JP2001281849A - Positive type resist composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive type resist composition having enhanced resolving power and improved process admissibility such as an improved margin for exposure and an improved depth of a focus in lithography using a short- wavelength light source for exposure capable of ultramicro-fabrication and a positive type chemical amplification type resist. SOLUTION: The positive type resist composition contains a resin having a group which is decomposed by the action of an acid and increases solubility in an alkali developing solution and a compound which generates an aliphatic or aromatic carboxylic acid substituted by at least one fluorine atom when irradiated with active light or radiation ray.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a lithographic printing plate or an IC.
The present invention relates to a positive photosensitive composition used in a semiconductor manufacturing process such as the above, a circuit substrate such as a liquid crystal and a thermal head, and other photofabrication processes.

[0002]

2. Description of the Related Art Semiconductor manufacturing processes for lithographic printing plates and ICs,
Liquid crystal, the manufacture of circuit boards such as thermal heads, as well as other photosensitive compositions used in the photofabrication process, there are various compositions, generally a photoresist photosensitive composition is used, it is Broadly speaking, there are two types: positive and negative. As one of the positive photoresist photosensitive compositions, there is a chemically amplified resist composition described in US Pat. No. 4,491,628, European Patent 249,139 and the like. Chemically amplified positive resist compositions are
Irradiation with radiation such as deep ultraviolet light generates an acid in the exposed area, and a reaction using this acid as a catalyst changes the solubility of the active radiation-irradiated area and the non-irradiated area in the developing solution to form a pattern on the substrate. It is a pattern forming material to be made.

Examples of such a combination include a combination of a compound capable of generating an acid by photolysis with an acetal or an O, N-acetal compound (Japanese Patent Application Laid-Open No. 48-89003), a combination of an orthoester or an amide acetal compound ( Combination with a polymer having an acetal or ketal group in the main chain (JP-A-53-172014).
3429), a combination with an enol ether compound (JP-A-55-12995), a combination with an N-acyliminocarbonate compound (JP-A-55-126236),
Combination with a polymer having an orthoester group in the main chain (JP-A-56-17345), combination with a tertiary alkyl ester compound (JP-A-60-3625), combination with a silyl ester compound (JP-A-60-3625) Showa 60-10247
No.) and a combination with a silyl ether compound (Japanese Unexamined Patent Publication No.
0-37549, JP-A-60-112446) and the like. These have high photosensitivity because the quantum yield exceeds 1 in principle.

Similarly, systems which are stable under aging at room temperature, but are decomposed by heating in the presence of an acid and solubilized in alkali are disclosed in, for example, JP-A-59-45439, JP-A-60-3625, JP-A-62-2229242, JP-A-63-27829, JP-A-63-36240, JP-A-63-250542, Polym.Eng.Sce., Vol. 23, 101
2 (1983); ACS.Sym. 242, 11 (1984); Semicond
uctor World 1987, November, p. 91; Macromolecules, 2
Vol. 1, p. 1475 (1988); SPIE, vol. 920, p. 42 (1988);
Combination systems with esters or carbonate compounds of primary or secondary carbons (eg t-butyl, 2-cyclohexenyl). Since these systems also have high sensitivity and low absorption in the far ultraviolet region, they can be effective systems for shortening the light source wavelength capable of ultrafine processing.

The positive chemically amplified resist comprises an alkali-soluble resin, a compound which generates an acid upon exposure to radiation (photoacid generator), and a compound having an acid-decomposable group and inhibiting the dissolution of the alkali-soluble resin. It can be roughly classified into a two-component system comprising a component system, a resin having a group which is decomposed by the reaction with an acid and becomes alkali-soluble, and a photoacid generator. These two
In a three-component or three-component positive chemically amplified resist, the acid from the photoacid generator is interposed by exposure,
After the heat treatment, development is performed to obtain a resist pattern.

As described above, these positive-type chemically amplified resists can be effective systems for shortening the wavelength of a light source capable of ultra-fine processing. However, such resists further improve resolution, exposure margin and depth of focus. There is a need for improved process tolerance. JP-A-6-242606 describes a basic sulfonium compound as a photoacid generator, and JP-A-7-333844 describes a basic iodonium compound as a photoacid generator. Also, Japanese Unexamined Patent Application Publication No.
-125907 describes the use of a compound that generates a carboxylic acid and a compound that generates an acid other than the carboxylic acid as the photoacid generator.

[0007]

However, even the above-mentioned technology cannot sufficiently cope with the current fine processing, and there is room for improvement in the improvement of the resolution and the process tolerance such as the exposure margin and the depth of focus. . An object of the present invention is a lithography technique using a short wavelength exposure light source capable of ultrafine processing and a positive chemically amplified resist,
It is an object of the present invention to provide a positive resist composition having improved resolving power and improved process tolerance such as an exposure margin and a depth of focus.

[0008]

According to the present invention, a positive resist composition having the following constitution is provided to achieve the above object of the present invention. (1) (A) a resin having a group which is decomposed by the action of an acid and increases the solubility in an alkali developing solution, and (B)
A positive resist composition comprising a compound that generates an aliphatic or aromatic carboxylic acid substituted with at least one fluorine atom upon irradiation with actinic rays or radiation. (2) The positive resist composition as described in (1) above, further comprising (D) a compound having a molecular weight of 3000 or less, which is decomposed by the action of an acid and increases the solubility in an alkali developer.

(3) (B) a compound which generates an aliphatic or aromatic carboxylic acid substituted by at least one fluorine atom upon irradiation with actinic rays or radiation;
(D) a compound having a molecular weight of 3000 or less, which is decomposed by the action of an acid to increase solubility in an alkali developing solution, and (E)
A positive resist composition comprising an alkali-soluble resin. (4) The positive resist composition according to any one of (1) to (3), further comprising (C) a compound that generates a sulfonic acid upon irradiation with actinic rays or radiation.

(5) The positive type according to any one of claims 1 to 4, further comprising (F) a nitrogen-containing basic compound, and (G) a fluorine-based or silicon-based surfactant. Resist composition. (6) (B) a compound capable of generating an aliphatic or aromatic carboxylic acid substituted by at least one fluorine atom upon irradiation with actinic rays or radiation, which is selected from any of the following formulas (I) to (III): The positive resist composition according to any one of the above (1) to (5), which is a compound having a structure represented by the following formula:

[0011]

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(In the above formula, R ₁ To R ₃₇ are each independently
Hydrogen atom, straight chain, branched or cyclic alkyl group, straight chain,
Represents a branched or cyclic alkoxy group, a hydroxy group, a halogen atom, or a —S—R ₃₈ group. Here, R ₃₈ represents a linear, branched, or cyclic alkyl group or an aryl group. X
^- is an anion of at least one aliphatic or aromatic carboxylic acid substituted with a fluorine atom. (7) The positive resist composition as described in (6) above, wherein X ⁻ is an anion of a perfluoroaliphatic carboxylic acid or a perfluoroaromatic carboxylic acid. (8) The positive resist composition according to (6), wherein X ⁻ is an anion of a fluorine-substituted alkyl carboxylic acid having 4 or more carbon atoms. (9) (A) a resin having a group that is decomposed by the action of an acid and increases the solubility in an alkali developer is a resin containing a repeating structural unit represented by the following general formulas (IV) and (V): The positive resist composition according to any one of the above (1), (2) and (4) to (8).

[0013]

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(In the above general formula (IV), L is a hydrogen atom,
It represents a linear, branched or cyclic alkyl group which may be substituted, or an aralkyl group which may be substituted. Z represents a linear, branched or cyclic alkyl group which may be substituted, or an aralkyl group which may be substituted. Further, Z and L may combine to form a 5- or 6-membered ring. (10) The positive resist composition as described in (9) above, wherein Z in the general formula (IV) is a substituted alkyl group or a substituted aralkyl group. (11) The above (1) to (1), further comprising (B ′) a compound that generates a carboxylic acid not substituted by a fluorine atom upon irradiation with actinic rays or radiation.
0) The positive resist composition according to any one of the above.

As described above, JP-A-11-125907 describes the use of a compound that generates a carboxylic acid and a compound that generates an acid other than the carboxylic acid as the photoacid generator. Since the generated carboxylic acid compound is a carboxylic acid and a weak acid, it does not directly contribute to the decomposition of the acid-decomposable group. Therefore, when this carboxylic acid-generating compound is used alone as a photoacid generator, there is a serious problem that an image cannot be formed or the sensitivity is significantly reduced. That is, the carboxylic acid generating compound cannot be used alone, and it is necessary to use a photoacid generator that generates a strong acid. In the present invention, this problem has been successfully solved, and a carboxylic acid-generating compound can be used alone by introducing a specific substituent, and a resist composition having excellent performance has been found. Further, in the present invention, excellent performance can be exhibited even with an electron beam as an energy beam for exposure. When exposing with an electron beam, the incident electrons have electric charges and interact with the nuclei and electrons of the substances that make up the resist. There was a problem of deterioration. In addition, even if exposure is performed with a reduced beam diameter in order to resolve a fine pattern, there is a problem in that the exposure area is enlarged due to the scattering and the resolution is deteriorated. The composition of the present invention successfully solved these problems caused by electron beam exposure.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention provides: (A) a resin having a group which is decomposed by the action of an acid to increase the solubility in an alkali developer, and (B) an aliphatic or aromatic substituted with at least one fluorine atom by irradiation with actinic rays or radiation. 1. a positive resist composition (hereinafter also referred to as a “first composition”) containing a compound that generates a group carboxylic acid as an essential component; (B) a compound that generates an aliphatic or aromatic carboxylic acid substituted with at least one fluorine atom upon irradiation with actinic rays or radiation, (D) decomposes by the action of an acid, and is soluble in an alkali developing solution. And (E) a positive resist composition containing an alkali-soluble resin as an essential component (hereinafter, also referred to as a “second composition”). Hereinafter, the term “positive resist composition” or “composition” refers to the first resist composition.
It includes both a composition and a second composition.

