JP2000186118A - Novel ester compound, polymer compound, resist material, and pattern forming method - Google Patents

Abstract

(57) Abstract: An ester compound represented by the following general formula (1). Embedded image (In the formula, R ¹ represents a hydrogen atom, a methyl group or CH ₂ CO ₂ R ^4. R ² represents a hydrogen atom, a methyl group or CO ₂ R ⁴ .
R ³ represents a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms or an optionally substituted aryl group having 6 to 20 carbon atoms. R ⁴ represents a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms. k is 0 or 1. m is 0 or 1, n is 0, 1, 2, 3, 2m
+ N = 2 or 3 is satisfied. [Effect] The resist material using the polymer compound of the present invention as a base resin is sensitive to high-energy rays and excellent in sensitivity, resolution, and etching resistance, and thus is useful for fine processing by electron beams or far ultraviolet rays. It is. 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.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to (1) a specific ester compound, and (2) high sensitivity, good resolution and high etching when this compound is contained in a resist material as a base resin and contains this compound as a constituent unit. (3) a method for producing the polymer compound, (4) a resist material containing the polymer compound, which exhibits resistance and particularly provides a resist material suitable as a fine pattern forming material for VLSI production; And (5) 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 become higher and higher, the pattern rules have been required to be finer. Among them, KrF excimer laser light, A
Photolithography using an rF excimer laser beam as a light source is required to be realized as a technology indispensable 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-5-80515, 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 desorption 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; In addition, polymer compounds that achieve sensitivity, resolution, and etching resistance that greatly exceed conventional products,
(3) A method for producing the polymer compound, (4) a resist material using the polymer compound as a base resin, and (5) a pattern forming method using the resist material.

[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, high resolution and high etching resistance, 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).

[0009]

Embedded image (In the formula, R ¹ represents a hydrogen atom, a methyl group or CH ₂ CO ₂ R ^4. R ² represents a hydrogen atom, a methyl group or CO ₂ R ⁴ .
R ³ represents a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms or an optionally substituted aryl group having 6 to 20 carbon atoms. R ⁴ represents a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms. k is 0 or 1. m is 0 or 1, n is 0, 1, 2, 3, 2m
+ N = 2 or 3 is satisfied. The present invention also provides the following polymer compound. [II] A weight average molecular weight of 1,000 to 500,000, characterized by containing an ester compound represented by the following general formula (1a-1) or (1a-2) as a constituent unit.
High molecular compound.

[0010]

Embedded image (In the formula, R ¹ , R ² , R ³ , k, m, and n have the same meaning as described above.)

[III] Further, the following formulas (2a) to (10)
The polymer compound according to [II], containing one or more of the repeating units represented by a).

[0012]

Embedded image(Where R¹, R^TwoIs the same as above. R^FiveIs hydrogen field
Containing a carboxy group or a hydroxyl group having 1 to 15 carbon atoms.
A monovalent hydrocarbon group. R⁶~ R⁹At least one of
Contains a carboxy group or a hydroxyl group having 1 to 15 carbon atoms.
A monovalent hydrocarbon group, and the rest independently represent hydrogen sources
Linear or branched or cyclic alkyl having 1 to 15 carbon atoms
Represents a kill group. R⁶~ R⁹May form a ring with each other
In that case, R⁶~ R⁹At least one has 1 carbon atom
Divalent carbonization containing 15 to 15 carboxy or hydroxyl groups
Represents a hydrogen group, and the remainder each independently has 1 to 15 carbon atoms.
It represents a linear, branched or cyclic alkylene group. R^TenIs
-CO having 3 to 15 carbon atoms_TwoMonovalent containing partial structures
Shows a hydrocarbon group. R¹¹~ R¹⁴At least one of is carbon
-CO of Formulas 2 to 15_Two-Monovalent carbonization containing a partial structure
Represents a hydrogen group, and the rest are each independently a hydrogen atom or carbon
Represents a linear, branched or cyclic alkyl group of the formulas 1 to 15
You. R¹¹~ R¹⁴May form a ring with each other,
R in case¹¹~ R ¹⁴At least one has 1 to 15 carbon atoms
-CO_Two-Represents a divalent hydrocarbon group containing a partial structure
And the rest are each independently a straight-chain having 1 to 15 carbon atoms.
Shows a branched or cyclic alkylene group. R¹⁵Has 7 or more carbon atoms
Containing 15 polycyclic hydrocarbon groups or polycyclic hydrocarbon groups
Represents an alkyl group. R¹⁶Represents an acid labile group. k is 0
Or 1. )

The present invention also provides a method for producing the following polymer compound. [IV] The ester compound of the above general formula (1) and carbon-
A method for producing a polymer compound, comprising subjecting another compound containing a carbon double bond to radical polymerization, anionic polymerization or coordination polymerization.

Further, the present invention provides the following resist material. [V] A resist material comprising the polymer compound described in the above [II] or [III]. [VI] A resist material comprising the polymer compound described in [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. [VII] a step of applying the resist material of [V] or [VI] on the substrate, a step of exposing with a high energy beam or an electron beam through a photomask after the heat treatment, and Developing using a developing solution.

In the ester compound represented by the general formula (1) or the high molecular compound having the structural unit represented by the formula (1a-1) or (1a-2), the acid-labile protecting group is represented by the following formula (1b). Alkylcycloalkyl or alkylcycloalkenyl is used, and tert-butoxycarbonyl and tert-butyl have low reactivity to acid, 2-tetrahydropyranyl and 1-ethoxyethyl have too high reactivity to acid and alkali. All of the weak points of the resistance to the developer are eliminated.

[0017]

Embedded image (In the formula, R ³ , m, and n have the same meanings as described above.)

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 above 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.
Further, since this polymer compound has a rigid alicyclic ring in its main chain, it also exhibits extremely strong etching resistance.

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).

[0021]

Embedded image

Here, R ¹ is a hydrogen atom, a methyl group or a C
H ₂ CO ₂ R ⁴ is shown. It will be described later examples of R ^4.
R ² represents a hydrogen atom, a methyl group or CO ₂ R ⁴ . R ³ represents a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms or an optionally substituted aryl group having 6 to 20 carbon atoms, and is represented by a linear, branched or cyclic alkyl group. Specifically, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-amyl, n-pentyl, n-hexyl, cyclopentyl, Examples thereof include a cyclohexyl group, a cyclopentylmethyl group, a cyclopentylethyl group, a cyclohexylmethyl group, and a cyclohexylethyl group.Specific examples of the optionally substituted aryl group include a phenyl group, a methylphenyl group, a naphthyl group, an anthryl group, and a phenanthryl. Group, pyrenyl group and the like.
R ⁴ 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, and tert. -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. k is 0 or 1. 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.

