JP2002249520A - Polymer compound, resist material and pattern forming method - Google Patents

Abstract

(57) [Summary] (With correction) [Solution] A polymer compound having a group represented by (1). (R ¹ is a fluorine atom or a fluorinated alkyl group, R ² is a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. R ³ and R ⁴ are a hydrogen atom, a fluorine atom, or a carbon number. A linear, branched or cyclic alkyl group or a fluorinated alkyl group having 1 to 20. R ³ and R ⁴ may form a ring, in which case, the linear or branched alkyl group has 1 to 20 carbon atoms, respectively. A or b is an integer of 0 to 2; c is an integer of 1 to 3; a + b + c = 3; k is an integer of 1 to 5; It is an integer of 0 to 4 and k + k '= 5.) [Effect] The resist material is excellent in sensitivity to high energy rays, particularly those having a wavelength of 170 nm or less, and plasma etching resistance is improved by introducing a fluorine-containing aromatic ring. Improve and at the same time excel Having resolution.

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, 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.

[0003] The background of the rapid progress of 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 particularly popular resist material in deep ultraviolet lithography (Japanese Patent Publication No. 2-27660, Japanese Patent Application Laid-Open No. Sho 63-63). -2782
No. 9, etc.). 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
Starting from the micron process, the 0.25 micron rule is being applied, and now the 0.18 micron rule is being applied to mass production. In addition, studies on the 0.15 micron rule have begun, and the pace of miniaturization is accelerating increasingly.

In the case of ArF (193 nm), it is expected that the design rule will be reduced to 0.13 μm or less. Therefore, it cannot be used as a base resin for a resist. Therefore, in order to ensure transparency and required dry etching resistance, acrylic and cycloolefin-based alicyclic resins have been studied (Japanese Patent Application Laid-Open No. 9-73173,
JP-A-10-10739, JP-A-9-230595, WO97 / 33198).

For F ₂ (157 nm), 0.10 μm
m or less is expected, but it is increasingly difficult to ensure transparency, and acrylic resins, which are base polymers for ArF, do not transmit light at all, and cycloolefin-based polymers 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.

[0006] 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
A novel polymer compound useful as a base polymer of a chemically amplified resist material, and a resist material containing the same and a pattern forming method using the same. Aim.

[0007]

Means for Solving the Problems and Embodiments of the Invention The present inventors have conducted intensive studies in order to achieve the above object, and as a result, found that an ester group having a fluorine-containing aromatic ring in an acid-eliminable unit in a base polymer. It has been found that a resist material having transparency and dry etching resistance, particularly a chemically amplified resist material, can be obtained without impairing the acid desorbing ability by introducing the compound, thereby leading to the present invention.

That is, the present invention provides the following polymer compound, resist material and pattern forming method. [I] A polymer compound having a group represented by the following general formula (1).

Embedded image (Wherein, R ¹ is a fluorine atom or a fluorinated alkyl group, and R ² is a hydrogen atom or a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms. R ³ , R
⁴ 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 ³ and R ⁴ may form a ring, in which case they each represent a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms or a fluorinated alkylene group. a and b are integers of 0 to 2, c is an integer of 1 to 3, and a + b + c = 3. k is an integer of 1 to 5, k 'is an integer of 0 to 4, and k + k' = 5. [II] The polymer compound according to claim 1, which has any one of the repeating units represented by the following general formulas (2-1) to (2-5).

Embedded image (Wherein, R ¹ is a fluorine atom or a fluorinated alkyl group, and R ² is a hydrogen atom or a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms. R ³ , R
⁴ 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 ³ and R ⁴ may form a ring, in which case they each represent a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms or a fluorinated alkylene group. R ^{5 to} 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. R ⁸ and R ⁹ are a hydrogen atom, a methyl group, or CH ₂ CO ₂ R ¹¹
Is shown. R ¹¹ is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, or a substituted alkyl group. R
¹⁰ is a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms or a fluorinated alkylene group.
a and b are integers of 0 to 2; c is an integer of 1 to 3;
b + c = 3. k is an integer of 1 to 5, k 'is an integer of 0 to 4, and k + k' = 5. m is 0 or 1. [III] A resist material comprising the polymer compound described in [I] or [II]. [IV] A chemically amplified positive resist composition comprising (A) the polymer compound according to [I] or [II], (B) an organic solvent, and (C) an acid generator. [V] The resist material according to [IV], further comprising a basic compound. [VI] [IV] or [V] further containing a dissolution inhibitor
The resist material as described. [VII] (1) Any one of [III] to [VI]
Step of applying the resist material according to the paragraph on the substrate,
(2) After the heat treatment, the wavelength 1
A pattern forming method comprising: a step of exposing with a high energy ray in a band of 00 to 180 nm or a band of 1 to 30 nm; and (3) a step of performing a heat treatment as necessary and then developing with a developing solution. . [VIII] The pattern forming method according to [VII], wherein the high energy ray is an F ₂ excimer laser, an Ar ₂ excimer laser, or a soft X-ray.

