JP2001109154A - Positive type photoresist composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a chemical amplification type positive type photoresist composition having high sensitivity, high resolving power and good adhesion to a substrate and ensuring improved edge roughness of a pattern. SOLUTION: The positive type photoresist composition contains a compound which generates an acid when irradiated with active light or radiation and a resin containing repeating units each having a specified lactone structure and having alkali solubility increased by decomposition by the action of the acid.

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 high-definition pattern by using light having a wavelength of not more than 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. Generally, chemically amplified resists are commonly known as two-component, 2.5-component,
It can be roughly classified into three types of three-component systems. 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, and among them, it is necessary to further meet the required characteristics in use. For example,
When using 248 nm light of a KrF excimer laser, a hydroxystyrene-based polymer having a low light absorption is particularly used.
There has been proposed a resist composition using a polymer having an acetal group or a ketal group introduced as a protective group. JP-A-2-141636, JP-A-2-19847, JP-A-4-219775, JP-A-5-281745 and the like are examples thereof. In addition, similar compositions using a t-butoxycarbonyloxy group or a p-tetrahydropyranyloxy group as an acid-decomposable group are disclosed in JP-A-2-209977, JP-A-3-206458, JP-A-2-19847, and the like. Proposed. These are suitable when using KrF excimer laser light of 248 nm,
When an ArF excimer laser is used as the light source, the sensitivity is low because the absorbance is still essentially too high. Further, there are other disadvantages associated therewith, such as deterioration of resolution, deterioration of focus tolerance, deterioration of pattern profile, and the like, and many points still need improvement. As a photoresist composition for an ArF light source, a resin into which an alicyclic hydrocarbon site has been introduced for the purpose of imparting dry etching resistance has been proposed. As such a resin, 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 is copolymerized with a monomer having an alicyclic hydrocarbon group. Resin.

On the other hand, besides the method of introducing an alicyclic hydrocarbon moiety into the side chain of the acrylate monomer, a method of imparting dry etching resistance utilizing an alicyclic hydrocarbon moiety as a polymer main chain has also been studied. ing. In addition, Japanese Patent Application Laid-Open
-73173, JP-A-9-90637 and JP-A-10
JP-A-161313 discloses the use of an alkali-soluble group protected by a structure containing an alicyclic group, and an acid-sensitive compound containing a structural unit capable of leaving the alkali-soluble group with an acid to render it alkali-soluble. Resist material is described. Further, a resin in which a hydrophilic 5- or 6-membered lactone group is introduced into the resin having an alicyclic group for the purpose of improving the affinity for an alkali developing solution and the adhesion to a substrate is disclosed in JP-A-9-90637, JP-A-10-20769, JP-A-10-274852
And JP-A-10-239846. Even with the techniques described above, in photoresist compositions (particularly photoresists for deep ultraviolet exposure), there are still improvements due to resins containing acid-decomposable groups, and further improvements in sensitivity, resolution, and molecular There are still many insufficient points such as improvement in adhesion to a substrate due to simultaneous inclusion of an aliphatic cyclic hydrocarbon group therein, and improvement is desired. Furthermore,
In recent years, with a demand for miniaturization of a semiconductor chip, the design pattern of the fine semiconductor has reached a fine region of 0.13 to 0.35 μm. However, these compositions have a problem that the resolution of the pattern is hindered by factors such as the edge roughness of the line pattern. Here, the edge roughness means that the top and bottom edges of the resist line pattern are caused by the characteristics of the resist.
This means that an edge looks irregular when viewed from directly above, because the pattern fluctuates irregularly in a direction perpendicular to the line direction.

[0005]

As described above, according to the known techniques of the conventional photoresist composition, sensitivity, resolution,
Since the adhesion to the substrate does not meet the recent required performance, the edge of the pattern has roughness, and a stable pattern cannot be obtained. Therefore, further improvement has been desired. Accordingly, an object of the present invention is to provide a chemically amplified positive photoresist composition having high sensitivity, high resolution, good adhesion to a substrate, and improved pattern edge roughness. .

[0006]

Means for Solving the Problems As a result of intensive studies on the constituent materials of the resist composition in the positive type chemical amplification system, the present inventors have found that by using an acid-decomposable resin having a lactone structure of a specific structure, Knowing that the object of the present invention is achieved, the present invention has been achieved. That is, the above object is achieved by the following constitutions. (1) (A) a compound that generates an acid upon irradiation with actinic rays or radiation, and (B) a compound represented by the following general formula (I-1)
A positive photoresist composition comprising a resin containing a repeating unit having a group represented by at least one of (I-4) and decomposed by the action of an acid to increase the solubility in alkali. .

[0007]

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In the general formulas (I-1) to (I-4), R ₁ to
R ₅ may be the same or different and represents a hydrogen atom, an optionally substituted alkyl group, cycloalkyl group or alkenyl group. Two of R _{1 to} R ₅ may combine to form a ring. (2) The resin of (B) further has the following general formula (pI) to
(2) The composition according to the above (2), which contains a repeating unit having an alkali-soluble group protected by at least one of groups having an alicyclic hydrocarbon structure represented by (pVI). Positive photoresist composition.

