KR20020070800A - Positive electron beam resist composition - Google Patents

Abstract

PURPOSE: A positive electron beam resist composition is provided to improve the resist pattern profile and the changes in the line width by the post-exposure in a vacuum chamber. CONSTITUTION: The positive electron beam resist composition comprises a resin which contains a structural unit represented by the formula X, and whose solubility to an alkaline developing solution increases by the action of an acid; and a compound generating an acid by the irradiation of electron beam, wherein R1 and R2 which are the same and different each other, are H or an alkyl group of C1-C4; R3 and R4 which are the same and different each other, are H or a substituted or unsubstituted straight, branched or cyclic alkyl group; R5 is a substituted or unsubstituted straight, branched or cyclic alkyl group or a substituted or unsubstituted aryl group; m is an integer of 1-20; and n is an integer of 0-5.

Description

Positive electron beam resist composition {POSITIVE ELECTRON BEAM RESIST COMPOSITION}

The present invention relates to a positive electron beam resist composition used in the manufacture of semiconductor integrated circuit devices, integrated circuit manufacturing mugs and the like.

As positive photoresist compositions, there are chemical amplification resist compositions described in US Pat. No. 4,491,628, European Patent No. 29,139, and the like. The chemically amplified positive resist composition generates an acid in the exposed portion by irradiation with radiation such as far ultraviolet light, and changes the solubility of the active radiation in the developer and the non-irradiated developer by the reaction using the acid to form a pattern. It is a pattern formation material formed on a board | substrate.

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

In Japanese Patent Laid-Open No. 9-319092, it is disclosed that a resin incorporating an acetal group having an oxy linkage is effective in reducing standing waves and the like.

In addition, Japanese Patent Laid-Open No. 10-221854 discloses a resin having a unit of a substituted acetal group.

However, in the resin having these acetal groups, when used as an electron beam resist, the influence of electron beam backscattering appeared strongly, and the resulting resist pattern became an inverse tapered profile. In addition, improvement of line width fluctuation caused by the standing time in the vacuum chamber of the electron beam irradiation apparatus has been desired.

SUMMARY OF THE INVENTION An object of the present invention is to provide a chemically amplified positive electron beam resist composition which is excellent in the shape of a pattern profile to be obtained as an electron beam irradiation resist and also has improved line width fluctuation caused by the standing time in a vacuum chamber of an electron beam irradiation apparatus. It is to offer.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in view of such a phenomenon, the said objective was achieved by using the positive electron beam resist composition which has a compound which has an acid-decomposable group of a specific structure, and came to complete this invention.

That is, the positive electron beam resist composition which concerns on this invention is the following structures.

(1) (a) a resin having a structural unit containing a group represented by the following general formula (X) and decomposed by the action of an acid to increase its solubility in an alkaline developer; and

(b) A positive electron beam resist composition comprising a compound that generates an acid by irradiation with an electron beam.

(In general formula (X), R <1>, R <2> may be same or different, and may represent a hydrogen atom and a C1-C4 alkyl group, R <3>, R <4> may be same or different, and may have a hydrogen atom and a substituent, Branched, cyclic alkyl group, R5 represents a straight chain which may have a substituent, branched, cyclic alkyl group, an aryl group which may have a substituent, and an aralkyl group which may have a substituent. An integer, and n represents an integer of 0 to 5.)

(2) (a) a resin having structural units represented by the following general formulas (I), (II) and (III), which is decomposed by the action of an acid to increase its solubility in an alkaline developer; And

(b) A positive electron beam resist composition comprising a compound that generates an acid by irradiation with an electron beam.

(In formulas (I) to (III), R21 represents a hydrogen atom or a methyl group, R22 represents a group which is not decomposed by the action of an acid, and R23 represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or an alkoxy group. And an acyl group or an acyloxy group, n represents an integer of 1 to 3. W represents a group represented by the general formula (X).)

(3) to (1) or (2), wherein the ratio of the structural units represented by the following general formulas (I), (II) and (III) satisfies the following conditions (1) to (4). Positive electron beam resist composition of a base material.

① 0.10 <(I) / (I) + (II) + (III) <0.25

② 0.01 <(II) / (I) + (II) + (III) <0.15

③ (I)> (II)

④ 0.5 <(I) / (I) + (II) <0.85

(In formula, (I), (II), and (III) represent the mole fraction of the structural unit represented by general formula (I), general formula (II), and general formula (III), respectively.)

(4) The following general formulas (A-1), (A-2), (A-3), and (b) in which a compound that generates an acid by irradiation of the electron beam (s) generates sulfonic acid by irradiation of an electron beam; A positive electron beam resist composition as described in (1)-(3) characterized by one or more of the compounds represented by A-4), (A-5), (A-6), and (A-7).

In Formulas (A-1) and (A-2), R ₁ to R ₅ may be the same or different and represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a hydroxy group, a halogen atom, or a -SR ₆ group. R ₆ represents an alkyl group or an aryl group X ⁻ has at least one group selected from the group of branched or cyclic alkyl groups having 8 or more carbon atoms and alkoxy groups, or linear, branched or cyclic carbon atoms 4-7. Two or more groups selected from the group of alkyl groups and alkoxy groups, or three or more groups selected from the group of linear or branched C1-C3 alkyl groups and alkoxy groups, or 1 to 5 halogens Anion of benzenesulfonic acid, naphthalenesulfonic acid or anthracenesulfonic acid having an atom or having a linear or branched ester group having 1 to 10 carbon atoms.)

(In formula (A-3), R <_7> -R <_10> may be same or different and shows a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a hydroxyl group, or a halogen atom, respectively. X <^-> is the same as said. M , n, p and q each represent an integer of 1 to 3.)

(Formula (A-4) of, R ₁₁ ~R ₁₃ may be the same or different, represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a hydroxy group, a halogen atom or a -SR ₆ R _6, X ^-. And is the L, m and n may be the same or different and represent an integer of 1 to 3. When l, m and n are each 2 or 3, each of 2 to 3 R ₁₁ to R ₁₃ You may combine with each other and form the ring which consists of 5-8 elements containing a carbocyclic ring, a heterocyclic ring, or an aromatic ring.)

(Formula (A-5) of, R ₁₄ ~R ₁₆ may be the same or different, represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a hydroxy group, a halogen atom or a -SR ₆ R _6, X ^-. And is the L, m and n may be the same or different and represent an integer of 1 to 3. When l, m and n are each 2 or 3, each of 2 to 3 R ₁₄ to R ₁₆ You may combine with each other and form the ring which consists of 5-8 elements containing a carbocyclic ring, a heterocyclic ring, or an aromatic ring.)

(In formula (A-6), Y is a linear, branched, cyclic alkyl group which may have a substituent, an aralkyl group which may be substituted,

(R ₃₁ to R ₅₁ may be the same or different and represent a hydrogen atom, a straight chain, branched, cyclic alkyl group which may have a substituent, an alkoxy group, an acyl group, an acylamino group, a sulfonylamino group, an aryl group, An acyloxy group, an aralkyl group or an alkoxycarbonyl group, or a formyl group, a nitro group, a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, or a cyano group, and R ₃₁ to R ₃₅ , R ₃₆ to R ₄₂ and R ₄₃ to R Or ₅₁ in each group may combine to form a 5- to 8-membered ring consisting of carbon atoms and / or heteroatoms). Or Y may be combined with the residue of another imide sulfonate compound.

X may be a linear, branched alkylene group which may have a substituent, a monocyclic or polycyclic cyclic alkylene group which may have a substituent or may contain a hetero atom, a linear, branched alkenylene group which may be substituted, or may be substituted or hetero The monocyclic or polycyclic cyclic alkenylene group which may contain the atom, the arylene group which may be substituted, and the aralkylene group which may be substituted are shown. X may be bonded to another imidesulfonate residue.)

Ar _One -SO ₂ -SO ₂ -Ar ₂ (A-7)

In Formula (A-7), Ar ₁ and Ar ₂ may be the same or different and represent a substituted or unsubstituted aryl group.

(5) The positive electron beam resist composition as described in any one of said (1)-(4) characterized by further containing a cyclic amine compound.

(6) The positive electron beam resist composition according to any one of (1) to (5), further comprising a fluorine-based surfactant or a silicone-based surfactant.

(7) The positive electron beam resist composition according to any one of (1) to (6) above, further comprising a compound which is decomposed by the action of an acid and increases in solubility in an alkali developer.

Hereinafter, the present invention will be described in detail.

(a) -1: Resin which has group represented by said general formula (X), decomposes by action of acid, and increases solubility to alkaline developing solution

As an alkyl group of R <1>, R <2> in general formula (X), C1, such as a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, etc. There are -4 alkyl groups.

R <3>, R <4> may be same or different, and represents a hydrogen, a linear, branched, cyclic alkyl group which may have a substituent.

As a linear alkyl group, Preferably it is C1-C30, More preferably, it is 1-20, For example, a methyl group, an ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group , n-octyl group, n-nonyl group, n-decanyl group and the like.

As a branched alkyl group, Preferably it is C1-C30, More preferably, it is 1-20, For example, i-propyl group, i-butyl group, i-pentyl group, t-pentyl group, i-hexyl group, t-hex And a real group, n-heptyl group, t-heptyl group, i-octyl group, t-octyl group, i-nonyl group, t-decanoyl group and the like.

As a cyclic alkyl group, Preferably it is C3-C30, More preferably, it is 3-20, For example, Cyclopropyl group, Cyclobutyl group, Cyclopentyl group, Cyclohexyl group, Cycloheptyl group, Cyclooctyl group, Cyclononyl group, Cyclodecanoyl group, and the like.

R <5> represents the linear, branched, cyclic alkyl group which may have a substituent, the aryl group which may have a substituent, and the aralkyl group which may have a substituent.

As a linear or branched alkyl group of R <5>, Preferably it is C1-C30, More preferably, it is C1-C20, For example, a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, i- Butyl group, t-butyl group, n-pentyl group, i-pentyl group, t-pentyl group, n-hexyl group, i-hexyl group, t-hexyl group, n-heptyl group, i-heptyl group, t- Heptyl group, n-octyl group, i-octyl group, t-octyl group, n-nonyl group, i-nonyl group, t-nonyl group, n-decanyl group, i-decanyl group, t-decanyl group, 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, n-octadecyl group, i-octadecyl group, n-nonadecyl group, i-nonadec Practical skills etc. can be illustrated.

As a cyclic alkyl group of R <5>, Preferably it is C1-C30, More preferably, it is C1-C20, Even if a ring is formed by C20, you may be cyclic alkyl which has a substituent, For example, a cyclopropyl group, Cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecanyl group, cycloundecyl group, cyclododecyl group, cyclotridecyl group, cyclotetradecyl group, cyclopentadecyl group , Cyclohexadecyl group, cycloheptadecyl group, cyclooctadecyl group, cyclonondecyl group, 4-cyclohexylcyclohexyl group, 4-n-hexylcyclohexyl group, pentanylcyclohexyl group, hexyloxycyclohexyl group And fentanyloxycyclohexyl group. Substituted cyclic alkyl groups other than those exemplified herein may be used as long as they are within the above range.

