JPH11305443A - Positive type photoresist composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive type photoresist compsn. excellent in the shape of pattern profile, in particular the smoothness of the side wall shape of a pattern, having high dry etching resistance, high sensitivity and high resolving power and free from the occurrence of a stationary wave by incorporating a compd. having specified acid-decomposable groups. SOLUTION: The photoresist compsn. contains a resin which has groups represented by the formula, is decomposed by the action of an acid and increases its solubility to an alkali developer and a compd. which generates the acid when irradiated with active rays of light or radiation. In the formula, R1 and R2 are each H or 1-4C alkyl, W is a divalent org. group and R3 is chain alkyl optionally having a substituent and having a total carbon number of 11-20, cycloalkyl optionally having a substituent and having a total carbon number of 11-20, aryl optionally having a substituent and having a total carbon number of 11-30 or aralkyl optionally having a substituent and having a total carbon number of 12-20. Preferably the photoresist compsn. further contains a compd. which is decomposed by the action of the acid and increases its solubility to the alkali developer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive photoresist composition used for manufacturing semiconductor integrated circuit devices, masks for manufacturing integrated circuits, printed wiring boards, liquid crystal panels, and the like.

[0002]

2. Description of the Related Art As a positive photoresist composition, there is a chemically amplified resist composition described in U.S. Pat. No. 4,491,628 and European Patent No. 29,139. The chemically amplified positive resist composition produces an acid in the exposed area by irradiation with radiation such as deep ultraviolet light, and the acid-catalyzed reaction causes the active and non-irradiated parts of the active radiation to dissolve in the developing solution. Is a pattern forming material for forming a pattern on a substrate by changing the pattern.

The above chemically amplified positive resist composition comprises an alkali-soluble resin, a compound that generates an acid upon exposure to radiation (photoacid generator), and a compound that inhibits dissolution of the alkali-soluble resin having an acid-decomposable group. A three-component system, a two-component system composed of a resin having a group which becomes alkali-soluble by being decomposed by reaction with an acid, and a resin having a group which becomes alkali-soluble by being decomposed by a reaction with an acid; It can be broadly classified into a hybrid system comprising a low molecular weight dissolution inhibiting compound having an acid-decomposable group and a photoacid generator.

Japanese Patent Application Laid-Open No. Hei 2-19847 discloses poly (p
-Hydroxystyrene) which contains a resin in which the phenolic hydroxyl group of phenolic hydroxyl group is wholly or partially protected by a tetrahydropyranyl group. Japanese Patent Application Laid-Open No. 219957/1992 also discloses a resist composition containing a resin in which 20 to 70% of phenolic hydroxyl groups of poly (p-hydroxystyrene) are substituted with acetal groups. ing. Furthermore, JP-A-5-249682 discloses a photoresist composition using a similar acetal-protected resin. Also, Japanese Patent Application Laid-Open No.
Japanese Patent Application Publication No. JP-A-2002-133873 discloses a photoresist composition using a ternary copolymer containing a group substituted with an acetal group. Further, JP-A-8-253534 discloses a photoresist composition using a partially crosslinked polymer containing a group substituted with an acetal group.

Japanese Patent Application Laid-Open No. 8-15864 discloses that
The resin component is a mixture of polyhydroxystyrene in which 10 to 60 mol% of hydroxyl groups are substituted with t-butoxycarbonyloxy groups and polyhydroxystyrene in which 10 to 60 mol% of hydroxyl groups are substituted with ethoxyethoxy groups or the like. Certain positive resist compositions have been disclosed.

Further, Japanese Patent Application Laid-Open No. 9-319092 discloses that a resin into which an acetal group into which an oxy linkage has been introduced is effective in reducing standing waves.

However, these conventional photoresist compositions containing a resin having an acid-decomposable group have problems with respect to the pattern profile, such as significant generation of standing waves and dirty side walls of the pattern. , Improvement was desired.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide an excellent pattern profile shape, particularly excellent pattern wall shape smoothness, high dry etching resistance,
An object of the present invention is to provide an excellent chemically amplified positive photoresist composition which has high sensitivity and high resolution and does not generate a standing wave.

[0009]

Means for Solving the Problems In view of the present situation, the present inventors have made intensive studies and as a result, have found that the use of a positive photoresist composition having a compound having an acid-decomposable group having a specific structure has led to the above object. Have been achieved, and the present invention has been completed. That is, the positive photoresist composition according to the present invention has the following constitution. (1) (a) having a group represented by the following general formula (I),
A positive photoresist composition comprising: a resin that decomposes under the action of an acid to increase solubility in an alkali developer; and (b) a compound that generates an acid upon irradiation with actinic rays or radiation.

[0010]

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In the formula (I), R ₁ and R ₂ may be the same or different and each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; W represents a divalent organic group; ₃ is total carbon number 1
A chain alkyl group which may have 1 to 20 substituents, a cyclic alkyl group which may have a substituent having 11 to 20 carbon atoms in total, and a substituent which has 11 to 30 carbon atoms in total. It represents a good aryl group or an aralkyl group which may have a substituent having 12 to 30 carbon atoms in total.

(2) In the general formula (I), R ₁ and R ₂ may be the same or different and each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and W represents a divalent organic group. R ₃ represents an aryl group which may have a substituent having a total of 11 to 30 carbon atoms,
The positive photoresist composition according to claim 1, which represents an aralkyl group which may have a substituent having 12 to 30 carbon atoms in total.

(3) The positive photoresist composition as described in the above (1) or (2), further comprising a compound which is decomposed by the action of an acid to increase solubility in an alkali developing solution.

[0014]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. (A) a compound having a group represented by the above general formula (I), which decomposes under the action of an acid to increase solubility in an alkali developing solution. As the alkyl group of R ₁ and R ₂ in the general formula (I), Examples thereof include an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group and a t-butyl group. As the divalent organic group for W, preferably a linear, branched or cyclic alkylene group, an arylene group, a heteroarylene group, which may have a substituent,
An aralkylene group and —S—, —C (＝ O) —, —N
_{(R 4) -, - SO} -, - SO 2 -, - CO 2 -, - N
(R ₄ ) SO ₂ — or a divalent group obtained by combining two or more of these groups. Here, R ₄ can be a hydrogen atom or an alkyl group (specific examples of the alkyl group include the same as those described above for R ₁ ).

The above-mentioned chain alkyl having 11 to 20 carbon atoms, preferably 11 to 18 carbon atoms, for R ₃ may be linear or branched, for example, n-undecyl group, i -Undecyl group, n-dodecyl group, i-dodecyl group, n-tridecyl group, i-tridecyl group, n-tetradecyl group, i-tetradecyl group, n-pentadecyl group,
i-pentadecyl group, n-hexadecyl group, i-hexadecyl group, n-heptadecyl group, i-heptadecyl group,
Examples thereof include an n-octadecyl group, an i-octadecyl group, an n-nonadecyl group, and an i-nonadecyl group.

The cyclic alkyl having 11 to 20 carbon atoms, preferably 11 to 18 carbon atoms, of R ₃ may be a cyclic alkyl having a substituent or a cyclic alkyl having a substituent. Cycloundecyl group, cyclododecyl group, cyclotridecyl group, cyclotridecyl group,
Cyclotetradecyl group, cyclopentadecyl group, cyclohexadecyl group, cycloheptadecyl group, cyclooctadecyl group, cyclononadecyl group, 4-cyclohexylcyclohexyl group, 4-n-hexylcyclohexyl group,
Examples thereof include a pentanylcyclohexyl group, a hexyloxycyclohexyl group, and a pentanyloxycyclohexyl group. Substituted cyclic alkyl groups other than those listed here can also be used within the above range.