[0024]

Embedded image

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.

[0026]

Embedded image

Here, R ¹ , R ² , R ³ , k, m, and n are the same as described above. M represents a metal.

In the first step, 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, a Grignard reaction, a reaction using an organolithium compound, and the like, but are not limited thereto. The reaction proceeds easily under known conditions, but preferably in a solvent such as tetrahydrofuran or diethyl ether, the starting material cyclic ketone compound, alkyl halide or aryl halide, M
It is preferable to mix magnesium, lithium, or the like as the metal and heat or cool as necessary.

The second step 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 preferably a tertiary alcohol such as methylene chloride, a carboxylic acid halide such as acrylic acid chloride and methacrylic acid chloride, and a base such as triethylamine are mixed. It is preferable to perform cooling according to the conditions.

The third step is a step of constructing an alicyclic skeleton by the Diels-Alder reaction. The reaction proceeds easily under known conditions, but preferably, an ester of a raw material unsaturated acid and cyclopentadiene are mixed in a solvent such as a solvent or a solvent such as benzene, and a catalyst such as boron trifluoride is added as necessary. It is preferable to mix them, and if necessary, heat or cool them.

The present invention is characterized by containing, as a structural unit, a unit of the following general formula (1a-1) or (1a-2) obtained by using the ester compound of the general formula (1) as a monomer. Weight average molecular weight 1,000-500,00
0, preferably 5,000 to 100,000 high molecular compounds are provided.

[0032]

Embedded image

Here, R ¹ , R ² , R ³ , k, m, and n are the same as described above.

In this case, the polymer compound of the present invention comprises one or more units of the following general formulas (2a) to (10a) obtained by using the following general formulas (2) to (10) as a monomer: Can also be contained.

[0035]

Embedded image

[0036]

Embedded image

In the above equation, k is 0 or 1, and therefore, equations (6a-1) to (9a-2) are
a-1-1) to (9a-2-2).

[0038]

Embedded image

Here, R ¹ and R ² are the same as above. R
⁵ represents a hydrogen atom or a monovalent hydrocarbon group containing a carboxy group having 1 to 15 carbon atoms or a hydroxyl group, and specifically, carboxyethyl, carboxybutyl, carboxycyclopentyl, carboxycyclohexyl, carboxynorbornyl, carboxyadamantyl , Hydroxyethyl, hydroxybutyl, hydroxycyclopentyl, hydroxycyclohexyl, hydroxynorbornyl, hydroxyadamantyl and the like. At least one of R ^{6 to} R ⁹ represents a carboxy group having 1 to 15 carbon atoms or a monovalent hydrocarbon group containing a hydroxyl group, and the rest are each independently a hydrogen atom or a linear group having 1 to 15 carbon atoms; It represents a branched or cyclic alkyl group. Specific examples of the monovalent hydrocarbon group having a carboxy group or a hydroxyl group having 1 to 15 carbon atoms include carboxy, carboxymethyl, carboxyethyl, carboxybutyl, hydroxymethyl, hydroxyethyl, hydroxybutyl, and 2-carboxyethoxy. Carbonyl, 4-carboxybutoxycarbonyl, 2-
Hydroxyethoxycarbonyl, 4-hydroxybutoxycarbonyl, carboxycyclopentyloxycarbonyl, carboxycyclohexyloxycarbonyl, carboxynorbornyloxycarbonyl, carboxyadamantyloxycarbonyl, hydroxycyclopentyloxycarbonyl, hydroxycyclohexyloxycarbonyl, hydroxynorbornyloxycarbonyl, hydroxy Adamantyloxycarbonyl and the like can be exemplified. Specific examples of the linear, branched, or cyclic alkyl group having 1 to 15 carbon atoms are the same as those exemplified for R ⁴ . R ^{6 to} R ⁹ may form a ring with each other, in which case at least one of R ^{6 to} R ⁹ is a divalent hydrocarbon group having a carboxy group or a hydroxyl group having 1 to 15 carbon atoms. And the rest are independently carbon number 1 to
It represents 15 linear, branched or cyclic alkylene groups.
2 containing a carboxy group or a hydroxyl group having 1 to 15 carbon atoms
Specific examples of the monovalent hydrocarbon group include those obtained by removing one hydrogen atom from those exemplified above as the monovalent hydrocarbon group containing a carboxy group or a hydroxyl group. Specific examples of the linear, branched, or cyclic alkylene group having 1 to 15 carbon atoms include those exemplified for R ⁴ with one hydrogen atom removed.

R ¹⁰ represents a monovalent hydrocarbon group having a —CO ₂ — partial structure having 3 to 15 carbon atoms.
Oxooxolan-3-yl, 4,4-dimethyl-2-
Examples include oxooxolan-3-yl, 4-methyl-2-oxooxan-4-yl, 2-oxo-1,3-dioxolan-4-ylmethyl, 5-methyl-2-oxooxolan-5-yl, and the like. it can. At least one of R ^{11 to} R ^{14 represents} a monovalent hydrocarbon group having a —CO ₂ — partial structure having 2 to 15 carbon atoms, and the rest are each independently a hydrogen atom or a linear chain having 1 to 15 carbon atoms. A branched, branched or cyclic alkyl group. Specific examples of the monovalent hydrocarbon group having a —CO ₂ — partial structure having 2 to 15 carbon atoms include 2-oxooxolan-3-yloxycarbonyl and 4,4-
Dimethyl-2-oxooxolan-3-yloxycarbonyl, 4-methyl-2-oxooxan-4-yloxycarbonyl, 2-oxo-1,3-dioxolane-
Examples thereof include 4-ylmethyloxycarbonyl, 5-methyl-2-oxooxolan-5-yloxycarbonyl and the like. Specific examples of the linear, branched, or cyclic alkyl group having 1 to 15 carbon atoms are the same as those exemplified for R ⁴ . R ^{11 to} R ¹⁴ may form a ring with each other, and in that case, at least one of R ^{11 to} R ¹⁴ is a divalent hydrocarbon containing a —CO ₂ — partial structure having 1 to 15 carbon atoms. And the remainder are each independently 1 to 1 carbon atoms
5 represents a linear, branched, or cyclic alkylene group. Specific examples of the divalent hydrocarbon group having a —CO ₂ — partial structure having 1 to 15 carbon atoms include 1-oxo-2-oxapropane-1,3-diyl and 1,3-dioxo-2. - oxa-1,3-diyl, 1-oxo-2-Okisabutan-1,4-diyl, other like 1,3-dioxo-2-Okisabutan-1,4-diyl, the -CO ₂ - partial structure And those in which one hydrogen atom has been removed from those exemplified for the monovalent hydrocarbon group containing. 1 to 1 carbon atoms
Specific examples of the linear, branched, or cyclic alkylene group of 5 include those exemplified for R ⁴ with one hydrogen atom removed.

