JP2000019734A - Positive photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition excellent in a residual film ratio, resist profile, and the like to deep ultraviolet rays by containing a polymer with specific partial structure. SOLUTION: This positive photosensitive resin composition contains a compound producing acid by active light, a polymer with partial structure expressed by a formula, a nitrogen contained basic compound, and a fluorinated and/or silicone surfactant. In the formula, R1-R4 independently represent hydrogen atom. hydroxyl group, carboxyl group or alkyl group. R1 and R3, or R2 and R4 can be bonded to each other to form a ring. X represents a bivalent organic residual group of 2-20 in the number of carbon, R5 represents hydrogen atom, alkyl group, substitutional alkyl group or a group expressed by -COOR5 and composing a group decomposed under the action of acid. Z represents an atom group forming a cyclohexane ring or a decalin ring together with a carbon atom. Y is expressed by a formula II, where R6, R7 independently represent hydrogen atom or methyl group, and n represents 1 or 2.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive photosensitive resin composition used in a process for producing semiconductors such as ICs, a circuit substrate for liquid crystals and thermal heads, and other photofabrication processes. is there. More specifically, the present invention relates to a positive photosensitive resin composition suitably used for fine processing of a semiconductor device using light energy rays having a short wavelength such as far ultraviolet rays, X-rays, and electron beams.
The positive photosensitive resin composition is preferably used for fine processing of a semiconductor element using an F excimer laser.

[0002]

2. Description of the Related Art In recent years, high integration of semiconductor integrated circuits has progressed.
With the practical use of LSIs and VLSIs, the minimum pattern width of integrated circuits has reached the sub-half micron range, and further miniaturization has been progressing. Therefore, the demand for photolithography technology for forming a fine pattern is becoming more and more severe. As one of means for miniaturizing a pattern, it is known to shorten the wavelength of exposure light used when forming a resist pattern. For example, in the manufacture of a DRAM having a degree of integration of up to 64 Mbits, the i-line (365 nm) of a high-pressure mercury lamp has been used as a light source until now. 25
In the mass production process of 6 Mbit DRAM, a KrF excimer laser (248 nm) has been put into practical use as an exposure light source instead of i-line, and a DRA having an integration degree of 1 Gbit or more.
For the purpose of manufacturing M, a light source having a shorter wavelength has been studied, and use of an ArF excimer laser (193 nm), an F ₂ excimer laser (157 nm), X-rays, and an electron beam is considered to be effective ( Takumi Ueno et al., "Short Wavelength Photoresist Materials-Microfabrication for ULSI", Bunshin Publishing, 1988).

In particular, an ArF excimer laser is positioned as a next-generation exposure technology, and development of a resist for ArF excimer laser exposure having high sensitivity, high resolution, and excellent dry etching resistance has been desired. Conventional i-line and K
As a resist material for rF excimer laser exposure,
In order to obtain high dry etching resistance, a resist containing an aromatic polymer is widely used. For example, a novolak resin-based resist or a polyvinyl phenol-based chemically amplified resist is known. However, since the aromatic ring introduced for the purpose of imparting dry etching resistance hardly transmits light in the wavelength range of ArF excimer laser light, it is difficult to expose even the bottom of the resist film. A good pattern with no cross-sectional shape could not be obtained.

It is known that one of the solutions to the problem of resist transparency is to use an aliphatic polymer containing no aromatic ring, for example, polymethyl methacrylate (J. Vac. Sci. Technol. , B9, 3357 (1991)). However, such a polymer cannot be practically used because sufficient dry etching resistance cannot be expected. Thus, Ar
In developing a resist material for F excimer laser exposure, the greatest challenge is to achieve both improved transparency and high dry etching resistance. Therefore, a resist containing an alicyclic hydrocarbon group instead of an aromatic ring shows the same dry etching resistance as an aromatic group, and
Proc. SPIE, 1672, 66 (199
In recent years, the use of this polymer has been studied vigorously.

