JP2002003537A - New ester compound, polymer compound, resist material and method of pattern forming - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resist material, a base resin of which is a polymer compound by this invention, which is useful for the microfabrication by the electron beam or far ultraviolet ray because the material is sensitive to a high energy beam and is excellent in a sensitivity, a resolving power, and an etching resistance. Especially, the same has the characteristic which forms a perpendicular pattern to a substrate because there is little absorption on the wavelength of an ArF excimer laser or a KrF excimer laser. SOLUTION: The objective ester compound is shown by formula (1). (In the formula, R1 shows hydrogen, a methyl group, or CH2CO2R3, R2 shows a hydrogen atom, a methyl group, or CO2R3, R3 shows a 1-15C straight chain, branched, or cyclic alkyl group, Z is a 2-20C divalent hydrocarbon group which may have a hetero atom and forms a single ring or a crosslinked ring together with the combined carbon atom, m is 0 or 1, n is 0, 1, 2, or 3 and the number with which is satisfied of 2m+n=2 or 3).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to (1) a specific ester compound, and (2) a compound containing this compound as a structural unit and exhibiting high sensitivity and good resolution when incorporated into a resist material as a base resin. In particular, the present invention relates to a polymer compound that provides a resist material suitable as a fine pattern forming material for VLSI manufacturing, (3) a resist material containing the polymer compound, and (4) a pattern forming method using the resist material.

[0002]

2. Description of the Related Art In recent years, as the integration and speed of LSIs have been increased and the pattern rules have been required to be finer, far-ultraviolet lithography has been regarded as a promising next-generation fine processing technology. Among them, KrF excimer laser light, A
Photolithography using an rF excimer laser beam as a light source has been eagerly sought to be realized as an indispensable technique for ultrafine processing of 0.3 μm or less.

[0003] In a resist material for a KrF excimer laser, polyhydroxystyrene, which has a practical level of transparency and etching resistance, has become a practically standard base resin. As the resist material for ArF excimer laser, a material such as a derivative of polyacrylic acid or polymethacrylic acid or a polymer compound containing an aliphatic cyclic compound in a main chain thereof has been studied. In each case, the basic form is to protect a part or all of the alkali-soluble portion of the alkali-soluble resin with an appropriate acid-eliminable group, and by variously selecting an acid-eliminable protective group, The overall performance of the resist material is adjusted.

Examples of acid-labile protecting groups include tert-
Butoxycarbonyl (described in Japanese Patent Publication No. 27660/1990), tert-butyl (Japanese Unexamined Patent Publication No. 62-115440, J. Photopolym. Sci. Techn.)
ol. 7 [3], 507 (1994), etc.), 2-tetrahydropyranyl (described in JP-A-2-80515, JP-A-5-88367, etc.), 1-ethoxyethyl (described in JP-A-2-19847, Described in Japanese Unexamined Patent Publication No. 4-215661). However, as further miniaturization of the pattern rule is required, none of these acid-labile protecting groups can be said to exhibit satisfactory performance.

That is, tert-butoxycarbonyl and t
Ert-butyl has a remarkably low reactivity to acid, and in order to secure a difference in dissolution rate before and after exposure, a considerable amount of energy ray irradiation must be performed to generate a sufficient amount of acid. If the acid generator is of a strong acid generating type, the reaction proceeds even if the amount of generated acid is small, so that the exposure amount can be kept relatively low. However, in this case, the influence of the deactivation of the generated acid by the basic substance in the air becomes relatively large, causing problems such as a T-top pattern. On the other hand, 2-tetrahydropyranyl and 1-ethoxyethyl have an excessively high reactivity to an acid, so that the elimination reaction proceeds randomly only by the generation of an acid by exposure without waiting for a heat treatment. Large dimensional change between developments. Furthermore, when used as a protecting group for carboxylic acid, the dissolution inhibitory effect on alkali is low, so that the dissolution rate of the unexposed portion is high, and the film is reduced during development. It also has the disadvantage that its properties are extremely reduced. In any case, a difference in dissolution rate between before and after exposure cannot be ensured, and as a result, the resist material has an extremely low resolution.

[0006]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above circumstances, and (1) an ester compound which gives a polymer compound having excellent acid-decomposability; And (3) a resist material using the polymer compound as a base resin, and (4) a pattern forming method using the resist material. The purpose is to.

[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, obtained by the method described below, a novel ester compound represented by the following general formula (1) Is useful as a raw material for a polymer compound having excellent acid decomposability, and a weight average molecular weight of 1,000 to 500,
It has been found that a resist material using 000 new polymer compounds as a base resin has high sensitivity and high resolution, and that this resist material is extremely effective for precise fine processing.

That is, the present invention provides the following ester compounds. [I] An ester compound represented by the following general formula (1).

Embedded image (Wherein, R ¹ is a hydrogen atom, a methyl group or CH ₂ CO ₂ R
³ is shown. R ² represents a hydrogen atom, a methyl group or CO ₂ R ³ . R ³ represents a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms. Z is a divalent hydrocarbon group which may contain a heteroatom having 2 to 20 carbon atoms to form a single ring or a bridged ring together with the carbon atom to be bonded. m is 0 or 1, n
Is 0, 1, 2, or 3, and is a number satisfying 2m + n = 2 or 3. The present invention also provides the following polymer compound. [II] A weight average molecular weight of 1,000, characterized by containing a repeating unit represented by the following general formula (1a) using an ester compound represented by the above general formula (1) as a raw material.
~ 500,000 high molecular compounds.

Embedded image (In the formula, R ¹ , R ² , Z, m, and n have the same meanings as described above.) [III] Further, at least one repeating unit represented by the following formulas (2a) to (10a) is contained. The polymer compound according to [II].

Embedded image (Wherein R ¹ and R ² are the same as above. K is 0 or 1)
It is. R ⁴ represents a hydrogen atom or a monovalent hydrocarbon group having a carboxy group or a hydroxyl group having 1 to 15 carbon atoms.
At least one of R ^{5 to} R ⁸ represents a monovalent hydrocarbon group having a carboxy group or a hydroxyl group having 1 to 15 carbon atoms,
The rest each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms. R ^{5 to} R ^8
May form a ring with each other, in which case, R ⁵ to
At least one of R ⁸ is a divalent hydrocarbon group having a carboxy group or a hydroxyl group having 1 to 15 carbon atoms, and the rest is each independently a single bond or a linear, branched or branched group having 1 to 15 carbon atoms. Shows a cyclic alkylene group. R ⁹ has 3 to 3 carbon atoms.
15 of -CO ₂ - represents a monovalent hydrocarbon group containing a partial structure. At least one of R ^{10 to} R ¹³ has 2 to 2 carbon atoms.
15 of -CO 2 _- represents a monovalent hydrocarbon group containing a partial structure, while the remaining R's are independently hydrogen or 1 carbon atoms
It represents 15 linear, branched or cyclic alkyl groups. R
^{10 to} R ¹³ may form a ring with each other, in which case at least one of R ^{10 to} R ¹³ has 1 to 1 carbon atoms.
5 represents a divalent hydrocarbon group containing a —CO ₂ — partial structure, and the rest are each independently a single bond or a C 1 to C 15
Represents a linear, branched or cyclic alkylene group. R
¹⁴ represents a polycyclic hydrocarbon group having 7 to 15 carbon atoms or an alkyl group containing a polycyclic hydrocarbon group. R ¹⁵ represents an acid labile group. X is -CH ₂ - shows a or -O-. Y is-
O- or - ^{(NR 16)} - ^{indicates, R 16} is a straight, branched or cyclic alkyl group of hydrogen or 1 to 15 carbon atoms. )

Further, the present invention provides the following resist material. [IV] A resist material comprising the polymer compound described in [II] or [III]. [V] A resist material comprising the polymer compound described in the above [II] or [III], a compound generating an acid in response to a high energy beam or an electron beam, and an organic solvent. Further, the present invention provides the following pattern forming method. [VI] a step of applying the resist material of [IV] or [V] on the substrate, a step of exposing with a high energy beam or an electron beam through a photomask after the heat treatment, and, if necessary, after a heat treatment Developing using a developer.

In the ester compound of the general formula (1) or the high molecular compound having the formula (1a) as a structural unit, a cycloalkylcycloalkyl or cycloalkylcycloalkyl represented by the following formula (1b) is used as an acid-eliminable protecting group. Alkenyl is used, and tert-butoxycarbonyl or tert
This solves any of the following problems: low reactivity of -butyl with acid, too high reactivity of 2-tetrahydropyranyl or 1-ethoxyethyl with acid, and weak resistance to alkali developing solution.

[0011]

Embedded image (Wherein, Z, m and n have the same meanings as above.
The chain line indicates a bond (the same applies hereinafter). )

The ester compound of the general formula (1) is decomposed while generating an olefin compound under acidic conditions to generate a carboxylic acid. This mechanism itself is not different from the decomposition of tertiary alkyl esters such as tert-butyl ester, but there is a great difference in the speed of its progress. That is, in the decomposition of a tertiary alkyl ester by an acid,
First, a carboxylic acid and a tertiary alkyl cation are generated, and then the cation is released by proton release to form an olefin compound, and the reaction is completed. The rate-determining step of this decomposition reaction is the elimination of the cations in the latter half. However, in the ester compound of the general formula (1), the reduction of ring distortion and the formation of a conjugated system are probably very powerful driving forces. The progress of this stage is very fast. In addition, the re-activity of the resulting olefin is very low, resulting in an acid decomposability far exceeding that of other tertiary alkyl esters.