As an aryl group of R <5>, Preferably it is C6-C30, More preferably, it is C6-C20, For example, a phenyl group, 4-methylphenyl group, 3-methylphenyl group, 2-methylphenyl group, 4-ethylphenyl group, 3-ethylphenyl group, 2-ethylphenyl group, 4-n-propylphenyl group, 3-n-propylphenyl group, 2-n-propylphenyl group, 4-i-propylphenyl group, 3-i-propylphenyl group, 2-i-propyl Phenyl group, 4-cyclopropylphenyl group, 3-cyclopropylphenyl group, 2-cyclopropylphenyl group, 4-n-butylphenyl group, 3-n-butylphenyl group, 2-n-butylphenyl group, 4-i-butylphenyl group, 3- i-butylphenyl group, 2-i-butylphenyl group, 4-t-butylphenyl group, 3-t-butylphenyl group, 2-t-butylphenyl group, 4-cyclobutylphenyl group, 3-cyclobutylphenyl group, 2-cyclobutylphenyl group , 4-cyclopentylphenyl group, 4-cyclohexylphenyl group, 4-cycloheptenylphenyl group, 4-cyclooctanylphenyl group, 2-cyclopentylphenyl group, 2-cyclohexylphenyl group, 2-cycloheptenylphenyl group, 2-cycloocta Nilphenyl group, 3 -Cyclopentylphenyl group, 3-cyclohexylphenyl group, 3-cycloheptenylphenyl group, 3-cyclooctanylphenyl group, 4-cyclopentyloxyphenyl group, 4-cyclohexyloxyphenyl group, 4-cycloheptenyloxyphenyl group, 4-cyclo Octanyloxyphenyl 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-pentylphenyl group, 4-n-hexylphenyl group, 4-n-heptenylphenyl group, 4-n-octanylphenyl group, 2-n-pentyl Phenyl 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 , 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-isoboroylphenyl group, 3-isoboroylphenyl group, 2-isoboroylphenyl group, 4-cyclopentyloxyphenyl group, 4-cyclohexyloxyphenyl group, 4-cycloheptenyl Oxyphenyl group, 4-cyclooctanyloxyphenyl group, 2-cyclopentyloxyphenyl group, 2-cyclohexyloxyphenyl group, 2-cycloheptenyloxyphenyl group, 2-cyclooctanyl Cyphenyl 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-isopropyloxyphenyl group, 2,6-di-t-butyloxyphenyl group, 2,3-di-t-butyl Oxyphenyl 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- Yloxyphenyl group, 3,4-di-i-butyloxyphenyl group, 2,6-di-t-amyloxyphenyl group, 2,3-di-t-amyloxyphenyl group, 2,4-di-t-amyloxy Phenyl 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-isoboroyloxyphenyl group, 3-isoboroyloxy And a phenyl group, a 2-isoboroyloxyphenyl group, and the like, and these may be further substituted as long as it is within the above range, and is not limited to substituents other than the above examples.

As the aralkyl group of R5, Preferably it is C7-30, More preferably, it is C7-20, For example, a phenylethyl group, 4-methylphenylethyl group, 3-methylphenylethyl group, 2-methylphenylethyl group, 4-ethylphenylethyl group , 3-ethylphenylethyl group, 2-ethylphenylethyl group, 4-n-propylphenylethyl group, 3-n-propylphenylethyl group, 2-n-propylphenylethyl group, 4-i-propylphenylethyl group, 3-i-propyl Phenylethyl group, 2-i-propylphenylethyl group, 4-cyclopropylphenylethyl group, 3-cyclopropylphenylethyl group, 2-cyclopropylphenylethyl group, 4-n-butylphenylethyl group, 3-n-butylphenylethyl group, 2- n-butylphenylethyl group, 4-i-butylphenylethyl group, 3-i-butylphenylethyl group, 2-i-butylphenylethyl group, 4-t-butylphenylethyl group, 3-t-butylphenylethyl group, 2-t- Butylphenylethyl group, 4-cyclobutylphenylethyl group, 3-cyclobutylphenylethyl group, 2-cyclobutylphenylethyl group, 4-cyclopentylphenylethyl group, 4-cyclohexylphenylethyl group, 4-cycloheptenylphenylethyl group, 4-cyclooctanylphenylethyl group, 2-cyclopentylphenylethyl group, 2-cyclohexylphenylethyl group, 2-cycloheptenylphenylethyl group, 2-cyclooctanylphenylethyl group, 3-cyclopentyl Phenylethyl group, 3-cyclohexylphenylethyl group, 3-cycloheptenylphenylethyl group, 3-cyclooctanylphenylethyl group, 4-cyclopentyloxyphenylethyl group, 4-cyclohexyloxyphenylethyl group, 4-cyclohepkenyloxyphenylethyl group , 4-cyclooctanyloxyphenylethyl group, 2-cyclopentyloxyphenylethyl group, 2-cyclohexyloxyphenylethyl group, 2-cycloheptenyloxyphenylethyl group, 2-cyclooctanyloxyphenylethyl group, 3-cyclopentyloxyphenyl Ethyl group, 3-cyclohexyloxyphenylethyl group, 3-cycloheptenyloxyphenylethyl group, 3-cyclooctanyloxyphenylethyl group, 4-n-pentylphenylethyl group, 4-n-hexylphenylethyl group, 4-n-heptenyl Phenylethyl 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-isopropylphenyl Ethyl 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, 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 group, 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, 2,4-di-i-amylphenylethyl group, 3,4-di-i-am Phenylethyl group, 2,6-di-n-pentylphenylethyl group, 2,3-di-n-pentylphenylethyl group, 2,4-di-n-pentylphenylethyl group, 3,4-di-n-pentylphenylethyl group , 4-adamantylphenylethyl group, 3-adamantylphenylethyl group, 2-adamantylphenylethyl group, 4-isoboroylphenylethyl group, 3-isoboroylphenylethyl group, 2-isoboroylphenyl Ethyl group, 4-cyclopentyloxyphenylethyl group, 4-cyclohexyloxyphenylethyl group, 4-cycloheptenyloxyphenylethyl group, 4-cyclooctanyloxyphenylethyl group, 2-cyclopentyloxyphenylethyl group, 2-cyclohexyloxyphenyl Ethyl group, 2-cycloheptenyloxyphenylethyl group, 2-cyclooctanyloxyphenylethyl group, 3-cyclopentyloxyphenylethyl group, 3-cyclohexyloxyphenylethyl group, 3-cycloheptenyloxyphenylethyl group, 3-cyclooctanyl Oxyphenylethyl group, 4-n-pentyloxyphenylethyl group, 4-n-hexyloxyphenylethyl group, 4-n-heptenyloxyphenylethyl group, 4-n-octanyloxyphenylethyl group, 2-n-pentyloxy Nylethyl 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-di-isopropyloxyphenylethyl group, 2,3-di-isopropyloxyphenylethyl group, 2,4-di- Isopropyloxyphenylethyl group, 3,4-di-isopropyloxyphenylethyl group, 2,6-di-t-butyloxyphenylethyl group, 2,3-di-t-butyloxyphenylethyl 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- Miloxyphenylethyl 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 -Isoboroyloxyphenylethyl group, 3-isoboroyloxyphenylethyl group, 2-isoboroyloxyphenylethyl group, or the alkyl substituted with a methyl group, a propyl group, a butyl group, etc. are mentioned.

Moreover, as another substituent of the said group, a hydroxyl group, a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, said alkyl group, a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, a hydroxide Alkoxy groups such as oxypropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, t-butoxy group, alkoxycarbonyl group such as methoxycarbonyl group and ethoxycarbonyl group, benzyl group, phenethyl group and cumyl group Acyloxy groups, such as an acyl group, such as an aralkyl group, an aralkyloxy group, a formyl group, an acetyl group, butyryl group, a benzoyl group, a cyanyl group, a valeryl group, and a butyryloxy group, said alkenyl group, vinyloxy group, and propenyl Alkenyloxy groups, such as an oxy group, an allyloxy group, and a butenyloxy group, aryloxy groups, such as the said aryl group and phenoxy group, and aryloxycarbonyl groups, such as a benzoyloxy group, can be illustrated.

As a substituent of said R <5>, Preferably, they are a C1-C20 alkyl group, a C6-C20 aryl group, or a C7-20 aralkyl group. These substituents may further have a substituent.

Although the specific example of group represented by general formula (X) is shown below, it is not limited to these.

Resin which has group represented by general formula (X) in this invention, and decomposes by the action of an acid, and the solubility to alkaline developing solution increases (henceforth called resin which has group represented by general formula (X)). Is a compound obtained by superposing | polymerizing a monomer, having the structure which introduce | transduced the acid-decomposable group represented by general formula (X) into the compound which has molecular weight distribution, and becomes alkali-soluble by the action of an acid.

As resin which has group represented by general formula (X), it is resin which has group represented by general formula (X) in the main chain or side chain of resin, or both a main chain and a side chain. Among them, a resin having a group represented by the general formula (X) in the side chain is more preferable.

Next, as the matrix resin in the case a group represented by the general formula (X) which combines as a side chain, the -OH or -COOH, preferably in the side chain is an alkali-soluble resin for holding a group -R ^O -COOH or -Ar-OH . For example, alkali-soluble resin which does not contain the acid-decomposable group mentioned later can be illustrated. Here, -R ⁰ -represents a divalent or higher aliphatic or aromatic hydrocarbon which may have a substituent, and -Ar- represents a divalent or higher aromatic group which may have a monocyclic or polycyclic substituent.

Preferred mother resins in the present invention are alkali-soluble resins having phenolic hydroxyl groups.

Alkali-soluble resin which has phenolic hydroxyl group used for this invention is o-, m- or p-hydroxy styrene (collectively these are called hydroxy styrene), or o-, m- or p-hydroxy- Copolymer or homopolymer thereof containing 30 mol% or more, preferably 50 mol% or more, of repeating units corresponding to α-methylstyrene (collectively referred to as hydroxy-α-methylstyrene), or benzene of the unit It is preferred that the nucleus is a partially hydrogenated resin, more preferably a p-hydroxystyrene homopolymer.

As monomers other than hydroxy styrene and hydroxy- (alpha) -methylstyrene for preparing the said copolymer by copolymerization, acrylic acid ester, methacrylic acid ester, acrylamide, methacrylamide, acrylonitrile, meta Krylonitrile, maleic anhydride, styrene, α-methylstyrene, acetoxy styrene and alkoxy styrenes are preferable, and styrene, acetoxy styrene and t-butoxy styrene are more preferable.

In this invention, as content of the repeating unit (structural unit) which has group represented by general formula (X) in such resin, 5 mol%-50 mol% are preferable with respect to all the repeating units, More preferably, Is 5 mol%-30 mol%.

In the present invention, the resin having a group represented by the general formula (X) may contain an acid-decomposable group other than the group represented by the general formula (X).

Resin containing the group represented by the said general formula (X) can be obtained by synthesize | combining a corresponding vinyl ether, and making it react by alkali method with the phenolic hydroxyl group containing alkali-soluble resin melt | dissolved in suitable solvents, such as tetrahydrofuran. . The reaction is usually carried out in the presence of an acidic catalyst, preferably an acidic ion exchange resin, or a salt such as hydrochloric acid, p-toluenesulfonic acid or pyridinium tosylate. The corresponding vinyl ether can be synthesized from an active raw material such as chloroethyl vinyl ether by a method such as nucleophilic substitution reaction, or can be synthesized using a mercury or a palladium catalyst.

As another method, it can also be synthesized by acetal exchange using a corresponding alcohol and vinyl ether. In this case, having the substituent to be introduced into the alcohol, the vinyl ether is mixed in a relatively unstable vinyl ether such as t-butyl vinyl ether, and is carried out in the presence of an acid such as p-toluenesulfonic acid or pyridium tosylate.

As for the weight average molecular weight of resin containing group represented by the said General formula (X), 3000-80000 are preferable, More preferably, it is 5000-50000. The molecular weight distribution (Mn / Mw) is in the range of 1.01 to 4.0, preferably 1.05 to 3.00. In order to obtain the polymer of such molecular weight distribution, it is preferable to use methods such as anionic polymerization and radical polymerization.

Although the specific structure of resin containing group represented by such general formula (X) is illustrated below, this invention is not limited to these.

Resin (resin containing group represented by general formula (X) and resin which has structural units represented by general formula (I), general formula (II), and general formula (III)) used by this invention is alkali In order to adjust the dissolution rate and improve the heat resistance, a polyhydroxy compound may be added in the synthesis step to introduce a crosslinking site connecting the polymer main chain to the polyfunctional acetal group.

The amount of the polyhydroxy compound added is 0.01 to 10 mol%, preferably 0.05 to 8 mol%, more preferably 0.1 to 5 mol% with respect to the number of hydroxyl groups in the resin.

The polyhydroxy compound may have 2 to 6 phenolic hydroxyl groups or alcoholic hydroxyl groups, preferably 2 to 4 hydroxyl groups, and more preferably 2 or 3 hydroxyl groups. Although a specific example is shown below, this invention is not limited to these.

(a) -2: Resin having the structural units represented by the general formulas (I), (II) and (III) and decomposed by the action of an acid to increase its solubility in an alkaline developer

R21 represents a hydrogen atom or a methyl group.