The aryl group of R ₃ having 11 to 30 carbon atoms, preferably 11 to 25 carbon atoms, includes a 4-cyclopentylphenyl group, a 4-cyclohexylphenyl group,
4-cycloheptenylphenyl group, 4-cyclooctanylphenyl group, 2-cyclopentylphenyl group, 2-cyclohexylphenyl group, 2-cycloheptenylphenyl group, 2-cyclooctanylphenyl group, 3-cyclopentylphenyl group, 3-cyclohexylphenyl group, 3
-Cycloheptenylphenyl group, 3-cyclooctanylphenyl group, 4-cyclopentyloxyphenyl group, 4
-Cyclohexyloxyphenyl group, 4-cycloheptenyloxyphenyl group, 4-cyclooctanyloxyphenyl group, 2-cyclopentyloxyphenyl group,
Cyclohexyloxyphenyl group, 2-cycloheptenyloxyphenyl group, 2-cyclooctanyloxyphenyl group, 3-cyclopentyloxyphenyl group, 3-cyclohexyloxyphenyl group, 3-cycloheptenyloxyphenyl group, 3-cycloocta Nyloxyphenyl group, 4-n-pentylphenyl group, 4-n-hexylphenyl group, 4-n-heptenylphenyl group, 4-n-
An octanylphenyl group, a 2-n-pentylphenyl group,
2-n-hexylphenyl group, 2-n-heptenylphenyl group, 2-n-octanylphenyl group, 3-n-pentylphenyl group, 3-n-hexylphenyl group, 3-n
-Heptenylphenyl group, 3-n-octanylphenyl group, 2,6-di-isopropylphenyl group, 2,3-di-isopropylphenyl group, 2,4-di-isopropylphenyl group, 3,4-di -Isopropylphenyl group,
3,6-di-t-butylphenyl group, 2,3-di-t-
Butylphenyl group, 2,4-di-t-butylphenyl group, 3,4-di-t-butylphenyl group, 2,6-di-
n-butylphenyl group, 2,3-di-n-butylphenyl group, 2,4-di-n-butylphenyl group, 3,4-di-n-butylphenyl group, 2,6-di-i- Butylphenyl group, 2,3-di-i-butylphenyl group, 2,4-
Di-i-butylphenyl group, 3,4-di-i-butylphenyl group, 2,6-di-t-amylphenyl group, 2,3
-Di-t-amylphenyl group, 2,4-di-t-amylphenyl group, 3,4-di-t-amylphenyl group, 2,
6-di-i-amylphenyl group, 2,3-di-i-amylphenyl group, 2,4-di-i-amylphenyl group,
3,4-di-i-amylphenyl group, 2,6-di-n-
Pentylphenyl group, 2,3-di-n-pentylphenyl group, 2,4-di-n-pentylphenyl group, 3,4-
Di-n-pentylphenyl group, 4-adamantylphenyl group, 2-adamantylphenyl group, 4-isobornylphenyl group, 3-isobornylphenyl group, 2-isoboronylphenyl group, 4-cyclopentyloxyphenyl group , 4-cyclohexyloxyphenyl group, 4-cycloheptenyloxyphenyl group, 4-cyclooctanyloxyphenyl group, 2-cyclopentyloxyphenyl group, 2-cyclohexyloxyphenyl group, 2-cycloheptenyloxyphenyl group, 2 -Cyclooctanyloxyphenyl group, 3-cyclopentyloxyphenyl group, 3-cyclohexyloxyphenyl group, 3-cycloheptenyloxyphenyl group, 3-cyclooctanyloxyphenyl group, 4-n-pentyloxyphenyl group,
4-n-hexyloxyphenyl group, 4-n-heptenyloxyphenyl group, 4-n-octanyloxyphenyl group, 2-n-pentyloxyphenyl group, 2-n-hexyloxyphenyl group, 2-n -Heptenyloxyphenyl group, 2-n-octanyloxyphenyl group, 3-
n-pentyloxyphenyl group, 3-n-hexyloxyphenyl group, 3-n-heptenyloxyphenyl group,
3-n-octanyloxyphenyl group, 2,6-di-isopropyloxyphenyl group, 2,3-di-isopropyloxyphenyl group, 2,4-di-isopropyloxyphenyl group, 3,4-di-isopropyl Oxyphenyl group, 2,6-di-t-butyloxyphenyl group, 2,3
-Di-t-butyloxyphenyl group, 2,4-di-t-
Butyloxyphenyl group, 3,4-di-t-butyloxyphenyl group, 2,6-di-n-butyloxyphenyl group, 2,3-di-n-butyloxyphenyl group, 2,4
-Di-n-butyloxyphenyl group, 3,4-di-n-
Butyloxyphenyl group, 2,6-di-i-butyloxyphenyl group, 2,3-di-i-butyloxyphenyl group, 2,4-di-i-butyloxyphenyl group, 3,4
-Di-i-butyloxyphenyl group, 2,6-di-t-
Amyloxyphenyl group, 2,3-di-t-amyloxyphenyl group, 2,4-di-t-amyloxyphenyl group, 3,4-di-t-amyloxyphenyl group, 2,6
-Di-i-amyloxyphenyl group, 2,3-di-i-
Amyloxyphenyl group, 2,4-di-i-amyloxyphenyl group, 3,4-di-i-amyloxyphenyl group, 2,6-di-n-pentyloxyphenyl group, 2,
3-di-n-pentyloxyphenyl group, 2,4-di-
n-pentyloxyphenyl group, 3,4-di-n-pentyloxyphenyl group, 4-adamantyloxyphenyl group, 3-adamantyloxyphenyl group, 2-adamantyloxyphenyl group, 4-isobornyloxyphenyl group, Examples thereof include a 3-isoboronyloxyphenyl group and a 2-isoboronyloxyphenyl group, and these may be further substituted within the above range, and are not limited to substituents other than those described above.

The aralkyl group having 12 to 30 carbon atoms, preferably 12 to 25 carbon atoms, of R ₃ includes 4-cyclopentylphenylethyl group, 4-cyclohexylphenylethyl group, 4-cycloheptenylphenylethyl group,
-Cyclooctanylphenylethyl, 2-cyclopentylphenylethyl, 2-cyclohexylphenylethyl, 2-cycloheptenylphenylethyl, 2-
Cyclooctanylphenylethyl group, 3-cyclopentylphenylethyl group, 3-cyclohexylphenylethyl group, 3-cycloheptenylphenylethyl group, 3-cyclooctanylphenylethyl group, 4-cyclopentyloxyphenylethyl group, 4-cyclohexyl Oxyphenylethyl group, 4-cycloheptenyloxyphenylethyl group, 4-cyclooctanyloxyphenylethyl group, 2-cyclopentyloxyphenylethyl group, 2-
Cyclohexyloxyphenylethyl group, 2-cycloheptenyloxyphenylethyl group, 2-cyclooctanyloxyphenylethyl group, 3-cyclopentyloxyphenylethyl group, 3-cyclohexyloxyphenylethyl group, 3-cycloheptenyloxyphenylethyl Group, 3-cyclooctanyloxyphenylethyl group, 4
-N-pentylphenylethyl group, 4-n-hexylphenylethyl group, 4-n-heptenylphenylethyl group, 4-n-octanylphenylethyl group, 2-n-pentylphenylethyl group, 2-n- Hexylphenylethyl group, 2-n-heptenylphenylethyl group, 2-n
-Octanylphenylethyl group, 3-n-pentylphenylethyl group, 3-n-hexylphenylethyl group, 3
-N-heptenylphenylethyl group, 3-n-octanylphenylethyl group, 2,6-di-isopropylphenylethyl group, 2,3-di-isopropylphenylethyl group, 2,4-di-isopropylphenylethyl Group, 3,
4-di-isopropylphenylethyl group, 2,6-di-
t-butylphenylethyl group, 2,3-di-t-butylphenylethyl group, 2,4-di-t-butylphenylethyl group, 3,4-di-t-butylphenylethyl group,
2,6-di-n-butylphenylethyl group, 2,3-di-n-butylphenylethyl group, 2,4-di-n-butylphenylethyl group, 3,4-di-n-butylphenylethyl group Group, 2,6-di-i-butylphenylethyl group,
2,3-di-i-butylphenylethyl group, 2,4-di-i-butylphenylethyl group, 3,4-di-i-butylphenylethyl group, 2,6-di-t-amylphenylethyl A 2,3-di-t-amylphenylethyl group,
2,4-di-t-amylphenylethyl group, 3,4-di-t-amylphenylethyl group, 2,6-di-i-amylphenylethyl group, 2,3-di-i-amylphenylethyl group Group, 2,4-di-i-amylphenylethyl group,
3,4-di-i-amylphenylethyl group, 2,6-di-n-pentylphenylethyl group, 2,3-di-n-pentylphenylethyl group, 2,4-di-n-pentylphenylethyl group Group, 3,4-di-n-pentylphenylethyl group, 4-adamantylphenylethyl group, 3-adamantylphenylethyl group, 2-adamantylphenylethyl group, 4-isobornylphenylethyl group, 3-isoboronyl Phenylethyl group, 2-isoboronylphenylethyl group, 4-cyclopentyloxyphenylethyl group, 4-cyclohexyloxyphenylethyl group, 4-
Cycloheptenyloxyphenylethyl group, 4-cyclooctenyloxyphenylethyl group, 2-cyclopentyloxyphenylethyl group, 2-cyclohexyloxyphenylethyl group, 2-cycloheptenyloxyphenylethyl group, 2-cyclooctanyloxy Phenylethyl group, 3-cyclopentyloxyphenylethyl group, 3
-Cyclohexyloxyphenylethyl group, 3-cycloheptenyloxyphenylethyl group, 3-cyclooctanyloxyphenylethyl group, 4-n-pentyloxyphenylethyl group, 4-n-hexyloxyphenylethyl group, 4- n-heptenyloxyphenylethyl group,
4-n-octanyloxyphenylethyl group, 2-n-
Pentyloxyphenylethyl group, 2-n-hexyloxyphenylethyl group, 2-n-heptenyloxyphenylethyl group, 2-n-octanyloxyphenylethyl group, 3-n-pentyloxyphenylethyl group, 3-
n-hexyloxyphenylethyl group, 3-n-heptenyloxyphenylethyl group, 3-n-octanyloxyphenylethyl group, 2,6-diisopropyloxyphenylethyl group, 2,3-di-isopropyloxyphenyl Ethyl group, 2,4-di-isopropyloxyphenylethyl group, 3,4-diisopropyloxyphenylethyl group, 2,6-di-t-butyloxyphenylethyl group, 2,3-di-t-butyloxy Phenylethyl group, 2,4-di-t-butyloxyphenylethyl group,
3,4-di-t-butyloxyphenylethyl group, 2,
6-di-n-butyloxyphenylethyl group, 2,3-
Di-n-butyloxyphenylethyl group, 2,4-di-
n-butyloxyphenylethyl group, 3,4-di-n-
Butyloxyphenylethyl group, 2,6-di-i-butyloxyphenylethyl group, 2,3-di-i-butyloxyphenylethyl group, 2,4-di-i-butyloxyphenylethyl group, 3, 4-di-i-butyloxyphenylethyl group, 2,6-di-t-amyloxyphenylethyl group, 2,3-di-t-amyloxyphenylethyl group, 2,4-di-t-amyloxy Phenylethyl group, 3,4-di-t-amyloxyphenylethyl group,
2,6-di-i-amyloxyphenylethyl group, 2,
3-di-i-amyloxyphenylethyl group, 2,4-
Di-i-amyloxyphenylethyl group, 3,4-di-
i-amyloxyphenylethyl group, 2,6-di-n-
Pentyloxyphenylethyl group, 2,3-di-n-pentyloxyphenylethyl group, 2,4-di-n-pentyloxyphenylethyl group, 3,4-di-n-pentyloxyphenylethyl group, 4- Adamantyloxyphenylethyl group, 3-adamantyloxyphenylethyl group, 2-adamantyloxyphenylethyl group, 4-
An isobornyloxyphenylethyl group, a 3-isobornyloxyphenylethyl group, a 2-isobornyloxyphenylethyl group, or the above alkyl is a methyl group,
Examples thereof include those substituted with a propyl group, a butyl group and the like.

