JP2003082030A - Polymer compound, resist material and method for pattern formation - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resist material which is sensitive to high-energy beam, has excellent sensitivity to high-energy beam at <=200 nm, especially <=170 nm wavelength, improved transparency of resist and excellent plasma etching resistance at the same time. SOLUTION: This polymer compound has repeating units of formula (1a), formula (1b) and formula (1c) (R<1> , R<2> , R<5> and R<6> are each H, F, an alkyl or a fluorinated alkyl; R<3> and R<7> are each F or a fluorinated alkyl; R<4> is an acid- unstable group; R<8> is an adhesive group, H, an alkyl or a fluorinated alkyl; R<10> is a single bond, an alkylene or a fluorinated alkylene; R<11> and R<12> are each H, an alkyl or a fluorinated alkyl; R<13> is H, F, an alkyl or a fluorinated alkyl; R<14> is H, an alkyl or an acid-unstable group; 0<a<1, 0<b<1, 0<c<1, 0<a+b+c<=1; m and n are each an integer of 1<=m<=5, 0<=n<=4 and m+n=5).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resist material suitable for a microfabrication technique, particularly a polymer compound useful as a base polymer of a chemically amplified resist material, a resist material and a pattern forming method using the same.

[0002]

2. Description of the Related Art In recent years,
Along with high integration and high speed of LSI, miniaturization of pattern rules is required.

Background of the rapid progress in miniaturization is to increase the NA of the projection lens, improve the performance of the resist, and shorten the wavelength. Regarding high resolution and high sensitivity of resist,
A chemically amplified positive resist material using an acid generated by light irradiation as a catalyst has excellent performance and has become a mainstream resist material in deep ultraviolet lithography (Japanese Patent Publication No. 27660/1990). -2782
9). Also, from i-line (365 nm) to K
Shortening the wavelength to rF (248 nm) has brought about a great change, and the resist material for KrF excimer laser is 0.30.
It started with the micron process, went through the 0.25 micron rule, and is now being applied to mass production of the 0.18 micron rule. Furthermore, studies on the 0.15 micron rule have begun, and the momentum for miniaturization is accelerating.

With ArF (193 nm), it is expected that the finer design rule will be 0.13 μm or less. However, the conventionally used resins such as novolac and polyvinylphenol have a very strong absorption around 193 nm. Therefore, it cannot be used as a base resin for resist. Therefore, in order to ensure transparency and required dry etching resistance, acrylic and cycloolefin-based alicyclic resins have been investigated (Japanese Patent Laid-Open No. 9-73173).
JP-A-10-10739, JP-A-9-23059
5 publication, WO 97/33198).

For F ₂ (157 nm) 0.10 μ
Although miniaturization of m or less is expected, it becomes more and more difficult to secure transparency, and acrylic resins, which are base polymers for ArF, do not transmit light at all, and cycloolefin-based compounds that have carbonyl bonds It turned out to have a strong absorption. Further, it has been found that polyvinylphenol, which is the base polymer for KrF, has an absorption window near 160 nm and the transmittance is slightly improved, but it is far from a practical level.

According to the study of the present inventor, as a method of improving the transmittance around 157 nm, it is considered that reducing the number of carbonyl groups or carbon-carbon double bonds is also one method. It has been found that the introduction of fluorine atoms into the glass also greatly contributes to the improvement of the transmittance. In fact, a polymer in which fluorine was introduced into the aromatic ring of polyvinylphenol could obtain a transmittance close to practical use. However, it has become clear that this base polymer is notably put into practical use as a resist because it becomes remarkable that the base polymer is made negative by irradiation with high energy light such as an F ₂ laser. On the other hand, it was found that a polymer obtained by introducing fluorine into a polymer compound containing an acrylic resin or an alicyclic compound derived from a norbornene derivative in its main chain can suppress absorption to a low level and can also solve the problem of negative reaction. . Here, it has been reported that a copolymer of α-trifluoromethylacrylic acid and hexafluoroalcohol pendant styrene has high dry etching resistance and is promising as a highly transparent resist (SPIE. Vol. 4345).
-31, 2001 now printing; Po
lymer design for 157nm ch
emally amplified resist
s). However, when the copolymerization ratio of styrene is increased, the etching resistance is improved but the transmittance is lowered. Further, when the copolymerization ratio of α-trifluoromethylacrylic acid substituted with an acid labile group was increased, the transmittance was improved, but there were problems such as repelling of the developer and residue left in the space.

The present invention has been made in view of the above circumstances, and is 300 nm or less, particularly F ₂ (157 nm), Kr.
₂ (146 nm), KrAr (134 nm), Ar ₂ (1
To provide a novel polymer compound useful as a base polymer of a chemically amplified resist material having excellent transmittance in vacuum ultraviolet light (26 nm), a resist material containing the same, and a pattern forming method using the resist material. To do.

[0008]

Means for Solving the Problems and Modes for Carrying Out the Invention As a result of intensive studies to achieve the above object, the present inventor has found that an acrylate monomer containing fluorine at the α-position and hexafluoroalcohol are pendant. By using a styrene copolymer as a base polymer,
It has been found that a resist material, particularly a chemically amplified resist material, which can drastically improve transparency and developing characteristics and can also secure dry etching resistance can be obtained. Particularly, a repeating unit in which α-trifluoromethylacrylic acid carboxylate is substituted with an acid labile group and a repeating unit in which α-trifluoromethyl acrylic acid carboxylate is substituted with an adhesive group, and styrene with hexafluoroalcohol are used. A terpolymer containing pendant repeating units, or a repeating unit in which trifluoromethylacrylic acid carboxylate is substituted with an acid labile group and α-trifluoromethylacrylic acid carboxylate in which a perfluoroalkyl group is substituted. Repeating units,
The inventors have found that a terpolymer containing a repeating unit in which styrene is pendant with hexafluoroalcohol is useful, and have completed the present invention.

That is, the present invention provides the following polymer compound, resist material and pattern forming method. Claim 1: A polymer compound having repeating units represented by the following general formulas (1a), (1b) and (1c).

[Chemical 2] (In the formula, R ¹ , R ² , R ⁵ and R ⁶ are a hydrogen atom, a fluorine atom,
Alternatively, it is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms or a fluorinated alkyl group. R ³ ,
R ⁷ is a fluorine atom or a linear, branched or cyclic fluorinated alkyl group having 1 to 20 carbon atoms. R
⁴ is an acid labile group, R ⁸ is an adhesive group, a hydrogen atom, or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms or a fluorinated alkyl group. R ¹⁰ is a single bond, an alkylene group having 1 to 20 carbon atoms, or a fluorinated alkylene group. R ¹¹ and R ¹² are a hydrogen atom, a fluorine atom, or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms or a fluorinated alkyl group,
^At least one of ¹¹ and R ¹² contains at least one fluorine atom. R ¹³ is the same or different hydrogen atom, fluorine atom, or a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, and may be a fluorinated alkyl group. R ¹⁴ is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms or an acid labile group, and may contain an ether group, a carbonyl group, an ester group or a lactone ring. a, b, c are 0 <a <1, 0 <b <
1, 0 <c <1 and 0 <a + b + c ≦ 1. Further, m and n are integers of 1 ≦ m ≦ 5 and 0 ≦ n ≦ 4,
m + n = 5. ) Claim 2: In the repeating unit of general formula (1a), R ⁴
Is an acid labile group, and R ^{8 in} the repeating unit of the general formula (1b) is an adhesive group.
The high molecular compound described. Claim 3: In the repeating unit of general formula (1a), R ⁴
Is an acid labile group, and in the repeating unit of the general formula (1b), R ⁸ is a linear, branched or cyclic fluorinated alkyl group having 1 to 20 carbon atoms. 1. The polymer compound according to 1. Claim 4: R ³ and R ⁷ are each a straight, claim 1, 2 or 3 polymer, wherein the fluorinated alkyl group branched or cyclic Compound. Claim 5: The polymer compound according to claim 4, wherein R ³ and R ⁷ are each a trifluoromethyl group. [6] A resist material comprising the polymer compound according to any one of [1] to [5]. Claim 7: (A) A chemically amplified resist material containing the polymer compound according to any one of claims 1 to 5, (B) an organic solvent, and (C) an acid generator. [8] The resist material according to [7], which further contains a basic compound. Claim 9: The resist material according to claim 7 or 8, further comprising a dissolution inhibitor. Claim 10: (1) A step of applying the resist material according to any one of claims 6 to 9 onto a substrate, and (2) a heat treatment followed by a wavelength range of 100 to 180 nm through a photomask, or A step of exposing with a high energy ray in the band of 1 to 30 nm,
(3) A method of forming a pattern, which comprises a step of performing a heating treatment as needed and then developing with a developing solution. Claim 11: The high energy rays are F ₂ laser and Ar _2.
A laser or soft X-ray is used.
The pattern forming method described in 0.

The present invention will be described in more detail below. The polymer compound of the present invention has the following general formula (1a):
It contains the repeating units represented by (1b) and (1c).

[0011]

[Chemical 3]

In the formula, R ¹ , R ² , R ⁵ and R ⁶ are a hydrogen atom, a fluorine atom, or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms or a fluorinated alkyl group. However, a hydrogen atom and a fluorine atom are preferable. R ³ and R ⁷ are a fluorine atom or a linear, branched or cyclic fluorinated alkyl group having 1 to 20 carbon atoms, and a fluorine atom or a trifluoromethyl group is preferably used. R ⁴ is an acid labile group, R ⁸ is an adhesive group, a hydrogen atom, or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms described below or a fluorinated alkyl group. R ¹⁰
Is a single bond, an alkylene group having 1 to 20 carbon atoms, or a fluorinated alkylene group. R ¹¹ and R ¹² are a hydrogen atom, a fluorine atom, or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms or a fluorinated alkyl group, and at least one of R ¹¹ and R ¹² Contains at least one fluorine atom. R ¹³ is the same or different hydrogen atom, fluorine atom, or a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, and may be a fluorinated alkyl group. R ¹⁴ is hydrogen atom or 1 to 10 carbon atoms
A linear, branched or cyclic alkyl group or an acid labile group of, an ether group, a carbonyl group, an ester group,
It may contain a lactone ring. a, b, c are 0 <a
<1, 0 <b <1, 0 <c <1, and 0 <a + b + c
≦ 1. Further, m and n are 1 ≦ m ≦ 5 and 0 ≦ n ≦ 4.
Is an integer and m + n = 5.

R ⁸ is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, n-propyl group and s
Examples thereof include an ec-butyl group, a tert-butyl group, a cyclopentyl group, a cyclohexyl group, a 2-ethylhexyl group, and an n-octyl group, and those having 1 to 12 carbon atoms, particularly those having 1 to 10 carbon atoms are particularly preferable. Further, the fluorinated alkyl group is one in which some or all of the hydrogen atoms of the above alkyl group are substituted with fluorine atoms, and a trifluoromethyl group, 2,2,2-trifluoroethyl group, 3,
3,3-trifluoropropyl group, 1,1,1,3
3,3-hexafluoroisopropyl group, 1,1,2,
2,3,3,3-heptafluoropropyl group, 2,2
In addition to the 3,3,4,4,5,5-octafluoropentyl group and the like, a group represented by the following formula is also used.

[0014]

[Chemical 4] (In the formula, R ¹³ is a hydrogen atom, a fluorine atom, or a carbon number of 1 to 20.
Is a linear, branched or cyclic alkyl group or a fluorinated alkyl group, and 0 ≦ f ≦ 10. )

Further, the alkylene group having 1 to 20 carbon atoms as R ¹⁰ and the fluorinated alkylene group have one hydrogen atom removed from the alkyl group having 1 to 20 carbon atoms and the fluorinated alkyl group. The carbon number is 1 to 1
12, especially those having 1 to 10 carbon atoms are preferable.