First, components such as a compound and a resin contained in the positive photosensitive composition will be described in detail.

[Explanation of each component contained in the composition] [1] (B) A compound which generates an aliphatic or aromatic carboxylic acid substituted by at least one fluorine atom upon irradiation with actinic rays or radiation. (Component (B)) The positive resist composition of the present invention contains the component (B) as an essential component. As the fluorine-substituted aliphatic carboxylic acid of the component (B), acetic acid, propionic acid, n-
Fatty acids such as butyric acid, isobutyric acid, valeric acid, trimethylacetic acid, caproic acid, heptanoic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, undecanoic acid, dodecanoic acid, and tridecanoic acid And fluorinated carboxylic acids. These may have a hydroxyl group, an alkoxy group, or a halogen atom as a substituent. Further, it is preferable that the aliphatic chain contains a linking group such as an oxygen atom, a sulfur atom, a carbonyl group, a carboxyl group, and a sulfonyl group.
Preferred examples of the fluorine-substituted aliphatic carboxylic acid include those represented by the following general formula. _{L- (CH 2) p (CF} 2) q (CH 2) r-COOH general formula, L is a hydrogen atom or a fluorine atom. p and r each independently represent an integer of 0 to 15, and q represents an integer of 1 to 15. In the general formula, a hydrogen atom or a fluorine atom of the alkyl chain is an alkyl group (preferably having 1 to 5 carbon atoms) which may be substituted by a fluorine atom, or an alkoxy group (preferably carbon atom) which may be substituted by a fluorine atom. Number 1
To 5) or may be substituted with a hydroxyl group. The fluorine-substituted aliphatic carboxylic acid is preferably a fluorine-substituted saturated aliphatic carboxylic acid having preferably 2 to 20, more preferably 4 to 20 carbon atoms. By setting the number of carbon atoms to 4 or more, the diffusibility of the generated carboxylic acid decomposability is reduced, and the line width change due to aging from exposure to post-heating can be further suppressed. Above all,
Preferred are fluorine-substituted linear or branched saturated aliphatic carboxylic acids having 4 to 18 carbon atoms.

The fluorine-substituted aromatic carboxylic acid as the component (B) is preferably an aromatic carboxylic acid having 7 to 20, more preferably 7 to 15, and still more preferably 7 to 11 carbon atoms. It is preferably a fluorine-substituted acid. Specifically, benzoic acid, substituted benzoic acid, naphthoic acid, substituted naphthoic acid, anthracene carboxylic acid, substituted anthracene carboxylic acid (where the substituent is an alkyl group, an alkoxy group, a hydroxyl group, a halogen atom, an aryl group, an acyl group Groups, acyloxy groups, nitro groups, alkylthio groups, and arylthio groups). Above all, benzoic acid and fluorine-substituted substituted benzoic acid are preferred.

These aliphatic or aromatic carboxylic acids substituted with a fluorine atom are those in which one or more of the hydrogen atoms present in the skeleton other than the carboxyl group have been substituted with a fluorine atom, and particularly preferably a carboxyl group. Other aliphatic carboxylic acids (perfluorosaturated aliphatic carboxylic acids or perfluoroaromatic carboxylic acids) in which all of the hydrogen atoms present in the skeleton other than those are substituted with fluorine atoms. Thereby, the sensitivity is further improved.

The preferred component (B) is an onium salt compound (sulfonium salt, iodonium salt, etc.) having an anion of an aliphatic or aromatic carboxylic acid substituted by a fluorine atom as a counter anion as described above, carboxylic acid Examples include an imidocarboxylate compound having an ester group or a nitrobenzyl ester compound. As the component (B), more preferably, compounds represented by the above general formulas (I) to (III) are exemplified. Thereby, the sensitivity, the resolving power, and the exposure margin are further improved. By irradiating this compound with actinic rays or radiation, a saturated aliphatic or aromatic carboxylic acid substituted with at least one fluorine atom corresponding to X ⁻ in formulas (I) to (III) is generated, Functions as a photoacid generator.

In general formulas (I) to (III), R _{1 to} R
The straight-chain or branched alkyl group of ₃₈ may have a substituent and has 1 carbon atom such as methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group and t-butyl group.
To four. As the cyclic alkyl group,
What has a C3-C8 group which may have a substituent, such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group, is mentioned. As the alkoxy group for R _{1 to} R ₃₇ ,
Methoxy, ethoxy, hydroxyethoxy, propoxy, n-butoxy, isobutoxy, sec-
Those having 1 to 4 carbon atoms such as a butoxy group and a t-butoxy group are exemplified. Examples of the halogen atom for R _{1 to} R ₃₇ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. _Examples of the aryl group represented by R38 include those having 6 to 14 carbon atoms such as a phenyl group, a tolyl group, a methoxyphenyl group, and a naphthyl group. The aryl group may have a substituent. Preferably as these substituents,
C 1-4 alkoxy group, halogen atom (fluorine atom, chlorine atom, iodine atom), C 6-10 aryl group, C 2-6 alkenyl group, cyano group, hydroxy group, carboxy Group, alkoxycarbonyl group,
And a nitro group.

The general formulas (I) to (II) used in the present invention
The iodonium compound or sulfonium compound represented by I) has at least 1 as a counter anion X ^−.
It has an anion of a saturated aliphatic or aromatic carboxylic acid substituted with two fluorine atoms. These anions are anions (—COO ⁻ ) from which a hydrogen atom of the carboxylic acid (—COOH) has been eliminated.

Hereinafter, specific examples of the component (B) (photoacid generator) will be shown, but the present invention is not limited thereto. Specific examples of the photoacid generator represented by the general formula (I) (I-
1) to (I to 36):

[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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Specific examples (II-1) to (II-67) of the photoacid generator represented by the general formula (II):

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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Specific examples (III-1) to (III-4) of the photoacid generator represented by the general formula (III):

[0040]

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Specific examples of other photoacid generators (IV-1)
(V-4):

[0042]

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The compounds of the above (B) may be used alone or
More than one species can be used in combination.

The compound represented by the general formula (I), which is the above-mentioned component (B), is obtained by reacting an aromatic compound with a periodate and converting the obtained iodonium salt into a corresponding carboxylic acid. Can be synthesized. General formula (I
I), the compound represented by the general formula (III) is obtained, for example, by reacting an aryl Grignard reagent such as arylmagnesium bromide with a substituted or unsubstituted phenyl sulfoxide, and converting the obtained triaryl sulfonium halide with a corresponding carboxylic acid. It can be synthesized by salt exchange. Also,
A method in which substituted or unsubstituted phenyl sulfoxide and the corresponding aromatic compound are condensed and salt-exchanged using an acid catalyst such as methanesulfonic acid / diphosphorus pentoxide or aluminum chloride, and a diaryliodonium salt and a diarylsulfide are converted to copper acetate or the like. It can be synthesized by a method such as condensation and salt exchange using a catalyst. The salt exchange can be carried out by converting the salt into a halide salt and then converting the salt into a carboxylate using a silver reagent such as silver oxide, or by using an ion exchange resin. The carboxylic acid or carboxylate used for the salt exchange may be a commercially available one, or may be obtained by hydrolysis of a commercially available carboxylic acid halide.

The fluorine-substituted carboxylic acid as the anion part of the component (B) is obtained from a fluoroaliphatic compound produced by a telomerization method (also called a telomer method) or an oligomerization method (also called an oligomer method). It is also preferable to use one derived. Regarding the method for producing these fluoroaliphatic compounds, see, for example, one of “Synthesis and Function of Fluorine Compounds” (supervised by Nobuo Ishikawa, published by CMC Corporation, 1987).
Pages 17-118 and "Chemistry of OrganicFluori
ne Compounds II "(Monograph 187, Ed by Milos Hud
licky and Attila E. Pavlath, American Chemical Socie
ty 1995), pages 747-752.
The telomerization method is a method of synthesizing a telomer by radically polymerizing a fluorine-containing vinyl compound such as tetrafluoroethylene using an alkyl halide having a large chain transfer constant such as iodide as a telogen (Scheme-1).
Examples are shown in In the synthesis by the telomer method, a mixture of a plurality of compounds having different carbon chain lengths is obtained. The mixture may be used as it is or may be used after purification.

[0046]

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The terminal iodinated telomer obtained is usually
For example, an appropriate terminal chemical modification such as [Scheme 2] is performed, and the compound is led to a fluoroaliphatic compound. These compounds are further converted to a desired structure as necessary, and are used for producing a fluoroaliphatic group-containing compound.

[0048]

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The content of the compound (B) in the positive resist composition of the present invention is based on the solid content of the composition.
0.1-20% by weight is preferred, more preferably 0.5%
10 to 10% by weight, more preferably 1 to 7% by weight.

