JP2003140350A - Polymer compound, resist material and method for forming pattern - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resist material by using a polymer compound such as a chemically amplifying resist material which shows significantly high contrast in the alkali solubility rate before and after exposure, which has high sensitivity, high resolution and excellent etching durability and which is suitable as a material to form a fine pattern, in particular, for the manufacture of a VLSI. SOLUTION: The polymer compound has an end molecular structure expressed by general formula (1). In the formula (1), R<1> represents a single bond or a group selected from among 1-10C straight-chain, branched or cyclic alkylene groups, bridged cyclic alkylene groups or 6-10C arylene groups and R<2> represents an acid unstable group.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention has a significantly high alkali dissolution rate contrast before and after exposure, has high sensitivity and high resolution, exhibits excellent etching resistance and substrate adhesion,
In particular, the present invention relates to a polymer compound effective as a base resin for a chemically amplified positive resist material suitable for VLSI manufacturing and as a fine pattern forming material for photomasks, a resist material containing the polymer compound, and a pattern forming method.

[0002]

2. Description of the Related Art In recent years,
With the higher integration and higher speed of LSIs, deep-UV lithography has been put into practical use in response to the demand for finer pattern rules. Deep UV lithography is 0.3μ
Processing of m or less is also possible, and when a resist material having low light absorption is used, it becomes possible to form a pattern having a side wall that is nearly vertical to the substrate.

For example, a chemically amplified positive resist material using an acid catalyst (Japanese Patent Publication No. 27660/1990, JP-A-63).
-27829 gazette) is a resist material for deep UV lithography, which uses a high-intensity KrF excimer laser as a deep UV light source and has high sensitivity, resolution, and dry etching resistance, and has excellent characteristics. is there.

As such a chemically amplified positive resist material, a two-component system comprising a base polymer and an acid generator,
A three-component system comprising a base polymer, an acid generator and a dissolution inhibitor having an acid labile group is known.

For example, Japanese Patent Application Laid-Open No. 62-115440 proposes a resist material comprising poly-p-tert-butoxystyrene and an acid generator, and Japanese Patent Application Laid-Open No. 3-223858 discloses a resist material similar to this proposal. T in the molecule
A two-component resist material comprising an ert-butoxy group-containing resin and an acid generator, and further, JP-A-4-21258 discloses a methyl group, an isopropyl group, a tert-butyl group, a tetrahydropyranyl group, a trimethylsilyl group-containing poly A two-component resist material composed of hydroxystyrene and an acid generator has been proposed.

Further, JP-A-6-100488 discloses that poly [3,4-bis (2-tetrahydropyranyloxy) styrene], poly [3,4-bis (tert-butoxycarbonyloxy) styrene], poly A resist material comprising a polydihydroxystyrene derivative such as [3,5-bis (2-tetrahydropyranyloxy) styrene] and an acid generator has been proposed.

However, the base resin of these resist materials has an acid labile group in the side chain, and the acid labile group is decomposed by a strong acid such as tert-butyl group and tert-butoxycarbonyl group. Then, the pattern shape of the resist material is likely to be a T-top shape, and on the other hand, an alkoxyalkyl group such as an ethoxyethyl group is decomposed by a weak acid. Therefore, with the passage of time from exposure to heat treatment, There is a problem that the pattern shape is extremely thin, or because it has a bulky group in the side chain, heat resistance is lowered, sensitivity and resolution are not satisfactory, both have problems, Studies have been made to compensate for the drawbacks by using these plural substituents.

In addition, a copolymer of hydroxystyrene and a (meth) acrylic acid tertiary ester is used in order to realize higher transparency and adhesion to the substrate, improve footing up to the substrate, and improve etching resistance. The above resist materials have also been reported (JP-A-3-275149, JP-A-6-
No. 289608), however, this type of resist material has problems such as heat resistance and a poor pattern shape after exposure, and it is not satisfactory in etching resistance.

The present invention has been made in view of the above circumstances.
A resist material having higher sensitivity and resolution than conventional resist materials, exposure allowance, process adaptability, a good pattern shape after exposure, and excellent etching resistance, particularly a chemically amplified positive resist material. It is an object of the present invention to provide a polymer compound effective as a base resin of the above, a resist material containing the polymer compound, and a pattern forming method.

[0010]

Means for Solving the Problems and Modes for Carrying Out the Invention As a result of intensive studies conducted by the present inventors in order to achieve the above object, the polymer main chain has an acid labile group represented by the formula (1) at the terminal. It was found that the addition of a polymer having an end group structure having a radically improved dissolution contrast of the resist and enhanced resolution. This polymer is
Particularly, in the following general formula (2), a polymer compound having a repeating unit represented by n and an end having an acid labile group represented by the formula (1) and having a weight average molecular weight of 1,000 to 500,000 is used. Yes, it is effective as a base resin for a positive resist material, particularly a chemically amplified positive resist material, and a chemically amplified positive resist material containing this polymer compound, an acid generator and an organic solvent is used for the dissolution contrast and solution of the resist film. High image quality, good exposure latitude, excellent process adaptability, good pattern shape after exposure, and better etching resistance. Or we found that it is very effective as a photomask pattern forming material,
The present invention has been completed.

Therefore, the present invention provides the following polymer compounds,
A resist material and a pattern forming method are provided. Claim 1: A polymer compound having a terminal structure represented by the following general formula (1).

[Chemical 3] (In the formula, R ¹ is a single bond, or a straight chain having 1 to 10 carbon atoms,
It is a group selected from branched and cyclic alkylene groups, bridged cyclic alkylene groups and arylene groups having 6 to 10 carbon atoms, and R ² is an acid labile group. ) Claim 2: Repeating unit n represented by the following general formula (2)
The polymer compound according to claim 1, which has a terminal structure of

[Chemical 4] (In the formula, R ¹ and R ² are as described above, R ³ is a hydrogen atom or an acid labile group. R ⁴ is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. R ⁵ is a hydrogen atom or a methyl group, R ⁶ is an aromatic ring having 6 to 20 carbon atoms, and m of the hydrogen atoms are substituted with OR ^3. Z is a single bond or (p + 1). ) A valent aliphatic or aromatic hydrocarbon group which may contain a carbonyl group, an ester group or an ether group, m is an integer of 1 to 3, and p
Is 1 or 2. ) Claim 3: The polymer compound according to claim 2, wherein the aromatic ring represented by R ⁶ in the general formula (2) is a benzene ring, a naphthalene ring or an anthracene ring. Claim 4: The polymer compound represented by the general formula (2) is synthesized by anionic polymerization.
Alternatively, the polymer compound according to item 3. [5] A resist material comprising the polymer compound according to any one of [1] to [4]. [6] A chemical amplification comprising: (A) an organic solvent, (B) a base resin, the polymer compound according to any one of [1] to [4], and (C) an acid generator. Positive resist material. Claim 7: (A) An organic solvent, (B) A base resin comprising the polymer compound according to any one of claims 1 to 4, (C) an acid generator, and (D) a dissolution inhibitor. A chemically amplified positive resist material characterized by the following. [8] The chemically amplified positive resist composition according to [6] or [7], further comprising a basic compound as an additive (E). Claim 9: A step of applying the resist material according to any one of claims 5 to 8 on a substrate, and a step of exposing with a high energy beam or an electron beam through a photomask after heat treatment, which are necessary. And then developing with a developing solution.

The present invention will be described in more detail below.
The polymer compound of the present invention has a terminal structure represented by the following general formula (1). In this case, as the polymer compound, those represented by the following general formula (2) are preferable.

[0013]

[Chemical 5] (In the formula, R ¹ is a single bond, or a linear, branched, or cyclic alkylene group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, a bridged cyclic alkylene group, and an arylene having 6 to 10 carbon atoms. R ² is an acid labile group, R ³ is a hydrogen atom or an acid labile group, and R ⁴ has 1 to 2 carbon atoms.
It is a linear, branched or cyclic alkyl group of 0, preferably 3 to 10, and R ⁵ is a hydrogen atom or a methyl group.
R ⁶ is an aromatic ring having 6 to 20 carbon atoms, and m hydrogen atoms thereof are substituted with OR ³ . Z is a single bond or (p
It is a +1) -valent aliphatic or aromatic hydrocarbon group, which may contain a carbonyl group, an ester group or an ether group. m is an integer of 1 to 3, and p is 1 or 2. )

R¹The alkylene group of is methylene
Group, ethylene group, n-propylene group, isopropylene
Group, n-butylene group, isobutylene group, sec-butyle
Group, cyclohexylene group, norbornylene, adaman
Examples thereof include bridged cyclic groups such as tylene, particularly methylene group,
Ethylene group and n-propylene group are preferably used.
R ¹Examples of the arylene group include a phenylene group and the like.
Be done.

Examples of the alkyl group represented by R ⁴ include methyl group, ethyl group, n-propyl group, isopropyl group and n-
Examples thereof include a butyl group, an isobutyl group, a sec-butyl group and a t-butyl group.

As R ⁶ , a benzene ring is preferably used for KrF excimer laser exposure, but a naphthalene ring or anthracene ring can also be used for EB exposure. At the wavelength of 248 nm of the KrF excimer laser, the naphthalene ring and the anthracene ring have strong absorption and thus cannot form a pattern, but the EB has no absorption, so that a vertical pattern can be formed. Further, the naphthalene ring and the anthracene ring are more advantageous than the benzene ring for the dry etching resistance.

Z is a single bond or (p + 1) valence (ie,
A divalent or trivalent) aliphatic or aromatic hydrocarbon group. In this case, the aliphatic hydrocarbon group is preferably one having 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms. Those having 6 to 20 carbon atoms, particularly those having 6 to 10 carbon atoms are preferable. As the divalent aliphatic hydrocarbon group, a straight chain,
Examples thereof include branched, cyclic, or bridged cyclic alkylene groups, examples of the divalent aromatic hydrocarbon group include arylene groups such as a phenylene group, and examples of these alkylene groups and arylene groups include R ¹ . What was illustrated can be illustrated concretely. Examples of the trivalent aliphatic or aromatic hydrocarbon group are those in which one of the hydrogen atoms bonded to the carbon atom of the above divalent aliphatic or aromatic hydrocarbon group (alkylene group, arylene group) is eliminated. Can be mentioned. In addition, (p +
The 1) -valent aliphatic or aromatic hydrocarbon group may include a carbonyl group (= C = O), an ester group (-COO-), or an ether group (-O-). Examples of Z include the followings.

[0018]

[Chemical 6]

However, R ⁰ is a single bond, or a linear, branched, cyclic or bridged alkylene group having 1 to 10 carbon atoms similar to R ¹ or an arylene group having 6 to 10 carbon atoms. And may contain a carbonyl group, an ester group or an ether group. R represents a trivalent aliphatic hydrocarbon group obtained by removing one hydrogen atom from a linear or branched alkylene group having 1 to 6 carbon atoms. Or

[Chemical 7] The group forming is shown.

The terminal acid labile group R ² and the side chain acid labile group R ³ in the above polymer compound may be the same or different, and various selections are made. In particular, the following formula (AL-10),
A group represented by (AL-11), a tertiary alkyl group having 4 to 40 carbon atoms represented by the following formula (AL-12), a trialkylsilyl group having 1 to 6 carbon atoms in each alkyl group, and 4 carbon atoms. It is preferably an oxoalkyl group of -20. The acid labile group R ³ on the side chain of the polymer may be one type or two or more different types.