Further, as further substituents of the above groups, a hydroxyl group, a halogen atom (fluorine, chlorine, bromine, iodine),
Nitro group, cyano group, the above alkyl group, methoxy group
Alkoxy groups such as ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, t-butoxy group, alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group, and benzyl An aralkyl group such as a group, a phenethyl group or a cumyl group, an aralkyloxy group, an acyl group such as a formyl group, an acetyl group, a butyryl group, a benzoyl group, a cyanamyl group, or a valeryl group, an acyloxy group such as a butyryloxy group, or the above alkenyl group; Alkenyloxy group such as vinyloxy group, propenyloxy group, allyloxy group, butenyloxy group, the above aryl group,
Examples include an aryloxy group such as a phenoxy group and an aryloxycarbonyl group such as a benzoyloxy group.

The substituent of R ₃ is preferably an aryl group having 11 to 25 carbon atoms or an aralkyl group having 12 to 25 carbon atoms. These substituents may further have a substituent, provided that the carbon number of the substituted aryl group or the substituted aralkyl group is within this range.

Specific examples of the group represented by formula (I) are shown below, but it should not be construed that the invention is limited thereto.

[0022]

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[0023]

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[0024]

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The compound having the group represented by the general formula (I) as described above, which is decomposed by the action of an acid to increase the solubility in an alkali developing solution includes the group represented by the general formula (I). It contains an alkali-soluble resin (polymer type dissolution inhibiting compound) and a non-polymer type dissolution inhibiting compound. Preferred embodiments of the positive photoresist composition of the present invention include the following. Photoacid generator and polymer-type dissolution inhibiting compound Photoacid generator, non-polymeric dissolution-inhibiting compound and alkali-soluble resin Photoacid generator, polymer-type dissolution-inhibiting compound and non-polymeric dissolution-inhibiting compound Photoacid generator and polymer-type dissolving Inhibiting Compound, Non-polymeric Dissolution Inhibiting Compound and Alkali-Soluble Resin

Hereinafter, the polymer type dissolution inhibiting compound will be described. The polymer-type dissolution inhibiting compound in the present invention has a structure in which an acid-decomposable group represented by the general formula (I) is introduced into a compound obtained by polymerizing a monomer and having a molecular weight distribution. Is a compound which becomes alkali-soluble. The polymer-type dissolution inhibiting compound is a resin having a group represented by the general formula (I) in the main chain or side chain of the resin, or in both the main chain and the side chain.
Among them, a resin having a group represented by the general formula (I) in a side chain is more preferable. Next, as a base resin when the group represented by the general formula (I) is bonded as a side chain, -O is added to the side chain.
H or -COOH, preferably an alkali-soluble resin having a -R ⁰ -COOH or -A _r -OH group. For example, an alkali-soluble resin not containing an acid-decomposable group described below can be mentioned.

In the present invention, a preferable base resin is an alkali-soluble resin having a phenolic hydroxyl group. The alkali-soluble resin having a phenolic hydroxyl group used in the present invention is o-, m- or p-hydroxystyrene (these are collectively referred to as hydroxystyrene), or o-, m- or p-hydroxy-α-. A copolymer containing at least 30 mol%, preferably 50 mol% or more of a repeating unit corresponding to methylstyrene (collectively referred to as hydroxy-α-methylstyrene) or a homopolymer thereof, or a benzene nucleus of the unit Is preferably a partially hydrogenated resin, and more preferably a p-hydroxystyrene homopolymer. As monomers other than hydroxystyrene and hydroxy-α-methylstyrene for preparing the copolymer by copolymerization, acrylates, methacrylates, acrylamides, methacrylamides, acrylonitrile, methacrylonitrile, Maleic anhydride, styrene, α-methylstyrene, acetoxystyrene, alkoxystyrenes are preferred, styrene,
Acetoxystyrene and t-butoxystyrene are more preferred.

In the present invention, the content of the repeating unit having a group represented by the general formula (I) in such a resin is preferably from 5 mol% to 50 mol%, more preferably, to all the repeating units. Is from 5 mol% to 30 mol%.

In the present invention, in the above-mentioned polymer-type dissolution inhibiting compound, in addition to the group represented by the above general formula (I),
It may contain another acid-decomposable group.

The resin containing a group represented by the above general formula (I) is prepared by synthesizing a corresponding vinyl ether and reacting the resin with a phenolic hydroxyl group-containing alkali-soluble resin dissolved in an appropriate solvent such as tetrahydrofuran by a known method. Can be obtained at The reaction is usually an acidic catalyst,
Preferably, the reaction is performed in the presence of an acidic ion exchange resin, hydrochloric acid, p-toluenesulfonic acid, or a salt such as pyridinium tosylate. The corresponding vinyl ether can be synthesized from an active substance such as chloroethyl vinyl ether by a method such as a nucleophilic substitution reaction.

The weight average molecular weight of the group containing the group represented by the general formula (I) is preferably 3,000 to 80,000,
More preferably, it is 7000 to 50,000. The range of the molecular weight distribution (Mw / Mn) is 1.01 to 4.0,
Preferably it is 1.05 to 3.00. In order to obtain a polymer having such a molecular weight distribution, it is preferable to use a technique such as anionic polymerization or radical polymerization.

Specific examples of such a polymer-type dissolution-inhibiting compound are shown below, but the present invention is not limited thereto.

[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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Next, the non-polymer type dissolution inhibiting compound will be described. The non-polymeric dissolution inhibiting compound is 300
A compound having a constant molecular weight of 0 or less, a compound having a structure having a single structure and a group represented by the above general formula (I) introduced therein, and being alkali-soluble by the action of an acid. The non-polymeric dissolution inhibiting compound used in the present invention has at least one group represented by the above general formula (I) as an acid-decomposable group. In each compound,
At least two acid-decomposable groups are present in the structure, and at the position where the distance between the acid-decomposable groups is the longest,
At least 10, preferably at least 11, and more preferably at least 12 bonding atoms excluding the acid-decomposable group.
Compounds having at least three acid-decomposable groups, or at a position where the distance between the acid-decomposable groups is the longest,
It is advantageous to use compounds that have at least 9, preferably at least 10, and more preferably at least 11 linking atoms exclusive of the acid-decomposable groups.

