JP2000267282A - Positive photosensitive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a positive photosensitive compsn. which has high resolution and high sensitivity, which hardly produces a rough surface state, which has high dry etching durability and which gives an excellent resist pattern having a good squareness property of the profile by using a ternary resin having a specified structure and a specified compd. which produces an acid. SOLUTION: This compsn. contains (a) at least one kind of compd. expressed by formula I, II or the like which produces sulfonic acid by irradiation of active rays or radiation and (b) a resin which contains recurring units or the like expressed by formulae III and IV and which decomposes by the effect of an acid to increase solubility in an alkali developer. In formulae I, II, each of R1 to R5 may be same as or different from others, and is a hydrogen atom, alkyl group or the like, X is a specified anion of benzene sulfonic acid, naphthalene sulfonic acid or anthracene sulfonic acid, in formulae III, IV, R21 is a hydrogen atom or methyl group, R24 is a hydrogen atom, halogen atom or the like,(n)is an integer 1 to 3, each of R'1 and R'2 is a hydrogen atom or alkyl group, W is a divalent org. group, and R'3 is a chain alkyl group, cyclic alkyl group or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a lithographic printing plate or an IC.
The present invention relates to a positive photosensitive composition used in a semiconductor manufacturing process such as the above, a circuit substrate such as a liquid crystal and a thermal head, and other photofabrication processes.

[0002]

2. Description of the Related Art Positive photoresist compositions include:
There is a chemically amplified resist composition described in U.S. Pat. No. 4,491,628 and European Patent No. 249,139. The chemically amplified positive resist composition generates an acid in the exposed portion by irradiation with radiation such as far ultraviolet light, and the reaction using the acid as a catalyst dissolves the active radiation-irradiated portion and the non-irradiated portion in the developing solution. This is a pattern forming material that changes the properties and forms a pattern on a substrate.

The above-mentioned positive chemically amplified resist comprises three components comprising an alkali-soluble resin, a compound capable of generating an acid upon exposure to radiation (photoacid generator), and a compound inhibiting dissolution of the alkali-soluble resin having an acid-decomposable group. It can be roughly classified into a two-component system comprising a resin having a group which is decomposed by the reaction with an acid and becomes alkali-soluble and a photoacid generator. In these two-component or three-component positive chemically amplified resists, a resist pattern is obtained by heat treatment and development with an acid from a photoacid generator being exposed by exposure.

Here, as a resin having a group which is decomposed by reaction with an acid used in a positive chemically amplified resist as described above and becomes alkali-soluble, JP-A-8-123
No. 032 discloses a monomer containing an acetal group as an acid-decomposable group, hydroxystyrene, a halogen atom,
A ternary copolymer containing styrene having an alkyl group, an alkoxy group, or the like substituted on a benzene ring has been used.
However, even if this resin is used as an acid-decomposable group-containing resin in a positive chemically amplified resist, there is still room for improvement in resolution. In recent years, with higher integration of semiconductor devices, further improvement in resolution of positive chemically amplified resists has been desired.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a positive photosensitive film having a high resolution, a high sensitivity, a small surface roughness, a high dry etching resistance, and an excellent resist pattern having good rectangularity. It is to provide a composition.

[0006]

Means for Solving the Problems The inventors of the present invention have made intensive studies while paying attention to the above-mentioned characteristics, and as a result, the object of the present invention is to provide a positive type chemically amplified system with a ternary resin having a specific structure. It has been found that this can be achieved by using certain compounds that generate the following acids. That is, the present invention has the following configuration. (1) (a) The following general formulas (A-1), (A-2), which generate sulfonic acid upon irradiation with actinic rays or radiation;
(A-3), (A-4), (A-5), (A-6) and at least one of the compounds represented by (A-7), and (b) the following general formula (I) And a repeating structural unit represented by the general formula (II) or a repeating structural unit represented by the following general formulas (I), (II) and (III). A positive photosensitive composition comprising: a resin having an increased solubility in a developer.

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In the formulas (A-1) and (A-2), R _{1 to} R ₅
May be the same or different, a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a hydroxy group,
A halogen atom, or -S-R ₆ group. R ₆ represents an alkyl group or an aryl group. X ⁻ has at least one group selected from the group consisting of a branched or cyclic alkyl group and an alkoxy group having 8 or more carbon atoms, or has a linear or
A branched or cyclic alkyl group having 4 to 7 carbon atoms and at least two groups selected from the group of alkoxy groups, or a linear or branched alkyl group having 1 to 3 carbon atoms and It has at least three groups selected from the group of alkoxy groups, has 1 to 5 halogen atoms, or has a linear, branched or cyclic carbon number of 1 to
The anion of benzenesulfonic acid, naphthalenesulfonic acid or anthracenesulfonic acid having 10 ester groups is shown.

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In the formula (A-3), R _{7 to} R ₁₀ may be the same or different and represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a hydroxy group, or a halogen atom. X ⁻ has at least one group selected from the group consisting of a branched or cyclic alkyl group having 8 or more carbon atoms and an alkoxy group, or has 4 to 7 linear, branched or cyclic carbon atoms. Having at least two groups selected from the group of alkyl groups and alkoxy groups, or a group selected from the group of linear or branched alkyl groups and alkoxy groups having 1 to 3 carbon atoms. The anion of benzenesulfonic acid, naphthalenesulfonic acid or anthracenesulfonic acid having at least three is shown. m, n, p and q each represent an integer of 1 to 3.

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In the formula (A-4), R _{11 to} R ₁₃ 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 —S—R ₆ Represents a group. R ₆ and X ⁻ are as defined above. l, m and n may be the same or different;
Indicates an integer. when l, m and n are each 2 or 3, 2
To three two are bonded to each other in each of R ₁₁ to R _13, they may form a ring consisting of five to eight elements including carbocyclic, heterocyclic or aromatic ring.

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In the formula (A-5), R _{14 to} R ₁₆ may be the same or different and each represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a hydroxy group, a halogen atom, or —S—R ₆ Represents a group. R ₆ and X ⁻ are as defined above. l, m and n may be the same or different;
Indicates an integer. when l, m and n are each 2 or 3, 2
Two each of the to three R ₁₄ to R ₁₆ are bonded to each other, they may form a ring consisting of five to eight elements including carbocyclic, heterocyclic or aromatic ring.

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

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The group represented by the formula (R)₃₁~ R₅₁Are the same
And may have a hydrogen atom or a substituent.
Straight-chain, branched, cyclic alkyl, alkoxy,
Acyl group, acylamino group, sulfonylamino group, ant
Group, acyloxy group, aralkyl group or alkoxy
Sicarbonyl group, formyl group, nitro group, chlorine atom
Atom, bromine atom, iodine atom, hydroxyl group, or cyano group
And R₃₁~ R₃₅, R₃₆ ~ R₄₂And R₄₃~ R₅₁Is it
Two of each group are bonded to form carbon and / or hetero
And may form a 5- to 8-membered ring composed of atoms). Also,
Y is bonded to the residue of another imidosulfonate compound
You may. X represents a linear or branched group which may have a substituent;
Alkylene group, which may have a substituent and
A monocyclic or polycyclic alkylene group which may be substituted;
Optionally substituted straight-chain, branched alkenylene, substituted
Monocyclic or polycyclic, optionally containing heteroatoms
Cyclic alkenylene group, optionally substituted arylene
And an aralkylene group which may be substituted. Ma
In addition, even if X is bonded to another imidosulfonate residue,
Good. Ar₁-SO_Two-SO_Two-Ar_Two (A-7) In the formula (A-7), Ar₁, Ar_TwoAre the same but different
And represents a substituted or unsubstituted aryl group.

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In the formulas (I) to (III), R ₂₁ represents a hydrogen atom or a methyl group, R ₂₃ represents a group which is not decomposed by the action of an acid, and R ₂₄ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group. Represents a group, an alkoxy group, an acyl group or an acyloxy group. n represents an integer of 1 to 3. In the formula (II), R ′ ₁ ,
R ′ ₂ may be the same or different and represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, W represents a divalent organic group, and R ′ ₃ represents a total of 1 to 20 carbon atoms. A chain alkyl group which may have a substituent, a cyclic alkyl group which may have a substituent having 3 to 20 carbon atoms in total, an aryl group which may have a substituent having 6 to 30 carbon atoms in total, Or an aralkyl group which may have a substituent having 7 to 30 carbon atoms in total. (2) In the formula (II), R ′ ₃ is a chain alkyl group which may have a substituent having 11 to 20 carbon atoms in total, and a cyclic group which may have a substituent having 11 to 20 carbon atoms in total. An alkyl group, an aryl group which may have a substituent having a total of 11 to 30 carbon atoms, or a total of 12 to 3 carbon atoms
The positive photosensitive composition according to the above (1), which represents an aralkyl group optionally having 0 substituents. (3) the formula R _'3 are also good chain alkyl group having a total substitution group having a carbon number of 11 to 18 of (II), carbon atoms in total 11-1
Cyclic alkyl group optionally having 8 substituents, total carbon number 1
(1) or (2), which represents an aryl group optionally having 1 to 25 substituents or an aralkyl group optionally having 12 to 25 carbon atoms. Positive photosensitive composition. (4) having a group decomposable by an acid, and having a molecular weight of 3,000, in which the solubility in an alkali developer is increased by the action of an acid.
The positive photosensitive composition according to any one of the above (1) to (3), comprising the following low-molecular acid-decomposable dissolution inhibiting compound.

As described above, by using the compound having the specific structure and the resin having the specific three types of repeating units as the photoacid generator, a superbly high resolving power can be obtained in a chemically amplified resist. And high light sensitivity,
An excellent resist pattern having high rectangularity was obtained.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the compounds used in the present invention will be described in detail. (A) Photoacid Generator Photoacid Generators Represented by General Formulas (A-1) to (A-3) R _{1 to} R in the General Formulas (A-1) to (A-3)
The alkyl group of ₆ and R _{7 to} R ₁₀ may have a substituent and may have a carbon number such as a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group and a t-butyl group. 1-4 are mentioned. 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 those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group and a t-butoxy group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an 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, a tolyl group, a methoxyphenyl group and a naphthyl group.