As the acid labile group, R ⁴ or R
There are ¹⁴ cases, and various selections are made. Especially, the following formula (A-
1), a group represented by (A-2), a tertiary alkyl group having 4 to 40 carbon atoms represented by the following formula (A-3), and a trialkylsilyl group in which each alkyl group has 1 to 6 carbon atoms. A group and an oxoalkyl group having 4 to 20 carbon atoms are preferable.

[0017]

[Chemical 5]

In the formula (A-1), R ³⁰ has 4 to 4 carbon atoms.
40, preferably 4 to 15 tertiary alkyl groups, each alkyl group is a C1 to C6 trialkylsilyl group,
An oxoalkyl group having 4 to 20 carbon atoms or the above general formula (A
-3), and specifically as a tertiary alkyl group, a tert-butyl group, a tert-amyl group,
1,1-diethylpropyl group, 1-ethylcyclopentyl group, 1-butylcyclopentyl group, 1-ethylcyclohexyl group, 1-butylcyclohexyl group, 1-ethyl-2-cyclopentenyl group, 1-ethyl-2-cyclohexenyl group Group, a 2-methyl-2-adamantyl group, and the like. Specific examples of the trialkylsilyl group include a trimethylsilyl group, a triethylsilyl group, and dimethyl-ter.
Examples thereof include a t-butylsilyl group, and specific examples of the oxoalkyl group include a 3-oxocyclohexyl group, a 4-methyl-2-oxooxan-4-yl group, and a 5-methyl- group.
Examples include 2-oxooxolan-5-yl group. a
1 is an integer of 0-6.

In the formula (A-2), R ³¹ and R ³² represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, and specifically, Methyl group, ethyl group, propyl group, isopropyl group, n-
Examples thereof include a butyl group, sec-butyl group, tert-butyl group, cyclopentyl group, cyclohexyl group, 2-ethylhexyl group, n-octyl group and the like. R ³³ has 1 carbon atom
To 30, preferably 1 to 10 monovalent hydrocarbon groups which may have a hetero atom such as an oxygen atom, wherein a linear, branched or cyclic alkyl group, and some of these hydrogen atoms are Examples thereof include those substituted with a hydroxyl group, an alkoxy group, an oxo group, an amino group, an alkylamino group and the like, and specific examples include the following substituted alkyl groups.

[0020]

[Chemical 6]

[0021] R ³¹ and R ^32, and R ³¹ and R ^33, R ³² and R ³³ may form a ring, R ³¹ in the case of forming the ring,
R ³² and R ³³ each have 1 to 18 carbon atoms, preferably 1 to
10 represents a linear or branched alkylene group.

As the acid labile group of the above formula (A-1),
Specifically, a tert-butoxycarbonyl group, tert
-Butoxycarbonylmethyl group, tert-amyloxycarbonyl group, tert-amyloxycarbonylmethyl group, 1,1-diethylpropyloxycarbonyl group,
1,1-diethylpropyloxycarbonylmethyl group,
1-ethylcyclopentyloxycarbonyl group, 1-ethylcyclopentyloxycarbonylmethyl group, 1-ethyl-2-cyclopentenyloxycarbonyl group, 1-
Examples thereof include an ethyl-2-cyclopentenyloxycarbonylmethyl group, a 1-ethoxyethoxycarbonylmethyl group, a 2-tetrahydropyranyloxycarbonylmethyl group and a 2-tetrahydrofuranyloxycarbonylmethyl group.

Further, the following formulas (A-1) -1 to (A-1)
The substituent shown by -9 can also be mentioned.

[0024]

[Chemical 7] (A2 is an integer of 0 to 6)

Here, R ³⁷ is the same or different from each other and has a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and R ³⁸ is a hydrogen atom or a carbon atom. It is a linear, branched or cyclic alkyl group of the number 1 to 10.

R ³⁹ is the same or different from each other, and is a linear, branched or cyclic alkyl group having 2 to 10 carbon atoms,
Alternatively, it is an aryl group having 6 to 20 carbon atoms.

Among the acid labile groups represented by the above formula (A-2), those having a linear or branched structure are represented by the following formula (A-
2) -1 to (A-2) -23 can be exemplified.

[0028]

[Chemical 8]

[0029]

[Chemical 9]

Among the acid labile groups represented by the above formula (A-2), the cyclic one is tetrahydrofuran-2-
Yl group, 2-methyltetrahydrofuran-2-yl group,
Examples thereof include a tetrahydropyran-2-yl group and a 2-methyltetrahydropyran-2-yl group.

Further, the general formula (A-2a) or (A-
The base resin may be intermolecularly or intramolecularly crosslinked by the acid labile group represented by 2b).

[0032]

[Chemical 10]

In the formula, R ⁴⁰ and R ⁴¹ are hydrogen atoms or have 1 carbon atom.
8 represents a linear, branched or cyclic alkyl group. Alternatively, R ⁴⁰ and R ⁴¹ may combine with each other to form a ring, and when forming a ring, R ⁴⁰ and R ^{41 each} represent a linear or branched alkylene group having 1 to 8 carbon atoms. R ⁴² is a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, b and d are 0 or 1 to 10, preferably an integer of 0 or 1 to 5 and c is 1 to
It is an integer of 7. A is a (c + 1) -valent carbon number 1 to 50
Represents an aliphatic or alicyclic saturated hydrocarbon group, an aromatic hydrocarbon group or a heterocyclic group, and these groups may have a heteroatom interposed, or a part of hydrogen atoms bonded to the carbon atom It may be substituted with a hydroxyl group, a carboxyl group, a carbonyl group or a fluorine atom. B is -CO-
O-, -NHCO-O- or -NHCONH- is shown.

In this case, A is preferably a divalent to tetravalent C1-C20 linear, branched or cyclic alkylene group, an alkyltriyl group, an alkyltetrayl group and a C6-C30. It is an arylene group, and these groups may have a heteroatom interposed, and a part of hydrogen atoms bonded to the carbon atom may be substituted with a hydroxyl group, a carboxyl group, an acyl group or a halogen atom. Further, c is preferably an integer of 1 to 3.

The cross-linking acetal groups represented by formulas (A-2a) and (A-2b) are specifically represented by the following formula (A-
2) -24 to (A-2) -31.

[0036]

[Chemical 11]

Next, in the formula (A-3), R ³⁴ , R ³⁵ ,
R ³⁶ is a straight, a monovalent hydrocarbon group, branched or cyclic alkyl group, oxygen, sulfur, nitrogen, which may contain a hetero atom such as fluorine, R ³⁴ and R
³⁵ , R ³⁴ and R ³⁶ , and R ³⁵ and R ³⁶ may be bonded to each other to form a ring having 3 to 20 carbon atoms together with the carbon atom to which they are bonded.

The tertiary alkyl group represented by the formula (A-3) includes a tert-butyl group, a triethylcarbyl group,
1-ethylnorbornyl group, 1-methylcyclohexyl group, 1-ethylcyclopentyl group, 2- (2-methyl)
Adamantyl group, 2- (2-ethyl) adamantyl group,
Examples thereof include a tert-amyl group.

Specific examples of the tertiary alkyl group include the following formulas (A-3) -1 to (A-3) -18.

[0040]

[Chemical 12]

In formulas (A-3) -1 to (A-3) -18,
R ⁴³ is the same or different, and is a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, or an aryl group such as phenyl group having 6 to 20 carbon atoms. R ^44, R ⁴⁶ is a hydrogen atom, or a straight, an alkyl group branched or cyclic. R ⁴⁵ represents an aryl group having 6 to 20 carbon atoms such as a phenyl group.

Further, the following formulas (A-3) -19 and (A-3)
As shown in -20, the polymer may be crosslinked intramolecularly or intermolecularly by including R ⁴⁷ which is a divalent or higher valent alkylene group or an arylene group. Formula (A-3) -19,
In (A-3) -20, R ⁴³ is the same as described above, R ⁴⁷ is a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms, or an arylene group such as a phenylene group, and an oxygen atom or It may contain a hetero atom such as a sulfur atom or a nitrogen atom. b1 is an integer of 1 to 3.

[0043]

[Chemical 13]

Further, R ³⁴ , R ³⁵ and R ^{36 in the} formula (A-3) are
May have a hetero atom such as oxygen, nitrogen or sulfur, and specific examples thereof include those represented by the following formulas (A) -1 to (A) -7.

R ³⁰ , R ³³ and R ³⁶ in the formulas (A-1), (A-2) and (A-3) are phenyl group, p-methylphenyl group, p-ethylphenyl group and p- Unsubstituted or substituted aryl groups such as alkoxy-substituted phenyl groups such as methoxyphenyl group, aralkyl groups such as benzyl group, phenethyl group, etc., and those groups having an oxygen atom or a hydrogen atom bonded to a carbon atom is a hydroxyl group. An alkyl group represented by the following formulas (A) -1 to (A) -7, which is substituted or two hydrogen atoms are substituted with oxygen atoms to form a carbonyl group, or a formula (A) -8, The oxoalkyl group shown by (A) -9 can be mentioned.

[0046]

[Chemical 14]

Examples of the trialkylsilyl group in which each alkyl group has 1 to 6 carbon atoms include trimethylsilyl group, triethylsilyl group and dimethyl-tert-butylsilyl group. Examples of the oxoalkyl group having 4 to 20 carbon atoms include 3-oxocyclohexyl group, 5-methyl-2-oxooxolan-5-yl group, 2-oxooxan-4-yl group and the like.

Next, various adhesive groups for R ⁸ are selected, but the groups represented by the following formulas are particularly preferable.

[0049]

[Chemical 15]

In the polymer compound of the present invention, R ⁴ is an acid labile group in the repeating unit of general formula (1a), and R ⁸ is an adhesive group in the repeating unit of general formula (1b). And R ⁴ in the repeating unit of the general formula (1a) is an acid labile group, and R ^{8 in} the repeating unit of the general formula (1b) has 1 to 20 carbon atoms.
Is preferably a linear, branched or cyclic fluorinated alkyl group, and R ³ and R ⁷ are each a linear, branched or cyclic fluorinated alkyl group having 1 to 20 carbon atoms. A group, especially a trifluoromethyl group, is preferred.

Next, as a concrete example of the above formula (1c), the following formula can be given.

[Chemical 16]

The polymer compound of the present invention has a repeating unit in which α-trifluoromethylacrylic acid carboxylate is substituted with an acid labile group, and an α-trifluoromethylacrylic acid carboxylate is substituted with an adhesive group. A terpolymer of a repeating unit and a repeating unit in which hexafluoroalcohol is pendant on styrene, or a repeating unit in which α-trifluoromethylacrylic acid carboxylate is substituted with an acid labile group, and α-trifluoro A terpolymer of a repeating unit in which methyl acrylic acid carboxylate is substituted with a perfluoroalkyl ester and a repeating unit in which hexafluoroalcohol is pendant on styrene can be used, and α-
A repeating unit in which trifluoromethylacrylic acid carboxylate is substituted with an acid labile group, a repeating unit in which α-trifluoromethylacrylic acid carboxylate is substituted with an adhesive group, and α-trifluoromethylacrylic acid carboxylate It may be a quaternary or quaternary or more copolymer of a repeating unit in which is substituted with a perfluoroalkyl ester, and a repeating unit in which hexafluoroalcohol is pendant on styrene. Also,
Molecular weight, polydispersity, do not may be blended two or more different polymers of copolymerization ratio, (1b) units of R ⁸
May be blended with a polymer having adhesiveness with a polymer in which R ^{8 of the} unit (1b) is a perfluoroalkyl group.

The polymer compound of the present invention has the above R ⁸
The above-mentioned adhesive group alone has sufficient adhesiveness, but from the viewpoint of further improving the adhesiveness, the repeating unit represented by the following formula can be introduced.

