JP2008299351A - Positive photoresist composition for exposure with far ultraviolet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a positive photoresist composition having superior sensitivity in the resolution of contact holes in the production of a semiconductor device, the photoresist composition preventing the occurrence of particles in the dissolution of solid components in a solvent or during storage with time and also preventing a variation of sensitivity due to storage with time. <P>SOLUTION: The positive photoresist composition for exposure with far ultraviolet contains: a compound which generates an acid when irradiated with active rays or radiation; a resin having a specified structure and a velocity of dissolution in an alkali developing solution increased by the action of the acid; and a specified mixed solvent. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a positive photoresist composition for deep ultraviolet exposure used in an ultramicrolithography process such as the manufacture of VLSI and high-capacity microchips and other photofabrication processes. More particularly, the present invention relates to a positive photoresist composition for far ultraviolet exposure that can form a highly refined pattern using light in the far ultraviolet region including excimer laser light, particularly light having a wavelength of 250 nm or less.

In recent years, the degree of integration of integrated circuits has been increasing, and in the manufacture of semiconductor substrates such as VLSI, processing of ultrafine patterns having a line width of less than half a micron has been required. In order to satisfy this need, the operating wavelength of an exposure apparatus used for photolithography has been increasingly shortened, and now it is considered to use excimer laser light (XeCl, KrF, ArF, etc.) having a short wavelength among far ultraviolet rays. It is becoming.
A chemical amplification type resist is used for lithography pattern formation in this wavelength region.

  In general, chemically amplified resists can be broadly classified into three types, commonly called two-component systems, 2.5-component systems, and 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 by the action of an acid and increases the solubility of the resin in an alkaline developer. The 2.5 component system further contains a low molecular weight compound having an acid-decomposable group in the two component system. A three-component system contains a photoacid generator, an alkali-soluble resin, and the low molecular weight compound.

The chemical amplification resist is suitable as a photoresist for irradiation with ultraviolet rays or far ultraviolet rays, but among them, it is necessary to cope with the required characteristics in use. As a photoresist composition for an ArF light source, a photoresist composition in which a (meth) acrylic resin that absorbs less light than a partially hydroxylated styrene resin is combined with a compound that generates an acid by light is used. Proposed.
For example, there are Patent Document 1, Patent Document 2, and the like. In particular, Patent Document 3 discloses a resin in which a tertiary carbon organic group is ester-bonded to oxygen of a carboxyl group of acrylic acid.

  Furthermore, Patent Document 4 discloses an acid-decomposable resin having an acrylic ester or fumarate ester as a repeating structural unit, but the pattern profile, substrate adhesion, etc. are insufficient, and satisfactory performance is not obtained. Is the actual situation.

  Lithographic processes that produce devices using 0.18 μm and 0.13 μm design rules often use light with a wavelength of 193 nm as exposure radiation, so resist polymers that do not contain much ethylenic unsaturation are desired. .

  As a photoresist composition for an ArF light source, a resin in which an alicyclic hydrocarbon moiety is introduced has been proposed for the purpose of imparting dry etching resistance, but the system is extremely hydrophobic as an adverse effect of the introduction of the alicyclic hydrocarbon moiety. Therefore, it is difficult to develop with a tetramethylammonium hydroxide (hereinafter, TMAH) aqueous solution that has been widely used as a resist developer, and the resist is peeled off from the substrate during development. It can be seen.

In response to the hydrophobization of the resist, measures such as mixing an organic solvent such as isopropyl alcohol with the developer have been studied, and although some results are seen, the concern about the swelling of the resist film and the process become complicated. The problem is not necessarily solved. In the approach of improving the resist, many measures have been taken to supplement various hydrophobic alicyclic hydrocarbon sites by introducing hydrophilic groups.
Patent Document 5 discloses an energy sensitive resist material containing a polymer obtained by polymerizing a monomer having an alicyclic structure such as a norbornene ring in the main chain, a maleic anhydride, and a monomer having a carboxyl group. Although the transparency with respect to the wavelength of 193 nm has been improved, it cannot be said that the sensitivity is necessarily high, and when considering lithography of 0.13 μm or later, resist performance such as insufficient resolution is insufficient.

  Patent Document 6 discloses a radiation-sensitive resin composition containing a resin having an alicyclic skeleton in the main chain and a radiation-sensitive acid generator. Patent Document 7 discloses a radiation-sensitive resin composition containing a polymer containing a norbornene derivative and an androstane-17-carboxylic acid ester compound.

  Patent Documents 8 to 10 disclose an acid-sensitive compound containing an alkali-soluble group protected with a structure containing an alicyclic group, and a structural unit in which the alkali-soluble group is eliminated by an acid to make it alkali-soluble. A resist material using is described.

Patent Documents 11 to 13 describe resist compositions containing an acid-decomposable resin having a specific lactone structure.
Patent Document 14 discloses a chemically amplified resist containing a terpolymer having a specific repeating structural unit having a norbornene structure in the main chain.
Patent Document 15 discloses a resin containing a repeating structural unit having an adamantane structure in the side chain and maleic anhydride as a repeating structural unit.
Patent Document 16 discloses a repeating unit composed of norbornene having a specific acid-decomposable group, a repeating unit composed of an anhydride, for the purpose of improving storage stability, transparency, dry etching property, sensitivity, resolution, pattern shape, and the like. And a composition containing a resin having a repeating unit having an alicyclic group.

However, these resist compositions have problems such as generation of particles at the time of dissolving a solid content in a solvent or storage with time, or sensitivity fluctuation due to storage with time. In addition to these, an improvement in sensitivity in resolution of contact holes has also been desired.
Japanese Unexamined Patent Publication No. 7-199467 JP 7-252324 A JP-A-6-289615 JP-A-7-234511 Japanese Patent Laid-Open No. 10-10739 JP 10-1111569 A JP-A-11-202491 JP-A-9-73173 JP-A-9-90637 JP-A-10-161313 JP-A-9-90637 JP-A-10-207069 JP-A-10-274852 JP-A-10-130340 JP-A-11-305444 European Patent Application No. 1048883

  Accordingly, the object of the present invention is to provide excellent sensitivity in the resolution of contact holes in the manufacture of semiconductor devices, as well as to prevent generation of particles when the solid content is dissolved in a solvent or when stored over time. It is an object of the present invention to provide a positive photoresist composition for far-ultraviolet light exposure that can prevent the fluctuations of

As a result of intensive studies on the constituent materials of the resist composition in the positive chemical amplification system, the present inventors have found that the object of the present invention can be achieved by using a specific resin and a specific solvent. It came.
That is, the object is (A) a compound that generates an acid upon irradiation with actinic rays or radiation, and (B) a repeating structural unit represented by the following general formula (I), a repeating structure represented by the general formula (II): A far-ultraviolet light exposure comprising a resin containing a unit and a repeating structure represented by the general formula (III), which increases the dissolution rate in an alkaline developer by the action of an acid, and (C) a specific mixed solvent This is achieved by a positive photoresist composition for use.

In general formula (I):
R _{11 to} R ₁₄ are each independently a group capable of decomposing by the action of an acid, a hydrogen atom, a halogen atom, a cyano group, —COOH, —COOR ₁₅ , —C (═O) —XA—R ₁₆ , or It represents an alkyl group or a cyclic hydrocarbon group, and at least one of R _{11 to} R ₁₄ represents a group that decomposes by the action of an acid. In addition, at least two of R _{11 to} R ₁₄ may be bonded to form a ring. n represents 0 or 1. Here, R ₁₅ represents an alkyl group, cyclic hydrocarbon group, or -Y group shown below. X represents an oxygen atom, a sulfur _{atom, -NH -, - NHSO 2 -} , or an -NHSO ₂ NH-. A represents a single bond, an alkylene group, a cycloalkylene group, an ether group, a thioether group, a carbonyl group, or a group of two or more groups selected from the group consisting of ester groups. R ₁₆ represents —COOH, —COOR ₁₅ , —CN, a hydroxyl group, an alkoxy group, —CO—NH—R ₁₇ , —CO—NH—SO ₂ —R _17, or the following —Y group. R ₁₇ represents an alkyl group or a cyclic hydrocarbon group.
The -Y group;

In the -Y group, R _{21 to} R ₃₀ each independently represents a hydrogen atom or an alkyl group. a and b represent 1 or 2;

In general formula (II):
Z ₂ represents —O— or —N (R ₄₁ ) —. Here, R ₄₁ represents a hydrogen atom, a hydroxyl group, an alkyl group, a haloalkyl group, or —OSO ₂ —R ₄₂ . _R42 represents an alkyl group, a haloalkyl group, a cycloalkyl group or a camphor residue.
In general formula (III):
R ₉₁ represents a hydrogen atom, a lower alkyl group, a halogen atom or —CN.
X ₅ is, -O -, - S -, - NR 93 -, or -NR ₉₃ SO ₂ - represents a. R ₉₃ represents a hydrogen atom, a chain or cyclic alkyl group.
B represents a single bond or a linking group.
R ₉₂ represents a hydrogen atom, a chain or cyclic alkyl group, an alkoxy group, a hydroxyl group, a carboxy group, a cyano group, —COOR ₉₄ , or a group represented by any one of the following general formulas (IV) to (X). . R ₉₄ represents a hydrogen atom or a chain or cyclic alkyl group.

_{^{-N + (R 95) (R}} 96) (R 97) · X - (VIII)
-R ₉₈ -A ₅₀ -R ₉₉ (IX)
-SO ₃ R ₁₀₀ (X)

In the formula (IV), Ra ₁ , Rb ₁ , Rc ₁ , Rd ₁ , and Re ₁ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. m and n each independently represents an integer of 0 to 3, and m + n is 2 or more and 6 or less.
In formulas (V-1) to (V-4), R _{1b to} R _5b each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an alkenyl group. Two of R _{1b to} R _5b may combine to form a ring.
In formula (VII), R _{1d to} R _8d each independently represents a hydrogen atom or an alkyl group. R _d0 represents a hydrogen atom, a chain or cyclic alkyl group, an aryl group or an aralkyl group. m represents an integer of 1 to 10.
In formula (VIII), R _{95 to} R ₉₇ each independently represents a hydrogen atom, a chain or cyclic alkyl group, an alkenyl group, an aryl group, or an aralkyl group. However, R _{95 to} R ₉₇ may be bonded to each other to form a non-aromatic ring or an aromatic ring. X ⁻ represents R—SO ₃ ^— . R represents an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
In formula (IX), R ₉₈ represents a single bond, an alkylene group, an arylene group, or a divalent group obtained by combining these.
A ₅₀ represents any of the functional groups shown below.

R ₉₉ represents a hydrogen atom or an alkyl group.
In the formula (X), R ₁₀₀ represents a chain or cyclic alkyl group, an aryl group or an aralkyl group.

(1) In the above structure, the solvent of (C) further contains at least one of propylene glycol monoalkyl ether, alkyl lactate and alkyl alkoxypropionate and heptanone, and is a positive photoresist. Composition.

