JP2003015299A - 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 more specifically to provide a positive type resist composition having improved surface roughness and scum. SOLUTION: Each of the positive type resist compositions contains (A) a resin which has specified repeating units (1), repeating units (2) which are decomposed by the action of an acid to increase the solubility of the resin in an alkali developing solution and repeating units (3) inert to the action of the acid, having no alkali-soluble group and containing at least one fluorine atom and is decomposed by the action of the acid to increase its solubility in the alkali developing solution and (B) a compound which generates the acid when irradiated with active light or radiation.

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, a compound having an aromatic group essentially has a large absorption in the wavelength region of 193 nm, and therefore the chemical amplification type resist described above cannot provide sufficient performance. .

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.

In the SPIE 2001 Microlithography Symposium, a resist using 4- [bis (trifluoromethyl) -hydroxymethyl] styrene and a t-butyl methacrylate copolymer was reported. However, the resist using this has a problem that the roughness of the pattern surface after development is large. In addition, there is a problem that scum is often generated in the space portion of the line & space pattern. Also DE1005
The 4996A specification discloses an F ₂ resist resin obtained by copolymerizing an acrylate monomer containing a fluorine atom at the α-position or the ester portion with a (meth) acrylate containing p-hydroxystyrene or a tertiary ester. However, this also has a problem that scum is often generated in the space portion of the line and space pattern.

[0009]

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, and more specifically to provide a positive resist composition having improved surface roughness and scum.

[0010]

Means for Solving the Problems As a result of intensive studies made by the present inventors while paying attention to the above-mentioned various characteristics, the object of the present invention was satisfactorily achieved by using the following specific fluorine atom-containing resin. And has reached the present invention. That is, the present invention has the following configuration.

(1) (A) copolymerizable with at least one repeating unit (1) represented by the following general formula (I) and at least one repeating unit represented by the general formula (I),
A repeating unit (2) which decomposes by the action of an acid to increase the solubility of the resin in an alkaline developer,
And at least one repeating unit (3) which is inert to the action of an acid and does not have an alkali-soluble group and contains at least one fluorine atom and which is decomposed by the action of an acid and has a solubility in an alkali developing solution. A positive resist composition, which comprises a resin that increases the amount of (B) and (B) a compound that generates an acid upon irradiation with actinic rays or radiation.

[0012]

[Chemical 7]

In the general formula (I), R ₅ represents a hydrogen atom, a halogen atom, a cyano group or an alkyl group which may have a substituent. R ₆ and R ₇ may be the same or different, and may have a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group or a substituent, an alkyl group, a cycloalkyl group, an alkoxy group, an acyl group, Acyloxy group,
It represents an alkenyl group, an aryl group or an aralkyl group. R ₅₀ to R ₅₅ may be the same or different, represent a hydrogen atom, an alkyl group which may have a fluorine atom or a substituent. However, at least one of R _{50 to} R ₅₅ represents a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom.

(2) The positive photoresist composition as described in (1) above, wherein the repeating unit (2) is represented by the following general formula (II).

[0015]

[Chemical 8]

In the general formula (II), R ₁ represents a hydrogen atom, a halogen atom, a cyano group or an alkyl group which may have a substituent. R ₂ and R ₃ may be the same or different, and may have a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group or a substituent, an alkyl group, a cycloalkyl group, an alkoxy group, an acyl group, It represents an acyloxy group, an alkenyl group, an aryl group or an aralkyl group. R ₄ represents a group represented by the following general formula (IV) or (V).

[0017]

[Chemical 9]

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. Two of R _{11 to} R ₁₃ may combine to form a ring. 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 to form a ring.

(3) The positive photoresist composition as described in (1) or (2) above, wherein the repeating unit (2) is represented by the following general formula (III).