On the other hand, since the ester compound of the formula (1) is basically a tertiary alkyl ester, decomposition proceeds indefinitely during exposure and development like 2-tetrahydropyranyl and 1-ethoxyethyl. It does not cause film loss during development. Therefore, when a high molecular compound containing this compound as a constituent unit is blended into a resist material as a base resin, the dissolution rate of the unexposed portion is extremely slow, and the region irradiated with light at an appropriate exposure dose is rapidly alkali-soluble. Thus, a highly sensitive and high resolution resist material having high dissolution contrast can be obtained.

Hereinafter, the present invention will be described in more detail.
The novel ester compound of the present invention is represented by the following general formula (1).

[0015]

Embedded image

Here, R ¹ is a hydrogen atom, a methyl group or a C
H ₂ CO ₂ R ³ is shown. It will be described later examples of R ^3. R ² represents a hydrogen atom, a methyl group or CO ₂ R ³ .
R ³ represents a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert group -Butyl group, tert-amyl group, n-pentyl group, n-hexyl group, cyclopentyl group, cyclohexyl group, ethylcyclopentyl group, butylcyclopentyl group, ethylcyclohexyl group, butylcyclohexyl group, adamantyl group, ethyladamantyl group, butyladamantyl And the like. Z is a divalent hydrocarbon group which may include a heteroatom having 2 to 20 carbon atoms that forms a monocyclic or bridged ring with the carbon atom to be bonded, and specifically, cyclopropane, cyclobutane, cyclopentane, cyclohexane, A hydrocarbon group forming a single ring such as cycloheptane and cyclooctane, bicyclo [2.2.
1] heptane, bicyclo [2.2.2] octane, bicyclo [4.4.0] decane, tricyclo [5.2.1.
[0 ^2,6 ] decane and the like, and a part of the hydrogen atoms contained therein are substituted with alkyl, hydroxy, alkoxy, acyloxy, alkylcarbonyl, hydroxycarbonyl, alkoxycarbonyl, oxo, etc. And a hydrocarbon group forming a ring. m is 0 or 1, n is 0, 1, 2, or 3, and 2m + n = 2 or 3.

Specific examples of the ester compound of the present invention are shown below, but the invention is not limited thereto.

[0018]

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The production of the ester compound of the present invention can be carried out, for example, by the following steps, but is not limited thereto.

[0020]

Embedded image

Here, R ¹ , R ² , Z, m and n are the same as described above. Hal is bromine or chlorine.

Step A is a step in which a nucleophilic addition reaction is performed on the carbonyl of the cyclic ketone compound to obtain a tertiary alcohol. Specific examples of this stage include, for example, Grignard reaction, but are not limited thereto. The reaction proceeds easily under known conditions, but preferably in a solvent such as tetrahydrofuran or diethyl ether,
It is preferable that the starting material is mixed with a cyclic ketone compound, an alkyl halide, and magnesium, and heated or cooled as necessary.

Step B is a step in which the tertiary alcohol obtained in the previous step is converted into an unsaturated acid ester. The reaction proceeds easily under known conditions, but it is preferable to mix a raw material of a tertiary alcohol, an unsaturated carboxylic acid halide such as methacrylic acid chloride, or a base such as triethylamine in a solvent such as methylene chloride. Then, it is preferable to perform cooling if necessary.

The present invention is characterized by containing a repeating unit represented by the following general formula (1a) using the ester compound represented by the above general formula (1) as a raw material, and having a weight average molecular weight of 1,000 to 500, 000, preferably 5,000
0-100,000 high molecular compounds are provided.

[0025]

Embedded image

Here, R ¹ , R ² , Z, m and n are the same as above. In this case, the polymer compound of the present invention contains, as a structural unit, at least one of the units of the following general formulas (2a) to (10a) obtained by using the following general formulas (2) to (10) as a monomer. You can also.

[0027]

Embedded image

[0028]

Embedded image

[0029] In the above formulas, X is -CH ₂ - shows a or -O-. Y is -O- or - ^{(NR 16)} - ^{indicates, R 16} is a hydrogen atom or a C15 straight, a branched or cyclic alkyl group. k is 0 or 1. Therefore, the expressions (6a) to (9a) are obtained by the following expression (6a-1)
To (9a-2).

[0030]

Embedded image

Where R¹, R², X are the same as above
You. R⁴Is a hydrogen atom or a carboxy group having 1 to 15 carbon atoms
Or a monovalent hydrocarbon group containing a hydroxyl group.
Contains carboxyethyl, carboxybutyl, carboxy
Cyclopentyl, carboxycyclohexyl, carboxy
Cinorbornyl, carboxyadamantyl, hydroxy
Ethyl, hydroxybutyl, hydroxycyclopent
, Hydroxycyclohexyl, hydroxynorborny
And hydroxyadamantyl. R ⁵~ R
⁸At least one is a carboxy group having 1 to 15 carbon atoms or
Represents a monovalent hydrocarbon group containing a hydroxyl group, and the rest represents
Each is independently a hydrogen atom or a straight-chain having 1 to 15 carbon atoms.
Shows a branched or cyclic alkyl group. C 1-15
A monovalent hydrocarbon group containing a ruboxyl group or a hydroxyl group
Specifically, carboxy, carboxymethyl,
Boxyethyl, carboxybutyl, hydroxymethyl,
Hydroxyethyl, hydroxybutyl, 2-carboxy
Ethoxycarbonyl, 4-carboxybutoxycarboni
, 2-hydroxyethoxycarbonyl, 4-hydroxy
Sibutoxycarbonyl, carboxycyclopentyloxy
Cicarbonyl, carboxycyclohexyloxycarbo
Nil, carboxynorbornyloxycarbonyl, car
Boxyadamantyloxycarbonyl, hydroxycycl
Lopentyloxycarbonyl, hydroxycyclohexyl
Leoxycarbonyl, hydroxynorbornyloxyca
Rubonyl, hydroxyadamantyloxycarbonyl, etc.
Can be exemplified. C1-C15 linear, branched, cyclic
Specific examples of the alkyl group of R³What was exemplified in
The same can be exemplified. R⁵~ R⁸Form a ring with each other
In which case R⁵~ R⁸At least
One contains a carboxy group or a hydroxyl group having 1 to 15 carbon atoms.
The divalent hydrocarbon group having
A single bond or a linear, branched or cyclic C1-C15
Shows an alkylene group. A carboxy group having 1 to 15 carbon atoms or
Is a specific example of a divalent hydrocarbon group containing a hydroxyl group.
Is a monovalent carbon having a carboxy group or a hydroxyl group.
Those excluding one hydrogen atom from those exemplified for the hydrogen group
Can be exemplified. C1-C15 linear, branched, cyclic
Specific examples of the alkylene group of³Also illustrated in
From which one hydrogen atom has been removed.

R⁹Is -CO having 3 to 15 carbon atoms₂-Partial structure
A monovalent hydrocarbon group containing
Oxooxolan-3-yl, 4,4-dimethyl-2-
Oxooxolan-3-yl, 4-methyl-2-oxo
Oxan-4-yl, 2-oxo-1,3-dioxola
N-4-ylmethyl, 5-methyl-2-oxooxola
N-5-yl and the like. R¹⁰~ R¹³Less of
One is -CO having 2 to 15 carbon atoms₂-Contains partial structure
And the rest are each independently water
Linear or branched or cyclic, having 1 to 15 carbon atoms
Shows an alkyl group. -CO having 2 to 15 carbon atoms₂-Partial structure
Specific examples of the monovalent hydrocarbon group containing
-Oxooxolan-3-yloxycarbonyl, 4,
4-dimethyl-2-oxooxolan-3-yloxy
Carbonyl, 4-methyl-2-oxooxan-4-i
Ruoxycarbonyl, 2-oxo-1,3-dioxola
4-N-ylmethyloxycarbonyl, 5-methyl-2
-Oxooxolan-5-yloxycarbonyl and the like
Can be shown. A linear, branched, or cyclic carbon having 1 to 15 carbon atoms
Specific examples of the alkyl group include R³Same as the one exemplified in
Can be exemplified. R¹⁰~ R¹³Form a ring with each other
In which case R¹⁰~ R ¹³Few
At least one is -CO having 1 to 15 carbon atoms.₂-Including partial structures
The divalent hydrocarbon group having
A single bond or a linear, branched, or cyclic
Represents a alkylene group. -CO having 1 to 15 carbon atoms₂-Partial structure
Specific examples of the divalent hydrocarbon group containing
-Oxo-2-oxapropane-1,3-diyl, 1,
3-dioxo-2-oxapropane-1,3-diyl,
1-oxo-2-oxabutane-1,4-diyl, 1,
3-dioxo-2-oxabutane-1,4-diyl and the like
In addition, the above -CO₂A monovalent hydrocarbon containing a partial structure
For example, one hydrogen atom removed from those exemplified in the group
Can be shown. A linear, branched, or cyclic carbon having 1 to 15 carbon atoms
Specific examples of the alkylene group include R³Is it exemplified in
From which one hydrogen atom has been removed.

R ¹⁴ represents a polycyclic hydrocarbon group having 7 to 15 carbon atoms or an alkyl group containing a polycyclic hydrocarbon group;
Specifically, norbornyl, bicyclo [3.3.1] nonyl, tricyclo [5.2.1.0 ^2,6 ] decyl, adamantyl, ethyladamantyl, butyladamantyl,
Norbornylmethyl, adamantylmethyl and the like can be exemplified. R ¹⁵ represents an acid labile group. k is 0 or 1.
X is -CH ₂ - indicates a or -O-, Y is -O- or -
(NR ¹⁶ ) —, wherein R ¹⁶ is a hydrogen atom or carbon atom 1
Represents a linear, branched or cyclic alkyl group of from 15 to 15,
Specifically exemplified the same ones as exemplified for R ^3.