[0009]

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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. (3) The group having an alicyclic hydrocarbon structure represented by any one of the general formulas (pI) to (pVI) is a group represented by the following general formula (II). 4. The positive photoresist composition according to item 1.

[0011]

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In the general formula (II), R₂₈Has a substituent
Represents an optionally substituted alkyl group. R ₂₉~ R₃₁Is the same
May also be different, a hydroxy group, a halogen atom,
A carboxy group or an optionally substituted
Alkyl group, cycloalkyl group, alkenyl group, alkoxy
Represents a silyl group, an alkoxycarbonyl group or an acyl group.
p, q, and r each independently represent an integer of 0 or 1-3.
You. (4) The resin of (B) is represented by the following general formula (a).
Wherein the repeating unit contains
Positive photoresist according to any one of (1) to (3)
Strike composition.

[0013]

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In the general formula (a), R represents a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms. R ₃₂ to R ₃₄ may be the same or different, represent a hydrogen atom or a hydroxyl group. At least one of R ₃₂ to R ₃₄ represents a hydroxyl group. (5) The positive photoresist composition as described in any of (1) to (4) above, further comprising (C) an acid diffusion inhibitor. (6) The positive photoresist composition as described in any of (1) to (5) above, wherein the compound (A) is a sulfonium or iodonium sulfonate compound. (7) The positive photoresist composition as described in any of (1) to (5) above, wherein the compound (A) is a sulfonate compound of N-hydroxyimide or a disulfonyldiazomethane compound. (8) The above-mentioned (1) to (7), wherein far-ultraviolet light having a wavelength of 150 nm to 220 nm is used as the exposure light.
The positive photoresist composition according to any one of the above.

[0015]

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 (A) photoacid generator used in the present invention is a compound which generates an acid upon irradiation with actinic rays or radiation. is there. As the photoacid generator used in the present invention, a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization, a photodecolorant for dyes, a photochromic agent, or a microresist is used. Known light (400 to 200
nm ultraviolet light, far ultraviolet light, particularly preferably g-line, h
Ray, i-ray, KrF excimer laser light), ArF excimer laser light, an electron beam, an X-ray, a compound generating an acid by a molecular beam or an ion beam, and a mixture 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 and arsonium salts, organic halogen compounds, and organic metal / organic compounds. Halides, photoacid generators having an o-nitrobenzyl-type protecting group, compounds that generate sulfonic acid upon photolysis typified by iminosulfonate, disulfone compounds, diazoketosulfones, diazodisulfone compounds, and the like. Can be. 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, V. N. R. Pilai, Syn
thesis, (1), 1 (1980); Abad
et al, Tetrahedron Lett. , (4
7) 4555 (1971); H. R. Barton
et al. Chem. Soc. , (C), 329
(1970), U.S. Pat. No. 3,779,778, European Patent 126,712, and the like, which can generate an acid by light can also be used.

Among the compounds capable of decomposing upon irradiation with actinic rays or radiation to generate an acid, those which are used particularly effectively are 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).

[0018]

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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.

[0020]

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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).

[0022]

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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, B
F ₄ ⁻ , AsF ₆ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , SiF ₆ ²⁻ , Cl
Perfluoroalkanesulfonic acid anions such as O ₄ ⁻ and CF ₃ SO ₃ ^— , substituted benzenesulfonic acid anions such as toluenesulfonic acid anion, dodecylbenzenesulfonic acid anion and pentafluorobenzenesulfonic acid anion, naphthalene-1-sulfonic acid anion And condensed polynuclear aromatic sulfonic acid anions such as anthraquinone sulfonic acid anions, and sulfonic acid group-containing dyes, but are not limited thereto. R ²⁰³ , R
Two of ²⁰⁴ and R ²⁰⁵ and Ar ¹ and Ar ² may be bonded via a single bond or a substituent. Specific examples include the following compounds, but are not limited thereto.

[0024]

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[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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[0030]

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The above-mentioned onium salts represented by the general formulas (PAG3) and (PAG4) are known. W. Kn
apczyketal, J.A. Am. Chem. So
c. , 91, 145 (1969); L. Mayco
ketal, J.M. Org. Chem. , 35,253
2, (1970); Goethaetal, Bu
ll. Soc. Chem. Belg. , 73, 546,
(1964); M. Leicester, J.A. Am
e. Chem. Soc. , 51, 3587 (192)
9); V. Crivello et al, J. Mol. Po
lym. Chem. Ed. , 18, 2677 (198
0), U.S. Pat. Nos. 2,807,648 and
No. 47,473, JP-A-53-101,331 and the like.

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

[0033]

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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.

[0035]

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[0036]

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[0037]

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

[0039]

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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.

[0041]

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In the present invention, as the photoacid generator, a sulfonium or iodonium sulfonate compound (particularly preferably, a compound represented by (PAG3) or (PAG4)) and an N-hydroxyimide sulfonate compound (particularly preferable) Is a compound represented by (PAG6) or a disulfonyldiazomethane compound (particularly preferably (P
AG7). Thereby, the sensitivity and the resolving power are excellent, and the edge roughness of a fine pattern is also excellent. The amount of these photoacid generators to be added is generally in the range of 0.001 to 40% by weight, preferably 0.01 to 20% by weight, more preferably 0.1 to 20% by weight, based on the solid content in the composition. It is used in the range of 1 to 5% by weight. When the addition amount of the photoacid generator is 0.0
When the amount is less than 01% by weight, the sensitivity is lowered, and when the amount is more than 40% by weight, the light absorption of the resist becomes too high, and the profile is deteriorated and the process (especially baking) margin is unpreferably reduced.