The substituent is preferably an alkoxy group having 1 to 4 carbon atoms, a halogen atom (a fluorine atom, a chlorine atom or an iodine atom), an aryl group having 6 to 10 carbon atoms, or an alkenyl having 2 to 6 carbon atoms. Group, cyano group, hydroxy group,
Examples thereof include a carboxy group, an alkoxycarbonyl group, and a nitro group. General formulas (A-1) to used in the present invention
The sulfonium or iodonium compound represented by (A-3) has at least one or more branched or cyclic, preferably 8 or more, preferably 10 or more alkyl or alkoxy groups as a counter anion, X ^−. Or at least two or more linear, branched or cyclic alkyl or alkoxy groups having 4 to 7 carbon atoms, or linear or branched alkyl groups or alkoxy groups having 1 to 3 carbon atoms Benzenesulfonic acid, naphthalenesulfonic acid or anthracenesulfonic acid having at least three groups, having 1 to 5 halogen atoms, or having a linear, branched or cyclic ester group having 1 to 10 carbon atoms Has an acid anion. This reduces the diffusivity of the acid (benzenesulfonic acid, naphthalenesulfonic acid or anthracenesulfonic acid having the above group) generated after exposure, and improves the solvent solubility of the sulfonium or iodonium compound. In particular, from the viewpoint of reducing diffusivity, a branched or cyclic alkyl group, alkoxy group, or ester group is more preferable as the above group than a linear alkyl group or alkoxy group. Further, those having a halogen atom are also preferable. When the number of the above groups is one, the difference in diffusivity between a straight chain and a branched or cyclic one becomes more remarkable.

C8 or more, preferably C8 to C2
Examples of the zero alkyl group include a branched or cyclic octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group,
Examples include a tridecyl group, a tetradecyl group, and an octadecyl group. 8 or more carbon atoms, preferably 8 to 20 carbon atoms
As the alkoxy group, a branched or cyclic octyloxy group, a nonyloxy group, a decyloxy group, an undecyloxy group, a dodecyloxy group, a tridecyloxy group,
Examples include a tetradecyloxy group and an octadecyloxy group. Examples of the alkyl group having 4 to 7 carbon atoms include a linear, branched, or cyclic butyl group, a pentyl group, a hexyl group, and a heptyl group. 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, and a heptyloxy group. Examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. Examples of the alkoxy group having 1 to 3 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, and an isopropoxy group.

Further, X ^- in the aromatic sulfonic acid represented by, in addition to the above specific substituent, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), C6-10
It may contain as substituents aryl groups, cyano groups, sulfide groups, hydroxy groups, carboxy groups, nitro groups and the like.

Hereinafter, specific examples of these compounds (A-1)
-1) to (A-1-66), (A-2-1) to (A-2)
-59) and (A-3-1) to (A-3-35), but are not limited thereto.

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In the specific examples, n is linear, s is secondary, t
Represents tertiary and i represents branching. The general formula (A-
1) - (a compound represented by A-3), for example the corresponding Cl ^- salt (formula (A-1) X at ~ (A-3) ^- the Cl
^And a compound represented by X ^- Y ⁺ (X ^- has the same meaning as in formulas (A-1) to (A-3);
Y ⁺ is H ⁺ , Na ⁺ , K ⁺ , NH ₄ ⁺ , N (CH ₃ ) ₄ ⁺
And the like. ) Can be synthesized by salt exchange in an aqueous solution.

Photoacid generators represented by formulas (A-4) and (A-5) In formulas (A-4) and (A-5), R _{11 to} R ₁₃ ,
Specific examples of the alkyl group, cycloalkyl group, alkoxy group and halogen atom in R _{14 to} R ₁₆ are the same as those described above for R _{1 to} R ₅ . R ₆ , X
^- have the same meanings as described above.

When l, m, and n are each 2 or 3,
Two or two of each of R _{11 to} R ₁₃ or R _{14 to} R ₁₆ are bonded to each other to form a ring composed of 5 to 8 elements including a carbon ring, a heterocyclic ring or an aromatic ring May be.

Hereinafter, specific examples of the compound represented by the general formula (A-4) (A-4-1) to (A-4-28) and the compound represented by the general formula (A-5) Specific example (A-5-1)-
(A-5-30) is shown, but the invention is not limited to this.

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In the specific examples, n is linear, s is secondary, t
Represents tertiary and i represents branching. The general formula (A-
4) (a compound represented by A-5) may, for example, the corresponding Cl ^- salt (formula (A-4), X in (A-5) ^- a Cl
^- a compound) which was replaced by, X ^- Y ⁺ in the compound represented by (X ^- is the general formula (A-4), synonymous with the case of (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.

The photoacid generator represented by the general formula (A-6) The linear, branched or cyclic alkyl group of Y and R _{31 to} R _{51 in} the general formula (A-6) is a methyl group or an ethyl group. , A propyl group, an isopropyl group, a n-butyl group, a sec-butyl group, a t-butyl group, a hexyl group, a linear or branched alkyl group having 1 to 20 carbon atoms such as an octyl group and a cyclopropyl group, a cyclopentyl group Or a cyclic alkyl group such as a cyclohexyl group. Preferred substituents of the alkyl group include an alkoxy group, an acyl group, an acyloxy group, a chlorine atom, a bromine atom, an iodine atom and the like.

The aralkyl group for Y includes an aralkyl group having 7 to 12 carbon atoms 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 and 1 carbon atom.
And lower alkoxy groups, nitro groups, acetylamino groups, and halogen atoms.

The alkoxy groups represented by R _{31 to} R ₅₁ include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group,
n-butoxy group, isobutoxy group, sec-butoxy group, t-butoxy group, octyloxy group, alkoxy group having a substituent such as an alkoxy group having 1 to 20 carbon atoms such as dodecyloxy group or ethoxyethoxy group. No. Examples of the acyl group include an acetyl group, a propionyl group, and a benzoyl group. Examples of the acylamino group include an acetylamino group, a propionylamino group and a benzoylamino group. Examples of the sulfonylamino group include a substituted or unsubstituted benzenesulfonylamino group such as a methanesulfonylamino group, an ethanesulfonylamino group, a sulfonylamino group having 1 to 4 carbon atoms, and a p-toluenesulfonylamino group. Examples of the aryl group include a phenyl group, a tolyl group, and a naphthyl group. Examples of the alkoxycarbonyl group include an alkoxycarbonyl group having 2 to 20 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group, an ethoxyethoxycarbonyl group, an octyloxycarbonyl group, and a dodecyloxycarbonyl group.

Examples of the acyloxy group include an acyloxy group having 2 to 20 carbon atoms such as an acetoxy group, a propanoyloxy group, an octanoyloxy group and a benzoyloxy group. The aralkyl group has 7 to 15 carbon atoms such as a substituted or unsubstituted benzyl group and a substituted or unsubstituted phenethyl group.
Aralkyl groups. Preferred substituents on the aralkyl group are the same as those described above.

In R _{31 to} R ₅₁ , R _{31 to} R ₃₅ and R ₃₆
To R ₄₂ and R ₄₃ to R ₅₁ is two may be combined with each other to form a 5-8 membered ring consisting of carbon and / or hetero atoms of the each group. Examples of such a 5- to 8-membered ring include cyclohexane, pyridine, furan and pyrrolidine. X and Y may be bonded to a residue of another imide sulfonate compound, or may form a dimer or a trimer. As another imide sulfonate, a compound represented by the general formula (A-6) which is a monovalent group at X or Y can be mentioned.

Examples of the alkylene group represented by X include a linear or branched alkylene group having 1 to 10 carbon atoms or a monocyclic or polycyclic alkylene group which may contain a hetero atom. Examples of the linear or branched alkylene group include a methylene group, an ethylene group, a propylene group, and an octylene group. Preferred substituents on the alkylene group include 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. Here mentioned alkoxy group, an acyl group, a nitro group, an acylamino group, a sulfonylamino group, an aryl group, alkoxycarbonyl group have the same meanings as those mentioned in R ₃₁ to R _51. As the halogen atom, a fluorine atom, a chlorine atom, a bromine atom,
An iodine atom can be mentioned.

Examples of the cyclic alkylene group include a monocyclic cycloalkylene group having 4 to 8 carbon atoms such as a cyclopentylene group and a cyclohexylene group, and 7-oxabicyclo [2.2.1].
Examples include a polycyclic cycloalkylene group having 5 to 15 carbon atoms such as a 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, and a nitro group. Group, acylamino group, sulfonylamino group, halogen atom, aryl group,
An alkoxycarbonyl group. Here mentioned alkoxy group, an acyl group, a nitro group, an acylamino group, a sulfonylamino group, an aryl group, alkoxycarbonyl group have the same meanings as those mentioned in R ₃₁ to R _51. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of the arylene group include a phenylene group and a naphthylene group. Preferred substituents of the arylene group include an alkyl group, a cycloalkyl group, an alkoxy group, an acyl group, a formyl group, a nitro group, an acylamino group, a sulfonylamino group, a halogen atom, an aryl group,
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
₃₁ those mentioned to R ₅₁ is as defined above. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of the alkenylene group include alkenylene groups having 2 to 4 carbon atoms, such as an ethenylene group and a butenylene group. Preferred examples of the alkenylene group include an alkyl group, a cycloalkyl group, an alkoxy group and an acyl group. Group, formyl group, nitro group, acylamino group, sulfonylamino group, halogen atom, aryl group,
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
₃₁ those mentioned to R ₅₁ is as defined above. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. As the cyclic alkenylene group, a cyclopentenylene group, a cyclohexenylene group, etc.
And a polycyclic cycloalkenylene group having 5 to 15 carbon atoms, such as a monocyclic cycloalkenylene group of 8 to 8, a 7-oxabicyclo [2,2,1] heptenylene group and a norbornenylene group. Examples of the aralkylene group include a tolylene group and a xylylene group, and examples of the substituent include the substituents described for the arylene group. Hereinafter, specific examples of the compound represented by Formula (A-6) (A-
6-1) to (A-6-49), but the invention is not limited thereto.