Examples of the group (also called an acid stabilizer) which are not decomposed by the action of an acid at R22 include a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, and an alkyloxy group (however, -O-tertiary alkyl group). An acyl group, a cycloalkyloxy group, an alkenyloxy group, an aryloxy group, an alkylcarbonyloxy group, an alkylamide methyloxy group, an alkylamide group, an arylamide methyl group, an arylamide group, and the like. The acid stabilizer is preferably an acyl group, an alkylcarbonyloxy group, an alkyloxy group, a cycloalkyloxy group, an aryloxy group, an alkylamideoxy group or an alkylamide group, and more preferably an acyl group or an alkylcarbonyl jade. It is a time period, an alkyloxy group, a cycloalkyloxy group, and an aryloxy group.

In the acid stabilizer of R22, as the alkyl group, one having 1 to 4 carbon atoms such as methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group and t-butyl group is preferable, and cycloalkyl group is cyclopropyl group and cyclobutyl Groups having 3 to 10 carbon atoms such as groups, cyclohexyl groups, and adamantyl groups are preferable, and as alkenyl groups, those having 2 to 4 carbon atoms such as vinyl groups, propenyl groups, allyl groups, and butenyl groups are preferable, and as alkenyl groups, vinyl groups And C2-C4, such as a propenyl group, an allyl group, and a butenyl group, and a C6-C14 thing like a phenyl group, xylyl group, toluyl group, cumenyl group, naphthyl group, and aceracenyl group is preferable as an aryl group. Do. As an alkoxy group, C1-C4 alkoxy groups, such as a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, a hydroxypropoxy group, n-butoxy group, an isobutoxy group, and a sec-butoxy group, are preferable.

The halogen atom in R23 is preferably fluorine, chlorine, bromine or iodine, and the alkyl group preferably has 1 to 8 carbon atoms such as methyl, ethyl, propyl, n-butyl, sec-butyl, t-butyl, hexyl or octyl. In addition, as the aryl group, those having 6 to 14 carbon atoms such as phenyl, xylyl, toluyl, cumenyl, naphthyl, acetracenyl, and the like are preferable. As the alkoxy group, those having 1 to 4 carbon atoms such as methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy, n-butoxy, isobutoxy, sec-butoxy, t-butoxy, and the like are preferable. As the acyl group, those having 1 to 7 carbon atoms, such as formyl, acetyl, propanoyl, butanoyl and benzoyl, are preferable. As the acyloxy group, carbon atoms such as acetoxy, propnoyloxy, butanoyloxy and benzoyloxy -7 things are preferable.

The substituent W in general formula (I) is a thing of the said general formula (X), and general formula (X) is as having mentioned above.

Although the specific structure of the structural unit represented by such a general formula (I) is illustrated below, this invention is not limited to these.

By containing the structural unit represented by the general formula (II) in the resin, the resin can be decomposed by the action of an acid to control the solubility in the alkaline developer. Moreover, the profile excellent in rectangularity can be achieved by introducing this structural unit. It is also effective to adjust the amount of the structural unit represented by the general formula (I).

Although the following can be illustrated as a specific example of the polymerizable monomer of the structural unit represented by such general formula (II), It is not limited to these.

Resin containing the structural unit represented by these general formula (II) or general formula (III) is a phenolic resin or its monomer, reacted with an acid anhydride in presence of a base, or a corresponding halide in presence of a base. It can obtain by making it react.

In the present invention, the resin having a group that is decomposed by the action of an acid to increase the solubility in the alkaline developer is, in addition to the structural units represented by the formulas (I), (II) and (III). Another monomer unit may be included as a copolymerization component.

In this invention, it is preferable that the ratio of the structural unit represented by general formula (I), general formula (II), and general formula (III) satisfy | fills the conditions of following (1)-(4).

① 0.10 <(I) / (I) + (II) + (III) <0.25

② 0.01 <(II) / (I) + (II) + (III) <0.15

③ (I)> (II)

④ 0.5 <(I) / (I) + (II) <0.85

(In formula, (I), (II), and (III) represent the mole fraction of the structural unit represented by general formula (I), general formula (II), and general formula (III), respectively.)

By satisfying the above conditions, the resin of the present invention improves the rectangularity of the profile, and in particular, the development defect is further improved.

The repeating structural unit represented by general formula (I), general formula (II), and general formula (III), or the repeating structural unit from another polymerizable monomer exists in resin individually by combining 1 type (s) or 2 or more types, respectively. You may have to.

In addition, the resin contained in the positive photosensitive composition of the present invention may be copolymerized with other polymerizable monomers suitable for introducing alkali-soluble groups such as phenolic hydroxyl groups and carboxyl groups in order to maintain good developability with respect to alkaline developing solutions. You may be.

The molecular weight of the resin having a repeating structural unit represented by the above general formula (I), general formula (II) and general formula (III) synthesized by the above method is 2,000 or more in terms of weight average (Mw: polystyrene standard), Preferably it is 3,000-200,000, More preferably, it is 5,000-70,000. Moreover, dispersion degree (Mw / Mn) becomes like this. Preferably it is 1.0-4.0, More preferably, it is 1.0-3.5, Especially preferably, it is 1.0-3.0, The smaller the dispersion degree, the more heat resistance and image formability (pattern profile, defocusing) Latitude and the like).

Although the specific example of resin which has a repeating structural unit of general formula (I), general formula (II), and general formula (III) is shown below, this invention is not limited to these.

In a positive photosensitive composition of a resin having a group represented by the above formula (X) (including a resin having a repeating structural unit of formula (I), (II) or formula (III)) (coating solvent is The content of Ex.) Is preferably 50 to 99% by weight, more preferably 70 to 97% by weight.

Moreover, in this invention, you may use together resin which has another acid-decomposable group. As a resin having a group which is decomposed by another acid used in the chemically amplified resist in the present invention to increase the solubility in an alkaline developer, it is decomposed to an acid in both the main chain or the side chain of the resin, or both the main chain and the side chain. Resins capable of retaining groups. Among them, a resin having a group capable of decomposing into an acid in the side chain is more preferable.

Preferable groups as the acid decomposable group are -COOA ^O and -OB ^O groups, and examples of groups containing these groups include groups represented by -R ^O -COOA ⁰ or -Ar-OB ^O.

Wherein A ^O is a -C (R ⁰¹ ) (R ⁰² ) (R ⁰³ ) group, -Si (R ⁰¹ ) (R ⁰² ) (R ⁰³ ) group, or -C (R ⁰⁴ ) (R ⁰⁵ ) -OR It represents ⁰⁶ group. B ^O represents an -A ^O or -CO-OA ^O group (R ^O , R ^O1 to R ^O6 and Ar have the same meanings as described later).

As the acid-decomposable group, a silyl ether group, cumyl ester group, acetal group, tetrahydropyranyl ether group, tetrahydropyranyl ester group, enol ether group, enol ester group, tertiary alkyl ether group, agent Tertiary alkyl ester groups, tertiary alkyl carbonate groups and the like. More preferably, they are a tertiary alkyl ester group, tertiary alkyl carbonate group, cumyl ester group, acetal group, and tetrahydropyranyl ether group.

Next, a matrix resin when coupled as a side chain group that can be decomposed by these acids is, groups containing an -OH or -COOH group in the side chain, preferably a -COOH group or an ^O -R -Ar-OH groups It is alkali-soluble resin holding. For example, alkali-soluble resin described below can be enumerated.

The alkali dissolution rate of these alkali-soluble resins is measured by 0.261N tetramethylammonium hydroxide (TMAH) (23 ° C), and preferably 170 Pa / sec or more. Especially preferably, it is 330 kPa / sec or more.

Moreover, alkali-soluble resin with high transmittance | permeability with respect to far ultraviolet light and an excimer laser light is preferable at the point which achieves a rectangular profile. Preferably, the transmittance | permeability at 248 nm of 1 micrometer film thickness is 20 to 90%.

In view of this, particularly preferred alkali-soluble resins are o-, m-, p-poly (hydroxystyrene) and copolymers thereof, hydrogenated poly (hydroxystyrene), halogen- or alkyl-substituted poly (hydroxystyrene). , Some O-alkylated or O-acylates of poly (hydroxystyrene), styrene-hydroxystyrene copolymers, α-methylstyrene-hydroxystyrene copolymers and hydrogenated novolac resins.

The resin having a group that can be decomposed into an acid used in the present invention may be reacted with an alkali-soluble resin by reacting a precursor of a group that can be decomposed into an acid, or an alkali-soluble resin monomer having a group that can be decomposed into an acid. It can obtain by copolymerizing with various monomers.

You may mix the acid-decomposable low molecular weight dissolution inhibiting compound described later with the said acid generator and resin which has group which can decompose | disassemble into an acid.

The acid-decomposable dissolution inhibiting compound used in the present invention includes two or more groups capable of decomposing into acids in the structure, and has eight bonding atoms excluding the acid-decomposable group at a position where the distance between the acid-decomposable groups is farthest. It is a compound passing through the above.

In addition, the acid-decomposable low molecular weight soluble blocking compound used in the present invention may contain at least one acid-decomposable group represented by the general formula (X).

In the present invention, preferably, the acid-decomposable dissolution inhibiting compound has two or more groups that can be decomposed into an acid in its structure, and bonds excluding the acid-decomposable group at a position where the distance between the acid-decomposable groups is farthest away. A compound having at least 10 atoms, preferably at least 11, more preferably at least 12 atoms, or at least 3 acid-decomposable groups, and the acid at a position where the distance between the acid-decomposable groups is farthest It is a compound which carries out 9 or more, preferably 10 or more, more preferably 11 or more coupling atoms except a decomposable group. The upper limit of the number of the binding atoms is preferably 50, more preferably 30.

In the present invention, even when the acid-decomposable dissolution inhibiting compound has three or more acid-decomposable groups, preferably four or more, or two acid-decomposable groups, the acid-decomposable groups are separated from each other by a predetermined distance or more. If present, the dissolution inhibiting property to the alkali-soluble resin is remarkably improved.

In addition, the distance between the acid-decomposable groups in the present invention is represented by the number of light-linked atoms, except for the acid-decomposable group. For example, in the following compounds (1) and (2), the distance between the acid-decomposable groups is 4 binding atoms, and in compound (3), 12 binding atoms are each.

The acid-decomposable dissolution inhibiting compound of the present invention may have a plurality of acid-decomposable groups on one benzene ring, but is preferably a compound composed of a skeleton having one acid-decomposable group on one benzene ring. . The molecular weight of the acid-decomposable dissolution inhibiting compound of the present invention is 3,000 or less, preferably 500 to 3,000, more preferably 1,000 to 2,500.

In a preferred embodiment of the present invention, groups which can be decomposed by an acid, that is, groups containing -COO-A ^O or -OB ^O groups are represented by -R ^O -COO-A ^O or -Ar-OB ^O You can enumerate the groups.

Wherein A ^O represents -C (R ⁰¹ ) (R ⁰² ) (R ⁰³ ), -Si (R ⁰¹ ) (R ⁰² ) (R ⁰³ ) or -C (R ⁰⁴ ) (R ⁰⁵ ) -OR ⁰⁶ Display. B ^O represents A ^O or -CO-OA ^O.

R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ may be the same or different and represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group, and R ⁰⁶ represents an alkyl group or an aryl group. However, two or more of R ⁰¹ to R ⁰³ may be a group other than a hydrogen atom, and two groups of R ⁰¹ to R ⁰³ and R ⁰⁴ to R ⁰⁶ may combine to form a ring. R <^0> represents the bivalent or more aliphatic or aromatic hydrocarbon group which may have a substituent, and -Ar- represents the bivalent or more aromatic group which may have a monocyclic or polycyclic substituent.

The alkyl group is preferably one having 1 to 4 carbon atoms such as methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group and t-butyl group, and cycloalkyl group is cyclopropyl group, cyclobutyl group and cyclohex. C3-C10 things, such as a real group and an adamantyl group, are preferable, C2-C4 things, such as a vinyl group, a propenyl group, an allyl group, and a butenyl group, are preferable, and as an aryl group, a phenyl group and a xylyl group The C6-C14 thing like a toluyl group, cumenyl group, a naphthyl group, and anthracenyl group is preferable.

