JP2001278919A - Polymeric compound for resist and resist composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymeric compound for a resist having a superior film forming property as well as keeping resist characteristics such as an alkali- solubility and an adhesiveness to substrate. SOLUTION: The polymeric compound for a resist comprises a repetition unit having an acid-eliminating group, a repetition unit having an adhesion group to substrate, and a repetition unit expressed by formula (1), wherein R1 represents a hydrogen atom or a methyl group, R2 represents a 3-8C alkyl group (provided that a tertiary alkyl group is excluded). The repetition unit expressed by formula (1) is about 0.01-30 mol % of all the repetition units composing a polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resist polymer compound and a resist composition for use in fine processing of a semiconductor, and a method for producing a semiconductor using the resist composition.

[0002]

2. Description of the Related Art A resist used in a semiconductor manufacturing process does not have characteristics such as a property that an irradiated portion changes to alkali-soluble due to light irradiation, adhesion to a silicon wafer, plasma etching resistance, and transparency to light used. must not. The resist is generally used as a solution containing a polymer as a main agent, a photoacid generator, and several additives for adjusting the above properties. It is extremely important that the polymer has the above-mentioned properties in a well-balanced manner.

[0003] The exposure light source for lithography used in the manufacture of semiconductors has become shorter in wavelength year by year, and an ArF excimer laser having a wavelength of 193 nm is expected as a next-generation exposure light source. It has been proposed to use a unit containing an alicyclic hydrocarbon skeleton having high transparency to the wavelength and etching resistance as a monomer unit of a resist polymer used in the ArF excimer laser exposure machine (Patent) No. 2776273). It is also known that a polymer having an adamantane skeleton which is particularly excellent in etching resistance among alicyclic hydrocarbon skeletons is used as a resist polymer. However, although the alicyclic hydrocarbon skeleton is excellent in etching resistance as described above, it has a disadvantage that adhesion to a substrate is low due to high hydrophobicity. Therefore, the above-mentioned literature proposes a copolymer in which a highly hydrophilic monomer unit having a carboxyl group or a lactone ring (adhesion imparting monomer unit) is incorporated for the purpose of improving the above.

On the other hand, Japanese Patent Application Laid-Open No. 11-109632 discloses a monomer unit having an adamantane skeleton into which a hydroxyl group is introduced to impart hydrophilicity (adhesion imparting monomer unit), and an alkali-soluble monomer produced by irradiation with light. A copolymer having the following monomer unit (alkali-soluble monomer unit) is disclosed.

Further, an attempt has been made to use a monomer unit having an adamantane skeleton itself as an alkali-soluble monomer unit (JP-A-9-73173,
JP-A-9-90637, JP-A-10-27485
No. 2, JP-A-10-319595, JP-A-10-319595
1-112326, JP-A-11-119434).

However, the above copolymer having an alicyclic hydrocarbon skeleton, particularly a copolymer having a monomer unit having an adamantane skeleton, generally has a glass transition point (Tg).
Therefore, there is a problem that the coating film is brittle and hard, and it is not easy to select the resist manufacturing conditions when processing it into a resist thin film (it is difficult to form a thin film). Although this glass transition point can be adjusted by the composition ratio of the copolymer, conventionally, there is no known method capable of controlling the glass transition point in a wide range while maintaining resist properties such as alkali solubility and substrate adhesion. .

[0007]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a resist polymer having excellent film-forming properties while maintaining resist properties such as alkali solubility and substrate adhesion. And a resist composition containing the same. Another object of the present invention is to provide a resist polymer compound and a resist composition capable of forming a resist thin film having improved brittleness. Still another object of the present invention is to provide a method of manufacturing a semiconductor which can easily and efficiently form a uniform and low-brittle resist thin film.

[0008]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, when a polymer containing a repeating unit (monomer unit) having a specific structure is used as a resin for a chemically amplified resist, alkali The present inventors have found that the glass transition point can be adjusted to a wide range while maintaining solubility and adhesion to a substrate, and film properties such as film formability and film brittleness can be greatly improved, and the present invention has been completed.

That is, the present invention provides a repeating unit having an acid leaving group and a repeating unit having a substrate adhesive group, represented by the following formula (1):

Embedded image [Wherein R ¹ represents a hydrogen atom or a methyl group, and R ² represents a C _3-8 alkyl group (excluding a tertiary alkyl group)]. A polymer compound is provided.

The repeating unit having an acid leaving group is represented by the following formula (2)

Embedded image [Wherein, R ³ is a hydrogen atom or a methyl group, and R ⁴ is a compound represented by the following formulas (4) to (7)]

Embedded image (Wherein R ^{7 to} R ¹² are the same or different and each is a C _1-6 alkyl group, X and Y are substituents bonded to an adamantane ring, and are protected by an oxo group, an alkyl group, or a protecting group. Represents a hydroxyl group which may be protected, a hydroxymethyl group which may be protected by a protecting group, or a carboxyl group which may be protected by a protecting group, and m and n each represent 0 to 3
And p represents 1 or 2), and a repeating unit represented by the following formula:

The repeating unit having the substrate adhesive group is represented by the following formula (3)

Embedded image [Wherein, R ⁵ is a hydrogen atom or a methyl group, and R ⁶ is a compound represented by the following formula (8) or (9)

Embedded image(Wherein ring A is an alicyclic hydrocarbon ring, Z is bonded to ring A
Substituents, such as oxo, alkyl, and protecting groups
Hydroxyl groups, which may be protected, protected with protecting groups
Protected by an optionally protected hydroxymethyl group or a protecting group.
Represents a carboxyl group which may be
Even if at least one is protected by an oxo group or a protecting group
Good hydroxyl groups,
A group that may be protected by a droxymethyl group or a protecting group
It is a ruboxyl group. R¹³Is a hydrogen atom or a methyl group, R
¹⁴~ R¹⁷Are the same or different and each represents a hydrogen atom or an alkyl
Represents a group. t is 0 or 1, q is an integer of 1 to 3, r is 1 to
An integer of 3, s represents an integer of 0 to 2, and r + s = 2 to 4
is there. However, when ring A is an adamantane ring,-(C
H _Two)_t-Is attached to the bridgehead of the adamantane ring)
Represents a group represented by the formula]
You.

The repeating unit represented by the above formula (1) is
For example, 0.01 of all repeating units constituting the polymer
３０30 mol%. The present invention also provides a resist composition comprising the above resist polymer compound and a photoacid generator. The present invention further provides a method for producing a semiconductor, comprising a step of forming a resist coating film by applying the above-described resist composition on a substrate or a substrate, and forming a pattern through exposure and development.

In the present specification, the term "acid-eliminable group" means a group which is eliminated at a specific site by an acid to form an alkali-soluble group such as a carboxyl group. The term “substrate adhesive group” means a group having a polar group and improving the adhesiveness to a substrate such as a silicon wafer. Furthermore, in this specification, “acryl” and “methacryl” may be collectively referred to as “(meth) acryl”, and “acryloyl” and “methacryloyl” may be collectively referred to as “(meth) acryloyl”.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The resist polymer compound of the present invention comprises, as a repeating unit (monomer unit) constituting a polymer molecule, a repeating unit having an acid-labile group,
It is composed of a repeating unit having a substrate adhesive group and a repeating unit represented by the formula (1). Each of the repeating units may be one type or two or more types. Further, the repeating unit having an acid leaving group and the repeating unit having a substrate adhesive group may be the same. That is, one repeating unit may contain an acid leaving group and a substrate adhesion group. In this case, the resist polymer compound of the present invention can be composed of a repeating unit containing an acid-labile group and a substrate adhesion group, and a repeating unit represented by the formula (1). The resist polymer compound of the present invention may be any of a random copolymer, an alternating copolymer, a block copolymer and the like.

The repeating unit having an acid leaving group (hereinafter, may be simply referred to as “repeating unit 2”) is
Since a free carboxyl group or the like is generated by the acid generated from the photoacid generator, it functions as an alkali-soluble unit solubilized during alkali development. Further, the repeating unit having a substrate adhesion group (hereinafter, may be simply referred to as “repeating unit 3”) functions as an adhesion imparting unit that enhances adhesion to a substrate. The repeating unit represented by the formula (1) (hereinafter, may be simply referred to as “repeating unit 1”) adjusts the glass transition temperature of the polymer and adjusts the film forming property and the brittleness of the resist film. It functions as a resist film characteristic adjustment unit that improves.