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The compound represented by formula (A-6) is described in G.
28,360 (1895), DEAmes et al., J. Chem. Soc. 3518 (1955), or MAStol
berg et al., J. Am. Chem. Soc. 79, 2615 (1957), etc., using an N-hydroxyimide compound synthesized with a sulfonic acid chloride under basic conditions, for example, L. Bauer et al., J. Am. .
It can be synthesized according to the method of Org. Chem .. 24, 1294 (1959).

The photoacid generator represented by the general formula (A-7) In the general formula (A-7), Ar ₁ and Ar ₂ may be the same or different, and represent a substituted or unsubstituted aryl group. Show. Here, examples of the aryl group include a phenyl group, a tolyl group, and a naphthyl group. Examples of the substituent of the aryl group include an alkyl group, a cycloalkyl group, an alkoxy group, an acyl group, a formyl group, a nitro group, an acylamino group, a sulfonylamino group, a halogen atom, an aryl group,
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 mentioned above have the same meanings as those described above for R _{31 to} R _51. is there. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Specific examples of the photoacid generator represented by the general formula (A-7) include the following compound (A-7-
1) to (A-7-14), but are not limited thereto.

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The synthesis of the photoacid generator represented by the general formula (A-7) is described in G. C. Dencer. Junior.
"Journal of Organic Chemistry"
(GC Denser, Jr. et al., `` Journal of Organic Chemi
stry ") 31, 3418-3419 (1966). P. Hilditch, `` Journal of the Chemical Society '' (TP Hilditch, `` Journal of the C
Chemical Society ") 93, 1524-1527 (1908). Hinsberg, "Berichtedea Deutschen Hemisie Geserschaft" (O. Hinsberg
Author, "Berichteder Deutschen Chemischen Gesellschaf
t ") 49, 2593-2594 (1918). That is, in an aqueous sulfuric acid solution, a method of synthesizing from a sulfinic acid represented by the general formula (a) using cobalt sulfate, a method of synthesizing from a sulfonic acid chloride represented by the general formula (b) using ethyl xanthate, or Under basic conditions, a method of synthesizing the sulfinic acid represented by the general formula (a) and the sulfonic acid chloride represented by the general formula (b) can be exemplified. Ar ₁ —SO ₂ H (a) Ar ₂ —SO ₂ Cl (b) (where Ar ₁ and Ar ₂ have the same meaning as defined in formula (A-7).)

In the present invention, the above-mentioned general formula (A-1)
Of the photoacid generators represented by formulas (A) to (A-7),
-1) to a photoacid generator represented by (A-5) are preferred,
More preferred are photoacid generators represented by formulas (A-1) to (A-4). As a result, the resolution and sensitivity are further improved. The content of the compounds represented by formulas (A-1) to (A-7) in the composition is preferably from 0.1 to 20% by weight, more preferably from 0.1 to 20% by weight, based on the solid content of the whole composition. It is 5 to 10% by weight, more preferably 1 to 7% by weight.

(B) Formulas (I), (II) and (II)
A resin that contains a repeating unit having the structure represented by (I) and decomposes under the action of an acid to increase solubility in an alkaline developer.

R ₂₁ in the general formulas (I), (II) and (III) is a hydrogen atom or a methyl group.

In formula (II), examples of the alkyl group of R ′ ₁ and R ′ ₂ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group and a s.
Examples thereof include an alkyl group having 1 to 4 carbon atoms such as an ec-butyl group and a t-butyl group. The divalent organic group represented by W may preferably have a substituent, and may be a linear, branched or cyclic alkylene group, an arylene group, a heteroarylene group, an aralkylene group, and -S-, -C ( =
O) -, - N (R '4) -, - SO -, - SO 2 -, -
CO ₂ —, —N (R ′ ₄ ) SO ₂ —, or a divalent group obtained by combining two or more of these groups can be exemplified.
Here, R ′ ₄ can be a hydrogen atom or an alkyl group (specific examples of the alkyl group include the same as those described above for R ′ ₁ ).

The chain alkyl having 1 to 20 carbon atoms, preferably 11 to 20 carbon atoms, more preferably 11 to 18 carbon atoms of R ′ ₃ may be linear or branched. Well, for example, a methyl group, an ethyl group, an 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-nonadecyl group and the like.

[0102] The R _'3 of 3 to 20 carbon atoms, preferably 11 to 20 carbon atoms, more preferably a cyclic alkyl of 11 to 18 carbon atoms, up to 20 substituents, even when they form a ring with the carbon number May be a cyclic alkyl having, for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecanyl group, cycloundecyl group, cyclododecyl group, cyclotridecyl group,
Cyclotridecyl group, cyclotetradecyl group, cyclopentadecyl group, cyclohexadecyl group, cycloheptadecyl group, cyclooctadecyl group, cyclononadecyl group,
Examples thereof include a 4-cyclohexylcyclohexyl group, a 4-n-hexylcyclohexyl group, a pentanylcyclohexyl group, a hexyloxycyclohexyl group, and a pentanyloxycyclohexyl group. Substituted cyclic alkyl groups other than those listed here can also be used within the above range.

[0102] 6-30 carbon atoms in the R _'3, as is preferably 11 to 30 carbon atoms, more preferably an aryl group having 11 to 25 carbon atoms, e.g., phenyl, 4-methylphenyl, 3-methylphenyl Phenyl 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-propylphenyl group, 4-cyclopropylphenyl group, 3-cyclopropyl Phenyl 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 −
A cyclopentylphenyl group, a 4-cyclohexylphenyl group, a 4-cycloheptenylphenyl group, a 4-cyclooctanylphenyl group, a 2-cyclopentylphenyl group,
2-cyclohexylphenyl group, 2-cycloheptenylphenyl group, 2-cyclooctanylphenyl group, 3-cyclopentylphenyl group, 3-cyclohexylphenyl group, 3-cycloheptenylphenyl group, 3-cyclooctanylphenyl group, 4-cyclopentyloxyphenyl group, 4-cyclohexyloxyphenyl group, 4-cycloheptenyloxyphenyl group, 4-cyclooctanyloxyphenyl group, 2-cyclopentyloxyphenyl group, 2-cyclohexyloxyphenyl group, 2-cyclohep A phenyloxyphenyl group, a 2-cyclooctanyloxyphenyl group, a 3-cyclopentyloxyphenyl group, a 3-cyclohexyloxyphenyl group, a 3-cycloheptenyloxyphenyl group, a 3-cyclooctanyloxyphenyl group, - pentylphenyl group, 4-n
-Hexylphenyl group, 4-n-heptenylphenyl group, 4-n-octanylphenyl group, 2-n-pentylphenyl group, 2-n-hexylphenyl group, 2-n-heptenylphenyl group, 2- n-octanylphenyl group,
3-n-pentylphenyl group, 3-n-hexylphenyl group, 3-n-heptenylphenyl group, 3-n-octanylphenyl group, 2,6-di-isopropylphenyl group, 2,3-di- Isopropylphenyl group, 2,4-di-isopropylphenyl group, 3,4-di-isopropylphenyl group, 3,6-di-t-butylphenyl group, 2,
3-di-t-butylphenyl group, 2,4-di-t-butylphenyl group, 3,4-di-t-butylphenyl group,
2,6-di-n-butylphenyl group, 2,3-di-n-
Butylphenyl group, 2,4-di-n-butylphenyl group, 3,4-di-n-butylphenyl group, 2,6-di-
i-butylphenyl group, 2,3-di-i-butylphenyl group, 2,4-di-i-butylphenyl group, 3,4-di-i-butylphenyl group, 2,6-di-t- Amylphenyl group, 2,3-di-t-amylphenyl group, 2,4-
Di-t-amylphenyl group, 3,4-di-t-amylphenyl group, 2,6-di-i-amylphenyl group, 2,3
-Di-i-amylphenyl group, 2,4-di-i-amylphenyl group, 3,4-di-i-amylphenyl group, 2,
6-di-n-pentylphenyl group, 2,3-di-n-pentylphenyl group, 2,4-di-n-pentylphenyl group, 3,4-di-n-pentylphenyl group, 4-adamantylphenyl Group, 2-adamantylphenyl group, 4-
Isobornylphenyl group, 3-isobornylphenyl group, 2-isobornylphenyl group, 4-cyclopentyloxyphenyl group, 4-cyclohexyloxyphenyl group, 4-cycloheptenyloxyphenyl group, 4-cyclooctanyl An oxyphenyl group, a 2-cyclopentyloxyphenyl group, a 2-cyclohexyloxyphenyl group, a 2-cycloheptenyloxyphenyl group, a 2-cyclooctanyloxyphenyl group, a 3-cyclopentyloxyphenyl group, a 3-cyclohexyloxyphenyl group, 3-cycloheptenyloxyphenyl group, 3-cyclooctanyloxyphenyl group, 4-n-pentyloxyphenyl group, 4-n-hexyloxyphenyl group, 4
-N-heptenyloxyphenyl group, 4-n-octenyloxyphenyl 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- Butyloxyphenyl group,
2,4-di-t-butyloxyphenyl group, 3,4-di-t-butyloxyphenyl group, 2,6-di-n-butyloxyphenyl group, 2,3-di-n-butyloxyphenyl Group, 2,4-di-n-butyloxyphenyl group,
3,4-di-n-butyloxyphenyl group, 2,6-di-i-butyloxyphenyl group, 2,3-di-i-butyloxyphenyl group, 2,4-di-i-butyloxyphenyl Group, 3,4-di-i-butyloxyphenyl group,
2,6-di-t-amyloxyphenyl group, 2,3-di-t-amyloxyphenyl group, 2,4-di-t-amyloxyphenyl group, 3,4-di-t-amyloxyphenyl A 2,6-di-i-amyloxyphenyl group,
2,3-di-i-amyloxyphenyl group, 2,4-di-i-amyloxyphenyl group, 3,4-di-i-amyloxyphenyl group, 2,6-di-n-pentyloxyphenyl Group, 2,3-di-n-pentyloxyphenyl group, 2,4-di-n-pentyloxyphenyl group, 3,
4-di-n-pentyloxyphenyl group, 4-adamantyloxyphenyl group, 3-adamantyloxyphenyl group, 2-adamantyloxyphenyl group, 4-isobornyloxyphenyl group, 3-isobornyloxyphenyl group, Examples thereof include a 2-isoboronyloxyphenyl group, and these may be further substituted within the above range, and are not limited to substituents other than the above examples.

