JPH11258802A - Negative resist composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the negative resist composition suitable for use of light from a <=220 nm exposure light source, especially, ArF excimer laser beams (193 nm) by incorporating specified compounds and resin. SOLUTION: This negative resist composition contains the compound to be allowed to produce an acid by irradiation with activated rays or radiation and the polycycloolefin resin having hydroxy and carboxy groups, and alicyclic groups on the main chain, and at least one kind of cyclic imido compound represented by the formula in which A is a divalent alkylene group or the like optionally having a hetero atom; B is an optionally substituted trivalent alkylene group or the like; Z1 is an H atom or the like; Z2 is an optionally substituted (m+1)-valent alkylene group or the like; Z3 is an optionally substituted n-valent alkylene group or the like; (m) is an integer of >=1; and (n) is an integer of >=2.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a negative resist composition used in the process of manufacturing semiconductors such as ICs, the manufacture of circuit boards such as liquid crystals and thermal heads, and other photofabrication processes. More specifically, the present invention relates to a negative resist composition suitable for using deep ultraviolet light having a wavelength of 220 nm or less as an exposure light source.

[0002]

2. Description of the Related Art As a positive photoresist composition, there is a chemically amplified resist composition described in U.S. Pat. No. 4,491,628 and EP 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. It is a pattern forming material that changes the properties and forms a pattern on a substrate.

[0003] Examples of such a combination include a combination of a compound that generates an acid by photolysis and an acetal or an O, N-acetal compound (JP-A-48-89003).
Combination with an orthoester or amide acetal compound (JP-A-5120714), combination with a polymer having an acetal or ketal group in the main chain (JP-A-53-133429), combination with an enol ether compound (JP-A-53-133429) No. 55-12995), a combination with an N-acyliminocarbonate compound (Japanese Patent Laid-Open No.
No. 5-126236), a combination with a polymer having an orthoester group in the main chain (JP-A-56-17345).
), A combination with a tertiary alkyl ester compound (JP-A-60-3625), a combination with a silyl ester compound (JP-A-60-10247), and a combination with a silyl ether compound (JP-A-60-1985). -37549
No. JP-A-60-112446). These have high photosensitivity because the quantum yield exceeds 1 in principle.

[0004] Similarly, a system which is decomposed by heating in the presence of an acid and solubilized in an alkali is disclosed in, for example,
-45439, JP-A-60-3625, JP-A-62
JP-A-229242, JP-A-63-27829, JP-A-63-36240, JP-A-63-250642, JP-A-5-181279, Polym.Eng.Sce., Vol. 23, 1012
Page (1983); ACS. Sym. 242, 11 (1984); Semicondu
ctor World 1987, November, p. 91; Macromolecules, 21,
Vol., P. 1475 (1988); SPIE, vol. 920, p. 42 (1988), etc., and a compound capable of generating an acid upon exposure to a tertiary or secondary carbon (for example, t-butyl, 2-cyclohexenyl). )
And JP-A-4-219775, JP-A-5-249682, and JP-A-6-219572.
Combination systems with acetal compounds described in JP-A-65332 and JP-A-4-21258 and JP-A-6-65.
No. 333, etc., in combination with a t-butyl ether compound.

Since these systems mainly use a resin having a poly (hydroxystyrene) basic skeleton, which has a small absorption in the 248 nm region, as a main component, when a KrF excimer laser is used as an exposure light source, a high sensitivity is obtained. A high-resolution and good pattern can be formed, and it can be a good system as compared with the conventional naphthoquinonediazide / novolak resin system. On the other hand, similarly, a negative-type chemical amplification system using a crosslinking reaction by a photo-generated acid catalyst has been studied.
As such an example, for example, JP-A-4-226458
Nos. 4-291258, 4-291259, 4-291260, 4-291261, and 4-3
No. 14055, No. 4-358155, No. 4-3678
No. 64, No. 4-369865, No. 5-5991, No. 5-67431, No. 5-88366, No. 5-113
No. 666, No. 5-134411, No. 5-134412
Nos. 5-173333, 5-210239, 5-233706, 5-281715, and 5-3
No. 13370, No. 6-3825, No. 6-43647
No. 6-67413, No. 6-67431, No. 6-
No. 19137, No. 6-130666, No. 6-1386
No. 51, No. 6-138660, No. 6-194838
No. 6-214392, No. 6-214393, No. 6-236024, No. 7-33855, No. 7-13
No. 4412, No. 7-140660, No. 7-18167
No. 8, No. 7-244378, No. 7-295220,
8-29981, 8-152717, 8-1
No. 66870, No. 8-184966, No. 8-2409
No. 11, 8-292559, 8-292564
And JP-A-8-339087.

However, a light source of an even shorter wavelength, for example, Ar
When an F excimer laser (193 nm) is used as an exposure light source, a compound having an aromatic group is essentially 19
Because of the large absorption in the 3 nm region, the above chemical amplification system was not sufficient. As a polymer having a small absorption in the 193 nm region, use of poly (meth) acrylate has been promoted.
As described in J. Vac. Sci. Technol., B9, 3357 (1991), this polymer is generally more resistant to dry etching in semiconductor manufacturing processes than conventional phenolic resins having aromatic groups. There was a problem of low.

On the other hand, the polymer having an alicyclic group has the same dry etching resistance as an aromatic group and has a small absorption in the 193 nm region.
1672, 66 (1992). In recent years, the use of this polymer for positive-type photosensitive systems has been energetically studied. Specifically, JP-A-4-39665 and JP-A-5-8
0515, 5-265212, 5-29759
No. 1, 5-346668, 6-289615,
6-324494, 7-49568, 7-1
No. 85046, No. 7-191463, No. 7-1994
No. 67, No. 7-234511, No. 7-252324
And the polymers described in the specifications such as JP-A No. 8-259626. On the other hand, in a negative photosensitive system, a stable system that achieves both reduction in absorption of light having a wavelength of 193 nm and resistance to dry etching has not yet been achieved.

[0008]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a negative resist composition suitable for use with an exposure light source having a wavelength of 220 nm or less, particularly an ArF excimer laser beam (193 nm). Specifically, 22
Good sensitivity when using an exposure light source with a wavelength of 0 nm or less,
An object of the present invention is to provide a negative resist composition having resolution, having sufficient dry etching resistance, and having sufficient stability during storage.

[0009]

Means for Solving the Problems The inventors of the present invention have made intensive studies while paying attention to the above-mentioned properties, and as a result, the object of the present invention is to use a resin having an alicyclic group and a hydroxyl group and a cyclic imide compound as described below. Find that it is achieved brilliantly,
The present invention has been reached. That is, the present invention has the following configuration. (1) (A) a compound that generates an acid upon irradiation with actinic rays or radiation, (B) a polycycloolefin resin having a hydroxyl group and a carboxyl group and having an alicyclic group in the main chain, and (C) A negative resist composition comprising a cyclic imide compound. (2) The component (C) is at least one cyclic imide compound selected from the group consisting of compounds represented by the following general formulas (I), (II) and (III). The negative resist composition according to the above (1).

[0010]

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In general formulas (I), (II) and (III):
A represents a divalent alkylene group, alkenylene group, cycloalkylene group or cycloalkenylene group which may contain a hetero atom and may have a substituent. B represents a trivalent alkylene group, alkenylene group, cycloalkylene group or cycloalkenylene group which may contain a hetero atom and may have a substituent. Z ₁ is a hydrogen _{atom, -OH, -O-R a,} -O-
SO ₂ —R _a , —O—CO—R _a , —O—CO—O—R _a ,
Or an _{-O-CO-NH-R a} . Where _Ra is
Represents an alkyl group or a cycloalkyl group which may have a substituent. Z ₂ may have a substituent, (m
+1) valent alkylene group, alkenylene group or cycloalkylene _{group, -O-R b (-O-)} m, -O-SO 2
_{-R b (-SO 2 -O-) m} , -O-CO-R b (-CO
-O-) m, -O-CO- O-R b (-O-CO-O
-) M, or -O-CO-NH- _Rb (-NH-CO-
O-) m. Here, R _b represents a (m + 1) -valent alkylene group or cycloalkylene group which may have a substituent. Z ₃ may have a substituent, n
Represents a valent alkylene group, alkenylene group or cycloalkylene group. m represents an integer of 1 or more. n represents an integer of 2 or more. Further, a plurality of B and Z _{3 in the} general formula (III) are 2
It may combine at more than one position to form a ring structure composed of 3 to 10 carbon atoms and heteroatoms.

(3) The resin as the component (B) comprises at least one structural unit selected from the group consisting of repeating structural units having an alicyclic group represented by the following general formulas (IV) and (V): The negative resist composition according to the above (1) or (2), which is contained in a main chain.

[0013]

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In general formulas (IV) and (V), R _{4 to} R
₇ each independently represents a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a carboxyl group, -CO-OR ₃₈
An alkyl group, which may have a group or a substituent,
Represents a hydroxyalkyl group, a haloalkyl group, or an alkoxy group. Here, R ₃₈ represents an alkyl group, a cycloalkyl group or an alkenyl group which may have a substituent.
Further, two of R _{4 to} R ₇ may be bonded to each other to form an alkylene chain. A _{1 to} A ₃ each independently represent a divalent alkylene group, an alkenylene group, or a monocyclic or polycyclic cycloalkylene group which may have a substituent. X represents a single bond, a divalent alkylene group, an alkenylene group, or a —SO ₂ — group. p and q represent an integer of 0 to 4. (4) The repeating structural units having an alicyclic group represented by the general formulas (IV) and (V) are represented by the following general formulas (VI) to (VI).
(3) The negative resist composition as described in (3) above, which is at least one structural unit selected from the group consisting of repeating structural units represented by (X).