In the above formula (1), R ¹ represents a hydrogen atom or a methyl group, and R ² is a C _3-8 alkyl group (however,
Excluding a lower alkyl group). Examples of the C _3-8 alkyl group for R ² include propyl, isopropyl,
Butyl, isobutyl, s-butyl, pentyl, isopentyl, 1-methylbutyl, 1-ethylpropyl, hexyl, isohexyl, 1-methylpentyl, 1-ethylbutyl, heptyl, 1-methylhexyl, octyl, 1-
And a methylheptyl group. Among these,
R ² is preferably a C _4-6 alkyl group, particularly a C ₄ alkyl group such as a butyl group. R ² is preferably a linear alkyl group.

The repeating unit having an acid-eliminable group is not particularly limited as long as it is a repeating unit having a group in which a specific site is eliminated by an acid to produce an alkali-soluble group. For example, a repeating unit represented by the formula (2) can be mentioned.

In the above formula (2), R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents a group represented by the above formulas (4) to (7). In the formulas (4) to (7), R ^{7 to} R ¹² are the same or different and each represent a C _1-6 alkyl group, and X and Y are substituents bonded to an adamantane ring, and are oxo groups. An alkyl group, a hydroxyl group which may be protected with a protecting group, a hydroxymethyl group which may be protected with a protecting group, or a carboxyl group which may be protected with a protecting group, and m and n each represent Represents an integer of 0 to 3,
p represents 1 or 2.

The C _1-6 alkyl group for R ^{7 to} R ¹² includes methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, pentyl, isopentyl, 1-methylbutyl, 1-ethylpropyl, hexyl, Examples include isohexyl, 1-methylpentyl, and 1-ethylbutyl. Among these, a C _1-4 alkyl group, particularly a methyl group and an ethyl group, are preferred.

Examples of the alkyl group for X and Y include the C _1-6 alkyl group exemplified above. Preferred alkyl groups include a methyl group and an ethyl group.

As the protecting group for the hydroxyl group and the carboxyl group in X and Y, a protecting group commonly used in the field of organic synthesis can be used. For example, protected forms of hydroxyl groups include methyl ether, methoxymethyl ether, 2
Ethers such as -methoxyethoxymethyl ether, 2-tetrahydropyranyl ether, 2-tetrahydrofuranyl ether, 1-ethoxyethyl ether, 1-methyl-1-methoxyethyl ether, t-butyl ether and benzyl ether; formate esters, acetate esters, Esters such as benzoic acid esters; carbonates such as methyl carbonate, ethyl carbonate and benzyl carbonate; hemiacetals with aldehydes such as acetaldehyde and benzaldehyde.

Examples of the protected form of the carboxyl group include, for example, methyl ester, methoxymethyl ester, 2-tetrahydropyranyl ester, 2-tetrahydrofuranyl ester, 2-methoxyethoxymethyl ester, benzyloxymethyl ester, ethyl ester, t -Butyl ester, cyclohexyl ester, allyl ester, phenyl ester, benzyl ester,
Esters such as triphenylmethyl ester, diphenylmethyl ester, trimethylsilyl ester and N-hydroxysuccinimidoyl ester; and amides such as N, N-dimethylamide.

When X and Y are plural, each may be a different substituent. Of X and Y, groups other than the oxo group are often bonded to the bridgehead of the adamantane ring.
In addition, substituents other than those described above may be bonded to the adamantane rings of the formulas (4) and (5) as long as the resist properties are not impaired.

The repeating unit represented by the above formula (2)
Chi, R^FourIs a group represented by the formula (4), and m is 1 to
In 3, at least one of X is protected with an oxo group and a protecting group.
Hydroxyl group, which may be protected
May be protected by a hydroxymethyl group or a protecting group.
A repeating unit which may be a carboxyl group, and R ^Four
Is a group represented by the formula (5), and n is 1 to 3, and Y is
At least one of which is protected by an oxo group or a protecting group;
May be protected with a hydroxyl group or a protecting group.
May be protected with a hydroxymethyl group or a protecting group
Carboxyl repeating units are alkali soluble
Not only as a unit but also as an adhesion-imparting unit
Function.

The repeating unit having the substrate adhesive group is not particularly limited as long as it has a group that improves the adhesiveness to the substrate, and a typical example thereof is, for example, a compound represented by the above formula (3). Repeating unit to be used.

In the above formula (3), R ⁵ represents a hydrogen atom or a methyl group, and R ⁶ represents a group represented by the above formula (8) or (9). In the formulas (8) and (9), ring A represents an alicyclic hydrocarbon ring, and Z is a substituent bonded to ring A, and is protected by an oxo group, an alkyl group, or a protecting group. A hydroxyl group, a hydroxymethyl group which may be protected with a protecting group, or a carboxyl group which may be protected with a protecting group, wherein at least one of q Zs is an oxo group or a protecting group. A hydroxyl group which may be protected, a hydroxymethyl group which may be protected by a protecting group, or a carboxyl group which may be protected by a protecting group. R ¹³ represents a hydrogen atom or a methyl group, R ¹⁴ to R
¹⁷ is the same or different and represents a hydrogen atom or an alkyl group. t is 0 or 1, q is an integer of 1 to 3, r is an integer of 1 to 3, s is an integer of 0 to 2, and r + s is 2 to 4.
However, when the ring A is adamantane ring, - (CH _{2) t} - is bonded to a bridgehead position of the adamantane ring. In the formula (9), the group -CR ¹⁴ (R ¹⁵ )-or the group -CR
^{When 16} (R ¹⁷ )-is 2 or more, each group may be the same or different.

The alicyclic hydrocarbon ring in the ring A includes:
For example, monocyclic alicyclic hydrocarbon rings (cycloalkane ring, cycloalkene ring) such as cyclopentane ring, cyclohexane ring, cyclohexene ring, cycloheptane ring, cyclooctane ring, cyclodecane ring and cyclododecane ring; perhydronaphthalene Ring (decalin ring), perhydrofluorene ring, perhydroindene ring, isobornane ring, pinane ring, norpinane ring, bornan ring, norbornane ring,
A norbornene ring, a bicyclo [2.2.2] octane ring,
Adamantane ring, tricyclo [5.2.1.0 ^2,6 ] decane ring, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ]
Polycyclic alicyclic hydrocarbon ring such as dodecane ring (bridged ring)
And the like. Among these alicyclic hydrocarbon rings, a cyclohexane ring and a bridged ring (particularly, an adamantane ring, etc.) are preferred.

The protective groups for the alkyl group, hydroxyl group and carboxyl group in Z are the same as those in X and Y described above. When Z is plural, each may be a different substituent. Note that a substituent other than those described above may be bonded to the ring A of the formula (8) as long as the resist properties are not impaired.

Examples of the alkyl group for R ^{14 to} R ¹⁷ include the C _1-6 alkyl group exemplified above. Preferred alkyl groups include a methyl group and an ethyl group. r is often 1 or 2, and s is 0 or 1.
Often it is. R + s is preferably 2 or 3.

In the repeating unit represented by the formula (3), R ⁶ is a group represented by the formula (8), and at least one of Z is a 2-tetrahydropyranyloxycarbonyl group or 2-tetrahydrofuran. Nyloxycarbonyl group,
The repeating unit which is an acid-eliminable group such as a t-butoxycarbonyl group functions not only as an adhesion-imparting unit but also as an alkali-soluble unit.

In the present invention, a particularly great effect is obtained when at least one of the repeating units 2 and 3 has a bulky and rigid adamantane skeleton. Further, a copolymer containing a repeating unit having an adamantane skeleton, for example, about 30 to 100 mol% (particularly, 50 to 100 mol%) of the repeating unit having the adamantane skeleton is contained in all the repeating units constituting the polymer. When the copolymer is used as a resin for a resist, it is excellent in transparency and exhibits extremely high etching resistance.

The proportion of the repeating unit 1 can be appropriately selected according to the desired physical properties, but is usually about 0.01 to 30 mol% based on all repeating units constituting the polymer.
Preferably it is about 0.05 to 10 mol%, more preferably about 0.05 to 5 mol%.

The ratio of the repeating unit 2 to the repeating unit 3 is, for example, the former / the latter (molar ratio) = 1/9.
It is about 9-99 / 1, preferably about 20 / 80-90 / 10, and more preferably about 35 / 65-80 / 20.

The polymer compound for resist of the present invention may have a repeating unit other than the above in order to fine-tune the balance of various properties as a resin for resist. The proportion of the repeating units other than the repeating units 1 to 3 is, for example, 0% of all the repeating units constituting the polymer.
About 30 mol%, preferably about 0 to 20 mol%.

The polymer compound for resist of the present invention has a weight average molecular weight (Mw) of, for example, about 3,000 to 200,000, preferably about 3,000 to 20,000, and a molecular weight distribution (Mw / Mn) of, for example, 1.8 to 3,000. It is about 0.0. Here, Mn indicates a number average molecular weight (in terms of polystyrene).

