JP2001022072A - Positive type photoresist composition for exposure with far ultraviolet ray - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a positive type resist composition for exposure with far UV excellent in shelf stability of a resist solution by using a specified acid decomposable resin and a specified mixed solvent. SOLUTION: The positive type photoresist composition for exposure with far UV contains a compound which generates an acid when irradiated with active light or radiation, a resin which contains repeating units each having an alkali-soluble group protected with a group containing an alicyclic hydrocarbon structure of formula I, formula II or the like and is decomposed by the action of the acid to enhance its alkali solubility and a mixed solvent containing heptanone and γ-butyrolactone or the like. In the formula I, R11 is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or secondary butyl and Z is an atomic group required to form an alicyclic hydrocarbon group together with C. In the formula II, R12-R14 are each 1-4C linear or branched alkyl or an alicyclic hydrocarbon group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive photoresist composition used in an ultra microlithography process such as the production of an ultra LSI or a high-capacity micro chip, and other photofabrication processes. More specifically, the present invention relates to a positive photoresist composition capable of forming a highly fine pattern by using light having a wavelength of 250 nm, particularly a deep ultraviolet region including excimer laser light.

[0002]

2. Description of the Related Art In recent years, the degree of integration of integrated circuits has been increasing more and more, and in the manufacture of semiconductor substrates such as ultra LSIs, processing of ultrafine patterns having a line width of less than half a micron is required. It has become In order to meet this need, the wavelength of an exposure apparatus used for photolithography is becoming shorter and shorter, and now excimer laser light (XeCl, KrF, ArF, etc.) having a short wavelength among far ultraviolet rays is used.
The use of is being considered. A chemically amplified resist is used for forming a pattern in lithography in this wavelength region.

In general, chemically amplified resists can be broadly classified into three types: so-called two-component, 2.5-component and three-component resists. The two-component system combines a compound that generates an acid by photolysis (hereinafter referred to as a photoacid generator) and a binder resin. The binder resin is a resin having in its molecule a group (also referred to as an acid-decomposable group) that decomposes under the action of an acid to increase the solubility of the resin in an alkaline developer. The 2.5-component system further contains a low-molecular compound having an acid-decomposable group in such a two-component system. The three-component system contains a photoacid generator, an alkali-soluble resin, and the above low molecular compound.

The above-mentioned chemically amplified resist is suitable for a photoresist for irradiating ultraviolet rays or far ultraviolet rays, but among them, it is necessary to further meet the required characteristics in use. When an ArF excimer laser is used as a light source, a photoresist composition in which a (meth) acrylic resin having less absorption than a partially hydroxylated styrene resin is combined with a compound capable of generating an acid by light is proposed. Have been. For example, JP-A-7-199467, 7-25
No. 2324 and the like. Among them, JP-A-6-28961
No. 5 discloses a resin in which a tertiary carbon organic group is ester-bonded to oxygen of a carboxyl group of acrylic acid.

Further, Japanese Patent Application Laid-Open No. Hei 7-234511 discloses an acid-decomposable resin having an acrylate ester or a fumarate ester as a repeating unit. The fact is that performance has not been obtained.

Further, a resin into which an alicyclic hydrocarbon moiety has been introduced for the purpose of imparting dry etching resistance has been proposed. However, the introduction of an alicyclic hydrocarbon moiety has a disadvantage that the system becomes extremely hydrophobic. In addition, there are phenomena such as difficulty in developing with an aqueous solution of tetramethylammonium hydroxide (hereinafter referred to as TMAH), which has been widely used as a resist developing solution, and peeling of the resist from the substrate during the development. In response to such hydrophobicity of the resist, measures such as mixing an organic solvent such as isopropyl alcohol in a developing solution have been studied. Although some results have been obtained, concerns about the swelling of the resist film and the process become complicated. Etc. are not necessarily solved. In the approach of improving the resist, many measures have been taken to supplement various hydrophobic alicyclic hydrocarbon sites by introducing a hydrophilic group.

In general, a monomer having a carboxylic acid moiety such as acrylic acid or methacrylic acid or a monomer having a hydroxyl group or a cyano group in a molecule such as HEMA or acrylonitrile is replaced with an alicyclic hydrocarbon group. The aim was to solve the developability by copolymerizing with a monomer having the compound, but it was completely insufficient.

On the other hand, in addition to the method of introducing an alicyclic hydrocarbon site into the side chain of the acrylate monomer, a method of imparting dry etching resistance utilizing an alicyclic hydrocarbon site as a polymer main chain has also been studied. I have. However, this system also has the above problem, and improvement by a similar approach is being studied.

Further, Japanese Patent Application Laid-Open No. 9-73173,
JP-A-90637 and JP-A-10-161313 each disclose an alkali-soluble group protected by a structure containing an alicyclic group, and a structural unit which is made to be alkali-soluble when the alkali-soluble group is eliminated by an acid. A resist material using an acid-sensitive compound is described. JP-A-10-2
No. 54139 discloses an acid-decomposable group-containing resin having an alicyclic skeleton, a radiation-sensitive acid generator, a linear ketone, a cyclic ketone, a propylene glycol monoalkyl ether acetate and an alkyl 2-hydroxypropionate. A resin composition containing a solvent comprising a mixture with at least one member selected from the group is described. This system also has the above problems, and improvements by a similar approach are being studied.

Although various resins containing acid-decomposable groups have been studied as described above in a chemically amplified photoresist for deep ultraviolet exposure, there is still room for improvement due to the hydrophobicity of the resin. did. That is, when the chemically amplified photoresist is stored in a liquid state, the compatibility between the resin and the photoacid generator is poor, particles are generated in the liquid, and the resist performance is deteriorated. Still present (deterioration of storage stability of resist solution).