[2] Photoacid generator which may be used in combination with component (B) (component (C)) A photoacid generator other than component (B) is used in combination with the positive resist composition of the present invention. can do. Known photoacid generators that can be used in combination include photoinitiators for photocationic polymerization, photoinitiators for photoradical polymerization, photodecolorants for dyes, photochromic agents, and microresists. (Ultraviolet light of 400 to 200 nm, far ultraviolet light, particularly preferably g-ray, h-ray, i-ray, KrF excimer laser light), ArF excimer laser light, electron beam, X-ray,
A compound that generates an acid by a molecular beam or an ion beam and a mixture thereof can be appropriately selected and used.

Other photoacid generators that can be used in combination include, for example, onium salts such as diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenonium salts and arsonium salts, organic halogen compounds, and organic metal compounds. Organic halides, photoacid generators having an o-nitrobenzyl-type protecting group, compounds that generate sulfonic acid upon photolysis represented by iminosulfonate, disulfone compounds, diazoketosulfones, diazodisulfone compounds, etc. be able to. In addition, a group in which an acid is generated by these lights or a compound in which a compound is introduced into a main chain or a side chain of a polymer can be used in combination.

Further, VNRPillai, Synthesis, (1), 1 (198
0), A. Abad etal, Tetrahedron Lett., (47) 4555 (1971),
The compounds described in DHR Barton et al., J. Chem. Soc., (C), 329 (1970), U.S. Pat. No. 3,779,778, and EP 126,712, which can generate an acid by light can also be used in combination. Among the compounds capable of decomposing upon irradiation with actinic rays or radiation to generate an acid, particularly effective compounds include the following general formula (PAG3), general formula (PAG4), general formula (PAG6) or general formula (PAG6). PAG7).

[0053]

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In the general formulas (PAG3) and (PAG4), A
r ¹ and Ar ² are the same or different and represent a substituted or unsubstituted aryl group. Preferred substituents include an alkyl group, a haloalkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a nitro group, a carboxyl group, an alkoxycarbonyl group, a hydroxy group, a mercapto group, and a halogen atom. R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ are
The same or different, substituted or unsubstituted alkyl group,
Indicates an aryl group. Preferably, it is an aryl group having 6 to 14 carbon atoms, an alkyl group having 1 to 8 carbon atoms, or a substituted derivative thereof. Preferred substituents are an alkoxy group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms, a nitro group, a carboxyl group, a hydroxy group and a halogen atom for the aryl group, and a substituent for the alkyl group. Carbon number 1
To 8 alkoxy groups, carboxyl groups, and alkoxycarbonyl groups.

[0055] Z ^- represents a counter anion, for example BF ₄ ^{-,
_{AsF 6 -, PF 6 -,}} SbF 6 -, SiF 6 2-, ClO 4 -,
Alkanesulfonic acid which may be substituted, perfluoroalkanesulfonic acid, benzenesulfonic acid which may be substituted, naphthalenesulfonic acid, anthracenesulfonic acid,
Examples include but are not limited to camphor sulfonic acid. Preferred are alkanesulfonic acid, perfluoroalkanesulfonic acid, alkyl-substituted benzenesulfonic acid, and pentafluorobenzenesulfonic acid. Two of R ²⁰³ , R ²⁰⁴ , and R ²⁰⁵ and Ar ¹ , Ar ²
May be bonded via each single bond or a substituent.

In the general formulas (PAG6) and (PAG7), R
²⁰⁶ represents a substituted or unsubstituted alkyl group or aryl group. A represents a substituted or unsubstituted alkylene group, alkenylene group, or arylene group. R represents a linear, branched or cyclic alkyl group, or an optionally substituted aryl group. Specific examples thereof include the following compounds, but are not limited thereto.

[0057]

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[0058]

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[0059]

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In the present invention, among the photoacid generators used in combination, (C) a compound capable of generating a sulfonic acid upon irradiation with actinic rays or radiation is preferred from the viewpoint of excellent sensitivity and resolution. Further, the positive resist composition of the present invention comprises, as the component (B ′), a compound that generates a carboxylic acid upon irradiation with actinic rays or radiation other than the component (B) (hereinafter, particularly referred to as “component (B ′)”). (Also referred to as). Thereby, the density dependency is improved. Examples of such a component (B ′) include compounds in which X ⁻ is an anion of a saturated aliphatic carboxylic acid or aromatic carboxylic acid that is not substituted with a fluorine atom in the general formulas (I) to (III). . Specific examples thereof include those in which the fluorine atom in the anion portion is replaced with a hydrogen atom in the specific example of the component (B).

In the composition of the present invention, the photoacid generator used in combination with the above formula (PAG-3) or (PAG-
4), those represented by the formula (PAG-7) and the component (B ') are preferred. The component (C) or the component (B ′) which can be used in combination is used in an amount of 5% by weight or less based on the solid content in the positive resist composition.
Preferably, it is used in a range of 4% by weight or less.

[3] (A) Resin having a group that decomposes under the action of an acid to increase solubility in an alkali developer (component (A)) The component (A) is used in the first composition of the present invention. Used as an essential component. Component (A) is a resin having a group that decomposes with an acid and increases solubility in an alkali developer (also referred to as a group that can be decomposed with an acid), such as a main chain or a side chain of the resin,
Alternatively, it is a resin having an acid-decomposable group in both the main chain and the side chain. Among them, a resin having a group which can be decomposed by an acid in a side chain is more preferable. Preferred groups that can be decomposed by an acid are —COOA ⁰ and —O—B ⁰ groups, and further containing these groups include —R ⁰ —COOA ⁰ and —Ar
Include groups represented by -O-B ^0. Where A ⁰ is −
C ( ^R01 ) ( ^R02 ) ( ^R03 ), -Si ( ^R01 ) ( ^R02 )
Shows the (R ^{0 3)} or ^{-C (R 04) (R 05} ) -O-R 06 group. B ⁰ indicates the A ⁰ or -CO-O-A ⁰ group (R ^0, R ⁰¹ ~R ⁰⁶ and Ar are same as those described later).

The acid-decomposable group is preferably a silyl ether group, a cumyl ester group, an acetal group, a tetrahydropyranyl ether group, an enol ether group, an enol ester group, a tertiary alkyl ether group, or a tertiary alkyl ester. And tertiary alkyl carbonate groups. More preferred are a tertiary alkyl ester group, a tertiary alkyl carbonate group, a cumyl ester group, an acetal group, and a tetrahydropyranyl ether group. Particularly preferred is an acetal group.

Next, when the group decomposable by these acids is bonded as a side chain, the base resin has -OH or -COOH, preferably -R ⁰ -COOH or -Ar-OH group in the side chain. It is an alkali-soluble resin. For example, an alkali-soluble resin described below can be used.

The alkali dissolution rate of these alkali-soluble resins was measured with a 0.261N tetramethylammonium hydroxide (TMAH) (at 23 ° C.) and measured at 170 ° C.
A / sec or more is preferable. Particularly preferably 330A
Per second or more (where A is Angstroms). From the viewpoint of achieving a rectangular profile, an alkali-soluble resin having a high transmittance to far ultraviolet light or excimer laser light is preferable. Preferably, a 1 μm film thickness of 24
The transmittance at 8 nm is 20 to 90%. From such a viewpoint, particularly preferred alkali-soluble resins are o-, m
-, P-poly (hydroxystyrene) and copolymers thereof, hydrogenated poly (hydroxystyrene), halogen or alkyl-substituted poly (hydroxystyrene), part of poly (hydroxystyrene), O-alkylated or O- An acylated product, a styrene-hydroxystyrene copolymer, an α-methylstyrene-hydroxystyrene copolymer, and a hydrogenated novolak resin.

The resin having a group that can be decomposed by an acid used in the present invention is disclosed in European Patent No. 254853 and JP-A No. 2-25 / 1990.
No. 850, No. 3-223860, No. 4-251259
As disclosed in US Pat. No. 6,086,098, an alkali-soluble resin is reacted with a precursor of an acid-decomposable group, or an alkali-soluble resin monomer having an acid-decomposable group bonded thereto is copolymerized with various monomers. Can be obtained.

Specific examples of the resin having a group capable of being decomposed by an acid used in the present invention are shown below, but the present invention is not limited thereto.