[0015]

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In the general formulas (VI) to (X), R _{4 to} R ₇ , R
₃₈ and X have the same meanings as in the above general formulas (IV) to (V). R ₈ to R ₃₇ each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group, an alkyl group, a hydroxyalkyl group, a cycloalkyl group, an alkenyl group, -CO-OR ₃₈ group, or a carboxyl group. Further, two of R _{4 to} R ₃₇ may be bonded to form an alkylene group having 1 to 5 carbon atoms which may contain a hetero atom. a to j each independently represent an integer of 0 to 4; (5) The resin of the component (B) is represented by the following general formula (XI):
(1) to (4), which is a resin having at least one structural unit selected from the group consisting of repeating structural units having a hydroxyl group represented by (XII) and (XIII). The negative resist composition according to any one of the above.

[0017]

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In the general formulas (XI) to (XIII), R₃₉, R
₄₀, R₄₂~ R₄₄Are each independently a hydrogen atom or a halogen atom
, A cyano group, an alkyl group which may have a substituent
Or a haloalkyl group. R₄₁Is a cyano group, -CO
-OR₄₅Or -CO-NR₄₆R₄₇Represents X₁~ X
_ThreeAre each independently a single bond or -CO-R₄₈−,
-CO-OR ₄₉-, -CO-NR₅₀-R₅₁-, Substituent
Optionally having a divalent alkylene group, alkenylene
Or a cycloalkylene group alone or
Represents a divalent group in which two or more are combined. Where R₄₅~ R
₄₇, R₅₀Each independently has a hydrogen atom or a substituent
Alkyl, cycloalkyl or alkenyl
Represents a hydroxyl group. Also R₄₆, R₄₇Bond to form a ring
Good. R₄₈, R₄₉, R₅₁Is a single bond or an ether group,
Has ester group, amide group, urethane group, ureido group
Or a divalent alkylene group, alkenylene group or
Represents a cycloalkylene group. (6) The resin of the component (B) is represented by the following general formula (XIV):
Carboxyl groups represented by (XV) and (XVI)
Selected from the group consisting of repeating structural units having
Characterized by a resin having at least one type of structural unit
The negative-working laser according to any one of the above (1) to (5)
Dist composition.

[0019]

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In general formulas (XIV) to (XVI): R ₅₂ ,
R ₅₃ and R _{55 to} R ₅₇ each independently represent a hydrogen atom, a halogen atom, a cyano group, or an alkyl group or a haloalkyl group which may have a substituent. R ₅₄ represents a cyano group, —C
It represents an O-OR ₅₈ or -CO-NR ₅₉ R _60. X _{4 to} X
₆ are each independently a single bond or -CO-R ₆₁ -, - C
O—O—R ₆₂ —, —CO—NR ₆₃ —R ₆₄ —, an optionally substituted divalent alkylene group, alkenylene group or cycloalkylene group alone or
Represents a divalent group in which two or more are combined. Where R ₅₈ is
Represents a hydrogen atom, an alkyl group, a cycloalkyl group or an alkenyl group which may have a substituent. R ₅₉ , R ₆₀ ,
R ₆₃ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group or an alkenyl group which may have a substituent. R ₅₉ and R ₆₀ may combine to form a ring. R ₆₁ , R ₆₂ and R ₆₄ each independently represent a single bond, or a divalent alkylene group, alkenylene group or cycloalkylene which may have an ether group, ester group, amide group, urethane group or ureido group. Represents a group. (7) The above (1) to (6), wherein far ultraviolet light having a wavelength of 220 nm or less is used as an exposure light source.
A negative resist composition according to any one of the above.

The cyclic imide compound of the present invention (C) crosslinks efficiently with the resin of the present invention (A) under an acid catalyst and becomes insoluble in an alkali developing solution. Therefore, a negative image is formed by exposure. Since the resin of the present invention (A) has an alicyclic group in the main chain, it has low absorption at 220 nm or less, and particularly low absorption in ArF excimer laser light (193 nm).
In addition, it shows sufficient characteristics for dry etching resistance.

[0022]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments will be described below.
The present invention is not limited to this embodiment. The negative resist composition of the present invention comprises a compound capable of generating an acid upon irradiation with actinic rays or radiation (hereinafter referred to as “compound of component (A)”), an alicyclic group in the main chain, and a hydroxyl group. It contains a polycycloolefin resin having a group and a carboxyl group (hereinafter, referred to as “resin of component (B)”) and a cyclic imide compound (hereinafter, referred to as “compound of component (C)”). First, the resin of the component (B) will be described in detail, followed by the compound of the component (C) and the compound of the component (A).

[1] Regarding resin of component (B) The resin of component (B) is a polycycloolefin resin.
It has an alicyclic group in the main chain, and further has a hydroxyl group and a carboxyl group. The alicyclic group which the resin of the component (B) has in the main chain may be monocyclic or polycyclic. Specific examples include a divalent group having a monocyclo, bicyclo, tricyclo, tetracyclo structure or the like having 5 or more carbon atoms. The number of carbon atoms is preferably from 6 to 30, particularly preferably a polycyclic group having from 7 to 25 carbon atoms. The substituent may or may not have. Representative structural examples of the alicyclic portion of the polycyclic alicyclic group constituting the main chain are shown below.

[0024]

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[0025]

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[0026]

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The repeating unit containing an alicyclic group forming the main chain is preferably a repeating unit represented by the general formula (IV) or (V), and more preferably a repeating unit represented by the general formulas (VI) to (X). Can be mentioned. The hydroxyl group and the carboxyl group may be respectively contained in the repeating structural units represented by the general formulas (IV) or (V), more preferably, the general formulas (VI) to (X). It may be included in another repeating unit. As such other repeating units, general formulas (XI) to (XIII) and (XI)
V) to (XVI).

The carboxyl group, hydroxy group and acid-decomposable group may be contained in a plurality of positions in the above repeating unit, or may be unevenly distributed in a chain molecule.
It may be dispersed.

In the general formulas (IV) to (X), R _{4 to} R
₇ is a hydrogen atom, a halogen atom, a cyano group, a hydroxy group, an alkyl group, a haloalkyl group, a hydroxyalkyl group, and an alkoxy group, group can be represented by -CO-OR _38, or a carboxy group. R _{4 to} R
Examples of the alkyl group represented by ₇ include, for example, those having 1 to 4 carbon atoms.
Can be mentioned. For example, a methyl group,
Ethyl, propyl, n-butyl and sec-butyl groups are preferred. The haloalkyl group is an alkyl group partially or wholly substituted with a halogen atom, preferably substituted with a fluorine atom, a chlorine atom or a bromine atom, and preferably has 1 to 4 carbon atoms. For example, a fluoromethyl group, a chloromethyl group, a bromomethyl group, a fluoroethyl group, a chloroethyl group, a bromoethyl group and the like can be mentioned. Examples of the hydroxyalkyl group include a hydroxymethyl group, a 2-hydroxyethyl group, a 2-hydroxypropyl group, a C1-C4 group such as a 4-hydroxybutyl group.
Six things can be mentioned. Examples of the alkoxy group include an alkoxy group having 1 to 8 carbon atoms. For example, a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, a hydroxypropoxy group, a butoxy group and the like are preferable. Any of the following alkyl groups may or may not have a substituent. In addition, any two of R _{4 to} R ₇ may be bonded to each other to form an alkylene group having 1 to 5 carbon atoms. This alkylene group may contain a hetero atom in the skeleton structure.

R ₃₈ in the above formula represents an alkyl group, a cycloalkyl group or an alkenyl group. The alkyl group represented by R ₃₈ is, for example, an alkyl group having 1 to 8 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group,
Preferred examples include an n-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group, and an octyl group. The cycloalkyl group may be monocyclic or polycyclic. Preferred examples of the monocyclic type include a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group having 3 to 8 carbon atoms. Preferred examples of the polycyclic type include an adamantyl group, a norbornyl group, an isobornyl group, a dicyclopentyl group, a σ-pinel group, and a tricyclodecanyl group. The alkenyl group is, for example, an alkenyl group having 2 to 6 carbon atoms,
Preferable examples include a vinyl group, a propenyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group and a cyclohexenyl group. Each of these may or may not have a substituent.

A _{1 to} A ₃ are divalent groups and include, for example, an alkylene group, an alkenylene group and a cycloalkylene group. Specific examples include an alkylene group having 1 to 8 carbon atoms, an alkenylene group having 2 to 6 carbon atoms, and a cycloalkylene group having 4 to 8 carbon atoms. A
₁ As the alkylene group represented to A _3, for example, methylene group, ethylene group, propylene group, butylene group, hexylene group, and preferably an octylene group.
Preferred examples of the alkenylene group include an ethenylene group, a propenylene group, and a butenylene group. Preferred examples of the cycloalkylene group include a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, and a norbornylene group. Such an alkylene group, alkenylene group, and cycloalkylene group may or may not have a substituent.

The alkylene group represented by X includes, for example, an alkylene group having 1 to 4 carbon atoms, and preferably includes a methylene group and an ethylene group. Examples of the alkenylene group include alkenylene groups having 2 to 4 carbon atoms, and preferably include an ethenylene group, a propenylene group, and a butenylene group.
The alkylene group and alkenylene group may or may not have a substituent.