Originally, attempts to apply a polymer containing an alicyclic hydrocarbon group to a resist have been made for a long time. For example, Japanese Patent Application Laid-Open Nos. 60-195542, 1-217453, 2-59751
Discloses a norbornene-based polymer, and JP-A-2-46045 discloses various alkali-soluble resins having a cyclic aliphatic hydrocarbon skeleton and a maleic anhydride unit. Further, JP-A-5-80515 discloses a copolymer of norbornene and an acrylic acid ester protected with an acid-decomposable group, JP-A-4-39665, JP-A-5-265212, JP-A-5-80515, JP-A-7-234511 discloses a copolymer having an adamantane skeleton in a side chain, and JP-A-7-252324
In JP-A-9-221526, a compound in which an aliphatic cyclic hydrocarbon group having a carbon number of 7 to 12 having a bridged cyclic hydrocarbon group is linked to a side chain of a polymer, for example, tricyclo [5.2. 1.0
2.6] Decane dimethylene group, tricyclo [5.2.1.02.6]
A decanediyl group, a norbornanediyl group, a norbornanedimethyl group, an adamantanediyl group, are disclosed. Are linked to the side chain of the polymer.

Further, JP-A-9-325498 discloses a polymer having a cyclohexane and isobornyl skeleton in the main chain, and further disclosed in JP-A-9-230595, JP-A-9-244247, JP-A-10-10739 and WO97. -33198, EP794458, EP789278
Discloses a polymer in which various cyclic olefins such as dicycloolefin are introduced into the main chain, JP-A-8-82925
JP-A-9-230597 discloses that a compound having a menthyl group or a menthyl derivative group is preferable among terpenoid skeletons.

[0007] Further, a device has been devised to increase the resolving power by adding a low-molecular dissolution inhibitor. JP-A-8-15865
Discloses a dissolution inhibitor for t-butyl ester of androstan, and JP 9-265177 discloses a norbornyl group,
A low-molecular dissolution inhibitor in which an acid-decomposable group is linked to an adamantyl group, a decanyl group, or a cyclohexyl group is disclosed. Further, Proc. SPIE 3049, 84, (1997) reports that adhesion and contrast can be improved by using a lithocholic acid t-butyl ester oligomer as a dissolution inhibitor.

Further, in a conventional positive type chemically amplified resist for KrF using an aromatic polymer, for example, Prooc.
PIE 1672,46, (1992), Prooc.SPIE 2438,551, (1995), P
rooc.SPIE, 2438,563 (1995), Prooc.SPIE 1925,14, (199
3), J. Photopolym.Sci.Tech.Vol.8.No.4,535 (1995), J.
Photopolym.Sci.Tech.Vol.5.No.1,207 (1992), J.Photop
olym.Sci.Tech.Vol.8.No.4,561 (1995), Jpn.J.Appl.Phy
As reported in s.33, 7023 (1994), etc., as the standing time from exposure to heat treatment (PEB) becomes longer, the generated acid diffuses, and the resist is exposed to basic impurities in the atmosphere. There is a problem that the acid on the surface is deactivated and the sensitivity and the profile and line width of the resist pattern after development are changed. As means for solving these problems, a technique of adding an amine to a chemically amplified resist using an aromatic polymer is disclosed in JP-A-63-149640, JP-A-5-149640.
-249662, JP-A-5-127369, JP-A-5-289322, JP-A-5-249683, JP-A-5-289340, JP-A-5-232706
No., JP-A-5-257282, JP-A-6-242605, JP-A-6-24
No. 2606, JP-A-6-266100, JP-A-6-266110, JP
6-317902, JP-A-7-120929, JP-A-7-146558, JP-A-7-319163, JP-A-7-508840, JP-A-7-333844
No., JP-A-7-219217, JP-A-7-92678, JP-A-7-282
No. 47, JP-A-8-22120, JP-A-8-110638, JP-A-8-1
No. 23030, JP-A-9-274312, JP-A-9-66871, JP-A-9-292708, JP-A-9-325496, JP-T-7-508840,
Many are disclosed in US Pat. No. 5,525,453, US Pat. No. 5,629,134, US Pat.

However, when these amines are added to a chemically amplified resist for ArF using a non-aromatic polymer having a cyclic aliphatic hydrocarbon skeleton structure,
As in the case of using an aromatic polymer, it is effective against a change in sensitivity, a change in profile of a resist pattern after development, and a change in line width, but results in extremely poor development defects.

[0010]

SUMMARY OF THE INVENTION An object of the present invention has been made in view of the above problems, and has been made in consideration of the problems of deep ultraviolet light, particularly
An object of the present invention is to provide a positive photosensitive resin composition which is excellent in the residual film ratio, the resist profile, the resolving power, the dry etching resistance, and does not cause a problem of development defects, with respect to an ArF excimer laser beam.