Pt-butoxystyrene / p-hydroxystyrene copolymer, p- (t-butoxycarbonyloxy) styrene / p-hydroxystyrene copolymer, p
-(T-butoxycarbonylmethyloxy) styrene /
p-hydroxystyrene copolymer, 4- (t-butoxycarbonylmethyloxy) -3-methylstyrene / 4
Hydroxy-3-methylstyrene copolymer, p- (t-
(Butoxycarbonylmethyloxy) styrene / p-hydroxystyrene (10% hydrogenated) copolymer, m-
(T-butoxycarbonylmethyloxy) styrene / m
-Hydroxystyrene copolymer, o- (t-butoxycarbonylmethyloxy) styrene / o-hydroxystyrene copolymer, p- (cumyloxycarbonylmethyloxy) styrene / p-hydroxystyrene copolymer, cumyl methacrylate / Methyl methacrylate copolymer,
4-t-butoxycarbonylstyrene / dimethyl maleate copolymer, benzyl methacrylate / tetrahydropyranyl methacrylate,

P- (t-butoxycarbonylmethyloxy) styrene / p-hydroxystyrene / styrene copolymer, pt-butoxystyrene / p-hydroxystyrene / fumaronitrile copolymer, t-butoxystyrene / hydroxyethyl methacrylate Copolymer, styrene / N- (4-hydroxyphenyl) maleimide / N-
(4-t-butoxycarbonyloxyphenyl) maleimide copolymer, p-hydroxystyrene / t-butyl methacrylate copolymer, styrene / p-hydroxystyrene / t-butyl methacrylate copolymer p-hydroxystyrene / t-butyl Acrylate copolymer, styrene / p-hydroxystyrene / t-butyl acrylate copolymer p- (t-butoxycarbonylmethyloxy) styrene / p-hydroxystyrene / N-methylmaleimide copolymer, t-butyl methacrylate / 1 -Adamantyl methyl methacrylate copolymer, p-hydroxystyrene / t-butyl acrylate / p-acetoxystyrene copolymer, p-hydroxystyrene / t-butyl acrylate / p- (t-butoxycarbonyloxy) styrene copolymer , P-hydroxystyrene / t-butyl acrylate / p- (t-butoxycarbonylmethyloxy)
Styrene copolymer,

In the present invention, as the resin having an acid-decomposable group (component (A)), a resin containing a repeating structural unit represented by the above general formulas (IV) and (V) is preferable. Thereby, it has a high resolution and the performance change over time from exposure to heating is reduced.

The alkyl group in L and Z in the general formula (IV) includes methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, cyclopentyl, hexyl Group, cyclohexyl group, octyl group, dodecyl group, etc.
Straight-chain, branched or cyclic ones.

Preferred substituents for the alkyl group include an alkyl group, an alkoxy group, a hydroxyl group, a halogen atom, a nitro group, an acyl group, an acylamino group, a sulfonylamino group,
Examples include an alkylthio group, an arylthio group, and an aralkylthio group.Examples include a cyclohexylethyl group, an alkylcarbonyloxymethyl group, an alkylcarbonyloxyethyl group, an arylcarbonyloxyethyl group, an aralkylcarbonyloxyethyl group, an alkyloxymethyl group, and an aryloxy group. Methyl group, aralkyloxymethyl group, alkyloxyethyl group, aryloxyethyl group, aralkyloxyethyl group, alkylthiomethyl group, arylthiomethyl group, aralkylthiomethyl group,
Examples thereof include an alkylthioethyl group, an arylthioethyl group, and an aralkylthioethyl group. The alkyl in this case is not particularly limited, but may be any of a chain, a ring, and a branch, and examples thereof include a group such as a cyclohexylcarbonyloxyethyl group, a t-butylcyclohexylcarbonyloxyethyl group, and an n-butylcyclohexylcarbonyloxyethyl group. Can be mentioned. Also, the aryl is not limited, but includes, for example, a phenyloxyethyl group and the like, and may be further substituted, for example, a cyclohexylphenyloxyethyl group. The aralkyl is not particularly limited, but examples thereof include a benzylcarbonyloxyethyl group.

Examples of the aralkyl group in L and Z include those having 7 to 15 carbon atoms, such as a substituted or unsubstituted benzyl group and a substituted or unsubstituted phenethyl group. Preferred substituents of the aralkyl group include an alkoxy group, a hydroxyl group, a halogen atom, a nitro group, an acyl group, an acylamino group, a sulfonylamino group, an alkylthio group, an arylthio group, an aralkylthio group, and the like. Examples include a benzyl group and a phenylthiophenethyl group. It is preferred that Z is a substituted alkyl group or a substituted aralkyl group, since further improvement in edge roughness is recognized. Here, the substituent of the alkyl group is preferably a cyclic alkyl group, an aryloxy group, an alkylcarboxy group, an arylcarboxy group, or an aralkylcarboxy group, and the substituent of the aralkyl group is an alkyl group, a cyclic alkyl group, or a hydroxyl group. preferable.

5 or 6 formed by combining L and Z with each other
Examples of the member ring include a tetrahydropyran ring and a tetrahydrofuran ring.

The ratio of the repeating structural unit represented by the general formula (IV) to the repeating structural unit represented by the general formula (V) in the resin is preferably from 1/99 to 60/40, and more preferably from 1/99 to 60/40. It is 5/95 to 50/50, more preferably 10/90 to 40/60.

The resin containing the repeating structural units represented by the general formulas (IV) and (V) may include structural units derived from other monomers. Other monomers include hydrogenated hydroxystyrene; halogen, alkoxy or alkyl-substituted hydroxystyrene; styrene; halogen, alkoxy, acyloxy or alkyl-substituted styrene; maleic anhydride; acrylic acid derivative; methacrylic acid derivative; Examples include, but are not limited to:
The ratio between the structural units of the general formulas (IV) and (V) and the structural units of the other monomers is represented by a molar ratio of [(IV) +
(V)] / [other monomer components] = 100/0 to 50 /
50, preferably 100/0 to 60/40, and more preferably 100/0 to 70/30.

Specific examples of the resin containing a repeating structural unit represented by the above general formulas (IV) and (V) and other resins that can be used in the present invention include:
The following are mentioned.

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In the above specific examples, Me is a methyl group, E
t represents an ethyl group, nBu represents an n-butyl group, iso-Bu represents an isobutyl group, and tBu represents a t-butyl group.

When an acetal group is used as the acid-decomposable group, a polyhydroxy compound is added at the synthesis stage to adjust the alkali dissolution rate and improve heat resistance to introduce a cross-linking site connecting the polymer main chain with a polyfunctional acetal group. May be. The amount of the polyhydroxy compound to be added is 0.01 to 5 mol%, more preferably 0.05 to 4 mol%, based on the amount of hydroxyl groups of the resin. Examples of the polyhydroxy compound include those having 2 to 6 phenolic hydroxyl groups or alcoholic hydroxyl groups, preferably 2 to 4 hydroxyl groups, and more preferably 2 to 4 hydroxyl groups.
Or three. Specific examples of the polyhydroxy compound are shown below, but the present invention is not limited thereto.

[0092]

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(A) The weight average molecular weight (Mw) of the resin having an acid-decomposable group is from 2,000 to 300,000.
Is preferably within the range. If it is less than 2,000, the film thickness is greatly reduced due to the development of the unexposed portion. Here, the weight average molecular weight is defined as a polystyrene equivalent value of gel permeation chromatography.

Further, the component (A) of the positive resist composition of the present invention, that is, the resin having a group decomposable by an acid, is
You may mix and use more than one type. The amount of the component (A) used is 40 to 40% based on the solid content of the first composition of the present invention.
It is 99% by weight, preferably 60 to 98% by weight.

[4] (D) A compound having a molecular weight of 3000 or less which is decomposed by the action of an acid to increase the solubility in an alkali developer ((D) component) The (D) component is an essential component of the second composition. And a component to be added to the first composition as needed. The component (D) has a group that can be decomposed by an acid, and the solubility in an alkali developing solution is increased by the action of an acid.
00, more preferably 300 to 1,500 low molecular weight compounds. The component (D) functions as a dissolution inhibitor for an alkali developing solution in a non-exposed area. In the following description, “acid-decomposable dissolution inhibiting compound” has the same meaning as component (D).

The preferred component (D), that is, the preferred acid-decomposable dissolution-inhibiting compound has at least two acid-decomposable groups in its structure, and the distance between the acid-decomposable groups is the longest. A compound that has at least 8 bonding atoms in position except for the acid-decomposable group. A more preferred acid-decomposable dissolution-inhibiting compound is (A) an acid-decomposable compound having at least two groups capable of being decomposed by an acid in its structure, and wherein the distance between the acid-decomposable groups is the farthest. At least 10 and preferably at least 11
, More preferably at least 12 compounds,
And (ii) at least three acid-decomposable groups, and the distance between the acid-decomposable groups is at least 9, and preferably at least 10, excluding the acid-decomposable groups at the farthest position. More preferably, it is a compound passing through at least 11. The upper limit of the number of the bonding atoms is preferably 50, and more preferably 30.

When the acid-decomposable dissolution-inhibiting compound has three or more, preferably four or more acid-decomposable groups, and also when it has two acid-decomposable groups, the acid-decomposable groups are mutually fixed at a certain level. If the distance is not less than the distance, the dissolution inhibiting property with respect to the alkali-soluble resin is significantly improved. The distance between the acid-decomposable groups is represented by the number of via bond atoms excluding the acid-decomposable groups. For example, in the case of the following compounds (1) and (2), the distance between the acid-decomposable groups is four bonding atoms each,
In compound (3), it has 12 bonding atoms.

[0098]

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The acid-decomposable dissolution inhibiting compound may have a plurality of acid-decomposable groups on one benzene ring, but preferably one acid-decomposable group on one benzene ring. It is a compound composed of a skeleton having a group.

A group which can be decomposed by an acid, ie, —COO-A
⁰ and a group containing a —O—B ⁰ group include —R ⁰ —COO—
A ⁰ or a group represented by —Ar—O—B ⁰ is exemplified.
Here, A ⁰ represents -C (R ⁰¹ ) (R ⁰² ) (R ⁰³ ), -Si
^{(R 01) (R 02)} (R 0 3) or -C (R ⁰⁴⁾
It represents a (R ⁰⁵ ) -OR ⁰⁶ group. B ⁰ is A ⁰ or -CO-
It represents an ^OA group. R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R
⁰⁵ is the same or different and represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group, and R ⁰⁶ represents an alkyl group or an aryl group. However, at least two of R ^{01 to} R ⁰³ are groups other than hydrogen atoms, and even when two groups of R ^{01 to} R ⁰³ and R ^{04 to} R ⁰⁶ are bonded to form a ring. Good. R ⁰ represents a divalent or higher valent aliphatic or aromatic hydrocarbon group which may have a substituent, and -Ar- represents a divalent or higher valent which may have a monocyclic or polycyclic substituent. Shows an aromatic group.

