KR19990088140A - Novel Ester Compounds, Polymers, Resist Composition and Patterning Process - Google Patents

Abstract

The present invention relates to an ester compound represented by the following formula (1).

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 a substitutable 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 any one of 0, 1, 2, and 3, and is a number which satisfy | fills 2m + n = 2 or 3.

Moreover, since the resist material using the high molecular compound of this invention as a base resin is excellent in sensitivity, resolution, and etching tolerance in response to high energy rays, it is useful for the fine processing by an electron beam and far ultraviolet rays. In particular, since the absorption at the exposure wavelengths of the ArF excimer laser and the KrF excimer laser is small, it is possible to easily form a fine pattern perpendicular to the substrate.

Description

Novel Ester Compounds, Polymers, Resist Composition and Patterning Process

The present invention provides (1) a specific ester compound and (2) a compound as a structural unit, and when blended with a resist material as a base resin, it exhibits high sensitivity, good resolution, and high etching resistance, and in particular, fine patterns for producing ultra LSI. It relates to a high molecular compound which provides a resist material suitable as a forming material, (3) the manufacturing method of this high molecular compound, (4) the resist material containing this high molecular compound, and (5) the pattern formation method using this resist material.

In recent years, with the higher integration and higher speed of LSI, finer pattern rules have been required, and far-ultraviolet lithography is promising as a next-generation fine processing technology. Among them, photolithography using KrF excimer laser light and ArF excimer laser light as a light source is an indispensable technique for ultrafine processing of 0.3 μm or less, and the implementation thereof is urgently desired.

In the resist material for KrF excimer laser, polyhydroxy styrene which has a practically acceptable level of permeability and etching resistance has become a de facto standard base resin. In the resist material for ArF excimer laser, materials, such as a high molecular compound which contains the derivative of polyacrylic acid or polymethacrylic acid, and an aliphatic cyclic compound in a principal chain, are examined. In any case, the basic form is to protect some or all of the alkali-soluble part of the alkali-soluble resin with a suitable acid leaving group, and adjust the performance as a whole resist material by selecting various acid leaving protecting groups. Doing.

Examples of acid leaving protecting groups include tert-butoxycarbonyl (described in Japanese Patent Publication No. 90-27660, etc.), tert-butyl (Japanese Patent Publication No. 87-115440, J. Photopolym, Sci.Technol. 3], 507 (1994) and the like, 2-tetrahydropyranyl (described in Japanese Patent Laid-Open No. 93-80515, Japanese Patent Laid-Open No. 93-88367, etc.), 1-ethoxyethyl (Japanese Patent Laid-Open) 90-19847, the patent publication 92-215661, etc.) etc. are mentioned. However, while further refinement of the pattern rule is required, none of these acid leaving protecting groups can be said to exhibit satisfactory performance.

That is, tert-butoxycarbonyl and tert-butyl have a remarkably low reactivity with acid, and in order to secure a difference in dissolution rate immediately after exposure, a considerable amount of energy ray irradiation must be performed to generate a sufficient amount of acid. When the acid generator is a strong acid generating type, since the amount of acid generated is at least in reaction, the exposure can be relatively low. However, in that case, the influence of inactivation of the generated acid by the basic substance in air becomes relatively large, causing a problem such that the pattern becomes a T-top shape. On the other hand, since 2-tetrahydropyranyl and 1-ethoxyethyl are highly reactive with acids, the desorption reaction proceeds indiscriminately only by generating acid by exposure without waiting for heat treatment. Dimensional change is large. In addition, when used as a protecting group of the carboxylic acid, since the dissolution inhibiting effect against alkali is low, the dissolution rate of the unexposed portion is high and the film decreases during development. It also has drawbacks such as falling. In any case, the dissolution rate difference before and after exposure cannot be ensured, and as a result, the resist material has a very low resolution.

The present invention has been made in view of the above circumstances, and (1) an ester compound which provides a polymer compound having excellent acid decomposability, and (2) a sensitivity, resolution and etching resistance far exceeding conventional products when blended into a resist material as a base resin. It is an object of the present invention to provide a polymer compound for realizing the present invention, (3) a method for producing this polymer compound, (4) a resist material using this polymer compound as a base resin, and (5) a pattern forming method using the resist material.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to achieve the said objective, it is found that the novel ester compound represented by following General formula (1) obtained by the method mentioned later is useful as a raw material of the high molecular compound which has excellent acid decomposability, and uses this compound. It was found that the resist material using a novel high molecular compound having a weight average molecular weight of 1,000 to 500,000 obtained as a base resin has high sensitivity, high resolution and high etching resistance, and that the resist material is very effective for precise microfabrication.

That is, the present invention provides the following ester compound.

[I] An ester compound represented by the following general formula (1).

<Formula 1>

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 a substitutable 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 any one of 0, 1, 2, and 3, and is a number which satisfy | fills 2m + n = 2 or 3.

[II] A polymer compound having a weight average molecular weight of 1,000 to 500,000, comprising an ester compound represented by the following general formula 1aa or 1ab as a structural unit.

In the formula, R ¹ , R ² , R ³ , k, m, and n represent the same meanings as described above.

[III] The polymer compound according to [II], containing any one kind or two or more kinds of repeating units represented by the following Formulas 2a to 10a.

In the formula,

R ¹ and R ² are the same as above,

R <^5> represents a monovalent hydrocarbon group containing a hydrogen atom, a C1-C15 carboxyl group, or a hydroxyl group,

At least one of R ⁶ to R ⁹ represents a monovalent hydrocarbon group containing a carboxyl group or a hydroxyl group having 1 to 15 carbon atoms, and the rest are each independently a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms. Indicate,

R ⁶ to R ⁹ may form a ring with each other, in which case at least one of R ⁶ to R ⁹ represents a divalent hydrocarbon group containing a carboxyl group or a hydroxyl group having 1 to 15 carbon atoms, and the others are each independently carbon atoms. 1 to 15 linear, branched or cyclic alkylene groups,

R ¹⁰ represents a monovalent hydrocarbon group containing a -CO ₂ -partial structure having 3 to 15 carbon atoms,

At least one of R ¹¹ to R ¹⁴ represents a monovalent hydrocarbon group containing a -CO ₂ -substructure having 2 to 15 carbon atoms, and the others are each independently a hydrogen atom or a straight, branched or cyclic ring having 1 to 15 carbon atoms. An alkyl group of

R ¹¹ to R ¹⁴ may form a ring with each other, in which case at least one of R ¹¹ to R ¹⁴ represents a divalent hydrocarbon group containing a -CO ₂ -substructure having 1 to 15 carbon atoms, the remainder of which is respectively Independently a linear, branched or cyclic alkylene group having 1 to 15 carbon atoms,

R ¹⁵ represents an alkyl group containing a polycyclic hydrocarbon group or a polycyclic hydrocarbon group having 7 to 15 carbon atoms,

R ¹⁶ represents an acid labile group,

k is 0 or 1;

This invention also provides the manufacturing method of the following high molecular compound.

[IV] A method for producing a polymer compound, characterized in that radical polymerization, anion polymerization or coordination polymerization of the ester compound of the formula (1) and a separate compound containing a carbon-carbon double bond are carried out.

In addition, the present invention provides the following resist material.

[V] A resist material comprising the polymer compound according to the above [II] or [III].

[VI] A resist material comprising a polymer compound according to the above-mentioned [II] or [III], a compound which generates an acid in response to a high energy ray or an electron beam, and an organic solvent.

Moreover, this invention provides the following pattern formation method.

[VII] A process of applying the resist material of [V] or [VI] onto a substrate, a process of exposing with a high energy ray or an electron beam through a photo mask after heat treatment, and after heat treatment as necessary, a developer is used. And a step of developing the pattern.

In the high molecular compound comprising the ester compound of Formula 1 and Formula 1aa or 1ab as a structural unit, alkylcycloalkyl or alkylcycloalkenyl represented by the following Formula 1b is used as the acid leaving protecting group, and tert-butoxycarbonyl and The low reactivity with tert-butyl acid, the high reactivity with 2-tetrahydropyranyl and 1-ethoxyethyl acid, and the weak resistance with alkaline developing solution were all eliminated.

In formula, R <^3> , m and n show the same meaning as the above.

The ester compound of Formula 1 is decomposed to generate an olefin compound under acidic conditions to generate carboxylic acid. This mechanism itself is not at all different from decomposition of tertiary alkyl esters such as tert-butyl ester, but there is a big difference in the progression speed. That is, in the decomposition by tertiary alkyl ester acid, carboxylic acid and tertiary alkyl cation are first generated, and then olefin compound is formed by dissolution of the cation by proton release, and the reaction is terminated. The rate-limiting step of this decomposition reaction eliminates the latter cation, but since the reduction of the distortion of the ring and the formation of a conjugated system are very powerful driving force in the ester compound of Formula 1, the progress of this step is very fast. In addition, the reactivity of the resulting olefins is also very low, resulting in acid degradability far exceeding other tertiary alkylesters.

On the other hand, since the ester compound of Formula 1 is basically a tertiary alkyl ester, the decomposition proceeds indefinitely between exposure and development, such as 2-tetrahydropyranyl and 1-ethoxyethyl, or the film decreases during development. It doesn't cause it. Therefore, when the high molecular compound containing this compound as a structural unit is blended into the resist material as the base resin, the dissolution rate of the unexposed portion is very slow, and the high dissolution contrast in which the region irradiated with light at an appropriate exposure dose quickly becomes alkali-soluble. A highly sensitive to high resolution resist material can be obtained. Moreover, since this high molecular compound has a rigid alicyclic ring in a main chain, it also exhibits very 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 formula (1).