<(B) Resin which decomposes under the action of acid and increases solubility in alkali> The resin used in the composition of the present invention, which decomposes under the action of acid (B) and increases solubility in alkali (hereinafter referred to as resin) , Simply referred to as “resin of (B)”) includes a repeating unit having a group represented by the above general formulas (I-1) and (I-4). General formula (I-1)
In (I-4), examples of the alkyl group for R _{1 to} R ₅ 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 a methyl group, an ethyl group, a propyl group, an isopropyl group, n
-Butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, and decyl group. The cycloalkyl group represented by R _{1 to} R ₅ is preferably a cycloalkyl group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and the like. R
₁ to R Examples of the alkenyl group at the _5, vinyl group, propenyl group, butenyl group, 2 to 6 carbon atoms such as a hexenyl group
Are preferred. Examples of the ring formed by combining two members out of R _{1 to} R ₅ include a 3- to 8-membered ring such as a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, and a cyclooctane ring. In the general formulas (I-1) and (I-2), R _{1 to} R ₅ may be connected to any of the seven carbon atoms constituting the cyclic skeleton.

Further, as the further substituent of the above-mentioned alkyl group, cycloalkyl group and alkenyl group, there are 1 to 1 carbon atoms.
Examples include four 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. Preferred examples of the repeating unit having a group represented by any of formulas (I-1) to (I-4) include a repeating unit represented by the following formula (AI).

[0045]

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In the general formula (AI), R has the same meaning as R in the following general formula (a). A ′ represents a single bond, an ether group, an ester group, a carbonyl group, an alkylene group, or a divalent group obtained by combining these. B represents a group represented by any of formulas (I-1) to (I-4). In A ′, examples of the combined divalent group include those represented by the following formulas.

[0047]

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In the above formula, Ra, Rb, and r1 have the same meanings as those described below. m represents an integer of 1 to 3.
Hereinafter, specific examples of the repeating unit represented by the general formula (AI) will be shown, but the present invention is not limited thereto.

[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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In the present invention, the resin (B) is further protected by at least one of the groups having an alicyclic hydrocarbon structure represented by the general formulas (pI) to (pVI). It is preferable to contain a repeating unit having an alkali-soluble group in that the effects of the present invention become more remarkable.
In the general formulas (pI) to (pVI), the alkyl group for R _{12 to} R ₂₅ may be substituted or unsubstituted, and may be a linear or branched alkyl group having 1 to 4 carbon atoms. Represents 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, a sec-butyl group and a t-butyl group. Further, as a further substituent of the alkyl group, an alkoxy group having 1 to 4 carbon atoms, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an acyl group, an acyloxy group, a cyano group, a hydroxyl group, Carboxy group, alkoxycarbonyl group,
Examples thereof include a nitro group. The alicyclic hydrocarbon group in R _{11 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.

As the substituent of these alicyclic hydrocarbon groups, an alkyl group, a substituted alkyl group, a cycloalkyl group,
Examples include an alkenyl group, an acyl group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group, and an alkoxycarbonyl group. As the alkyl group, a methyl group, an ethyl group,
A lower alkyl group such as a propyl group, an isopropyl group, and a butyl group is preferable, and a methyl group, an ethyl group, and more preferably
A propyl group and an isopropyl group. Examples of the substituent of the substituted alkyl group include a hydroxyl group, a halogen atom and an alkoxy group. An alkoxy group (including an alkoxy group of an alkoxycarbonyl group) includes a methoxy group,
C1-C1 such as ethoxy, propoxy and butoxy groups
Four things can be mentioned. Examples of the cycloalkyl group include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, and the like. Examples of the alkenyl group include alkenyl groups having 2 to 6 carbon atoms, and specific examples include a vinyl group, a propenyl group, an allyl group, a butenyl group, a pentenyl group, and a hexenyl group. Examples of the acyl group include an acetyl group, an ethylcarbonyl group, and a propylcarbonyl group. Examples of the halogen atom include a chlorine atom, a bromine atom, an iodine atom and a fluorine atom.

Among the structures represented by the general formulas (pI) to (pVI), the group represented by the general formula (pI) is preferable, and the group represented by the general formula (II) is more preferable. In formula (II), the alkyl group represented by R ₂₈ , the halogen atom represented by R _{29 to} R ₃₁ , an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, and an acyl group are the aforementioned alicyclic hydrocarbon groups. Examples of the substituent described above are exemplified.

The general formulas (pI) to (pV)
Examples of the alkali-soluble group protected by the structure represented by I) include various groups known in this technical field. Specific examples include a carboxylic acid group, a sulfonic acid group, a phenol group, a thiol group and the like, and preferred are a carboxylic acid group and a sulfonic acid group. The alkali-soluble group protected by the structure represented by the general formulas (pI) to (pVI) in the above resin is preferably the following general formula (pVI)
Groups represented by I) to (pXI).