R ¹⁵ represents a polycyclic hydrocarbon group having 7 to ¹⁵ carbon atoms or an alkyl group containing a polycyclic hydrocarbon group, and specific examples include norbornyl, bicyclo [3.3.1] nonyl, and tricyclo. [5.2.1.0 ^2,6 ] decyl, adamantyl, ethyl adamantyl, butyl adamantyl, norbornylmethyl, adamantylmethyl and the like. R ¹⁶ represents an acid labile group. k is 0 or 1.

Specific examples of the acid labile group represented by R ¹⁶ include a group represented by the following general formula (11) or (12),
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.

[0043]

Embedded image

In the formula, R ¹⁷ and R ¹⁸ are a hydrogen atom or a carbon atom
To 18, preferably 1 to 10 linear, branched or cyclic alkyl groups, specifically methyl, ethyl,
Propyl group, isopropyl group, n-butyl group, sec-
Examples thereof include a butyl group, a tert-butyl group, a cyclopentyl group, a cyclohexyl group, a 2-ethylhexyl group, and an n-octyl group. R ¹⁹ represents a monovalent hydrocarbon group which may have a heteroatom such as an oxygen atom having 1 to 18 carbon atoms, and preferably 1 to 10 carbon atoms, and may be a linear, branched or cyclic alkyl group; Some of the hydrogen atoms are hydroxyl, alkoxy,
Examples thereof include those substituted with an oxo group, an amino group, an alkylamino group, and the like, and specific examples include the following substituted alkyl groups.

[0045]

Embedded image

[0046] R ¹⁷ and R ^18, R ^17, R ^19, and R ¹⁸ and R ¹⁹ may form a ring, when they form a ring R ^17,
R ¹⁸ and R ¹⁹ each have 1 to 18 carbon atoms, preferably 1 to 18 carbon atoms.
And 10 linear or branched alkylene groups.

R ²⁰ has 4 to ²⁰ carbon atoms, preferably 4 to 1 carbon atoms.
5 tertiary alkyl groups, each alkyl group having 1 carbon atom
A trialkylsilyl group, an oxoalkyl group having 4 to 20 carbon atoms, or a group represented by the general formula (11). a is an integer of 0 to 6.

The tertiary alkyl group includes te
rt-butyl group, tert-amyl group, 1,1-diethylpropyl group, 1-ethylcyclopentyl group, 1-butylcyclopentyl group, 1-ethylcyclohexyl group, 1
-Butylcyclohexyl group, 1-ethyl-2-cyclopentenyl group, 1-ethyl-2-cyclohexenyl group, 2
-Methyl-2-adamantyl group and the like. Examples of the trialkylsilyl group include those having 1 to 6 carbon atoms in each alkyl group such as a trimethylsilyl group, a triethylsilyl group, and a dimethyl-tert-butylsilyl group. Examples of the oxoalkyl group include a 3-oxocyclohexyl group, a 4-methyl-2-oxooxan-4-yl group, a 5-methyl-2-oxooxolan-5-yl group, and the like.

Specific examples of the linear or branched acid labile group represented by the above formula (11) include the following groups.

[0050]

Embedded image

Specific examples of the cyclic groups among the acid labile groups represented by the above formula (11) include the following groups.

[0052]

Embedded image

Specific examples of the acid labile group of the above formula (12) 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.

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: (i) a monomer of the above formula (1); (ii) a monomer of the above formulas (2) to (10); Monomers containing a carbon-carbon double bond other than (i) and (ii), for example, methyl methacrylate;
Substituted acrylates such as methyl crotonate, dimethyl maleate and dimethyl itaconate; unsaturated carboxylic acids such as maleic acid, fumaric acid and itaconic acid; substituted norbornenes such as norbornene and methyl norbornene-5-carboxylate; anhydrous Unsaturated acid anhydrides such as itaconic acid 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 is contained in an amount of 30 to 80 mol%, and (II) the formulas (2a) to (1) based on the monomers of the above 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 500,000.
00 to 100,000. Outside this range, the etching resistance may be extremely reduced, or the difference in dissolution rate before and after exposure may not be ensured, resulting in reduced resolution.

The present invention also relates to a method of subjecting 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)) to radical polymerization. The present invention provides a method for producing a polymer compound, which comprises conducting anionic polymerization or coordination 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 reaction conditions for the anionic polymerization reaction are as follows: (a) a hydrocarbon such as benzene, an ether such as tetrahydrofuran, or liquid ammonia as a solvent; and (a) a metal such as sodium or potassium as a polymerization initiator; Using an alkyl metal such as -butyllithium or sec-butyllithium, ketyl, or Grignard reagent, (c) maintaining the reaction temperature at about -78 ° C to 0 ° C, and (d) reducing the reaction time from 0.5 hour to 48 hours. It is preferable to use about a time, and (e) a proton-donating compound such as methanol, a halide such as methyl iodide, or another electrophilic substance is preferably used as a terminator, but a case outside this range is not excluded.

The reaction conditions for the coordination polymerization are as follows: (a) using hydrocarbons such as n-heptane and toluene as a solvent;
As a catalyst, a Ziegler-Natta catalyst comprising a transition metal such as titanium and an alkylaluminum, a Phillips catalyst in which chromium and nickel compounds are supported on a metal oxide, an olefin-metathesis mixed catalyst represented by a tungsten and rhenium mixed catalyst, and the like ( C) The reaction temperature is 0 ° C
To about 100 ° C., and (d) the reaction time is preferably about 0.5 to 48 hours, but a case outside this range is not excluded.