In the polymer compound for resist of the present invention, the following are preferred combinations of the repeating unit 2 and the repeating unit 3. (A) In the repeating unit 2, R ⁴ is a group represented by the formula (4) or (5), and in the repeating unit 3, R ⁶ is a group represented by the formula (9). Combination with repeating unit (b) In repeating unit 2, R ⁴ is a group represented by formula (6) or (7), and in repeating unit 3, R ⁶ is represented by formula (8) In which the ring A in the formula (8) is a bridged ring (for example, an adamantane ring or the like). (C) In the repeating unit 2, R ⁴ is a group represented by the formula (4) or the formula ( A repeating unit which is a group represented by 5) and a repeating unit 3 in which R ⁶ is a group represented by formula (8) and ring A in formula (8) is a monocyclic alicyclic hydrocarbon Combination with a repeating unit that is a ring (eg, a cyclohexane ring)

Each of the repeating units represented by the above formulas (1) to (3) can be formed by subjecting the corresponding (meth) acrylic acid ester as a comonomer to polymerization.

[Repeating Unit Represented by Formula (1)] The monomer corresponding to the repeating unit 1 is represented by the following formula (10)

Embedded image (Wherein R ¹ and R ² are the same as described above), and typical examples thereof include the following compounds. [1-1] propyl (meth) acrylate [1-2] butyl (meth) acrylate [1-3] isobutyl (meth) acrylate [1-4] s-butyl (meth) acrylate [1-5] ] Pentyl (meth) acrylate [1-6] Hexyl (meth) acrylate [1-7] Isohexyl (meth) acrylate [1-8] Heptyl (meth) acrylate [1-9] (meth) acrylic acid Octyl [1-10] 2-ethylhexyl (meth) acrylate

[Repeating Unit Represented by Formula (2)] The monomer corresponding to the repeating unit 2 is represented by the following formula (11)

Embedded image (Wherein, R ³ and R ⁴ are the same as described above).

Of the monomers represented by the above formula (11),
Typical examples of the compound in which R ⁴ is a group represented by the above formula (4) include the following compounds. [2-1] 1- (1- (meth) acryloyloxy-1-
Methylethyl) adamantane (R ³ ＨH or CH ₃ , R ^{7
_{= R 8 = CH 3, m}} = 0) [2-2] 1- hydroxy-3- (1- (meth) acryloyloxy-1-methylethyl) adamantane (R ³ =
H or _{^{CH 3, R 7 = R 8}} = CH 3, X = OH, m = 1) [2-3] 1,3- dihydroxy-5- (1- (meth) acryloyloxy-1-methylethyl) adamantane (R ³ = H or _{^{CH 3, R 7 = R 8}} = CH 3, X = OH, m
= 2) [2-4] 1- (1-ethyl-1- (meth) acryloyloxypropyl) adamantane (R ³ ＨH or CH ₃ , R
⁷ = R ⁸ = ethyl, m = 0) [2-5] 1- (1- ethyl-1 (meth) acryloyloxy propyl) -3-hydroxy adamantane (R ³
= H or CH ₃ , R ⁷ = R ⁸ = ethyl group, X = OH, m =
1) [2-6] 1- (1- (meth) acryloyloxy-1-)
Methylpropyl) adamantane (R ³ ＨH or CH ₃ , R
⁷ = CH ₃ , R ⁸ = ethyl group, m = 0) [2-7] 1- (1- (meth) acryloyloxy-1-)
Methylpropyl) -3-hydroxyadamantane (R ³
ＨH or CH ₃ , R ⁷ ＣＨCH ₃ , R ⁸ = ethyl group, X ＝ O
H, m = 1) [2-8] 1- (1- (meth) acryloyloxy-1,
2-dimethylpropyl) adamantane (R ³ = H or C
_{^{H 3, R 7 = CH 3}} , R 8 = isopropyl, m = 0) [2-9] 1- (1- ( meth) acryloyloxy-1,
2-dimethylpropyl) -3-hydroxy-adamantane (R ³ = H or _{^{CH 3, R 7 = CH 3}} , R 8 = isopropyl, X = OH, m = 1 ) [2-10] 1- (1- ethyl 1- (meth) acryloyloxy propyl) -3,5-dihydroxy-adamantane (R ³ = H or _{^{CH 3, R 7 = R 8}} = ethyl, X = OH,
m = 2) [2-11] 1,3- dihydroxy-5- (1- (meth) acryloyloxy-1-methylpropyl) adamantane (R ³ = H or _{^{CH 3, R 7 = CH 3}} , R 8 = Ethyl group, X
= OH, m = 2) [ 2-12] 1,3- dihydroxy-5- (1- (meth) acryloyloxy-1,2-dimethylpropyl) adamantane (R ³ = H or CH _3, R ⁷ = CH ₃ , R ⁸ = isopropyl group, X = OH, m = 2)

Of the monomers represented by the above formula (11), R
^The compound (11a) in which 4 is a group represented by the formula (4) can be obtained, for example, according to the following reaction step formula.

Embedded image (Wherein, X ¹ represents a halogen atom, R ^X represents a halogen atom, a hydroxyl group, an alkoxy group or an alkenyloxy group. R ³ , R ⁷ , R ⁸ , X and m are the same as described above)

In this reaction scheme, a compound of the adamantane derivative (13) used as a raw material, wherein X is a hydroxyl group, can be obtained by introducing a hydroxyl group into the adamantane ring. For example, an adamantane compound is contacted with oxygen in the presence of an N-hydroxyimide catalyst such as N-hydroxyphthalimide and, if necessary, a metal promoter such as a cobalt compound (eg, cobalt acetate, cobalt acetylacetonate, etc.). By doing so, a hydroxyl group can be introduced into the adamantane ring. In this method, the amount of the N-hydroxyimide-based catalyst used is, for example, from 0.0001 to 1 mol, preferably from 0.001 to 0.5, per mol of the adamantane compound.
It is about a mole. The amount of the metal promoter used is, for example, from 0.0001 to 1 mol of the adamantane compound.
0.7 mol, preferably about 0.001 to 0.5 mol. Oxygen is often used in excess with respect to the adamantane compound. The reaction is performed, for example, in a solvent such as an organic acid such as acetic acid, a nitrile such as acetonitrile, or a halogenated hydrocarbon such as dichloroethane, at normal pressure or under pressure, from 0 to 0.
The reaction is performed at a temperature of about 200 ° C, preferably about 30 to 150 ° C. By selecting the reaction conditions, a plurality of hydroxyl groups can be introduced into the adamantane ring.

Further, among the adamantane derivatives (13) used as raw materials, compounds wherein X is a carboxyl group can be produced by introducing a carboxyl group into the adamantane ring. For example, an adamantane compound is treated with an N-hydroxyimide-based catalyst such as N-hydroxyphthalimide,
If necessary, a carboxyl group is introduced into the adamantane ring of the adamantane compound by contacting with carbon monoxide and oxygen in the presence of a metal-based cocatalyst such as a cobalt compound (eg, cobalt acetate, cobalt acetylacetonate, etc.). it can. In this carboxylation reaction,
The amount of the N-hydroxyimide-based catalyst to be used is, for example, 0.0001 to 1 mol per 1 mol of the adamantane compound,
Preferably it is about 0.001-0.5 mol. Also,
The amount of the metal promoter used is, for example, about 0.0001 to 0.7 mol, preferably about 0.001 to 0.5 mol, per 1 mol of the adamantane compound. The amounts of carbon monoxide and oxygen used are, for example, 1 mol or more and 0.5 mol or more, respectively, per 1 mol of the adamantane compound.
The ratio of carbon monoxide to oxygen is, for example, the former / latter (molar ratio) = about 1/99 to 99/1, preferably 50/50.
It is about 95/5. The carboxylation reaction is, for example, an organic acid such as acetic acid, a nitrile such as acetonitrile, a solvent such as a halogenated hydrocarbon such as dichloroethane, at normal pressure or under pressure, at about 0 to 200 ° C., preferably about 10 to 150 ° C. At a temperature of By selecting reaction conditions, a plurality of carboxyl groups can be introduced into the adamantane ring.

The reaction of the adamantane derivative (13) with a 1,2-dicarbonyl compound (eg, biacetyl) (14) and oxygen is carried out by reacting a metal compound such as a cobalt compound (eg, cobalt acetate, cobalt acetylacetonato). And / or in the presence of an N-hydroxyimide-based catalyst such as N-hydroxyphthalimide. 1,
The amount of the 2-dicarbonyl compound (14) used is 1 mol or more per 1 mol of the adamantane derivative (13) (for example, 1 to 1 mol).
50 mol), preferably 1.5 to 20 mol, more preferably about 3 to 10 mol. The amount of the metal compound to be used is, for example, about 0.0001 to 0.1 mol per 1 mol of the adamantane derivative (13). The amount of the N-hydroxyimide-based catalyst used is determined based on the adamantane derivative (13).
The amount is, for example, about 0.001 to 0.7 mol per 1 mol. Oxygen is often used in excess with respect to the adamantane derivative (13). The reaction is usually performed in an organic solvent. Examples of the organic solvent include nitriles such as benzonitrile, an organic acid such as acetic acid, and halogenated hydrocarbons such as trifluoromethylbenzene. The reaction is carried out at normal pressure or under pressure, for example, at a temperature of about 30 to 250 ° C, preferably about 40 to 200 ° C.

