JP2003015298A - Positive type resist composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive type resist composition suitable for use under a light source for exposure which emits light of <=160 nm, particularly F2 excimer laser light (157 nm) and specifically to provide a positive type resist composition exhibiting satisfactory transmittance when a light source which emits light of 157 nm is used and having good contrast by dissolution. SOLUTION: Each of the positive type resist compositions contains (A) a resin which has repeating units with a specified structure and is decomposed by the action of an acid to increase its solubility in an alkali developing solution, (B) a compound which generates the acid when irradiated with active light or radiation and (C) a solvent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive resist composition suitable for use in microlithography processes such as manufacturing of ultra-LSIs and high-capacity microchips, and other photofabrication processes. More specifically, the present invention relates to a positive resist composition capable of forming a highly refined pattern using vacuum ultraviolet light of 160 nm or less.

[0002]

2. Description of the Related Art The degree of integration of integrated circuits is increasing more and more, and in the manufacture of semiconductor substrates such as VLSI, it has become necessary to process ultrafine patterns having a line width of less than quarter micron. It was As one of means for achieving a finer pattern, it is known to shorten the wavelength of an exposure light source used when forming a resist pattern.

For example, to manufacture a semiconductor device with an integration degree of up to 64 Mbits, up to now, the i-line (365n) of a high pressure mercury lamp has been used.
m) has been used as a light source. As a positive resist compatible with this light source, many compositions containing a novolac resin and a naphthoquinonediazide compound as a photosensitive material have been developed, and have achieved sufficient results in processing line widths up to about 0.3 μm. . Further, KrF excimer laser light (248 nm) has been adopted as an exposure light source instead of the i-line in the manufacture of a semiconductor device having an integration degree of 256 Mbits or more. Furthermore, for the purpose of manufacturing semiconductors with a degree of integration of 1 Gbit or more, the use of ArF excimer laser light (193 nm), which is a light source with a shorter wavelength in recent years, has a
The use of F ₂ excimer laser light (157 nm) has been studied to form a pattern of m or less.

With the shortening of the wavelength of these light sources, the constituent components of the resist material and the compound structure thereof have changed greatly. That is, in the conventional resist containing a novolac resin and a naphthoquinonediazide compound, since absorption in the far ultraviolet region of 248 nm is large, it is difficult for light to reach the bottom of the resist, and only a tapered pattern with low sensitivity can be obtained. To solve such problems, 24
Composition in which a compound (photo-acid generator) that generates an acid by irradiation with far-ultraviolet light is used by using as a main component a resin that has a basic skeleton of poly (hydroxystyrene) having a small absorption in the 8 nm region and is protected by an acid-decomposing group. The thing, what is called a chemically amplified resist, came to be developed. Since the chemically amplified resist changes its solubility in a developing solution due to the catalytic decomposition reaction of the acid generated in the exposed portion, a highly sensitive and high resolution pattern can be formed.

However, when ArF excimer laser light (193 nm) is used, since the compound having an aromatic group essentially has a large absorption in the wavelength region of 193 nm, sufficient performance cannot be obtained even with the above chemically amplified resist. It was

To solve this problem, an acid-decomposable resin having a basic skeleton of poly (hydroxystyrene) is used as an acid-decomposable resin in which an alicyclic structure having no absorption at 193 nm is introduced into the polymer main chain or side chain. Instead, the chemically amplified resist is being improved.

However, the absorption of F ₂ excimer laser light (157 nm) in the 157 nm region is large even in the alicyclic resin described above, and the target 0.1 μm
It was found to be insufficient to obtain the following pattern. On the other hand, a resin having a fluorine atom (perfluoro structure) introduced may have sufficient transparency at 157 nm.
Proc. SPIE. Vol.3678. 13 (1999), the structure of the effective fluororesin is Proc. SPIE. Vol.3999. 330 (2000), 357 (2000), 365 ( 2000), WO-
It has been proposed in No. 00/17712. However, the resist containing these fluororesins,
The dissolution contrast of the exposed and unexposed areas was not always sufficient.

[0008]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is to obtain a light of 160 nm or less, especially F ₂ excimer laser light (1
57 nm) exposure light source suitable for use as a positive resist composition. Specifically, a positive resist composition exhibiting sufficient transmissivity when using a 157 nm light source and having good dissolution contrast is provided. Is to provide.

[0009]

Means for Solving the Problems The inventors of the present invention, as a result of diligent study in consideration of the above-mentioned various characteristics, have found that the object of the present invention can be successfully achieved by using the following specific composition. Has reached the present invention. That is, the present invention has the following configuration.

(1) (A) The following general formulas (I) and (I
A resin having at least one repeating unit represented by I) and (VI), which decomposes by the action of an acid and increases the solubility in an alkali developing solution, and (B) generates an acid by irradiation with actinic rays or radiation. A positive resist composition comprising a compound and a solvent (C).

[0011]

[Chemical 6]

In the general formulas (I), (II) and (VI),
R₁, R_Five, R_17aAnd R₁₇Are the same or different
Often, hydrogen atom, halogen atom, cyano group or substituent
It represents an alkyl group which may have. R₂, R₃, R₆Over
And R₇May be the same or different and may be a hydrogen atom,
Possess a rogen atom, cyano group, hydroxyl group or substituent
Optionally, an alkyl group, a cycloalkyl group, an
Coxy group, acyl group, acyloxy group, alkenyl group,
Represents a reel group or an aralkyl group. R₅₀~ R ₅₅Is
They may be the same or different and may be hydrogen atom, fluorine atom or
Represents an alkyl group which may have a substituent. However,
R₅₀~ R₅₅Of these, at least one is a fluorine atom or
At least one hydrogen atom is replaced by a fluorine atom
Represents a kill group. R_FourIs the following general formula (IV) or (V)
Represents the group of. R₁₈Is -C (R_18d) (R_18e)
(R_18f) Or -C (R_18d) (R_18e) (OR_{18 g}) Table
You R_18d~ R _{18 g}Can be the same or different, water
An alkyl group, optionally substituted with an atom or a substituent,
Chloroalkyl group, alkenyl group, aralkyl group or
Represents an aryl group. R_18d, R_18e, R_18fTwo of the
Is R_18d, R_18e, R_{18 g}Two of them combine to form a ring
You may.

[0013]

[Chemical 7]

In the general formula (IV), R ₁₁ , R ₁₂ and R
₁₃ represents an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group or an aryl group, which may be the same or different and may have a substituent. General formula (V)
R ₁₄ and R _{15, which} may be the same or different, each represent a hydrogen atom or an alkyl group which may have a substituent. R ₁₆ is an alkyl group which may have a substituent,
It represents a cycloalkyl group, an aralkyl group or an aryl group. Two of R _{14 to} R ₁₆ may combine with each other to form a ring.

(2) In the general formula (VI), R ₁₈ is
The positive resist composition as described in (1), which is represented by the following general formula (VI-A).

[0016]

[Chemical 8]

In the general formula (VI-A), R _18a and R _18
18b may be the same or different and represents an alkyl group which may have a substituent. R _18c represents a cycloalkyl group which may have a substituent.

(3) In the general formula (VI), R ₁₈ is
The positive resist composition as described in (1), which is represented by the following general formula (VI-B).

[0019]

[Chemical 9]

In the general formula (VI-B), R _18h represents an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group or an aryl group which may have a substituent. Z is
It represents an atomic group constituting a monocyclic or polycyclic alicyclic group together with the carbon atom in the general formula (VI-B).

