JP2001302726A - Polymeric compound, resist material and pattern-forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resist material comprising a polymeric compound bearing a group represented by general formula (1) (wherein R1, R2, R3 and R4 are each hydrogen atom, fluorine atom, a 1-20C linear, branched or cyclic alkyl group or a fluoroalkyl group; and at least one of R1, R2, R3 and R4 contains a fluorine atom). SOLUTION: The resist material is sensitive to high energy beams, excellent is sensitivity, resolution and plasma etching resistance at a wavelength of 200 nm or less, particularly 170 nm or less, and furthermore capable of suppressing progress of crosslinking. These features allow the resist material to have low absorption at an exposure wavelength of the F2 excimer laser in particular and to easily form a pattern fine and perpendicular to the substrate. The resist material is therefore suitable as a fine pattern-forming material for manufacturing a very large-scale integrated circuit.

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 to 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 rapid progress in miniaturization is an increase in NA of a projection lens, an improvement in resist performance, and a reduction in 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 major change, and the resist material for KrF excimer laser has been reduced to 0.30.
Beginning with the micron process, passing through the 0.25 micron rule, it is currently expanding to the application of the 0.18 micron rule to mass production. In addition, studies on the 0.15 micron rule have begun, and the pace of miniaturization is accelerating.

In the case of ArF (193 nm), the miniaturization of the design rule is expected to be 0.13 μm or less, but conventionally used resins such as novolak and polyvinylphenol have very strong absorption around 193 nm. Therefore, it cannot be used as a base resin for a resist. 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 becomes more and more 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.

[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
It is an object of the present invention to provide a novel polymer compound useful as a base polymer of a chemically amplified resist material having excellent transmittance in vacuum ultraviolet light such as 21 nm) and a pattern forming method using the chemically amplified resist material containing the same.

[0007]

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, by using a resin containing a fluorinated ester group as a base polymer, a transparent resin was obtained. The present inventors have found that a chemically amplified resist material having sufficient solubility and alkali solubility can be obtained, and have accomplished the present invention.

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

Embedded image (Wherein R ¹ , R ² , R ³ , and R ⁴ represent a hydrogen atom, a fluorine atom,
A linear, branched or cyclic alkyl group having 1 to 20 carbon atoms or a fluorinated alkyl group, wherein R ¹ , R ² ,
At least one of R ³ and R ⁴ contains a fluorine atom. [II] The following general formulas (2-1), (2-2), (2-
3) The polymer compound according to [I], containing any of the repeating units represented by (2-4) and (2-5).

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. R ⁸ and R ⁹ represents a hydrogen atom, a methyl group or CH ₂ CO ₂ R ^11. R ¹¹ is a linear, branched or cyclic alkyl group or substituted alkyl group having 1 to 20 carbon atoms, and R ¹⁰ is a carbon atom. Number 1-2
It is 0 linear, branched or cyclic alkylene group or fluorinated alkylene group. k is 0 or 1. R ^{1 to} R ⁴ are the same as above. [III] A resist material comprising the polymer compound according to [I] or [II]. [IV] A chemically amplified positive resist material 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 according to 1. [VII] (1) Any one of [III] to [VI]
(2) applying a chemically amplified resist material as described in (1) above on a substrate, (2) then exposing with a high energy beam or an electron beam having a wavelength of 300 nm or less through a photomask after a heat treatment, and (3) necessary After heat treatment according to
Developing using a developing solution.

As a method for improving the transmittance near 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 it greatly contributes to the improvement of the rate. In fact, a polymer in which fluorine was introduced into the aromatic ring of polyvinylphenol was able to obtain practically close transmittance. However, it was found that this base polymer became more negative due to irradiation with high-energy light such as an F ₂ laser, 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 able to suppress the absorption low and solve the problem of negative conversion. . In particular, the esters into which the fluorinated alkyl group of the present invention has been introduced further increase the transmittance around 157 nm, have acid instability, and have the effect of increasing the alkali-soluble contrast. It is.

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 the following general formula (2-1)
It has any of the repeating units represented by-(2-5).

[0011]

Embedded image

[0012]

Embedded image

Here, R¹, R^Two, R^Three, R^FourIs a hydrogen atom,
Fluorine atom, C1-C20 linear, branched or
A cyclic alkyl group or a fluorinated alkyl group
R ¹, R^Two, R^Three, R^FourAt least one of which is fluorine
Including atoms. R^Five, R⁶, R⁷Is a hydrogen atom, a fluorine atom,
C1-C20 linear, branched or cyclic alkyl
Or a fluorinated alkyl group. R⁸And R⁹
Is a hydrogen atom, a methyl group, or CH_TwoCO_TwoR¹¹Is shown. R
¹¹Is a linear, branched or cyclic C 1-20
It is a alkyl group or a substituted alkyl group. R^TenIs 1 carbon
Up to 20 linear, branched or cyclic alkylene groups or
Is a fluorinated alkylene group. k is 0 or 1
is there.