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 compound used in the present invention that generates an acid in response to a high energy beam or an electron beam (hereinafter, referred to as an acid generator) 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.

[0066]

Embedded image (Wherein, R ^101a , R ^101b , and R ^101c each have 1 to 1 carbon atoms)
A straight-chain, branched, or cyclic alkyl group, alkenyl group, oxoalkyl group, or oxoalkenyl group of 12; an aryl group having 6 to 20 carbon atoms; or an aralkyl group or an aryloxoalkyl group having 7 to 12 carbon atoms. A part or all of the hydrogen atoms of these groups may be substituted by an alkoxy group or the like. R ^101b and R ^101c may form a ring, and when forming a ring, R ^101b and R ^101c
Represents an alkylene group having 1 to 6 carbon atoms. K ^- represents a non-nucleophilic counter ion. )

The above R ^101a , R ^101b and R ^101c may be the same or different from each other. Specifically, as the alkyl group, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclopropylmethyl group, 4-methylcyclohexyl group, cyclohexylmethyl group, norbornyl group, An adamantyl group and the like can be mentioned. 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 and a 2-oxocyclohexyl group.
-Oxopropyl group, 2-cyclopentyl-2-oxoethyl group, 2-cyclohexyl-2-oxoethyl group,
A 2- (4-methylcyclohexyl) -2-oxoethyl group and the like can be mentioned. Examples of the aryl group include a phenyl group, a naphthyl group, a p-methoxyphenyl group, m
-Methoxyphenyl group, o-methoxyphenyl group, ethoxyphenyl group, p-tert-butoxyphenyl group,
alkoxyphenyl groups such as m-tert-butoxyphenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, ethylphenyl group, 4-t
alk-naphthyl groups such as tert-butylphenyl group, 4-butylphenyl group and dimethylphenyl group, alkylnaphthyl groups such as methylnaphthyl group and ethylnaphthyl group, methoxynaphthyl group and ethoxynaphthyl group, and dimethylnaphthyl group And dialkylnaphthyl groups such as diethylnaphthyl group, and dialkoxynaphthyl groups such as dimethoxynaphthyl group and diethoxynaphthyl group. Examples of the aralkyl group include a benzyl group, a phenylethyl group, a phenethyl group and the like. Examples of the aryloxoalkyl group include a 2-phenyl-2-oxoethyl group, a 2- (1-naphthyl) -2-oxoethyl group,
And 2-aryl-2-oxoethyl groups such as-(2-naphthyl) -2-oxoethyl 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.

[0068]

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

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

[0070]

Embedded image (Wherein, R ¹⁰⁵ and R ¹⁰⁶ are linear, branched, or cyclic alkyl groups or halogenated alkyl groups having 1 to 12 carbon atoms, aryl groups or halogenated aryl groups 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 methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl and the like. Group, amyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, norbornyl group, adamantyl group and the like. Examples of the halogenated alkyl group include a trifluoromethyl group, a 1,1,1-trifluoroethyl group, and a 1,1,1-
Examples thereof include a 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. Examples thereof include an alkylphenyl group such as a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, an ethylphenyl group, a 4-tert-butylphenyl group, a 4-butylphenyl group, and a dimethylphenyl group. Examples of the halogenated aryl group include a fluorophenyl group, a chlorophenyl group, a 1,2,3,4,5-pentafluorophenyl group, and the like. Examples of the aralkyl group include a benzyl group and a phenethyl group.

[0072]

Embedded image (Wherein, R ¹⁰⁷ , R ¹⁰⁸ , and R ¹⁰⁹ 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 20 carbon atoms, Or an aralkyl group having 7 to 12 carbon atoms.
^108, R ¹⁰⁹ may form a cyclic structure bonded to each other, indicating when they form a ring, R ^108, R ¹⁰⁹ each represent 1-6 linear, a branched alkylene group. )

Examples of the alkyl group, halogenated alkyl group, aryl group, halogenated aryl group and aralkyl group of R ¹⁰⁷ , R ¹⁰⁸ and R ¹⁰⁹ include the same groups as described for R ¹⁰⁵ and R ¹⁰⁶ . The alkylene group represented by R ¹⁰⁸ and R ¹⁰⁹ includes a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group and the like.

[0074]

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

[0075]

Embedded image (Wherein, 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 some or all of the hydrogen atoms of these groups further have carbon atoms. It may be substituted by 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; Or a phenyl group which may be 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 for R ¹¹⁰ includes:
1,2-phenylene group, 1,8-naphthylene group and the like, alkylene groups include methylene group, 1,2-ethylene group, 1,3-propylene group, 1,4-butylene group, 1-
Phenyl-1,2-ethylene group, norbornane-2,3
Examples of the -diyl group and the alkenylene group include a 1,2-vinylene group, a 1-phenyl-1,2-vinylene group, and a 5-norbornene-2,3-diyl group. R ^111
Examples of the alkyl group are the same as R ^{101a to} R ^101c, and examples of the alkenyl group include a vinyl group, a 1-propenyl group, an allyl group, a 1-butenyl group, a 3-butenyl group, an isoprenyl group and a 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, etc. , Methoxymethyl group, ethoxymethyl group, propoxymethyl group, butoxymethyl group, pentoxymethyl group, hexyloxymethyl group, heptyloxymethyl group, methoxyethyl group, ethoxyethyl group, propoxyethyl group, butoxyethyl group, pli Roxyethyl, hexyloxyethyl, methoxypropyl, ethoxypropyl, propoxypropyl, butoxypropyl, methoxybutyl, ethoxybutyl, propoxybutyl, methoxypentyl, ethoxypentyl, methoxyhexyl, methoxy Heptyl Etc. The.

It is to be noted that carbon atoms 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.

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-p-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; nitro 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 methanesulfonic acid ester, N-hydroxyglutarimide methanesulfonic acid ester 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 hydroxyimide compounds, such as triphenylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, and tris (trifluoromethanesulfonic acid) pts (pt)
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 per 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, and if the amount is more than 15 parts, the resolution of the resist material may decrease due to a decrease in the alkali dissolution rate. May deteriorate.

The organic solvent used in the present invention may be any organic solvent that can dissolve the base resin, the acid generator, and other additives. 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 and the like 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.