[0054]

[Chemical 17] (In the formula, R ²⁴ is a hydrogen atom, a hydroxy group, or a carbon number 1
10 represents a linear, branched or cyclic alkyl group of 10
0 ≦ h ≦ 4 and 0 ≦ i ≦ 4. )

When synthesizing the polymer compound of the present invention, the monomer giving the repeating unit represented by the above formulas (1a), (1b) and (1c) and, if necessary, the adhesion improving monomer are dissolved in a solvent. The catalyst is added, and the polymerization reaction is carried out while heating or cooling as the case may be. The polymerization reaction is also governed by the type of initiator (or catalyst), the method of initiation (light, heat, radiation, plasma, etc.), the polymerization conditions (temperature, pressure, concentration, solvent, additives) and the like. In the polymerization of the polymer compound of the present invention, radical copolymerization in which polymerization is initiated by radicals such as AIBN and ionic polymerization (anionic polymerization) using a catalyst such as alkyllithium are generally used. These polymerizations can be performed according to the usual method.

The radical polymerization initiator is not particularly limited, but as an example, 2,2'-azobis (4-
Methoxy-2,4-dimethylvaleronitrile), 2,
2'-azobis (2,4-dimethylvaleronitrile),
Azo compounds such as 2,2′-azobisisobutyronitrile and 2,2′-azobis (2,4,4-trimethylpentane), tert-butylperoxypivalate, lauroyl peroxide, benzoyl peroxide, t
Peroxide compounds such as ert-butyl peroxylaurate, water-soluble initiators such as persulfates such as potassium persulfate, and peroxides such as potassium persulfate and hydrogen peroxide and sodium sulfite. A redox-based initiator composed of a combination of such reducing agents is exemplified. The amount of the polymerization initiator used can be appropriately changed depending on the type, the polymerization reaction conditions, etc., but usually 0.001 to 5% by weight, particularly 0.01 to 2% by weight based on the total amount of the monomers to be polymerized. Weight percent is adopted.

A polymerization solvent may be used in the polymerization reaction. As the polymerization solvent, those which do not inhibit the polymerization reaction are preferable, and typical ones include esters such as ethyl acetate and n-butyl acetate, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, toluene, xylene, cyclohexane and the like. The aliphatic or aromatic hydrocarbons, alcohols such as isopropyl alcohol and ethylene glycol monomethyl ether, and ether solvents such as diethyl ether, dioxane and tetrahydrofuran can be used. These solvents may be used alone or in 2
It can be used by mixing more than one kind. Also, a known molecular weight modifier such as dodecyl mercaptan may be used in combination.

The reaction temperature of the polymerization reaction is appropriately changed depending on the kind of the polymerization initiator or the boiling point of the solvent, and usually 20 to 2
00 ° C is preferable, and 50 to 140 ° C is particularly preferable. The reaction vessel used for such a polymerization reaction is not particularly limited.

As a method for removing the organic solvent or water as a medium from the solution or dispersion of the polymer according to the present invention thus obtained, any known method can be used. There are methods such as reprecipitation filtration or heat distillation under reduced pressure.

The weight average molecular weight of the above polymer compound is 1,
000 to 1,000,000, especially 2,000 to 10
It is desirable to set it to 10,000.

In the formulas (1a), (1b) and (1c), a, b and c are positive numbers and a + b + c = 1, but a / (a + b + c) is 0.05 to 0.7, preferably. Is 0.1 to 0.6, and b / (a + b + c) is 0.1 to 0.
4, preferably 0.15 to 0.2, c / (a + b + c)
Is 0.3 to 0.9, preferably 0.35 to 0.8. Furthermore, equations (1a), (1b), (1
When a repeating unit derived from an adhesive monomer is included in addition to the unit of c), and this unit is (Q) _h , (a +
It is desirable that b + c) / (a + b + c + h) is 0.6 to 1, preferably 0.7 to 1.

The polymer compound of the present invention is a resist material,
In particular, it can be used as a base resin for a chemically amplified resist composition, especially a chemically amplified positive resist material, but it is mixed with another polymer compound for the purpose of changing the mechanical properties, thermal properties, alkali solubility, and other properties of the film. You can also At this time, the range of the polymer compound to be mixed is not particularly limited, but the polymer compound may be mixed with a known polymer compound for resist or the like in an arbitrary range.

The resist material of the present invention can be prepared using known components except that the polymer compound of the present invention is used as a base resin. Particularly, the chemically amplified positive resist material is
It may contain (A) the polymer compound (base resin), (B) an organic solvent, and (C) an acid generator. In this case, these resist materials may further contain (D) a basic compound and (E) a dissolution inhibitor.

The organic solvent of the component (B) used in the present invention may be any one as long as it can dissolve the base resin, acid generator, other additives and the like. Examples of such an organic solvent include cyclohexanone and methyl-2-n-
Ketones such as amyl ketone, 3-methoxybutanol,
3-methyl-3-methoxybutanol, 1-methoxy-
Alcohols such as 2-propanol and 1-ethoxy-2-propanol, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether and other ethers, propylene Glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol mono ter
Esters such as t-butyl ether acetate are mentioned.

Fluorinated organic solvents can also be used. Specifically, 2-fluoroanisole, 3-fluoroanisole, 4-fluoroanisole, 2,3-difluoroanisole, 2,4-difluoroanisole, 2,5-difluoroanisole, 5,8
-Difluoro-1,4-benzodioxane, 2,3-difluorobenzyl alcohol, 1,3-difluoro-2
-Propanol, 2 ', 4'-difluoropropiophenone, 2,4-difluorotoluene, trifluoroacetaldehyde ethyl hemiacetal, trifluoroacetamide, trifluoroethanol, 2,2,2-trifluoroethylbutyrate, ethylhepta Fluorobutyrate, ethylheptafluorobutylacetate, ethylhexafluoroglutarylmethyl, ethyl-3-hydroxy-4,4,4-trifluorobutyrate, ethyl-2-methyl-4,4,4-trifluoroacetoacetate , Ethyl pentafluorobenzoate, ethyl pentafluoropropionate, ethyl pentafluoropropynyl acetate, ethyl perfluorooctanoate, ethyl-4,4,4-trifluoroacetoacetate, ethyl-4,4,4 -Trifluorobutyrate, ethyl-4,4,4-trifluorocrotonate, ethyltrifluorosulfonate, ethyl-3- (trifluoromethyl) butyrate, ethyltrifluoropyruvate, sec-ethyltrifluoroacetate, fluorocyclohexane , 2,2,3,3,4,4,4-heptafluoro-1-butanol, 1,1,1,2,2,3
3-heptafluoro-7,7-dimethyl-4,6-octanedione, 1,1,1,3,5,5,5-heptafluoropentane-2,4-dione, 3,3,4,4 5,
5,5-heptafluoro-2-pentanol, 3,3
4,4,5,5,5-heptafluoro-2-pentanone, isopropyl 4,4,4-trifluoroacetoacetate, methyl perfluorodenanoate, methyl perfluoro (2-methyl-3-oxahexanoate ),
Methyl perfluorononanoate, methyl perfluorooctanoate, methyl-2,3,3,3-tetrafluoropropionate, methyltrifluoroacetoacetate, methyltrifluoroacetoacetate, 1,1,
1,2,2,6,6,6-octafluoro-2,4-hexanedione, 2,2,3,3,4,4,5,5-octafluoro-1-pentanol, 1H, 1H, 2H, 2
H-perfluoro-1-decanol, perfluoro (2,5-dimethyl-3,6-dioxane anionic) acid methyl ester, 2H-perfluoro-5-methyl-3,6-dioxanonane, 1H, 1H, 2H , 3
H, 3H-perfluorononane-1,2-diol, 1
H, 1H, 9H-perfluoro-1-nonanol, 1
H, 1H-perfluorooctanol, 1H, 1H, 2
H, 2H-perfluorooctanol, 2H-perfluoro-5,8,11,14-tetramethyl-3,6
9,12,15-pentaoxaoctadecane, perfluorotributylamine, perfluorotrihexylamine, perfluoro-2,5,8-trimethyl-3,6,6.
9-trioxadodecanoic acid methyl ester, perfluorotripentylamine, perfluorotripropylamine, 1H, 1H, 2H, 3H, 3H-perfluoroundecane-1,2-diol, trifluorobutanol,
1,1,1-trifluoro-5-methyl-2,4-hexanedione, 1,1,1-trifluoro-2-propanol, 3,3,3-trifluoro-1-propanol,
1,1,1-trifluoro-2-propyl acetate,
Perfluoro (butyltetrahydrofuran), perfluorodecalin, perfluoro (1,2-dimethylcyclohexane), perfluoro (1,3-dimethylcyclohexane), propylene glycol trifluoromethyl ether acetate, propylene glycol methyl ether trifluoromethyl acetate, Butyl trifluoromethyl acetate, methyl 3-trifluoromethoxypropionate, perfluorocyclohexanone, propylene glycol trifluoromethyl ether, butyl trifluoroacetate, 1,1,1-trifluoro-5,5-dimethyl-2,4- Hexanedione and the like can be mentioned.

These solvents may be used alone or in admixture of two or more, but are not limited thereto. In the present invention, among these organic solvents, in addition to diethylene glycol dimethyl ether and 1-ethoxy-2-propanol, which have the best solubility of the acid generator in the resist component, propylene glycol monomethyl acetate which is a safety solvent and a mixed solvent thereof. Is preferably used.

The amount of the above solvent used is 300 to 10,000 parts with respect to 100 parts by weight of the base resin (weight part, hereinafter the same).
In particular, it can be 500 to 5,000 parts.

Examples of the acid generator as the component (C) include an onium salt represented by the following general formula (2), a diazomethane derivative represented by the formula (3), a glyoxime derivative represented by the formula (4), a β-ketosulfonic acid derivative, a disulfone derivative and a nitro compound. Examples thereof include a benzyl sulfonate derivative, a sulfonate ester derivative, and an imidoyl sulfonate derivative.

One of onium salts used as an acid generator
The general formula is represented by the following formula (2). (R⁵¹)_iM⁺K^-        (2) (In the formula, R⁵¹Are linear and branched having 1 to 12 carbon atoms, respectively.
Or cyclic alkyl group, aryl having 6 to 20 carbon atoms
A group or an aralkyl group having 7 to 12 carbon atoms, M ⁺Is
Represents iodonium and sulfonium, K^-Is a non-nucleophilic pair
It represents a counterion, and i is 2 or 3. )

Examples of the alkyl group represented by R ⁵¹ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a 2-oxocyclopentyl group, a norbornyl group and an adamantyl group. As the aryl group, a phenyl group, p
-Methoxyphenyl group, m-methoxyphenyl group, o-
Methoxyphenyl group, ethoxyphenyl group, p-ter
Alkoxyphenyl groups such as t-butoxyphenyl group and m-tert-butoxyphenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, ethylphenyl group, 4-tert-butylphenyl group, 4
Examples thereof include an alkylphenyl group such as a butylphenyl group and a dimethylphenyl group. Examples of the aralkyl group include a benzyl group and a phenethyl group. As the non-nucleophilic counter ion of K ⁻ , chloride ion, halide ion such as bromide ion, triflate, fluoroalkyl sulfonate such as 1,1,1-trifluoroethane sulfonate, nonafluorobutane sulfonate, tosylate, benzene sulfonate. Examples include aryl sulfonates such as 4-fluorobenzene sulfonate and 1,2,3,4,5-pentafluorobenzene sulfonate, and alkyl sulfonates such as mesylate and butane sulfonate.

Specific examples of the onium salt include diphenyliodonium trifluoromethanesulfonate, (p-tert-butoxyphenyl) phenyliodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, and p-toluenesulfonic acid (p-
tert-butoxyphenyl) phenyliodonium,
Triphenylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonate (p-tert-butoxyphenyl) diphenylsulfonium, bis (p-tert-butoxyphenyl) phenylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonate tris (p-tert-butoxy) (Phenyl) sulfonium, p-toluenesulfonate triphenylsulfonium, p-toluenesulfonate (p-tert-butoxyphenyl) diphenylsulfonium, p-toluenesulfonate bis (p-tert-butoxyphenyl) phenylsulfonium, p-toluenesulfone Acid tris (p-tert-butoxyphenyl) sulfonium, nonafluorobutanesulfonic acid triphenylsulfonium, butanesulfonic acid Li phenyl trifluoromethanesulfonate, trimethylsulfonium, p
-Trimethylsulfonium toluenesulfonate, cyclohexylmethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, cyclohexylmethyl (2-oxocyclohexyl) sulfonium p-toluenesulfonate, dimethylphenylsulfonium trifluoromethanesulfonate, dimethyl p-toluenesulfonate Phenylsulfonium, dicyclohexylphenylsulfonium trifluoromethanesulfonate, dicyclohexylphenylsulfonium p-toluenesulfonate, trinaphthylsulfonium trifluoromethanesulfonate, cyclohexylmethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, trifluoromethanesulfonic acid (2-norbornyl ) Methyl (2-oxosik Hexyl) sulfonium, ethylenebis [methyl (2-oxocyclopentyl) sulfonium trifluoromethanesulfonate na - DOO], 1,2'-naphthyl carbonyl methyl tetrahydrothiophenium triflate, and the like.