[0021]

[Chemical 8]

In the formulas (AL-10) and (AL-11), R ⁷ and R ¹⁰ are linear, branched or cyclic alkyl groups having 1 to 20 carbon atoms, such as oxygen, sulfur, nitrogen and fluorine. May include a heteroatom of

R ⁸ and R ⁹ are hydrogen atoms or have 1 to 20 carbon atoms.
Is a linear, branched or cyclic alkyl group, and may contain a hetero atom such as oxygen, sulfur, nitrogen or fluorine, and a is an integer of 0-10. R ⁸ and R ^9, R ⁸ and R ^10, R ⁹ and R ¹⁰ are 3 to 12 carbon atoms with the carbon and oxygen atoms to respectively bond to which they are attached, in particular 3 to 8
May form a ring. Specific examples of the compound represented by the formula (AL-10) include tert-butoxycarbonyl group, tert-butoxycarbonylmethyl group, te.
rt-amyloxycarbonyl group, tert-amyloxycarbonylmethyl group, 1-ethoxyethoxycarbonylmethyl group, 2-tetrahydropyranyloxycarbonylmethyl group, 2-tetrahydrofuranyloxycarbonylmethyl group, and the following general formula (AL- 10) -1 to (A
Examples of the substituent include L-10) -9.

[0024]

[Chemical 9]

Formulas (AL-10) -1 to (AL-10)-
Among 9, R ¹⁴ represents the same or different number 1-8 straight, branched or cyclic alkyl group, or an aryl group or an aralkyl group having 6 to 20 carbon atoms. R ¹⁵ represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. R ¹⁶ represents an aryl group or an aralkyl group having 6 to 20 carbon atoms. a is the same as above.

The acetal group represented by the formula (AL-11) is represented by the formulas (AL-11) -1 to (AL-11) -2.
An example is shown by 3.

[0027]

[Chemical 10]

[0028]

[Chemical 11]

In the case of R ³ as the acid labile group having an acetal structure, it is intermolecularly or intramolecularly crosslinked by the acid labile group represented by the following general formula (AL-11a) or (AL-11b). May be.

[0030]

[Chemical 12]

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

General formulas (AL-11a) and (AL-11
Specific examples of the cross-linked acetal represented by b) include those represented by the following formulas (AL-11) -24 to (AL-11) -31.

[0033]

[Chemical 13]

The tertiary alkyl group represented by the formula (AL-12) includes tert-butyl group, triethylcarbyl group, 1-ethylnorbornyl group, 1-methylcyclohexyl group, 1-ethylcyclopentyl group, 2- (2-methyl) adamantyl group, 2- (2-ethyl) adamantyl group, tert-amyl group, etc. or the following general formula (AL-
12) -1 to (AL-12) -18 can be mentioned.

[0035]

[Chemical 14]

In the formula, R ³⁰ is the same or different and has 1 to 8 carbon atoms.
Linear, branched or cyclic alkyl group of 6 or 6 carbon atoms
To 20 aryl groups or aralkyl groups. R ³¹ , R
³³ represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. R ³² represents an aryl group or an aralkyl group having 6 to 20 carbon atoms.

Furthermore, formulas (AL-12) -19 and (AL-
12) As shown in -20, the polymer may contain R ³⁴ which is a divalent or higher alkylene group or an arylene group, and may be cross-linked within or between the molecules of the polymer. Formula (AL-1
2) -19, R ³⁰ is the same as above, and R ³⁴ is a carbon number of 1 to 2.
0 represents a linear, branched or cyclic alkylene group or an arylene group, and may contain a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom. b is an integer of 1 to 3.

[0038]

[Chemical 15]

Further, R ³⁰ , R ³¹ , R ³² , and R ³³ may have a hetero atom such as oxygen, nitrogen, and sulfur. Specifically, they are specifically represented by the following formulas (AL-13) -1 to (AL- 13) -7.

[0040]

[Chemical 16]

Examples of the trialkylsilyl group in which each alkyl group has 1 to 6 carbon atoms include trimethylsilyl group, triethylsilyl group and dimethyl-tert-butylsilyl group.

Examples of the method for producing the phenol residue polymer having an acid labile group at the terminal according to the present invention include a method of reacting with a compound having an acid labile group as a terminating component during living anionic polymerization. For example, in the general formula (2), when R ⁶ is a benzene ring, the general formula (3)-
A hydroxystyrene derivative represented by 1, a hydroxyvinylnaphthalene derivative represented by the general formula (3) -2 when R ⁶ is a naphthalene ring, and a hydroxyvinyl derivative represented by the general formula (3) -3 when R ⁶ is an anthracene ring. A method is preferred in which living anion polymerization is started using a vinyl anthracene derivative, a predetermined amount is polymerized, and then the compound represented by the general formula (4) is reacted to terminate the polymerization.

[0043]

[Chemical 17]

Here, R ⁵ and m are as described above, and R ^5
40 is a linear, branched or cyclic primary having 2 to 6 carbon atoms, 2
And a tertiary alkyl group, an acetal group represented by the formula (AL-11), and a trialkylsilyl group.

As the polymerization terminator having an acid labile group,
The compounds represented by formula (4), particularly formulas (4) -1 to (4) -3, are preferable.

[Chemical 18]

Here, R ¹ , R ² , Z, R ⁰ and R are as described above, and X is a halogen atom, an aldehyde group, a hydroxyl group, a carboxyl group or the like.

Further, the polymerization terminators represented by the general formulas (4) -1 to (4) -3 are specifically the following formulas (4) -1-1 to
(4) -1-18, (4) -2-1 to (4) -2-1
4, (4) -3-1.

[0048]

[Chemical 19]

[0049]

[Chemical 20]

When performing living anionic polymerization, the reaction solvent is preferably a solvent such as toluene, benzene, tetrahydrofuran, dioxane or ethyl ether,
In particular, polar solvents such as tetrahydrofuran, dioxane and ethyl ether are preferable, and they may be used alone or in combination of two or more kinds.

Alkyl lithium is used as the initiator, and among them, sec-butyl lithium and n-butyl lithium are particularly preferable, and the amount used is proportional to the designed molecular weight. The reaction temperature is −80 to 100 ° C., preferably −70 to 0 ° C., and the reaction time is 0.1 to 50 hours, preferably 0.5 to 5 hours.

In the above method, the weight average molecular weight is 1,000 to 100,000, and the general formula (2)
A polymer compound represented by

The reaction formula (5) is shown below as an example of the synthesis of the polymer compound of the present invention.

[Chemical 21]

In this case, sec-butyllithium was used as the polymerization initiator, and t-butyl 3-bromopropionate was used as the polymerization terminator.

After the polymerization, R ⁴⁰ is deprotected to replace the hydrogen atom of the hydroxyl group of phenol with an acid labile group. It should be noted here that R ⁴⁰ is deprotected during the deprotection reaction.
^{The two} must not be deprotected. In the case of deprotection with an acid, R ⁴⁰ should be selected from a protective group that is more easily deprotected than R ² , such as an acetal group or a trimethylsilyl group. Deprotection under alkaline conditions is preferred if possible.

Further, after the polymer compound thus obtained is isolated, it is represented by the general formulas (AL-10), (AL-11) and (AL-12) with respect to the phenolic hydroxyl group moiety. It is also possible to introduce acid labile groups. For example, it is possible to react the phenolic hydroxyl group of a polymer compound with an alkenyl ether compound in the presence of an acid catalyst to obtain a polymer compound in which the phenolic hydroxyl group is partially protected by an alkoxyalkyl group.

At this time, the reaction solvent is preferably an aprotic polar solvent such as dimethylformamide, dimethylacetamide, tetrahydrofuran or ethyl acetate,
You may use it individually or in mixture of 2 or more types. Examples of the catalyst acid include hydrochloric acid, sulfuric acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, p
-Toluenesulfonic acid pyridinium salt and the like are preferable, and the amount thereof is 0.1 to 1 with respect to 1 mol of all the hydroxyl groups of hydrogen atoms of the phenolic hydroxyl group of the polymer compound which reacts.
It is preferably 0 mol%. The reaction temperature is -2
It is 0 to 100 ° C, preferably 0 to 60 ° C, and the reaction time is 0.2 to 100 hours, preferably 0.5 to 20.
It's time.

It is also possible to obtain a polymer compound in which a phenolic hydroxyl group is partially protected by an alkoxyalkyl group by reacting a halogenated alkyl ether compound with a polymer compound in the presence of a base. Is.

At this time, the reaction solvent is preferably an aprotic polar solvent such as acetonitrile, acetone, dimethylformamide, dimethylacetamide, tetrahydrofuran or dimethylsulfoxide, and may be used alone or in combination of two or more kinds. As the base, triethylamine, pyridine, diisopropylamine, potassium carbonate and the like are preferable, and the amount of the base used is such that the hydrogen atom of the phenolic hydroxyl group of the polymer compound to be reacted is 1
It is preferably 10 mol% or more based on mol. The reaction temperature is -50 to 100 ° C, preferably 0 to 60
The reaction time is 0.5 to 100 hours, preferably 1 to 20 hours.

Further, the introduction of the acid labile group of the above formula (AL-10) can be carried out by reacting a dialkyl dicarbonate compound or an alkoxycarbonylalkyl halide with a polymer compound in a solvent in the presence of a base. Is. The reaction solvent is preferably an aprotic polar solvent such as acetonitrile, acetone, dimethylformamide, dimethylacetamide, tetrahydrofuran or dimethylsulfoxide, and may be used alone or in combination of two or more.

As the base, triethylamine, pyridine, imidazole, diisopropylamine, potassium carbonate and the like are preferable, and the amount of the base used is 10 moles of hydrogen atoms of the phenolic hydroxyl group of the original polymer compound to 1 mole of all the hydroxyl groups. % Or more is preferable.

The reaction temperature is 0 to 100 ° C, preferably 0 to 60 ° C. The reaction time is 0.2 to 100
The time is preferably 1 to 10 hours.

Examples of the dialkyl dicarbonate compound include di-tert-butyl dicarbonate and di-tert-amyl dicarbonate, and examples of the alkoxycarbonylalkyl halide include tert-butoxycarbonylmethyl chloride.
tert-amyloxycarbonylmethyl chloride, t
ert-butoxycarbonylmethyl bromide, ter
Examples thereof include t-butoxycarbonylethyl chloride. However, it is not limited to these synthesizing methods.

The polymer compound of the present invention is a resist material,
Particularly, it is preferably used as a base resin in a chemically amplified resist material, and the resist material of the present invention has the formula (1)
The present invention is characterized in that a polymer material having an acid labile group-containing terminal group represented by is added. In this case, the conventional polymer material having no acid labile group at the terminal is added to the compound of the present invention. Can be further added, that is, a polymer blend can be added. Conventional polymeric materials include substituted or unsubstituted novolacs, polyhydroxystyrenes, polyhydroxystyrene- (meth) acrylic acid derivatives, (meth) acrylic derivatives, norbornene derivatives, maleic anhydride, maleimide derivatives, acenaphthene derivatives, vinyl. Naphthalene derivative, vinyl anthracene derivative, vinyl ether derivative, allyl ether derivative, vinyl acetate, (meth) acrylonitrile, vinylpyrrolidone, tetrafluoroethylene, or indene derivative, indole derivative, benzofuran derivative, benzothiophene derivative, or the like. It is a polymer. The method of polymerizing the polymer may be anionic polymerization, radical polymerization or cationic polymerization. Further, in the resist material of the present invention, two or more kinds of polymer blends having different molecular weights and dispersities, or two or more kinds of polymer blends having different main chain acid labile groups and different terminal acid labile groups are possible. .