As the substituent, a hydroxy group, a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, the alkyl group, a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, a hydroxypropoxy group, alkoxy groups such as alkoxy groups such as n-butoxy group, isobutoxy group, sec-butoxy group and t-butoxy group, alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group, aralkyl groups such as benzyl group, phenethyl group and cumyl group, and aralkyl jade Acyl groups, such as acyl groups, such as a time period, a formyl group, an acetyl group, butyryl group, benzoyl group, a cyanyl group, and a valeryl group, and a butyryloxy group, said alkenyl group, vinyloxy group, propenyloxy group, and allyloxy group And alkenyloxy groups such as butenyloxy group, aryloxy groups such as aryl group and phenoxy group, and aryloxycarbonyl groups such as benzoyloxy group.

As the group which can be decomposed by an acid, a silyl ether group, cumyl ester group, acetal group, tetrahydropyranyl ether group, enol ether group, enol ester group, tertiary alkyl ether group, and third A grade alkyl ester group and a tertiary alkyl carbonate group can be illustrated. More preferably, they are a tertiary alkyl ester group, tertiary alkyl carbonate group, cumyl ester group, and tetrahydropyranyl ether group.

As the acid-decomposable dissolution inhibiting compound, Japanese Patent Application Laid-Open No. H12-289946, Japanese Patent Application Laid-Open No. Hei 1-289947, Japanese Patent Application Laid-Open No. 2-2560, Japanese Patent Application Laid-Open No. 3-128959, and Japanese Patent Application Laid-Open No. 3-158855 Patent Publication No. Hei 3-179353, Patent Publication Hei 3-191351, Patent Publication Hei 3-200251, Patent Publication Hei 3-200252, Patent Publication Hei 3-200253, Patent Publication Hei 3-200254, Patent Publication No. 3-200255, Patent Publication No. 3-259149, Patent Publication No. 3-279958, Patent Publication No. 3-279959, Patent Publication No. 4-1650, Patent Publication No. 4-1651, Patent Publication No. 4-11260, Patent Publication No. 4-12356, Patent Publication No. 4-12357, Patent Application No. 3-33229, Patent Application No. 3-230790, Patent Application No. 3-320438, Patent Application No. 4- No. 25157, No. 4-52732, No. 4-103215, No. 4-104542, No. 4-107885, No. 4-107889 and No. 4-152195 Some or all of the phenolic OH groups of the polyhydroxy compound described in the specification It includes a compound protected by combining with the group shown above, -R ^O -COO-A ^O group or B ^O group.

More preferably, Japanese Patent Application Laid-Open No. H12-289946, Japanese Patent Laid-Open No. 3-128959, Japanese Patent Laid-Open No. 3-158855, Japanese Patent Laid-Open No. 3-179353, Japanese Patent Laid-Open No. 3-200251, Japanese Patent Laid-Open No. 3 -200252, Patent Publication No. 3-200255, Patent Publication No. 3-259149, Patent Publication No. 3-279958, Patent Publication No. 4-1650, Patent Publication No. 4-11260, Patent Publication No. 4-12356 Japanese Patent Application Laid-Open No. 4-12357, Japanese Patent Application No. 4-25157, Japanese Patent Application No. 4-103215, Japanese Patent Application No. 4-104542, Japanese Patent Application No. 4-107885, Japanese Patent Application No. 4-107889 and The use of the polyhydroxy compound described in the specification of patent application No. 4-152195 is mentioned.

More specifically, there are compounds represented by general formulas [I] to [XVI].

R ¹⁰¹ , R ¹⁰² , R ¹⁰⁸ , R ¹³⁰ : which may be the same or different, a hydrogen atom, -R ^O -COO-C (R ⁰¹ ) (R ⁰² ) (R ⁰³ ) or -CO-OC (R ⁰¹ ) (R ⁰² ) (R ⁰³ ), except that R ^O , R ⁰¹ , R ⁰² and R ⁰³ are defined as above.

R ¹⁰⁰ : -CO-, -COO-, -NHCONH-, -NHCOO-, -O-, -S-, -SO-, -SO _2- , -SO ₃ -or

Here, G is 2-6, However, when G = 2, at least 1 of R <^150> , R <^151> is an alkyl group,

R ¹⁵⁰ and R ^{151 may be the} same or different and represent a hydrogen atom, an alkyl group, an alkoxy group, -OH, -COOH, -CN, a halogen atom, -R ¹⁵² -COOR ¹⁵³ or -R ¹⁵⁴ -OH,

R ¹⁵² , R ¹⁵⁴ : alkylene group,

R ¹⁵³ : hydrogen atom, alkyl group, aryl group or aralkyl group,

R ⁹⁹ , R ¹⁰³ to R ¹⁰⁷ , R ¹⁰⁹ , R ¹¹¹ to R ¹¹⁸ , R ¹³¹ to R ¹³⁴ : may be the same or different and represent a hydrogen atom, a hydroxy group, an alkyl group, an alkoxy group, an acyl group, an acyloxy group, an aryl group, or an aryl Oxy group, aralkyl group, aralkyloxy group, halogen atom, nitro group, carboxyl group, cyano group or -N (R ¹⁵⁵ ) (R ¹⁵⁶ ) (R ¹⁵⁵ , R ¹⁵⁶ : H, alkyl group or aryl group)

R ¹¹⁰ : single bond, alkylene group, or

R ¹⁵⁷ , R ¹⁵⁹ : may be the same or different and are a single bond, an alkylene group, -O-, -S-, -CO- or a carboxyl group,

R ¹⁵⁸ : a hydrogen atom, an alkyl group, an alkoxy group, an acyl group, an acyloxy group, an aryl group, a nitro group, a hydroxy group, a cyano group or a carboxyl group, except that the hydroxy group is an acid-decomposable group (e.g., t-butoxycarbonylmethyl group, tetra Hydropyranyl group, 1-ethoxy-1-ethyl group, 1-t-butoxy-1-ethyl group) may be substituted.

R ¹¹⁹ and R ^{120 may be the} same or different and are a methylene group, a lower alkyl substituted methylene group, a halomethylene group or a haloalkylene group, except that in the present invention, a lower alkyl group represents an alkyl group having 1 to 4 carbon atoms,

A: methylene group, lower alkyl substituted methylene group, halomethylene group or haloalkylene group,

a to v, g 1 to n 1: when there are a plurality of groups, the groups in () may be the same or different,

a to q, s, t, v, g1 to i1, k1 to m1: an integer of 0 or 1 to 5,

r, u: 0 or an integer of 1 to 4,

j1, n1: 0 or an integer of 1 to 3,

(a + b), (e + f + g), (k + l + m), (q + r + s), (g1 + h1 + i1 + j1) ≥ 2,

(j1 + n1) ≤ 3,

(r + u) ≤4,

(a + c), (b + d), (e + h), (f + i), (g + j), (k + n), (l + o), (m + p), (q + t), (s + v), (g1 + k1), (h1 + l1), (i1 + m1) ≤5

Indicates.

From here,

R ¹⁶⁰ : organic group, single bond, -S-, -SO- or

R ¹⁶¹ : hydrogen atom, monovalent organic group or

R ¹⁶² to R ^{166 may be the} same or different and represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group

, Alkoxy group, alkenyl group, -OR ^O -COO-C (R ⁰¹ ) (R ⁰² ) (R ⁰³ ) or -O-CO-O-

C (R ⁰¹ ) (R ⁰² ) (R ⁰³ ), but two or more are -OR ^O -COO-C (R ⁰¹ ) (R ⁰² )

(R ⁰³ ) or -O-CO-OC (R ⁰¹ ) (R ⁰² ) (R ⁰³ ), also four each or six

Substituents of the same symbol may be the same or different,

X: divalent organic group,

e2: 0 or 1 is displayed.

From here,

R ¹⁶⁷ to R ^{170 may be the} same or different and represent a hydrogen atom, a hydroxyl group, a halogen atom,

An alkyl group, an alkoxy group, or an alkenyl group is represented, but each 4-6

The substituents of the same symbol may not be the same,

R ¹⁷¹ , R ¹⁷² : hydrogen atom, alkyl group or

R ¹⁷³ : two or more of -OR ^O -COO- (R ⁰¹ ) (R ⁰² ) (R ⁰³ ) or -O-CO-OC (R ⁰¹ ) (R ⁰² ) (R ⁰³ )

And the rest are hydroxy groups,

f2, h2: 0 or 1,

g2: 0 or an integer of 1 to 4,

Is displayed.

From here,

R ¹⁷⁴ to R ^{180 may be the} same or different and represent a hydrogen atom, a hydroxyl group, a halogen atom, or an alkyl group.

Group, alkoxy group, nitro group, alkenyl group, aryl group, aralkyl group, alkoxycar

Carbonyl, arylcarbonyl, acyloxy, acyl, aralkyloxy or

An aryloxy group, provided that the substituents of each of the same symbol are the same

Not a flag,

R ¹⁸¹ : two or more of -OR ^O -COO-C (R ⁰¹ ) (R ⁰² ) (R ⁰³ ) or -O-CO-OC (R ⁰¹ ) (R ⁰² ) (R ⁰³ )

Groups, the rest being hydroxy groups,

Is displayed.

The specific example of a preferable compound skeleton is shown below.

R in compounds (1) to (43) is a hydrogen atom,

Is displayed. However, at least two or three may be groups other than a hydrogen atom, and each substituent R may not be the same group.

In this case, the content of the dissolution inhibiting compound is 3 to 45% by weight, preferably 5 to 30% by weight, more preferably 10 to 20% by weight, based on the total weight of the photosensitive composition (excluding the solvent). to be.

Moreover, in order to adjust alkali solubility, you may mix alkali-soluble resin which does not have group which can be decomposed | dissolved into an acid.

As such alkali-soluble resin, a novolak resin, a hydrogenated novolak resin, acetone pyrogarol resin, o-polyhydroxy styrene, m-polyhydroxy styrene, p-polyhydroxy styrene, hydrogenated polyhydroxy Styrene, halogen or alkyl-substituted polyhydroxystyrenes, hydroxystyrene-N-substituted maleimide copolymers, o / p- and m / p-hydroxystyrene copolymers, some O-alkyls for the hydroxy groups of polyhydroxystyrene Cargoes (e.g., 5-30 mole% O-methylate) or O-acylates (e.g., 5-30 mole% o-acetylate, etc.), styrene-maleic anhydride copolymer, styrene-hydride A hydroxy styrene copolymer, (alpha) -methylstyrene-hydroxy styrene copolymer, carboxyl group-containing methacryl-type resin, and its derivative (s) are mentioned, However, It is not limited to these.

Particularly preferred alkali-soluble resins are novolak resins and o-polyhydroxystyrenes, m-polyhydroxystyrenes, p-polyhydroxystyrenes and copolymers thereof, alkyl substituted polyhydroxystyrenes, and some O of polyhydroxystyrenes. -Alkylated or O-acylates, styrene-hydroxystyrene copolymers, α-methylstyrene-hydroxystyrene copolymers. The novolak resin is obtained by addition condensation with aldehydes in the presence of an acidic catalyst, with a predetermined monomer as a main component.

Predetermined monomers include cresols such as phenol, m-cresol, p-cresol, and o-cresol, 2,5-xylenol, 3,5-xylenol, 3,4-xylenol, 2,3 Alkyl phenols such as xylenols such as xylenol, m-ethylphenol, p-ethylphenol, o-ethylphenol, pt-butylphenol, p-octylphenol, and 2,3,5-trimethylphenol; Methoxyphenol, m-methoxyphenol, 3,5-dimethoxyphenol, 2-methoxy-4-methylphenol, m-ethoxyphenol, p-ethoxyphenol, m-propoxyphenol, p-propoxy Alkoxyphenols such as phenol, m-butoxyphenol and p-butoxyphenol, bisalkylphenols such as 2-methyl-4-isopropylphenol, m-chlorophenol, p-chlorophenol, o-chlorophenol and dihydride Although hydroxy aromatic compounds, such as oxybiphenyl, bisphenol A, phenylphenol, resorcinol, and naphthol, can be used individually or in mixture of 2 or more types, it is not limited to these.

Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p -Hydroxybenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde Although p-ethylbenzaldehyde, pn-butylbenzaldehyde, furfural, chloroacetaldehyde and their acetals such as chloroacetaldehyde diethylacetal and the like can be used, among these, it is preferable to use formaldehyde.

These aldehydes are used independently or in combination of 2 or more types. As the acidic catalyst, hydrochloric acid, sulfuric acid, formic acid, acetic acid, oxalic acid and the like can be used.

It is preferable that the weight average molecular weight of the novolak resin obtained in this way exists in the range of 1,000-30,000. If it is less than 1,000, the film loss after development of a non-exposed part is large, and when it exceeds 30,000, the developing speed will fall. Especially preferable is the range of 2,000-20,000.

The weight average molecular weight of the above-mentioned polyhydroxy styrene, derivatives and copolymers other than the novolac resin is 2,000 or more, preferably 5,000 to 200,000, and more preferably 10,000 to 100,000. Moreover, 25000 or more are preferable from a viewpoint of improving the heat resistance of a resist film.

Here, a weight average molecular weight is defined using the conversion value of the polystyrene of a gel permeation chromatography.

You may use these alkali-soluble resin in this invention in mixture of 2 or more types.

As addition amount in the composition of these alkali-soluble resin in this invention, Preferably it is 5-30 weight%.

The acid generator (b) used in the present invention is a compound that generates an acid by irradiation of an electron beam.

As a compound which generates an acid by irradiation of an electron beam used in the present invention, any compound can be used as long as it is decomposed by irradiation of an electron beam to generate an acid, but a photoinitiator of photocationic polymerization, a photoinitiator of photoradical polymerization, and a photochromic agent of a pigment are used. Known light used in photochromic agents, microresists, and the like (ultraviolet rays of 400 to 200 nm, far ultraviolet rays, particularly preferably g rays, h rays, i rays, KrF excimer laser light), ArF excimer laser light, X Among compounds and mixtures thereof that generate acids by rays, molecular beams, or ion beams, those which decompose upon irradiation with an electron beam to generate an acid can be appropriately selected and used.

Moreover, as a compound which generate | occur | produces an acid by the irradiation of the electron beam used for other this invention, Onium salts, such as a diazonium salt, an ammonium salt, a phosphonium salt, an iodonium salt, a sulfonium salt, a selenium salt, an arsonium salt, The compound which produces | generates sulfonic acid by photolysis represented by an organic halogen compound, an organometallic / organic halide, a photoacid generator which has o-nitrobenzyl type protecting group, an imino sulfonate, etc. can be mentioned.

Moreover, the compound which introduce | transduced the group or compound which generate | occur | produces an acid by these electron beams in the main chain or side chain of a polymer can be used.

See also V.N.R.Pillai, Synthesis, (1), 1 (1980), A. Abab et al, Tetrahedron Lett., (47) 4555 (1971), D. H. R. Barton et al, J. Chem. Compounds which generate an acid by light described in Soc., (C), 329 (1970), US Pat. No. 3,779,778, EP 126,712 and the like can also be used.

Among the compounds which decompose by irradiation of the electron beam and generate an acid, compounds represented by the above general formulas (A-1) to (A-7) and which generate sulfonic acid by irradiation of an electron beam are preferably used.

Hereinafter, the compound represented by general formula (A-1)-(A-7) is demonstrated in detail.

Acid generators represented by general formulas (A-1) to (A-3)

As an alkyl group of R <_1> -R <_6> and R <_7> -R <_10> in said general formula (A-1)-(A-3), the methyl group, ethyl group, propyl group, n-butyl group which may have a substituent, There exists a C1-C4 thing like sec-butyl group and t-butyl group. Examples of the cycloalkyl group include those having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group and a cyclohexyl group which may have a substituent. Examples of the alkoxy group include one to four carbon atoms such as methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, n-butoxy group, isobutoxy group, sec-butoxy group and t-butoxy group. Examples of the halogen atom include fluorine atom, chlorine atom, bromine atom and iodine atom. Examples of the aryl group include those having 6 to 14 carbon atoms which may have a substituent such as a phenyl group, tolyl group, methoxyphenyl group or naphthyl group.

As a substituent, Preferably, it is a C1-C4 alkoxy group, a halogen atom (fluorine atom, a chlorine atom, an iodine atom), a C6-C10 aryl group, a C2-C6 alkenyl group, a cyano group, a hydroxyl group, a carboxy group, An alkoxycarbonyl group, a nitro group, and the like.

The sulfonium and iodonium compounds represented by the general formulas (A-1) to (A-3) used in the present invention are, as the monoanions, X ⁻ , having 8 or more branched or cyclic carbon atoms, preferably At least one alkyl group or alkoxy group having at least 10, at least two linear, branched, or cyclic alkyl groups having 4 to 7 carbon atoms or at least two alkoxy groups, linear or branched alkyl groups having 1 to 3 carbon atoms, or It has at least three alkoxy groups, has 1 to 5 halogen atoms, or has an anion of benzenesulfonic acid, naphthalenesulfonic acid or anthracenesulfonic acid having a linear, branched or cyclic C1-10 ester group. Thereby, the diffusivity of the acid (benzene sulfonic acid, naphthalene sulfonic acid, or anthracene sulfonic acid containing the said group) which generate | occur | produces after exposure becomes small, and the solvent solubility of the sulfonium and an iodonium compound improves. In particular, from the viewpoint of decreasing the diffusibility, the group is a linear alkyl group or an alkoxy group, and a branched or cyclic alkyl group or an alkoxy group is more preferable. In the case where there is one group, the difference in diffusivity between linear and branched or annular becomes more remarkable.

Examples of the alkyl group having 8 or more carbon atoms, preferably 8 to 20 carbon atoms include branched or cyclic octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, and octadecyl group. .

As the alkoxy group having 8 or more carbon atoms, and preferably 8 to 20 carbon atoms, a branched or cyclic octyloxy group, nonyloxy group, decyloxy group, undecyloxy group, dodecyloxy group, tridecyloxy group, tetradecyloxy Period, an octadecyloxy group, and the like.

Examples of the alkyl group having 4 to 7 carbon atoms include a linear, branched or cyclic butyl group, pentyl group, hexyl group, heptyl group and the like.

Examples of the alkoxy group having 4 to 7 carbon atoms include a linear, branched or cyclic butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, and the like.

Examples of the alkyl group having 1 to 3 carbon atoms include methyl group, ethyl group, n-propyl group and isopropyl group.

Examples of the alkoxy group having 1 to 3 carbon atoms include methoxy group, ethoxy group, n-propoxy group and isopropoxy group.

As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom can be illustrated, Preferably it is a fluorine atom.

Examples of the linear, branched or cyclic C1-10 esters include methyl ester groups, ethyl ester groups, n-propyl ester groups, i-propyl ester groups, n-butyl ester groups, i-butyl ester groups and t- Butyl ester group, n-hexyl ester group, i-hexyl ester group, t-hexyl ester group, n-heptyl ester group, i-heptyl ester group, t-heptyl ester group, n-octyl ester group, i-octyl ester Group, t-octyl ester group, n-nonyl ester group, i-nonyl ester group, t-nonyl ester group, n-decanyl ester group, i-decanyl ester group, t-decanyl ester group, cyclopropyl ester Groups, cyclobutyl ester groups, cyclopentyl ester groups, cyclohexyl ester groups, cycloheptyl ester groups, cyclooctyl ester groups, cyclononyl ester groups, cyclodecanyl ester groups, and the like.

The aromatic sulfonic acid represented by X ⁻ includes halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom), C6-C10 aryl group, cyano group, sulfide group, hydroxy group, carboxy group, You may contain a nitro group etc. as a substituent.

Specific examples (A-1-1) to (A-1-66), (A-2-1) to (A-2-59), and (A-3-1) to (A) of these compounds below -3-35), but the present invention is not limited thereto.

In addition, in a specific example, it shows that n is linear, s is class 2, t is class 3, and i is branching.

Compounds represented by general formulas (A-1) to (A-3) include, for example, a corresponding Cl ⁻ salt (substituted with Cl ⁻ in X ⁻ in general formulas (A-1) to (A-3)). Compound) and a compound represented by X ^- Y ⁺ (X ^- is the same meaning as in the general formula (A-1) to (A-3), Y ⁺ is H ⁺ , Na ⁺ , K ⁺ , NH ₄ Cations such as ⁺ , N (CH ₃ ) ₄ ^+, etc.) can be synthesized by salt exchange in an aqueous solution.

Acid generators represented by general formulas (A-4) and (A-5)

In general formula (A-4) and (A-5), the alkyl group, cycloalkyl group, alkoxy group, and halogen atom in R <_11> -R <_13> , R <_14> -R <_16> are the same as those of said R <_1> -R <_5> . It can enumerate as a specific example. R ₆ and X ⁻ have the same meaning as described above.

When l, m and n are each 2 or 3, 5 each of two or three of R ₁₁ to R ₁₃ or R ₁₄ to R ₁₆ are bonded to each other to contain a carbocyclic ring, a heterocyclic ring, or an aromatic ring; You may form the ring which consists of -8 elements.

Specific examples of the compound represented by General Formula (A-4-1) to (A-4-28) and General Formula (A-5) below (A-) 5-1)-(A-5-30) are shown, but it is not limited to this.

In addition, in a specific example, it shows that n is linear, s is class 2, t is class 3, and i is branching.

Compounds represented by the general formulas (A-4) and (A-5) are, for example, substituted X ⁻ with Cl ⁻ in the corresponding Cl ⁻ salts (General Formulas (A-4) and (A-5)). Compound) and a compound represented by X ^- Y ⁺ (X ^- means the same as in the general formula (A-4), (A-5), Y ⁺ is H ⁺ , Na ⁺ , K ⁺ , NH ₄ ⁺ , N (CH ₃ ) ₄ ⁺ and the like.) Can be synthesized by salt exchange in an aqueous solution.

Acid generator represented by general formula (A-6)

As Y and R <_31> -R <_51> linear, branched, and cyclic alkyl groups in said general formula (A-6), a methyl group, an ethyl group, a propyl group, an isopropyl group, n-butyl group, sec-butyl group, t-butyl group And a linear or branched alkyl group having 1 to 20 carbon atoms such as a hexyl group and an octyl group and a cyclic alkyl group such as a cyclopropyl group, a cyclopentyl group or a cyclohexyl group. Preferred substituents of the alkyl group include an alkoxy group, acyl group, acyloxy group, chlorine atom, bromine atom and iodine atom.

Moreover, as an aralkyl group of Y, there are C7-12 aralkyl groups, such as a benzyl group or a phenethyl group. Preferable substituents for the aralkyl group include a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxy group having 1 to 4 carbon atoms, a nitro group, an acetylamino group, a halogen atom and the like.

As an alkoxy group of R <_31> -R <_51> , a methoxy group, an ethoxy group, a propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, t-butoxy group, octyloxy group, and dodecyl oxy There exists an alkoxy group which has substituents, such as a C1-C20 alkoxy group or an ethoxyethoxy group like time. Examples of the acyl group include an acetyl group, propionyl group, and benzoyl group. Examples of the acylamino group include an acetylamino group, propionylamino group, and benzoylamino group. The sulfonylamino group includes a substituted or unsubstituted benzenesulfonylamino group, such as a C1-4 sulfonylamino group such as methanesulfonylamino group and ethanesulfonylamino group and p-toluenesulfonylamino group. Examples of the aryl group include a phenyl group, tolyl group, and naphthyl group. Examples of the alkoxycarbonyl group include an alkoxycarbonyl group having 2 to 20 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group, ethoxyethoxycarbonyl group, octyloxycarbonyl group and dodecyloxycarbonyl group.

As an acyloxy group, there are C2-C20 acyloxy groups, such as an acetoxy group, a propanoyloxy group, an octanoyloxy group, and a benzoyloxy group.

Aralkyl groups include C7-15 aralkyl groups, such as substituted or unsubstituted benzyl groups and substituted or unsubstituted phenethyl groups. Preferable substituents for the aralkyl group include those exemplified above.

In R <_31> -R <_51> , R <_31> -R <_35> , R <_36> -R <_42> and R <_43> -R <_51> may combine with each other, and may form the 5-8 membered ring which consists of carbon and / or a hetero atom. . Such 5- to 8-membered rings include, for example, cyclohexane, pyridine, furan or pyrrolidine.