According to the study of the present inventor, one of the methods for improving the transmittance around 157 nm is considered to be a method of reducing 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, the base polymer becomes remarkable that negative upon exposure to high-energy light such as F ₂ laser, the practical application of the resist was found to be difficult. On the other hand, it has been found that a polymer in which fluorine is introduced into a polymer compound containing an aliphatic cyclic compound derived from an acrylic resin or a norbornene derivative in the main chain can suppress the absorption and solve the problem of negative conversion. . In particular,
Esters having a fluorinated aromatic ring introduced into the side chain of the present invention have improved transmittance at around 157 nm and dry etching resistance, and also have excellent acid desorption properties.

Hereinafter, the present invention will be described in more detail. The polymer compound according to the present invention has a group represented by the following general formula (1), and particularly has any one of the repeating units represented by the following general formulas (2-1) to (2-5). Things.

[0011]

Embedded image

Here, R¹Is a fluorine atom or fluorinated
Alkyl group, R²Is a hydrogen atom or carbon number 1
20 linear, branched or cyclic alkyl groups
You. R ³, R⁴Is a hydrogen atom, a fluorine atom, or a carbon atom 1
-20 linear, branched or cyclic alkyl groups or
It is a fluorinated alkyl group. R³, R⁴Forms a ring
And in that case, each of them may have a carbon number of 1-20.
Chain, branched or cyclic alkylene group or fluorinated
Represents an alkylene group. R⁵~ R⁷Is a hydrogen atom,
A nitrogen atom, or a straight-chain, branched or branched carbon atom having 1 to 20 carbon atoms
Is a cyclic alkyl group or a fluorinated alkyl group
You. R⁸And R⁹Is a hydrogen atom, a methyl group, or CH₂C
O₂R¹¹Is shown. R¹¹Is a linear chain having 1 to 20 carbon atoms,
Branched or cyclic alkyl group or substituted alkyl group
It is. R¹⁰Is linear or branched having 1 to 20 carbon atoms
Or cyclic alkylene group or fluorinated alkylene
Group. a and b are integers of 0 to 2; c is an integer of 1 to 3
And a + b + c = 3. k is an integer of 1 to 5, k '
Is an integer of 0 to 4 and k + k ′ = 5. m is 0 or
Is 1.

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-
An octyl group can be exemplified, 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-described alkyl group has been substituted with fluorine atoms, and is a trifluoromethyl group, a 2,2,2-trifluoroethyl group,
3,3-trifluoropropyl group, 1,1,1,3,
3,3-hexafluoroisopropyl group, 1,1,2,2
2,3,3,3-heptafluoropropyl group and the like. Examples of the substituted alkyl group include the above-mentioned fluorinated alkyl group. Furthermore, carbon number 1
20 alkylene groups, fluorinated alkylene group,
The above-mentioned alkyl groups having 1 to 20 carbon atoms and those obtained by removing one hydrogen atom from a fluorinated alkyl group are exemplified, and those having 1 to 12 carbon atoms, particularly those having 1 to 10 carbon atoms, are preferred.

Specific examples of the substituent represented by the general formula (1) include the following.

Embedded image

The polymer compound of the present invention has the formula (2-
Although repeating units 1) to (2-5) alone have acid elimination properties, the following repeating units (3-1) to (3-5) may be introduced from the viewpoint of further improving acid elimination properties. it can.

[0016]

Embedded image

In the formula, R ^{5 to} R ¹⁰ and m are the same as described above, and R represents an acid labile group. Formulas (3-1) to (3-5)
The acid labile group in the above is variously selected, and is particularly preferably a group represented by the following formulas (4) to (6).

[0018]

Embedded image

In the formula (4), R ¹² has 4 to 2 carbon atoms.
0, preferably a tertiary alkyl group having 4 to 15 carbon atoms, wherein each alkyl group is represented by a trialkylsilyl group having 1 to 6 carbon atoms, an oxoalkyl group having 4 to 20 carbon atoms, or the above general formula (5). 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, 2-methyl-2-adamantyl group, and the like. Specific examples of the trialkylsilyl group include a trimethylsilyl group, a triethylsilyl group, and a dimethyl-ter
t-butylsilyl group and the like; specific examples of the oxoalkyl group include a 3-oxocyclohexyl group, a 4-methyl-2-oxooxan-4-yl group, and a 5-methyl-
And a 2-oxooxolan-5-yl group. d
Is an integer of 0 to 6.

R ¹³ and R ¹⁴ in the formula (5) are a hydrogen atom or a linear group having 1 to 18, preferably 1 to 10 carbon atoms;
A branched or cyclic alkyl group, specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, cyclopentyl group, cyclohexyl group, 2-ethylhexyl And an n-octyl group. R ¹⁵ has 1 carbon atom
Represents a monovalent hydrocarbon group which may have a hetero atom such as an oxygen atom such as 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.