[0064]

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

[0066]

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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. Examples of the halogen atom and the alkyl group for R include the same examples as those for R in the general formula (a) described below. A ′ has the same meaning as described above. Ra is
Represents a group of any 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.

[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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[0073]

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The resin (B) may further contain another repeating unit. The resin (B) in the present invention preferably contains, as another copolymerization component, a repeating unit represented by the general formula (a). Thereby, the developability and the adhesion to the substrate are improved. The alkyl optionally having a substituent of R in the general formula (a) includes the alkyl represented by the general formula (I-
Examples similar to R ₁ in 1) to (I-4) can be given. Examples of the halogen atom for R include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. At least one of R ₃₂ to R ₃₄ in the general formula (a) is a hydroxyl group, preferably a dihydroxy form or a monohydroxy form, more preferably a monohydroxy body. Further, the resin (B) in the present invention preferably contains, as another copolymerization component, a repeating unit represented by the following general formulas (III-a) to (III-d). This allows
The resolution of the contact hole pattern is improved.

[0075]

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In the above formula, R₁Has the same meaning as R described above.
R_Five~ R₁₂Each independently has a hydrogen atom or a substituent
Represents an optionally substituted alkyl group. R represents a hydrogen atom or
Is an alkyl group which may have a substituent,
Represents a kill group, an aryl group or an aralkyl group. m is 1
Represents an integer of 10 to 10. X has a single bond or a substituent
An alkylene group, a cyclic alkylene group,
-Ene group, ether group, thioether group,
Bonyl group, ester group, amide group, sulfonamide
Group, a urethane group, or a urea group.
Germany or a combination of at least two of these groups
And represents a divalent group that is not decomposed by the action of an acid. Z
Is a single bond, an ether group, an ester group, an amide group,
Represents a kylene group or a divalent group obtained by combining them.
R₁₃Is a single bond, an alkylene group, an arylene group, or
It represents a divalent group obtained by combining these. R_FifteenIs an archille
Group, arylene group, or divalent
Represents a group. R₁₄Is an alkyl which may have a substituent
Group, cyclic alkyl group, aryl group or aralkyl group
You. R ₁₆Represents a hydrogen atom or a substituent
Good, alkyl group, cyclic alkyl group, alkenyl group,
Represents a reel group or an aralkyl group. A is the official
Represents any functional group.

[0077]

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Examples of the alkyl group of R _{5 to} R ₁₂ , R, R ₁₄ and R ₁₆ 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. More preferably methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group,
t-butyl group, pentyl group, hexyl group, heptyl group,
An octyl group, a nonyl group, and a decyl group. R, R _14, R
_Examples of the cyclic alkyl group of ₁₆ include those having 3 to 30 carbon atoms, and specifically, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a norbornyl group, a boronyl group, a tricyclodecanyl group , Dicyclopentenyl group, nobornane epoxy group, menthyl group, isomenthyl group, neomenthyl group, tetracyclododecanyl group, steroid residue and the like.

The aryl group represented by R, R ₁₄ and R ₁₆ 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, R ₁₄ and R ₁₆ 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 R ₁₆ 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 X, 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. Z
Represents a single bond, an ether group, an ester group, an amide group, an alkylene group, or a divalent group obtained by combining these.
R ₁₃ represents a single bond, an alkylene group, an arylene group, or a divalent group obtained by combining these. R ₁₅ represents an alkylene group, an arylene group, or a divalent group obtained by combining them. Examples of the arylene group in X, R ₁₃ and R ₁₅ include those having 6 to 10 carbon atoms, which may have a substituent. Specifically, phenylene group, tolylene group,
And a naphthylene group. Examples of the cyclic alkylene group for X include those in which the above-mentioned cyclic alkyl group is divalent. Examples of the alkylene group in X, Z, R ₁₃ and R ₁₅ include groups represented by the following formulas. -[C (Ra) (Rb)] r1- 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. r1 represents an integer of 1 to 10. Specific examples of the linking group X are shown below, but the content of the present invention is not limited thereto.

[0081]

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Further substituents in the above 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, specific examples of the structure of the terminal other than X are shown below as specific examples of the structure of the side chain in the general formula (III-b), but the present invention is not limited thereto. .

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Specific examples of the monomer corresponding to the repeating structural unit represented by the general formula (III-c) are shown below.
The content of the present invention is not limited to these.

[0085]

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[0086]

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[0087]

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

[0089]

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[0090]

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[0091]

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In the general formula (III-b), R _{5 to} R
_{As 12} , a hydrogen atom and a methyl group are preferable. 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), R ₁₃ is preferably a single bond, an alkylene group such as a methylene group, an ethylene group, a propylene group, or a butylene group, and R ₁₄ is a group having 1 carbon atom such as a methyl group or an ethyl group.
Preferred are 10 to 10 alkyl groups, cyclopropyl groups, cyclohexyl groups, cyclic alkyl groups such as camphor residues, naphthyl groups, and naphthylmethyl groups. Z 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 Formula (III-d), R ₁₅ is preferably an alkylene group having 1 to 4 carbon atoms. As R ₁₆ , an alkyl group having 1 to 8 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a neopentyl group, an octyl group, a cyclohexyl group, which may have a substituent; Adamantyl group, norbornyl group, boronyl group, isobornyl group,
Menthyl, morpholino, 4-oxocyclohexyl, and optionally substituted phenyl, toluyl, mesityl, naphthyl, and camphor residues are preferred. As these further substituents, a halogen atom such as a fluorine atom, an alkoxy group having 1 to 4 carbon atoms and the like are preferable. In the present invention, general formulas (III-a) to (III-a)
-D), general formula (III-b) and general formula (II
The repeating unit represented by Id) is preferred.

