- (tri) fluoromethyl acrylate methoxymethyl α- (tri) fluoromethyl acrylate, ethoxyethyl α- (tri) fluoromethyl acrylate, n-propoxyethyl α- (tri) fluoromethyl acrylate, iso-propoxy α- (tri) fluoromethyl acrylate Linear or branched structure such as ethyl, n-butoxyethyl α- (tri) fluoromethyl acrylate, iso-butoxyethyl α- (tri) fluoromethyl acrylate, tert-butoxyethyl α- (tri) fluoromethyl acrylate (Meth) acrylic acid ester having

  Styrene, α-methylstyrene, vinyltoluene, p-hydroxystyrene, p-tert-butoxycarbonylhydroxystyrene, 3,5-di-tert-butyl-4-hydroxystyrene, 3,5-dimethyl-4-hydroxystyrene, aromatic alkenyl compounds such as p-tert-perfluorobutylstyrene and p- (2-hydroxy-iso-propyl) styrene;

Unsaturated carboxylic acids and carboxylic anhydrides such as (meth) acrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride;
Examples include ethylene, propylene, norbornene, tetrafluoroethylene, acrylamide, N-methylacrylamide, N, N-dimethylacrylamide, vinyl chloride, vinyl fluoride, vinylidene fluoride, and vinylpyrrolidone.

  The content of the structural unit (E1) and the structural unit (E2) is not particularly limited, but is preferably in the range of 20 mol% or less in the structural unit of the resist polymer.

  Preferred combinations of the structural unit (B) and the structural unit (C) in the resist polymer are listed in Tables 1 to 4.

  In addition, the structural unit (B) includes at least one selected from the group consisting of the formula (10-1) and the formula (10-3), the formula (10-7), (10-8), ( 10-10), (10-12), (10-17) and one or more selected from the group consisting of the formula (10-19) may be used in combination. Furthermore, in addition to the combinations listed in Table 1, as the structural unit (D), the formula (13-1), the formula (13-26), the formula (13-27), and the formula (13-30) In addition, a combination obtained by adding one monomer selected from the group consisting of the formula (13-31) and the formula (13-68) (hereinafter referred to as “combination A”) is also preferable. Then, with respect to the combinations listed in Table 1 or combination A, as the structural unit (E1), at least one unit selected from the group consisting of the formula (14-1) and the formula (14-3) is used. A combination including a monomer is also preferable.

  The weight average molecular weight of the resist polymer of the present invention is not particularly limited, but is preferably 2,000 or more, more preferably 3,000 or more, from the viewpoint of dry etching resistance and resist pattern shape, It is particularly preferably 4,000 or more, more preferably 5,000 or more. Further, the mass average molecular weight of the resist polymer of the present invention is preferably 100,000 or less, more preferably 50,000 or less, and more preferably 30,000, from the viewpoints of solubility in a resist solution and resolution. The following is particularly preferable, and 20,000 or less is more preferable.

  The molecular weight distribution of the resist polymer of the present invention is not particularly limited, but is preferably 2.5 or less, more preferably 2.0 or less, from the viewpoint of solubility in a resist solution and resolution. .8 or less is particularly preferable.

Next, a method for producing the resist polymer of the present invention will be described.
The method for producing the resist polymer of the present invention is not particularly limited as long as it is performed by solution polymerization. The polymerization method for solution polymerization is not particularly limited, and may be batch polymerization or dropping polymerization. Among these, a polymerization method called dropping polymerization in which a monomer is dropped into a polymerization vessel is preferable from the viewpoint that a polymer having a narrow composition distribution and / or molecular weight distribution can be easily obtained. The monomer to be dropped may be a monomer alone or a solution in which the monomer is dissolved in an organic solvent.

  In the drop polymerization method, for example, an organic solvent is charged in a polymerization vessel in advance (this organic solvent is also referred to as a “charged solvent”), heated to a predetermined polymerization temperature, and then a monomer and a polymerization initiator are each independently or A solution dissolved in an organic solvent in an arbitrary combination (this organic solvent is also referred to as “dropping solvent”) is dropped into the charged solvent. The monomer may be dropped without being dissolved in the dropping solvent. In that case, the polymerization initiator may be dissolved in the monomer, or a solution in which only the polymerization initiator is dissolved in the organic solvent is organic. It may be dropped into a solvent. Further, the monomer or the polymerization initiator may be dropped into the polymerization vessel in a state where the charged solvent is not in the polymerization vessel.

  The monomer and the polymerization initiator may be directly dropped from an independent storage tank to a charged solvent heated to a predetermined polymerization temperature, or dropped from an independent storage tank to a charged solvent heated to a predetermined polymerization temperature. They may be mixed immediately before the addition and dropped into the charged solvent.

  Furthermore, the timing at which the monomer or the polymerization initiator is dropped into the charging solvent may be dropped after the monomer has been dropped first, or the polymerization initiator may be dropped after the monomer has been dropped. Then, the monomer may be dropped with a delay, or the monomer and the polymerization initiator may be dropped at the same timing. These dropping speeds may be constant until the dropping is completed, or may be changed in multiple stages according to the consumption speed of the monomer or polymerization initiator, or intermittently. The dripping may be stopped or started.

  Although the polymerization temperature in the dropping polymerization method is not particularly limited, it is usually preferably in the range of 50 to 150 ° C.

  As an organic solvent used in the dropping polymerization method, a known solvent can be used as a polymerization solvent. For example, a chain ether such as ether (diethyl ether, propylene glycol monomethyl ether (hereinafter also referred to as “PGME”), tetrahydrofuran ( (Hereinafter also referred to as “THF”), cyclic ethers such as 1,4-dioxane), esters (methyl acetate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, propylene glycol monomethyl ether acetate (hereinafter also referred to as “PGMEA”). ), Ketone (acetone, methyl ethyl ketone (hereinafter also referred to as “MEK”), methyl isobutyl ketone (hereinafter also referred to as “MIBK”), amide (N, N-dimethylacetamide, N, N-dimethylformamide). ), Sulfoxide Such as dimethyl sulfoxide), hydrocarbons (benzene, toluene, xylene and like aromatic hydrocarbons, aliphatic hydrocarbons such as hexane, and alicyclic hydrocarbons such as cyclohexane), and mixtures of these solvents.

  These solvents may be used alone or in combination of two or more.

  The amount of the polymerization solvent used is not particularly limited and may be determined as appropriate. Usually, it is preferable to use within the range of 30-700 mass parts with respect to 100 mass parts of monomer whole quantity used for copolymerization.

  In the dropping polymerization method, when two or more polymerization solvents are used, the mixing ratio of the polymerization solvent in the dropping solvent and the charged solvent can be set at an arbitrary ratio.

  The monomer concentration of the monomer solution dropped into the organic solvent is not particularly limited, but is preferably in the range of 5 to 50% by mass.

  In addition, the amount of the charged solvent is not particularly limited and may be determined as appropriate. Usually, it is preferable to use within the range of 30-700 mass parts with respect to 100 mass parts of monomer whole quantity used for copolymerization.

  The resist polymer of the present invention is usually obtained by polymerizing a monomer composition containing one or more monomers having a naphthalene skeleton represented by the formula (1) in the presence of a polymerization initiator. can get. The polymerization initiator is preferably one that generates radicals efficiently by heat. Examples of such a polymerization initiator are 2,2′-azobisisobutyronitrile (hereinafter also referred to as AIBN) and dimethyl-2,2′-azobisisobutyrate (hereinafter also referred to as DAIB). ), 2,2′-azobis [2- (2-imidazolin-2-yl) propane] and the like; 2,5-dimethyl-2,5-bis (tert-butylperoxy) hexane, di (4 -Tert-butylcyclohexyl) peroxydicarbonate and other organic peroxides.

  In addition, when producing a resist polymer used in ArF excimer laser (wavelength: 193 nm) lithography, the light transmittance of the resulting resist polymer (transmittance for light with a wavelength of 193 nm) is not reduced as much as possible. The polymerization initiator preferably has no aromatic ring in the molecular structure. Furthermore, in consideration of safety during polymerization, the polymerization initiator preferably has a 10-hour half-life temperature of 60 ° C. or higher.

