JP2002327013A - High molecular compound, resist material and pattern forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resist material which is sensitive to high energy beams, particularly excellent in sensitivity at <=170 nm wavelength and which has improved transparency of a resist and excellent plasma etching resistance. SOLUTION: A high polymer compound contains a group of the formula (I) [R<1> -R<3> are H, F or an alkyl group or a fluorinated alkyl group; R<4> and R<5> are H or F; R<6> and R<7> are H, F or an alkyl group or a fluorinated alkyl group; at least one of R<6> and R<7> contains one or more F; a is 0 or 1].

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 microfabrication technology, particularly a polymer compound useful as a base polymer of a chemically amplified resist material, a resist material containing the same, and a pattern forming method using the same. .

[0002]

2. Description of the Related Art In recent years,
With the increase in integration and speed of LSIs, miniaturization of pattern rules is required. Background of the rapid progress of miniaturization include higher NA of the projection lens, improved resist performance, and shorter wavelength. Regarding high resolution and high sensitivity of resist, chemically amplified positive resist material catalyzed by acid generated by light irradiation has excellent performance, and has become the mainstream resist material especially in deep ultraviolet lithography (Japanese Patent Publication No. 27660/1990,
3-27829). The i-line (365)
nm) to KrF (248 nm) has brought about a major change, and the resist material for KrF excimer laser has started from the 0.30 micron process, passed the 0.25 micron rule, and is now mass-produced at the 0.18 micron rule. It has been expanded to apply to. Furthermore, the study of the 0.15 micron rule has begun, and the pace of miniaturization is accelerating increasingly.

In the case of ArF (193 nm), the miniaturization of the design rule is expected to be 0.13 μm or less. However, a conventionally used resin such as novolak or polyvinyl phenol has 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 necessary dry etching resistance, acrylic and cycloolefin-based alicyclic resins have been studied (JP-A-9-73173, JP-A-10-10739, and JP-A-9-230595). No., WO 97/33198).

For F ₂ (157 nm), 0.10 μm
m or less is expected, but it is increasingly difficult to ensure transparency. Acrylic resin, which is a base polymer for ArF, does not transmit light at all, and even cycloolefin-based resins having carbonyl bonds It was found to have strong absorption. In addition, it was found that polyvinyl phenol as a base polymer for KrF has an absorption window near 160 nm, and although the transmittance is slightly improved, it is far from a practical level.

[0005] The present invention has been made in view of the above circumstances, and it has been found that 300 nm or less, particularly F ₂ (157 nm), Kr
₂ (146 nm), KrAr (134 nm), Ar ₂ (1
A novel polymer compound useful as a base polymer of a resist material having excellent transmittance in vacuum ultraviolet light such as 26 nm), particularly a chemically amplified resist material, a resist material containing the same, and a pattern forming method using the same. To the purpose.

[0006]

Means for Solving the Problems and Embodiments of the Invention The present inventors have made intensive studies to achieve the above object, and as a result, introduced an ester group having a fluorine-containing alicyclic unit into a base polymer. As a result, the present inventors have found that a resist material, in particular, a chemically amplified resist material which can ensure dry etching resistance while dramatically improving transparency can be obtained, and the present invention has been accomplished.

That is, the present invention provides the following polymer compound, resist material, and pattern forming method. Claim 1: A weight average molecular weight of 1,000 to 500, containing a group represented by the following general formula (1).
000 high molecular compounds.

[0008]

Embedded image (Wherein, R ^{1 to} R ³ 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. R ² and R ³ are It may form a ring, in which case it represents an alkylene group having 1 to 20 carbon atoms which may contain a hetero atom such as oxygen, sulfur, nitrogen, etc. R ⁴ and R ⁵ are a hydrogen atom or a fluorine atom.
⁶ and R ⁷ 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 ⁶ and R ⁷ is one or more Containing a fluorine atom. R ⁶ and R ⁷ may form a ring, in which case they represent a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms or a fluorinated alkylene group. a is 0 or 1. Claim 2: The polymer compound according to claim 1, which contains a group represented by the following general formula (1a).

Embedded image

Wherein R ^{1 to} R ³ 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.
² and R ³ may form a ring, in which case oxygen, sulfur,
Represents an alkylene group having 1 to 20 carbon atoms which may contain a hetero atom such as nitrogen. a is 0 or 1. b is an integer of 1 to 4. Claim 3: The polymer compound according to claim 1, wherein the polymer compound has any of partial structures represented by the following general formulas (2-1) to (2-5).

Embedded image (In the formula, R ⁰ represents a group represented by the formula (1) in claim 1 or the formula (1a) in claim 2. R ^{8 to} R ¹⁰ represent a hydrogen atom, a fluorine atom, or a C 1 to C 1 atom. A linear, branched or cyclic alkyl group or a fluorinated alkyl group of 20. R ¹¹ represents a methylene group, an oxygen atom or a sulfur atom, R ¹² and R ¹³ represent a hydrogen atom, a methyl group, Or CH
₂ CO ₂ R ¹⁵ is shown. R ¹⁵ is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, or a substituted alkyl group. R ¹⁴ is a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms or a fluorinated alkylene group. c is 0 or 1. (4) A resist material comprising the polymer compound according to any one of (1) to (3). Claim 5: A chemically amplified positive type comprising (A) the polymer compound according to any one of Claims 1 to 3, (B) an organic solvent, and (C) an acid generator. Resist material. In a preferred embodiment, the resist composition further comprises a basic compound. (7) The resist material according to the above (5) or (6), further comprising a dissolution inhibitor. Claim 8: (1) a step of applying the resist material according to any one of claims 4 to 7 on a substrate; and (2) a heat treatment, followed by a wavelength of 100 to 18 via a photomask.
A pattern forming method, comprising: a step of exposing with a high-energy ray in a 0 nm band or a 1 to 30 nm band; and (3) a step of performing a heat treatment as necessary and then developing with a developer. In a preferred embodiment, the high energy ray is an F ₂ laser, an Ar ₂ laser, or a soft X-ray.

According to the study of the present inventor, as a method of improving the transmittance around 157 nm, it is considered that one method is to reduce the number of carbonyl groups and carbon-carbon double bonds. It has been found that the introduction of fluorine atoms into the metal also greatly contributes to improving the transmittance. In fact, a polymer in which fluorine was introduced into the aromatic ring of polyvinylphenol was able to obtain a practically close transmittance. However, it was found that the application of high-energy light such as an F ₂ laser to this base polymer significantly progressed to negative conversion, and it was found that practical application as a resist was difficult. On the other hand, it was found that a polymer in which fluorine was introduced into a polymer compound containing an aliphatic cyclic compound derived from an acrylic resin or a norbornene derivative in the main chain was capable of suppressing absorption and solving the problem of negative conversion. . In particular, it has been found that polymers having a fluorine-containing alicyclic unit introduced into an ester side chain as in the present invention have a high transmittance near 157 nm and an excellent dry etching resistance.

Hereinafter, the present invention will be described in more detail. The polymer compound according to the present invention has the following general formula (1)
Weight average molecular weight having a group represented by 1,000 to 50
000.

Embedded image (Wherein, R ^{1 to} R ³ 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. R ² and R ³ are It may form a ring, in which case it represents an alkylene group having 1 to 20 carbon atoms which may contain a hetero atom such as oxygen, sulfur, nitrogen, etc. R ⁴ and R ⁵ are a hydrogen atom or a fluorine atom. ⁶
And R ⁷ are a hydrogen atom, a fluorine atom, or a C 1-20
Is a linear, branched or cyclic alkyl group or a fluorinated alkyl group, and at least one of R ⁶ and R ⁷ contains one or more fluorine atoms. R ⁶ and R ⁷ may combine to form a ring, in which case they represent a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms or a fluorinated alkylene group. a is 0 or 1. )

In this case, examples of the group in which R ⁶ and R ⁷ are bonded to form a ring include a group represented by the following general formula (1a).

Embedded image (Wherein, R ^{1 to} R ³ are a hydrogen atom, a fluorine atom, or a linear, branched or cyclic alkyl group or a fluorinated alkyl group having 1 to 20 carbon atoms. R ² and R ³ are A ring may be formed, and in that case, it represents an alkylene group having 1 to 20 carbon atoms which may contain a hetero atom such as oxygen, sulfur, nitrogen, etc. a is 0 or 1. b is an integer of 1 to 4. Is.)

Here, R ^{1 to} R ³ are a hydrogen atom, a fluorine atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms or a fluorinated alkyl group. R
² and R ³ may be bonded to each other to form a ring, and in this case, they are an alkylene group having 1 to 20 carbon atoms which may contain a hetero atom such as oxygen, sulfur or nitrogen. R ⁴ and R ⁵ are a hydrogen atom or a fluorine atom. R ⁶ and R ⁷ 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 ⁶ and R ⁷ is It contains one or more fluorine atoms. R ⁶ and R ⁷ may combine to form a ring, in which case they represent a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms or a fluorinated alkylene group. A is 0 or 1, and b is 1 to
It is an integer of 4.