In this case, the linear, branched or cyclic alkyl group having 1 to 20 carbon atoms includes methyl, ethyl, propyl, isopropyl, n-butyl and s.
Examples thereof include an ec-butyl group, a tert-butyl group, a cyclopentyl group, a cyclohexyl group, a 2-ethylhexyl group, an n-octyl group, and the like, and particularly preferably those having 1 to 12 carbon atoms, particularly preferably 1 to 10 carbon atoms. 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, 1,1,2,2
3,3,3-heptafluoropropyl group and the like. Examples of the substituted alkyl group include the above-mentioned fluorinated alkyl group. 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. 1
To 12, particularly preferably 1 to 10.

Examples of the group represented by the above formula (1) include groups represented by the following (3-1) to (3-3).

[0016]

Embedded image

The polymer compound of the present invention may further comprise, in addition to the above units, the following repeating unit (4) from the viewpoint of improving adhesion.
~ (39) can be introduced.

[0018]

Embedded image

[0019]

Embedded image

[0020]

Embedded image (In the formula, R ⁵ , R ⁶ , and R ⁷ are the same as above.)

Further, in order to further improve the contrast, it is possible to introduce, for example, repeating units of the following formulas (i) to (v) having an acid labile group containing no fluorine.

[0022]

Embedded image (In the formula, R ^{5 to} R ¹⁰ and k are the same as described above, and R is an acid labile group.)

As the acid labile group R, various types are selected, and in particular, groups represented by the following formulas (40) and (41) and tertiary alkyl groups having 4 to 40 carbon atoms represented by the following formula (42) A trialkylsilyl group having 1 to 6 carbon atoms, 4 to 4 carbon atoms
It is preferably 20 oxoalkyl groups or the like.

[0024]

Embedded image

R ¹² has 4 to 20 carbon atoms, preferably 4 to 1 carbon atoms.
5 tertiary alkyl groups, each alkyl group having 1 carbon atom
A trialkylsilyl group, an oxoalkyl group having 4 to 20 carbon atoms or a group represented by the above formula (42), and specific examples of the tertiary alkyl group include a tert-butyl group and a tert-amyl group. , 1,1-diethylpropyl, 1-ethylcyclopentyl, 1-butylcyclopentyl, 1-ethylcyclohexyl, 1-butylcyclohexyl, 1-ethyl-2-cyclopentenyl, 1-ethyl-2-cyclo Examples include a hexenyl group and a 2-methyl-2-adamantyl group, and specific examples of the trialkylsilyl group include a trimethylsilyl group, a triethylsilyl group, and a dimethyl-tert-butylsilyl group, and specific examples of the oxoalkyl group. Include a 3-oxocyclohexyl group, a 4-methyl-2-oxooxan-4-yl group, Chill-2-oxo-oxo-run -
5-yl group and the like. a is an integer of 0 to 6.

R ¹³ and R ^{14 each} represent a hydrogen atom or a group having 1 to 1 carbon atoms.
8, preferably 1 to 10 linear, branched or cyclic alkyl groups, specifically methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert- Examples thereof include a butyl group, a cyclopentyl group, a cyclohexyl group, a 2-ethylhexyl group, and an n-octyl group. R ¹⁵ has 1 to 18 carbon atoms, preferably 1 to
10 represents a monovalent hydrocarbon group which may have a hetero atom such as an oxygen atom, and is a linear, branched, or cyclic alkyl group;
Examples thereof include those in which some of these hydrogen atoms are substituted with a hydroxyl group, an alkoxy group, an oxo group, an amino group, an alkylamino group, and the like, and specific examples include the following substituted alkyl groups.

[0027]

Embedded image

[0028] R ¹³ and R ^14, and R ¹³ and R ^15, R ¹⁴ and R ¹⁵ may form a ring, when they form a ring R ^13,
R ¹⁴ and R ¹⁵ each have 1 to 18 carbon atoms, preferably 1 to
And 10 linear or branched alkylene groups.

Specific examples of the acid labile group of the above formula (40) include a tert-butoxycarbonyl group and a tert-butoxycarbonyl group.
Butoxycarbonylmethyl group, tert-amyloxycarbonyl group, tert-amyloxycarbonylmethyl group, 1,1-diethylpropyloxycarbonyl group,
1,1-diethylpropyloxycarbonylmethyl group,
1-ethylcyclopentyloxycarbonyl group, 1-ethylcyclopentyloxycarbonylmethyl group, 1-ethyl-2-cyclopentenyloxycarbonyl group, 1-
Examples thereof include an ethyl-2-cyclopentenyloxycarbonylmethyl group, a 1-ethoxyethoxycarbonylmethyl group, a 2-tetrahydropyranyloxycarbonylmethyl group, and a 2-tetrahydrofuranyloxycarbonylmethyl group.

Specific examples of the linear or branched acid labile group represented by the above formula (41) include the following groups.

[0031]

Embedded image

Specific examples of the cyclic group among the acid labile groups represented by the above formula (41) include a tetrahydrofuran-2-yl group, a 2-methyltetrahydrofuran-2-yl group and a tetrahydropyran-2-yl group. And 2-methyltetrahydropyran-2-yl group. Equation (4
1) includes an ethoxyethyl group, a butoxyethyl group,
An ethoxypropyl group is preferred.

Next, in the equation (42), R ¹⁶ , R ¹⁷ , R
¹⁸ is a monovalent hydrocarbon group, typically a straight, branched or cyclic alkyl group of 1 to 20 carbon atoms, oxygen, sulfur, nitrogen, which may contain a hetero atom such as fluorine, R ¹⁶ and R
^17, R ¹⁶ and R ^18, may be bonded to each other and R ¹⁷ and R ¹⁸ combine ring.