<Formula 1>

Here, R ¹ represents a hydrogen atom, a methyl group or CH ₂ CO ₂ R ⁴ . Specific examples of R ⁴ will be described later. 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 a substituted aryl group having 6 to 20 carbon atoms, and is a linear, branched or cyclic alkyl group, specifically, methyl, ethyl, propyl or iso. Propyl group, n-butyl group, sec-butyl group, tert-butyl group, tert-amyl group, n-pentyl group, n-hexyl group, cyclopentyl group, cyclohexyl group, cyclopentylmethyl group, cyclopentylethyl group, cyclo Hexylmethyl group, a cyclohexylethyl group, etc. can be illustrated, A phenyl group, methylphenyl group, naphthyl group, anthryl group, phenanthryl group, pyrenyl group etc. can be illustrated specifically as a substitutable aryl group. R ⁴ represents a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms, specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, 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, ethyl adamantyl group And a butyl adamantyl group etc. can be illustrated. k is 0 or 1; m is 0 or 1, n is 0, 1, 2, 3, and is a number which satisfy | fills 2m + n = 2 or 3.

Although the specific example of the ester compound of this invention is shown below, it is not limited to this.

Although the manufacture of the ester compound of this invention can be performed by following Reaction Formula 1, it is not limited to this, for example.

In formula, R <^1> , R <^2> , R <^3> , k, m, and n are the same as the above, and M represents a metal.

The first step is a step of performing nucleophilic addition reaction to carbonyl of the cyclic ketone compound to form a tertiary alcohol. As a specific example of this step, although the Grignard reaction, the reaction using an organolithium compound, etc. are mentioned, it is not limited to this, for example. The reaction proceeds easily under known conditions, but preferably, in a solvent such as tetrahydrofuran, diethyl ether or the like, a cyclic ketone compound of the raw material, an alkyl halide or an aryl halide, magnesium, lithium or the like as a M metal is mixed and required. Therefore, it is good to perform heating or cooling.

The second process is to make the tertiary alcohol obtained in the previous step into an unsaturated acid ester. The reaction proceeds easily under known conditions, but preferably, in a solvent such as methylene chloride, bases such as carboxylic acid halides such as tertiary alcohols, acrylic acid chlorides and methacrylic acid chlorides, and triethylamine, etc. are mixed, It is good to carry out by cooling as needed.

The third step is a step of constructing an alicyclic skeleton by Diels Alder reaction. The reaction proceeds easily under known conditions, but preferably, an unsaturated acid ester of a raw material and cyclopentadiene are mixed in a solvent such as solvent-free or benzene, and a catalyst such as boron trifluoride is mixed as necessary, and furthermore, It is good to carry out by heating or cooling according to this.

The present invention provides a polymer compound having a weight average molecular weight of 1,000 to 500,000, preferably 5,000 to 100,000, comprising a unit of formula 1aa or 1ab obtained by using the ester compound of formula 1 as a monomer as a structural unit. .

<Formula 1aa>

<Formula 1ab>

In formula, R <^1> , R <^2> , R <^3> , k, m, and n are the same as the above.

In this case, the high molecular compound of this invention may contain as a structural unit 1 or more types of units of the following general formula (2a-10a) obtained by making following formula (2-10) as a monomer.

In addition, k is 0 or 1 in the above formula, and thus, the formulas 6a-1 to 9a-2 may be represented by the following formulas 6a-1-1 to 9a-2-2.

Here, R ¹ and R ² are the same as above. R ⁵ represents a hydrogen atom or a monovalent hydrocarbon group containing a carboxyl group or a hydroxyl group having 1 to 15 carbon atoms, 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 monovalent hydrocarbon group containing a carboxyl group or a hydroxyl group having 1 to 15 carbon atoms, and the rest are each independently a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms. Indicates. As a monovalent hydrocarbon group containing a C1-C15 carboxyl group or a hydroxyl group, specifically, carboxy, carboxymethyl, carboxyethyl, carboxybutyl, hydroxymethyl, hydroxyethyl, hydroxybutyl, 2-carboxyethoxycarbonyl , 4-carboxybutoxycarbonyl, 2-hydroxyethoxycarbonyl, 4-hydroxybutoxycarbonyl, carboxycyclopentyloxycarbonyl, carboxycyclohexyloxycarbonyl, carboxynorbornyloxycarbonyl, Carboxyadamantyloxycarbonyl, hydroxycyclopentyloxycarbonyl, hydroxycyclohexyloxycarbonyl, hydroxy norbornyloxycarbonyl, hydroxyadamantyloxycarbonyl and the like can be exemplified. Specifically as a C1-C15 linear, branched, cyclic alkyl group, the thing similar to what was illustrated by R <^4> can be illustrated. R ⁶ to R ⁹ may form a ring with each other, in which case at least one of R ⁶ to R ⁹ represents a divalent hydrocarbon group containing a carboxy group or hydroxyl group having 1 to 15 carbon atoms, and the remaining ones each independently have 1 carbon atom. To linear, branched or cyclic alkylene groups of 15 to 15; As a bivalent hydrocarbon group containing a C1-C15 carboxyl group or a hydroxyl group, the thing etc. which removed one hydrogen atom from what was illustrated by the monovalent hydrocarbon group containing the said carboxyl group or a hydroxyl group specifically, etc. can be illustrated. As a C1-C15 linear, branched, cyclic alkylene group, what specifically removed R <^1> from what was illustrated by R <^4> , etc. can be illustrated.

R ¹⁰ represents a monovalent hydrocarbon group containing a C3-C15 -CO ₂ -partial structure, and specifically 2-oxooxolane-3-yl, 4,4-dimethyl-2-oxooxolane-3- Days, 4-methyl-2-oxooxan-4-yl, 2-oxo-1,3-dioxolan-4-ylmethyl, 5-methyl-2-oxooxanran-5-yl and the like can be exemplified. have. At least one of R ¹¹ to R ¹⁴ represents a monovalent hydrocarbon group containing a -CO ₂ -substructure having 2 to 15 carbon atoms, and the others are each independently a hydrogen atom or a straight, branched or cyclic ring having 1 to 15 carbon atoms. An alkyl group of. -CO ₂ of 2 to 15 carbon atoms - particularly Examples of the monovalent hydrocarbon group containing a partial structure include 2-oxo-3-yloxy dioxolane Brassica Viterbo carbonyl, 4,4-dimethyl-2-oxo-3-yloxy dioxolane Cycarbonyl, 4-methyl-2-oxooxan-4-yloxycarbonyl, 2-oxo-1,3-dioxolan-4-ylmethyloxycarbonyl, 5-methyl-2-oxooxolane- 5-yloxycarbonyl etc. can be illustrated. Specifically as a C1-C15 linear, branched, cyclic alkyl group, the thing similar to what was illustrated by R <^4> can be illustrated. R ¹¹ to R ¹⁴ may form a ring with each other, in which case at least one of R ¹¹ to R ¹⁴ represents a divalent hydrocarbon group containing a -CO ₂ -substructure having 1 to 15 carbon atoms, the remainder of which is respectively The C1-C15 linear, branched, cyclic alkylene group is represented independently. 1 to 15 carbon atoms of -CO ₂ - _2-valent hydrocarbon group containing a partial structure as the 1-oxo-2-oxa Specifically, propane-1,3-diyl, 1,3-dioxo-2-oxa-propane -1 , -Diyl, 1-oxo-2-oxabutane-1,4-diyl, 1,3-dioxo-2-oxabutane-1,4-diyl and the like, in addition to containing the above-CO ₂ -partial structure The thing remove | excluding one hydrogen atom from what was illustrated by monovalent hydrocarbon group etc. can be illustrated. As a C1-C15 linear, branched, cyclic alkylene group, what specifically removed one hydrogen atom from what was illustrated by R <^4> , etc. can be illustrated.

R ¹⁵ represents a polycyclic hydrocarbon group having 7 to 15 carbon atoms or an alkyl group containing a polycyclic hydrocarbon group, and specifically, norbornyl, bicyclo [3.3.1] nonyl, 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 of R ¹⁶ include a group represented by the following formula (11) or (12), a C 4-20, preferably a 3-15 alkyl group, a trialkylsilyl group each having 1 to 6 carbon atoms, And an oxoalkyl group having 4 to 20 carbon atoms.

In the formula, R ¹⁷ and R ¹⁸ represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, specifically methyl, ethyl, propyl, isopropyl, n-butyl group, sec-butyl group, tert-butyl group, cyclopentyl group, cyclohexyl group, 2-ethylhexyl group, n-octyl group, etc. can be illustrated. R ¹⁹ represents a monovalent hydrocarbon group which may have a hetero atom such as an oxygen atom having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, and a linear, branched, cyclic alkyl group, and a part of these hydrogen atoms are hydroxyl, alkoxy The thing substituted by group, an oxo group, an amino group, an alkylamino group, etc. are mentioned, Specifically, the following substituted alkyl group etc. can be illustrated.

Here, R ¹⁷ and R ¹⁸ , R ¹⁷ and R ¹⁹ , R ¹⁸ and R ¹⁹ may form a ring, and in the case of forming a ring, R ¹⁷ , R ¹⁸ and R ¹⁹ each have 1 to 18 carbon atoms, preferably Preferably a linear or branched alkylene group of 1 to 10.

R ²⁰ represents a C 4-20, preferably a 4-15 tertiary alkyl group, a trialkylsilyl group each having 1 to 6 carbon atoms, an oxoalkyl group having 4 to 20 carbon atoms, or a group represented by Formula 11 above. a is an integer of 0-6.