A polymer compound different from the polymer compound of the present invention can be further added to the resist material of the present invention.

Specific examples of the polymer compound different from the polymer compound of the present invention include a weight average molecular weight of 1, having a unit represented by the following formula (R1) and / or the following formula (R2).
000 to 500,000, preferably 5,000 to 10
However, the present invention is not limited to these.

[0084]

Embedded image

[0085]

Embedded image (Wherein, R ⁰⁰¹ is a hydrogen atom, a methyl group or CH ₂ CO ₂ R
⁰⁰³ is shown. R ⁰⁰² is a hydrogen atom, a methyl group or CO ₂ R ⁰⁰³
Is shown. R ⁰⁰³ represents a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms. R ⁰⁰⁴ 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 ^{005 to} R ⁰⁰⁸ represents a carboxy group having 1 to 15 carbon atoms or a monovalent hydrocarbon group containing a hydroxyl group, and the rest each independently represents a hydrogen atom or a linear group having 1 to 15 carbon atoms; It represents a branched or cyclic alkyl group. R ^{005 to} R ⁰⁰⁸ may form a ring with each other, in which case at least one of R ^{005 to} R ⁰⁰⁸ is a divalent hydrocarbon group having a carboxy group or a hydroxyl group having 1 to 15 carbon atoms. And the rest are each independently 1 to 1 carbon atoms
5 represents a linear, branched, or cyclic alkylene group. R
⁰⁰⁹ is 1 having a —CO ₂ — partial structure having 3 to 15 carbon atoms.
Represents a monovalent hydrocarbon group. At least one of R ^{010 to} R ^{013 represents} a monovalent hydrocarbon group having a —CO ₂ — partial structure having 2 to 15 carbon atoms, and the rest are each independently a hydrogen atom or a linear chain having 1 to 15 carbon atoms. A branched, branched or cyclic alkyl group. R ^{010 to} R ⁰¹³ may form a ring with each other, in which case at least one of R ^{010 to} R ⁰¹³ is a divalent hydrocarbon containing a —CO ₂ — partial structure having 1 to 15 carbon atoms. And the rest each independently represent a linear, branched or cyclic alkylene group having 1 to 15 carbon atoms. R ⁰¹⁴
Represents a polycyclic hydrocarbon group having 7 to 15 carbon atoms or an alkyl group containing a polycyclic hydrocarbon group. R ⁰¹⁵ represents an acid labile group. R ⁰¹⁶ represents a hydrogen atom or a methyl group. R ⁰¹⁷ represents a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. k ′ is 0 or 1. a1 ', a2', a
3 ′, b1 ′, b2 ′, b3 ′, c1 ′, c2 ′, c
3 ′, d1 ′, d2 ′, d3 ′, e ′ are numbers of 0 or more and less than 1, and a1 ′ + a2 ′ + a3 ′ + b1 ′ + b2 ′ +
b3 '+ c1' + c2 '+ c3' + d1 '+ d2' + d
3 ′ + e ′ = 1 is satisfied. f ', g', h ', i',
j ′ is a number from 0 to less than 1, and f ′ + g ′ + h ′ +
i ′ + j ′ = 1 is satisfied. )

In addition, specific examples of each group include:
This is the same as that described for R ^{1 to} R ¹⁶ .

The compounding ratio of the polymer compound other than the polymer compound of the present invention is from 10:90 to 90:10, especially 20:90.
It is preferable that the weight ratio is in the range of 80 to 80:20. If the compounding ratio of the polymer compound of the present invention is less than the above range, preferable performance as a resist material may not be obtained. The performance of the resist material can be adjusted by appropriately changing the above mixing ratio.

The polymer compound is not limited to one kind,
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 in which the hydrogen atom of the phenolic hydroxyl group has an average of 0 to 100 mol% as a whole or an carboxy group in the molecule by an acid labile group The carboxy group has an average of 80 to 1
The substituted compound is blended at a ratio of 00 mol%.

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

In this case, such a phenolic hydroxyl group is
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.

[0092]

Embedded image (Wherein, R ²⁰¹ and R ²⁰² each represent a hydrogen atom or a linear or branched alkyl or alkenyl group having 1 to 8 carbon atoms. R ²⁰³ represents a hydrogen atom or a 1 to 8 carbon atom. Represents a linear or branched alkyl or alkenyl group or — (R ²⁰⁷ ) _h COOH, wherein R ²⁰⁴ is — (CH ₂ ) _i
-(I = 2 to 10), an arylene group having 6 to 10 carbon atoms,
It represents a carbonyl group, a sulfonyl group, an oxygen atom or a sulfur atom. R ^{20 5} 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 ²⁰⁶ is a hydrogen atom,
It represents a linear or branched alkyl group or alkenyl group having 1 to 8 carbon atoms, or a phenyl group or a naphthyl group each substituted with a hydroxyl group. 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 0-5. u and h are 0
Or 1. s, t, s ′, t ′, s ″, and t ″ are s + t = 8, s ′ + t ′ = 5, and s ″ + t ″, respectively.
= 4 and having at least one hydroxyl group in each phenyl skeleton. α is the equation (D8),
The number is such that the molecular weight of the compound (D9) is 100 to 1,000. )

In the above formula, R²⁰¹, R²⁰²As, for example, water
Element atom, methyl group, ethyl group, butyl group, propyl group,
Ethynyl group, cyclohexyl group, R²⁰³For example,
R^{Two 01}, R²⁰²The same as above, or -COOH, -C
H_TwoCOOH, R²⁰⁴Are, for example, ethylene group,
Nylene, carbonyl, sulfonyl, oxygen, sulfur
Yellow atom, R²⁰⁵As, for example, a methylene group, or
R²⁰⁴The same as R ²⁰⁶As a hydrogen atom,
Tyl, ethyl, butyl, propyl, ethynyl
Group, cyclohexyl group, and hydroxyl-substituted
Phenyl, naphthyl and the like.

The acid labile group of the dissolution controlling agent includes a group represented by the following general formula (11) and a group represented by the following general formula (1)
A group represented by 2), a tertiary alkyl group having 4 to 20 carbon atoms,
Examples of the alkyl group include a trialkylsilyl group having 1 to 6 carbon atoms and an oxoalkyl group having 4 to 20 carbon atoms.