  The amount of the polymerization initiator used is not particularly limited, but is preferably 0.3 mol parts or more with respect to 100 mol parts of the total amount of monomers used for copolymerization, from the viewpoint of increasing the yield of the copolymer. More than the molar part is more preferable, and from the point of narrowing the molecular weight distribution of the copolymer, the molar amount is preferably 30 parts by mole or less with respect to 100 parts by mole of the total amount of monomers used for copolymerization.

  When producing the resist polymer of the present invention, a chain transfer agent (hereinafter referred to as a chain transfer agent) may be used as long as the storage stability of the resist composition is not impaired. Examples of such chain transfer agents include 1-butanethiol, 2-butanethiol, 1-octanethiol, 1-decanethiol, 1-tetradecanethiol, cyclohexanethiol, 2-methyl-1-propanethiol, 2- Examples include hydroxyethyl mercaptan.

  ArF excimer laser (wavelength: 193 nm) When producing a resist polymer used in lithography, chain transfer from the point that the light transmittance (transmittance to light with a wavelength of 193 nm) of the resulting resist polymer is not lowered as much as possible. The agent preferably has no aromatic ring.

  The polymer solution produced by solution polymerization is diluted to a suitable solution viscosity with a good solvent such as 1,4-dioxane, acetone, THF, MEK, MIBK, γ-butyrolactone, PGMEA, and PGME as necessary. Then, it is dropped into a large amount of poor solvent such as methanol, water, hexane, heptane, etc. to precipitate the polymer. This process is generally called reprecipitation and is very effective for removing unreacted monomers, polymerization initiators, and the like remaining in the polymerization solution. If these unreacted substances remain as they are, there is a possibility of adversely affecting the resist performance. Therefore, it is preferable to remove them as much as possible. The reprecipitation process may be unnecessary depending on circumstances. Thereafter, the precipitate is filtered off and sufficiently dried to obtain the polymer of the present invention. Moreover, after filtering off, it can also be used with a wet powder, without drying.

  The produced polymer solution can be used as a resist composition as it is or after diluting with an appropriate solvent. At that time, additives such as a storage stabilizer may be appropriately added.

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

  The resist composition of the present invention is obtained by dissolving the resist polymer of the present invention in a solvent. The chemically amplified resist composition of the present invention is obtained by dissolving the resist polymer of the present invention and a photoacid generator in a solvent. The resist polymer of the present invention may be used alone or in combination of two or more. In addition, without separating the polymer from the polymer solution obtained by solution polymerization or the like, the polymer solution is used as it is for the resist composition, or the polymer solution is diluted with an appropriate solvent, or It can also be concentrated and used in a resist composition.

  Examples of the solvent include linear or branched ketones such as methyl ethyl ketone, methyl isobutyl ketone, 2-pentanone and 2-hexanone; cyclic ketones such as cyclopentanone and cyclohexanone; propylene glycol monomethyl ether acetate, propylene glycol monoethyl Propylene glycol monoalkyl acetates such as ether acetate; Ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether and propylene glycol monoethyl ether Class: ethylene glycol monomethyl ether, ethylene glycol monoe Ethylene glycol monoalkyl ethers such as ether; diethylene glycol alkyl ethers such as diethylene glycol dimethyl ether and diethylene glycol monomethyl ether; esters such as ethyl acetate and ethyl lactate; n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, cyclohexanol, 1 -Alcohols such as octanol; 1,4-dioxane, ethylene carbonate, γ-butyrolactone and the like. These solvents may be used alone or in combination of two or more.

  The content of the solvent is usually 200 to 5000 parts by mass and more preferably 300 to 2000 parts by mass with respect to 100 parts by mass of the resist polymer.

  When the resist polymer of the present invention is used for a chemically amplified resist, it is necessary to use a photoacid generator.

  The photoacid generator contained in the chemically amplified resist composition of the present invention can be arbitrarily selected from those that can be used as the acid generator of the chemically amplified resist composition. A photo-acid generator may use 1 type or may use 2 or more types together.

  Examples of such a photoacid generator include onium salt compounds, sulfonimide compounds, sulfone compounds, sulfonic acid ester compounds, quinonediazide compounds, diazomethane compounds, and the like. As the photoacid generator, among them, onium salt compounds such as sulfonium salts, iodonium salts, phosphonium salts, diazonium salts, pyridinium salts are preferable, specifically, triphenylsulfonium triflate, triphenylsulfonium hexafluoroantimonate, Triphenylsulfonium naphthalenesulfonate, (hydroxyphenyl) benzylmethylsulfonium toluenesulfonate, diphenyliodonium triflate, diphenyliodonium pyrenesulfonate, diphenyliodonium dodecylbenzenesulfonate, diphenyliodonium hexafluoroantimonate, p-methylphenyldiphenylsulfonium nonafluorobutanesulfonate, Tri (tert-butylphenyl) sulfonium trifluor B methanesulfonate, and the like.

  The content of the photoacid generator is appropriately determined depending on the type of the photoacid generator selected, but is usually 0.1 parts by mass or more and 0.5 parts by mass with respect to 100 parts by mass of the resist polymer. More preferably. By setting the content of the photoacid generator within this range, a chemical reaction due to the catalytic action of the acid generated by exposure can be sufficiently caused. Moreover, content of a photo-acid generator is 20 mass parts or less normally with respect to 100 mass parts of resist polymers, and it is more preferable that it is 10 mass parts or less. By setting the content of the photoacid generator within this range, the stability of the resist composition is improved, and the occurrence of uneven coating during application of the composition and scum during development is sufficiently reduced.

  Furthermore, a nitrogen-containing compound can also be mix | blended with the chemically amplified resist composition of this invention. By containing a nitrogen-containing compound, the resist pattern shape, the stability over time, and the like are further improved. In other words, the cross-sectional shape of the resist pattern is closer to a rectangle, and the resist film is exposed, post-exposure baked (PEB), and left for several hours before the next development process. However, the deterioration of the cross-sectional shape of the resist pattern is further suppressed when such leaving (aging) is performed.

  As the nitrogen-containing compound, any known compounds can be used, but amines are preferable, and among them, secondary lower aliphatic amines and tertiary lower aliphatic amines are more preferable.

  Here, the “lower aliphatic amine” refers to an alkyl or alkyl alcohol amine having 5 or less carbon atoms.

  Examples of the secondary lower aliphatic amine and tertiary lower aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, tripentylamine, diethanolamine, triethanolamine and the like. Is mentioned. Among these nitrogen-containing compounds, tertiary alkanolamines such as triethanolamine are more preferable.

  The nitrogen-containing compound may be used alone or in combination of two or more.

  The content of the nitrogen-containing compound is appropriately determined depending on the type of the selected nitrogen-containing compound, but is usually preferably 0.01 parts by mass or more with respect to 100 parts by mass of the resist polymer. By setting the content of the nitrogen-containing compound within this range, the resist pattern shape can be made more rectangular. Moreover, it is preferable that content of a nitrogen-containing compound is 2 mass parts or less normally with respect to 100 mass parts of resist polymers. By setting the content of the nitrogen-containing compound within this range, it is possible to reduce the sensitivity deterioration.

  In addition, the chemically amplified resist composition of the present invention may contain an organic carboxylic acid, a phosphorus oxo acid, or a derivative thereof. By containing these compounds, it is possible to prevent sensitivity deterioration due to the compounding of the nitrogen-containing compound, and further improve the resist pattern shape, the stability with time of standing, and the like.

  As the organic carboxylic acid, for example, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid and the like are preferable.

  Phosphorus oxoacids or derivatives thereof include, for example, phosphoric acid, phosphoric acid di-n-butyl ester, phosphoric acid diphenyl ester and other phosphoric acid and derivatives thereof; phosphonic acid, phosphonic acid dimethyl ester Phosphonic acids such as phosphonic acid di-n-butyl ester, phenylphosphonic acid, phosphonic acid diphenyl ester, phosphonic acid dibenzyl ester, etc. and derivatives thereof; phosphinic acids such as phosphinic acid, phenylphosphinic acid and their Examples thereof include derivatives such as esters, and among them, phosphonic acid is preferable.

  These compounds (organic carboxylic acid, phosphorus oxo acid, or derivatives thereof) may be used alone or in combination of two or more.

  The content of these compounds (organic carboxylic acid, phosphorus oxo acid, or derivative thereof) is appropriately determined depending on the type of the selected compound and the like. It is preferably 01 parts by mass or more. By setting the content of these compounds within this range, the resist pattern shape can be made more rectangular. Further, the content of these compounds (organic carboxylic acid, phosphorus oxo acid, or a derivative thereof) is usually preferably 5 parts by mass or less with respect to 100 parts by mass of the resist polymer. By reducing the content of these compounds within this range, the film loss of the resist pattern can be reduced.