[0011]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to solve the problem of the performance improvement technology inherent in microphotofabrication using far ultraviolet light, particularly ArF excimer laser light. Specifically, it is an object of the present invention to provide a positive resist composition for exposure to deep ultraviolet light, which has excellent storage stability of a resist solution.

[0012]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies on constituent materials of a resist composition in a positive-type chemical amplification system, and have found that a specific acid-decomposable resin and a specific mixed solvent are used. Knowing that the purpose of the invention is achieved,
The present invention has been reached. That is, the above object is achieved by the following constitutions.

(1) (a) a compound capable of generating an acid upon irradiation with actinic rays or radiation, (b) (a) containing an alicyclic hydrocarbon structure represented by the following general formulas (pI) to (pVI) A repeating unit having an alkali-soluble group protected by at least one of the groups; (b) a repeating unit represented by the following general formula (II); and (c) a repeating unit represented by the following general formula (III-a) to A resin containing at least one of the repeating units represented by (III-d) and decomposing under the action of an acid to increase the solubility in alkali; (c) (1) heptanone; and (2) γ-butyrolactone , At least one of ethylene carbonate and propylene carbonate
A positive photoresist composition for deep ultraviolet exposure, comprising a mixed solvent containing a seed.

[0014]

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In the general formulas (pI) to (pVI), R ₁₁ is
Represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a sec-butyl group, and Z represents an atomic group necessary for forming an alicyclic hydrocarbon group together with a carbon atom. Represents R _{12 to} R ₁₆ each independently represent a linear or branched alkyl group or an alicyclic hydrocarbon group having 1 to 4 carbon atoms, provided that R _{12 to} R ₁₄
And at least one of R ₁₅ and R ₁₆ represents an alicyclic hydrocarbon group. R ₁₇ to R ₂₁ each independently represent a hydrogen atom, 1 to 4 carbon atoms, a straight-chain or branched alkyl group or an alicyclic hydrocarbon group, provided that, R ₁₇
At least one of to R ₂₁ represents an alicyclic hydrocarbon group. Further, any one of R ₁₉ and R ₂₁ has 1 to 4 carbon atoms,
Represents a linear or branched alkyl group or an alicyclic hydrocarbon group. R _{22 to} R ₂₅ each independently represent a linear or branched alkyl group or an alicyclic hydrocarbon group having 1 to 4 carbon atoms, provided that at least one of R _{22 to} R ₂₅ is an aliphatic group; Represents a cyclic hydrocarbon group.

[0016]

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In the general formula (II), R 1 represents a hydrogen atom, a halogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms. X1 represents a divalent linking group. Lc represents a lactone group.

[0018]

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In the above formula, R 1 represents a hydrogen atom, a halogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms. R30 to R37 each independently represent a hydrogen atom or an alkyl group which may have a substituent. R represents a hydrogen atom or an optionally substituted alkyl group, cyclic alkyl group, aryl group or aralkyl group. m represents an integer of 1 to 10. X2
Is a single bond, or an optionally substituted alkylene group, a cyclic alkylene group, an arylene group, or an ether group, a thioether group, a carbonyl group, an ester group,
A single group selected from the group consisting of an amide group, a sulfonamide group, a urethane group, and a urea group, or a combination of at least two or more of these groups and represents a divalent group that is not decomposed by the action of an acid. Z1 represents a single bond, an ether group, an ester group, an amide group, an alkylene group, or a divalent group obtained by combining these. R38 represents a single bond, an alkylene group, an arylene group, or a divalent group obtained by combining these. R40 represents an alkylene group, an arylene group, or a divalent group obtained by combining them. R39
Represents an alkyl group, a cyclic alkyl group, an aryl group or an aralkyl group which may have a substituent. R41 is
A hydrogen atom or an alkyl group, a cyclic alkyl group, an alkenyl group, an aryl group or an aralkyl group which may have a substituent. A represents any of the functional groups shown below.

[0020]

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(2) (d) The positive photoresist composition for deep UV exposure according to the above (1), which contains an organic basic compound. (3) (e) The above (1) or (2), which contains a fluorine-based and / or silicon-based surfactant.
4. The positive photoresist composition for deep ultraviolet exposure according to item 1.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the compounds used in the present invention will be described in detail. <(A) Compound that generates an acid upon irradiation with actinic rays or radiation (photoacid generator)> The photoacid generator used in the present invention is a compound which generates an acid upon irradiation with actinic rays or radiation. As the photoacid generator used in the present invention, a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization,
Known light (eg, ultraviolet light having a wavelength of 400 to 200 nm, far ultraviolet light, particularly preferably g-line, h-line, i-line)
X-rays, KrF excimer laser light), ArF excimer laser light, electron beams, X-rays, compounds generating an acid by a molecular beam or an ion beam, and mixtures thereof can be appropriately selected and used.

Other photoacid generators used in the present invention include, for example, onium salts such as diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenonium salts, arsonium salts, and the like.
Organic halogen compound, organic metal / organic halide, o
A photoacid generator having a nitrobenzyl-type protecting group; a compound represented by photolysis such as iminosulfonate that generates sulfonic acid; a disulfone compound; a diazoketosulfone; and a diazodisulfone compound.
Further, a group in which an acid is generated by such light or a compound in which a compound is introduced into a main chain or a side chain of a polymer can be used.

Further, VNRPillai, Synthesis, (1), 1 (198
0), A. Abad etal, Tetrahedron Lett., (47) 4555 (1971),
Compounds that generate an acid by light described in DHR Barton et al., J. Chem. Soc., (C), 329 (1970), U.S. Pat. No. 3,779,778, and EP 126,712 can also be used.

Among the compounds capable of decomposing upon irradiation with an electron beam to generate an acid, those particularly effectively used will be described below. (1) The following general formula (PAG) substituted with a trihalomethyl group
The oxazole derivative represented by 1) or the general formula (PA)
An S-triazine derivative represented by G2).