[0095]

Embedded image (Wherein, R ¹⁷ and R ¹⁸ represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms. R ¹⁹ may have a heteroatom having 1 to 18 carbon atoms) R ¹⁷ and R ¹⁸ , R ¹⁷ and R ¹⁹ , and R ¹⁸ and R ¹⁹ may form a ring, and when forming a ring, R ¹⁷ and R ¹⁸ ,
R ¹⁹ represents a linear or branched alkylene group having 1 to 18 carbon atoms. R ²⁰ is a tertiary alkyl group having 4 to ²⁰ carbon atoms, each alkyl group is 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 general formula (11). Is shown. A is 0
6 to an integer. )

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, a basic compound can be added to the resist composition of the present invention. As the basic compound, a compound that can suppress the diffusion rate when the acid generated from the acid generator diffuses into the resist film is suitable. By blending a basic compound, the diffusion rate of acid in the resist film is suppressed and the resolution is improved. 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-pyridone, 4-pyrrolidinopyridine, 1-methyl- 4-phenylpyridine, 2- (1-ethylpropyl) pyridine,
Aminopyridine, dimethylaminopyridine, etc.), pyridazine derivatives, pyrimidine derivatives, pyrazine derivatives, pyrazoline derivatives, pyrazolidine derivatives, piperidine derivatives, piperazine derivatives, morpholine derivatives, indole derivatives, isoindole derivatives, 1H-indazole derivatives, indoline derivatives, quinoline derivatives (Eg, quinoline, 3-quinolinecarbonitrile), isoquinoline derivatives, cinnoline derivatives, quinazoline derivatives, quinoxaline derivatives, phthalazine derivatives, purine derivatives, pteridine derivatives, carbazole derivatives, phenanthridine derivatives, acridine derivatives, phenazine derivatives, 1,1
Examples thereof include 0-phenanthroline derivatives, adenine derivatives, adenosine derivatives, guanine derivatives, guanosine derivatives, uracil derivatives, uridine derivatives and the like.

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), and the like; 3-pyridinesulfonic acid as a nitrogen-containing compound having a sulfonyl group; Examples of pyridinium p-toluenesulfonate include a nitrogen-containing compound having a hydroxyl group, a nitrogen-containing compound having a hydroxyphenyl group, and alcoholic nitrogen-containing compounds such as 2-hydroxypyridine, aminocresol, 2,4-quinolinediol, 3-indole methanol 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 formulas (B1) and (B2) can be blended.

[0104]

Embedded image(Where R³⁰¹, R³⁰², R³⁰³, R³⁰⁷, R³⁰⁸Each
Independently, linear, branched or cyclic, having 1 to 20 carbon atoms
An alkylene group of R³⁰⁴, R³⁰⁵, R³⁰⁶, R³⁰⁹, R³¹⁰
Is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an amino group
And R³⁰⁴And R ³⁰⁵, R³⁰⁴And R³⁰⁶, R³⁰⁵And R³⁰⁷,
R³⁰⁴And R³⁰⁵And R³⁰⁶, R³⁰⁹And R³¹⁰Are combined
To form a ring. S, T and U are each 0 to 20
Is an integer. However, when S, T, U = 0, R³⁰⁴,
R³⁰⁵, R³⁰⁶, R³⁰⁹, R³¹⁰Does not contain a hydrogen atom. )

Here, R ³⁰¹ , R ³⁰² , R ³⁰³ , R ³⁰⁷ , R
^{The 308} alkylene group has 1 to 20, preferably 1 to 10, and more preferably 1 to 8 carbon atoms, specifically, a methylene group, an ethylene group, an n-propylene group, an isopropylene group, Examples thereof include an n-butylene group, an isobutylene group, an n-pentylene group, an isopentylene group, a hexylene group, a nonylene group, a decylene group, a cyclopentylene group, and a cyclohexylene group.

Further, R ³⁰⁴ , R ³⁰⁵ , R ³⁰⁶ , R ³⁰⁹ , R
^{The 310} alkyl group has 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms, and more preferably 1 to 6 carbon atoms, and these 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,
Examples include a cyclopentyl group and a cyclohexyl group.

Further, R ³⁰⁴ and R ³⁰⁵ , R ³⁰⁴ and R ³⁰⁶ , R
^{When 305} and R ³⁰⁶ , R ³⁰⁴ and R ³⁰⁵ and R ³⁰⁶ , and R ³⁰⁹ and R ³¹⁰ form a ring, the ring has 1 to 20, preferably 1 to 8, more preferably 1 to 6, carbon atoms. In these rings, an alkyl group having 1 to 6 carbon atoms, 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 (B1) and (B2) include tris {2- (methoxymethoxy) ethyl}.
Amine, tris {2- (methoxyethoxy) ethyl} amine, 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) ethoxydiethyl] amine, 4,
7,13,16,21,24-hexaoxa-1,10
-Diazabicyclo [8.8.8] hexacosan, 4,
7,13,18-tetraoxa-1,10-diazabicyclo [8.5.5] eicosan, 1,4,10,13-
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 amine, aniline derivative, pyrrolidine derivative, pyridine derivative, quinoline derivative, amino acid derivative, nitrogen-containing compound having hydroxyl group, nitrogen-containing compound having hydroxyphenyl group, alcoholic nitrogen-containing compound, amide derivative, imide derivative, tris {2- (methoxymethoxy) ethyl} amine, tris} (2- (2-
Methoxyethoxy) ethyl} amine, tris [2-
{(2-methoxyethoxy) methyl} ethyl] amine,
1-aza-15-crown-5 and the like are preferred.

The compounding amount of the above-mentioned basic compound is based on the amount of the acid generator 1
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 ≡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 combining 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).

[0113]

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 -C
OOR 'group (R' is a hydrogen atom or -R ⁴⁰⁹ -COOH)
Is shown. R ⁴⁰⁵ represents — (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 has 1 carbon atom
Represents an alkylene group having 10 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 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 represents a linear or branched alkylene group having 1 to 10 carbon atoms. 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 is shown. 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, t
2, s3, t3, s4, and t4 are respectively s1 + t1 =
8, s2 + t2 = 5, s3 + t3 = 4, s4 + t4 = 6
And 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 1,000.
This is a number from 0 to 10,000. )

[0114]

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.