The tertiary alkyl group represented by the formula (42) 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, te
An rt-amyl group and the like can be mentioned.

Further, specific examples of the tertiary alkyl group include the following formulas (43) to (58).

[0036]

Embedded image

Here, R ¹⁹ 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 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, 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. Examples of the hetero atom include an oxygen atom, a sulfur atom, and a nitrogen atom, and -OH, -OR (R is an alkyl group, and the same applies hereinafter),-
O -, - S -, - S (= O) -, - NH 2, -NHR,
It can be contained or intervened as —NR ₂ , —NH—, and —NR—.

Examples of R ²¹ and R ²² include a hydrogen atom, an alkyl group, a hydroxyalkyl group, an alkoxyalkyl group, an alkoxy group, an alkoxyalkyl group and the like. These may be linear, branched or cyclic. But yes.
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.

When synthesizing the polymer compound of the present invention, a monomer having a carbon-carbon double bond having the group of the above formula (1), particularly units of the formulas (2-1) to (2-5), is provided. In the case of a monomer, for example, of the formula (2-1):

Embedded image And, if necessary, formulas (4) to (3)
A monomer that gives the unit of 9) or a monomer that gives the unit of the formula (i) to (v) is mixed with a solvent, a catalyst is added, and a polymerization reaction is carried out while heating or cooling in some cases. 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, additives). In the polymerization of the polymer compound of the present invention, AIBN
Radical copolymerization in which polymerization is initiated by a radical such as ionic polymerization (anionic polymerization) using a catalyst such as alkyllithium, and the like are common. These polymerizations can be carried out according to the usual methods.

Here, a unit having a group of the formula (1) is represented by A,
A unit represented by Formulas (4) to (39) is represented by B, and Formulas (i) to
When the unit represented by (v) is C, the polymer compound of the present invention can be represented by the following formula. (A) _a (B) _b (C) _{c In} this case, a is a positive number, and b and c are 0 or positive numbers, and are preferably as follows. 0.1 ≦ a / (a + b + c) ≦ 0.8, more preferably 0.3 ≦ a / (a + b + c) ≦ 0.60 ≦ b / (a + b + c) ≦ 0.8, more preferably 0.1 ≦ a / (a + b + c) ≦ 0.8.
1 ≦ b / (a + b + c) ≦ 0.6 0 ≦ c / (a + b + c) ≦ 0.5, more preferably 0 ≦
c / (a + b + c) ≦ 0.3

The above-mentioned polymer compound has a weight average molecular weight of 1,000 to 1,000,000, particularly 2,000 to 1
Preferably it is 100,000.

The polymer compound of the present invention comprises a resist material,
In particular, it can be used as a base resin of a chemically amplified positive resist material, especially a chemically amplified positive resist material.

Accordingly, the present invention provides a chemically amplified positive resist composition comprising (A) the above-mentioned polymer compound (base resin), (B) an organic solvent, and (C) an acid generator. .

In this case, these resist materials may further contain (D) a basic compound and (E) a dissolution inhibitor.

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, other additives and the like 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, 1,1,1,2,2,6,6 6-octafluoro-2,4-hexanedione, 2,2,3,3,4,4,
5,5-octafluoro-1-pentanol, 1H, 1
H, 2H, 2H-perfluoro-1-decanol, perfluoro (2,5-dimethyl-3,6-dioxananionic) acid methyl ester, 2H-perfluoro-5
-Methyl-3,6-dioxanonane, 1H, 1H, 2
H, 3H, 3H-perfluorononane-1,2-diol, 1H, 1H, 9H-perfluoro-1-nonanol, 1H, 1H-perfluorooctanol, 1H, 1
H, 2H, 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, trifluoro Butyl methyl acetate, methyl 3-trifluoromethoxypropionate, perfluorocyclohexanone, propylene glycol trifluoromethyl ether, butyl trifluoroacetate, 1,1,1-triethyl Ruoro-5,5-dimethyl -
2,4-hexanedione and the like can be mentioned.

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 acid generator of the component (C) includes an onium salt of the following general formula (59), a diazomethane derivative of the formula (60), a glyoxime derivative of the formula (61), 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.

[0049] _{^{(R 23) m M + K}} - (59) ( provided that wherein R ²³ each represent 1 to 12 linear,
Branched or cyclic alkyl group, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having a carbon number of 7 to 12, M ⁺
Represents iodonium or sulfonium, K ⁻ represents a non-nucleophilic counter ion, and m is 2 or 3. )

Examples of the alkyl group represented by R ²³ 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.

[0051]

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, an aryl group or a halogenated aryl group having 6 to 12 carbon atoms, or a 7 to 12 carbon atoms. 12 represents an aralkyl group.)

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 an adamantyl group. 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.