The non-polymer type dissolution inhibiting compound suppresses the solubility of the alkali-soluble resin in alkali, and the acid generated when exposed to light deprotects the acid-decomposable group, and conversely, the solubility of the resin in alkali. Has the effect of promoting JP-A-63-27829 and JP-A-3-198059 disclose a dissolution inhibiting compound having a skeleton compound of naphthalene, biphenyl and diphenylcycloalkane, but have a small dissolution inhibiting property for an alkali-soluble resin, and have a high profile and resolution. Is not enough.

In the present invention, the preferred non-polymeric dissolution inhibiting compound is a compound having a single structure having a molecular weight of 3,000 or less having at least three alkali-soluble groups in one molecule and having at least 1/2 of the alkali-soluble group represented by the general formula ( Compounds protected by the acid-decomposable group represented by I) can be mentioned. The use of such a non-polymeric dissolution inhibiting compound having an alkali-soluble group is preferable in that the solvent solubility of the non-polymeric dissolution inhibiting compound is improved and the effect of the present invention is further enhanced.

In the present invention, the preferred upper limit of the number of the bonding atoms is 50, more preferably 30. In the present invention, when the non-polymer type dissolution inhibiting compound has three or more, preferably four or more acid-decomposable groups, and even if it has two acid-decomposable groups, the acid-decomposable groups are mutually present. If they are separated by a certain distance or more, the dissolution inhibiting property with respect to the alkali-soluble resin is significantly improved.

In the present invention, the distance between the acid-decomposable groups is represented by the number of via bond atoms excluding the acid-decomposable groups. For example, in the case of the following compounds (1) and (2), the distance between the acid-decomposable groups is 4 bonding atoms, and in the compound (3), the bonding atom is 12 bonding atoms.

[0044]

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The non-polymeric dissolution-inhibiting compound of the present invention may have a plurality of acid-decomposable groups on one benzene ring, but preferably has one acid-decomposable group on one benzene ring.
It is a compound composed of a skeleton having two acid-decomposable groups. Further, the molecular weight of the non-polymeric dissolution inhibiting compound of the present invention is 3,500 or less, preferably 500 to 3,0.
00, more preferably 1,000 to 2,500.
When the molecular weight of the non-polymeric dissolution inhibiting compound of the present invention is in the above range, it is preferable in terms of high resolution.

Preferred non-polymeric dissolution inhibiting compounds are
JP-A-1-289946, JP-A-1-289947
JP-A-2-2560, JP-A-3-128959
JP-A-3-158855, JP-A-3-17935
No. 3, JP-A-3-191351, JP-A-3-2002
No. 51, JP-A-3-200252, JP-A-3-200
No. 253, JP-A-3-200254, JP-A-3-20
0255, JP-A-3-259149, JP-A-3-2
No. 79958, JP-A-3-279959, JP-A-4-
1650, JP-A-4-1651, JP-A-4-112
No. 60, JP-A-4-12356, JP-A-4-1235
No. 7, Japanese Patent Application No. 3-33229, Japanese Patent Application No. 3-23079
No. 0, Japanese Patent Application No. 3-320438, Japanese Patent Application No. 4-2515
7, Japanese Patent Application No. 4-52732, Japanese Patent Application No. 4-10321
No. 5, Japanese Patent Application No. 4-104542, Japanese Patent Application No. 4-1078
No. 85, Japanese Patent Application Nos. 4-107889 and 4-15219
Compounds in which some or all of the phenolic OH groups of the polyhydroxy compound described in the specification such as No. 5 are protected with the group represented by the above general formula (I) are included.

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

More specifically, the following general formulas [I] to [X]
IV].

[0049]

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[0050]

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[0051]

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[0052]

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Here, R ¹⁰¹ , R ¹⁰² , R ¹⁰⁸ ,
R ¹³⁰ : may be the same or different, a hydrogen atom, -C
(R ₁ ) (R ₂ ) —O—W—R ₃ (R ₁ , R ₂ ,
W and R ₃ are as defined above. R ¹⁰⁰ : -CO-, -COO-, -NHCONH-,-
NHCOO-, -O-, -S-, -SO-, -SO
_2- , -SO _3- , or

[0054]

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[0055] Here, G = 2 to 6, provided that at least one alkyl group of R ^0.99, R ¹⁵¹ when the ^{G = 2, R 150, R} 151: may be the same or different, a hydrogen atom, an alkyl Group, alkoxy group, -OH, -COOH,
-CN, halogen atom, -R ¹⁵² -COOR ^{15 3} or ^{-R 154 -OH, R 152, R} 154: an alkylene group, R ^153: a hydrogen atom, an alkyl group, an aryl group or an aralkyl group,, R ^99, R ¹⁰³ To R ¹⁰⁷ , R ¹⁰⁹ , R ^{111 to} R ¹¹⁸ , R
^{121 to} R ¹²³ , R ^{128 to} R ¹²⁹ , R ^{131 to} R ¹³⁴ , R
^{138 to} R ¹⁴¹ and R ¹⁴³ may be the same or different and include a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an acyl group, an acyloxy group, an aryl group, an aryloxy group, an aralkyl group, an aralkyloxy group, a halogen atom, nitro Group, carboxyl group, cyano group, or -N ( ^R155 )
( ^R156 ) ( ^R155 , ^R156 : H, alkyl group or aryl group) ^R110 : single bond, alkylene group, or

[0056]

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R ¹⁵⁷ and R ¹⁵⁹ may be the same or different, and represent a single bond, an alkylene group, —O—, —S—, —CO
— Or carboxyl group, R ¹⁵⁸ : hydrogen atom, alkyl group, alkoxy group, acyl group, acyloxy group, aryl group, nitro group, hydroxyl group, cyano group, or carboxyl group, provided that the hydroxyl group is replaced with an acid-decomposable group. You may.

R ¹¹⁹ and R ¹²⁰ may be the same or different and each represents a methylene group, a lower alkyl-substituted methylene group, a halomethylene group or a haloalkyl group, provided that the lower alkyl group is an alkyl group having 1 to 4 carbon atoms. R ^{124 to} R ¹²⁷ may be the same or different and may be a hydrogen atom or an alkyl group; R ^{135 to} R ¹³⁷ may be the same or different and a hydrogen atom;
Alkyl group, alkoxy group, acyl group, or acyloxy group, R ¹⁴² : hydrogen atom, —C (R ₁ ) (R ₂ ) —O—W—R
₃ (R ₁ , R ₂ , W and R ₃ are as defined above), or

[0059]

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R ¹⁴⁴ and R ¹⁴⁵ may be the same or different and represent a hydrogen atom, a lower alkyl group, a lower haloalkyl group,
Or an aryl group, R ^{146 to} R ¹⁴⁹ : may be the same or different, and may be hydrogen, hydroxyl, halogen, nitro, cyano, carbonyl, alkyl, alkoxy, alkoxycarbonyl, aralkyl, aralkyloxy A group, an acyl group, an acyloxy group, an alkenyl group, an alkenyloxy group, an aryl group, an aryloxy group, or an aryloxycarbonyl group, provided that the four substituents having the same symbols do not have to be the same group. : —CO— or —SO ₂ —, Z, B: single bond or —O—, A: methylene group, lower alkyl-substituted methylene group, halomethylene group, or haloalkyl group; E: single bond or oxymethylene group , A to z, a1 to y1: when plural, the groups in () may be the same or different; a to q, s, t, v, g1 to i1, k1 m1, o1, q1, s1, u1: 0 or an integer of 1 to 5, r, u, w, x, y, z, a1~f1, p1, r1, t1, v1~x1: 0 or 1
An integer of 4, j1, n1, z1, a2, b2, c2, d2: an integer of 0 or 1 to 3, at least one of z1, a2, c2, d2 is 1 or more, y1: an integer of 3 to 8, (a + b), (e + f + g), (k + l + m), (q + r + s), (w
+ x + y), (c1 + d1), (g1 + h1 + i1 + j1), (o1 + p1), (s1 + t1) ≧ 2,
(j1 + n1) ≦ 3, (r + u), (w + z), (x + a1), (y + b1), (c1 + e1), (d1
+ f1), (p1 + r1), (t1 + v1), (x1 + w1) ≦ 4, provided that the general formula [V]
In the case of (w + z), (x + a1) ≦ 5, (a + c), (b + d), (e + h), (f + i),
(g + j), (k + n), (l + o), (m + p), (q + t), (s + v), (g1 + k1), (h1 + l
1), (i1 + m1), (o1 + q1), (s1 + u1) ≦ 5.

[0061]

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[0062]

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[0063]

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[0064]

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Specific examples of preferred compound skeletons are shown below.