Specific examples of the acid labile group represented by R ¹⁵ include groups represented by the following formulas (L1) to (L4), and those having 4 carbon atoms.
To 20, preferably 4 to 15, tertiary alkyl groups, each alkyl group having 1 to 6 carbon atoms, a trialkylsilyl group, and 4 to 20 carbon atoms oxoalkyl group.

[0035]

Embedded image

In the formula, R ^L01 and R ^L02 represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms. , Propyl group, isopropyl group, n-butyl group,
sec-butyl group, tert-butyl group, cyclopentyl group, cyclohexyl group, 2-ethylhexyl group, n-
An octyl group can be exemplified. ^RL03 has 1 to 1 carbon atoms
8, preferably a monovalent hydrocarbon group which may have a hetero atom such as 1 to 10 oxygen atoms, such as a linear, branched or cyclic alkyl group, and a part of these hydrogen atoms is a hydroxyl group , An alkoxy group, an oxo group, an amino group, an alkylamino group and the like, and specific examples thereof include the following substituted alkyl groups.

[0037]

Embedded image

R ^L01 and R ^L02 , R ^L01 and R ^L03 , R ^L02 and R ^L03 may form a ring, and when a ring is formed, R ^L01 , R ^L02 , R
^L03 has 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms.
Represents a linear or branched alkylene group.

R ^L04 has 4 to 20 carbon atoms, preferably 4 carbon atoms.
A tertiary alkyl group having 1 to 15 carbon atoms, each alkyl group being a trialkylsilyl group having 1 to 6 carbon atoms, an oxoalkyl group having 4 to 20 carbon atoms or a group represented by the above formula (L1); Specific examples of the group include a tert-butyl group, a tert-amyl group, a 1,1-diethylpropyl group, a 1-ethylcyclopentyl group, a 1-butylcyclopentyl group, a 1-ethylcyclohexyl group, a 1-butylcyclohexyl group, -Ethyl-2-cyclopentenyl group, 1-ethyl-2-cyclohexenyl group, 2-methyl-2-adamantyl group, and the like. Specific examples of the trialkylsilyl group include a trimethylsilyl group, a triethylsilyl group, and dimethyl. -Tert-butylsilyl group and the like, and specific examples of the oxoalkyl group include 3-oxocyclohexyl. Group, 4-methyl-2-oxooxan-4-yl group, 5-methyl-5-oxo-dioxolane -
4-yl group and the like. y is an integer of 0-6.

R ^L05 represents a linear or branched alkyl group having 1 to 8 carbon atoms or an optionally substituted aryl group having 6 to 20 carbon atoms, and is a linear, branched or cyclic alkyl group. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a tert-amyl group, an n-pentyl group, and an n-hexyl group. Specific examples of the optionally substituted aryl group include a phenyl group, a methylphenyl group, a naphthyl group, an anthryl group, a phenanthryl group, and a pyrenyl group. m is 0 or 1, n
Is 0, 1, 2, or 3, and is a number satisfying 2m + n = 2 or 3.

R^L06Is a linear or branched C1-C8
Or a cyclic alkyl group or substituted with 6 to 20 carbon atoms
Represents an optionally substituted aryl group, specifically R^L05Same as
Can be exemplified. R^L07~ R^L16Are each
Independently contains a hydrogen atom or a heteroatom having 1 to 15 carbon atoms
A monovalent hydrocarbon group which may be a methyl group, an ethyl group
Group, propyl group, isopropyl group, n-butyl group, se
c-butyl group, tert-butyl group, tert-amyl
Group, n-pentyl group, n-hexyl group, n-octyl
Group, n-nonyl group, n-decyl group, cyclopentyl group,
Cyclohexyl, cyclopentylmethyl, cyclope
Ethyl group, cyclopentylbutyl group, cyclohexyl
Silmethyl group, cyclohexylethyl group, cyclohexyl
A linear, branched or cyclic alkyl group such as a rubutyl group,
Some of these hydrogen atoms are hydroxyl, alkoxy,
Boxy group, alkoxycarbonyl group, oxo group, amino
Group, alkylamino group, cyano group, mercapto group,
Examples include those substituted with a thio group, a sulfo group, or the like.
You. R^L07~ R^L16May form a ring with each other
(For example, R^L07And R^L08, R^L07When
R^L09, R^L08And R^L10, R ^L09And R^L10,
R^L11And R^L12, R^L13And R^L14Etc.), on the spot
Divalent optionally containing a heteroatom having 1 to 15 carbon atoms
And a hydrocarbon group represented by the above-mentioned monovalent hydrocarbon group.
Examples thereof include those in which one hydrogen atom has been removed therefrom. Ma
R^L07~ R^L16Is bonded to adjacent carbon
May bond to each other without any intervention to form a double bond
(For example, R^L07And R^L09, R^L09And R ^L15,
R^L13And R^L15etc).

Specific examples of the linear or branched acid labile group represented by the formula (L1) include the following groups.

[0043]

Embedded image

Specific examples of the cyclic acid labile group represented by the above formula (L1) include a tetrahydrofuran-2-yl group, a 2-methyltetrahydrofuran-2-yl group and a tetrahydropyran-2-yl group. And 2-methyltetrahydropyran-2-yl group.

Specific examples of the acid labile group of the above formula (L2) 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 acid labile group of the above formula (L3) include 1-methylcyclopentyl, 1-ethylcyclopentyl, 1-n-propylcyclopentyl, 1-isopropylcyclopentyl, 1-n-butylcyclopentyl, -Sec-butylcyclopentyl, 1-methylcyclohexyl, 1-ethylcyclohexyl, 3-methyl-1-cyclopenten-3-yl, 3-ethyl-1-cyclopenten-3-yl, 3-methyl-1-cyclohexene-3- Yl, 3-ethyl-1-cyclohexene-3
-Yl and the like.

Specific examples of the acid labile group of the formula (L4) include the following groups.

[0048]

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In the production of the polymer compound of the present invention, the ester compound of the above general formula (1) is used as a first monomer, and one kind of compound selected from the compounds of the above general formulas (2) to (10) is used. The above can be performed by a copolymerization reaction using the second and subsequent monomers.

In the copolymerization reaction, by appropriately adjusting the proportion of each monomer, it is possible to obtain a polymer compound capable of exhibiting preferable performance when used as a resist material.

In this case, the polymer compound of the present invention comprises, in addition to (i) the monomer of the above formula (1), (ii) at least one monomer of the above formulas (2) to (10), iii) Monomers containing a carbon-carbon double bond other than the above (i) and (ii), for example, substituted acrylates such as methyl methacrylate, methyl crotonate, dimethyl maleate, and dimethyl itaconate; Unsaturated carboxylic acids such as maleic acid, fumaric acid and itaconic acid, norbornene, norbornene-5
Substituted norbornenes such as methyl carboxylate, unsaturated acid anhydrides such as itaconic anhydride, and other monomers may be copolymerized.

The polymer compound of the present invention may contain (I) a structural unit of the formula (1a) based on the monomer of the above formula (1) in an amount of more than 0 mol% to 100 mol%, preferably 20 to 90 mol%;
More preferably, it contains 30 to 80 mol%, and (II) the formulas (2a) to (1) based on the monomers of the formulas (2) to (10)
0 mol% or more of one or more structural units of 0a);
It contains less than 100 mol%, preferably 1 to 95 mol%, more preferably 5 to 90 mol%.
I) One or more structural units based on the monomer (iii) may be contained in an amount of 0 to 80 mol%, preferably 0 to 70 mol%, more preferably 0 to 50 mol%.

The polymer of the present invention has a weight average molecular weight of 1,000 to 500,000, preferably 3.0 to 500.
00 to 100,000. If the ratio is outside this range, the etching resistance may be extremely lowered, or the difference in dissolution rate before and after the exposure may not be secured, and the resolution may be reduced.

The polymer compound of the present invention comprises the above-mentioned ester compound of the general formula (1) and another compound containing a carbon-carbon double bond (monomer of the above (ii) and / or (iii)). It can be produced by radical polymerization.

The reaction conditions for the radical polymerization reaction are as follows. An azo compound such as 2,2'-azobisisobutyronitrile or a peroxide such as benzoyl peroxide or lauroyl peroxide is used as an initiator.
(D) The reaction time is 0.5 to 48 hours.
It is preferable to set the time to about the time, but it is not excluded that the time is out of this range.

The polymer compound of the present invention is effective as a base polymer of a resist material, and the present invention provides a resist material containing the polymer compound.

Further, the present invention can provide a resist material comprising the polymer compound, a compound which generates an acid in response to a high energy beam or an electron beam, and an organic solvent.

The acid generator used in the present invention includes: i. An onium salt of the following general formula (P1a-1), (P1a-2) or (P1b); ii. A diazomethane derivative represented by the following general formula (P2), iii. A glyoxime derivative of the following general formula (P3), iv. A bissulfone derivative represented by the following general formula (P4); A sulfonic acid ester of an N-hydroxyimide compound represented by the following general formula (P5), vi. β-ketosulfonic acid derivatives, vii. Disulfone derivatives, viii. A nitrobenzylsulfonate derivative, ix. And sulfonic acid ester derivatives.

