JP2002220416A - High polymer compound, resist material and pattern- forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resist material which is sensitive to high energy beams and excellent in the sensitivity, resolution and plasma etching resistance at a wavelength of 200 nm or less, especially 190 nm or less. SOLUTION: The high polymer compound comprises a recurring unit represented by the formula (I) [R1, R2 and R3 are H, F, an alkyl or a fluorinated alkyl; R4 is H or an alkyl; R5 is a single bond or an alkylene; R6 and R7 are H, F or an alkyl and at least one of them contains a fluorine atom; X is -O-or -C(=O)-O-; R8 is an acid labile group; 0<d+e<5, 0<g+h<=5, 0<(a+b)/(a+b+ c)<1, 0<c/(a+b+c)<0.8].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

2. Description of the Related Art LSI
With the increase in integration and speed of devices, pattern rules are rapidly becoming finer. Background of the rapid progress of miniaturization include higher NA of the projection lens, improved resist performance, and shorter wavelength. Especially from i-line (365 nm) to KrF
(248nm) has brought about a major change,
Mass production of devices with the 0.18 μm rule has become possible. In order to increase the resolution and sensitivity of resist, a chemically amplified positive resist material using acid as a catalyst (Japanese Patent Publication 2-
No. 27660, and JP-A-63-27829) have excellent characteristics and have become a mainstream resist material particularly in deep ultraviolet lithography.

[0003] Resist materials for KrF excimer lasers have generally begun to be used in 0.3 micron processes,
After the 0.25 micron rule, the application of the 0.18 micron rule to mass production and the study of the 0.15 micron rule have also begun, and the pace of miniaturization is accelerating increasingly. Shortening of the wavelength from KrF to ArF (193 nm) is expected to reduce the design rule to 0.13 μm or less. Since it has very strong absorption, it cannot be used as a base resin for 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. 9-1997).
73173, JP-A-10-10739, JP-A-9-107
230595, WO97 / 33198). Further, F ₂ (157n) in which miniaturization of 0.10 μm or less can be expected
Regarding m), it is increasingly difficult to ensure transparency,
It was found that the acrylic type did not transmit light at all, and the cycloolefin type having a carbonyl bond had strong absorption. 16 for polyvinylphenol
Although there is an absorption window near 0 nm and the transmittance is slightly improved, it is far from a practical level, and reducing the double bond between carbonyl and carbon is a necessary condition for securing the transmittance. It turned out that a solution to this was desired.

The present invention has been made in order to meet the above-mentioned demands, and has been made to have a thickness of 300 nm or less, especially F ₂ (157 nm), K
r ₂ (146 nm), KrAr (134 nm), Ar
( ₂ ) A novel polymer compound useful as a base polymer of a chemically amplified resist material having excellent transmittance and resolution in vacuum ultraviolet light such as (126) nm and dry etching resistance, a resist material containing the same and a resist material containing the same It is an object to provide a pattern forming method.

[0005]

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, have found that a fluorinated styrene derivative and an acrylic monomer having a fluorinated alcohol substituent Further, the present inventors have found that by using a polymer obtained by copolymerizing vinyl alcohol as a base resin, it is possible to provide a resist material which ensures transparency, resolution and dry etching resistance, and forms the present invention. It has been reached.

That is, the present invention provides the following polymer compound, resist material and pattern forming method. Claim 1: A polymer compound comprising a repeating unit represented by the following general formula (1).

Embedded image (Wherein R ¹ , R ² and R ³ are the same or different hydrogen atoms, fluorine atoms, or linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms or fluorinated alkyl groups) , R ⁴ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
R ⁵ is a single bond or a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, and R ⁶ and R ⁷ are a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms. ⁶ ,
At least one of R ⁷ contains one or more fluorine atoms.
X is -O- or -C (= O) -O-. R ⁸ is an acid labile group, 0 ≦ d <5, 0 ≦ e <5, 0 <f <5,
0 ≦ g ≦ 5, 0 ≦ h ≦ 5, and 0 <d + e <
5, 0 <g + h ≦ 5. Also, 0 ≦ a / (a + b +
c) <1, 0 ≦ b / (a + b + c) <1, 0 <(a +
b) / (a + b + c) <1 and 0 <c / (a + b +
c) <0.8. Claim 2: A resist material comprising the polymer compound according to claim 1. Claim 3: (A) the polymer compound according to claim 1, (B)
A chemically amplified positive resist composition comprising an organic solvent and (C) an acid generator. In a preferred embodiment, the resist composition further comprises a basic compound. Claim 5: Claim 3 or 4 further containing a dissolution inhibitor
The resist material as described. Claim 6: (1) a step of applying the resist material according to any one of claims 2 to 5 on a substrate, and (2) a high energy having a wavelength of 300 nm or less via a photomask after a heat treatment. Exposing with a beam or an electron beam;
(3) a step of performing heat treatment as needed, and then developing with a developer. In a preferred embodiment, the exposure wavelength is vacuum ultraviolet light having a wavelength of 180 nm or less and 100 nm or more, or soft X-ray light or an electron beam having a wavelength of 1 to 30 nm.

That is, as described above, polyvinyl phenol has an absorption window at around 160 nm and slightly improves transmittance, but is far from a practical level, and reduces double bonds between carbonyl and carbon-carbon. It turned out that this was a necessary condition for ensuring transmittance, but phenol exhibited excellent properties in terms of etching resistance and alkali solubility with respect to acrylic, and was further substituted with halogen, especially fluorine-substituted. It was found that by increasing the size of the window, there was an effect of improving the transmittance, and a practically close transmittance could be obtained.

However, as a problem in F ₂ exposure, when a phenol compound is used as a base polymer, the exposed portion is dissolved once when the exposure amount is increased.
In some cases, the dissolution rate was negatively reduced immediately, and the negative conversion was observed not only when phenol but also an alicyclic polymer was used. On the other hand, it has been found that α-methylphenol and a polymer obtained by fluorinating phenol suppress the behavior of negative conversion, but this is not sufficient. However, it was found that the (meth) acrylic polymer did not become negative at all.
Furthermore, it was found that the (meth) acrylic polymer was excellent in dissolution contrast, and that a rectangular pattern could be obtained even if the transmittance was low.

As a solubilizing group having the highest transparency, a fluorinated alcohol can be mentioned. Examples of pattern formation of cycloolefin-based resist with fluorinated alcohol are http
p /// ce055. cm. utexas. edu / r
essearch / 157 / 157_etch. htm,
Proc. SPIE, 3999 37 (2000), P
olym. Mater. Sci. Eng. 1997, 7
7, 449-450. Fluorinated alcohols do not have carbonyl bonds and have high transmittance because they are substituted by fluorine.

[0010] Further, the fluorinated alcohol has the same alkali solubility as the hydroxyl group of phenol, and also has adhesion to the substrate. Carboxylic acid also has good substrate adhesion,
Alkali solubility and good wettability of the developer is a functional group, but since the acidity is higher than fluorinated alcohol, the characteristics are greatly changed by a slight difference in the amount of carboxylic acid,
It was very difficult to control the characteristics. However,
Fluorinated alcohols have lower acidity than carboxylic acids,
Since it is comparable to phenol, it is a functional group that can easily control alkali solubility. Furthermore, the fluorinated alcohol can introduce a substituent after polymerizing the polymer, and the same method of synthesizing an acid labile group as phenol can be used. It is also possible to copolymerize a monomer having a double bond, in which a fluorinated alcohol is substituted with an acid labile group, and a fluorinated styrene derivative. However, a cycloolefin-based resist having a fluorinated alcohol is not sufficient for practical use in dry etching resistance. The present invention has responded to such a demand by using a polymer compound containing a repeating unit of the above formula (1).

Hereinafter, the present invention will be described in more detail.
The polymer compound of the present invention contains a repeating unit represented by the following general formula (1).