[0026]

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In the formula, R ²⁰¹ is a substituted or unsubstituted aryl group or alkenyl group, and R ²⁰² is a substituted or unsubstituted aryl group, alkenyl group, alkyl group, —C (Y) ₃
Show Y represents a chlorine atom or a bromine atom. Specific examples include the following compounds, but the present invention is not limited thereto.

[0028]

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(2) An iodonium salt represented by the following general formula (PAG3) or a sulfonium salt represented by the following general formula (PAG4).

[0030]

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Here, the formulas Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aryl group. R ²⁰³ , R ²⁰⁴ , R
²⁰⁵ is each independently a substituted or unsubstituted alkyl group,
Indicates an aryl group.

Z^-Represents a counter anion, for example, BF_Four ^-,
AsF₆ ^-, PF₆ ^-, SbF₆ ^-, SiF₆ ^2-, ClO_Four ^-,
CF_ThreeSO_Three ^-Perfluoroalkanesulfonic acid ani
On, pentafluorobenzenesulfonate anion, na
Condensed polynuclear aromatics such as phthalene-1-sulfonic acid anion
Sulfonic acid anion, anthraquinone sulfonic acid ani
And sulfonic acid group-containing dyes.
It is not limited to these.

Further, two of R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ and Ar ¹ and Ar ² may be bonded through a single bond or a substituent.

Specific examples include the following compounds, but are not limited thereto.

[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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The above onium salts represented by the general formulas (PAG3) and (PAG4) are known, for example, JWKnapczyk
etal, J. Am. Chem. Soc., 91, 145 (1969), ALMaycok eta
l, J. Org. Chem., 35, 2532, (1970), E. Goethas et al., Bul
l.Soc.Chem.Belg., 73,546, (1964), HM Leicester, J. Am
e.Chem.Soc., 51,3587 (1929), JVCrivello etal, J.Pol
18, 2677 (1980), U.S. Pat. Nos. 2,807,648 and 4,247,473, and JP-A-53-101,331.

(3) Disulfone derivatives represented by the following formula (PAG5) or iminosulfonate derivatives represented by the following formula (PAG6).

[0044]

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Where Ar^Three, Ar^FourAre each independently substituted
Or an unsubstituted aryl group. R ²⁰⁶Is replaced or
It represents an unsubstituted alkyl group or aryl group. A is a substitution
Or unsubstituted alkylene, alkenylene, arylene
Shows a substituent group. Specific examples include the compounds shown below.
However, the present invention is not limited to these.

[0046]

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[0047]

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[0048]

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(4) A diazodisulfone derivative represented by the following general formula (PAG7).

[0050]

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Here, R represents a linear, branched or cyclic alkyl group or an optionally substituted aryl group. Specific examples include the following compounds, but are not limited thereto.

[0052]

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The amount of the photoacid generator to be added is usually in the range of 0.001 to 40% by weight, preferably 0.01 to 20% by weight, more preferably 0.01 to 20% by weight, based on the solid content in the composition. Is used in the range of 0.1 to 5% by weight. When the addition amount of the photoacid generator is less than 0.001% by weight, the sensitivity is lowered. When the addition amount is more than 40% by weight, the light absorption of the resist becomes too high, and the profile deteriorates,
The process (especially baking) margin is unfavorably reduced.

<Resin which decomposes under the action of (b) acid to increase solubility in alkali> Resin which decomposes under the action of (b) acid and increases solubility in alkali used in the composition of the present invention (hereinafter referred to as "resin") , Simply referred to as “(b) alkali-soluble resin”) is represented by (a) the general formula (pI) to
(PVI) a repeating unit having an alkali-soluble group protected by at least one of groups having an alicyclic hydrocarbon structure, (b) a repeating unit represented by the above general formula (II), and (C) The above general formulas (III-a) to general formulas
It contains at least one of the repeating units represented by (III-d).

In the general formulas (pI) to (pVI), R
The alkyl group for _{12 to} R ₂₅ represents a linear or branched alkyl group having 1 to 4 carbon atoms, which may be substituted or unsubstituted. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group,
Examples include a sec-butyl group and a t-butyl group. Further, as a further substituent of the above alkyl group, one having 1 carbon atom
And 4 to 4 alkoxy groups, halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom), acyl group, acyloxy group, cyano group, hydroxyl group, carboxy group, alkoxycarbonyl group, nitro group and the like.

The alicyclic hydrocarbon group for R _{12 to} R _{25 or} the alicyclic hydrocarbon group formed by Z and a carbon atom may be monocyclic or polycyclic. Specific examples include groups having a monocyclo, bicyclo, tricyclo, tetracyclo structure or the like having 5 or more carbon atoms. The number of carbon atoms is preferably from 6 to 30, particularly preferably from 7 to 25. These alicyclic hydrocarbon groups may have a substituent. Hereinafter, structural examples of the alicyclic portion of the group containing the alicyclic hydrocarbon structure will be described.

[0057]

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[0058]

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[0059]

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In the present invention, preferred examples of the alicyclic moiety include an adamantyl group, a noradamantyl group, a decalin residue, a tricyclodecanyl group, a tetracyclododecanyl group, a norbornyl group, a cedrol group, and a cyclohexyl group. , Cycloheptyl group, cyclooctyl group,
Examples thereof include a cyclodecanyl group and a cyclododecanyl group. More preferred are an adamantyl group, a decalin residue, a norbornyl group, a cedrol group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecanyl group, and a cyclododecanyl group.

Examples of the substituent of these alicyclic hydrocarbon groups include an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group and an alkoxycarbonyl group. As the alkyl group, a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group is preferable, and a methyl group, an ethyl group, a propyl group, and an isopropyl group are more preferable. Examples of the substituent of the substituted alkyl group include a hydroxyl group, a halogen atom and an alkoxy group. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group.