[0066]

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[0067]

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[0068]

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[0069]

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[0070]

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[0071]

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[0072]

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[0073]

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[0074]

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[0075]

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[0076]

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[0077]

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[0078]

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[0079]

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[0080]

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[0081]

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[0082]

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[0083]

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[0084]

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R in the compounds (1) to (63) represents a hydrogen atom or

[0086]

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This is a group selected from However, at least two, or three depending on the structure, are groups other than hydrogen atoms, and each substituent R may not be the same group.

In the present invention, the amount of the compound having a group represented by the general formula (I), which decomposes under the action of an acid and increases the solubility in an alkali developing solution, is shown below. When the photoacid generator and the polymer-type dissolution-inhibiting compound are contained, the content of the polymer-type dissolution-inhibiting compound is preferably 5 to 40% by weight based on the total weight of the composition (in terms of solid content),
More preferably, it is 10 to 30% by weight. When the photoacid generator, the non-polymeric dissolution inhibiting compound and the alkali-soluble resin are contained, the content of the non-polymeric dissolution inhibiting compound is 3 to the total weight (in terms of solid content) of the composition.
It is preferably from 50 to 50% by weight, more preferably from 5 to 35% by weight.

When the photoacid generator, the polymer-type dissolution-inhibiting compound and the non-polymer-type dissolution-inhibiting compound are contained, the content of the non-polymeric dissolution-inhibiting compound is 3 to the total weight (in terms of solid content) of the composition. The content of the polymer-type dissolution inhibiting compound is preferably from 2 to 40% by weight based on the total weight (in terms of solid content) of the composition, More preferably 5 to 30
When the photoacid generator, the polymer-type dissolution-inhibiting compound, the non-polymer-type dissolution-inhibiting compound, and the alkali-soluble resin are contained, the content of the non-polymer-type dissolution-inhibiting compound is the total weight of the composition (in terms of solid content). 3) to 40% by weight based on
The content is more preferably 5 to 30% by weight, and the content of the polymer-type dissolution inhibiting compound is preferably 2 to 40% by weight, more preferably 5 to 30% by weight, based on the total weight (in terms of solid content) of the composition. %

In the present invention, an alkali-soluble resin containing no acid-decomposable group can be used in the composition, whereby the sensitivity is improved. The alkali-soluble resin containing no acid-decomposable group (hereinafter, simply referred to as an alkali-soluble resin) is a resin that is soluble in alkali, and preferably includes polyhydroxystyrene, novolak resin, and derivatives thereof. A copolymer resin containing a p-hydroxystyrene unit can also be used as long as it is alkali-soluble. Among them, poly (p-hydroxystyrene), poly (p / m-hydroxystyrene)
A copolymer, a poly (p / o-hydroxystyrene) copolymer, and a poly (p-hydroxystyrene-styrene) copolymer are preferably used. Furthermore, poly (4-hydroxy-3-methylstyrene) resin, poly (4-hydroxy-
A poly (alkyl-substituted hydroxystyrene) resin such as a 3,5-dimethylstyrene) resin, and a resin in which a part of the phenolic hydroxyl groups of the above resin is alkylated or acetylated are also preferably used as long as they are alkali-soluble.

Further, when a part of the phenol nucleus (30 mol% or less of all phenol nuclei) of the above resin is hydrogenated, the transparency of the resin is improved, and sensitivity, resolution and profile formation in a rectangular shape are preferable. . As the alkali-soluble resin used in the present invention, for example, novolak resin,
Hydrogenated novolak resin, acetone-pyrogallol resin,
Polyhydroxystyrene, alkyl-substituted polyhydroxystyrene, poly (hydroxystyrene-N-substituted maleimide) copolymer, partially O-alkylated or O-acylated polyhydroxystyrene, poly (styrene-
Examples thereof include (maleic anhydride) copolymer, carboxyl group-containing methacrylic resin and derivatives thereof, poly (styrene-hydroxystyrene) copolymer, and hydrogenated polyhydroxystyrene, but are not limited thereto.

Particularly preferred alkali-soluble resins used in the present invention are novolak resins and alkali-soluble resins containing p-hydroxystyrene units (preferably poly (p-hydroxystyrene), poly (p / m-hydroxystyrene)). Copolymer, poly (p / o-hydroxystyrene) copolymer, poly (p-hydroxystyrene-styrene) copolymer, poly (4-hydroxy-3-methylstyrene) resin, poly (4-hydroxy-3) Poly (alkyl-substituted hydroxystyrene) resin, such as poly (alkyl-substituted hydroxystyrene) resin, a resin in which a part of the phenolic hydroxyl groups of the above resin is alkylated or acetylated, a partially hydrogenated polyhydroxystyrene resin, a polyhydroxystyrene resin , With partially hydrogenated novolak resin, partially hydrogenated polyhydroxystyrene resin That.

In the present invention, polyhydroxystyrene is a p-hydroxystyrene monomer, an m-hydroxystyrene monomer, an o-hydroxystyrene monomer and an alkyl having 1 to 4 carbon atoms at the ortho-position from the bonding position of the hydroxyl group of the monomer. This shows a polymer obtained by polymerizing at least one monomer selected from the group consisting of substituted hydroxystyrene monomers.

The novolak resin is obtained by subjecting a predetermined monomer as a main component to addition condensation with an aldehyde in the presence of an acidic catalyst.

As the predetermined monomer, phenol, m
Cresols such as -cresol, p-cresol and o-cresol, xylenols such as 2,5-xylenol, 3,5-xylenol, 3,4-xylenol and 2,3-xylenol, m-ethylphenol, p- Alkylphenols such as ethylphenol, o-ethylphenol, pt-butylphenol, p-octylphenol, 2,3,5-trimethylphenol, p-methoxyphenol, m-methoxyphenol, 3,5-dimethoxyphenol, Alkoxyphenols such as -methoxy-4-methylphenol, m-ethoxyphenol, p-ethoxyphenol, m-propoxyphenol, p-propoxyphenol, m-butoxyphenol and p-butoxyphenol, 2-methyl-4-isopropyl Fenault Bis alkylphenols etc., dihydroxybiphenyl, bisphenol A, phenylphenol, resorcinol, and the hydroxyaromatic compounds of naphthol or the like can be used alone or two or more kinds, but the invention is not limited thereto.

Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propylaldehyde, benzaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde , O-nitrobenzaldehyde,
m-nitrobenzaldehyde, p-nitrobenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, p-ethylbenzaldehyde, pn-butylbenzaldehyde,
Furfural and acetal forms thereof can be used, but among these, formaldehyde is preferably used.

These aldehydes are used alone or in combination of two or more. As the acidic catalyst, sulfuric acid, formic acid, acetic acid, oxalic acid and the like can be used. The content of the alkali-soluble resin not containing an acid-decomposable group is 50% by weight or less, preferably 30% by weight or less, more preferably 20% by weight, based on the total of the resin and the acid-decomposable group-containing resin. % By weight or less.

The photoacid generator (b) used in the present invention comprises:
A compound that generates an acid upon irradiation with actinic rays or radiation. Examples of the compound used in the present invention, which decomposes upon irradiation with actinic rays or radiation to generate an acid, include a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization, a photobleaching agent for dyes, and a photodiscoloration agent. Or known light used in micro-resists (ultraviolet rays of 400 to 200 nm, far ultraviolet rays, particularly preferably g-line, h-line, i-line, K-line).
rF excimer laser light), an ArF excimer laser light, an electron beam, an X-ray, a molecular beam or a compound capable of generating an acid by an ion beam, and a mixture thereof can be appropriately selected and used.