In this case, the linear, branched or cyclic alkyl group having 1 to 20 carbon atoms includes methyl, ethyl, propyl, isopropyl, n-propyl,
sec-butyl group, tert-butyl group, cyclopentyl group, cyclohexyl group, 2-ethylhexyl group, n-
Examples thereof include an octyl group and the like, and particularly those having 1 to 12 carbon atoms, particularly 1 to 10 carbon atoms are preferable. Note that the fluorinated alkyl group is a group in which part or all of the hydrogen atoms of the above alkyl group has been substituted with fluorine atoms, and is a trifluoromethyl group, a 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 and the like. Further, the alkylene group having 1 to 20 carbon atoms and the fluorinated alkylene group include those in which one hydrogen atom is eliminated from the alkyl group having 1 to 20 carbon atoms and the fluorinated alkyl group. Those having a number of 1 to 12, especially 1 to 10 carbon atoms are preferred.

The high molecular compound having a group represented by the above formula (1) or (1a) includes the following general formulas (2-1) to
Those having any of the repeating units shown in (2-5) are preferable.

Embedded image (Wherein, R ⁰ is .R ⁸ ~ to a group of the formula (1) or (1a)
R ¹⁰ is 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. R ¹¹ represents a methylene group, an oxygen atom or a sulfur atom. R ¹² and R ¹³ represent a hydrogen atom, a methyl group, or CH ₂ CO ₂ R ¹⁵ . R ¹⁵ has 1 to 20 carbon atoms
Is a linear, branched or cyclic alkyl group or a substituted alkyl group. R ¹⁴ is a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms or a fluorinated alkylene group. c is 0 or 1. )

The above-mentioned alkyl group, fluorinated alkyl group, alkylene group and fluorinated alkylene group are the same as those exemplified above.

Specific examples of the substituent represented by the general formula (1) or (1a) include the following. In the following examples, Et represents an ethyl group.

[0018]

Embedded image

The polymer compound of the present invention has an acid-eliminating property only by any one of the repeating units (2-1) to (2-5), but from the viewpoint of improving the resolution of a resist, the above-mentioned unit is preferred. And the following repeating units (3-1) to (3-5)
Any one or more units can be introduced.

[0020]

Embedded image (In the formula, R ^{8 to} R ¹⁵ and c are the same as described above, and R ¹⁶ represents an acid labile group.) The acid labile group of R ¹⁶ is variously selected. ) To (6).

[0021]

Embedded image

In the formula (4), R ¹⁷ has 4 to 2 carbon atoms.
0, preferably a tertiary alkyl group having 4 to 15 carbon atoms,
20 represents an oxoalkyl group or a group represented by the above general formula (6).
t-butyl group, 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, 2-
Examples thereof include a methyl-2-adamantyl group, and specific examples of the oxoalkyl group include a 3-oxocyclohexyl group, a 4-methyl-2-oxooxan-4-yl group,
-Methyl-5-oxooxolan-4-yl group and the like. d is an integer of 0-6.

Specific examples of the acid labile group of the above formula (4) include a tert-butoxycarbonyl group, a tert-butoxycarbonylmethyl group, a tert-amyloxycarbonyl group, a tert-amyloxycarbonylmethyl group,
1,1-diethylpropyloxycarbonyl group, 1,1
-Diethylpropyloxycarbonylmethyl group, 1-ethylcyclopentyloxycarbonyl group, 1-ethylcyclopentyloxycarbonylmethyl group, 1-ethyl-
2-cyclopentenyloxycarbonyl group, 1-ethyl-2-cyclopentenyloxycarbonylmethyl group, 1
-Ethoxyethoxycarbonylmethyl group, 2-tetrahydropyranyloxycarbonylmethyl group, 2-tetrahydrofuranyloxycarbonylmethyl group and the like.

In the formula (5), R ¹⁸ and R ^{19 each} represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms. , Ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, cyclopentyl, cyclohexyl, 2-ethylhexyl, n-octyl and the like. R ²⁰ is 1 to carbon atoms
18, preferably a monovalent hydrocarbon group which may have 1 to 10 hetero atoms such as an oxygen atom, and is a linear, branched or cyclic alkyl group, and a part of these hydrogen atoms is a hydroxyl group , An alkoxy group, an oxo group, an amino group, an alkylamino group and the like, and specific examples thereof include the following substituted alkyl groups.

[0025]

Embedded image

R ¹⁸ and R ¹⁹ , R ¹⁸ and R ²⁰ , and R ¹⁹ and R ²⁰ may form a ring, and when forming a ring, R ¹⁸ ,
R ¹⁹ and R ²⁰ each have 1 to 18 carbon atoms, preferably 1 to
And 10 linear or branched alkylene groups.

Specific examples of the linear or branched acid labile group represented by the above formula (5) include the following groups.

[0028]

Embedded image

As the cyclic group among the acid labile groups represented by the above formula (5), specifically, tetrahydrofuran-
Examples thereof include a 2-yl group, a 2-methyltetrahydrofuran-2-yl group, a tetrahydropyran-2-yl group, and a 2-methyltetrahydropyran-2-yl group. Equation (5)
Preferred are an ethoxyethyl group, a butoxyethyl group and an ethoxypropyl group.

Next, in the formula (6), R ²¹ , R ²² , R ²³
Is a monovalent hydrocarbon group such as a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and oxygen, sulfur, nitrogen,
It may contain a hetero atom such as fluorine, and R ²¹ and R ²² ,
R ²¹ and R ²³ , or R ²² and R ²³ may combine with each other to form a ring.

The tertiary alkyl group represented by the formula (6) includes a tert-butyl group, a triethylcarbyl group,
Ethyl norbornyl group, 1-methylcyclohexyl group,
1-ethylcyclopentyl group, 2- (2-methyl) adamantyl group, 2- (2-ethyl) adamantyl group, te
rt-amyl group, 1,1,1,3,3,3-hexafluoro-2-methyl-isopropyl group, 1,1,1,3,
In addition to the 3,3-hexafluoro-2-cyclohexyl-isopropyl group, the following groups can be specifically mentioned.

[0032]

Embedded image

Here, R ²⁴ represents a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, Examples thereof include a sec-butyl group, an n-pentyl group, an n-hexyl group, a cyclopropyl group, a cyclopropylmethyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. R ²⁵ represents a linear, branched or cyclic alkyl group having 2 to 6 carbon atoms, specifically, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and an n-pentyl group. , N-hexyl group, cyclopropyl group, cyclopropylmethyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and the like. R ²⁶
And R ^{27 each} represent a hydrogen atom, a monovalent hydrocarbon group which may contain a heteroatom having 1 to 6 carbon atoms, or a monovalent hydrocarbon group which may intervene through a heteroatom having 1 to 6 carbon atoms. Shape,
It may be branched or cyclic. In this case, examples of the hetero atom include an oxygen atom, a sulfur atom, and a nitrogen atom, and —OH, —OR ²⁸ , —O—, —S—, and —S (=
_{O) -, - NH 2,} -NHR 28, -N (R 28) 2, -NH
-, -NR ^28- can be contained or interposed (R ²⁸ represents an alkyl group). As R ²⁶ and R ²⁷ ,
Specifically, methyl, hydroxymethyl, ethyl, hydroxyethyl, propyl, isopropyl, n-butyl, sec-butyl, n-pentyl, n-hexyl, methoxy, methoxymethoxy Group, ethoxy group, tert-butoxy group and the like.

The polymer compound of the present invention has the following repeating unit (7-
Any one or more units of 1) to (7-5) can be introduced.

[0035]

Embedded image (In the formula, R ^{8 to} R ¹⁵ and c are the same as described above, and R ²⁹ represents a fluorinated alkyl group having 2 to 20 carbon atoms.)

R ²⁹ is a fluorinated alkyl group,
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, 2,2,3,3,4,4
5,5-octafluoropentyl group and the like.

The polymer compound of the present invention may further comprise the following repeating unit (8-
Any one or more units of 1) to (8-5) can be introduced.

[0038]

Embedded image (In the formula, R ^{8 to} R ¹⁵ and c are the same as described above, and R ³⁰ represents a hydrogen atom or an adhesive group.)

[0039] Specific examples of the adhesive group represented by R ³⁰ include those as represented below.

[0040]

Embedded image

Further, the polymer compound of the present invention comprises (8-1)
In addition to the units (8-5), the following adhesive groups can be introduced from the viewpoint of improving the adhesiveness.