In addition to the above, the resin (B) controls dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and resolution, heat resistance, sensitivity, and the like, which are general requirements for resists. It can be used as a copolymer with various monomer repeating units for the purpose.

Examples of such a repeating unit include repeating units corresponding to the following monomers, but are not limited thereto. Thereby, the performance required for the resin, particularly (1) solubility in a coating solvent, (2) film forming property (glass transition point), (3)
Alkali developability, (4) film loss (hydrophilic / hydrophobic, alkali-soluble group selection), (5) adhesion of unexposed portion to substrate,
(6) Fine adjustment of dry etching resistance becomes possible.
Examples of such a copolymerizable monomer include, for example, an acrylate, a methacrylate, an acrylamide, a methacrylamide, an allyl compound, a vinyl ether, and an addition-polymerizable unsaturated bond selected from vinyl esters. And the like.

Specifically, for example, acrylic esters such as alkyl (the alkyl group has 1 to 1 carbon atoms)
Acrylates (for example, methyl acrylate, ethyl acrylate, propyl acrylate, amyl acrylate, cyclohexyl acrylate, ethylhexyl acrylate, octyl acrylate, acrylate-
t-octyl, chloroethyl acrylate, 2-hydroxyethyl acrylate 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate, Tetrahydrofurfuryl acrylate, etc.);

Methacrylic esters, for example, alkyl (preferably having 1 to 10 carbon atoms in the alkyl group) methacrylate (for example, methyl methacrylate,
Ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate,
Benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate,
5-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, etc.); acrylamides such as acrylamide, N-alkylacrylamide , (Alkyl groups having 1 to 1 carbon atoms
0, for example, methyl, ethyl, propyl, butyl, t-butyl, heptyl, octyl, cyclohexyl, hydroxyethyl and the like. ), N,
N-dialkylacrylamide (an alkyl group having 1 to 10 carbon atoms, for example, a methyl group, an ethyl group,
There are a butyl group, an isobutyl group, an ethylhexyl group, a cyclohexyl group and the like. ), N-hydroxyethyl-N-methylacrylamide, N-2-acetamidoethyl-N
-Acetylacrylamide and the like;

Methacrylamides, for example, methacrylamide, N-alkyl methacrylamide (alkyl having 1 to 10 carbon atoms, for example, methyl, ethyl, t-butyl, ethylhexyl, hydroxyethyl, cyclohexyl) Groups, etc.), N, N-dialkyl methacrylamide (an alkyl group such as ethyl group, propyl group, butyl group, etc.), N-hydroxyethyl-N-methyl methacrylamide, etc .; allyl compounds, for example, allyl esters ( For example, allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate and the like, allyloxyethanol and the like; vinyl ethers such as alkyl vinyl ether (for example, Hexy Vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether,
1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, etc.);

Vinyl esters such as vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxy acetate, vinyl butoxy acetate, Vinyl acetoacetate, vinyl lactate, vinyl-β-phenylbutyrate, vinylcyclohexylcarboxylate, etc .; dialkyl itaconates (eg, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, etc.); dialkyl esters of fumaric acid (eg, dibutyl) Fumarate etc.) or monoalkyl esters; other acrylic acid, methacrylic acid,
Examples thereof include crotonic acid, itaconic acid, maleic anhydride, maleimide, acrylonitrile, methacrylonitrile, and maleilenitrile. In addition, any addition-polymerizable unsaturated compound copolymerizable with the above various repeating units may be used. In the resin (B), the molar ratio of each repeating unit structure is determined by the acid value, the dry etching resistance of the resist, the suitability for a standard developer, the substrate adhesion, the dependency of the resist profile on the density of the resist, and the general requirements of the resist. It is set appropriately in order to adjust the resolution, heat resistance, sensitivity and the like.

In the resin (B), the compounds represented by the general formulas (I-1) to (I)
-4) The content of the repeating unit having a group represented by
The content is 30 to 70 mol%, preferably 35 to 65 mol%, more preferably 40 to 60 mol% in all the repeating units. The content of the repeating unit having a group represented by any one of formulas (pI) to (pVI) is defined as
Usually, it is 20 to 75 mol%, preferably 25 to 70 mol%, more preferably 30 to 65 mol%. (B)
In the resin, the content of the repeating unit represented by the general formula (a) is usually 0 mol% to 70 mol% in all monomer repeating units.
, Preferably 10 to 40 mol%, more preferably 15 to 30 mol%. In the resin (B), the content of the repeating units represented by the general formulas (III-a) to (III-d) is usually 0.1% in all the monomer repeating units.
1 mol% to 30 mol%, preferably 0.5 to 25 mol%.
Mol%, more preferably 1 to 20 mol%.