Other compounds that generate an acid upon irradiation with actinic rays or radiation used in the present invention include, for example, SI Schlesinger, Photogr. Sci. Eng., 18, 3
87 (1974), TSBetal, Polymer, 21,423 (1980) and the like diazonium salts, U.S. Pat.Nos. 4,069,055 and 4,06
9,056, the same Re 27,992, ammonium salts described in JP-A-3-140,140, etc., DCNecker et al., Macromolecules, 1,
7,2468 (1984), CSWenetal, Teh, Proc.Conf.Rad.Curing
ASIA, p478 Tokyo, Oct (1988), U.S. Pat.No. 4,069,055
No. 4,069,056, etc.
vello etal, Macromorecules, 10 (6), 1307 (1977), Chem.
& Eng.News, Nov. 28, p31 (1988), EP 104,143,
No. 339,049, No. 410,201, JP-A-2-150,848, JP-A-2-296,514 and the like iodonium salts, JVCriv
ello etal, Polymer J. 17, 73 (1985), JVCrivello eta
lJOrg.Chem., 43, 3055 (1978), WRWatt et al., J. Polym
er Sci., Polymer Chem. Ed., 22, 1789 (1984), JVCrivel
lo etal, Polymer Bull., 14,279 (1985), JVCrivello e
tal, Macromorecules, 14 (5), 1141 (1981), JVCrivelloe
tal, J. PolymerSci., Polymer Chem. Ed., 17, 2877 (1979),
European Patent Nos. 370,693, 161,811, 410,201,
339,049, 233,567, 297,443, 297,442,
U.S. Pat.Nos. 4,933,377, 3,902,114, 4,760,013
No. 4,734,444, No. 2,833,827, Dokoku Patent No. 2,904,
Nos. 626, 3,604,580 and 3,604,581, etc., sulfonium salts described in JVCrivello et al., Macromorecules, 10
(6), 1307 (1977), JVCrivello etal, J. PolymerSci., Po
selmerium salts described in lymer Chem.Ed., 17, 1047 (1979), CSwen et al., Teh, Proc. Conf. Rad. Curing ASIA, p.
Onium salts such as arsonium salts described in 478 Tokyo, Oct (1988), U.S. Pat.No. 3,905,815, JP-B-46-4605,
JP-A-48-36281, JP-A-55-32070, JP-A-60-23973
No. 6, JP-A-61-169835, JP-A-61-169837, JP-A-61-69837
2-58241, JP-A-62-212401, JP-A-63-70243, Organic halogen compounds described in JP-A-63-298339, etc., K. Mei
er et al, J. Rad. Curing, 13 (4), 26 (1986), TPGill et
al, Inorg.Chem., 19,3007 (1980), D.Astruc, Acc.Chem.R
es., 19 (12), 377 (1896), organometallic / organic halides described in JP-A-2-14145, S. Hayase et al., J. Polymer
Sci., 25, 753 (1987), E. Reichmanis et al., J. Phlymer Sc
i., Polymer Chem. Ed., 23, 1 (1985), QQ Zhu et al., J. Phot
ochem., 36, 85, 39, 317 (1987), B. Amit etal, Tetrahedron
Lett., (24) 2205 (1973), DHR Barton et al., J. Chem So
c., 3571 (1965), PMCollins et al, J. Chem.SoC., Perkin
I, 1695 (1975), M. Rudinstein et al., Tetrahedron Lett.,
(17), 1445 (1975), JWWalker etal J. Am. Chem. Soc., 110,
7170 (1988), SCBusman et al., J. Imaging Technol., 11
(4), 191 (1985), HM Houlihan et al, Macormolecules, 21,
2001 (1988), PM Collins et al., J. Chem. Soc., Chem. Comm.
un., 532 (1972), S. Hayase etal, Macromolecules, 18, 1799
(1985), E. Reichmanis et al., J. Electrochem. Soc., Solid
State Sci.Technol., 130 (6), FMHoulihan et al, Macrom
olcules, 21, 2001 (1988), European Patent Nos. 0290,750 and 046,
No. 083, No. 156,535, No. 271,851, No. 0,388,343, U.S. Pat.Nos. 3,901,710, 4,181,531, JP-A-60-19853
No. 8, a photoacid generator having a 0-nitrobenzyl-type protecting group described in JP-A-53-133022, M. TUNOOKA etal, Polyme
r Preprints Japan, 35 (8), G. Berner et al., J. Rad. Curin
g, 13 (4), WJMijs etal, Coating Technol., 55 (697), 45
(1983), Akzo, H. Adachi et al, Polymer Preprints, Japa
n, 37 (3), European Patent Nos. 0199,672, 84515, 044,11
No. 5, No. 618,564, No. 0101,122, U.S. Pat.No. 4,371,60
No. 5, 4,431,774, JP-A-64-18143, JP-A-2-245
No. 756, compounds that generate sulfonic acid upon photodecomposition, such as iminosulfonates described in JP-A-3-140109 and the like, and disulfone compounds described in JP-A-61-166544, etc. .

Further, a group that generates an acid by these lights,
Alternatively, a compound having a compound introduced into a main chain or a side chain of a polymer, for example, MEWoodhouse et al., J. Am. Chem.
c., 104, 5586 (1982), SPPappas etal, J. Imaging Sc
i., 30 (5), 218 (1986), S. Kondoetal, Makromol.Chem., Rap
id Commun., 9,625 (1988), Y.Yamadaetal, Makromol.Che
m., 152, 153, 163 (1972), JVCrivello etal, J. PolymerS
ci., Polymer Chem. Ed., 17, 3845 (1979), U.S. Pat.
No. 9,137, Dokoku Patent No. 3914407, JP-A-63-26653, JP-A-55-164824, JP-A-62-69263, JP-A-63-146038
JP-A-63-163452, JP-A-62-153853, JP-A-63-163452
Compounds described in No. 146029 can be used.

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

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

[0103]

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

[0105]

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[0106]

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[0107]

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

[0109]

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Here, the formulas Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aryl group. Preferred substituents include an alkyl group, a haloalkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a nitro group, a carboxyl group, an alkoxycarbonyl group, a hydroxy group, a mercapto group, and a halogen atom.

R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ each independently represent
It represents a substituted or unsubstituted alkyl group or aryl group.
Preferably, an aryl group having 6 to 14 carbon atoms, 1 to 1 carbon atoms
8 and substituted derivatives thereof. As a preferred substituent, the aryl group has 1 to 1 carbon atoms.
An alkoxy group having 8 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group, a nitro group, a carboxyl group, a mercapto group, a hydroxy group and a halogen atom; A carboxyl group and an alkoxycarbonyl group.

[0112] Z ^- represents a counter anion, for example BF ₄ ^{-,
_{AsF 6 -, PF 6 -,}} SbF 6 -, SiF 6 2-, ClO 4 -,
CF ₃ SO ₃ ^-, etc. perfluoroalkane sulfonate anion, pentafluorobenzenesulfonic acid anion, condensed polynuclear aromatic sulfonic acid anion such as naphthalene-1-sulfonic acid anion, anthraquinone sulfonic acid anion, a sulfonic acid group-containing dyes Examples include, but are not limited to:

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

Further, a photo-acid generator which has little change in performance (T-Top formation, line width change, etc.) over time from exposure to heat treatment is preferred. As such a photoacid generator, for example, in the general formulas (PAG3) and (PAG4), Ar ₁ , Ar ₂ , and R ^{203 to} R ²⁰⁵ each represent a substituted or unsubstituted aryl group, and Z ⁻ represents light. Has relatively low diffusivity in the resist film when it is generated as an acid by the irradiation. Specifically, Z ^- has at least one group selected from the group consisting of a branched or cyclic alkyl group or an alkoxy group having 8 or more carbon atoms, or a linear, branched or cyclic carbon group. It has at least two groups selected from the group consisting of an alkyl group or an alkoxy group having 4 to 7 carbon atoms, or a straight or branched alkyl group or an alkoxy group having 1 to 3 carbon atoms. And an anion of benzenesulfonic acid, naphthalenesulfonic acid or anthracenesulfonic acid having at least three groups selected from

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

[0116]

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[0117]

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[0118]

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[0119]

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[0120]

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[0121]

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[0122]

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[0123]

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[0124]

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[0125]

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[0126]

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[0127]

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[0128]

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[0129]

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[0130]

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

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

[0133]

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

[0135]

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[0136]

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[0137]

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[0138]

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[0139]

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In the present invention, the compound (b) which generates an acid upon irradiation with actinic rays or radiation is preferably an onium salt, a disulfone, a 4-position DNQ sulfonic acid ester, or a triazine compound. In addition, two or more of these compounds may be mixed. In this case, similar structures such as onium salts may be mixed, or compounds having different skeletons such as onium salts and disulfone may be mixed.

The amount of the compound (b) which decomposes upon irradiation with actinic rays or radiation to generate an acid is usually determined based on the total weight (excluding the coating solvent) of the positive photoresist composition of the present invention. It is used in the range of 0.001 to 40% by weight, preferably 0.01 to 20% by weight, and more preferably 0.1 to 5% by weight. If the amount of the compound that decomposes upon irradiation with actinic rays or radiation to generate an acid is less than 0.001% by weight, the sensitivity is low, and if the amount is more than 40% by weight, the light absorption of the resist is high. This is not preferable because the profile is deteriorated and the process (especially baking) margin is narrowed.

An organic basic compound can be used in the composition of the present invention. This is preferable because the storage stability is improved and the line width change due to PED is reduced. Preferred organic basic compounds that can be used in the present invention are compounds that are more basic than phenol. Among them, a nitrogen-containing basic compound is preferable. Preferred chemical environments include the structures of the following formulas (A) to (E).