[0059]

Embedded image (Wherein, R ^101a , R ^101b , and R ^101c each represent a linear, branched, or cyclic alkyl group, alkenyl group, oxoalkyl group, or oxoalkenyl group having 1 to 12 carbon atoms, and aryl having 6 to 20 carbon atoms. Group or 7 to carbon atoms
12 represents an aralkyl group or an aryloxoalkyl group, and a part or all of the hydrogen atoms of these groups may be substituted with an alkoxy group or the like. Also, R ^101b
And may be the ^{R 101 c} to form a ring, when they form a ^ring, R ^{101b, R 101c} are each 1 to carbon atoms
6 represents an alkylene group. K ^- is a non-nucleophilic counter ion. )

The above R ^101a , R ^101b , R ^101c
May be the same or different from each other, and specifically, as an alkyl group, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group , Hexyl group, heptyl group, octyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclopropylmethyl group,
Examples include a 4-methylcyclohexyl group, a cyclohexylmethyl group, a norbornyl group, and an adamantyl group.
Examples of the alkenyl group include a vinyl group, an allyl group, a propenyl group, a butenyl group, a hexenyl group, and a cyclohexenyl group. Examples of the oxoalkyl group include a 2-oxocyclopentyl group, a 2-oxocyclohexyl group, and the like. A 2-oxopropyl group, a 2-cyclopentyl-2-oxoethyl group, a 2-cyclohexyl-2-oxoethyl group, a 2- (4 -Methylcyclohexyl) -2-
An oxoethyl group and the like can be mentioned. Examples of the aryl group include a phenyl group, a naphthyl group, a p-methoxyphenyl group, an m-methoxyphenyl group, an o-methoxyphenyl group, an ethoxyphenyl group, a p-tert-butoxyphenyl group, and an m-tert-butoxyphenyl group. Alkylphenyl groups such as alkoxyphenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, ethylphenyl group, 4-tert-butylphenyl group, 4-butylphenyl group and dimethylphenyl group ,
Methylnaphthyl group, alkylnaphthyl group such as ethylnaphthyl group, methoxynaphthyl group, alkoxynaphthyl group such as ethoxynaphthyl group, dimethylnaphthyl group, dialkylnaphthyl group such as diethylnaphthyl group, dimethoxynaphthyl group, diethoxynaphthyl group and the like And alkoxynaphthyl groups. Examples of the aralkyl group include a benzyl group, a phenylethyl group, and a phenethyl group.
As the aryloxoalkyl group, 2-phenyl-2
And 2-aryl-2-oxoethyl groups such as -oxoethyl group, 2- (1-naphthyl) -2-oxoethyl group and 2- (2-naphthyl) -2-oxoethyl group. K ^- a non-nucleophilic counter as the ionic chloride ions,
Halide ion such as bromide ion, triflate, 1,
Fluoroalkylsulfonates such as 1,1-trifluoroethanesulfonate and nonafluorobutanesulfonate; arylsulfonates such as tosylate, benzenesulfonate, 4-fluorobenzenesulfonate, 1,2,3,4,5-pentafluorobenzenesulfonate, and mesylate And alkylsulfonates such as butanesulfonate.

[0061]

Embedded image (Wherein, R ^102a and R ^102b each have 1 to 1 carbon atoms.
8 represents a linear, branched or cyclic alkyl group. R
¹⁰³ represents a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms. R ^104a and R ^104b each represent a 2-oxoalkyl group having 3 to 7 carbon atoms. K ^- is a non-nucleophilic counter ion. )

Specific examples of R ^102a and R ^102b include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, and heptyl. Octyl group, cyclopentyl group, cyclohexyl group, cyclopropylmethyl group, 4-methylcyclohexyl group, cyclohexylmethyl group and the like. R ¹⁰³ includes methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, 1,4-cyclohexylene,
-Cyclohexylene group, 1,3-cyclopentylene group,
Examples thereof include a 1,4-cyclooctylene group and a 1,4-cyclohexanedimethylene group. R ^104a , R ^104b
Examples thereof include a 2-oxopropyl group, a 2-oxocyclopentyl group, a 2-oxocyclohexyl group, and a 2-oxocycloheptyl group. K ^- is the formula (P1a-
Examples similar to those described in 1) and (P1a-2) can be given.

[0063]

Embedded image (Wherein, R ¹⁰⁵ and R ¹⁰⁶ are a linear, branched or cyclic alkyl group or halogenated alkyl group having 1 to 12 carbon atoms, an aryl group or halogenated aryl group having 6 to 20 carbon atoms, or And 7 to 12 aralkyl groups.)

Examples of the alkyl group for R ¹⁰⁵ and R ¹⁰⁶ include a methyl group, an ethyl group, a propyl group, an isopropyl group, and an n group.
-Butyl group, sec-butyl group, tert-butyl group,
Pentyl, hexyl, heptyl, octyl, amyl, cyclopentyl, cyclohexyl, cycloheptyl, norbornyl, adamantyl and the like. Examples of the halogenated alkyl group include a trifluoromethyl group, a 1,1,1-trifluoroethyl group,
Examples thereof include a 1-trichloroethyl group and a nonafluorobutyl group. Examples of the aryl group include an alkoxyphenyl group such as a phenyl group, a p-methoxyphenyl group, an m-methoxyphenyl group, an o-methoxyphenyl group, an ethoxyphenyl group, a p-tert-butoxyphenyl group, and a m-tert-butoxyphenyl group. 2-methylphenyl group, 3-
Examples thereof include alkylphenyl groups such as a methylphenyl group, a 4-methylphenyl group, an ethylphenyl group, a 4-tert-butylphenyl group, a 4-butylphenyl group, and a dimethylphenyl group. As the halogenated aryl group, a fluorophenyl group, a chlorophenyl group, 1,2,3,4,5
-Pentafluorophenyl group and the like. Examples of the aralkyl group include a benzyl group and a phenethyl group.

[0065]

Embedded image (Wherein, R ¹⁰⁷ , R ¹⁰⁸ and R ^{109 each} have 1 to 1 carbon atoms.
2 represents a linear, branched or cyclic alkyl group or halogenated alkyl group, an aryl group or halogenated aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms. R ^{108, R 109} may be bonded to each other to form a cyclic structure, when they form a ^{ring, R 108,}
R ¹⁰⁹ represents a linear or branched alkylene group having 1 to 6 carbon atoms. )

The alkyl group, halogenated alkyl group, aryl group, halogenated aryl group and aralkyl group represented by R ¹⁰⁷ , R ¹⁰⁸ and R ¹⁰⁹ are R ¹⁰⁵ , R ¹⁰⁶
And the same groups as described in the above. Note that R
^As the alkylene group for ¹⁰⁸ and R ^109, a methylene group,
Examples include an ethylene group, a propylene group, a butylene group, and a hexylene group.

[0067]

Embedded image (In the formula, R ^101a and R ^101b are the same as described above.)

[0068]

Embedded image (In the formula, R ¹¹⁰ represents an arylene group having 6 to 10 carbon atoms, an alkylene group having 1 to 6 carbon atoms or an alkenylene group having 2 to 6 carbon atoms, and a part or all of the hydrogen atoms of these groups further have carbon atoms. R ¹¹¹ may be substituted with a linear or branched alkyl or alkoxy group, a nitro group, an acetyl group, or a phenyl group having from 1 to 4. R ¹¹¹ has 1 to 8 carbon atoms. Or a substituted alkyl group, alkenyl group or alkoxyalkyl group, phenyl group or naphthyl group, and a part or all of the hydrogen atoms of these groups are further an alkyl group or alkoxy group having 1 to 4 carbon atoms; ~ 4
A phenyl group optionally substituted by an alkyl group, an alkoxy group, a nitro group or an acetyl group; a heteroaromatic group having 3 to 5 carbon atoms; or a chlorine atom or a fluorine atom. )

Here, the arylene group of R ¹¹⁰ is 1,2-phenylene group, 1,8-naphthylene group or the like, and the alkylene group is methylene group, 1,2-ethylene group, 1,3-propylene group. Group, 1,4-butylene group,
1-phenyl-1,2-ethylene group, norbornane-
When the 2,3-diyl group or the like is an alkenylene group,
2-vinylene group, 1-phenyl-1,2-vinylene group,
5-norbornene-2,3-diyl group and the like.
As the alkyl group for R ¹¹¹ , R ^{101a to} R ^{10
The same} alkenyl groups as those described in ^{1c except} for a vinyl group, a 1-propenyl group, an allyl group, a 1-butenyl group,
-Butenyl group, isoprenyl group, 1-pentenyl group, 3
-Pentenyl group, 4-pentenyl group, dimethylallyl group, 1-hexenyl group, 3-hexenyl group, 5-hexenyl group, 1-heptenyl group, 3-heptenyl group, 6-heptenyl group, 7-octenyl group and the like, Examples of the alkoxyalkyl group include a methoxymethyl group, an ethoxymethyl group,
Propoxymethyl group, butoxymethyl group, pentoxylmethyl group, hexyloxymethyl group, heptyloxymethyl group, methoxyethyl group, ethoxyethyl group, propoxyethyl group, butoxyethyl group, pentoxyloxy group,
Hexyloxyethyl group, methoxypropyl group, ethoxypropyl group, propoxypropyl group, butoxypropyl group, methoxybutyl group, ethoxybutyl group, propoxybutyl group, methoxypentyl group, ethoxypentyl group,
Examples include a methoxyhexyl group and a methoxyheptyl group.

It is to be noted that carbon atom 1 which may be further substituted
Examples of the alkyl group having 4 to 4 include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group. Group, propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, tert-butoxy group, etc. may be substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group, a nitro group or an acetyl group. A phenyl group, a tolyl group, a p-tert-butoxyphenyl group, a p-acetylphenyl group, a p-nitrophenyl group, etc.
Examples of the heteroaromatic group 5 include a pyridyl group and a furyl group.