Here, the alkyl group is preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group and a t-butyl group. Preferred are those having 3 to 10 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclohexyl group and adamantyl group, and alkenyl groups having 2 to 2 carbon atoms such as vinyl group, propenyl group, allyl group and butenyl group. Preferably, the aryl group has 6 to 1 carbon atoms such as phenyl, xylyl, toluyl, cumenyl, naphthyl and anthracenyl.
Four are preferred. Further, as a substituent, a hydroxyl group,
Halogen atom (fluorine, chlorine, bromine, iodine), nitro group, cyano group, the above alkyl group, methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group, n-butoxy group, isobutoxy group, s
an alkoxy group such as an ec-butoxy group and a t-butoxy group,
Methoxycarbonyl group, alkoxycarbonyl group such as ethoxycarbonyl group, benzyl group, aralkyl group such as phenethyl group, cumyl group, aralkyloxy group, formyl group, acetyl group, butyryl group, benzoyl group, cyanyl group, acyl such as valeryl group Group, acyloxy group such as butyryloxy group, the above alkenyl group, vinyloxy group,
Examples thereof include an alkenyloxy group such as a propenyloxy group, an allyloxy group and a butenyloxy group, an aryloxy group such as the above-mentioned aryl group and phenoxy group, and an aryloxycarbonyl group such as a benzoyloxy group.

The acid-decomposable group is preferably a silyl ether group, a cumyl ester group, an acetal group, a tetrahydropyranyl ether group, an enol ether group, an enol ester group, a tertiary alkyl ether group, or a tertiary alkyl ester group. And tertiary alkyl carbonate groups. More preferred are a tertiary alkyl ester group, a tertiary alkyl carbonate group, a cumyl ester group, and a tetrahydropyranyl ether group.

The component (D) is preferably selected from JP-A No. 1-2
89946, JP-A-1-289947, JP-A-2-
2560, JP-A-3-128959, JP-A-3-1
58855, JP-A-3-179353, JP-A-3-179
191351, JP-A-3-200251, JP-A-3-3
JP-A-200252, JP-A-3-200253, JP-A-3-200254, JP-A-3-200255, JP-A-3-259149, JP-A-3-279958, JP-A-3-279959, JP-A-4-200 1650, JP-A-4-1651, JP-A-4-11260, JP-A-4
-12356, JP-A-4-12357, Japanese Patent Application No. 3-
No. 33229, Japanese Patent Application No. 3-230790, Japanese Patent Application No. 3-230
No. 320438, Japanese Patent Application No. 4-25157, Japanese Patent Application No. 4-
No. 52732, No. 4-103215, No. 4-
104542, Japanese Patent Application No. 4-107885, Japanese Patent Application No. 4
No. -107889, groups shown above some or all of the phenolic OH groups of the polyhydroxy compounds described herein, such as Nos. 4-152195, -R ⁰ -COO-
Protected compounds linked by A ⁰ or B ⁰ groups are included.

More preferably, JP-A-1-289946
JP-A-3-128959, JP-A-3-15885
5, JP-A-3-179353, JP-A-3-2002
No. 51, JP-A-3-200252, JP-A-3-200
255, JP-A-3-259149, JP-A-3-27
9958, JP-A-4-1650, JP-A-4-112
No. 60, JP-A-4-12356 and JP-A-4-1235
7, Japanese Patent Application No. 4-25157, Japanese Patent Application No. 4-10321
No. 5, Japanese Patent Application No. 4-104542, Japanese Patent Application No. 4-1078
No. 85, Japanese Patent Application Nos. 4-107889 and 4-15219
No. 5 using the polyhydroxy compound described in the specification.

In the present invention, specific examples of the preferable compound skeleton of the component (D) are shown below.

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[0115]

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[0117]

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R in the compounds (1) to (44) represents a hydrogen atom,

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Represents the following. However, at least two or three depending on the structure are groups other than hydrogen atoms, and each substituent R
May not be the same group.

In the case of the first composition, the content of the component (D) is
Based on the solids content of the first composition, preferably from 3 to 45
%, More preferably 5 to 30% by weight, and still more preferably 10 to 20% by weight. (D) in the case of the second composition
The contents of the components are the same as in the first composition.

[5] (E) Alkali-soluble resin ((E)
Component) (E) The alkali-soluble resin is an essential component of the second composition of the present invention. It is a component that may be added to the first composition of the present invention. (E) The alkali-soluble resin is a resin that is insoluble in water and soluble in an alkali developer, and is used to adjust the alkali solubility of the second composition. This resin has substantially no acid-decomposable groups. As the component (E), for example, novolak resin, hydrogenated novolak resin, acetone-pyrogallol resin, o-polyhydroxystyrene, m-polyhydroxystyrene, p-polyhydroxystyrene, hydrogenated polyhydroxystyrene, halogenated or alkyl-substituted polystyrene Hydroxystyrene, hydroxystyrene-N-substituted maleimide copolymer, o /
p- and m / p-hydroxystyrene copolymers, partially O-alkylated compounds based on hydroxyl groups of polyhydroxystyrene (for example, 5 to 30 mol% of O-methylated products, O-
(1-methoxy) ethylated product, O- (1-ethoxy) ethylated product, O-2-tetrahydropyranylated product, O-
(T-butoxycarbonyl) methylated compound) or O
-Acylated (for example, 5 to 30 mol% of O-acetylated product, O- (t-butoxy) carbonylated product, etc.), styrene-maleic anhydride copolymer, styrene-hydroxystyrene copolymer, α-methylstyrene -Hydroxystyrene copolymers, carboxyl group-containing methacrylic resins and derivatives thereof, and polyvinyl alcohol derivatives, but are not limited thereto.

Particularly preferred (E) alkali-soluble resins are novolak resins and o-polyhydroxystyrene, m-
Polyhydroxystyrene, p-polyhydroxystyrene and copolymers thereof, alkyl-substituted polyhydroxystyrene, partially O-alkylated or O-acylated polyhydroxystyrene, styrene-hydroxystyrene copolymer, α-methyl It is a styrene-hydroxystyrene copolymer. The novolak resin is obtained by subjecting a given monomer as a main component to addition condensation with an aldehyde in the presence of an acidic catalyst.

The weight average molecular weight of the novolak resin is 1,
It is preferably in the range of 000 to 30,000.
If it is less than 1,000, the film loss of the unexposed portion after development is large, and if it exceeds 30,000, the developing speed is reduced. Particularly preferred is the range of 2,000 to 20,000. In addition, the weight average molecular weight of the polyhydroxystyrene other than the novolak resin, its derivative, and the copolymer is 2,000 or more, preferably 5,000 to 20,000.
0, more preferably 8,000 to 100,000. Further, from the viewpoint of improving the heat resistance of the resist film, it is preferably 10,000 or more. Here, the weight average molecular weight is defined as a value in terms of polystyrene by gel permeation chromatography. In the present invention, these alkali-soluble resins may be used as a mixture of two or more kinds.

The amount of the alkali-soluble resin used is preferably from 40 to 97% by weight, more preferably from 60 to 90% by weight, based on the solid content of the second composition.

[6] (F) Nitrogen-containing basic compound ((F)
Component) The preferred nitrogen-containing basic compound (F) that can be compounded in the positive resist composition of the present invention is a compound having a higher basicity than phenol. Above all (A) ~
A nitrogen-containing basic compound having a structure represented by (E) is preferable. By using the nitrogen-containing basic compound, the performance change is small even with the lapse of time from exposure to post-heating.

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Here, R ²⁵⁰ , R ²⁵¹ and R ²⁵² are the same or different and are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aminoalkyl group having 1 to 6 carbon atoms, a hydroxy group having 1 to 6 carbon atoms. It is an alkyl group or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. Also, where R ²⁵¹ and R
²⁵² may combine with each other to form a ring.

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Wherein R ²⁵³ , R ²⁵⁴ , R ²⁵⁵ and R ²⁵⁶
Is the same or different and represents an alkyl group having 1 to 6 carbon atoms). Preferred specific examples include substituted or unsubstituted guanidine, substituted or unsubstituted aminopyridine, substituted or unsubstituted aminoalkylpyridine, substituted or unsubstituted aminopyrrolidine, substituted or unsubstituted indazol, substituted or unsubstituted Pyrazole, substituted or unsubstituted pyrazine, substituted or unsubstituted pyrimidine, substituted or unsubstituted purine, substituted or unsubstituted imidazoline, substituted or unsubstituted pyrazoline, substituted or unsubstituted piperazine, substituted or unsubstituted amino Examples include morpholine, substituted or unsubstituted aminoalkyl morpholine, and the like, and include mono, di, trialkylamine, substituted or unsubstituted aniline, substituted or unsubstituted piperidine, mono and diethanolamine, and the like. Preferred substituents are an amino group, aminoalkyl group, alkylamino group, aminoaryl group, arylamino group, alkyl group, alkoxy group, acyl group, acyloxy group, aryl group, aryloxy group, nitro group, hydroxyl group, cyano group It is.