The aralkyl group having 7 to 30 carbon atoms, preferably 12 to 30 carbon atoms, more preferably 12 to 25 carbon atoms for R ′ ₃ includes, for example, phenylethyl group, 4-methylphenylethyl group, 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-propylphenylethyl 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-cyclopentylphenylethyl group, 3-cyclohexylphenylethyl group, 3-cycloheptenylphenylethyl group, 3-cycloocta Nylphenylethyl group, 4-cyclopentyloxyphenylethyl group, 4
-Cyclohexyloxyphenylethyl group, 4-cycloheptenyloxyphenylethyl group, 4-cyclooctanyloxyphenylethyl group, 2-cyclopentyloxyphenylethyl group, 2-cyclohexyloxyphenylethyl group, 2-cycloheptenyloxyphenyl Ethyl group, 2-cyclooctanyloxyphenylethyl group,
3-cyclopentyloxyphenylethyl group, 3-cyclohexyloxyphenylethyl group, 3-cycloheptenyloxyphenylethyl group, 3-cyclooctanyloxyphenylethyl group, 4-n-pentylphenylethyl group, 4-n-hexyl Phenylethyl group, 4-n-heptenylphenylethyl group, 4-n-octanylphenylethyl group, 2-n-pentylphenylethyl group, 2-
n-hexylphenylethyl group, 2-n-heptenylphenylethyl group, 2-n-octanylphenylethyl group, 3-n-pentylphenylethyl group, 3-n-hexylphenylethyl group, 3-n-heptane Thenylphenylethyl group, 3-n-octanylphenylethyl group, 2,6
-Di-isopropylphenylethyl group, 2,3-di-isopropylphenylethyl group, 2,4-di-isopropylphenylethyl group, 3,4-di-isopropylphenylethyl group, 2,6-di-t-butyl Phenylethyl 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-amylphenylethyl 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-isobornylphenylethyl group, 3-isoboronylphenylethyl group, 2- Isobornylphenylethyl group, 4-cyclopentyloxyphenylethyl group, 4-cyclohexyloxyphenylethyl group, 4-cycloheptenyloxyphenylethyl group, 4-cyclooctanyloxyphenylethyl group, 2-cyclopentyloxyphenylethyl group A 2-cyclohexyloxyphenylethyl group, 2-
Cycloheptenyloxyphenylethyl group, 2-cyclooctenyloxyphenylethyl group, 3-cyclopentyloxyphenylethyl group, 3-cyclohexyloxyphenylethyl group, 3-cycloheptenyloxyphenylethyl group, 3-cyclooctanyloxy Phenylethyl group, 4-n-pentyloxyphenylethyl group, 4-
n-hexyloxyphenylethyl group, 4-n-heptenyloxyphenylethyl group, 4-n-octanyloxyphenylethyl group, 2-n-pentyloxyphenylethyl group, 2-n-hexyloxyphenylethyl group ,
2-n-heptenyloxyphenylethyl group, 2-n-
An octanyloxyphenylethyl group, a 3-n-pentyloxyphenylethyl group, a 3-n-hexyloxyphenylethyl group, a 3-n-heptenyloxyphenylethyl group, a 3-n-octanyloxyphenylethyl group,
2,6-diisopropyloxyphenylethyl group,
2,3-di-isopropyloxyphenylethyl group,
2,4-di-isopropyloxyphenylethyl group,
3,4-diisopropyloxyphenylethyl 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-butyloxy Phenylethyl group, 2,6-di-t-amyloxyphenylethyl group,
2,3-di-t-amyloxyphenylethyl group, 2,
4-di-t-amyloxyphenylethyl 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- An adamantyloxyphenylethyl group, a 2-adamantyloxyphenylethyl group, a 4-isobornyloxyphenylethyl group, a 3-isobornyloxyphenylethyl group, a 2-isoboronyloxyphenylethyl group, or the above alkyl is methyl Group, propyl group,
Those substituted with a butyl group and the like can be mentioned.

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

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

When the resin contains the structural unit represented by the general formula (II), the resin is decomposed by the action of an acid, and the resin has an increased solubility in an alkaline developer.

Examples of the group which is not decomposed by the action of an acid at R ₂₃ (also referred to as an acid stable group) include a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, and an alkyloxy group (provided that —O -Excluding tertiary alkyl), acyl group, cycloalkyloxy group, alkenyloxy group, aryloxy group, alkylcarbonyloxy group, alkylamidomethyloxy group, alkylamido group, arylamidomethyl group, arylamido group and the like. No. The acid stabilizer is preferably an acyl group, an alkylcarbonyloxy group, an alkyloxy group, a cycloalkyloxy group, an aryloxy group, an alkylamidooxy group or an alkylamido group, more preferably an acyl group or an alkylcarbonyloxy group. , An alkyloxy group, a cycloalkyloxy group, and an aryloxy group.

In the acid-stable group represented by R ₂₃ , the alkyl group may be a group having 1 to carbon atoms such as a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group and a t-butyl group.
The cycloalkyl group is preferably a group having 3 to 10 carbon atoms such as a cyclopropyl group, a cyclobutyl group, a cyclohexyl group, or an adamantyl group. The alkenyl group is preferably a vinyl group, a propenyl group, or an allyl group. And a butenyl group having 2 to 4 carbon atoms are preferable, and as the alkenyl group, a vinyl group, a propenyl group,
Those having 2 to 4 carbon atoms such as an allyl group and a butenyl group are preferable. As the aryl group, a phenyl group, a xylyl group,
Those having 6 to 14 carbon atoms such as a toluyl group, a cumenyl group, a naphthyl group and an anthracenyl group are preferred. Examples of the alkoxy group include a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, a hydroxypropoxy group, n
An alkoxy group having 1 to 4 carbon atoms such as -butoxy group, isobutoxy group and sec-butoxy group is preferred.

As the halogen atom for R ₂₄ ,
Fluorine, chlorine, bromine and iodine are preferred. As the alkyl group, methyl, ethyl, propyl, n-butyl, sec.
Those having 1 to 8 carbon atoms such as -butyl, t-butyl, hexyl, octyl and the like are preferable. As the aryl group, those having 6 to 14 carbon atoms such as phenyl, xylyl, toluyl, cumenyl, naphthyl, anthracenyl and the like are preferable. Are preferred. 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, Preferred are those having 1 to 7 carbon atoms such as formyl, acetyl, propanoyl, butanoyl and benzoyl. As the acyloxy group, acetoxy,
Those having 2 to 7 carbon atoms, such as propnoyloxy, butanoyloxy and benzoyloxy, are preferred.

The resins containing the repeating units represented by the general formulas (I) to (III) are synthesized, for example, by the following method. That is, an OH group in a resin obtained by homopolymerizing or copolymerizing a polymerizable monomer corresponding to the structural unit represented by the general formula (I) is converted into a group represented by the following formula (II):

[0111]

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Further, a method for modifying and converting the compound to a group represented by R ₂₃ in the general formula (III), a polymerizable monomer corresponding to the general formula (I) and a polymerizable monomer corresponding to the general formula (II) A method of copolymerizing a monomer and a polymerizable monomer corresponding to general formula (III), or after homopolymerizing or copolymerizing a polymerizable monomer corresponding to general formulas (II) and (III),
The group of formula (II), can be synthesized by the method of converting by hydrolyzing a part of the groups represented by R ₂₃ in the structure of the general formula (I).

Specifically, a polymerizable monomer corresponding to the above general formula (I) is prepared by using a suitable solvent and catalyst, for example,
JP-A-2-25850, JP-A-3-223860, JP-A-4
After homopolymerization or copolymerization with another polymerizable monomer by a radical polymerization method described in, for example, JP-A-212258 and JP-A-5-249682, the OH group in the obtained resin is subjected to, for example, JP-A-60-52845. JP-A-5-19482, JP-A-4-219775, JP-A-4-251259, JP-A-5-192
No. 49682, No. 4-21258, No. 5-1812
79 items, the 6-83059 JP, by the method described in the 6-194841 Patent etc., the group of formula (II), modified group represented by R _23, it is synthesized by a method of converting. Further, it is synthesized by copolymerizing monomers corresponding to the general formulas (I), (II) and (III) and, if necessary, other polymerizable monomers by the above-mentioned radical polymerization method or the like. Further, monomers corresponding to the general formulas (II) and / or (III) and, if necessary, other polymerizable monomers are obtained by the above-mentioned radical polymerization method or JP-A-4-350657.
4-350658, 6-41221, 6-4
After homopolymerization or copolymerization by the living anionic polymerization method described in No. 1222, No. 6-65332, No. 6-65333, etc., the compound is represented by the above group of the general formula (II) and / or R _23. Part of the group is hydrolyzed to form a compound of the general formula (I)
The method of converting to the structure of
Said groups and / or modifications to the group represented by R ₂₃ again formula (II), it is synthesized by a method of converting.

Specific examples of the polymerizable monomer corresponding to the general formula (I) include the following, but are not limited thereto.

[0115]

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[0116]

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Specific examples of the polymerizable monomer represented by the general formula (II) include the above compound examples (I-1) to (I-2).
Those obtained by substituting the OH group of 3) with the following groups are mentioned.

[0118]

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[0119]

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[0120]

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Further, specific examples of the polymerizable monomer represented by the general formula (III) include, but are not limited to, the following.

[0122]

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[0123]

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In the present invention, it is decomposed by the action of an acid,
The resin having a group that increases the solubility in an alkaline developer contains other monomer units as copolymer components in addition to the structural units represented by the general formulas (I), (II) and (III). Is also good.