R _{4 to} R _{7 of} the general formulas (VI) to (X), X
Is synonymous with any of those represented by the general formulas (IV) to (V). R _{8 to} R ₃₇ include a hydrogen atom, a halogen atom, a hydroxy group, a hydroxyalkyl group, an alkoxy group, an alkyl group, a cycloalkyl group, an alkenyl group,
A -CO-OR ₃₈ group or a carboxy group can be mentioned. Examples of the alkyl group represented by R _{8 to} R ₃₇ include the same alkyl groups as the alkyl groups represented by R ₃₈ described above. The above cycloalkyl group, alkenyl group, hydroxyalkyl group, alkoxy group, -CO-O
Examples for R ₃₈ groups may be the same group as each example of R ₄ to R ₇ shown both by the general formula (IV) ~ (V).

Furthermore, at least two of R _{4 to} R ₁₇ in the formula (VI), R _{4 to} R ₁₀ , R ₁₂ , R ₁₃ and R _{4 to} R ₁₀ in the formulas (VII), (IX) and (X) R _{15 to} R
₂₇ or at least two of R _{4 to} R ₁₀ , R ₁₂ , R ₁₃ , R _{15 to} R ₂₀ , R ₂₂ , R ₂₃ in formula (VIII)
And at least two of R _{25 to} R ₃₇ may combine to form an alkylene group having 1 to 5 carbon atoms. In this case, the alkylene group may include a hetero atom in the skeleton structure. Specific examples of the repeating structural units represented by formulas (VI) to (X) are shown below, but the present invention is not limited thereto.

[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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As described above, the resin of the component (B) has a hydroxyl group and a carboxyl group. As the repeating unit having a hydroxyl group and a carboxyl group, general formulas (XI) to (XIII) and general formulas (XIV) to (X
The repeating unit represented by VI) may be used. The repeating units represented by formulas (XI) to (XVI) are included by copolymerizing with the repeating units represented by formulas (VI) to (X).

R ₃₉ , R ₄₀ , R _{42 to} R ₄₄ , R ₅₂ , R ₅₃ , R
_{55 to} R ₅₇ each represent a hydrogen atom, a halogen atom, a cyano group,
Represents an alkyl group or a haloalkyl group. R ₃₉ , R ₄₀ , R
Examples of the alkyl group represented by _{42 to} R ₄₄ , R ₅₂ , R ₅₃ , and R _{55 to} R ₅₇ include, for example, an alkyl group having 1 to 4 carbon atoms, and specifically, for example, a methyl group, an ethyl group, Preferred examples include a propyl group, an n-butyl group, and a sec-butyl group. Examples of the haloalkyl group include an alkyl group having 1 to 4 carbon atoms in which a halogen atom is partially or entirely substituted. As the halogen atom in that case, a fluorine atom, a chlorine atom or a bromine atom can be preferably mentioned. Preferred examples of such a haloalkyl group include a fluoromethyl group, a chloromethyl group, a bromomethyl group, a fluoroethyl group, a chloroethyl group, and a bromoethyl group. These alkyl groups or haloalkyl groups may or may not further have a substituent.

R ₄₁ is a cyano group or —CO—OR ₄₅ ,
It represents the -CO-NR ₄₆ R _47. R in -CO-OR _45
45 is an alkyl group, a cycloalkyl group of R ₃₈ described above,
The same as those described for the alkenyl group can be used. R _46, R ₄₇ in -CO-NR ₄₆ R ₄₇ represents a hydrogen atom or an alkyl group, a cycloalkyl group, an alkenyl group. The alkyl group, cycloalkyl group, and alkenyl group may have a substituent or may not have a substituent.

Examples of the alkyl group represented by R ₄₆ and R ₄₇ include an alkyl group having 1 to 8 carbon atoms, and particularly, a methyl group, an ethyl group, a propyl group, an n-butyl group and a se
C-butyl, hexyl, 2-ethylhexyl and octyl are preferred. The cycloalkyl group may be monocyclic or polycyclic. As the monocyclic type, for example, carbon atoms of 3
To 8 cycloalkyl groups, and specifically, preferably, a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group. Preferred examples of the polycyclic type include an adamantyl group, a norbornyl group, an isobornyl group, a dicyclopentyl group, a σ-pinel group, and a tricyclodecanyl group. Examples of the alkenyl group include an alkenyl group having 2 to 6 carbon atoms, particularly a vinyl group, a propenyl group,
Allyl group, butenyl group, pentenyl group, hexenyl group,
Preferable examples include a cyclohexenyl group.
These alkyl group, cycloalkyl group, and alkenyl group may or may not have a substituent.

R ₄₆ and R ₄₇ may be bonded to each other to form a ring containing a nitrogen atom. Examples of such a ring include pyrrolidine, piperidine, and piperazine.
An 8-membered ring can be preferably mentioned.

Examples of the alkylene group represented by X _{1 to} X ₃ include an alkylene group having 1 to 8 carbon atoms.
Particularly, a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, an octylene group and the like can be preferably mentioned. Examples of the alkenylene group include an alkenylene group having 2 to 6 carbon atoms, and in particular, an ethenylene group, a propenylene group, a butenylene group, and the like are preferable. As the cycloalkylene group, a cyclopentylene group optionally having a substituent, a cyclohexylene group, a dicyclodecaneylene group, a tricyclodecaneylene group, a tetracyclododecylene group, an adamantylene group, Monocyclic or polycyclic ones having 5 to 20 carbon atoms such as an androstannylene group are exemplified. Alkylene group, alkenylene group, cycloalkylene group,
Both may have a substituent or may not have a substituent.

R₄₈, R₄₉, R₅₁An alkylene group represented by
As the rukenylene group and the cycloalkylene group, X has already been used.₁
~ X_ThreeAlkylene group, alkenylene group, cyclo
The same as the alkylene group can be mentioned. Like this
Alkylene, alkenylene, cycloalkylene
Is an ether group, an ester group, an amide group, a urethane group,
Even if the ureido group is contained in a part of its main chain or side chain
Well, it need not be included. -CO-NR₅₀-R₅₁−
R in the group₅₀As R₄₁-CO-NR₄₅R₄₆of
R ₄₅, R₄₆Examples of the same group can be mentioned.

R ₅₄ represents a cyano group or —CO—OR ₅₈ ,
It represents the -CO-NR ₅₉ R _60. R in -CO-OR _58
58 is an alkyl group for R ₃₈ described above, a cycloalkyl group,
The same as those described for the alkenyl group can be used. R _59, R ₆₀ in -CO-NR ₅₉ R ₆₀ represents a hydrogen atom or an alkyl group, a cycloalkyl group, an alkenyl group. The alkyl group, cycloalkyl group, and alkenyl group may have a substituent or may not have a substituent.

Examples of the alkyl group represented by R ₅₉ and R ₆₀ include an alkyl group having 1 to 8 carbon atoms, and particularly, a methyl group, an ethyl group, a propyl group, an n-butyl group, and a
C-butyl, hexyl, 2-ethylhexyl and octyl are preferred. The cycloalkyl group may be monocyclic or polycyclic. As the monocyclic type, for example, carbon atoms of 3
To 8 cycloalkyl groups, and specifically, preferably, a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group. Preferred examples of the polycyclic type include an adamantyl group, a norbornyl group, an isobornyl group, a dicyclopentyl group, a σ-pinel group, and a tricyclodecanyl group. Examples of the alkenyl group include an alkenyl group having 2 to 6 carbon atoms, particularly a vinyl group, a propenyl group,
Allyl group, butenyl group, pentenyl group, hexenyl group,
Preferable examples include a cyclohexenyl group.
These alkyl group, cycloalkyl group, and alkenyl group may or may not have a substituent.

R ₅₉ and R ₆₀ may be bonded to each other to form a ring containing a nitrogen atom. Examples of such a ring include pyrrolidine, piperidine, and piperazine.
An 8-membered ring can be preferably mentioned.

Examples of the alkylene group represented by X _{4 to} X ₆ include an alkylene group having 1 to 8 carbon atoms.
Particularly, a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, an octylene group and the like can be preferably mentioned. Examples of the alkenylene group include an alkenylene group having 2 to 6 carbon atoms, and in particular, an ethenylene group, a propenylene group, a butenylene group, and the like are preferable. As the cycloalkylene group, a cyclopentylene group optionally having a substituent, a cyclohexylene group, a dicyclodecaneylene group, a tricyclodecaneylene group, a tetracyclododecylene group, an adamantylene group, Monocyclic or polycyclic ones having 5 to 20 carbon atoms such as an androstannylene group are exemplified. Alkylene group, alkenylene group, cycloalkylene group,
Both may have a substituent or may not have a substituent.

R₆₁, R₆₂, R₆₄An alkylene group represented by
As the rukenylene group and the cycloalkylene group, X has already been used.₁
~ X_ThreeAlkylene group, alkenylene group, cyclo
The same as the alkylene group can be mentioned. Like this
Alkylene, alkenylene, cycloalkylene
Is an ether group, an ester group, an amide group, a urethane group,
Even if the ureido group is contained in a part of its main chain or side chain
Well, it need not be included. -CO-NR₆₃-R₆₄−
R in the group₆₃As R₅₄-CO-NR₅₉R₆₀of
R ₅₉, R₆₀Examples of the same group can be mentioned.

Specific examples of the repeating structural units represented by formulas (XI) to (XVI) are shown below, but the invention is not limited thereto.

[0053]

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[0054]

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[0055]

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[0056]

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[0057]

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In addition, specific examples of the further substituents mentioned as needed in each of the above substituents include a hydroxyl group, a halogen atom, a nitro group, a cyano group, an amide group,
Examples thereof include a sulfonamide group, and further include an alkyl group and an alkoxy group represented by R _{8 to} R ₄₇ , or an alkoxycarbonyl group, an acyl group, and an acyloxy group represented by R _{51 to} R _53. And a carboxy group. Examples of the acyloxy group include an acetoxy group and a butyryloxy group. Examples of the halogen atom include fluorine, chlorine, bromine, and iodine.