In addition, X and Y may be combined with the residue of another imide sulfonate compound, and may form a dimer and a trimer. As another imide sulfonate, it is a compound represented by general formula (A-6), and the thing which became monovalent group in the part of X or Y.

As an alkylene group of X, there exists a monocyclic or polycyclic cyclic alkylene group which may contain a linear or branched C1-C10 alkylene group or hetero atom. Examples of the linear or branched alkylene group include a methylene group, an ethylene group, a propylene group or an octylene group. Preferred substituents of the alkylene group include an alkoxy group, acyl group, formyl group, nitro group, acylamino group, sulfonylamino group, halogen atom, aryl group and alkoxycarbonyl group. The alkoxy group, acyl group, nitro group, acylamino group, sulfonylamino group, aryl group, and alkoxycarbonyl group which were illustrated here are the same meaning as what was illustrated by R <_31> -R <_51> . Examples of the halogen atom include fluorine atom, chlorine atom, bromine atom and iodine atom.

As a cyclic alkylene group, there are C5-C15 polycyclic cycloalkylene groups, such as C4-C8 monocyclic cycloalkylene group, such as a cyclopentylene group and a cyclohexylene group, and 7-oxabicyclo [2.2.1] heptylene group, Preferred substituents of the cycloalkylene group include an alkyl group having 1 to 4 carbon atoms, an alkoxy group, an acyl group, a formyl group, a nitro group, an acylamino group, a sulfonylamino group, a halogen atom, an aryl group, and an alkoxycarbonyl group. The alkoxy group, acyl group, nitro group, acylamino group, sulfonylamino group, aryl group, and alkoxycarbonyl group which were illustrated here are the same meaning as what was illustrated by R <_31> -R <_51> . Examples of the halogen atom include fluorine atom, chlorine atom, bromine atom and iodine atom.

Examples of the arylene group include a phenylene group and a naphthylene group. Preferred substituents of the arylene group include alkyl groups, cycloalkyl groups, alkoxy groups, acyl groups, formyl groups, nitro groups, acylamino groups, sulfonylamino groups, halogen atoms, aryl groups, and alkoxycarbonyl groups. The alkyl group, cycloalkyl group, alkoxy group, acyl group, formyl group, nitro group, acylamino group, sulfonylamino group, aryl group and alkoxycarbonyl group exemplified here are the same as those exemplified for R ₃₁ to R ₅₁ . Examples of the halogen atom include fluorine atom, chlorine atom, bromine atom and iodine atom.

Alkenylene groups include alkenylene groups having 2 to 4 carbon atoms, for example, ethenylene groups, butenylene groups, and the like. Preferable substituents for alkenylene groups include alkyl groups, cycloalkyl groups, alkoxy groups, acyl groups, formyl groups, nitro groups, And an acylamino group, a sulfonylamino group, a halogen atom, an aryl group, and an alkoxycarbonyl group. The alkyl group, cycloalkyl group, alkoxy group, acyl group, formyl group, nitro group, acylamino group, sulfonylamino group, aryl group and alkoxycarbonyl group exemplified here are the same as those exemplified for R ₃₁ to R ₅₁ . Examples of the halogen atom include fluorine atom, chlorine atom, bromine atom and iodine atom.

As cyclic alkenylene group, C4-C8 monocyclic cycloalkenylene group, such as a cyclopentenylene group and a cyclohexenylene group, 7-oxabicyclo [2.2.1] heptenylene group, and a norbornenylene group, etc. There are 15 polycyclic cycloalkenylene groups.

As an aralkylene group, there are a tolylene group, a xylylene group, etc., As the substituent, the substituent illustrated by the arylene group can be illustrated.

Although the specific example (A-6-1)-(A-6-49) of the compound represented by these general formula (A-6) is shown below, it is not limited to these.

Compounds represented by general formula (A-6) include GF Jaubert, Ber .. 28,360 (1895), DEAmes et al., J. Chem. Soc .. 3518 (1955), MAStolberg et al. N-hydroxyimide compounds and sulfonic acid chlorides synthesized according to the method of J. Am. Chem. Soc. 79, 2615 (1957) and the like under basic conditions, for example, L. Bauer et al., J. Org. It is possible to synthesize according to the method of Chem .. 24, 1294 (1959).

Acid generator represented by general formula (A-7)

In General Formula (A-7), Ar ₁ and Ar ₂ are the same or different and represent a substituted or unsubstituted aryl group.

Here, as an aryl group, a phenyl group, a tolyl group, a naphthyl group, etc. are mentioned. Substituents for the aryl group include alkyl groups, cycloalkyl groups, alkoxy groups, acyl groups, formyl groups, nitro groups, acylamino groups, sulfonylamino groups, halogen atoms, aryl groups, and alkoxycarbonyl groups.

The alkyl group, cycloalkyl group, alkoxy group, acyl group, formyl group, nitro group, acylamino group, sulfonylamino group, aryl group and alkoxycarbonyl group exemplified herein are the same as those exemplified in the above R ₃₁ to R ₅₁ . Examples of the halogen atom include fluorine atom, chlorine atom, bromine atom and iodine atom.

Although the compound (A-7-1)-(A-7-14) shown below as a specific example of the acid generator represented by general formula (A-7) is not limited to these.

As a synthesis | combination of the acid generator represented by the said General formula (A-7), D.-C.-D.S.-Junia. Et al. "Journal of Organic Chemistry" (GCDenser, Jr. et al., "Journal of Organic" 31, 3418-3419 (1966), D. P. Hilditch, Journal of the Chemical Society (TPHildichi, Journal of the Chemical Society, 93, 1524-1527 (1908). Method of description, or O. H. Berg et al. (Berrichte der Deutschen Hemisie Gegelshaft) (O.Hinsberg, `` Berichte der Dentschen Chemischen Gesellschaft '') 49, 2593-2594 (1918) That is, a method of synthesizing with sulfinic acid represented by general formula (a) using cobalt sulfate in aqueous sulfuric acid solution, and sulfonic acid chloride represented by general formula (b) using ethyl xtogenate A method of synthesizing or a table of sulfinic acid represented by the general formula (a) and general formula (b) under basic conditions Being and a method of synthesizing a sulfonic acid chloride.

Ar _One SO ₂ H (a)

Ar ₂ SO ₂ Cl (b)

(Here, Ar ₁ , Ar ₂ have the same meaning as defined by the general formula (A-7).)

In this invention, the acid generator represented by general formula (A-1)-(A-5) is preferable among the acid generator represented by said general formula (A-1)-(A-7), and Preferably, it is an acid generator represented by general formula (A-1)-(A-4). This makes the resolution and sensitivity even more excellent.

In the present invention, the content of the acid generator (preferably the compound represented by general formulas (A-1) to (A-7)) in the composition is preferably 0.1 to 25% by weight based on the solids of the entire composition. More preferably, it is 1-15 weight%, More preferably, it is 2-10 weight%.

An organic basic compound can be used for the composition of this invention. This is preferable because the stability at the time of storage is further improved and the line width change by PED is further reduced.

Preferred organic basic compounds which can be used in the present invention are compounds which are more basic than phenol. Among these, nitrogen-containing basic compounds are preferable.

As a preferable chemical environment, the following formula (A)-(E) structure can be mentioned.

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 a substituent having 6 to 20 carbon atoms. Or an unsubstituted aryl group, wherein R ²⁵¹ and R ²⁵² may combine with each other to form a ring.

(Wherein, R ²⁵³ , R ²⁵⁴ , R ²⁵⁵ and R ²⁵⁶ may be the same or different and represent an alkyl group having 1 to 6 carbon atoms.)

Further preferred compounds are nitrogen-containing cyclic compounds (also called cyclic amine compounds) or nitrogen-containing basic compounds having two or more nitrogen atoms of different chemical environments in one molecule.

As a cyclic amine compound, it is more preferable that it is polycyclic structure. Preferable specific examples of the cyclic amine compound include compounds represented by the following general formula (F).

In formula (F), Y and Z respectively independently represent the linear, branched, and cyclic alkylene group which may contain the hetero atom and may be substituted.

Here, the hetero atom includes a nitrogen atom, a sulfur atom and an oxygen atom. As an alkylene group, C2-C10 is preferable, More preferably, it is a 2-5 thing. As a substituent of an alkylene group, a halogen atom and a halogen substituted alkyl group are mentioned besides a C1-C6 alkyl group, an aryl group, and an alkenyl group. Moreover, the compound shown below is mentioned as a specific example of a compound represented by general formula (F).

Among the above, 1,8- diazabicyclo [5.4.0] undeca-7-ene and 1, 5- diazabicyclo [4.3.0] nona-5-ene are especially preferable.

As the nitrogen-containing basic compound having two or more nitrogen atoms in different chemical environments in one molecule, particularly preferably, a compound or an alkylamino group including both of a substituted or unsubstituted amino group and a ring structure containing nitrogen atoms It is a compound having. Preferred embodiments 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 aminomorpholine, substituted or unsubstituted aminoalkylmorpholine, and the like. 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 and cyano group.

Particularly preferred compounds include guanidine, 1,1-dimethylguanidine, 1,1,3,3-tetramethylguanidine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethyl Aminopyridine, 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, trimethylimidazole, triphenylimidazole, methyldiphenylimidazole and the like are listed, but are not limited thereto.

These nitrogen-containing basic compounds are used alone or in combination of two or more thereof. The usage-amount of a nitrogen-containing basic compound is 0.001-10 weight part normally, Preferably it is 0.01-5 weight part with respect to 100 weight part of photosensitive resin compositions (excluding a solvent). If it is less than 0.001 weight part, the said effect cannot be acquired. On the other hand, when it exceeds 10 weight part, there exists a tendency for the fall of a sensitivity and the developability of a non-exposed part to deteriorate.

The chemically amplified positive resist composition of the present invention may further contain a compound having two or more phenolic OH groups that promote solubility in surfactants, dyes, pigments, plasticizers, photosensitizers, and developing solutions, if necessary. .

It is preferable to contain surfactant in the photosensitive resin composition of this invention. Specifically, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether, polyoxyethylene nonyl Polyoxyethylene alkyl allyl ethers such as phenol ethers, polyoxyethylene polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan tree Sorbitan fatty acid esters such as oleate and sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan triol Polyoxyethylene sorbitan fatty acid esters such as latex and polyoxyethylene sorbitan tristearate Nonionic surfactants such as leu, Eftop EF301, EF303, EF352 (manufactured by Shin-Akita Kasei Co., Ltd.), Megapack F171, F173, F176, F189, R08 (Dainippon Ink Co., Ltd.) Products), Florade FC430, FC431 (manufactured by Sumitomo 3M, Inc.), Asahiguide AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd.) Fluorine-based surfactants such as fluorine-based surfactants, and organosiloxane polymers KP431 (manufactured by Shin-Etsukagaku Kogyo Co., Ltd.) and acrylic or methacrylic acid-based (poly) polymerized polyflours No. 75 and No. 95 High School Co., Ltd. product, Troisol S-366 (Troy Chemical Co., Ltd. product), etc. are mentioned.

Among these surfactants, fluorine-based or silicone-based surfactants are preferable in view of applicability and development defect reduction.

The compounding quantity of surfactant is 0.01 weight%-2 weight% normally with respect to the total composition solid content in the composition of this invention, Preferably they are 0.01 weight%-1 weight%.

These surfactant can be used individually by 1 type or in combination of 2 or more types.

In addition, by adding a spectroscopic sensitizer as exemplified below, the chemically amplified positive resist of the present invention can be made sensitive to i or g-rays by increasing or decreasing the photoacid generator to be used in a longer wavelength region than in the outside which does not have absorption. Can be. Specific examples of the preferred spectroscopic sensitizer include benzophenone, p, p'-tetramethyldiaminobenzophenone, p, p'-tetraethylethylaminobenzophenone, 2-chlorothioxanthone, anthrone and 9- Ethoxyanthracene, anthracene, pyrene, perylene, phenothiazine, benzyl, acridine orange, benzoprabin, cetopravin-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-naphthyl Amines, picclamids, anthraquinones, 2-ethylanthraquinones, 2-tert-butylanthraquinones, 1,2-benzanthraquinones, 3-methyl-1,3-diaza-1,9-benzanthrones, Dibenzalacetone, 1,2-naphthoquinone, 3,3'-carbonyl-bis (5,7-dimethoxycarbonylcoumarin), coronene, and the like, but are not limited thereto.