The resin used in the present invention may be prepared by adding a polyhydroxy compound at the synthesis stage to adjust the alkali dissolution rate and improve the heat resistance, and introducing a cross-linking site connecting the polymer main chain with a polyfunctional acetal group. Good. The amount of polyhydroxy compound added to the number of hydroxyl groups of the resin,
0.01 to 10 mol%, preferably 0.05 to 8 mol
%, More preferably 0.1 to 5 mol%. Examples of the polyhydroxy compound include those having 2 to 6 phenolic hydroxyl groups or alcoholic hydroxyl groups, preferably 2 to 4 hydroxyl groups, and more preferably 2 or 3 hydroxyl groups. is there. Specific examples are shown below, but the present invention is not limited to these.

[0126]

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The repeating structural units represented by formulas (I) to (III) or the repeating structural units derived from other polymerizable monomers may be present in the resin alone or in combination of two or more. . The content of the repeating structural unit represented by the general formula (I) in the resin is preferably from 30 to 90.
Mol%, more preferably 40 to 85 mol%, even more preferably 50 to 80 mol%. The general formula (I
The content of the repeating structural unit represented by I) is preferably 3 to 40 mol%, more preferably 5 to 40 mol%, and still more preferably 10 to 40 mol%. The content of the repeating structural unit represented by the general formula (III) in the resin is preferably 5 to 40 mol%, more preferably 7 to 35 mol%,
More preferably, it is 7 to 30 mol%. Further, the resin contained in the positive photosensitive composition of the present invention is suitable so that an alkali-soluble group, for example, a phenolic hydroxyl group or a carboxyl group can be introduced in order to maintain good developability in an alkali developing solution. Other polymerizable monomers may be copolymerized.

The molecular weight of the resin having a repeating structural unit of the above general formulas (I) to (III) synthesized by the above method has a weight average (Mw: polystyrene standard) of 2,000.
It is 0 or more, preferably 3,000 to 200,000, and more preferably 5,000 to 70,000.
The degree of dispersion (Mw / Mn) is preferably 1.0 to
4.0, more preferably 1.0 to 2.0, particularly preferably 1.0 to 1.6. The smaller the degree of dispersion, the higher the heat resistance.
Image formability (pattern profile, defocus latitude, etc.) is improved. The above general formulas (I) to (III)
The content of the resin having a repeating structural unit of (a) excluding the coating solvent in the positive photosensitive composition is preferably 50 to 9
It is 9% by weight, more preferably 70 to 97% by weight. Specific examples of the resin having the repeating structural units of the general formulas (I) to (III) are shown below, but the present invention is not limited thereto.

[0129]

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[0130]

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[0131]

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[0132]

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[0133]

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[0134]

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[0135]

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[0136]

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[0137]

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[0138]

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[0139]

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[0140]

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[0141]

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A resin having an acid-decomposable group may be used in combination with the resin having a repeating structural unit represented by the general formulas (I) to (III). The resin having a group which is decomposed by another acid used in the chemically amplified resist according to the present invention and which increases the solubility in an alkali developing solution includes a main chain or a side chain of the resin, or a main chain and a side chain. Is a resin having an acid-decomposable group. Among them, a resin having a group which can be decomposed by an acid in a side chain is more preferable. Preferred groups which can be decomposed by an acid are -COOA ⁰ , -OB
⁰ groups, and further containing these groups include -R ⁰ -C
OOA ⁰ or a group represented by -A _r -O-B ⁰ . Here, A ⁰ is -C (R ⁰¹ ) (R ⁰² ) (R ⁰³ ),
-Si (R ⁰¹ ) (R ⁰² ) (R ⁰³ ) or -C (R ⁰⁴ )
It represents a (R ⁰⁵ ) -OR ⁰⁶ group. B ⁰ is -A ⁰ or -C
Shows the O-O-A ⁰ group ^{(R 0, R 01 ~R 06} , and Ar is same meaning as described later).

The acid-decomposable group is preferably a silyl ether group, a cumyl ester group, an acetal group, a tetrahydropyranyl ether group, a tetrahydropyranyl ester group, an enol ether group, an enol ester group,
And a tertiary alkyl ester group and a tertiary alkyl carbonate group. More preferred are a tertiary alkyl ester group, a tertiary alkyl carbonate group, a cumyl ester group, an acetal group, and a tetrahydropyranyl ether group.

[0144] Next, as the matrix resin in the case where the group capable of decomposing by an acid is bonded as a side chain, -OH or -COOH in the side chain, preferably -R ⁰ -COOH or -A _r -OH group It is an alkali-soluble resin having. For example, an alkali-soluble resin described below can be used.

The alkali dissolution rate of these alkali-soluble resins was measured (at 23 ° C.) using 0.261N tetramethylammonium hydroxide (TMAH).
A / sec or more is preferable. Particularly preferably 330A
/ Sec or more (A is angstroms). From the viewpoint of achieving a rectangular profile, an alkali-soluble resin having a high transmittance to far ultraviolet light or excimer laser light is preferable. Preferably, the transmittance at a wavelength of 248 nm with a thickness of 1 μm is 20 to 90%. From this perspective,
Particularly preferred alkali-soluble resins are o-, m-, p-
Poly (hydroxystyrene) and copolymers thereof, hydrogenated poly (hydroxystyrene), halogen- or alkyl-substituted poly (hydroxystyrene), part of poly (hydroxystyrene), O-alkylated or O-acylated product, styrene -Hydroxystyrene copolymer, α
-Methylstyrene-hydroxystyrene copolymer and hydrogenated novolak resin.

The resin having an acid-decomposable group used in the present invention may be obtained by reacting an alkali-soluble resin with a precursor of an acid-decomposable group, or by bonding an acid-decomposable group to an alkali-soluble resin. It can be obtained by copolymerizing a monomer with various monomers.

It is preferable to mix an acid-decomposable low-molecular-weight dissolution-inhibiting compound described later together with the photoacid generator and the resin having an acid-decomposable group. The acid-decomposable dissolution inhibiting compound used in the present invention has at least two acid-decomposable groups in its structure, and at the position where the distance between the acid-decomposable groups is farthest away, the acid-decomposable group Is a compound having at least 8 bonding atoms excluding. In the present invention, the acid-decomposable dissolution-inhibiting compound preferably has at least two groups capable of being decomposed by an acid in its structure, and at the position where the distance between the acid-decomposable groups is farthest away, the acid-decomposable group A compound having at least 10, preferably at least 11, and more preferably at least 12 bonding atoms excluding the above, or a position where the distance between the acid-decomposable groups is the longest, having at least three acid-decomposable groups Has at least 9, preferably at least 1, bonding atoms excluding an acid-decomposable group.
It is a compound via 0, more preferably via at least 11. The preferred upper limit of the number of the bonding atoms is 50, more preferably 30. In the present invention, when the acid-decomposable dissolution-inhibiting compound has three or more, preferably four or more acid-decomposable groups, and even when the compound has two acid-decomposable groups, the acid-decomposable groups are mutually present. If they are separated by a certain distance or more, the dissolution inhibiting property with respect to the alkali-soluble resin is significantly improved. In addition, the distance between the acid-decomposable groups in the present invention is represented by the number of via bond atoms excluding the acid-decomposable groups. For example, in the case of the following compounds (1) and (2), the distance between the acid-decomposable groups is 4 bonding atoms, and in the compound (3), the bonding atom is 12 bonding atoms.

[0148]

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

In a preferred embodiment of the present invention, an acid-decomposable group, ie, —COO-A ⁰ , —O-B ⁰
The group containing a group, -R ⁰ -COO-A ^0, or -A
include groups represented by the r-O-B ^0. Where A
⁰ is -C (R ⁰¹ ) (R ⁰² ) (R ⁰³ ), -Si (R ⁰¹ )
(R ⁰² ) (R ⁰³ ) or -C (R ⁰⁴ ) (R ⁰⁵ ) -O-
R represents a ⁰⁶ group. B ⁰ represents A ⁰ or a —CO—OA ⁰ group. R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ may be the same or different and each represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group, and R ⁰⁶ represents an alkyl group Alternatively, it represents an aryl group. However, at least two of R ^{01 to} R ⁰³ are groups other than a hydrogen atom, and two groups of R ^{01 to} R ⁰³ and R ^{04 to} R ⁰⁶ are bonded to form a ring. Is also good. R ⁰ represents a divalent or higher valent aliphatic or aromatic hydrocarbon group which may have a substituent, and -Ar- represents a divalent or higher valent which may have a monocyclic or polycyclic substituent. Shows an aromatic group.

Here, the alkyl group is preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group and a t-butyl group. Preferred are those having 3 to 10 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclohexyl group and adamantyl group, and alkenyl groups having 2 to 2 carbon atoms such as vinyl group, propenyl group, allyl group and butenyl group. Preferably, the aryl group has 6 to 1 carbon atoms such as phenyl, xylyl, toluyl, cumenyl, naphthyl and anthracenyl.
Four are preferred. Further, as a substituent, a hydroxyl group,
Halogen atom (fluorine, chlorine, bromine, iodine), nitro group, cyano group, the above alkyl group, methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group, n-butoxy group, isobutoxy group, s
an alkoxy group such as an ec-butoxy group and a t-butoxy group,
Alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group, aralkyl groups such as benzyl group, phenethyl group and cumyl group, aralkyloxy groups, acyl groups such as formyl group, acetyl group, butyryl group, benzoyl group, cyanamyl group, and valeryl group. Group, an acyloxy group such as a butyryloxy group, the above alkenyl group, a vinyloxy group.
Examples thereof include an alkenyloxy group such as a propenyloxy group, an allyloxy group, and a butenyloxy group, an aryloxy group such as the above-described aryl group and phenoxy group, and an aryloxycarbonyl group such as a benzoyloxy group.

The group decomposable with an acid is preferably a silyl ether group, a cumyl ester group, an acetal group, a tetrahydropyranyl ether group, an enol ether group, an enol ester group, a tertiary alkyl ether group, or a tertiary alkyl ether group. Alkyl ester groups, tertiary alkyl carbonate groups and the like. More preferred are a tertiary alkyl ester group, a tertiary alkyl carbonate group, a cumyl ester group, and a tetrahydropyranyl ether group.