[0012]

Embedded image (Wherein R ¹ , R ² and R ³ are the same or different hydrogen atoms, fluorine atoms, or linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms or fluorinated alkyl groups) , R ⁴ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
R ⁵ is a single bond or a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, and R ⁶ and R ⁷ are a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms. ⁶ ,
At least one of R ⁷ contains one or more fluorine atoms.
X is -O- or -C (= O) -O-. R ⁸ is an acid labile group, 0 ≦ d <5, 0 ≦ e <5, 0 <f <5,
0 ≦ g ≦ 5, 0 ≦ h ≦ 5, and 0 <d + e <
5, 0 <g + h ≦ 5. Also, 0 ≦ a / (a + b +
c) <1, 0 ≦ b / (a + b + c) <1, 0 <(a +
b) / (a + b + c) <1 and 0 <c / (a + b +
c) <0.8. )

The linear, branched or cyclic alkyl group having 1 to 20 carbon atoms of R ^{1 to} R ³ includes methyl, ethyl, n-propyl, isopropyl and n-alkyl.
Examples thereof include a butyl group, a sec-butyl group, a tert-butyl group, a cyclopentyl group, a cyclohexyl group, a 2-ethylhexyl group, and an n-octyl group.
2, especially those having 1 to 10 carbon atoms are preferred. The fluorinated alkyl group is a group in which part or all of the hydrogen atoms of the above-mentioned alkyl group have been substituted with fluorine atoms, and is a trifluoromethyl group, a 2,2,2-trifluoroethyl group, , 3-trifluoropropyl group, 1,
Examples thereof include a 1,2,2,3,3,3-heptafluoropropyl group.

The alkyl group for R ^4, R ⁶ and R ⁷ includes methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-
Examples of the alkylene group for R ⁵ include alkyl groups having 1 to 10 carbon atoms among the alkyl groups for R ^{1 to} R ³ exemplified above, and a hydrogen atom is removed from these alkyl groups. And separated groups.

The acid labile groups represented by R ⁸ include:
Although various selections are made, in particular, groups represented by the following formulas (2) and (3), tertiary alkyl groups having 4 to 40 carbon atoms, and trialkylsilyl groups having 1 to 6 carbon atoms represented by the following formula (4) And an oxoalkyl group having 4 to 20 carbon atoms.

[0016]

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In the formula (2), R ⁹ has 4 to 2 carbon atoms.
0, preferably a tertiary alkyl group of 4 to 15, each alkyl group being a trialkylsilyl group having 1 to 6 carbon atoms, an oxoalkyl group having 4 to 20 carbon atoms, or the above general formula (4)
Wherein the tertiary alkyl group is specifically a tert-butyl group, a tert-amyl group,
-Diethylpropyl group, 1-ethylcyclopentyl group,
1-butylcyclopentyl group, 1-ethylcyclohexyl group, 1-butylcyclohexyl group, 1-ethyl-2-
A cyclopentenyl group, a 1-ethyl-2-cyclohexenyl group, a 2-methyl-2-adamantyl group, and the like;
Specific examples of the trialkylsilyl group include a trimethylsilyl group, a triethylsilyl group, and a dimethyl-tert-butylsilyl group. Specific examples of the oxoalkyl group include a 3-oxocyclohexyl group and a 4-methyl-
A 2-oxooxan-4-yl group, a 5-methyl-2-oxooxolan-5-yl group, and the like. a1 is 0
6 to an integer.

In the formula (3), R ¹⁰ and R ¹¹ represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms. , Ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, cyclopentyl, cyclohexyl, 2-ethylhexyl, n-octyl and the like. R ¹² has 1 to 1 carbon atoms
18, preferably a monovalent hydrocarbon group which may have 1 to 10 hetero atoms such as an oxygen atom, and is a linear, branched or cyclic alkyl group, and a part of these hydrogen atoms is a hydroxyl group , An alkoxy group, an oxo group, an amino group, an alkylamino group or the like, and specific examples thereof include the following substituted alkyl groups.

[0019]

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R ¹⁰ and R ¹¹ , R ¹⁰ and R ¹² , and R ¹¹ and R ¹² may form a ring, and when forming a ring, R ¹⁰ ,
R ¹¹ and R ¹² 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 (2) 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.

Further, substituents represented by the following formulas (2) -1 to (2) -9 can also be mentioned.

[0023]

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Here, R ¹⁶ is a linear chain having 1 to 10 carbon atoms;
A branched or cyclic alkyl group, R ¹⁷ is a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms.

R ¹⁸ is a linear, branched or cyclic alkyl group having 2 to 10 carbon atoms.

As an example of the compound represented by the formula (3),
1-methoxyethyl group, 1-ethoxyethyl group, 1-n
-Propoxyethyl group, 1-isopropoxyethyl group,
1-n-butoxyethyl group, 1-isobutoxyethyl group, 1-sec-butoxyethyl group, 1-tert-butoxyethyl group, 1-tert-amyloxyethyl group,
Linear such as 1-ethoxy-n-propyl group, 1-cyclohexyloxyethyl group, methoxypropyl group, ethoxypropyl group, 1-methoxy-1-methyl-ethyl group, 1-ethoxy-1-methyl-ethyl group, etc. Alternatively, a cyclic acetal group such as a branched acetal group, a tetrahydrofuranyl group, and a tetrahydropyranyl group may be mentioned, and an ethoxyethyl group, a butoxyethyl group, and an ethoxypropyl group are preferable.

Further, it may be cross-linked between molecules or between molecules by an acid labile group represented by the general formula (3a) or (3b).

[0028]

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In the formula, R ¹⁹ and R ^{20 each} represent a hydrogen atom or a carbon atom
Represents a straight-chain, branched-chain or cyclic alkyl group of 1 to 8;
Alternatively, R ¹⁹ and R ²⁰ may combine to form a ring, and when forming a ring, R ¹⁹ and R ²⁰ represent a linear or branched alkylene group having 1 to 8 carbon atoms. R ²¹ has 1 to 10 carbon atoms
Is a linear, branched or cyclic alkylene group;
Or an integer of 1 to 10, preferably 0 or 1 to 5, c is 1
-7. A is a (c + 1) -valent carbon number of 1 to 5
0 represents an aliphatic or alicyclic saturated hydrocarbon group, an aromatic hydrocarbon group or a heterocyclic group, and these groups may have a hetero atom interposed or a part of a hydrogen atom bonded to the carbon atom; May be substituted by a hydroxyl group, a carboxyl group, a carbonyl group or a fluorine atom. B is -CO
-O-, -NHCO-O- or -NHCONH- is shown.

In this case, A is preferably a divalent or tetravalent linear, branched or cyclic alkylene group having 1 to 20 carbon atoms, an alkyltriyl group, an alkyltetrayl group, or a 6 to 30 carbon atoms. These are arylene groups, and these groups may have a hetero atom interposed, and a part of the hydrogen atom bonded to the carbon atom may be substituted with a hydroxyl group, a carboxyl group, an acyl group or a halogen atom. C is preferably an integer of 1 to 3.

Particularly preferably, in the formula (3a), R
¹⁹ is a methyl or ethyl group, R ²⁰ is a hydrogen atom or a methyl group, b and d are 0, c is 1, and A is ethylene, 1,4-butylene or 1,4-cyclohexylene.

Next, in the formula (4), R ¹³ , R ¹⁴ , R ¹⁵
Is a monovalent hydrocarbon group such as a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and oxygen, sulfur, nitrogen,
It may contain a hetero atom such as fluorine, and R ¹³ and R ¹⁴ ,
R ¹³ and R ¹⁵ , and R ¹⁴ and R ¹⁵ may be bonded to each other to form a ring.

The tertiary alkyl group represented by the formula (4) 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.

As the tertiary alkyl group, the following formulas (4) -1 to (4) -18 can be specifically mentioned.

[0035]

Embedded image

In the formulas (4) -1 to (4) -18, R ²² is the same or different and is a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, or phenyl having 6 to 20 carbon atoms. And an aryl group such as a group. R ²³ and R ^{25 each} represent a hydrogen atom or a carbon atom
And 20 linear, branched or cyclic alkyl groups. R
²⁴ represents an aryl group having 6 to 20 carbon atoms such as a phenyl group.

Furthermore the following formula (4) -19, as shown in (4) -20, divalent or more alkylene groups, including R ²⁶ is an arylene group, within the molecule or between molecules of the polymer are crosslinked You may. Formulas (4) -19 and (4) -20
Among, similarly to R ²² are described above, R ²⁶ is a straight, branched or cyclic alkylene group or arylene group such as phenylene group, an oxygen atom or a sulfur atom, such as nitrogen atom It may contain a hetero atom. b1 is 1
-3.