(2) The positive photoresist composition as described in (1) above, wherein the solvent of (C) further contains at least one of γ-butyrolactone, ethylene carbonate, and propylene carbonate.

(3) In the above configuration, the resin of component (B) further contains a repeating unit represented by the following formula (XI), for far ultraviolet exposure according to the above (1) or (2) Positive type photoresist composition.

In general formula (XI):
R ₉₁ c represents a hydrogen atom, a lower alkyl group, a halogen atom or —CN.
X ₅ c is, -O -, - S -, - NR 93 c-, or -NR ₉₃ CSO ₂ - represents a. R ₉₃ c represents a hydrogen atom, a chain or cyclic alkyl group.
Bc represents a single bond or a linking group.
R ₉₂ c represents a group represented by the following general formula (XI ′).

In General Formula (XI ′), R ₂ c to R ₄ c each independently represent a hydrogen atom or a hydroxyl group. However, at least one of R ₂ c to R ₄ c represents a hydroxyl group.

Furthermore, the following aspects are also preferable.
(4) The positive photoresist composition for far ultraviolet exposure according to any one of (1) to (3) above, further comprising a fluorine-based and / or silicon-based surfactant.

(5) The positive photoresist composition for far ultraviolet exposure according to any one of (1) to (4), further comprising an organic basic compound.

  The present invention has excellent sensitivity in the resolution of contact holes in the manufacture of semiconductor devices, and can prevent the generation of particles when dissolving the solid content in a solvent or storage over time, and prevents fluctuations in sensitivity due to storage over time A positive photoresist composition that can be provided can be provided.

  Hereinafter, the compounds used in the present invention will be described in detail.

[1] (A) Compound that generates acid upon irradiation with actinic ray or radiation The composition of the present invention contains (A) a compound that generates acid upon irradiation with an actinic ray or radiation (photoacid generator).

  Examples of the photoacid generator include photoinitiators for photocationic polymerization, photoinitiators for photoradical polymerization, photodecolorants for dyes, photochromic agents, and known light (400 to 400) used for microresists. 200 nm ultraviolet rays, far ultraviolet rays, particularly preferably g-line, h-line, i-line, KrF excimer laser beam), ArF excimer laser beam, electron beam, X-ray, molecular beam or ion beam, and compounds These mixtures can be appropriately selected and used.

Examples of other photoacid generators used in the present invention include diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenonium salts, onium salts such as arsonium salts, organic halogen compounds, organic metals / organics. Examples include halides, photoacid generators having an o-nitrobenzyl-type protecting group, compounds that generate photosulfonic acid by photolysis, such as iminosulfonates, disulfone compounds, diazoketosulfones, diazodisulfone compounds, etc. Can do.
Moreover, the group which generate | occur | produced the acid by these light, or the compound which introduce | transduced the compound into the principal chain or side chain of the polymer can be used.

  Furthermore, VNRPillai, Synthesis, (1), 1 (1980), A. Abad etal, Tetrahedron Lett., (47) 4555 (1971), DHR Barton etal, J. Chem. Soc., (C), 329 (1970) ), Compounds capable of generating an acid by light described in US Pat. No. 3,779,778, European Patent 126,712 and the like can also be used.

Among the compounds that generate acids that can be used in combination, those that are particularly effectively used will be described below.
(1) An oxazole derivative represented by the following general formula (PAG1) substituted with a trihalomethyl group or an S-triazine derivative represented by the general formula (PAG2).

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

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

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

Z ⁻ represents a counter anion, for example, a perfluoroalkanesulfonic acid anion such as BF ₄ ⁻ , AsF ₆ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , SiF ₆ ²⁻ , ClO ₄ ⁻ , CF ₃ SO ₃ ⁻ , penta Examples include, but are not limited to, condensed polynuclear aromatic sulfonate anions such as fluorobenzene sulfonate anion and naphthalene-1-sulfonate anion, anthraquinone sulfonate anion, and sulfonate group-containing dyes.

Two of R ²⁰³ , R 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.

In the above, Ph represents a phenyl group.
The above onium salts represented by the general formulas (PAG3) and (PAG4) are known and can be synthesized, for example, by the methods described in U.S. Pat. Nos. 2,807,648 and 4,247,473, JP-A-53-101,331, etc. .

(3) A disulfone derivative represented by the following general formula (PAG5) or an iminosulfonate derivative represented by the general formula (PAG6).

In the formula, Ar ³ and Ar ⁴ each independently represent a substituted or unsubstituted aryl group. R ²⁰⁶ represents a substituted or unsubstituted alkyl group or aryl group. A represents a substituted or unsubstituted alkylene group, alkenylene group, or arylene group.
Specific examples include the following compounds, but are not limited thereto.

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

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

  The addition amount of the photoacid generator is usually used in the range of 0.001 to 30% by weight, preferably 0.3 to 20% by weight, more preferably 0.5 to 0.5%, based on the solid content in the composition. It is used in the range of 10% by weight. If the addition amount of the photoacid generator is less than 0.001% by weight, the sensitivity becomes low, and if the addition amount is more than 30% by weight, the light absorption of the resist becomes too high, resulting in deterioration of the profile and process (especially baking). ) Margin becomes narrow, which is not preferable.

[2] (B) Resin Next, (B) the repeating unit represented by the general formula (I), the repeating unit represented by the general formula (II), and the general formula (III) An acid-decomposable resin having a repeating unit (hereinafter abbreviated as “acid-decomposable resin according to the present invention”) will be described.

In the above general formula (I), R _{11 to} R ₁₄ are each independently a group that decomposes by the action of an acid, a hydrogen atom, a halogen atom, a cyano group, —COOH, —COOR ₁₅ , —C (═O ) —X—A—R ₁₆ , an alkyl group or a cyclic hydrocarbon group, and at least one of R _{11 to} R ₁₄ represents a group that decomposes by the action of an acid. In addition, at least two of R _{11 to} R ₁₄ may be bonded to form a ring. n represents 0 or 1. Here, R ₁₅ represents an alkyl group, a cyclic hydrocarbon group, or the above-Y group. X represents an oxygen atom, a sulfur _{atom, -NH -, - NHSO 2 -} , or an -NHSO ₂ NH-. A represents a single bond, an alkylene group, a cycloalkylene group, an ether group, a thioether group, a carbonyl group, or a group of two or more groups selected from the group consisting of ester groups. R ₁₆ represents —COOH, —COOR ₁₅ , —CN, a hydroxyl group, an alkoxy group, —CO—NH—R ₁₇ , —CO—NH—SO ₂ —R _17, or —Y
Represents a group. R ₁₇ represents an alkyl group or a cyclic hydrocarbon group.
In the above -Y group, R _{21 to} R ₃₀ each independently represents a hydrogen atom or an alkyl group. a and b represent 1 or 2;

The structure of a group that is decomposed by the action of an acid is represented by —C (═O) —X ₁ —R _p .
In the formula, R _p is a tertiary alkyl group such as t-butyl group or t-amyl group, isobornyl group, 1-ethoxyethyl group, 1-butoxyethyl group, 1-isobutoxyethyl group, 1-cyclohexyloxy 1-alkoxyethyl group such as ethyl group, 1-methoxymethyl group, alkoxymethyl group such as 1-ethoxymethyl group, 3-oxoalkyl group, tetrahydropyranyl group, tetrahydrofuranyl group, trialkylsilyl ester group, 3- Examples thereof include an oxocyclohexyl ester group, a 2-methyl-2-adamantyl group, a mevalonic lactone residue, and a 2- (γ-butyrolactonyloxycarbonyl) -2-propyl group. X ₁ represents an oxygen atom, a sulfur atom, -NH -, - NHSO ₂ - or an -NHSO ₂ NH-.

Examples of the halogen atom in R _{11 to} R ₁₄ include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom.
The alkyl group in R _{11 to} R ₁₄ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, more preferably a linear or branched alkyl group having 1 to 6 carbon atoms. More preferred are methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and t-butyl group.
Examples of the cyclic hydrocarbon group in R _{11 to} R ₁₄ include a cyclic alkyl group and a bridged hydrocarbon group, such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a 2-methyl-2-adamantyl group, and norbornyl. Group, boronyl group, isobornyl group, tricyclodecanyl group, dicyclopentenyl group, nobornane epoxy group, menthyl group, isomenthyl group, neomenthyl group, tetracyclododecanyl group and the like.

Examples of the ring formed by combining at least two of R _{11 to} R ₁₄ include rings having 5 to 12 carbon atoms such as cyclopentene, cyclohexene, cycloheptane, and cyclooctane.
Examples of the alkoxy group for R ₁₆ include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.
Each of the above alkyl groups, cyclic hydrocarbon groups, and alkoxy groups may further have a substituent. Examples of the substituent include a hydroxyl group, a carboxyl group, a cyano group, and a halogen atom (for example, a chlorine atom, a bromine atom, Fluorine atom, iodine atom, etc.), alkoxy group (preferably having 1 to 4 carbon atoms, such as methoxy group, ethoxy group, propoxy group, butoxy group, etc.), acyl group (eg, formyl group, acetyl group, etc.), acyloxy group ( For example, an acetoxy group etc.) can be mentioned.

Examples of the alkylene group in A include groups represented by the following formulas.
− [C (R _b ) (R _c )] _r −
In the formula, R _b and R _c represent a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, or an alkoxy group, and both may be the same or different. The alkyl group is preferably a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group, and more preferably selected from a methyl group, an ethyl group, 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 (preferably having 1 to 4 carbon atoms).
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.

In the -Y group, R _{21 to} R ₃₀ each independently represents a hydrogen atom or an alkyl group. a and b represent 1 or 2;
Examples of the alkyl group in R _{21 to} R ₃₀ include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group.
The alkyl group as R _{21 to} R ₃₀ may have a substituent. Examples of the substituent include a hydroxyl group, a carboxyl group, a cyano group, a halogen atom (for example, a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom), an alkoxy group (preferably having 1 to 4 carbon atoms, for example, a methoxy group, Ethoxy group, propoxy group, butoxy group, etc.), acyl group (preferably having 2 to 5 carbon atoms, such as formyl group, acetyl group, etc.), acyloxy group (preferably having 2 to 5 carbon atoms, such as acetoxy group), aryl group (Preferably having 6 to 14 carbon atoms, such as a phenyl group).

  Specific examples of the repeating unit represented by the general formula (I) include the following, but the present invention is not limited to these specific examples.

In the general formula (II), Z ₂ represents —O— or —N (R ₄₁ ) —. Here, R ₄₁ represents a hydrogen atom, a hydroxyl group, an alkyl group, a haloalkyl group, or —OSO ₂ —R ₄₂ . _R42 represents an alkyl group, a haloalkyl group, a cycloalkyl group or a camphor residue.

The alkyl group in R ₄₁ and R ₄₂ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, more preferably a linear or branched alkyl group having 1 to 6 carbon atoms. More preferred are methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and t-butyl group.
Examples of the haloalkyl group in R ₄₁ and R ₄₂ include a trifluoromethyl group, a nanofluorobutyl group, a pentadecafluorooctyl group, and a trichloromethyl group. Examples of the cycloalkyl group for R ₄₂ include a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.