[0042]

Embedded image (Wherein, R ³¹ and R ^{32 each} represent a hydrogen atom or a group having 1 to 20 carbon atoms)
Is a linear, branched or cyclic alkyl group or a fluorinated alkyl group. e is an integer of 0-4. )

When synthesizing the polymer compound of the present invention, a monomer having a group represented by the above formula (1) or (1a), particularly a monomer giving units of (2-1) to (2-5), and if necessary, Acid-eliminable monomers (3-1) to (3-5),
The monomers for improving transparency (7-1) to (7-5) and the monomers for improving adhesion (8-1) to (8-5) are dissolved in a solvent, a catalyst is added thereto, and in some cases, heating or cooling is performed. The polymerization reaction is carried out while performing. Polymerization reaction is initiator (or catalyst)
Type, method of initiation (light, heat, radiation, plasma, etc.),
It is also governed by the polymerization conditions (temperature, pressure, concentration, solvent, additives) and the like. In the polymerization of the polymer compound of the present invention, 2,2′-azobisisobutyronitrile (hereinafter referred to as A
Radical copolymerization in which polymerization is initiated by a radical such as IBN), ionic polymerization (anionic polymerization) using a catalyst such as alkyllithium, and the like are common. These polymerizations can be carried out according to a conventional method.

The radical polymerization initiator is not particularly restricted but includes, for example, the above-mentioned AIBN, 2,2 ′
-Azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4,4-trimethylpentane) and the like Peroxides such as azo compounds, tert-butylperoxypivalate, lauroyl peroxide, benzoyl peroxide, tert-butylperoxylaurate and the like, and water-soluble initiators such as potassium persulfate such as potassium persulfate A redox initiator comprising a combination of a salt and further a peroxide such as potassium persulfate or hydrogen peroxide and a reducing agent such as sodium sulfite is exemplified. The amount of the polymerization initiator used can be appropriately changed depending on the type, polymerization reaction conditions and the like, but is usually 0.001 to 5% by weight, especially 0.01 to 2% by weight based on the total amount of the monomers to be polymerized. % By weight is employed.

In the polymerization reaction, a polymerization solvent may be used. As the polymerization solvent, those that do not inhibit the polymerization reaction are preferable, and typical examples include esters such as ethyl acetate and n-butyl acetate, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, toluene, xylene and cyclohexane. Aliphatic or aromatic hydrocarbons, alcohols such as isopropyl alcohol and ethylene glycol monomethyl ether, and ether solvents such as diethyl ether, dioxane and tetrahydrofuran. These solvents can be used alone or
It can be used even if it mixes more than kinds. A known molecular weight regulator such as dodecyl mercaptan may be used in combination.

The reaction temperature of the polymerization reaction is appropriately changed depending on the type of the polymerization initiator or the boiling point of the solvent.
00 ° C is preferable, and particularly preferably 50 to 140 ° C. 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 distillation under heat under reduced pressure.

The polymer compound of the present invention comprises a unit having a group represented by the formula (1) or (1a) [formulas (2-1) to (2-5)
And the unit having an acid leaving group represented by the formulas (3-1) to (3-5) are represented by U2, and the units having the formula (7-1) to (7)
The unit of the transparency unit represented by -5) is U3, and the unit of the formula (8)
When the unit of the adhesive group or other adhesive unit represented by -1) to (8-5) is U4,-(U1) _f1- (U2) _f2- (U3) _f3- (U4) _f4 Where f1 to f4 are f1 + f2 + f
3 + f4 = 1, 0.1 ≦ f1 / (f1 + f2 + f3 + f4) ≦ 0.9,
More preferably, 0.2 ≦ f1 / (f1 + f2 + f3 + f
4) ≦ 0.5 0.1 ≦ f2 / (f1 + f2 + f3 + f4) ≦ 0.8,
More preferably, 0.2 ≦ f2 / (f1 + f2 + f3 + f
4) ≦ 0.5 0 ≦ f3 / (f1 + f2 + f3 + f4) ≦ 0.5, more preferably 0 ≦ f3 / (f1 + f2 + f3 + f4) ≦
0.30 ≦ f4 / (f1 + f2 + f3 + f4) ≦ 0.5, more preferably 0 ≦ f4 / (f1 + f2 + f3 + f4) ≦
It is preferably 0.3.

The weight average molecular weight of the high molecular compound is 1,
000 to 1,000,000, especially 2,000 to 10
Desirably, it is set to 0000.

The polymer compound of the present invention comprises a resist material,
In particular, it can be used as a base resin for chemically amplified type, especially chemically amplified positive type resist material, but mixes other polymer compounds for the purpose of changing the film's mechanical properties, thermal properties, alkali solubility, and other physical properties. You can also. At this time, the range of the polymer compound to be mixed is not particularly limited, but it can be mixed with a known polymer compound for a resist 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.
(A) The polymer compound (base resin), (B) an organic solvent, and (C) an acid generator. In this case, (D) a basic compound and (E) a dissolution inhibitor may be further added to these resist materials.

The organic solvent of the component (B) used in the present invention may be any as long as the base resin, the acid generator, and other additives can be dissolved. Such organic solvents include, for example, cyclohexanone, 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, ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether and diethylene glycol dimethyl ether; 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 exemplified.

Further, a fluorinated organic solvent 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-trifluoroethyl butyrate , Ethyl heptafluorobutyrate, ethyl heptafluorobutyl acetate, ethyl hexafluoroglutarylmethyl, ethyl-3-hydroxy-4,4,4-trifluorobutyrate, ethyl-2-methyl-4,4,4-triethyl Fluoroacetoacetate, ethylpentafluorobenzoate, ethylpentafluoropropionate, ethylpentafluoropropynyl acetate, ethyl perfluorooctanoate, ethyl-4,4,4-trifluoroacetoacetate, ethyl-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-oxahexano Ethate), methyl perfluorononanoate, methyl perfluorooctanoate, methyl-2,3,3,3-tetrafluoropropionate, 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, 2H-perfluoro-1-decanol, perfluoro (2,5-dimethyl-3,6-dioxaneanionic) acid methyl ester, 2H-perfluoro-5-methyl-3,6-dioxanonane , 1H, 1
H, 2H, 3H, 3H-perfluorononane-1,2-
Diol, 1H, 1H, 9H-perfluoro-1-nonanol, 1H, 1H-perfluorooctanol, 1
H, 1H, 2H, 2H-perfluorooctanol, 2
H-perfluoro-5,8,11,14-tetramethyl-3,6,9,12,15-pentaoxaoctadecane, perfluorotributylamine, perfluorotrihexylamine, perfluoro-2,5,8- Trimethyl-3,6,9-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, perfluorobutyltetrahydrofuran, perfluorodecalin, perfluoro (1,2-dimethylcyclohexane), perfluoro (1,3-dimethylcyclohexane), propylene glycol tri Fluoromethyl 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.

These solvents can be used singly or as a mixture 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 in which the solubility of the acid generator in the resist component is the most excellent, propylene glycol monomethyl acetate as a safe solvent and a mixed solvent thereof Is preferably used.

The amount of the solvent used is determined by the amount of base resin 1
300 to 10,000 per 100 parts (parts by weight, hereinafter the same)
0 parts, especially 500 to 5,000 parts are preferred.

Examples of the acid generator (C) include an onium salt of the following general formula (9), a diazomethane derivative of the formula (10), a glyoxime derivative of the formula (11), a β-ketosulfonic acid derivative, a disulfone derivative, and a nitro compound. Benzylsulfonate derivatives, sulfonic acid ester derivatives, imidoylsulfonate derivatives and the like can be mentioned.

(R³³)_gM⁺K^- (9) (where R³³Is a straight-chain or branched having 1 to 12 carbon atoms, respectively.
Or cyclic alkyl group, aryl having 6 to 20 carbon atoms
A aralkyl group having 7 to 12 carbon atoms; ⁺Is
Represents iodonium or sulfonium, K^-Is non-nucleophilic
Represents a counter ion, and g is 2 or 3. )

Examples of the alkyl group for R ³³ 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, m-tert-butoxyphenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, ethylphenyl group, 4-tert-butylphenyl group, 4
-Alkylphenyl groups such as -butylphenyl group and dimethylphenyl group. Examples of the aralkyl group include a benzyl group and a phenethyl group. K ^- a non-nucleophilic counter chloride ions as the ion, halide ions such as bromide ion, triflate, 1,1,1-trifluoroethane sulfonate, fluoroalkyl sulfonate such as nonafluorobutanesulfonate, tosylate, benzenesulfonate , 4-fluorobenzenesulfonate, arylsulfonates such as 1,2,3,4,5-pentafluorobenzenesulfonate, and alkylsulfonates such as mesylate and butanesulfonate.

[0059]

Embedded image (Wherein R ³⁴ and R ³⁵ are a linear, branched or cyclic alkyl group or halogenated alkyl group having 1 to 12 carbon atoms, an aryl group or halogenated aryl group having 6 to 12 carbon atoms or 7 carbon atoms) ~ 12 aralkyl groups are shown.)