More specifically, for example, diphenyliodonium trifluoromethanesulfonate, phenyliodonium trifluoromethanesulfonate (p-tert-butoxyphenyl), diphenyliodonium p-toluenesulfonate, p-toluenesulfonate (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 , 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, bisnaphthylsulfonylmethane,
Bissulfone derivatives such as bistrifluoromethylsulfonylmethane, bismethylsulfonylmethane, bisethylsulfonylmethane, bispropylsulfonylmethane, bisisopropylsulfonylmethane, bis-p-toluenesulfonylmethane, and bisbenzenesulfonylmethane;
-Cyclohexylcarbonyl-2- (p-toluenesulfonyl) propane, 2-isopropylcarbonyl-2-
Β-ketosulfone derivatives such as (p-toluenesulfonyl) propane, disulfone derivatives such as diphenyldisulfone and dicyclohexyldisulfone, nitros such as 2,6-dinitrobenzyl p-toluenesulfonate and 2,4-dinitrobenzyl p-toluenesulfonate Benzyl sulfonate derivatives, 1,2,3-tris (methanesulfonyloxy) benzene, 1,2,3-tris (trifluoromethanesulfonyloxy) benzene, 1,2,3-tris (p-toluenesulfonyloxy) benzene and the like Sulfonic acid ester derivatives, N-hydroxysuccinimide methanesulfonic acid ester, N-hydroxysuccinimide trifluoromethanesulfonic acid ester, N-hydroxysuccinimide ethanesulfonic acid ester, N-
Hydroxysuccinimide 1-propanesulfonic acid ester, N-hydroxysuccinimide 2-propanesulfonic acid ester, N-hydroxysuccinimide 1-pentanesulfonic acid ester, N-hydroxysuccinimide 1-octanesulfonic acid ester, N-hydroxysuccinimide p-toluenesulfone Acid ester, N-
Hydroxysuccinimide p-methoxybenzenesulfonate, N-hydroxysuccinimide 2-chloroethanesulfonate, N-hydroxysuccinimidebenzenesulfonate, N-hydroxysuccinimide-2,4,6-trimethylbenzenesulfonate, N-hydroxy Succinimide 1-naphthalenesulfonic acid ester, N-hydroxysuccinimide 2-naphthalenesulfonic acid ester, N-hydroxy-2-phenylsuccinimide methanesulfonic acid ester, N-hydroxymaleimide methanesulfonic acid ester, N-hydroxymaleimidoethanesulfonic acid ester, N-hydroxy-2-phenylmaleimide methanesulfonate, N-hydroxyglutarimide methanesulfonate Ether, N- hydroxy glutarimide benzenesulfonate ester, N- hydroxyphthalimide methanesulfonate ester, N- hydroxyphthalimide benzenesulfonate ester, N- hydroxyphthalimide trifluoromethanesulfonate ester,
N-hydroxyphthalimide p-toluenesulfonic acid ester, N-hydroxynaphthalimide methanesulfonic acid ester, N-hydroxynaphthalimidebenzenesulfonic acid ester, N-hydroxy-5-norbornene-2,3-dicarboximide methanesulfonic acid ester N-hydroxy-5-norbornene-2,3-dicarboximide trifluoromethanesulfonic acid ester, N-hydroxy-5-norbornene-2,3-dicarboximide p-toluenesulfonic acid ester, etc.
Sulfonic acid ester derivatives of a hydroxyimide compound, such as triphenylsulfonium trifluoromethanesulfonate, (p-tert-butoxyphenyl) diphenylsulfonium trifluoromethanesulfonate, and tris (pt) trifluoromethanesulfonate;
tert-butoxyphenyl) sulfonium, triphenylsulfonium p-toluenesulfonate, diphenylsulfonium p-toluenesulfonate (p-tert-butoxyphenyl), tris (p-toluenesulfonate)
-Tert-butoxyphenyl) sulfonium, trinaphthylsulfonium trifluoromethanesulfonate, cyclohexylmethyl trifluoromethanesulfonate (2
Onium salts such as -oxocyclohexyl) sulfonium, (2-norbonyl) methyl trifluoromethanesulfonate (2-oxocyclohexyl) sulfonium, 1,2'-naphthylcarbonylmethyltetrahydrothiophenium triflate, bis (benzenesulfonyl) diazomethane, Bis (p-toluenesulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane,
Bis (n-butylsulfonyl) diazomethane, bis (isobutylsulfonyl) diazomethane, bis (sec-butylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, etc. Diazomethane derivative of bis-O-
Glyoxime derivatives such as (p-toluenesulfonyl) -α-dimethylglyoxime, bis-O- (n-butanesulfonyl) -α-dimethylglyoxime, bissulfone derivatives such as bisnaphthylsulfonylmethane, N-hydroxysuccinimide methanesulfonic acid Ester, N-hydroxysuccinimide trifluoromethanesulfonic acid ester, N-hydroxysuccinimide 1-propanesulfonic acid ester, N-hydroxysuccinimide 2
-Propanesulfonic acid ester, N-hydroxysuccinimide 1-pentanesulfonic acid ester, N-hydroxysuccinimide p-toluenesulfonic acid ester,
Sulfonate derivatives of N-hydroxyimide compounds such as N-hydroxynaphthalimide methanesulfonate and N-hydroxynaphthalimidobenzenesulfonate are preferably used. In addition, the said acid generator can be used individually by 1 type or in combination of 2 or more types. Onium salts are excellent in the effect of improving rectangularity, and diazomethane derivatives and glyoxime derivatives are excellent in the effect of reducing standing waves. Therefore, fine adjustment of the profile can be performed by combining the two.

The acid generator is preferably added in an amount of 0.1 to 15 parts by weight based on 100 parts (parts by weight, hereinafter the same) of the base resin.
Parts, more preferably 0.5 to 8 parts. If the amount is less than 0.1 part, the sensitivity may be poor. If the amount is more than 15 parts, the transparency may be reduced and the resolution may be reduced.

The organic solvent used in the present invention may be any organic solvent which can dissolve the base resin, acid generator, other additives and the like. Examples of such an organic solvent include ketones such as cyclohexanone and methyl-2-n-amyl ketone, 3-methoxybutanol,
-Methyl-3-methoxybutanol, 1-methoxy-2
Alcohols such as -propanol, 1-ethoxy-2-propanol, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethers such as ethylene 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, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol monoter
Esters such as t-butyl ether acetate can be mentioned, and one of these can be used alone or a mixture of two or more thereof, but is 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 ether acetate as a safe solvent and a mixture thereof Solvents are preferably used.

The amount of the organic solvent to be used is preferably 200 to 1,000 parts, more preferably 400 to 800 parts per 100 parts of the base resin.

In the resist composition of the present invention, a polymer compound different from the polymer compound having a repeating unit represented by the above formula (1a) can be added.

Specific examples of the high molecular compound include a weight average molecular weight represented by the following formula (R1) and / or (R2) of 1,000 to 500,000, preferably 5,
000 to 100,000, but are not limited thereto.

[0077]

Embedded image(Wherein X is the same as above. R⁰⁰¹Is a hydrogen atom, methyl
Group or CH₂CO₂R^{0 03}Is shown. R⁰⁰²Is hydrogen field
Child, methyl group or CO₂R⁰⁰³Is shown. R^{00 3}Is charcoal
A linear, branched or cyclic alkyl group having a prime number of 1 to 15
Show. R⁰⁰⁴Is a hydrogen atom or a C 1 -C 15
Shows a monovalent hydrocarbon group containing a ruboxyl group or a hydroxyl group.
You. R⁰⁰⁵~ R⁰⁰⁸At least one has 1 to 1 carbon atoms
Monovalent hydrocarbon containing 15 carboxy or hydroxyl groups
And the rest are each independently a hydrogen atom or carbon number
Represents a linear, branched or cyclic alkyl group of 1 to 15
You. R ⁰⁰⁵~ R⁰⁰⁸May form a ring with each other
In that case, R⁰⁰⁵~ R ⁰⁰⁸At least one of
Contains a carboxy group or a hydroxyl group having 1 to 15 carbon atoms.
Shows a divalent hydrocarbon group, and the rest are each independently a single bond
Or a linear, branched or cyclic alkyl having 1 to 15 carbon atoms
Represents a len group. R⁰⁰⁹Is -CO having 3 to 15 carbon atoms₂−
Shows a monovalent hydrocarbon group containing a partial structure. R⁰¹⁰
~ R⁰¹³At least one is -CO having 2 to 15 carbon atoms.
₂-Represents a monovalent hydrocarbon group containing a partial structure,
Are each independently a hydrogen atom or a straight chain having 1 to 15 carbon atoms
A branched, branched or cyclic alkyl group. R⁰¹⁰~ R
⁰¹³May form a ring with each other, in which case
R⁰¹⁰~ R⁰¹³At least one has 1 to 15 carbon atoms
-CO₂-Represents a divalent hydrocarbon group containing a partial structure
And the rest are each independently a single bond or a C 1-15
It represents a linear, branched or cyclic alkylene group. R^01
4Is a polycyclic hydrocarbon group having 7 to 15 carbon atoms or polycyclic hydrocarbon
Shows an alkyl group containing a hydrogen group. R⁰¹⁵Is acid anxious
Indicates a fixed group. R⁰¹⁶Represents a hydrogen atom or a methyl group.
R⁰¹⁷Is a linear, branched or cyclic C 1-8
Represents a alkyl group. k 'is 0 or 1. a1 ', a
2 ', a3', b1 ', b2', b3 ', c1', c
2 ', c3', d1 ', d2', d3 ', e' are 0 or more
A1 '+ a2' + a3 '+ b1' +
b2 '+ b3' + c1 '+ c2' + c3 '+ d1' + d
2 ′ + d3 ′ + e ′ = 1 is satisfied. f ', g',
h ', i', and j 'are numbers from 0 to less than 1, and f' +
g ′ + h ′ + i ′ + j ′ = 1 is satisfied. x ', y',
z ′ is an integer of 0 to 3, and x ′ + y ′ + z ′ ≦ 5, 1
It is a number that satisfies ≦ y ′ + z. )

For specific examples of each group,
This is the same as that described for R ^{1 to} R ¹⁵ .