[0020]

[Chemical 10]

In the general formula (III), R _17a and R ₁₇ may be the same or different and each represents a hydrogen atom, a halogen atom, a cyano group or an alkyl group which may have a substituent. R _{18 is, -C (R 18d) (R} 18e) (R 18f) or -
Represents C (R _18d ') (R _18e ') (OR _18f '). R _18d ~
R _18f may be the same or different and each represents an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group or an aryl group, which may have a substituent. R
_18d 'to _R18f ' may be the same or different and each represents an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group or an aryl group, which may have a hydrogen atom or a substituent. Two of R _{18d to} R _18f or R _18d 'to R _18f
Two of _18f 'may combine to form a ring. A is
It represents a single bond or a divalent linking group.

(4) The positive resist composition as described in (3) above, wherein R _{18 in the} above general formula (III) is represented by the following general formula (III-B).

[Chemical 11]

In the general formula (III-B), R _18h represents an _optionally substituted alkyl group, cycloalkyl group, alkenyl group, alkynyl group, aralkyl group or aryl group. Z represents an atomic group forming a monocyclic or polycyclic alicyclic group together with the carbon atom in the general formula (VI-B).

(5) The repeating unit (3) is an α-trifluoroacrylic acid ester, a fluorine-containing alkyl ester of (meth) acrylic acid, a benzenesulfonic acid ester of vinylphenol having a fluorine atom or a fluorine-substituted alkyl group. Or a repeating unit represented by the following general formula (IV): (1) to (4)
The positive resist composition as described in any one of 1.

[0025]

[Chemical 12]

R ₅ represents a hydrogen atom, a halogen atom, a cyano group or an alkyl group which may have a substituent. R ₆
And R ₇ may be the same or different, and is a hydrogen atom,
Halogen atom, cyano group, hydroxyl group or optionally having an alkyl group, cycloalkyl group, alkoxy group, acyl group, acyloxy group, alkenyl group,
It represents an aryl group or an aralkyl group. R ₅₀ ~ R
₅₅ may be the same or different and represents a hydrogen atom, a fluorine atom or an alkyl group which may have a substituent.
However, at least one of R _{50 to} R ₅₅ represents a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. R ₆₀ is an optionally substituted alkyl group, alkylcarbonyl group, monocyclic or polycyclic cycloalkyl group, monocyclic or polycyclic cycloalkylcarbonyl group, alkenyl group, alkenylcarbonyl group, aralkyl Represents a group, an aralkylcarbonyl group, an aryl group or an arylcarbonyl group. In addition, each group represented by R ₆₀ is preferably one in which at least one hydrogen atom is substituted with a fluorine atom.

The following constitutions can be mentioned as more preferable embodiments. (6) The above-mentioned (1) to (5), which further comprises a resin that decomposes by the action of an acid containing the repeating units (1) and (2) and increases the solubility in an alkali developing solution. The positive resist composition as described in any one of 1.

(7) The positive resist composition as described in any of (1) to (6) above, which further comprises (D) a fluorine-based and / or silicon-based surfactant.

(8) The positive resist composition as described in any one of (1) to (7) above, which further comprises (E) an acid diffusion inhibitor containing a basic compound having a nitrogen atom. object.

(9) The above (1) to (1), which is for irradiation with F ₂ laser light having a wavelength of 157 nm.
The positive resist composition as described in any of (8).

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 fluorine atom-containing resin as the component (A) used in the present invention comprises at least one repeating unit (1) represented by the above general formula (I) and at least one repeating unit (1). A repeating unit (2) copolymerizable with the unit represented by the general formula (I) and having a function of decomposing by the action of an acid to increase the solubility of the resin in an alkali developing solution, and at least one of: A resin which is inert to the action of an acid, has no alkali-soluble group, and has a repeating unit (3) containing at least one fluorine atom, which decomposes by the action of an acid and increases the solubility in an alkali developing solution. is there.

The repeating unit (1) has the general formula (I) above.
Is a repeating unit represented by.

The repeating unit (2) is copolymerizable with the unit represented by the general formula (I) and has a function of decomposing by the action of an acid to increase the solubility of the resin in an alkali developing solution, For example, it may be any repeating unit having a group which is decomposed by the action of an acid to be described later and exhibits alkali solubility, and is preferably the above formula (II) or formula (II
It is a repeating unit represented by I).