The resist material of the present invention is particularly favorably used as a positive type and contains the above-mentioned polymer compound. In this case, the resist material of the present invention comprises (A) an organic solvent and (B) a base resin. As the above polymer compound,
It is preferably used as a chemically amplified positive resist material containing (C) an acid generator, and optionally (D) a dissolution inhibitor, preferably (E) a basic compound.

Here, in the chemically amplified positive resist composition of the present invention, the organic solvent of the component (A) is butyl acetate, amyl acetate, cyclohexyl acetate, 3-methoxybutyl acetate, methyl ethyl ketone, methyl amyl ketone, cyclohexanone, Cyclopentanone, 3-ethoxyethyl propionate, 3-ethoxymethyl propionate, 3-methoxymethyl propionate, methyl acetoacetate, ethyl acetoacetate, diacetone alcohol,
Methyl pyruvate, ethyl pyruvate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether,
Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methyl-3-methoxybutanol, N-methylpyrrolidone, dimethyl sulfoxide, γ-butyrolactone, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, methyl lactate, Examples thereof include ethyl lactate, propyl lactate, and tetramethylene sulfone, but are not limited to these. Particularly preferred are propylene glycol alkyl ether acetate and alkyl lactate. These solvents may be used alone or in combination of two or more. An example of a preferable mixed solvent is a mixed solvent of propylene glycol alkyl ether acetate and alkyl lactate.

The alkyl group of propylene glycol alkyl ether acetate in the present invention has 1 carbon atoms.
To 4 groups, for example, a methyl group, an ethyl group, a propyl group and the like, among which a methyl group and an ethyl group are preferable. The propylene glycol alkyl ether acetate has 1,2-substitution products and 1,3-substitution products, and there are three isomers depending on the combination of substitution positions, but either one or a mixture may be used.

Examples of the alkyl group of the above-mentioned alkyl lactate include those having 1 to 4 carbon atoms, such as methyl group, ethyl group and propyl group. Of these, methyl group and ethyl group are preferred.

When propylene glycol alkyl ether acetate is added as a solvent, 1 is added to all the solvents.
It is preferably 0% by weight or more. When a mixed solvent of propylene glycol alkyl ether acetate and alkyl lactate is used as a solvent, the total amount thereof is preferably 50% by weight or more based on all the solvents. In this case, more preferably, 20 to 100% by weight of propylene glycol alkyl ether acetate,
It is preferable that the proportion of the alkyl lactate is 0 to 80% by weight. When the amount of propylene glycol alkyl ether acetate is small, there are problems such as deterioration of coating properties, and when the amount is too large, there are problems of insufficient solubility, generation of particles and foreign substances. When the amount of alkyl lactate is small, there are problems such as insufficient solubility, especially when an onium salt is added as an acid generator, and increase in particles and foreign substances. However, there are problems such as deterioration of storage stability.

The amount of these solvents added is 300 to 100 parts by weight of the base resin of the chemically amplified positive resist material.
Although it is 2,000 parts by weight, preferably 400 to 1,000 parts by weight, it is not limited to this as long as it is a concentration that can be achieved by the existing film forming method.

The photo-acid generator as the component (C) may be any compound as long as it is a compound capable of generating an acid upon irradiation with high energy rays. Suitable photoacid generators include sulfonium salts, iodonium salts, sulfonyldiazomethane, N-
There are sulfonyloxyimide type acid generators and the like. As described in detail below, these may be used alone or in combination of two or more.

The sulfonium salt is a salt of a sulfonium cation and a sulfonate, and as the sulfonium cation, triphenylsulfonium, (4-tert-butoxyphenyl) diphenylsulfonium, bis (4-ter).
t-butoxyphenyl) phenylsulfonium, tris (4-tert-butoxyphenyl) sulfonium,
(3-tert-butoxyphenyl) diphenylsulfonium, bis (3-tert-butoxyphenyl) phenylsulfonium, tris (3-tert-butoxyphenyl) sulfonium, (3,4-ditert-butoxyphenyl) diphenylsulfonium, bis ( 3,4-
Ditert-butoxyphenyl) phenylsulfonium, tris (3,4-ditert-butoxyphenyl)
Sulfonium, diphenyl (4-thiophenoxyphenyl) sulfonium, (4-tert-butoxycarbonylmethyloxyphenyl) diphenylsulfonium, tris (4-tert-butoxycarbonylmethyloxyphenyl) sulfonium, (4-tert-butoxyphenyl) bis ( 4-dimethylaminophenyl) sulfonium, tris (4-dimethylaminophenyl) sulfonium, 2-naphthyldiphenylsulfonium, dimethyl 2-naphthylsulfonium, 4-hydroxyphenyldimethylsulfonium, 4-methoxyphenyldimethylsulfonium, trimethylsulfonium, 2-oxo Examples thereof include cyclohexylcyclohexylmethylsulfonium, trinaphthylsulfonium, tribenzylsulfonium, and the like. Examples of trifluoromethane sulfonate, nonafluorobutane sulfonate, heptadecafluorooctane sulfonate, 2,2,2-trifluoroethane sulfonate, pentafluorobenzene sulfonate, 4-trifluoromethylbenzene sulfonate, 4-fluorobenzene sulfonate, toluene Examples thereof include sulfonates, benzene sulfonates, 4- (4-toluenesulfonyloxy) benzene sulfonates, naphthalene sulfonates, camphor sulfonates, octane sulfonates, dodecyl benzene sulfonates, butane sulfonates, methane sulfonates and the like, and sulfonium salts of combinations thereof.

The iodonium salt is a salt of an iodonium cation and a sulfonate, and includes diphenyliodonium, bis (4-tert-butylphenyl) iodonium and 4
-Tert-butoxyphenylphenyliodonium,
Aryl iodonium cation such as 4-methoxyphenylphenyl iodonium and trifluoromethane sulfonate, nonafluorobutane sulfonate, heptadecafluorooctane sulfonate as sulfonate, 2,
2,2-trifluoroethane sulfonate, pentafluorobenzene sulfonate, 4-trifluoromethylbenzene sulfonate, 4-fluorobenzene sulfonate, toluene sulfonate, benzene sulfonate, 4
-(4-Toluenesulfonyloxy) benzene sulfonate, naphthalene sulfonate, camphor sulfonate, octane sulfonate, dodecyl benzene sulfonate, butane sulfonate, methane sulfonate, etc. are mentioned, and the iodonium salt of these combinations is mentioned.

Examples of the sulfonyldiazomethane include bis (ethylsulfonyl) diazomethane, bis (1-methylpropylsulfonyl) diazomethane, bis (2-methylpropylsulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, bis (cyclohexyl). Sulfonyl) diazomethane, bis (perfluoroisopropylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (4-methylphenylsulfonyl) diazomethane, bis (2,4-dimethylphenylsulfonyl) diazomethane, bis (2-naphthylsulfonyl) diazomethane , 4-methylphenylsulfonylbenzoyldiazomethane, tert-butylcarbonyl-4-methylphenylsulfonyldiazomethane, 2-naphthylsulfur Sulfonyl benzoyl diazomethane,
4-methylphenylsulfonyl-2-naphthoyldiazomethane, methylsulfonylbenzoyldiazomethane, t
Examples thereof include bissulfonyldiazomethane and sulfonylcarbonyldiazomethane such as ert-butoxycarbonyl-4-methylphenylsulfonyldiazomethane.

Examples of the N-sulfonyloxyimide type photoacid generator include succinimide, naphthalenedicarboxylic acid imide, phthalic acid imide, cyclohexyldicarboxylic acid imide, 5-norbornene-2,3-dicarboxylic acid imide, and 7-oxabicyclo. [2.2.1] -5-Heptene-2,3-dicarboxylic acid imide or other imide skeleton and trifluoromethanesulfonate, nonafluorobutanesulfonate, heptadecafluorooctanesulfonate, 2,
2,2-trifluoroethane sulfonate, pentafluorobenzene sulfonate, 4-trifluoromethylbenzene sulfonate, 4-fluorobenzene sulfonate, toluene sulfonate, benzene sulfonate, naphthalene sulfonate, camphor sulfonate, octane sulfonate, dodecyl benzene sulfonate, butane sulfonate, A combination of compounds such as methanesulfonate may be mentioned.

Examples of the benzoin sulfonate type photoacid generator include benzoin tosylate, benzoin mesylate,
Examples thereof include benzoin butane sulfonate.

As the pyrogallol trisulfonate-type photoacid generator, all the hydroxyl groups of pyrogallol, phloroglycine, catechol, resorcinol, and hydroquinone are trifluoromethanesulfonate, nonafluorobutanesulfonate, heptadecafluorooctanesulfonate, 2,2,2. -Trifluoroethane sulfonate, pentafluorobenzene sulfonate, 4-trifluoromethylbenzene sulfonate, 4-fluorobenzene sulfonate, toluene sulfonate, benzene sulfonate, naphthalene sulfonate, camphor sulfonate, octane sulfonate, dodecyl benzene sulfonate, butane sulfonate, methane sulfonate, etc. The compound substituted by is mentioned.

Examples of the nitrobenzyl sulfonate type photoacid generator include 2,4-dinitrobenzyl sulfonate and 2
-Nitrobenzyl sulfonate, 2,6-dinitrobenzyl sulfonate, and the sulfonate includes
Specifically, trifluoromethane sulfonate, nonafluorobutane sulfonate, heptadecafluorooctane sulfonate, 2,2,2-trifluoroethane sulfonate, pentafluorobenzene sulfonate, 4-trifluoromethylbenzene sulfonate, 4-fluorobenzene sulfonate, toluene sulfonate , Benzene sulfonate, naphthalene sulfonate, camphor sulfonate, octane sulfonate, dodecyl benzene sulfonate, butane sulfonate, methane sulfonate and the like. A compound in which the nitro group on the benzyl side is replaced with a trifluoromethyl group can also be used in the same manner.

Examples of the sulfone type photoacid generator include bis (phenylsulfonyl) methane, bis (4-methylphenylsulfonyl) methane, bis (2-naphthylsulfonyl) methane and 2,2-bis (phenylsulfonyl) propane. , 2,2-bis (4-methylphenylsulfonyl)
Propane, 2,2-bis (2-naphthylsulfonyl) propane, 2-methyl-2- (p-toluenesulfonyl)
Propiophenone, 2- (cyclohexylcarbonyl)
-2- (p-toluenesulfonyl) propane, 2,4-
Dimethyl-2- (p-toluenesulfonyl) pentane-
3-on and the like can be mentioned.

Examples of the glyoxime derivative type photoacid generator include bis-o- (p-toluenesulfonyl) -α-
Dimethylglyoxime, bis-o- (p-toluenesulfol) -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- (t
ert-butanesulfonyl) -α-dimethylglyoxime, bis-o- (perfluorooctanesulfonyl)-
α-dimethylglyoxime, bis-o- (cyclohexylsulfonyl) -α-dimethylglyoxime, bis-o
-(Benzenesulfonyl) -α-dimethylglyoxime, bis-o- (p-fluorobenzenesulfonyl)-
α-dimethylglyoxime, bis-o- (p-tert
-Butylbenzenesulfonyl) -α-dimethylglyoxime, bis-o- (xylenesulfonyl) -α-dimethylglyoxime, bis-o- (camphorsulfonyl)
Examples include -α-dimethylglyoxime.