[0021]

Embedded image

R ¹³ and R ¹⁴ , R ¹³ and R ¹⁵ , R ¹⁴
And R ¹⁵ may form a ring, and when forming a ring, R ¹³ , R ¹⁴ and R ¹⁵ each have 1 to 18 carbon atoms;
It preferably represents 1 to 10 linear or branched alkylene groups.

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.

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

[0025]

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 ¹⁶ , R ¹⁷ ,
R ¹⁸ is a monovalent hydrocarbon group such as a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and oxygen, sulfur,
It may contain a hetero atom such as nitrogen or fluorine, and R ¹⁶
And R ¹⁷ , R ¹⁶ and R ¹⁸ , and R ¹⁷ and R ¹⁸ 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,
Ethylnorbonyl group, 1-methylcyclohexyl group, 1
-Ethylcyclopentyl group, 2- (2-methyl) adamantyl group, 2- (2-ethyl) adamantyl group, ter
A t-amyl group and the like can be mentioned.

Further, specific examples of the tertiary alkyl group of the formula (6) include tertiary alkyl groups of the following formulas (7) to (22).

[0030]

Embedded image

Here, R ¹⁹ is a straight-chain having 1 to 6 carbon atoms,
Shows a branched or cyclic alkyl group, specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, n-pentyl group, n-hexyl group, cyclopropyl group, Examples thereof include a cyclopropylmethyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. R ²⁰ 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 ²¹ and R ^{22 each} represent a hydrogen atom, having 1 to 6 carbon atoms.
A monovalent hydrocarbon group optionally containing a heteroatom, having 1 carbon atom
And represents a monovalent hydrocarbon group which may have up to 6 hetero atoms. Examples of the hetero atom include an oxygen atom, a sulfur atom, and a nitrogen atom. —OH, —OR ′ (R ′ is an alkyl group, the same applies hereinafter), —O—, —S—, and —S (（O)
_{-, - NH 2, -NHR '} , - NR' 2, -NH -, -
It can be contained or intervened as NR'-.
Examples of R ²¹ and R ²² include a hydrogen atom, an alkyl group, a hydroxyalkyl group, an alkoxyalkyl group, an alkoxy group, and an alkoxyalkoxy group.
These may be linear, branched or cyclic. Specifically, methyl, hydroxymethyl, ethyl, hydroxyethyl, propyl, isopropyl, n-
Examples thereof include a butyl group, sec-butyl group, n-pentyl group, n-hexyl group, methoxy group, methoxymethoxy group, ethoxy group, tert-butoxy group and the like.

The polymer compound of the present invention may further comprise the following repeating unit (2)
3) to (59) can be introduced.

[0034]

Embedded image

[0035]

Embedded image

[0036]

Embedded image (Wherein, R ⁵ , R ⁶ , and R ⁷ 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. It is an integer of 4. Me is a methyl group.)

When synthesizing the polymer compound of the present invention, a monomer having a carbon-carbon double bond having a group represented by the above formula (1), particularly a monomer giving units (2-1) to (2-5) And, if necessary, mixing a solvent to give a unit of (3-1) to (3-5) and a monomer to give a unit of (23) to (59) with a solvent, adding a catalyst, and optionally heating. Alternatively, the polymerization reaction is performed while cooling. The polymerization reaction depends on the type of initiator (or catalyst), the method of initiation (light, heat, radiation, plasma, etc.), and the polymerization conditions (temperature, pressure, concentration,
Solvent and additives). In the polymerization of the polymer compound of the present invention, radical polymerization in which polymerization is initiated by a radical such as AIBN, ionic polymerization (anionic polymerization) using a catalyst such as alkyllithium, and the like are general. These polymerizations can be carried out according to a conventional method.

The radical polymerization initiator is not particularly limited. For 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 tert-butyl peroxy laurate, and water-soluble initiators such as persulfates such as potassium persulfate; and peroxides such as potassium persulfate and hydrogen peroxide and sodium sulfite. Redox initiators comprising combinations of such reducing agents are 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 ones are ethyl acetate,
Ester type such as n-butyl acetate, ketone type such as acetone, methyl ethyl ketone, methyl isobutyl ketone,
Aliphatic or aromatic hydrocarbons such as toluene, xylene and cyclohexane, alcohols such as isopropyl alcohol and ethylene glycol monomethyl ether, and ethers such as diethyl ether, dioxane and tetrahydrofuran can be used. These solvents can be used alone or in combination of two or more. Further, 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 an 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 weight average molecular weight of the above-mentioned high molecular compound is 1,000 to 1,000,000, particularly 2,000 to 1
Desirably, 100,000.