Examples of the alkyl group for R ³⁴ and R ³⁵ 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, a nonafluorobutyl group, and the like. Examples of the aryl group include phenyl, p-methoxyphenyl, m-methoxyphenyl, o-methoxyphenyl, ethoxyphenyl, p-tert-butoxyphenyl, and m-tert.
An alkoxyphenyl group such as -butoxyphenyl group, 2-
Examples thereof include an alkylphenyl group such as a methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, an ethylphenyl group, a 4-tert-butylphenyl group, a 4-butylphenyl group, and a 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.

[0061]

Embedded image (Wherein, R ^{36 to} R ³⁸ are a linear, branched or cyclic alkyl group or halogenated alkyl group having 1 to 12 carbon atoms, an aryl group or halogenated aryl group having 6 to 12 carbon atoms, or And represents an aralkyl group of 7 to 12. R ³⁷ and R ³⁸
May combine with each other to form a cyclic structure, and in the case of forming a cyclic structure, R ³⁷ and R ³⁸ each have 1 to 6 carbon atoms.
Represents a linear or branched alkylene group. )

As the alkyl group, halogenated alkyl group, aryl group, halogenated aryl group and aralkyl group represented by R ^{36 to} R ^38, the same groups as those described for R ³⁴ and R ³⁵ can be mentioned. The alkylene group for R ³⁷ and R ³⁸ includes a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group and the like.

Specific examples of the acid generator include diphenyliodonium trifluoromethanesulfonate, phenyliodonium trifluoromethanesulfonate (p-tert-butoxyphenyl), diphenyliodonium p-toluenesulfonate, and p-toluenesulfonic acid (p-toluenesulfonic acid). -Tert-butoxyphenyl) phenyliodonium, triphenylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonic acid (p-ter
t-butoxyphenyl) diphenylsulfonium, bis (p-tert-butoxyphenyl) phenylsulfonium trifluoromethanesulfonate, tris (p-tert-butoxyphenyl) sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, p- Toluenesulfonic acid (p-ter
t-butoxyphenyl) diphenylsulfonium, p-
Bis (p-tert-butoxyphenyl) phenylsulfonium toluenesulfonate, tris (p-tert-butoxyphenyl) sulfonium p-toluenesulfonate, triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium butanesulfonate,
Trimethylsulfonium trifluoromethanesulfonate, trimethylsulfonium p-toluenesulfonate,
Cyclohexylmethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, cyclohexylmethyl (2-oxocyclohexyl) sulfonium p-toluenesulfonate, dimethylphenylsulfonium trifluoromethanesulfonate, dimethylphenylsulfonium p-toluenesulfonate, trifluoromethanesulfonate Dicyclohexylphenylsulfonium, dicyclohexylphenylsulfonium p-toluenesulfonate, trinaphthylsulfonium trifluoromethanesulfonate, cyclohexylmethyl trifluoromethanesulfonate (2-oxocyclohexyl) sulfonium, (2-norbonyl) methyl trifluoromethanesulfonate (2-oxocyclohexyl) ) Sulfonium, ethylenebis [meth (2-oxo-cyclopentyl) sulfonium trifluoromethanesulfonate na - DOO,
Onium salts such as 1,2′-naphthylcarbonylmethyltetrahydrothiophenium triflate, 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- (tert-butylsulfonyl) diazomethane, 1-cyclohexylsulfonyl-1- (tert-amylsulfonyl) diazomethane, 1-tert-amylsulfonyl-1- (tert
-Butylsulfonyl) diazomethane derivatives such as diazomethane, bis-O- (p-toluenesulfonyl) -α-dimethylglyoxime, 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- (trifluoromethanesulfonyl) -α-dimethylglyoxime , Bis-O- (1,1,1-trifluoroethanesulfonyl) -α-dimethylglyoxime, bis-O- (t
ert-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- (xylenesulfonyl) -α-dimethylglyoxime, bis-O- (camphor-sulfonyl)
Glyoxime derivatives such as -α-dimethylglyoxime,
2-cyclohexylcarbonyl-2- (p-toluenesulfonyl) propane, 2-isopropylcarbonyl-2
Β-ketosulfone derivatives such as-(p-toluenesulfonyl) propane, disulfone derivatives such as diphenyldisulfone and dicyclohexyldisulfone, 2,6-dinitrobenzyl p-toluenesulfonate, 2,4-dinitrobenzyl p-toluenesulfonate and the like Nitrobenzylsulfonate derivatives, 1,2,3-tris (methanesulfonyloxy) benzene, 1,2,3-tris (trifluoromethanesulfonyloxy) benzene, 1,2,3-tris (p-toluenesulfonyloxy) benzene, etc. Sulfonic acid ester derivative, phthalimido-yl-triflate, phthalimido-yl-tosylate, 5-norbornene-2,3-dicarboximido-yl-triflate, 5-norbornen-2,3-dicarboximido-yl- Tossilet 5-norbornene-2,3-dicarboximide - yl -n- butyl preparative reflation although imidoyl sulfonate derivatives such as sulfonates, trifluoromethane sulfonic acid triphenylsulfonium trifluoromethanesulfonic acid (p-tert
-Butoxyphenyl) diphenylsulfonium, tris (p-tert-butoxyphenyl) sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, p-toluenesulfonate (p
-Tert-butoxyphenyl) diphenylsulfonium, tris (p-tert-butoxyphenyl) sulfonium p-toluenesulfonate, trinaphthylsulfonium trifluoromethanesulfonate, cyclohexylmethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, trifluoromethanesulfone Onium salts such as acid (2-norbornyl) methyl (2-oxocyclohexyl) sulfonium, 1,2′-naphthylcarbonylmethyltetrahydrothiophenium triflate, bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, Bis (cyclohexylsulfonyl) diazomethane, bis (n-butylsulfonyl) diazomethane, bis (isobutylsulfonyl) diazometa Diazomethane derivatives such as bis (sec-butylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, bis-O- (p-toluenesulfonyl) -Α-dimethylglyoxime, bis-O-
Glyoxime derivatives such as (n-butanesulfonyl) -α-dimethylglyoxime are preferably used. In addition,
The acid generators can be used alone or in combination of two or more. Onium salts are excellent in the effect of improving rectangularity, and diazomethane derivatives and glyoxime derivatives are excellent in the effect of reducing standing waves. Therefore, fine adjustment of the profile can be performed by combining the two.

The amount of the acid generator to be added is preferably 0.2 to 15 parts with respect to 100 parts of the base resin. In some cases, when the amount is more than 15 parts, the transparency is reduced and the resolution may be reduced.

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 into the resist film is suitable. By blending such a basic compound, the diffusion rate of the acid in the resist film is suppressed and the resolution is improved. And pattern profiles can be improved (see JP-A-5-232706, JP-A-5-249683, and JP-A-5-249683).
No. 158239, No. 5-249662, No. 5-25
No. 7282, No. 5-289322, No. 5-28934
0 publication etc.).

Examples of such basic compounds include ammonia, primary, secondary, and tertiary aliphatic amines, hybrid amines, aromatic amines, heterocyclic amines, and carboxyl-containing amines. Examples include a nitrogen compound, a nitrogen-containing compound having a sulfonyl group, a nitrogen-containing compound having a hydroxyl group, a nitrogen-containing compound having a hydroxyphenyl group, an alcoholic nitrogen-containing compound, an amide derivative, and an imide derivative.

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

Specific examples of the 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 Examples include tetraethylenepentamine.

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 '-Tetramethylmethylenediamine, N, N, N', N'-tetramethylethylenediamine, N, N, N ', N'-tetramethyltetraethylenepentamine and the like are exemplified.

Specific examples of the hybrid amines include, for example, dimethylethylamine, methylethylpropylamine, benzylamine, phenethylamine, benzyldimethylamine and the like.

Specific examples of the aromatic amines include aniline, N-methylaniline, N-ethylaniline, N-propylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methylaniline, and 4-methylaniline. Aniline, ethyl aniline, propyl aniline, trimethyl aniline, 2-nitroaniline, 3-nitroaniline,
-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 pyrrole derivatives such as pyrrole, 2H-pyrrole, 1-methylpyrrole, 2,4-dimethylpyrrole, 2,5-dimethylpyrrole, N-methylpyrrole, oxazole, isopyrrole and the like. Oxazole derivatives such as oxazole, thiazole derivatives such as thiazole and isothiazole, imidazole, 4-
Imidazole derivatives such as methylimidazole and 4-methyl-2-phenylimidazole, pyrazole derivatives, furazane 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 derivatives, indole derivatives, isoindole derivatives, 1H-indazole derivatives, indoline derivatives, quinolines, quinoline derivatives such as 3-quinolinecarbonitrile, isoquinoline derivatives, cinnoline derivatives,
Quinazoline derivatives, quinoxaline derivatives, phthalazine derivatives, purine derivatives, pteridine derivatives, carbazole derivatives, phenanthridine derivatives, acridine derivatives,
Examples include phenazine derivatives, 1,10-phenanthroline derivatives, adenine derivatives, adenosine derivatives, guanine derivatives, guanosine derivatives, uracil derivatives, uridine derivatives and the like.