[0053]

Embedded image (Wherein, R ²⁶ , R ²⁷ and R ²⁸ are a linear, branched or cyclic alkyl group or halogenated alkyl group having 1 to 12 carbon atoms, an aryl group or aryl halide having 6 to 12 carbon atoms) And a aralkyl group having 7 to 12 carbon atoms.
R ²⁷ and R ²⁸ may combine with each other to form a cyclic structure. In the case where a cyclic structure is formed, R ²⁷ and R ²⁸ each represent a linear or branched alkylene group having 1 to 6 carbon atoms. . )

Examples of the alkyl group, halogenated alkyl group, aryl group, halogenated aryl group, and aralkyl group represented by R ²⁶ , R ²⁷ , and R ²⁸ include the same groups as those described for R ²⁴ and R ²⁵ . The alkylene group of R ²⁷ and R ²⁸ includes a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group and the like.

Specifically, for example, diphenyliodonium trifluoromethanesulfonate, phenyliodonium trifluoromethanesulfonate (p-tert-butoxyphenyl), diphenyliodonium p-toluenesulfonate, p-toluenesulfonic acid (p-tert-sulfonic acid)
(Butoxyphenyl) phenyliodonium, triphenylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, bis (p-tert-butoxyphenyl) phenylsulfonium trifluoromethanesulfonate, tris trifluoromethanesulfonate (P-tert-butoxyphenyl) sulfonium,
triphenylsulfonium p-toluenesulfonate, p
-(P-tert-butoxyphenyl) diphenylsulfonium toluenesulfonate, bis (p-tert-butoxyphenyl) phenylsulfonium p-toluenesulfonate, tris (p-tert-toluenesulfonate)
(t-butoxyphenyl) sulfonium, triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium butanesulfonate, trimethylsulfonium trifluoromethanesulfonate, trimethylsulfonium p-toluenesulfonate, cyclohexylmethyl trifluoromethanesulfonate (2-oxocyclohexyl) Sulfonium, cyclohexylmethyl p-toluenesulfonate (2-oxocyclohexyl) sulfonium, dimethylphenylsulfonium trifluoromethanesulfonate, dimethylphenylsulfonium p-toluenesulfonate, dicyclohexylphenylsulfonium trifluoromethanesulfonate, dicyclohexylphenylsulfonium p-toluenesulfonate , Trifluoromethane sulfone Trinaphthylsulfonium, cyclohexylmethyl trifluoromethanesulfonate (2-oxocyclohexyl) sulfonium, (2-norbonyl) methyl (2-oxocyclohexyl) sulfonium, ethylenebis [methyl (2-oxocyclopentyl) 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 (isobutyl) Ruhoniru)
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-
Diazomethane derivatives such as amylsulfonyl) diazomethane, 1-tert-amylsulfonyl-1- (tert-butylsulfonyl) 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- (tert-butanesulfonyl)-
α-dimethylglyoxime, bis-O- (perfluorooctanesulfonyl) -α-dimethylglyoxime, bis-O- (cyclohexanesulfonyl) -α-dimethylglyoxime, bis-O- (benzenesulfonyl) -α
-Dimethylglyoxime, bis-O- (p-fluorobenzenesulfonyl) -α-dimethylglyoxime, bis-O- (p-tert-butylbenzenesulfonyl)-
Glyoxime derivatives such as α-dimethylglyoxime, bis-O- (xylenesulfonyl) -α-dimethylglyoxime, bis-O- (camphorsulfonyl) -α-dimethylglyoxime, 2-cyclohexylcarbonyl-
Β-ketosulfone derivatives such as 2- (p-toluenesulfonyl) propane and 2-isopropylcarbonyl-2- (p-toluenesulfonyl) propane; disulfone derivatives such as diphenyldisulfone and dicyclohexyldisulfone; Nitrobenzylsulfonate derivatives such as dinitrobenzyl and 2,4-dinitrobenzyl p-toluenesulfonate;
Tris (methanesulfonyloxy) benzene, 1,2,2
Sulfonate derivatives such as 3-tris (trifluoromethanesulfonyloxy) benzene and 1,2,3-tris (p-toluenesulfonyloxy) benzene, phthalimido-yl-triflate, phthalimido-yl-
Tosylate, 5-norbornene-2,3-dicarboximido-yl-triflate, 5-norbornene-2,
Imido-ylsulfonate derivatives such as 3-dicarboximido-yl-tosylate and 5-norbornene-2,3-dicarboximido-yl-butyl trifluorosulfonate; and the like, such as triphenylsulfonium trifluoromethanesulfonate, trifluoromethane (P-tert-butoxyphenyl) diphenylsulfonium methanesulfonate, tris (p-tert-butoxyphenyl) sulfonium trifluoromethanesulfonate, p
-Triphenylsulfonium toluenesulfonate, p-
Toluenesulfonate (p-tert-butoxyphenyl) diphenylsulfonium, tris (p-tert-butoxyphenyl) sulfonium p-toluenesulfonate, trinaphthylsulfonium trifluoromethanesulfonate, cyclohexylmethyl trifluoromethanesulfonate (2-oxocyclohexyl) Sulfonium, (2-norbornyl) methyl trifluoromethanesulfonate (2-oxocyclohexyl) sulfonium, 1,2 ′
-Onium salts such as naphthylcarbonylmethyltetrahydrothiophenium triflate, bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl)
Diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (n-butylsulfonyl) diazomethane, bis (isobutylsulfonyl) diazomethane, bis (sec-butylsulfonyl) diazomethane, bis (n
Diazomethane derivatives such as -propylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, and bis (tert-butylsulfonyl) diazomethane;
Bis-O- (p-toluenesulfonyl) -α-dimethylglyoxime, bis-O- (n-butanesulfonyl)-
Glyoxime derivatives such as 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 have excellent rectangularity improving effect, and diazomethane derivatives and glyoxime derivatives have excellent standing wave reducing effect.
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 low and the resolution may be low.