[0011]

Means for Solving the Problems The present inventors have conducted intensive studies on the constituent materials of a positive type chemically amplified resist composition, and as a result, have found that a polymer containing a specific alicyclic hydrocarbon skeleton structure and a photoacid generator It has been found that the object can be achieved by a combination of a nitrogen-containing basic compound, a fluorine-based surfactant and / or a silicon-based surfactant. That is, the present invention has the following configuration. (1) (A) a compound generating an acid by actinic rays, (B) a polymer having a partial structure represented by the following general formula (I), (C)
A positive photosensitive resin composition comprising a nitrogen-containing basic compound and (D) a fluorine-based and / or silicon-based surfactant.

[0012]

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(In the above general formula (I), R _{1 to} R
₄ independently represents a hydrogen atom, a hydroxyl group, a carboxyl group, an alkyl group, an alkoxy group, a substituted alkyl group, a substituted alkoxy group, or a cyclic alkyl group. Also, R
₁ and R ₃ or R ₂ and R ₄ may combine with each other to form a ring. X represents a divalent organic residue having 2 to 20 carbon atoms. R ₅ represents a hydrogen atom, an alkyl group, a substituted alkyl group, cyclic alkyl group, a substituted cyclic alkyl group, or -C
OOR ₅ represents a group constituting a group decomposed by the action of an acid. Z represents a group of atoms forming a cyclohexane ring or a decalin ring together with the carbon atoms. Y is

[0014]

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Wherein R ₆ and R ₇ each independently represent a hydrogen atom or a methyl group, and n represents 1 or 2. (2) The positive photosensitive resin composition according to (1), wherein the polymer (B) has a group that is decomposed by the action of an acid. (3) The low-molecular-weight acid-decomposable dissolution-inhibiting compound having a group decomposable by the action of an acid and having an alkali solubility increased by the action of an acid and having a molecular weight of 2000 or less. Or the positive photosensitive resin composition according to (2). (4) The positive photosensitive resin composition according to any one of (1) to (3), wherein the actinic ray is far ultraviolet light having a wavelength of 220 nm or less.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the compounds used in the present invention will be described in detail. First, the polymer (B) of the present invention containing a specific structural unit will be described. The above general formula
Examples of the alkyl group of R _{1 to} R ₄ in (I) include a linear or branched alkyl group having 1 to 10 carbon atoms, which may be substituted. Specifically, methyl, ethyl, propyl, isopropyl, n-butyl, t-
Butyl group, hydroxymethyl group, hydroxyethyl group,
Examples include a norbornylmethyl group and an adamantylmethyl group. Examples of the cyclic alkyl group for R _{1 to} R ₄ include a cyclopentyl group and a cyclohexyl group. R _{1 to} R ₄
Examples of the alkoxy group include an alkoxy group having 1 to 10 carbon atoms, which may have a substituent. Specific examples include a methoxy group, an ethoxy group, an n-butoxy group, a t-butoxy group, a propoxy group and an isopropoxy group.

Further substituents in the above groups include:
Examples include a halogen atom, a cyano group, and a nitro group. R
_As the alkyl group and substituted alkyl group in _5, the above R ₁
It includes the same as those in to R _4. Examples of the cyclic alkyl group for R ₅ include those having 4 to 20 carbon atoms, specifically, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a norbornyl group, a tricyclodecanyl group, a tetracyclododecanyl group, And a tricyclopentyl group. Further substituents of these cyclic alkyl groups include a hydroxyl group, a halogen atom, a carboxyl group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group.

[0018] R ₁ and Examples of the ring and R ₃ or R ₂ and R ₄ is formed by combining, R ₁ and R ₃ or R ₂ and R ₄ are bonded to -C (= O) -O-C (= O)-, -C (= O) -N
H-C (= O) - , - CH 2 -C (= O) -O-C (=
O)-, and the like to form a ring.

R ₅ constituting a group decomposed by the action of an acid represented by —COOR ₅ is a hydrocarbon group having 2 to 20 carbon atoms (the hydrocarbon group is a t-butyl group,
Norbornyl group, cyclodecanyl group, etc.),
Represents an alkoxyethyl group such as a tetrahydrofuranyl group, a tetrahydropyranyl group, an ethoxyethyl group, an isopropylethyl group, a lactone group, or a cyclohexyloxyethyl group.