Further, as the tertiary alkyl group, tert-butyl group, tert-amyl group, 1,1-diethylpropyl group, 1-ethylcyclopentyl group, 1-butylcyclopentyl group, 1-ethylcyclohexyl group, 1-butyl Cyclohexyl 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 trimethylsilyl group, triethylsilyl group, and 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-oxooxoran-5-yl group, and the like.

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

Among the acid labile groups represented by the above formula (11), the following groups can be specifically exemplified as cyclic ones.

Specific examples of the acid labile group represented by Formula 12 include tert-butoxycarbonyl group, tert-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-ethyl-2-cyclopentenyl Oxycarbonylmethyl group, 1-ethoxyethoxycarbonylmethyl group, 2-tetrahydropyranyloxycarbonylmethyl group, 2-tetrahydrofuranyloxycarbonylmethyl group, etc. can be illustrated.

The preparation of the polymer compound of the present invention can be carried out by a copolymerization reaction using the ester compound of Formula 1 as the first monomer and at least one selected from the compounds represented by Formulas 2 to 10 as the second or more monomer.

In a copolymerization reaction, by adjusting the presence ratio of each monomer suitably, it can be made into the high molecular compound which can exhibit the favorable performance when used as a resist material.

In this case, the polymer compound of the present invention

(i) the monomer of Formula 1

(ii) monomers of Chemical Formulas 2 to 10

In addition to more

(iii) Substituted acrylic esters, such as a monomer containing carbon-carbon double bonds other than said (i) and (ii), for example, methyl methacrylate, methyl crotonate, dimethyl maleate, and dimethyl itaconic acid, , Unsaturated carboxylic acids such as fumaric acid and itaconic acid, substituted norbornenes such as norbornene and norbornene-5-carboxylic acid methyl, unsaturated acid anhydrides such as itaconic anhydride, and other monomers may be copolymerized. There is no

The polymer compound of the present invention,

(I) more than 0 mol% and 100 mol% or less, preferably 20 to 90 mol%, more preferably 30 to 80 mol% of the structural unit of formula 1a based on the monomer of formula 1,

(II) 0 mol% or more and less than 100 mol%, preferably 1 to 95 mol%, more preferably 5 or more of the structural units of the formulas 2a to 10a based on the monomers of the formulas 2 to 10a. To 90 mol%, if necessary

(III) 0 to 80 mol%, preferably 0 to 70 mol%, more preferably 0 to 50 mol% of one or two or more of the structural units based on the monomer of (iii) can be contained.

In addition, the weight average molecular weight of the high molecular compound of this invention is 1,000-500,000, Preferably it is 3,000-100,000. If it is out of this range, etching resistance may fall extremely, or it may become impossible to ensure the dissolution rate difference before and after exposure, and resolution may fall.

In another aspect, the present invention is characterized by radical polymerization, anion polymerization or coordination polymerization of the ester compound of Formula 1 and a separate compound containing a carbon-carbon double bond (the monomers of (ii) and / or (iii)) A method for producing a polymer compound is provided.

The reaction conditions of the radical polymerization reaction include (a) hydrocarbons such as benzene, ethers such as tetrahydrofuran, alcohols such as ethanol, and ketones such as methyl isobutyl ketone, and (b) polymerization initiators. As azo compounds such as 2,2'-azobisisobutyronitrile or peroxides such as benzoyl peroxide and lauroyl peroxide, (c) the reaction temperature is maintained at 0 to 100 ℃, (d) Although it is preferable to make reaction time about 0.5 to 48 hours, it does not exclude the case out of this range.

The reaction conditions for the anionic polymerization reaction include (a) hydrocarbons such as benzene, ethers such as tetrahydrofuran, or liquid ammonia as the solvent, and (b) metals such as sodium and potassium as the polymerization initiator, n-butyllithium and alkyl metal such as sec-butyllithium, ketyl, or Grignard reactant, (c) the reaction temperature is maintained at -78 ℃ to 0 ℃, (d) the reaction time is about 0.5 to 48 hours , (E) Proton donor compounds such as methanol, halides such as methyl iodide, and other electromagnetic substances are preferably used as the terminator, but the case outside this range is not excluded.

Reaction conditions for coordination polymerization include (a) using hydrocarbons such as n-heptane and toluene as solvents, and (b) a Ziegler-Natta catalyst consisting of transition metals such as titanium and alkylammonium, chromium and nickel compounds as catalysts. Using an olefin-methacesis mixed catalyst such as a Phillips catalyst supported on an oxide, a tungsten and rhenium mixed catalyst, and the like, (C) the reaction temperature is maintained at 0 ° C to 100 ° C, and (D) the reaction time is 0.5 hour. Although it is preferable to set it as about 48 hours, it does not exclude the case 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 comprising the polymer compound.

Moreover, this invention can be set as the resist material containing this high molecular compound, the compound which generate | occur | produces an acid in response to an high energy ray, or an electron beam, and an organic solvent.

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

i. An onium salt of the formula P1a-1, P1a-2 or P1b,

ii. A diazomethane derivative of the formula P2,

iii. Glyoxime derivatives of the formula

iv. A bissulphone derivative of the formula P4,

v. Sulfonic acid esters of N-hydroxyimide compounds of the formula

vi. β-ketosulfonic acid derivatives,

vii. Disulfone derivatives,

viii. Nitrobenzylsulfonate derivatives,

ix. Sulfonic acid ester derivatives;

In formula, ^R101a , ^R101b, and ^R101c are C1-C12 linear, branched, cyclic alkyl group, alkenyl group, oxoalkyl group, or oxoalkenyl group, C6-C20 aryl group, or C7-C8 respectively An aralkyl group or an aryloxoalkyl group of 12 may be substituted, and some or all of the hydrogen atoms of these groups may be substituted by an alkoxy group or the like. In addition, R ^101b and R ^101c may form a ring. When forming a ring, R ^101b and R ^101c each represent an alkylene group having 1 to 6 carbon atoms. K ⁻ represents a non-nucleophilic counter ion.

R ^101a , R ^101b, and R ^101c may be the same as or different from each other, and specifically, as an alkyl group, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, Pentyl, hexyl, heptyl, octyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norbornyl, adamantyl have. Examples of the alkenyl group include vinyl group, allyl group, propenyl group, butenyl group, hexenyl group, cyclohexenyl group and the like. Examples of the oxoalkyl group include 2-oxocyclopentyl group, 2-oxocyclohexyl group, and the like. 2-oxopropyl group, 2-cyclopentyl-2-oxoethyl group, 2-cyclohexyl-2-oxoethyl group, 2 -(4-methylcyclohexyl) -2-oxoethyl group etc. are mentioned. Examples of the aryl group include a phenyl group, a naphthyl group, and alkoxyphenyl groups such as p-methoxyphenyl group, m-methoxyphenyl group, o-methoxyphenyl group, ethoxyphenyl group, p-tert-butoxyphenyl group, and m-tert-butoxyphenyl group. , Alkylphenyl groups such as 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, ethylphenyl group, 4-tert-butylphenyl group, 4-butylphenyl group and dimethylphenyl group, alkylnaphthyl groups such as methylnaphthyl group and ethylnaphthyl group And dialkoxy naphthyl groups such as alkoxy naphthyl groups such as methoxy naphthyl group and ethoxy naphthyl group, dimethyl naphthyl group and diethyl naphthyl group, and dialkoxy naphthyl groups such as dimethoxy naphthyl group and diethoxy naphthyl group. have. Examples of the aralkyl group include benzyl group, phenylethyl group and phenethyl group. As an aryl oxo alkyl group, 2-aryl-2-oxo, such as a 2-phenyl- 2-oxo ethyl group, 2- (1-naphthyl) -2-oxoethyl group, 2- (2-naphthyl) -2-oxoethyl group, etc. Ethyl group etc. are mentioned. Examples of non-nucleophilic counter ions of K ⁻ include halide ions such as chloride ions and bromide ions, triflate, fluoroalkylsulfonates such as 1,1,1-trifluoroethanesulfonate and nonafluorobutanesulfonate, and tosyl Alkyl sulfonates, such as aryl sulfonates, a mesylate, butane sulfonate, such as a late, a benzene sulfonate, 4-fluorobenzene sulfonate, a 1,2,3,4,5-pentafluorobenzene sulfonate, are mentioned. have.

In the formula, 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 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 ⁻ represents a non-nucleophilic counter ion.

Specific examples of the R ^102a and R ^102b include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl and cyclophene A methyl group, a cyclohexyl group, a cyclopropylmethyl group, 4-methylcyclohexyl group, a cyclohexylmethyl group, etc. are mentioned. ^Examples of R ¹⁰³ include methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, 1,4-cyclohexylene group, 1,2-cyclohexylene group, 1 A, 3-cyclopentylene group, a 1, 4- cyclooctylene group, a 1, 4- cyclohexane dimethylene group, etc. are mentioned. ^{Examples of} R ^104a and R ^104b include a 2-oxopropyl group, a 2-oxocyclopentyl group, a 2-oxocyclohexyl group, a 2-oxocycloheptyl group, and the like. K ^- may be the same as described in the formulas P1a-1 and P1a-2.

In formula, R <^105> , R <^106> represents a C1-C12 linear, branched, cyclic alkyl group or a halogenated alkyl group, a C6-C20 aryl group or a halogenated aryl group, or a C7-C12 aralkyl group.