A repeating unit having an alicyclic group in the main chain (preferably a repeating unit represented by formula (IV) or (V), more preferably any of formulas (VI) to (X)) The content in the resin is usually at least 30 mol%, preferably 40 to 100 mol%, more preferably 50 to 100 mol%.
Molar%, especially the range of 70 to 100 molar% is good. In practice, it may be adjusted by the balance between dry etching resistance, alkali developability and the like.

The resin (B) has a hydroxyl group and a carboxyl group. The content of the repeating structural unit having a hydroxyl group and a carboxyl group in the resin is preferably 10 to 70 mol% in all the repeating structural units.
More preferably, it is 20 to 60 mol%, and still more preferably 30 to
５０50 mol%. In addition, these content rates,
The content may be adjusted in consideration of the content of the compound of the component (C) and the performance such as alkali developability, substrate adhesion, and sensitivity.
The content of each of the repeating structural units having a hydroxyl group or a carboxyl group in the resin is the total content of the resin, including those contained in the repeating unit having an alicyclic group in the main chain. is there.

For the purpose of improving the performance of the resin of component (B), another polymerizable monomer may be further copolymerized within a range that does not significantly impair the transmittance of the resin of 220 nm or less and the dry etching resistance. Good. Copolymerizable monomers that can be used include those shown below. For example, it has one addition-polymerizable unsaturated bond selected from acrylates, acrylamides, methacrylates, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, crotonates, and the like. Compound.

Specifically, for example, acrylic esters such as alkyl (the alkyl group has 1 to 1 carbon atoms)
Acrylates (eg, methyl acrylate, ethyl acrylate, propyl acrylate, t-butyl acrylate, amyl acrylate, cyclohexyl acrylate, ethylhexyl acrylate, octyl acrylate, tert-octyl acrylate) , Chloroethyl acrylate, 2-hydroxyethyl acrylate 2,2
-Dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, glycidyl acrylate, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, etc.) aryl acrylate (for example, phenyl acrylate) , Hydroxyphenyl acrylate, etc.);

Methacrylic esters, for example, alkyl (alkyl having preferably 1 to 10 carbon atoms) methacrylate (for example, methyl methacrylate,
Ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, t-butyl methacrylate,
Amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate,
Chlorbenzyl methacrylate, octyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, glycidyl methacrylate , Furfuryl methacrylate, tetrahydrofurfuryl methacrylate, etc.), aryl methacrylates (eg, phenyl methacrylate, hydroxyphenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, etc.); acrylamides such as acrylamide, N-alkylacrylamide, , Having 1 to 10 carbon atoms
Such as methyl, ethyl, propyl, butyl, t-butyl, heptyl, octyl, cyclohexyl, benzyl, hydroxyethyl and benzyl groups. ), N-arylacrylamides (aryl groups include, for example, phenyl, tolyl, nitrophenyl, naphthyl, cyanophenyl, hydroxyphenyl, carboxyphenyl, etc.),
N, N-dialkylacrylamide (an alkyl group having 1 to 10 carbon atoms, for example, a methyl group, an ethyl group, a butyl group, an isobutyl group, an ethylhexyl group,
And a cyclohexyl group. ), N, N-arylacrylamide (aryl groups include, for example, phenyl group), N-methyl-N-phenylacrylamide, N-hydroxyethyl-N-methylacrylamide, N-2-acetamidoethyl-N Methacrylamides, for example, methacrylamide, N-alkyl methacrylamide (an alkyl group having 1 to 10 carbon atoms, for example, a methyl group, an ethyl group, a t-butyl group, an ethylhexyl group; A hydroxyethyl group, a cyclohexyl group, etc.), N-
Aryl methacrylamide (aryl group includes phenyl group, hydroxyphenyl group, carboxyphenyl group, etc.), N, N-dialkylmethacrylamide (alkyl group includes ethyl group, propyl group, butyl group, etc.) ), N, N-diarylmethacrylamide (an aryl group includes a phenyl group and the like), N-
Hydroxyethyl-N-methylmethacrylamide, N-
Methyl-N-phenylmethacrylamide, N-ethyl-
N-phenyl methacrylamide and the like; allyl compounds, for example, allyl esters (eg, allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl acetoacetate) Allyl, etc.), allyloxyethanol, etc .;

Vinyl ethers such as alkyl vinyl ethers (eg, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether,
Ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, Tetrahydrofurfuryl vinyl ether, etc.), vinyl aryl ethers (eg, vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,
4-dichlorophenyl ether, vinyl naphthyl ether, vinyl anthranyl ether, etc.); vinyl esters such as vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl barate, vinyl caproate, and vinyl chloride Acetate, vinyl dichloroacetate, vinyl methoxy acetate, vinyl butoxy acetate, vinyl phenyl acetate, vinyl aceto acetate, vinyl lactate, vinyl-β-phenyl butyrate, vinyl cyclohexyl carboxylate, vinyl benzoate,
Vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate, and the like;

Styrenes such as styrene, alkyl styrene (eg, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl Styrene, trifluoromethylstyrene, ethoxymethylstyrene, acetoxymethylstyrene, etc., alkoxystyrene (eg, methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene, etc.), halogen styrene (eg, chlorostyrene, dichlorostyrene) , Trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorstyrene , Trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene, etc., hydroxystyrene (for example, 4-hydroxystyrene, 3-hydroxystyrene, 2-hydroxystyrene, -Hydroxy-3-methylstyrene, 4-hydroxy-3,5-dimethylstyrene, 4-hydroxy-3-methoxystyrene, 4-hydroxy-3- (2-hydroxybenzyl)
Crotonates; for example, alkyl crotonates (eg, butyl crotonate, hexyl crotonate, glycerin monocrotonate); dialkyl itaconates (eg, dimethyl itaconate, diethyl itaconate; And dialkyl esters of maleic acid or fumaric acid (eg, dimethyl maleate, dibutyl fumarate, etc.), maleic anhydride, maleimide, acrylonitrile, methacrylonitrile, maleilenitrile and the like. In addition, generally, any addition-polymerizable unsaturated compound that can be copolymerized may be used.

Among them, monomers having a carboxyl group such as carboxystyrene, N- (carboxyphenyl) acrylamide, N- (carboxyphenyl) methacrylamide, hydroxystyrene, N- (hydroxyphenyl) acrylamide, N- ( Monomers having a phenolic hydroxyl group, such as (hydroxyphenyl) methacrylamide, hydroxyphenyl acrylate, and hydroxyphenyl methacrylate, and monomers that improve alkali solubility, such as maleimide, are preferred as the copolymerization component.

The content of the other polymerizable monomer in the resin as the component (B) is 50 mol% based on all the repeating units.
Or less, more preferably 30 mol% or less.

The molecular weight of the resin as the component (B) is 2,000 or more, preferably 3,000 to 1,000,000, more preferably 5,000 to 200,000 by weight average (Mw: polystyrene standard). More preferably, 20,0
The range is from 00 to 100,000. The larger the value, the better the heat resistance and the like, but the lower the developability and the like. The degree of dispersion (M
w / Mn) is preferably 1.0 to 5.0, more preferably 1.0 to 3.0, and the smaller the value, the better the heat resistance and image performance (pattern profile, defocus latitude, etc.). . In the present invention, the amount of the resin (B) added to the negative resist composition is 50 to 99.7% by weight, preferably 70 to 9% by weight, based on the total solid content.
99% by weight.

The resin (B) is synthesized by radical, cationic or anionic polymerization of unsaturated monomers corresponding to each structure. More specifically, each monomer is blended based on the preferred composition shown above, and is mixed in an appropriate solvent with about 1%.
A polymerization catalyst is added at a monomer concentration of 0 to 40% by weight,
It is heated and polymerized as needed. For example, there is the following method. Typically, the following three methods are mentioned.

(1) Ring-opening metathesis polymerization of a monocyclic or polycyclic cycloolefin using a coordination polymerization catalyst such as a transition metal complex. (2) Addition polymerization of a monocyclic or polycyclic cycloolefin using an electrophilic transition metal catalyst. (3) Free-radical copolymerization of a monocyclic or polycyclic cycloolefin with an electrophilic olefin (such as maleic acid). The specific synthesis method is 'Olefin Metathesis' by KJIvin.
(1983, Academic Press), V. Draguton et al. 'Olefin Me
tathesis and Ring-Opening Polymerization of Cyclo-
Olefins' (1985, Wiley-Interscience), S. Matsumoto
'ACS Symposium Series, No. 59, 303 (1977)', J. Am. C
hem., 110, 960 (1988); J. Am. Chem., 112, 8378 (199).
0)., J. Am. Chem., 113, 6899 (1991)., J. Organomat. Ch.
em., 358, 567 (1988); Makromol. Chem., 193, 2917 (1
992)., J. Mol. Cat., 74, 109 (1992)., Polym. Bull., 3
1, 175 (1993), J. Macromol. Sci. Chem., A5, 1339 (19
71)., J. Photopolym. Sci. Tech., 7, 141 (1994). In addition, J. Am. Chem., 79, 5771 (195
7)., J. Am. Chem., 81, 984 (1959)., Makromol.
134, 147 (1970)., J. Org.Chem., 26, 4658 (1961).,
J. Polym. Sci., 61, 538 (1962)., J. Polym. Sci. Part A
3, 723 (1965), J. Polym. Sci. Part A3, 1609 (1965), and also British Patent No. 1255838, JP-B-48-2063.
No. 2, 48-43191, 55-5525, 57-16130, 58
-50270, 58-50272, Tokuhei 2-9619, 2-42094
No. 6-18817, JP-A-51-6300, JP-A-51-31800,
No. 53-71200, JP-A No. 1-197460, No. 1-217453, No. 1-31
No. 8023, No. 1-318025, No. 2-146045, No. 2-59751,
4-63810, 4-249509, 4-353507, 5-80515
And can be synthesized by the method described in the specification such as JP-A No. 5-97591.