Among these, photoacid generators preferably used include sulfonium salts, bissulfonyldiazomethane,
It is N-sulfonyloxyimide.

The optimum anion of the generated acid varies depending on the ease of cleavage of the acid labile group used in the polymer, but generally, anion having no volatility or extremely high diffusibility is selected. Suitable anions in this case are benzenesulfonate anion, toluenesulfonate anion, 4- (4
-Toluenesulfonyloxy) benzenesulfonate anion, pentafluorobenzenesulfonate anion,
2,2,2-trifluoroethanesulfonic acid anion,
Nonafluorobutane sulfonate anion, heptadecafluorooctane sulfonate anion, and camphor sulfonate anion.

The addition amount of the photoacid generator (C) in the chemically amplified positive resist composition of the present invention is 0.5 to 20 parts by weight, preferably 1 to 100 parts by weight of the base resin in the resist material. 10 parts by weight. The photoacid generator (C) may be used alone or in combination of two or more. Further, it is also possible to use a photo-acid generator having a low transmittance at the exposure wavelength and control the transmittance in the resist film by adjusting the amount added.

The dissolution inhibitor of the component (D) is a compound having a weight average molecular weight of 100 to 1,000 and having two or more phenolic hydroxyl groups in the molecule, and the hydrogen atom of the phenolic hydroxyl group is acid labile. Average 1 as a whole
A compound substituted at a ratio of 0 to 100 mol% is preferable.
The weight average molecular weight of the above compound is 100 to 1,000.
It is 0, preferably 150 to 800. The content of the dissolution inhibitor is 0 to 50 parts by weight, preferably 5 to 50 parts by weight, more preferably 10 to 100 parts by weight of the base resin.
It is 30 parts by weight and can be used alone or in combination of two or more kinds. If the blending amount is small, the resolution may not be improved in some cases, and if the blending amount is too large, the film thickness of the pattern may decrease and the resolution tends to decrease.

Examples of such a dissolution inhibitor of the component (D) which is preferably used are bis (4- (2'-tetrahydropyranyloxy) phenyl) methane and bis (4-
(2'-tetrahydrofuranyloxy) phenyl) methane, bis (4-tert-butoxyphenyl) methane,
Bis (4-tert-butoxycarbonyloxyphenyl) methane, bis (4-tert-butoxycarbonylmethyloxyphenyl) methane, bis (4- (1′-ethoxyethoxy) phenyl) methane, bis (4- (1 ′)
-Ethoxypropyloxy) phenyl) methane, 2,2
-Bis (4 '-(2''-tetrahydropyranyloxy)) propane, 2,2-bis (4'-(2 ''-tetrahydrofuranyloxy) phenyl) propane, 2,2
-Bis (4'-tert-butoxyphenyl) propane, 2,2-bis (4'-tert-butoxycarbonyloxyphenyl) propane, 2,2-bis (4-te
rt-Butoxycarbonylmethyloxyphenyl) propane, 2,2-bis (4 ′-(1 ″ -ethoxyethoxy) phenyl) propane, 2,2-bis (4′-
(1 ″ -Ethoxypropyloxy) phenyl) propane, 4,4-bis (4 ′-(2 ″ -tetrahydropyranyloxy) phenyl) tert-butylvalerate, 4,4
-Bis (4 '-(2''-tetrahydrofuranyloxy) phenyl) valerate tert-butyl, 4,4-bis (4'-tert-butoxyphenyl) valerate tert
Butyl, tert-butyl 4,4-bis (4-tert-butoxycarbonyloxyphenyl) valerate, 4,4-
Bis (4′-tert-butoxycarbonylmethyloxyphenyl) valerate tert-butyl, 4,4-bis (4 ′-(1 ″ -ethoxyethoxy) phenyl) valerate tert-butyl, 4,4-bis (4 ′) Tert-butyl- (1 ''-ethoxypropyloxy) phenyl) valerate, tris (4- (2'-tetrahydropyranyloxy) phenyl) methane, tris (4- (2'-tetrahydrofuranyloxy) phenyl) methane, Tris (4-
tert-butoxyphenyl) methane, tris (4-t
ert-butoxycarbonyloxyphenyl) methane,
Tris (4-tert-butoxycarbonyloxymethylphenyl) methane, tris (4- (1′-ethoxyethoxy) phenyl) methane, tris (4- (1′-ethoxypropyloxy) phenyl) methane, 1,1,2 −
Tris (4 ′-(2 ″ -tetrahydropyranyloxy) phenyl) ethane, 1,1,2-tris (4′-
(2 ″ -tetrahydrofuranyloxy) phenyl) ethane, 1,1,2-tris (4′-tert-butoxyphenyl) ethane, 1,1,2-tris (4′-ter
t-butoxycarbonyloxyphenyl) ethane, 1,
1,2-tris (4′-tert-butoxycarbonylmethyloxyphenyl) ethane, 1,1,2-tris (4 ′-(1′-ethoxyethoxy) phenyl) ethane, 1,1,2-tris (4 Examples include '-(1'-ethoxypropyloxy) phenyl) ethane and the like.

As the basic compound as the component (E), a compound which can suppress the diffusion rate when the acid generated from the photo-acid generator diffuses in the resist film is suitable. With the combination of, the acid diffusion rate in the resist film is suppressed and the resolution is improved, the sensitivity change after exposure is suppressed, the dependency on the substrate and the environment is reduced, and the exposure margin and pattern profile are improved. can do.

Examples of the basic compound as the component (E) include primary, secondary and tertiary aliphatic amines, mixed amines, aromatic amines, heterocyclic amines and carboxy groups. And a nitrogen-containing compound having a sulfonyl group, a nitrogen-containing compound having a hydroxy group, a nitrogen-containing compound having a hydroxyphenyl group, an alcoholic nitrogen-containing compound, an amide derivative, an imide derivative and the like.

Specifically, as the primary aliphatic amines, ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, ter.
t-butylamine, pentylamine, tert-amylamine, cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine,
Nonylamine, decylamine, dodecylamine, cetylamine, methylenediamine, ethylenediamine, tetraethylenepentamine, etc. are exemplified, and secondary aliphatic amines include 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 are exemplified, and as tertiary aliphatic amines, trimethylamine, triethylamine, tri-n-propylamine, 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, 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 -Melaniline, 4-methylaniline,
Ethylaniline, propylaniline, trimethylaniline, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2,4-dinitroaniline, 2,6-dinitroaniline, 3,5-dinitroaniline, N, N-
Dimethyltoluidine), diphenyl (p-tolyl) amine, methyldiphenylamine, triphenylamine,
Phenylenediamine, naphthylamine, diaminonaphthalene, pyrrole derivative (for example, pyrrole, 2H-pyrrole, 1-methylpyrrole, 2,4-dimethylpyrrole, 2,5-dimethylpyrrole, N-methylpyrrole, etc.), oxazole derivative (for example, Oxazole, isoxazole etc.), thiazole derivative (eg thiazole, isothiazole etc.), imidazole derivative (eg imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole etc.), pyrazole derivative, furazan derivative, pyrroline derivative (Eg, pyrroline, 2-methyl-1-pyrroline, etc.), pyrrolidine derivative (eg, pyrrolidine, N-methylpyrrolidine, pyrrolidinone, N-methylpyrrolidone, etc.), imidazoline derivative, imidazolidine derivative Body, pyridine derivatives (for example,
Pyridine, methylpyridine, ethylpyridine, propylpyridine, butylpyridine, 4- (1-butylpentyl) pyridine, dimethylpyridine, trimethylpyridine, triethylpyridine, phenylpyridine, 3-methyl-2-phenylpyridine, 4-tert-butyl. Pyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine,
1-methyl-2-pyridine, 4-pyrrolidinopyridine,
1-methyl-4-phenylpyridine, 2- (1-ethylpropyl) pyridine, aminopyridine, dimethylaminopyridine, etc.), pyridazine derivative, pyrimidine derivative,
Pyrazine derivative, pyrazoline derivative, pyrazolidine derivative, piperidine derivative, piperazine derivative, morpholine derivative, indole derivative, isoindole derivative, 1
H-indazole derivative, indoline derivative, quinoline derivative (eg, quinoline, 3-quinolinecarbonitrile, etc.), isoquinoline derivative, cinnoline derivative, quinazoline derivative, quinoxaline derivative, phthalazine derivative, purine derivative, pteridine derivative, carbazole derivative, phenanthridine Derivative, acridine derivative, phenazine derivative, 1,10-phenanthroline derivative,
Adenine derivative, adenosine derivative, guanine derivative,
Examples include guanosine derivatives, uracil derivatives, uridine derivatives and the like.

Further, examples of the nitrogen-containing compound having a carboxyl group include aminobenzoic acid, indolecarboxylic acid, amino acid derivatives (eg, nicotinic acid, alanine, arginine, aspartic acid, glutamic acid, glycine, histidine, isoleucine, glycyl. Leucine,
Leucine, methionine, phenylalanine, threonine, lysine, 3-aminopyrazine-2-carboxylic acid, methoxyalanine, etc.) are exemplified, and as the nitrogen-containing compound having a sulfonyl group, 3-pyridinesulfonic acid, p
-Pyridinium toluenesulfonate and the like are exemplified, and as the nitrogen-containing compound having a hydroxy group, the nitrogen-containing compound having a hydroxyphenyl group, and the alcoholic nitrogen-containing compound, 2-hydroxypyridine, aminocresol,
2,4-quinoline diol, 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, piperidine ethanol, 1- (2-hydroxyethyl) pyrrolidine, 1- (2-hydroxyethyl) -2-
Pyrrolidinone, 3-piperidino-1,2-propanediol, 3-pyrrolidino-1,2-propanediol, 8
-Hydroxyjulolidine, 3-cuinclidinol, 3
-Tropanol, 1-methyl-2-pyrrolidine ethanol, 1-aziridine ethanol, N- (2-hydroxyethyl) phthalimide, N- (2-hydroxyethyl)
Isonicotinamide and the like are exemplified. As the amide derivative, formamide, N-methylformamide, N, N
-Dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide and the like are exemplified. Examples of the imide derivative include phthalimide, succinimide, and maleimide.

Further, one kind or two or more kinds selected from the basic compounds represented by the following general formula (B) -1 can be added. N (X) _n (Y) _3-n (B) -1 In the formula, n = 1, 2 or 3. The side chains X may be the same or different and can be represented by the following general formulas (X) -1 to (X) -3. The side chain Y represents the same or different hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and may contain an ether group or a hydroxyl group. In addition, Xs may combine with each other to form a ring.

[0092]

[Chemical formula 22]

Here, R ³⁰⁰ , R ³⁰² and R ³⁰⁵ have 1 carbon atom.
4 is a linear or branched alkylene group,
R ³⁰¹ and R ³⁰⁴ are a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and may contain one or more hydroxy group, ether group, ester group, lactone ring. .

R ³⁰³ is a single bond or a linear or branched alkylene group having 1 to 4 carbon atoms, and R ³⁰⁶ is 1 carbon atom.
20 straight chain, branched or cyclic alkyl groups,
It may contain one or more hydroxy groups, ether groups, ester groups, and lactone rings.