^{Examples of the} alkyl group ^of R ¹⁰⁵ and R ¹⁰⁶ include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, amyl and cyclo A pentyl group, a cyclohexyl group, a cycloheptyl group, a norbornyl group, an adamantyl group etc. are mentioned. Examples of the halogenated alkyl group include trifluoromethyl group, 1,1,1-trifluoroethyl group, 1,1,1-trichloroethyl group, and nonafluorobutyl group. As an aryl group, alkoxyphenyl groups, such as a phenyl group, p-methoxyphenyl group, m-methoxyphenyl group, o-methoxyphenyl group, ethoxyphenyl group, p-tert-butoxyphenyl group, and m-tert-butoxyphenyl group, 2-methylphenyl Alkylphenyl groups, such as group, 3-methylphenyl group, 4-methylphenyl group, ethylphenyl group, 4-tert- butylphenyl group, 4-butylphenyl group, and a dimethylphenyl group, are mentioned. Examples of the halogenated aryl group include a fluorophenyl group, a chlorophenyl group, 1,2, 3,4,5-pentafluorophenyl group, and the like. As an aralkyl group, a benzyl group, a phenethyl group, etc. are mentioned.

In formula, R <^107> , R <^108> , R <^109> is a C1-C12 linear, branched, cyclic alkyl group or a halogenated alkyl group, a C6-C20 aryl group, or a halogenated aryl group, or C7-C12 aral Indicates a kill group. R ¹⁰⁸ and R ¹⁰⁹ may be bonded to each other to form a cyclic structure, and when forming a cyclic structure, R ¹⁰⁸ and R ¹⁰⁹ each represent a linear or branched alkylene group having 1 to 6 carbon atoms.

Examples of the alkyl group, halogenated alkyl group, aryl group, halogenated aryl group, and aralkyl group for R ¹⁰⁷ , R ¹⁰⁸ and R ¹⁰⁹ include the same groups as described for R ¹⁰⁵ and R ¹⁰⁶ . Examples of the alkylene group of R ¹⁰⁸ and R ¹⁰⁹ may be mentioned methylene group, ethylene group, propylene group, butylene group, hexylene group and the like.

In formula, ^R101a and ^R101b are the same as the above.

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 some or all of the hydrogen atoms of these groups are again linear 1 to 4 carbon atoms. Or a branched alkyl group or alkoxy group, nitro group, acetyl group, or phenyl group. R ¹¹¹ represents a linear, branched or substituted alkyl, alkenyl or alkoxyalkyl, phenyl or naphthyl group having 1 to 8 carbon atoms, and some or all of the hydrogen atoms of these groups are again alkyl groups having 1 to 4 carbon atoms or An alkoxy group; Phenyl group which may be substituted by the C1-C4 alkyl group, the alkoxy group, the nitro group, or the acetyl group; Hetero aromatic groups having 3 to 5 carbon atoms; Or a chlorine atom or a fluorine atom.

Here, as the arylene group of R ¹¹⁰ , a 1,2-phenylene group, a 1,8-naphthylene group, and the like, and as an alkylene group, a methylene group, a 1,2-ethylene group, a 1,3-propylene group, 1,4- The butylene group, 1-phenyl-1,2-ethylene group, norbornane-2,3-diyl group, etc. As an alkenylene group, 1,2-vinylene group, 1-phenyl-1,2-vinylene group, 5 And norbornene-2,3-diyl groups. ^Examples of the alkyl group of R ¹¹¹ are the same as those of R ^101a to R ^{101c. Examples} of the alkenyl group include a vinyl group, 1-propenyl group, allyl group, 1-butenyl group, 3-butenyl group, isofurenyl group, 1-pentenyl group, and 3-pente. A nilyl 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. As the alkoxyalkyl group, methoxymethyl group, ethoxymethyl group, propoxymethyl group, butoxymethyl group, pentyloxymethyl group, hexyloxymethyl group, heptyloxymethyl group, methoxyethyl group, ethoxyethyl group, propoxyethyl group, butoxyethyl group, pentyloxy Ethyl group, hexyloxyethyl group, methoxypropyl group, ethoxypropyl group, propoxypropyl group, butoxypropyl group, methoxybutyl group, ethoxybutyl group, propoxybutyl group, methoxypentyl group, ethoxypentyl group , Methoxyhexyl group, methoxyheptyl group and the like.

Moreover, as a C1-C4 alkyl group which may be substituted again, a methyl group, an ethyl group, a propyl group, isopropyl group, n-butyl group, isobutyl group, tert- butyl group, etc. are mentioned, and a C1-C4 alkoxy group is a methoxy group. , Ethoxy group, propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, tert-butoxy group and the like as the phenyl group which may be substituted with an alkyl group, alkoxy group, nitro group or acetyl group having 1 to 4 carbon atoms A phenyl group, tolyl group, p-tert-butoxyphenyl group, p-acetylphenyl group, p-nitrophenyl group etc. are mentioned as a pyridyl group, a furyl group, etc. as a C3-C5 hetero aromatic group.

Specifically, for example, trifluoromethanesulfonic acid diphenyliodium, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) phenyliodium, p-toluenesulfonic acid diphenyliodium, p-toluenesulfonic acid (p -tert-butoxyphenyl) phenyliodonium, trifluoromethanesulfonic acid triphenylsulfonium, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, trifluoromethanesulfonic acid bis (p-tert -Butoxyphenyl) phenylsulfonium, trifluoromethanesulfonic acid tris (p-tert-butoxyphenyl) sulfonium, p-toluenesulfonic acid triphenylsulfonium, p-toluenesulfonic acid (p-tert-butoxyphenyl) di Phenylsulfonium, p-toluenesulfonic acid bis (p-tert-butoxyphenyl) phenylsulfonium, p-toluenesulfonic acid tris (p-tert-butoxyphenyl) sulfonium, nonafluorobutanesulfonic acid triphenylsulfonium, butane Sulfonic acid triphenylsulfonium, trifluoromethanesulfonic acid trimethylsulfonium, p-toluenesulfonic acid trimethyl Sulfonium, trifluoromethanesulfonic acid cyclohexylmethyl (2-oxocyclohexyl) sulfonium, p-toluenesulfonic acid cyclohexylmethyl (2-oxocyclohexyl) sulfonium, trifluoromethanesulfonic acid dimethylphenylsulfonium, p- Toluenesulfonic acid dimethylphenylsulfonium, trifluoromethanesulfonic acid dicyclohexylphenylsulfonium, p-toluenesulfonic acid dicyclohexylphenylsulfonium, trifluoromethanesulfonic acid trinaphthylsulfonium, trifluoromethanesulfonic acid cyclohexylmethyl (2 -Oxocyclohexyl) sulfonium, trifluoromethanesulfonic acid (2-norbornyl) methyl (2-oxocyclohexyl) sulfonium, ethylenebis [methyl (2-oxocyclopentyl) sulfonium trifluoromethanesulfonate] , Onium salts such as 1,2'-naphthylcarbonylmethyltetrahydrothiophenium triplate, bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (xylenesulfonyl Diazomethane, bis (cyclohex) Silsulfonyl) diazomethane, bis (cyclopentylsulfonyl) diazomethane, bis (n-butylsulfonyl) diazomethane, bis (isobutylsulfonyl) diazomethane, bis (sec-butylsulfonyl) dia Crude methane, 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 such as diazomethane, 1-cyclohexylsulfonyl-1- (tert-amylsulfonyl) diazomethane, 1-tert-amylsulfonyl-1- (tert-butylsulfonyl) diazomethane Derivatives, bis-O- (p-toluenesulfonyl) -α-dimethylglyoxime, bis-O- (p-toluenesulfonyl) -α-diphenylglyoxime, bis-O- (p-toluenesulfonyl) -α-dicyclohexylglyoxime, bis-O- (p-toluenesulfonyl) -2,3-pentanedionegly Shim, bis-O- (p-toluenesulfonyl) -2-methyl-3,4-pentanedioneglyoxime, bis-O- (n-butanesulfonyl) -α-dimethylglyoxime, bis-O- ( n-butanesulfonyl) -α-diphenylglyoxime, bis-O- (n-butanesulfonyl) -α-dicyclohexylglyoxime, bis-O- (n-butanesulfonyl) -2,3- Pentanedionoglyoxime, bis-O- (n-butanesulfonyl) -2-methyl-3,4-pentanedioneglyoxime, 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- (benzene Sulfonyl) -α-dimethylglyoxime, bis-O- (p-fluorobenzenesulfonyl) -α-dimethylglyoxime, bis-O- (p-tert-butylbenzenesulfonyl) -α-dimethylglyoxime , Bis-O- (xylenesulfonyl) -α-dimethylglycol Glyoxime derivatives such as lyoxime, bis-O- (camphorsulfonyl) -α-dimethylglyoxime, bisnaphthylsulfonylmethane, bistrifluoromethylsulfonylmethane, bismethylsulfonylmethane, bisethylsulfonylmethane , Bissulfon derivatives such as bispropylsulfonylmethane, bisisopropylsulfonylmethane, bis-p-toluenesulfonylmethane and bisbenzenesulfonylmethane, 2-cyclohexylcarbonyl-2- (p-toluenesulfonyl) Β-ketosulfone derivatives such as propane and 2-isopropylcarbonyl-2- (p-toluenesulfonyl) propane, disulfone derivatives such as diphenyldisulfone and dicyclohexyl disulfone, p-toluenesulfonic acid 2,6 -Nitrobenzylsulfonate derivatives such as dinitrobenzyl and p-toluenesulfonic acid 2,4-dinitrobenzyl, 1,2,3-tris (methanesulfonyloxy) benzene, 1,2,3-tris (trifluoro Sulfonic acid ester derivatives such as methanesulfonyloxy) benzene, 1,2,3-tris (p-toluenesulfonyloxy) benzene, and N-hydroxysuccinimide Dmethanesulfonic acid ester, N-hydroxysuccinimidetrifluoromethanesulfonic acid ester, N-hydroxysuccinimideethanesulfonic acid ester, N-hydroxysuccinimide1-propanesulfonic acid ester, N-hydroxysuccinimide 2-propanesulfonic acid ester, N-hydroxysuccinimide 1-pentanesulfonic acid ester, N-hydroxysuccinimide 1 -octane sulfonic acid ester, N-hydroxysuccinimide p-toluenesulfonic acid ester, N-hydroxysuccinate Imide p-methoxybenzenesulfonic acid ester, N-hydroxysuccinimide 2-chloroethanesulfonic acid ester, N-hydroxysuccinimidebenzenesulfonic acid ester, N-hydroxysuccinimide-2,4,6-trimethyl Benzenesulfonic acid ester, N-hydroxysuccinimide 1-naphthalenesulfonic acid ester, N-hydroxysuccinimide 2-naphthalenesulfonic acid ester, N-hydroxy-2-phenylsuccinimidemethanesulfonic acid ester, N-hydroxymalee Midmethane Phonic acid ester, N-hydroxy maleimide ethane sulfonic acid ester, N-hydroxy-2-phenyl maleimide methane sulfonic acid ester, N-hydroxy glutimide methane sulfonic acid ester, N-hydroxy glutalimide benzene sulfonic acid ester , N-hydroxyphthalimide methanesulfonic acid ester, N-hydroxyphthalimide benzene sulfonic acid ester, N-hydroxyphthalimide trifluoromethanesulfonic acid ester, N-hydroxyphthalimide p-toluenesulfonic acid ester, N-hydroxynaphthalimidemethanesulfonic acid ester, N-hydroxynaphthalimidebenzenesulfonic acid ester, N-hydroxy-5-norbornene-2,3-dicarboxyimidemethanesulfonic acid ester, N-hydroxy N-hydroxys such as -5-norbornene-2,3-dicarboxyimidetrifluoromethanesulfonic acid ester and N-hydroxy-5-norbornene-2,3-dicarboxyimide p-toluenesulfonic acid ester Sulfone of mede compound Acid ester derivatives; trifluoromethanesulfonic acid triphenylsulfonium, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, trifluoromethanesulfonic acid tris (p-tert-part Methoxyphenyl) sulfonium, p-toluenesulfonic acid triphenylsulfonium, p-toluenesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, p-toluenesulfonic acid tris (p-tert-butoxyphenyl) sulfonium, Trifluoromethanesulfonic acid trinaphthylsulfonium, trifluoromethanesulfonic acid cyclohexylmethyl (2-oxocyclohexyl) sulfonium, trifluoromethanesulfonic acid (2-norbornyl) methyl (2-oxocyclohexyl) sulfonium, Onium salts such as 1,2'-naphthylcarbonylmethyltetrahydrothiophenium triplate, bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (cyclohexylsulfonyl ) Diazomethane, bis (n-butylsulfonyl) diazomethane, bis (isobutylsulfonyl) diazom Dias, such as bis (sec-butylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane and bis (tert-butylsulfonyl) diazomethane Glyoxime derivatives, such as bis-O- (p-toluenesulfonyl) -α-dimethylglyoxime, bis-O- (n-butanesulfonyl) -α-dimethylglyoxime, bisnaphthylsulfonylmethane Bissulfon derivatives, such as N-hydroxysuccinimidemethanesulfonic acid ester, N-hydroxysuccinimide trifluoromethanesulfonic acid ester, N-hydroxysuccinimide 1-propanesulfonic acid ester, and N-hydroxysuccinate Mid 2-propanesulfonic acid ester, N-hydroxysuccinimide 1-pentanesulfonic acid ester, N-hydroxysuccinimide p-toluenesulfonic acid ester, N-hydroxy naphthalimide methanesulfonic acid ester, N-hydroxy naph Sulfonic acid s of N-hydroxyimide compounds such as deimidebenzenesulfonic acid ester Le derivative is preferably used. In addition, the said acid generator can be used individually by 1 type or in combination of 2 or more types. Since the onium salt is excellent in the rectangularity improving effect, and the diazomethane derivative and the glyoxime derivative are excellent in standing wave reduction effect, it is possible to fine-tune a profile by combining both.