The alkyl group and haloalkyl group as R ₄₁ and R ₄₂ , the cycloalkyl group as R ₄₂ , or the camphor residue may have a substituent. Examples of such a substituent include a hydroxyl group, a carboxyl group, a cyano group, a halogen atom (for example, a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom), an alkoxy group (preferably having 1 to 4 carbon atoms, for example, methoxy Group, ethoxy group, propoxy group, butoxy group, etc.), acyl group (preferably having 2 to 5 carbon atoms, such as formyl group, acetyl group, etc.), acyloxy group (preferably having 2 to 5 carbon atoms, such as acetoxy group), An aryl group (preferably having 6 to 14 carbon atoms, for example, a phenyl group) and the like can be mentioned.

  Specific examples of the repeating unit represented by the general formula (II) include the following [I′-1] to [I′-7], but the present invention is not limited to these specific examples. .

Next, the repeating unit represented by formula (III) will be described.
In the formula (III), R ₉₁ represents a hydrogen atom, a lower alkyl group, a halogen atom, or a cyano group.
The lower alkyl group for R ₉₁ is preferably one having 1 to 5 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. This lower alkyl group may further have a substituent. Examples of such a substituent include a hydroxyl group, a carboxyl group, a cyano group, a halogen atom (for example, a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom), an alkoxy group (preferably having 1 to 4 carbon atoms, for example, methoxy Group, ethoxy group, propoxy group, butoxy group, etc.), acyl group (preferably having 2 to 5 carbon atoms, such as formyl group, acetyl group, etc.), acyloxy group (preferably having 2 to 5 carbon atoms, such as acetoxy group), An aryl group (preferably having 6 to 14 carbon atoms, for example, a phenyl group) and the like can be mentioned.

X ₅ is, -O -, - S -, - NR 93 -, or -NR ₉₃ SO ₂ - represents a. R ₉₃ represents a hydrogen atom, a chain or cyclic alkyl group. The chain alkyl group as R ₉₃ is a lower alkyl group, preferably having 1 to 5 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. Examples of the cyclic alkyl group include those having 3 to 12 carbon atoms. These may further have a substituent. Examples of the substituent include a hydroxyl group, a carboxyl group, a cyano group, a halogen atom (for example, a chlorine atom, a bromine atom, a fluorine atom, an iodine atom), an alkoxy group ( Preferably it has 1 to 4 carbon atoms, such as methoxy group, ethoxy group, propoxy group, butoxy group, etc., acyl group (preferably 2 to 5 carbon atoms, such as formyl group, acetyl group, etc.), acyloxy group (preferably carbon Examples thereof include 2 to 5, for example, an acetoxy group, an aryl group (preferably 6 to 14 carbon atoms, for example, a phenyl group), and the like.

B represents a single bond or a linking group. Examples of the linking group for B include, for example, a single group selected from the group consisting of an alkylene group, a cycloalkylene group, an ether group, a thioether group, a carbonyl group, and an ester group, or a combination of two or more groups.
Preferred examples of the cycloalkylene group for B include those having 3 to 10 carbon atoms, and examples thereof include a cyclopentylene group, a cyclohexylene group, and a cyclooctylene group.
Examples of the alkylene group for B include groups represented by the following formulas.
− [C (R _X ) (R _Y )] _Z −
Rx and Ry each independently represents a hydrogen atom, a hydroxyl group, a halogen atom, or a linear or cyclic alkyl group, alkoxy group, alkenyl group, aryl group, or aralkyl group, which may have a substituent. However, Rx and Ry may combine with each other to form a cyclic alkyl ring.
Examples of the linear alkyl group for Rx or Ry include a linear or branched alkyl group, which may have a substituent. The linear or branched alkyl group is preferably a linear or branched alkyl group having 1 to 12 carbon atoms, more preferably a linear or branched alkyl group having 1 to 10 carbon atoms. More preferably, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group is there.
Examples of the cyclic alkyl group include those having 3 to 30 carbon atoms, and may contain a hetero atom such as an oxygen atom or a nitrogen atom. Specifically, 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, tetra A cyclododecanyl group, a steroid residue, a tetrahydropyranyl group, a morpholino group and the like can be mentioned.
Examples of the alkoxy group generally include those having 1 to 12 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms, such as methoxy group, ethoxy group, propoxy group, butoxy group. Groups and the like.
Examples of the alkenyl group include alkenyl groups having 2 to 6 carbon atoms, which may have a substituent. Specifically, vinyl group, propenyl group, allyl group, butenyl group, pentenyl group, hexenyl group, cyclopentenyl group, cyclohexenyl group, 3-oxocyclohexenyl group, 3-oxocyclopentenyl group, 3-oxoindenyl group, etc. Can be mentioned. Of these, the cyclic alkenyl group may contain an oxygen atom.
Examples of the aryl group include those having 6 to 10 carbon atoms, which may have a substituent. Specifically, a phenyl group, a tolyl group, a naphthyl group, etc. are mentioned.
Examples of the aralkyl group include a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, and a mesitylmethyl group.
Examples of the substituent that the chain or cyclic alkyl group, alkoxy group, alkenyl group, aryl group, or aralkyl group may have include a carboxyl group, a cyano group, a hydroxyl group, and a halogen atom (chlorine atom, bromine atom). Fluorine atom, iodine atom, etc.), alkoxy group (preferably having 1 to 4 carbon atoms, such as methoxy group, ethoxy group, propoxy group, butoxy group), acetylamide group, alkoxycarbonyl group, acyl group (preferably having 2 carbon atoms) -10, for example, formyl group, acetyl group, propionyl group), acyloxy group (preferably having 2 to 10 carbon atoms such as acetoxy group), and aryl group (preferably having 6 to 14 carbon atoms such as phenyl group). As for Rx or Ry, an aryl group or an aralkyl group is further substituted with an alkyl group (preferably having a carbon number of 1 to 5, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a cyclopropyl group, a cyclobutyl group. , A cyclopentyl group, etc.). The alkyl group as the substituent may further have a substituent such as a hydroxyl group, a halogen atom, or an alkoxy group (preferably having 1 to 4 carbon atoms, such as a methoxy group, an ethoxy group, a propoxy group, or a butoxy group). .
Z is an integer of 1 to 10, preferably 1 to 4.

R ₉₂ represents a hydrogen atom, a chain or cyclic alkyl group, an alkoxy group, a hydroxyl group, a carboxy group,
A cyano group, —COOR ₉₄ , or a group represented by any one of the above general formulas (IV) to (X) is represented.
_Examples of the chain alkyl group as R ₉₂ and R ₉₄ generally include those having 1 to 30 carbon atoms, preferably 6 to 20 carbon atoms. For example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group , Dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group and the like.
_Examples of the cyclic alkyl group as R ₉₂ and R ₉₄ generally include those having 3 to 40 carbon atoms, preferably 6 to 20 carbon atoms. For example, 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 Groups, steroid residues, tetrahydropyranyl groups, morpholino groups and the like.

The chain alkyl group as R ₉₂ and R ₉₄ may have a substituent. Examples of the substituent include a hydroxyl group, a carboxyl group, a cyano group, a halogen atom (for example, a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom), an alkoxy group (preferably having 1 to 4 carbon atoms, for example, a methoxy group, an ethoxy group). Group, propoxy group, butoxy group, etc.), alkoxycarbonyl group, acyl group (preferably having 2 to 5 carbon atoms, such as formyl group, acetyl group, etc.), acyloxy group (preferably having 2 to 5 carbon atoms, such as acetoxy group) , An aryl group (preferably having 6 to 14 carbon atoms, for example, a phenyl group), an acetylamide group, and the like. Examples of the alkoxy group in the alkoxycarbonyl group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.
The cyclic alkyl group as R ₉₂ and R ₉₄ includes, as a substituent, a carboxyl group, a cyano group, a halogen atom (chlorine atom, bromine atom, fluorine atom, iodine atom), an alkoxy group (preferably having 1 to 4 carbon atoms, For example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, etc.), an alkoxycarbonyl group, an acyl group (preferably having 2 to 5 carbon atoms, such as a formyl group, an acetyl group), an acyloxy group (preferably having 2 to 5 carbon atoms). , For example, an acetoxy group), an aryl group (preferably having 6 to 14 carbon atoms, such as a phenyl group), and an acetylamide group. Examples of the alkoxy group in the alkoxycarbonyl group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.

As the repeating unit represented by the general formula (III) in which R ₉₂ is a cyclic alkyl group, the repeating unit represented by the following general formula (IIIa) or the general formula (IIIb) is preferable.

In general formula (IIIa) and general formula (IIIb), R ₀ represents a hydrogen atom, a lower alkyl group, a halogen atom, or a cyano group. R ₆₁ and R ₆₂ represent a lower alkyl group. R _{63 to} R ₆₈ each independently represents a hydrogen atom, a lower alkyl group, a lower alkoxy group or a halogen atom. R ₆₃ and R ₆₄ or R ₆₅ and R ₆₆ may be combined to form a carbonyl group. R ₆₃ and R ₆₅ may be linked to form an alkylene chain. k and l are integers of 2 to 5.

In the repeating units represented by the general formulas (IIIa) and (IIIb), acid decomposability is exhibited due to the presence of a tertiary carbon atom to which R ₆₁ is bonded.
R ₀ is preferably a hydrogen atom.
The lower alkyl group as R ₀ and R _{61 to} R ₆₈ has 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. Specific examples include a methyl group, an ethyl group, a linear or branched propyl group, and a linear or branched butyl group.
The lower alkoxy group as R _{63 to} R ₆₈ has 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. Specific examples include a methoxy group, an ethoxy group, a linear or branched propoxy group, and a linear or branched butoxy group.
The lower alkyl group as R ₀ and R _{61 to} R ₆₈ and the lower alkoxy group as R _{63 to} R ₆₈ may have a substituent. Examples of the substituent include halogen atoms such as chlorine atom and bromine atom, alkoxy groups such as methoxy group and ethoxy group (preferably having 1 to 3 carbon atoms), and the like.

R ₆₃ and R ₆₄ , or R ₆₅ and R ₆₆ may be combined to form a carbonyl group.
k and l are preferably 2 to 4, more preferably 2 or 3.
The alkylene chain that may be formed by linking R ₆₃ and R ₆₅ has a methylene chain, an ethylene chain, a propylene chain, or the like, and preferably has 3 or less carbon atoms.

The alkoxy group for R ₉₂ generally has 1 to 30 carbon atoms, preferably 3 to 20 carbon atoms, more preferably 4 to 15 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Can be mentioned.
The alkoxy group of R ₉₂ may further have a substituent, and examples of the substituent are the same as those described as the substituent for the chain or cyclic alkyl group as R ₉₂ .

Specific examples of the repeating unit represented by the general formula (III) in which R ₉₂ is an alkyl group, an alkoxy group, or a hydrogen atom, and the repeating units represented by the general formula (IIIa) and the general formula (IIIb) will be given below. However, it is not limited to these.