Examples of the above-mentioned 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. The alkyl group, cycloalkyl group, aralkyl group and aryl group as R _{22c are the same} as those described above.

Examples of the alkylene group include linear and branched alkylene groups, and 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.

[0039] Two of _{R 18d ~R 18f, R 18d '} ~R 18f'
2 out of R 2, 2 out of R _{14 to} R ₁₆ , R ₂₅ and R ₂₆ , R ₂₇
The ring formed by R and R ₂₈ or R ₂₉ and R ₃₀ is, for example, a 3- to 8-membered ring, and specific examples thereof include a cyclopropane ring, a cyclopentane ring, a cyclohexane ring, a tetramethylene oxide ring, and a pentane ring. Examples thereof include a methylene oxide ring, a hexamethylene oxide ring, a furan ring, a pyran ring, a dioxonol ring and a 1,3-dioxolane ring.

Z represents an atomic group constituting a monocyclic or polycyclic alicyclic group together with the carbon atom in the general formula (III-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 which these groups may have 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). 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, benzoyloxy group, etc.), alkoxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, etc.), alkyl Examples thereof include groups (methyl group, ethyl group, propyl group, butyl group), cycloalkyl group (cyclohexyl group), aryl group (phenyl group), cyano group, nitro group and the like.

The group contained in the resin of the present invention (A) and decomposed by the action of an acid to be alkali-soluble includes, for example, —O—C (R _18d ) (R _18e ) (R _18f ), —O—C. (R
_18d ) ( _R18e ) ( _OR18f ), _-O -COO-C
(R _18d ) (R _18e ) (R _18f ), _—O —C (R ₀₁ ) (R
₀₂ ) COO-C ( _R18d ) ( _R18e ) ( _R18f ), _-CO
OC ( _R18d ) ( _R18e ) ( _R18f ), -COO-C
(R _18d ) (R _18e ) (OR _18f ), and the like. R _18d
~ R _18f has the same _{meaning as} described above. R ₀₁ and R ₀₂ represent a hydrogen atom or an alkyl group, cycloalkyl group, alkenyl group, aralkyl group or aryl group which may have a substituent as described above.

As a preferred specific example, 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.

Specific examples of the repeating unit (1) include, but are not limited to, the followings.

[0046]

[Chemical 13]

[0047]

[Chemical 14]

Specific examples of the repeating unit represented by formula (II) which is the repeating structural unit (2) are shown below, but the repeating units are not limited thereto.

[0049]

[Chemical 15]

[0050]

[Chemical 16]

[0051]

[Chemical 17]

[0052]

[Chemical 18]

[0053]

[Chemical 19]

[0054]

[Chemical 20]

[0055]

[Chemical 21]

Specific examples of the repeating structural unit represented by formula (III) which is the repeating unit (2) are shown below, but the repeating unit is not limited thereto.

[0057]

[Chemical formula 22]

[0058]

[Chemical formula 23]

[0059]

[Chemical formula 24]

[0060]

[Chemical 25]

[0061]

[Chemical formula 26]

The repeating unit (3) is a repeating unit which is inert to the action of an acid and does not have an alkali-soluble group and contains at least one fluorine atom. It is a unit that does not have a soluble group. The alkali-soluble group not contained in the repeating unit (3) is, for example, a group having a pKa of 11 or less, and examples thereof include a phenolic hydroxyl group, an active methylene group, an imide group, a carboxyl group, a sulfonic acid group and a sulfinic acid group. .

As the repeating unit (3), an α-trifluoroacrylic acid ester, a fluorine-containing alkyl ester of (meth) acrylic acid, a fluorine atom or a fluorine-substituted alkyl group (for example, a trifluoromethyl group) of vinylphenol is used. Examples thereof include a benzenesulfonic acid ester having a substituent and a repeating unit represented by the following general formula (IV). The ester portion of the α-trifluoroacrylic acid ester preferably has 1 to 1 carbon atoms.
It is a linear, branched or cyclic alkyl group having 20 carbon atoms, more preferably a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, or a cyclic alkyl group having 6 to 14 carbon atoms.