The addition amount of an acid generator becomes like this. Preferably it is 0.1-15 parts, More preferably, it is 0.5-8 parts with respect to 100 parts (weight part, below same) of base resin. When less than 0.1 part, a sensitivity may fall, and when more than 15 parts, the alkali dissolution rate may fall and the resolution of a resist material may fall, and since low molecular weight components become excess, heat resistance may fall.

As the organic solvent used in the present invention, any organic solvent may be used as long as it can dissolve a base resin, an acid generator, and other additives. As such an organic solvent, for example, ketones such as cyclohexanone and methyl-2-n-amyl ketone, 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1 Alcohols such as ethoxy-2-propanol, ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether and 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 And esters such as monotert-butyl ether acetate, and one of these may be used alone or in combination of two or more thereof. However, it is not limited to these. In the present invention, among these organic solvents, in addition to diethylene glycol dimethyl ether and 1-ethoxy-2-propanol having the highest solubility of the acid generator in the resist component, propylene glycol monomethyl ether acetate as a safety solvent and a mixed solvent thereof are preferably used. do.

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

The resist material of the present invention may further contain a polymer compound separate from the polymer compound of the present invention.

Specific examples of the polymer compound separate from the polymer compound of the present invention include those having a weight average molecular weight of 1,000 to 500,000, preferably 5,000 to 100,000, having units represented by the following general formula R1 and / or the following general formula R2, It is not limited to these.

Wherein, R ¹ is a hydrogen atom, a methyl group or ^{_{CH 2 CO 2 R 3, R}} 2 represents a hydrogen atom, a methyl group or CO ₂ R ^3, R ³ is a straight, branched or cyclic having 1 to 15 carbon atoms Represents an alkyl group, R ⁴ represents a hydrogen atom or a monovalent hydrocarbon group containing 1 to 15 carbon atoms or a carboxyl group, and at least one of R ⁵ to R ⁰⁰⁸ contains 1 to 15 carbon atoms or a hydroxyl group A hydrocarbon group, and the rest each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms, and R ⁵ to R ⁸ may form a ring with each other, in which case R ⁵ to at least one of R ⁰⁰⁸ represents a divalent hydrocarbon group containing a carboxyl or hydroxyl group of a carbon number of 1 to 15, the remains are each independently C 1 -C 15 straight chain, branched of , Represents a group of cyclic alkylene, R ⁹ is -CO ₂ having a carbon number of 3 to 15 - represents a monovalent hydrocarbon-containing partial structure, R ¹⁰ to R ⁰¹³ of at least one dog of a carbon number of 2 to 15 -CO ₂ - A monovalent hydrocarbon group containing a partial structure, the remainder each independently represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms, and R ¹⁰ to R ¹³ may form a ring with each other, In that case, at least one of R ¹⁰ to R ¹³ represents a divalent hydrocarbon group containing a -CO ₂ -substructure having 1 to 15 carbon atoms, and the others are each independently a linear, branched or cyclic group having 1 to 15 carbon atoms. represents an alkylene group, R ¹⁴ represents an alkyl group containing a polycyclic hydrocarbon group or polycyclic hydrocarbon group having 7 to ^15, R 15 represents an acid labile, R ¹⁶ is also hydrogen Represents a methyl group, R ¹⁷ represents a straight chain, branched alkyl or cyclic group having 1 to 8, k 'is 0 or 1, a1', a2 ', a3', b1 ', b2', b3 ', c1 ', c2', c3 ', d1', d2 ', d3' and e 'are numbers of 0 or more and less than 1, and a1' + a2 '+ a3' + b1 '+ b2' + b3 '+ c1' + c2 '+ c3' + d1 '+ d2' + d3 '+ e' = 1, f ', g', h ', i' and j 'are numbers of 0 or more and less than 1, and f' + g satisfies '+ h' + i '+ j' = 1

In addition, about the specific example of each group, it is the same as that of R <^1> -R <^16> .

It is preferable that the compounding ratio of the high molecular compound separate from the high molecular compound of this invention exists in the weight ratio range of 10: 90-90: 10, especially 20: 80-80: 20. When the compounding ratio of the high molecular compound of this invention is less than this, the performance which is preferable as a resist material may not be obtained. The performance of a resist material can be adjusted by changing said compounding ratio suitably.

In addition, the said high molecular compound is not limited to 1 type, It can add 2 or more types. By using a plurality of high molecular compounds, the performance of the resist material can be adjusted.

The dissolution control agent can also be added to the resist material of the present invention. As a dissolution control agent, the average molecular weight is 100-1,000, Preferably it is 150-800, At the same time, the hydrogen atom of this phenolic hydroxyl group of the compound which has two or more phenolic hydroxyl groups in a molecule | numerator is averaged 0-100 overall by acid instability group. The compound which substituted the hydrogen atom of this carboxyl group of the compound which has a carboxyl group in the ratio of mol% or in a molecule | numerator as a whole at the ratio of an average of 80-100 mol% by acid labile group is mix | blended.

In addition, the substitution rate by the acid labile group of the hydrogen atom of a phenolic hydroxyl group or a carboxyl group is 0 mol% or more, Preferably it is 30 mol% or more of the whole phenolic hydroxyl group or carboxyl group, The upper limit is 100 mol%, More preferably, It is 80 mol%.

In this case, as a compound which has 2 or more of these phenolic hydroxyl groups, or a compound which has a carboxyl group, what is represented by following formula (D1-D14) is preferable.