Specific examples of the compound represented by the above general formula (B) -1 are shown below. Tris (2-
Methoxymethoxyethyl) amine, tris {2- (2-
Methoxyethoxy) ethyl} amine, tris {2- (2
-Methoxyethoxymethoxy) ethyl} amine, tris {2- (1-methoxyethoxy) ethyl} amine, tris {2- (1-ethoxyethoxy) ethyl} amine, tris {2- (1-ethoxypropoxy) ethyl} amine , Tris [2- {2- (2-hydroxyethoxy) ethoxy} ethyl] amine, 4,7,13,16,21,
24-hexaoxa-1,10-diazabicyclo [8.
8.8] Hexacosane, 4,7,13,18-Tetraoxa-1,10-diazabicyclo [8.5.5] eicosane, 1,4,10,13-Tetraoxa-7,16-
Diazabicyclooctadecane, 1-aza-12-crown-4, 1-aza-15-crown-5, 1-aza-1
8-crown-6, tris (2-formyloxyethyl) amine, tris (2-formyloxyethyl) amine, tris (2-acetoxyethyl) amine, tris (2-propionyloxyethyl) amine, tris (2
-Butyryloxyethyl) amine, tris (2-isobutyryloxyethyl) amine, tris (2-valeryloxyethyl) amine, tris (2-pivaloyloxyxyethyl) amine, N, N-bis (2 -Acetoxyethyl) 2- (acetoxyacetoxy) ethylamine, tris (2-methoxycarbonyloxyethyl) amine, tris (2-tert-butoxycarbonyloxyethyl) amine, tris [2- (2-oxopropoxy) ethyl] amine, Tris [2- (methoxycarbonylmethyl) oxyethyl] amine, tris [2- (tert-
Butoxycarbonylmethyloxy) ethyl] amine, tris [2- (cyclohexyloxycarbonylmethyloxy) ethyl] amine, tris (2-methoxycarbonylethyl) amine, tris (2-ethoxycarbonylethyl) amine, N, N-bis ( 2-hydroxyethyl)
2- (methoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (methoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2- (ethoxycarbonyl) ethylamine, N, N
-Bis (2-acetoxyethyl) 2- (ethoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2- (2-methoxyethoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2 −
(2-methoxyethoxycarbonyl) ethylamine,
N, N-bis (2-hydroxyethyl) 2- (2-hydroxyethoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (2-acetoxyethoxycarbonyl) ethylamine, N, N-bis ( 2-hydroxyethyl) 2-[(methoxycarbonyl) methoxycarbonyl] ethylamine, N, N-bis (2-acetoxyethyl) 2-[(methoxycarbonyl) methoxycarbonyl] ethylamine, N, N-bis (2-hydroxyethyl) ) 2- (2-oxopropoxycarbonyl)
Ethylamine, N, N-bis (2-acetoxyethyl)
2- (2-oxopropoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2- (tetrahydrofurfuryloxycarbonyl) ethylamine,
N, N-bis (2-acetoxyethyl) 2- (tetrahydrofurfuryloxycarbonyl) ethylamine, N,
N-bis (2-hydroxyethyl) 2-[(2-oxotetrahydrofuran-3-yl) oxycarbonyl] ethylamine, N, N-bis (2-acetoxyethyl) 2
-[(2-oxotetrahydrofuran-3-yl) oxycarbonyl] ethylamine, N, N-bis (2-hydroxyethyl) 2- (4-hydroxybutoxycarbonyl) ethylamine, N, N-bis (2-formyloxyethyl) ) 2- (4-formyloxybutoxycarbonyl) ethylamine, N, N-bis (2-formyloxyethyl) 2- (2-formyloxyethoxycarbonyl) ethylamine, N, N-bis (2-methoxyethyl) 2- (Methoxycarbonyl) ethylamine, N-
(2-hydroxyethyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (2-acetoxyethyl)
Bis [2- (methoxycarbonyl) ethyl] amine, N
-(2-hydroxyethyl) bis [2- (ethoxycarbonyl) ethyl] amine, N- (2-acetoxyethyl) bis [2- (ethoxycarbonyl) ethyl] amine, N- (3-hydroxy-1-propyl) Screw [2-
(Methoxycarbonyl) ethyl] amine, N- (3-acetoxy-1-propyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (2-methoxyethyl) bis [2- (methoxycarbonyl) ethyl] amine , N-
Butylbis [2- (methoxycarbonyl) ethyl] amine, N-butylbis [2- (2-methoxyethoxycarbonyl) ethyl] amine, N-methylbis (2-acetoxyethyl) amine, N-ethylbis (2-acetoxyethyl) amine , N-methylbis (2-pivaloyloxyxyethyl) amine, N-ethylbis [2- (methoxycarbonyloxy) ethyl] amine, N-ethylbis [2- (tert-butoxycarbonyloxy) ethyl] amine, tris (methoxy Carbonylmethyl) amine, tris (ethoxycarbonylmethyl) amine, N-
Butylbis (methoxycarbonylmethyl) amine, N-
Hexylbis (methoxycarbonylmethyl) amine, β
Examples thereof include, but are not limited to,-(diethylamino) -δ-valerolactone.

Furthermore, one or more basic compounds having a cyclic structure represented by the following general formula (B) -2 can be added.

[Chemical formula 23] (In the formula, X is as described above, R ³⁰⁷ is a linear or branched alkylene group having 2 to 20 carbon atoms, a carbonyl group,
It may contain one or more ether groups, ester groups and sulfides. )

The above formula (B) -2 is specifically 1- [2
-(Methoxymethoxy) ethyl] pyrrolidine, 1- [2
-(Methoxymethoxy) ethyl] piperidine, 4- [2
-(Methoxymethoxy) ethyl] morpholine, 1- [2
-[(2-methoxyethoxy) methoxy] ethyl] pyrrolidine, 1- [2-[(2-methoxyethoxy) methoxy] ethyl] piperidine, 4- [2-[(2-methoxyethoxy) methoxy] ethyl] morpholine, Acetic acid 2-
(1-pyrrolidinyl) ethyl, 2-piperidinoethyl acetate, 2-morpholinoethyl acetate, 2- (1-pyrrolidinyl) ethyl formate, 2-piperidinoethyl propionate,
Acetoxyacetic acid 2-morpholinoethyl, methoxyacetic acid 2
-(1-Pyrrolidinyl) ethyl, 4- [2- (methoxycarbonyloxy) ethyl] morpholine, 1- [2-
(T-Butoxycarbonyloxy) ethyl] piperidine, 4- [2- (2-methoxyethoxycarbonyloxy) ethyl] morpholine, methyl 3- (1-pyrrolidinyl) propionate, methyl 3-piperidinopropionate, 3- Methyl morpholino propionate, methyl 3- (thiomorpholino) propionate, 2-methyl-3- (1
-Methyl pyrrolidinyl) propionate, ethyl 3-morpholinopropionate, methoxycarbonylmethyl 3-piperidinopropionate, 2-hydroxyethyl 3- (1-pyrrolidinyl) propionate, 2-acetoxyethyl 3-morpholinopropionate, 3 -(1-Pyrrolidinyl) propionic acid 2-oxotetrahydrofuran-3-
Yl, tetrahydrofurfuryl 3-morpholinopropionate, glycidyl 3-piperidinopropionate, 2-methoxyethyl 3-morpholinopropionate, 3- (1-
2- (2-methoxyethoxy) ethyl pyrrolidinyl) propionate, butyl 3-morpholinopropionate, 3-
Cyclohexyl piperidinopropionate, α- (1-pyrrolidinyl) methyl-γ-butyrolactone, β-piperidino-γ-butyrolactone, β-morpholino-δ-valerolactone, methyl 1-pyrrolidinyl acetate, methyl piperidinoacetate, methyl morpholinoacetate , Methyl thiomorpholino acetate, ethyl 1-pyrrolidinyl acetate, and 2-methoxyethyl morpholino acetate.

Further, a basic compound containing a cyano group represented by the general formulas (B) -3 to (B) -6 can be added.

[Chemical formula 24] (In the formula, X, R ³⁰⁷ , and n are as described above, and R ³⁰⁸ and R ³⁰⁹ are the same or different and are linear or branched alkylene groups having 1 to 4 carbon atoms.)

The base containing a cyano group is specifically 3-
(Diethylamino) propiononitrile, N, N-bis (2-hydroxyethyl) -3-aminopropiononitrile, N, N-bis (2-acetoxyethyl) -3-aminopropiononitrile, N, N-bis (2-formyloxyethyl) -3-aminopropiononitrile, N,
N-bis (2-methoxyethyl) -3-aminopropiononitrile, N, N-bis [2- (methoxymethoxy)
Ethyl] -3-aminopropiononitrile, N- (2-
Cyanoethyl) -N- (2-methoxyethyl) -3-methylaminopropionate, N- (2-cyanoethyl)-
Methyl N- (2-hydroxyethyl) -3-aminopropionate, N- (2-acetoxyethyl) -N- (2-
Methyl cyanoethyl) -3-aminopropionate, N-
(2-Cyanoethyl) -N-ethyl-3-aminopropiononitrile, N- (2-cyanoethyl) -N- (2-
Hydroxyethyl) -3-aminopropiononitrile,
N- (2-acetoxyethyl) -N- (2-cyanoethyl) -3-aminopropiononitrile, N- (2-cyanoethyl) -N- (2-formyloxyethyl) -3-
Aminopropiononitrile, N- (2-cyanoethyl)
-N- (2-methoxyethyl) -3-aminopropiononitrile, N- (2-cyanoethyl) -N- [2- (methoxymethoxy) ethyl] -3-aminopropiononitrile, N- (2-cyanoethyl) ) -N- (3-Hydroxy-1-propyl) -3-aminopropiononitrile,
N- (3-acetoxy-1-propyl) -N- (2-cyanoethyl) -3-aminopropiononitrile, N-
(2-Cyanoethyl) -N- (3-formyloxy-1
-Propyl) -3-aminopropiononitrile, N-
(2-Cyanoethyl) -N-tetrahydrofurfuryl-
3-aminopropiononitrile, N, N-bis (2-cyanoethyl) -3-aminopropiononitrile, diethylaminoacetonitrile, N, N-bis (2-hydroxyethyl) aminoacetonitrile, N, N-bis (2-
Acetoxyethyl) aminoacetonitrile, N, N-bis (2-formyloxyethyl) aminoacetonitrile, N, N-bis (2-methoxyethyl) aminoacetonitrile, N, N-bis [2- (methoxymethoxy) ethyl] amino Acetonitrile, N-cyanomethyl-N-
Methyl (2-methoxyethyl) -3-aminopropionate, N-cyanomethyl-N- (2-hydroxyethyl)
Methyl-3-aminopropionate, N- (2-acetoxyethyl) -N-cyanomethyl-3-aminopropionate methyl, N-cyanomethyl-N- (2-hydroxyethyl) aminoacetonitrile, N- (2-acetoxyethyl) ) -N- (cyanomethyl) aminoacetonitrile,
N-cyanomethyl-N- (2-formyloxyethyl)
Aminoacetonitrile, N-cyanomethyl-N- (2-
Methoxyethyl) aminoacetonitrile, N-cyanomethyl-N- [2- (methoxymethoxy) ethyl] aminoacetonitrile, N- (cyanomethyl) -N- (3-hydroxy-1-propyl) aminoacetonitrile, N-
(3-acetoxy-1-propyl) -N- (cyanomethyl) aminoacetonitrile, N-cyanomethyl-N-
(3-formyloxy-1-propyl) aminoacetonitrile, N, N-bis (cyanomethyl) aminoacetonitrile, 1-pyrrolidinepropiononitrile, 1-piperidinepropiononitrile, 4-morpholinepropiononitrile, 1-pyrrolidineacetonitrile, 1-piperidine acetonitrile, 4-morpholine acetonitrile,
Cyanomethyl 3-diethylaminopropionate, N, N
-Bis (2-hydroxyethyl) -3-aminopropionate cyanomethyl, N, N-bis (2-acetoxyethyl) -3-aminopropionate cyanomethyl, N, N-
Bis (2-formyloxyethyl) -3-aminopropionate cyanomethyl, N, N-bis (2-methoxyethyl) -3-aminopropionate cyanomethyl, N, N-
Bis [2- (methoxymethoxy) ethyl] -3-aminopropionic acid cyanomethyl, 3-diethylaminopropionic acid (2-cyanoethyl), N, N-bis (2-hydroxyethyl) -3-aminopropionic acid (2-cyanoethyl) ), N, N-bis (2-acetoxyethyl) -3
-Aminopropionic acid (2-cyanoethyl), N, N-
Bis (2-formyloxyethyl) -3-aminopropionic acid (2-cyanoethyl), N, N-bis (2-methoxyethyl) -3-aminopropionic acid (2-cyanoethyl), N, N-bis [2 -(Methoxymethoxy) ethyl] -3-aminopropionic acid (2-cyanoethyl),
1-Pyrrolidine propionate cyanomethyl, 1-piperidine propionate cyanomethyl, 4-morpholine cyanomethyl propionate, 1-pyrrolidine propionate (2
-Cyanoethyl), 1-piperidinepropionic acid (2-
Examples are cyanoethyl) and 4-morpholinepropionic acid (2-cyanoethyl).