Examples of the divalent organic residue having 2 to 20 carbon atoms in X include an alkylene group having 2 to 20 carbon atoms such as an ethylene group and a propylene group, a carbon number such as a cyclobutylene group and a cyclohexylene group. Examples thereof include an arylene group having 6 to 20 carbon atoms such as a 4 to 20 cycloalkylene group and a phenylene group, and a divalent cycloolefin group which may be bridged.

The partial structure represented by the above general formula (I) is
It may be contained in the main chain of the polymer or in its side chain, but in the present invention, it is preferably contained in the main chain of the polymer. Specific examples of the polymer containing the partial structure represented by the general formula (I) include those represented by the following (a-1) to (a-24).

[0022]

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[0023]

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[0024]

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As an example of the synthesis of a polymer having a partial structure represented by the general formula (I), first, Japanese Patent Application Laid-Open No. 5-163328
I.e., 4-vinylcyclohexene and / or
Or polymerize 5-vinylnorbornene and phenols,
After synthesizing a polymer having a structural unit represented by the following general formula (II), by hydrogenating the polymer, the following general formula (I
A polymer represented by II) is obtained. The polymer represented by the general formula (V) is obtained by further subjecting the carboxylic acid anhydride represented by the general formula (IV) to an esterification reaction with the polymer represented by the general formula (III). The polymer represented by the general formula (V) is further subjected to an esterification reaction with a predetermined monomer as necessary, and the specific examples (a-1) to
A polymer represented by (a-24) is obtained.

[0026]

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(In the above formula, Z ₀ represents — (CH ₂ ) m—, R ₆ and R ₇ each represent a hydrogen atom or a methyl group. M represents 0 or 1, and n represents 1 or .Z ₁ representing a 2 represents a divalent organic residue .R ₁ to R _4, has the same meaning as R ₁ to R ₄ in the general formula (I).)

The synthesis method will be described in more detail. The synthesis of the polymer represented by the general formula (II) can be easily obtained by reacting the 4-vinylhexene and / or 5-vinylnorbornene with a phenol in the presence of an acid catalyst. Phenols include phenol, o-cresol,
m-cresol, p-cresol, t-butylphenol, cyclohexylphenol, p-cumylphenol, xylenols, and naphthols.

The proportion of the phenols to be reacted when 4-vinylcyclohexene and / or 5-vinylnorbornene is reacted with the phenol is determined by the amount of phenols charged to the amount of 4-vinylcyclohexene and / or 5-vinylnorbornene. The molar equivalent is preferably 0.8 to 12 times the molar equivalent, more preferably 2 to 10 times the molar equivalent. When the charged amount of the phenols is less than 0.8 times the molar equivalent, it is difficult to obtain a polymer having a desired molecular weight, and when the charged amount exceeds 12 times the molar equivalents, enormous effort is required to remove unreacted phenols. Not preferred.

The acid catalyst used in the reaction of 4-vinylcyclohexene and / or 5-vinylnorbornene with phenols includes boron trifluoride; an ether complex of boron trifluoride, a water complex, an amine complex, and phenol. Complexes or boron trifluoride complexes such as alcohol complexes; aluminum compounds such as aluminum trichloride and diethylaluminum monochloride; iron chloride; titanium tetrachloride; sulfuric acid; hydrogen fluoride; trifluoromethanesulfonic acid and the like can be preferably used. In particular, boron trifluoride, boron trifluoride
Preferred are ether complexes, boron trifluoride / phenol complexes, boron trifluoride / water complexes, boron trifluoride / alcohol complexes, boron trifluoride / amine complexes, and more preferably boron fluoride, boron trifluoride / phenol complexes Is most preferred. The amount of the acid catalyst used depends on the catalyst used. For example, in the case of boron trifluoride / phenol complex, 0.1 to 100 parts by weight of the 4-vinylcyclohexene and / or 5-vinylnorbornene is used. ~
The amount is preferably 20 parts by weight, particularly preferably 0.5 to 10 parts by weight.