In formula, R <^201> , R <^202> represents a hydrogen atom or a C1-C8 linear or branched alkyl group or an alkenyl group, respectively, R <^203> represents a hydrogen atom or a C1-C8 linear or branched form Alkyl group or alkenyl group, or-(R ²⁰⁷ ) _h COOH, R ²⁰⁴ is-(CH ₂ ) _i- (i = 2 to 10), arylene group having 6 to 10 carbon atoms, carbonyl group, sulfonyl group, oxygen atom or A sulfur atom, R ²⁰⁵ 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, and R ²⁰⁶ represents a hydrogen atom or a straight chain having 1 to 8 carbon atoms Or a branched alkyl group, an alkenyl group, 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, and R ²⁰⁸ represents a hydrogen atom or a hydroxyl group , j is from 0 to 5 Is an integer, u and h are 0 or 1, and s, t, s ', t', s "and t" are s + t = 8, s '+ t' = 5, s "+ t" = 4 Is a number having at least one hydroxyl group in each phenyl skeleton, and? Is a number having a molecular weight of 100 to 1,000 of the compounds of the formulas D8 and D9.

In the formula, R ²⁰¹ and R ^{202 are,} for example, a hydrogen atom, a methyl group, an ethyl group, a butyl group, a propyl group, an ethynyl group and a cyclohexyl group, and R ^{203 is} , for example, the same as R ²⁰¹ and R ²⁰² , or examples of -COOH and -CH ₂ COOH, R ^204, for example an ethylene group, a phenylene group, a carbonyl group, a sulfonyl group, an oxygen atom, a sulfur atom, R ²⁰⁵ as the example would equal to the methylene group, or R ^204, R ²⁰⁶ As a hydrogen atom, a methyl group, an ethyl group, a butyl group, a propyl group, an ethynyl group, a cyclohexyl group, the phenyl group substituted by the hydroxyl group, naphthyl group, etc. are mentioned, for example.

Here, as the acid labile group of the dissolution control agent, a group represented by the following formula (11), a group represented by the following formula (12), a tertiary alkyl group having 4 to 20 carbon atoms, a trialkylsilyl group having 1 to 6 carbon atoms of each alkyl group, And an oxoalkyl group having 4 to 20 carbon atoms.

<Formula 11>

<Formula 12>

In the formula, 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 represents a monovalent hydrocarbon group which may have a hetero atom having 1 to 18 carbon atoms, and R ¹⁷ and R ¹⁸ , R ¹⁷ and R ¹⁹ , R ¹⁸ and R ¹⁹ may form a ring, and in the case of forming a ring, R ¹⁷ , R ¹⁸ and R ¹⁹ may be linear or branched, each having 1 to 18 carbon atoms. An alkylene group of R 3, R ²⁰ represents a tertiary alkyl group having 4 to 20 carbon atoms, a trialkylsilyl group having 1 to 6 carbon atoms each, an oxoalkyl group having 4 to 20 carbon atoms, or a group represented by the above formula (11) a is an integer of 0-6.

The compounding quantity of the said dissolution control agent is 0-50 parts with respect to 100 parts of base resin, Preferably it is 5-50 parts, More preferably, it is 10-30 parts, It can use individually or in mixture of 2 or more types. If the blending amount is less than 5 parts, the resolution may not be improved. If the blending amount is more than 50 parts, the film may be reduced in pattern and resolution may be lowered.

Furthermore, such dissolution control agents are synthesized by introducing acid labile groups using organic chemical formulations for compounds having phenolic hydroxyl groups or carboxyl groups.

In addition, a basic compound can be mix | blended with the resist material of this invention.

As a basic compound, the compound which can suppress the diffusion rate at the time of the acid which generate | occur | produces from an acid generator in a resist film is suitable. By compounding the basic compound, the diffusion rate of the acid in the resist film is suppressed, the resolution is improved, the change in sensitivity after exposure can be suppressed, or the exposure margin and the pattern profile can be improved by reducing the substrate and the environmental dependency.

As such basic compounds, primary, secondary and tertiary aliphatic amines, hybrid amines, aromatic amines, heterocyclic amines, nitrogen-containing compounds having a carboxyl group, nitrogen-containing compounds having a sulfonyl group, and nitrogen-containing compounds having a hydroxyl group And nitrogen-containing compounds having hydroxyphenyl groups, alcoholic nitrogen-containing compounds, amide derivatives, imide derivatives and the like.

Specifically, as the primary aliphatic amines, ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, pentylamine, tert -Amylamine, cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, cetylamine, methylenediamine, ethylenediamine, tetraethylenepentamine and the like are exemplified, and As secondary aliphatic amines, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, dipentylamine, dicyclopentyl Amine, dihexylamine, dicyclohexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, didodecylamine, dicetylamine, N, N-dimethylmethylenediamine, N, N-dimethylethylenediamine , N, N-dimethyltetraethylenepentamine and the like, tertiary aliphatic Trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tripentylamine, tricyclopentylamine, tri Hexylamine, tricyclohexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, tridodecylamine, tricetylamine, N, N, N ', N'-tetramethylmethylenediamine, N, N, N ', N'-tetramethylethylenediamine, N, N, N', N'-tetramethyltetraethylenepentamine, etc. are illustrated.

In addition, examples of the mixed amines include dimethylethylamine, methylethylpropylamine, benzylamine, phenethylamine, benzyldimethylamine, and the like. Specific examples of aromatic amines and heterocyclic amines include aniline derivatives (eg, 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-di Nitroaniline, N, N-dimethyltoluidine, etc.), diphenyl (p-tolyl) amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, pyrrole derivatives (e.g. pyrrole , 2H-pyrrole, 1-methylpyrrole, 2,4-dimethylpyrrole, 2,5-dimethylpyrrole, N-methylpyrrole and the like), oxazole derivatives (e.g. oxazole, isoxazole, etc.), thiazole Derivatives (e.g. thiazole, isothiazole, etc.), imidazole derivatives (e.g. imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, etc.), Lazole derivatives, furazane derivatives, pyrroline derivatives (e.g., pyrroline, 2-methyl-1-pyrroline, etc.), pyrrolidine derivatives (e.g., pyrrolidine, N-methylpyrrolidine, py Rorizinone, N-methylpyrrolidone, etc.), imidazoline derivatives, imidazolidine derivatives, pyridine derivatives (e.g. pyridine, methylpyridine, ethylpyridine, propylpyridine, butylpyridine, 4- (1-butyl) Pentyl) pyridine, dimethylpyridine, trimethylpyridine, triethylpyridine, phenylpyridine, 3-methyl-2-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxy Pyridine, 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, indolin derivatives, quinoline derivatives (e.g. quinoline, 3-quinolinecarbonitrile etc.), isoquinoline derivatives, cinnoline derivatives, quinazoline derivatives, Quinoxaline derivatives, phthalazine derivatives, purine derivatives, pteridine derivatives, carbazole derivatives, phenanthridine derivatives, acridine derivatives, phenadine derivatives, 1,10-phenanthroline derivatives, adenine derivatives, adenosine derivatives, Guanine derivatives, guanosine derivatives, uracil derivatives, uridine derivatives and the like.

As the nitrogen-containing compound having a carboxyl group, for example, aminobenzoic acid, indolecarboxylic acid, amino acid derivatives (e.g., nicotinic acid, alanine, arginine, aspartic acid, glutamic acid, glycine, histidine, isoleucine, glycylosin, leucine , Methionine, phenylalanine, threonine, lysine, 3-aminopyrazine-2-carboxylic acid, methoxyalanine), and the like, and nitrogen-containing compounds having a sulfonyl group include 3-pyridine sulfonic acid, p-toluene sulfonic acid pyridinium, and the like. Illustrative 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, 2,4-quinolinediol, 3-indolmethanol hydrate, and monoethanol. Amine, diethanolamine, triethanolamine, N-ethyldiethanolamine, N, N-diethylethanolamine, triisopropanolamine, 2,2'-iminodie Ol, 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-hydroxy Hydroxyethyl) -2-pyrrolidinone, 3-piperidino-1,2-propanediol, 3-pyrrolidino-1,2-propanediol, 8-hydroxyurorizine, 3-quinuclidinol, 3 -Tropanol, 1-methyl-2-pyrrolidineethanol, 1-aziridineethanol, N- (2-hydroxyethyl) phthalimide, N- (2-hydroxyethyl) isonicotinamide, etc. are illustrated. . Examples of the amide derivatives include formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide and the like. Phthalimide, succinimide, maleimide, etc. are illustrated as an imide derivative.

Moreover, you may mix | blend the basic compound represented by following formula (13) and (14).

In formula, R ³⁰¹ , R ³⁰² , R ³⁰³ , R ³⁰⁷ and R ³⁰⁸ each independently represent a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms, R ³⁰⁴ , R ³⁰⁵ , R ³⁰⁶ , R ³⁰⁹ And R ³¹⁰ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an amino group, and R ³⁰⁴ and R ³⁰⁵ , R ³⁰⁴ and R ³⁰⁶ , R ³⁰⁵ and R ³⁰⁷ , R ³⁰⁴ and R ³⁰⁵ and R ³⁰⁶ , R ³⁰⁹ and R ³¹⁰ May combine with each other to form a ring. S, T and U are each an integer of 0 to 20, but when S, T, U = 0, R ³⁰⁴ , R ³⁰⁵ , R ³⁰⁶ , R ³⁰⁹ and R ³¹⁰ do not contain a hydrogen atom.