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, the sensitivity change after exposure is suppressed, the dependence on the substrate and the environment is reduced, and the exposure margin is reduced. And pattern profiles can be improved (see JP-A-5-232706, JP-A-5-249683 and JP-A-5-249683, and
No. 158239, No. 5-249662, No. 5-25
No. 7282, No. 5-289322, No. 5-28934
No. 0 publication).

Such basic compounds include primary, secondary and tertiary aliphatic amines, hybrid amines,
Aromatic amines, heterocyclic amines, nitrogen-containing compounds having a carboxy group, nitrogen-containing compounds having a sulfonyl group,
Examples include 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.

Specifically, as primary aliphatic amines, ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tertiary amine
t-butylamine, pentylamine, tert-amylamine, cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine,
Nonylamine, decylamine, dodecylamine, cetylamine, methylenediamine, ethylenediamine, tetraethylenepentamine and the like are exemplified. As secondary aliphatic amines, 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-dimethyltetraethylenepentamine, and the like. Examples of the tertiary aliphatic amines include trimethylamine, triethylamine, tri-n-propylamine, and 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'-tetra Examples include methylethylenediamine, N, N, N ', N'-tetramethyltetraethylenepentamine and the like.

Examples of the mixed amines include dimethylethylamine, methylethylpropylamine, benzylamine, phenethylamine and benzyldimethylamine. Specific examples of aromatic amines and heterocyclic amines include aniline derivatives (for example, aniline,
N-methylaniline, N-ethylaniline, N-propylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, ethylaniline, propylaniline, trimethylaniline, 2-nitroaniline , 3-nitroaniline, 4-nitroaniline, 2,4-dinitroaniline, 2,6-dinitroaniline, 3,5-dinitroaniline, N, N-
Dimethyl toluidine, etc.), diphenyl (p-tolyl) amine, methyl diphenylamine, triphenylamine,
Phenylenediamine, naphthylamine, diaminonaphthalene, pyrrole derivatives (e.g., pyrrole, 2H-pyrrole, 1-methylpyrrole, 2,4-dimethylpyrrole,
2,5-dimethylpyrrole, N-methylpyrrole, etc.),
Oxazole derivatives (eg, oxazole, isoxazole, etc.), thiazole derivatives (eg, thiazole, isothiazole, etc.), imidazole derivatives (eg, imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, etc.), pyrazole derivatives, furazane derivatives, Pyrroline derivatives (eg, pyrroline, 2-methyl-1-pyrroline, etc.), pyrrolidine derivatives (eg, pyrrolidine, N-methylpyrrolidine, pyrrolidinone, N-methylpyrrolidone, etc.), imidazoline derivatives, imidazolidine derivatives, pyridine derivatives (eg, pyridine, methyl) Pyridine, ethylpyridine, propylpyridine, butylpyridine, 4- (1-butylpentyl) pyridine, dimethylpyridine, trimethylpyridine, triethylpyridine, phenylpyridyl , 3-methyl-2-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 1-methyl-2-pyridone, 4-pyrrolidinopyridine, 1-methyl- 4-phenylpyridine, 2- (1-ethylpropyl) pyridine,
Aminopyridine, dimethylaminopyridine, etc.), 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, quinoline derivatives (Eg, quinoline, 3-quinolinecarbonitrile), isoquinoline derivatives, cinnoline derivatives, quinazoline derivatives, quinoxaline derivatives, phthalazine derivatives, purine derivatives, pteridine derivatives, carbazole derivatives, phenanthridine derivatives, acridine derivatives, phenazine derivatives, 1,1
Examples thereof include 0-phenanthroline derivatives, adenine derivatives, adenosine derivatives, guanine derivatives, guanosine derivatives, uracil derivatives, uridine derivatives and the like.

Examples of the nitrogen-containing compound having a carboxy group include aminobenzoic acid, indolecarboxylic acid, and amino acid derivatives (eg, nicotinic acid, alanine, arginine, aspartic acid, glutamic acid, glycine,
Histidine, isoleucine, glycylleucine, leucine, methionine, phenylalanine, threonine, lysine, 3-aminopyrazine-2-carboxylic acid, methoxyalanine, etc.). , Pyridinium p-toluenesulfonate, and the like. Examples of the nitrogen-containing compound having a hydroxyl group, the nitrogen-containing compound having a hydroxyphenyl group, and the alcoholic nitrogen-containing compound include 2-hydroxypyridine, aminocresol, and 2,4-quinolinediol. , 3-indolemethanol hydrate, monoethanolamine, diethanolamine, triethanolamine, N-ethyldiethanolamine, N, N-diethylethanolamine, triisopropanolamine,
2,2'-iminodiethanol, 2-aminoethanol
3-amino-1-propanol, 4-amino-1-
Butanol, 4- (2-hydroxyethyl) morpholine, 2- (2-hydroxyethyl) pyridine, 1- (2
-Hydroxyethyl) piperazine, 1- [2- (2-hydroxyethoxy) ethyl] piperazine, 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,
Examples thereof include 1-methyl-2-pyrrolidineethanol, 1-aziridineethanol, N- (2-hydroxyethyl) phthalimide, and N- (2-hydroxyethyl) isonicotinamide. Examples of the amide derivative include formamide, N-methylformamide, N, N-dimethylformamide, acetamido, N-methylacetamido,
N-dimethylacetamide, propionamide, benzamide and the like are exemplified. Examples of the imide derivative include phthalimide, succinimide, and maleimide.