The ester portion in the fluorine-containing alkyl ester of (meth) acrylic acid is a straight chain having 1 to 20 carbon atoms, in which at least one hydrogen atom is replaced by a fluorine atom,
It is a branched or cyclic alkyl group, and more preferably, at least one hydrogen atom is replaced by a fluorine atom, and a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, or at least one hydrogen atom is fluorine. It is a cyclic alkyl group having 6 to 14 carbon atoms, which is substituted with atoms. The number of fluorine atoms is usually 1 to 38, preferably 2 to 19. The alkyl group having a fluorine atom preferably has no fluorine atom on the carbon atom bonded to the ester group.

R ₅ , R ₆ , R ₇ and R ₅₀ in the formula (IV)
The definition and specific examples of R ₅₅ are the same as those in formula (I). R ₆₀ is an alkyl group, an alkylcarbonyl group, a monocyclic or polycyclic cycloalkyl group, a monocyclic or polycyclic cycloalkylcarbonyl group, an alkenyl group, an alkenylcarbonyl group, an aralkyl group, an aralkylcarbonyl group, an aryl group, or Represents an arylcarbonyl group. Alkyl in these groups, cycloalkyl,
The alkenyl, aralkyl and aryl moieties are each represented by the formula (I) to
What was demonstrated as a substituent of (III) can be applied.
In addition, each group represented by R ₆₀ is preferably one in which at least one hydrogen atom is substituted with a fluorine atom.

Specific examples of the repeating unit (3) are shown below, but the repeating unit (3) is not limited thereto.