[0038]

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Further, R ¹³ , R ¹⁴ and R ¹⁵ in the formula (4) may have a hetero atom such as oxygen, nitrogen and sulfur.
Specific examples include those represented by the following formulas (5) -1 to (5) -7.

R ⁹ in the formulas (2), (3) and (4)
R ¹² and R ¹⁵ are a phenyl group, a p-methylphenyl group, p
-Ethylphenyl group, unsubstituted or substituted aryl group such as alkoxy-substituted phenyl group such as p-methoxyphenyl group,
Aralkyl groups such as benzyl group and phenethyl group, or those groups having an oxygen atom, or a hydrogen atom bonded to a carbon atom being replaced with a hydroxyl group, or a carbonyl group having two hydrogen atoms being replaced with oxygen atoms An alkyl group represented by the following formulas (5) -1 to (5) -7,
Alternatively, oxoalkyl groups represented by formulas (5) -8 and (5) -9 can be mentioned.

[0041]

Embedded image

Examples of the trialkylsilyl group in which each alkyl group used as the acid labile group of R ⁸ has 1 to 6 carbon atoms include a trimethylsilyl group, a triethylsilyl group, and a tert-butyldimethylsilyl group. .

The oxoalkyl group having 4 to 20 carbon atoms includes a 3-oxocyclohexyl group and a group represented by the following formula.

[0044]

Embedded image

The above general formulas (2), (3) and (4)
The acid labile group described in (1) can also replace the hydrogen atom of the hydroxyl group of the fluorinated hydroxystyrene [unit (a)].

When the fluorinated styrene is copolymerized with a monomer having an acid labile group-substituted fluoroalcohol, the polymer compound of the present invention provides a practically sufficient dissolution contrast due to the alkali solubility of the fluoroalcohol. However, in order to further improve the dissolution contrast, it may have a repeating unit in which a phenol or carboxyl group represented by the following formulas (6) -1 to (6) -6 is substituted with an acid labile group.

[0047]

Embedded image

Here, in the formulas (6) -1 to (6) -6, R
¹ , R ² , R ³ and R ⁸ are the same as described above, and R ²⁷ is a single bond or a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms. Also, d, e, and f are 0 ≦ d <5, 0
≦ e <5, 1 ≦ f <5.

The polymer compound of the present invention is derived from, in addition to the above-mentioned units, a monomer having a substituent for further improving adhesion, a monomer for improving dry etching resistance, and a (meth) acrylate monomer. Units can be included. The monomer for improving adhesion is
Phenol, acid anhydride, ester (lactone), carbonate, alcohol, carboxylic acid, carboxylic amide,
It contains a hydrophilic substituent such as sulfonic amide and ketone, and includes, for example, those represented by the following formulas (7) -1 to (7) -60.

[0050]

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[0051]

Embedded image

[0052]

Embedded image

[0053]

Embedded image

R ¹ , R ² , R ³ , and R ⁴ are the same as described above;
R ²⁸ , R ²⁹ and R ³⁰ 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 ′ is a single bond or an alkylene group having 1 to 4 carbon atoms, and R ″ and R ′ ″ are a hydrogen atom, a fluorine atom, an alkyl group having 1 to 4 carbon atoms or a fluorinated alkyl group. i and j are 1 or 2.

In the above formulas (1) and (2), a, b,
c is 0 ≦ a / (a + b + c) <1, preferably 0 ≦ a
/(A+b+c)≦0.9, more preferably 0 ≦ a /
(A + b + c) ≦ 0.8, 0 ≦ b / (a + b + c) <
1, 0 ≦ b / (a + b + c) ≦ 0.7, more preferably 0 ≦ b / (a + b + c) ≦ 0.5, 0 <(a + b) /
(A + b + c) <1, preferably 0.05 ≦ (a + b)
/(A+b+c)≦0.9, more preferably 0.1 ≦
(A + b) / (a + b + c) ≦ 0.8, 0 <c / (a +
b + c) <0.8, preferably 0.1 ≦ c / (a + b +
c) ≦ 0.7, more preferably 0.2 ≦ c / (a + b +
c) ≦ 0.6.

In this case, when another unit exemplified above other than the units a, b, and c is represented by (Q) _x , x / (a +
b + c + x) is from 0 to 0.5, especially from 0 to 0.4;
+ B + c + x = 1.

The weight average molecular weight of the polymer compound of the present invention is 2,000 to 200,000, especially 3,000.
~ 100,000.

When the above-mentioned polymer compound is produced, generally, a monomer and a solvent which give the above-mentioned units are mixed, a catalyst is added, and a polymerization reaction is carried out while heating or cooling as the case may be. The polymerization reaction depends on the type of initiator (or catalyst), the method of initiation (light, heat, radiation, plasma, etc.),
It is also governed by polymerization conditions (temperature, pressure, concentration, solvent, additives) and the like. 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 the usual methods.

The monomer giving the unit c is represented by the following formula (C) -1.

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The method for synthesizing the monomer (C) -1 is as follows.
The following method is mentioned.

Embedded image

The polymer compound of the present invention is suitably used as a base resin for a resist material. Therefore, the resist material of the present invention contains the above polymer compound as a base resin. In this case, the resist material of the present invention is particularly effectively used as a chemically amplified type, and is particularly preferably used as a chemically amplified positive type.

The chemically amplified positive resist material according to the present invention comprises (A) the above-mentioned polymer compound, (B) an organic solvent, and (C)
It contains an acid generator, and preferably contains (D) a basic compound and / or (E) a dissolution inhibitor.

The organic solvent (B) used in the present invention may be any organic solvent in which an acid generator, a base resin, a dissolution inhibitor and the like can be dissolved. Parts (parts by weight, hereinafter the same)
-5,000 parts, especially 200-3,000 parts, are used. 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 Ethers such as glycol 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-ethoxypropion Ethyl acid, acetic acid ter
Esters such as t-butyl, tert-butyl propionate, and propylene glycol-mono-tert-butyl ether acetate are exemplified. Further, a fluorinated organic solvent can also be used. Specifically, 2-fluoroanisole, 3-fluoroanisole, 4-fluoroanisole, 2,3-difluoroanisole, 2,4-difluoroanisole, 2,5-difluoroanisole, 5,8-difluoro-1, 4-benzodioxane, 2,3-difluorobenzyl alcohol, 1,3-difluoro-2-propanol, 2 ′,
4'-difluoropropiophenone, 2,4-difluorotoluene, trifluoroacetaldehyde ethyl hemiacetal, trifluoroacetamide, trifluoroethanol, 2,2,2-trifluoroethyl butyrate, ethyl heptafluorobutyrate, ethyl hepta Fluorobutyl 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-4,4,4-
Trifluorobutyrate, ethyl-4,4,4-trifluorocrotonate, ethyltrifluorosulfonate, ethyl-3- (trifluoromethyl) butyrate,
Ethyl trifluoropyruvate, ethyl trifluoroacetate, 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, 2H-perfluoro-1-
Decanol, perfluoro (2,5-dimethyl-3,6
-Dioxane anionic) acid methyl ester, 2H-
Perfluoro-5-methyl-3,6-dioxanonane,
1H, 1H, 2H, 3H, 3H-perfluorononane-
1,2-diol, 1H, 1H, 9H-perfluoro-
1-nonanol, 1H, 1H-perfluorooctanol, 1H, 1H, 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, butyl trifluoromethylacetate, methyl 3-trifluoromethoxypropionate, perfluorocyclohexanone, propylene glycol trifluoromethyl ether, trifluoro Butyl acetate, 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione and the like. One of these can be used alone, or two or more can be used as a mixture, but the present invention is not limited thereto. In the present invention, among these organic solvents, in addition to diethylene glycol dimethyl ether, 1-ethoxy-2-propanol, and ethyl lactate, which have the highest solubility of the acid generator in the resist component, propylene glycol monomethyl ether acetate, which is a safe solvent, And a mixed solvent thereof are preferably used.