The amount of the basic compound is 0.001 to 2 parts, especially 0.01 to 2 parts, based on 100 parts of the total base resin.
1 part is preferred. If the blending amount is less than 0.001 part, the blending effect may not be obtained, and if it exceeds 2 parts, the sensitivity may be lowered too much.

A surfactant for improving coatability can be further added to the chemically amplified positive resist composition of the present invention.

Examples of the surfactant include, but are not limited to, polyoxyethylene alkyls such as polyoxyethylene lauryl ether, polyoxyethylene sterial ether, polyoxyethylene cetyl ether and polyoxyethylene olein ether. Ethers, polyoxyethylene octylphenol ether,
Polyoxyethylene alkyl allylic ethers such as polyoxyethylene nonylphenol ether, polyoxyethylene polyoxypropylene block copolymers,
Sorbitan monolaurate, sorbitan monopalmitate, sorbitan fatty acid esters such as sorbitan monostearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate,
Nonionic surfactants of polyoxyethylene sorbitan fatty acid ester such as polyoxyethylene sorbitan trioleate and polyoxyethylene sorbitan tristearate, Ftop EF301, EF303, EF35
2 (Tochem Products), Megafac F171, F
172, F173 (Dainippon Ink and Chemicals), Florard FC430, FC431 (Sumitomo 3M), Asahi Guard AG710, Surflon S-381, S-38
2, SC101, SC102, SC103, SC10
4, SC105, SC106, Surfynol E100
4, KH-10, KH-20, KH-30, KH-40
(Asahi Glass) and other fluorine-containing surfactants, organosiloxane polymer KP341, X-70-092, X-70-
093 (Shin-Etsu Chemical Co., Ltd.), acrylic acid-based or methacrylic acid-based Polyflow No. 75, No. 95 (Kyoeisha Yushi Kagaku Kogyo), among them FC430, Surflon S
-381, Surfynol E1004, KH-20, K
H-30 is preferred. These can be used alone or in combination of two or more.

The addition amount of the surfactant in the chemically amplified positive resist composition of the present invention is 2 parts by weight or less, preferably 1 part by weight or less, relative to 100 parts by weight of the base resin in the resist material composition. .

Various chemically amplified positive resist compositions containing the organic solvent (A) of the present invention, the polymer compound (B) represented by the general formula (2), and the acid generator (C) are manufactured into various integrated circuits. When it is used for, the known lithography technique can be used, although not particularly limited thereto.

Substrates for manufacturing integrated circuits (Si, SiO ₂ ,
SiN, SiON, TiN, WSi, BPSG, SO
G, organic antireflection film, various LowK materials, etc.), mask pattern manufacturing substrate (Cr, CrN, CrO, CrON,
MoSi, SiO ₂ etc.) spin coating, roll coating, flow coating, dip coating, spray coating,
It is applied by a suitable coating method such as doctor coating or nozzle scanning so that the coating film thickness is 0.1 to 2.0 μm, and is 60 to 150 ° C. on a hot plate for 1 to 10 minutes, preferably 80 to 120 ° C. Pre-bake for 1-5 minutes. Then, the desired pattern is exposed through a predetermined mask with a light source selected from ultraviolet rays, far ultraviolet rays, vacuum ultraviolet rays, electron beams, X-rays, excimer lasers, γ rays, synchrotron radiation, etc., preferably with an exposure wavelength of 300 nm or less. To do. The exposure amount is about 1 to 200 mJ / cm ² ,
It is preferable that the exposure is performed at a dose of preferably about 1 to 100 mJ / cm ² . 60-18 on hot plate
0 ° C, 10 seconds to 5 minutes, preferably 80 to 150 ° C, 3
Post exposure bake (PEB) for 0 seconds to 3 minutes.

Further, 0.1 to 5%, preferably 1 to 3%
Using a developer of an aqueous alkaline solution such as tetramethylammonium hydroxide (TMAH) for 10 seconds to 3 minutes, preferably 20 seconds to 2 minutes, dipping method, paddle method, spray method, etc. Then, the target pattern is formed on the substrate by developing in the usual manner. In addition, the resist material of the present invention is particularly suitable for deep ultraviolet rays of 254 to 193 nm among high energy rays, and
It is most suitable for fine patterning by vacuum ultraviolet ray of 57 nm, electron beam, soft X-ray, X-ray, excimer laser, γ-ray and synchrotron radiation. If the above range falls outside the upper and lower limits, the desired pattern may not be obtained.

[0107]

The resist material using the polymer compound of the present invention has a significantly high alkali dissolution rate contrast before and after exposure, has high sensitivity and high resolution, and exhibits particularly excellent etching resistance. In particular, it is possible to provide a resist material such as a chemically amplified resist material which is suitable as a fine pattern forming material for manufacturing a VLSI.

[0108]

EXAMPLES The present invention will be specifically described below with reference to synthesis examples, comparative synthesis examples, examples and comparative examples, but the present invention is not limited to the following examples.

[Synthesis Example 1] t-butyl terminal propionate
Synthesis of p-hydroxystyrene polymer Tetrahydrofuran 1,0 as a solvent in a 1 L flask
00 mL, sec-butyllithium 0.0 as an initiator
1 mol was charged. To this mixed solution, 173 g of p-trimethylsiloxystyrene was added at -78 ° C, and polymerization was carried out while stirring for 30 minutes. The reaction solution turned red.
A polymerization termination reaction was performed by adding 0.1 mol of t-butyl 3-bromopropionate to the reaction solution. Then, in order to purify the polymer, the reaction mixture was poured into methanol, and the obtained polymer was precipitated, separated, and dried to obtain 164 g of a white polymer. Furthermore, p
-To give a hydroxystyrene polymer, 164 g of the above polymer are dissolved in 1,000 mL of acetone, 20
After adding a small amount of concentrated hydrochloric acid at 0 ° C. and stirring for 7 hours, the mixture was poured into water to precipitate the polymer, which was washed and dried to obtain 92 g of a polymer. In addition, analysis by GPC, ¹ H-N
No peak derived from trimethylsilyl group was observed in MR, p of Mw11,000, Mw / Mn1.03
-Hydroxystyrene polymer was confirmed.

[Synthesis Example 2] Synthesis of terminal methyl propionate-cyclopentyl p-hydroxystyrene polymer In a 1 L flask, tetrahydrofuran 1,0 was used as a solvent.
00 mL, sec-butyllithium 0.0 as an initiator
1 mol was charged. To this mixed solution, 173 g of p-trimethylsiloxystyrene was added at -78 ° C, and polymerization was carried out while stirring for 30 minutes. The reaction solution turned red.
A polymerization termination reaction was carried out by adding 0.1 mol of methylcyclopentyl 3-bromopropionate to the reaction solution.
Then, in order to purify the polymer, the reaction mixture was poured into methanol, and the obtained polymer was precipitated, separated, and dried to obtain 164 g of a white polymer. Further, in order to obtain a p-hydroxystyrene polymer, 164 g of the above polymer was dissolved in 1,000 mL of acetone, a small amount of concentrated hydrochloric acid was added at 20 ° C., and the mixture was stirred for 7 hours.
When it was poured into water to precipitate the polymer, which was washed and dried, 92 g of the polymer was obtained. In addition, no peak derived from a trimethylsilyl group was observed by GPC analysis or ¹ H-NMR, Mw 11,000, Mw / M
It was confirmed to be a p-hydroxystyrene polymer having n1.03.

[Synthesis Example 3] Terminal methyl-2 propionate
Synthesis of adamantane p-hydroxystyrene polymer Tetrahydrofuran 1,0 as a solvent in a 1 L flask
00 mL, sec-butyllithium 0.0 as an initiator
1 mol was charged. To this mixed solution, 173 g of p-trimethylsiloxystyrene was added at -78 ° C, and polymerization was carried out while stirring for 30 minutes. The reaction solution turned red.
A polymerization termination reaction was carried out by adding 0.1 mol of methyl-2-adamantane 3-bromopropionate to the reaction solution. Then, in order to purify the polymer, the reaction mixture was poured into methanol, and the obtained polymer was precipitated, separated, and dried to obtain 168 g of a white polymer. Further, to obtain a p-hydroxystyrene polymer, 168 g of the above polymer was added to 1,000 mL of acetone.
Was dissolved in water, a small amount of concentrated hydrochloric acid was added at 20 ° C., the mixture was stirred for 7 hours, poured into water to precipitate the polymer, which was washed and dried to obtain 94 g of a polymer. Further, no peak derived from a trimethylsilyl group was observed by GPC analysis or ¹ H-NMR, Mw 11,000, Mw /
It was confirmed to be a p-hydroxystyrene polymer having Mn of 1.03.

[Synthesis Example 4] Synthesis of terminal t-butoxycarbonyl norbornene p-hydroxystyrene polymer Tetrahydrofuran 1,0 was used as a solvent in a 1 L flask.
00 mL, sec-butyllithium 0.0 as an initiator
1 mol was charged. To this mixed solution, 173 g of p-trimethylsiloxystyrene was added at -78 ° C, and polymerization was carried out while stirring for 30 minutes. The reaction solution turned red.
The polymerization termination reaction was carried out by adding 0.1 mol of 2-t-butoxycarbonyl-5-bromonorbornene to the reaction solution. Then, in order to purify the polymer, the reaction mixture was poured into methanol to precipitate the resulting polymer,
When separated and dried, 168 g of a white polymer was obtained. Further, in order to obtain a p-hydroxystyrene polymer, 168 g of the above polymer was added to 1,000 m of acetone.
It was dissolved in L, a small amount of concentrated hydrochloric acid was added at 20 ° C., the mixture was stirred for 7 hours, poured into water to precipitate the polymer, which was washed and dried to obtain 94 g of a polymer. Further, no peak derived from a trimethylsilyl group was observed by GPC analysis or ¹ H-NMR, Mw 11,000, Mw /
It was confirmed to be a p-hydroxystyrene polymer having Mn of 1.03.