*) This is a mixture of units with different numbers of groups in parentheses, and represents an average of 1.4 groups in parentheses.

Furthermore, the repeating structural unit in which R ₉₂ in the formula (III) is a structure represented by the following general formula (IV) will be described.

Ra ₁ , Rb ₁ , Rc ₁ , Rd ₁ and Re ₁ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. m and n each independently represents an integer of 0 to 3, and m + n is 2 or more and 6 or less.
Examples of the alkyl group having 1 to 4 carbon atoms of Ra _{1 to} Re ₁ include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a t-butyl group. Can do. These alkyl groups may be substituted with a substituent such as an alkoxy group (preferably having 1 to 4 carbon atoms).

  Specific examples of the repeating structural unit having the structure of the general formula (IV) are shown below, but are not limited thereto.

In the specific example of the repeating unit having the structure of the general formula (IV), (IV-17) to (IV-36) are preferable from the viewpoint that the exposure margin becomes better.
Further, as the structure of the general formula (IV), those having an acrylate structure are preferable from the viewpoint that the edge roughness becomes good.

  Furthermore, the repeating unit structure which has group represented by either of the following general formula (V-1)-(V-4) is demonstrated.

In General Formulas (V-1) to (V-4), R _{1b to} R _5b each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an alkenyl group. Two of R _{1b to} R _5b may combine to form a ring.

In the general formulas (V-1) to (V-4), examples of the alkyl group in R _{1b to} R _5b include linear and branched alkyl groups. The linear or branched alkyl group is preferably a linear or branched alkyl group having 1 to 12 carbon atoms, more preferably a linear or branched alkyl group having 1 to 10 carbon atoms. 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, octyl group, nonyl group, decyl It is a group.
As a cycloalkyl group in R _<1b > -R < _5b >, C3-C8 things, such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, are preferable.
As an alkenyl group in R _<1b > -R < _5b >, C2-C6 things, such as a vinyl group, a propenyl group, a butenyl group, a hexenyl group, are preferable, for example.
Examples of the ring formed by combining two of R _{1b to} R _5b include 3- to 8-membered rings such as a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, and a cyclooctane ring.

Further, the ring alkyl group as R _1b to R _5b, a cycloalkyl group, two of the alkenyl groups and R _1b to R _5b formed by bonding may have a substituent. Preferred substituents include a hydroxyl group, a carboxy group, a nitro group, a cyano group, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), an alkoxy group having 1 to 4 carbon atoms, and an alkyl group having 2 to 5 carbon atoms. Examples thereof include an alkoxycarbonyl group, an acyl group having 2 to 5 carbon atoms, and an acyloxy group having 2 to 5 carbon atoms.
In the general formulas (V-1) to (V-4), R _{1b to} R _5b may be connected to any carbon atom constituting the cyclic skeleton.

  As a preferable repeating unit having a group represented by general formulas (V-1) to (V-4), a repeating unit represented by the following general formula (AI) can be given.

In general formula (AI), R _b0 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. The alkyl group of R _b0 may have a substituent, and as a preferable substituent, an alkyl group as R _1b in the general formulas (V-1) to (V-4) may have. Preferred examples of the substituent include those exemplified above.
Examples of the halogen atom for R _b0 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. R _b0 is preferably a hydrogen atom.
B ₂ represents a group represented by any one of the general formulas (V-1) to (V-4).
A ′ is the same as the definition of B in the formula (III). In A ′, examples of the combined divalent group include those represented by the following formulae.

In the above formula, Rab and Rbb represent a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, and an alkoxy group, and both may be the same or different.
The alkyl group is preferably a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group, and more preferably selected from a methyl group, an ethyl group, 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 having 1 to 4 carbon atoms.
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, preferably an integer of 1 to 4. m represents an integer of 1 to 3, preferably 1 or 2.

  Although the specific example of the repeating unit represented by general formula (AI) is given to the following, the content of this invention is not limited to these.

Next, the repeating structural unit having a structure represented by the following general formula (VI) will be described.

The bridged alicyclic ring containing Z may have a substituent. Examples of the substituent include a carboxyl group, a hydroxyl group, a halogen atom, an alkyl group (preferably having 1 to 4 carbon atoms), an alkoxy group (preferably having 1 to 4 carbon atoms), and an alkoxycarbonyl group (preferably having 2 to 5 carbon atoms). ), An acyl group (for example, formyl group, benzoyl group), an acyloxy group (for example, propylcarbonyloxy group, benzoyloxy group), an alkylsulfonylsulfamoyl group (-CONHSO ₂ CH ₃ etc.). In addition, the alkyl group as a substituent may be further substituted with a hydroxyl group, a halogen atom, an alkoxy group (preferably having 1 to 4 carbon atoms), or the like.

  B in the general formula (III) may be bonded at any position of the carbon atom constituting the bridged alicyclic ring structure containing Z in the general formula (VI).

  Although the specific example of the repeating unit which has a structure represented by general formula (VI) below is given, it is not limited to these.

Furthermore, the repeating structural unit in which R ₉₂ in the formula (III) has a structure represented by the following general formula (VII) will be described.

In General Formula (VII), R _{1d to} R _8d each independently represent a hydrogen atom or a chain alkyl group.
R _d0 represents a hydrogen atom, a chain or cyclic alkyl group, an aryl group, or an aralkyl group.
m represents an integer of 1 to 10.

_Examples of the linear alkyl group represented by R _{1d to} R _8d and R _d0 in the general formula (VII) include a linear, branched, or cyclic alkyl group, which may have a substituent. The linear or branched alkyl group is preferably a linear or branched alkyl group having 1 to 12 carbon atoms, more preferably a linear or branched alkyl group having 1 to 10 carbon atoms. 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, octyl group, nonyl group, decyl It is a group.
_Examples of the cyclic alkyl group represented by R _d0 include those having 3 to 30 carbon atoms, specifically, 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 residue and the like.

_Examples of the aryl group for R _d0 include those having 6 to 20 carbon atoms, which may have a substituent. Specifically, a phenyl group, a tolyl group, a naphthyl group, etc. are mentioned.
_Examples of the aralkyl group for R _d0 include those having 7 to 20 carbon atoms, which may have a substituent. Examples include a benzyl group, a phenethyl group, and a cumyl group.
In the present invention, R _{1d to} R _8d are preferably a hydrogen atom or a methyl group. R _d0 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. m is preferably 1-6.

  Further substituents in the chain or cyclic alkyl group, aryl group, aralkyl group, alkylene group, cyclic alkylene group, and arylene group include a carboxyl group, a cyano group, a hydroxyl group, a halogen atom (for example, a chlorine atom, a bromine atom, a fluorine atom). Atoms, iodine atoms, etc.), alkyl groups, substituted alkyl groups, alkoxy groups (preferably having 1 to 4 carbon atoms, such as methoxy group, ethoxy group, propoxy group, butoxy group, etc.), alkoxycarbonyl groups, acyl groups, acyloxy groups ( Examples thereof include an acetoxy group) and an acetylamide group. 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 (preferably having 1 to 4 carbon atoms).

  Specific examples of the repeating unit having the structure represented by the general formula (VII) will be given below, but the invention is not limited thereto.

Next, the repeating structural unit in which R ₉₂ in the formula (III) has a structure represented by the following general formula (VIII) will be described.
_{^{-N + (R 95) (R}} 96) (R 97) · X - (VIII)

In general formula (VIII):
R _{95 to} R ₉₇ each independently represents a hydrogen atom, a chain or cyclic alkyl group, an alkenyl group, an aryl group, or an aralkyl group. However, R _{95 to} R ₉₇ may be bonded to each other to form a non-aromatic ring or an aromatic ring.
Examples of the chain alkyl group include a linear or branched alkyl group, which may have a substituent. A linear or branched alkyl group having 1 to 12 carbon atoms is preferable, a linear or branched alkyl group having 1 to 10 carbon atoms is more preferable, and a methyl group, an ethyl group, or a propyl group is more preferable. , Isopropyl group, n-butyl group, isobutyl group, sec-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, and decyl group.

Examples of the cyclic alkyl group include those having 3 to 30 carbon atoms, and may contain a hetero atom such as an oxygen atom or a nitrogen atom. Specifically, 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, tetra A cyclododecanyl group, a steroid residue, a tetrahydropyranyl group, a morpholino group and the like can be mentioned.

Examples of the alkenyl group include alkenyl groups having 2 to 6 carbon atoms, which may have a substituent. Specifically, vinyl group, propenyl group, allyl group, butenyl group, pentenyl group, hexenyl group, cyclopentenyl group, cyclohexenyl group, 3-oxocyclohexenyl group, 3-oxocyclopentenyl group, 3-oxoindenyl group, etc. Can be mentioned. Of these, the cyclic alkenyl group may contain an oxygen atom.
Examples of the aryl group include those having 6 to 10 carbon atoms, which may have a substituent. Specifically, a phenyl group, a tolyl group, a naphthyl group, etc. are mentioned.

  Examples of the aralkyl group include a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, and a mesitylmethyl group.

Chain or cyclic alkyl group as R ₉₅ to R _97, an alkenyl group, an aryl group, or an aralkyl group, and R ₉₅ to R ₉₇ are combined to form and may be non-aromatic ring, have an aromatic ring Examples of the substituent may be a carboxyl group, a cyano group, a hydroxyl group, a halogen atom (a chlorine atom, a bromine atom, a fluorine atom, an iodine atom, etc.), an alkoxy group (preferably having 1 to 4 carbon atoms, such as a methoxy group, ethoxy group). Group, propoxy group, butoxy group), acetylamide group, alkoxycarbonyl group, acyl group (preferably having 2 to 10 carbon atoms, for example, formyl group, acetyl group, propionyl group), acyloxy group (preferably having 2 to 10 carbon atoms). For example, an acetoxy group) and an aryl group (preferably having 6 to 14 carbon atoms, for example, a phenyl group). R ₉₅ as to R ₉₇ aryl group or an aralkyl group, and R ₉₅ to R ₉₇ are combined to form and may be non-aromatic ring, for the aromatic ring, as a substituent, an alkyl group (preferably 1 to 5 carbon atoms For example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, etc.). The alkyl group as the substituent may further have a substituent such as a hydroxyl group, a halogen atom, or an alkoxy group (preferably having 1 to 4 carbon atoms, such as a methoxy group, an ethoxy group, a propoxy group, or a butoxy group). .

X ⁻ has a specific structure R—SO ₃ ^— as described above.
The aliphatic hydrocarbon group for R is preferably a linear or branched alkyl group having 1 to 20 carbon atoms or a cyclic alkyl group, and may have a substituent.
The aromatic hydrocarbon group for R is preferably an aromatic group having 6 to 14 carbon atoms and may have a substituent.

Examples of the alkyl group for R include a methyl group, an ethyl group, a propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-octyl group, and 2-ethylhexyl, which may have a substituent. Group, decyl group, dodecyl group and the like, and the cyclic alkyl group may have a substituent, cyclopentyl group, cyclohexyl group, cyclooctyl group, cyclododecyl group, adamantyl group, norbornyl group, camphor group, A tricyclodecanyl group, a menthyl group, etc. can be mentioned.
Examples of the aromatic group include a phenyl group and a naphthyl group which may have a substituent.