Further, the above reaction can be carried out with or without using a solvent. When no solvent is used, the amount of phenols charged can be reduced to the amount of 4-vinylcyclohexene and / or 5-vinylnorbornene. It is preferable to use an equivalent or more, particularly 3 to 10 times equivalent to the charged amount. When a solvent is used, the solvent is not particularly limited as long as the solvent does not inhibit the reaction,
Specifically, for example, aromatic hydrocarbon compounds such as benzene, toluene, and xylene can be preferably mentioned. The reaction temperature varies depending on the type of the acid catalyst to be used. For example, when a boron trifluoride / phenol complex is used, the reaction temperature is preferably in the range of 20 to 170C, more preferably 40 to 150C. The reaction temperature is 170
If the temperature is higher than 20 ° C., decomposition or side reaction of the catalyst occurs. If the temperature is lower than 20 ° C., the reaction is delayed, which is economically disadvantageous.

In the case where a method of successively adding 4-vinylcyclohexene and / or 5-vinylnorbornene is used in carrying out the above reaction, homopolymerization of the 4-vinylcyclohexene and / or 5-vinylnorbornene may be used. Can also be prevented.

In the above reaction, after completion of the reaction, the catalyst is filtered off or deactivated, and the resulting solution is concentrated to obtain the polymer represented by the general formula (II). The method of removing the catalyst varies depending on the type of the catalyst used. For example, in the case of boron trifluoride / phenol complex, 1 to 10 times the molar amount of calcium hydroxide,
After deactivating the catalyst by adding magnesium hydroxide, etc.,
Preferably, the catalyst is filtered. It is desirable to improve the workability by adding a solvent or performing a treatment such as raising the temperature of the filtrate during the filtration.

Hydrogenation of the polymer of the general formula (II)
As a hydrogenation method for obtaining the polymer (III), a known method can be used. For example, a polymer of the general formula (II) is dissolved in a solvent and brought into contact with hydrogen in the presence of a metal catalyst.

The solvent is preferably a solvent which can easily dissolve the polymer of the general formula (II), is stable during the hydrogenation treatment, and can be easily removed after the hydrogenation treatment.
Suitable are lower alcohols such as propanol and butanol, lower ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, and cyclic ethers such as tetrahydrofuran and dioxane.Phenols such as cresols can also be used. preferable.

The metal catalyst is preferably nickel, cobalt, palladium, platinum or rhodium. The form may be either a simple metal or a metal oxide carrier. Normally, nickel or cobalt is used as a Raney type metal alone, or used by being supported on a porous carrier such as silica, alumina, carbon or diatomaceous earth. The noble metals are usually used in the form of oxides or carriers. The amount of catalyst used depends on the type of catalyst used, but generally the following is appropriate. That is, it can be carried out by a batch system using an autoclave or the like, or a continuous system such as a fixed bed flow system.

In the case of the batch type, about 0.01 to 10% by weight of a metal is suitable for the polymer to be treated, and in the case of the continuous flow type, the WHSV of the polymer relative to the catalyst is 0.1 to 10 kg / kg.
A suitable value is about kg · hr. Also, in the case of continuous distribution,
The catalyst is usually a supported catalyst. The hydrogenation temperature is 50 ~
300 ° C is suitable, preferably 150-250 ° C. Hydrogen pressure should be 10 to 20 due to problems such as reaction temperature and pressure resistance of equipment.
0 kg / cm ² are suitable, preferably from 50 to 100 / cm ^2. The treatment time can be arbitrarily selected according to the treatment conditions such as the kind and amount of the catalyst to be used, the treatment temperature, and the properties of the polymer to be treated. In the present invention, the degree of nuclear hydrogenation of the aromatic nucleus is preferably 60% or more, more preferably 70% or more, and particularly preferably 80% or more. If the degree of nuclear hydrogenation is less than 60%, the optical absorption at 193 nm increases and the profile of the resist deteriorates, which is not preferable.