As the acid-decomposable dissolution-inhibiting compound, those described in JP-A-1-289946 and JP-A-1-2899 are preferred.
No. 47, JP-A-2-2560, JP-A-3-12895
9, JP-A-3-158855, JP-A-3-1793
No. 53, JP-A-3-191351, JP-A-3-200
No. 251, JP-A-3-200252, JP-A-3-20
0253, JP-A-3-200254, JP-A-3-2
0255, JP-A-3-259149, JP-A-3-259
279958, JP-A-3-279959, JP-A-4
JP-A-1650, JP-A-4-1651, JP-A-4-11
No. 260, JP-A-4-12356, JP-A-4-123
No. 57, Japanese Patent Application No. 3-33229, Japanese Patent Application No. 3-2307
No. 90, Japanese Patent Application No. 3-320438, Japanese Patent Application No. 4-251
No. 57, Japanese Patent Application No. 4-52732, Japanese Patent Application No. 4-1032
No. 15, Japanese Patent Application No. 4-104542, Japanese Patent Application No. 4-107
No. 885, Japanese Patent Application No. 4-107889 and No. 4-1521
Compounds in which some or all of the phenolic OH groups of the polyhydroxy compound described in the specification such as No. 95 are bonded and protected by the above-mentioned groups, -R ⁰ -COO-A ⁰ or B ⁰ groups, included.

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

More specifically, general formulas [I] to [XV]
The compound represented by I] is mentioned.

[0156]

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[0157]

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[0158]

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[0159]

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R ¹⁰¹ , R ¹⁰² , R ¹⁰⁸ , R ¹³⁰ : may be the same or different, and represent a hydrogen atom, -R ⁰ -COO-C
( ^R01 ) ( ^R02 ) ( ^R03 ) or -CO-OC ( ^R01 )
^{(R 0 2) (R 03} ), provided that the definition of R ^0, R ^01, R ⁰² and R ⁰³ are as defined above.

R ¹⁰⁰ : -CO-, -COO-, -NHC
ONH-, -NHCOO-, -O-, -S-, -SO
-, -SO _2- , -SO _3- , or

[0162]

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[0163] Here, G = 2 to 6, provided that at least one alkyl group of R ^0.99, R ¹⁵¹ when the ^{G = 2, R 150, R} 151: may be the same or different, a hydrogen atom, an alkyl Group, alkoxy group, -OH, -COOH,
-CN, halogen atom, -R ¹⁵² -COOR ^{15 3} or ^{-R 154 -OH, R 152, R} 154: an alkylene group, R ^153: a hydrogen atom, an alkyl group, an aryl group or an aralkyl group,, R ^99, R ¹⁰³ To R ¹⁰⁷ , R ¹⁰⁹ , R ^{111 to} R ¹¹⁸ , R
^{121 to} R ¹²³ , R ^{128 to} R ¹²⁹ , R ^{131 to} R ¹³⁴ , R
^{138 to} R ¹⁴¹ and R ¹⁴³ may be the same or different and include a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an acyl group, an acyloxy group, an aryl group, an aryloxy group, an aralkyl group, an aralkyloxy group, a halogen atom, nitro Group, carboxyl group, cyano group, or -N ( ^R155 )
(R ¹⁵⁶ ) (R ¹⁵⁵ , R ¹⁵⁶ : H, alkyl group or aryl group) R ¹¹⁰ : single bond, alkylene group, or

[0164]

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R ¹⁵⁷ and R ¹⁵⁹ may be the same or different, and represent a single bond, an alkylene group, —O—, —S—, —CO
— Or 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 hydroxyl group, a cyano group, or a carboxyl group, provided that the hydroxyl group is an acid-decomposable group (for example, t-butoxycarbonylmethyl group, tetrahydropyranyl group, 1-ethoxy-1-ethyl group,
(1-t-butoxy-1-ethyl group).

R ¹¹⁹ and R ¹²⁰ may be the same or different and each represents a methylene group, a lower alkyl-substituted methylene group, a halomethylene group, or a haloalkylene group, provided that the lower alkyl group is an alkyl group having 1 to 4 carbon atoms. R ^{124 to} R ¹²⁷ may be the same or different and may be a hydrogen atom or an alkyl group; R ^{135 to} R ¹³⁷ may be the same or different and a hydrogen atom;
An alkyl group, an alkoxy group, an acyl group, or an acyloxy group, R ¹⁴² : a hydrogen atom, —R ⁰ —COO—C (R ⁰¹ )
( ^R02 ) ( ^R03 ) or -CO-OC ( ^R01 ) ( ^R02 )
(R ⁰³ ), or

[0167]

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R ¹⁴⁴ and R ¹⁴⁵ may be the same or different and represent a hydrogen atom, a lower alkyl group, a lower haloalkyl group,
Or an aryl group, R ^{146 to} R ¹⁴⁹ : may be the same or different, and may be hydrogen, hydroxyl, halogen, nitro, cyano, carbonyl, alkyl, alkoxy, alkoxycarbonyl, aralkyl, aralkyloxy A group, an acyl group, an acyloxy group, an alkenyl group, an alkenyloxy group, an aryl group, an aryloxy group, or an aryloxycarbonyl group, provided that the four substituents having the same symbols need not be the same group. : —CO— or —SO ₂ —, Z, B: single bond or —O—, A: methylene group, lower alkyl-substituted methylene group, halomethylene group, or haloalkylene group; E: single bond or oxymethylene Groups, a to z, a1 to y1: when plural, the groups in parentheses may be the same or different; a to q, s, t, v, g1 to i1, k1 m1, o1, q1, s1, u1: 0 or an integer of 1 to 5, r, u, w, x, y, z, a1~f1, p1, r1, t1, v1~x1: 0 or 1
An integer of 4, j1, n1, z1, a2, b2, c2, d2: an integer of 0 or 1 to 3, z1, a
2, at least one of c2, d2 is 1 or more, y1: an integer of 3 to 8, (a + b), (e + f + g), (k + l + m), (q + r + s ), (w + x + y), (c1 + d1), (g1 +
h1 + i1 + j1), (o1 + p1), (s1 + t1) ≧ 2, (j1 + n1) ≦ 3, (r + u), (w + z), (x + a1), (y + b1), (c1 + e1), (d1 + f1), (p1 + r1),
(t1 + v1), (x1 + w1) ≦ 4, provided that (w +
z), (x + a1) ≦ 5, (a + c), (b + d), (e + h), (f + i), (g + j), (k + n), (l + o), (m + p), (q
+ t), (s + v), (g1 + k1), (h1 + l1), (i1 + m1), (o1 + q1), (s1 + u1)
≦ 5.

[0169]

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[0170]

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[0171]

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[0172]

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Specific examples of preferred compound skeletons are shown below.

[0174]

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[0175]

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[0176]

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[0177]

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[0178]

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[0179]

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[0180]

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[0181]

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[0182]

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[0183]

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[0184]

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[0185]

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[0186]

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[0187]

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[0188]

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[0189]

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[0190]

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[0191]

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[0192]

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R in the compounds (1) to (63) is a hydrogen atom,

[0194]

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Represents the following. However, at least two or three depending on the structure are groups other than hydrogen atoms, and each substituent R
May not be the same group. In this case, the content of the dissolution inhibiting compound is 3 to 45% by weight, preferably 5 to 30% by weight, based on the total weight of the photosensitive composition (excluding the solvent).
More preferably, it is 10 to 20% by weight.

Further, in order to adjust the alkali solubility,
An alkali-soluble resin having no acid-decomposable group may be mixed. As such an alkali-soluble resin,
For example, novolak resin, hydrogenated novolak resin, acetone-pyrogallol resin, o-polyhydroxystyrene,
m-polyhydroxystyrene, p-polyhydroxystyrene, hydrogenated polyhydroxystyrene, halogen- or alkyl-substituted polyhydroxystyrene, hydroxystyrene-N-substituted maleimide copolymer, o / p- and m
/ P-hydroxystyrene copolymer, partially O-alkylated product (for example, 5 to 30 mol% of O-methylated product) to the hydroxyl group of polyhydroxystyrene or O-
Acylated product (for example, 5 to 30 mol% o-acetylated product), styrene-maleic anhydride copolymer, styrene-hydroxystyrene copolymer, α-methylstyrene-
Hydroxystyrene copolymer, carboxyl group-containing methacrylic resin and its derivatives can be mentioned,
It is not limited to these. Particularly preferred alkali-soluble resins are novolak resins and o-polyhydroxystyrene, m-polyhydroxystyrene, p-polyhydroxystyrene and copolymers thereof, alkyl-substituted polyhydroxystyrene, partial O-alkylation of polyhydroxystyrene, Or O-acylated product, styrene-
Hydroxystyrene copolymer and α-methylstyrene-hydroxystyrene copolymer. The novolak resin is obtained by subjecting a given monomer as a main component to addition condensation with an aldehyde in the presence of an acidic catalyst.

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

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, p-ethylbenzaldehyde, pn-butylbenzaldehyde, furfural, chloroacetaldehyde, and their acetal compounds, such as chloroacetaldehyde diethyl acetal, among which formaldehyde is used Is preferred. These aldehydes are used alone or in combination of two or more. As the acidic catalyst, hydrochloric acid, sulfuric acid, formic acid, acetic acid, oxalic acid and the like can be used.

The weight average molecular weight of the novolak resin thus obtained is preferably in the range of 1,000 to 30,000. If it is less than 1,000, the film loss of the unexposed portion after development is large, and if it exceeds 30,000, the developing speed is reduced. Particularly preferred are 2,000-20,
000. In addition, the weight average molecular weight of the polyhydroxystyrene other than the novolak resin, its derivative, and the copolymer is 2,000 or more, preferably 5,000.
~ 200,000, more preferably 10,000-1000
00. Further, from the viewpoint of improving the heat resistance of the resist film, 25,000 or more is preferable. here,
The weight average molecular weight is defined as a value in terms of polystyrene by gel permeation chromatography. These alkali-soluble resins in the present invention may be used as a mixture of two or more kinds. The addition amount of these alkali-soluble resins in the composition of the present invention is preferably 5
３０30% by weight.