The compounding ratio of the polymer compound having a repeating unit represented by the above general formula (1a) to another polymer compound is 100: 0 to 10:90, particularly 100: 0 to 2
It is preferable that the weight ratio is in the range of 0:80. If the compounding ratio of the polymer compound having a repeating unit represented by the above general formula (1a) is less than this, favorable performance as a resist material may not be obtained in some cases. The performance of the resist material can be adjusted by appropriately changing the above mixing ratio.

The above-mentioned polymer compound is not limited to one kind but may be 2
More than one species can be added. By using a plurality of types of polymer compounds, the performance of the resist material can be adjusted.

The resist composition of the present invention may further contain a dissolution controlling agent. The dissolution controlling agent has an average molecular weight of 100 to 1,000, preferably 150 to 80.
0 and a compound having two or more phenolic hydroxyl groups in the molecule, wherein a hydrogen atom of the phenolic hydroxyl group is substituted by an acid labile group at an average rate of 0 to 100 mol% or a carboxy group in the molecule. And a compound in which the hydrogen atom of the carboxy group of the compound having the formula (1) is substituted with an acid labile group at an average ratio of 50 to 100 mol% as a whole.

Incidentally, the substitution rate of the hydrogen atom of the phenolic hydroxyl group by the acid labile group is 0 mol% or more, preferably 30 mol% or more of the entire phenolic hydroxyl group on average.
The upper limit is 100 mol%, more preferably 80 mol%. The substitution rate of the hydrogen atom of the carboxy group by the acid labile group is 50 mol% or more, preferably 70 mol% or more of the entire carboxy group on average, and the upper limit is 100 mol%.
It is.

In this case, the phenolic hydroxyl group is 2
As the compound having one or more compounds or the compound having a carboxy group, compounds represented by the following formulas (D1) to (D14) are preferable.

[0084]

Embedded image (Wherein, R ²⁰¹ and R ²⁰² are each a hydrogen atom,
Or a linear or branched alkyl group or alkenyl group having 1 to 8 carbon atoms. R ²⁰³ represents a hydrogen atom, a linear or branched alkyl group or alkenyl group having 1 to 8 carbon atoms, or — (R ²⁰⁷ ) _h COOH. R
The _{^{204 - (CH 2) i -}} (i = 2~10), a carbon number 6
-10 arylene groups, carbonyl groups, sulfonyl groups,
Indicates an oxygen atom or a sulfur atom. R ²⁰⁵ has 1 to 1 carbon atoms
0 represents an alkylene group, an arylene group having 6 to 10 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen atom or a sulfur atom. R ^{2 06} represents a hydrogen atom, a linear or branched alkyl group, alkenyl group, or a phenyl group or a naphthyl group which is a hydroxyl-substituted having 1 to 8 carbon atoms. R
²⁰⁷ represents a linear or branched alkylene group having 1 to 10 carbon atoms. R ²⁰⁸ represents a hydrogen atom or a hydroxyl group. j
Is an integer of 0 to 5. u and h are 0 or 1. s,
t, s ′, t ′, s ″, and t ″ are respectively s + t =
8, a number satisfying s ′ + t ′ = 5, s ″ + t ″ = 4, and having at least one hydroxyl group in each phenyl skeleton. α is a number such that the molecular weight of the compounds of formulas (D8) and (D9) is 100 to 1,000. )

In the above formula, R ²⁰¹ and R ²⁰² are, for example, hydrogen atom, methyl group, ethyl group, butyl group, propyl group, ethynyl group, cyclohexyl group, and R ²⁰³ are, for example, the same as R ²⁰¹ and R ^202. mono- or _-COOH, as the -CH 2 ^{COOH, R 204,} an ethylene group, a phenylene group, a carbonyl group, a sulfonyl group, an oxygen atom, a sulfur atom, ^etc., as ^{R 205,} for example similar to the methylene group or ^{R 204,,} What, R
^{As 206} , for example, a hydrogen atom, a methyl group, an ethyl group,
Examples thereof include a butyl group, a propyl group, an ethynyl group, a cyclohexyl group, a phenyl group and a naphthyl group each substituted with a hydroxyl group.

Here, the acid labile group of the dissolution controlling agent includes groups represented by the following general formulas (L1) to (L4), tertiary alkyl groups having 4 to 20 carbon atoms, and carbon atoms of each alkyl group. 1 to 6 trialkylsilyl groups, 4 to 2 carbon atoms
And an oxoalkyl group of 0.

[0087]

Embedded image(Where R^L01, R^L02Is a hydrogen atom or carbon number 1
It represents 18 linear, branched or cyclic alkyl groups. R
^L03Has a heteroatom such as an oxygen atom having 1 to 18 carbon atoms.
And a monovalent hydrocarbon group which may be used. R^L01And R
^L02, R^L01And R ^L03, R^L02And R^L03What is
A ring may be formed, and when a ring is formed, R ^L01,
R^L02, R^L03Is a linear group having 1 to 18 carbon atoms
Or a branched alkylene group. R^L04Is carbon number 4
-20 tertiary alkyl groups, each alkyl group being carbon
A trialkylsilyl group having 1 to 6 carbon atoms,
A xoalkyl group or a group represented by the above general formula (L1)
Show. R^L05Is a linear, branched or cyclic C1-8
Alkyl group or substituted with 6 to 20 carbon atoms
Shows good aryl groups. R^L06Is a linear chain having 1 to 8 carbon atoms
, Branched or cyclic alkyl groups or C6-C20
It shows the aryl group which may be substituted. R^L07~ R
^L16Are each independently a hydrogen atom or a group having 1 to 15 carbon atoms.
It represents a monovalent hydrocarbon group which may contain a hetero atom. R
^L07~ R^L16May form a ring with each other,
May contain a heteroatom having 1 to 15 carbon atoms
Shows a divalent hydrocarbon group. Also, R^L07~ R^L16Is
Bonds between adjacent carbons without any intervention
Then, a double bond may be formed. y is an integer from 0 to 6
You. m is 0 or 1, and n is 0, 1, 2, or 3.
2m + n = 2 or 3. )

The blending amount of the above-mentioned dissolution controlling agent was
It is 0 to 50 parts, preferably 5 to 50 parts, more preferably 10 to 30 parts with respect to 00 parts, and can be used alone or in combination of two or more. If the amount is less than 5 parts, the resolution may not be improved. If the amount is more than 50 parts, the pattern may be reduced in film thickness and the resolution may be reduced.

The dissolution controlling agent as described above is used for the compound having a phenolic hydroxyl group or a carboxy group.
It is synthesized by introducing an acid labile group using an organic chemical formulation.

Further, the resist composition of the present invention may contain a basic compound. As the basic compound, a compound capable of suppressing the diffusion rate when the acid generated from the acid generator diffuses into the resist film is suitable. By compounding a basic compound, the diffusion rate of acid in the resist film is suppressed and the resolution is improved, the sensitivity change after exposure is suppressed, the dependence on the substrate and environment is reduced, and the exposure margin and pattern profile are reduced. Etc. can be improved.

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, 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.). , 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 amide derivatives 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, one or more kinds of basic compounds represented by the following general formula (B1) may be blended.

Embedded image (In the formula, n = 1, 2, or 3. Each Y independently represents a hydrogen atom or a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms, and may include a hydroxy group or an ether. X each independently represents any one of the groups represented by the following formulas (X1) to (X3), and two or three Xs may combine to form a ring.)

Embedded image (Wherein ^{R 300, R 302, R 305} is a straight or branched alkylene group of 1 to 4 carbon atoms ^{.R 301,} R
^{Reference numeral 304} denotes a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, which may contain one or more hydroxy groups, ethers, esters or lactone rings. R ³⁰³ represents a single bond or a linear or branched alkylene group having 1 to 4 carbon atoms. )