CF ₃ CH ₂ OCO (CH ₃ ) C = CH ₂ CF ₃ CF ₃ CH ₂ OCO (CH ₃ ) C = CH ₂ F (CF ₂ ) ₄ CH ₂ CH ₂ OCO (CH ₃ ) C = CH ₂ F (CF ₂ ) ₄ CH ₂ CH (OH) CH ₂ OCO (CH ₃ ) C = CH ₂ F (CF ₂ ) ₆ CH ₂ CH ₂ OCO (CH ₃ ) C = CH ₂ F (CF ₂ ) ₆ CH ₂ CH (OH) CH ₂ OCO (CH ₃ ) C = CH ₂ F (CF ₂ ) ₈ CH ₂ CH ₂ OCO (CH ₃ ) C = CH ₂ F (CF ₂ ) ₈ CH ₂ CH (OH) CH ₂ OCO ( CH ₃ ) C = CH ₂ F (CF ₂ ) ₁₀ CH ₂ CH ₂ OCO (CH ₃ ) C = CH ₂ CF ₃ CF (CF ₂ ) ₂ CH ₂ CH ₂ OCO (CH ₃ ) C = CH ₂ CF ₃ CF (CF ₂ ) ₂ CH ₂ CH (OH) CH ₂ OCO (CH ₃ ) C = CH ₂ CF ₃ CF (CF ₂ ) ₄ CH ₂ CH ₂ OCO (CH ₃ ) C = CH ₂ CF ₃ CF (CF ₂ ) ₄ CH ₂ CH (OH) CH ₂ OCO (CH ₃ ) C = CH ₂ CF ₃ CF (CF ₂ ) ₆ CH ₂ CH ₂ OCO (CH ₃ ) C = CH ₂ CF ₃ CF (CF ₂ ) ₆ CH ₂ CH (OH) CH ₂ OCO (CH ₃ ) C = CH ₂ H (CF ₂ ) ₂ CH ₂ OCO (CH ₃ ) C = CH ₂ H (CF ₂ ) ₄ CH ₂ OCO (CH ₃ ) C = CH ₂ H ( CF ₂ ) ₆ CH ₂ OCO (CH ₃ ) C = CH ₂ H (CF ₂ ) ₈ CH ₂ OCO (CH ₃ ) C = CH ₂ (CF ₃ ) ₂ CHOCO (CH ₃ ) C = CH ₂ CF ₃ CHFCF ₂ CH ₂ OCO (CH ₃ ) C = CH ₂ CF ₃ CH ₂ OCOCH = CH ₂ CF ₃ CF ₃ CH ₂ OCOCH = CH ₂ F (CF ₂ ) ₄ CH ₂ CH ₂ OCOCH = CH ₂ F (CF ₂ ) ₄ CH ₂ CH (OH) CH ₂ OCOCH = CH ₂ F (CF ₂ ) ₆ CH ₂ CH ₂ OCOCH = CH ₂ F (CF ₂ ) ₆ CH ₂ CH (OH) CH ₂ OCOCH = CH ₂ F (CF ₂ ) ₈ CH ₂ CH ₂ OCOCH = CH ₂ F (CF ₂ ) ₈ CH ₂ CH (OH) CH ₂ OCOCH = CH ₂ F (CF ₂ ) ₁₀ CH ₂ CH ₂ OCOCH = CH ₂ CF ₃ CF (CF ₂ ) ₂ CH ₂ CH ₂ OCOCH = CH ₂ CF ₃ CF (CF ₂ ) ₂ CH ₂ CH (OH) CH ₂ OCOCH = CH ₂ CF ₃ CF (CF ₂ ) ₄ CH ₂ CH ₂ OCOCH = CH ₂ CF ₃ CF (CF ₂ ) ₄ CH ₂ CH (OH) CH ₂ OCOCH = CH ₂ CF ₃ CF (CF ₂ ) ₆ CH ₂ CH ₂ OCOCH = CH ₂ CF ₃ CF ( CF ₂ ) ₆ CH ₂ CH (OH) CH ₂ OCOCH = CH ₂ H (CF ₂ ) ₂ CH ₂ OCOCH = CH ₂ H (CF ₂ ) ₄ CH ₂ OCOCH = CH ₂ H (CF ₂ ) ₆ CH ₂ OCOCH = CH ₂ H (CF ₂ ) ₈ CH ₂ OCO (CH ₃ ) C = CH ₂ (CF ₃ ) ₂ CHOCOCH = CH ₂ CF ₃ CHFCF ₂ CH ₂ OCOCH = CH ₂ CH ₃ OCO (CF ₃ ) C = CH ₂ CH ₃ CH ₂ OCO (CF ₃ ) C = CH ₂ CH ₃ CH ₂ CH ₂ OCO (CF ₃ ) C = CH ₂ (CH ₃ ) ₂ CHOCO (CF ₃ ) C = CH ₂ (CH ₃ ) ₂ CHCH ₂ OCO ( CF ₃ ) C = CH ₂ CH ₃ CH ₂ CH ₂ CH ₂ OCO (CF ₃ ) C = CH ₂ C ₆ F ₅ CH = CH ₂ C ₆ H ₄ FCH = CH ₂

[0068]

[Chemical 27]

The content of the repeating unit (1) represented by the general formula (I) is generally 30 to 30 in the resin (A).
It is used in the range of 85 mol%, preferably 40 to 80 mol%, more preferably 50 to 70 mol%. The content of the repeating unit (2) is generally 10 in the resin (A).
˜50 mol%, preferably 20 to 40 mol%, more preferably 25 to 35 mol%. The content of the repeating unit (3) is generally 2 in the resin (A).
-40 mol%, preferably 3-30 mol%, more preferably 5-20 mol%.

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. .

The repeating structural units represented by 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),
ArF excimer laser light, F ₂ excimer laser light,
A compound that generates an acid by an electron beam, an X-ray, a molecular beam or an ion beam and a mixture thereof can be appropriately selected and used.

Further, other compounds that 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.

Further, 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).

[0077]

[Chemical 28]

In the formula, R ²⁰¹ is a substituted or unsubstituted aryl group or alkenyl group, and R ²⁰² is a substituted or unsubstituted aryl group, alkenyl group, alkyl group 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.