[2] Compound of Component (C) The cyclic imide compound of the present invention (C) is represented by the general formula (I):
It is preferably a compound represented by (II) or (III). In the formula, the divalent alkylene group in A preferably has 2 to 8 carbon atoms such as an ethylene group, a propylene group, a butylene group, a hexylene group, and an octylene group which may have a substituent. . The divalent alkenylene group preferably has 2 to 2 carbon atoms such as an optionally substituted ethenylene group, a propenylene group and a butenylene group.
There are six. Examples of the divalent cycloalkylene group preferably include those having 5 to 8 carbon atoms such as a cyclopentylene group and a cyclohexylene group which may have a substituent. Examples of the divalent cycloalkenylene group include those having 5 to 10 carbon atoms such as a cyclopentenylene group and a cyclohexenylene group.

The trivalent alkylene group, the trivalent alkenylene group, the trivalent cycloalkylene group, and the trivalent cycloalkenylene group of B are the above-mentioned divalent ones in which one bond is increased. Can be mentioned. In addition, A,
Each substituent in the definition of B may contain a heteroatom. Examples of such a hetero atom include an oxygen atom, a sulfur atom, and a nitrogen atom.

[0073] Further, the Z ₂ (m + 1) valent alkylene group, alkenylene group, a cycloalkylene group, 2
Examples of the valence group include those described above, and those having a valence of more than 2 include a group obtained by further attaching one or more bonds to the divalent group. As the n-valent alkylene group, alkenylene group and cycloalkylene group for Z ₃ , those described above are mentioned as divalent ones, and those having more than two valences are further bonded to the divalent group by one or more bonds. Those that have been modified.

The alkyl group represented by _Ra is preferably an optionally substituted methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, hexyl group,
1 to 8 carbon atoms such as ethylhexyl group and octyl group
Individual ones. As the cycloalkyl group, preferably a cyclopropyl group optionally having a substituent,
3 carbon atoms such as cyclopentyl and cyclohexyl
To 8 items. Examples of the (m + 1) -valent alkylene group and cycloalkylene group for R _b include those described above for Z ₂ . m is an integer of 1 or more, preferably 2 to 10, more preferably 2 to 5. n is an integer of 2 or more, preferably 2 to 1
0, and more preferably an integer of 2 to 5.

Further preferred substituents of the above substituents include a hydroxyl group and a halogen atom (fluorine, chlorine, bromine,
Iodine), a nitro group, a cyano group, an amide group, a sulfonamide group, an alkyl group of the above Ra, _a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, a hydroxypropoxy group, a butoxy group, and the like. Examples include an alkoxycarbonyl group such as an alkoxy group, a methoxycarbonyl group and an ethoxycarbonyl group, an acyl group such as a formyl group and an acetyl group, and an acyloxy group such as an acetoxy group and a butyryloxy group.

A plurality of B and Z _{3 in the} general formula (III) may be bonded at two or more positions to form a ring structure composed of 3 to 10 carbon atoms and hetero atoms. Examples of such a ring structure include monocyclic or polycyclic structures such as cyclopentane, cyclohexane, cyclooctane, dicyclooctane, dicyclodecane, tricycloheptane, tricyclooctane, and tricyclodecane.

The content of the compound (C) used in the composition of the present invention is adjusted in accordance with the hydroxy group in the resin of the present invention (B), and furthermore, such as alkali developability, substrate adhesion and sensitivity. It is prepared from the viewpoint of performance. Preferably, it is in the range of 3 to 50 wt%, more preferably 5 to 40 wt%, and still more preferably 10 to 30 wt%, based on the solid content of the whole composition.

The specific examples of the compounds used in the present invention (C) are shown below, but are not limited thereto.

[0079]

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[0080]

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[0081]

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[0082]

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[0083]

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[0084]

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[3] Compound of Component (A) (Compound that Decomposes by Irradiation with Actinic Rays or Radiation to Generate Acid) As the compound of component (A) used in the present invention, photoinitiation of cationic photopolymerization Agents, photoinitiators for photoradical polymerization, photodecolorants for dyes, photochromic agents, or known light-generating compounds used in microresist and the like, and compounds and mixtures thereof are appropriately selected. Can be used.

For example, SISchlesinger, Photogr.Sci.E
ng., 18,387 (1974), TSBal etal, Polymer, 21,423 (198
0) etc., U.S. Pat.No.4,069,055
No. 4,069,056, Re 27,992, Japanese Patent Application No. 3-140,140
Salt, DCNecker etal, Macrom
olecules, 17, 2468 (1984), CSwen et al, Teh, Proc. Con
f.Rad.Curing ASIA, p478 Tokyo, Oct (1988), U.S. Patent No.
Nos. 4,069,055 and 4,069,056, and phosphonium salts described in JVCrivello et al., Macromorecules, 10 (6), 1307 (19
77), Chem. & Eng. News, Nov. 28, p31 (1988), European Patent No. 10
No. 4,143, U.S. Pat.Nos. 339,049, 410,201, JP-A-2-150,848, iodonium salts described in JP-A-2-296,514, etc., JVCrivello et al., Polymer J. 17, 73 (1985),
JVCrivello et al. J. Org.Chem., 43, 3055 (1978), WRW
att etal, J. Polymer Sci., Polymer Chem. Ed., 22, 1789 (1
984), JVCrivello etal, Polymer Bull., 14,279 (198
5), JVCrivello etal, Macromorecules, 14 (5), 1141 (19
81), JVCrivello etal, J. PolymerSci., Polymer Chem.
Ed., 17,2877 (1979), European Patent Nos. 370,693, 3,902,1
No. 14, 233,567, 297,443, 297,442, U.S. Patent Nos. 4,933,377, 161,811, 410,201, 33
9,049, 4,760,013, 4,734,444, 2,833,827
No. 2,904,626, 3,604,580, 3,604,
No. 581 etc., sulfonium salt, JVCrivello etal, M
acromorecules, 10 (6), 1307 (1977), JVCrivello etal,
J. Polymer Sci., Polymer Chem. Ed., 17, 1047 (1979), etc., selenonium salts, CSwen et al., Teh, Proc. Conf.R
onium salts such as arsonium salts described in ad.Curing ASIA, p478 Tokyo, Oct (1988), U.S. Pat.No. 3,905,815,
JP-B-46-4605, JP-A-48-36281, JP-A-55-32070
No., JP-A-60-239736, JP-A-61-169835, JP-A-61-169835
No. 1-169837, JP-A-62-58241, JP-A-62-212401,
JP-A-63-70243, organic halogen compounds described in JP-A-63-298339, etc., K. Meier et al., J. Rad.Curing, 13 (4), 26
(1986), TPGill et al., Inorg.Chem., 19,3007 (1980),
D. Astruc, Acc.Chem.Res., 19 (12), 377 (1896), JP-A-2-1
Organometallics / organic halides described in No. 61445, S. Hay
ase etal, J. Polymer Sci., 25, 753 (1987), E. Reichmanis
etal, J.Pholymer Sci., Polymer Chem. Ed., 23, 1 (1985),
QQZhu et al., J. Photochem., 36, 85, 39, 317 (1987), B. Ami
t etal, Tetrahedron Lett., (24) 2205 (1973) 、 DHRBart
on etal, J. Chem Soc., 3571 (1965), PMCollins etal,
J. Chem.SoC., Perkin I, 1695 (1975), M. Rudinstein et al.
Tetrahedron Lett., (17), 1445 (1975), JWWalker etal
J. Am. Chem. Soc., 110, 7170 (1988), SCBusman et al., J. Im
aging Technol., 11 (4), 191 (1985), HM Houlihan et al, M
acormolecules, 21, 2001 (1988), PM Collins et al, J. Che
m.Soc., Chem.Commun., 532 (1972), S.Hayase et al, Macrom
olecules, 18, 1799 (1985), E. Reichmanis et al., J. Electro
chem.Soc., Solid State Sci.Technol., 130 (6), FMHou
lihan et al, Macromolcules, 21, 2001 (1988), European Patent No.
0290,750, 046,083, 156,535, 271,851
No. 0,388,343, U.S. Pat.Nos. 3,901,710, 4,181,
No. 531, JP-A-60-198538, a photoacid generator having an o-nitrobenzyl-type protecting group described in JP-A-53-133022, etc.
M.TUNOOKA etal, Polymer Preprints Japan, 35 (8), G.Be
rner etal, J. Rad. Curing, 13 (4), WJMijs etal, Coating
Technol., 55 (697), 45 (1983), Akzo, H. Adachi et al, Pol
ymer Preprints, Japan, 37 (3), European Patent No. 0199,672,
No. 84515, No. 199,672, No. 044,115, No. 0101,122
Nos., U.S. Pat.Nos. 618,564, 4,371,605, 4,431,77
No. 4, JP-A-64-18143, JP-A-2-245756, Japanese Patent Application No. 3-1
Compounds which generate sulfonic acid upon photolysis, such as iminosulfonate described in JP 40109, etc.
66544 and the like.