Preferred compounds are guanidine, 1,1,
1-dimethylguanidine, 1,1,3,3-tetramethylguanidine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2-diethylaminopyridine, 2- (aminomethyl) pyridine, 2-amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-5-methylpyridine, 2-amino-6
-Methylpyridine, 3-aminoethylpyridine, 4-aminoethylpyridine, 3-aminopyrrolidine, piperazine, N- (2-aminoethyl) piperazine, N- (2-
Aminoethyl) piperidine, 4-amino-2,2,6,
6-tetramethylpiperidine, 4-piperidinopiperidine, 2-iminopiperidine, 1- (2-aminoethyl)
Pyrrolidine, pyrazole, 3-amino-5-methylpyrazole, 5-amino-3-methyl-1-p-tolylpyrazole, pyrazine, 2- (aminomethyl) -5-methylpyrazine, pyrimidine, 2,4-diaminopyrimidine ,
4,6-dihydroxypyrimidine, 2-pyrazoline, 3
-Pyrazolin, N-aminomorpholine, N- (2-aminoethyl) morpholine, 1,5-diazabicyclo [4,3,0] non-5-ene, 1,8-diazabicyclo [5,4,0] Undec-7-ene, 2,4,5-triphenylimidazole, tri (n-butyl) amine,
Tri (n-octyl) amine, N-phenyldiethanolamine, N-hydroxyethylpiperidine, 2,6-
Diisopropylaniline, N-cyclohexyl-N'-
Examples include, but are not limited to, morpholinoethylthiourea, N-hydroxyethylmorpholine, and the like.

Of these, particularly preferred compounds include 1,5-diazabicyclo [4.3.0] non-5-
Ene, 1,8-diazabicyclo [5.4.0] undec-7ene, 2,4,5-triphenylimidazole, tri (n-butyl) amine, tri (n-octyl) amine, N-phenyldiethanolamine, N-hydroxyethylpiperidine, 2,6-diisopropylaniline,
N-cyclohexyl-N'-morpholinoethylthiourea and N-hydroxyethylmorpholine. These nitrogen-containing basic compounds can be used alone or in combination of two or more.

The amount of the nitrogen-containing basic compound used is usually 0.001 to 10% by weight, based on the solid content of the composition.
Preferably it is 0.01 to 5% by weight. If the amount is less than 0.001% by weight, the effect of the addition of the nitrogen-containing basic compound cannot be obtained. On the other hand, if it exceeds 10% by weight, the sensitivity tends to decrease and the developability of the unexposed portion tends to deteriorate.

[7] (G) Fluorine and / or Silicon Surfactant ((G) Component) The positive resist composition of the present invention preferably contains (G) component. The component (G) is at least one surfactant selected from a fluorine-based surfactant, a silicon-based surfactant, and a surfactant containing both a fluorine atom and a silicon atom. When the positive resist composition of the present invention contains the above surfactant, the sensitivity, resolution, substrate adhesion, and dry etching resistance are excellent when using an exposure light source of 250 nm or less, particularly 220 nm or less, and storage over time. It is possible to obtain a resist pattern with less subsequent particles and with less development defects and scum. As these surfactants, for example, JP-A-62-36663, JP-A-61-226
No. 746, JP-A-61-226745, JP-A-62-170950, JP-A-63-34540, JP-A-7-230165, JP-A-8-62834,
The surfactants described in JP-A-9-54432 and JP-A-9-5988 can be exemplified, and the following commercially available surfactants can be used as they are. As commercially available surfactants that can be used, for example, F-top EF301, EF303, (Shin-Akita Chemical Co., Ltd.)
), Florado FC430, 431 (manufactured by Sumitomo 3M Limited),
Megafac F171, F173, F176, F189, R08 (Dai Nippon Ink Co., Ltd.), Surflon S-382, SC101, 102, 10
3, 104, 105, 106 (manufactured by Asahi Glass Co., Ltd.), Troysol S
-366 (manufactured by Troy Chemical Co., Ltd.) or a silicon-based surfactant. Also, polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can be used as a silicon-based surfactant.

The amount of the surfactant is usually 0.001% by weight to 2% by weight based on the solid content in the composition of the present invention.
% By weight, preferably 0.01% to 1% by weight.
These surfactants can be used alone or in combination of two or more.

[8] Other Components Used in the Present Invention The positive photosensitive composition of the present invention may further contain, if necessary, a dye, a pigment, a plasticizer, a surfactant other than those described above, and a photosensitizer. ,
And phenolic O that promotes solubility in developing solutions
A compound having two or more H groups can be contained.

The compound having two or more phenolic OH groups that can be used in the present invention is preferably a phenol compound having a molecular weight of 1,000 or less. Further, it is necessary to have at least two phenolic hydroxyl groups in the molecule. If the number exceeds 10, the effect of improving the development latitude is lost. When the ratio of the phenolic hydroxyl group to the aromatic ring is less than 0.5, the film thickness dependency is large, and the development latitude tends to be narrow. If this ratio exceeds 1.4, the stability of the composition deteriorates, and it becomes difficult to obtain high resolution and good film thickness dependency, which is not preferable.

The preferred addition amount of this phenol compound is 2 to 50% by weight, more preferably 5 to 30% by weight, based on the alkali-soluble resin. 50% by weight
If the addition amount exceeds the above range, the development residue becomes worse and a new defect that the pattern is deformed at the time of development occurs, which is not preferable.

Such a phenol compound having a molecular weight of 1,000 or less can be prepared by, for example, referring to the methods described in JP-A-4-122938, JP-A-2-28531, US Pat. No. 4,916,210, European Patent 219294, and the like. ,
It can be easily synthesized by those skilled in the art. Specific examples of the phenol compound are shown below, but the compounds that can be used in the present invention are not limited to these.

Resorcin, phloroglucin, 2, 3, 4
-Trihydroxybenzophenone, 2,3,4,4'-
Tetrahydroxybenzophenone, 2,3,4,3 ',
4 ', 5'-hexahydroxybenzophenone, acetone-pyrogallol condensation resin, fluoroglucoside,
4,2 ', 4'-biphenyltetrol, 4,4'-thiobis (1,3-dihydroxy) benzene, 2,2',
4,4'-tetrahydroxydiphenyl ether, 2,
2 ', 4,4'-tetrahydroxydiphenylsulfoxide, 2,2', 4,4'-tetrahydroxydiphenylsulfone, tris (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) Cyclohexane, 4,4- (α-methylbenzylidene) bisphenol, α, α ′, α ″ -tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene,
α, α ', α "-tris (4-hydroxyphenyl)-
1-ethyl-4-isopropylbenzene, 1,2,2-
Tris (hydroxyphenyl) propane, 1,1,2-
Tris (3,5-dimethyl-4-hydroxyphenyl)
Propane, 2,2,5,5-tetrakis (4-hydroxyphenyl) hexane, 1,2-tetrakis (4-hydroxyphenyl) ethane, 1,1,3-tris (hydroxyphenyl) butane, para [α, α , Α ', α'-tetrakis (4-hydroxyphenyl)]-xylene.

[Preparation of Positive Resist Composition and Use Thereof] The components contained in the positive resist composition of the present invention have been described above. Next, a method for preparing the positive resist composition of the present invention and a method for using the same will be described. The composition of the present invention is applied to a support by dissolving the above components in the above-mentioned solvent. As the solvent used here,
Ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, γ-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol Monomethyl ether acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N, N-dimethylformamide, dimethylsulfoxide, N-methyl Pyrrolidone, tetrahydrofuran and the like are preferable, and these solvents are used alone or in combination.

Among the above, preferred solvents are 2-
Heptanone, γ-butyrolactone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl lactate, ethyl lactate, methoxypropion And methyl ethoxypropionate, N-methylpyrrolidone and tetrahydrofuran.

In this case, it is preferable to add the above-mentioned (G) fluorine-based and / or silicon-based surfactant to the solvent. Further, a surfactant other than the component (G) can be added. As such a surfactant, specifically, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether , Polyoxyethylene alkyl allyl ethers such as polyoxyethylene nonylphenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate , Sorbitan fatty acid esters such as sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxo Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as ethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate; acrylic acid Alternatively, methacrylic acid (co) polymerized polyflow No. 75, no. 9
5 (manufactured by Kyoeisha Yushi Kagaku Kogyo KK) and the like. The amount of these surfactants is usually 2 parts by weight or less per 100 parts by weight of the solids in the composition of the present invention,
It is preferably at most 1 part by weight.

The above composition is applied on a substrate (eg, silicon / silicon dioxide coating) to be used in the manufacture of precision integrated circuit devices by an appropriate application method such as a spinner or a coater, and then exposed through a predetermined mask. A good resist pattern can be obtained by baking and developing.

As the developer for the photosensitive composition of the present invention,
Sodium hydroxide, potassium hydroxide, sodium carbonate,
Inorganic alkalis such as sodium silicate, sodium metasilicate and aqueous ammonia, primary amines such as ethylamine and n-propylamine, secondary amines such as diethylamine and di-n-butylamine, and triethylamine and methyldiethylamine Use alkaline aqueous solutions such as triamines, alcoholamines such as dimethylethanolamine and triethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, and cyclic amines such as pyrrole and pichelidine. be able to. Further, an appropriate amount of an alcohol or a surfactant may be added to the above alkaline aqueous solution.