[0079]

[Chemical 29]

[0080]

[Chemical 30]

[0081]

[Chemical 31]

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

[0083]

[Chemical 32]

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 to each other via a single bond or a substituent.

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

[0089]

[Chemical 33]

[0090]

[Chemical 34]

[0091]

[Chemical 35]

[0092]

[Chemical 36]

[0093]

[Chemical 37]

[0094]

[Chemical 38]

[0095]

[Chemical Formula 39]

[0096]

[Chemical 40]

[0097]

[Chemical 41]

[0098]

[Chemical 42]

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).

[0101]

[Chemical 43]

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.

[0103]

[Chemical 44]

[0104]

[Chemical formula 45]

[0105]

[Chemical formula 46]

[0106]

[Chemical 47]

[0107]

[Chemical 48]

[0108]

[Chemical 49]

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

[0110]

[Chemical 50]

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.

[0112]

[Chemical 51]

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

[0114]

[Chemical 52]

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.

[0116]

[Chemical 53]

Among the above photo-acid generators, acid generators represented by the formulas (PAG3) to (PAG8) which generate an organic sulfonic acid are preferable, and among them, benzene having a fluorine atom or a fluorine-substituted alkyl group as a substituent. A photoacid generator that generates a sulfonic acid or an alkylsulfonic acid containing a fluorine atom is preferable, and nonaphlate, pentafluorobenzene sulfonate, and 3,5-bis (trifluoromethyl) benzene sulfonate are more preferable.

The addition amount of the compound capable of generating an acid upon irradiation with actinic rays or radiation of the present invention (B) is usually 0.1 to 20% by weight based on the total solid content of the composition of the present invention. %, 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) The positive resist composition of the present invention preferably contains a fluorine-based and / or silicon-based surfactant. 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 Addition of these fluorine-based and / or silicon-based surfactants 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 The composition of the present invention has a 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.

[0124]

[Chemical 54]

Here, R ²⁵⁰ , R ²⁵¹ and R ²⁵² may be the same or different and each represents 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 a resist film in the production of precision integrated circuit devices, etc., a positive electrode of the present invention is formed on a 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.

The developer for the positive resist composition of the present invention includes sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, inorganic alkalis such as 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.

[0132]

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.

[Synthesis Example 1] 18.9 g of 4- [bis (trifluoromethyl) -hydroxymethyl] styrene (0.
07 mol), 3.52 g of 4-t-butoxystyrene
(0.02 mol), pentafluorostyrene 1.94 g
(0.01 mol) of 1-methoxy-2-propanol 6
It was dissolved in 0 ml and 0.25 g of 2,2'-azobis (2,4-dimethylvaleronitrile) (Wako Pure Chemical Industries, Ltd .; trade name V-65) was added as a polymerization initiator. This solution was heated to 70 ° C. under a nitrogen stream to give 1-methoxy-2.
-Drop to 10 ml of propanol with stirring over 2 hours. After the dropping, stirring was continued for another 4 hours. Then, the reaction solution was poured into 1 L of methanol / ion-exchanged water (1/1) with vigorous stirring. The precipitated resin was washed with ion-exchanged water, filtered, and dried under vacuum to obtain 16.1 g of a white resin. By NMR measurement, this resin was
A resin having a structure of -1 (the molar ratio of repeating units shown in Table 1, from the repeating unit on the left, 70/20/10), and having a weight average molecular weight (polystyrene standard) of 19,000 by GPC measurement. It was confirmed. )) In the same manner, the resins of the present invention shown in Table 1 were synthesized.

[0134]

[Table 1]

[0135]

[Table 2]

Resins (P-1) to (P- shown in Table 1 above.
Regarding 6), 1.36 g of each resin was added with 0.02 of triphenylsulfonium nonaflate salt (PAG4-3).
g, imidosulfonate compound (PAG6-19) 0.
02 g was added and dissolved in 8.5 g of 1-methoxy-2-propanol acetate. The resist composition of the present invention was prepared by adding it. For resins (P-7) to (P-12), each resin 1.36
g of triphenylsulfonium nonaflate salt (PA
G4-3) 0.04 g was added and dissolved in 8.5 g of 1-methoxy-2-propanol acetate.
(Produced) was added to prepare a resist composition of the present invention.