Examples of the alkali-soluble group protected by the structure represented by the general formulas (pI) to (pVI) in the above (b) alkali-soluble resin include various groups known in this technical field. Specifically, a carboxylic acid group,
Examples thereof include a sulfonic acid group, a phenol group, and a thiol group, and preferred are a carboxylic acid group and a sulfonic acid group. As the alkali-soluble group protected by the structure represented by any of the general formulas (pI) to (pVI) in the above resin, preferably, groups represented by the following general formulas (pVII) to (pXI) are exemplified.

[0063]

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Here, R _{11 to} R ₂₅ and Z are the same as defined above. (B) Constituting the alkali-soluble resin (b), (a) general formulas (pI) to (pVI)
As the repeating unit having an alkali-soluble group protected by the structure represented by the following formula, a repeating unit represented by the following general formula (pA) is preferable.

[0065]

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In the general formula (pA), R represents a hydrogen atom, a halogen atom or a substituted or unsubstituted linear or branched alkyl group having 1 to 4 carbon atoms. A plurality of Rs may be the same or different. A ′ is a single bond or two or more selected from the group consisting of a single bond, an alkylene group, a substituted alkylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a sulfonamide group, a urethane group, and a urea group. Represents a combination of the above groups. Ra represents any one of the above formulas (pI) to (pVI). Hereinafter, specific examples of the monomer corresponding to the repeating unit represented by the general formula (pA) are shown.

[0067]

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[0068]

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[0069]

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[0070]

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[0071]

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[0072]

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(B) The alkali-soluble resin contains (b) a repeating unit represented by the above general formula (II). The alkyl group of R1 in the above general formula (II) may have 1 to 1 carbon atoms.
4 are linear or branched. Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl and the like. The alkyl group may be substituted,
Examples of the substituent include an alkoxy group having 1 to 4 carbon atoms, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), an acyl group, an acyloxy group, a cyano group, a hydroxyl group, a carboxy group, an alkoxycarbonyl group, Examples thereof include a nitro group. Examples of the halogen atom for R1 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

X1 in the general formula (II) represents a divalent linking group. Examples of the divalent linking group include a single bond, an alkylene group, a substituted alkylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a sulfonamide group,
Examples thereof include a divalent group in which one or a combination of two or more types selected from the group consisting of a urethane group and a urea group can be given. Preferred X1 is a single bond, having 1 to 1 carbon atoms.
Examples include a single alkylene group, an ether group, a carbonyl group, and an ester group, or a divalent group obtained by combining two or more of these groups. The combination of two or more
Preferred structures as the valent groups include the following.

[0075]

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In the above formula, Ra and Rb each independently represent a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom,
Represents a hydroxyl group or an alkoxy group. As the alkyl group, a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group is preferable, and a methyl group, an ethyl group, a propyl group, and an isopropyl group are more preferable. As a substituent of the substituted alkyl group, a hydroxyl group,
Examples include a halogen atom and an alkoxy group. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom.
r1 represents an integer of 1 to 10. m represents the number of 1-3. Lc in the general formula (II) represents a lactone group. Specific examples of the lactone group are described below, but are not limited thereto.

[0077]

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Ra, Rb, Rc, Rd of the above lactone group
Each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms which may have a substituent,
m and n each independently represent an integer of 0 to 3, and m + n is 2 or more and 6 or less. Specific examples of the repeating unit represented by the general formula (II) are described below.

[0079]

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[0080]

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(C) In the general formulas (III-a) to (III-d),
R1 has the same meaning as R1. R30-R37, R, R3
Examples of the alkyl group of R41 include a linear or branched alkyl group, which may have a substituent. As the linear or branched alkyl group, a linear or branched alkyl group having 1 to 12 carbon atoms is preferable, and a linear or branched alkyl group having 1 to 10 carbon atoms is more preferable. And more preferably methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl Group. Examples of the cyclic alkyl group for R, R39 and R41 include those having 3 to 30 carbon atoms.
Cyclopropyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group, tricyclodecanyl group, dicyclopentenyl group, nobornane epoxy group, menthyl group, isomenthyl group, neomenthyl group, tetracyclododecanyl group, Steroid residues and the like can be mentioned.

The aryl group represented by R, R39 and R41 has 6 to 20 carbon atoms, and may have a substituent. Specific examples include a phenyl group, a tolyl group, and a naphthyl group. Examples of the aralkyl group represented by R, R39 and R41 include those having 7 to 20 carbon atoms, such as a benzyl group, a phenethyl group and a cumyl group which may have a substituent. The alkenyl group for R41 has 2 carbon atoms.
To 6 alkenyl groups, specifically, a vinyl group, a propenyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, a cyclopentenyl group, a cyclohexenyl group, a 3-oxocyclohexenyl group, and a 3-oxo group. A cyclopentenyl group, a 3-oxoindenyl group and the like. Among these, the cyclic alkenyl group may contain an oxygen atom.

As the linking group X2, an alkylene group, a cyclic alkylene group, an arylene group or an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a sulfonamide group, a urethane group which may have a substituent. A group selected from the group consisting of urea groups, or a combination of at least two or more of these groups;
Examples include divalent groups that do not decompose under the action of an acid. Z1
Represents a single bond, an ether group, an ester group, an amide group, an alkylene group, or a divalent group obtained by combining these.
R38 represents a single bond, an alkylene group, an arylene group, or a divalent group obtained by combining these. R40 represents an alkylene group, an arylene group, or a divalent group obtained by combining them. Examples of the arylene group in X 2, R 38 and R 40 include those having 6 to 10 carbon atoms, which may have a substituent. Specific examples include a phenylene group, a tolylene group, and a naphthylene group. As the cyclic alkylene group for X 2, those in which the above-mentioned cyclic alkyl group is divalent are exemplified. Examples of the alkylene group represented by X2, Z1, R38 and R40 include groups represented by the following formula. -[C (Ra) (Rb)] r- wherein Ra and Rb represent a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, or an alkoxy group;
Both may be the same or different. As the alkyl group, a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group is preferable, and a methyl group, an ethyl group, a propyl group, and an isopropyl group are more preferable. As the substituent of the substituted alkyl group,
Examples include a hydroxyl group, a halogen atom and an alkoxy group. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. r represents an integer of 1 to 10. Specific examples of the linking group X2 are shown below, but the present invention is not limited thereto.