(4) In the general formula (VI), R ₁₈ is
The positive resist composition as described in (1), which is represented by the following general formula (VI-C).

[0022]

[Chemical 10]

In formula (VI-C), R _{18 '} represents an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group or an aryl group which may have a substituent.

(5) At least one of R _{1 of} the general formula (I), R ₅ of the general formula (II) and R ₁₇ of the general formula (VI) is a trifluoromethyl group ( The positive resist composition as described in any one of 1) to (4).

The preferred embodiments of the present invention will be further described below. (6) The resin of (A) further has at least one repeating unit represented by the following general formula (III) or (VII). (1) to (5) Positive resist composition.

[0026]

[Chemical 11]

In the general formula (III), R ₈ is a hydrogen atom,
It represents a halogen atom, a cyano group or an alkyl group which may have a substituent. R ₉ and R ₁₀ may be the same or different, and may have a hydrogen atom, a halogen atom, a cyano group or a substituent, an alkyl group, a cycloalkyl group, an alkoxy group, an acyl group, an acyloxy group, It represents an alkenyl group, an aryl group or an aralkyl group. In formula (VII), R ₁₉ and R _{20, which} may be the same or different, each represents a hydrogen atom, a halogen atom, a cyano group or an alkyl group which may have a substituent. R ₂₁ represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent or a -A ₁ -CN group. A ₁ represents a single bond or a divalent linking group.

(7) The resin (A) further comprises at least one repeating unit represented by the following general formulas (VIII) to (XVII), (1) to (6)
The positive resist composition as described in any one of 1.

[0029]

[Chemical 12]

In the general formulas (VIII) to (XVII), R
_{twenty five}, R₂₆And R₂₇Can be the same or different, water
An elementary atom, a fluorine atom or an optionally substituted group,
Represents a alkyl group, a cycloalkyl group or an aryl group.
You R₂₈, R₂₉And R₃₀Can be the same or different
, Optionally substituted alkyl group, cycloalkyl group
It represents a alkyl group or an aryl group. Also, R_{twenty five}And R₂₆, R
₂₇And R₂₈, R₂₉And R₃₀And are linked together to form a ring
May be. R₃₁, R₃₅, R₃₇, R₄₀And R₄₄Is the same
May be different from each other and have a hydrogen atom or a substituent.
May be alkyl group, cycloalkyl group, acyl group
Specifically, it represents an alkoxycarbonyl group. R ₃₂, R₃₃, R
₃₄, R₄₁, R₄₂And R₄₃Can be the same or different
Even if it has a hydrogen atom, a halogen atom or a substituent
Represents an alkyl group or an alkoxy group. R₃₆Over
And R₃₉May be the same or different and may be a hydrogen atom,
Rogen atom, cyano group or an optionally substituted group
Represents a rukyl group. R₃₈May have a substituent,
Alkyl group, cycloalkyl group, aralkyl group or ari
Group. B₁And B₂Is a single bond or a divalent linking group
Represents B₃Represents a divalent linking group. n is 0 or 1
Represents

(8) The positive resist composition as described in any of (1) to (7), which further comprises (D) a fluorine-based and / or silicon-based surfactant. (9) The invention further comprises (E) an acid diffusion inhibitor containing a basic compound having a nitrogen atom (1)
The positive resist composition as described in any of (8) to (8). (10) The positive resist composition as described in any of (1) to (9), which is for irradiation with an F ₂ laser beam having a wavelength of 157 nm.

[0032]

BEST MODE FOR CARRYING OUT THE INVENTION The compounds used in the present invention are described in detail below. [1] Resin (A) of the Present Invention The resin (A) of the present invention has the general formulas (I) and (I
A resin having at least one repeating unit represented by each of I) and (VI), which decomposes by the action of an acid and increases the solubility in an alkali developing solution. In the resin (A) of the present invention, R ₁₈ in the general formula (VI) is preferably represented by the above general formula (VI-A), (VI-B) or (VI-C). The resin (A) in the present invention further has the above general formulas (III) and (VII) to (XVI).
It may have at least one repeating unit represented by I).

In the general formulas (I), (II) and (VI),
R₁, R_Five, R_17aAnd R₁₇Are the same or different
Often, hydrogen atom, halogen atom, cyano group or substituent
It represents an alkyl group which may have. R₂, R₃, R₆Over
And R₇May be the same or different and may be a hydrogen atom,
Possess a rogen atom, cyano group, hydroxyl group or substituent
Optionally, an alkyl group, a cycloalkyl group, an
Coxy group, acyl group, acyloxy group, alkenyl group,
Represents a reel group or an aralkyl group. R₅₀~ R ₅₅Is
They may be the same or different and may be hydrogen atom, fluorine atom or
Represents an alkyl group which may have a substituent. However,
R₅₀~ R₅₅Of these, at least one is a fluorine atom or
At least one hydrogen atom is replaced by a fluorine atom
Represents a kill group. R_FourIs the following general formula (IV) or (V)
Represents the group of. R₁₈Is -C (R_18d) (R_18e)
(R_18f) Or -C (R_18d) (R_18e) (OR_{18 g}) Table
You R_18d~ R _{18 g}Can be the same or different, water
An alkyl group, optionally substituted with an atom or a substituent,
Chloroalkyl group, alkenyl group, aralkyl group or
Represents an aryl group. R_18d, R_18e, R_18fTwo of the
Is R_18d, R_18e, R_{18 g}Two of them combine to form a ring
You may.

In the general formula (IV), R ₁₁ , R ₁₂ and R
₁₃ represents an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group or an aryl group, which may be the same or different and may have a substituent. General formula (V)
R ₁₄ and R _{15, which} may be the same or different, each represent a hydrogen atom or an alkyl group which may have a substituent. R ₁₆ is an alkyl group which may have a substituent,
It represents a cycloalkyl group, an aralkyl group or an aryl group. Two of R _{14 to} R ₁₆ may combine with each other to form a ring.

In the general formula (VI-A), R _18a and R _18
18b may be the same or different and represents an alkyl group which may have a substituent. R _18c represents a cycloalkyl group which may have a substituent. General formula (VI-
In B), R _18h represents an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group or an aryl group, which may have a substituent. Z represents an atomic group forming a monocyclic or polycyclic alicyclic group together with the carbon atom in the general formula (VI-B). In general formula (VI-C), R _{18 ′} represents an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group or an aryl group, which may have a substituent.

In the general formula (III), R ₈ is a hydrogen atom,
It represents a halogen atom, a cyano group or an alkyl group which may have a substituent. R ₉ and R ₁₀ may be the same or different, and may have a hydrogen atom, a halogen atom, a cyano group or a substituent, an alkyl group, a cycloalkyl group, an alkoxy group, an acyl group, an acyloxy group, It represents an alkenyl group, an aryl group or an aralkyl group. In formula (VII), R ₁₉ and R _{20, which} may be the same or different, each represents a hydrogen atom, a halogen atom, a cyano group or an alkyl group which may have a substituent. R ₂₁ represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent or a -A ₁ -CN group. A ₁ represents a single bond or a divalent linking group.