As Comparative Example 1, the resin component was
-[Bis (trifluoromethyl) -hydroxymethyl]
Styrene and t-butyl methacrylate (copolymerization composition molar ratio 65/35, weight average molecular weight 17,000) (Resin C
A resist solution was prepared in the same manner as in Example 1 except that the resist changed to -1) was used. In Comparative Example 2, the above resin components were used as 4- (hydroxymethyl) styrene and 4- (t-
Butoxy) styrene and 2,2,2-trifluoromethylmethacrylate (copolymerization composition molar ratio 40/40/2
0, weight average molecular weight 18,000) (resin C-2) was used as the resist, and a resist solution was prepared in the same manner as in Example 1.

The resist solution was filtered through a 0.1 μm Teflon (registered trademark) filter, and then coated on a hexamethyldisilazane-treated silicon wafer by a spin coater, and vacuum contact type hot at 110 ° C. for 90 seconds. It was heated and dried on the plate to obtain a resist film having a film thickness of 0.3 μm. For the obtained resist film, Canon
Company KrF excimer stepper (FPA-3000EX
5) was used for image exposure, post-heating was performed at 110 ° C. for 90 seconds, and then development was performed with a 0.262N TMAH aqueous solution to form a 0.13 μm L / S pattern.

[Surface Roughness] Line / Space (0.
(13 μm / 0.13 μm) The roughness of the top surface of the line portion of the pattern was observed by SEM and visually evaluated. The line surface was evaluated as A, where almost no roughness was observed, the slightly observed one was B, and the significantly observed one was C. [Scum] Line / Space (0.13 μm / 0.13
(μm) The space of the pattern was observed and evaluated by SEM. The one in which scum was hardly observed was designated as A, the one in which slight scum was observed was designated as B, and the one in which it was remarkably observed was designated as C. The results are shown in Table 2.

[0140]

[Table 3]

It can be seen that the resist composition using the fluorine atom-containing resin of the present invention is excellent in surface roughness and scum.

[0142]

By using the specific fluorine atom-containing resin of the present invention, it is possible to provide a positive resist composition having reduced surface roughness and scum.

   ─────────────────────────────────────────────────── ─── Continued front page    F term (reference) 2H025 AC04 AC08 AD03 BE00 BG00                       FA03 FA12 FA17                 4J100 AB07P AB07Q AB07R AB07S                       AB10R AC22R AL03R AL08Q                       AL08R BA02Q BA02R BA03P                       BA05Q BA16H BA20Q BA58R                       BB07R BB07S BB10R BB18P                       BB18Q BB18R BC04R BC09Q                       BC43R CA05 CA06 HA08                       HC64 HC71 HE22 JA38

Claims (5)