Examples of the acid generator (C) include an onium salt of the following general formula (8), a diazomethane derivative of the formula (9), a glyoxime derivative of the formula (10), a β-ketosulfone derivative, a disulfone derivative, and nitrobenzyl. Sulfonate derivatives, sulfonic acid ester derivatives, imido-yl sulfonate derivatives, and the like.

[0065] _{^{(R 30) b M + K}} - (8) ( where, R ³⁰ is a straight-chain having 1 to 12 carbon atoms, branched or cyclic alkyl group, an aryl group or a carbon number of 6 to 12 carbon atoms Represents an aralkyl group of 7 to 12, M ⁺ represents iodonium or sulfonium, K ⁻ represents a non-nucleophilic counter ion, and b is 2 or 3.)

As the alkyl group for R ^30, a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group, a 2-
An oxocyclohexyl group, a norbornyl group, an adamantyl group and the like can be mentioned. 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. 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.

[0067]

Embedded image (However, R ³¹ and R ³² 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 carbon atom having 7 to 12 carbon atoms. 12 represents an aralkyl group.)

Examples of the alkyl group for R ³¹ and R ³² 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 fluorobenzene group, a chlorobenzene group, a 1,2,3,4,5-pentafluorobenzene group, and the like. Examples of the aralkyl group include a benzyl group and a phenethyl group.

[0069]

Embedded image (Provided that R ³³ , R ³⁴ and R ³⁵ are linear having 1 to 12 carbon atoms;
It represents a branched or cyclic alkyl group or a halogenated alkyl group, an aryl group having 6 to 12 carbon atoms or an aryl group, or an aralkyl group having 7 to 12 carbon atoms. Also,
R ³⁴ and R ³⁵ may be bonded to each other to form a cyclic structure. In the case of forming a cyclic structure, R ³⁴ and R ³⁵ each represent a linear or branched alkylene group having 1 to 6 carbon atoms. . )

As the alkyl group, halogenated alkyl group, aryl group, halogenated aryl group and aralkyl group of R ³³ , R ³⁴ and R ³⁵ , the same groups as those described for R ³¹ and R ³² can be mentioned. The alkylene group for R ³⁴ and R ³⁵ 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-
(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 Onium salts such as bis (benze) Sulfonyl) diazomethane, bis (p- toluenesulfonyl) diazomethane, bis (xylene sulfonyl) diazomethane, bis (cyclohexyl sulfonyl) diazomethane, bis (cyclopentyl sulfonyl) diazomethane, bis (n- butylsulfonyl)
Diazomethane, bis (isobutylsulfonyl) diazomethane, bis (sec-butylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis (t
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-
Diazomethane derivatives such as cyclohexylsulfonyl-1- (tert-amylsulfonyl) diazomethane and 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) -α
Glyoxime derivatives such as -dimethylglyoxime, bis-o- (xylenesulfonyl) -α-dimethylglyoxime, bis-o- (camphorsulfonyl) -α-dimethylglyoxime, 2- (cyclohexylcarbonyl)
-2- (p-toluenesulfonyl) propane, 2-isopropylcarbonyl-2- (p-toluenesulfonyl)
Β-ketosulfone derivatives such as propane, diphenyldisulfone, disulfone derivatives such as dicyclohexyldisulfone, nitrobenzylsulfonate derivatives such as 2,6-dinitrobenzyl p-toluenesulfonate and 2,4-dinitrobenzyl p-toluenesulfonate; 2,3-
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-yl-sulfonate derivatives such as 3-dicarboximido-yl-tosylate, 5-norbornene-2,3-dicarboximido-yl-n-butylsulfonate, etc., and triphenylsulfonium trifluoromethanesulfonate; Triphenylmethanesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, trifluoromethanesulfonic acid tris (p-
Onium such as tert-butoxyphenyl) sulfonium, triphenylsulfonium p-toluenesulfonate, diphenylsulfonium p-toluenesulfonate (p-tert-butoxyphenyl), and tris (p-tert-butoxyphenyl) sulfonium p-toluenesulfonate Salt, bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (n-butylsulfonyl) diazomethane, bis (isobutylsulfonyl) diazomethane, bis (sec-butylsulfonyl) diazomethane, Bis (n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl)
Diazomethane derivatives such as diazomethane and bis (tert-butylsulfonyl) diazomethane; bis-o- (p-
Glyoxime derivatives such as 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. The onium salt is excellent in the effect of improving the rectangularity, and the diazomethane derivative and the glyoxime derivative are excellent in the standing wave reducing effect. However, the fine adjustment of the profile can be performed by combining the two.

The compounding amount of the acid generator is 100
Parts to 0.2 to 15 parts, particularly preferably 0.5 to 8 parts, and if less than 0.2 part, the amount of acid generated at the time of exposure is small, and sensitivity and resolution may be poor. If the amount exceeds 15 parts, the transmittance of the resist is reduced, and the resolution may be poor.

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 the compounding, the diffusion rate of the acid in the resist film is suppressed, the resolution is improved, the sensitivity change after exposure is suppressed, the dependency on the substrate and the environment is reduced, and the exposure margin and the pattern profile are improved. (JP-A-5-232706, JP-A-5-249683 and JP-A-5-249683).
No. 158239, No. 5-249662, No. 5-25
No. 7282, No. 5-289322, No. 5-28934
0 publication etc.).

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 of the compound include a nitrogen-containing compound having a hydroxy group, a nitrogen-containing compound having a hydroxyphenyl group, an alcoholic nitrogen-containing compound, an amide derivative, and an imide derivative, and an aliphatic amine is particularly preferably used.

Specifically, the primary aliphatic amines include ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tertiary aliphatic amines.
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), 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-pyridine, 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.

Further, 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.). , P-toluenesulfonate and the like. Examples of the nitrogen-containing compound having a hydroxy group, the nitrogen-containing compound having a hydroxyphenyl group, and the alcoholic nitrogen-containing compound include 2-hydroxypyridine, aminocresol, and 2,4-quinoline. Diol, 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,
Examples include N-dimethylacetamide, propionamide, benzamide and the like. Examples of the imide derivative include phthalimide, succinimide, and maleimide.

Further, basic compounds represented by the following general formulas (11) and (12) can be blended.

[0079]

Embedded image (Wherein, R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁷ , and R ⁴⁸ are each independently a linear, branched, or cyclic alkylene group having 1 to 20 carbon atoms, R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R ⁴⁹ and R ^{50 each} represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an amino group, R ⁴⁴ and R ⁴⁵ , R ⁴⁵ and R ⁴⁶ , R ⁴⁴ and R ⁴⁶ , R ⁴⁴ and R ⁴⁵ and R ⁴⁶ ; R
⁴⁹ and R ⁵⁰ may be combined with each other to form a ring. S,
T and U each represent an integer of 0 to 20. Where S,
When T and U = 0, R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R ⁴⁹ and R ⁵⁰ do not contain a hydrogen atom. )

Here, the alkylene group of R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁷ and R ⁴⁸ has 1 to 20 carbon atoms, preferably 1 carbon atom.
-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 ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R ⁴⁹ and R ⁵⁰ 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 ⁴⁴ and R ⁴⁵ , R ⁴⁵ and R ⁴⁶ , R ⁴⁴ and R ^46
46, if R ⁴⁴ and R ⁴⁵ and R ^46, R ⁴⁹ and R ⁵⁰ form rings, the number of carbon atoms in the ring is 1 to 20, more preferably 1 to
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.

S, T and U are each an integer of 0 to 20, more preferably 1 to 10, further preferably 1 to 8.

Specific examples of the compounds represented by the above formulas (11) and (12) 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.

In particular, tertiary amines, aniline derivatives, pyrrolidine derivatives, pyridine derivatives, quinoline derivatives, amino acid derivatives, nitrogen-containing compounds having a hydroxy group, nitrogen-containing compounds having a hydroxyphenyl group, alcoholic nitrogen-containing compounds, amide derivatives, Imide derivative, tris {2- (methoxymethoxy) ethyl} amine, tris {2- (2-methoxyethoxy) ethyl} amine, tris [2-{(2-methoxyethoxy) methyl} ethyl]
Amines, 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, preferably 0.01 to 2 parts, based on 100 parts of the total base resin. ~ 1 part is preferred. If the amount is less than 0.01 part, the effect of the compounding is not obtained, and if it exceeds 2 parts, the sensitivity may be excessively lowered.