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, and the like. Amino acid derivatives such as methionine, phenylalanine, threonine, lysine, 3-aminopyrazine-2-carboxylic acid, and methoxyalanine are exemplified. 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-quinolinediol, 3-indolemethanol hydrate, monoethanolamine, diethanolamine, triethanolamine, N-ethyldiethanolamine, N, N-diethylethanolamine, triisopropanolamine, 2,2′-iminodiethanol,
-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, piperidineethanol, 1- (2-hydroxyethyl) pyrrolidine, 1- (2-hydroxyethyl) -2-
Pyrrolidinone, 3-piperidino-1,2-propanediol, 3-pyrrolidino-1,2-propanediol, 8
-Hydroxyurolidine, 3-quinuclidinol, 3
-Tropanol, 1-methyl-2-pyrrolidineethanol, 1-aziridineethanol, N- (2-hydroxyethyl) phthalimide, N- (2-hydroxyethyl)
Examples include isonicotinamide.

Specific examples of the amide derivative include formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide,
N, N-dimethylacetamide, propionamide, benzamide and the like are exemplified. Specific examples of the imide derivative include phthalimide, succinimide, and maleimide.

Further, one or more selected from basic compounds represented by the following general formula (12) can be added.

[0077]

Embedded image (In the formula, h = 1, 2, and 3. The side chains R ³⁹ may be the same or different, and can be bonded to each other to form a ring, and the above general formulas (12a), (12b), (12
c). The side chains R ⁴⁰ are the same or different,
Hydrogen atom or linear, branched or cyclic carbon number 1
Represents 20 alkyl groups and may contain an ether group or a hydroxyl group. R ⁴¹ , R ⁴³ and R ⁴⁶ have 1 to 1 carbon atoms
4, a linear or branched alkylene group represented by R ⁴² and R ⁴⁵
Is a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms, and may include one or more hydroxy groups, ether groups, ester groups, and lactone rings.
R ⁴⁴ is a single bond, a linear or branched alkylene group having 1 to 4 carbon atoms, and R ⁴⁷ is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a hydroxy group, It may contain one or more ether, ester groups and lactone rings. )

The compounds represented by the above general formula (12) are specifically exemplified 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) ethoxydiethyl] amine,
4,7,13,16,21,24-hexaoxa-1,
10-diazabicyclo [8.8.8] hexacosan,
4,7,13,18-tetraoxa-1,10-diazabicyclo [8.5.5] eicosan, 1,4,10,1
3-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
-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 ( 2
-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 -δ-valerolactone, but are not limited thereto. Further, one or more of the basic compounds having a cyclic structure represented by the following general formula (13) may be added.

[0080]

Embedded image (Wherein, R ³⁹ is as defined above, R ⁴⁸ represents a linear C2-20, branched alkylene group, a carbonyl group, an ether group, an ester group, contain one or more sulfide It may be.)

Specific examples of the base represented by the general formula (13) include 1- [2- (methoxymethoxy) ethyl] pyrrolidine, 1- [2- (methoxymethoxy) ethyl] piperidine, and 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, 2- (1-pyrrolidinyl) ethyl acetate, 2-piperidinoethyl acetate, 2-morpholinoethyl acetate, 2- (1-pyrrolidinyl) ethyl formate, propion 2-piperidinoethyl acid, 2-morpholinoethyl acetoxyacetate, 2- (1-pyrrolidinyl) ethyl methoxyacetate, 4- [2- (methoxycarbonyloxy) ethyl] morpholine, 1- [2- (t-butoxycarbonyloxy) ethyl ] Piperidine, 4- [2- (2-methoxyethoxycarbonyloxy) ethyl] morpholine,
Methyl- (1-pyrrolidinyl) propionate, methyl 3-piperidinopropionate, methyl 3-morpholinopropionate, methyl 3- (thiomorpholino) propionate, methyl 2-methyl-3- (1-pyrrolidinyl) propionate Ethyl 3-morpholinopropionate, methoxycarbonylmethyl 3-piperidinopropionate,
2-hydroxyethyl (1-pyrrolidinyl) propionate, 2-acetoxyethyl 3-morpholinopropionate, 2-oxotetrahydrofuran-3-yl 3- (1-pyrrolidinyl) propionate, tetrahydrofurfuryl 3-morpholinopropionate, 3 -Glycidyl piperidinopropionate, 2-methoxyethyl 3-morpholinopropionate, 2- (2-methoxyethoxy) ethyl 3- (1-pyrrolidinyl) propionate, butyl 3-morpholinopropionate, 3-piperidinopropion Acid cyclohexyl, α- (1-pyrrolidinyl) methyl-γ-butyrolactone, β-piperidino-γ-butyrolactone,
Examples thereof include β-morpholino-δ-valerolactone, methyl 1-pyrrolidinyl acetate, methyl piperidinoacetate, methyl morpholino acetate, methyl thiomorpholino acetate, ethyl 1-pyrrolidinyl acetate, and 2-methoxyethyl morpholino acetate.

Further, basic compounds containing a cyano group represented by the following general formulas (14) to (17) can be added.

[0083]

Embedded image (In the formula, R ³⁹ , R ⁴⁸ , and h are the same as described above for R ⁴⁹ and R
⁵⁰ is the same or different linear or branched alkylene group 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-
Methyl cyanoethyl) -N- (2-methoxyethyl) -3-aminopropionate, 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, 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
-Cyanomethyl bis (2-hydroxyethyl) -3-aminopropionate, cyanomethyl N, N-bis (2-acetoxyethyl) -3-aminopropionate, N, N-
Cyanomethyl bis (2-formyloxyethyl) -3-aminopropionate, cyanomethyl N, N-bis (2-methoxyethyl) -3-aminopropionate, N, N-
Cyanomethyl bis [2- (methoxymethoxy) ethyl] -3-aminopropionate, 2-cyanoethyl 3-diethylaminopropionate, 2-cyanoethyl N, N-bis (2-hydroxyethyl) -3-aminopropionate ), 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),
Cyanomethyl 1-pyrrolidinepropionate, cyanomethyl 1-piperidinepropionate, cyanomethyl 4-morpholinepropionate, 1-pyrrolidinepropionate (2
-Cyanoethyl), 1-piperidinepropionic acid (2-
Cyanoethyl) and 4-morpholinepropionic acid (2-cyanoethyl).

The above-mentioned basic compounds can be used alone or in combination of two or more. The compounding amount is 0.01 to 2 parts with respect to 100 parts of the total base resin.
Particularly, 0.01 to 1 part is preferable. If the amount is less than 0.01 part, the effect as an additive may not be sufficiently obtained, and if it exceeds 2 parts, the resolution and sensitivity may be reduced.

The dissolution inhibitor of component (E) has a molecular weight of 3,000, the solubility of which in an alkali developing solution is changed by the action of an acid.
Compounds having a molecular weight of 0 or less, particularly compounds in which some or all of the hydroxyl groups of a phenol or carboxylic acid derivative having a molecular weight of 2,500 or less are substituted with an acid labile group are suitable. The acid labile group may be a group containing fluorine mentioned in the present invention, or may be a conventional group containing no fluorine.

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 ′
-Methylene bis [2,6-difluorophenol],
4,4 ′-(4-fluorophenyl) methylenebis [2,6-difluorophenol], 2,6-bis [(2-hydroxy-5-fluorophenyl) methyl]
-4-fluorophenol, 2,6-bis [(4-hydroxy-3-fluorophenyl) methyl] -4-fluorophenol, 2,4-bis [(3-hydroxy-4-
Hydroxyphenyl) methyl] -6-methylphenol; examples of the acid-labile substituent include those represented by formula (4)
And (6).

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
tert-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′-
Tert-Butyl (2 ″ -tetrahydropyranyloxy) phenyl) valerate, 4,4-bis (4 ′-(2 ″
-Tetrahydrofuranyloxy) phenyl) valeric acid te
tert-butyl, tert-butyl 4,4-bis (4′-tert-butoxyphenyl) valerate, 4,4-bis (4-tert-butoxycarbonyloxyphenyl)
Tert-butyl valerate, 4,4-bis (4′-ter
tert-butyl t-butoxycarbonylmethyloxyphenyl) valerate, tert-butyl 4,4-bis (4 ′-(1 ″ -ethoxyethoxy) phenyl) 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-trifluoromethylbenzenecarboxylate, 2-trifluoro Tert-butyl methylcyclohexanecarboxylate, tert-butyl decahydronaphthalene-2,6-dicarboxylate, tert-butyl cholate, te-deoxycholate
tert-butyl, tert-butyl adamantane carboxylate, tert-butyl adamantane acetate, tetratert-butyl 1,1′-bicyclohexyl-3,3 ′, 4,4′-tetracarboxylate and the like.