Next, the diazomethane derivative is represented by the following formula (3):
Indicated by.

[Chemical 18] (In the formula, R ⁵² and R ⁵³ are a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms or a halogenated alkyl group, an aryl group having 6 to 12 carbon atoms, a halogenated aryl group or a carbon number. 7 to 12 aralkyl groups are shown.)

Examples of the alkyl group of R ⁵² and R ⁵³ include a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group and an adamantyl group. Examples of the halogenated alkyl group include a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 2,2,2-trichloroethyl group and a nonafluorobutyl group. The aryl group is a phenyl group, p-methoxyphenyl group, m-methoxyphenyl group, o-methoxyphenyl group, ethoxyphenyl group, p-tert-butoxyphenyl group, m-tert.
-Alkoxyphenyl groups such as butoxyphenyl group, 2-
Examples thereof include alkylphenyl groups such as methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, ethylphenyl group, 4-tert-butylphenyl group, 4-butylphenyl group and dimethylphenyl group. Examples of the halogenated aryl group include a fluorophenyl group, a chlorophenyl group, a 1,2,3,4,5-pentafluorophenyl group and the like. Examples of the aralkyl group include a benzyl group and a phenethyl group.

Specific examples of the diazomethane derivative include bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (xylenesulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (cyclopentylsulfonyl).
Diazomethane, bis (n-butylsulfonyl) diazomethane, bis (isobutylsulfonyl) diazomethane, bis (sec-butylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis (tert-
Butylsulfonyl) diazomethane, bis (n-amylsulfonyl) diazomethane, bis (isoamylsulfonyl) diazomethane, bis (sec-amylsulfonyl)
Diazomethane, bis (tert-amylsulfonyl) diazomethane, 1-cyclohexylsulfonyl-1- (t
ert-Butylsulfonyl) diazomethane, 1-cyclohexylsulfonyl-1- (tert-amylsulfonyl) diazomethane, 1-tert-amylsulfonyl-
1- (tert-butylsulfonyl) diazomethane and the like can be mentioned.

The glyoxime derivative is represented by the following formula (4)
Indicated by.

[Chemical 19] (In the formula, R ^{54 to} R ⁵⁶ are a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms or a halogenated alkyl group, an aryl group having 6 to 12 carbon atoms or a halogenated aryl group, or a carbon number. 7 represents an aralkyl group of 7 to 12. R ⁵⁵ and R ⁵⁶ may be bonded to each other to form a cyclic structure, and in the case of forming a cyclic structure, R ⁵⁵ and R ⁵⁶ are each a straight chain having 1 to 6 carbon atoms. Represents a branched or branched alkylene group.)

Examples of the alkyl group, halogenated alkyl group, aryl group, halogenated aryl group and aralkyl group for R ^{54 to} R ⁵⁶ include the same groups as those described for R ⁵² and R ⁵³ . The alkylene group for R ⁵⁵ and R ⁵⁶ is a methylene group, an ethylene group, a propylene group, a butylene group,
Hexylene group and the like can be mentioned.

Specific examples of the glyoxime derivative include bis-O- (p-toluenesulfonyl) -α-dimethylglyoxime and bis-O- (p-toluenesulfonyl)-.
α-diphenylglyoxime, bis-O- (p-toluenesulfonyl) -α-dicyclohexylglyoxime,
Bis-O- (p-toluenesulfonyl) -2,3-pentanedione glyoxime, bis-O- (p-toluenesulfonyl) -2-methyl-3,4-pentanedione glyoxime, bis-O- (n -Butanesulfonyl) -α-
Dimethylglyoxime, bis-O- (n-butanesulfonyl) -α-diphenylglyoxime, bis-O- (n
-Butanesulfonyl) -α-dicyclohexylglyoxime, bis-O- (n-butanesulfonyl) -2,3-
Pentanedione glyoxime, bis-O- (n-butanesulfonyl) -2-methyl-3,4-pentanedione glyoxime, bis-O- (methanesulfonyl) -α-dimethylglyoxime, bis-O- (trifluoro Rmethanesulfonyl) -α-dimethylglyoxime, bis-O-
(1,1,1-trifluoroethanesulfonyl) -α-
Dimethylglyoxime, bis-O- (tert-butanesulfonyl) -α-dimethylglyoxime, bis-O-
(Perfluorooctanesulfonyl) -α-dimethylglyoxime, bis-O- (cyclohexanesulfonyl)
-Α-dimethylglyoxime, bis-O- (benzenesulfonyl) -α-dimethylglyoxime, bis-O-
(P-Fluorobenzenesulfonyl) -α-dimethylglyoxime, bis-O- (p-tert-butylbenzenesulfonyl) -α-dimethylglyoxime, bis-O
Examples include-(xylenesulfonyl) -α-dimethylglyoxime and bis-O- (camphor-sulfonyl) -α-dimethylglyoxime.

Other acid generators used include β-cyclohexylcarbonyl-2- (p-toluenesulfonyl) propane and 2-isopropylcarbonyl-2- (p-toluenesulfonyl) propane.
Ketosulfone derivatives, disulfone derivatives such as diphenyldisulfone and dicyclohexyldisulfone, 2,6-dinitrobenzyl p-toluenesulfonate, nitrobenzylsulfonate derivatives such as 2,4-dinitrobenzyl p-toluenesulfonate, 1,2,3-tris (Methanesulfonyloxy) benzene, 1,2,3-tris (trifluoromethanesulfonyloxy) benzene, 1,2,
Sulfonic acid ester derivatives such as 3-tris (p-toluenesulfonyloxy) benzene, phthalimido-yl-
Triflate, phthalimido-yl-tosylate, 5-
Norbornene-2,3-dicarboximido-yl-triflate, 5-norbornene-2,3-dicarboximido-yl-tosylate, 5-norbornene-2,3
Examples include imidoyl sulfonate derivatives such as -dicarboximido-yl-n-butyl triflate.

Among the acid generators described above, trifluoromethanesulfonate triphenylsulfonium, trifluoromethanesulfonate (p-tert-butoxyphenyl) diphenylsulfonium, trifluoromethanesulfonate tris (p-tert-butoxyphenyl) sulfonium, Triphenylsulfonium p-toluenesulfonate, p-toluenesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, p-toluenesulfonate tris (p-tert-butoxyphenyl) sulfonium, trifluoromethanesulfonate trinaphthylsulfonium, trifluoromethane Cyclomethanemethyl sulfonate (2-oxocyclohexyl) sulfonium, trifluoromethanesulfonate (2-norbornyl) methyl (2 Oxocyclohexyl) sulfonium, onium salts such as 1,2′-naphthylcarbonylmethyltetrahydrothiophenium triflate, bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (n) -Butylsulfonyl) diazomethane, bis (isobutylsulfonyl) diazomethane, bis (sec-butylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane,
Diazomethane derivatives such as bis (isopropylsulfonyl) diazomethane and bis (tert-butylsulfonyl) diazomethane, bis-O- (p-toluenesulfonyl) -α-dimethylglyoxime, bis-O- (n-butanesulfonyl) -α- Glyoxime derivatives such as dimethylglyoxime are preferably used. In addition, the said acid generator can be used individually by 1 type or in combination of 2 or more types. Since the onium salt is excellent in the rectangularity improving effect and the diazomethane derivative and the glyoxime derivative are excellent in the standing wave reducing effect, it is possible to finely adjust the profile by combining them.

The amount of the acid generator added is preferably 0.2 to 15 parts with respect to 100 parts of the base resin. When it is less than 0.2 part, the acid generation amount at the time of exposure is small and the sensitivity and resolution are poor. In some cases, if it exceeds 15 parts, the transparency may be lowered and the resolution may be lowered.

As the basic compound as the component (D), a compound capable of suppressing the diffusion rate when the acid generated from the acid generator diffuses in the resist film is suitable. By blending such a basic compound, the diffusion rate of acid in the resist film is suppressed and the resolution is improved, the sensitivity change after exposure is suppressed, the dependency on the substrate and the environment is reduced, and the exposure margin And pattern profile, etc. can be improved (Japanese Patent Laid-Open Nos. 5-232706, 5-249683, 5 and 5).
-158239, 5-249662, 5-25
7282, 5-289322, 5-28934
No. 0 etc. description).

Such basic compounds include ammonia, primary, secondary and tertiary aliphatic amines, mixed amines, aromatic amines, heterocyclic amines, and carboxyl group-containing compounds. Examples thereof include nitrogen compounds, nitrogen-containing compounds having a sulfonyl group, nitrogen-containing compounds having a hydroxyl group, nitrogen-containing compounds having a hydroxyphenyl group, alcoholic nitrogen-containing compounds, amide derivatives and imide derivatives.

Specific examples of primary aliphatic amines include methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, pentylamine and tert-amine. Examples include amylamine, cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, cetylamine, methylenediamine, ethylenediamine, tetraethylenepentamine and the like.

Specific examples of secondary aliphatic amines include dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine,
Dipentylamine, dicyclopentylamine, dihexylamine, dicyclohexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, didodecylamine, dicetylamine, N, N-dimethylmethylenediamine, N, N-dimethylethylenediamine, N, N-dimethyl Tetraethylene pentamine and the like are exemplified. Specific examples of the tertiary aliphatic amines include trimethylamine, triethylamine, tri-n-
Propylamine, triisopropylamine, tri-n-
Butylamine, triisobutylamine, tri-sec-
Butylamine, tripentylamine, tricyclopentylamine, trihexylamine, tricyclohexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, tridodecylamine, tricetylamine, N, N, N ', N Examples include'-tetramethylmethylenediamine, N, N, N ', N'-tetramethylethylenediamine, N, N, N', N'-tetramethyltetraethylenepentamine and the like.

Specific examples of the mixed amines include dimethylethylamine, methylethylpropylamine, benzylamine, phenethylamine, benzyldimethylamine and the like.

Specific examples of aromatic amines include aniline, N-methylaniline, N-ethylaniline, N-propylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methylaniline and 4-methyl. Aniline, ethylaniline, propylaniline, trimethylaniline, 2-nitroaniline, 3-nitroaniline, 4
-Nitroaniline, 2,4-dinitroaniline, 2,6
-Dinitroaniline, 3,5-dinitroaniline, N,
Aniline derivatives such as N-dimethyltoluidine, diphenyl (p-tolyl) amine, methyldiphenylamine,
Examples include triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene and the like.