[0143]

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Further preferred compounds are nitrogen-containing cyclic compounds or two nitrogen atoms having different chemical environments in one molecule.
It is a nitrogen-containing basic compound having at least one compound. The nitrogen-containing cyclic compound more preferably has a polycyclic structure.
Preferred specific examples of the nitrogen-containing polycyclic compound include a compound represented by the following general formula (F).

[0145]

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In the formula (F), Y and Z each independently represent a linear, branched or cyclic alkylene group which may contain a hetero atom and may be substituted. Here, examples of the hetero atom include a nitrogen atom, a sulfur atom, and an oxygen atom. The alkylene group preferably has 2 to 10 carbon atoms, and more preferably has 2 to 5 carbon atoms. Examples of the substituent of the alkylene group include an alkyl group having 1 to 6 carbon atoms, an aryl group, an alkenyl group, a halogen atom, and a halogen-substituted alkyl group. Further, specific examples of the compound represented by the general formula (F) include the following compounds.

[0147]

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Among them, 1,8-diazabicyclo [5.4.0] undec-7-ene and 1,5-diazabicyclo [4.3.0] non-5-ene are particularly preferable.

As the nitrogen-containing basic compound having two or more nitrogen atoms having different chemical environments in one molecule, a compound containing both a substituted or unsubstituted amino group and a ring structure containing a nitrogen atom is particularly preferable. Or a compound having an alkylamino group. Preferred specific examples include substituted or unsubstituted guanidine, substituted or unsubstituted aminopyridine, substituted or unsubstituted aminoalkylpyridine, substituted or unsubstituted aminopyrrolidine, substituted or unsubstituted indersol, 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 Morpholine, substituted or unsubstituted aminoalkylmorpholine and the like. Preferred substituents are an amino group, an aminoalkyl group, an alkylamino group, an aminoaryl group, an arylamino group, an alkyl group, an alkoxy group, an acyl group, an acyloxy group, an aryl group, an aryloxy group, a nitro group, a hydroxyl group, a cyano group It is.

As particularly preferred compounds, guanidine and
1,1-dimethylguanidine, 1,1,3,3-tetramethylguanidine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2-diethylamino Pyridine, 2- (aminomethyl) pyridine, 2-amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-5-methylpyridine, 2-amino-6-methylpyridine, 3-aminoethyl Pyridine, 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-
Examples include (2-aminoethyl) morpholine, trimethylimidazole, triphenylimidazole, methyldiphenylimidazole, and the like, but are not limited thereto.

These nitrogen-containing basic compounds are used alone or in combination of two or more. The amount of the nitrogen-containing basic compound to be used is generally 0.001-10 parts by weight, preferably 0.01-5 parts by weight, per 100 parts by weight of the photosensitive resin composition (excluding the solvent). If the amount is less than 0.001 part by weight, the above effects cannot be obtained. On the other hand, if it exceeds 10 parts by weight, the sensitivity tends to decrease and the developability of the unexposed part tends to deteriorate.

The chemically amplified positive resist composition of the present invention may further contain, if necessary, a phenolic OH group which promotes solubility in a surfactant, a dye, a pigment, a plasticizer, a photosensitizer and a developing solution. A compound having two or more compounds can be contained.

Suitable surfactants include, specifically, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether,
Polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether; polyoxyethylene alkyl allyl ethers such as polyoxyethylene octyl phenol ether and polyoxyethylene nonyl phenol ether; polyoxyethylene / polyoxypropylene block copolymers; sorbitan monolaurate ,
Sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate and other sorbitan fatty acid esters, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxy Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as ethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; EFTOP EF301, EF303;
EF352 (manufactured by Shin-Akita Chemical Co., Ltd.), MegaFac F1
71, F173 (manufactured by Dainippon Ink Co., Ltd.), Flora
Do FC430, FC431 (Sumitomo 3M Limited)
Made), Asahi Guard AG710, Surflon S-38
2, SC101, SC102, SC103, SC10
Fluorinated surfactants such as 4, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.), and organosiloxane polymer KP3
No. 41 (manufactured by Shin-Etsu Chemical Co., Ltd.) or acrylic acid-based or methacrylic acid-based (co) polymerized polyflow No. 41 75, N
o. 95 (manufactured by Kyoeisha Yushi Kagaku Kogyo KK) and the like.

These surfactants may be added alone or in some combination. A preferable addition amount is 100 parts of the composition (excluding the solvent).
0.0005 to 0.01 parts by weight with respect to parts by weight. Suitable dyes include oily dyes and basic dyes. Specifically, Oil Yellow # 101, Oil Yellow # 103, Oil Pink # 312, Oil Green B
G, oil blue BOS, oil blue # 603, oil black BY, oil black BS, oil black T-505 (manufactured by Orient Chemical Industries, Ltd.), crystal violet (CI42555), methyl violet (CI42535), rhodamine B (CI45)
170B), malachite green (CI42000),
Methylene blue (CI52015) and the like can be mentioned.

Further, the following spectral sensitizers are added to sensitize the photoacid generator to be used in the wavelength region longer than the deep ultraviolet where the photoacid generator used has no absorption, thereby obtaining the chemically amplified positive resist of the present invention. Can be made sensitive to the i or g line. Examples of suitable spectral sensitizers include benzophenone, p, p'-tetramethyldiaminobenzophenone, p, p'-tetraethylethylaminobenzophenone, 2-chlorothioxanthone, anthrone, 9-ethoxyanthracene, anthracene, and pyrene. , Perylene,
Phenothiazine, benzyl, acridine orange, benzoflavin, cetoflavin-T, 9,10-diphenylanthracene, 9-fluorenone, acetophenone, phenanthrene, 2-nitrofluorene, 5-nitroacenaphthene, benzoquinone, 2-chloro-4-nitroaniline N-acetyl-p-nitroaniline, p-nitroaniline, N-acetyl-4-nitro-1-naphthylamine, picramide, anthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone 1,2-
Benzanthraquinone, 3-methyl-1,3-diaza-
1,9-benzanthrone, dibenzalacetone, 1,
2-naphthoquinone, 3,3′-carbonyl-bis (5,
7-dimethoxycarbonylcoumarin) and coronene, but are not limited thereto.

Examples of the compound having two or more phenolic OH groups which promote the solubility in a developing solution include polyhydroxy compounds. Preferably, the polyhydroxy compound includes phenols, resorcin, phloroglucin, phloroglucid, 3,4-trihydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, α, α ′, α ″ -tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene,
Tris (4-hydroxyphenyl) methane, Tris (4
-Hydroxyphenyl) ethane, 1,1′-bis (4-
(Hydroxyphenyl) cyclohexane.

The chemically amplified positive resist composition of the present invention is prepared by dissolving each of the above components in a solvent that dissolves the components and coating the solution on a support. Examples of usable solvents include ethylene dichloride, cyclohexanone and cyclohexanone. Pentanone, 2-heptanone, γ-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene, Ethyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate,
Propyl pyruvate, N, N-dimethylformamide,
Dimethyl sulfoxide, N-methylpyrrolidone, tetrahydrofuran and the like are preferable, and these solvents are used alone or in combination.

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

Examples of the developer for the chemically amplified positive resist composition of the present invention include, for example, inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium phosphate, sodium metasilicate and aqueous ammonia. Primary amines such as ethylamine and n-propylamine, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, dimethylethanolamine,
Alcoholamines such as triethanolamine, amides such as formamide and acetamide, tetramethylammonium hydroxide, trimethyl (2-hydroxyethyl) ammonium hydroxide, tetraethylammonium hydroxide, tributylmethylammonium hydroxide, and tetraethanolammonium hydroxide , Methyltriethanol ammonium hydroxide,
Quaternary ammonium salts such as benzylmethyldiethanolammonium hydroxide, benzyldimethylethanolammonium hydroxide, benzyltriethanolammonium hydroxide, tetrapropylammonium hydroxide and tetrabutylammonium hydroxide, and alkalis such as cyclic amines such as pyrrole and piperidine And the like.

[0160]

The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. [Synthesis Example I-1 Synthesis of vinyl ether] 83.1 g (0.5 mol) of p-cyclohexylphenol was added to 300 m
l of toluene, 150 g of 2-chloroethyl vinyl ether is added, and sodium hydroxide 25
g, 5 g of tetrabutylammonium bromide and 60 g of triethylamine, and the mixture was heated and stirred at 120 ° C. for 5 hours. The reaction solution was washed with water, and excess chlororetyl vinyl ether and toluene were removed by distillation under reduced pressure. From the obtained oil component, p-cyclohexylphenoxyethyl vinyl ether (X-1) was obtained by distillation under reduced pressure. [Synthesis Example I-2, 3, 4, 5, 6, 7, 8, 9] In the same manner as in Synthesis Example I-1, vinyl ether X-
2, X-3, X-4, X-5, X-6, X-7, X-
8, X-9 were obtained, respectively.