  Note that both the nitrogen-containing compound and the organic carboxylic acid, phosphorus oxoacid, or a derivative thereof can be contained in the chemically amplified resist composition of the present invention, or only one of them can be contained. .

  Furthermore, the resist composition of the present invention may contain various additives such as surfactants, other quenchers, sensitizers, antihalation agents, storage stabilizers, and antifoaming agents as necessary. it can. Any of these additives can be used as long as it is known in the art. Moreover, the compounding quantity of these additives is not specifically limited, What is necessary is just to determine suitably.

  The resist polymer of the present invention may be used as a resist composition for metal etching, photofabrication, plate making, hologram, color filter, retardation film and the like.

  Next, an example of the manufacturing method of the board | substrate with which the pattern of this invention was formed is demonstrated.

  First, the resist composition of the present invention is applied to the surface of a substrate to be processed such as a silicon wafer on which a pattern is formed by spin coating or the like. And the to-be-processed board | substrate with which this resist composition was apply | coated is dried by baking processing (prebaking) etc., and a resist film is manufactured on a board | substrate.

Next, the resist film thus obtained is irradiated with light through a photomask (exposure). The light used for exposure is preferably a KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (157 nm), or EUV excimer laser (13.5 nm) having a wavelength of 250 nm or less, An ArF excimer laser is particularly preferable. It is also preferable to expose with an electron beam.

  On the other hand, immersion exposure in which exposure is performed with a high refractive index liquid such as pure water, perfluoro-2-butyltetrahydrofuran, or perfluorotrialkylamine interposed between the resist film and the final lens of the exposure apparatus. May be performed.

  After exposure, heat treatment is appropriately performed (post-exposure baking, PEB), the substrate is immersed in an alkaline developer, and the exposed portion is dissolved and removed in the developer (development). Any known alkaline developer may be used. Then, after development, the substrate is appropriately rinsed with pure water or the like. In this way, a resist pattern is manufactured on the substrate to be processed.

  Then, the processed substrate on which the resist pattern has been manufactured is appropriately heat-treated (post-baked) to strengthen the resist and selectively etch the portion without the resist. After the etching, the resist is removed with a release agent to obtain a substrate on which a pattern is formed.

  Finally, the production method of the polymerizable monomer of the present invention will be described with reference to formula (8-1), formula (8-2), formula (8-25), and formula (8-113).

  First, the polymerizable monomer represented by the formula (8-1) is (meth) acrylic acid 2-methanesulfonyloxyethyl (the following formula (15-2)) or (meth) acrylic acid 2-p-toluenesulfonyloxyethyl. (Formula (15-3) below) and 2,3-dihydroxynaphthalene (Formula (15-1) below) are reacted under basic conditions to form an ether bond with one hydroxyl group of 2,6-dihydroxynaphthalene. Can be obtained.

(R represents a hydrogen atom or a methyl group.)

  The basic compound is not particularly limited, but includes bases containing alkali metals such as potassium carbonate, sodium hydroxide, potassium hydroxide, sodium (meth) acrylate, potassium (meth) acrylate, sodium methoxide, sodium ethoxide. Side, alkali metal alkoxides such as potassium tert-butoxide, organic amines such as triethylamine, diisopropylethylamine, pyridine and dimethylaminopyridine, and organic metals such as sodium hydride, methyllithium and n-butyllithium. Although the usage-amount in particular of a basic compound is not restrict | limited, (Meth) acrylic acid 2-methanesulfonyloxyethyl (15-2) or (meth) acrylic acid 2-p-toluenesulfonyloxyethyl (15-3) 100 The range of 20 to 400 mol is preferable with respect to mol. When the usage-amount of a basic compound is 50 mol or more, it exists in the tendency which can obtain the polymerizable monomer of Formula (8-6) with a sufficient yield. Moreover, when the usage-amount is 200 mol or less, it exists in the tendency which can suppress the production | generation of the di (meth) acrylate body which is a by-product.

  The amount of 2,3-dihydroxynaphthalene (15-1) used is not particularly limited, but 2-methanoxyloxyethyl (meth) acrylate (15-2) or 2-p-toluene (meth) acrylate. The range of 10-400 mol is preferable with respect to 100 mol of sulfonyloxyethyl (15-3). When the amount of 2,3-dihydroxynaphthalene (15-1) used is 50 mol or more, the polymerizable monomer (8-1) tends to be obtained with good yield. Moreover, when the usage-amount is 200 mol or less, it exists in the tendency which can suppress the production | generation of the di (meth) acrylate body which is a by-product.

  The reaction temperature is not particularly limited, but is preferably in the range of −20 ° C. to 200 ° C. When the reaction temperature is −20 ° C. or higher, the polymerizable monomer of the formula (8-1) tends to be obtained with good yield. Moreover, when reaction temperature is 200 degrees C or less, it exists in the tendency which can suppress the production | generation of the di (meth) acrylate body which is a by-product. The reaction temperature is particularly preferably in the range of 0 to 160 ° C.

  Further, this reaction may be carried out using a solvent, and examples thereof include methanol, ethanol, tert-butanol, toluene, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, acetonitrile, dichloromethane, chloroform, benzene and the like. From the viewpoint of the solubility of 2,6-dihydroxynaphthalene, methanol, tert-butanol, toluene, tetrahydrofuran, dimethylformamide, dimethylsulfoxide, and acetonitrile are more preferable.

  The synthetic reaction of the polymerizable monomer represented by the formula (8-1) was carried out by using 2-methansulfonyloxyethyl (meth) acrylate (15-2) or 2-p-toluenesulfonyloxyethyl (meth) acrylate (15-3). ) And 2,3-dihydroxynaphthalene (15-1) and a basic compound may be charged at once, but after preparing a solution of 2,3-dihydroxynaphthalene (15-1) and a basic compound Then, the reaction was carried out while dropping (meth) acrylic acid 2-methanesulfonyloxyethyl (15-2), (meth) acrylic acid 2-p-toluenesulfonyloxyethyl (15-3), or a solution thereof dropwise into this solution. It may be carried out, and (meth) acrylic acid 2-methanesulfonyloxyethyl (15-2) or (meth) acrylic acid 2-p-toluene Solution 2,3-dihydroxynaphthalene (15-1) and a basic compound solution ho oxy ethyl (15-3) may be performed dropwise while reacting.

  Next, a method for producing the polymerizable monomer represented by the formula (8-2) will be described. The polymerizable monomer represented by the formula (8-2) is (meth) acrylic acid 2-methanesulfonyloxyethyl (the following formula (15-2)) or (meth) acrylic acid 2-p-toluenesulfonyloxyethyl (the following). Formula (15-3)) and 2,6-dihydroxynaphthalene (following formula (15-4)) are reacted under basic conditions to form an ether bond with one hydroxyl group of 2,6-dihydroxynaphthalene. be able to.

(R represents a hydrogen atom or a methyl group.)

  The reaction conditions are not particularly limited. For example, the polymerizable monomer represented by the formula (8-2) can be obtained under the same conditions as those for synthesizing the polymerizable monomer represented by the formula (8-1) described above.

  Further, the polysynthetic monomer represented by the formula (8-2) can be produced by another method besides the above method. For example, 2-methansulfonyloxyethyl (meth) acrylate (following formula (15-2)) or 2-p-toluenesulfonyloxyethyl (meth) acrylate (following formula (15-3)) and 2-acetoxy It reacts with -6-hydroxynaphthalene (following formula (15-8)) to form an ether bond to obtain 2- (6-acetoxynaphthaleneoxy) ethyl (meth) acrylate of the following formula (15-5). After deprotecting the acetyl group of the formula (15-5) compound by a deprotection reaction, a polymerizable monomer represented by the formula (8-2) can be obtained.

(R represents a hydrogen atom or a methyl group.)