In the general formulas (VIII) to (XVII), R
_{twenty five}, R₂₆And R₂₇Can be the same or different, water
An elementary atom, a fluorine atom or an optionally substituted group,
Represents a alkyl group, a cycloalkyl group or an aryl group.
You R₂₈, R₂₉And R₃₀Can be the same or different
, Optionally substituted alkyl group, cycloalkyl group
It represents a alkyl group or an aryl group. Also, R_{twenty five}And R₂₆, R
₂₇And R₂₈, R₂₉And R₃₀And are linked together to form a ring
May be. R₃₁, R₃₅, R₃₇, R₄₀And R₄₄Is the same
May be different from each other and have a hydrogen atom or a substituent.
May be alkyl group, cycloalkyl group, acyl group
Specifically, it represents an alkoxycarbonyl group. R ₃₂, R₃₃, R
₃₄, R₄₁, R₄₂And R₄₃Can be the same or different
Even if it has a hydrogen atom, a halogen atom or a substituent
Represents an alkyl group or an alkoxy group. R₃₆Over
And R₃₉May be the same or different and may be a hydrogen atom,
Rogen atom, cyano group or an optionally substituted group
Represents a rukyl group. R₃₈May have a substituent,
Alkyl group, cycloalkyl group, aralkyl group or ari
Group. B₁And B₂Is a single bond or a divalent linking group
Represents B₃Represents a divalent linking group. n is 0 or 1
Represents

Examples of the above alkyl group include linear and branched alkyl groups, for example, having 1 to 8 carbon atoms.
Specific examples of the alkyl group include methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, and octyl group. The cycloalkyl group may be monocyclic or polycyclic. The monocyclic type has 3 to 8 carbon atoms, and preferred examples thereof include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.
The polycyclic type has 6 to 20 carbon atoms and includes, for example, an adamantyl group, a norbornyl group, an isobornyl group,
Camphanyl group, dicyclopentyl group, a-pinel group,
Preferable examples include tricyclodecanyl group, tetracyclododecyl group, androstanyl group. still,
The cycloalkyl group is intended to include those in which a part of carbon atoms constituting the ring is substituted with a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom.

The aryl group has, for example, 6 to 1 carbon atoms.
5 aryl groups, specifically, a phenyl group,
Tolyl group, dimethylphenyl group, 2,4,6-trimethylphenyl group, naphthyl group, anthryl group, 9,10-
Preferred examples thereof include a dimethoxyanthryl group. The aralkyl group is, for example, an aralkyl group having a carbon number of 7 to 12, and specific examples thereof include a benzyl group, a phenethyl group and a naphthylmethyl group.

The alkenyl group has, for example, 2 to 2 carbon atoms.
8 alkenyl groups, specifically vinyl groups,
An allyl group, a butenyl group, and a cyclohexenyl group can be preferably mentioned. The alkoxy group is, for example, an alkoxy group having 1 to 8 carbon atoms, and specifically, a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, a butoxy group, a pentoxy group, an allyloxy group, an octoxy group. A group and the like can be preferably mentioned.

The acyl group has, for example, 1 to 10 carbon atoms.
Specific examples of the acyl groups include formyl group, acetyl group, propanoyl group, butanoyl group, pivaloyl group, octanoyl group and benzoyl group. The acyloxy group has 2 to 1 carbon atoms.
Two acyloxy groups are preferable, and examples thereof include an acetoxy group, a propionyloxy group, and a benzoyloxy group. The alkynyl group is preferably an alkynyl group having 2 to 5 carbon atoms, and examples thereof include an ethynyl group, a propynyl group and a butynyl group. Examples of the alkoxycarbonyl group include t-butoxycarbonyl group and t-
Examples thereof include tertiary alkoxycarbonyl groups such as amyloxycarbonyl group and 1-methyl-1-cyclohexyloxycarbonyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.

The divalent linking group means a divalent alkylene group, cycloalkylene group, alkenylene group or arylene group or -O-CO-R which may have a substituent.
_22a -,-CO-O- _R22b -,-CO-N ( _R22c )-
Represents _R22d- . R _22a, R _{22 b} and R _{22 d} may be the same or different, a single bond or an ether group, an ester group, which may have an amide group, a urethane group or a ureido group, a divalent alkylene group Represents a cycloalkylene group, an alkenylene group or an arylene group. R
_22c represents a hydrogen atom or an alkyl group, cycloalkyl group, aralkyl group or aryl group which may have a substituent.

Examples of the alkylene group include linear and branched alkylene groups. Examples thereof include a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and an octylene group having 1 to 8 carbon atoms. There are things. Examples of the cycloalkylene group include those having 5 to 8 carbon atoms such as a cyclopentylene group and a cyclohexylene group. As the alkenylene group, those having 2 to 6 carbon atoms such as an ethenylene group, a propenylene group and a butenylene group, which may have a substituent, can be mentioned. The arylene group is preferably an arylene group having a carbon number of 6 to 15, such as a phenylene group, a tolylene group and a naphthylene group which may have a substituent.

Two of R _{18d to} R _18f , R _18d , R _18e ,
The ring formed by combining two of R _18g , two of R _{14 to} R ₁₆ , R ₂₅ and R ₂₆ , R ₂₇ and R ₂₈ or R ₂₉ and R ₃₀ with each other is, for example, 3 to 8-membered ring, specifically, cyclopropane ring, cyclopentane ring, cyclohexane ring, tetramethylene oxide ring, pentamethylene oxide ring, hexamethylene oxide ring, furan ring, pyran ring, dioxonol ring, 1,3-dioxolane Examples include rings.

Z represents an atomic group constituting a monocyclic or polycyclic alicyclic group together with the carbon atom in the general formula (VI-B).
The monocyclic alicyclic group preferably has 3 to 8 carbon atoms, and examples thereof include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. As the polycyclic alicyclic group, those having 6 to 20 carbon atoms are preferable, and examples thereof include an adamantyl group, a norbornyl group, an isobornyl group, a camphanyl group, a dicyclopentyl group, an α-pinel group, a tricyclodecanyl group, and tetracyclododecyl. Group, androstanyl group and the like.

The above alkyl group, cycloalkyl group, alkoxy group, acyl group, acyloxy group, alkynyl group,
The alkenyl group, aryl group, aralkyl group, alkoxycarbonyl group, alkylene group, cycloalkylene group, alkenylene group, arylene group and the like may have a substituent. Substituents substituted on these groups include those having active hydrogen such as amino group, amide group, ureido group, urethane group, hydroxyl group and carboxyl group, and halogen atoms (fluorine atom, chlorine atom, bromine atom, Iodine atom), alkoxy group (methoxy group, ethoxy group, propoxy group, butoxy group, etc.), thioether group, acyl group (acetyl group, propanoyl group, benzoyl group, etc.), acyloxy group (acetoxy group, propanoyloxy group, benzoyl) Oxy group, etc.), alkoxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, etc.), alkyl group (methyl group, ethyl group,
Propyl group, butyl group), cycloalkyl group (cyclohexyl group), aryl group (phenyl group), cyano group, nitro group and the like.

In the present invention, at least one of R ₁ of general formula (I), R ₅ of general formula (II) and R ₁₇ of general formula (VI) is preferably a trifluoromethyl group.