Examples of the substituent that the aliphatic hydrocarbon group and the aromatic hydrocarbon group may have include a halogen atom, a hydroxyl group, an alkoxy group, an alkoxycarbonyl group, and a camphor group. Group, t-butyl group, methoxy group, ethoxy group, t-butoxy group, fluorine atom, chlorine atom, bromine atom, cyano group, hydroxyl group, methoxycarbonyl group, ethoxycarbonyl group, t-butoxycarbonyl group, t-amyloxy group A carbonyl group etc. are mentioned. Further, for aliphatic hydrocarbon groups, aryl groups (preferably having 6 to 14 carbon atoms) can be cited as substituents, and for aromatic hydrocarbon groups, alkyl groups (1 to 15 carbon atoms) can be cited as substituent groups.

  Specific examples of the repeating unit having the structure represented by the general formula (VIII) are shown below. However, the contents of the present invention are not limited to these.

Furthermore, the repeating structural unit in which R ₉₂ in the formula (III) has a structure represented by the following general formula (IX) or (X) will be described.
-R ₉₈ -A ₅₀ -R ₉₉ (IX)
-SO ₃ R ₁₀₀ (X)

In General Formula (IX), R ₉₈ represents a single bond, an alkylene group, an arylene group, or a divalent group obtained by combining these.
Examples of the arylene group 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.

Examples of the alkylene group include the groups shown below.
-[C (Rf) (Rg)] r-
In the formula, Rf and Rg represent a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, and an alkoxy group, both of which may be the same or different. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, A lower alkyl group such as an isopropyl group and a butyl group is preferable, and a substituent selected from the group consisting of a methyl group, an ethyl group, a propyl group, and an isopropyl group is 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. r represents an integer of 1 to 10.
In the above, examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom.

A ₅₀ represents any of the functional groups shown below.

R ₉₉ represents a hydrogen atom or an alkyl group.
The linear alkyl group for R ₉₉ may be either linear or branched, and may have a substituent. The linear or branched alkyl group is preferably one having 1 to 12 carbon atoms, more preferably one having 1 to 10 carbon atoms, specifically a methyl group, an ethyl group, a propyl group, an isopropyl group, Preferred examples include n-butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group and decyl group.

R ₁₀₀ in the general formula (X) represents a chain or cyclic alkyl group, an aryl group or an aralkyl group, and may have a substituent.
The linear alkyl group for R ₁₀₀ may be linear or branched and may have a substituent. The linear or branched alkyl group is preferably one having 1 to 12 carbon atoms, more preferably one having 1 to 10 carbon atoms, specifically a methyl group, an ethyl group, a propyl group, an isopropyl group, Preferred examples include 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 cyclic alkyl group of R _100, include those having 3 to 30 carbon atoms, specifically, cyclopropyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, bornyl group, tricyclodecanyl group , Dicyclopentenyl group, nobornane epoxy group, menthyl group, isomenthyl group, neomenthyl group, tetracyclododecanyl group, steroid residue and the like. The ring structure may have a hetero atom or a double bond. Examples thereof include tetrahydropyran and pentene rings.

The aryl group of R _100, include those having 6 to 20 carbon atoms, which may have a substituent. Specifically, a phenyl group, a tolyl group, a naphthyl group, etc. are mentioned.
Examples of the aralkyl group for R ₁₀₀ include those having 7 to 20 carbon atoms, which may have a substituent. Specific examples include a benzyl group, a phenethyl group, and a cumyl group.

Examples of the substituent that the linear alkyl group of R _99, the linear or cyclic alkyl group of R ₁₀₀ , an alkoxy group, an aryl group, or an aralkyl group may have include a carboxyl group, a cyano group, a hydroxyl group, and a halogen Atom (chlorine atom, bromine atom, fluorine atom, iodine atom, etc.), alkoxy group (preferably having 1 to 4 carbon atoms, eg methoxy group, ethoxy group, propoxy group, butoxy group), acetylamide group, alkoxycarbonyl group, acyl A group (preferably having 2 to 10 carbon atoms, such as formyl group, acetyl group, propionyl group), an acyloxy group (preferably having 2 to 10 carbon atoms such as acetoxy group), an aryl group (preferably having 6 to 14 carbon atoms, such as Phenyl group). The aryl group or an aralkyl group as R _100, as a substituent, further the alkyl group (preferably having from 1 to 5, for example, a methyl group carbon, an ethyl group, a propyl group, an isopropyl group, a butyl group, a cyclopropyl group, a cyclobutyl group, A cyclopentyl group or the like). The alkyl group as the substituent may further have a substituent such as a hydroxyl group, a halogen atom, or an alkoxy group (preferably having 1 to 4 carbon atoms, such as a methoxy group, an ethoxy group, a propoxy group, or a butoxy group). . The ring structure may form a condensed ring.

Hereinafter, specific examples (2) to (5) of the monomer corresponding to the repeating unit represented by the general formula (III) containing —NH—SO ₂ — and the structure represented by the general formula (IX) are included. Specific examples (6) to (15) of the monomer corresponding to the repeating structural unit are shown, but not limited thereto.

  Hereinafter, although the specific example of the monomer corresponding to the repeating structural unit which has a structure represented by general formula (X) is shown, it is not limited to these.

  The acid-decomposable resin used in the present invention can further contain a repeating unit represented by the following formula (XI).

With respect to general formula (XI), R ₉₁ c, X ₅ c, R ₉₃ c, and B c are the same as R ₉₁ , X ₅ , R ₉₃ , and B for general formula (III), respectively.
R ₉₂ c represents a group represented by the following general formula (XI ′).

In General Formula (XI ′), R ₂ c to R ₄ c each independently represent a hydrogen atom or a hydroxyl group. However, at least one of R ₂ c to R ₄ c represents a hydroxyl group.

  The structure represented by the general formula (XI) is preferably a dihydroxy body or a monohydroxy body, and more preferably a dihydroxy body.

  Although the specific example of the repeating unit which has a structure represented by general formula (XI) below is given, it is not limited to these.

  The resin according to the present invention may further contain a repeating unit represented by the following general formula (XI-A) or (XI-B).

In General Formula (XI-A), R _{13h to} R _16h each independently represent a hydrogen atom, a halogen atom, a cyano group, —COOH, —COOR _17h , —C (═O) —X _h —A _h —. R _18h represents an alkyl group or a cyclic hydrocarbon group which may have a substituent.
Also, it may form a ring of at least two members to one of the _R l3h ~R _16h. n represents 0 or 1. However, each of R _{13h to} R _16h does not have a group that is decomposed by an acid.
R _17h represents an alkyl group, a cyclic hydrocarbon group or the —Y group, which may have a substituent.
X _h represents an oxygen atom, a sulfur atom, -NH -, - NHSO ₂ - or an -NHSO ₂ NH-.
A _h represents a single bond or a divalent linking group.
R _18h is —COOH, —COOR _17h , —CN, a hydroxyl group, an optionally substituted alkoxy group, —CO—NH—R _19h , —CO—NH—SO ₂ —R _19h or the above — Y group is represented. R _19h represents an alkyl group or a cyclic hydrocarbon group which may have a substituent.

As the halogen atom in the above R _{13h to} R _16h , a chlorine atom, a bromine atom, a fluorine atom,
An iodine atom etc. can be mentioned.

The alkyl group for R _{13h to} R _16h is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, more preferably a linear or branched alkyl group having 1 to 6 carbon atoms. More preferred are methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and t-butyl group.

Examples of the cyclic hydrocarbon group in R _{13h to} R _16h include a cyclic alkyl group and a bridged hydrocarbon group, such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a 2-methyl-2-adamantyl group, and norbornyl. Group, boronyl group, isobornyl group, tricyclodecanyl group, dicyclopentenyl group, nobornane epoxy group, menthyl group, isomenthyl group, neomenthyl group, tetracyclododecanyl group and the like.
Examples of the ring formed by combining at least two of R _{13h to} R _16h include rings having 5 to 12 carbon atoms such as cyclopentene, cyclohexene, cycloheptane, and cyclooctane.

Examples of the alkoxy group for R _18h 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 further substituents in the alkyl group, cyclic hydrocarbon group, and alkoxy group include a hydroxyl group, a halogen atom, a carboxyl group, an alkoxy group, an acyl group, a cyano group, and an acyloxy group. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. 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 acyl group include a formyl group and an acetyl group. Examples thereof include an acetoxy group.

Examples of the divalent linking group for A _h 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, a urethane group, and a urea group. Examples thereof include a single selected group or a combination of two or more groups.

Examples of the alkylene group and substituted alkylene group for A _h include groups represented by the following formulae.
− [C (R _bh ) (R _ch )] _r −
In the formula, R _bh and R _{ch each} represent a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, or an alkoxy group, and both may be the same or different. The alkyl group is preferably a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group, and more preferably selected from a methyl group, an ethyl group, 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. 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.

In general formula (XI-B), each of R _{13i to} R _16i independently represents a hydrogen atom, a halogen atom, a cyano group, —COOH, —COOR _17i , a group that decomposes by the action of an acid, —C (═O) —X _i —A _i —R _18i , or an alkyl group or a cyclic hydrocarbon group which may have a substituent.
Further, at least two of R _{13i to} R _16i may be bonded to form a ring. n represents 0 or 1.
R _17i represents an alkyl group, a cyclic hydrocarbon group, or the aforementioned —Y group, which may have a substituent.
X _i represents an oxygen atom, a sulfur atom, -NH -, - NHSO ₂ - or an -NHSO ₂ NH-.
A _i represents a single bond or a divalent linking group.
R _18i represents —COOH, —COOR _17i , —CN, a hydroxyl group, an optionally substituted alkoxy group, —CO—NH—R _19i , —CO—NH—SO ₂ —R _19i, or — Y group is represented. R _19i represents an alkyl group or a cyclic hydrocarbon group which may have a substituent.
In the -Y group, R _{21 to} R ₃₀ each independently represent a hydrogen atom or an alkyl group which may have a substituent. a and b represent 1 or 2;

The structure of the group decomposing by the action of an acid is represented by —C (═O) —X _1i —R _pi .
In the formula, R _pi represents a tertiary alkyl group such as t-butyl group or t-amyl group, isobornyl group, 1-ethoxyethyl group, 1-butoxyethyl group, 1-isobutoxyethyl group, 1-cyclohexyloxy 1-alkoxyethyl group such as ethyl group, 1-methoxymethyl group, alkoxymethyl group such as 1-ethoxymethyl group, 3-oxoalkyl group, tetrahydropyranyl group, tetrahydrofuranyl group, trialkylsilyl ester group, 3- Examples thereof include an oxocyclohexyl ester group, a 2-methyl-2-adamantyl group, a mevalonic lactone residue, and a 2- (γ-butyrolactonyloxycarbonyl) -2-propyl group.
X _1i represents an oxygen atom, a sulfur atom, -NH -, - NHSO ₂ - or an -NHSO ₂ NH-.