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 materials, 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) A chemically amplified positive resist composition comprising the polymer compound (base resin), (B) an organic solvent, and (C) an acid generator. In this case, a basic compound (D) and a dissolution inhibitor (E) may be further added to these resist materials.

Here, the organic solvent of the component (B) used in the present invention may be any organic solvent in which the base resin, the acid generator, and other additives can be dissolved.
Examples of such an organic solvent include ketones such as cyclohexanone and methyl-2-n-amyl ketone;
Alcohols such as methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol Ethers such as monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, and 3-ethoxypropionic acid Ethyl, tert-acetic acid
Esters such as -butyl, tert-butyl propionate and propylene glycol monotert-butyl ether acetate.

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 hepta Fluorobutyrate, ethylheptafluorobutyl acetate, ethylhexafluoroglutarylmethyl, ethyl-3-hydroxy-4,4,4-trifluorobutyrate, ethyl-2-methyl-4,4,4-trifluoroacetoacetate , 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, S-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, methyl trifluoroacetoacetate, 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-dioxananionic) 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,
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, 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 combination 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 are used. It is preferably used.

The acid generator of the component (C) includes an onium salt of the following general formula (60), a diazomethane derivative of the formula (61), a glyoxime derivative of the formula (62), 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. (R ²³ ) _j M ⁺ K ⁻ (60) (wherein, R ²³ is a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, or carbon Represents an aralkyl group of the formulas 7 to 12,
M ⁺ represents iodonium or sulfonium, K ⁻ represents a non-nucleophilic counter ion, and j is 2 or 3. )

As the alkyl group for R ²³ , a methyl group,
Examples include 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-te
an alkoxyphenyl group such as an rt-butoxyphenyl group, an m-tert-butoxyphenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group,
Ethylphenyl group, 4-tert-butylphenyl group,
Examples thereof include an alkylphenyl group such as a 4-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, 1,1,1-trifluoroethane sulfonate, fluoroalkyl sulfonate such as nonafluorobutane sulfonate, tosylate,
Examples include arylsulfonates such as benzenesulfonate, 4-fluorobenzenesulfonate, 1,2,3,4,5-pentafluorobenzenesulfonate, and alkylsulfonates such as mesylate and butanesulfonate.

[0050]

Embedded image (However, R ²⁴ and R ²⁵ are a linear, branched or cyclic alkyl group or halogenated alkyl group having 1 to 12 carbon atoms,
It represents an aryl group having 6 to 12 carbon atoms, an aryl halide group or an aralkyl group having 7 to 12 carbon atoms. )

Examples of the alkyl group of R ²⁴ and R ²⁵ 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 adamantyl groups. Examples of the halogenated alkyl group include a trifluoromethyl group, a 1,1,1-trifluoroethyl group, a 1,1,1-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.

[0052]

Embedded image(However, in the formula, R²⁶, R²⁷, R²⁸Is carbon number 1 to 1
2 linear, branched or cyclic alkyl groups or halogens
Alkyl group, aryl group having 6 to 12 carbon atoms or halogen
An aryl group or an aralkyl group having 7 to 12 carbon atoms
Show. R²⁷, R ²⁸Combine with each other to form a ring structure
When forming a cyclic structure, R ²⁷, R²⁸
Is a linear or branched alkylene having 1 to 6 carbon atoms, respectively.
Represents a group. )

As the alkyl group, halogenated alkyl group, aryl group, halogenated aryl group and aralkyl group of R ²⁶ , R ²⁷ and R ²⁸ , the same groups as described for R ²⁴ and R ²⁵ can be mentioned. In addition, as an alkylene group of R ²⁷ and R ^28, a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group and the like can be mentioned.