  The basic compound is not particularly limited, but includes bases containing alkali metals such as potassium carbonate, sodium hydroxide, potassium hydroxide, sodium (meth) acrylate, potassium (meth) acrylate, sodium methoxide, sodium ethoxide. Side, alkali metal alkoxides such as potassium tert-butoxide, organic amines such as triethylamine, diisopropylethylamine, pyridine and dimethylaminopyridine, and organic metals such as sodium hydride, methyllithium and n-butyllithium. Although the usage-amount in particular of a basic compound is not restrict | limited, (Meth) acrylic-acid 2-methanesulfonyloxyethyl (15-2) or (meth) acrylic-acid 2-p-toluenesulfonyloxyethyl (15-3) 100 mol The range of 20 to 200 mol is preferable, and the range of 50 to 150 mol is more preferable. Within this range, 2- (6-acetoxynaphthaleneoxy) ethyl (15-5) (meth) acrylate can be obtained with good yield.

  The amount of 2-acetoxy-6-hydroxynaphthalene (15-8) used is not particularly limited, but is 2-methanoxylethyl (meth) acrylate (15-2) or 2-p- (meth) acrylic acid. The range of 50-200 mol is preferable with respect to 100 mol of toluenesulfonyloxyethyl (15-3), and the range of 50-150 mol is more preferable. Within this range, 2- (6-acetoxynaphthaleneoxy) ethyl (15-5) (meth) acrylate can be obtained with good yield.

  The reaction temperature is not particularly limited, but is preferably in the range of −20 ° C. to 200 ° C. When the reaction temperature is −20 ° C. or higher, the polymerizable monomer tends to be obtained with good yield. Moreover, when reaction temperature is 200 degrees C or less, it exists in the tendency which can suppress side reactions, such as deacetylation. The reaction temperature is particularly preferably in the range of 0 to 140 ° C.

  Further, this reaction may be carried out using a solvent, and examples thereof include methanol, ethanol, tert-butanol, toluene, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, acetonitrile, dichloromethane, chloroform, benzene and the like. From the viewpoint of the solubility of 2-acetoxy-6-hydroxynaphthalene (15-8), methanol, tert-butanol, toluene, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, and acetonitrile are more preferable.

  The synthesis reaction of 2- (6-acetoxynaphthaleneoxy) ethyl (15-5) (meth) acrylic acid was carried out using 2-methanoxyloxyethyl (15-2) or (meth) acrylic acid 2-p. -Toluenesulfonyloxyethyl (15-3), 2-acetoxy-6-hydroxynaphthalene (15-8) and a basic compound may be charged all at once, but 2-acetoxy-6-hydroxynaphthalene (15 -8) and a basic compound solution were prepared, and then 2-methansulfonyloxyethyl (meth) acrylate (15-2) or 2-p-toluenesulfonyloxyethyl (meth) acrylate (15-3) was added to this solution. ), Or the reaction may be carried out while dropping the solution, and 2-mesyloxyethyl (meth) acrylate 15-2) or 2-tosyloxyethyl (meth) acrylic acid ester (15-3) may be reacted while 2-acetoxy-6-hydroxynaphthalene (15-8) and a base compound solution are added dropwise. good.

  The deprotection reaction of the acetyl group is not particularly limited, and examples thereof include a method of performing an ester hydrolysis reaction in the presence of an acid or a base or a biocatalyst exhibiting ester hydrolysis activity. The acidic compound is not particularly limited, and examples thereof include acids such as hydrochloric acid, sulfuric acid, methanesulfonic acid, tosylic acid and acetic acid, and Lewis acids containing atoms such as boron and tin. Although it does not restrict | limit especially as the usage-amount of an acid catalyst, The range of 0.1-10 mol is preferable with respect to 100 mol of 2- (6-acetoxynaphthaleneoxy) ethyl (15-5) (meth) acrylic acid. When the amount of the acid catalyst used is 0.1 mol or more, the reaction rate tends to be increased, and when it is 10 mol or less, the formation of by-products tends to be suppressed. The lower limit of the amount of the acid catalyst used is more preferably 0.5 mol or more, and the upper limit is more preferably 3 mol or less.

  Further, the basic compound is not particularly limited, but a base containing an alkali metal such as potassium carbonate, sodium hydroxide, potassium hydroxide, sodium (meth) acrylate, potassium (meth) acrylate, sodium methoxide, Examples include alkali metal alkoxides such as sodium ethoxide and potassium tert-butoxide, and organic bases such as triethylamine, diisopropylethylamine, pyridine and dimethylaminopyridine. Although the usage-amount of a basic compound is not restrict | limited in particular, The range of 10-200 mol is preferable with respect to 100 mol of 2- (6-acetoxynaphthaleneoxy) ethyl (15-5) (meth) acrylic acid.

  Although it does not restrict | limit especially as a biocatalyst which shows ester hydrolysis activity, A lipase, esterase, etc. are mentioned. Although the usage-amount of a biocatalyst is not restrict | limited in particular, 0.1-100 weight part is preferable with respect to 100 weight part of (meth) acrylic acid 2- (6-acetoxynaphthaleneoxy) ethyl (15-5).

  The reaction temperature for the deprotection reaction is not particularly limited, but is preferably in the range of -20 to 100 ° C. When the reaction temperature is −20 ° C. or higher, the reaction time tends to be shortened, and when it is 100 ° C. or lower, the formation of by-products tends to be suppressed. The reaction temperature is more preferably in the range of 0 to 70 ° C.

  Next, a method for producing the polymerizable monomer represented by the formula (8-25) will be described. The polymerizable monomer represented by the formula (8-25) is (meth) acrylic acid 3-methanesulfonyloxy-n-propyl (the following formula (15-6)) or (meth) acrylic acid 3-p-toluenesulfonyloxy. -N-propyl (following formula (15-7)) and 2,6-dihydroxynaphthalene (following formula (15-4)) are reacted under basic conditions, and one hydroxyl group of 2,6-dihydroxynaphthalene and ether It can be obtained by forming a bond.

(R represents a hydrogen atom or a methyl group.)

  Although the reaction conditions are not particularly limited, for example, the polymerizable monomer represented by the formula (8-25) can be obtained under the same conditions as those for synthesizing the polymerizable monomer represented by the formula (8-1) described above. Moreover, after obtaining the compound which has an acetoxy group similarly to Formula (8-2), the method of deprotecting may be used.

  Finally, a method for producing the polymerizable monomer represented by the formula (8-113) of the present invention will be described. The polymerizable monomer represented by formula (8-113) is, for example, 2-bromo-6-t-butoxycarbonyloxynaphthalene represented by formula (15-9) or 2-chloro-6-t represented by formula (15-10). It can be obtained by reacting -butoxycarbonyloxynaphthalene with sodium (meth) acrylate ethyl oxide of the following formula (15-11) or potassium (meth) acrylate ethyl oxide of the following formula (15-12). it can.

(R represents a hydrogen atom or a methyl group.)

  The amount of sodium (meth) acrylate ethyl oxide (15-11) or potassium (meth) acrylate ethyl oxide (15-12) is not particularly limited, but 2-bromo-6--6 of formula (15-9) is not limited. The range of 70-500 mol is preferable with respect to 100 mol of t-butoxycarbonyloxynaphthalene or 2-chloro-6-t-butoxycarbonyloxynaphthalene of the formula (15-10). When the amount used is 70 mol or more, the polymerizable monomer of the formula (8-113) tends to be obtained with good yield. Moreover, when this usage-amount is 500 mol or less, it exists in the tendency which can suppress a by-product production | generation. The amount used is particularly preferably in the range of 100 to 200 mol.

  The reaction temperature is not particularly limited, but is preferably in the range of −20 ° C. to 100 ° C. When the reaction temperature is −20 ° C. or higher, the polymerizable monomer of the formula (8-113) tends to be obtained with good yield. Moreover, when reaction temperature is 100 degrees C or less, it exists in the tendency which can suppress the production | generation of the dimethacrylate body which is a by-product. The reaction temperature is particularly preferably in the range of 0 to 50 ° C.

  In addition, this reaction may be carried out using a solvent, and examples thereof include toluene, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, acetonitrile, dichloromethane, chloroform, benzene and the like. In view of the solubility of 2-bromo-6-t-butoxycarbonyloxynaphthalene of the formula (15-9) or 2-chloro-6-t-butoxycarbonyloxynaphthalene of the formula (15-10), toluene, tetrahydrofuran, More preferred are dimethylformamide, dimethyl sulfoxide, and acetonitrile.