[0084]

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Further substituents in the alkyl group, cyclic alkyl group, alkenyl group, aryl group, aralkyl group, alkylene group, cyclic alkylene group and arylene group include carboxyl group, acyloxy group, cyano group,
Alkyl group, substituted alkyl group, halogen atom, hydroxyl group,
Examples include an alkoxy group, an acetylamide group, an alkoxycarbonyl group, and an acyl group. Here, examples of the alkyl group include lower alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a cyclopropyl group, a cyclobutyl group, and a cyclopentyl group. Examples of the substituent of the substituted alkyl group include a hydroxyl group, a halogen atom and an alkoxy group. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group. Examples of the acyloxy group include an acetoxy group. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom.

Hereinafter, as specific examples of the structure of the side chain in the general formula (III-b), specific examples of the terminal structure excluding X2 are shown below, but the present invention is not limited thereto. .

[0087]

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Hereinafter, specific examples of the monomer corresponding to the repeating structural unit represented by the general formula (III-c) are shown, but the present invention is not limited thereto.

[0089]

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[0090]

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[0091]

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Hereinafter, specific examples of the repeating structural unit represented by the general formula (III-d) will be shown, but the present invention is not limited thereto.

[0093]

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[0094]

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[0095]

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In formula (III-b), R30 to R37 are preferably a hydrogen atom or a methyl group. R is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. m
Is preferably 1 to 6. In the general formula (III-c), R38
Is preferably an alkylene group such as a single bond, a methylene group, an ethylene group, a propylene group, or a butylene group. As R39, an alkyl group having 1 to 10 carbon atoms such as a methyl group or an ethyl group, a cyclopropyl group, a cyclohexyl Groups, cyclic alkyl groups such as camphor residues, naphthyl groups, and naphthylmethyl groups are preferred. Z1 is preferably a single bond, an ether bond, an ester bond, an alkylene group having 1 to 6 carbon atoms, or a combination thereof, and more preferably a single bond or an ester bond. In the formula (III-d), R40 is preferably an alkylene group having 1 to 4 carbon atoms. R41
May have a substituent, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a neopentyl group, an alkyl group having 1 to 8 carbon atoms such as an octyl group, a cyclohexyl group, an adamantyl group , A norbornyl group, a boronyl group, an isobornyl group, a mentyl group, a morpholino group, a 4-oxocyclohexyl group, and a phenyl group, a toluyl group, a mesityl group, a naphthyl group, and a camphor residue which may have a substituent are preferable. These further substituents include a halogen atom such as a fluorine atom, a carbon atom having 1 to 4 carbon atoms.
Are preferred.

In the present invention, general formulas (III-a) to (III-a)
Among (III-d), repeating units represented by formulas (III-b) and (III-d) are preferable.

(B) The alkali-soluble resin includes (a)
A repeating unit other than (b) and (c) may be included.

(B) In the alkali-soluble resin, the molar ratio of each repeating unit is determined by the acid value, the dry etching resistance of the resist, the suitability for a standard developer, the substrate adhesion, the density dependence of the resist profile, and the general It is appropriately set in order to adjust the resolution, heat resistance, sensitivity, and the like, which are required in a global manner.

(B) In the alkali-soluble resin, (a) the content of the repeating unit having an alkali-soluble group protected by the structure represented by any of formulas (pI) to (pVI) is preferably Is 20 to 70 mol%
, More preferably 25 to 65 mol%, still more preferably 30 to 60 mol%. (A) If there are too many repeating units, it becomes difficult to form an image, and if there are too few, the dry etching resistance is impaired. (B) The content of the repeating unit represented by the above general formula (II) is preferably 20 to 70 mol% in all the repeating units.
, More preferably 25 to 65 mol%, still more preferably 30 to 60 mol%. (B) If the repeating unit is excessively present, the dry etching resistance is impaired, and if it is too small, image formation becomes difficult. (C) The content of the repeating units represented by formulas (III-a) to (III-d) is 0.1 to 2 in all the repeating units.
0 mol%, preferably 0.3 to 18 mol%, more preferably 0.5 to 16 mol%. (C) When the repeating unit is present in an amount exceeding 20 mol%, the positive photoresist composition of the present invention causes non-negligible film loss of the resist after exposure and development. Is unfavorable due to the density dependence of

(B) The weight-average molecular weight Mw of the alkali-soluble resin is, as a value measured by gel permeation chromatography, a polystyrene standard, preferably 1,000 to 1,000,000, more preferably 1, 500 to 500,000, more preferably 2,0
00 to 200,000, particularly preferably 2,500 to 1
The larger the weight average molecular weight, the higher the heat resistance and the like, while the lower the developability and the like.

The (b) alkali-soluble resin used in the present invention can be synthesized according to a conventional method, for example, by a radical polymerization method.

In the positive photoresist composition for deep ultraviolet exposure according to the present invention, (b) the amount of the alkali-soluble resin added to the whole composition is 40 to 99.
It is preferably 99% by weight, more preferably 50 to 99.9.
7% by weight.

The composition of the present invention comprises, together with (a) the photoacid generator and (b) the alkali-soluble resin, (c)
(1) heptanone (hereinafter also referred to as a solvent of (1)),
(2) at least one of γ-butyrolactone, ethylene carbonate and propylene carbonate (hereinafter, referred to as
(Also referred to as the solvent of (2)).
In the present invention, examples of heptanone include 2-heptanone, 3-heptanone, and 4-heptanone, and preferred is 2-heptanone. As for the use ratio of the solvent (1) and the solvent (2), the amount of the solvent (2) is preferably 0.5 to the total weight of the solvent (1) and the solvent (2). -30% by weight, more preferably 1-20% by weight, even more preferably 3-10% by weight.