Specific examples of the heterocyclic amines include pyro-
, 2H-pyrrole, 1-methylpyrrole, 2,4-dimethylpyrrole, 2,5-dimethylpyrrole, N-methylpyrrole, and other pyrrole derivatives, oxazole and isoxazole, and other oxazole derivatives, thiazole , Isothiazole and other thiazole derivatives, imidazole, 4-
Imidazole derivatives such as methylimidazole and 4-methyl-2-phenylimidazole, pyrazole derivatives, flazane derivatives, pyrroline, pyrroline derivatives such as 2-methyl-1-pyrroline, pyrrolidine, N-methylpyrrolidine, pyrrolidinone, N-methylpyrrolidone, etc. Pyrrolidine derivative, imidazoline derivative, imidazolidine derivative, pyridine, methylpyridine, ethylpyridine, propylpyridine, butylpyridine, 4- (1-butylpentyl) pyridine, dimethylpyridine, trimethylpyridine, triethylpyridine, phenylpyridine, 3-methyl 2-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine,
1-methyl-2-pyridine, 4-pyrrolidinopyridine,
Pyridine derivatives such as 1-methyl-4-phenylpyridine, 2- (1-ethylpropyl) pyridine, aminopyridine, dimethylaminopyridine, pyridazine derivatives, pyrimidine derivatives, pyrazine derivatives, pyrazoline derivatives, pyrazolidine derivatives, piperidine derivatives, piperazine derivatives , Morpholine derivative, indole derivative, isoindole derivative, 1H-indazole derivative, indoline derivative, quinoline, quinoline derivative such as 3-quinolinecarbonitrile, isoquinoline derivative, cinnoline derivative,
Quinazoline derivative, quinoxaline derivative, phthalazine derivative, purine derivative, pteridine derivative, carbazole derivative, phenanthridine derivative, acridine derivative,
Examples thereof include a phenazine derivative, a 1,10-phenanthroline derivative, an adenine derivative, an adenosine derivative, a guanine derivative, a guanosine derivative, a uracil derivative and a uridine derivative.

Specific examples of the nitrogen-containing compound having a carboxyl group include aminobenzoic acid, indolecarboxylic acid, nicotinic acid, alanine, arginine, aspartic acid, glutamic acid, glycine, histidine, isoleucine, glycylleucine, leucine, Examples thereof include amino acid derivatives such as methionine, phenylalanine, threonine, lysine, 3-aminopyrazine-2-carboxylic acid, and methoxyalanine.

Specific examples of the nitrogen-containing compound having a sulfonyl group include 3-pyridinesulfonic acid and pyridinium p-toluenesulfonate.

Specific examples of the nitrogen-containing compound containing a hydroxyl group and a hydroxyphenyl group and the alcoholic nitrogen-containing compound include 2-hydroxypyridine, aminocresol,
2,4-quinoline diol, 3-indole methanol hydrate, monoethanolamine, diethanolamine, triethanolamine, N-ethyldiethanolamine, N, N-diethylethanolamine, triisopropanolamine, 2,2'-iminodiethanol, 2
-Aminoethanol, 3-amino-1-propanol,
4-amino-1-butanol, 4- (2-hydroxyethyl) morpholine, 2- (2-hydroxyethyl) pyridine, 1- (2-hydroxyethyl) piperazine, 1-
[2- (2-hydroxyethoxy) ethyl] piperazine, piperidine ethanol, 1- (2-hydroxyethyl) pyrrolidine, 1- (2-hydroxyethyl) -2-
Pyrrolidinone, 3-piperidino-1,2-propanediol, 3-pyrrolidino-1,2-propanediol, 8
-Hydroxyjulolidine, 3-cuinclidinol, 3
-Tropanol, 1-methyl-2-pyrrolidine ethanol, 1-aziridine ethanol, N- (2-hydroxyethyl) phthalimide, N- (2-hydroxyethyl)
Isonicotinamide and the like are exemplified.

Specific examples of the amide derivative include formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide,
Examples are N, N-dimethylacetamide, propionamide, benzamide and the like.

Specific examples of the imide derivative include phthalimide, succinimide, maleimide and the like.

Further, one kind or two or more kinds selected from the basic compounds represented by the following general formula (B) -1 can be added. N (X) _n (Y) _3-n (B) -1 In the formula, n = 1, 2 or 3. The side chains X may be the same or different and can be represented by the following general formulas (X) -1 to (X) -3. The side chain Y represents the same or different hydrogen atom or a linear, branched or cyclic C1-C20 alkyl group, and may contain an ether group or a hydroxyl group. In addition, Xs may combine with each other to form a ring.

Here, R ³⁰⁰ , R ³⁰² and R ³⁰⁵ have 1 carbon atom.
4 is a linear or branched alkylene group,
R ³⁰¹ and R ³⁰⁴ are a hydrogen atom, or a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms, a hydroxy group,
It may contain one or more ether groups, ester groups, and lactone rings.

R ³⁰³ is a single bond or a linear or branched alkylene group having 1 to 4 carbon atoms, and R ³⁰⁶ is 1 carbon atom.
20 straight chain, branched or cyclic alkyl groups,
1 hydroxy group, ether group, ester group, lactone ring
Alternatively, a plurality of them may be included.

[0096]

[Chemical 20]

Specific examples of the compound represented by formula (B) -1 are shown below. Tris (2-methoxymethoxyethyl) amine, tris {2- (2-methoxyethoxy) ethyl} amine, tris {2- (2-methoxyethoxymethoxy) ethyl} amine, tris {2- (1-methoxyethoxy) ethyl } Amine, Tris {2- (1-
Ethoxyethoxy) ethyl} amine, tris {2- (1
-Ethoxypropoxy) ethyl} amine, tris [2-
{2- (2-hydroxyethoxy) ethoxy} ethyl]
Amine, 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo [8.8.8] hexacosane, 4,7,13,18-tetraoxa-1,10-
Diazabicyclo [8.5.5] eicosane, 1,4,1
0,13-tetraoxa-7,16-diazabicyclooctadecane, 1-aza-12-crown-4, 1-aza-15-crown-5, 1-aza-18-crown-
6, tris (2-formyloxyethyl) amine, tris (2-formyloxyethyl) amine, tris (2
-Acetoxyethyl) amine, tris (2-propionyloxyethyl) amine, tris (2-butyryloxyethyl) amine, tris (2-isobutyryloxyethyl) amine, tris (2-valeryloxyethyl) amine, Tris (2-pivaloyloxyxyethyl) amine, N, N-bis (2-acetoxyethyl) 2- (acetoxyacetoxy) ethylamine, tris (2-methoxycarbonyloxyethyl) amine, tris (2-te
rt-Butoxycarbonyloxyethyl) amine, tris [2- (2-oxopropoxy) ethyl] amine, tris [2- (methoxycarbonylmethyl) oxyethyl] amine, tris [2- (tert-butoxycarbonylmethyloxy) ethyl] Amine, tris [2- (cyclohexyloxycarbonylmethyloxy) ethyl]
Amine, tris (2-methoxycarbonylethyl) amine, tris (2-ethoxycarbonylethyl) amine,
N, N-bis (2-hydroxyethyl) 2- (methoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (methoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2 -(Ethoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (ethoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2- (2
-Methoxyethoxycarbonyl) ethylamine, N, N
-Bis (2-acetoxyethyl) 2- (2-methoxyethoxycarbonyl) ethylamine, N, N-bis (2-
Hydroxyethyl) 2- (2-hydroxyethoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (2-acetoxyethoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2
-[(Methoxycarbonyl) methoxycarbonyl] ethylamine, N, N-bis (2-acetoxyethyl) 2-
[(Methoxycarbonyl) methoxycarbonyl] ethylamine, N, N-bis (2-hydroxyethyl) 2-
(2-oxopropoxycarbonyl) ethylamine,
N, N-bis (2-acetoxyethyl) 2- (2-oxopropoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2- (tetrahydrofurfuryloxycarbonyl) ethylamine, N, N-bis ( Two
-Acetoxyethyl) 2- (tetrahydrofurfuryloxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2-[(2-oxotetrahydrofuran-3-yl) oxycarbonyl] ethylamine, N,
N-bis (2-acetoxyethyl) 2-[(2-oxotetrahydrofuran-3-yl) oxycarbonyl] ethylamine, N, N-bis (2-hydroxyethyl) 2
-(4-Hydroxybutoxycarbonyl) ethylamine, N, N-bis (2-formyloxyethyl) 2-
(4-formyloxybutoxycarbonyl) ethylamine, N, N-bis (2-formyloxyethyl) 2-
(2-Formyloxyethoxycarbonyl) ethylamine, N, N-bis (2-methoxyethyl) 2- (methoxycarbonyl) ethylamine, N- (2-hydroxyethyl) bis [2- (methoxycarbonyl) ethyl] amine, N -(2-acetoxyethyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (2-hydroxyethyl) bis [2- (ethoxycarbonyl) ethyl] amine, N- (2-acetoxyethyl) bis [2 -(Ethoxycarbonyl) ethyl] amine, N- (3-hydroxy-1-propyl) bis [2- (methoxycarbonyl)
Ethyl] amine, N- (3-acetoxy-1-propyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (2-methoxyethyl) bis [2- (methoxycarbonyl) ethyl] amine, N-butylbis [2-
(Methoxycarbonyl) ethyl] amine, N-butylbis [2- (2-methoxyethoxycarbonyl) ethyl]
Amine, N-methylbis (2-acetoxyethyl) amine, N-ethylbis (2-acetoxyethyl) amine,
N-methylbis (2-pivaloyloxyxyethyl) amine, N-ethylbis [2- (methoxycarbonyloxy) ethyl] amine, N-ethylbis [2- (tert.
-Butoxycarbonyloxy) ethyl] amine, tris (methoxycarbonylmethyl) amine, tris (ethoxycarbonylmethyl) amine, N-butylbis (methoxycarbonylmethyl) amine, N-hexylbis (methoxycarbonylmethyl) amine, β- (diethylamino) Examples thereof include, but are not limited to, -δ-valerolactone.

Further, one or more basic compounds having a cyclic structure represented by the following general formula (B) -2 can be added.

[0099]

[Chemical 21] (In the formula, X is as described above, R ³⁰⁷ is a linear or branched alkylene group having 2 to 20 carbon atoms, a carbonyl group,
It may contain one or more ether groups, ester groups and sulfides. )

The formula (B) -2 is specifically 1- [2-
(Methoxymethoxy) ethyl] pyrrolidine, 1- [2-
(Methoxymethoxy) ethyl] piperidine, 4- [2-
(Methoxymethoxy) ethyl] morpholine, 1- [2-
[(2-Methoxyethoxy) methoxy] ethyl] pyrrolidine, 1- [2-[(2-methoxyethoxy) methoxy] ethyl] piperidine, 4- [2-[(2-methoxyethoxy) methoxy] ethyl] morpholine, acetic acid 2-
(1-pyrrolidinyl) ethyl, 2-piperidinoethyl acetate, 2-morpholinoethyl acetate, 2- (1-pyrrolidinyl) ethyl formate, 2-piperidinoethyl propionate,
Acetoxyacetic acid 2-morpholinoethyl, methoxyacetic acid 2
-(1-Pyrrolidinyl) ethyl, 4- [2- (methoxycarbonyloxy) ethyl] morpholine, 1- [2-
(T-Butoxycarbonyloxy) ethyl] piperidine, 4- [2- (2-methoxyethoxycarbonyloxy) ethyl] morpholine, methyl 3- (1-pyrrolidinyl) propionate, methyl 3-piperidinopropionate, 3- Methyl morpholino propionate, methyl 3- (thiomorpholino) propionate, 2-methyl-3- (1
-Methyl pyrrolidinyl) propionate, ethyl 3-morpholinopropionate, methoxycarbonylmethyl 3-piperidinopropionate, 2-hydroxyethyl 3- (1-pyrrolidinyl) propionate, 2-acetoxyethyl 3-morpholinopropionate, 3 -(1-Pyrrolidinyl) propionic acid 2-oxotetrahydrofuran-3-
Yl, tetrahydrofurfuryl 3-morpholinopropionate, glycidyl 3-piperidinopropionate, 2-methoxyethyl 3-morpholinopropionate, 3- (1-
2- (2-methoxyethoxy) ethyl pyrrolidinyl) propionate, butyl 3-morpholinopropionate, 3-
Cyclohexyl piperidinopropionate, α- (1-pyrrolidinyl) methyl-γ-butyrolactone, β-piperidino-γ-butyrolactone, β-morpholino-δ-valerolactone, methyl 1-pyrrolidinyl acetate, methyl piperidinoacetate, methyl morpholinoacetate , Methyl thiomorpholino acetate, ethyl 1-pyrrolidinyl acetate, and 2-methoxyethyl morpholino acetate.