The reaction between the acyladamantane derivative (15) thus obtained and the Grignard reagent (16) can be carried out according to a usual Grignard reaction. The amount of the Grignard reagent (16) to be used is, for example, about 0.7 to 3 mol, preferably about 0.9 to 1.5 mol, per 1 mol of the acyladamantane derivative (15). When the acyl adamantane derivative (15) has a hydroxyl group or a carboxyl group on the adamantane ring, the amount of the Grignard reagent is increased according to the number thereof. The reaction is performed, for example, in ethers such as diethyl ether and tetrahydrofuran. The reaction temperature is, for example, about 0 to 150 ° C, preferably about 20 to 100 ° C.

The reaction (esterification reaction) between the adamantane methanol derivative (17) produced by the above reaction and (meth) acrylic acid or its derivative (18) is carried out by a conventional method using an acid catalyst or a transesterification catalyst. be able to. Further, an adamantane methanol derivative (17) and an alkenyl (meth) acrylate such as vinyl (meth) acrylate and 2-propenyl (meth) acrylate are combined with a catalyst of a Group 3 element compound of the periodic table (for example, samarium acetate, trifluorofluoride). Reaction (transesterification reaction) in the presence of samarium compounds such as samarium methanesulfonate and samarium complex), the formula (11) can be efficiently obtained under mild conditions.
The compound represented by a) can be obtained. in this case,
The amount of the alkenyl (meth) acrylate used is, for example, 0.1 mol per 1 mol of the adamantane methanol derivative (17).
It is about 8 to 5 mol, preferably about 1 to 1.5 mol. The amount of the catalyst of the Group 3 element compound of the periodic table is, for example, 0.001 mol per mol of the adamantane methanol derivative (17).
It is about 1 to 1 mol, preferably about 0.01 to 0.25 mol. This reaction is carried out in a solvent inert to the reaction, for example, from 0 to
The reaction is performed at a temperature of 150 ° C, preferably about 25 to 120 ° C.

Incidentally, by introducing a protecting group into a hydroxyl group or a carboxyl group at an appropriate stage of the above reaction step, X of the compound (11a) is protected by a hydroxyl group or a protecting group in which X is protected by a protecting group. A compound which is a carboxyl group obtained can be obtained. Introduction of the protecting group can be performed by a conventional method.

Further, among the compounds represented by the above formula (11a), the compound (11a ') wherein R ⁷ and R ⁸ are the same group
Can be obtained, for example, according to the following reaction scheme.

Embedded image (Wherein, R ^y represents a hydrocarbon group. R ³ , R ⁷ , X, X ¹ ,
R ^x and m are the same as above.

Examples of the hydrocarbon group for R ^y include a C _1-6 aliphatic hydrocarbon group such as a methyl, ethyl, propyl, and isopropyl group; and a phenyl group.

In this reaction scheme, the adamantanecarboxylic acid derivative (19) used as a raw material can be produced in the same manner as in the case of the adamantane derivative (13). Adamantanecarboxylic acid derivative (19) and hydroxy compound (2
The reaction with 0) can be carried out, for example, according to a conventional esterification method using an acid catalyst or the like. The reaction between the adamantanecarboxylic acid ester represented by the formula (21) and the Grignard reagent (16) is usually performed in a solvent inert to the reaction, for example, ethers such as diethyl ether and tetrahydrofuran. The reaction temperature is, for example, 0 to 10
The temperature is about 0 ° C, preferably about 10 to 40 ° C. The amount of the Grignard reagent (16) used is, for example, about 2 to 4 equivalents based on the adamantanecarboxylic acid ester (21).

The reaction (esterification reaction) between the adamantane methanol derivative (17a) and (meth) acrylic acid or its derivative (18) is carried out by reacting the compound represented by the formula (17) with (meth) acrylic acid or its derivative. The reaction can be carried out according to the reaction with (18). In this way, the compound (11a ′) in which R ⁷ and R ⁸ are the same group (for example, R ⁷ = R ⁸ = ethyl group) among the compounds represented by the formula (11a) can be easily prepared. Can be.

Of the monomers represented by the above formula (11),
Typical examples of the compound in which R ⁴ is a group represented by the above formula (5) include the following compounds. [2-13] 1,3-dihydroxy-2- (meth) acryloyloxy-2-methyladamantane (R ³ = H or C
_{^{H 3, R 9 = CH 3}} , Y = 1-OH, 3-OH, n = 2) [2-14] 1,5- dihydroxy-2- (meth) acryloyloxy-2-methyl-adamantane (R ³ = H or C
_{^{H 3, R 9 = CH 3}} , Y = 1-OH, 5-OH, n = 2) [2-15] 1,3- dihydroxy-6 (meth) acryloyloxy-6-methyl-adamantane (R ³ = H or C
H ₃ , R ⁹ ＣＨCH ₃ , Y = 1-OH, 3-OH, n = 2) [2-16] 1-hydroxy-2- (meth) acryloyloxy-2-methyladamantane (R ³又 は H or CH ₃ , R
⁹ ＣＨCH ₃ , Y = 1-OH, n = 1) [2-17] 5-hydroxy-2- (meth) acryloyloxy-2-methyladamantane (R ³ ＨH or CH ₃ , R
_{^{9 = CH 3, Y = 5}} -OH, n = 1) [2-18] 2- ( meth) acryloyloxy-2-methyl-adamantane (R ³ = H or _{^{CH 3, R 9 = CH 3}} , n =
0)

Of the monomers represented by the above formula (11), R
^The compound (11b) in which ⁴ is a group represented by the formula (5) can be obtained, for example, according to the following reaction step formula.

Embedded image (Wherein, R ³ , R ⁹ , R ^X , X ¹ , Y and n are the same as above)

In this reaction scheme, the reaction between the adamanthanone derivative (22) and the Grignard reagent (23) can be carried out according to a conventional Grignard reaction. The amount of the Grignard reagent (23) to be used is, for example, about 0.7 to 3 mol, preferably about 0.9 to 1.5 mol, per 1 mol of the adamantanone derivative (22). When the adamantane derivative (22) has a hydroxyl group or a carboxyl group on the adamantane ring, the amount of the Grignard reagent is increased according to the number thereof. The reaction is carried out in a solvent inert to the reaction, for example, ethers such as diethyl ether and tetrahydrofuran. The reaction temperature is, for example, about 0 to 150 ° C, preferably about 20 to 100 ° C.

The 2-adamantanol derivative (24) thus obtained is converted from (meth) acrylic acid or its derivative (18)
(Esterification reaction) to give a compound of the formula (11)
The compound represented by b) can be obtained. The esterification reaction can be performed according to the reaction between the compound of the formula (17) and (meth) acrylic acid or its derivative (18).

The adamantane derivative (22) having a hydroxyl group on the adamantane ring of the adamantanone derivative (22) used as a raw material in the above method can be obtained by converting 2-adamantanone into an N-hydroxyimide catalyst such as N-hydroxyphthalimide. If necessary, it can be produced by bringing into contact with oxygen in the presence of a metal-based cocatalyst such as a cobalt compound, a manganese compound and a vanadium compound to introduce a hydroxyl group into the adamantane ring. In this method, the amount of the N-hydroxyimide-based catalyst used is, for example, 0.0001 to 1 with respect to 1 mol of the 2-adamantanones.
Mol, preferably about 0.001 to 0.5 mol.
The amount of the metal promoter used is, for example, about 0.0001 to 0.7 mol, and preferably about 0.001 to 0.5 mol, per 1 mol of the 2-adamantanones. Oxygen is 2
-Often used in excess with respect to adamantanones.
The reaction is, for example, an organic acid such as acetic acid, a nitrile such as acetonitrile, a solvent such as a halogenated hydrocarbon such as dichloroethane, at normal pressure or under pressure, at about 0 to 200 ° C.
Preferably, it is performed at a temperature of about 30 to 150 ° C.

Among the adamantanone derivatives (22), compounds having a hydroxyl group on the adamantane ring include the adamantane and oxygen, the N-hydroxyimide-based catalyst and a strong acid (eg, hydrogen halide, sulfuric acid or the like). ,
If necessary, it can be produced by reacting in the presence of the metal-based cocatalyst. The amount of the strong acid used is
For example, 0.00001 per mole of adamantane
To 1 mol, preferably about 0.0005 to 0.7 mol. Other reaction conditions are the same as the above-mentioned hydroxyl group introduction reaction.