  The method for recovering the generated polymerizable monomers of the formulas (8-1), (8-2), (8-25), and (8-113) from the reaction solution is not particularly limited, but the solvent is distilled off under reduced pressure. And recovering crystals by crystallization. The crystallization operation is preferable in terms of chemical purity of the polymerizable monomers of the recovered formulas (8-1), (8-2), (8-25), and (8-113). Although polymerizable monomer crystals of the formulas (8-1), (8-2), (8-25), and (8-113) may be precipitated from the reaction solution, the points such as the yield and chemical purity are usually used. After substituting the solvent with a suitable solvent, the desired polymerizable monomer crystal is precipitated.

  Solvents include water, methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, 2-butanol, tert-butanol, n-amyl alcohol, cyclopropanol, n-hexyl alcohol, cyclohexanol, 1-octanol, Alcohol solvents such as octanol, or ester solvents such as methyl acetate, ethyl acetate, propyl acetate, methyl lactate, and ethyl lactate, or ketone solvents such as acetone, methyl ethyl ketone, MIBK, cyclopentanone, cyclohexanone, petroleum ether, dimethyl ether , Ethers such as diethyl ether, dimethoxymethane, diethoxyethane, diisopropyl ether, methyl tert-butyl ether, 1,4-dioxane, tetrahydrofuran Agents, or n- pentane, n- hexane, n- heptane, n- octane, isooctane, cyclopentane, cyclohexane, benzene, toluene, xylene, chloroform, methylene chloride, and a hydrocarbon-based solvent such as dichloroethane. After replacing the solvent of the reaction solution with a solution containing at least one of these solvents, polymerization of formulas (8-1), (8-2), (8-25), and (8-113) A crystalline monomer crystal. The solvent is preferably at least one solvent selected from water, alcohols, esters, ethers or hydrocarbons in terms of recovery yield and chemical purity. Moreover, you may perform impurity removal operation, such as filtration, washing | cleaning, adsorption | suction, before depositing a crystal | crystallization.

  The precipitated crystals are isolated by a known method, for example, vacuum filtration, pressure filtration, centrifugation, etc., and have the formulas (8-1), (8-2), (8-25), and (8-113). The polymerizable monomer is recovered. The isolation temperature is not particularly limited, but is preferably in the range of -40 to 40 ° C. When the isolation temperature is −40 ° C. or higher, the chemical purity of the polymerizable monomer recovered tends to increase, and when the isolation temperature is 40 ° C. or lower, the recovery yield of the polymerizable monomer tends to increase. .

  Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto. In addition, “part” in each example and comparative example means “part by mass” unless otherwise specified.

  Moreover, the copolymerizability of the resist polymer, the resist polymer, and the resist composition were evaluated as follows.

1. Evaluation of resist polymer <content of each structural unit>
The content of the constituent units of the resist polymer is determined by ^{1 H-NMR} in the case where it can be determined by ^{the 1 H-NMR} measurement, can not be determined by ^{the 1 H-NMR} measurement by such overlapping proton peak In some cases, it was determined by ¹³ C-NMR measurement.

The measurement of ¹ H-NMR was carried out using JNM-GX270 type FT-NMR (trade name) manufactured by JEOL Ltd., and a resist polymer sample solution (deuterated chloroform solution or deuterium) of about 5% by mass. Hydrogenated dimethyl sulfoxide solution) was put in a test tube having a diameter of 5 mmφ, and the measurement was performed at an observation frequency of 270 MHz and a single pulse mode with 64 integrations. The measurement temperature was 40 ° C. when deuterated chloroform was used as the solvent, and 60 ° C. when deuterated dimethyl sulfoxide was used as the solvent.

^In the case of ¹³ C-NMR measurement, using a UNITY-INOVA type FT-NMR (trade name) manufactured by Varian Technologies, an approximately 20% by mass resist polymer sample solution of deuterated dimethyl sulfoxide has a diameter of 5 mmφ. And 50000 times of integration using a proton complete decoupling method in which the measurement temperature is 60 ° C., the observation frequency is 125 MHz, and the nuclear overhauser effect (NOE) is removed.

<Mass average molecular weight>
About 20 mg of the resist polymer is dissolved in 5 mL of tetrahydrofuran (THF), filtered through a 0.5 μm membrane filter to prepare a sample solution, and this sample solution is subjected to Tosoh gel permeation chromatography (GPC). And measured. In this measurement, a separation column is manufactured by Showa Denko, Shodex GPC K-805L (trade name) in series, the solvent is THF, the flow rate is 1.0 mL / min, the detector is a differential refractometer, the measurement temperature Measurements were made using polystyrene as the standard polymer at 40 ° C. and an injection volume of 0.1 mL.

<Light transmittance>
5 parts of the produced resist polymer and 45 parts of PGMEA as a solvent were mixed to obtain a uniform solution, and then filtered through a membrane filter having a pore size of 0.1 μm to prepare a polymer composition solution.

  The prepared polymer composition solution was spin-coated on a quartz wafer and prebaked at 120 ° C. for 60 seconds using a hot plate to produce a resist film having a thickness of 1 μm.

  A polymer thin film produced on a quartz wafer is placed on the sample side, and an untreated quartz wafer is placed on the reference side, and a wavelength range using an ultraviolet / visible absorptiometer UV-3100 (trade name) manufactured by Shimadzu Corporation. Was measured at 192 to 194 nm, the scan speed was set to medium speed, the sampling pitch was automatically set, and the slit width was set to 2.0, and the light transmittance at 193 nm was obtained.

2. Evaluation of Resist Composition Using the produced polymer, a resist composition was prepared as follows, and its performance was evaluated.

<Preparation of resist composition>
100 parts of the prepared resist polymer, 2 parts of triphenylsulfonium triflate as a photoacid generator, 720 parts of PGMEA as a solvent and 180 parts of ethyl lactate were mixed to obtain a uniform solution, and then the pore size was 0.1 μm. It filtered with the membrane filter and prepared the resist composition solution.

<Sensitivity>
The prepared resist composition solution was spin-coated on a silicon wafer and prebaked at 120 ° C. for 60 seconds using a hot plate to produce a resist film having a thickness of 0.3 μm. Next, after exposure using an ArF excimer laser exposure machine (wavelength: 193 nm) using a line-and-space pattern mask, post-exposure baking was performed at 110 ° C. for 60 seconds using a hot plate. Subsequently, development was performed at room temperature using a 2.38% tetramethylammonium hydroxide aqueous solution, washed with pure water, and dried to form a resist pattern.

At this time, the exposure amount (mJ / cm ² ) at which the mask pattern of 0.16 μm was transferred to the resist line width of 0.16 μm was measured as sensitivity.

<Resolution>
Further, the minimum dimension (μm) of the resist pattern resolved when exposed with the above exposure amount was defined as the resolution.

<Defect amount>
About the resist pattern obtained above, the number of development defects was measured using a surface defect observation apparatus KLA2132 (trade name) manufactured by KLA Tencor Co., Ltd., and used as a defect amount.

<Dry etching resistance>
A silicon wafer coated with a resist film having a thickness of 0.3 μm was dry-etched with an SPE-220T dry etching apparatus (trade name) manufactured by Showa Vacuum Co., Ltd. The processing conditions were such that the gas type and gas flow rate were CF ₄ / O ₂ = 95 sccm / 5.0 sccm, the processing chamber pressure was 15 Pa, the plasma power was 400 W, and the processing time was 2 minutes. The film thickness of the resist film before and after the dry etching treatment was measured using a Lambda Ace VM-8000J type optical interference type film thickness measuring device (trade name) manufactured by Dainippon Screen Mfg. Co., Ltd. The measurement method was to measure the film thickness at a total of five points including the wafer center and points moved 25 mm up, down, left and right from the center, and the average value was defined as the resist film thickness. The dry etching resistance is the film thickness (T) of the sample before the dry etching process, the film thickness (t) after the process, the film thickness (T ₀ ) of the reference cresol novolac resin before the dry etching process, From the film thickness (t ₀ ), the value represented by the following formula (ER) was used.
ER = (T−t) / (T ₀ −t ₀ )

<Example 1>
Into a flask equipped with a nitrogen inlet, a stirrer, a condenser, and a thermometer, 71.9 parts of ethyl lactate was added at room temperature, and then nitrogen was blown into the ethyl lactate for 30 minutes using a ball filter. Thereafter, the temperature of the hot water bath was raised to 80 ° C. while stirring under a nitrogen atmosphere.