Specific examples of the acid generator include diphenyliodonium trifluoromethanesulfonate, (p-tert-butoxyphenyl) phenyliodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, and p-toluenesulfonic acid (p-toluenesulfonate). -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],
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- (camphorsulfonyl)
Glyoxime derivatives such as -α-dimethylglyoxime,
2- (cyclohexylcarbonyl-2- (p-toluenesulfonyl) propane, 2-isopropylcarbonyl-
Β-ketosulfone derivatives such as 2- (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-
Sulfonate derivatives such as tris (p-toluenesulfonyloxy) benzene, phthalimido-yl-triflate, phthalimido-yl-tosylate, 5-norbornene-2,3-dicarboximido-yl-triflate, 5-norbornene- Imido-ylsulfonate derivatives such as 2,3-dicarboximido-yl-tosylate and 5-norbornene-2,3-dicarboximido-yl-N-butyl trifluorosulfonate; Phenylsulfonium, trifluoromethanesulfonic acid (p-te
rt-butoxyphenyl) diphenylsulfonium, tris (p-tert-butoxyphenyl) sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, p-toluenesulfonate (p-tert-butoxyphenyl) diphenylsulfonium, p- Tris toluenesulfonic acid (p-tert
-Butoxyphenyl) sulfonium, trinaphthylsulfonium trifluoromethanesulfonate, cyclohexylmethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, (2-norbonyl) methyl (2-oxocyclohexyl) sulfonium, 1,2 ′ Onium salts such as naphthylcarbonylmethyltetrahydrothiophenium triflate, bis (benzenesulfonyl) diazomethane,
Bis (p-toluenesulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (n
Diazomethane derivatives such as -butylsulfonyl) diazomethane, bis (isobutylsulfonyl) diazomethane, bis (sec-butylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, and bis (tert-butylsulfonyl) diazomethane And glyoxime derivatives such as bis-O- (p-toluenesulfonyl) -α-dimethylglyoxime and bis-O- (n-butanesulfonyl) -α-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. 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 (parts by weight, the same applies hereinafter) of the base resin.
The sensitivity and the resolution may be poor, and if it is more than 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 rate of diffusion of the acid generated from the acid generator 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 (Japanese Patent Laid-Open Nos. 5-232706, 5-249683, 5
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 carboxy-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 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 mixed amines include, for example, 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-methylaniline. Aniline, ethylaniline, propylaniline, trimethylaniline, 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, 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-pyridone, 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,
Phenazine derivatives, 1,10-phenanthroline derivatives, adenine derivatives, adenosine derivatives, guanine derivatives, guanosine derivatives, uracil derivatives, uridine derivatives and the like are exemplified.

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, acetamido, N-methylacetamido,
N, N-dimethylacetamide, propionamide, benzamide and the like are exemplified.

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

Further, the following general formulas (63) and (64)
And a basic compound represented by the formula:

[0070]

Embedded image (Wherein, R ^{29 to} R ³¹ , R ³⁵ , and R ³⁶ are each independently a linear, branched, or cyclic alkylene group having 1 to 20 carbon atoms, R ^{32 to} R ³⁴ , R ³⁷ , and R ^38. Represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an amino group,
^R32 and ^R33 , ^R32 and ^R34 , ^R33 and ^R34 , R
³² and R ³³ and R ³⁴ , and R ³⁷ and R ³⁸ may be respectively bonded to form a ring. m, n and o are each 0 to 2
It is an integer of 0. However, when m, n, o = 0, R ²⁹
To R ³¹ , R ³⁵ and R ³⁶ do not contain a hydrogen atom. )

Here, R ^{29 to} R ³¹ , R ³⁵ and R ³⁶
The alkylene group has 1 to 20, preferably 1 to 10, more preferably 1 to 8 carbon atoms. Specifically, methylene group, ethylene group, n-propylene group, isopropylene group, n -Butylene group, isobutylene group, n
-A pentylene group, an isopentylene group, a hexylene group, a nonylene group, a decylene group, a cyclopentylene group, a cyclohexylene group and the like.

The alkyl group of R ^{32 to} R ³⁴ , R ³⁷ and R ³⁸ has 1 to 20 carbon atoms, preferably 1 to 20 carbon atoms.
8, more preferably 1 to 6, which may be linear, branched or cyclic. Specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, hexyl, nonyl, decyl, dodecyl Group, tridecyl group, cyclopentyl group, cyclohexyl group and the like.

R ³² and R ³³ , R ³² and R ³⁴ , R ³³
And when R ³⁴ , R ^{32 to} R ³⁴ , R ³⁷ and R ³⁸ form a ring, the ring has from 1 to 20, more preferably from 1 to 8, still more preferably from 1 to 6, and May have a branched alkyl group having 1 to 6 carbon atoms, particularly 1 to 4 carbon atoms. m, n, and o are each an integer of 0 to 20, more preferably 1 to 10, and further preferably an integer of 1 to 8.

Specific examples of the compounds of the above formulas (63) and (64) include tris {2- (methoxymethoxy) ethyl} amine, tris {2- (methoxyethoxy) ethyl} amine, and tris [2-{( 2-methoxyethoxy)
Methoxy {ethyl} amine, tris {2- (2-methoxyethoxy) ethyl} amine, tris {2- (1-methoxyethoxy) ethyl} amine, tris {2- (1-ethoxyethoxy) ethyl} amine, tris 2- (1-
Ethoxypropoxy) ethyl} amine, tris [2-
{(2-hydroxyethoxy) ethoxy} ethyl] 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, 1,4,1
0,13-tetraoxa-7,16-diazabicyclooctadecane, 1-aza-12-crown-4, 1-aza-15-crown-5, 1-aza-18-crown-6
And the like.

Among the above basic compounds, tertiary amines, aniline derivatives, pyrrolidine derivatives, pyridine derivatives, quinoline derivatives, amino acid derivatives, nitrogen-containing compounds having a hydroxyl group, nitrogen-containing compounds having a hydroxyphenyl group, alcoholic compounds Nitrogen-containing compounds, amide derivatives, imide derivatives, tris {2- (methoxymethoxy) ethyl} amine, tris {2- (2-methoxyethoxy) ethyl} amine, tris [2-{(2-methoxyethoxy) methyl} ethyl Amine, 1-aza-15-crown-5 and the like are preferred.