Next, a method for obtaining the polymer represented by the general formula (V) will be described. The polymer represented by the general formula (V) is obtained by subjecting the polymer represented by the general formula (III) to an esterification reaction with a carboxylic anhydride represented by the general formula (IV). Here, as the carboxylic anhydride used, for example, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, citraconic anhydride, α
-Methylglutaconic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chloromaleic anhydride, d-
Phenyl maleic anhydride, pyromellitic anhydride, hymic anhydride, 3,6-endomethylene-phthalic anhydride, terpene maleic anhydride adduct, α-terpinene-maleic anhydride adduct, 4,5-cyclohexene-dicarboxylic anhydride Product, 1-methyl-4,5-cyclohexene-dicarboxylic anhydride, 3,6-methylene 1,2,3,6-tetrahydro-cisphthalic anhydride, (4-carboxy-4
-Cyclohexenyl) acetic anhydride, 4-methyl-4,5
-Cyclohexenedicarboxylic anhydride, (4-carboxy-5-cyclohexenyl) acetic anhydride, 3,6-methylene-1,2,3,6-tetrahydro-cis-phthalic anhydride, 6- (5-carboxy -Bicyclo [2,2,1] -hepta-2-enyl) acetic anhydride,
3,6-methano-1-methyl 1,2,3,6-tetrahydrocisphthalic anhydride, 2-oxa-1,4-dioxo-5,8-methano-1,2,3,4,4a, 5,8,
8a-octahydronaphthalene, 5,8-methanol 1,
2,3,4,4a, 5,8,8a-octahydronaphthalene-1,2-dicarboxylic anhydride, 5,8-methano-
1-methyl-1,2,3,4,4a, 5,8,8a-octahydronaphthalene-2,3-dicarboxylic anhydride,
1,4,5,8-dimethano-1,2,3,4,4a,
5,8,8a-octahydronaphthalene-2,3-dicarboxylic anhydride, 2-oxa-1,3-dioxo-1,
2,3,4,4a, 5,8,8a, 9,9a, 10,1
0a-dodecahydroanthracene, 4- (5-bicyclo [2,2,1] -hepta-2-enyl) phthalic anhydride, phenolphthalein, 4- (2,5-dioxotetrahydrofuran-3-yl) -Tetralin-1,2-
Dicarboxylic anhydride, 5- (2,5-dioxotetrahydrofuranyl) -3-methyl-3-cyclohexene-
1,2-dicarboxylic anhydride, 4-methylcyclohexane-1,2-dicarboxylic anhydride, methylcyclohexene-1,2-dicarboxylic anhydride, endo-bicyclo [2,2,2] oct-5-ene -2,3-dicarboxylic anhydride and the like. The carboxylic anhydrides can be used alone or in combination of two or more.

The esterification reaction used here is described, for example, in RPHanzilik: Org. Synth., VI, 560 (1988) and J. Cason:
Org. Synth., III, 169 (1955). That is, in the presence of a catalyst, a polymer represented by the general formula (III) and a carboxylic acid anhydride represented by the general formula (IV) are dissolved in a solvent, and the mixture is reacted under the temperature condition of 5 ° C to 150 ° C. It is obtained by doing. Examples of the solvent used include benzene, toluene, xylene, DMF, THF and the like. Examples of the basic catalyst include pyridine, sodium acetate, 4-dimethylaminopyridine, triethylamine and the like.

Here, the molar concentration of the charged polymer represented by the general formula (III) and the carboxylic anhydride represented by the general formula (IV) is 1.0 The carboxylic anhydride represented by the general formula (IV) is preferably in a range of 0.5 to 2.0 mol per mol. When the molar concentration of the charged carboxylic anhydride is less than 0.5 mol%, the alkali solubility of the polymer represented by the general formula (V) is insufficient, and the sensitivity of the resist is reduced, and the resolution of the resist is reduced. Not preferred. On the other hand, the molar concentration of the charged carboxylic anhydride is 2.0
If the amount exceeds mol%, the acid anhydride becomes a diester by alcoholysis, and the polymer represented by the general formula (V) tends to be insufficient in alkali solubility and the sensitivity of the resist tends to decrease. Therefore, it is preferable to control the reaction so that the acid anhydride becomes a half ester by alcoholysis. The present invention has the general formula (V)
Positive photoresist composition comprising a polymer represented by the formula (a polymer having a partial structure represented by the general formula (I) and not containing an acid-decomposable group), an acid-decomposable dissolution inhibitor, and a photoacid generator: Including things. Polymer represented by the general formula (V) (general formula (I)
It is preferable to further introduce an acid-decomposable group into the polymer having a structure represented by

In the method of introducing an acid-decomposable group into the polymer represented by the general formula (V), the acid-decomposable group is protected by an esterification reaction at the carboxyl group of the polymer represented by the general formula (V). It is obtained by doing. The esterification reaction used here is, for example, a method of esterifying a polymer represented by the general formula (V) and a tertiary alcohol with 4-dimethylaminopyridine (DMAP) or the like (G. Hoefle, W. Steglich , and Vorbruegge
n, Angew.Chem.Int.Ed.Engle., 17,569 (1978)) and a method using trifluoroacetic anhydride (RCParish and LMStoc
k, J. Org. Chem., 30, 927 (1965)) or a method using DCC (dicyclohexylcarbodiimide) (B. Neises and WS
teglich, Org. Synth., 63, 183 (1985)). Further, the carboxyl group of the polymer represented by the general formula (V)
After converting to a carboxylic acid chloride by SOCl ₂ or the like, an esterification reaction with an alcohol or metal alkoxide may be performed, or a DCC-DMAP method may be used.