Further, basic compounds represented by the following formulas (62) and (63) can be blended.

[0063]

Embedded image(Where R²⁹, R³⁰, R³¹, R³⁵, R³⁶Are independent
Linear, branched or cyclic C 1-20 alkyl
Kylene group, R³², R³³, R³⁴, R³⁷, R³⁸Is a hydrogen atom,
An alkyl group or an amino group having 1 to 20 carbon atoms;³²
And R³³, R³³And R ³⁴, R³²And R³⁴, R³²And R³³And R³⁴,
R³⁷And R³⁸May combine with each other to form a ring.
m, n, and o are each an integer of 0 to 20. However,
When m, n, o = 0, R²⁹, R³⁰, R³¹, R³⁵, R³⁶
Does not contain a hydrogen atom. )

Here, the alkylene group of R ²⁹ , R ³⁰ , R ³¹ , R ³⁵ and R ³⁶ has 1 to 20 carbon atoms, preferably 1 to 20 carbon atoms.
-10, more preferably 1-8, and specifically, methylene, ethylene, n-propylene, isopropylene, n-butylene, isobutylene, n-
Examples include a pentylene group, an isopentylene group, a hexylene group, a nonylene group, a decylene group, a cyclopentylene group, and a cyclohexylene group.

The alkyl group of R ³² , R ³³ , 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.

Further, R ³² and R ³³ , R ³³ and R ³⁴ , R ³² and R
^When R ³⁴ , R ³² and R ³³ and R ³⁴ , and R ³⁷ and R ³⁸ form a ring, the ring has 1 to 20 carbon atoms, and preferably 1 to 20 carbon atoms.
8, more preferably 1 to 6, and in these rings, an alkyl group having 1 to 6, particularly 1 to 4 carbon atoms may be branched.

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 (62) and (63) 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. Especially 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 nitrogen-containing compounds, amide derivatives, imide derivatives, Tris ｛2
-(Methoxymethoxy) ethyl} amine, tris-2-
(2-methoxyethoxy) ethyldiamine, tris [2
-{(2-methoxyethoxy) methyl} ethyl] amine, 1-aza-15-crown-5 and the like are preferred.

The above basic compounds can be used alone or in combination of two or more. The compounding amount is 0.01 to 2 parts, especially 0.01 to 2 parts with respect to 100 parts of the base resin. One part is preferred. 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 decrease.

Next, as a dissolution inhibitor, a molecular weight of 3,000, whose solubility in an alkali developing solution is changed by the action of an acid.
0 or less compounds, in particular, compounds in which part or all of 2,500 or less low molecular weight phenol or carboxylic acid derivatives are substituted with acid-labile substituents. 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'-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)
0) to (42).

Examples of suitable 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, 4,4-bis (4 ′-(2 ″ -tetrahydropyranyloxy) phenyl) Tert-butyl valerate, tert-butyl 4,4-bis (4 ′-(2 ″ -tetrahydrofuranyloxy) phenyl) valerate,
Tert-butyl 4,4-bis (4′-tert-butoxyphenyl) valerate, 4,4-bis (4-tert-butyl)
Butoxycarbonyloxyphenyl) valeric acid tert-
Butyl, tert-butyl 4,4-bis (4′-tert-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-butoxycarbonyloxyphenyl) methane, tris (4-tert-butoxycarbonyloxyphenyl) methane, tris (4-tert-butoxycarbonyloxymethylphenyl) methane, tris (4 -(1′-ethoxyethoxy) phenyl) methane, tris (4- (1′-ethoxypropyl) ) 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,
1,2-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, 2-trifluoromethylbenzenecarboxylic acid 1,1-t-butyl ester, 2-trifluoromethylcyclohexanecarboxylic acid-t-butyl ester, decahydronaphthalene-2,6-dicarboxylic acid-t-butyl ester, coal Acid-t-butyl ester, deoxycholic acid-t-butyl ester, adamantanecarboxylic acid-t-butyl ester, adamantaneacetic acid-t-butyl ester, [1,1′-bicyclohexyl-3,3 ′,
4,4'-tetracarboxylic acid tetra-t-butyl ester] and the like.

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, per 100 parts of the solids in the resist composition. 2
If the amount is more than 0 parts, the monomer component increases, so that the heat resistance of the resist material decreases.

The resist composition of the present invention may further contain, as an optional component, a surfactant which is commonly used for improving 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.

Here, 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.).