Of the monomers represented by the above formula (11),
The compounds in which R ⁴ is a group represented by the above formula (6) include the following compounds. [2-19] 2-tetrahydropyranyl (meth) acrylate (R ³ ＨH or CH ₃ , p = 2) [2-20] 2-tetrahydrofuranyl (meth) acrylate (R ¹ 1H or CH ₃ , p = 1)

Of the monomers represented by the above formula (11),
R^FourIs a compound represented by the formula (7):
The compounds described above are included. [2-21] t-butyl (meth) acrylate (R^Three= H or
CH_Three, R^Ten= R¹¹= R¹²= CH_Three) [2-22] t-amyl (meth) acrylate (R^Three= H or
CH_Three, R^Ten= R¹¹= CH _Three, R¹²= Ethyl group)

[Repeating Unit Represented by Formula (3)] The monomer corresponding to the repeating unit 3 is represented by the following formula (12)

Embedded image (Wherein, R ⁵ and R ⁶ are the same as described above).

Of the monomers represented by the above formula (12),
Typical examples of the compound in which R ⁶ is a group represented by the above formula (8) include the following compounds. [3-1] 1-hydroxy-3- (meth) acryloyloxy adamantane (R ⁵ = H or CH _3, t = 0, A ring =
Adamantane ring, Z = OH, q = 1 ) [3-2] 1,3- dihydroxy-5- (meth) acryloyloxy adamantane (R ⁵ = H or CH _3, t = 0,
A ring = adamantane ring, Z = OH, q = 2 ) [3-3] 1- carboxy-3- (meth) acryloyloxy adamantane (R ⁵ = H or CH _3, t = 0, A ring =
Adamantane ring, Z = COOH, q = 1 ) [3-4] 1,3- dicarboxy-5- (meth) acryloyloxy adamantane (R ⁵ = H or CH _3, t = 0,
A ring = adamantane ring, Z = COOH, q = 2) [3-
5] 1-carboxy-3-hydroxy-5- (meth) acryloyloxy adamantane (R ⁵ = H or CH _3, t
= 0, A ring = adamantane ring, Z = COOH, OH, q
= 2) [3-6] 1- (meth) acryloyloxy-4-oxo-adamantane (R ⁵ = H or CH _3, t = 0, A ring = adamantane ring, Z = oxo group, q = 1) [3 -7] 3-hydroxy-1- (meth) acryloyloxy-4-oxoadamantane (R ⁵ ＨH or CH ₃ , t
= 0, ring A = adamantane ring, Z = OH, oxo group, q
= 2) [3-8] 7-hydroxy-1- (meth) acryloyloxy-4-oxo-adamantane (R ⁵ = H or CH _3, t
= 0, ring A = adamantane ring, Z = OH, oxo group, q
= 2) [3-9] 1- t- butoxycarbonyl-3- (meth) acryloyloxy adamantane (R ⁵ = H or CH _3, t
= 0, ring A = adamantane ring, Z = t-butoxycarbonyl group, q = 1) [3-10] 1,3-bis (t-butoxycarbonyl) -5
- (meth) acryloyloxy adamantane (R ⁵ = H
Or CH ₃ , t = 0, ring A = adamantane ring, Z = t-
Butoxycarbonyl group, t-butoxycarbonyl group, q
= 2) [3-11] 1- t- butoxycarbonyl-3-hydroxy-5- (meth) acryloyloxy adamantane (R ⁵
= H or CH ₃ , t = 0, ring A = adamantane ring, Z =
OH, t-butoxycarbonyl group, q = 2) [3-12] 1- (2- tetrahydropyranyloxy) -3- (meth) acryloyloxy adamantane (R ⁵ = H or CH _3, t = 0, A ring = adamantane ring,
Z = 2-tetrahydropyranyloxycarbonyl group, q
= 1) [3-13] 1,3-bis (2-tetrahydropyranyloxy carbonyl) -5- (meth) acryloyloxy adamantane (R ⁵ = H or CH _3, t = 0, A ring = adamantane ring, Z = 2-tetrahydropyranyloxycarbonyl group, 2-tetrahydropyranyloxycarbonyl group,
q = 2) [3-14] 1- hydroxy-3- (2-tetrahydropyranyloxy carbonyl) -5- (meth) acryloyloxy adamantane (R ⁵ = H or CH _3, t = 0, A ring =
Adamantane ring, Z = OH, 2-tetrahydropyranyloxycarbonyl group, q = 2) [3-15] 8-hydroxymethyl-4- (meth) acryloyloxymethyltricyclo [5.2.1.0 ^{2, 6} ] decane (R ⁵ ＨH or CH ₃ , t = 1, ring A = tricyclo [5.2.1.0 ^2,6 ] decane ring, Z = hydroxymethyl group, q = 1) [3-16] 4-hydroxymethyl-8- (meth) acryloyloxymethyltricyclo [5.2.1.0 ^2,6 ] decane (R ⁵ = H or CH ₃ , t = 1, Ring A = tricyclo [5.2. 1.0 ^2,6 ] decane ring, Z = hydroxymethyl group, q = 1) [3-17] 3-oxocyclohexyl (meth) acrylate (R ⁵ ＨH or CH ₃ , t = 0, ring A = cyclohexane Ring, Z = oxo group, q = 1)

Of the monomers represented by the above formula (12), R
^The compound in which ⁶ is a group represented by the formula (8) can be obtained, for example, according to the following reaction step formula.

Embedded image (Wherein, A ring, R ⁵ , R ^x , Z, t, and q are the same as described above)

In this reaction scheme, among the compounds represented by the formula (25) used as a raw material, the compound in which the ring A is an adamantane ring is obtained by introducing a hydroxyl group, a carboxyl group or the like into the adamantane ring of the adamantane compound. can get. A hydroxyl group to the adamantane ring,
Examples of the method for introducing a carboxyl group or the like include the above-described methods. The reaction (esterification reaction) between the compound (25) and (meth) acrylic acid or its derivative (26) is carried out according to the above formula (1)
The reaction can be carried out according to the reaction of the compound represented by 7) with (meth) acrylic acid or its derivative (18).

Of the monomers represented by the above formula (12),
Representative examples of the compound in which R ⁶ is a group represented by the above formula (9) include the following compounds. [3-18] 2- (meth) acryloyloxy-γ-butyrolactone [3-19] 2- (meth) acryloyloxy-2-methyl-
γ-butyrolactone [3-20] 2- (meth) acryloyloxy-4,4-dimethyl-γ-butyrolactone [3-21] 2- (meth) acryloyloxy-2,4,4-
Trimethyl-γ-butyrolactone [3-22] 2- (meth) acryloyloxy-3,4,4-
Trimethyl-γ-butyrolactone [3-23] 2- (meth) acryloyloxy-2,3,4
4-tetramethyl-γ-butyrolactone [3-24] 2- (meth) acryloyloxy-3,3,4-
Trimethyl-γ-butyrolactone [3-25] 2- (meth) acryloyloxy-2,3,3
4-tetramethyl-γ-butyrolactone [3-26] 2- (meth) acryloyloxy-3,3,4,4
4-tetramethyl-γ-butyrolactone [3-27] 2- (meth) acryloyloxy-2,3,3
4,4-pentamethyl-γ-butyrolactone [3-28] 3- (meth) acryloyloxy-γ-butyrolactone [3-29] 3- (meth) acryloyloxy-3-methyl-γ-butyrolactone [3-30] 3- (meth) acryloyloxy-4-methyl-γ-butyrolactone [3-31] 3- (meth) acryloyloxy-3,4-dimethyl-γ-butyrolactone [3-32] 3- (meth) acryloyloxy- 4,4-dimethyl-γ-butyrolactone [3-33] 3- (meth) acryloyloxy-3,4,4
-Trimethyl-γ-butyrolactone

Of the monomers represented by the above formula (12),
R ⁶ is a group represented by the formula (9), and s = 0, r
= 2 can be obtained, for example, according to the following reaction scheme.

Embedded image (Wherein, R ^z represents a hydrocarbon group. R ^14a , R ^14b ,
R ^15a and R ^15b are the same or different and each represent a hydrogen atom or an alkyl group. R ⁵ , R ¹³ and ^RX are the same as described above)

In the above reaction ^scheme, the hydrocarbon group for R ^z includes methyl, ethyl, propyl, s-butyl,
aliphatic hydrocarbon groups having about 1 to 6 carbon atoms such as t-butyl, vinyl and allyl groups (alkyl groups, alkenyl groups or alkynyl groups); aromatic hydrocarbon groups such as phenyl group and naphthyl group; cycloalkyl groups And an alicyclic hydrocarbon group. The alkyl group for R ^14a , R ^14b , R ^15a and R ^15b is the same as the alkyl group for R ¹⁴ and R ¹⁵ .