Specific examples of the compound represented by formula (B1) include tris (2-methoxymethoxyethyl)
Amine, tris {2- (2-methoxyethoxy) ethyl} amine, tris {2- (2-methoxyethoxymethoxy) ethyl} amine, tris {2- (1-methoxyethoxy) ethyl} amine, tris {2- ( 1-ethoxyethoxy) ethyl} amine, tris {2- (1-ethoxypropoxy) ethyl} amine, tris [2- {2-
(2-hydroxyethoxy) ethoxydiethyl] amine, 4,7,13,16,21,24-hexaoxa-
1,10-diazabicyclo [8.8.8] hexacosan, 4,7,13,18-tetraoxa-1,10-diazabicyclo [8.5.5] eicosan, 1,4,1
0,13-tetraoxa-7,16-diazabicyclooctadecane, 1-aza-12-crown-4, 1-aza-15-crown-5, 1-aza-18-crown-
6, tris (2-formyloxyethyl) amine, tris (2-formyloxyethyl) amine, tris (2
-Acetoxyethyl) amine, tris (2-propionyloxyethyl) amine, tris (2-butyryloxyethyl) amine, tris (2-isobutyryloxyethyl) amine, tris (2-valeryloxyethyl) amine, Tris (2-pivaloyloxyxyethyl) amine, N, N-bis (2-acetoxyethyl) 2- (acetoxyacetoxy) ethylamine, tris (2-methoxycarbonyloxyethyl) amine, tris (2-te
rt-butoxycarbonyloxyethyl) amine, tris [2- (2-oxopropoxy) ethyl] amine, tris [2- (methoxycarbonylmethyl) oxyethyl] amine, tris [2- (tert-butoxycarbonylmethyloxy) ethyl] Amine, tris [2- (cyclohexyloxycarbonylmethyloxy) ethyl]
Amine, tris (2-methoxycarbonylethyl) amine, tris (2-ethoxycarbonylethyl) amine,
N, N-bis (2-hydroxyethyl) 2- (methoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (methoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2 -(Ethoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (ethoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2- (2
-Methoxyethoxycarbonyl) ethylamine, N, N
-Bis (2-acetoxyethyl) 2- (2-methoxyethoxycarbonyl) ethylamine, N, N-bis (2-
(Hydroxyethyl) 2- (2-hydroxyethoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (2-acetoxyethoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2
-[(Methoxycarbonyl) methoxycarbonyl] ethylamine, N, N-bis (2-acetoxyethyl) 2-
[(Methoxycarbonyl) methoxycarbonyl] ethylamine, N, N-bis (2-hydroxyethyl) 2-
(2-oxopropoxycarbonyl) ethylamine,
N, N-bis (2-acetoxyethyl) 2- (2-oxopropoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2- (tetrahydrofurfuryloxycarbonyl) ethylamine, N, N-bis ( 2
-Acetoxyethyl) 2- (tetrahydrofurfuryloxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2-[(2-oxotetrahydrofuran-3-yl) oxycarbonyl] ethylamine, N,
N-bis (2-acetoxyethyl) 2-[(2-oxotetrahydrofuran-3-yl) oxycarbonyl] ethylamine, N, N-bis (2-hydroxyethyl) 2
-(4-hydroxybutoxycarbonyl) ethylamine, N, N-bis (2-formyloxyethyl) 2-
(4-formyloxybutoxycarbonyl) ethylamine, N, N-bis (2-formyloxyethyl) 2-
(2-formyloxyethoxycarbonyl) ethylamine, N, N-bis (2-methoxyethyl) 2- (methoxycarbonyl) ethylamine, N- (2-hydroxyethyl) bis [2- (methoxycarbonyl) ethyl] amine, N -(2-acetoxyethyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (2-hydroxyethyl) bis [2- (ethoxycarbonyl) ethyl] amine, N- (2-acetoxyethyl) bis [2 -(Ethoxycarbonyl) ethyl] amine, N- (3-hydroxy-1-propyl) bis [2- (methoxycarbonyl)
Ethyl] amine, N- (3-acetoxy-1-propyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (2-methoxyethyl) bis [2- (methoxycarbonyl) ethyl] amine, N-butylbis [2-
(Methoxycarbonyl) ethyl] amine, N-butylbis [2- (2-methoxyethoxycarbonyl) ethyl]
Amine, N-methylbis (2-acetoxyethyl) amine, N-ethylbis (2-acetoxyethyl) amine,
N-methylbis (2-pivaloyloxyxyethyl) amine, N-ethylbis [2- (methoxycarbonyloxy) ethyl] amine, N-ethylbis [2- (tert
-Butoxycarbonyloxy) ethyl] amine, tris (methoxycarbonylmethyl) amine, tris (ethoxycarbonylmethyl) amine, N-butylbis (methoxycarbonylmethyl) amine, N-hexylbis (methoxycarbonylmethyl) amine, β- (diethylamino) -Δ-valerolactone and the like.

The compounding amount of the above-mentioned basic compound is as follows.
0.001 to 10 parts, preferably 0.01 to 10 parts by weight
One copy. If the amount is less than 0.001 part, the effect as an additive may not be sufficiently obtained, and if it exceeds 10 parts, the resolution and sensitivity may be reduced.

Further, a compound having a group represented by ΔC—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 (A branched alkylene group)
And a phenolic hydroxyl group (C) in the molecule and ΔC-COO
The molar ratio with the group (D) represented by H is C / (C + D) =
A compound which is 0.1 to 1.0. [Group II] Compounds represented by the following general formulas (A11) to (A15).

[0100]

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 group having 1 to 1 carbon atoms.
8 represents a linear or branched alkyl group or alkenyl group. R ⁴⁰⁴ is a hydrogen atom, a linear or branched alkyl or alkenyl group having 1 to 8 carbon atoms, or-
( ^R409 ) _h- COOR 'group (R' is a hydrogen atom or-
R ⁴⁰⁹ -COOH). R ^{405 is-} (CH ₂ )
_i- (i = 2 to 10), an arylene group having 6 to 10 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen atom or a sulfur atom. R ⁴⁰⁶ is an alkylene group having 1 to 10 carbon atoms,
It represents 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, a phenyl group or a naphthyl group each substituted with a hydroxyl group. R ⁴⁰⁹ has 1 to 10 carbon atoms
Represents a linear or branched alkylene group. R ⁴¹⁰ represents a hydrogen atom, a linear or branched alkyl group or alkenyl group having 1 to 8 carbon atoms, or —R ⁴¹¹ —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, s2, t2, s3, t
3, s4 and t4 are s1 + t1 = 8 and s2 + t2, respectively.
= 5, s3 + t3 = 4, s4 + t4 = 6, and a number having 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 is the formula (A
The compound of 7) above is used in a weight-average molecular weight of 1,000 to 10,000.
This is a number that is set to 0. )

[0101]

Embedded image (R ⁴⁰² , R ⁴⁰³ and R ⁴¹¹ have the same meaning as described above. R ⁴¹² represents a hydrogen atom or a hydroxyl group. S5, t
5 is a number that s5 ≧ 0 and t5 ≧ 0, and 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.

[0103]

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. )

[0104]

Embedded image

The compound having a group represented by ≡C—COOH in the molecule may be used alone or in combination of two or more.

The amount of the compound having a group represented by ≡C-COOH in the molecule is 0 to 5 parts, preferably 0.1 to 5 parts, more preferably 0.1 to 5 parts, based on 100 parts of the base resin. To 3 parts, more preferably 0.1 to 2 parts. 5
If the number is more than the number, the resolution of the resist material may be reduced.

Further, an acetylene alcohol derivative can be added to the resist composition of the present invention as an additive, whereby the storage stability can be improved.

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

[0109]

Embedded image (Wherein R ⁵⁰¹ , R ⁵⁰² , R ⁵⁰³ , R ⁵⁰⁴ , R
⁵⁰⁵ is a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, X and Y each represent 0 or a positive number, and satisfy the following values. 0 ≦ X ≦ 30, 0 ≦
Y ≦ 30 and 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
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 effect of improving coating properties and storage stability may not be sufficiently obtained, and if the amount is more than 2% by weight, the resolution of the resist material may decrease.

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

The surfactant is preferably a nonionic surfactant, and is preferably a perfluoroalkylpolyoxyethylene ethanol, a fluorinated alkyl ester, a perfluoroalkylamine oxide, a perfluoroalkyl EO adduct, or a fluorine-containing organosiloxane-based surfactant. And the like. For example, Florad “FC-430”, “F
C-431 "(all manufactured by Sumitomo 3M Limited), Surflon" S-141 "," S-145 "(all manufactured by Asahi Glass Co., Ltd.), Unidyne" DS-401 "," DS
-403 "," DS-451 "(all manufactured by Daikin Industries, Ltd.), MegaFac" F-8151 "(manufactured by Dainippon Ink Industries, Ltd.)," X-70-092 "," X-7 "
0-093 "(all manufactured by Shin-Etsu Chemical Co., Ltd.) and the like. Preferably, Florad “FC-4”
30 "(manufactured by Sumitomo 3M Limited)," X-70-09 "
3 "(manufactured by Shin-Etsu Chemical Co., Ltd.).

A pattern can be formed using the resist material of the present invention by a known lithography technique. For example, a film having a thickness of 0 is formed on a substrate such as a silicon wafer by spin coating or the like. 0.3-2.0μ
m on a hot plate.
１５０150 ° C., 1-10 minutes, preferably 80-130
Pre-bake at 1 ° C for 1-5 minutes. Next, a mask for forming a target pattern is held over the above resist film, and a high energy ray such as far ultraviolet ray, excimer laser, or X-ray or an electron beam is exposed at a dose of about 1 to 200 mJ / cm ² , preferably about 10 to 10 mJ / cm ^2. After irradiating so as to be about 100 mJ / cm ² , on a hot plate at 60 to 150 ° C.
Perform post-exposure bake (PEB) for 1 to 5 minutes, preferably 80 to 130 ° C. for 1 to 3 minutes. Furthermore, 0.
Dip for 0.1 to 3 minutes, preferably 0.5 to 2 minutes, using a developer of 1 to 5%, preferably 2 to 3% of an aqueous alkali solution such as tetramethylammonium hydroxide (TMAH). A target pattern is formed on the substrate by developing using a conventional method such as a paddle method, a puddle method, or a spray method. In addition, the material of the present invention is 248 to 193, especially among high energy rays.
It is most suitable for fine patterning by deep ultraviolet light of nm or 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.

[0115]

The resist material using the polymer compound of the present invention as a base resin is sensitive to high-energy rays and has excellent sensitivity, resolution and etching resistance. Useful. In particular, since the absorption at the exposure wavelength of an ArF excimer laser or a KrF excimer laser is small, a fine pattern perpendicular to the substrate can be easily formed.

[0116]

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] The ester compound of the present invention and a polymer compound containing the same were synthesized according to the following formulation.

Synthesis Example 1-1 Synthesis of Monomer 1 168.0 g of chlorocyclohexane was dissolved in 500 ml of diethyl ether. The reaction mixture was added to 26.4
g of metallic magnesium was dropped at 60 ° C. or lower over 1 hour. After continuing stirring at room temperature for 2 hours, 84.0 g of cyclopentanone was added dropwise at 65 ° C. or lower over 45 minutes.
After continuing stirring at room temperature for 1 hour, usual post-reaction treatment was carried out, and the obtained oily substance was distilled under reduced pressure.
3 g of 1-cyclohexylcyclopentanol were obtained. The yield was 57.9%.