[0147]

EXAMPLES The present invention will be described below in more detail with reference to examples, but the scope of the present invention is not limited in any way by these examples.

Synthesis Example 1 [Component (B): synthesis of compound generating fluorine-substituted carboxylic acid] (1) <Synthesis of bis (4-t-amylphenyl) iodonium heptafluorobutyrate (compound I-3)> 10 g of bis (4-t-amylphenyl) iodonium iodide was dissolved in 500 ml of methanol, and 4.44 g of silver oxide was added thereto, followed by stirring at room temperature for 4 hours. After filtering the reaction solution to remove silver compounds, 4.67 g of heptafluorobutyric acid was added to this solution. This solution was concentrated, and the obtained solid was recrystallized from acetone / water (4/6) to obtain 6 g of the desired product.

(2) Using the same method as in the above (1) and using the corresponding iodonium iodide and carboxylic acid, the compounds (I) to (I)
-24) and the following (Compound B′-3) and (Compound B′-4) which generate unsubstituted carboxylic acids shown below were synthesized.

(3) <Synthesis of triphenylsulfonium nonafluoropentanoate (compound II-4)> 20 g of triphenylsulfonium iodide was dissolved in 500 ml of methanol, and 12.5 g of silver oxide was added thereto. Stirred in the clear. After filtering the reaction solution to remove the silver compound, 14.9 g of nonafluoropentanoic acid was added to the solution, and the solution was concentrated. After adding 300 ml of diisopropyl ether to the obtained oily substance and sufficiently stirring, an operation of removing diisopropylpropyether by decanting was repeated twice. The obtained oil was dried under reduced pressure to obtain 18 g of the desired product.

(4) Using the same method as in the above (3) and using the corresponding sulfonium iodide and carboxylic acid, the components (B) (compounds II-1) to (II-48) and The following (Compound B'-1) and (Compound B'-2) which generate unsubstituted carboxylic acids were synthesized.

[0152]

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(5) <triarylsulfonium heptafluorobutyrate (compound II-24), (compound III-
Synthesis of mixture containing 3) as main component> Fluka 45% aqueous solution of triphenylsulfonium chloride (mixture of triarylsulfonium chloride) 10
100 g of methanol was added to the mixture, and 3.4 g of silver oxide was added thereto.
4 g was added and stirred for 4 hours. After filtering the reaction solution to remove silver compounds, 3.38 g of heptafluorobutyric acid was added to the solution, and the solution was concentrated. After adding 300 ml of diisopropyl ether to the obtained oily substance and sufficiently stirring, an operation of removing the diisopropyl ether by decantation was repeated twice. The obtained oil was dried under reduced pressure to obtain 4.2 g of the desired product.

(6) <Synthesis of N-pentafluorobenzoyloxyphthalimide (Compound IV-1)> N-hydroxyphthalimide (10 g) was dehydrated in THF200.
and cooled to 0 ° C. To this solution, 13.6 g of pentafluorobenzoyl chloride was added dropwise. To this solution was added 7.0 g of triethylamine, and the mixture was stirred for 2 hours. The reaction solution was slowly poured into 1.5 L of distilled water, and the precipitated powder was collected by filtration and washed with water to obtain 17 g of the desired product.

(7) Using the same method as in the above (6), the corresponding hydroxyimide is reacted with carboxylic acid chloride under basic conditions to obtain the component (B) (compound IV-2), (compound IV-3) was synthesized.

(8) Synthesis of 2-nitro-6-trifluoromethylbenzylpentafluorobenzoate (Compound V-2) 10 g of 2-nitro-6-trifluoromethylbenzyl alcohol and 9.8 g of dicyclohexylamine were added to acetone 1
The solution was dissolved in 50 ml, and 11.5 g of pentafluorobenzoyl chloride was slowly added dropwise to the solution. After reacting at room temperature for 2 hours, the reaction solution was slowly poured into 1 L of distilled water, and the precipitated solid was washed with distilled water to obtain the target substance.
g were obtained.

(9) By using the same method to react the corresponding benzyl alcohol and carboxylic acid chloride under basic conditions, the (B) component (compounds V-1) to (compound V) -4) was obtained.

Compounds (I-25) and (I-3)
1), (I-33), (II-49), (II-50),
(II-56), (II-59), (II-61), (II-6)
4) was similarly synthesized. However, with respect to these compounds, the anion portion is a mixture of a compound having an anion shown in each formula of 50% or more synthesized with a telomer method and a compound having an anion different in carbon chain length.

Synthesis Example 2 [Synthesis of Resin as Component (A)] (1) <p- (1- (cyclohexylethoxy) ethoxy) styrene / p-hydroxystyrene (30/70)
Synthesis of (Resin A-25)> p-hydroxystyrene (VP-8000 manufactured by Nippon Soda)
70 g was heated and dissolved in 320 g of propylene glycol monomethyl ether acetate (PGMEA), dehydrated by distillation under reduced pressure, and then cooled to 20 ° C. To this solution was added 0.35 g of pyridinium-p-toluenesulfonate and 22.4 g of cyclohexaneethanol. To this solution, 17.5 g of t-butyl vinyl ether was slowly added, and reacted at 20 ° C. for 5 hours. 0.28 g of triethylamine and 320 ml of ethyl acetate were added to the reaction solution, which was washed three times with 150 ml of distilled water. The solvent was distilled off and concentrated. The obtained oil was dissolved in 100 ml of acetone, and this was slowly poured into 2 L of distilled water. The precipitated powder was collected by filtration and dried to obtain 54 g of the desired product.

(2) <p- (1- (cyclohexylethoxy) ethoxy) styrene / p-acetoxystyrene /
p-Hydroxystyrene (30/10/60) resin A-
Synthesis of 38> p-hydroxystyrene (VP-8000 manufactured by Nippon Soda)
70 g was heated and dissolved in 320 g of propylene glycol monometer ether acetate (PGMEA), dehydrated by distillation under reduced pressure, and then cooled to 20 ° C. To this solution, 0.35 g of viridinium-p-toluenesulfonate and 22.4 g of cyclohexaneethanol were added. To this solution, 17.5 g of t-butyl vinyl ether was slowly added, and reacted at 20 ° C. for 5 hours. 5.53 g of pyridine was added to the reaction solution, and 5.9 g of acetic anhydride was slowly added thereto. The reaction was carried out at room temperature for 1 hour, and 320 ml of ethyl acetate was added to the solution, which was washed three times with 150 ml of distilled water. The solvent was distilled off and concentrated. The obtained oil was dissolved in 100 ml of acetone, and this was slowly poured into 2 L of distilled water. The precipitated powder is collected by filtration and dried to obtain 5
8 g were obtained.

(3) The following resin was synthesized by using the same method as in the above (1) and (2). A-3; p- (1-ethoxyethoxy) styrene / p-
Hydroxystyrene (35/65) molecular weight 15,000,
Dispersion degree (Mw / Mn) 1.1 A-7; p- (1-isobutoxyethoxy) styrene / p-hydroxystyrene (30/70) molecular weight 600
0, dispersity (Mw / Mn) 1.2 A-36; p- (1-phenethyloxyethoxy) styrene / p-acetoxystyrene / p-hydroxystyrene (30/10/60) molecular weight 11,000, dispersity (M
w / Mn) 1.2 A-41; p- (1- (4-t-butylcyclohexylcarboxyethoxy) ethoxystyrene / p-acetoxystyrene / p-hydroxystyrene (30/10/6)
0) Molecular weight 12000, degree of dispersion (Mw / Mn) 1.1 A-43; p- (1- (cyclohexylethoxy) ethoxy) styrene / pt-butylstyrene / p-hydroxystyrene (30/8/62) Molecular weight 18000, degree of dispersion (Mw / Mn) 2.3 A-22; p- (1-benzyloxyethoxy) styrene / p-hydroxystyrene (25/75) molecular weight 13
000, dispersity (Mw / Mn) 1.3 A-35; p- (1-benzyloxyethoxy) styrene / p-hydroxystyrene / p-acetoxystyrene (20/70/10) molecular weight 9000, dispersity (Mw) /
Mn) 1.2

A-14: p- (1-isobutoxyethoxy) styrene / p- (t-butoxycarbonylmethyleneoxy) styrene / p-hydroxystyrene (20 /
10/70), molecular weight 13000, degree of dispersion (Mw / M
n) 1.3 A-50: Styrene / p-hydroxystyrene / p-
(T-butoxycarbonyloxy) styrene (10/7
0/20), molecular weight 13000, degree of dispersion (Mw / Mn)
1.4 A-52: p-hydroxystyrene / p-ethoxyethoxystyrene / cyclohexyl acrylate (20/7
0/10), molecular weight 18000, degree of dispersion (Mw / Mn)
1.9

Further, the following resin as the component (A) was synthesized. (4) <A-48; Synthesis of p-hydroxystyrene / t-butyl acrylate (79/21)> 84.1 g of p-vinylphenol, t-butyl acrylate
22.4 g was dissolved in 150 g of dioxane, and a nitrogen stream was introduced for 1 hour. Dimethyl 2,2'-azobisisobutyrate 6.9
1 g, and the mixture was heated to 75 ° C.
Polymerization was carried out for hours. After completion of the polymerization, the reaction solution was cooled to room temperature, 150 g of acetone was added thereto, and the mixture was diluted and dropped into a large amount of hexane to obtain a solid polymer. Acetone dilution,
The introduction into hexane was repeated three times to remove the residual monomer. The obtained polymer was dried under reduced pressure at 60 ° C. to obtain a polymer A-48. As a result of NMR analysis, the composition ratio of p-vinylphenol: t-butyl acrylate was 79:21. Mw is 12,000 and the degree of dispersion (M
(w / Mn) was 2.6.