Here, as an alkylene group of R ³⁰¹ , R ³⁰² , R ³⁰³ , R ³⁰⁷ and R ³⁰⁸ , carbon atoms are 1 to 20, preferably 1 to 10, more preferably 1 to 8, specifically methylene group, Ethylene group, n-propylene group, isopropylene group, n-butylene group, isobutylene group, n-pentylene group, isopentylene group, hexylene group, nonylene group, decylene group, cyclopentylene group, cyclohexylene group, etc. Can be mentioned.

The alkyl groups of R ³⁰⁴ , R ³⁰⁵ , R ³⁰⁶ , R ³⁰⁹ and R ³¹⁰ are those having 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, which are linear, branched or cyclic. Any may be sufficient. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, hexyl group, nonyl group, decyl group and dodecyl group , Tridecyl group, cyclopentyl group, cyclohexyl group and the like.

In addition, when R ³⁰⁴ and R ³⁰⁵ , R ³⁰⁴ and R ³⁰⁶ , R ³⁰⁵ and R ³⁰⁶ , R ³⁰⁴ and R ³⁰⁵ and R ³⁰⁶ , R ³⁰⁹ and R ³¹⁰ form a ring, the carbon number of the ring is 1 to 20, Preferably it is 1-8, More preferably, it is 1-6, and these rings may have the C1-C6, especially 1-4 alkyl group branched.

S, T and U are each an integer of 0-20, More preferably, they are 1-10, More preferably, they are integers of 1-8.

Specific examples of the compounds of the formulas (13) and (14) include tris {2- (methoxymethoxy) ethyl} amine, tris {2- (methoxyethoxy) ethyl} amine and tris [2-{(2-methoxy Methoxy) methoxy} ethyl] amine, tris {2- (2-methoxyethoxy) ethyl} amine, tris {2- (1-methoxyethoxy) ethyl} amine, tris {2- (1-ethoxy Ethoxy) ethyl} amine, tris {2- (1-ethoxypropoxy) ethyl} amine, tris [2-{(2-hydroxyethoxy) ethoxy} ethyl] amine, 4,7,13,16 , 21,24-hexaoxa-1,10-diazabicyclo [8.8.8] hexacoic acid, 4,7,13,18-tetraoxa-1,10-diazabicyclo [8.5.5] eichoic acid, 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 Can be mentioned. Tertiary amines, aniline derivatives, pyrrolidine derivatives, pyridine derivatives, quinoline derivatives, amino acid derivatives, nitrogen-containing compounds having hydroxyl groups, nitrogen-containing compounds having hydroxyphenyl groups, alcoholic nitrogen-containing compounds, amide derivatives, imide derivatives , Tris {2- (methoxymethoxy) ethyl} amine, tris {(2- (2-methoxyethoxy) ethyl} amine, tris [2-{(2-methoxyethoxy) methyl} ethyl] amine , 1-aza-15-crown-5 and the like are preferred.

The compounding quantity of the said basic compound is 0.001-10 parts with respect to 1 part of acid generators, Preferably it is 0.01-1 part. If the amount is less than 0.001 part, the effect as an additive may not be sufficiently obtained, while if it is more than 10 parts, resolution and sensitivity may be lowered.

In addition, a compound having a group represented by ≡C-COOH in the molecule can be blended into the resist material of the present invention.

As a compound which has group represented by -C-COOH in a molecule | numerator, 1 type (s) or 2 or more types of compounds chosen from the following group I and II can be used, for example, It is not limited to these. 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]

Some or all of the hydrogen atoms of the phenolic hydroxyl groups of the compounds represented by formulas A1 to A10 are substituted by -R ⁴⁰¹ -COOH (R ⁴⁰¹ is a linear or branched alkylene group having 1 to 10 carbon atoms); And at the same time the molar ratio between the phenolic hydroxyl group (C) in the molecule and the group (D) represented by ≡C-COOH is C / (C + D) = 0.1 to 1.0.

In the formula, 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, and R ⁴⁰⁴ represents a hydrogen atom or 1 to C atoms A linear or branched alkyl group or an alkenyl group of 8 or a-(R ⁴⁰⁹ ) _h -COOR 'group (R' represents a hydrogen atom or -R ⁴⁰⁹ -COOH), and 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 is an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, a carbonyl group, A sulfonyl group, an oxygen atom or a sulfur atom, R ⁴⁰⁷ represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms, an alkenyl group, a phenyl group or a naphthyl group each substituted with a hydroxyl group, and R ⁴⁰⁹ has 1 carbon atom Straight or branched eggs of from 10 to 10 Represents a chelene group, R ⁴¹⁰ represents a hydrogen atom or a linear or branched alkyl group or alkenyl group having 1 to 8 carbon atoms or an -R ⁴¹¹ -COOH group, and R ⁴¹¹ represents a linear or branched alkylene having 1 to 10 carbon atoms Group, j is an integer from 0 to 5, u and h are 0 or 1, s1, t1, s2, t2, s3, t3, s4 and t4 are s1 + t1 = 8, s2 + t2 = 5, satisfies s3 + t3 = 4, s4 + t4 = 6, and at the same time has at least one hydroxyl group in each phenyl skeleton, κ is a number having a weight average molecular weight of 1,000 to 5,000, and λ is a formula It is a number which uses the compound of A7 as a weight average molecular weight 1,000-10,000.

[Group II]

Compounds represented by the following formulas A11 to A15.

Wherein R ⁴⁰² , R ⁴⁰³ and R ⁴¹¹ represent the same meaning as described above, R ⁴¹² represents a hydrogen atom or a hydroxyl group, s5 and t5 represent s5 ≧ 0, t5 ≧ 0, and satisfy s5 + t5 = 5. Number, h 'is 0 or 1.

Although the compound specifically, shown by following formula (AI-1-14) and AII-1-10 is mentioned as this component, It is not limited to these.

In the formula, R ″ represents a hydrogen atom or a CH ₂ COOH group, 10 to 100 mol% of R ″ in each compound is a CH ₂ COOH group, and α and κ represent the same meanings as described above.

In addition, the compound which has group represented by -C-COOH in the said molecule can be used individually by 1 type or in combination of 2 or more types.

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 3 parts, still more preferably 0.1 to 5 parts based on 100 parts of the base resin. Part two. When more than 5 parts, the resolution of a resist material may fall.

Moreover, an acetylene alcohol derivative can be mix | blended with the resist material of this invention as an additive, and, thereby, storage stability can be improved.

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

In the formula, R ⁵⁰¹ , R ⁵⁰² , R ⁵⁰³ , R ⁵⁰⁴ and R ⁵⁰⁵ each represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, X, Y represents 0 or a positive number, and 0 ≤ X ≤ 30, 0 ≤ Y ≤ 30, 0 ≤ X + Y ≤ 40 is satisfied.

As the acetylene alcohol derivative, preferably, quinolin 61, sufinol 82, sufinol 104, sufinol 104E, sufinol 104H, sufinol 104A, sufinol TG, sufinol PC, sufinol 440, sufinol 465, sufinol 485 (Air Products and Chemicals Inc.), Sufinol E1004 (made by Nisshin Chemical Industries, Ltd.), etc. are mentioned.

The amount of the acetylene alcohol derivative added is 0.01 to 2% by weight, more preferably 0.02 to 1% by weight in 100% by weight of the resist composition. When less than 0.01 weight%, the effect of improving coating property and storage stability may not be fully acquired, and when more than 2 weight%, the resolution of a resist material may fall.

The resist material of this invention can add the surfactant normally used in order to improve applicability as an arbitrary component other than the said component. In addition, the addition amount of an arbitrary component can be made into the normal amount in the range which does not impair the effect of this invention.

Here, as surfactant, a nonionic thing is preferable, and a perfluoroalkyl polyoxyethylene ethanol, a fluorinated alkyl ester, a perfluoroalkylamine oxide, a perfluoroalkyl EO adduct, a fluorine-containing organosiloxane type compound, etc. Can be mentioned. For example, Floride "FC-430", "FC-431" (all, Sumitomo 3M Co., Ltd.), Supron "S-141", "S-145" (All Asahi Glass Co., Ltd. product) ), "DS-401", "DS-403", "DS-451" (all manufactured by Daikin Kogyo Co., Ltd.), Megapack "F-8151" (manufactured by Dainippon Ink Kogyo Co., Ltd.), And "X-70-092" and "X-70-093" (both manufactured by Shin-Etsu Chemical Co., Ltd.). Preferably, fluoride "FC-430" (made by Sumitomo 3M) and "X-70-093" (made by Shin-Etsu Chemical Co., Ltd.) are mentioned.

In order to form a pattern using the resist material of this invention, well-known lithography can be employ | adopted, for example, so that a film thickness may be set to 0.5-2.0 micrometers by methods, such as rotational coating, on the board | substrate, such as a silicon wafer. It is applied and it is prebaked on a hot plate for 1 to 10 minutes at 60 to 150 ° C, preferably at 80 to 120 ° C. Subsequently, a mask for forming a desired pattern is covered on the resist film, and high-energy rays or electron beams such as far ultraviolet rays, excimer lasers, X-rays or the like are exposed at an exposure dose of about 1 to 200 mJ / cm 2, preferably 10 to 100 mJ. After irradiating to about / cm 2, post exposure baking (PEB) is carried out on a hot plate at 60 to 150 ° C. for 1 to 5 minutes, preferably at 80 to 120 ° C. for 1 to 3 minutes. 0.1 to 5%, preferably 2 to 3% of an aqueous alkali solution developer such as tetramethylammonium hydroxide (TMAH) for 0.1 to 3 minutes, preferably 0.5 to 2 minutes, immersion method, puddle method, By developing by conventional methods, such as the spraying method, the desired pattern is formed on a board | substrate. In addition, the material of the present invention is particularly suitable for fine patterning by far ultraviolet rays or excimer lasers, X-rays and electron beams of 248 to 193 nm, even among high energy rays. In addition, when out of the upper limit and the lower limit of the above range, the desired pattern may not be obtained.