The content of the repeating unit based on the monomer of the additional copolymer component in the resin can be appropriately set according to the desired resist properties. A repeating unit containing a group represented by any one of (I-1) to (I-4), and a compound represented by any one of formulas (pI) to (pI)
It is preferably at most 99 mol%, more preferably at most 90 mol%, even more preferably at most 80 mol%, based on the total number of moles of the repeating units having the group represented by VI). The weight average molecular weight Mw of the resin (B) is preferably from 1,000 to 1,000,000 by gel permeation chromatography based on polystyrene standards.
0, more preferably from 1,500 to 500,000, still more preferably from 2,000 to 200,000, particularly preferably from 2,500 to 100,000. The larger the weight average molecular weight, the better the heat resistance and the like. While improving, the developability and the like decrease, and the balance is adjusted to a preferable range. The resin (B) used in the present invention can be synthesized according to a conventional method, for example, by a radical polymerization method. Hereinafter, specific examples of the resin (B) of the present invention will be described, but the content of the present invention is not limited thereto.

[0101]

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[0102]

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[0103]

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[0104]

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[0105]

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[0106]

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[0107]

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[0108]

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[0109]

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[0110]

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[0111]

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[0112]

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[0113]

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[0114]

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[0115]

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[0116]

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In the above formula, m, n, p and n1, n
2 and n3 each represent a molar ratio of the number of repetitions. (I-
N represents a repeating unit having a group represented by any of 1) to (I-4), and n represents a combination of two or more kinds.
1, n2, etc. The repeating unit having a group containing an alicyclic hydrocarbon structure represented by (pI) to (pVI) is indicated by m. Formulas (III-a) to (III-
The repeating unit represented by d) is represented by p. When repeating units represented by formulas (III-a) to (III-d) are included, m / n / p is (25-70) / (25
-65) / (3-40). General formula (III-a)
M / n is (30-70) / (70-30) when the repeating unit represented by-(III-d) is not included. It may be a block copolymer or a random copolymer.
It may be a regular polymer or an irregular polymer. In the positive photoresist composition for deep ultraviolet exposure according to the present invention, the amount of the resin (B) added to the whole composition is preferably 40 to 99.99% by weight, more preferably 50 to 99.99% by weight, based on the total solid content of the resist. 99.97% by weight.

The positive resist composition of the present invention may further contain an acid-decomposable dissolution inhibiting compound, a dye, a plasticizer,
A surfactant, a photosensitizer, an organic basic compound, and a compound that promotes solubility in a developer can be contained. In the positive photoresist composition of the present invention,
It may contain a fluorine-based and / or silicon-based surfactant. The positive photoresist composition of the present invention may contain a fluorine-based surfactant, a silicon-based surfactant, or a surfactant containing both a fluorine atom and a silicon atom, or may contain two or more kinds. it can. Examples of these surfactants include JP-A-62-36663, JP-A-61-226746, and JP-A-61-226745.
JP-A-62-170950, JP-A-63-345
No. 40, JP-A-7-230165, JP-A-8-628
No. 34, JP-A-9-54432, JP-A-9-5988
And the commercially available surfactants described below can be used as they are. Commercially available surfactants that can be used include, for example, F-Top EF301,
EF303, (Shin-Akita Chemical Co., Ltd.), Florard FC
430, 431 (manufactured by Sumitomo 3M Limited), MegaFac F171, F173, F176, F189, R08
(Dainippon Ink Co., Ltd.), Surflon S-382, S
C101, 102, 103, 104, 105, 106
(Asahi Glass Co., Ltd.) and the like, or a fluorine-based surfactant or a silicon-based surfactant. Further, polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as the 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 in the composition of the present invention. These surfactants may be added alone or in some combination. As the surfactant that can be used in addition to the above, specifically,
Polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkyl allyl such as polyoxyethylene octyl phenol ether and polyoxyethylene nonyl phenol ether Ethers, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan fatty acid esters such as sorbitan tristearate, poly Oxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, Polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, it may be mentioned nonionic surfactants of polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan tristearate and the like. The amount of these other 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.

The acid diffusion inhibitor (C) which can be used in the present invention is preferably added from the viewpoint of suppressing fluctuations in sensitivity and resolution over time from exposure to heating and development, and preferably an organic base. Compound. Examples of the organic basic compound include a nitrogen-containing basic compound having the following structure.

[0121]

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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 combine with each other to form a ring.

[0123]

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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 include guanidine, 1,1-dimethylguanidine,
1,3,3, -tetramethylguanidine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine,
-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-amino Ethyl) 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-pyrazoline, N-
Aminomorpholine, N- (2-aminoethyl) morpholine, 1,5-diazabicyclo [4,3,0] nona-
5-ene, 1,8-diazabicyclo [5,4,0] undec-7-ene, 2,4,5-triphenylimidazole, N-methylmorpholine, N-ethylmorpholine, N
-Hydroxyethylmorpholine, N-benzylmorpholine, cyclohexylmorpholinoethylthiourea (CH
Tertiary morpholine derivatives such as METU);
Hindered amines described in Japanese Patent No. 2575 (for example, those described in the Japanese Patent Publication [0005]), etc., are 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,
Hindered amines such as (2,2,6,6-pentamethyl-4-piperidyl) sebagate and the like can be mentioned. Among them, 1,5-diazabicyclo [4,3,0] non-5-ene and 1,8-diazabicyclo [5,4,0]
Undec-7-ene, 1,4-diazabicyclo [2,
2,2] octane, 4-dimethylaminopyridine, hexamethylenetetramine, CHMETU, bis (1,2,2
(2,6,6-pentamethyl-4-piperidyl) sebagate is preferred.