[Claims] 1. (A) A repeating unit (1) represented by the following general formula (I) and a unit represented by the general formula (I) can be copolymerized and decomposed by the action of an acid to form a resin. An acid having a repeating unit (2) having an action of increasing solubility in an alkaline developer and a repeating unit (3) which is inert to the action of an acid and has no alkali-soluble group and which contains at least one fluorine atom. A resin that decomposes due to the action of the solvent to increase the solubility in an alkaline developer, and (B)
A positive resist composition comprising a compound that generates an acid upon irradiation with actinic rays or radiation. [Chemical 1] In formula (I), R ₅ represents a hydrogen atom, a halogen atom, a cyano group or an alkyl group which may have a substituent.
R ₆ and R ₇ may be the same or different, and may have a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group or a substituent, an alkyl group, a cycloalkyl group, an alkoxy group, an acyl group, It represents an acyloxy group, an alkenyl group, an aryl group or an aralkyl group. R ₅₀ ~
R ₅₅ may be the same or different and represents a hydrogen atom, a fluorine atom or an alkyl group which may have a substituent. However, at least one of R _{50 to} R ₅₅ represents a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. 2. The repeating unit (2) has the following general formula (II):
The positive photoresist composition according to claim 1, wherein the positive photoresist composition is represented by: [Chemical 2] In formula (II), R ₁ represents a hydrogen atom, a halogen atom, a cyano group or an alkyl group which may have a substituent. R ₂ and R ₃ may be the same or different, and may have a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group or a substituent, an alkyl group, a cycloalkyl group, an alkoxy group, an acyl group, It represents an acyloxy group, an alkenyl group, an aryl group or an aralkyl group. R
₄ represents a group of the following general formula (IV) or (V). [Chemical 3] In formula (IV), R ₁₁ , R ₁₂ and R ₁₃ may be the same or different and may have a substituent, which may be an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group or an aryl group. Represents Two of R _{11 to} R ₁₃ may combine to form a ring. In the general formula (V), R ₁₄ and R
_15's may be the same or different and represent a hydrogen atom or an alkyl group which may have a substituent. R ₁₆ represents an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group which may have a substituent. R ₁₄ ~ R
Two of ₁₆ may combine to form a ring. 3. The repeating unit (2) is represented by the following general formula (III):
It is what is represented by these 1 or 2 characterized by the above-mentioned.
The positive photoresist composition described in 1. [Chemical 4] In formula (III), R _17a and R ₁₇ may be the same or different and represent a hydrogen atom, a halogen atom, a cyano group or an alkyl group which may have a substituent. R ₁₈ is-
C ( _R18d ) ( _R18e ) ( _R18f ) or -C ( _R18d ')
It represents (R _18e ') (OR _18f '). R _{18d to} R _18f may be the same or different and may have a substituent,
It represents an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group or an aryl group. R _18d 'to R _18f ' are
The same or different, and represents an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group or an aryl group, which may have a hydrogen atom or a substituent. R
Two of _{18d to R18f} or two of _R18d 'to _R18f ' may combine to form a ring. A represents a single bond or a divalent linking group. 4. The general formula (III), wherein R ₁₈ is represented by the following general formula (III-B).
The positive resist composition as described in 1. [Chemical 5] In the general formula (III-B), R _18h represents an alkyl group, a cycloalkyl group, an alkenyl group, which may have a substituent,
It represents an alkynyl group, an aralkyl group or an aryl group. Z
Represents an atomic group constituting a monocyclic or polycyclic alicyclic group together with the carbon atom in the general formula (VI-B). 5. The repeating unit (3) is an α-trifluoroacrylic acid ester, a fluorine-containing alkyl ester of (meth) acrylic acid, a benzenesulfonic acid ester of vinylphenol having a fluorine atom or a fluorine-substituted alkyl group, Alternatively, the positive resist composition according to any one of claims 1 to 4, which is a repeating unit represented by the following general formula (IV). [Chemical 6] R ₅ represents a hydrogen atom, a halogen atom, a cyano group or an alkyl group which may have a substituent. R ₆ and R _{7, which} may be the same or different, each represent a hydrogen atom, a halogen atom,
A cyano group, a hydroxyl group or an optionally substituted alkyl group, cycloalkyl group, alkoxy group, acyl group, acyloxy group, alkenyl group, aryl group or aralkyl group. R ₅₀ to R ₅₅ may be the same or different, represent a hydrogen atom, an alkyl group which may have a fluorine atom or a substituent. However, at least one of R _{50 to} R ₅₅ represents a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. R ₆₀ is an alkyl group which may have a substituent,
An alkylcarbonyl group, a monocyclic or polycyclic cycloalkyl group, a monocyclic or polycyclic cycloalkylcarbonyl group,
It represents an alkenyl group, an alkenylcarbonyl group, an aralkyl group, an aralkylcarbonyl group, an aryl group or an arylcarbonyl group.