The addition amount of the dissolution inhibitor in the resist material of the present invention is determined by the amount of base resin 10 in the resist material.
It is 20 parts or less, preferably 15 parts or less based on 0 parts. If the amount is more than 20 parts, the monomer component increases, and the heat resistance of the resist material decreases.

The resist composition of the present invention may contain, as an optional component, a surfactant which is commonly used for improving coating properties, in addition to the above components. In addition, the addition amount of the optional component can be a normal amount as long as the effect of the present invention is not hindered.

The surfactant is preferably a nonionic surfactant, and is preferably a perfluoroalkylpolyoxyethylene ethanol, a fluorinated alkyl ester, a perfluoroalkylamine oxide, a perfluoroalkyl EO adduct, or a fluorine-containing organosiloxane. And the like. For example, Florad “FC-430”, “F
C-431 "(all manufactured by Sumitomo 3M Limited), 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 Industries, Ltd.)," X-70-092 "," X-7 "
0-093 "(all manufactured by Shin-Etsu Chemical Co., Ltd.). Preferably, Florad “FC-4”
30 "(manufactured by Sumitomo 3M Limited)," X-70-09 "
3 "(manufactured by Shin-Etsu Chemical Co., Ltd.).

The formation of a pattern using the resist material of the present invention can be performed by employing a known lithography technique. For example, a film thickness of 0.1 to 1.0 is applied on a substrate such as a silicon wafer by a method such as spin coating.
μm and apply it on a hot plate for 6 μm.
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 target pattern is held over the resist film, and a high energy ray such as far ultraviolet ray, excimer laser, or X-ray or an electron beam is exposed at an exposure amount of 1 to 200 mJ / c.
m ^2, preferably about after irradiation so that 10 to 100 mJ / cm ² or so, on a hot plate at 60 to 150
C, 10 seconds to 5 minutes, preferably 80 to 130 C, 30
Post-exposure bake (PEB) for seconds to 3 minutes. Further, using a developing solution of 0.1 to 5%, preferably 2 to 3% of an alkaline aqueous solution such as tetramethylammonium hydroxide (TMAH), dipping for 10 seconds to 3 minutes, preferably 30 seconds to 2 minutes ( dip method, paddle (pud)
A target pattern is formed on the substrate by performing development using a conventional method such as a ble) method or a spray method. It should be noted that the material of the present invention is preferably a deep ultraviolet ray or a laser of 254 to 120 nm, especially 19
3 nm ArF, 157 nm F ₂ , 146 nm K
r _2, 134 nm of KrAr, the optimal laser for Ar ₂ or the like 126 nm, the fine patterning by X-ray and electron beam. Further, when the above range is out of the upper limit and the lower limit, a desired pattern may not be obtained.

[0093]

The resist material of the present invention is sensitive to high-energy rays, has excellent sensitivity at wavelengths of 200 nm or less, particularly 170 nm or less, and furthermore, the transparency of the resist is improved by introducing a fluorine-containing alicyclic unit. And at the same time have excellent plasma etching resistance. Accordingly, the resist material of the present invention can be a resist material having a small absorption particularly at the exposure wavelength of the F ₂ laser due to these characteristics, and can easily form a fine and perpendicular pattern to the substrate. Therefore, it is suitable as a fine pattern forming material for VLSI manufacturing.

[0094]

EXAMPLES The present invention will be specifically described below with reference to Synthesis Examples and Examples, but the present invention is not limited to the following Examples.

Synthesis Example 1 Copolymerization of the following monomer 1, methacrylic acid (2-ethyladamantyl) and the following monomer 2 (4: 4: 2) 26.2 g of the following monomer 1 in a 500 mL flask
And 17.9 g of methacrylic acid (2-ethyladamantyl) and 6.1 g of the following monomer 2 in 100 mL of toluene
After sufficient removal of oxygen in the system, the initiator A
0.34 g of IBN was charged, and the temperature was raised to 60 ° C. to carry out a polymerization reaction for 24 hours.

To purify the obtained polymer,
The mixture was poured into hexane to precipitate the resulting polymer.
Was. Further dissolve the obtained polymer in tetrahydrofuran
And pour it into 10 L of hexane to precipitate the polymer.
After repeating the cropping twice, the polymer was separated and dried.
35.2 g of the white polymer thus obtained was light-diffusing.
According to the random method, the weight average molecular weight is 14,000 and GP
Polymerization with dispersity (= Mw / Mn) of 1.4 from C elution curve
It was confirmed that it was a body. The resulting polymer is ¹H-
From the NMR measurement results, it was found that the monomer 1 and the methacrylic acid (2
-Ethyladamantyl) and monomer 2 at 41: 39: 2
It was found to be included at a ratio of 0.

[0097]

Embedded image

Synthesis Example 2 Copolymerization of monomer 1, methacrylic acid (2,2,3,3,4,4,5,5-octafluoropentyl), methacrylic acid (2-ethyladamantyl) and monomer 2 ( 4: 2: 3: 1) 24.6 g of monomer 1, 1 in a 500 mL flask.
0.1 g of methacrylic acid (2, 2, 3, 3, 4, 4,
5,5-octafluoropentyl), 12.6 g of methacrylic acid (2-ethyladamantyl), 2.9 g of the following monomer 2 were dissolved in 100 mL of toluene, and oxygen in the system was sufficiently removed. Was charged, and the temperature was raised to 60 ° C. to carry out a polymerization reaction for 24 hours.

To purify the obtained polymer,
The mixture was poured into hexane to precipitate the resulting polymer.
Was. Further dissolve the obtained polymer in tetrahydrofuran
And pour it into 10 L of hexane to precipitate the polymer.
After repeating the cropping twice, the polymer was separated and dried.
32.3 g of the white polymer thus obtained was light-diffusing.
According to the random method, the weight average molecular weight is 13,000,
Polymerization with dispersity (= Mw / Mn) of 1.4 from C elution curve
It was confirmed that it was a body. The resulting polymer is ¹H-
According to the NMR measurement results, monomer 1, methacrylic acid
(2,2,3,3,4,4,5,5-octafluorope
Methyl), methacrylic acid (2-ethyladamantyl) and
And monomer 2 in a ratio of 39: 20: 31: 10
It turned out to be.

[Synthesis Example 3] Copolymerization of monomer 1, methacrylic acid (2,2,3,3,4,4,5,5-octafluoropentyl), methacrylic acid (2-ethyladamantyl) and monomer 2 ( 3.5: 1.5: 3: 2) 22.8 g of monomer 1, in a 500 mL flask,
8.0 g of methacrylic acid (2, 2, 3, 3, 4, 4,
After dissolving 5,5-octafluoropentyl), 13.3 g of methacrylic acid (2-ethyladamantyl) and 6.1 g of monomer 2 in 100 mL of toluene and sufficiently removing oxygen in the system, the initiator AIBN was added. 0.34 g was charged, and the temperature was raised to 60 ° C. to carry out a polymerization reaction for 24 hours.

To purify the obtained polymer,
The mixture was poured into hexane to precipitate the resulting polymer.
Was. Further dissolve the obtained polymer in tetrahydrofuran
And pour it into 10 L of hexane to precipitate the polymer.
After repeating the cropping twice, the polymer was separated and dried.
34.3 g of the white polymer thus obtained was light-diffusing.
According to the random method, the weight average molecular weight is 14,000 and GP
Polymerization with dispersity (= Mw / Mn) of 1.5 from C elution curve
It was confirmed that it was a body. The resulting polymer is ¹H-
According to the NMR measurement results, monomer 1, methacrylic acid
(2,2,3,3,4,4,5,5-octafluorope
Methyl), methacrylic acid (2-ethyladamantyl) and
And monomer 2 in a ratio of 33: 16: 31: 20
It turned out to be.

[Synthesis Example 4] Copolymerization reaction of the following monomer 3, methacrylic acid (2-ethyladamantyl) and monomer 2 (4.5: 4: 1.5) In a 500 mL flask, 13.0 of the following monomer 3 was added.
g, 5.6 g of methacrylic acid (2-ethyladamantyl).
g, 1.4 g of monomer 2 was dissolved in 100 mL of toluene, and oxygen in the system was sufficiently removed.
Was charged, and the temperature was raised to 60 ° C. to carry out a polymerization reaction for 24 hours. To purify the obtained polymer, the reaction mixture was poured into methanol, and the obtained polymer was precipitated.