Examples of the halogen atom in R _{13i to} R _16i include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom.

The alkyl group in R _{13i to} R _16i is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, more preferably a linear or branched alkyl group having 1 to 6 carbon atoms. More preferred are methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and t-butyl group.

Examples of the cyclic hydrocarbon group in R _{13i to} R _16i include a cyclic alkyl group and a bridged hydrocarbon group, such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a 2-methyl-2-adamantyl group, and norbornyl. Group, boronyl group, isobornyl group, tricyclodecanyl group, dicyclopentenyl group, nobornane epoxy group, menthyl group, isomenthyl group, neomenthyl group, tetracyclododecanyl group and the like.
Examples of the ring formed by combining at least two of R _{13i to} R _16i include rings having 5 to 12 carbon atoms such as cyclopentene, cyclohexene, cycloheptane, and cyclooctane.

Examples of the alkoxy group for R _18i 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 further substituents in the alkyl group, cyclic hydrocarbon group, and alkoxy group include a hydroxyl group, a halogen atom, a carboxyl group, an alkoxy group, an acyl group, a cyano group, and an acyloxy group. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. 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 acyl group include a formyl group and an acetyl group. Examples thereof include an acetoxy group.

Examples of the divalent linking group for A _i 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, a urethane group, and a urea group. Examples thereof include a single selected group or a combination of two or more groups.

Examples of the alkylene group and substituted alkylene group in A _i include groups represented by the following formulae.
− [C (R _bi ) (R _ci )] _r −
In the formula, R _bi and R _ci represent a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, and an alkoxy group, and both may be the same or different. The alkyl group is preferably a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group, and more preferably selected from a methyl group, an ethyl group, 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. 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 repeating unit represented by the general formula (XI-A) or (XI-B) include the following, but the present invention is not limited to these specific examples. .

  Preferred examples of the copolymer component that the acid-decomposable resin according to the present invention may further include include a repeating unit represented by the following general formula (XII-A) or (XII-B).

Here, in the formula, Z _j represents an oxygen atom, —NH—, —N (—R _50j ) —, —N (—OSO ₂ R _50j ) —, and R _50j represents a (substituted) alkyl group or a (substituted) cyclic group. Means a hydrocarbon group.

The alkyl group for R _50j is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, more preferably a linear or branched alkyl group having 1 to 6 carbon atoms, still more preferably. Are a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a t-butyl group.

Examples of the cyclic hydrocarbon group in R _50j include a cyclic alkyl group and a bridged hydrocarbon group, such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a 2-methyl-2-adamantyl group, a norbornyl group, and a boronyl group. Group, isobornyl group, tricyclodecanyl group, dicyclopentenyl group, nobornane epoxy group, menthyl group, isomenthyl group, neomenthyl group, tetracyclododecanyl group and the like.
Specific examples of the repeating unit represented by the above general formula (XII-A) or (XII-B) include the following [XII-A-9] to [XII-A-16], [XII-B-9]. To [XII-B-16], but is not limited to these specific examples.

The acid-decomposable resin according to the present invention may be copolymerized within the range where the effects of the present invention can be obtained effectively, and further the following monomers giving the repeating unit constituting the resin. However, it is not limited to the following monomers.
As a result, the performance required for the resin, in particular (1) solubility in coating solvents, (2) film-formability (glass transition point), (3) alkali developability, (4) film slippage (hydrophobic and alkaline) (Soluble group selection), (5) Adhesion of unexposed part to substrate, (6) Dry etching resistance can be finely adjusted.
Examples of such a comonomer include an addition polymerizable unsaturated bond selected from acrylic esters, methacrylic esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, and the like. Examples thereof include a compound having one.

  Specifically, for example, acrylic esters, for example, alkyl (the alkyl group preferably has 1 to 10 carbon atoms) acrylate (for example, methyl acrylate, ethyl acrylate, propyl acrylate, amyl acrylate, acrylic Cyclohexyl acid, ethyl hexyl acrylate, octyl acrylate, tert-octyl acrylate, 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 acid esters, for example, alkyl (the alkyl group preferably has 1 to 10 carbon atoms) 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, full Furyl methacrylate, tetrahydrofurfuryl methacrylate Rate, etc.);

  Acrylamides such as acrylamide, N-alkyl acrylamide (the alkyl group having 1 to 10 carbon atoms, such as methyl, ethyl, propyl, butyl, t-butyl, heptyl, octyl, cyclohexyl Group, hydroxyethyl group, etc.), N, N-dialkylacrylamide (alkyl group having 1 to 10 carbon atoms, for example, methyl group, ethyl group, butyl group, isobutyl group, ethylhexyl group, cyclohexyl group, etc. N-hydroxyethyl-N-methylacrylamide, N-2-acetamidoethyl-N-acetylacrylamide, etc .;

  Methacrylamide, for example, methacrylamide, N-alkyl methacrylamide (alkyl groups having 1 to 10 carbon atoms such as methyl, ethyl, t-butyl, ethylhexyl, hydroxyethyl, cyclohexyl, etc. N, N-dialkylmethacrylamide (there are alkyl groups such as ethyl, propyl and butyl), N-hydroxyethyl-N-methylmethacrylamide and the like;

  Allyl compounds such as allyl esters (eg allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, etc.), allyloxyethanol, etc .;

  Vinyl ethers such as alkyl vinyl ethers (eg hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethyl hexyl 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 methoxyacetate, vinyl butoxyacetate, vinyl acetoacetate , Vinyl lactate, vinyl-β-phenylbutyrate, vinylcyclohexylcarboxylate, etc .;

Dialkyl itaconates (eg dimethyl itaconate, diethyl itaconate, dibutyl itaconate, etc.);
There are acrylic acid, methacrylic acid, crotonic acid, itaconic acid, acrylonitrile, methacrylonitrile and the like.

  The ratio of each repeating unit takes into consideration the dry etching resistance of the desired resist, sensitivity, pattern cracking prevention, substrate adhesion, resist profile, and resolving power, heat resistance, etc. which are general resist requirements. It can be set appropriately.

The content of the repeating structural unit represented by the general formula (I) in the acid-decomposable resin is preferably from 10 to 60 mol%, more preferably from 15 to 55 mol%, still more preferably from 20 to 20 in all repeating structural units. 50 mol%.
In the acid-decomposable resin, the content of the repeating structural unit represented by the general formula (II) is preferably 10 to 70 mol%, more preferably 15 to 60 mol%, still more preferably 20 to 50 in all repeating structural units. Mol%.
In the acid-decomposable resin, the content of the repeating structural unit represented by the general formula (III) is preferably 2 to 50 mol%, more preferably 4 to 45 mol%, and still more preferably 6 to 6 in all repeating structural units. 40 mol%.

  In the acid-decomposable resin, the total number of repeating units having an acid-decomposable group such as the repeating structural units represented by formulas (I) and (III) is preferably 15 to 90 mol%, more preferably 15 to 85 mol. %, And more preferably 20 to 80 mol%.

In addition, the content in the resin of the repeating structural unit based on the monomer of the additional copolymerization component other than the repeating structural unit represented by the above (I), (II) or (III) also contributes to the desired resist performance. Depending on the total number of moles of the repeating structural units represented by the general formulas (I), (II), and (III), other additional repeating structures are generally available. The total number of units is preferably 99 mol% or less, more preferably 90 mol% or less, and still more preferably 80 mol% or less.
Moreover, when the composition of this invention is an object for ArF exposure, it is preferable that an acid-decomposable resin does not contain an aromatic ring from the point of transparency with respect to ArF light.

The acid-decomposable resin used in the present invention can be synthesized according to a conventional method (for example, radical polymerization). For example, as a general synthesis method, monomer species are charged into a reaction vessel in a batch or in the course of reaction, and if necessary, a reaction solvent such as ethers such as tetrahydrofuran, 1,4-dioxane, diisopropyl ether, methyl ethyl ketone, A ketone such as methyl isobutyl ketone, an ester solvent such as ethyl acetate, and the composition of the present invention such as propylene glycol monomethyl ether acetate described below are dissolved in a solvent that dissolves uniformly and then nitrogen, argon, etc. Polymerization is started using a commercially available radical initiator (azo initiator, peroxide, etc.) as necessary under an inert gas atmosphere. If desired, an initiator is added or added in portions, and after completion of the reaction, it is put into a solvent and a desired polymer is recovered by a method such as powder or solid recovery. The concentration of the reaction is 20% by weight or more, preferably 30% by weight or more, more preferably 40% by weight or more.
The reaction temperature is 10 ° C to 150 ° C, preferably 30 ° C to 120 ° C, more preferably 50-100 ° C.

  The weight average molecular weight of the acid-decomposable resin according to the present invention is preferably 1,000 to 200,000 as a polystyrene conversion value by the GPC method. When the weight average molecular weight is less than 1,000, heat resistance and dry etching resistance are deteriorated, which is not preferable. When the weight average molecular weight exceeds 200,000, developability is deteriorated, and the viscosity is extremely high, so that the film forming property is deteriorated. Produces less favorable results.

  In the positive photoresist composition for deep ultraviolet exposure according to the present invention, the blending amount of the acid-decomposable resin according to the present invention in the entire composition is preferably 40 to 99.99% by weight in the total resist solid content, more preferably. Is 50 to 99.97% by weight.

  It is preferable to dissolve 3 to 25% by weight, more preferably 5 to 22% by weight, and still more preferably solid content such as (A) photoacid generator and (B) resin in the above solvent as a solid content concentration. 7 to 20% by weight.

[3] (C) Mixed solvent The positive photoresist composition of the present invention contains a mixed solvent as the component (C).

  Furthermore, as the component (C) of the present invention, at least one of propylene glycol monoalkyl ether, alkyl lactate and alkyl alkoxypropionate (also referred to as (5) solvent) and heptanone (also referred to as (4) solvent). It is a solvent containing. Thereby, the sensitivity in the resolution of the contact hole is excellent, and the initial particle generation in the resist solution is improved. Examples of heptanone include 2-heptanone, 3-heptanone and 4-heptanone, and 2-heptanone is preferred.

  Preferred examples of the propylene glycol monoalkyl ether include propylene glycol monomethyl ether and propylene glycol monoethyl ether. Preferable examples of the alkyl lactate include methyl lactate and ethyl lactate. Preferred examples of the alkyl alkoxypropionate include ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, and methyl 3-ethoxypropionate.

  The amount of the solvent (4) used is usually 30% by weight or more, preferably 40% by weight or more, more preferably 50% by weight or more with respect to the total solvent. The amount of the solvent (5) used is usually 5 to 70% by weight, preferably 10 to 60% by weight, and more preferably 15 to 50% by weight with respect to the total solvent. If the amount of the solvent (5) used is less than the above range, the effect of addition is reduced, and if it exceeds 70% by weight, the coating property may be deteriorated.