The 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 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.

Next, as the dissolution inhibitor of the component (E),
A compound having a molecular weight of 3,000 or less, whose solubility in an alkali developing solution is changed by the action of an acid, particularly a part or all of a low-molecular-weight phenol or carboxylic acid derivative of 2,500 or less is substituted with an acid-labile substituent. The following compounds can be mentioned. 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 phenol or carboxylic acid derivatives having a molecular weight of 2,500 or less include 4,4 '-(1-methylethylidene) bisphenol and [1,1'-biphenyl-4,4'-diol] 2,2'-diol. Methylene bis [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'-diol [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).

Examples of preferably used dissolution inhibitors include 3,3 ′, 5,5′-tetrafluoro [(1,1 ′
-Biphenyl) -4,4'-di-t-butoxycarbonyl], 4,4 '-[2,2,2-trifluoro-1-
(Trifluoromethyl) ethylidene] bisphenol-
4,4'-di-t-butoxycarbonyl, bis (4-
(2′-tetrahydropyranyloxy) phenyl) methane, bis (4- (2′-tetrahydrofuranyloxy)
Phenyl) methane, bis (4-tert-butoxyphenyloxy) 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′-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, tert-butyl 4,4-bis (4 '-(2'-tetrahydropyranyloxy) phenyl) valerate, 4,4
-Bis (4 '-(2'-tetrahydrofuranyloxy)
Tert-butyl phenyl) valerate, tert-butyl 4,4-bis (4′-tert-butoxyphenyl) valerate
-Butyl, tert-butyl 4,4-bis (4-tert-butoxycarbonyloxyphenyl) valerate, 4,
Tert-butyl 4-bis (4′-tert-butoxycarbonylmethyloxyphenyl) valerate, tert-butyl 4,4-bis (4 ′-(1′-ethoxyethoxy) phenyl) valerate, 4,4-bis (4 '-(1'-ethoxypropyloxy) phenyl) tert-butyl valerate, tris (4- (2'-tetrahydropyranyloxy) phenyl) methane, tris (4- (2'-tetrahydrofuranyloxy) phenyl ) Methane, Tris (4-
tert-butoxyphenyl) methane, tris (4-t
tert-butoxycarbonyloxyphenyl) methane,
Tris (4-tert-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-t-butyl 2-trifluoromethylbenzenecarboxylate, t-butyl 2-trifluoromethylcyclohexanecarboxylate Esters, decahydronaphthalene-2,6-dicarboxylic acid-t-butyl ester, cholic acid-t-butyl ester, deoxycholic acid-t-butyl ester, adamantanecarboxylic acid-t-butyl ester, adamantane acetate-t-butyl ester Ester, [1,1′-bicyclohexyl-3,3 ′, 4,4′-tetracarboxylic acid tetra-t
-Butyl ester].

The amount of the dissolution inhibitor added to the resist composition of the present invention is 20 parts or less, preferably 15 parts or less, based on 100 parts of the solids in the resist composition. 2
If the amount is more than 0 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, other than the above components, a surfactant which is commonly used to improve coating properties. 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 impaired.

The surfactant is preferably a nonionic surfactant, and is preferably a perfluoroalkylpolyoxyethylene ethanol, a fluorinated alkyl ester, a perfluoroalkylamine oxide, a perfluoroalkylEO adduct, or a fluorine-containing organosiloxane-based surfactant. 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.) and the like. Preferably, Florad “FC-4”
30 "(manufactured by Sumitomo 3M Limited)," X-70-09 "
3 "(manufactured by Shin-Etsu Chemical Co., Ltd.).

A pattern can be formed using the resist material of the present invention by employing a known lithography technique. For example, the film thickness is 0.1 to 1.0 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
Prebake at 50 ° C. for 30 seconds to 5 minutes. Next, a mask for forming a target pattern is held over the above 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 from 60 to 15
0 ° C, 10 seconds to 5 minutes, preferably 80 to 130 ° C, 3
Post-exposure bake (PEB) for 0 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), immersing 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 dle method or a spray method. In addition, the material of the present invention is a deep ultraviolet ray or excimer laser of 254 to 120 nm, especially among high energy rays,
In particular, 193nm of ArF, _F of 157nm 2, 146n
m Kr ₂ , 134 nm KrAr, 121 nm Ar
It is most suitable for fine patterning by excimer laser such as No. ₂ , X-ray and electron beam. In addition, when the above range is out of the upper limit and the lower limit, a desired pattern may not be obtained.