Preferred examples of the combination of the solvent (1) and the solvent (2) are 2-heptanone + γ-butyrolactone, 2-heptanone + ethylene carbonate,
2-heptanone + propylene carbonate. The solid content of the (a) photoacid generator and (b) the alkali-soluble resin is added to the mixed solvent as a solid content concentration of 5% to 25%.
Preferably dissolved, more preferably 8% to 20%
It is.

The positive photoresist composition for deep ultraviolet exposure according to the present invention preferably contains (C) a fluorine-based and / or silicon-based surfactant. Thereby, the storage stability of the resist solution becomes more excellent. Examples of the fluorine-based and / or silicon-based surfactant include a fluorine-based surfactant, a silicon-based surfactant, and at least one type of surfactant containing both a fluorine atom and a silicon atom. As these surfactants, for example, JP-A-62-36663, JP-A-61-226746, JP-A-61-226745
No., JP-A-62-170950, JP-A-63-34540, JP-A-7-2
No. 30165, JP-A-8-62834, JP-A-9-54432, JP-A-9
No. -5988, and the following commercially available surfactants can be used as they are. As a commercially available surfactant that can be used, for example, F-top EF30
1, EF303, (Shin-Akita Chemical Co., Ltd.), Florard FC430, 431
(Manufactured by Sumitomo 3M Limited), Mega Fuck F171, F173, F1
76, F189, R08 (Dainippon Ink Co., Ltd.), Surflon S
-382, SC101, 102, 103, 104, 105, 106 (manufactured by Asahi Glass Co., Ltd.) and the like. 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 to 2% by weight, preferably 0.01 to 1% by weight, based on the solid content of the composition of the present invention. These surfactants can be used alone or in combination of two or more.

Examples of the other surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; Polyoxyethylene alkyl allyl ethers such as oxyethylene octyl phenol ether, polyoxyethylene nonyl phenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate Fatty acid esters such as sorbitan trioleate, sorbitan tristearate, polyoxyethylene sorbitan monolaurate Nonionic surfactants such as polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan tristearate, etc. Can be mentioned. The amount of these surfactants is usually 2 parts by weight or less, preferably 1 part by weight or less, per 100 parts by weight of the solids in the composition of the present invention. These surfactants may be added alone or in some combination.

In the present invention, it is preferable to use an organic basic compound in that the storage stability of the resist solution becomes more excellent. The organic basic compound is a compound having a higher basicity than phenol, and among them, a nitrogen-containing basic compound is preferable. Examples of the nitrogen-containing basic compound include those having the following structure.

[0110]

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Here, R ²⁵⁰ , R ²⁵¹ and R ²⁵² are the same or different and are a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aminoalkyl group having 1 to 6 carbon atoms, a hydroxyalkyl having 1 to 6 carbon atoms. Or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, wherein R ²⁵¹ and R ²⁵² may be bonded to each other to form a ring.

[0112]

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Wherein R ²⁵³ , R ²⁵⁴ , R ²⁵⁵ and R ²⁵⁶
Are the same or different and represent an alkyl group having 1 to 6 carbon atoms.) Further preferred compounds are nitrogen-containing basic compounds having two or more nitrogen atoms having different chemical environments in one molecule,
Particularly preferred are compounds containing both a substituted or unsubstituted amino group and a ring structure containing a nitrogen atom, or compounds having an alkylamino group. 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 aminomorpholine, substituted or unsubstituted amino And alkyl morpholine. Preferred substituents are an amino group, an aminoalkyl group, an alkylamino group, an aminoaryl group, an arylamino group, an alkyl group, an alkoxy group, an acyl group, an acyloxy group, an aryl group, an aryloxy group, a nitro group,
A hydroxyl group and a cyano group.

Preferred specific compounds are guanidine, 1,1-dimethylguanidine, 1,1,3,3,-
Tetramethylguanidine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2-diethylaminopyridine, 2- (aminomethyl) pyridine,
-Amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-5-methylpyridine, 2-amino-6-methylpyridine, 3-aminoethylpyridine, 4-aminoethylpyridine, 3-amino Pyrrolidine, piperazine, N- (2-aminoethyl) piperazine, N- (2-aminoethyl) piperidine, 4-amino-2,2,6,6-tetramethylpiperidine, 4-piperidinopiperidine, 2-imino Piperidine, 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,
-Pyrazoline, 3-pyrazoline, N-aminomorpholine, N- (2-aminoethyl) morpholine, 1,5-
Diazabicyclo [4,3,0] non-5-ene, 1,8
-Diazabicyclo [5,4,0] undec-7-ene,
3,4,5-triphenylimidazole, N-methylmorpholine, N-ethylmorpholine, N-hydroxyethylmorpholine, N-benzylmorpholine, cyclohexylmorpholinoethylthiourea (CHMETU), etc.
Grade morpholine derivatives, hindered amines described in JP-A-11-52575 (for example, [0005]
, Etc.) and the like, but is not limited thereto.

Particularly preferred specific examples are 1,5-diazabicyclo [4.3.0] -5-nonene, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,4-diazabicyclo [2 .2.2] octane, 4-dimethylaminopyridine,
Hexamethylenetetramine, 4,4-dimethylimidazoline, pyrroles, pyrazoles, imidazoles, pyridazines, pyrimidines, tertiary morpholines such as CHMETU, bis (1,2,2,6,6-pentamethyl-
Hindered amines such as (4-piperidyl) sebagate and the like can be mentioned.

Among them, 1,5-diazabicyclo [4,
3,0] non-5-ene, 1,8-diazabicyclo [5,4,0] undec-7-ene, 1,4-diazabicyclo [2,2,2] octane, 4-dimethylaminopyridine, hexamethylene Preferred are tetramine, CHMETU, and bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate.