In the polymer of the above (B) in the present invention,
The content of the repeating unit having the partial structure represented by the general formula (I) is 50 mol% based on all repeating units.
Or more, more preferably 60 mol% or more. When the polymer of the above (B) in the present invention contains an acid-decomposable group, the content of the repeating unit having an acid-decomposable group in the polymer is preferably at least 20 mol% based on all repeating units. It is preferably at least 30 mol%, more preferably 30 to 60 mol%. The polymer (B) in the present invention may contain other repeating units in addition to the repeating unit having a partial structure represented by the general formula (I).

The polymer (B) has a weight average molecular weight of 150
It is preferably in the range of 0 to 100,000, more preferably in the range of 2000 to 70000, and particularly preferably in the range of 3000 to 50,000. Molecular weight 150
If the molecular weight is less than 0, the dry etching resistance, heat resistance, and adhesion to the substrate are insufficient, and if the molecular weight exceeds 100,000, the resist sensitivity is undesirably reduced. Further, the molecular weight distribution (Mw / Mn) is preferably 1.0 to 6.0,
The heat resistance and the image performance (resist profile, defocus latitude and the like) are more preferably 1.0 to 4.0, and the smaller the smaller, the better. The weight average molecular weight and molecular weight distribution (Mw / Mn) of the polymer (B) are measured by gel permeation chromatography equipped with a refractive index detector in terms of polystyrene.

In the positive photosensitive resin composition of the present invention, the content of the polymer (B) is from 50 to 9 in terms of solid content.
It is 9.7% by weight, preferably 70 to 99% by weight. The positive photosensitive resin composition of the present invention may contain, if necessary, other polymers in addition to the polymer (B).
The content of the other polymer is preferably 30 parts by weight or less, more preferably 2 parts by weight, per 100 parts by weight of the polymer (B).
It is at most 0 parts by weight, particularly preferably at most 10 parts by weight.

The other polymer that can be contained in the positive photosensitive resin composition of the present invention may be any polymer that is compatible with the polymer of the present invention, such as poly-p-hydroxyethylene and hydrogenated poly-p. -Hydroxyethylene, novolak resins, alicyclic polymers described in Japanese Patent Application No. 10-112219, and the like.

Next, the compound (A) contained in the positive photosensitive resin composition of the present invention, which decomposes upon irradiation with actinic rays to generate an acid (hereinafter, also referred to as "(A) photoacid generator") ) Will be described. Examples of the photoacid generator (A) used in the present invention include photoinitiators for photocationic polymerization, photoinitiators for photoradical polymerization, photodecolorants for dyes, photochromic agents, ultraviolet light, UV light, KrF excimer laser light, ArF excimer laser light, electron beam, X-ray, molecular beam, known photo-acid generator for micro-photoresist which generates acid by ion beam, etc. can do. In the present invention, the actinic ray is used in a broad concept including radiation as described above.

The photoacid generator (A) is not particularly limited as long as it is soluble in the below-mentioned organic solvent used in the positive photosensitive resin composition of the present invention, but generates an acid with light of 220 nm or less. It is preferably a photoacid generator. Also,
They may be used alone or in combination of two or more, or may be used in combination with a suitable sensitizer.

Examples of usable (A) photoacid generators include triphenylsulfonium salt derivatives described in, for example, J. Org. Chem. Vol. 43, N0.15, 3055 (1978) -2790
Other onium salts described in No. 71 (sulfonium salts, iodonium salts, phosphonium salts, diazonium salts, ammonium salts) can also be used. Specific examples of the onium salt include diphenyliodonium triflate, diphenyliodonium pyrene sulfonate, diphenyliodonium dodecylbenzenesulfonate, triphenylsulfonium triflate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium hexafluoroantimonate, and triphenylsulfonium naphthalene sulfonate. , Triphenylsulfonyumcamphorsulfonium, (4-methoxyphenyl) phenyliodonium trifluoromethanesulfonate, bis (t-butylphenyl) iodonium trifluoromethanesulfonate, and the like.