[0116]

Embedded image

[0117]

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

[0118]

Embedded image

The compounds having a group represented by ≡C—COOH in the molecule can 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.

[0123]

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 the 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, more preferably 0.02 to 1% by weight, based on 100% by weight of the resist composition. 0.0
If the amount is less than 1% 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, other than the above components, a surfactant which is commonly used to improve coating properties. In addition, the addition amount of the optional component can be a normal amount as long as the effect of the present invention is not impaired.

The surfactant is preferably a nonionic surfactant, and is preferably a perfluoroalkylpolyoxyethylene ethanol, a fluorinated alkyl ester, a perfluoroalkylamine oxide, a 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 by 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 a method such as spin coating. 0.5-2.0μ
m on a hot plate.
１５０150 ° C., 1〜１０10 minutes, preferably 80〜120
Pre-bake at 1 ° C for 1-5 minutes. Next, a mask for forming a target pattern is held over the resist film, and a high-energy ray such as far ultraviolet rays, an excimer laser, or an X-ray or an electron beam is exposed at a dose of about 1 to 200 mJ / cm ² , preferably 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) at 1 to 5 minutes, preferably at 80 to 120 ° C. for 1 to 3 minutes. Furthermore, 0.
Using a developer of an aqueous alkali solution such as 1-5%, preferably 2-3% tetramethylammonium hydroxide (TMAH), for 0.1 to 3 minutes, preferably 0.5 to 2 minutes, a dip method A target pattern is formed on the substrate by developing using a conventional method such as a paddle 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. Further, when the above range is out of the upper limit and the lower limit, a desired pattern may not be obtained.

[0129]

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.

[0130]

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 1 778.6 g of ethyl bromide was dissolved in 3 L of tetrahydrofuran. The reaction mixture was added dropwise to 171.4 g of magnesium metal at 60 ° C. or lower over 1 hour. After continuing stirring at room temperature for 2 hours, 300.0 g of cyclopentanone was added dropwise at 65 ° C. or lower over 45 minutes. After stirring at room temperature for 1 hour, the usual post-reaction treatment was carried out, and the obtained oily substance was distilled under reduced pressure to obtain 209.2 g of 1-.
Ethyl cyclopentanol was obtained. Yield 51.4
%Met.

197.0 g of 1-ethylcyclopentanol was dissolved in 2 L of methylene chloride. 204.0 g of acrylic acid chloride was added to the reaction mixture at -20 ° C.
The following was added dropwise over 10 minutes. 2.1 g of 4- (N,
N-dimethylamino) pyridine was added, followed by 263.
0 g of triethylamine was added dropwise at -20 ° C or lower over 1 hour. After continuing stirring at room temperature for 15 hours, a usual post-reaction treatment was carried out to obtain about 300 g of an oily substance. This was used for the next reaction without purification.

The oil obtained in the preceding step was dissolved in 300 ml of benzene. To this reaction mixture, 172.
0 g of cyclopentadiene was added dropwise at 10 ° C. or lower over 10 minutes. After stirring at room temperature for 17 hours and then at 70 ° C. for 1 hour, the mixture was concentrated under reduced pressure. When the obtained oily substance was distilled under reduced pressure, 269.9 g of 1-ethylcyclopentyl 5-norbornene-2-carboxylate (Mono) was obtained.
mer1) was obtained. The yield was 66.7%. Boiling point: 108-116 ° C / 1 mmHg ¹ H-NMR (CDCl ₃ , 270 MHz): δ 0.78
-0.90 (m, 3H), 1.20-2.18 (m, 1
4H), 2.83-3.20 (m, 3H), 5.89-
6.20 (m, 2H) FT-IR: 1726 cm ^-1

[Synthesis Examples 1-2 to 16] Monomer2
Synthesis of １６16 Monomers 2 to 16 were synthesized in the same manner as described above.

[0136]

Embedded image

[Synthesis Example 2-1] Synthesis of Polymer 1 117.0 g of Monomer 1 and 49.0 g of maleic anhydride were dissolved in 2 L of tetrahydrofuran, and 3.5
g of 2,2'-azobisisobutyronitrile was added.
After stirring at 60 ° C. for 15 hours, the mixture was concentrated under reduced pressure. The obtained residue was dissolved in 800 ml of tetrahydrofuran,
It was added dropwise to 0 L of n-hexane. The resulting solid was collected by filtration, washed with 20 L of n-hexane, and dried in vacuum at 40 ° C. for 6 hours.
A polymer compound represented by ymer1 was obtained. The yield was 53.2%.

[Synthesis Examples 2-2 to 48] Polymer 2
Synthesis of -48 In the same manner as above, Polymers 2-48 were synthesized.

[0139]

Embedded image

[0140]

Embedded image

[0141]

Embedded image

[0142]

Embedded image

[0143]

Embedded image

[0144]

Embedded image

[0145]

Embedded image

[0146]

Embedded image

[0147]

Embedded image

[0148]

Embedded image

[0149]

Embedded image

[0150]

Embedded image

[Example I] The polymers (Polymers 1 to 48) obtained in the above synthesis examples were evaluated for resolution when used as a resist material.

[Examples I-1 to 82] Evaluation of resolution of resist Polymers obtained in the above synthesis examples (Polymer 1 to Polymer 4)
8) and a polymer represented by the following formula (Polymer4)
9-56) as a base resin, an acid generator (PAG1-8) represented by the following formula, a dissolution controlling agent (DRR1-4) represented by the following formula, a basic compound, and an intramolecular compound represented by the following formula A compound having a group represented by ΔC-COOH (ACC1) was dissolved in a solvent containing 0.05% by weight of FC-430 (manufactured by Sumitomo 3M Ltd.) in the composition shown in the table to prepare a resist material. , And 0.2% of each resist material
Each of the resist solutions was prepared by filtration through a μm Teflon filter.

[0153]

Embedded image

[0154]

Embedded image

[0155]

Embedded image

[0156]

Embedded image

[0157]

Embedded image

A resist solution was spin-coated on a silicon wafer and applied to a thickness of 0.5 μm. Next, the silicon wafer was placed on a hot plate for 1 hour.
Bake at 10 ° C for 90 seconds. This was exposed using an ArF excimer laser stepper (manufactured by Nikon Corporation, NA = 0.55) and baked at 110 ° C. for 90 seconds (PE
B) When development was carried out with a 2.38% aqueous solution of tetramethylammonium hydroxide, a positive pattern could be obtained.