[0084]

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

[0085]

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 2-pentafluorophenyl-isopropyl methacrylate and the following monomer 1 (1: 1) In a 500 ml flask, 12.7 g of 2-pentafluorophenyl-isopropyl methacrylate and monomer 1 were added. After 7.3 g was dissolved in 100 ml of toluene and oxygen in the system was sufficiently removed, 0.57 g of an AIBN 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 mixture was poured into methanol to precipitate the resulting polymer.
Was. Further dissolve the obtained polymer in tetrahydrofuran
And pouring into 5 L of methanol to precipitate the polymer.
After repeating the cropping twice, the polymer was separated and dried.
15.2 g of the white polymer thus obtained was light-diffusing.
The weight average molecular weight is 8,900 g / mol by a random method.
According to the GPC elution curve, the degree of dispersion (= Mw / Mn) was 1.
It was confirmed that the polymer was No. 77 polymer. Also, ¹H-N
From the measurement of MR, it was found that methacrylic acid 2-pe
N-fluorophenyl-isopropyl and monomer 1
It was found at 7:53.

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Synthesis Example 2 Copolymerization of {1,1-bis (pentafluorophenyl) -2-ethyl} methacrylate with Monomer 1 (1: 1) In a 500 ml flask, {1,1-bis} methacrylate was used. (Pentafluorophenyl) -2-ethyl−２14.5 g
And 5.5 g of Monomer 1 were dissolved in 100 ml of toluene, and oxygen in the system was sufficiently removed.
0.43 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 methanol to precipitate the resulting polymer.
Was. Further dissolve the obtained polymer in tetrahydrofuran
And pouring into 5 L of methanol to precipitate the polymer.
After repeating the cropping twice, the polymer was separated and dried.
14.6 g of the white polymer thus obtained was light scattered.
According to the random method, the weight average molecular weight is 9,200 g / mol.
According to the GPC elution curve, the degree of dispersion (= Mw / Mn) was 1.
It was confirmed that the polymer was No. 73. Also, ¹H-N
From the measurement of MR, methacrylic acid 本 1,
1-bis (pentafluorophenyl) -2-ethyl} and
It was found that monomer 1 was contained at 46:54.
Was.

[Synthesis Example 3] 2- (p-trifluoromethylphenyl) -isopropyl methacrylate and monomer 1
(1: 1) In a 500 ml flask, 12.3 g of 2- (p-trifluoromethylphenyl) -isopropyl methacrylate and 7.7 g of monomer 1 were dissolved in 100 ml of toluene, and oxygen in the system was sufficiently dissolved. After removal of the initiator AIBN
0.59 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 methanol to precipitate the resulting polymer.
Was. Further dissolve the obtained polymer in tetrahydrofuran
And pouring into 5 L of methanol to precipitate the polymer.
After repeating the cropping twice, the polymer was separated and dried.
14.1 g of the white polymer thus obtained was light-diffusing.
According to the random method, the weight average molecular weight is 9,500 g / mol.
According to the GPC elution curve, the degree of dispersion (= Mw / Mn) was 1.
It was confirmed that the polymer was No. 67. Also, ¹H-N
From the measurement of MR, it was found that methacrylic acid 2-
(P-trifluoromethylphenyl) -isopropyl
It was found that monomer 1 was contained at 48:52.
Was.

[Evaluation Example]Polymer transmittance measurement 1 g of the obtained polymer is mixed with propylene glycol monomethyl
Dissolves sufficiently in 20 g of ether ether (PGMEA)
And dissolve the polymer by filtration through a 0.2 μm filter.
A liquid was prepared. As a polymer for a comparative example, a molecular weight of 10,
000, polydispersity (Mw / Mn) 1.10
30% of the hydroxyl groups of the hydroxystyrene
Prepare a polymer substituted with a benzyl group, and use this for the comparative example.
It was designated as Rimmer 1. Similarly, molecular weight 15,000, dispersity
1.7 polymethyl methacrylate as a comparative polymer
2, molecular weight 9,000, meta / para ratio 40/60, dispersion
The novolak polymer having a degree of 2.5 was compared with the polymer 3 for the comparative example.
Then, a polymer solution was prepared in the same manner as described above. Poly
Solution with MgF₂Spin coating on substrate
After that, bake at 100 ° C for 90 seconds using a hot plate
And a polymer film having a thickness of 100 nm is ₂Work on board
Done. This substrate is attached to a vacuum ultraviolet photometer (manufactured by JASCO Corporation, VU
V-200S), 248 nm, 193 nm, 1
The transmittance at 57 nm was measured. Table 1 shows the measurement results.
Show.

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[Table 1]

Preparation of Resist 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 reduce resist thickness to 200n
m thickness. This was exposed to light with an F ₂ excimer laser (Lithotec, VUVES) while changing the exposure amount, and immediately after exposure, baked at 120 ° C. for 90 seconds, and then 2.3.
Development was performed for 60 seconds with an aqueous solution of 8% tetramethylammonium hydroxide to determine the relationship between the exposure amount and the residual film ratio. The sensitivity of the resist was determined by setting the exposure amount at which the film thickness became 0 as Eth.