26.5 parts of α-methacryloyloxy-γ-butyrolactone (hereinafter referred to as GBLMA) represented by the following formula (51);
32.8 parts of 2-methacryloyloxy-2-methyladamantane (hereinafter referred to as MAdMA) represented by the following formula (52);
9.4 parts of 1-methacryloyloxy-3-hydroxyadamantane (hereinafter referred to as HAdMA) represented by the following formula (53);
17.5 parts of 2-methacryloyloxyethoxy-6-hydroxynaphthalene (hereinafter referred to as HNEMA) represented by the following formula (54);

From a dropping device containing a monomer solution in which 129.4 parts of ethyl lactate and 2.21 parts of dimethyl-2,2′-azobisisobutyrate (hereinafter referred to as DAIB) were mixed, The solution was dropped into the flask at a constant rate over 4 hours. Then, the temperature of 80 degreeC was hold | maintained for 3 hours.

  Next, the obtained reaction solution was dropped into a mixed solvent of about 10 times the amount of methanol / water = 80% by volume / 20% by volume with stirring to precipitate a white precipitate (resist polymer A-1). Got. The resulting precipitate was filtered off, and again poured into a mixed solvent of about 10 times the amount of methanol / water = 90% by volume / 10% by volume with respect to the reaction solution, and the precipitate was washed with stirring. The washed precipitate was filtered off and dried under reduced pressure at 60 ° C. for about 40 hours. Table 5 shows the molecular characteristics of the resulting resist polymer A-1 and the results of evaluation of the resist composition using the polymer A-1.

<Example 2>
Into a flask equipped with a nitrogen inlet, a stirrer, a condenser, and a thermometer, 72.4 parts of ethyl lactate was added at room temperature, and then nitrogen was blown into the ethyl lactate for 30 minutes using a ball filter. Thereafter, the temperature of the hot water bath was raised to 80 ° C. while stirring under a nitrogen atmosphere.

8- or 9-acryloyloxy-4-oxatricyclo [5.2.1.0 ^2,6 ] decan-3-one represented by the following formula (55) (hereinafter referred to as OTDA) 28.4 Part,
32.1 parts of ethylcyclohexyl methacrylate (hereinafter referred to as ECHMA) represented by the following formula (56);
13.1 part of 2- and 3-cyano-5-norbornyl methacrylate (hereinafter referred to as CNNNMA) represented by the following formula (57);
13.2 parts of 2-methacryloyloxypropyloxy-6-hydroxynaphthalene (hereinafter referred to as HNPMA) represented by the following formula (58);

From a dropping device containing a monomer solution in which 130.4 parts of ethyl lactate and 1.66 parts of DAIB were mixed, the monomer solution was dropped into the flask at a constant rate over 4 hours. Then, the temperature of 80 degreeC was hold | maintained for 3 hours.

  The subsequent operations were carried out by changing the polymer precipitation solvent from methanol / water = 80 vol% / 20 vol% to methanol, and the resulting precipitation washing solvent from methanol / water = 90 vol% / 10 vol% to methanol, respectively. Resist polymer A-2 was obtained in the same manner as in Example 1 except for the change. Table 5 shows the molecular characteristics of the resulting resist polymer A-2 and the results of evaluation of the resist composition using the polymer A-2.

<Example 3>
Into a flask equipped with a nitrogen inlet, a stirrer, a condenser, and a thermometer, 73.5 parts of ethyl lactate was added at room temperature, and then nitrogen was blown into the ethyl lactate for 30 minutes using a ball filter. Thereafter, the temperature of the hot water bath was raised to 80 ° C. while stirring under a nitrogen atmosphere.

28.6 parts of 2-adamantyloxymethyl methacrylate (hereinafter referred to as AdOMMA) represented by the following formula (59);
13.5 parts of 2-methacryloyloxy-2-cyanomethyladamantane (hereinafter referred to as CMAMA) represented by the following formula (60);
7.2 parts of 2-methacryloyloxyethoxy-6-ethoxynaphthalene (hereinafter referred to as EONEMA) represented by the following formula (61),

From a dropping apparatus containing a monomer solution in which 28.6 parts of GBLMA (formula (51)), 132.3 parts of ethyl lactate, and 6.0 parts of DAIB were mixed, the monomer solution was added at a constant rate of 4 It was dropped into the flask over time. Then, the temperature of 80 degreeC was hold | maintained for 3 hours.

  Subsequent operations were performed by changing the polymer precipitation solvent from methanol / water = 80% by volume / 20% by volume to methanol / water = 90% by volume / 10% by volume, and the resulting washing solvent for precipitation by methanol / water = 90% by volume. Polymer for resist A-3 was obtained in the same manner as in Example 1 except that the content was changed from% / 10% by volume to methanol. Table 5 shows the molecular characteristics of the resulting resist polymer A-3 and the results of evaluation of the resist composition using the polymer A-3.

<Example 4>
17.5 parts of 2-methacryloyloxyethoxy-3-hydroxynaphthalene (hereinafter referred to as OHNEMA) represented by the following formula (62) for HNEMA (formula (54)),

Resist polymer A-4 was obtained in the same manner as in Example 1 except for changing to. Table 5 shows the molecular characteristics of the resulting resist polymer A-4 and the results of evaluation of the resist composition using the polymer A-4.

<Example 5>
17.5 parts of 1-methacryloyloxyethoxy-6-hydroxynaphthalene (hereinafter referred to as 1HNEMA) represented by the following formula (63) for HNEMA (formula (54)),

Resist polymer A-5 was obtained in the same manner as in Example 1 except for changing to. Table 5 shows the molecular characteristics of the resulting resist polymer A-5 and the results of evaluation of the resist composition using the polymer A-5.

<Example 6>
Into a flask equipped with a nitrogen inlet, a stirrer, a condenser, and a thermometer, 75.0 parts of ethyl lactate was added at room temperature, and then nitrogen was blown into the ethyl lactate for 30 minutes using a ball filter. Thereafter, the temperature of the hot water bath was raised to 80 ° C. while stirring under a nitrogen atmosphere.

  39.0 parts of AdOMMA (formula (59)), 13.5 parts of CMAMA (formula (60)), 2-methacryloyloxyethoxy-6- (tert-butoxycarbonyloxy) represented by the following formula (64) 8.9 parts of naphthalene (hereinafter referred to as BCNEMA),

From a dropping apparatus containing a monomer solution in which 28.6 parts of GBLMA (formula (51)), 134.9 parts of ethyl lactate, and 5.52 parts of DAIB were mixed, the monomer solution was added at a constant rate. It was dropped into the flask over time. Then, the temperature of 80 degreeC was hold | maintained for 3 hours.

  Subsequent operations were performed in the same manner as in Example 3 to obtain a resist polymer A-6. Table 5 shows the molecular characteristics of the resulting resist polymer A-6 and the results of evaluation of the resist composition using the polymer A-6.

<Comparative Example 1>
Into a flask equipped with a nitrogen inlet, a stirrer, a condenser, and a thermometer, 68.9 parts of ethyl lactate was added at room temperature, and then nitrogen was blown into the ethyl lactate for 30 minutes using a ball filter. Thereafter, the temperature of the hot water bath was raised to 80 ° C. while stirring under a nitrogen atmosphere.

  29.2 parts of GBLMA (Formula (51)), 39.3 parts of MAdMA (Formula (52)), 14.2 parts of HAdMA (Formula (53)), 124.1 parts of ethyl lactate and 2 parts of DAIB From the dropping device containing the monomer solution mixed with .58 parts, the monomer solution was dropped into the flask at a constant rate over 4 hours. Then, the temperature of 80 degreeC was hold | maintained for 3 hours.

  The subsequent operations were the same as those in Example 1, and a resist polymer B-1 was obtained. The molecular properties of the resulting resist polymer B-1 and the results of evaluating the resist composition using the polymer B-1 are shown in Table 5.

<Comparative example 2>
Into a flask equipped with a nitrogen inlet, a stirrer, a condenser, and a thermometer, 69.5 parts of ethyl lactate was added at room temperature, and then nitrogen was blown into the ethyl lactate for 30 minutes using a ball filter. Thereafter, the temperature of the hot water bath was raised to 80 ° C. while stirring under a nitrogen atmosphere.