Further, a group capable of generating an acid by these lights,
Alternatively, a compound having a compound introduced into the main chain or side chain of a polymer, for example, MEWoodhouse et al., J. Am. Chem.
c., 104, 5586 (1982), SPPappas etal, J. Imaging Sc
i., 30 (5), 218 (1986), S. Kondo et al., Makromol.Chem., Ra.
pid Commun., 9,625 (1988), Y.Yamadaetal, Makromol.Che
m., 152, 153, 163 (1972), JVCrivello etal, J. Polymer
Sci., Polymer Chem. Ed., 17,3845 (1979), U.S. Pat.
No. 849,137, Dokoku Patent No. 3914407, JP-A-63-26653,
JP-A-55-164824, JP-A-62-69263, JP-A-63-1460
No. 38, JP-A-63-163452, JP-A-62-153853, JP-A-63-146029 and the like can be used.

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

Among the compounds (A) which decompose upon irradiation with actinic rays or radiation to generate an acid, those which are particularly effectively used are described below. (1) The following general formula (PAG) substituted with a trihalomethyl group
The oxazole derivative represented by 1) or the general formula (PAG)
An S-triazine derivative represented by 2).

[0090]

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In the formula, R ¹ represents a substituted or unsubstituted aryl group, alkenyl group, and R ² represents a substituted or unsubstituted aryl group, alkenyl group, alkyl group, or —CY ₃ . Y represents a chlorine atom or a bromine atom. Specific examples include the following compounds, but the present invention is not limited thereto.

[0092]

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[0093]

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[0094]

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

[0096]

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In the formula, Ar ¹ and Ar ² are the same or different and each represents a substituted or unsubstituted aryl group. here,
Preferred substituents include an alkyl group, a haloalkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a nitro group, a carboxyl group, an alkoxycarbonyl group, a hydroxy group, a mercapto group, and a halogen atom.

R ³ , R ⁴ and R ⁵ are the same or different and each represents a substituted or unsubstituted alkyl group or aryl group. Preferably an aryl group having 6 to 14 carbon atoms, 1 carbon atom
To 8 alkyl groups and substituted derivatives thereof. Here, preferable substituents are an alkoxy group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms, a nitro group, a carboxyl group, a hydroxy group and a halogen atom with respect to the aryl group. In contrast, an alkoxy group having 1 to 8 carbon atoms, a carboxyl group, and an alkoxycarbonyl group.

[0099] Z ^- represents a counter anion, for example BF ₄ ^{-,
_{AsF 6 -, PF 6 -,}} SbF 6 -, SiF 6 2 -, ClO 4 -,
Perfluoroalkanesulfonic acid anions such as CF ₃ SO ₃ ⁻ and C ₄ F ₉ SO ₃ ⁻ and halogen-substituted benzenesulfonic acid anions such as pentafluorobenzenesulfonic acid anion, linear, branched or cyclic alkyl groups, alkoxy Examples thereof include, but are not limited to, a group-substituted benzenesulfonate anion, a condensed polynuclear aromatic sulfonic acid anion, and a sulfonic acid group-containing dye.

Further, two of R ³ , R ⁴ and R ⁵ and A
r ¹ and Ar ² may be bonded via a single bond or a substituent.

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

[0102]

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[0103]

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[0104]

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[0105]

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[0106]

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[0107]

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[0108]

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[0109]

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[0110]

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[0111]

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[0112]

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[0113]

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

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

[0116]

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In the formula, Ar ³ and Ar ⁴ each independently represent a substituted or unsubstituted aryl group. R ⁶ represents a substituted or unsubstituted alkyl group or aryl group. A represents a substituted or unsubstituted alkylene group, alkenylene group, or arylene group. Specific examples include the following compounds, but are not limited thereto.

[0118]

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[0119]

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[0120]

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[0121]

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[0122]

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The amount of the compound (A) is usually in the range of 0.01 to 20% by weight based on the total weight of the negative resist composition of the present invention (excluding the coating solvent).
Preferably 0.1 to 10% by weight, more preferably 1 to 5%
Used in the range of weight percent.

[5] Other components used in the present invention The composition of the present invention may further contain, if necessary, an acid-decomposable dissolution inhibiting compound, a dye, a plasticizer, a surfactant, a photosensitizer, and an organic compound. It may contain a basic compound, a compound that promotes solubility in a developer, and the like. As the acid-decomposable dissolution inhibiting compound used in the present invention, for example,
At least one acid-decomposable group represented by (XII) or (XIII);
It is a low molecular compound having a molecular weight of 3,000 or less.
In particular, Proc does not decrease the transmittance at 220 nm or less.
Alicyclic or aliphatic compounds such as the cholic acid derivatives described in eeding of SPIE, 2724, 355 (1996) are preferred. In the present invention, when an acid-decomposable dissolution inhibiting compound is used, its addition amount is preferably 3 to 50% by weight, more preferably 5 to 40% by weight, based on the total weight of the composition (excluding the solvent). Preferably it is in the range of 10 to 35% by weight.

Examples of the compound capable of accelerating dissolution in a developer that can be used in the present invention include two or more phenolic OH groups.
Alternatively, it is a low-molecular compound having at least one carboxy group and a molecular weight of 1,000 or less. When it has a carboxy group, an alicyclic or aliphatic compound is preferable for the same reason as described above.
The preferred addition amount of these dissolution promoting compounds is 2 to 50% by weight, more preferably 5 to 30% by weight, based on the resin of the component (B). An addition amount exceeding 50% by weight is not preferable because new development defects such as development residue deterioration and pattern deformation during development occur.

A phenol compound having a molecular weight of 1,000 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. 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.

The preferred organic basic compound that can be used in the present invention is a compound that is 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).

[0129]

Embedded image

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 to 10 parts by weight, preferably 0.01 to 5 parts by weight, per 100 parts by weight of the negative resist composition (excluding the solvent) of the present invention. is there. 0.00
If the amount is less than 1 part by weight, the effect of the addition of the nitrogen-containing basic compound 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.

Suitable 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.

In order to improve the acid generation rate upon exposure, a photosensitizer as described below can be further added. Examples of suitable photosensitizers include benzophenone, p, p'-tetramethyldiaminobenzophenone,
p, p'-tetraethylethylaminobenzophenone,
2-chlorothioxanthone, anthrone, 9-ethoxyanthracene, anthracene, pyrene, perylene, phenothiazine, benzyl, acridine orange, benzoflavin, setoflavin-T, 9,10-diphenylanthracene, 9-fluorenone, acetophenone, phenanthrene, 2-nitro Fluorene, 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. These photosensitizers can also be used as a light absorbing agent for far ultraviolet light as 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 negative resist composition of the present invention is dissolved in a solvent capable of dissolving each of the above components and applied on a support. As the solvent used here, ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone,
γ-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene, ethyl acetate, methyl lactate, lactic acid Ethyl, methyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N, N-
Dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, tetrahydrofuran and the like are preferable, and these solvents are used alone or in combination.

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 and 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 above-mentioned negative resist composition is applied onto a substrate (eg, silicon / silicon dioxide coating) to be used for the production of precision integrated circuit devices by an appropriate application method such as a spinner or a coater, and then coated with a predetermined mask. Exposure through
A good resist pattern can be obtained by baking and developing. Here, it is preferable to perform a heat treatment for drying and forming a coating film after the application. By this heat treatment, the resin of the component (B) and the compound of the component (C) form a crosslinked structure. Here, the heating temperature is preferably 80 ° C. or higher, more preferably 100 ° C. or higher,
The temperature is more preferably 120 to 160 ° C., and the heating time is preferably 30 seconds or more, more preferably 1 minute or more,
More preferably, it is 1 minute to 10 minutes. The exposure light is preferably 250 nm or less, more preferably 22 nm or less.
It is far ultraviolet light having a wavelength of 0 nm or less. Specifically, Kr
F excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (157
nm), X-rays, electron beams and the like.

Examples of the developing solution for the negative resist composition of the present invention include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, and n-propylamine. Primary amines such as diethylamine, di-
secondary amines such as n-butylamine, triethylamine, tertiary amines such as methyldiethylamine, dimethylethanolamine, alcoholamines such as triethanolamine, tetramethylammonium hydroxide,
An alkaline aqueous solution such as a quaternary ammonium salt such as tetraethylammonium hydroxide, or a cyclic amine such as pyrrole or pichelidine can be used. Further, an appropriate amount of an alcohol or a surfactant may be added to the above alkaline aqueous solution.

[0138]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the contents of the present invention are not limited thereto.

[Synthesis Example 1 (Example of compound (d2
Synthesis of 2)) 20.8 g of hydroxyamine hydrochloride
(0.30 mol) was dissolved in 80 ml of ion-exchanged water, and 50 ml of 109.4 g (0.30 mol) of 25% tetramethylammonium hydroxide was added to this solution.
The solution was added over 30 minutes under ice cooling. Further, 46.3 g (0.30 mol) of hexahydrophthalic anhydride was added, and the mixture was stirred at room temperature for 1 hour and refluxed for 4 hours. The reaction solution was cooled on ice, and the precipitated powder was filtered and washed with water. The obtained crude crystals were recrystallized from acetone / water to obtain 27.9 g of N-hydroxyhexahydrophthalimide.

[Synthesis Example 2 (Example of compound (d3
Synthesis of 2))] In place of hexahydrophthalic anhydride in Synthesis Example 1, 49.2 g (0.30 mol) of 5-norbornene-2,3-dicarboxylic anhydride was used. N-hydroxy-5-norbornene-
29.4 g of 2,3-dicarboximide were obtained.

[Synthesis Example 3 (Compound example of component (C) (d3
Synthesis of 7))] Instead of hexahydrophthalic anhydride in Synthesis Example 1, 49.8 g (0.30 mol) of 3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride was used. Others were the same as in Synthesis Example 1 except for N-hydroxy-
28.7 g of 3,6-epoxy-1,2,3,6-tetrahydrophthalimide were obtained.