[Synthesis Example 5] Terminal t-butyl phenylacetate-
Synthesis of p-hydroxystyrene polymer Tetrahydrofuran 1,0 as a solvent in a 1 L flask
00 mL, sec-butyllithium 0.0 as an initiator
1 mol was charged. To this mixed solution, 173 g of p-trimethylsiloxystyrene was added at -78 ° C, and polymerization was carried out while stirring for 30 minutes. The reaction solution turned red.
The polymerization termination reaction was performed by adding 0.1 mol of t-butyl 3-bromophenylacetate to the reaction solution. Then, in order to purify the polymer, the reaction mixture was poured into methanol, and the obtained polymer was precipitated, separated, and dried to obtain 171 g of a white polymer. Furthermore, p
-To give the hydroxystyrene polymer, 171 g of the above polymer are dissolved in 1,000 ml of acetone,
After adding a small amount of concentrated hydrochloric acid at 0 ° C. and stirring for 7 hours, the mixture was poured into water to precipitate the polymer, which was washed and dried to obtain 94 g of a polymer. In addition, analysis by GPC, ¹ H-N
No peak derived from trimethylsilyl group was observed in MR, p of Mw11,000, Mw / Mn1.03
-Hydroxystyrene polymer was confirmed.

[Synthesis Example 6] Synthesis of t-butyl-terminal ethylmalonate-p-hydroxystyrene polymer Tetrahydrofuran 1,0 was used as a solvent in a 1 L flask.
00 mL, sec-butyllithium 0.0 as an initiator
1 mol was charged. To this mixed solution, 173 g of p-trimethylsiloxystyrene was added at -78 ° C, and polymerization was carried out while stirring for 30 minutes. The reaction solution turned red.
A polymerization termination reaction was carried out by adding 0.1 mol of t-butyl 2-bromoethylmalonate to the reaction solution. Then, in order to purify the polymer, the reaction mixture was poured into methanol, and the obtained polymer was precipitated, separated, and dried to obtain 174 g of a white polymer. Furthermore, p
-To obtain a hydroxystyrene polymer, 174 g of the above polymer is dissolved in 1,000 mL of acetone, 20
After adding a small amount of concentrated hydrochloric acid at 0 ° C. and stirring for 7 hours, the mixture was poured into water to precipitate a polymer, which was washed and dried to obtain 102 g of a polymer. In addition, analysis by GPC, ¹ H-
It was confirmed by NMR that no peak derived from a trimethylsilyl group was observed, and that it was a p-hydroxystyrene polymer having Mw 11,000 and Mw / Mn 1.03.

[Synthesis Example 7] Terminal 2-t-butoxycarbonyl-2-t-butoxycarbonylmethylnorbornene-p
Synthesis of Hydroxystyrene Polymer Tetrahydrofuran 1,0 as a solvent in a 1 L flask
00 mL, sec-butyllithium 0.0 as an initiator
1 mol was charged. To this mixed solution, 173 g of p-trimethylsiloxystyrene was added at -78 ° C, and polymerization was carried out while stirring for 30 minutes. The reaction solution turned red.
A polymerization termination reaction was performed by adding 0.1 mol of 2-t-butoxycarbonyl-2-t-butoxycarbonylmethyl-5-bromonorbornene to the reaction solution. Then, in order to purify the polymer, the reaction mixture was poured into methanol, and the obtained polymer was precipitated, separated, and dried to obtain 178 g of a white polymer. Furthermore, p
-To give a hydroxystyrene polymer, 178 g of the above polymer are dissolved in 1,000 mL of acetone, 20
After adding a small amount of concentrated hydrochloric acid at 0 ° C. and stirring for 7 hours, the mixture was poured into water to precipitate the polymer, which was washed and dried to obtain 109 g of a polymer. In addition, analysis by GPC, ¹ H-
It was confirmed by NMR that no peak derived from a trimethylsilyl group was observed, and that it was a p-hydroxystyrene polymer having Mw 11,000 and Mw / Mn 1.03.

[Synthesis Example 8] t-butyl terminal propionate
Ethoxyethylation of p-hydroxystyrene polymer t-butyl terminal propionate obtained in Synthesis Example 1 10 g of p-hydroxystyrene polymer was dissolved in 100 mL of tetrahydrofuran, and a catalytic amount of methanesulfonic acid was added, followed by stirring at 20 ° C. While adding 3 g of ethyl vinyl ether. After reacting for 1 hour, the mixture was neutralized with concentrated aqueous ammonia, and the neutralization reaction solution was added dropwise to 5 L of water to obtain a white solid. After filtering this, acetone 10
It was dissolved in 0 mL, added dropwise to 5 L of water, filtered, and vacuum dried. The polymer obtained was identified by ¹ H-NMR for the substitution ratio of the ethoxyethyl group of polyhydroxystyrene,
Polymer 1 was used.

[Synthesis Example 9] Terminal t-butyl propionate
ethoxyethylation of p-hydroxystyrene polymer,
Butanediol divinyl ether crosslinking 10 g of t-butyl terminal propionate p-hydroxystyrene polymer obtained in Synthesis Example 1 was dissolved in 100 mL of tetrahydrofuran, a catalytic amount of methanesulfonic acid was added, and then ethyl vinyl ether 2 was stirred at 20 ° C. 0.5 g, butanediol divinyl ether 0.75 g
Was added. After reacting for 1 hour, the mixture was neutralized with concentrated aqueous ammonia, and the neutralization reaction solution was added dropwise to 5 L of water to obtain a white solid. After filtering this, 100 mL of acetone
Dissolved in water, added dropwise to 5 L of water, filtered, and vacuum dried.
The polymer obtained was identified as Polymer 2 by identifying the substitution rate of the ethoxyethyl group of polyhydroxystyrene from ¹ H-NMR.

[Synthesis Example 10] t-BOC conversion of t-butyl p-hydroxystyrene polymer with terminal t-propionate at the terminal t-butyl t-propionate terminal p-hydroxystyrene polymer obtained in Synthesis Example 2 was added to 200 mL of pyridine.
And di-tert dicarbonate with stirring at 45 ° C.
-Butyl 11.6 g was added. After reacting for 1 hour,
When the reaction solution was added dropwise to 3 L of water, a white solid was obtained. This was filtered, dissolved in 100 mL of acetone, added dropwise to 5 L of water, filtered, and vacuum dried to obtain a polymer. The t-BOC conversion rate of the hydrogen atom of the hydroxyl group of polyhydroxystyrene was identified from ¹ H-NMR, and it was designated as Polymer 3.

[Synthesis Example 11] Terminal methyl propionate-
Cyclopentyl p-hydroxystyrene polymer t
-BOC-ized 20 g of terminal methyl propionate-cyclopentyl p-hydroxystyrene polymer obtained in Synthesis Example 2 was dissolved in 200 mL of pyridine, and 11.6 g of di-tert-butyl dicarbonate was added with stirring at 45 ° C. After reacting for 1 hour, the reaction solution was added dropwise to 3 L of water to obtain a white solid. This was filtered, dissolved in 100 mL of acetone, added dropwise to 5 L of water, filtered, and vacuum dried to obtain a polymer. The t-BOC conversion rate of the hydrogen atom of the hydroxyl group of polyhydroxystyrene was identified from ¹ H-NMR, and it was designated as Polymer 4.

[Synthesis Example 12] Terminal methyl propionate-
T-BOC Conversion of 2-Adamantane p-Hydroxystyrene Polymer 20 g of the terminal methyl-2-adamantane propionate p-hydroxystyrene polymer obtained in Synthesis Example 3 was dissolved in 200 mL of pyridine, and dicarbonic acid dicarbonate was stirred at 45 ° C. 11.6 g of -tert-butyl were added. After reacting for 1 hour, the reaction solution was added dropwise to 3 L of water to obtain a white solid. After filtering this, 100 mL of acetone
Dissolved in water, added dropwise to 5 L of water, filtered, and vacuum dried,
A polymer was obtained. The t-BOC conversion ratio of the hydrogen atom of the hydroxyl group of polyhydroxystyrene was identified from ¹ H-NMR, and polymer 5 was obtained.

[Synthesis Example 13] t-terminal t-butoxycarbonylnorbornene p-hydroxystyrene polymer t-
20 g of terminal t-butoxycarbonylnorbornene p-hydroxystyrene polymer obtained in BOC-modified Synthesis Example 4 was dissolved in 200 mL of pyridine, and 11.6 g of di-tert-butyl dicarbonate was added with stirring at 45 ° C. After reacting for 1 hour, the reaction solution was added dropwise to 3 L of water to obtain a white solid. This was filtered, dissolved in 100 mL of acetone, added dropwise to 5 L of water, filtered, and vacuum dried to obtain a polymer. The t-BOC conversion ratio of the hydrogen atom of the hydroxyl group of polyhydroxystyrene was identified from ¹ H-NMR, and the polymer 6 was obtained.

[Synthesis Example 14] t-BOC conversion of t-butylphenyl-acetate-p-hydroxystyrene polymer having a terminal terminal t-butylphenyl-p-hydroxystyrene polymer having a t-butylacetate terminal obtained in Synthesis Example 5 was added to 200 mL of pyridine.
And di-tert dicarbonate with stirring at 45 ° C.
-Butyl 11.6 g was added. After reacting for 1 hour,
When the reaction solution was added dropwise to 3 L of water, a white solid was obtained. This was filtered, dissolved in 100 mL of acetone, added dropwise to 5 L of water, filtered, and vacuum dried to obtain a polymer. The t-BOC conversion ratio of the hydrogen atom of the hydroxyl group of polyhydroxystyrene was identified from ¹ H-NMR, and it was designated as Polymer 7.

[Synthesis Example 15] t-BOC conversion of t-butyl-ethyl ethylmalonate-p-hydroxystyrene polymer at the terminal t-butyl-terminal ethylmalonate-p-obtained in Synthesis Example 6
Hydroxystyrene polymer 20g to pyridine 200m
Dissolve in L and stir at 45 ° C with di-tercarbonate.
11.6 g of t-butyl was added. After reacting for 1 hour, the reaction solution was added dropwise to 3 L of water to obtain a white solid. After filtering this, it is dissolved in 100 mL of acetone,
The mixture was added dropwise to 5 L of water, filtered, and vacuum dried to obtain a polymer. The t-BOC conversion rate of the hydrogen atom of the hydroxyl group of polyhydroxystyrene was identified from ¹ H-NMR, and polymer 8 was obtained.