Α, β-unsaturated carboxylic acid ester (27)
The reaction between alcohol and alcohol (28) with oxygen is carried out by an N-hydroxyimide-based catalyst such as N-hydroxyphthalimide and, if necessary, a metal-based cocatalyst such as a cobalt compound (eg, cobalt acetate, cobalt acetylacetonate, etc.). Done in the presence of The ratio between the α, β-unsaturated carboxylic acid ester (27) and the alcohol (28) can be appropriately selected depending on the type (price, reactivity, etc.) of both compounds. For example, the alcohol (28) may be used in excess (for example, about 2 to 50 times by mole) with respect to the α, β-unsaturated carboxylic acid ester (27). The ester (27) may be used in excess with respect to the alcohol (28). The amount of the N-hydroxyimide-based catalyst used is α, β-
For example, 0.1 mol of the unsaturated carboxylic acid ester (27) and the alcohol (28) may be used with respect to 1 mol of the compound used in a small amount.
It is about 0001 to 1 mol, preferably about 0.001 to 0.5 mol. The amount of the metal promoter used is α, β-
For example, 0.1 mol of the unsaturated carboxylic acid ester (27) and the alcohol (28) may be used with respect to 1 mol of the compound used in a small amount.
0001-0.7 mol, preferably 0.001-0.5
It is about a mole. Oxygen is often used in excess of the α, β-unsaturated carboxylic acid ester (27) and the alcohol (28), which are used in small amounts. The reaction is, for example, in a solvent such as an organic acid such as acetic acid, a nitrile such as acetonitrile, a halogenated hydrocarbon such as trifluoromethylbenzene, or an ester such as ethyl acetate, at about 0 to 150 ° C. under normal pressure or pressure. , Preferably 30 to 10
This is performed at a temperature of about 0 ° C.

The reaction of the α-hydroxy-γ-butyrolactone derivative (29) thus obtained with (meth) acrylic acid or its derivative (26) is carried out by the above-mentioned 1-adamantanol derivative (17) and (meth) acrylic acid. Or its derivative (1
8).

Of the monomers represented by the above formula (12),
R ⁶ is a group represented by the above formula (9), and s = r
= 1 and R ¹⁶ = R ¹⁷ = H can be obtained, for example, according to the following reaction scheme.

Embedded image (Wherein, R ⁵ , R ¹³ , R ¹⁴ , R ¹⁵ and R ^X are the same as described above)

In the above reaction scheme, the α-hydroxy-γ-butyrolactone represented by the formula (30) is represented by the formula (3
The conversion (isomerization) to the β-hydroxy-γ-butyrolactone represented by 1) is performed by converting the compound of the formula (30) into a solvent to which a small amount of an acid such as water or sulfuric acid or hydrochloric acid is added, if necessary. Can be performed. As the solvent,
There is no particular limitation, and for example, acetonitrile, acetic acid, ethyl acetate and the like can be used. The reaction temperature is, for example, 0 to 15
0 ° C., preferably about 20 to 100 ° C. Α-Hydroxy-γ-butyrolactones used as raw materials (30)
Can be produced in the same manner as in the compound represented by the formula (29). The compound of the formula (31) is obtained by reacting the compound of the formula (30) with phosphorus pentoxide (dehydration reaction) to obtain the corresponding α, β
-Unsaturated-γ-butyrolactone, which is reacted with hydrogen peroxide or a peracid such as m-chloroperbenzoic acid to epoxidize the double bond, and then hydrogenated in the presence of a catalyst such as Pd-C Can also be obtained. Equation (3
The compound of 1) can also be produced by a known method for obtaining β-hydroxy-γ-butyrolactones.

The reaction of β-hydroxy-γ-butyrolactones (31) with (meth) acrylic acid represented by the formula (26) or a derivative thereof is carried out by reacting the compound of the above formula (17) with (meth)
The reaction can be carried out according to the reaction with acrylic acid or its derivative (18).

The following compounds can be exemplified as monomers which may be used for finely adjusting the resist properties of the polymer compound of the present invention. [4-1] 1- (meth) acryloyloxyadamantane [4-2] 1- (meth) acryloyloxy-3,5-dimethyladamantane [4-3] 4- (meth) acryloyloxymethyltetracyclo [4. 4.0.1 ^2,5 . 1 ^7,10 ] dodecane [4-4] 2- (meth) acryloyloxynorbornane [4-5] 2- (meth) acryloyloxyisobornane [4-6] 2- (meth) acryloyloxymethylnorbornane [4 -7] (Meth) acrylic acid The copolymerization of the monomer may be ionic polymerization or living polymerization, but is usually performed by radical polymerization.
As the polymerization initiator used in the case of radical polymerization,
Not particularly limited, for example, potassium persulfate, ammonium persulfate, t-butyl peroxide, cumene hydroperoxide, acetyl peroxide, benzoyl peroxide, lauroyl peroxide, azobisisobutyronitrile, azobiscyclohexanecarbonitrile, Examples include methyl azobisisobutyrate, azobisisobutylamidine hydrochloride, and azobiscyanovaleric acid.

The polymerization method may be any of solution polymerization, bulk polymerization, emulsion polymerization and the like, but is usually solution polymerization. The polymerization temperature varies depending on the polymerization system, but is usually 50 to 12
0 ° C., preferably about 60 to 90 ° C.

The produced polymer can be purified by a conventional method. For example, after the polymerization reaction is completed, a hydrocarbon solvent such as pentane, hexane, heptane, petroleum ether or the like is added to the polymer solution to precipitate the polymer, the polymer is separated by filtration, and then dissolved in a solvent such as tetrahydrofuran (THF). A high-purity polymer can be obtained by re-precipitation by adding the above-mentioned hydrocarbon solvent or the like again.

The resist composition of the present invention contains the polymer compound of the present invention and a photoacid generator. Examples of the photoacid generator include commonly used or known compounds that efficiently generate an acid upon exposure to light, such as diazonium salts, iodonium salts (eg, diphenyliodohexafluorophosphate), and sulfonium salts (eg, triphenylsulfonium hexafluoroantimony). , Triphenylsulfonium hexafluorophosphate, triphenylsulfonium methanesulfonate, etc.), sulfonic acid esters [for example, 1-phenyl-1- (4-methylphenyl) sulfonyloxy-1-benzoylmethane,
1,2,3-trisulfonyloxymethylbenzene,
1,3-dinitro-2- (4-phenylsulfonyloxymethyl) benzene, 1-phenyl-1- (4-methylphenylsulfonyloxymethyl) -1-hydroxy-
1-benzoylmethane, etc.], oxathiazole derivatives, s-triazine derivatives, disulfone derivatives (eg, diphenyldisulfone), imide compounds, oxime sulfonates, diazonaphthoquinone, benzoin tosylate, and the like. These photoacid generators can be used alone or in combination of two or more.

The amount of the photoacid generator to be used can be appropriately selected according to the strength of the acid generated by light irradiation, the ratio of each monomer unit in the polymer compound, and the like. 0.1 to 30 parts by weight, preferably 1 to 25 parts by weight, more preferably about 2 to 20 parts by weight.

The resist composition includes an alkali-soluble component such as an alkali-soluble resin (eg, a novolak resin, a phenol resin, an imide resin, a carboxyl group-containing resin), a coloring agent (eg, a dye), and an organic solvent (eg, a dye). Hydrocarbons, halogenated hydrocarbons, alcohols, esters, amides, ketones, ethers, cellosolves, carbitols, glycol ether esters, mixed solvents thereof, and the like). .

The resist composition is applied on a substrate or a substrate, dried, and then exposed to light (or a post-exposure bake) on the coating film (resist film) through a predetermined mask. By forming a latent image pattern and then developing it, a fine pattern can be formed with high precision.

In the present invention, since the polymer compound contains the repeating unit 1 having a specific structure, the polymer compound is excellent in film formability, and a uniform resist film can be easily formed with good workability. Also,
The formed resist film has excellent characteristics that the brittleness is improved and the film is hard to be broken.

As the substrate or substrate, a silicon wafer,
Examples include metal, plastic, glass, and ceramic. The application of the resist composition can be performed using a conventional application means such as a spin coater, a dip coater, and a roller coater. The thickness of the coating film is, for example, 0.1 to 20.
μm, preferably about 0.3 to 2 μm.

Light of various wavelengths, for example, ultraviolet rays, X-rays, etc., can be used for exposure. For semiconductor resists, g-rays, i-rays, excimer lasers (eg, XeC
1, KrF, KrCl, ArF, ArCl, etc.) are used. Exposure energy is, for example, 1 to 1000 m
J / cm ² , preferably about 10 to 500 mJ / cm ² .