The operation of dissolving the obtained polymer in tetrahydrofuran and pouring it into 5 L of methanol to precipitate the polymer was repeated twice, and then the polymer was separated and dried. 14.0 g of the white polymer thus obtained had a weight average molecular weight of 8,500 by a light scattering method, and a dispersity (= Mw / Mn) of 1.0 from a GPC elution curve.
It was confirmed that the polymer was No. 7. Also, ¹ H-NM
The R results indicated that the resulting polymer contained monomer 3, methacrylic acid (2-ethyladamantyl) and monomer 2 in a ratio of 45:37:18.

[0104]

Embedded image

[Synthesis Example 5] Copolymerization reaction of the following monomer 4, methacrylic acid (2-ethyladamantyl) and monomer 2 (4.5: 4: 1.5). 8
g, 5.7 g of methacrylic acid (2-ethyladamantyl)
g, Monomer 2 and 1.5 g were dissolved in 100 mL of toluene, and oxygen in the system was sufficiently removed.
Was charged, and the temperature was raised to 60 ° C. to carry out a polymerization reaction for 24 hours. To purify the obtained polymer, the reaction mixture was poured into methanol, and the obtained polymer was precipitated.

Further, the operation of dissolving the obtained polymer in tetrahydrofuran and pouring it into 5 L of methanol to precipitate the polymer was repeated twice, then the polymer was separated and dried. 14.3 g of the white polymer thus obtained had a weight-average molecular weight of 8,900 as measured by a light scattering method and a dispersity (= Mw / Mn) of 1.90 according to a GPC elution curve.
It was confirmed that the polymer was No. 8. Also, ¹ H-NM
The results of R indicated that the resulting polymer contained monomer 4, methacrylic acid (2-ethyladamantyl) and monomer 2 in a ratio of 44:42:14.

[0107]

Embedded image

Synthesis Example 6 Copolymerization reaction of the following monomer 5, methacrylic acid (2-ethyladamantyl) and monomer 2 (4.5: 4: 1.5) 12.9 of the following monomer 5 in a 500 mL flask.
g, 5.7 g of methacrylic acid (2-ethyladamantyl)
g, Monomer 2 and 1.5 g were dissolved in 100 mL of toluene, and oxygen in the system was sufficiently removed.
Was charged, and the temperature was raised to 60 ° C. to carry out a polymerization reaction for 24 hours. To purify the obtained polymer, the reaction mixture was poured into methanol, and the obtained polymer was precipitated.

Further, the operation of dissolving the obtained polymer in tetrahydrofuran and pouring it into 5 L of methanol to precipitate the polymer was repeated twice, and then the polymer was separated and dried. 13.2 g of the white polymer thus obtained had a weight average molecular weight of 8,100 by a light scattering method, and a dispersity (= Mw / Mn) of 1.100 from a GPC elution curve.
It was confirmed that the polymer was No. 6. Also, ¹ H-NM
The results of R indicated that the resulting polymer contained monomer 5, methacrylic acid (2-ethyladamantyl) and monomer 2 in a ratio of 44:37:19.

[0110]

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[Synthesis Example 7] Copolymerization reaction of monomer 4, methacrylic acid (1-ethylcyclopentyl) and monomer 2 (4.5: 4: 1.5) In a 500 mL flask, 13.9 g of monomer 4 and methacrylic acid were added. 4.5 g of acid (1-ethylcyclopentyl)
Dissolve monomer 2 in 1.6 g toluene 100 mL,
After the oxygen in the system was sufficiently removed, 0.31 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 obtained polymer, the reaction mixture was poured into methanol, and the obtained polymer was precipitated.

Further, the operation of dissolving the obtained polymer in tetrahydrofuran and pouring it into 5 L of methanol to precipitate the polymer was repeated twice, then the polymer was separated and dried. The thus obtained 13.9 g of a white polymer had a weight average molecular weight of 8,200 by a light scattering method, and a dispersity (= Mw / Mn) of 1. based on a GPC elution curve.
It was confirmed that the polymer was No. 59. Also, ¹ H-N
The MR results indicated that the resulting polymer contained monomer 4, methacrylic acid (1-ethylcyclopentyl) and monomer 2 in a ratio of 42:40:18.

[Reference Example 1] Synthesis of Monomer 1 In a nitrogen stream, 747 was placed in a SUS autoclave having a capacity of 2 L.
g of octafluorocyclopentene and 74 g of cyclopentadiene were charged, the vessel was sealed, heated to 170 ° C. and maintained at the temperature for 72 hours. After cooling with ice and lowering the internal pressure,
The contents were transferred to a 2L mold flask and subjected to vacuum distillation.
193 g of the following compound (18) was obtained.

Under a nitrogen atmosphere, 100 g of the obtained compound (18) and 1.2 L of dichloromethane were added to a 2 L eggplant type flask. Subsequently, m-chloroperbenzoic acid 2 was added at room temperature.
66 g was added, and the mixture was stirred at room temperature for 48 hours. Next, an aqueous solution of sodium hydrogen sulfite is added dropwise at room temperature to decompose the excess reagent, diluted with a large excess of ethyl acetate, and washed with a 0.5N aqueous solution of sodium hydroxide, a saturated aqueous solution of sodium hydrogen carbonate, ion-exchanged water, and a saturated saline solution. did. The obtained organic layer was dried over an appropriate amount of magnesium sulfate, concentrated under reduced pressure by an evaporator, and then separated and purified by silica gel column chromatography to obtain 53 g of the following compound (19).

Under a nitrogen atmosphere, the entire amount of compound (19) and 1.8 L of tetrahydrofuran were added to a 2 L eggplant type flask. Subsequently, 6.8 lithium aluminum hydride was added under ice cooling.
g was added and stirred at 0 ° C. for 3 hours and at room temperature for 12 hours. Next, after dilution with a large amount of tetrahydrofuran, 10 mL of ion-exchanged water was added, and the mixture was stirred at room temperature for 1 hour to decompose excess reagent. Subsequently, the precipitate was separated by filtration through silica gel, concentrated under reduced pressure by an evaporator, and then separated and purified by silica gel column chromatography to obtain 36 g of the following compound (2).
0).

Under a nitrogen atmosphere, the total amount of the compound (20), 157 mL of methacrylic acid and 1.
3 g of hydroquinone was added. Then 18.8g at room temperature
Of concentrated sulfuric acid was added, and the mixture was stirred at 60 ° C for 5 hours. Next, after dilution with a large amount of ethyl acetate, an appropriate amount of ion-exchanged water was added to extract an organic layer. Subsequently, the organic layer was washed with a saturated aqueous solution of sodium hydrogen carbonate, ion-exchanged water, and saturated saline.
The obtained organic layer was dried over magnesium sulfate, concentrated under reduced pressure by an evaporator, and then separated and purified by silica gel column chromatography to obtain 28.3 g of Monomer 1.

[0117]

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Reference Example 2 Monomer 3, Monomer 4
And synthesis of monomer 5 in a 2 L SUS autoclave under a stream of nitrogen.
The container was charged with 2 g of perfluorohexylethylene and 100 g of dicyclopentadiene and sealed at 170 ° C.
And maintained at the temperature for 24 hours. After cooling with ice and lowering the internal pressure, the content was transferred to a 2 L mold flask and subjected to distillation under reduced pressure to obtain 109.5 g of the following compound (21).

Under a nitrogen atmosphere, 80 g of the obtained compound (21) was placed in a 1-L eggplant type flask, and 130 g of trifluoroacetic acid was added dropwise little by little. After the completion of the dropwise addition, the reaction was carried out at 50 ° C. for 6 hours. After completion of the reaction, the mixture was cooled to room temperature, and 400 mL of hexane was added.
Washed twice. Next, the organic layer was washed with 400 mL of a 26% aqueous sodium hydroxide solution, and the organic layer was dried by an evaporator. The obtained organic matter was dissolved in 400 mL of methanol, potassium carbonate was added, and the mixture was stirred at room temperature for 12 hours.
After removing methanol with an evaporator, the organic matter was dissolved in 400 mL of ether, and washed twice with 400 mL of water. The organic layer was dried over magnesium sulfate, and the solvent was removed with an evaporator and a vacuum pump.
81 g of a crude product of 2) was obtained.

The whole amount of the obtained compound (22) was dissolved in 160 g of acetone as a crude product, and Jones was dissolved in an ice bath.
An oxidation reaction was performed with the reagent. After quenching the excess reagent by adding 30 mL of isopropanol, the organic matter was diluted with hexane 3.
Dissolved in 00 mL and washed with 300 mL of water. After washing the organic layer with saturated aqueous sodium hydrogen carbonate solution and saturated saline,
After drying over magnesium sulfate, hexane was removed with an evaporator to obtain 78 g of a crude product of the following compound (23).