In the present invention, the solvent (C) preferably further contains at least one of γ-butyrolactone, ethylene carbonate, and propylene carbonate (also referred to as the solvent (6)). By adding the solvent (6), an increase in particles and sensitivity fluctuations are suppressed with the lapse of time of the resist solution, and a resist having excellent stability over time can be obtained.
The used weight ratio of the solvent (6) is preferably 0.1 to 25% by weight, more preferably 1 to 20% by weight, and more preferably 3 to 15% with respect to the total solvent.
In the present invention, the solid content of the resist composition containing each of the above components is preferably dissolved in the mixed solvent in a solid content concentration of 3 to 25% by weight, more preferably 5 to 22% by weight, still more preferably. 7 to 20% by weight.

Preferred combinations of the mixed solvent containing heptanone in the present invention include 2-heptanone + propylene glycol monomethyl ether, 2-heptanone + ethyl lactate, 2-heptanone + ethyl 3-ethoxypropionate, 2-heptanone + γ-butyrolactone, 2- Heptanone + ethylene carbonate, 2-heptanone + propylene carbonate, 2-heptanone + propylene glycol monomethyl ether + γ-butyrolactone, 2-heptanone + ethyl lactate + γ-butyrolactone, 2-heptanone + ethyl 3-ethoxypropionate + γ-butyrolactone, 2-heptanone + Propylene glycol monomethyl ether + ethylene carbonate, 2-heptanone + ethyl lactate + ethylene carbonate, 2-heptanone + 3-ethoxy Acid ethyl + ethylene carbonate, 2-
Heptanone + propylene glycol monomethyl ether + propylene carbonate, 2-heptanone + ethyl lactate + propylene carbonate, 2-heptanone + ethyl 3-ethoxypropionate + propylene carbonate. More preferably, 2-heptanone + propylene glycol monomethyl ether + γ-butyrolactone, 2-heptanone + ethyl lactate + γ-butyrolactone, 2-heptanone + ethyl 3-ethoxypropionate + γ-butyrolactone, 2-heptanone + propylene glycol monomethyl ether + ethylene carbonate 2-heptanone + ethyl lactate + ethylene carbonate, 2-heptanone + ethyl 3-ethoxypropionate + ethylene carbonate, 2-heptanone + propylene glycol monomethyl ether + propylene carbonate, 2-heptanone + ethyl lactate + propylene carbonate, 2-heptanone + 3 -Ethyl ethoxypropionate + propylene carbonate.

  Each of the above mixed solvents of the present invention may be added with other non-essential solvents as long as the effects of the present invention are not hindered. The addition amount of such other solvents is generally 30 parts by weight or less with respect to 100 parts by weight of each mixed solvent of the present invention. As other solvents, in addition to the solvents exemplified as the essential solvents for the above mixed solvents, ethylene dichloride, cyclohexanone, cyclopentanone, methyl ethyl ketone, toluene, N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, Tetrahydrofuran and the like can be mentioned.

[4] Surfactant The positive photoresist composition for deep ultraviolet exposure of the present invention preferably contains a fluorine-based and / or silicon-based surfactant.
The fluorine-based and / or silicon-based surfactant is at least one surfactant selected from fluorine-based surfactants, silicon-based surfactants, and surfactants containing both fluorine atoms and silicon atoms.
When the positive photoresist composition for far ultraviolet exposure according to the present invention contains the acid-decomposable resin and the surfactant, the sensitivity, resolution, and adhesion to the substrate when using an exposure light source of 250 nm or less, particularly 220 nm or less. Resist pattern with less development defects and scum can be obtained.
As these surfactants, for example, JP-A-62-36663, JP-A-61-226746, JP-A-61-226745, JP-A-62-170950, JP-A-63-34540, JP-A-63-34540 7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, U.S. Patents 5405720, 5360692, 5529881, 5296330, 5436098, 5576143 No. 5945511 and No. 5842451, and the following commercially available surfactants can be used as they are.
Commercially available surfactants that can be used include, for example, F-top EF301, EF303 (made by Shin-Akita Kasei Co., Ltd.), Florard FC430, 431 (made by Sumitomo 3M Ltd.), MegaFuck F171, F173, F176, F189, R08 (Dainippon Ink Chemical Co., Ltd.), Surflon S-382, SC101, 102, 103, 104, 105, 106 (Asahi Glass Co., Ltd.) and other fluorine-based surfactants or silicon-based surfactants be able to. Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon surfactant.

The compounding 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 can be used alone or in combination of two or more.

Specific examples of the other surfactants include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, and polyoxyethylene octylphenol. Ether, polyoxyethylene alkyl allyl ethers such as polyoxyethylene nonylphenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate Sorbitan fatty acid esters such as sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxy Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as ethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, etc. Can do.
The amount of these surfactants to be added is usually 2 parts by weight or less, preferably 1 part by weight or less per 100 parts by weight of the solid content in the composition of the present invention.
These surfactants may be added alone or in some combination.

[5] Organic Basic Compound A preferred organic basic compound that can be used in the present invention is a compound that is more basic than phenol. Of these, nitrogen-containing basic compounds are preferred.

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 group having 1 to 6 carbon atoms, or carbon. A substituted or unsubstituted aryl group of formula 6 to 20, wherein R ²⁵¹ and R ²⁵² may be bonded to each other to form a ring.

(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 of different chemical environments in one molecule, and particularly preferably both a substituted or unsubstituted amino group and a ring structure containing a nitrogen atom. Or a compound having an alkylamino group. Preferred examples include substituted or unsubstituted guanidine, substituted or unsubstituted aminopyridine, substituted or unsubstituted aminoalkylpyridine, substituted or unsubstituted aminopyrrolidine, substituted or unsubstituted indazole, substituted or unsubstituted Pyrazole, substituted or unsubstituted pyrazine, substituted or unsubstituted pyrimidine, substituted or unsubstituted purine, substituted or unsubstituted imidazoline, substituted or unsubstituted pyrazoline, substituted or unsubstituted piperazine, substituted or unsubstituted amino Examples include morpholine and substituted or unsubstituted aminoalkylmorpholine. Preferred substituents are amino group, aminoalkyl group, alkylamino group, aminoaryl group, arylamino group, alkyl group, alkoxy group, acyl group, acyloxy group, aryl group, aryloxy group, nitro group, hydroxyl group, cyano group It is.

Preferred specific compounds include guanidine, 1,1-dimethylguanidine, 1,1,3,3-tetramethylguanidine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4 -Dimethylaminopyridine, 2-diethylaminopyridine, 2- (aminomethyl) pyridine, 2-amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-5-methylpyridine, 2-amino-6 -Methylpyridine, 3-aminoethylpyridine, 4-aminoethylpyridine, 3-aminopyrrolidine, piperazine, N- (2-aminoethyl) piperazine, N- (2-aminoethyl) piperidine, 4-amino-2,2 , 6,6-tetramethylpiperidine, 4-piperidinopiperidine, 2-iminopiperidine 1- (2-aminoethyl) pyrrolidine, pyrazole, 3-amino-5-methylpyrazole, 5-amino-3-methyl-1-p-tolylpyrazole, pyrazine, 2- (aminomethyl) -5-methylpyrazine , Pyrimidine, 2,4-diaminopyrimidine, 4,6-dihydroxypyrimidine, 2-pyrazoline, 3-pyrazoline,
N-aminomorpholine, N- (2-aminoethyl) morpholine, 1,5-diazabicyclo [4,3,0] non-5-ene, 1,8-diazabicyclo [5,4,0] undec-7 Tertiary morpholine derivatives such as -ene, 2,4,5-triphenylimidazole, N-methylmorpholine, N-ethylmorpholine, N-hydroxyethylmorpholine, N-benzylmorpholine, cyclohexylmorpholinoethylthiourea (CHMETU), Examples thereof include, but are not limited to, hindered amines described in JP-A-11-52575 (for example, those described in the publication [0005]).

  Particularly preferred 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, And hindered amines such as 2,6,6-pentamethyl-4-piperidyl) sebagate. By using these, the density dependency is improved.

  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, hexamethylenetetramine, CHMETU, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebagate are preferred.

  These nitrogen-containing basic compounds are used alone or in combination of two or more. The usage-amount of a nitrogen-containing basic compound is 0.001-10 weight% normally with respect to solid content of the whole composition of the photosensitive resin composition, Preferably it is 0.01-5 weight%. If it is less than 0.001% by weight, the effect of adding the nitrogen-containing basic compound cannot be obtained. On the other hand, when it exceeds 10% by weight, there is a tendency for the sensitivity to deteriorate and the developability of the non-exposed area to deteriorate.

[6] Other Additives The positive photoresist composition of the present invention further includes an acid-decomposable dissolution inhibiting compound, a dye, a plasticizer, a sensitizer, and a compound that promotes solubility in a developer, if necessary. Can be contained.

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

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 absorber 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 a condensate of a diphenylamine derivative and a formaldehyde-modified melamine resin described in JP-B-7-69611, an alkali-soluble resin, a light absorber, and a maleic anhydride copolymer described in US Pat. No. 5,294,680. A reaction product of a diamine type light absorber, a resin binder described in JP-A-6-186863 and a methylolmelamine-based thermal crosslinking agent, a carboxylic acid group described in JP-A-6-118656, an epoxy group, and a light-absorbing group. Acrylic resin-type antireflection film in the same molecule, composed of methylol melamine and a benzophenone light absorber described in JP-A-8-87115, and a low-molecular light absorber on a polyvinyl alcohol resin described in JP-A-8-179509. Additions etc. are mentioned.
Further, as the organic antireflection film, DUV30 series, DUV-40 series manufactured by Brewer Science, AC-2, AC-3 manufactured by Shipley, etc. can be used.

Appropriate use of the resist solution on a substrate (eg, silicon / silicon dioxide coating) used for the manufacture of precision integrated circuit elements (on a substrate provided with the antireflection film if necessary), spinner, coater, etc. A good resist pattern can be obtained by applying through a predetermined coating method, exposing through a predetermined mask, baking and developing. Here, the exposure light is preferably light having a wavelength of 150 nm to 250 nm. Specific examples include a KrF excimer laser (248 nm), an ArF excimer laser (193 nm), an F ₂ excimer laser (157 nm), an X-ray, and an electron beam.

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, and di-n. -Secondary amines such as butylamine; tertiary amines such as triethylamine and methyldiethylamine; alcohol amines such as dimethylethanolamine and triethanolamine; quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. An alkaline aqueous solution of cyclic amines such as pyrrole and pihelidine can be used.
Furthermore, an appropriate amount of alcohol or surfactant may be added to the alkaline aqueous solution.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example.