Upon irradiation with light, an acid is generated from the photoacid generator,
With this acid, the acid-eliminable group in the polymer compound is quickly eliminated to form a carboxyl group or the like that contributes to solubilization. Therefore, a predetermined pattern can be accurately formed by development with water or an alkali developing solution.

[0083]

According to the present invention, since the polymer compound has a repeating unit having a specific structure capable of adjusting the glass transition temperature in a wide range, the resist properties such as alkali solubility and substrate adhesion can be maintained. And film properties such as film formability and brittleness of the resist film can be greatly improved. Therefore, a uniform and low brittle resist thin film can be easily and efficiently formed.

[0084]

The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the invention thereto. In addition, "acrylate" after the compound number (monomer number) indicates a compound having an acryloyloxy group among two compounds corresponding to the compound number described in the specification, and "methacrylate" means And a compound having a methacryloyloxy group among the above two compounds. The number at the lower right of the parenthesis in the structural formula indicates the mol% of the monomer unit. "N-B
“u” represents an n-butyl group, and “n-Pr” represents an n-propyl group.

Production Example 1 (2-methacryloyloxy-4,4-dimethyl-γ-
Production of butyrolactone [3-20 (methacrylate)] Ethyl acrylate 3 mmol, 2-propanol 3 m
1, a mixture of 0.6 mmol of N-hydroxyphthalimide, 0.003 mmol of cobalt (II) acetate, 0.015 mmol of cobalt acetylacetonato (III), and 1 ml of acetonitrile under an oxygen atmosphere (1 atm.)
Stirred at 0 ° C. for 12 hours. The reaction mixture is concentrated and the concentrate is subjected to silica gel chromatography to give 2
-Hydroxy-4,4-dimethyl-γ-butyrolactone was obtained in a yield of 75%. [Spectral data of 2-hydroxy-4,4-dimethyl-γ-butyrolactone] ¹ H-NMR (CDCl ₃ ) δ: 1.42 (s, 3)
H), 1.51 (s, 3H), 2.06 (dd, 1
H), 2.52 (dd, 1H), 3.03 (brs, 1
H), 4.63 (t, 1H) A mixture of 100 mmol of 2-hydroxy-4,4-dimethyl-γ-butyrolactone, 150 mmol of methacrylic acid chloride, 150 mmol of triethylamine and 300 ml of toluene obtained by the above method was added at 25 ° C. For 4 hours. After water was added to the reaction mixture, the organic layer was concentrated, and the concentrate was subjected to silica gel column chromatography to obtain 2-methacryloyloxy-4,4-dimethyl-γ-butyrolactone in a yield of 85%. . [2-methacryloyloxy-4,4-dimethyl-γ-
Spectrum data of butyrolactone] ¹ H-NMR (CDCl ₃ ) δ: 1.42 (s, 3
H), 1.48 (s, 3H), 1.90 (s, 3H),
2.15 (dd, 1H), 2.62 (dd, 1H),
5.66 (brs, 1H), 6.18 (brs, 1H)

Example 1 Synthesis of a resin having the structure shown below

Embedded image In an Erlenmeyer flask, 0.0003 g (0.002 mmol) of n-butyl methacrylate [1-2] (methacrylate),
2.31 g (10 mmol) of 2-methacryloyloxy-2-methyladamantane [2-18] (methacrylate), 2-methacryloyloxy-4,4-dimethyl-
γ-butyrolactone [3-20] (methacrylate) 1.9
9 g (10 mmol) and 0.43 g of an initiator (V-65 manufactured by Wako Pure Chemical Industries, Ltd.) were added, and dissolved in 25 g of tetrahydrofuran (THF) to obtain a monomer solution. On the other hand, 100 ml with a reflux tube and a three-way cock
The flask was charged with 15 g of THF, and the monomer solution prepared above was added to the flask under a nitrogen atmosphere using a liquid sending pump.
Introduced over 0 minutes. After the completion of the liquid feeding, the temperature was maintained at 60 ° C., and the mixture was stirred for 10 hours. Then, the reaction solution was dropped into 500 ml of hexane, and the generated precipitate was separated by filtration. The reprecipitation purification operation was performed once again to obtain 3 g of the target resin. GPC analysis of the recovered polymer showed a Mw of 7,200 and a molecular weight distribution (Mw / Mn) of 1.8.

Example 2 Synthesis of resin having the following structure

Embedded image As a monomer, 0.0028 g (0.02 mmol) of n-butyl methacrylate [1-2] (methacrylate),
2.31 g (10 mmol) of 2-methacryloyloxy-2-methyladamantane [2-18] (methacrylate), 2-methacryloyloxy-4,4-dimethyl-
γ-butyrolactone [3-20] (methacrylate)
The same operation as in Example 1 was performed except that 99 g (10 mmol) and 0.4303 g of an initiator (V-65 manufactured by Wako Pure Chemical Industries, Ltd.) were used, to obtain 2.9 g of a target resin. . GPC analysis of the recovered polymer showed a Mw of 8,600 and a molecular weight distribution (Mw / Mn) of 2.1.

Example 3 Synthesis of a resin having the following structure

Embedded image 0.0284 g (0.2 mmol) of n-butyl methacrylate [1-2] (methacrylate) as a monomer,
-Methacryloyloxy-2-methyladamantane [2-
18] (methacrylate), 2.31 g (10 mmol), 2-methacryloyloxy-4,4-dimethyl-
γ-butyrolactone [3-20] (methacrylate)
The same operation as in Example 1 was carried out except that 99 g (10 mmol) and 0.4328 g of an initiator (V-65 manufactured by Wako Pure Chemical Industries, Ltd.) were used, to obtain 3.3 g of a target resin. . GPC analysis of the recovered polymer showed a Mw of 8,300 and a molecular weight distribution (Mw / Mn) of 1.9.

Example 4 Synthesis of resin having the following structure

Embedded image As a monomer, 0.3124 g (2.2 mmol) of n-butyl methacrylate [1-2] (methacrylate), 2
-Methacryloyloxy-2-methyladamantane [2-
18] (methacrylate), 2.31 g (10 mmol), 2-methacryloyloxy-4,4-dimethyl-
γ-butyrolactone [3-20] (methacrylate)
The same operation as in Example 1 was carried out except that 99 g (10 mmol) and 0.4612 g of an initiator (V-65 manufactured by Wako Pure Chemical Industries, Ltd.) were used to obtain 2.8 g of a target resin. . GPC analysis of the recovered polymer showed a Mw of 9000 and a molecular weight distribution (Mw / Mn) of 2.6.

Example 5 Synthesis of a resin having the following structure

Embedded image As monomers, 0.0026 g (0.02 mmol) of n-propyl methacrylate [1-1] (methacrylate) and 2.31 g of 2-methacryloyloxy-2-methyl adamantane [2-18] (methacrylate) (10 Mmol), 1.99 g (10 mmol) of 2-methacryloyloxy-4,4-dimethyl-γ-butyrolactone [3-20] (methacrylate), and an initiator (V-65 manufactured by Wako Pure Chemical Industries, Ltd.) Was used in the same manner as in Example 1 except that 0.4303 g of the resin was used to obtain 2.7 g of a target resin. GPC analysis of the recovered polymer showed a Mw of 7,700 and a molecular weight distribution (Mw / Mn) of 2.4.

Example 6 Synthesis of a resin having the structure shown below

Embedded image 0.0256 g (0.2 mmol) of n-propyl methacrylate [1-1] (methacrylate) as a monomer,
2.31 g (10 mmol) of 2-methacryloyloxy-2-methyladamantane [2-18] (methacrylate), 2-methacryloyloxy-4,4-dimethyl-
γ-butyrolactone [3-20] (methacrylate)
The same operation as in Example 1 was performed except that 99 g (10 mmol) and 0.4326 g of an initiator (V-65 manufactured by Wako Pure Chemical Industries, Ltd.) were used, to obtain 3.1 g of a target resin. . GPC analysis of the recovered polymer showed a Mw of 8,600 and a molecular weight distribution (Mw / Mn) of 2.7.

Example 7 Synthesis of a resin having the following structure

Embedded image As a monomer, 0.0028 g (0.02 mmol) of n-butyl methacrylate [1-2] (methacrylate),
1- (1-methacryloyloxy-1-methylethyl)
2.6 g of adamantane [2-1] (methacrylate)
(10 mmol), 2-methacryloyloxy-4,4
Example 1 except that 1.99 g (10 mmol) of -dimethyl-γ-butyrolactone [3-20] (methacrylate) was used and 0.4593 g of an initiator (V-65 manufactured by Wako Pure Chemical Industries, Ltd.) was used. The same operation as described above was carried out to obtain the desired resin 3.0.
g was obtained. GPC analysis of the recovered polymer revealed that
Mw was 9,300 and molecular weight distribution (Mw / Mn) was 2.9.