These nitrogen-containing basic compounds are used alone or in combination of two or more. The amount of the nitrogen-containing basic compound used is based on the total solid content of the resist composition.
Usually, 0.001 to 10% by weight, preferably 0.01 to 10% by weight.
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.

The positive photoresist composition of the present invention may further contain an acid-decomposable dissolution inhibiting compound, a dye,
A plasticizer, a sensitizer, a compound that promotes solubility in a developer, and the like can be contained.

The positive resist composition of the present invention is applied on a substrate to form a thin film. The thickness of this coating film is preferably from 0.2 to 1.2 μm. In the present invention,
If necessary, a commercially available inorganic or organic antireflection film can be used.

As the antireflection film, an inorganic film type such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon and α-silicon, and an organic film type comprising a light absorbing agent and a polymer material can be used. The former requires equipment such as a vacuum deposition apparatus, a CVD apparatus, and a sputtering apparatus for film formation. As the organic antireflection film, for example, Japanese Patent Publication No. 7-69
611, a condensate of a formaldehyde-modified melamine resin with a diphenylamine derivative, an alkali-soluble resin,
A light absorbing agent or a reaction product of a maleic anhydride copolymer and a diamine type light absorbing agent described in US Pat. No. 5,294,680;
JP-A-6-118631, containing a resin binder and a methylolmelamine-based thermal crosslinking agent;
Acrylic resin type antireflection coating having a carboxylic acid group, an epoxy group and a light absorbing group in the same molecule as described in 18656, one comprising a methylolmelamine and a benzophenone-based light absorbing agent described in JP-A-8-87115, and described in JP-A-8-179509. Examples thereof include those obtained by adding a low-molecular-weight light absorbing agent to a polyvinyl alcohol resin. Also, as an organic anti-reflection film,
DUV30 series manufactured by Brewer Science,
DUV-40 series, Shipley's AC-2, AC
-3 can also be used.

The resist solution is applied on a substrate (eg, a silicon / silicon dioxide coating) used for manufacturing precision integrated circuit devices (on a substrate provided with the above antireflection film if necessary), a spinner, a coater, and the like. After coating by an appropriate coating method such as that described above, exposure through a predetermined mask, baking and development can provide a good resist pattern. Here, the exposure light is preferably 150
It is light having a wavelength of nm to 250 nm. Specifically, Kr
F excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (157
nm), X-rays, electron beams and the like.

Examples of the developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia.
Primary amines such as ethylamine and n-propylamine;
Secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcoholamines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide and the like An alkaline aqueous solution such as a quaternary ammonium salt, a cyclic amine such as pyrrole, or pyrhelidine can be used. Further, an appropriate amount of an alcohol or a surfactant may be added to the above alkaline aqueous solution.

[0123]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples. Synthesis Example (1) Synthesis of Resin (1) -1 2-methyl-2-adamantyl methacrylate, butyrolactone methacrylate, and methacrylic acid were converted to 40/48 /
Charged at a ratio of 12 and dissolved in N, N-dimethylacetamide / tetrahydrofuran = 5/5, solid content concentration 20%
Was prepared. The solution was added to Wako Pure Chemical V
-65 was added at 4 mol%, and this was added dropwise to 10 mL of N, N-dimethylacetamide heated to 60 ° C over 2 hours under a nitrogen atmosphere. After completion of the dropwise addition, the reaction solution was heated for 3 hours, 2 mol% of V-65 was added again, and the mixture was stirred for 3 hours. After completion of the reaction, the reaction solution is cooled to room temperature, and 3 L of distilled water is added.
The white powder crystallized and precipitated was recovered. The polymer composition ratio determined from C ¹³ NMR was 40/47/13. The weight average molecular weight in terms of standard polystyrene determined by GPC measurement was 6,800. By the same operation as in the above synthesis example, a resin having the following structure and the composition ratio and the molecular weight shown in the following table was synthesized. (Repeatable units 1, 2, and 3 are from the left in the structural formula.)

[0124]

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[0125]

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[0126]

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[0127]

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[0128]

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[0129]

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[0130]

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[0131]

[Table 1]

Examples 1 to 34 and Comparative Examples Resins shown in Tables 2 and 3 synthesized above were each used in 1.4.
g, photoacid generator 0.18 g and organic basic compound 1
0 mg and 1% by weight of a surfactant were blended, and each was dissolved in a mixed solvent shown in Tables 2 and 3 at a solid content of 14% by weight. A positive photoresist composition solution was prepared. As a comparative example, in the above example, as the resin, a resin (A4) synthesized by the method described in Synthesis Example 4 of JP-A-10-254139 [0073] was used, and as a solvent, 2-heptanone ( S1) and ethyl 2-hydroxypropionate (ethyl lactate) (S5)
Using a solvent mixed at a ratio of 0:30 (weight ratio), Table 3
In the same manner as in the above example, a positive photoresist composition solution for deep ultraviolet exposure was prepared according to the formulation described in Example 1.

In Table 2 below, photoacid generator 1 represents triphenylsulfonium triflate, and photoacid generator 2
Represents the above (PAG4-35), and the photoacid generator 3 is
The above (PAG4-36) is represented, and the photoacid generator 4 represents the above (PAG4-37). As the surfactant, W-1: Megafac F176 (Dainippon Ink Co., Ltd.)
(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: Polyoxyethylene nonylphenyl ether

As an organic basic compound, 1 is 1,5-
Diazabicyclo [4.3.0] -5-nonene (DBN)
2 represents bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebagate 3 represents tri-n-butylamine.