Examples of the compound having two or more phenolic OH groups which promote solubility in a developer include polyhydroxy compounds. Preferably, the polyhydroxy compounds include phenols, resorcin, phloroglucin, phlorogluside, and the like. , 3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, α, α ', α "-tris (4-hydroxyphenyl) -1,3,5-tri Isopropylbenzene, 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 dissolved in a solvent for dissolving each of the above components and applied onto a support. Examples of the solvent that can be used include ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, γ-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene , Ethyl acetate, methyl lactate, ethyl lactate, methyl methoxy propionate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N, N-dimethylformamide, dimethyl sulfoxide, N-methyl Pyrrolidone, tetrahydrofuran, etc. are preferable, and these solvent is used individually or in mixture.

The chemically amplified positive resist composition is coated on a substrate (e.g., silicon / silicon dioxide coating) as used in the manufacture of precision integrated circuit devices by a suitable coating method such as a spinner, a coater, and then a predetermined mask. By exposing through light and baking to develop, a good resist pattern can be formed.

As a developing solution of the chemically amplified positive resist composition of the present invention, for example, inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium phosphate, sodium metasilicate and aqueous ammonia, ethylamine, n-propylamine and the like Second amines such as amines, diethylamine and di-n-butylamine, third amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, formamide and acetamide Amides, tetramethylammonium hydroxide, trimethyl (2-hydroxyethyl) ammonium hydroxide, tetraethylammonium hydroxide, tributylmethylammonium hydroxide, tetraethanolammonium hydroxide, methyltriethanolammonium hydroxide Seed, benzyl methyl diethanol ammonium hydroxide, benzyl dimethyl ethanol ammonium hydroxide, benzyl triethanol ammonium hydroxide, tetra Ropil ammonium hydroxide is an aqueous solution, such as alkali hydroxide such as tetrabutylammonium hydroxide, etc. of quaternary ammonium salts, pyrrole, piperidine and so on of the cyclic amine.

Hereinafter, although this invention demonstrates more concretely, this invention is not limited to these.

(Resin, Acid Generator, Organic Base, Surfactant Used in Examples)

The synthesis of the resin of the present invention can be synthesized using either a method of using vinyl ether or acetal exchange using alcohol and alkyl vinyl ether for acetalization.

Synthesis Example I-1 Synthesis of Vinyl Ether

Ethyl vinyl ether was mixed in phenethyl alcohol, mercury acetate was added thereto, and the mixture was stirred at room temperature for 12 hours. After extraction with ethyl acetate and water and washing with water, distillation under reduced pressure afforded phenethyl vinyl ether (X-1).

Synthesis Example I-2 Synthesis of Vinyl Ether

Ethyl vinyl ether was mixed in phenethyl alcohol, and the paradium-1,10 phenanthroline complex was mixed there, and it stirred at room temperature for 20 hours. After extraction with ethyl acetate and water and washing with water, distillation under reduced pressure afforded phenethyl vinyl ether (X-1).

Synthesis Example I-3 Synthesis of Vinyl Ether

2-Chloroethyl vinyl ether was added to THF solution of phenylmagnesium bromide or phenyl lithium and heated and refluxed for 16 hours. After extraction with ethyl acetate and water and washing with water, distillation under reduced pressure afforded phenethyl vinyl ether (X-1).

Synthesis Example I-4-10

The method similar to the synthesis example I-1 was selected suitably, and the vinyl ether of X-2 to X-6 was obtained, respectively.

Synthesis Example II-1

32.4 g (0.2 mol) of p-acetoxystyrene was dissolved in 120 ml of butyl acetate, and 0.033 g of azobisisobutylonitrile (AIBN) was added three times at 2.5 hour intervals at 80 ° C. under nitrogen stream and stirring. The polymerization reaction was carried out by continuing stirring for 5 hours. The reaction solution was poured into 1200 ml of hexane to precipitate white resin. The obtained resin was dried and then dissolved in 150 ml of methanol. An aqueous solution of 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 thereto to dilute, neutralized with hydrochloric acid to precipitate a white resin. The resin was filtered, washed with water and dried. Furthermore, it was dissolved in 200 ml of tetrahydrofuran, and dripped and reprecipitation was carried out in 5 L of ultrapure water with vigorous stirring. This reprecipitation operation was repeated three times. The obtained resin was dried in a vacuum dryer at 120 ° C. for 12 hours to obtain poly (p-hydroxystyrene) alkali-soluble resin R-1.

The weight average molecular weight of obtained resin was 15000.

Synthesis Example II-2

Based on the general method, 35.2 g (0.2 mol) of p-tert-butoxystyrene monomers dehydrated and distilled and 5.21 g (0.05 mol) of t-Bu styrene monomers were dissolved in 100 ml of tetrahydrofuran. 0.033 g of azobisisobutyronitrile (AIBN) was added three times at an interval of 2.5 hours at 80 ° C under nitrogen stream and stirring, and finally, the polymerization reaction was carried out by continuing stirring for 5 hours. The reaction solution was poured into 1200 ml of hexane to precipitate white resin. The obtained resin was dried and then dissolved in 150 ml of tetrahydrofuran.

4N hydrochloric acid was added thereto, hydrolyzed by heating under reflux for 6 hours, and then reprecipitated in 5 L of ultrapure water, and the resin was filtered and washed with water and dried. The solution was further dissolved in 200 ml of tetrahydrofuran and dripped in 5 L of ultrapure water with vigorous stirring, followed by reprecipitation. 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 / t-butylstyrene) copolymer alkali-soluble resin R-2.

The weight average molecular weight of obtained resin was 12000.

Synthesis Example II-3

Nippon Sodatsu Co., Ltd. product, poly (p-hydroxy styrene) (VP8000) was made into alkali-soluble resin R-3. The weight average molecular weight was 9800.

Synthesis Example III-1

20 g of alkali-soluble resin R-3 obtained in Synthesis Example II-3

Propylene Glycol Monomethyl Ether Acetate (PGMEA) 80ml

Was dissolved in a flask, distilled under reduced pressure, and azeotropic distillation of water and PGMEA.

After confirming that the moisture content was sufficiently low, 7.0 g of vinyl ether X-1 obtained in Synthesis Example I-1 and 50 mg of p-toluenesulfonic acid were added thereto, stirred at room temperature for 1 hour, and triethylamine was added to carry out the reaction. Finished.

Ethyl acetate was added to the reaction solution, and the mixture was washed with water, and then distilled off ethyl acetate, water and azeotrope PGMEA by distillation under reduced pressure to obtain an alkali-soluble resin B-1 having a substituent according to the present invention. . The weight average molecular weight of obtained resin was 11000.

Synthesis Example III-2

20 g of alkali-soluble resin R-3 obtained in Synthesis Example II-3

Propylene Glycol Monomethyl Ether Acetate (PGMEA) 80ml

Was dissolved in a flask, distilled under reduced pressure, and azeotropic distillation of water and PGMEA.

After confirming that the water content was sufficiently low, 7.0 g of phenethyl alcohol, 6.5 g of t-butyl vinyl ether, and 50 mg of p-toluenesulfonic acid were added, stirred at room temperature for 1 hour, and triethylamine was added to terminate the reaction. It was.

Ethyl acetate was added to the reaction solution, and the mixture was washed with water, followed by distillation to remove PGMEA of ethyl acetate and water azeotrope by distillation under reduced pressure to obtain an alkali-soluble resin B-1 having a substituent according to the present invention. The weight average molecular weight of obtained resin was 11000.

In the same manner, resins B-2 to B-12 having a substituent according to the present invention were obtained using alkali-soluble resins and vinyl ethers shown in Table 1 below. In the same manner, alkali-soluble resins and vinyl ethers shown in Table 1 were used to synthesize the above resins, and 1.5 g of pyridine and 1.5 g of acetic anhydride were added thereto, followed by stirring at room temperature for 1 hour. Alkali-soluble resins B-13 to B-24 having a substituent related thereto were obtained.

Moreover, even using the acetal exchange method mentioned above, B-2-B-24 were similarly obtained from the corresponding alcohol and t-butyl vinyl ether.

Synthesis Example IV-1

Resin C-1 was obtained using alkali-soluble resin shown in following Table 2 and ethyl vinyl ether (Y-1) represented by a following formula.

Suzy Used vinyl ether Gun polymer C-1 Y-1 R-3

As resin C-2, poly (p-1-benzyloxy-1-methylethoxystyrene / p-hydroxystyrene / p-tert-butoxystyrene) described in JP-A-8-123032 was used. Used.

Synthesis Example V-1 (Synthesis of D-1)

19.9 g of mixture aqueous solution of commercially available triarylsulfonium Cl salt (50% aqueous solution of triphenylsulfonium chloride made by Fluka), triphenylsulfonium, and 4,4'-bis (diphenylsulfonio) diphenylsulphide (0.030 mol) was dissolved in 200 ml of ion-exchanged water. To this solution, a 400 mL solution of 10.5 g (0.030 mol) of Na salt of hard-type (branched) dodecylbenzenesulfonic acid having the following structure was added under stirring at room temperature.

The precipitated viscous solid was separated by decanter and washed with 1 L of ion-exchanged water.

The obtained viscous solid was dissolved in 100 ml of acetone, and poured into 500 ml of ion-exchanged water under stirring to recrystallize it. The precipitate was dried under vacuum at 50 ° C. to give 15.5 g of a glassy solid. NMR measurement confirmed that this solid was an acid generator (D-1) as the target product.

Synthesis Example V-2 (Synthesis of D-2)

68 g (0.174 mol) of triphenylsulfonium iodine and 42.5 g (0.183 mol) of silver oxide were dissolved in 500 ml of methanol, and the mixture was stirred at room temperature for 5 hours. Insoluble content was filtered, 59.4 g (0.209 mol) of triisopropylbenzenesulfonic acid were added, and it stirred at room temperature for 3 hours, concentrated, it was made into powder, and it was wash | cleaned with water. The obtained powder was recrystallized from ethyl acetate / acetone = 6/4 to obtain 50 g of an acid generator (D-2) as a target product. The structure was confirmed by NMR.

Synthesis Example V-3 (Synthesis of D-3)

7 g of phosphorus pentoxide and 70 g of methanesulfonic acid were stirred and mixed to dissolve and stirred at room temperature. 25 g (0.124 mol) of diphenyl sulfoxide and 20.4 g (0.136 mol) of n-butoxybenzene were added and stirred, and it stirred at 50 degreeC for 4 hours. The obtained reaction solution was poured into 500 ml of ice water, washed twice with 150 ml of toluene, and weakly alkaline with tetramethylammonium hydroxide to obtain an aqueous solution of butoxyphenyldiphenylsulfonium methanesulfonate.

After adding and stirring 1000 ml of ethyl acetate to this, the solution which added butanol to 26 g (0.14 mol) of 2-sulfobenzoic acid cyclic anhydrides was added and stirred. The solution was separated into an organic phase and an aqueous phase, washed twice with 500 ml of 10% aqueous tetramethylammonium hydroxide solution, washed three times with water, and the organic phase was dried and concentrated to obtain an acid generator (D-3) as a target product. .

Synthesis Example V-4 (Synthesis of D-4)

1) Synthesis of Pentafluorobenzenesulfonic Acid Tetramethylammonium Salt

25 g of pentafluorobenzenesulfonyl chloride was dissolved in 100 ml of methanol under ice cooling, and 100 g of 25% tetramethylammonium hydroxide aqueous solution was slowly added thereto. After stirring for 3 hours at room temperature, a solution of pentafluorobenzenesulfonic acid tetramethylammonium salt was obtained. This solution was used for salt exchange with sulfonium salts and iodonium salts.