The following items were evaluated for the resist. First, the sensitivity (Eth, mJ / cm ² ) was determined. Next, an exposure amount for resolving a 0.25 μm line and space at 1: 1 is defined as an optimum exposure amount (Eop, mJ / cm ² ), and a minimum line width (μm ) Is the resolution of the evaluation resist. The shape of the resolved resist pattern was observed using a scanning electron microscope.

Tables 1 to 5 show the composition and evaluation results of each resist.
Shown in In addition, in Tables 1-5, the solvent and the basic compound are as follows. PGMEA: Propylene glycol methyl ether acetate PG / EL: Mixed solvent of 70% PGMEA and 30% ethyl lactate TBA: Tributylamine TEA: Triethanolamine TMMEA: Trismethoxymethoxyethylamine TMMEA: Trismethoxyethoxymethoxyethylamine

[0161]

[Table 1]

[0162]

[Table 2]

[0163]

[Table 3]

[0164]

[Table 4]

[0165]

[Table 5]

From the results shown in Tables 1 to 5, it is clear that the polymer compound having the ester compound of the present invention as a structural unit has extremely high reactivity to an acid, and thus the resist material of the present invention has extremely high sensitivity. It was confirmed that the film had image properties.

Example II The etching resistance of the polymers (Polymers 1 to 48) obtained in the above synthesis examples was evaluated.

[Examples II-1 to 48] Evaluation of etching resistance of polymer The polymers (Polymer 1 to Polymer 4) obtained in the above synthesis examples were obtained.
8) and a polymer for comparison (polymethyl methacrylate, molecular weight 10,000) were dissolved in cyclohexanone, spin-coated on a silicon wafer, and coated to a thickness of 1.0 μm. Next, the silicon wafer was baked at 110 ° C. for 90 seconds using a hot plate. For these, the etching rate (レ ー ト / min) in etching with a chlorine-based gas and a fluorine-based gas was measured.

Tables 6 and 7 show the evaluation results, and Table 8 shows the conditions of the measuring equipment. From the results in Tables 6 and 7, it was confirmed that the polymer compound of the present invention had extremely high etching resistance.

[0170]

[Table 6]

[0171]

[Table 7]

[0172]

[Table 8]

Continuing on the front page (72) Inventor Tsunehiro Nishi 28-1 Nishifukushima, Oku-ku, Nakakushiro-mura, Niigata Prefecture Inside the Synthetic Research Laboratory, Shin-Etsu Chemical Co., Ltd. 28-1 Fukushima, Shin-Etsu Chemical Co., Ltd., Synthetic Technology Research Laboratory (72) Inventor Koji Hasegawa 28-1, Nishifukushima, Oku, Nukujuku-mura, Niigata Prefecture Niigata Synthetic Technology Research Laboratory, Shin-Etsu Chemical Co., Ltd. 28-1 Nishifukushima, Kushiro-mura, Nakakubijo-gun, Japan Shin-Etsu Chemical Co., Ltd.

Claims (7)

[Claims] 1. An ester compound represented by the following general formula (1). Embedded image (In the formula, R ¹ represents a hydrogen atom, a methyl group or CH ₂ CO ₂ R ^4. R ² represents a hydrogen atom, a methyl group or CO ₂ R ⁴ .
R ³ represents a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms or an optionally substituted aryl group having 6 to 20 carbon atoms. R ⁴ represents a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms. k is 0 or 1. m is 0 or 1, n is 0, 1, 2, 3, 2m
+ N = 2 or 3 is satisfied. ) 2. The compound represented by the following general formula (1a-1) or (1a-
(2) A weight average molecular weight of 1,000 to 50, which contains the ester compound represented by 2) as a constituent unit.
000 high molecular compounds. Embedded image (In the formula, R ¹ , R ² , R ³ , k, m, and n have the same meaning as described above.) 3. Formulas (2a) to (10a) below
Contains one or more of the repeating units
The polymer compound according to claim 2, wherein Embedded image(Where R¹, R^TwoIs the same as above. R^FiveIs hydrogen field
Containing a carboxy group or a hydroxyl group having 1 to 15 carbon atoms.
A monovalent hydrocarbon group. R⁶~ R⁹At least one of
Contains a carboxy group or a hydroxyl group having 1 to 15 carbon atoms.
A monovalent hydrocarbon group, and the rest independently represent hydrogen sources
Linear or branched or cyclic alkyl having 1 to 15 carbon atoms
Represents a kill group. R⁶~ R⁹May form a ring with each other
In that case, R⁶~ R⁹At least one has 1 carbon atom
Divalent carbonization containing 15 to 15 carboxy or hydroxyl groups
Represents a hydrogen group, and the remainder each independently has 1 to 15 carbon atoms.
It represents a linear, branched or cyclic alkylene group. R^TenIs
-CO having 3 to 15 carbon atoms_TwoMonovalent containing partial structures
Shows a hydrocarbon group. R¹¹~ R¹⁴At least one of is carbon
-CO of Formulas 2 to 15_Two-Monovalent carbonization containing a partial structure
Represents a hydrogen group, and the rest are each independently a hydrogen atom or carbon
Represents a linear, branched or cyclic alkyl group of the formulas 1 to 15
You. R¹¹~ R¹⁴May form a ring with each other,
R in case¹¹~ R ¹⁴At least one has 1 to 15 carbon atoms
-CO_Two-Represents a divalent hydrocarbon group containing a partial structure
And the rest are each independently a straight-chain having 1 to 15 carbon atoms.
Shows a branched or cyclic alkylene group. R¹⁵Has 7 or more carbon atoms
Containing 15 polycyclic hydrocarbon groups or polycyclic hydrocarbon groups
Represents an alkyl group. R¹⁶Represents an acid labile group. k is 0
Or 1. ) 4. A method for producing a polymer compound, comprising subjecting the ester compound of the general formula (1) and another compound containing a carbon-carbon double bond to radical polymerization, anion polymerization or coordination polymerization. 5. A resist material comprising the polymer compound according to claim 2 or 3. 6. A resist material comprising the polymer compound according to claim 2 or 3, a compound capable of generating an acid in response to a high energy beam or an electron beam, and an organic solvent. 7. A step of applying the resist material according to claim 5 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 necessary, and then developing with a developer.