Other components used in the present invention If necessary, the photosensitive composition of the present invention may further contain a dye, a pigment, a plasticizer, a surfactant, a photosensitizer, an organic basic compound, and a developer. Phenolic O that promotes solubility in water
A compound having two or more H groups can be contained.

The compound having two or more phenolic OH groups that can be used in the present invention is preferably a phenol compound having a molecular weight of 1,000 or less. Further, it is necessary to have at least two phenolic hydroxyl groups in the molecule. If the number exceeds 10, the effect of improving the development latitude is lost. When the ratio of the phenolic hydroxyl group to the aromatic ring is less than 0.5, the film thickness dependency is large, and the development latitude tends to be narrow. If this ratio exceeds 1.4, the stability of the composition deteriorates, and it becomes difficult to obtain high resolution and good film thickness dependency, which is not preferable.

The preferable addition amount of the phenol compound is 2 to 50% by weight based on the resin, more preferably 5 to 50% by weight.
３０30% by weight. With an addition amount exceeding 50% by weight,
It is not preferable because a new defect that development residue is deteriorated and a pattern is deformed during development is generated.

Such a phenol compound having a molecular weight of 1000 or less can be prepared by those skilled in the art by referring to the methods described in, for example, JP-A-4-122938, JP-A-2-28531, US Pat. No. 4,916,210, and EP 219294. It can be easily synthesized at Specific examples of the phenol compound are shown below, but the compounds that can be used in the present invention are not limited to these.

Resorcin, phloroglucin, 2, 3, 4
-Trihydroxybenzophenone, 2,3,4,4'-
Tetrahydroxybenzophenone, 2,3,4,3 ',
4 ', 5'-hexahydroxybenzophenone, acetone-pyrogallol condensation resin, fluoroglucoside,
4,2 ', 4'-biphenyltetrol, 4,4'-thiobis (1,3-dihydroxy) benzene, 2,2',
4,4'-tetrahydroxydiphenyl ether, 2,
2 ', 4,4'-tetrahydroxydiphenylsulfoxide, 2,2', 4,4'-tetrahydroxydiphenylsulfone, tris (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) Cyclohexane, 4,4- (α-methylbenzylidene) bisphenol, α, α ′, α ″ -tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene,
α, α ', α "-tris (4-hydroxyphenyl)-
1-ethyl-4-isopropylbenzene, 1,2,2-
Tris (hydroxyphenyl) propane, 1,1,2-
Tris (3,5-dimethyl-4-hydroxyphenyl)
Propane, 2,2,5,5-tetrakis (4-hydroxyphenyl) hexane, 1,2-tetrakis (4-hydroxyphenyl) ethane, 1,1,3-tris (hydroxyphenyl) butane, para [α, α , Α ', α'-tetrakis (4-hydroxyphenyl)]-xylene.

Preferred organic basic compounds that can be used in the present invention are compounds that are more basic than phenol. Among them, a nitrogen-containing basic compound is preferable. Preferred chemical environments include the structures of the following formulas (A) to (E).

[0206]

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Further preferred compounds are nitrogen-containing basic compounds having two or more nitrogen atoms having different chemical environments in one molecule, and particularly preferred is a ring structure containing a substituted or unsubstituted amino group and a nitrogen atom. Or a compound having an alkylamino group. Preferred specific examples include substituted or unsubstituted guanidine, substituted or unsubstituted aminopyridine, substituted or unsubstituted aminoalkylpyridine, substituted or unsubstituted aminopyrrolidine, substituted or unsubstituted indazol,
Substituted or unsubstituted pyrazole, substituted or unsubstituted pyrazine, substituted or unsubstituted pyrimidine, substituted or unsubstituted purine, substituted or unsubstituted imidazoline, substituted or unsubstituted pyrazoline, substituted or unsubstituted piperazine, substituted Or, unsubstituted aminomorpholine, substituted or unsubstituted aminoalkylmorpholine and the like can be mentioned. Preferred substituents are an amino group,
An aminoalkyl group, an alkylamino group, an aminoaryl group, an arylamino group, an alkyl group, an alkoxy group, an acyl group, an acyloxy group, an aryl group, an aryloxy group, a nitro group, a hydroxyl group, and a cyano group. As particularly preferred compounds, guanidine, 1,1-dimethylguanidine, 1,1,3,3-tetramethylguanidine, 2-
Aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2-diethylaminopyridine, 2- (aminomethyl) pyridine, 2-amino-3-methylpyridine, 2-amino -4-methylpyridine, 2-amino-5
-Methylpyridine, 2-amino-6-methylpyridine,
3-aminoethylpyridine, 4-aminoethylpyridine, 3-aminopyrrolidine, piperazine, N- (2-aminoethyl) piperazine, N- (2-aminoethyl) piperidine, 4-amino-2,2,6,6 -Tetramethylpiperidine, 4-piperidinopiperidine, 2-iminopiperidine, 1- (2-aminoethyl) pyrrolidine, pyrazole, 3-amino-5-methylpyrazole, 5-amino-3-methyl-1-p- Tolylpyrazole, pyrazine, 2- (aminomethyl) -5-methylpyrazine, pyrimidine, 2,4-diaminopyrimidine, 4,6-dihydroxypyrimidine, 2-pyrazoline, 3-pyrazoline,
Examples include, but are not limited to, N-aminomorpholine, N- (2-aminoethyl) morpholine, and the like.

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

Preferred dyes include oil dyes and basic dyes. Specifically, Oil Yellow # 101, Oil Yellow # 103, Oil Pink # 312, Oil Green BG, Oil Blue BOS, Oil Blue # 60
3. Oil black BY, oil black BS, oil black T-505 (all manufactured by Orient Chemical Co., Ltd.), crystal violet (CI42555), methyl violet (CI42535), rhodamine B
(CI45170B), malachite green (CI42
000), methylene blue (CI52015) and the like.

Further, a spectral sensitizer as described below is added to sensitize the photosensitive composition of the present invention to a longer wavelength region than far ultraviolet where the photoacid generator used has no absorption. Sensitivity can be given to i or g rays. Suitable spectral sensitizers include, specifically, benzophenone, p,
p'-tetramethyldiaminobenzophenone, p, p '
-Tetraethylethylaminobenzophenone, 2-chlorothioxanthone, anthrone, 9-ethoxyanthracene, anthracene, pyrene, perylene, phenothiazine, benzyl, acridine orange, benzoflavin,
Cetoflavin-T, 9,10-diphenylanthracene, 9-fluorenone, acetophenone, phenanthrene, 2-nitrofluorene, 5-nitroacenaphthene,
Benzoquinone, 2-chloro-4-nitroaniline, N-
Acetyl-p-nitroaniline, p-nitroaniline, N-acetyl-4-nitro-1-naphthylamine, picramide, anthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone 1,2-benzanthraquinone, 3- Methyl-1,3-diaza-1,
9-benzanthrone, dibenzalacetone, 1,2-
Naphthoquinone, 3,3′-carbonyl-bis (5,7-
Dimethoxycarbonylcoumarin) and coronene, but are not limited thereto. Further, these spectral sensitizers can also be used as a light absorbing agent for far ultraviolet light of a light source. In this case, the light absorbing agent exerts the effect of improving the standing wave by reducing the reflected light from the substrate and reducing the influence of multiple reflection in the resist film.

The positive photosensitive composition of the present invention is dissolved in a solvent in which each of the above components is dissolved, and coated on a support. As the solvent used here, ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, γ
-Butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate , Methyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N, N-
Dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, tetrahydrofuran and the like are preferable, and these solvents are used alone or in combination.

A surfactant may be added to the above solvents. Specifically, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether,
Polyoxyethylene alkyl allyl ethers such as polyoxyethylene nonylphenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, Sorbitan fatty acid esters such as sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate Surfactants such as polyoxyethylene sorbitan fatty acid esters such as acrylates and the like, F-top EF301, E 303, EF352 (manufactured by Shin Akita Kasei Co., Ltd.), Megafac F171, F173 (manufactured by Dainippon Ink Co., Ltd.), Flora - de FC430, FC43
1 (manufactured by Sumitomo 3M Limited), Asahi Guard AG71
0, Surflon S-382, SC101, SC102,
Fluorinated surfactants such as SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), and acrylic or methacrylic (co) polymerized polyflow No. 75, no. 95 (manufactured by Kyoeisha Yushi Kagaku Kogyo KK) and the like. The amount of these surfactants is usually 2 parts by weight or less, preferably 1 part by weight or less, per 100 parts by weight of the solids in the composition of the present invention. These surfactants may be added alone or in some combination.

The photosensitive composition is applied on a substrate (eg, silicon / silicon dioxide coating) which is used for manufacturing precision integrated circuit devices by a suitable application method such as a spinner or a coater, and then passed through a predetermined mask. By exposing, baking and developing, a good resist pattern can be obtained.

The developer of the photosensitive composition of the present invention includes
Sodium hydroxide, potassium hydroxide, sodium carbonate,
Inorganic alkalis such as sodium silicate, sodium metasilicate and aqueous ammonia, primary amines such as ethylamine and n-propylamine, secondary amines such as diethylamine and di-n-butylamine, and triethylamine and methyldiethylamine Use alkaline aqueous solutions such as triamines, alcoholamines such as dimethylethanolamine and triethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, and cyclic amines such as pyrrole and pichelidine. be able to. Further, an appropriate amount of an alcohol or a surfactant may be added to the above alkaline aqueous solution.

[0215]

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

[0216]

Embedded image

[0219]

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

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

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

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

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

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

[Synthesis Example III-16] 20 g of alkali-soluble resin R-4 obtained in Synthesis Example II-4 80 ml of tetrahydrofuran 6.50 g of vinyl ether X-1 obtained in Synthesis Example I-1 were mixed in a flask. Then, 10 mg of p-toluenesulfonic acid was added, and the mixture was stirred at room temperature for 18 hours. Further, 1.6 g of pyridine and 1.72 g of acetic anhydride were added, and the mixture was stirred at room temperature for 6 hours. The reaction solution was dripped into 5 L of ultrapure water while vigorously stirring to reprecipitate. The obtained resin was dried in a vacuum dryer at 70 ° C. for 12 hours to obtain an alkali-soluble resin B-16 having a substituent according to the present invention.