The whole amount of the obtained compound (23) was dissolved in 80 g of THF as a crude product, and dropped in a 1 L flask in a THF solution of ethyl magnesium bromide synthesized separately in an ice bath. After completion of the dropwise addition, the mixture was aged for 5 hours, 300 mL of hexane was added to the system, and then 300 mL of a saturated aqueous ammonium chloride solution was added dropwise. The organic layer was washed with saturated saline, dried over magnesium sulfate, and hexane was removed by an evaporator, followed by distillation under reduced pressure to obtain 65 g of the following compound (24).

In a 1 L eggplant type flask under a nitrogen atmosphere, 63
g of compound (24), 14.1 g of acrylic acid chloride, 120 g of toluene, 0.5 g of phenothiazine and 0.5 g of dimethylaminopyridine were added. After dripping 17.7 g of triethylamine, aging was performed at 80 ° C. for 3 hours. After cooling to room temperature and adding 300 mL of ether, 300 mL of water was added. The organic layer was washed with a formic acid aqueous solution, a saturated potassium carbonate aqueous solution, and a saturated saline solution, dried over magnesium sulfate, concentrated under reduced pressure using an evaporator, and distilled under reduced pressure to obtain 59.3 g of monomer 3.

The monomer 4 was obtained by the reaction of the compound (22) with methacrylic acid chloride using the same method. Further, by replacing dicyclopentadiene as a raw material for the synthesis of the compound (21) with furan, an oxygen-bridged compound (25) was obtained, and the monomer 5 was obtained by using the same method as described above.

[0124]

Embedded image

[Evaluation Example] Measurement of Polymer Permeability 1 g of the obtained polymer was sufficiently dissolved in 20 g of propylene glycol monomethyl ether acetate (PGMEA) and filtered with a 0.2 μm filter to prepare a polymer solution. . As a polymer for a comparative example, a molecular weight of 10,
A polymer in which 30% of the hydroxyl groups of a monodisperse polyhydroxystyrene having a dispersity (Mw / Mn) of 1.1 were substituted with a tetrahydropyranyl group was prepared. Similarly, polymethyl methacrylate having a molecular weight of 15,000 and a dispersity of 1.7 was used as Comparative Polymer 2 and a novolak polymer having a meta / para ratio of 40/60 and having a molecular weight of 9,000 and a dispersity of 2.5 was used as a Comparative Polymer. 3, and a polymer solution was prepared in the same manner as described above.

When the polymer solution was MgF_TwoSpin coating on the substrate
100 ° C using a hot plate
Baked for 90 seconds to form a 100 nm thick polymer film
gF _TwoIt was created on a substrate. Place this substrate on a vacuum ultraviolet photometer
(VUV-200S, manufactured by JASCO) and 248n
m, the transmittance at 193 nm and 157 nm were measured.
Was. From the measurement results shown in Table 1, the polymer compound of the present invention was
The resist material used was F _Two(157 nm)
It has been found that sufficient transparency can be ensured even if it is used.

[0127]

[Table 1]

Resist Preparation and Exposure 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, DUV-3
0 (manufactured by Brewer Science) with a thickness of 55 nm was spin-coated with a resist solution obtained on a silicon wafer, and then coated on a hot plate using a hot plate.
Bake at 00 ° C for 90 seconds to make resist thickness 200n
m. This F ₂ laser (Risotekku, Inc.,
VUVES) while changing the exposure amount, baking immediately at 120 ° C. for 90 seconds after the exposure, and developing with a 2.38% aqueous solution of tetramethylammonium hydroxide for 60 seconds. Seeking a relationship. The sensitivity of the resist was determined by setting the exposure amount at which the film thickness became 0 as Eth. Table 2 shows the results.

As a result of the VUVES exposure, it was found that the resist material using the polymer compound of the present invention decreased in film thickness with an increase in the amount of exposure, and exhibited characteristics of a positive resist.

[0130]

[Table 2]

[0131]

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──────────────────────────────────────────────────続 き 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 (72) Inventor Yuji Harada Niigata 28-1 Nishifukushima, Kushiro-mura, Nakakushiki-gun, Shinagawa Prefecture Shin-Etsu Chemical Co., Ltd. Materials Technology Research Laboratory (72) Inventor Jun Hatakeyama 28-1 Nishifukushima, Oku-ku, Nakakushiro-gun, Niigata Prefecture Shin-Etsu Chemical Co., Ltd. 28-1 Nishifukushima Shin-Etsu Chemical Co., Ltd.New Functional Materials Technology Laboratory (72) Inventor Masaru Sasako Okamon, Kadoma-shi, Osaka 1006 Shin (72) Inventor Masataka Endo 1006 Kadoma Kadoma, Kadoma City, Osaka (72) Inventor Shinji Kishimura 1006 Odaka Kadoma, Kadoma City, Osaka (72) Inventor Mitsutaka Otani 2805 Imafukudaidai, Kawagoe-shi, Saitama Central Glass Co., Ltd. Chemical Research Laboratory (72) Inventor Satoru Miyazawa 2805, Imafuku Nakadai, Kawagoe City, Saitama Prefecture Central Glass Co., Ltd. Chemical Laboratory (72) Kentaro Tsutsumi 2805, Imafuku Nakadai, Kawagoe City, Saitama Prefecture Central Kazuhiko Maeda (72) Inventor Kazuhiko Maeda 3-7-1, Kandanishikicho, Chiyoda-ku, Tokyo F-term within Central Glass Corporation (reference) 2H025 AA01 AA09 AB16 AC04 AC08 AD03 BE00 BE10 BG00 CB08 CB14 CB25 CB41 CB55 CB56 CC03 FA17 4J032 BA02 BA07 BB01 BB03 CA32 CA34 CB01 CB03 CC03 4J100 AL08P AL08Q AL08R BB07P BB17P BB18P BC03Q BC08P BC09Q BC12P BC53P BC53R

Claims (9)

[Claims] A weight average molecular weight of from 1,000 to 50, containing a group represented by the following general formula (1):
000 high molecular compounds. Embedded image (Wherein, R ^{1 to} R ³ 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. R ² and R ³ are It may form a ring, in which case it represents an alkylene group having 1 to 20 carbon atoms which may contain a hetero atom such as oxygen, sulfur, nitrogen, etc. R ⁴ and R ⁵ are a hydrogen atom or a fluorine atom.
⁶ and R ⁷ 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 ⁶ and R ⁷ is one or more Containing a fluorine atom. R ⁶ and R ⁷ may form a ring, in which case they represent a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms or a fluorinated alkylene group. a is 0 or 1. ) 2. The polymer compound according to claim 1, comprising a group represented by the following general formula (1a). Embedded image (Wherein, R ^{1 to} R ³ are a hydrogen atom, a fluorine atom, or a linear, branched or cyclic alkyl group or a fluorinated alkyl group having 1 to 20 carbon atoms. R ² and R ³ are A ring may be formed, and in that case, it represents an alkylene group having 1 to 20 carbon atoms which may contain a hetero atom such as oxygen, sulfur, nitrogen, etc. a is 0 or 1. b is an integer of 1 to 4. Is.) 3. The polymer compound according to claim 1, having a partial structure represented by any of the following general formulas (2-1) to (2-5). Embedded image (In the formula, R ⁰ represents a group represented by the formula (1) in claim 1 or the formula (1a) in claim 2. R ^{8 to} R ¹⁰ represent a hydrogen atom, a fluorine atom, or a C 1 to C 1 atom. A linear, branched or cyclic alkyl group or a fluorinated alkyl group of 20. R ¹¹ represents a methylene group, an oxygen atom or a sulfur atom, R ¹² and R ¹³ represent a hydrogen atom, a methyl group, Or CH
₂ CO ₂ R ¹⁵ is shown. R ¹⁵ is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, or a substituted alkyl group. R ¹⁴ is a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms or a fluorinated alkylene group. c is 0 or 1. ) 4. A resist material comprising the polymer compound according to claim 1. 5. A chemically amplified positive electrode comprising (A) the polymer compound according to any one of claims 1 to 3, (B) an organic solvent, and (C) an acid generator. Mold resist material. 6. The resist material according to claim 5, further comprising a basic compound. 7. The resist material according to claim 5, further comprising a dissolution inhibitor. 8. A step of (1) applying the resist material according to claim 4 on a substrate; and (2)
Next, after the heat treatment, a wavelength of 100 to
A pattern forming method, comprising: a step of exposing with a 180 nm band or a high energy ray of 1 to 30 nm band; and (3) a step of performing a heat treatment as necessary and then developing with a developer. 9. The method according to claim 1, wherein the high energy beam is an F ₂ laser,
9. The pattern forming method according to claim 8, wherein the pattern is r ₂ laser or soft X-ray.