The formation of a pattern using the resist material of the present invention can be performed 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 resist film, and a high energy ray such as far ultraviolet rays, an excimer laser, or an X-ray or an electron beam is exposed at a dose 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 developer of an aqueous alkali solution such as 0.1 to 5%, preferably 2 to 3% tetramethylammonium hydroxide (TMAH), dipping (dip) for 10 seconds to 3 minutes, preferably 30 seconds to 2 minutes. ) Method, paddle (pudd)
The target pattern is formed on the substrate by developing by a conventional method such as le) method or spray method. In addition, the material of the present invention is 254 to 120 nm deep ultraviolet ray or excimer laser, especially among high energy rays,
In particular, 193nm of ArF, F of 157nm _2, 146n
m Kr ₂ , 134 nm KrAr, 121 nm Ar ₂
It is most suitable for fine patterning by excimer laser such as excimer laser, 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.

[0077]

The resist material of the present invention is sensitive to high-energy rays, is excellent in sensitivity, resolution and plasma etching resistance at a wavelength of 200 nm or less, especially 170 nm or less, and suppresses the progress of negative conversion. I knew it could be done. 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.

[0078]

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

[Synthesis Example 1-1] Synthesis of 1,1-bis (trifluoromethyl) ethyl methacrylate In a 500-mL flask, 100 mL of THF was placed.
After cooling to 78 ° C., 25 g of hexafluoroacetone was dissolved. A methyllithium THF solution (1.
0M) was dropped, and the mixture was aged for 2 hours. Then, 17.5 g of methacrylic acid chloride was added dropwise and aged for 2 hours. Thereafter, a usual post-treatment operation was carried out, and the obtained oily substance was distilled under reduced pressure to obtain 28.3 g of 1,1-bis (trifluoromethyl) ethyl methacrylate. The yield was 75%.

[Synthesis Example 1-2] Synthesis of 1,1-bis (heptafluoroisopropyl) ethyl methacrylate 100 mL of THF was placed in a 500 mL flask, and-
After cooling to 78 ° C., 25 g of bis (heptafluoroisopropyl) ketone was dissolved. 72 mL of a THF solution of methyllithium (1.0 M) was added dropwise thereto, and the mixture was aged for 2 hours. Then, 7.9 g of methacrylic acid chloride was added dropwise, and the mixture was aged for 2 hours. Thereafter, a usual post-treatment operation was performed, and the obtained oily substance was distilled under reduced pressure.
1.5 g of 1,1-bis (heptafluoroisopropyl) ethyl methacrylate were obtained. The yield was 70%.

[Synthesis Example 2-1] Polymerization of 1,1-bis (trifluoromethyl) ethyl methacrylate In a 500 mL flask, 20 g of 1,1-bis (trifluoromethyl) ethyl methacrylate was added to 100 ml of toluene.
After the oxygen in the system was sufficiently removed, 0.50 g of an initiator AIBN was charged, and the temperature was raised to 60 ° C.
The polymerization reaction was performed for 4 hours.

To purify the resulting polymer, the reaction mixture was poured into methanol and the resulting polymer was precipitated. Further, the operation of dissolving the obtained polymer in acetone and pouring it into 5 L of methanol to precipitate the polymer was repeated twice, and then the polymer was separated and dried. 17.2 g of the thus obtained white polymer poly {1,1-bis (trifluoromethyl) ethyl methacrylate} has a weight average molecular weight of 9,300 g / mol by a light scattering method, and a GPC elution curve. The degree of dispersion (= Mw / Mn) is 1.
It was confirmed that the polymer was 85.

[Synthesis Example 2-2] Polymerization of 1,1-bis (heptafluoroisopropyl) ethyl methacrylate In a 500 mL flask, 20 g of 1,1-bis (heptafluoroisopropyl) ethyl methacrylate was dissolved in 100 mL of toluene. After the oxygen in the system was sufficiently removed, 0.31 g of an initiator AIBN was charged, and the temperature was raised to 60 ° C. to carry out a polymerization reaction for 24 hours.

In order 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 acetone and pouring it into 5 L of methanol to precipitate the polymer was repeated twice, and then the polymer was separated and dried. 16.5 g of the white polymer poly {1,1-bis (heptafluoroisopropyl) ethyl methacrylate) thus obtained had a weight average molecular weight of 8,700 g / d by a light scattering method.
mol and the degree of dispersion (= Mw / M
n) was confirmed to be 1.80 polymer.

[Synthesis Example 2-3] Copolymerization of 1,1-bis (trifluoromethyl) ethyl methacrylate and monomer 1 (1: 1) 1,1-bis (trifluoromethacrylate) in a 500 mL flask After 10 g of methyl) ethyl and 8.4 g of the following monomer 1 were dissolved in 100 mL of toluene and oxygen in the system was sufficiently removed, 0.50 g of an initiator AIBN was charged, and the temperature was raised to 60 ° C. to carry out a polymerization reaction for 24 hours. went.

In order 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 acetone and pouring it into 5 L of methanol to precipitate the polymer was repeated twice, and then the polymer was separated and dried. The thus obtained 14.5 g of a white polymer had a weight average molecular weight of 8,500 g / mol by a light scattering method and was analyzed by GPC.
From the elution curve, it was confirmed that the polymer had a dispersity (= Mw / Mn) of 1.90. ¹ H-NMR measurement confirmed that this polymer contained 1,1-bis (trifluoromethyl) ethyl methacrylate and monomer 1 at a ratio of 48:52.