Further, a basic compound containing a cyano group represented by formulas (B) -3 to (B) -6 can be added.

[0102]

[Chemical formula 22] (In the formula, X, R ³⁰⁷ , and n are as described above, and R ³⁰⁸ and R ³⁰⁹ are the same or different and are linear or branched alkylene groups having 1 to 4 carbon atoms.)

The base containing a cyano group is specifically 3-
(Diethylamino) propiononitrile, N, N-bis (2-hydroxyethyl) -3-aminopropiononitrile, N, N-bis (2-acetoxyethyl) -3-aminopropiononitrile, N, N-bis (2-formyloxyethyl) -3-aminopropiononitrile, N,
N-bis (2-methoxyethyl) -3-aminopropiononitrile, N, N-bis [2- (methoxymethoxy)
Ethyl] -3-aminopropiononitrile, N- (2-
Cyanoethyl) -N- (2-methoxyethyl) -3-methylaminopropionate, N- (2-cyanoethyl)-
Methyl N- (2-hydroxyethyl) -3-aminopropionate, N- (2-acetoxyethyl) -N- (2-
Methyl cyanoethyl) -3-aminopropionate, N-
(2-Cyanoethyl) -N-ethyl-3-aminopropiononitrile, N- (2-cyanoethyl) -N- (2-
Hydroxyethyl) -3-aminopropiononitrile,
N- (2-acetoxyethyl) -N- (2-cyanoethyl) -3-aminopropiononitrile, N- (2-cyanoethyl) -N- (2-formyloxyethyl) -3-
Aminopropiononitrile, N- (2-cyanoethyl)
-N- (2-methoxyethyl) -3-aminopropiononitrile, N- (2-cyanoethyl) -N- [2- (methoxymethoxy) ethyl] -3-aminopropiononitrile, N- (2-cyanoethyl) ) -N- (3-Hydroxy-1-propyl) -3-aminopropiononitrile,
N- (3-acetoxy-1-propyl) -N- (2-cyanoethyl) -3-aminopropiononitrile, N-
(2-Cyanoethyl) -N- (3-formyloxy-1
-Propyl) -3-aminopropiononitrile, N-
(2-Cyanoethyl) -N-tetrahydrofurfuryl-
3-aminopropiononitrile, N, N-bis (2-cyanoethyl) -3-aminopropiononitrile, diethylaminoacetonitrile, N, N-bis (2-hydroxyethyl) aminoacetonitrile, N, N-bis (2-
Acetoxyethyl) aminoacetonitrile, N, N-bis (2-formyloxyethyl) aminoacetonitrile, N, N-bis (2-methoxyethyl) aminoacetonitrile, N, N-bis [2- (methoxymethoxy) ethyl] amino Acetonitrile, N-cyanomethyl-N-
Methyl (2-methoxyethyl) -3-aminopropionate, N-cyanomethyl-N- (2-hydroxyethyl)
Methyl-3-aminopropionate, N- (2-acetoxyethyl) -N-cyanomethyl-3-aminopropionate methyl, N-cyanomethyl-N- (2-hydroxyethyl) aminoacetonitrile, N- (2-acetoxyethyl) ) -N- (cyanomethyl) aminoacetonitrile,
N-cyanomethyl-N- (2-formyloxyethyl)
Aminoacetonitrile, N-cyanomethyl-N- (2-
Methoxyethyl) aminoacetonitrile, N-cyanomethyl-N- [2- (methoxymethoxy) ethyl] aminoacetonitrile, N- (cyanomethyl) -N- (3-hydroxy-1-propyl) aminoacetonitrile, N-
(3-acetoxy-1-propyl) -N- (cyanomethyl) aminoacetonitrile, N-cyanomethyl-N-
(3-formyloxy-1-propyl) aminoacetonitrile, N, N-bis (cyanomethyl) aminoacetonitrile, 1-pyrrolidinepropiononitrile, 1-piperidinepropiononitrile, 4-morpholinepropiononitrile, 1-pyrrolidineacetonitrile, 1-piperidine acetonitrile, 4-morpholine acetonitrile,
Cyanomethyl 3-diethylaminopropionate, N, N
-Bis (2-hydroxyethyl) -3-aminopropionate cyanomethyl, N, N-bis (2-acetoxyethyl) -3-aminopropionate cyanomethyl, N, N-
Bis (2-formyloxyethyl) -3-aminopropionate cyanomethyl, N, N-bis (2-methoxyethyl) -3-aminopropionate cyanomethyl, N, N-
Bis [2- (methoxymethoxy) ethyl] -3-aminopropionic acid cyanomethyl, 3-diethylaminopropionic acid (2-cyanoethyl), N, N-bis (2-hydroxyethyl) -3-aminopropionic acid (2-cyanoethyl) ), N, N-bis (2-acetoxyethyl) -3
-Aminopropionic acid (2-cyanoethyl), N, N-
Bis (2-formyloxyethyl) -3-aminopropionic acid (2-cyanoethyl), N, N-bis (2-methoxyethyl) -3-aminopropionic acid (2-cyanoethyl), N, N-bis [2 -(Methoxymethoxy) ethyl] -3-aminopropionic acid (2-cyanoethyl),
1-Pyrrolidine propionate cyanomethyl, 1-piperidine propionate cyanomethyl, 4-morpholine cyanomethyl propionate, 1-pyrrolidine propionate (2
-Cyanoethyl), 1-piperidinepropionic acid (2-
Examples are cyanoethyl) and 4-morpholinepropionic acid (2-cyanoethyl).

The basic compound of the present invention is incorporated in an amount of 0.001 to 2 parts, particularly 0.
01 to 1 part is preferred. If the blending amount is less than 0.001 part, the blending effect may not be obtained, and if it exceeds 2 parts, the sensitivity may be lowered too much.

The dissolution inhibitor of the component (E) has a molecular weight of 3,000 whose solubility in an alkali developing solution is changed by the action of an acid.
A compound having 0 or less, particularly a compound in which a part or all of the hydroxyl groups of a phenol or carboxylic acid derivative having a molecular weight of 2,500 or less is substituted with an acid labile group is suitable. The acid labile group may be a fluorine-containing group which is mentioned in the present invention, or may be a conventional fluorine-free group.

Examples of the phenol or carboxylic acid derivative having a molecular weight of 2,500 or less include 4,4 '-(1-methylethylidene) bisphenol and [1,1'-biphenyl-4,4'-diol] -2,2'. -Methylenebis [4
-Methylphenol], 4,4-bis (4'-hydroxyphenyl) valeric acid, tris (4-hydroxyphenyl) methane, 1,1,1-tris (4'-hydroxyphenyl) ethane, 1,1,2 -Tris (4'-hydroxyphenyl) ethane, phenolphthalein, thymolphthalein, 3,3'-difluoro [(1,1'-biphenyl) -4,4'-diol], 3,3 ', 5 5 '
-Tetrafluoro [(1,1'-biphenyl-4,
4'-diol], 4,4 '-[2,2,2-trifluoro-1- (trifluoromethyl) ethylidene] bisphenol, 4,4'-methylenebis [2-fluorophenol], 2,2'- Methylenebis [4-fluorophenol], 4,4′-isopropylidenebis [2-fluorophenol], cyclohexylidenebis [2-fluorophenol], 4,4 ′-[(4-fluorophenyl) methylene] bis [ 2-fluorophenol],
4,4'-methylenebis [2,6-difluorophenol], 4,4 '-(4-fluorophenyl) methylenebis [2,6-difluorophenol], 2,6-bis [(2-hydroxy-5-fluoro) Phenyl) methyl]
-4-fluorophenol, 2,6-bis [(4-hydroxy-3-fluorophenyl) methyl] -4-fluorophenol, 2,4-bis [(3-hydroxy-4-)
Hydroxyphenyl) methyl] -6-methylphenol and the like, and examples of the acid labile substituent include the same ones as described above.

Specific examples of the dissolution inhibitor preferably used include 3,3 ', 5,5'-tetrafluoro [(1,
1'-biphenyl) -4,4'-di-tert-butoxycarbonyl], 4,4 '-[2,2,2-trifluoro-1- (trifluoromethyl) ethylidene] bisphenol-4,4'- Di-tert-butoxycarbonyl, bis (4- (2′-tetrahydropyranyloxy)
Phenyl) methane, bis (4- (2'-tetrahydrofuranyloxy) phenyl) methane, bis (4-tert)
-Butoxyphenyl) methane, bis (4-tert-butoxycarbonyloxyphenyl) methane, bis (4-
tert-butoxycarbonylmethyloxyphenyl)
Methane, bis (4- (1'-ethoxyethoxy) phenyl) methane, bis (4- (1'-ethoxypropyloxy) phenyl) methane, 2,2-bis (4 '-(2'')
-Tetrahydropyranyloxy)) propane, 2,2-
Bis (4 '-(2''-tetrahydrofuranyloxy)
Phenyl) propane, 2,2-bis (4'-tert-
Butoxyphenyl) propane, 2,2-bis (4'-t
ert-butoxycarbonyloxyphenyl) propane, 2,2-bis (4-tert-butoxycarbonylmethyloxyphenyl) propane, 2,2-bis (4 ′)
-(1 ''-ethoxyethoxy) phenyl) propane,
2,2-bis (4 '-(1''-ethoxypropyloxy) phenyl) propane, 4,4-bis (4'-
(2 ″ -Tetrahydropyranyloxy) phenyl) tert-butyl valerate, 4,4-bis (4 ′-(2 ″)
-Tetrahydrofuranyloxy) phenyl) valeric acid te
rt-butyl, 4,4-bis (4′-tert-butoxyphenyl) valerate tert-butyl, 4,4-bis (4-tert-butoxycarbonyloxyphenyl)
Tert-Butyl valerate, 4,4-bis (4'-ter
t-butoxycarbonylmethyloxyphenyl) tert-butyl valerate, 4,4-bis (4 ′-(1 ″ -ethoxyethoxy) phenyl) tert-butyl valerate,
Tert-Butyl 4,4-bis (4 '-(1''-ethoxypropyloxy) phenyl) valerate, tris (4-
(2′-Tetrahydropyranyloxy) phenyl) methane, tris (4- (2′-tetrahydrofuranyloxy) phenyl) methane, tris (4-tert-butoxyphenyl) methane, tris (4-tert-butoxycarbonyloxyphenyl) ) Methane, Tris (4-te
rt-Butoxycarbonyloxymethylphenyl) methane, tris (4- (1′-ethoxyethoxy) phenyl) methane, tris (4- (1′-ethoxypropyloxy) phenyl) methane, 1,1,2-tris (4 '-
(2 ″ -Tetrahydropyranyloxy) phenyl) ethane, 1,1,2-tris (4 ′-(2 ″ -tetrahydrofuranyloxy) phenyl) ethane, 1,1,2-
Tris (4'-tert-butoxyphenyl) ethane,
1,1,2-Tris (4′-tert-butoxycarbonyloxyphenyl) ethane, 1,1,2-Tris (4′-tert-butoxycarbonylmethyloxyphenyl) ethane, 1,1,2-Tris (4 '-(1'-
Ethoxyethoxy) phenyl) ethane, 1,1,2-tris (4 ′-(1′-ethoxypropyloxy) phenyl) ethane, 1,1-tert-butyl 2-trifluoromethylbenzenecarboxylic acid, 2-trifluoro Tert-Butyl methylcyclohexanecarboxylate, tert-butyl decahydronaphthalene-2,6-dicarboxylate, tert-butyl cholate, te deoxycholate
Examples include rt-butyl, adamantanecarboxylate tert-butyl, adamantaneacetate tert-butyl, and 1,1′-bicyclohexyl-3,3 ′, 4,4′-tetracarboxylic acid tetratert-butyl.

The addition amount of the dissolution inhibitor in the resist material of the present invention is the base resin 10 in the resist material.
It is 20 parts or less, preferably 15 parts or less with respect to 0 part. If the amount is more than 20 parts, the heat resistance of the resist material is deteriorated because the monomer component increases.