[Synthesis Example 4 (Example of compound (d3
Synthesis of 3))] N-hydroxy- obtained in Synthesis Example 2
5-norbornene-2,3-dicarboximide 17.
9 g (0.10 mol) was dissolved in 100 ml of THF, and 7.9 g (0.10 mol) of acetyl chloride was added to this solution. Further, a solution of triethylamine in 20 ml of THF was added over 30 minutes under ice cooling. After stirring at room temperature for 3 hours, the mixture was poured into 1 L of ion-exchanged water. The precipitated viscous solid was purified by silica gel column chromatography (developing solution: hexane / ethyl acetate) to give N-acetoxy-5-
15.7 g of norbornene-2,3-dicarboximide
I got

[Synthesis Example 5 (Example of compound (d3
Synthesis of 4))] N-hydroxy- obtained in Synthesis Example 2
5-norbornene-2,3-dicarboximide 17.
9 g (0.10 mol) was dissolved in 100 ml of THF, and 10-camphorsulfonyl chloride 25.1 was added to this solution.
g (0.10 mol) was added. Further, a solution of triethylamine in 20 ml of THF was added over 30 minutes under ice cooling.
After stirring at room temperature for 3 hours, the mixture was poured into 1 L of ion-exchanged water. The precipitated viscous solid was purified by silica gel column chromatography (developing solution: hexane / ethyl acetate),
24.5 g of N-10-camphorsulfonyloxy-5-norbornene-2,3-dicarboximide were obtained.

Synthesis Example 6 (Synthesis of Component (B) Resin (p-1) Having Structural Units of (a3) / (a7)) 0.40 g (0.001 mol) of tungsten hexachloride was weighed out. Then, it was dissolved in 200 ml of chlorobenzene under a nitrogen stream. To this, 2.28 g of a 15% toluene solution of triethylaluminum was added.
(0.003 mol) was added dropwise with stirring under a nitrogen stream, and further 152 g of 2-carbomethoxynorbornene was added.
(1.00 mol) of a chlorobenzene solution (300 ml) was added. Thereafter, stirring was continued at 30 ° C. for 20 hours. The reaction solution was poured into 4 L of methanol with stirring to precipitate a polymer. The produced polymer is separated by filtration, and
Drying at 0 ° C. yielded 144 g. This polymer is THF
Dissolve in 500 ml and use Pd / C (10% P
d) 5 g were added. Further, a solution of hydrazine monohydrate (80 g) in ethanol (100 ml) was added, and the mixture was heated and stirred at 80 ° C. for 5 hours. After the catalyst was separated by filtration, the reaction solution was poured into 3 L of methanol with stirring to precipitate a white polymer. The produced polymer was separated by filtration and dried at 40 ° C. under reduced pressure to obtain 142 g. 30.8 g of this polymer was dispersed in 300 ml of methanol, 73.3 g of an aqueous solution of 25% tetramethylammonium OH salt was added, and the mixture was heated under reflux for 5 hours. The reaction solution was diluted with methanol / ion exchange water and neutralized with concentrated hydrochloric acid. The precipitated polymer was separated by filtration, washed thoroughly with ion-exchanged water, and then reduced pressure at 40 ° C.
Then, 25.7 g of a white polymer was obtained. Subsequently, 14.0 g of this polymer was added to 100 m of DMF.
and then added with 6.1 g of triethylamine, and the solution was stirred at 70 ° C. with 7.5 g of ethylene bromohydrin.
g was added dropwise, and stirring was continued at 70 ° C. for 3 hours. The reaction solution was poured into 1.5 L of ion-exchanged water with vigorous stirring to precipitate a polymer. The precipitated polymer is filtered off,
After sufficiently washing with deionized water, it was dried at 40 ° C. under reduced pressure. 14.8 g of a light brown polymer (resin (p-1) of the present invention) was obtained. When the molecular weight was measured by GPC, the weight average (Mw: converted to polystyrene) was 5.7 × 1.
0 ³ and the result of NMR measurement showed that (a3) / (a7)
Was confirmed to be 55/45 in molar ratio.

[Synthesis Examples 7 to 12 (Resin (p-
2) Synthesis of (p-7))] The resins (p-2) to (p-7) of the present invention were synthesized in the same manner as in Synthesis Example 1. The structure, composition ratio and molecular weight are shown in Table 1 below.

[0146]

[Table 1]

[Synthesis Example 13 ((a48) / (a49) / (a5
Synthesis of resin (p-8) of component (B) having structural unit 1))] 0.50 g of palladium chloride and 1.1 g of AgBF ₄
Was stirred in 40 ml of acetonitrile at room temperature for 1 hour. After the precipitated solid was filtered off, the reaction solution was concentrated.
Anhydrous ethyl ether was added thereto, and the precipitated yellow solid was separated by filtration and further recrystallized with acetonitrile / ethyl ether to give an addition polymerization catalyst [Pd (MeCN)
₆ ] (BF ₄ ) 21.1 g was obtained. 1.0 g of the same catalyst was dissolved in 200 ml of a nitromethane solution, and 30.4 g (0.20 mol) of 2-carbomethoxynorbornene was further added. Thereafter, stirring was continued at room temperature for 24 hours. The reaction solution was concentrated under reduced pressure, and the obtained polymer was sufficiently washed with acetonitrile. After drying, the polymer was dispersed in 200 ml of methanol, 43.8 g of an aqueous solution of 25% tetramethylammonium OH salt was added, and the mixture was heated under reflux for 5 hours. The reaction solution was diluted with methanol / ion exchange water and neutralized with concentrated hydrochloric acid. The precipitated polymer was separated by filtration, washed thoroughly with ion-exchanged water, and then reduced pressure at 40 ° C.
And dried. 25.4 g of a white polymer were obtained. Subsequently, 14.4 g of this polymer was dissolved in 100 ml of DMF, and 4.0 g of triethylamine was added.
Under stirring at ℃, 4.9 g of ethylene bromohydrin was added dropwise, and stirring was further continued at 70 ° C. for 3 hours. The reaction solution was poured into 1.5 L of ion-exchanged water with vigorous stirring to precipitate a polymer. The precipitated polymer was separated by filtration, sufficiently washed with ion-exchanged water, and dried at 40 ° C. under reduced pressure. 14.5 g of a light brown polymer (resin (p-
8)) got. The molecular weight measured by GPC was 6.4 × 10 ³ in terms of weight average (Mw: in terms of polystyrene). As a result of NMR measurement, (a48) / (a49) /
The molar ratio of the structural unit of (a51) is 41/38/21
Was confirmed.

[Synthesis Examples 14 to 17 (Synthesis of Resins (p-9) to (p-12) of Component (B)]] The resins of the invention (p-9) to (p-9) to (p-9) p-12) was synthesized. The structure, composition ratio and molecular weight are shown in Table 2 below.

[0149]

[Table 2]

[Synthesis Example 18 ((a46) / (b1) / (c14
Synthesis of Resin (p-13) as Component (B) Having Structural Unit of (B))] 33.0 g (0.35 mol) of norbornene / 34.3 g (0.35 mol) of maleic anhydride / hydroxyethyl methacrylate 0 g (0.30 mol) in TH
F2, F2, F2, F2, F2, F2, F2, F2, F2, F2, F2, F2, F2, F3, F2, F2, F2, F4, F2, F2, F2, F2 and F2, respectively, and the polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) (Wako Pure Chemical Industries, Ltd .;
5) 1.0 g was added. Two hours and four hours after the start of the reaction, 1.0 g of the same initiator was added. After further reacting for 3 hours, the temperature was raised to 90 ° C., and stirring was continued for 1 hour. After allowing the reaction solution to cool, it was poured into 4 L of ion-exchanged water with vigorous stirring to precipitate a polymer. The obtained polymer was dried at 40 ° C. under reduced pressure to obtain 102 g of a white polymer. 21.3 g of this polymer was dissolved in 100 ml of N, N-dimethylacetamide, and 38.5 g (0.39 mol) of cyclohexanol and 31.8 g of pyridine were added.
6 g (0.40 mol) was added, and the mixture was heated and stirred at 90 ° C. for 3 hours. After allowing the reaction solution to cool, it was poured into 1 L of ion-exchanged water with vigorous stirring to precipitate a polymer. The obtained polymer was dried at 40 ° C. under reduced pressure to obtain 24.5 g of a white resin. When the molecular weight was measured by GPC, it was 12.5 × 103 in weight average (Mw: in terms of polystyrene). As a result of NMR measurement, it was confirmed that the molar ratio of the structural units of (a46) / (b1) / (c14) was 35/30/35.

[Synthesis Examples 19 to 22 (Synthesis of Resins (p-14) to (p-17) of Component (B)]] Hereinafter, in the same manner as in Synthesis Example 18, the resin of component (B) (p-14) ) To (p-17) were synthesized. The structure, composition ratio and molecular weight are shown in Table 3 below.

[0152]

[Table 3]

Example 1 (Measurement of Thermal Crosslinking Property and Optical Density) As shown in Table 4, 1.0 g of the resin as the component (B), 0.35 g of the compound as the component (C), and tri as the compound as the component (A) were obtained. 0.01 g of phenylsulfonium triflate was dissolved in 6.0 g of propylene glycol monomethyl ether acetate and filtered with a 0.2 μm Teflon filter. It is applied uniformly on a quartz glass substrate by a spin coater, and heated on a hot plate at 130 ° C. for 2 minutes.
A 1 μm resist film was formed. When the optical absorption of these films was measured with an ultraviolet spectrophotometer, it was 193 nm.
Are as shown in Table 4.