Action of acid contained in the resin of the present invention (A)
Examples of the group that is decomposed by and shows alkali solubility include
-OC (R_18d) (R_18e) (R_18f), -OC (R
_18d) (R_18e) (OR_{18 g}), -O-COO-C
(R_18d) (R_18e) (R_18f), -OC (R₀₁) (R
₀₂) COO-C (R_18d) (R_18e) (R_18f), -CO
OC (R_18d) (R_18e) (R_18f), -COO-C
(R_18d) (R_18e) (OR_{18 g}) And the like. R_18d
~ R_{18 g}Is the same as defined above except for a hydrogen atom.
R₀₁, R ₀₂Has a hydrogen atom or a substituent shown above.
Optional alkyl group, cycloalkyl group, alkene
Represents an alkyl group, an aralkyl group or an aryl group.

A preferred specific example is a t-butyl group,
t-amyl group, 1-alkyl-1-cyclohexyl group,
2-alkyl-2-adamantyl group, 2-adamantyl-2-propyl group, 2- (4-methylcyclohexyl)
Ether group or ester group of tertiary alkyl group such as 2-propyl group, acetal group or acetal ester group such as 1-alkoxy-1-ethoxy group, tetrahydropyranyl group, t-alkyl carbonate group, t-alkylcarbonyl A methoxy group and the like are preferable. More preferably, it is an acetal group such as a 1-alkoxy-1-ethoxy group or a tetrahydropyranyl group. In the case of an acetal group, the acid decomposability is large, the range of selection of the acid generating compound to be used in combination is widened, and it is effective in terms of the improvement of sensitivity, performance fluctuation with the elapse of time after exposure and heating. Particularly preferred is an acetal group containing an alkoxy group derived from the above perfluoroalkyl group as the 1-alkoxy component of the acetal group. In this case, the transmittance of short-wave exposure light (for example, 157 nm of F ₂ excimer laser light) can be further improved.

The content of the repeating unit represented by the general formula (I) in the resin (A) is generally 5 to 80 mol%, preferably 7 to 75 mol%, more preferably 10 to
Used in the range of 70 mol%. The content of the repeating unit represented by the general formula (II) in the resin (A) is generally 5 to 80 mol%, preferably 7 to 70 mol%, more preferably 10 to 65 mol%. To be done. The content of the repeating unit represented by the general formula (VI) in the resin (A) is generally 1 to 70 mol%, preferably 1 to 65 mol%, more preferably 5 to 60 mol%. used. The content of the repeating unit represented by the general formula (III) is generally 1 to 4 in the resin (A).
It is used in an amount of 0 mol%, preferably 3 to 35 mol%, more preferably 5 to 30 mol%. General formula (VII)
The content of the repeating unit represented by is generally 1 to 40 mol%, preferably 3 to 35 mol%, more preferably 5 to 30 mol% in the resin (A). The content of the repeating units represented by the general formulas (VIII) to (X) is generally 1 to 40 in the resin (A).
Mol%, preferably 3 to 35 mol%, more preferably 5
It is used in the range of ˜30 mol%. General formula (XI)-
The content of the repeating unit represented by (XIII) in the resin (A) is generally 1 to 40 mol%, preferably 3 to 35 mol%, more preferably 5 to 30 mol%. It The content of the repeating unit represented by the general formula (XIV) is generally 1 to 4 in the resin (A).
It is used in an amount of 0 mol%, preferably 3 to 35 mol%, more preferably 5 to 30 mol%. The content of the repeating unit represented by the general formula (XV) in the resin (A) is generally 1 to 40 mol%, preferably 3 to 35 mol%, more preferably 5 to 30 mol%. used. The content of the repeating unit represented by the general formula (XVI) is generally 1 to 40 mol% in the resin (A),
It is preferably used in the range of 3 to 35 mol%, more preferably 5 to 30 mol%. The content of the repeating unit represented by the general formula (XVII) in the resin (A) is generally 1 to 40 mol%, preferably 3 to 35 mol%, more preferably 5 to 30 mol%. used.

The resin of the present invention (A) may be copolymerized with other polymerizable monomers in addition to the above repeating structural units for the purpose of further improving the performance of the positive resist of the present invention. .

Copolymerizable monomers that can be used include those shown below. For example, addition-polymerizable unsaturated bonds selected from acrylic acid esters, acrylamides, methacrylic acid esters, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, crotonic acid esters, etc. other than the above It is a compound having one.

Specifically, for example, acrylic acid esters such as alkyl (wherein the alkyl group has 1 to 1 carbon atoms).
0 is preferred) Acrylate (eg, methyl acrylate, ethyl acrylate, propyl acrylate, amyl acrylate, cyclohexyl acrylate, ethylhexyl acrylate, octyl acrylate, chloroethyl acrylate, 2-hydroxyethyl acrylate 2,
2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, glycidyl acrylate, benzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, etc.) Aryl acrylate (eg phenyl acrylate etc.);

Methacrylic acid esters, for example, alkyl (alkyl groups preferably having 1 to 10 carbon atoms) methacrylate (for example, methyl methacrylate,
Ethylmethacrylate, propylmethacrylate, isopropylmethacrylate, amylmethacrylate, hexylmethacrylate, cyclohexylmethacrylate,
Benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate,
5-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, glycidyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, etc., aryl methacrylate (for example, phenyl methacrylate) , Cresyl methacrylate, naphthyl methacrylate, etc.);

Acrylamides such as acrylamide, N-alkylacrylamide, and the like (alkyl groups having 1 to 10 carbon atoms, such as methyl, ethyl, propyl, butyl, t-butyl, and heptyl. Group, octyl group, cyclohexyl group, benzyl group, hydroxyethyl group, benzyl group, etc.), N-arylacrylamide (as the aryl group, for example, phenyl group, tolyl group, nitrophenyl group, naphthyl group,
There are cyanophenyl group, hydroxyphenyl group, carboxyphenyl group and the like. ), N, N-dialkylacrylamide (the alkyl group has 1 to 10 carbon atoms, for example, methyl group, ethyl group, butyl group, isobutyl group, ethylhexyl group, cyclohexyl group, etc.), N, N-diarylacrylamide (an aryl group includes, for example, a phenyl group), N-methyl-N-phenylacrylamide, N-hydroxyethyl-N-methylacrylamide, N-2-acetamidoethyl-N-acetylacrylamide, etc. ;

Methacrylamides, such as methacrylamide, N-alkylmethacrylamides (wherein the alkyl group is one having 1 to 10 carbon atoms, such as methyl group, ethyl group, t-butyl group, ethylhexyl group, hydroxyethyl group). Group, cyclohexyl group, etc.), N
-Aryl methacrylamide (an aryl group includes a phenyl group, etc.), N, N-dialkyl methacrylamide (an alkyl group includes an ethyl group, a propyl group, a butyl group, etc.), N, N-diaryl. Methacrylamide (such as a phenyl group as an aryl group), N-hydroxyethyl-N-methylmethacrylamide, N-methyl-N-phenylmethacrylamide, N-ethyl-N-phenylmethacrylamide, etc .;
Allyl compounds, such as allyl esters (eg, allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate), allyloxyethanol Such;

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 ether (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 barrate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate. , Vinyl phenylacetate, vinyl acetoacetate, vinyl lactate, vinyl-β-
Phenyl butyrate, vinyl cyclohexyl carboxylate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate, etc .;

Styrenes such as styrene, alkylstyrenes (eg methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethyl). Styrene, trifluoromethylstyrene, ethoxymethylstyrene, acetoxymethylstyrene, etc.), alkoxystyrene (eg, methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene, etc.), halogen styrene (eg, chlorostyrene, dichlorostyrene). , Trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromstyrene, dibromostyrene, iodostyrene, fluoros Ren, trifluoromethyl styrene, 2
-Bromo-4-trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene, etc.), carboxystyrene, vinylnaphthalene;

Crotonic acid esters, for example, alkyl crotonic acid (eg, butyl crotonic acid, hexyl crotonic acid, glycerin monocrotonate, etc.); Dialkyl itaconic acid (eg, dimethyl itaconic acid, diethyl itaconic acid, dibutyl itaconic acid, etc.) ); Dialkyl esters of maleic acid or fumaric acid (eg,
Dimethyl maleate, dibutyl fumarate, etc.) and the like. In addition, any addition-polymerizable unsaturated compound that is generally copolymerizable may be used.