In the present invention, if necessary, a dissolution inhibitor can be blended as the component (E). As the dissolution inhibitor of the component (E), compounds having a molecular weight of 3,000 or less, whose solubility in an alkali developing solution is changed by the action of an acid,
In particular, a compound in which a part or all of a low molecular weight phenol or carboxylic acid derivative having a molecular weight of 2,500 or less is substituted with an acid-labile substituent is mentioned.

Examples of the phenol or carboxylic acid derivative having a molecular weight of 2,500 or less include bisphenol A, bisphenol H, bisphenol S, 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 and the like can be mentioned, and examples of the acid-labile substituent include those similar to the above-mentioned acid-labile group.

Examples of the dissolution inhibitor preferably used include bis (4- (2'-tetrahydropyranyloxy)
Phenyl) methane, bis (4- (2′-tetrahydrofuranyloxy) phenyl) methane, bis (4-tert
-Butoxyphenyl) methane, bis (4-tert-butoxycarbonyloxyphenyl) methane, bis (4-
tert-butoxycarbonylmethyloxyphenyl)
Methane, bis (4- (1′-ethoxyethoxy) phenyl) methane, bis (4- (1′-ethoxypropyloxy) phenyl) methane, 2,2-bis (4 ′-(2 ″)
-Tetrahydropyranyloxy)) propane, 2,2-
Bis (4 '-(2 "-tetrahydrofuranyloxy)
Phenyl) propane, 2,2-bis (4′-tert-
Butoxyphenyl) propane, 2,2-bis (4′-t
tert-butoxycarbonyloxyphenyl) propane, 2,2-bis (4-tert-butoxycarbonylmethyloxyphenyl) propane, 2,2-bis (4 ′
-(1 ''-ethoxyethoxy) phenyl) propane,
2,2-bis (4 ′-(1 ″ -ethoxypropyloxy) phenyl) propane, 4,4-bis (4′-
Tert-butyl (2 ″ -tetrahydropyranyloxy) phenyl) valerate, 4,4-bis (4 ′-(2 ″
-Tetrahydrofuranyloxy) phenyl) valeric acid te
tert-butyl, 4,4-bis (4'-tert-butoxyphenyl) tert-butyl valerate, 4,4-bis (4-tert-butoxycarbonyloxyphenyl)
Tert-butyl valerate, 4,4-bis (4′-ter
tert-butyl t-butoxycarbonylmethyloxyphenyl) valerate, tert-butyl 4,4-bis (4 ′-(1 ″ -ethoxyethoxy) phenyl) valerate,
Tert-Butyl 4,4-bis (4 ′-(1 ″ -ethoxypropyloxy) phenyl) valerate, tris (4-
(2′-tetrahydropyranyloxy) phenyl) methane, tris (4- (2′-tetrahydrofuranyloxy) phenyl) methane, tris (4-tert-butoxyphenyl) methane, tris (4-tert-butoxycarbonyloxyphenyl) ) Methane, Tris (4-te
rt-butoxycarbonyloxymethylphenyl) methane, tris (4- (1′-ethoxyethoxy) phenyl) methane, tris (4- (1′-ethoxypropyloxy) phenyl) methane, 1,1,2-tris (4 '-
(2 ″ -tetrahydropyranyloxy) phenyl) ethane, 1,1,2-tris (4 ′-(2 ″ -tetrahydrofuranyloxy) phenyl) ethane, 1,1,2-
Tris (4′-tert-butoxyphenyl) ethane,
1,1,2-tris (4′-tert-butoxycarbonyloxyphenyl) ethane, 1,1,2-tris (4′-tert-butoxycarbonylmethyloxyphenyl) ethane, 1,1,2-tris (4 '-(1'-
Ethoxyethoxy) phenyl) ethane, 1,1,2-tris (4 ′-(1′-ethoxypropyloxy) phenyl) ethane and the like can be mentioned.

The addition amount of the dissolution inhibitor in the resist material of the present invention is not more than 20 parts, preferably not more than 15 parts with respect to 100 parts of solids in the resist material. If the amount is more than 20 parts, the monomer component increases and the heat resistance of the resist material decreases.

The resist composition of the present invention may further contain a solubility enhancer. The dissolution enhancer that can be used in the present invention is used for the purpose of improving the hydrophobicity of the fluorine-containing base polymer. In other words, even if the base polymer is rendered water-soluble or alkali-solubilized by irradiation with a VUV excimer laser, if the hydrophobicity of the portion that is not irradiated with light is too high, the wettability of the developer is low, and an efficient development process cannot be performed. is there. Therefore, adding a water-soluble compound in advance is an effective means for ensuring high resolution. As the dissolution enhancer that can be used in the present invention, any known water-soluble compounds, water-soluble resins, alkali-soluble compounds, alkali-soluble resins, and the like can be used without any particular limitation. On this occasion,
It may be a fluorinated compound to increase the transparency at the VUV wavelength. That is, alkylene glycol or an oligomer or polymer thereof, a carboxylic acid-containing compound or a resin having a high acid value, a hydroxy group-containing compound or a resin having a high hydroxy value, and the like are preferable. In addition, amine, amide, silanol, imide, and sulfone Compounds or resins containing water-soluble substituents such as acids can also be used.

In the resist composition of the present invention, a polyacrylic acid or a derivative thereof, a norbornene derivative-maleic anhydride alternating polymer, or a polyacrylic acid or a derivative thereof may be used as a base resin in addition to the composition of the present invention. Copolymer, tetracyclododecene derivative-maleic anhydride alternating polymer and tertiary or quaternary copolymer with polyacrylic acid or a derivative thereof, norbornene derivative-maleimide alternating polymer and polyacrylic acid or a derivative thereof with terpolymer Or one selected from a quaternary copolymer, a tetracyclododecene derivative-maleimide alternating polymer and a tertiary or quaternary copolymer of polyacrylic acid or a derivative thereof, or polynorbornene and a metathesis ring-opening polymer, or It is possible to blend two or more high molecular polymers.

Further, a compound having a group represented by ≡C—COOH in the molecule can be blended with the resist composition of the present invention.

As the compound having a group represented by ≡C-COOH in the molecule, for example, one or more compounds selected from the following groups I and II can be used, but are not limited thereto. Not something. By blending this component, the PED stability of the resist is improved, and the edge roughness on the nitride film substrate is improved. [Group I] Part or all of the hydrogen atoms of the phenolic hydroxyl group of the compounds represented by the following general formulas (A1) to (A10) is -R ⁴⁰¹ -COOH (R ⁴⁰¹ is a linear or And the molar ratio of the phenolic hydroxyl group (C) to the group (D) represented by ΔC—COOH in the molecule is C / (C + D) = 0.1.
-1.0. [Group II] Compounds represented by the following general formulas (A11) to (A15).

[0095]

Embedded image (Wherein, R ⁴⁰⁸ represents a hydrogen atom or a methyl group. R
⁴⁰² and R ⁴⁰³ each represent a hydrogen atom or a linear or branched alkyl or alkenyl group having 1 to 8 carbon atoms. R
⁴⁰⁴ represents a hydrogen atom, a linear or branched alkyl or alkenyl group having 1 to 8 carbon atoms, or — (R ⁴⁰⁹ ) _h −
COOR 'group (R' is a hydrogen atom or an -R ^{40 9} -COO
H). R ⁴⁰⁵ is-(CH ₂ ) _i- (i = 2 to 1
0), an arylene group having 6 to 10 carbon atoms, a carbonyl group,
It represents a sulfonyl group, an oxygen atom or a sulfur atom. R ⁴⁰⁶ represents an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen atom or a sulfur atom. R ⁴⁰⁷ represents a hydrogen atom, a linear or branched alkyl group or alkenyl group having 1 to 8 carbon atoms, or a phenyl group or a naphthyl group respectively substituted with a hydroxyl group. R ⁴⁰⁹ is a straight or branched alkylene of 1 to 10 carbon atoms. ^R410 represents a hydrogen atom, a linear or branched alkyl group or alkenyl group having 1 to 8 carbon atoms, or-
R ^{411 represents a} —COOH group. R ⁴¹¹ represents a linear or branched alkylene group having 1 to 10 carbon atoms. j is an integer of 0-5. u and h are 0 or 1. s1, t1, s
2, t2, s3, t3, s4, and t4 are respectively s1 + t
1 = 8, s2 + t2 = 5, s3 + t3 = 4, s4 + t4
= 6 and has at least one hydroxyl group in each phenyl skeleton. κ is a number that makes the compound of the formula (A6) have a weight average molecular weight of 1,000 to 5,000. λ represents the compound of the formula (A7) having a weight average molecular weight of 1,
It is a number between 000 and 10,000. )

[0096]

Embedded image ( ^R402 , ^R403 , and ^R411 have the same meaning as described above.
⁴¹² represents a hydrogen atom or a hydroxyl group. s5 and t5 are s5
≧ 0 and t5 ≧ 0, which are numbers that satisfy s5 + t5 = 5. h ′ is 0 or 1. )

As this component, specifically, the following general formula AI
Compounds represented by -1 to 14 and AII-1 to 10 can be exemplified, but are not limited thereto.