(Synthesis of acid-decomposable resin)
Norbornene carboxylic acid t-butyl ester, maleic anhydride, 2-methyl-2-adamantyl acrylate, norbornene lactone acrylate is charged into a reaction vessel at a molar ratio of 20/20/35/25, and dissolved in methyl ethyl ketone / tetrahydrofuran = 1/1 solvent. And a 60% solids solution was prepared. This was heated at 65 ° C. under a nitrogen stream. When the reaction temperature was stabilized, 3 mol% of radical initiator V-601 manufactured by Wako Pure Chemical Industries, Ltd. was added to initiate the reaction. After heating for 12 hours, the reaction mixture was poured into 5 times the amount of hexane to precipitate a white powder. The precipitated powder was again dissolved in methyl ethyl ketone / tetrahydrofuran = 1/1 solvent and charged into 5 volumes of hexane / methyl tBu ether to precipitate a white powder, which was taken out by filtration. This operation was repeated again and dried to obtain the target resin (1).
When molecular weight analysis (RI analysis) by GPC of the obtained resin (1) was attempted, it was 11600 (weight average) in terms of polystyrene, and the amount of residual monomer was 0.4%. From the NMR spectrum, the composition of the resin (1) was 18/23/34/25 in terms of the molar ratio of norbornene / maleic anhydride / 2-methyl-2-adamantyl acrylate / norbornene lactone acrylate of the present invention.
Resins (2) to (25) were synthesized in the same manner.
The structures of the acid-decomposable resins (1) to (25) are shown below.

Table 1 shows the molar ratio and weight average molecular weight of each of the repeating units of the acid-decomposable resins (1) to (25).

Examples 4, 5, 7, 9, 10, 12, 13, 16, 19, 24, 26, 28, 32, 34, 39, Reference Examples 1 to 3, 6, 8, 11, 14, 15, 17, 18, 20-23, 25, 27, 29-31, 33, 35-38, 40, Comparative Example 1
(Preparation and evaluation of positive photoresist composition)
As shown in Table 2, 1.4 g of acid-decomposable resin shown in Table 1 synthesized in the above synthesis example, photoacid generator (addition amount shown in Table 2), 4 mg of organic basic compound (amine), necessary 5 mg of a surfactant was mixed with each other, dissolved in a solvent at a solid content ratio of 14% by weight, filtered through a 0.1 μm microfilter, and the positive photoresist compositions of Examples and Reference Examples shown in Table 2 Was prepared.
In Table 2, those marked with * mean reference examples.
Further, as Comparative Example 1, a positive photoresist composition was prepared using the components shown in Table 2 including Comparative Resin R in the same manner as in the above Examples and Reference Examples.

Each compound in Table 2 is as follows.
〔solvent〕
S1: Propylene glycol monomethyl ether acetate S2: Ethyl lactate S3: Butyl acetate S4: 2-heptanone S5: Propylene glycol monomethyl ether S6: Ethyl ethoxypropionate S7: γ-butyrolactone S8: Ethylene carbonate S9: Propylene carbonate

[Surfactant]
W-1: Megafuck F176 (manufactured by Dainippon Ink & Chemicals, Inc.)
(Fluorine)
W-2: Megafuck R08 (Dainippon Ink Chemical Co., Ltd.) (fluorine and
Silicon system)
W-3: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.)
W-4: Polyoxyethylene nonylphenyl ether W-5: Troisol S-366 (manufactured by Troy Chemical Co., Ltd.)

[Organic basic compounds]
1: DBU (1,8-diazabicyclo [5.4.0] -7-undecene)
2: 4-DMAP (4-dimethylaminopyridine)
3: TPI (2,4,5-triphenylimidazole)
4: 2,6-diisopropylaniline 5: antipyrine 6: tri-n-octylamine

[Resin used in Comparative Example]
Resin R: Resin having the following structure used in Example 1 of EP1048983A1

(Evaluation test)
First, ARC-25 manufactured by Brewer Science was applied to a silicon wafer by 30 nm using a spin coater and dried, and then the obtained positive photoresist composition was applied thereon and dried at 130 ° C. for 90 seconds. A positive type photoresist film having a thickness of about 0.4 μm was prepared, and then a 1/2 pitch contact hole pattern (mask size: 0.16 micron) with an ArF excimer laser (ArF stepper made by ISI having a wavelength of 193 nm and NA = 0.6). ). Heat treatment after exposure is performed at 130 ° C. for 90 seconds, 2.38% by weight
The resist pattern profile was obtained by developing with an aqueous solution of tetramethylammonium hydroxide and rinsing with distilled water.
The resist pattern of the silicon wafer thus obtained was observed with a scanning microscope, and the resist was evaluated as follows.

[Sensitivity]: The minimum exposure amount that reproduces a contact hole of 0.16 μm is defined as sensitivity, and the relative exposure amount when the resist exposure amount in Reference Example 1 is 1.0 is relative sensitivity (exposure amount of other resist / reference (Exposure amount of Example 1).

[Number of particles and increased number of particles after storage over time]: The positive photoresist composition solution (coating solution) prepared as described above is immediately after preparation (particle initial value) and after being left at 4 ° C. for 1 week. The number of particles in the liquid (number of particles after aging) was counted with a particle counter manufactured by Rion. Along with the initial particle value, the number of increased particles calculated by (number of particles after time)-(initial particle value) was evaluated. The number of particles counted was 0.25 μm or more in 1 ml of the resist composition solution.

[Sensitivity fluctuation before and after storage over time]: Thus, the sensitivity (exposure amount before storage) of the positive photoresist composition solution (coating solution) immediately after preparation was evaluated, and the composition solution was measured at 4 ° C. The sensitivity after exposure for 1 week (exposure amount after storage) was evaluated, and the sensitivity fluctuation rate was evaluated by the following formula.
Sensitivity fluctuation rate (%) = | (exposure amount before storage) − (exposure amount after storage) | / (exposure amount before storage) × 100
These evaluation results are shown in Table 3.

  As is apparent from Table 3, the positive photoresist composition for ultraviolet exposure according to the present invention has improved sensitivity, storage stability, and sensitivity fluctuation.

Claims (5)

(A) a compound that generates an acid upon irradiation with an actinic ray or radiation,
(B) A repeating structural unit represented by the following general formula (I), a repeating structural unit represented by the general formula (II), and a repeating structure represented by the general formula (III). A resin whose dissolution rate increases, and
(C) A positive photoresist composition for deep ultraviolet exposure, comprising a solvent containing heptanone.

In general formula (I):
R _{11 to} R ₁₄ are each independently a group capable of decomposing by the action of an acid, a hydrogen atom, a halogen atom, a cyano group, —COOH, —COOR ₁₅ , —C (═O) —XA—R ₁₆ , or It represents an alkyl group or a cyclic hydrocarbon group, and at least one of R _{11 to} R ₁₄ represents a group that decomposes by the action of an acid. In addition, at least two of R _{11 to} R ₁₄ may be bonded to form a ring. n represents 0 or 1. Here, R ₁₅ represents an alkyl group, cyclic hydrocarbon group, or -Y group shown below. X represents an oxygen atom, a sulfur _{atom, -NH -, - NHSO 2 -} , or an -NHSO ₂ NH-. A represents a single bond, an alkylene group, a cycloalkylene group, an ether group, a thioether group, a carbonyl group, or a group of two or more groups selected from the group consisting of ester groups.
R ₁₆ represents —COOH, —COOR ₁₅ , —CN, a hydroxyl group, an alkoxy group, —CO—NH—R ₁₇ , —CO—NH—SO ₂ —R _17, or the following —Y group. R ₁₇ represents an alkyl group or a cyclic hydrocarbon group.
The -Y group;

In the -Y group, R _{21 to} R ₃₀ each independently represents a hydrogen atom or an alkyl group. a and b represent 1 or 2;
In general formula (II):
Z ₂ represents —O— or —N (R ₄₁ ) —. Here, R ₄₁ represents a hydrogen atom, a hydroxyl group, an alkyl group, a haloalkyl group, or —OSO ₂ —R ₄₂ . _R42 represents an alkyl group, a haloalkyl group, a cycloalkyl group or a camphor residue.
In general formula (III):
R ₉₁ represents a hydrogen atom, a lower alkyl group, a halogen atom or —CN.
X ₅ is, -O -, - S -, - NR 93 -, or -NR ₉₃ SO ₂ - represents a. R ₉₃ represents a hydrogen atom, a chain or cyclic alkyl group.
B represents a single bond or a linking group.
R ₉₂ represents a hydrogen atom, a chain or cyclic alkyl group, an alkoxy group, a hydroxyl group, a carboxy group, a cyano group, —COOR ₉₄ , or a group represented by any one of the following general formulas (IV) to (X). . R ₉₄ represents a hydrogen atom or a chain or cyclic alkyl group.

_{^{-N + (R 95) (R}} 96) (R 97) · X - (VIII)
-R ₉₈ -A ₅₀ -R ₉₉ (IX)
-SO ₃ R ₁₀₀ (X)

In the formula (IV), Ra ₁ , Rb ₁ , Rc ₁ , Rd ₁ , and Re ₁ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. m and n each independently represents an integer of 0 to 3, and m + n is 2 or more and 6 or less.
In formulas (V-1) to (V-4), R _{1b to} R _5b each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an alkenyl group. Two of R _{1b to} R _5b may combine to form a ring.
In formula (VII), R _{1d to} R _8d each independently represents a hydrogen atom or an alkyl group. R _d0 represents a hydrogen atom, a chain or cyclic alkyl group, an aryl group or an aralkyl group. m represents an integer of 1 to 10.
In formula (VIII), R _{95 to} R ₉₇ each independently represents a hydrogen atom, a chain or cyclic alkyl group, an alkenyl group, an aryl group, or an aralkyl group. However, R _{95 to} R ₉₇ may be bonded to each other to form a non-aromatic ring or an aromatic ring. X ⁻ represents R—SO ₃ ^— . R represents an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
In formula (IX), R ₉₈ represents a single bond, an alkylene group, an arylene group, or a divalent group obtained by combining these.
A ₅₀ represents any of the functional groups shown below.

R ₉₉ represents a hydrogen atom or an alkyl group.
In the formula (X), R ₁₀₀ represents a chain or cyclic alkyl group, an aryl group or an aralkyl group.   2. The positive photoresist composition for far ultraviolet exposure according to claim 1, wherein the solvent of (C) further contains at least one of propylene glycol monoalkyl ether, alkyl lactate and alkyl alkoxypropionate. object.   The positive photoresist composition for far ultraviolet exposure according to claim 1 or 2, wherein the solvent (C) further contains at least one of γ-butyrolactone, ethylene carbonate, and propylene carbonate. The positive photoresist composition for far ultraviolet exposure according to any one of claims 1 to 3, wherein the resin of component (B) further contains a repeating unit represented by the following formula (XI).

In general formula (XI):
R ₉₁ c represents a hydrogen atom, a lower alkyl group, a halogen atom or —CN.
X ₅ c is, -O -, - S -, - NR 93 c-, or -NR ₉₃ CSO ₂ - represents a. R ₉₃ c represents a hydrogen atom, a chain or cyclic alkyl group.
Bc represents a single bond or a linking group.
R ₉₂ c represents a group represented by the following general formula (XI ′).

In General Formula (XI ′), R ₂ c to R ₄ c each independently represent a hydrogen atom or a hydroxyl group. However, at least one of R ₂ c to R ₄ c represents a hydroxyl group.   A pattern forming method comprising: forming a resist film with the positive photoresist composition for deep ultraviolet exposure according to claim 1, and exposing and developing the resist film.