These nitrogen-containing basic compounds are used alone or in combination of two or more. The amount of the nitrogen-containing basic compound to be used is generally 0.001 to 10% by weight, preferably 0.01 to 5% by weight, based on the solid content of the entire photosensitive resin composition. 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 resist composition of the present invention is dissolved in a solvent capable of dissolving each of the above components and applied on a support. 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, lactic acid Ethyl, methyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N, N-
Dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, 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 monoethyl ether, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate , N-methylpyrrolidone and tetrahydrofuran. Such a 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, α-silicon, and an organic film type made of 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. Examples of the organic antireflection film include, for example, a condensate of a diphenylamine derivative and a formaldehyde-modified melamine resin described in JP-B-7-69611, an alkali-soluble resin, a light absorbing agent, and a maleic anhydride copolymer described in US Pat. No. 5,294,680. Reaction products of diamine-type light absorbing agents, those containing a resin binder and a methylolmelamine-based thermal crosslinking agent described in JP-A-6-118631, and a carboxylic acid group, an epoxy group, and a light-absorbing group described in JP-A-6-118656 in the same molecule. Acrylic resin type antireflection film, comprising a methylolmelamine and a benzophenone-based light absorbing agent described in JP-A-8-87115,
JP-A-8-179509 describes a polyvinyl alcohol resin to which a low-molecular-weight light absorbing agent is added. Further, as the organic antireflection film, DUV30 series and DUV-40 series manufactured by Brewer Science, and AC-2 and AC-3 manufactured by Shipley may be used.

The resist solution is coated on a substrate (eg, silicon / silicon dioxide coating) used for manufacturing precision integrated circuit devices (on a substrate provided with the 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), F2 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; diethylamine;
Secondary amines such as -butylamine, triethylamine,
Tertiary amines such as methyldiethylamine, alcoholamines such as dimethylethanolamine and triethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, and cyclic amines such as pyrrole and pichelidine. An alkaline aqueous solution can be used. Further, an appropriate amount of an alcohol or a surfactant may be added to the above alkaline aqueous solution.

[0129]

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 Example (1) of the Present Invention 2-Methyl-2-adamantyl methacrylate and 6-e
ndo-hydroxybicyclo [2.2.1] heptane-
5-exo of 2-endo-carboxylic acid-γ-lactone
-Methacrylate was charged at a molar ratio of 50/50, dissolved in N, N-dimethylacetamide / tetrahydrofuran = 5/5, and 100 m of a solution having a solid concentration of 20% was prepared.
1 was adjusted. 6-endo-hydroxybicyclo [2.2.1] heptane-2-endo-carboxylic acid-
5-exo-methacrylate of γ-lactone is 6-e
ndo-hydroxybicyclo [2.2.1] heptane-
After the 2-endo-carboxylic acid was acetoxy-lactonized, the one synthesized by alkali-hydrolyzing the acetoxy group to a hydroxy group and further esterifying with methacrylic acid chloride was used. J. Chem. Soc. ,
227 (1959), Tetrahedron, 21,
1501 (1965). 3 mol% of V-65 manufactured by Wako Pure Chemical Industries, Ltd. was added to this solution, and this was added dropwise to 10 ml of N, N-dimethylacetamide heated to 60 ° C. over 3 hours in a nitrogen atmosphere. After completion of the dropwise addition, the reaction solution was heated for 3 hours, and 1 mol /% of V-65 was added again.
Stir for 3 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and white powder crystallized and precipitated in 3 L of distilled water was recovered.
The polymer composition determined by C ¹³ NMR was 51/49. The weight average molecular weight in terms of standard polystyrene determined by GPC measurement was 7,200.

Synthesis Examples 2 to 10, Synthesis of Resin of the Present Invention Resin 2 to 10 having the composition ratio and molecular weight shown in Table 1 were formed in the same manner as in Synthesis Example 1.

[0131]

[Table 1]

Synthesis of Comparative Example (Resin A4) According to the synthesis method described on page 8 of JP-A-10-274852, a compound described as A4 in the same publication was synthesized as follows. 2-methyl-2-adamantyl methacrylate and α-methacryloyloxy-γ-butyrolactone were mixed at a 50:50 molar ratio (40.0 g: 29.0 g).
And methylisobutyl ketone twice the weight of all monomers was added to form a solution. There, azobisisobutyronitrile was used as an initiator in an amount of 2 mol% based on the total amount of monomers.
And heated at 80 ° C. for about 8 hours. Thereafter, an operation of pouring the reaction solution into a large amount of heptane to cause precipitation was performed twice, and purification was performed. As a result, a copolymer represented by the following formula was obtained. The composition molar ratio of each unit was 50:50, and the weight average molecular weight was about 8,000.