[0098]

Embedded image (R ″ represents a hydrogen atom or a CH ₂ COOH group, and in each compound, 10 to 100 mol% of R ″ is CH ₂ CO
OH group. α and κ have the same meanings as described above. )

[0099]

Embedded image

The compound having a group represented by ≡C—COOH in the molecule can be used alone or in combination of two or more. ≡C-
The amount of the compound having a group represented by COOH is from 0 to 5 parts, preferably from 0.1 to 100 parts, per 100 parts of the base resin.
5 parts, more preferably 0.1 to 3 parts, even more preferably 0.1 to 2 parts. If the amount is more than 5 parts, the resolution of the resist material may decrease.

In order to prevent the wettability of the developing solution and the pattern defects after the development, a hydrating compound such as a sulfonamide compound, a carboxylic acid amide compound and a polyether compound may be added.

Further, an acetylene alcohol derivative can be added to the resist material of the present invention as an additive, whereby the generation of microbubbles in the resist solution can be suppressed.

As the acetylene alcohol derivative, those represented by the following general formulas (S1) and (S2) can be suitably used.

[0104]

Embedded image (Wherein, R ⁵⁰¹ , R ⁵⁰² , R ⁵⁰³ , R ⁵⁰⁴ , and R ⁵⁰⁵ are each a hydrogen atom or a linear, branched, or cyclic alkyl group having 1 to 8 carbon atoms, and X and Y are 0 or Indicates a positive number and satisfies the following values: 0 ≦ X ≦ 30, 0 ≦ Y ≦ 30, 0 ≦ X
+ Y ≦ 40. )

As acetylene alcohol derivatives, Surfynol 61, Surfynol 82, Surfynol 104, Surfynol 104E, Surfynol 104H, Surfynol 104A, Surfynol TG, Surfynol PC, Surfynol 44 are preferred.
0, Surfynol 465, Surfynol 485 (A
ir Products and Chemicals
Inc. And Surfynol E1004 (manufactured by Nissin Chemical Industry Co., Ltd.).

The acetylene alcohol derivative is added in an amount of 0.01 to 2% by weight based on 100% by weight of the resist material.
More preferably, it is 0.02 to 1% by weight. If the amount is less than 0.01% by weight, the coatability and the effect of suppressing microbubbles may not be sufficiently obtained.

The resist composition of the present invention may contain, as an optional component, a surfactant which is commonly used for improving coating properties. In addition, 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 examples thereof include perfluoroalkylpolyoxyethylene ethanol, fluorinated alkyl esters, perfluoroalkylamine oxides, and fluorine-containing organosiloxane compounds. For example, Florard "F
C-430 "," FC-431 "(all manufactured by Sumitomo 3M Limited), Surflon" S-141 "," S-1 "
45, S-381, S-383 (all manufactured by Asahi Glass Co., Ltd.), Unidyne DS-401, DS
-403 "," DS-451 "(all manufactured by Daikin Industries, Ltd.), MegaFac" F-8151 "," F-1
71 "," F-172 "," F-173 "," F-17 "
7 "(all manufactured by Dainippon Ink and Chemicals, Inc.)," X-7
0-092 "and" X-70-093 "(all manufactured by Shin-Etsu Chemical Co., Ltd.). Preferably, Florard "FC-430" (manufactured by Sumitomo 3M Limited) and "X-70-093" (manufactured by Shin-Etsu Chemical Co., Ltd.) are exemplified. Further, in order to improve the wettability of the developer, a nonionic surfactant having various hydrocarbon chains can be added.

A pattern can be formed by using the resist material of the present invention by using a known lithography technique. .1 to 1.0 μ
m on a hot plate.
~ 200 ° C, 10 seconds ~ 10 minutes, preferably 80 ~ 15
Prebake at 0 ° C. for 30 seconds to 5 minutes. Next, a mask for forming a target pattern is held over the resist film, and a deep ultraviolet ray having a wavelength of 300 nm or less, an excimer laser, a high energy ray such as an X-ray or an electron beam is exposed at a dose of about 1 to 200 mJ / cm ² . Preferably 10 to 100
After irradiating to about mJ / cm ^2, post exposure bake (PEB) is performed on a hot plate at 60 to 150 ° C. for 10 seconds to 5 minutes, preferably at 80 to 130 ° C. for 30 seconds to 3 minutes. Further, using a developing solution of an aqueous alkali solution such as 0.1 to 5%, preferably 2 to 3% of tetramethylammonium hydroxide (TMAH),
Dipping for 10 seconds to 3 minutes, preferably 30 seconds to 2 minutes (d
ip) method, paddle method, spray method (sp
(ray) method to form a target pattern on the substrate by performing development. In addition, the material of the present invention is preferably a deep ultraviolet ray or excimer laser having a wavelength of 254 to 120 nm, particularly an ArF having a wavelength of 193 nm, among high energy rays.
57 nm F ₂ , 146 nm Kr ₂ , 134 nm Kr
Excimer laser such as Ar, 126 nm Ar ₂ ,
It is most suitable for fine patterning by 3 nm, 11 nm, and 8 nm soft X-rays, EBs, and X-rays. In addition, when the above range is out of the upper limit and the lower limit, a desired pattern may not be obtained.

[0110]

The resist material of the present invention is sensitive to high energy rays and has excellent sensitivity, resolution and plasma etching resistance at a wavelength of 200 nm or less, particularly 190 nm or less. 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 and perpendicular pattern to the substrate, Therefore, it is suitable as a fine pattern forming material for VLSI manufacturing.

[0111]

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] Polymer 1: (4-hydroxystyrene)-(2,6-difluoro-4-hydroxystyrene) -monomer 1 copolymer (0.5: 0.
2: 0.3) Synthesis of 4-acetoxystyrene in a 500 mL flask.
26 g, 4.06 g of 2,6-difluoro-4-acetoxystyrene, and 13.4 g of Monomer 1 shown below were charged and dissolved in 80 g of toluene. Next, after sufficiently removing oxygen from the system, 0.68 g of an initiator AIBN (azobisisobutyronitrile) was charged, and the temperature was raised to 60 ° C.
The polymerization reaction was performed for 4 hours.

The reaction mixture was treated with hexane / ether (3:
2) After pouring into a mixed solvent to precipitate the obtained polymer, the polymer was transferred to a 1 L flask, and methanol / TH
It was dissolved in 140 g of a mixed solvent of F (4: 1). 15 g of triethylamine and 5 g of distilled water were added to the system,
And the hydrolysis reaction was carried out for 24 hours.

After the reaction mixture was concentrated, it was poured into 1 L of a 2% aqueous solution of acetic acid to precipitate the obtained polymer. Further, the obtained polymer was dissolved in acetone, and the solution was dissolved in 1 L of a 1% aqueous acetic acid solution.
After pouring into the mixture to precipitate the polymer, it was sufficiently dried. 14.5 g of the title polymer thus obtained had a weight average molecular weight of 12,000 g /
mol from the GPC elution curve (= Mw / M
It was confirmed that n) was a polymer of 1.95. Further, by ¹ H-NMR measurement, the obtained polymer was 4
-Hydroxystyrene / 2,6-difluoro-4-hydroxystyrene / monomer 1 at 51:20:29.