[0087]

Embedded image

[Synthesis Example 2-4] Copolymerization of 1,1-bis (trifluoromethyl) ethyl methacrylate and monomer 2 (1: 1) 1,1-bis (trifluoromethyl methacrylate) in a 500 mL flask ) 10 g of ethyl and 6.4 g of the following monomer 2 were dissolved in 100 mL of toluene, oxygen in the system was sufficiently removed, 0.50 g of an initiator AIBN was charged, the temperature was raised to 60 ° C, and a polymerization reaction was performed for 24 hours. Was.

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 acetone 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 8,200 g / mol by a light scattering method, and was measured by GPC.
From the elution curve, it was confirmed that the polymer had a dispersity (= Mw / Mn) of 1.95. ¹ H-NMR measurement confirmed that the polymer contained 1,1-bis (trifluoromethyl) ethyl methacrylate and monomer 2 at a ratio of 49:51.

[0090]

Embedded image

Next, 1 g of the polymer obtained above was mixed with propylene glycol monomethyl ether acetate (PGM).
EA) The polymer solution was sufficiently dissolved in 10 g, and filtered through a 0.2 μm filter to prepare a polymer solution. On the other hand, a polymer in which 30% of monodisperse polyhydroxystyrene having a molecular weight of 10,000 and a degree of dispersion (= Mw / Mn) of 1.10 was substituted with a tetrahydropyranyl group was synthesized, and was used as Comparative Example 1 polymer. In addition, polymethyl methacrylate having a molecular weight of 15,000 and a dispersity of 1.7 was used as a comparative example 2 polymer, and a novolak polymer having a meta / para ratio of 40/60 and a molecular weight of 9,000 and a dispersity of 2.5 was used as a comparative example 3 polymer. . 1 g of the obtained polymer was sufficiently dissolved in 10 g of propylene glycol monomethyl ether acetate, and filtered with a 0.2 μm filter to prepare a polymer solution. These polymer solutions are spin-coated on MgF ₂ substrate,
Bake at 100 ° C for 90 seconds using a hot plate,
A 300 nm thick polymer layer was formed on a MgF ₂ substrate. The transmittance at 248 nm, 193 nm, and 157 nm was measured using a vacuum ultraviolet photometer (VUV200S, manufactured by JASCO Corporation). Table 1 shows the results.

[0092]

[Table 1]

Example 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, the obtained resist solution is formed on a silicon wafer by forming DUV-30 (manufactured by Nissan Chemical Industries, Ltd.) with a film thickness of 55 nm and suppressing the reflectance to 1% or less with KrF light (248 nm). The substrate was spin-coated and baked at 100 ° C. for 90 seconds using a hot plate to make the thickness of the resist 300 nm.

An excimer laser stepper (Nikon Corporation, NSR-2005EX8A, NA-0.5, σ)
0.7 ordinary illumination) and stepping exposure while changing the exposure amount over an exposure area of 4 mm square,
Baking was performed at 0 ° C. for 90 seconds, and development was performed with a 2.38% aqueous solution of tetramethylammonium hydroxide for 60 seconds, and the relationship between the exposure amount and the remaining film ratio was determined. 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.

[0095]

Embedded image

[0096]

[Table 2]

From Tables 1 and 2, it can be seen that a sufficient transparency can be ensured even at the wavelength of F ₂ (157 nm), and that the film thickness decreases as the exposure amount increases in KrF exposure, indicating the characteristics of a positive resist. I understood.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) G03F 7/004 501 G03F 7/004 501 7/039 601 7/039 601 H01L 21/027 H01L 21/30 502R (72) Inventor Jun Hatakeyama 28-1 Nishifukushima, Nishifukushima, Nakakushijo-gun, Niigata Pref. Shin-Etsu Chemical Co., Ltd. Synthetic Research Laboratory EV296 FD146 4J100 AK32P AL08P AR09P AR11P BA15P BB07P BB10P BB18P CA01 CA04 DA28 DA61 FA02

Claims (7)

[Claims] 1. A polymer compound containing a group represented by the following general formula (1). Embedded image (Wherein R ¹ , R ² , R ³ , and R ⁴ represent a hydrogen atom, a fluorine atom,
A linear, branched or cyclic alkyl group having 1 to 20 carbon atoms or a fluorinated alkyl group, wherein R ¹ , R ² ,
At least one of R ³ and R ⁴ contains a fluorine atom. ) 2. The following general formulas (2-1), (2-2),
2. The composition according to claim 1, comprising any of the repeating units represented by (2-3), (2-4), and (2-5).
3. The polymer compound according to item 1. 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. R ⁸ and R ⁹ represents a hydrogen atom, a methyl group or CH ₂ CO ₂ R ^11. R ¹¹ is a linear, branched or cyclic alkyl group or substituted alkyl group having 1 to 20 carbon atoms, and R ¹⁰ is a carbon atom. Number 1-2
It is 0 linear, branched or cyclic alkylene group or fluorinated alkylene group. k is 0 or 1. R ^{1 to} R ⁴ are the same as above. ) 3. A resist material comprising the polymer compound according to claim 1 or 2. 4. A chemically amplified positive resist material 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 (1) applying the resist material according to any one of claims 3 to 6 onto a substrate; and (2)
Next, after the heat treatment, a wavelength of 300 n is passed through a photomask.
A pattern forming method comprising: exposing with a high-energy ray or an electron beam of m or less; and (3) performing a heat treatment as necessary and then developing with a developer.