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[Table 2]

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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 a wavelength of F ₂ (157 nm). Also, V
As a result of the UVES exposure, it was found that the film thickness was reduced as the exposure amount was increased, and exhibited characteristics of a positive resist.

──────────────────────────────────────────────────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, Nakakubijo-gun, Shinagawa Prefecture Synthetic Technology Laboratory, Shin-Etsu Chemical Co., Ltd. (72) Inventor Jun Watanabe 28-1, Nishi-Fukushima, Daisuku-ku, Kushiro-mura, Niigata Prefecture (72) Inventor Jun Hatakeyama 28-1 Nishifukushima, Nishifukushima, Niigata Prefecture, Niigata Prefecture Shinsei Chemical Industry Co., Ltd. (72) Inventor Yoshio Kawai 28-1, Nishifukushima, Nishifukushima, Niigata Prefecture (72) Inventor Masaru Sasako 1-1, Yukicho, Takatsuki-shi, Osaka (72) Inventor Masataka Endo 1-1, Yukicho, Takatsuki-shi, Osaka (72) Inventor Shinji Kishimura 1-1-1, Yukicho, Takatsuki-shi, Osaka (72) Mitsutaka Otani 2805, Imafukunakadai, Kawagoe-shi, Saitama Central Glass Chemical Co., Ltd. In the laboratory (72) Inventor Satoru Miyazawa 2805 Imafukunakadai, Kawagoe-shi, Saitama Central Research Institute of Chemical Glass Co., Ltd. (72) Inventor Kentaro Tsutsumi 2805 Imafukunakadai, Kawagoe-shi, Saitama Central Chemical Glass Co., Ltd. (72) Inventor Kazuhiko Maeda 3-7-1, Kandanishikicho, Chiyoda-ku, Tokyo F-term in Central Glass Co., Ltd. (Reference) 2H025 AA01 AA02 AA09 AC04 AC08 AD03 BE00 BE10 BG00 CB08 CB10 CB14 CB41 CC20 FA01 FA12 4J002 AA051 BG031BG08 BK001 ED058 EH148 EJ018 EJ038 EJ048 EJ058 EL068 EL088 EN027 EN037 EN047 EN067 EN077 EN107 EN117 EN127 EP017 EU027 EU037 EU047 EU057 EU077 EU117 EU127 EU137 EU147 EU227 EU237 EV216 EV237 EV246 EV266 EV296 AR306 EV327 FP206 FD206 AL208 1P AR36P BA11P BA15P BA20P BB07P BB18P BC03P BC04P BC43P CA01 JA38

Claims (8)

[Claims] 1. A polymer compound having a group represented by the following general formula (1). Embedded image (Wherein, R ¹ is a fluorine atom or a fluorinated alkyl group, and R ² is a hydrogen atom or a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms. R ³ , R
⁴ 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 ³ and R ⁴ may form a ring, in which case they each represent a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms or a fluorinated alkylene group. a and b are integers of 0 to 2, c is an integer of 1 to 3, and a + b + c = 3. k is an integer of 1 to 5, k 'is an integer of 0 to 4, and k + k' = 5. ) 2. The polymer compound according to claim 1, comprising any of the repeating units represented by the following formulas (2-1) to (2-5). Embedded image (Wherein, R ¹ is a fluorine atom or a fluorinated alkyl group, and R ² is a hydrogen atom or a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms. R ³ , R
⁴ 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 ³ and R ⁴ may form a ring, in which case they each represent a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms or a fluorinated alkylene group. R ^{5 to} 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. R ⁸ and R ⁹ are a hydrogen atom, a methyl group, or CH ₂ CO ₂ R ¹¹
Is shown. R ¹¹ is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, or a substituted alkyl group. R
¹⁰ is a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms or a fluorinated alkylene group.
a and b are integers of 0 to 2; c is an integer of 1 to 3;
b + c = 3. k is an integer of 1 to 5, k 'is an integer of 0 to 4, and k + k' = 5. m is 0 or 1. ) 3. A resist material comprising the polymer compound according to claim 1 or 2. 4. A chemically amplified positive resist composition comprising: (A) the polymer compound according to claim 1 or 2; (B) an organic solvent; and (C) an acid generator. 5. The resist material according to claim 4, further comprising a basic compound. 6. The resist material according to claim 4, further comprising a dissolution inhibitor. 7. A step of applying the resist material according to claim 3 on a substrate, and (2) a step of applying a wavelength of 100 to 1 through a photomask after a heat treatment.
A pattern forming method, comprising: a step of exposing with a high-energy ray in an 80 nm band or a 1 to 30 nm band; and (3) a step of performing heat treatment as necessary and then developing with a developer. 8. The pattern forming method according to claim 7, wherein the high energy ray is an F ₂ excimer laser, an Ar ₂ excimer laser, or a soft X-ray.