[0115]

Embedded image

[Synthesis Example 2] Polymer 2: (4-hydroxystyrene)-(2,3,4,5,6-pentafluorostyrene) -monomer 1 copolymer (0.4: 0.
3: 0.3) Synthesis of 4-acetoxystyrene in a 500 mL flask.
52 g, 2.86 g of 2,3,4,5,6-pentafluorostyrene, and 13.4 g of the above monomer 1 were charged and dissolved in 80 g of toluene. Next, after sufficiently removing oxygen in the system, 0.66 g of an initiator AIBN was charged, and the temperature was raised to 60 ° C. to carry out a polymerization reaction for 24 hours.

The reaction mixture was treated with hexane / ether (3:
2) After pouring into a mixed solvent to precipitate the obtained polymer, the polymer was transferred to a 1 L flask, and methanol / TH
It was dissolved in 150 g of a mixed solvent of F (4: 1). 16 g of triethylamine and 5 g of distilled water were added to the system,
And the hydrolysis reaction was carried out for 24 hours.

After the reaction mixture was concentrated, it was poured into 1 L of a 2% acetic acid aqueous solution to precipitate the obtained polymer. Further, the obtained polymer was dissolved in acetone, and the solution was dissolved in 1 L of a 1% aqueous acetic acid solution.
After pouring into the mixture to precipitate the polymer, it was sufficiently dried. 16.2 g of the title polymer thus obtained had a weight average molecular weight of 13,000 g /
mol from the GPC elution curve (= Mw / M
It was confirmed that n) was a polymer of 2.1. Furthermore,
¹ H-NMR measurement showed that the obtained polymer contained 4-hydroxystyrene / 2,3,4,5,6-pentafluorostyrene / monomer 1 at 41:29:30.

[Synthesis Example 3] Polymer 3: (2, 6
-Difluoro-4-hydroxystyrene) -monomer 1
Synthesis of Copolymer (0.5: 0.5) In a 500 mL flask, 8.8 g of 2,6-difluoro-4-acetoxystyrene and 18.3 of the above monomer 1 were added.
g, and dissolved in 80 g of toluene. Next, after oxygen in the system was sufficiently removed, 0.58 g of an initiator AIBN was charged, and the temperature was raised to 60 ° C. to carry out a polymerization reaction for 24 hours.

The reaction mixture was treated with hexane / ether (3:
2) After pouring into a mixed solvent to precipitate the obtained polymer, the polymer was transferred to a 1 L flask, and methanol / TH
It was dissolved in 145 g of a mixed solvent of F (4: 1). 16 g of triethylamine and 5 g of distilled water were added to the system,
And the hydrolysis reaction was carried out for 24 hours.

After the reaction mixture was concentrated, it was poured into 1 L of a 2% aqueous solution of acetic acid to precipitate the obtained polymer. Further, the obtained polymer was dissolved in acetone, and the solution was dissolved in 1 L of a 1% aqueous acetic acid solution.
After pouring into the mixture to precipitate the polymer, it was sufficiently dried. 13.1 g of the title polymer thus obtained had a weight average molecular weight of 12,000 g /
mol from the GPC elution curve (= Mw / M
n) was confirmed to be 1.90 polymer. Further, by ¹ H-NMR measurement, the obtained polymer was 4
-Hydroxystyrene / monomer 1 at 51:49.

[Synthesis Example 4] Polymer 4: (2, 6
-Difluoro-4-hydroxystyrene) -monomer 2
Synthesis of Copolymer (0.5: 0.5) In a 500 mL flask, 7.82 g of 2,6-difluoro-4-acetoxystyrene and 19.1 g of Monomer 2 shown below were charged and dissolved in 80 g of toluene. Was. Next, after sufficiently removing oxygen from the system, the initiator AIBN 0.5
2 g was charged, the temperature was raised to 60 ° C., and a polymerization reaction was performed for 24 hours.

The reaction mixture was treated with hexane / ether (3:
2) After pouring into a mixed solvent to precipitate the obtained polymer, the polymer was transferred to a 1 L flask, and methanol / TH
It was dissolved in 150 g of a mixed solvent of F (4: 1). 17 g of triethylamine and 6 g of distilled water were added to the system,
And the hydrolysis reaction was carried out for 24 hours.

After the reaction mixture was concentrated, it was poured into 1 L of a 2% acetic acid aqueous solution to precipitate the obtained polymer. Further, the obtained polymer was dissolved in acetone, and the solution was dissolved in 1 L of a 1% aqueous acetic acid solution.
After pouring into the mixture to precipitate the polymer, it was sufficiently dried. 16.3 g of the title polymer thus obtained had a weight average molecular weight of 13,000 g /
mol from the GPC elution curve (= Mw / M
n) was confirmed to be 1.80 polymer. Further, ¹ H-NMR measurement showed that the obtained polymer contained 2,6-difluoro-4-hydroxystyrene / monomer 2 at a ratio of 50:50.

[0125]

Embedded image

[Synthesis Example 5] Polymer 5: (2,3
-Difluoro-4-hydroxystyrene) -monomer 2
Synthesis of Copolymer (0.5: 0.5) In a 500 mL flask, 7.82 g of 2,3-difluoro-4-acetoxystyrene and 19.
1 g was added and dissolved in 80 g of toluene. Next, after sufficient removal of oxygen in the system, 0.52 g of an initiator AIBN was charged, and the temperature was raised to 60 ° C. to carry out a polymerization reaction for 24 hours.

The reaction mixture was treated with hexane / ether (3:
2) After pouring into a mixed solvent to precipitate the obtained polymer, the polymer was transferred to a 1 L flask, and methanol / TH
It was dissolved in 150 g of a mixed solvent of F (4: 1). 17 g of triethylamine and 6 g of distilled water were added to the system,
And the hydrolysis reaction was carried out for 24 hours.

After the reaction mixture was concentrated, it was poured into 1 L of a 2% aqueous solution of acetic acid to precipitate the obtained polymer. Further, the obtained polymer was dissolved in acetone, and the solution was dissolved in 1 L of a 1% aqueous acetic acid solution.
After pouring into the mixture to precipitate the polymer, it was sufficiently dried. 16.1 g of the title polymer thus obtained had a weight average molecular weight of 12,000 g /
mol from the GPC elution curve (= Mw / M
n) was confirmed to be 1.90 polymer. Further, ¹ H-NMR measurement showed that the obtained polymer contained 2,3-difluoro-4-hydroxystyrene / monomer 2 at 51:49.

[Synthesis Example 6] Polymer 6: (2,3
-Difluoro-4-hydroxystyrene) -monomer 3
Synthesis of Copolymer (0.5: 0.5) In a 500 mL flask, 7.82 g of 2,3-difluoro-4-acetoxystyrene and 17.6 g of monomer 3 shown below were charged and dissolved in 80 g of toluene. Was. Next, after sufficiently removing oxygen from the system, the initiator AIBN 0.5
2 g was charged, the temperature was raised to 60 ° C., and a polymerization reaction was performed for 24 hours.

The reaction mixture was treated with hexane / ether (3:
2) After pouring into a mixed solvent to precipitate the obtained polymer, the polymer was transferred to a 1 L flask, and methanol / TH
It was dissolved in 150 g of a mixed solvent of F (4: 1). 17 g of triethylamine and 6 g of distilled water were added to the system,
And the hydrolysis reaction was carried out for 24 hours.

After the reaction mixture was concentrated, it was poured into 1 L of a 2% acetic acid aqueous solution to precipitate the obtained polymer. Further, the obtained polymer was dissolved in acetone, and the solution was dissolved in 1 L of a 1% aqueous acetic acid solution.
After pouring into the mixture to precipitate the polymer, it was sufficiently dried. 16.1 g of the title polymer thus obtained had a weight average molecular weight of 9,000 g / m 2 by light scattering.
ol and the degree of dispersion (= Mw / M) from the GPC elution curve.
n) was confirmed to be 2.01. Further, ¹ H-NMR measurement showed that the obtained polymer contained 2,3-difluoro-4-hydroxystyrene / monomer 3 in a ratio of 50:50.