92.4 g of 1-cyclohexylcyclopentanol were dissolved in 1 L of methylene chloride. To this reaction mixture, 74.3 g of acrylic acid chloride was added to -2.
The solution was added dropwise at 0 ° C. or lower over 10 minutes. 1.0 g of 4-
(N, N-dimethylamino) pyridine is added, then 1
25.0 g of triethylamine was added dropwise at -20 ° C or lower over 1 hour. After continuing stirring at room temperature for 15 hours, ordinary post-reaction treatment was performed, and the obtained oily substance was distilled under reduced pressure to obtain 110.5 g of 1-cyclohexylcyclopentyl acrylate (Monomer 1). The yield was 90.5%. Boiling point: 83 to 85 ° C./53.3 Pa ¹ H-NMR (CDCl ₃ , 300 MHz): 0.90
-1.33 (5H, m), δ1.45-1.90 (11
H, m), δ 1.95-2.10 (2H, m), δ 2.
40 (1H, tt, J = 2.9, 11.7 Hz), δ
5.71 (1H, dd, J = 1.5, 10.3 Hz),
δ 6.03 (1H, dd, J = 10.3, 17.1H
z), δ 6.28 (1H, dd, J = 1.5, 17.1)
Hz)

[Synthesis Examples 1-2-8] Monomer 2
Synthesis of 8 Monomer as described above or with a known formulation
2 to 8 were synthesized.

[0121]

Embedded image

[Synthesis Example 2-1] Synthesis of Polymer 1 66.6 g of 1-cyclohexylcyclopentyl acrylate (Monomer 1), 77.7 g of 2-norbornene-5-carboxylic acid 2-oxooxolan-3-yl, 34 0.3 g of maleic anhydride and 178.6 g of 1,4-dioxane were mixed. The reaction mixture is
C., and 7.4 g of 2,2'-azobis (2,4
-Dimethylvaleronitrile) and stirred at 60 ° C. for 15 hours. After cooling to room temperature, 500ml
And then added dropwise to 10 L of isopropyl alcohol with vigorous stirring. The resulting solid was collected by filtration and vacuum-dried at 40 ° C. for 15 hours to obtain a white powder solid polymer compound represented by the following formula Polymer 1. The yield was 80.9 g, 45.3%.
Met. Mw is GPC in terms of polystyrene.
Represents the weight average molecular weight measured using

[Synthesis Examples 2 to 12] Polymers 2-1
Synthesis of 2 In the same manner as described above or by a known formulation, Polymer
2 to 12 were synthesized.

[0124]

Embedded image

[0125]

Embedded image

[0126]

Embedded image

[Examples] The resist material of the present invention was evaluated for resolution in ArF excimer laser exposure. [Examples 1 to 21 and Comparative Examples 1 to 4] Evaluation of resolution of resist Polymer represented by the above formula (Polymers 1 to 12)
And a polymer represented by the following formula (Polym
er13-16) as a base resin, an acid generator (PAG1, 2) represented by the following formula, a dissolution controlling agent (DRR1-4) represented by the following formula, a basic compound, and a compound represented by the following formula: A compound having a group represented by C-COOH (ACC1, 2) and a solvent were mixed in the composition shown in Table 1. Next, they were filtered through a Teflon (registered trademark) filter (pore size: 0.2 μm) to obtain a resist material.

[0128]

Embedded image

[0129]

Embedded image

[0130]

Embedded image

[0131]

Embedded image

A resist solution was applied to an antireflection film (A manufactured by Nissan Chemical Industries, Ltd.)
(RC25, 77 nm) was applied on a silicon wafer by spin coating, and a heat treatment was performed at 130 ° C. for 90 seconds to form a 375 nm-thick resist film. This is an ArF excimer laser stepper (Nikon Corporation, NA = 0.5
Exposure was performed using 5), heat treatment was performed at 110 ° C. for 90 seconds, and paddle development was performed using a 2.38% aqueous solution of tetramethylammonium hydroxide for 60 seconds.
One line and space pattern was formed. The cross section of the developed wafer is observed by a cross-sectional SEM (scanning electron microscope), and an exposure amount for resolving a 0.20 μm line and space at a ratio of 1: 1 (optimal exposure amount = Eop, mJ /
The minimum line width (μm) of the separated lines and spaces in cm ² ) was taken as the resolution of the evaluation resist. In addition, the shape of the pattern at that time is classified into any of a rectangle, a round head, a T-top, a forward taper, and a reverse taper.

Tables 1 and 2 show the composition of each resist and the evaluation results.
Shown in In Tables 1 and 2, the solvent and the basic compound are as follows. All solvents are FC-43
0 (manufactured by Sumitomo 3M Limited) was used. PGMEA: Propylene glycol methyl ether acetate TEA: Triethanolamine TMMEA: Trismethoxymethoxyethylamine TMMEA: Trismethoxyethoxymethoxyethylamine

[0134]

[Table 1]

[0135]

[Table 2]

From the results shown in Tables 1 and 2, it was confirmed that the resist material of the present invention had higher sensitivity and higher resolution in ArF excimer laser exposure than the conventional product.

Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat II (reference) C08F 232/08 C08F 232/08 234/02 234/02 C08K 5/00 C08K 5/00 C08L 33/04 C08L 33/04 G03F 7/039 601 G03F 7/039 601 H01L 21/027 H01L 21/30 502R (72) Inventor Go Takeshi 28-1 Nishifukushima, Nishifukushima, Niigata Pref. 72) Inventor Takeshi Watanabe 28-1 Nishifukushima, Kushiro-mura, Nakakushijo-gun, Niigata Prefecture Inside the Synthetic Research Laboratory, Shin-Etsu Chemical Co., Ltd. (72) Inventor Seiichiro Tachibana Seiichiro Tachibana 28-1 Nishifukushima, larger section of Kushiro-mura, Nakakushiro-gun, Niigata Prefecture Shin-Etsu Chemical Co., Ltd. 28-1 Nishifukushima Shin-Etsu Chemical Co., Ltd. F-term in the laboratory (for reference) 2H025 AA01 AA02 AB16 AC06 AC08 AD03 BE00 BE10 BG00 CB08 CB10 CB14 CB55 FA01 FA12 4H006 AA01 AB46 BJ20 BJ30 KA14 4J002 AA031 BG021 BH021 BK001 EQ016 ES016 EV216 EV08 GP03 BC016 BA03 BC08Q BC09Q BC12P BC22P BC23P BC53Q CA04 CA05 DA01 JA38

Claims (6)

[Claims] 1. An ester compound represented by the following general formula (1). Embedded image (Wherein, R ¹ is a hydrogen atom, a methyl group or CH ₂ CO ₂ R
³ is shown. R ² represents a hydrogen atom, a methyl group or CO ₂ R ³ . R ³ represents a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms. Z is a divalent hydrocarbon group which may contain a heteroatom having 2 to 20 carbon atoms to form a single ring or a bridged ring together with the carbon atom to be bonded. m is 0 or 1, n
Is 0, 1, 2, or 3, and is a number satisfying 2m + n = 2 or 3. ) 2. A weight average molecular weight of 1, comprising a repeating unit represented by the following general formula (1a) starting from an ester compound represented by the above general formula (1).
000 to 500,000 high molecular compounds. Embedded image (In the formula, R ¹ , R ² , Z, m, and n have the same meanings as described above.) 3. The polymer compound according to claim 2, further comprising at least one repeating unit represented by the following formulas (2a) to (10a). Embedded image (Wherein R ¹ and R ² are the same as above. K is 0 or 1)
It is. R ⁴ represents a hydrogen atom or a monovalent hydrocarbon group having a carboxy group or a hydroxyl group having 1 to 15 carbon atoms.
At least one of R ^{5 to} R ⁸ represents a monovalent hydrocarbon group having a carboxy group or a hydroxyl group having 1 to 15 carbon atoms,
The rest each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms. R ^{5 to} R ^8
May form a ring with each other, in which case, R ⁵ to
At least one of R ⁸ is a divalent hydrocarbon group having a carboxy group or a hydroxyl group having 1 to 15 carbon atoms, and the rest is each independently a single bond or a linear, branched or branched group having 1 to 15 carbon atoms. Shows a cyclic alkylene group. R ⁹ has 3 to 3 carbon atoms.
15 of -CO ₂ - represents a monovalent hydrocarbon group containing a partial structure. At least one of R ^{10 to} R ¹³ has 2 to 2 carbon atoms.
15 of -CO 2 _- represents a monovalent hydrocarbon group containing a partial structure, while the remaining R's are independently hydrogen or 1 carbon atoms
It represents 15 linear, branched or cyclic alkyl groups. R
^{10 to} R ¹³ may form a ring with each other, in which case at least one of R ^{10 to} R ¹³ has 1 to 1 carbon atoms.
5 represents a divalent hydrocarbon group containing a —CO ₂ — partial structure, and the rest are each independently a single bond or a C 1 to C 15
Represents a linear, branched or cyclic alkylene group. R
¹⁴ represents a polycyclic hydrocarbon group having 7 to 15 carbon atoms or an alkyl group containing a polycyclic hydrocarbon group. R ¹⁵ represents an acid labile group. X is -CH ₂ - shows a or -O-. Y is-
O- or - ^{(NR 16)} - ^{indicates, R 16} is a straight, branched or cyclic alkyl group of hydrogen or 1 to 15 carbon atoms. ) 4. A resist material comprising the polymer compound according to claim 2 or 3. 5. A resist material comprising the polymer compound according to claim 2 or 3, a compound generating an acid in response to a high energy beam or an electron beam, and an organic solvent. 6. A step of applying the resist material according to claim 4 on a substrate, and a step of exposing the substrate to a high energy beam or an electron beam via a photomask after the heat treatment.
And b. Performing a heat treatment as needed, and then developing using a developer.