Specific examples of the repeating structural unit represented by formula (I) are shown below, but the invention is not limited thereto.

[0062]

[Chemical 13]

[0063]

[Chemical 14]

[0064]

[Chemical 15]

[0065]

[Chemical 16]

[0066]

[Chemical 17]

[0067]

[Chemical 18]

[0068]

[Chemical 19]

[0069]

[Chemical 20]

Specific examples of the repeating structural unit represented by the general formula (II) are shown below, but the invention is not limited thereto.

[0071]

[Chemical 21]

[0072]

[Chemical formula 22]

[0073]

[Chemical formula 23]

[0074]

[Chemical formula 24]

Specific examples of the repeating structural unit represented by the general formula (III) are shown below, but the invention is not limited thereto.

[0076]

[Chemical 25]

Specific examples of the repeating structural unit represented by the general formula (VII) are shown below, but the invention is not limited thereto.

[0078]

[Chemical formula 26]

In the following, general formulas (VIII) to (XII
Specific examples of the repeating structural unit represented by I) are shown below, but the invention is not limited thereto.

[0080]

[Chemical 27]

[0081]

[Chemical 28]

[0082]

[Chemical 29]

[0083]

[Chemical 30]

In the following, general formulas (VI) and (XVII)
Specific examples of the repeating structural unit represented by are shown below, but the present invention is not limited thereto.

[0085]

[Chemical 31]

[0086]

[Chemical 32]

[0087]

[Chemical 33]

[0088]

[Chemical 34]

[0089]

[Chemical 35]

[0090]

[Chemical 36]

[0091]

[Chemical 37]

[0092]

[Chemical 38]

Specific examples of the repeating structural unit represented by formula (XV) include the repeating structural unit formed by the vinyl ethers.

The repeating structural units shown in the above specific examples may be used alone or in combination of two or more. The preferred molecular weight of the resin (A) of the present invention having the repeating structural unit is 1,000 to 2 on a weight average basis.
0,000, and more preferably 3,000 to 2
Used in the range of 10,000. Molecular weight distribution is 1-10
And preferably in the range of 1 to 3, more preferably 1 to 2. The smaller the molecular weight distribution,
The resolution, the resist shape, and the side wall of the resist pattern are smooth, and the roughness is excellent. The addition amount of the resin (A) of the present invention is generally in the range of 50 to 99.5% by weight, preferably 60 to 98% by weight, more preferably 65 to 95% by weight, based on the total solid content of the composition. Used in.

[2] The compound of the present invention (B) which generates an acid upon irradiation with actinic rays or radiation. The compound used in the present invention which decomposes upon irradiation with actinic rays or radiation to generate an acid is light. Photoinitiators for cationic polymerization, photoinitiators for photoradical polymerization, photobleaching agents for dyes, photochromic agents, or known light used for micro resists (4
Ultraviolet rays of from 0 to 200 nm, deep ultraviolet rays, particularly preferably g rays, h rays, i rays, KrF excimer laser light),
A compound that generates an acid by ArF excimer laser light, an electron beam, an X-ray, a molecular beam or an ion beam, and a mixture thereof can be appropriately selected and used.

Other compounds which generate an acid upon irradiation with actinic rays or radiation used in the present invention include SI Schlesinger, Photogr. Sci. En.
g., 18,387 (1974), TS Bal et al, Polymer, 21, 4
23 (1980) and the like diazonium salt, U.S. Pat.No. 4,069,
055, 4,069,056, Re 27,992, JP-A-3-401
Ammonium salts described in No. 40, DC Necker et al,
Macromolecules, 17, 2468 (1984), CS Wen et al, T
eh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1
988), U.S. Pat.Nos. 4,069,055 and 4,069,056 and other phosphonium salts, JV Crivello et al, Macromorec
ules, 10 (6), 1307 (1977), Chem. & Eng. News, Nov. 2
8, p31 (1988), European Patent Nos. 104,143, 339,049, 410,201, JP-A 2-150848, JP-A-2-296514, etc., iodonium salts, JVCrivello et al, Polym
er J. 17, 73 (1985), JV Crivello et al., J. Org.
Chem., 43, 3055 (1978), WR Watt et al, J. Polyme.
r Sci., Polymer Chem. Ed., 22, 1789 (1984), JV Cr
ivello et al, Polymer Bull., 14, 279 (1985), JV
Crivello et al, Macromorecules, 14 (5), 1141 (198)
1), JV Crivello et al, J. Polymer Sci., Polymer
Chem. Ed., 17, 2877 (1979), European Patent No. 370,693,
161,811, 410,201, 339,049, 233,567
No. 297,443, 297,442, U.S. Pat.No. 4,933,377
Issue 3,902,114, Issue 4,760,013, Issue 4,734,444,
No. 2,833,827, Dokoku Patent No. 2,904,626, No. 3,604,580
Nos. 3,604,581, etc., sulfonium salts, JVC
rivello et al, Macromorecules, 10 (6), 1307 (1977),
JV Crivello et al, J. Polymer Sci., Polymer Che
m. Ed., 17, 1047 (1979) etc., selenonium salt, C.
S. Wen et al, Teh, Proc.Conf. Rad. Curing ASIA, p
478 Tokyo, Oct (1988) and other onium salts such as arsonium salts, U.S. Pat.No. 3,905,815, Japanese Patent Publication No. 46-4605,
JP-A-48-36281, JP-A-55-32070, JP-A-60-23973
6, JP 61-169835, JP 61-169837, JP 6
2-58241, JP-A-62-212401, JP-A-63-70243, JP-A-63-298339 and the like, organic halogen compounds, K. Me
ier et al, J. Rad. Curing, 13 (4), 26 (1986), TPG
ill et al, Inorg. Chem., 19, 3007 (1980), D. Astru
c, Acc. Chem. Res., 19 (12), 377 (1896), JP-A-2-161
No. 445, etc., Organometallic / Organohalide, S. Haya
se et al, J. Polymer Sci., 25, 753 (1987), E. Reich
manis et al, J. Pholymer Sci., Polymer Chem. Ed.,
23, 1 (1985), QQ Zhuetal, J. Photochem., 36, 85,
39, 317 (1987), B. Amit et al, Tetrahedron Lett., (2
4) 2205 (1973), DHR Barton et al, J. Chem Soc.,
3571 (1965), PM Collins et al, J. Chem. Soc., P
erkin I, 1695 (1975), M. Rudinstein et al, Tetrahed.
ron Lett., (17), 1445 (1975), JW Walker et al,
J. Am. Chem. Soc., 110, 7170 (1988), SC Busman e
t al, J. Imaging Technol., 11 (4), 191 (1985), HM
Houlihan et al, Macromolecules, 21, 2001 (1988),
PMCollins et al, J. Chem. Soc., Chem. Commun., 5
32 (1972), S. Hayase et al, Macromolecules, 18, 179.
9 (1985), E. Reichmanis et al, J. Electrochem. Soc.,
Solid State Sci. Technol., 130 (6), FM Houlihan
et al, Macromolcules, 21, 2001 (1988), European Patent No. 02
90,750, 046,083, 156,535, 271,851,
0,388,343, U.S. Pat.No. 3,901,710, 4,181,531
M.TU, a photoacid generator having a 0-nitrobenzyl type protective group described in JP-A No. 60-198538, JP-A No. 53-133022 and the like.
NOOKA et al, Polymer Preprints Japan, 35 (8), G. Be
rner et al, J. Rad. Curing, 13 (4), WJ Mijs et
al, Coating Technol., 55 (697), 45 (1983), Akzo, H.A.
dachi et al, Polymer Preprints, Japan, 37 (3), European Patents 0199,672, 84515, 044,115, 618,56.
4, No. 0101,122, U.S. Patent Nos. 4,371,605, 4,431,
774, JP-A-64-18143, JP-A-2-245756, JP-A
Compounds which generate sulfonic acid by photolysis, represented by iminosulfonates described in JP-A 3-140109, and the like.
-166544 etc. can be mentioned.