[0154]

[Table 4]

From the results shown in Table 4, the measured optical density of the resist obtained from the composition of the present invention was smaller than that of the resist using poly (hydroxystyrene) (weight average molecular weight: 12000) of the comparative example. It turns out that it has sufficient transmittance | permeability with respect to 193 nm light. Further, in order to confirm the crosslinking property of the obtained film, the film was entirely exposed to light of 193 nm, further heated at 130 ° C. for 1 minute, and then immersed in a 2.38% aqueous solution of tetramethylammonium hydroxide for 1 minute. In each case, the film loss was 5% or less, and it was found that the film was sufficiently cured by crosslinking.

Example 2 (Measurement of dry etching resistance) The negative type composition of the present invention prepared in Example 1 was uniformly applied on a silicon substrate in the same manner as in Example 1, and
Heat on a hot plate at 30 ° C for 2 minutes,
A μm resist film was formed. The obtained membrane is ULVA
C reactive ion etching system (CSE-11
The etching rate for CF ₄ / O ₂ (8/2) gas was measured using 10), and the result was as shown in Table 5 (etching conditions: Power = 500 W, Pre
ssure = 4.6Pa, GasFlow Rate =
10 sccm).

[0157]

[Table 5]

From the results shown in Table 5, it can be seen that the etching rate of the resin of the present invention is smaller than the value of poly (methyl methacrylate) (weight average molecular weight: 35500) of the comparative example, and that the resin has a sufficient dry etching resistance.

Example 3 (Evaluation of Image) 1.0 g of the resin of the present invention shown in Table 6, 0.35 g of the compound (c) of the present invention, and 0.01 g of triphenylsulfonium triflate were 6.0 g of propylene glycol monomethyl ether acetate. And filtered through a 0.2 μm Teflon filter. The solution was uniformly coated on a hexamethyldisilazane-treated silicon substrate by a spin coater, and dried by heating on a hot plate at 130 ° C. for 2 minutes to form a 0.4 μm resist film. A mask having a pattern drawn with chromium on a quartz plate is brought into close contact with the resist film, and ArF excimer laser light (1
93 nm). Immediately after exposure, heating was performed on a hot plate at 110 ° C. for 60 seconds. After further immersion development in a 2.38% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 60 seconds and rinsing with pure water for 30 seconds,
Dried. The sensitivity, resolution, and pattern shape of these photoresists were evaluated. The results are shown in Table 6.

[0160]

[Table 6]

From the results shown in Table 6, the resist using the negative resist composition of the present invention has high sensitivity and good resolution. Also, it can be seen that the pattern shape is good.

[0162]

As is apparent from the above description, the resist using the negative resist composition of the present invention is 2%.
It has high transparency to far ultraviolet light of 20 nm or less and good dry etching resistance. Even when far ultraviolet light of 220 nm or less (especially ArF excimer laser light) is used as an exposure light source, it exhibits high sensitivity, high resolution, and a good pattern profile, and can be effectively used for forming a fine pattern required for semiconductor device manufacturing. It is possible.

Claims (7)

[Claims] (A) a compound that generates an acid upon irradiation with actinic rays or radiation, (B) a polycycloolefin resin having a hydroxyl group and a carboxyl group, and having an alicyclic group in the main chain; C) A negative resist composition comprising a cyclic imide compound. 2. Component (C) is represented by the following general formulas (I) and (I)
The negative resist composition according to claim 1, wherein the negative resist composition is at least one kind of cyclic imide compound selected from the group consisting of compounds represented by I) and (III). Embedded image In the general formulas (I), (II), and (III), A is a divalent alkylene group, an alkenylene group, or a cycloalkylene which may contain a hetero atom and may have a substituent. Group or a cycloalkenylene group. B represents a trivalent alkylene group, alkenylene group, cycloalkylene group or cycloalkenylene group which may contain a hetero atom and may have a substituent. Z ₁ is
Hydrogen _{atom, -OH, -O-R a,} -O-SO 2 -R a, -
O-CO- _Ra , -O-CO-O- _Ra , or -O-CO
It represents an -NH-R _a. Here, R _a may have a substituent, an alkyl group, a cycloalkyl group. Z
₂ may have a substituent, (m + 1) valent alkylene group, alkenylene group or cycloalkylene _{group, -O-R b (-O-)} m, -O-SO 2 -R b (- S
O ₂ —O—) m, —O—CO—R _b (—CO—O—) m,
_{-O-CO-O-R b} (-O-CO-O-) m, or -
It represents O-CO-NH- _Rb (-NH-CO-O-) m. Here, R _b may have a substituent, (m
+1) represents a valent alkylene group or a cycloalkylene group. Z ₃ represents an n-valent alkylene group, alkenylene group or cycloalkylene group which may have a substituent. m represents an integer of 1 or more. n represents an integer of 2 or more. Further, a plurality of B and Z _{3 in the} general formula (III) may be bonded at two or more positions to form a ring structure composed of 3 to 10 carbon atoms and hetero atoms. 3. The resin of the component (B) has the following general formula (I)
The negative according to claim 1 or 2, wherein the main chain has at least one structural unit selected from the group consisting of repeating structural units having an alicyclic group represented by V) and (V). -Type resist composition. Embedded image In the general formulas (IV) and (V), R _{4 to} R ₇ each independently have a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a carboxyl group, a —CO—OR ₃₈ group, or a substituent. Represents an alkyl group, a hydroxyalkyl group, a haloalkyl group, or an alkoxy group which may be substituted. here,
R ₃₈ represents an optionally substituted alkyl group, cycloalkyl group or alkenyl group. Further, two of R _{4 to} R ₇ may be bonded to each other to form an alkylene chain. A _{1 to} A ₃ each independently represent a divalent alkylene group, an alkenylene group, or a monocyclic or polycyclic cycloalkylene group which may have a substituent. X represents a single bond, a divalent alkylene group, an alkenylene group, or -SO
Represents a _2- group. p and q represent an integer of 0 to 4. 4. The repeating structural unit having an alicyclic group represented by the general formulas (IV) and (V) is represented by the following general formula (V)
The negative resist composition according to claim 3, wherein the negative resist composition is at least one structural unit selected from the group consisting of repeating structural units represented by I) to (X). Embedded image In the general formulas (VI) to (X), R _{4 to} R ₇ , R ₃₈ and X have the same meanings as in the general formulas (IV) to (V), respectively. R
_{8 to} R ₃₇ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group, an alkyl group, a hydroxyalkyl group, a cycloalkyl group, an alkenyl group, -CO
—OR represents a ₃₈ group or a carboxyl group. Also, R _{4 to} R
Two of ₃₇ may combine to form an alkylene group having 1 to 5 carbon atoms which may contain a hetero atom. a to j
Represents an integer of 0 to 4 each independently. 5. The resin of the component (B) is represented by the following general formula (X)
Hydroxyl represented by I), (XII) and (XIII)
Selected from the group consisting of repeating structural units having a group
It is a resin having at least one type of structural unit.
The negative type resist according to any one of claims 1 to 4, wherein
Composition. Embedded imageIn the general formulas (XI) to (XIII), R₃₉, R₄₀, R₄₂~ R
₄₄Is independently a hydrogen atom, a halogen atom, a cyano
An alkyl group or haloa, which may have a group or a substituent
Represents a alkyl group. R₄₁Is a cyano group, -CO-OR₄₅,
Or -CO-NR₄₆R₄₇Represents X₁~ X_ThreeAre independent
A single bond or -CO-R₄₈-, -CO-OR
₄₉-, -CO-NR₅₀-R₅₁-, Even if it has a substituent
Good divalent alkylene, alkenylene or cyclo
Alkylene groups alone or in combination of two or more
Represents a divalent group. Where R₄₅~ R₄₇, R₅₀Is each
Each independently represents a hydrogen atom or an optionally substituted
Represents a kill group, a cycloalkyl group or an alkenyl group. Ma
R₄₆, R₄₇May combine with each other to form a ring. R₄₈, R
₄₉, R₅₁Is a single bond or an ether group, an ester group,
Divalent, which may have a mid group, a urethane group, or a ureido group
Alkylene, alkenylene or cycloalkyl
Represents a len group. 6. The resin of component (B) has the following general formula (XI)
A resin having at least one structural unit selected from the group consisting of a repeating structural unit having a carboxyl group, represented by V), (XV), and (XVI). 5. The negative resist composition according to any one of the above items 5. Embedded image In general formulas (XIV) to (XVI), R ₅₂ , R ₅₃ and R ₅₅
R ₅₇ each independently represents a hydrogen atom, a halogen atom, a cyano group, or an optionally substituted alkyl group or haloalkyl group. R ₅₄ represents a cyano group, —CO—OR ₅₈ or —CO—NR ₅₉ R ₆₀ . X _{4 to} X ₆ are each independently a single bond or —CO—R ₆₁ —, —CO—O—R
_62- , -CO-NR ₆₃ -R _64- , a divalent alkylene group, alkenylene group or cycloalkylene group which may have a substituent, or a divalent group obtained by combining two or more thereof. Represents Here, R ₅₈ is a hydrogen atom,
Represents an alkyl group, a cycloalkyl group or an alkenyl group which may have a substituent. R ₅₉ , R ₆₀ and R ₆₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group or an alkenyl group which may have a substituent. R ₅₉ and R ₆₀ may combine to form a ring. R ₆₁ , R
₆₂ and R ₆₄ each independently represent a single bond or a divalent alkylene group, alkenylene group or cycloalkylene group which may have an ether group, an ester group, an amide group, a urethane group, or a ureido group. 7. The exposure light source according to claim 1, wherein a far ultraviolet light having a wavelength of 220 nm or less is used.
A negative resist composition according to any one of the above.