Examples 1 to 10 and Comparative Examples [Preparation and Evaluation of Photosensitive Composition] 1.4 g of the resin synthesized in the above synthesis example, 0.03 g of photoacid generator, and 1,5-diazabicyclo [4.3. 0] -5-nonene in an amount of 0.002 g and dissolved in propylene glycol monomethyl ether acetate at a solid content of 14 wt%.
And the positive resists of Examples 1 to 10 and Comparative Example were prepared. Table 2 shows the resin of the present invention and the photoacid generator used.

[0134]

[Table 2]

(Evaluation Test) The obtained positive photoresist solution was applied on a silicon wafer using a spin coater, dried at 130 ° C. for 90 seconds, and a positive photoresist film of about 0.4 μm was formed. ArF excimer laser (193 nm Ar, NA = 0.6, manufactured by ISI)
F stepper). A heat treatment after the exposure was performed at 120 ° C. for 90 seconds, developed with a 2.38% aqueous solution of tetramethylammonium hydroxide, and rinsed with distilled water to obtain a resist pattern profile. For these, sensitivity, resolution, and edge roughness were evaluated as follows. Table 2 shows the evaluation results.

[Sensitivity] Sensitivity was evaluated based on the minimum exposure that reproduced a 0.15 μm line-and-space pattern. [Resolving power] The resolving power was evaluated by a limit resolving power capable of reproducing at a minimum exposure amount for reproducing a 0.15 μm line and space pattern. [Edge Roughness] The edge roughness is measured at the edge roughness of an isolated pattern using a length-measuring scanning electron microscope (SEM), and a line pattern edge is detected at a plurality of positions in a measurement monitor, and the detection position is determined. Is used as an index of the edge roughness, and the smaller the value, the better. As is clear from the results in Table 2, all of the positive resist compositions of the present invention are at a satisfactory level. That is, it is suitable for lithography using far ultraviolet rays such as ArF excimer laser exposure.

[0137]

The present invention can provide a positive resist composition which is suitable for far ultraviolet light, particularly ArF excimer laser light, has excellent sensitivity, resolution, and edge roughness, and has an excellent resist pattern profile.

 ────────────────────────────────────────────────── ─── Continuing from the front page (72) Kunihiko Kodama Inventor Kunihiko, Yoshida-cho, Haibara-gun, Shizuoka 4,000 Kawajiri, Fujisha Shin Film Co., Ltd. F-term (reference) 2H025 AA00 AA01 AA02 AA03 AA14 AB16 AC04 AC08 AD03 BE00 BE07 BE08 BE10 BG00 CC20 FA03 FA12 FA17

Claims (8)

[Claims] (1) a compound which generates an acid upon irradiation with actinic rays or radiation; and (B) a compound represented by the following general formula (I-
(1) A positive photo-type resin comprising a resin containing a repeating unit having a group represented by at least one of (I-4) and decomposing by the action of an acid to increase the solubility in alkali. Resist composition. Embedded image In general formulas (I-1) to (I-4), R _{1 to} R ₅ may be the same or different, and may be a hydrogen atom, an optionally substituted alkyl group, cycloalkyl group or alkenyl. Represents a group. Two of R _{1 to} R ₅ may combine to form a ring. 2. The resin of (B) further comprises the following general formula (p)
The composition according to claim 1, further comprising a repeating unit having an alkali-soluble group protected by at least one of the groups having an alicyclic hydrocarbon structure represented by (I) to (pVI). The positive photoresist composition according to any one of the preceding claims. 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. 3. The compound represented by any one of the general formulas (pI) to (pVI).
The group containing an alicyclic hydrocarbon structure is represented by the following general formula (I
The group according to claim 2, which is a group represented by I).
The positive photoresist composition described above. Embedded imageIn the general formula (II), R₂₈May have a substituent
Represents an alkyl group. R ₂₉~ R₃₁Are the same but different
May be a hydroxy group, a halogen atom, a carboxy group
Alternatively, an alkyl group which may have a substituent,
Chloroalkyl, alkenyl, alkoxy, alcohol
Represents a xycarbonyl group or an acyl group. p, q, r are
Each independently represents 0 or an integer of 1 to 3. 4. The resin of (B) is represented by the following general formula (a):
The positive photoresist composition according to claim 1, further comprising a repeating unit represented by the formula: Embedded image In the general formula (a), R represents a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms. R ₃₂ to R ₃₄ may be the same or different, represent a hydrogen atom or a hydroxyl group. At least one of R ₃₂ to R ₃₄
One represents a hydroxyl group. 5. The positive photoresist composition according to claim 1, further comprising (C) an acid diffusion inhibitor. 6. The positive photoresist composition according to claim 1, wherein the compound (A) is a sulfonium or iodonium sulfonate compound. 7. The positive photoresist composition according to claim 1, wherein the compound (A) is a sulfonate compound of N-hydroxyimide or a disulfonyldiazomethane compound. 8. An exposure light having a wavelength of 150 nm to 220 nm.
8. The method according to claim 1, wherein far ultraviolet light of nm is used.
The positive photoresist composition according to any one of the above.