[Synthesis Examples III-17 to III-21] Table 1 below
The alkali-soluble resins B-17 to B-21 having a substituent according to the present invention were obtained in the same manner as in Synthesis Example III-1 using the alkali-soluble resins, vinyl ethers, and acid anhydrides shown in (1).

[0226]

[Table 1]

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

[0228]

Embedded image

[0229]

[Table 2]

(Examples 1 to 21, Comparative Examples 1 to 4) [Preparation and Evaluation of Photosensitive Composition] Each of the materials shown in Table 3 below was dissolved in 8 g of PGMEA (propylene glycol monoethyl ether acetate). The solution was filtered through a 2 μm filter to prepare a resist solution. This resist solution was applied on a silicon wafer using a spin coater, and dried on a vacuum suction type hot plate at 130 ° C. for 60 seconds to obtain a resist film having a thickness of 0.8 μm.

[0231]

[Table 3]

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

[0233]

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This resist film was exposed using a 248 nm KrF excimer laser stepper (NA = 0.45). After the exposure, the film was heated on a hot plate at 100 ° C. for 60 seconds, immediately immersed in a 0.26 N aqueous solution of tetramethylammonium hydroxide (TMAH) for 60 seconds, rinsed with water for 30 seconds, and dried. The pattern on the silicon wafer thus obtained was observed with a scanning electron microscope, and the performance of the resist was evaluated. Table 3 shows the results. The resolving power indicates a limit resolving power at an exposure amount for reproducing a 0.30 μm line and space mask pattern. The resulting resist pattern was observed with an optical microscope or SEM to evaluate the roughness of the surface. A sample with a clean surface was rated as ○, a sample with slight roughness observed was rated as Δ, and a sample with marked roughness was rated as ×. Further, the dry etching resistance was evaluated by a relative value with the novolak resin being 1.0, after performing dry etching by an ordinary method. Those with numerical values approaching 1.0 are good. The rectangularity of the pattern profile was observed by SEM after exposure and development, and evaluated according to the following criteria. A: The angle between the pattern side wall and the substrate is 90 degrees (that is, perpendicular) and the angle between the pattern side wall and the pattern surface is right. O: The angle between the pattern side wall and the substrate is 85 to 95 degrees (substantially perpendicular) and the pattern side wall. The angle between the pattern surface and the pattern surface is almost right. ×: The angle between the pattern side wall and the substrate is 85 degrees or less or 95 degrees or more (taper or reverse taper) or the angle between the pattern side wall and the pattern surface is round.

[0235]

[Table 4]

As is clear from the results shown in Table 4, the positive photoresist compositions of the examples according to the present invention each obtained satisfactory results, but the photoresist compositions of the comparative examples did not. It was something.

[0237]

According to the present invention, the smoothness of the shape of the pattern profile, particularly the shape of the side wall of the pattern, is excellent.
High dry etching resistance, less surface roughness,
An excellent chemically amplified positive photoresist composition having high sensitivity and high resolution is provided.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H025 AA00 AA01 AA02 AA03 AA09 AB03 AB15 AB16 AB20 AC01 AC04 AC08 AD03 BE00 BE07 BE10 BG00 CB16 CB17 CB41 CB45 CB52 CC20 FA17 2H096 AA06 AA25 AA26 AA30 EA02 GA03 EA02

Claims (4)

[Claims] (1) by irradiation with actinic rays or radiation;
The following general formulas (A-1) and (A
-2), (A-3), (A-4), (A-5), (A-
6) and at least the compounds represented by (A-7)
One kind, and (b) the following general formulas (I) and (II)
A repeating structural unit represented by the following general formula (I),
The repeating structure represented by the general formula (II) and the general formula (III)
Decomposed by the action of acid containing unit
Characterized by containing a resin that increases the solubility in
Positive photosensitive composition. Embedded imageIn the formulas (A-1) and (A-2), R₁~ R_FiveIs the same
May be different and include a hydrogen atom, an alkyl group,
Alkyl group, alkoxy group, hydroxy group, halogen source
Child or -SR₆Represents a group. R₆Is an alkyl group, or
Indicates an aryl group. X^-Is a branched or cyclic carbon number 8
Selected from the group of more than one alkyl and alkoxy groups
Having at least one group, linear, branched or
Cyclic alkyl and alkoxy groups having 4 to 7 carbon atoms
Having at least two groups selected from the group
Or branched alkyl groups having 1 to 3 carbon atoms and alcohols
Having at least three groups selected from the group of xyl groups
Having 1 to 5 halogen atoms, or linear
Having a linear or branched ester group having 1 to 10 carbon atoms.
Benzene sulfonic acid, naphthalene sulfonic acid or anthra
Shows the anion of sensulfonic acid. Embedded imageIn the formula (A-3), R₇~ R_TenAre the same but different
Each may be a hydrogen atom, an alkyl group, a cycloalkyl
Group, an alkoxy group, a hydroxy group, or a halogen atom
Show. X^-Is a branched or cyclic alkyl having 8 or more carbon atoms.
Groups selected from the group consisting of
Having at least one, linear, branched or cyclic carbon number
Selected from the group of 4-7 alkyl and alkoxy groups
Having at least two groups,
Is a branched alkyl group having 1 to 3 carbon atoms and alkoxy
Bennes having at least three groups selected from the group of groups
Zensulfonic acid, naphthalenesulfonic acid or anthracene
3 shows the anion of sulfonic acid. m, n, p and q are
Each represents an integer of 1 to 3. Embedded imageIn the formula (A-4), R₁₁~ R₁₃Are the same but different
Hydrogen, alkyl, cycloalkyl,
Alkoxy group, hydroxy group, halogen atom or -SR
₆Represents a group. R₆, X^-Is as defined above. l, m and
And n may be the same or different and represent an integer of 1 to 3
You. When l, m and n are each 2 or 3, 2-3 R
₁₁~ R₁₃Two of each are bonded to each other to form a carbon
Ring consisting of 5 to 8 elements including ring, heterocycle or aromatic ring
May be formed. Embedded imageIn the formula (A-5), R₁₄~ R₁₆Are the same but different
Hydrogen, alkyl, cycloalkyl,
Alkoxy group, hydroxy group, halogen atom or -SR
₆Represents a group. R₆, X^-Is as defined above. l, m and
And n may be the same or different and represent an integer of 1 to 3
You. When l, m and n are each 2 or 3, 2-3 R
₁₄~ R₁₆Two of each are bonded to each other to form a carbon
Ring consisting of 5 to 8 elements including ring, heterocycle or aromatic ring
May be formed. Embedded imageIn the formula (A-6), Y represents a linear group which may have a substituent,
Branched or cyclic alkyl group, optionally substituted aralkyl
Group,Represents a group represented by (R₃₁~ R₅₁Are the same but different
And may have a hydrogen atom or a substituent.
Chain, branch, cyclic alkyl group, alkoxy group, acyl group,
Acylamino group, sulfonylamino group, aryl group,
Siloxy group, aralkyl group or alkoxycarbonyl
Group, formyl group, nitro group, chlorine atom, bromine atom
Represents an iodine atom, a hydroxyl group, or a cyano group;
₃₁~ R₃₅, R₃₆ ~ R₄₂And R₄₃~ R₅₁Is for each group
Two of which combine to form carbon and / or heteroatoms
Or a 5- to 8-membered ring). Y is another
It may be bonded to the residue of the midosulfonate compound.
X is a linear or branched alkylene which may have a substituent
Group, which may have a substituent and contains a hetero atom
A monocyclic or polycyclic alkylene group, which may be substituted
Linear or branched alkenylene group, which may be substituted
Monocyclic or polycyclic alkoyls which may contain heteroatoms
Kenylene group, optionally substituted arylene group, substituted
Represents an aralkylene group which may be substituted. Also, X is different
May be bonded to the imidosulfonate residue of Ar₁-SO_Two-SO_Two-Ar_Two (A-7) In the formula (A-7), Ar₁, Ar_TwoAre the same but different
And represents a substituted or unsubstituted aryl group. Embedded imageIn the formulas (I) to (III), R_{twenty one}Represents a hydrogen atom or a methyl group
Then R_{twenty three}Represents a group that is not decomposed by the action of an acid;_{twenty four}Is
Hydrogen atom, halogen atom, alkyl group, aryl group,
Represents a lucoxy group, an acyl group or an acyloxy group. n is 1
Represents an integer of 1 to 3. In the formula (II), R ′₁, R '_TwoAre the same
May be different, a hydrogen atom, or a group having 1 to 4 carbon atoms.
R represents an alkyl group; W represents a divalent organic group;_ThreeIs
Chain alkyl optionally having 1 to 20 carbon atoms
Group, a cyclic alkyl group which may have a substituent having 3 to 20 carbon atoms in total.
Ali group which may have a kill group or a substituent having 6 to 30 carbon atoms in total
Or a substituent having a total carbon number of 7 to 30.
Represents an aralkyl group. 2. The compound represented by the formula (II), wherein R ′ ₃ is a total of 11 to 11 carbon atoms.
A chain alkyl group optionally having 20 substituents, a cyclic alkyl group optionally having 11 to 20 carbon atoms, and an aryl optionally having 11 to 30 carbon atoms Group,
The positive photosensitive composition according to claim 1, which represents an aralkyl group which may have a substituent having 12 to 30 carbon atoms in total. 3. The compound represented by the formula (II), wherein R ′ ₃ has a total carbon number of 11 to 11.
A chain alkyl group optionally having 18 substituents, a cyclic alkyl group optionally having 11 to 18 carbon atoms, and an aryl optionally having 11 to 25 carbon atoms Group,
The positive photosensitive composition according to claim 1, wherein the positive photosensitive composition represents an aralkyl group which may have a substituent having 12 to 25 carbon atoms in total. 4. A low molecular weight acid-decomposable dissolution inhibiting compound having a molecular weight of 3,000 or less, which has a group decomposable by an acid and whose solubility in an alkaline developer is increased by the action of an acid. The positive photosensitive composition according to claim 1.