In addition to the above components, the resist composition of the present invention may contain, as an optional component, a surfactant which is commonly used for improving the coating property. In addition, the addition amount of the optional component can be a normal amount within a range that does not impair the effects of the present invention.

Here, the surfactant is preferably a nonionic one, such as perfluoroalkyl polyoxyethylene ethanol, fluorinated alkyl ester, perfluoroalkyl amine oxide, perfluoroalkyl EO adduct, fluorine-containing organosiloxane system. A compound etc. are mentioned. For example, Florard "FC-430", "F
C-431 "(all manufactured by Sumitomo 3M Ltd.), Surflon" S-141 "," S-145 "(all manufactured by Asahi Glass Co., Ltd.), Unidyne" DS-401 "," DS "
-403 "," DS-451 "(all manufactured by Daikin Industries, Ltd.), Megafac" F-8151 "(manufactured by Dainippon Ink and Industries Co., Ltd.)," X-70-092 "," X-7 ".
0-093 "(all manufactured by Shin-Etsu Chemical Co., Ltd.) and the like. Preferably, Florard "FC-4
30 "(manufactured by Sumitomo 3M Limited)," X-70-09 "
3 ”(manufactured by Shin-Etsu Chemical Co., Ltd.).

To form a pattern using the resist material of the present invention, a known lithography technique can be adopted. For example, a film thickness of 0.1 to 1.0 is formed on a substrate such as a silicon wafer by a method such as spin coating.
Apply it to a thickness of 6 μm, and apply it on a hot plate for 6
0 to 200 ° C., 10 seconds to 10 minutes, preferably 80 to 1
Pre-bake at 50 ° C. for 30 seconds to 5 minutes. Next, a mask for forming a desired pattern is held over the resist film, and a high-energy ray such as deep ultraviolet ray, excimer laser, or X-ray or electron beam is exposed at an exposure amount of 1 to 200 mJ / c.
After irradiating to about m ² , preferably about 10 to 100 mJ / cm ² , 60 to 150 on a hot plate.
C, 10 seconds to 5 minutes, preferably 80 to 130 ° C., 30
Post exposure bake (PEB) for seconds to 3 minutes. Further, using a developer of an alkali aqueous solution such as 0.1 to 5%, preferably 2 to 3% tetramethylammonium hydroxide (TMAH), it is immersed (dip) for 10 seconds to 3 minutes, preferably 30 seconds to 2 minutes. ) Law, paddle
The desired pattern is formed on the substrate by developing by a conventional method such as a le) method or a spray method. The material of the present invention is particularly suitable for deep ultraviolet rays or excimer laser of 254 to 120 nm among high energy rays.
Especially 193 nm ArF, 146 nm Kr ₂ , 134
It is optimal for fine patterning by excimer laser such as KrAr _{2 of} nm, F _{2 of} 157 nm, laser such as Ar _{2 of} 126 nm, X-ray and electron beam. If the above range falls outside the upper and lower limits, the desired pattern may not be obtained.

[0112]

Industrial Applicability The resist material of the present invention is sensitive to high energy rays and has excellent sensitivity at a wavelength of 200 nm or less, particularly 170 nm or less, and at the same time, the transparency of the resist is improved, and at the same time excellent plasma etching is performed. Have resistance. Therefore, the resist material of the present invention can be a resist material having small absorption at the exposure wavelength of the F ₂ laser due to these characteristics, and it is possible to easily form a fine pattern perpendicular to the substrate. For super L
It is suitable as a fine pattern forming material for SI production.

[0113]

EXAMPLES The present invention will be described in detail below with reference to synthesis examples and examples, but the present invention is not limited to the following examples.

[Synthesis Example 1] Copolymerization of Monomer 1 below, Monomer 2 below and Monomer 3 below (1: 1: 1) 19.6 g of Monomer 1 below in a 500 mL flask.
And 22.4 g of the following monomer 2 and 27.0 g of the following monomer 3 were dissolved in 100 mL of toluene to sufficiently remove oxygen in the system, and then 0.38 g of an initiator AIBN (azobisisobutyronitrile) was charged. The temperature was raised to 60 ° C. and the polymerization reaction was carried out for 24 hours.

To purify the polymer obtained, the reaction mixture was poured into hexane and the polymer obtained was precipitated. The polymer obtained is separated and dried, and then methanol 0.5
L and tetrahydrofuran (1.0 L) were dissolved again, triethylamine (70 g) and water (15 g) were added, the acetoxy group was deprotected, and the mixture was neutralized with acetic acid. After the reaction solution was concentrated, it was dissolved in 0.5 L of acetone and the same precipitation as above was performed.
Filtration and drying were performed to obtain a white polymer. The thus-obtained white polymer (55.0 g) has a weight average molecular weight of 14,000 as determined by a light scattering method, and has a dispersity (= Mw / Mn) of 1.8 from the GPC elution curve. I was able to confirm that. From the ¹ H-NMR measurement results, it was found that the obtained polymer contained the monomer 1, the monomer 2, and the monomer 3 from which the acetyl group had been eliminated in a content ratio of 35:30:35.

[0116]

[Chemical formula 23]

[Synthesis Example 2] Monomer 1 and Monomer 4 below
And 3: Copolymerization of Monomer 3 (3: 2: 5) 29.4 g of Monomer 1 and 1 in a 500 mL flask.
8.4 g of the following monomer 4 and 67.5 g of monomer 3
Was dissolved in 150 mL of toluene, and oxygen in the system was sufficiently removed, and then 0.35 g of AIBN as an initiator was charged.
The temperature was raised to ° C and a polymerization reaction was carried out for 24 hours.

To purify the polymer obtained, the reaction mixture was poured into hexane and the polymer obtained was precipitated. The polymer obtained is separated and dried, and then methanol 0.5
L and tetrahydrofuran (1.0 L) were dissolved again, triethylamine (70 g) and water (15 g) were added, the acetoxy group was deprotected, and the mixture was neutralized with acetic acid. After the reaction solution was concentrated, it was dissolved in 0.5 L of acetone and the same precipitation as above was performed.
Filtration and drying were performed to obtain a white polymer. The thus obtained 82.4 g of the white polymer was a polymer having a weight average molecular weight of 14,000 as determined by a light scattering method and a dispersity (= Mw / Mn) of 1.75 according to the GPC elution curve. I was able to confirm that. From the ¹ H-NMR measurement results, it was found that the obtained polymer contained the monomer 1 and the monomer 4 and the monomer 3 from which the acetyl group had been removed at a content ratio of 31:20:49.

[0119]

[Chemical formula 24]

[Synthesis Example 3] Monomer 1 and the following monomer 5
And Copolymerization of Monomer 3 (3: 2: 5) 29.4 g of Monomer 1 and 2 in a 500 mL flask.
After dissolving 7.6 g of the following monomer 5 and 67.5 g of the monomer 3 in 150 mL of toluene and sufficiently removing oxygen in the system, 0.35 g of the initiator AIBN was charged, and the temperature was changed to 60 ° C.
The temperature was raised to and the polymerization reaction was carried out for 24 hours.

To purify the polymer obtained, the reaction mixture was poured into hexane and the polymer obtained was precipitated. The polymer obtained is separated and dried, and then methanol 0.5
L and tetrahydrofuran (1.0 L) were dissolved again, triethylamine (70 g) and water (15 g) were added, the acetoxy group was deprotected, and the mixture was neutralized with acetic acid. After the reaction solution was concentrated, it was dissolved in 0.5 L of acetone and the same precipitation as above was performed.
Filtration and drying were performed to obtain a white polymer. 95.2 g of the white polymer thus obtained was a polymer having a weight average molecular weight of 15,000 by a light scattering method and a dispersity (= Mw / Mn) of 1.85 from a GPC elution curve. I was able to confirm that. From the ¹ H-NMR measurement results, it was found that the obtained polymer contained Monomer 1, Monomer 5, and Monomer 3 from which the acetyl group had been eliminated at a content ratio of 33:17:50.

[0122]

[Chemical 25]

[Synthesis Example 4] Monomer 6 and monomer 5 shown below
And Copolymerization of Monomer 3 (3: 2: 5) 45.3 g of Monomer 6 and 2 in a 500 mL flask.
After dissolving 7.6 g of Monomer 5 and 67.5 g of Monomer 3 in 150 mL of toluene and sufficiently removing oxygen in the system, 0.35 g of AIBN as an initiator was charged, and the temperature was raised to 60 ° C. to perform polymerization for 24 hours. The reaction was carried out.

To purify the polymer obtained, the reaction mixture was poured into hexane and the polymer obtained was precipitated. The polymer obtained is separated and dried, and then methanol 0.5
L and tetrahydrofuran (1.0 L) were dissolved again, triethylamine (70 g) and water (15 g) were added, the acetoxy group was deprotected, and the mixture was neutralized with acetic acid. After the reaction solution was concentrated, it was dissolved in 0.5 L of acetone and the same precipitation as above was performed.
Filtration and drying were performed to obtain a white polymer. The thus obtained 132.8 g of a white polymer is a polymer having a weight average molecular weight of 11,000 as determined by a light scattering method and a dispersity (= Mw / Mn) of 1.9 as determined by GPC elution curve. I was able to confirm that. From the ¹ H-NMR measurement result, it was found that the obtained polymer contains the monomer 6, the monomer 5, and the monomer 3 from which the acetyl group has been eliminated at a content ratio of 25:22:53.

[0125]

[Chemical formula 26]

[Synthesis Example 5] Copolymerization of Monomer 6, Monomer 5 and Monomer 7 (3: 2: 5) 45.3 g of Monomer 6 and 2 in a 500 mL flask.
After dissolving 7.6 g of Monomer 5 and 95.5 g of Monomer 7 in 150 mL of toluene and sufficiently removing oxygen in the system, 0.35 g of AIBN as an initiator was charged, and the temperature was raised to 60 ° C. to perform polymerization for 24 hours. The reaction was carried out.

To purify the polymer obtained, the reaction mixture was poured into hexane and the polymer obtained was precipitated. The polymer obtained is separated and dried, and then methanol 0.5
L and tetrahydrofuran (1.0 L) were dissolved again, triethylamine (70 g) and water (15 g) were added, the acetoxy group was deprotected, and the mixture was neutralized with acetic acid. After the reaction solution was concentrated, it was dissolved in 0.5 L of acetone and the same precipitation as above was performed.
Filtration and drying were performed to obtain a white polymer. 132.8 g of the white polymer thus obtained is a polymer having a weight average molecular weight of 9,500 by the light scattering method and a dispersity (= Mw / Mn) of 1.6 from the GPC elution curve. I was able to confirm that. From the results of ¹ H-NMR measurement, it was found that the obtained polymer contained Monomer 6, Monomer 5, and Monomer 7 from which an acetyl group had been removed at a content ratio of 25:22:53.

[0128]

[Chemical 27]

[Synthesis Example 6] Monomer 1 and the following monomer 8
And Copolymerization of Monomer 3 (3: 2: 5) 19.6 g of Monomer 1 and 1 in a 500 mL flask.
After dissolving 5.6 g of the monomer 8 and 42.0 g of the monomer 3 in 100 mL of toluene and sufficiently removing oxygen in the system, 0.38 g of the AIBN initiator was charged, the temperature was raised to 60 ° C., and polymerization was performed for 24 hours. The reaction was carried out.

To purify the polymer obtained, the reaction mixture was poured into hexane and the polymer obtained was precipitated. The polymer obtained is separated and dried, and then methanol 0.5
L and tetrahydrofuran (1.0 L) were dissolved again, triethylamine (70 g) and water (15 g) were added, the acetoxy group was deprotected, and the mixture was neutralized with acetic acid. After the reaction solution was concentrated, it was dissolved in 0.5 L of acetone and the same precipitation as above was performed.
Filtration and drying were performed to obtain a white polymer. 77.0 g of the white polymer thus obtained was a polymer having a weight average molecular weight of 11,000 by the light scattering method and a dispersity (= Mw / Mn) of 1.83 from the GPC elution curve. I was able to confirm that. From the ¹ H-NMR measurement results, it was found that the obtained polymer contained the monomer 1, the monomer 8, and the monomer 3 from which the acetyl group had been removed in a content ratio of 28:18:54.