Also, a group in which an acid-generating group or a compound is introduced into the main chain or side chain of a polymer, for example, ME Woodho
useet al, J. Am. Chem. Soc., 104, 5586 (1982), S.
P. Pappas et al, J. Imaging Sci., 30 (5), 218 (198
6), S. Kondo et al, Makromol. Chem., Rapid Commu
n., 9, 625 (1988), Y. Yamada et al, Makromol. Che
m., 152, 153, 163 (1972), JV Crivello et al, J.
Polymer Sci., Polymer Chem. Ed., 17, 3845 (1979),
U.S. Pat.No. 3,849,137, United States Patent No. 3914407, JP-A-63
-26653, JP-A-55-164824, JP-A-62-69263, JP-A-63-146038, JP-A-63-163452, JP-A-62-15385
The compounds described in JP-A No. 3 and JP-A No. 63-146029 can be used.

Further, VNR Pillai, Synthesis, (1),
1 (1980), A. Abad et al, Tetrahedron Lett., (47) 45.
55 (1971), DHR Barton et al, J. Chem. Soc.,
(C), 329 (1970), U.S. Patent No. 3,779,778, European Patent No. 1
The compounds which generate an acid by the light described in No. 26,712 and the like can also be used.

Among the compounds which decompose when exposed to 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
1) an oxazole derivative or a general formula (PAG
An S-triazine derivative represented by 2).

[0100]

[Chemical Formula 39]

In the formula, R ²⁰¹ is a substituted or unsubstituted aryl group or alkenyl group, R ²⁰² is a substituted or unsubstituted aryl group, alkenyl group, alkyl group or —C (Y) ₃
Indicates. Y represents a chlorine atom or a bromine atom. The following compounds can be specifically mentioned, but the compounds are not limited to these.

[0102]

[Chemical 40]

[0103]

[Chemical 41]

[0104]

[Chemical 42]

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

[0106]

[Chemical 43]

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

R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ each independently represent a substituted or unsubstituted alkyl group or aryl group. Preferably, an aryl group having 6 to 14 carbon atoms and 1 to 8 carbon atoms
Are alkyl groups and substituted derivatives thereof. Preferred substituents are an alkoxy group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group, a nitro group, a carboxyl group, a mercapto group, a hydroxy group and a halogen atom for an aryl group. For an alkyl group, an alkoxy group having 1 to 8 carbon atoms, a carboxyl group, and an alkoxycarbonyl group.

Z ⁻ represents an anion, specifically, an alkyl sulfonic acid which may have a substituent, a cycloalkyl sulfonic acid, a perfluoroalkyl sulfonic acid, an aryl sulfonic acid (for example, having a substituent) Examples of each anion include benzene sulfonic acid, naphthalene sulfonic acid, anthracene sulfonic acid).

Two of R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ and Ar ¹ and Ar ² may be bonded via a single bond or a substituent.

Specific examples include the compounds shown below, but the invention is not limited thereto.

[0112]

[Chemical 44]

[0113]

[Chemical formula 45]

[0114]

[Chemical formula 46]

[0115]

[Chemical 47]

[0116]

[Chemical 48]

[0117]

[Chemical 49]

[0118]

[Chemical 50]

[0119]

[Chemical 51]

[0120]

[Chemical 52]

[0121]

[Chemical 53]

The onium salts represented by the general formulas (PAG3) and (PAG4) are known, and for example, JW Knapcz.
yk et al, J. Am. Chem. Soc., 91, 145 (1969), AL
Maycok et al, J. Org. Chem., 35, 2532, (1970), E.
Goethas et al, Bull. Soc. Chem. Belg., 73, 546, (196
4), HM Leicester, J. Ame. Chem. Soc., 51, 3587.
(1929), JV Crivello et al, J. Polym. Chem. Ed.,
18, 2677 (1980), U.S. Pat.Nos. 2,807,648 and 4,247,
It can be synthesized by the method described in JP-A No. 473, JP-A-53-101331, etc.

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

[0124]

[Chemical 54]

In the formula, Ar³, Ar^FourReplace each independently
Or an unsubstituted aryl group. R ²⁰⁶Is replaced or
An unsubstituted alkyl group and an aryl group are shown. If A is replaced
Or unsubstituted alkylene group, alkenylene group, aryle
Group. Specific examples include the compounds shown below.
However, the present invention is not limited to these.

[0126]

[Chemical 55]

[0127]

[Chemical 56]

[0128]

[Chemical 57]

[0129]

[Chemical 58]

[0130]

[Chemical 59]

[0131]

[Chemical 60]

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

[0133]

[Chemical formula 61]

Here, R represents a linear, branched or cyclic alkyl group or an aryl group which may be substituted. Specific examples thereof include the compounds shown below, but the invention is not limited thereto.

[0135]

[Chemical formula 62]

(5) An oxime sulfonate derivative represented by the following general formula (PAG8).

[0137]

[Chemical formula 63]

In the formula, R ₂₀₇ represents a substituted or unsubstituted alkyl group, cycloalkyl group, aryl group or aralkyl group. R ₂₀₈ and R ₂₀₉ represent a substituted or unsubstituted alkyl group, cycloalkyl group, aryl group, aralkyl group, cyano group or acyl group. R ₂₀₈ and R ₂₀₉ may combine to form a carbon ring or a heterocycle having an oxygen atom, a nitrogen atom or a sulfur atom. Specific examples include the compounds shown below, but the invention is not limited thereto.

[0139]

[Chemical 64]

The amount of the compound which generates an acid upon irradiation with actinic rays or radiation of the present invention (B) is generally 0.1 to 20% by weight based on the total solid content of the composition of the present invention. And preferably 0.5 to 10% by weight, more preferably 1 to 7% by weight. These compounds may be used alone or in combination of two or more.