[Synthesis Example 16] Terminal 2-t-butoxycarbonyl-2-t-butoxycarbonylmethylnorbornene-
t-BOC conversion of p-hydroxystyrene polymer Terminal 2-t-butoxycarbonyl-2 obtained in Synthesis Example 7
20 g of -t-butoxycarbonylmethylnorbornene-p-hydroxystyrene polymer was dissolved in 200 mL of pyridine, and di-tert-dicarbonate was stirred at 45 ° C.
11.6 g of butyl was added. After reacting for 1 hour, the reaction solution was added dropwise to 3 L of water to obtain a white solid.
After filtering this, dissolve it in 100 mL of acetone and add 5 L of water.
Was dropped, filtered and then vacuum dried to obtain a polymer. ¹
The t-BOC conversion ratio of the hydrogen atom of the hydroxyl group of polyhydroxystyrene was identified from 1 H-NMR, and the polymer 9 was obtained.

[Comparative Synthesis Example 1] Synthesis of terminal methoxy p-hydroxystyrene polymer Tetrahydrofuran 1,0 was used as a solvent in a 1 L flask.
00 mL, sec-butyllithium 0.0 as an initiator
1 mol was charged. To this mixed solution, 173 g of p-trimethylsiloxystyrene was added at -78 ° C, and polymerization was carried out while stirring for 30 minutes. The reaction solution turned red.
0.1 mol of methanol in the reaction solution as a polymerization termination reaction
Was added. Then, to purify the polymer,
The reaction mixture was poured into methanol to precipitate the obtained polymer, which was then separated and dried to obtain 164 g of a white polymer. Further, in order to obtain a p-hydroxystyrene polymer, 164 g of the above polymer was dissolved in 1,000 mL of acetone, a small amount of concentrated hydrochloric acid was added at 20 ° C., the mixture was stirred for 7 hours, and then poured into water to precipitate the polymer, which was washed and washed. When dried, 92 g of polymer was obtained. Moreover, no peak derived from a trimethylsilyl group was observed by GPC analysis or ¹ H-NMR, Mw11,
It was confirmed that the polymer was a p-hydroxystyrene polymer having a Mw / Mn of 1.03.

[Comparative Synthesis Example 2] Synthesis of terminal phenyl p-hydroxystyrene polymer A 1 L flask was charged with 1,000 mL of tetrahydrofuran as a solvent and 0.01 mol of sec-butyllithium as an initiator. To this mixed solution, 173 g of p-trimethylsiloxystyrene was added at -78 ° C, and polymerization was carried out while stirring for 30 minutes.
The reaction solution turned red. The polymerization termination reaction was carried out by adding 0.1 mol of bromobenzene to the reaction solution.
Then, in order to purify the polymer, the reaction mixture was poured into methanol, and the obtained polymer was precipitated, separated, and dried to obtain 164 g of a white polymer. Further, in order to obtain a p-hydroxystyrene polymer, 164 g of the above polymer was dissolved in 1,000 mL of acetone, a small amount of concentrated hydrochloric acid was added at 20 ° C., and the mixture was stirred for 7 hours.
When it was poured into water to precipitate the polymer, which was washed and dried, 92 g of the polymer was obtained. In addition, no peak derived from a trimethylsilyl group was observed by GPC analysis or ¹ H-NMR, Mw 11,000, Mw / M
It was confirmed to be a p-hydroxystyrene polymer having n1.01.

[Comparative Synthesis Example 3] Terminal carboxyl group p
Synthesis of Hydroxystyrene Polymer Tetrahydrofuran 1,0 as a solvent in a 1 L flask
00 mL, sec-butyllithium 0.0 as an initiator
1 mol was charged. To this mixed solution, 173 g of p-trimethylsiloxystyrene was added at -78 ° C, and polymerization was carried out while stirring for 30 minutes. The reaction solution turned red.
A polymerization termination reaction was performed by adding 0.1 mol of tetrahydropyranyl 3-bromopropionate to the reaction solution.
Then, in order to purify the polymer, the reaction mixture was poured into methanol, and the obtained polymer was precipitated, separated, and dried to obtain 164 g of a white polymer. Further, in order to obtain a p-hydroxystyrene polymer, 164 g of the above polymer was dissolved in 1,000 mL of acetone, and a small amount of concentrated hydrochloric acid was added at 20 ° C. to eliminate the trimethylsilyl group and the tetrahydropyranyl group at the terminal, and then for 7 hours. After stirring, the mixture was poured into water to precipitate a polymer, which was washed and dried to obtain 92 g of a polymer. Also, GP
It was confirmed by C analysis and ¹ H-NMR that no peak derived from the trimethylsilyl group and the terminal tetrahydropyranyl group was observed, and that the polymer was a p-hydroxystyrene polymer having Mw of 11,000 and Mw / Mn of 1.01.

[Comparative Synthesis Example 4] t-BOC conversion of terminal methoxy group-p-hydroxystyrene polymer 20 g of terminal methoxy group-p-hydroxystyrene polymer obtained in Comparative Synthesis Example 1 was dissolved in 200 mL of pyridine, and 45 ° C. 11.6 g of di-tert-butyl dicarbonate was added with stirring. After reacting for 1 hour, 3 L of water
When the reaction solution was added dropwise to, a white solid was obtained. This was filtered, dissolved in 100 mL of acetone, added dropwise to 5 L of water, filtered, and vacuum dried to obtain a polymer. ¹ H-
The t-BOC conversion rate of the hydrogen atom of the hydroxyl group of polyhydroxystyrene was identified by NMR, and it was set as the comparative polymer 1.

[Comparative Synthesis Example 5] t-BOC conversion of terminal phenyl group-p-hydroxystyrene polymer 20 g of terminal phenyl group-p-hydroxystyrene polymer obtained in Comparative Synthesis Example 2 was dissolved in 200 mL of pyridine, and the mixture was heated at 45 ° C. 11.6 g of di-tert-butyl dicarbonate was added with stirring. After reacting for 1 hour, 3 L of water
When the reaction solution was added dropwise to, a white solid was obtained. This was filtered, dissolved in 100 mL of acetone, added dropwise to 5 L of water, filtered, and vacuum dried to obtain a polymer. ¹ H-
The t-BOC conversion rate of the hydrogen atom of the hydroxyl group of polyhydroxystyrene was identified by NMR, and it was set as the comparative polymer 2.

[Comparative Synthesis Example 6] Terminal carboxyl group -p
-T-BOC conversion of hydroxystyrene polymer 20 g of terminal carboxyl group-p-hydroxystyrene polymer obtained in Comparative Synthesis Example 3 was dissolved in 200 mL of pyridine, and dicarbonic acid di-tert- was stirred at 45 ° C.
11.6 g of butyl was added. After reacting for 1 hour, the reaction solution was added dropwise to 3 L of water to obtain a white solid.
After filtering this, dissolve it in 100 mL of acetone and add 5 L of water.
Was dropped, filtered and then vacuum dried to obtain a polymer. ¹
The t-BOC conversion rate of the hydrogen atom of the hydroxyl group of polyhydroxystyrene was identified from 1 H-NMR, and it was designated as Comparative Polymer 3.

[0131]

[Chemical 25]

[0132]

[Chemical formula 26]

[0133]

[Chemical 27]

[Examples and Comparative Examples] Exposure Patterning Evaluation Using the polymers obtained in the above-mentioned Synthesis Examples and Comparative Synthesis Examples,
A resist material having the composition shown in Table 1 was prepared, and the exposure patterning was evaluated by the following method. The results are shown in Table 1. A solution having the composition shown in Table 1 was filtered through a 0.2 μm size filter to prepare a resist solution. A resist solution was spin-coated on a substrate in which DUV-30 (manufactured by Nissan Chemical Industries, Ltd.) was formed into a film having a film thickness of 55 nm on a silicon wafer, and baked at 120 ° C. for 90 seconds using a hot plate to make the resist thickness 300 nm. . This is an excimer laser stepper (Nikon NSR-S202
A, NA-0.6, σ 0.75, 2/3 ring illumination), and immediately after the exposure, bake at 130 ° C. for 90 seconds, and then with a 2.38% tetramethylammonium hydroxide aqueous solution. Development was performed for a second to obtain a positive type pattern.

The obtained resist pattern was evaluated as follows. Evaluation method: 0.18 μm line and space 1:
The exposure amount resolved in 1 was taken as the sensitivity of the resist, and the minimum line width of the line and space separated at this exposure amount was taken as the resolution of the evaluation resist.

[0136]

[Table 1] PGMEA: Propylene glycol monomethyl ether acetate

[0137]

[Chemical 28]

It was found that the resist material of the present invention to which a polymer having an acid labile group at the end is added has high sensitivity and high resolution and is a promising material for achieving further fine processing.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Osamu Watanabe             28-1 Nishifukushima, Kubiki Village, Nakakubiki District, Niigata Prefecture             Shin-Etsu Chemical Co., Ltd.Research on new functional materials technology             In-house (72) Inventor Takanobu Takeda             28-1 Nishifukushima, Kubiki Village, Nakakubiki District, Niigata Prefecture             Shin-Etsu Chemical Co., Ltd.Research on new functional materials technology             In-house F term (reference) 2H025 AA03 AA09 AB16 AC04 AC08                       AD03 BE00 BE10 BG00 CB08                       CB17 CB41 CB43 CC03 CC20                       FA01 FA12 FA17                 4J100 AB07P BA02H BA03H BA06H                       BA15H BA20H BA22H BA76P                       BC03H BC08H BC43H CA01                       CA04 DA39 FA02 FA03 FA08                       HA08 HC08 JA38

Claims (9)

[Claims] 1. A polymer compound having a terminal structure represented by the following general formula (1). [Chemical 1] (In the formula, R ¹ is a single bond, or a straight chain having 1 to 10 carbon atoms,
It is a group selected from branched and cyclic alkylene groups, bridged cyclic alkylene groups and arylene groups having 6 to 10 carbon atoms, and R ² is an acid labile group. ) 2. The polymer compound according to claim 1, which has a repeating unit n represented by the following general formula (2) and a terminal structure. [Chemical 2] (In the formula, R ¹ and R ² are as described above, R ³ is a hydrogen atom or an acid labile group. R ⁴ is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. R ⁵ is a hydrogen atom or a methyl group, R ⁶ is an aromatic ring having 6 to 20 carbon atoms, and m of the hydrogen atoms are substituted with OR ^3. Z is a single bond or (p + 1). ) A valent aliphatic or aromatic hydrocarbon group which may contain a carbonyl group, an ester group or an ether group, m is an integer of 1 to 3, and p
Is 1 or 2. ) 3. The polymer compound according to claim 2, wherein the aromatic ring represented by R ⁶ in the general formula (2) is a benzene ring, a naphthalene ring or an anthracene ring. 4. The polymer compound according to claim 2, wherein the polymer compound represented by the general formula (2) is synthesized by anionic polymerization. 5. A resist material comprising the polymer compound according to any one of claims 1 to 4. 6. A polymer compound according to claim 1, which comprises (A) an organic solvent and (B) a base resin,
(C) A chemically amplified positive resist composition containing an acid generator. 7. A polymer compound according to claim 1, which comprises (A) an organic solvent and (B) a base resin,
A chemically amplified positive resist composition containing (C) an acid generator and (D) a dissolution inhibitor. 8. The chemically amplified positive resist composition according to claim 6, further comprising a basic compound as an additive (E). 9. A step of applying the resist material according to any one of claims 5 to 8 onto a substrate, and after heat treatment,
A pattern forming method comprising: a step of exposing with a high-energy beam or an electron beam through a photomask; and a step of performing a heat treatment as needed and then developing with a developing solution.