<Example>

Hereinafter, the present invention will be described in detail with reference to synthesis examples and examples, but the present invention is not limited to the following examples.

Synthesis Example

The ester compound of this invention and the high molecular compound containing it were synthesize | combined with the prescription shown below.

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 metal magnesium over 60 ° C. over 1 hour. After continuing stirring for 2 hours at room temperature, 300.0 g of cyclopentanone was added dropwise at 65 DEG C or lower over 45 minutes. After stirring at room temperature for 1 hour, normal post-treatment treatment was carried out, and the obtained oily substance was distilled off under reduced pressure, whereby 209.2 g of 1-ethylcyclopentanol was obtained. The yield was 51.4%.

197.0 g of 1-ethylcyclopentanol was dissolved in 2 L of methylene chloride. 204.0 g of acrylic acid chloride was added dropwise to the reaction mixture over -20 DEG C over 10 minutes. 2.1 g of 4- (N, N-dimethylamino) pyridine was added, followed by the dropwise addition of 263.0 g of triethylamine over -1 ° C over 1 hour. After stirring at room temperature for 15 hours, it was treated after the usual reaction to obtain about 300 g of an oily substance. It was used for the next reaction without purification.

The oily material obtained in the previous step was dissolved in 300 ml of benzene. 172.0 g of cyclopentadiene was added dropwise to the reaction mixture over 10 minutes at 10 占 폚 or lower. Stirring was continued for 17 hours at room temperature and then for 1 hour at 70 ° C, and then concentrated under reduced pressure. The resulting oily substance was distilled off under reduced pressure to obtain 269.9 g of 5-norbornene-2-carboxylic acid 1-ethylcyclopentyl (monomer 1). The yield was 66.7%.

Boiling Point: 108 to 116 ° C / 1 mmHg

¹ H-NMR (CDCl ₃ , 270 MHz): δ 0.78-0.90 (m, 3H), 1.20-2.18 (m, 14H), 2.83-3.20 (m, 3H), 5.89-6.20 (m, 2H)

FT-IR: 1726 cm ^-1

<Synthesis Examples 1-2-16>

Synthesis of Monomers 2-16 (Monomers 2-16)

In the same manner as described above, monomers 2 to 16 (Monomer 2 to 16) were synthesized.

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 and added dropwise to 20 L of n-hexane. The resulting solid was obtained by filtration, washed again with 20 L of n-hexane, and vacuum dried at 40 ° C. for 6 hours to obtain 88.3 g of a polymer compound represented by the following Formula 1 (Polymer 1). Yield 53.2%.

<Synthesis Examples 2-2 to 48>

Synthesis of Polymers 2 to 48

As described above, polymers 2 to 48 (Polymers 2 to 48) were synthesized.

Example I

Evaluation of the resolution at the time of manufacturing from the resist material was performed with respect to the polymer (Polymer 1-48) obtained by the additive synthesis example.

<Examples I-1 to 82>

Evaluation of the resolution of the resist

The acid generators (PAG1-8) represented by the following formula, and the solubilizer represented by the following formula using the polymer (Polymer 1-48) obtained by the said synthesis example, and the polymer (Polymer 49-56) represented by the following formula as base resins Yesterday (DRR1-4), basic compound, 0.05% by weight of FC-430 (Sumitomo 3M Co., Ltd.) in the composition shown in the table showing a compound (ACC1) having a group represented by ≡C-COOH in the molecule represented by the following formula: It dissolved in the solvent contained, the resist material was combined, and each resist material was filtered through the 0.2 micrometer Teflon filter, and the resist liquid was produced, respectively.

The resist liquid was applied to a silicon wafer with a thickness of 0.5 mu m by a spin coating method. This silicon wafer was then baked by a hot plate at 110 ° C. for 90 seconds. This was exposed using an ArF excimer laser stepper (NA = 0.55), baked at 110 ° C. for 90 seconds (PEB), and developed with an aqueous solution of 2.38% tetramethylammonium hydroxide to form a positive pattern. Could get

Evaluation of the resist was performed for the following items. First, sensitivity (Eth, mJ / cm ² ) was obtained. Subsequently, the exposure amount for resolving the line and space of 0.25 μm to 1: 1 is set to the optimum exposure amount (Eop, mJ / cm ² ), and the minimum line width (μm) of the line and space separated at this exposure amount is determined to evaluate the resolution of the resist. It was set as. The shape of the resolved resist pattern was observed using a scanning electron microscope.

The composition and evaluation results of each resist are shown in Tables 1 to 5 below. In Tables 1 to 5, solvents and basic compounds 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

TMEMEA: Trismethoxyethoxymethoxyethylamine

From the results of Tables 1 to 5, it was confirmed that the polymer compound containing the ester compound of the present invention as a structural unit has a very high reactivity with acid, and therefore the resist material of the present invention has a very high sensitivity and resolution.

Example II

The etching resistance evaluation was performed about the polymer (Polymer 1-48) obtained by the said synthesis example.

<Examples II-1 to 48>

Etching Resistance Evaluation of Polymers

The polymers (Polymers 1 to 48) and the comparative polymers (methyl polymethacrylate, molecular weight 10,000) obtained in the above synthesis example were dissolved in cyclohexanone and coated on a silicon wafer with a thickness of 1.0 mu m by spin coating. This silicon wafer was then baked at 110 ° C. for 90 seconds using a hot plate. About these, the etching rate (ms / min) in etching by chlorine gas and fluorine gas was measured.

The evaluation results are shown in Tables 6 and 7, and the conditions of the measuring instruments are shown in Table 8 below.

From the results in Tables 6 and 7, it was confirmed that the polymer compound of the present invention has a very high etching resistance.

Chlorine Etching Fluorine Etching manufacture company Nichiden Anerva Tokyo Electron product no L451D TE8500 Gas / flow rate Cl ₂ / 20sccm CHF ₃ / 7sccm O ₂ / 2sccm CF ₄ / 45sccm CHF ₃ / 15sccm O ₂ / 20sccm BCl ₃ / 100sccm Ar / 90sccm RF power 300 W 600 W pressure 2Pa 450 mTorr Temperature 23 ℃ -20 ℃ time 360 seconds 60 seconds

Since the resist material using the high molecular compound of this invention as a base resin is excellent in sensitivity, resolution, and etching resistance in response to high energy rays, it is useful for the fine processing by an electron beam and far ultraviolet rays. In particular, since absorption at the exposure wavelength of ArF excimer laser and KrF excimer laser is small, it has a characteristic that the pattern which is fine and perpendicular | vertical to a board | substrate can be formed easily.

Claims (7)

An ester compound represented by the following formula (1). <Formula 1> 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 a substitutable 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 any one of 0, 1, 2, and 3, and is a number which satisfy | fills 2m + n = 2 or 3. A polymer compound having a weight average molecular weight of 1,000 to 500,000, comprising an ester compound represented by the following formula 1aa or 1ab as a structural unit. <Formula 1aa> <Formula 1ab> In the formula, R ¹ , R ² , R ³ , k, m and n have the same meaning as defined in claim 1. The high molecular compound of Claim 2 containing any 1 type, or 2 or more types of repeating units represented by following General formula (2a)-(10a). In the formula, R ¹ and R ² have the same meaning as defined in claim 1, R <^5> represents a monovalent hydrocarbon group containing a hydrogen atom, a C1-C15 carboxyl group, or a hydroxyl group, At least one of R ⁶ to R ⁹ represents a monovalent hydrocarbon group containing a carboxyl group or a hydroxyl group having 1 to 15 carbon atoms, and the rest are each independently a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms. Indicate, R ⁶ to R ⁹ may form a ring with each other, in which case at least one of R ⁶ to R ⁹ represents a divalent hydrocarbon group containing a carboxyl group or a hydroxyl group having 1 to 15 carbon atoms, and the others are each independently carbon atoms. 1 to 15 linear, branched or cyclic alkylene groups, R ¹⁰ represents a monovalent hydrocarbon group containing a -CO ₂ -partial structure having 3 to 15 carbon atoms, At least one of R ¹¹ to R ¹⁴ represents a monovalent hydrocarbon group containing a -CO ₂ -substructure having 2 to 15 carbon atoms, and the others are each independently a hydrogen atom or a straight, branched or cyclic ring having 1 to 15 carbon atoms. An alkyl group of R ¹¹ to R ¹⁴ may form a ring with each other, in which case at least one of R ¹¹ to R ¹⁴ represents a divalent hydrocarbon group containing a -CO ₂ -substructure having 1 to 15 carbon atoms, the remainder of which is respectively Independently a linear, branched or cyclic alkylene group having 1 to 15 carbon atoms, R ¹⁵ represents an alkyl group containing a polycyclic hydrocarbon group or a polycyclic hydrocarbon group having 7 to 15 carbon atoms, R ¹⁶ represents an acid labile group, k is 0 or 1; A method for producing a polymer compound, characterized in that the radical polymerization, anion polymerization or coordination polymerization of the ester compound of the formula (1) according to claim 1 and other compounds containing carbon-carbon double bonds are carried out. A resist material comprising the polymer compound according to claim 2 or 3. A resist material comprising the polymer compound according to claim 2 or 3, a compound which generates an acid in response to a high energy ray or an electron beam, and an organic solvent. A step of applying a resist material according to claim 5 or 6 on a substrate, a step of exposing with a high energy ray or an electron beam through a photomask after heat treatment, and a step of developing using a developer after heat treatment if necessary. Pattern forming method comprising a.