Example 8 Synthesis of a resin having the following structure

Embedded image As a monomer, 0.0284 g (0.2 mmol) of n-butyl methacrylate [1-2] (methacrylate), 1
2.6 g (1) of-(1-methacryloyloxy-1-methylethyl) adamantane [2-1] (methacrylate)
0 mmol) and 1.99 g (10 mmol) of 2-methacryloyloxy-4,4-dimethyl-γ-butyrolactone [3-20] (methacrylate), and an initiator (V-65 manufactured by Wako Pure Chemical Industries, Ltd.) ) Was performed in the same manner as in Example 1 except that 0.4618 g of the target resin 2.9 was used.
g was obtained. GPC analysis of the recovered polymer revealed that
Mw was 7,900 and molecular weight distribution (Mw / Mn) was 2.4.

Comparative Example 1 Synthesis of a resin having the following structure

Embedded image As a monomer, 2.31 2-methacryloyloxy-2-methyladamantane [2-18] (methacrylate) was used.
g (10 mmol), 2-methacryloyloxy-4,
Example 1 except that 1.99 g (10 mmol) of 4-dimethyl-γ-butyrolactone [3-20] (methacrylate) was used and 0.43 g of an initiator (V-65 manufactured by Wako Pure Chemical Industries, Ltd.) was used. 1. Perform the same operation as in 1.
9 g were obtained. GPC analysis of the recovered polymer showed a Mw of 8000 and a molecular weight distribution (Mw / Mn) of 2.7.

Comparative Example 2 Synthesis of resin having the following structure

Embedded image As a monomer, 1- (1-methacryloyloxy-1)
2.6 g (10 mmol) of -methylethyl) adamantane [2-1] (methacrylate), 2-methacryloyloxy-4,4-dimethyl-γ-butyrolactone [3-20]
1.99 g (10 mmol) of (methacrylate) and 0.45 of an initiator (V-65 manufactured by Wako Pure Chemical Industries, Ltd.)
The same operation as in Example 1 was performed except that 9 g was used, to obtain 2.6 g of a target resin. GPC analysis of the recovered polymer showed a Mw of 8,800 and a molecular weight distribution (Mw / Mn).
Was 2.9.

Comparative Example 3 Synthesis of a resin having the following structure

Embedded image 0.02 g of methyl methacrylate as a monomer
(0.2 mmol), 2-methacryloyloxy-2-
1. Methyl adamantane [2-18] (methacrylate)
31 g (10 mmol), 2-methacryloyloxy-
Except that 1.99 g (10 mmol) of 4,4-dimethyl-γ-butyrolactone [3-20] (methacrylate) was used and 0.432 g of an initiator (V-65 manufactured by Wako Pure Chemical Industries, Ltd.) was used. The same operation as in Example 1 was performed to obtain 2.8 g of a target resin. GPC analysis of the recovered polymer showed a Mw of 7000 and a molecular weight distribution (Mw / Mn) of 2.8.
Met.

Comparative Example 4 Synthesis of a resin having the following structure

Embedded image 0.02 g of methyl methacrylate as a monomer
(0.2 mmol), 2.6 g (10 mmol) of 1- (1-methacryloyloxy-1-methylethyl) adamantane [2-1] (methacrylate), 2-methacryloyloxy-4,4-dimethyl-γ -Butyrolactone [3
-20] The same operation as in Example 1 was performed except that 1.99 g (10 mmol) of (methacrylate) and 0.461 g of an initiator (V-65 manufactured by Wako Pure Chemical Industries, Ltd.) were used. 3.3 g of a resin was obtained. GPC analysis of the recovered polymer showed a Mw of 7,200 and a molecular weight distribution (Mw / Mn) of 3.1.

Evaluation Test The following tests were performed on the polymers obtained in the examples and comparative examples. Table 1 shows the results. (Brittleness of Coating Film) Using the polymers obtained in Examples and Comparative Examples, a thin film having a thickness of 0.3 to 0.5 μm was formed on a silicon wafer by a coating method. A JIS K54 was applied to this thin film using a pencil with a load of 1 kg and 3H.
A scratch test was performed 10 times in accordance with the method described in “01 (pencil scratch tester for coating film)”, and the brittleness of the coating film was evaluated based on the following criteria. A: The thin film was not broken in all cases. ：: The thin film was not destroyed 5 to 9 times out of 10 times ×: The thin film was destroyed in any case.

(Resist Characteristics) 100 parts by weight of the polymer and 10 parts by weight of triphenylsulfonium hexafluoroantimonate were mixed with ethyl lactate as a solvent to prepare a resist composition having a polymer concentration of 17% by weight. This resist composition was applied to a silicon wafer by spin coating to form a 1.0 μm-thick photosensitive layer. After pre-baking on a hot plate at a temperature of 100 ° C. for 150 seconds, exposure was performed at a dose of 30 mJ / cm ² through a mask using a KrF excimer laser having a wavelength of 247 nm, followed by post-baking at a temperature of 100 ° C. for 60 seconds. Next, the film was developed with a 0.3 M aqueous solution of tetramethylammonium hydroxide for 60 seconds and rinsed with pure water,
The resist properties were evaluated according to the following criteria. ◎: A 0.3 μm line and space pattern was obtained. ：: A 0.5 μm line and space pattern was obtained. ×: Could not be resolved.

[Table 1]

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03F 7/039 601 G03F 7/039 601 H01L 21/027 H01L 21/30 502R F-term (Reference) 2H025 AA09 AA13 AA14 AB16 AC08 AD03 BE00 BG00 CB14 CB41 CB43 CB45 CB51 CB60 4J002 BG041 BG051 BG071 EQ036 EV296 EW176 FD206 GP03 GQ05 4J100 AL03R AL04P AL04R AL05P AL08P AL08Q BA03P BA04Q HC16 BC03 BC02 BC02 BC02 BC02 BC02

Claims (6)

[Claims] 1. A repeating unit having an acid-eliminable group, a repeating unit having a substrate adhesive group, and a compound represented by the following formula (1): [Wherein R ¹ represents a hydrogen atom or a methyl group, and R ² represents a C _3-8 alkyl group (excluding a tertiary alkyl group)]. High molecular compounds. 2. The repeating unit having an acid leaving group is represented by the following formula (2): [Wherein, R ³ is a hydrogen atom or a methyl group, and R ⁴ is a compound represented by the following formulas (4) to (7)] (Wherein R ^{7 to} R ¹² are the same or different and each is a C _1-6 alkyl group, X and Y are substituents bonded to an adamantane ring, and are protected by an oxo group, an alkyl group, or a protecting group. Represents a hydroxyl group which may be protected, a hydroxymethyl group which may be protected by a protecting group, or a carboxyl group which may be protected by a protecting group, and m and n each represent 0 to 3
And p represents 1 or 2).] The resist polymer compound according to claim 1, which is a repeating unit represented by the following formula: 3. A repeating unit having a substrate adhesive group,
The following formula (3)[Wherein, R^FiveIs a hydrogen atom or a methyl group, R⁶Is the following formula
(8) or (9)(Wherein ring A is an alicyclic hydrocarbon ring, Z is bonded to ring A
Substituents, such as oxo, alkyl, and protecting groups
Hydroxyl groups, which may be protected, protected with protecting groups
Protected by an optionally protected hydroxymethyl group or a protecting group.
Represents a carboxyl group which may be
Even if at least one is protected by an oxo group or a protecting group
Good hydroxyl groups,
A group that may be protected by a droxymethyl group or a protecting group
It is a ruboxyl group. R¹³Is a hydrogen atom or a methyl group, R
¹⁴~ R¹⁷Are the same or different and each represents a hydrogen atom or an alkyl
Represents a group. t is 0 or 1, q is an integer of 1 to 3, r is 1 to
An integer of 3, s represents an integer of 0 to 2, and r + s = 2 to 4
is there. However, when ring A is an adamantane ring,-(C
H _Two)_t-Is attached to the bridgehead of the adamantane ring)
A repeating unit represented by the following formula:
Item 4. The resist polymer compound according to Item 1. 4. The repeating unit represented by the formula (1) accounts for 0.01 to 30 mol% of all repeating units constituting the polymer.
The resist polymer compound according to claim 1, wherein 5. A resist composition comprising the polymer compound for a resist according to claim 1 and a photoacid generator. 6. A method for producing a semiconductor, comprising a step of applying the resist composition according to claim 5 on a substrate or a substrate to form a resist coating film, and forming a pattern through exposure and development.