(5) <A-16; p- (1-isobutoxyethoxy) styrene / p-hydroxystyrene / t
Synthesis of -butyl acrylate (20/59/21)> Dissolve 20 g of the above polymer (A-48) in 80 g of propylene glycol monoethyl ether acetate (PGMEA), heat to 60 ° C., gradually reduce the pressure of the system to 20 mmH
g, and PGMEA and water in the system were azeotropically dehydrated. After azeotropic dehydration, the mixture was cooled to 20 ° C, and isobutyl vinyl ether was
2.2 g were added, and 3 mg of p-toluenesulfonic acid was further added. After the addition, the reaction was carried out for 2 hours, and the acid was neutralized by adding a small amount of triethylamine. Thereafter, ethyl acetate was added to the reaction solution, and the salt was removed by washing with ion-exchanged water. Further, ethyl acetate and water were distilled off from the reaction solution under reduced pressure to obtain a target product, polymer A-16.

(6) A-51: p-hydroxystyrene / styrene / t-butyl acrylate (78/7/1
5) (molecular weight 13100, degree of dispersion (Mw / Mn)
7) was synthesized in the same manner as in the resin A-48. (7) <A-49; p-hydroxystyrene / p- (t
-Butoxycarbonyloxy) styrene (60/40)
Synthesis of poly-p-hydroxystyrene (VP-800 manufactured by Nippon Soda)
0, weight average molecular weight 11,000) was dissolved in 40 ml of pyridine, and di-t-butyl dicarbonate (1.
28 g were added. After reacting at room temperature for 3 hours, the mixture was added to a solution of 1 liter of ion-exchanged water / 20 g of concentrated hydrochloric acid. The precipitated powder was filtered, washed with water, and dried to obtain a p-hydroxystyrene / p- (t-butyloxycarbonyloxy) styrene copolymer (60/40).

Examples 1 to 42 and Comparative Examples 1 to 3 According to the formulations shown in Table 1, each component was dissolved in a solvent to prepare a solution having a solid content of 15%. The solution was filtered through a filter to prepare a resist solution. This resist solution was evaluated as follows.

A. KrF excimer laser exposure evaluation Using a spin coater, the resist solution was uniformly coated on a hexamethylsilazane-treated silicon wafer, and heated and dried on a hot plate at 120 ° C. for 90 seconds to form a 0.6 μm A resist film was formed. The resist film was subjected to pattern exposure using a KrF excimer laser stepper (NA = 0.63) using a line and space mask, and immediately after exposure, heated on a hot plate at 110 ° C. for 90 seconds. 2.38% more
2 with aqueous solution of tetramethylammonium hydroxide
The film was developed at 3 ° C. for 60 seconds, rinsed with pure water for 30 seconds, and then dried. From the pattern on the silicon wafer thus obtained, the performance of the resist was evaluated by the following method. Table 2 shows the results.

(Resolution) Indicates the limit resolution at an exposure amount for reproducing a 0.18 μm line-and-space (1/1) mask pattern. (Exposure margin) The exposure amount for reproducing a 0.16 μm line-and-space (1/1) mask pattern is the optimum exposure amount, and the exposure amount width for reproducing a line width of 0.16 μm ± 10% is the optimum exposure amount. The divided value was expressed as a percentage (%). The larger the number, the smaller the line width change with respect to the change in exposure.

(Depth of focus) A 0.15 μm line-and-space (1/1) at an exposure dose for reproducing a 0.15 μm line-and-space (1/1) mask pattern
The depth of focus of 1) was measured. The larger the value, the wider the depth of focus.

[0170]

[Table 1]

[0171]

[Table 2]

[0172]

[Table 3]

(Description of Components in Table 1) Component (A) (the blending amount is a value as a solid content) PHS / ST in Example 31 was p-hydroxystyrene / styrene (molar ratio: 85:15). ) A copolymer (weight average molecular weight: 20,000, dispersity: 2.9) and an alkali-soluble resin. (B) Component Example 8: A mixture mainly composed of (II-24) and (III-3) synthesized in Synthesis Examples 1 and (5) is used as the component (B). (C) Component (C-1): (PAG4-5) (C-2): (PAG4-4) (C-3): (PAG4-1) (C-4): (PAG7-2) (C-5) is a photoacid generator that generates a sulfonic acid having the following structure.

[0174]

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(D) Component (D-1): a compound having the following structure.

[0176]

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(F) Basic compound component (1); 1,5-diazabicyclo [4.3.0] -5-
Nonene (2); 2,4,5-triphenylimidazole (3); tri-n-butylamine (4); N-hydroxyethylpiperidine (G) Surfactant component W-1: Megafac F176 (Dainippon Ink (stock)
(Fluorine) W-2: Megafac R08 (Dai Nippon Ink Co., Ltd.)
(Fluorine and silicone type) W-3: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) W-4; Troysol S-366 (manufactured by Troy Chemical Co., Ltd.) (silicon-based) solvent PGMEA: propylene glycol Monomethyl ether acetate PGME; Propylene glycol monomethyl ether (1-methoxy-2-propanol) EL; Ethyl lactate EEP; Ethyl ethoxypropionate BL; γ-butyrolactone CH; Cyclohexanone

[0178]

[Table 4]

[0179]

[Table 5]

The following results are evident from the results shown in Table 2. The resist films of Examples 1-42, which are the positive resist compositions of the present invention, are exposed to KrF laser light, which is a deep ultraviolet light. As a result, a pattern is formed with a high resolution, a wide exposure margin and a wide depth of focus. On the other hand, in the case of Comparative Examples 1 to 3 not using the component (B), the exposure margin and the depth of focus are narrow.

B. Evaluation of electron beam exposure Some of the examples described in Table 1 above (Examples described in Table 3) were adjusted to a solid concentration of 17% to obtain a resist solution. The resist solution was uniformly applied to a hexamethyldisilazane-treated silicon substrate by a spin coater, and heated and dried on a hot plate at 120 ° C. for 60 seconds to form a 0.8 μm resist film. This resist film is exposed by an electron beam lithography system (acceleration voltage: 50 keV, beam diameter: 0.20 μm).
For 90 seconds on a hot plate. 2.38
The film was developed at 23 ° C. for 60 seconds with an aqueous solution of tetramethylammonium hydroxide having a concentration of% by weight, rinsed with pure water for 30 seconds, and then dried. From the pattern on the silicon wafer thus obtained, the performance of the resist was evaluated by the following method. Table 3 shows the results.

(Image Evaluation Method) The formed 0.20 μm contact hole pattern was observed with a scanning electron microscope.
Checked the profile.

(Sensitivity Evaluation Method) Evaluation was performed using an exposure amount (μC / cm ² ) for reproducing a contact hole pattern of 0.20 μm. (Resolving power evaluation method) The resolving power indicates a limit resolving power at an exposure amount for reproducing a 0.20 μm contact hole pattern.

[0184]

[Table 6]

From the results shown in Table 3 above, the composition of the present invention was further subjected to electron beam exposure with high sensitivity and high resolution.
An excellent rectangular profile pattern is formed without an inverse tapered profile caused by scattering peculiar to electron beam exposure.

[0186]

The positive resist composition of the present invention has an improved resolving power, an exposure margin and a focus in a lithography technique using a short wavelength exposure light source capable of ultrafine processing and a positive chemically amplified resist. Process tolerances such as depth have been improved. Also, excellent performance is exhibited even when an electron beam is used as the exposure energy beam.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Toshiaki Aoi 4,000 Kawajiri, Yoshida-cho, Haibara-gun, Shizuoka Prefecture F-term in Fujisha Shin Film Co., Ltd. FA17 4J002 AA03W AA03X AA05W AA05X BC12W BC12X BH01X CC03X EJ008 ER029 EU049 EU119 EU129 EV078 EV208 EV218 FD206 FD207 FD310 GP03

Claims (5)

[Claims] 1. A resin having a group which decomposes under the action of an acid to increase the solubility in an alkaline developer, and (B) which is substituted with at least one fluorine atom by irradiation with actinic rays or radiation. A positive resist composition comprising a compound that generates an aliphatic or aromatic carboxylic acid. 2. The positive resist composition according to claim 1, further comprising (D) a compound having a molecular weight of 3000 or less, which is decomposed by the action of an acid and increases the solubility in an alkali developing solution. . (B) a compound capable of generating an aliphatic or aromatic carboxylic acid substituted by at least one fluorine atom upon irradiation with actinic rays or radiation, (D) decomposing by the action of an acid, and alkali developing A positive resist composition comprising a compound having a molecular weight of 3000 or less, which increases solubility in a liquid, and (E) an alkali-soluble resin. 4. The positive resist composition according to claim 1, further comprising (C) a compound capable of generating a sulfonic acid upon irradiation with actinic rays or radiation. (F) a nitrogen-containing basic compound, and
The positive resist composition according to any one of claims 1 to 4, further comprising (G) a fluorine-based or silicon-based surfactant.