[0132]

Embedded image

[0133]

Embedded image

[0134]

Embedded image

Next, the above-mentioned polymer was evaluated as follows. 1 g of the polymer obtained in Synthesis Examples 1 to 6 above was sufficiently dissolved in 10 g of propylene glycol monomethyl ether acetate, and the solution was filtered through a 0.2 μm filter.
A polymer solution was prepared. On the other hand, as a comparative example,
A polymer in which 30% of a monodisperse polyhydroxystyrene having a dispersity (Mw / Mn) of 1.00 and a degree of dispersion (Mw / Mn) of 1.10 was replaced with a tetrahydropyranyl group was synthesized to obtain a transmittance comparison polymer 1. Further, the molecular weight is 15,000, and the degree of dispersion is 1.70.
The polymethyl methacrylate of Comparative Example Polymer 2, a molecular weight of 9,000 at a meta / para ratio of 40/60 and a dispersity of 2.5
The novolak polymer of No. 0 was designated as Comparative Example Polymer 3. 1 g of the obtained comparative polymer was sufficiently dissolved in 10 g of propylene glycol monomethyl ether acetate,
A polymer solution was similarly prepared by filtration through a 0.2 μm filter.

The above polymer solution was spin-coated on a MgF ₂ substrate, and heated at 100 ° C. for 9 hours using a hot plate.
Baking for 0 seconds, the polymer layer having a thickness of 200 nm is
Created on _two substrates. Vacuum ultraviolet photometer (manufactured by JASCO Corporation, V
UV 200S) using 248 nm, 193 nm, 15
The transmittance at 7 nm was measured. Table 1 shows the results.

[0137]

[Table 1]

The polymer solution was spin-coated on a Si substrate and baked at 100 ° C. for 90 seconds using a hot plate to form a polymer film having a thickness of 300 nm.
The wafer on which the polymer film was formed was evaluated under the following two conditions. Table 2 shows the results. (1) Etching test with CHF ₃ / CF ₄ system gas Dry etching equipment TE manufactured by Tokyo Electron Limited
Using -8500P, the difference in thickness of the polymer film before and after etching was determined. The etching conditions are as shown below. Chamber pressure 40.0 Pa RF power 1,300 W Gap 9 mm CHF ₃ gas flow rate 30 ml / min CF ₄ gas flow rate 30 ml / min Ar gas flow rate 100 ml / min Time 60 sec (2) Etching test with Cl ₂ / BCl ₃ gas Nikki Anelva Dry etching system L-50 manufactured by Co., Ltd.
Using 7DL, the difference in thickness of the polymer film before and after etching was determined. The etching conditions are as shown below. Chamber pressure 40.0 Pa RF power 300 W Gap 9 mm Cl ₂ gas flow rate 30 ml / min BCl ₃ gas flow rate 30 ml / min CHF ₃ gas flow rate 100 ml / min O ₂ gas flow rate 2 ml / min Time 60 sec

[0139]

[Table 2]

Evaluation of resist Next, the above polymer and an acid generator (PAG) shown below were used.
1, 2), a basic compound is converted to a fluorine-based surfactant FC-
430 (manufactured by Sumitomo 3M Limited) is sufficiently dissolved in propylene glycol monomethyl ether acetate (PGMEA) containing 100 ppm, and 0.1 μm PT
The solution was filtered through an FE filter to prepare a resist solution. Table 3 shows the composition. The obtained resist solution is formed into a film of DUV-30 (manufactured by Nissan Chemical Industries, Ltd.) with a thickness of 55 nm on a silicon wafer, and the reflectance is 1% with KrF light (248 nm).
The substrate was spin-coated on the following substrate, and baked at 100 ° C. for 90 seconds using a hot plate to reduce the thickness of the resist to 300 nm. This is excimer laser stepper (Nikon Corporation, NSR-S202A, NA
−0.6, σ0.75, 2/3 annular illumination), and immediately after exposure, baked at 110 ° C. for 90 seconds, 2.3
Developing with an aqueous solution of 8% tetramethylammonium hydroxide for 60 seconds, the line and space are 1:
1 was obtained.

The obtained resist pattern was evaluated as follows. Table 3 shows the results. Evaluation method: 0.25 μm line and space:
The exposure amount resolved at 1 was taken as the optimum exposure amount (sensitivity: Eop), and the minimum line width of the line and space separated at this exposure amount was taken as the resolution of the evaluation resist.

[0142]

[Table 3]

[0143]

Embedded image

From the results shown in Tables 1 to 3, it was found that the resist material using the polymer compound of the present invention was an F ₂ excimer laser (1
Sufficient transparency at a wavelength around 57 nm), resolution and sensitivity were satisfied, and the difference in film thickness after etching was small, indicating that the film had excellent dry etching resistance.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03F 7/38 G03F 7/38 H01L 21/027 H01L 21/30 502R (72) Inventor Jun Hatakeyama Naka Niigata 28-1 Nishifukushima, Kushiro-mura, Kushiro-gun Shin-Etsu Chemical Industry Co., Ltd. In-house (72) Inventor Atsushi Watanabe 28-1 Nishifukushima, Oku-ku, Nakatsugi-gun, Niigata Prefecture Shin-Etsu Chemical Co., Ltd. Inventor Masataka Endo 1006 Kadoma Kadoma, Kadoma City, Osaka (72) Inventor Shinji Kishimura 1006 Kadoma Kadoma, Kadoma City, Osaka (72) Inventor Mitsutaka Tani 2805 Imafukunakadai, Kawagoe City, Saitama Prefecture, Japan Chemical Research Laboratory (72) Inventor Satoru Satoru Miyazawa 2805 Imafukunakadai, Kawagoe City, Saitama Prefecture, Japan Chemical Research Laboratory (72) Inventor Kentaro Tsutsumi 2805, Imafukunakadai, Kawagoe-shi, Saitama Prefecture Central Glass Co., Ltd. Chemical Research Laboratory (72) Inventor Kazuhiko Maeda 3-7-1, Kandanishikicho, Chiyoda-ku, Tokyo Central Glass Co., Ltd. F-term (reference) 2H025 AA01 AA02 AA09 AB16 AC04 AC05 AC06 AC08 AD03 BE00 BG00 CC03 CC20 FA01 FA03 FA12 FA17 2H096 AA25 BA11 BA20 EA03 EA05 EA06 EA07 FA01 GA08 JA01 JA02 4J100 AB07P AB07Q AB10Q AC53P AC53Q AE09R AL08R BA02R BA03P BA03R BA03R BA04 BA03R BA03R BA02R BB18Q BB18R BC03R BC04R BC08R BC09R BC22R BC23R BC43R BC53R BC58R BC59R CA04 CA05 JA38

Claims (7)

[Claims] 1. A polymer compound comprising a repeating unit represented by the following general formula (1). Embedded image (Wherein R ¹ , R ² and R ³ are the same or different hydrogen atoms, fluorine atoms, or linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms or fluorinated alkyl groups) , R ⁴ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
R ⁵ is a single bond or a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, and R ⁶ and R ⁷ are a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms. ⁶ ,
At least one of R ⁷ contains one or more fluorine atoms.
X is -O- or -C (= O) -O-. R ⁸ is an acid labile group, 0 ≦ d <5, 0 ≦ e <5, 0 <f <5,
0 ≦ g ≦ 5, 0 ≦ h ≦ 5, and 0 <d + e <
5, 0 <g + h ≦ 5. Also, 0 ≦ a / (a + b +
c) <1, 0 ≦ b / (a + b + c) <1, 0 <(a +
b) / (a + b + c) <1 and 0 <c / (a + b +
c) <0.8. ) 2. A resist material comprising the polymer compound according to claim 1. (A) the polymer compound according to (1),
A chemically amplified positive resist composition comprising (B) an organic solvent and (C) an acid generator. 4. The method according to claim 3, further comprising a basic compound.
The resist material as described. 5. The resist material according to claim 3, further comprising a dissolution inhibitor. 6. A step of (1) applying the resist material according to any one of claims 2 to 5 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. 7. The pattern forming method according to claim 6, wherein the exposure wavelength is vacuum ultraviolet light having a wavelength of 180 nm or less and 100 nm or more, or soft X-ray light or an electron beam having a wavelength of 1 to 30 nm.