[3] Solvent of the present invention (C) The composition of the present invention is dissolved in a solvent that dissolves each of the above components and coated on a support. As the solvent used here,
1-methoxy-2-propanol acetate, 1-methoxy-2-propanol, 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 monoethyl ether, propylene glycol monomethyl ether acetate, toluene, ethyl acetate , Methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, tetrahydrofuran and the like are preferable, and 1 -Methoxy-
2-Propanol acetate and 1-methoxy-2-propanol are particularly preferable. These solvents may be used alone or as a mixture.

[4] Fluorine-based and / or silicon-based surfactant (D) that can be used in the present invention The positive resist composition of the present invention contains a fluorine-based and / or silicon-based surfactant. be able to. That is, the positive resist composition of the present invention contains at least one of a fluorine-based surfactant, a silicon-based surfactant, and a surfactant containing both a fluorine atom and a silicon atom, or two or more thereof. You can These fluorine-based and
The addition of a silicon-based surfactant is effective in suppressing development defects and improving coatability.

Examples of these surfactants include those disclosed in
62-36663, JP-A-61-226746, JP-A-61-226745,
JP 62-170950 A, JP 63-34540 A, JP 7-23016 A
5, JP 8-62834A, JP 9-54432A, JP 9-598A
8, U.S. Pat.No. 5,405,720, U.S. Pat.No. 5,360,692, U.S. Pat.No. 5,528,981, U.S. Pat.No. 5,296,330, U.S. Pat.
U.S. Patent No. 5576143, U.S. Patent No. 5296143, U.S. Patent
5294511 and US Pat. No. 5,824,451 can be mentioned, and the following commercially available surfactants can be used as they are. Examples of such commercially available surfactants include F-top EF301, EF303, EF352 (Shin-Akita Kasei)
Fluoro FC430, 431 (Sumitomo 3M Limited)
Made), MegaFac F171, F173, F176, F189, R08 (made by Dainippon Ink and Chemicals), Asahi Guard AG710, Surflon S
-382, SC101, 102, 103, 104, 105, 106 (manufactured by Asahi Glass Co., Ltd.), Troisol S-366 (manufactured by Troy Chemical Co., Ltd.) and the like fluorine-based surfactants or silicon-based surfactants can be mentioned. . Also polysiloxane polymer KP
-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as the silicon-based surfactant.

The content of the surfactant is usually 0.001% by weight to 2% by weight, preferably 0.01% by weight to 1% by weight, based on the solid content in the composition of the present invention. These surfactants may be added alone or in some combinations.

[5] Acid Diffusion Inhibitor (E) Applicable to the Present Invention In the composition of the present invention, the performance variation (T-to-pattern of the pattern) after irradiation with actinic rays or radiation and before heat treatment.
(P shape formation, sensitivity fluctuation, pattern line width fluctuation, etc.) and performance fluctuation with time after coating, and further, after irradiation with actinic rays or radiation, excessive diffusion of acid (deterioration of resolution) during heat treatment. Therefore, it is preferable to add an acid diffusion inhibitor. The acid diffusion inhibitor is an organic basic compound,
For example, an organic base compound containing basic nitrogen, and a compound having a pKa value of the conjugate acid of 4 or more is preferably used. Specifically, the structures of the following formulas (A) to (E) can be mentioned.

[0146]

[Chemical 65]

Here, R ²⁵⁰ , R ²⁵¹ and R ²⁵² may be the same or different and each is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aminoalkyl group having 1 to 6 carbon atoms, or 1 carbon atom. ~ 6 hydroxyalkyl group or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, wherein R is
²⁵¹ and R ²⁵² may combine with each other to form a ring. R
²⁵³ , R ²⁵⁴ , R ²⁵⁵ and R ^{256, which} may be the same or different, each represents an alkyl group having 1 to 6 carbon atoms. More preferred compounds are nitrogen-containing basic compounds having two or more nitrogen atoms having different chemical environments in one molecule, and particularly preferably both a substituted or unsubstituted amino group and a ring structure containing a nitrogen atom. It is a compound containing or a compound having an alkylamino group.

Preferred specific examples are substituted or unsubstituted guanidine, substituted or unsubstituted aminopyridine, substituted or unsubstituted aminoalkylpyridine, substituted or unsubstituted aminopyrrolidine, substituted or unsubstituted indazole, imidazole, 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 Alternatively, unsubstituted aminomorpholine, substituted or unsubstituted aminoalkylmorpholine and the like can be mentioned. Preferred substituents are amino group, aminoalkyl group, alkylamino group, aminoaryl group, arylamino group, alkyl group, alkoxy group, acyl group, acyloxy group, aryl group, aryloxy group, nitro group, hydroxyl group, cyano group. Is.

Particularly preferred compounds are guanidine,
1,1-dimethylguanidine, 1,1,3,3-tetramethylguanidine, imidazole, 2-methylimidazole, 4-methylimidazole, N-methylimidazole, 2-phenylimidazole, 4,5-diphenylimidazole, 2 , 4,5-Triphenylimidazole, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2-diethylaminopyridine, 2
-(Aminomethyl) pyridine, 2-amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-5-methylpyridine, 2-amino-6-methylpyridine, 3-aminoethylpyridine, 4 -Aminoethylpyridine,

3-aminopyrrolidine, piperazine, N-
(2-aminoethyl) piperazine, N- (2-aminoethyl) piperidine, 4-amino-2,2,6,6-tetramethylpiperidine, 4-piperidinopiperidine, 2-
Iminopiperidine, 1- (2-aminoethyl) pyrrolidine, pyrazole, 3-amino-5-methylpyrazole,
5-amino-3-methyl-1-p-tolylpyrazole,
Pyrazine, 2- (aminomethyl) -5-methylpyrazine, pyrimidine, 2,4-diaminopyrimidine, 4,6
-Dihydroxypyrimidine, 2-pyrazoline, 3-pyrazoline, N-aminomorpholine, N- (2-aminoethyl) morpholine and the like, but not limited thereto. These nitrogen-containing basic compounds may be used alone or in combination of two or more.

The ratio of the acid generator and the organic basic compound used in the composition is preferably (acid generator) / (organic basic compound) (molar ratio) = 2.5 to 300. If the molar ratio is less than 2.5, the sensitivity may be low and the resolution may be lowered. If the molar ratio is more than 300, the resist pattern may become thicker with the lapse of time after the post-exposure heat treatment, and the resolution may be lowered. . The (acid generator) / (organic basic compound) (molar ratio) is preferably 5.0 to 200, more preferably 7.0 to 150.

In the process of forming a pattern on the resist film in the production of precision integrated circuit elements, etc., the positive electrode of the present invention is formed on the substrate (eg, silicon / silicon dioxide covering, glass substrate, transparent substrate such as ITO substrate). A good resist pattern can be formed by applying a mold resist composition and then irradiating it with an actinic ray or radiation drawing device, followed by heating, developing, rinsing and drying.

As a developer for the positive resist composition of the present invention, there are used inorganic hydroxides such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine. Primary amines such as diethylamine, di-
Secondary amines such as n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and primary amines such as choline. An aqueous solution of alkali such as quaternary ammonium salt, cyclic amines such as pyrrole and piperidine, and the like can be used. Furthermore, alcohols such as isopropyl alcohol and surfactants such as nonionic surfactants may be added to the aqueous solution of the above alkalis in appropriate amounts. Of these developers, quaternary ammonium salts are preferable, and tetramethylammonium hydroxide and choline are more preferable.