As the solvent, S1: 2-heptanone S2: γ-butyrolactone S3: ethylene carbonate S4: propylene carbonate

(Evaluation Test) The obtained positive photoresist composition solution was applied on a silicon wafer by using a spin coater, dried at 140 ° C. for 90 seconds, and about 0.5 μm
Was formed and exposed to an ArF excimer laser (stepper having a wavelength of 193 nm and NA = 0.55). 9 post-exposure bake at 120 ° C
This was performed for 0 seconds, developed with a 2.38% aqueous solution of tetramethylammonium hydroxide, and rinsed with distilled water to obtain a resist pattern profile. For these, the storage stability of the resist composition was evaluated as follows.

[Storage Stability of Resist Composition] (Rate of Sensitivity Variation) After storing the prepared resist solution at 30 ° C. for one month, the sensitivity was evaluated, and the rate of variation from the sensitivity before storage was measured. . The sensitivity is 0.18 μm in line width.
Was measured as relative sensitivity with the sensitivity of Example 1 taken as 1 and the exposure amount reproducing the pattern No. 1 as the sensitivity. (Initial value and increase number of particles) The number of particles immediately after the preparation of the prepared resist solution is used as the initial value of the particles, and the initial value and the solution after storing the resist solution at 30 ° C. for one month. The number of particles in the medium was measured, and the number of particles increased before and after the storage with time was evaluated. Table 3 shows the results.

[0138]

[Table 2]

[0139]

[Table 3]

As is clear from the results, the comparative example was inferior in storage stability of the resist solution. On the other hand, the positive photoresist composition of the present invention has a satisfactory level of storage stability of the resist solution. That is, it is suitable for lithography using far ultraviolet rays such as ArF excimer laser exposure.

[0141]

The positive photoresist composition for deep ultraviolet exposure according to the present invention is sufficiently suitable especially for light in the wavelength region of 170 nm to 220 nm, and has excellent storage stability of the resist solution.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H025 AA00 AB16 AC04 AC08 AD03 BE00 BG00 CC03 CC04 CC20 FA03 FA12 FA17 4J002 BG071 BG081 CF021 CF101 CH022 CP032 EA029 EB068 EE037 EH007 EL057 EN029 EN049 EN00 EN099 EU0 EU099 EU0 EU029 EU139 EU186 EU216 EU239 EV216 EV296 EW176 EZ006 FD146 FD207 FD209 FD312 FD318 GP03 4J011 QB02 SA74 SA79 SA82 SA83 SA87 TA07 TA08 UA06 VA01 WA01

Claims (3)

[Claims] (1) a compound which generates an acid upon irradiation with actinic rays or radiation, (b) (a) a compound represented by the following general formula (p)
I) to (pVI), a repeating unit having an alkali-soluble group protected by at least one of the groups having an alicyclic hydrocarbon structure, (b) the following general formula (II)
And (c) a repeating unit represented by the following general formula (III)
(a) a resin containing at least one of the repeating units represented by (III-d) and decomposed by the action of an acid to increase the solubility in alkali; and (c) (1) heptanone; A) positive photoresist composition for deep ultraviolet exposure, comprising a mixed solvent containing γ-butyrolactone, ethylene carbonate and at least one of propylene carbonate. Embedded image In the general formulas (pI) to (pVI), R ₁₁ represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a sec-butyl group;
Represents an atomic group necessary for forming an alicyclic hydrocarbon group together with a carbon atom. R _{12 to} R ₁₆ each independently represent a linear or branched alkyl group or an alicyclic hydrocarbon group having 1 to 4 carbon atoms, provided that at least one of R _{12 to} R ₁₄ , or Either R ₁₅ or R ₁₆ represents an alicyclic hydrocarbon group. R _{17 to} R ₂₁ each independently represent a hydrogen atom,
It represents a linear or branched alkyl group or an alicyclic hydrocarbon group having 1 to 4 carbon atoms, provided that at least one of R _{17 to} R ₂₁ represents an alicyclic hydrocarbon group. Also, R ₁₉ ,
Any of R ₂₁ represents a linear or branched alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group. R ₂₂ ~R
₂₅ independently represents a linear or branched alkyl group or an alicyclic hydrocarbon group having 1 to 4 carbon atoms, provided that
At least one of R ₂₂ to R ₂₅ represents an alicyclic hydrocarbon group. Embedded image In the general formula (II), R1 represents a hydrogen atom, a halogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms. X1 represents a divalent linking group. Lc is
Represents a lactone group. Embedded image In the above formula, R 1 is a hydrogen atom, a halogen atom or 1 to
Represents a linear or branched alkyl group having 4 carbon atoms. R30 to R37 each independently represent a hydrogen atom or an alkyl group which may have a substituent. R represents a hydrogen atom or an optionally substituted alkyl group, cyclic alkyl group, aryl group or aralkyl group. m represents an integer of 1 to 10. X2 is a single bond or an optionally substituted alkylene group, cyclic alkylene group, arylene group, or ether group, thioether group, carbonyl group, ester group, amide group, sulfonamide group, urethane group, A urea group alone or at least two of these groups
One or more of them represent a divalent group that is not decomposed by the action of an acid. Z1 represents a single bond, an ether group, an ester group, an amide group, an alkylene group, or a divalent group obtained by combining these. R38 is a single bond, an alkylene group,
Represents an arylene group or a divalent group obtained by combining them. R40 represents an alkylene group, an arylene group, or a divalent group obtained by combining them. R39 represents an optionally substituted alkyl group, cyclic alkyl group, aryl group or aralkyl group. R41 represents a hydrogen atom or an alkyl group, a cyclic alkyl group, an alkenyl group, an aryl group or an aralkyl group which may have a substituent. A represents any of the functional groups shown below. Embedded image 2. The positive photoresist composition for deep ultraviolet exposure according to claim 1, wherein the composition further comprises (d) an organic basic compound. 3. The method according to claim 1, further comprising (e) a fluorine-based and / or silicon-based surfactant.
4. The positive photoresist composition for deep ultraviolet exposure according to item 1.