[0131]

[Chemical 28]

[Comparative Synthesis Example 1] Using a 2 L flask, polyhydroxystyrene (Mw = 11,000, M
w / Mn = 1.08) 40 g of tetrahydrofuran 40
Dissolve in 0 mL, add 1.4 g of methanesulfonic acid and 12.3 g of ethyl vinyl ether, react at room temperature for 1 hour,
2.5 g of ammonia water (30%) was added to stop the reaction, and the reaction solution was crystallized and precipitated using 5 L of acetic acid water,
Washing with water twice more and filtering the resulting white solid, 4
After drying under reduced pressure at 0 ° C., 47 g of a white polymer was obtained. The obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, and the following analysis results were obtained. Copolymerization composition ratio hydroxystyrene: p-ethoxyethoxystyrene =
63.5: 36.5 Weight average molecular weight (Mw) = 13,000 Molecular weight distribution (Mw / Mn) = 1.10 This is defined as (Comparative Synthesis Example 1 polymer).

Comparative Synthesis Example 2 To a 2 L flask, 43.0 g of tert-butyl methacrylate and 113.8 g of 4-acetoxystyrene were added, and 130 g of toluene was added as a solvent. This reaction vessel was cooled to −70 ° C. under a nitrogen atmosphere, and deaeration under reduced pressure and nitrogen blowing were repeated 3 times. After warming to room temperature, 4.1 g of AIBN as a polymerization initiator was added,
After raising the temperature to 0 ° C., the reaction was carried out for 15 hours. The reaction solution was concentrated to 1/2 and precipitated in a mixed solution of 4.5 L of methanol and 0.5 L of water.
After drying under reduced pressure at 0 ° C., 125 g of a white polymer was obtained. This polymer was added with 0.5 L of methanol and tetrahydrofuran 1.
Redissolve in 0 L, 70 g of triethylamine, 15 g of water
Was added to carry out a deprotection reaction, and the mixture was neutralized with acetic acid. The reaction solution was concentrated, dissolved in 0.5 L of acetone, and subjected to the same precipitation, filtration and drying as above to obtain 112 g of a white polymer.

The obtained polymer was measured by ¹³ C, ¹ H-NMR and GPC, and the following analysis results were obtained. Copolymerization composition ratio t-butyl methacrylate: 4-hydroxystyrene = 3
2:68 Weight average molecular weight (Mw) = 12,400 Molecular weight distribution (Mw / Mn) = 1.75 This is designated as (Comparative Synthesis Example 2 polymer).

[Comparative Synthesis Example 3] Monomer 1 and Monomer 3
Copolymerization of (1: 1) 19.6 g of monomers 1 and 2 in a 500 mL flask.
After 7.0 g of the following monomer 3 was dissolved in 100 mL of toluene to sufficiently remove oxygen in the system, the initiator AIBN was used.
Was charged in an amount of 0.38 g, and the temperature was raised to 60 ° C. to carry out a polymerization reaction for 24 hours.

To purify the polymer obtained, the reaction mixture was poured into hexane and the polymer obtained was precipitated. The polymer obtained is separated and dried, and then methanol 0.5
L and tetrahydrofuran (1.0 L) were dissolved again, triethylamine (70 g) and water (15 g) were added, the acetoxy group was deprotected, and the mixture was neutralized with acetic acid. After the reaction solution was concentrated, it was dissolved in 0.5 L of acetone and the same precipitation as above was performed.
Filtration and drying were performed to obtain a white polymer. The thus-obtained white polymer (35.0 g) has a weight average molecular weight of 9,300 by the light scattering method, and has a dispersity (= Mw / Mn) of 1.8 from the GPC elution curve. I was able to confirm that. From the ¹ H-NMR measurement results, it was found that the obtained polymer contained the monomer 1 and the monomer 3 from which the acetyl group had been eliminated in a content ratio of 48:52.

[Comparative Synthesis Example 4] Monomer 1 and Monomer 3
(2: 8) 13.1 g of monomers 1 and 7 in a 500 mL flask.
After 2.0 g of Monomer 3 was dissolved in 100 mL of toluene to sufficiently remove oxygen in the system, 0.38 g of AIBN as an initiator was charged, and the temperature was raised to 60 ° C. to carry out a polymerization reaction for 24 hours.

To purify the polymer obtained, the reaction mixture was poured into hexane and the polymer obtained was precipitated. The polymer obtained is separated and dried, and then methanol 0.5
L and tetrahydrofuran (1.0 L) were dissolved again, triethylamine (70 g) and water (15 g) were added, the acetoxy group was deprotected, and the mixture was neutralized with acetic acid. After the reaction solution was concentrated, it was dissolved in 0.5 L of acetone and the same precipitation as above was performed.
Filtration and drying were performed to obtain a white polymer. 63.0 g of the white polymer thus obtained is a polymer having a weight average molecular weight of 12,000 as determined by a light scattering method and a dispersity (= Mw / Mn) of 1.75 according to the GPC elution curve. I was able to confirm that. From the ¹ H-NMR measurement results, it was found that the obtained polymer contained the monomer 1 and the monomer 3 from which the acetyl group had been eliminated in a content ratio of 22:78.

[Evaluation Example] Polymer Permeability Measurement 1 g of the obtained polymer was sufficiently dissolved in 20 g of propylene glycol monomethyl ether acetate (PGMEA) and filtered through a 0.2 μm filter to prepare a polymer solution.

Polymer solution is MgF₂Spin coat on substrate
After coating and coating, use a hot plate to 100 ℃
Bake for 90 seconds at 100 ° C and apply a 100 nm thick polymer film to M
gF ₂Created on the substrate. This substrate is a vacuum ultraviolet photometer
(JUV, VUV-200S) installed, 248n
The transmittance at m, 193 nm, 157 nm was measured.
It was The measurement results are shown in Table 1.

[0141]

[Table 1]

Preparation and exposure of resist A resist solution was prepared by a conventional method using the above polymer and the components shown below in the amounts shown in Table 2. Next, AR-19
(Manufactured by Shipley Co., Ltd.) was spin-coated on a silicon wafer having a film thickness of 82 nm, and then baked at 100 ° C. for 90 seconds using a hot plate to make the resist thickness 200 nm. did. In addition to this, F ₂ laser (VISO, Lithotec Japan Co., Ltd.)
S-4500) while changing the exposure amount, and immediately after the exposure, bake at 120 ° C. for 90 seconds, and develop with a 2.38% tetramethylammonium hydroxide aqueous solution for 60 seconds to obtain the exposure amount and the residual film. The relationship of rates was sought. The exposure amount when the film thickness becomes 0 is Eth, the sensitivity of the resist,
The slope tan θ at that time was determined as γ.

[0143]

[Chemical 29]

[0144]

[Table 2]

From Tables 1 and 2, it was found that the resist material using the polymer compound of the present invention can secure sufficient transparency even at the wavelength of F ₂ (157 nm). Also,
As a result of the VUVES exposure, it was found that the film thickness decreased as the exposure amount increased and the characteristics of a positive resist were exhibited.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Jun Hatakeyama             28-1 Nishifukushima, Kubiki Village, Nakakubiki District, Niigata Prefecture             Shin-Etsu Chemical Co., Ltd.Research on new functional materials technology             In-house (72) Inventor Yuji Harada             28-1 Nishifukushima, Kubiki Village, Nakakubiki District, Niigata Prefecture             Shin-Etsu Chemical Co., Ltd.Research on new functional materials technology             In-house (72) Inventor Yoshio Kawai             28-1 Nishifukushima, Kubiki Village, Nakakubiki District, Niigata Prefecture             Shin-Etsu Chemical Co., Ltd.Research on new functional materials technology             In-house (72) Inventor Masaru Sasako             1006 Kadoma, Kadoma-shi, Osaka (72) Inventor Masataka Endo             1006 Kadoma, Kadoma-shi, Osaka (72) Inventor Shinji Kishimura             1006 Kadoma, Kadoma-shi, Osaka (72) Inventor Mitsutaka Otani             2805 Imafuku Nakadai Centra, Kawagoe City, Saitama Prefecture             Le Glass Co., Ltd. (72) Inventor Satoru Miyazawa             2805 Imafuku Nakadai Centra, Kawagoe City, Saitama Prefecture             Le Glass Co., Ltd. (72) Inventor Kentaro Tsutsumi             2805 Imafuku Nakadai Centra, Kawagoe City, Saitama Prefecture             Le Glass Co., Ltd. (72) Inventor Kazuhiko Maeda             3-7 Kandanishikicho, Chiyoda-ku, Tokyo             Within Central Glass Co., Ltd. F term (reference) 2H025 AA01 AA09 AB16 AC08 AD03                       BE00 BE10 BG00 CC20 FA03                       FA12 FA17                 4J100 AB07R AL26P AL26Q BA03Q                       BA10R BB07Q BB17R BC07P                       BC08Q BC53Q CA03 DA01                       DA04 JA38

Claims (11)

[Claims] 1. The following general formulas (1a), (1b) and (1
A polymer compound having a repeating unit represented by c). [Chemical 1] (In the formula, R ¹ , R ² , R ⁵ and R ⁶ are a hydrogen atom, a fluorine atom,
Alternatively, it is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms or a fluorinated alkyl group. R ³ ,
R ⁷ is a fluorine atom or a linear, branched or cyclic fluorinated alkyl group having 1 to 20 carbon atoms. R
⁴ is an acid labile group, R ⁸ is an adhesive group, a hydrogen atom, or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms or a fluorinated alkyl group. R ¹⁰ is a single bond, an alkylene group having 1 to 20 carbon atoms, or a fluorinated alkylene group. R ¹¹ and R ¹² are a hydrogen atom, a fluorine atom, or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms or a fluorinated alkyl group,
^At least one of ¹¹ and R ¹² contains at least one fluorine atom. R ¹³ is the same or different hydrogen atom, fluorine atom, or a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, and may be a fluorinated alkyl group. R ¹⁴ is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms or an acid labile group, and may contain an ether group, a carbonyl group, an ester group or a lactone ring. a, b, c are 0 <a <1, 0 <b <
1, 0 <c <1 and 0 <a + b + c ≦ 1. Further, m and n are integers of 1 ≦ m ≦ 5 and 0 ≦ n ≦ 4,
m + n = 5. ) 2. The repeating unit of the general formula (1a), R ⁴ is an acid labile group, and the repeating unit of the general formula (1b) is R ⁸ is an adhesive group. Polymer compounds. 3. In the repeating unit of the general formula (1a), R ⁴ is an acid labile group, and in the repeating unit of the general formula (1b), R ⁸ is a linear, branched or cyclic group having 1 to 20 carbon atoms. The polymer compound according to claim 1, which is a fluorinated alkyl group of 4. Higher according to claim 1, 2 or 3, wherein R ³ and R ⁷ are each a linear, branched or cyclic fluorinated alkyl group having 1 to 20 carbon atoms. Molecular compound. 5. The polymer compound according to claim 4, wherein R ³ and R ⁷ are each a trifluoromethyl group. 6. A resist material comprising the polymer compound according to any one of claims 1 to 5. 7. A chemically amplified resist material comprising (A) the polymer compound according to any one of claims 1 to 5, (B) an organic solvent, and (C) an acid generator. 8. The resist material according to claim 7, further containing a basic compound. 9. The resist material according to claim 7, further comprising a dissolution inhibitor. 10. (1) A step of applying the resist material according to claim 6 onto a substrate,
(2) Then, after heat treatment, a wavelength of 1 is passed through a photomask.
A pattern forming method comprising: a step of exposing with a high energy ray in a band of 0 to 180 nm or a band of 1 to 30 nm; and (3) a step of performing a heat treatment as needed and then developing with a developing solution. . 11. The high energy ray is an F ₂ laser,
The pattern forming method according to claim 10, wherein the pattern is Ar ₂ laser or soft X-ray.