  6.8 parts of 2-vinyl-6-hydroxynaphthalene (hereinafter referred to as HVN) represented by the following formula (75);

27.2 parts of GBLMA (Formula (51)), 37.4 parts of MAdMA (Formula (52)), 9.4 parts of HAdMA (Formula (53)), 125.0 parts of ethyl lactate and 2 DAIB The monomer solution was dropped into the flask at a constant rate for 4 hours from a dropping device containing the monomer solution mixed with 76 parts. Then, the temperature of 80 degreeC was hold | maintained for 3 hours.

  Subsequent operations were performed in the same manner as in Example 2 to obtain a resist polymer B-2. Table 5 shows the molecular characteristics of the resulting resist polymer B-2 and the results of evaluation of the resist composition using the polymer B-2.

<Comparative Example 3>
13.2 parts of HNPMA (formula (58)) 2-methacryloyloxy-iso-propyloxy-6-hydroxynaphthalene (hereinafter referred to as HNPIPMA) which is a mixture of formula (76) and formula (77)

Resist polymer B-3 was obtained in the same manner as in Example 2 except for changing to. Table 5 shows the molecular characteristics of the resulting resist polymer B-3 and the results of evaluating the resist composition using the polymer B-3.

  The resist polymer of the present invention (Examples 1 to 6) is compared with the resist polymer of Comparative Example 2 and Comparative Example 3 containing a structural unit having a naphthalene skeleton different from the structural unit (A). The light transmittance at the exposure wavelength was excellent.

  Furthermore, the resist composition (Examples 1 to 6) using the resist polymer of the present invention is compared with the resist composition using the resist polymer of Comparative Example 1 that does not contain the structural unit (A). It had sufficient resolution, few defects, and excellent dry etching resistance.

  Moreover, the resist composition (Examples 1-6) using the resist polymer of this invention is the resist polymer of the comparative example 2 containing the structural unit which has a naphthalene skeleton different from a structural unit (A). Compared with the resist composition used, it had sufficient sensitivity and resolution, and was excellent in dry etching resistance.

<Example 7>
The molar extinction constant (1 / mol · cm) of the following formula (65) (model structure of the structural unit obtained by polymerization using the monomer of formula (54)) is calculated by Fujitsu's computational chemistry software “MOPAC” (product) Name).

  Specifically, the molar absorption constant of the formula (65) is obtained by using the atoms constituting the formula (65) and the bond type (a bond type such as a single bond, a double bond, a triple bond, etc.) between the atoms as two-dimensional information. The input modeling is performed, and the structure optimization is performed based on the two-dimensional information by arranging the atoms and bond species in three dimensions so that the potential energy between atoms is minimized by the PM3 method. Then, by calculating the molar absorption constant in the ultraviolet-visible region between each atom whose structure is optimized by the ZINDO-CI PM3 method and summing up in all wavelength regions, the molar absorption constant at an arbitrary wavelength can be obtained. it can. The smaller the molar absorption constant, the better the light transmittance at that wavelength.

  The specific operation method of the structure optimization of the PM3 method by Fujitsu's computational chemistry software “MOPAC” (product name) (on the CAChe (product name) platform) is as follows. After modeling the structural unit on the Workspace screen, Select “New” from the pull-down menu of “Experiment”, and in the newly appearing screen, the item “Profession of ::” is “chemical sample”, the item “Property:” is “optimized geometry”, and “Usage: The item “” is to select “Start” after selecting “PM3 geometry”, and the structure can be optimized by this operation.

A specific operation method for obtaining the molar extinction constant according to the ZINDO-CI PM3 method is to appear newly by selecting “New” from the pull-down menu of “Experiment” with the structure optimized by the PM3. In the screen, the item “Profession of:” is “chemical sample”, the item “Property:” is “UV-visible transitions”, and the item “Using:” is “ZINDO-CI at PM3 geometry”. In the ultraviolet-visible absorption spectrum displayed by selecting “Start” after selecting, and selecting “UV-visible transitions” from the “Analyze” pull-down menu after completing the calculation. It can be determined molar extinction constant at 193 nm.
As a result of the above operation, the molar absorption constant at 193 nm of the compound of the formula (65) was 25 (1 / mol · cm).

<Example 8>
The molar absorption constant (1 / mol · cm) at 193 nm of the following formula (66) (a model structure of a structural unit obtained by polymerization using the monomer of formula (58)) is the same as in Example 7. As a result of calculation, it was 80 (1 / mol · cm).

<Example 9>
The molar absorption constant (1 / mol · cm) at 193 nm of the following formula (67) (a model structure of a structural unit obtained by polymerization using the monomer of formula (62)) is the same as in Example 7. As a result of calculation, it was 75 (1 / mol · cm).

<Example 10>
The molar absorption constant (1 / mol · cm) at 193 nm of the following formula (68) (model structure of the structural unit obtained by polymerization using the monomer of formula (61)) is the same as in Example 7. As a result of calculation, it was 100 (1 / mol · cm).

<Comparative Example 4>
The molar absorption constant (1 / mol · cm) at 193 nm of the following formula (78) (model structure of the structural unit obtained by polymerization using the monomer of formula (76)) is the same as in Example 7. As a result of calculation, it was 350 (1 / mol · cm).

<Comparative Example 5>
The molar absorption constant (1 / mol · cm) at 193 nm of the following formula (79) (model structure of the structural unit obtained by polymerization using the monomer of formula (77)) is the same as in Example 7. As a result of calculation, it was 1200 (1 / mol · cm).

  The structural units of the resist polymer of the present invention (Examples 7 to 10) were compared with the structural units (Comparative Examples 4 and 5) that were not the structural units of the resist polymer of the present invention, and the molar extinction coefficient at 193 nm. Was small. That is, it can be said that the light transmittance at 193 nm is good, and it can be expected that the sensitivity or resolution when used as a resist composition is good.

Example 11 Synthesis of 2-methacryloyloxyethoxy-6-hydroxynaphthalene [HNEMA: Formula (54)]
65.1 g (500.1 mmol) of 2-hydroxyethyl methacrylate (Mitsubishi Rayon Co., Ltd.) was put into a 1 L flask, and 165.0 g of toluene was further added and stirred at 25 ° C. After adding 66.0 g (652.2 mmol) of triethylamine while maintaining the internal temperature of the solution at 5 to 10 ° C., 69.0 g (606.7 mmol) of methanesulfonic acid chloride was added dropwise at an internal temperature of 5 to 15 ° C. . After completion of dropping, the mixture was aged at an internal temperature of 10 to 15 ° C. for 3 hours. 100 ml of pure water of the reaction solution was added dropwise at an internal temperature of 5 to 10 ° C. and stirred for 30 minutes after the addition. After separating the toluene layer, this was washed twice with 100 ml of 20 wt% saline, and the toluene layer was separated and dried over sodium sulfate. After removing sodium sulfate by filtration, toluene was distilled off from the filtrate using an evaporator under the conditions of 40 ° C. and 2660 Pa, and a crude product of 2-methanesulfonyloxyethyl methacrylate (hereinafter referred to as MsEMA) (100. 2 g) was obtained.

  Next, 48.1 g of 2,6-dihydroxynaphthalene (manufactured by Tokyo Chemical Industry Co., Ltd., 300.0 mmol) and 440 ml of anhydrous DMF were introduced into a 1 L flask and stirred to dissolve 2,6-dihydroxynaphthalene. To this solution, 41.5 g (300.0 mmol) of potassium carbonate (anhydrous) was added, and the temperature was raised to an internal temperature of 80 ° C. and stirred for 1 hour. After heating and stirring, a solution obtained by dissolving 41.6 g (200.0 mmol) of MsEMA crude material in 30.0 ml of anhydrous DMF was added for 1.1 hours at an internal temperature of 78 to 82 ° C. using a 100 ml dropping funnel. It was dripped over. After aging at 80 ° C. for 5 hours, the reaction solution was cooled to 10 ° C. This reaction solution was added to 1500 mL of water and stirred while maintaining the internal temperature at 0 to 10 ° C. Further, 700 m of toluene was added and stirred and mixed for 30 minutes, and then the toluene layer and the aqueous layer were separated. The aqueous layer was re-extracted with 700 ml of toluene and combined with the previously separated toluene layer. The whole toluene layer was washed twice with 400 mL of 5 wt% aqueous potassium carbonate solution and twice with 400 mL of pure water, and then the separated toluene layer was dried over sodium sulfate. After removing sodium sulfate by filtration, toluene was distilled off using an evaporator under the conditions of 35 ° C. and 2660 Pa to obtain a crude HNEMA (46.7 g). The resulting crude HNMMA was purified by column chromatography (filler: silica gel NH (manufactured by Fuji Serial Co., eluent: hexane: ethyl acetate = 1: 1), and further hexane: ethyl acetate = 1: 1). After recrystallization, 15.7 g of purified HNEMA was obtained, and an NMR chart of the obtained purified HNEMA is shown in FIG.