[0161]

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[0162]

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[Synthesis Example II-1] 32.4 g (0.2 mol) of p-acetoxystyrene was dissolved in 120 ml of butyl acetate, and azobisisobutyronitrile (AIBN) was added at 80 ° C. under a nitrogen stream and stirring. 0.033 g was added three times every 2.5 hours, and finally, stirring was continued for another 5 hours to carry out a polymerization reaction. The reaction solution was hexane 1200
Then, white resin was precipitated. After drying the obtained resin, it was dissolved in 150 ml of methanol. 7.7 g (0.19 mol) of sodium hydroxide / 50 ml of water
Was added thereto, and the mixture was hydrolyzed by heating under reflux for 3 hours. Thereafter, 200 ml of water was added for dilution, and neutralized with hydrochloric acid to precipitate a white resin. This resin was separated by filtration, washed with water and dried. Further tetrahydrofuran 200
The solution was dropped into 5 L of ultrapure water with vigorous stirring and reprecipitated. This reprecipitation operation was repeated three times. The obtained resin was dried in a vacuum dryer at 120 ° C. for 12 hours to obtain a poly (p-hydroxystyrene) alkali-soluble resin R-1. The weight average molecular weight of the obtained resin is 15
000.

[Synthesis Example II-2] p-tert-butoxystyrene monomer 3 dehydrated and purified by distillation according to a conventional method
5.25 g (0.2 mol) and styrene monomer
21 g (0.05 mol) in tetrahydrofuran 100 m
l. Under a nitrogen stream and stirring, at 80 ° C., 0.033 g of azobisisobutyronitrile (AIBN) was added three times every 2.5 hours, and finally, stirring was continued for another 5 hours to carry out a polymerization reaction. . The reaction solution was poured into 1200 ml of hexane to precipitate a white resin. After drying the obtained resin, it was dissolved in 150 ml of tetrahydrofuran. 4N hydrochloric acid was added thereto, and the mixture was hydrolyzed by heating under reflux for 6 hours, and then reprecipitated in 5 L of ultrapure water. The resin was separated by filtration, washed with water and dried. Further, it was dissolved in 200 ml of tetrahydrofuran, and dropped and reprecipitated in 5 L of ultrapure water with vigorous stirring. This reprecipitation operation was repeated three times. The obtained resin is dried in a vacuum dryer for 120 minutes.
C. and dried for 12 hours.
A (styrene) copolymer alkali-soluble resin R-2 was obtained.
The weight average molecular weight of the obtained resin was 12,000.

[Synthesis Example II-3] 32.4 g (0.2 mol) of p-acetoxystyrene and 7.01 g (0.07 mol) of methyl methacrylate were dissolved in 120 ml of butyl acetate. At 80 ° C., 0.033 g of azobisisobutyronitrile (AIBN) was added three times every 2.5 hours, and finally, stirring was continued for another 5 hours to carry out a polymerization reaction. The reaction solution was hexane 120
The solution was added to 0 ml to precipitate a white resin. After drying the obtained resin, it was dissolved in 200 ml of methanol. 7.7 g (0.19 mol) of sodium hydroxide / 50 m of water
l of an aqueous solution was added, and the mixture was hydrolyzed by heating under reflux for 1 hour. Then, add 200 ml of water and dilute,
Neutralized with hydrochloric acid to precipitate a white resin. This resin was separated by filtration, washed with water and dried. Furthermore, tetrahydrofuran 20
The solution was dissolved in 0 ml, dropped into 5 L of ultrapure water with vigorous stirring, and reprecipitated. This reprecipitation operation was repeated three times.
The obtained resin was dried in a vacuum dryer at 120 ° C. for 12 hours to obtain a poly (p-hydroxystyrene / methyl methacrylate) copolymer alkali-soluble resin R-3. The weight average molecular weight of the obtained resin was 10,000.

[Synthesis Example II-4] Poly (p-hydroxystyrene) (VP8000) manufactured by Nippon Soda Co., Ltd. was used as alkali-soluble resin R-4. Weight average molecular weight is 980
It was 0.

Synthesis Example III-1 20 g of alkali-soluble resin R-4 obtained in Synthesis Example II-4 80 ml of tetrahydrofuran 6.50 g of vinyl ether X-1 obtained in Synthesis Example I-1 were mixed in a flask. Then, 10 mg of p-toluenesulfonic acid was added, and the mixture was stirred at room temperature for 18 hours. The reaction solution was dripped into 5 L of ultrapure water while vigorously stirring to reprecipitate. The obtained resin was dried in a vacuum dryer at 70 ° C. for 12 hours to obtain an alkali-soluble resin B-1 having a substituent according to the present invention.

[Synthesis Examples III-2 to III-10] Using the alkali-soluble resin and vinyl ether shown in Table 1 below, the alkali-soluble resin B- having a substituent according to the present invention was prepared in the same manner as in Synthesis Example III-1. 2 to B-15 were obtained.

[0169]

[Table 1]

[Synthesis Examples IV-1 to IV-4] Alkali-soluble resins shown in Table 2 below, ethyl vinyl ether (Y-1), naphthyloxyethyl vinyl ether (Y-2) and (benzyl Using (oxyethoxy) ethyl vinyl ether (Y-3), resins C-1 to C-3
I got

[0171]

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[0172]

[Table 2]

(Examples 1 to 15 and Comparative Examples 1 to 4) [Preparation and Evaluation of Photosensitive Composition] Each of the materials shown in Table 3 below was dissolved in 8 g of PGMEA (propylene glycol monoethyl ether acetate). The solution was filtered through a 2 μm filter to prepare a resist solution. This resist solution was applied on a silicon wafer using a spin coater, and dried on a vacuum suction type hot plate at 130 ° C. for 60 seconds to obtain a resist film having a thickness of 0.8 μm.

[0174]

[Table 3]

The photoacid generators and organic base compounds used in the examples are shown below.

[0176]

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This resist film was exposed using a 248 nm KrF excimer laser stepper (NA = 0.45). After the exposure, the film was heated on a hot plate at 100 ° C. for 60 seconds, immediately immersed in a 0.26 N aqueous solution of tetramethylammonium hydroxide (TMAH) for 60 seconds, rinsed with water for 30 seconds, and dried. The pattern on the silicon wafer thus obtained was observed with a scanning electron microscope, and the performance of the resist was evaluated. Table 3 shows the results. The resolving power indicates a limit resolving power at an exposure amount for reproducing a 0.30 μm line and space mask pattern. The resulting resist pattern was observed with an optical microscope or SEM to evaluate the roughness of the surface.
A sample with a clean surface was rated as ○, a sample with slight roughness observed was rated as Δ, and a sample with marked roughness was rated as ×. Further, the dry etching resistance was evaluated by a relative value with the novolak resin being 1.0, after performing dry etching by an ordinary method. Those with numerical values approaching 1.0 are good.

[0178]

[Table 4]

As is evident from the results in Table 4, the positive photoresist compositions of the examples according to the present invention obtained satisfactory results, respectively, whereas the photoresist compositions of the comparative examples showed particularly satisfactory results. The surface roughness of the resist and the dry etching resistance were unsatisfactory.

[0180]

According to the present invention, the shape of the pattern profile is excellent, particularly the smoothness of the side wall shape of the pattern is excellent, the dry etching resistance is high, the sensitivity is high, the resolution is high, and the standing wave is generated. And an excellent chemically amplified positive photoresist composition free of any problem.

Claims (3)

[Claims] (1) a resin having a group represented by the following general formula (I), which is decomposed by the action of an acid and has increased solubility in an alkali developing solution; and (b) a resin which is irradiated with actinic rays or radiation. A positive photoresist composition comprising a compound that generates an acid. Embedded image Wherein _{(I), R 1, R} 2 , which may be the same or different, represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, W represents a divalent organic group, R ₃ is total carbon A chain alkyl group which may have a substituent having the number of 11 to 20, a total of 11 to 20 carbon atoms
A cyclic alkyl group optionally having a substituent, having a total carbon number of 11
Aryl group optionally having from 30 to 30 substituents, total carbon number 1
Represents an aralkyl group which may have 2 to 30 substituents; 2. In the general formula (I), R₁, R_TwoAre the same
May be different, a hydrogen atom, an alkyl having 1 to 4 carbon atoms.
W represents a divalent organic group; _ThreeIs total carbon
Aryl group optionally having substituents of formulas 11 to 30, total carbon
An aralkyl group which may have a substituent having a prime number of 12 to 30;
The positive type photoreceptor according to claim 1, wherein
Dist composition. 3. The positive photoresist composition according to claim 1, further comprising a compound which is decomposed by the action of an acid to increase the solubility in an alkali developing solution.