[0154]

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

1. Synthesis Example 1 (Synthesis of Resin (2)) 4- (2-hydroxyhexafluoroisopropyl) styrene (manufactured by Central Glass Co., Ltd.), 4- (in a 100 ml three-necked flask equipped with a reflux tube and a nitrogen introduction tube. 1-
(Methoxyethoxy) styrene (manufactured by Tosoh Corporation) and 1-adamantane-1-methyl-ethylmethacrylate (manufactured by Daicel) were charged at a molar ratio of 50/40/10, and then tetrahydrofuran was added to the mixture to prepare a monomer concentration of 30% by weight. A total of 30 g of the reaction solution of was prepared. It was stirred and heated to 65 ° C. under a stream of nitrogen. Azo polymerization initiator V-65
(Manufactured by Wako Pure Chemical Industries, Ltd.) was added in an amount of 5.0 mol% with respect to the total number of moles of the three monomers, and the mixture was reacted for 8 hours while stirring under a nitrogen stream. Hexane 200 was added to the obtained reaction solution.
ml was added, the produced polymer was precipitated from the solution, and the unreacted monomer was separated and purified. The polymer composition determined from C ¹³ NMR was 51/39/10. When the obtained polymer was analyzed by GPC (in THF solvent, converted to standard polystyrene), the weight average molecular weight was 8,400,
Dispersion degree 2.20, molecular weight 1000 contained in polymer
The following proportion was 15% by weight. Similarly, the resins of the present invention shown in Table 1 were synthesized.

[0156]

[Table 1]

2. Example (Measurement of Transmittance) 1.36 g of the resin shown in Table 1 and 0.04 g of triphenylsulfonium naphthalate salt were added to 6.0 g of 1-methoxy-2-propanol acetate and 1-methoxy-2-.
A polymer solution was prepared by dissolving it in a mixed solvent of 2.5 g of propanol. Each polymer solution was filtered through a 0.1 μm Teflon (registered trademark) filter, and then coated on a calcium fluoride disc by a spin coater, and 120
It was heated and dried at 90 ° C. for 90 minutes to obtain a resist film of 0.1 μm. The absorption of the coating film was measured with an Acton CAMS-507 spectrometer and the transmittance at 157 nm was calculated. The results are shown in Table 2. As Comparative Example 1, polymer A: p used in KrF resist
-Hydroxystyrene / p- (1-ethoxyethoxystyrene) (70/30) was similarly prepared and the transmittance was measured.

[0158]

[Table 2]

From the results shown in Table 2, it can be seen that the resist film using the composition of the present invention has sufficient transparency at 157 nm.

3. Example (Measurement of Dissolution Contrast) Using the resins shown in Table 1, a resist solution was prepared in the same manner as in the above example. After filtering each resist solution with a 0.1 μm Teflon filter, it was applied on a silicon wafer treated with hexamethyldisilazane by a spin coater and heated and dried on a vacuum type hot plate at 120 ° C. for 90 seconds, A resist film having a film thickness of 0.1 μm was obtained. The obtained resist film was exposed at 157 nm using a laser exposure / dissolution behavior analyzer VUVES-4500 (manufactured by Lithotec Japan) at 157 nm.
The dissolution contrast of the unexposed area was measured. The results are shown in Table 3.

[0161]

[Table 3]

From the results shown in Table 3, it can be seen that the composition of the present invention has a dissolution contrast, that is, an image forming property, which is equal to or higher than that of the resist practically used for the KrF excimer of the comparative example.

[0163]

According to the present invention, it is possible to provide a positive resist composition having sufficient transparency even at a short wavelength of 157 nm and having a good dissolution contrast.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 2H025 AA04 AC04 AC08 AD03 BE00                       BG00 CC03 FA03 FA12 FA17                 4J100 AB01S AB07P AB07Q AL02S                       AL08R AM14S AR11R BA02P                       BA02R BA03Q BA03R BB07Q                       BB10R BB12P BB12R BB18P                       BB18Q BB18R BC04P BC08P                       BC09P BC53P CA05 CA06                       JA38

Claims (5)

[Claims] 1. (A) The following general formulas (I), (II) and
At least one repeating unit represented by (VI)
Possesses, decomposes due to the action of acid, and reacts with alkaline developers
Resin that increases the solubility of (B) actinic rays or radiation
Contains a compound that generates acid upon irradiation and (C) solvent
A positive resist composition comprising: [Chemical 1] R in the general formulas (I), (II) and (VI)₁, R_Five, R
_17aAnd R₁₇Can be the same or different and
Child, a halogen atom, a cyano group or a substituent
Represents a good alkyl group. R₂, R₃, R₆And R₇Is the same
Or they may be different, such as hydrogen atom, halogen atom,
May have an ano group, a hydroxyl group or a substituent
Alkyl group, cycloalkyl group, alkoxy group,
Sil group, acyloxy group, alkenyl group, aryl group
Represents an aralkyl group. R₅₀~ R ₅₅Is the same but different
May have a hydrogen atom, a fluorine atom or a substituent.
Represents an optionally substituted alkyl group. However, R₅₀~ R₅₅of
At least one of them is a fluorine atom or at least one
Represents an alkyl group in which a hydrogen atom of is substituted with a fluorine atom.
You R_FourRepresents a group of the following general formula (IV) or (V)
You R₁₈Is -C (R_18d) (R_18e) (R_18f) Or −
C (R_18d) (R_18e) (OR_{18 g}) Represents. R_18d~ R
_{18 g}May be the same or different and may be a hydrogen atom or
Alkyl group, cycloalkyl, which may have a substituent
Group, alkenyl group, aralkyl group or aryl group
Represent R_18d, R_18e, R_18f2 of or R_18d, R
_18e, R_{18 g}Two of them may combine to form a ring. [Chemical 2] R in the general formula (IV)₁₁, R₁₂And R₁₃Is the same but different
An alkyl group which may have a substituent or may have a substituent.
Group, cycloalkyl group, alkenyl group, aralkyl group
Alternatively, it represents an aryl group. R in the general formula (V)₁₄And R₁₅
May be the same or different and each represents a hydrogen atom or a substituent.
Represents an alkyl group which may have. R₁₆Is a substituent
Which may have an alkyl group, a cycloalkyl group,
Represents an aralkyl group or an aryl group. R₁₄~ R₁₆of
Two of them may combine to form a ring. 2. The general formula (VI), wherein R ₁₈ is represented by the following general formula (VI-A).
The positive resist composition as described in 1. [Chemical 3] In formula (VI-A), R _18a and R _18b may be the same or different and represent an alkyl group which may have a substituent. R _18c represents a cycloalkyl group which may have a substituent. 3. The general formula (VI), wherein R ₁₈ is represented by the following general formula (VI-B).
The positive resist composition as described in 1. [Chemical 4] In formula (VI-B), R _18h represents an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group or an aryl group, which may have a substituent. Z is a general formula (VI
-B) represents an atomic group that constitutes a monocyclic or polycyclic alicyclic group together with the carbon atom in B). 4. The general formula (VI), wherein R ₁₈ is represented by the following general formula (VI-C).
The positive resist composition as described in 1. [Chemical 5] In general formula (VI-C), R _{18 ′} represents an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group or an aryl group, which may have a substituent. 5. R _{1 of} the above general formula (I) and the general formula (I
At least one of R _{5 of} I) and R ₁₇ of the general formula (VI) is a trifluoromethyl group, The positive resist composition as claimed in claim 1.