Example 12 Synthesis of 2-methacryloyloxypropyloxy-6-hydroxynaphthalene [MNPMA: Formula (58)]
In a 1 L flask, 45.6 g (600.0 mmol) of 1,3-propanediol, 47.4 g (600.0 mmol) of pyridine, and 200 mL of anhydrous THF were charged. To this solution, 62.7 g (600.0 mmol) of methacrylic acid chloride was added dropwise at an internal temperature of 5 to 15 ° C. over 1.5 hours. After completion of dropping, the mixture was aged at an internal temperature of 10 to 15 ° C. for 8 hours. 100 ml of pure water was added dropwise to the reaction solution at an internal temperature of 5 to 10 ° C., followed by stirring for 30 minutes. After extraction by adding 300 mL of ethyl acetate, the ethyl acetate layer was separated, the aqueous layer was re-extracted with 300 ml of ethyl acetate, and combined with the previously separated ethyl acetate layer. This was washed with 150 ml of 20% by weight brine, and the ethyl acetate layer was separated and dried over sodium sulfate. After removing sodium sulfate by filtration, the solvent was distilled off using an evaporator under the conditions of 35 ° C. and 2660 Pa to obtain a crude product of 3-hydroxypropyl methacrylate (78.0 g).

  Next, the same operation as in Example 11 was performed except that 72.1 g (500 mmol) of 3-hydroxypropyl methacrylate was used instead of 2-hydroxyethyl methacrylate, and MNPMA crude (102.2 g) was obtained. Obtained.

  Next, purification operation of 44.5 g (200.0 mmol) of crude MNPMA was performed in the same manner as in Example 11 to obtain 16.1 g of purified HNPMA.

Example 13 Synthesis of 2-methacryloyloxyethoxy-3-hydroxynaphthalene [OHNEMA: Formula (62)]
In Example 11, 48.1 g of 2,3-dihydroxynaphthalene (manufactured by Tokyo Chemical Industry Co., Ltd., 300.0 mmol) was used instead of 2,6-dihydroxynaphthalene, and anhydrous THF was used instead of anhydrous DMF. The solution was added dropwise at 60 ° C. over 1.3 hours. After aging at 60 ° C. for 8 hours, the same operation as in Example 11 was performed to obtain a crude OHNEMA (51.1 g). The obtained crude OHNEMA was purified by column chromatography (filler: silica gel, eluent: hexane: ethyl acetate = 5: 1) to obtain 17.8 g of purified OHNEMA. The NMR chart of the obtained purified OHNEMA is shown in FIG.

<Reference Example 1; Synthesis of 2-methacryloyloxy-iso-propyloxy-6-hydroxynaphthalene [HNIPMA: mixture of formula (76) and formula (77)] In place of crude 3-hydroxypropyl methacrylate, hydroxypropyl The same operation as in Example 12 was performed except that methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd., a mixture of 2-hydroxypropyl methacrylate and 2-hydroxy-1-methylethyl methacrylate) was obtained to obtain 2.1 g of purified HNIPMA. .

1 is an NMR chart of purified HNEMA obtained in Example 11. FIG. 1 is an NMR chart of purified OHNEMA obtained in Example 13. FIG.

Claims (7)

A resist composition containing a resist polymer containing a structural unit (A) having a naphthalene skeleton represented by the following formula (1-1).
(In Formula (1-1), R ¹⁰ represents a hydrogen atom or a methyl group. Y represents —C (═O) —OH, —CH ₂ —C (═O) —OH, —OH, —C ( ═O) —OR ¹³ , —CH ₂ —C (═O) —OR ¹³ , or —OR ¹³ , wherein R ¹³ represents a linear, branched, or cyclic hydrocarbon group having 1 to 20 carbon atoms. The hydrocarbon group may have a hetero atom, L ¹ represents —CH ₂ —R ¹⁴ —CH ₂ —O—, wherein R ¹⁴ represents a single bond or a straight chain having 1 to 20 carbon atoms. Represents a hydrocarbon group of a chain, and this hydrocarbon group may have a hetero atom between the chains, X ¹ is a linear or branched alkyl group having 1 to 6 carbon atoms, a hydroxyl group, a carboxyl group, Esterified with an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and an alcohol having 1 to 6 carbon atoms Carboxyl represents a group or an amino group,. A linear or branched alkyl group having 1 to 6 carbon atoms wherein X ¹ is a hydroxyl group as a substituent, a carboxyl group, an acyl group having 1 to 6 carbon atoms, 1 to 6 carbon atoms And at least one group selected from the group consisting of a carboxyl group esterified with an alcohol having 1 to 6 carbon atoms, a cyano group, and an amino group, and h11 represents an integer of 0 to 4. (In addition, when h11 is 2 or more, it includes that X ¹ has a plurality of different groups.) The resist composition according to claim 1, wherein the structural unit (A) represented by the formula (1-1) is a structural unit having a naphthalene skeleton represented by the following formula (1-2).
(In the formula ^{(1-2), R 10, Y} , L 1 is, ^R 10, Y in the formula (1-1) has the same meaning as ^{L 1.)} The resist composition according to claim 1, wherein the structural unit (A) represented by the formula (1-1) is a structural unit having a naphthalene skeleton represented by the following formula (1-3).
(In the formula ^{(1-3), R 10, Y} , L 1 is, ^R 10, Y in the formula (1-1) has the same meaning as ^{L 1.)}   A step of applying the resist composition according to any one of claims 1, 2, and 3 onto a substrate to be processed, a step of exposing with light having a wavelength of 250 nm or less, and a step of developing using a developer. A method for manufacturing a substrate on which a pattern is formed. A resist polymer containing a structural unit (A) having a naphthalene skeleton represented by the following formula (1-1).
(In Formula (1-1), R ¹⁰ represents a hydrogen atom or a methyl group. Y represents —C (═O) —OH, —CH ₂ —C (═O) —OH, —OH, —C ( ═O) —OR ¹³ , —CH ₂ —C (═O) —OR ¹³ , or —OR ¹³ , wherein R ¹³ represents a linear, branched, or cyclic hydrocarbon group having 1 to 20 carbon atoms. The hydrocarbon group may have a hetero atom, L ¹ represents —CH ₂ —R ¹⁴ —CH ₂ —O—, wherein R ¹⁴ represents a single bond or a straight chain having 1 to 20 carbon atoms. Represents a hydrocarbon group of a chain, and this hydrocarbon group may have a hetero atom between the chains, X ¹ is a linear or branched alkyl group having 1 to 6 carbon atoms, a hydroxyl group, a carboxyl group, Esterified with an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and an alcohol having 1 to 6 carbon atoms Carboxyl represents a group or an amino group,. A linear or branched alkyl group having 1 to 6 carbon atoms wherein X ¹ is a hydroxyl group as a substituent, a carboxyl group, an acyl group having 1 to 6 carbon atoms, 1 to 6 carbon atoms And at least one group selected from the group consisting of a carboxyl group esterified with an alcohol having 1 to 6 carbon atoms, a cyano group, and an amino group, and h11 represents an integer of 0 to 4. In addition, when h11 is 2 or more, it includes that X ¹ has a plurality of different groups, provided that when R ¹⁴ is a single bond and Y is other than 3 position, Y is —OH, acetyl group Except for substituted hydroxyl groups.) 6. The resist polymer according to claim 5, wherein the structural unit (A) represented by the formula (1-1) is a structural unit having a naphthalene skeleton represented by the following formula (1-2).
(In the formula ^{(1-2), R 10, Y} , L 1 is, ^R 10, Y in the formula (1-1) has the same meaning as ^{L 1.)} 6. The resist polymer according to claim 5, wherein the structural unit (A) represented by the formula (1-1) is a structural unit having a naphthalene skeleton represented by the following formula (1-3).
(In the formula ^{(1-3), R 10, Y} , L 1 is, ^R 10, Y in the formula (1-1) has the same meaning as ^{L 1.)}