2) Synthesis of Di (4-t-amylphenyl) iodoniumpentafluorobenzenesulfonate (D-4)

60 g of t-amylbenzene, 39.5 g of potassium iodide, 81 g of acetic anhydride, and 170 ml of dichloromethane were mixed, and 66.8 g of concentrated sulfuric acid was slowly added dropwise thereto under ice-cooling. After stirring for 2 hours under ice cooling, the mixture was stirred at room temperature for 10 hours. 500 ml of water was added to the reaction liquid under ice cooling, and this was extracted with dichloromethane, the organic phase was washed with sodium bicarbonate and water, and then concentrated to give di (4-t-amylphenyl) iodium sulfate. This sulfate was added to the solution of excess pentafluorobenzenesulfonic acid tetramethylammonium salt. 500 ml of water was added to the solution, which was extracted with dichloromethane, the organic phase was washed with 5% aqueous tetramethylammonium hydroxide solution, and washed with water and concentrated to give di (4-t-amylphenyl) iodiumpentafluorobenzene. Sulfonate (D-4) was obtained.

Synthesis Example V-5 (Synthesis of D-5)

50 g of diphenyl sulfoxide was dissolved in 800 ml of benzene, and 200 g of aluminum chloride was added thereto, and the mixture was refluxed for 24 hours. The reaction solution was slowly poured into 2 L of ice water, and 400 ml of concentrated hydrochloric acid was added thereto, followed by heating at 70 ° C. for 10 minutes. This aqueous solution was washed with 500 ml of ethyl acetate and filtered, and then 200 g of ammonium iodide dissolved in 400 ml of water was added. The precipitated powder was collected by filtration, washed with water, washed with ethyl acetate and dried to obtain 70 g of triphenylsulfonium iodine.

30.5 g of triphenylsulfonium iodine was dissolved in 1000 ml of methanol, 19.1 g of silver oxide was added to the solution, and the mixture was stirred at room temperature for 4 hours. The solution was filtered and an excess solution of pentafluorobenzenesulfonic acid tetramethylammonium salt was added thereto. The reaction solution was concentrated and dissolved in 500 ml of dichloromethane, and the solution was washed with 5% aqueous tetramethylammonium hydroxide solution and water. The organic phase was dried over anhydrous sodium sulfate, and then concentrated to give triphenylsulfonium pentafluorobenzenesulfonate (D-5).

Synthesis Example V-6 (Synthesis of D-6)

50 g of triarylsulfonium chloride (50% aqueous solution of triphenylsulfonium chloride made by Fluka) was dissolved in 500 ml of water, and when an excess solution of pentafluorobenzenesulfonate tetramethylammonium salt was added thereto, an oily substance was precipitated. come. What floated above was decanted and the oily substance obtained was wash | cleaned and dried with water, and triarylsulfonium pentafluorobenzenesulfonate (D-6) was obtained.

As the acid generator D-7, 1-diazo-1-methylsulfonyl-4-phenylbutan-2-one described in JP-A-8-123032 was used.

As the organic base, (E-1), (E-2) and (E-3) having the following structures were used.

As the surfactant (F-1), Mechapack R08 (manufactured by Dainippon Ink, Inc.) was used.

As the surfactant (F-2), Troisol S-366 (manufactured by Troy Chemical Co., Ltd.) was used.

(Examples 1-22, Comparative Examples 1-3)

[Preparation and Evaluation of Photosensitive Composition]

Each material shown in Table 3 below was dissolved in 8 g of PGMEA (propylene glycol monomethyl ether acetate), and filtered through a 0.2 µm filter to prepare a resist solution. In addition, the usage-amount of surfactant was 0.0035g.

This resist solution was applied onto a silicon wafer using a spin coater, dried at 130 ° C. for 60 seconds in a vacuum suction hot plate to obtain a resist film having a thickness of 0.3 μm.

In Table 3, the ratios of D-2 / D-3, D-2 / D-4, D-2 / D-6, D-2 / D-5, and D-4 / D-5 are all 50: It was 50.

The use ratio of F-2 / F-1 of Examples 17 and 18 was 50:50.

The use ratio of E-2 / E-3 of Examples 19 and 20 was 60:40. The use ratio of E-1 / E-2 of Example 22 was 50:50.

These usage rates are the same also in Table 5.

This resist film was irradiated using an electron beam irradiation apparatus (acceleration voltage 50 KeV). After irradiation, heating was carried out for 60 seconds on a 100 ° C. hot plate, immediately immersed for 60 seconds in an aqueous 0.26N tetramethylammonium hydroxide (TMAH) solution, rinsed with water for 30 seconds, and dried. The pattern on the silicon wafer thus obtained was observed with a scanning electron microscope to evaluate the performance of the resist. The results are shown in Table 4.

The resolution represents the limit resolution at the exposure amount for reproducing the mask pattern of the line and space of 0.15 mu m.

The obtained resist pattern was observed with an optical microscope or SEM to observe the degree of inverse taper of the resist pattern. (Circle) and the thing of (circle rectangular profile) which the degree of inclination of the reverse taper of a pattern is very small (circle), and the thing where (circle) and the reverse taper of a pattern were observed clearly were made into x.

The resist film obtained as described above was left to stand for 240 minutes under high vacuum in an electron beam irradiation apparatus, and then exposed and developed as described above to form a resist pattern. As described above, the marginal resolution line width (A) of the pattern obtained by leaving it under high vacuum for 240 minutes and the marginal resolution line width (B) of the pattern obtained without leaving it under high vacuum were measured, and the variation rate was calculated as follows. The smaller the value is, the better.

Change rate = {1- | (B)-(A) | / (B)} × 100

As apparent from the results in Table 4, the positive electron beam resist compositions of the Examples of the present invention had satisfactory results, but the electron beam resist compositions of the Comparative Examples were particularly affected by the line width variation caused by the resist pattern shape and the standing time. I was dissatisfied with it.

(Examples 23-56, Comparative Examples 4-6)

As shown in Table 5 below, a resist solution was prepared in the same manner as in Examples 1 to 22, except that resins of the structural units represented by the general formulas (I), (II) and (III) were prepared. A resist film was obtained.

Table 6 shows the results of evaluation of the line width fluctuation due to the resolution, the resist pattern profile, and the standing in the vacuum chamber in the same manner as in Examples 1 to 22.

As is apparent from the results in Table 6, the positive electron beam resist composition of each embodiment according to the present invention is further improved in particular with respect to line width fluctuations caused by standing in a resist pattern profile and a vacuum chamber, respectively, to obtain satisfactory results. Although the electron beam resist composition of each comparative example was obtained, it was especially unsatisfactory about the line width fluctuation by leaving in a resist pattern profile and a vacuum chamber.

According to the present invention, there is provided a chemically amplified positive electron beam resist composition having improved line width fluctuation caused by standing in a resist pattern profile and a vacuum chamber.

Claims (7)

(a) a resin having a structural unit containing a group represented by the following general formula (X) and decomposed by the action of an acid to increase its solubility in an alkali developer; and (b) A positive electron beam resist composition comprising a compound that generates an acid by irradiation with an electron beam. (In general formula (X), R <1>, R <2> may be same or different, and may represent a hydrogen atom and a C1-C4 alkyl group, R <3>, R <4> may be same or different, and may have a hydrogen atom and a substituent, Branched, cyclic alkyl group, R5 represents a straight chain which may have a substituent, branched, cyclic alkyl group, an aryl group which may have a substituent, and an aralkyl group which may have a substituent. An integer, and n represents an integer of 0 to 5.) (a) a resin having structural units represented by the following general formulas (I), (II) and (III), decomposed by the action of an acid and increasing solubility in an alkali developer; and (b) A positive electron beam resist composition comprising a compound that generates an acid by irradiation with an electron beam. (In formulas (I) to (III), R21 represents a hydrogen atom or a methyl group, R22 represents a group which is not decomposed by the action of an acid, and R23 represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or an alkoxy group. And an acyl group or an acyloxy group, n represents an integer of 1 to 3. W represents a group represented by the general formula (X).) The positive electron beam resist composition according to claim 2, wherein the ratio of the structural units represented by the following general formulas (I), (II) and (III) satisfies the following conditions (1) to (4). ① 0.10 <(I) / (I) + (II) + (III) <0.25 ② 0.01 <(II) / (I) + (II) + (III) <0.15 ③ (I)> (II) ④ 0.5 <(I) / (I) + (II) <0.85 (In formula, (I), (II), and (III) represent the mole fraction of the structural unit represented by general formula (I), general formula (II), and general formula (III), respectively.) The compound according to any one of claims 1 to 3, wherein the compound (b) which generates an acid by irradiation with an electron beam generates sulfonic acid by irradiation with an electron beam (A-1), (A). The positive electron beam resist composition characterized by at least one of the compounds represented by -2), (A-3), (A-4), (A-5), (A-6) and (A-7). In Formulas (A-1) and (A-2), R ₁ to R ₅ may be the same or different and represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a hydroxy group, a halogen atom, or a -SR ₆ group. R ₆ represents an alkyl group or an aryl group X ⁻ has at least one group selected from the group of branched or cyclic alkyl groups having 8 or more carbon atoms and alkoxy groups, or linear, branched or cyclic carbon atoms 4-7. Two or more groups selected from the group of alkyl groups and alkoxy groups, or three or more groups selected from the group of linear or branched C1-C3 alkyl groups and alkoxy groups, or 1 to 5 halogens Anion of benzenesulfonic acid, naphthalenesulfonic acid or anthracenesulfonic acid having an atom or having a linear or branched ester group having 1 to 10 carbon atoms.) (In formula (A-3), R <_7> -R <_10> may be same or different and shows a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a hydroxyl group, or a halogen atom, respectively. X <^-> is the same as said. M , n, p and q each represent an integer of 1 to 3.) (Formula (A-4) of, R ₁₁ ~R ₁₃ may be the same or different, represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a hydroxy group, a halogen atom or a -SR ₆ R _6, X ^-. And is the L, m and n may be the same or different and represent an integer of 1 to 3. When l, m and n are each 2 or 3, each of 2 to 3 R ₁₁ to R ₁₃ You may combine with each other and form the ring which consists of 5-8 elements containing a carbocyclic ring, a heterocyclic ring, or an aromatic ring.) (Formula (A-5) of, R ₁₄ ~R ₁₆ may be the same or different, represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a hydroxy group, a halogen atom or a -SR ₆ R _6, X ^-. And is the L, m and n may be the same or different and represent an integer of 1 to 3. When l, m and n are each 2 or 3, each of 2 to 3 R ₁₄ to R ₁₆ You may combine with each other and form the ring which consists of 5-8 elements containing a carbocyclic ring, a heterocyclic ring, or an aromatic ring.) (In formula (A-6), Y is a linear, branched, cyclic alkyl group which may have a substituent, an aralkyl group which may be substituted, (R ₃₁ to R ₅₁ may be the same or different and represent a hydrogen atom, a straight chain, branched, cyclic alkyl group which may have a substituent, an alkoxy group, an acyl group, an acylamino group, a sulfonylamino group, an aryl group, An acyloxy group, an aralkyl group or an alkoxycarbonyl group, or a formyl group, a nitro group, a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, or a cyano group, and R ₃₁ to R ₃₅ , R ₃₆ to R ₄₂ and R ₄₃ to R Or ₅₁ in each group may combine to form a 5- to 8-membered ring composed of carbon atoms and / or heteroatoms). In addition, Y may be bonded with the residue of another imide sulfonate compound. X may be a linear, branched alkylene group which may have a substituent, a monocyclic or polycyclic cyclic alkylene group which may have a substituent or may contain a hetero atom, a linear, branched alkenylene group which may be substituted, or may be substituted. The monocyclic or polycyclic cyclic alkenylene group which may contain the atom, the arylene group which may be substituted, and the aralkylene group which may be substituted are shown. X may be bonded to another imidesulfonate residue.) Ar _One -SO ₂ -SO ₂ -Ar ₂ (A-7) (In Formula (A-7), Ar ₁ and Ar ₂ may be the same or different and represent a substituted or unsubstituted aryl group.) The positive electron beam resist composition according to any one of claims 1 to 4, further comprising a cyclic amine compound. The positive electron beam resist composition according to any one of claims 1 to 5, further comprising a fluorine-based surfactant or a silicone-based surfactant or both thereof. The positive electron beam resist composition according to any one of claims 1 to 6, further comprising a compound which is decomposed by the action of an acid to increase its solubility in an alkaline developing solution.