Also, JP-A-3-103854 and JP-A-3-103856
Diazodisulfones and diazoketosulfones disclosed in JP-A-4-1210960, JP-A-64-18143, JP-A-2-
Iminosulfonates described in 245756, JP-A-2-7127
Disulfones described in No. 0 can also be suitably used. Further, USP 3849137, JP-A-63-26653, JP-A-62
-69263, JP-A-63-146038, JP-A-63-163452, JP-A-62-153853, JP-A-63-146029, etc. Compounds introduced into a chain or a side chain can also be used, and have a 2-oxocyclohexyl group described in JP-A-7-25846, JP-A-7-28237, JP-A-7-92675, and JP-A-8-27120. Aliphatic alkyl sulfonium salts, and N-hydroxysuccinimide sulfonates, and also J. Photopolym. Sci., Tech.,
Vol. 7, No. 3, 423 (1994), a sulfonium salt and the like can also be suitably used, and they are used alone or in combination of two or more.

The content of the compound (A) which decomposes upon irradiation with actinic rays to generate an acid is usually 0.001 to 40, based on the total weight (solid content) of the photosensitive resin composition.
%, Preferably 0.01 to 20% by weight, more preferably 0.1 to 5% by weight. (A) If the amount of the photoacid generator is less than 0.001% by weight, the sensitivity is lowered, and if it is more than 40% by weight, the light absorption of the resist becomes too high, and the profile is deteriorated and the process margin, especially the bake margin is narrowed. Not preferred.

Next, the nitrogen-containing basic compound (C) contained in the positive photosensitive resin composition of the present invention will be described.
As the nitrogen-containing basic compound (C), an organic amine, a basic ammonium salt, a sulfonium salt or the like is used.
Any material that does not deteriorate sublimation or resist performance may be used.
For example, JP-A-63-149640, JP-A-5-249662, JP-A-5-249662
-127369, JP-A-5-289322, JP-A-5-249683, JP-A-5-289340, JP-A-5-232706, JP-A-5-257282
No., JP-A-6-242605, JP-A-6-242606, JP-A-6-26
No. 6100, JP-A-6-266110, JP-A-6-317902, JP-A-6-317902
7-120929, JP-A-7-146558, JP-A-7-319163, JP-A-7-508840, JP-A-7-333844, JP-A-7-219217
No., JP-A-7-92678, JP-A-7-28247, JP-A-8-2212
No. 0, JP-A-8-110638, JP-A-8-123030, JP-A-9-2
No. 74312, JP-A-9-66871, JP-A-9-292708, JP-A-9-325496, JP-T7-508840, USP5525453, USP5
Basic compounds described in 629134, US Pat. No. 5,667,938 and the like can be used.

Particularly preferred are 1,5-diazabicyclo [4.3.0] -5-nonene, 1,8-diazabicyclo [5.4.0] -7-undecene and 1,4-diazabicyclo [2.2]. .2] octane, 4-dimethylaminopyridine, 1-naphthylamine, piperidine, hexamethylenetetramine, imidazoles, hydroxypyridines, pyridines, 4,4'-diaminodiphenylether, pyridinium p-toluenesulfonate, 2,4,
Examples thereof include 6-trimethylpyridinium p-toluenesulfonate, tetramethylammonium p-toluenesulfonate, and tetrabutylammonium lactate. (C) The basic compound may be used alone or in combination of two or more.
More than one species can be used in combination.

The content of the nitrogen-containing basic compound (C) is usually in the range of 100 parts by weight of the photosensitive resin composition (solid content).
It is 0.001 to 10 parts by weight, preferably 0.01 to 5 parts by weight. If the amount is less than 0.001 part by weight, the effect cannot be sufficiently obtained. On the other hand, if it exceeds 10 parts by weight, the sensitivity tends to decrease and the developability of the unexposed part tends to be remarkably deteriorated.

Next, the fluorine-containing and / or silicon-containing surfactant contained in the positive photosensitive resin composition of the present invention will be described. In the photosensitive resin composition of the present invention,
A fluorine-based surfactant, a silicon-based surfactant Any surfactant containing both a fluorine atom and a silicon atom, or two or more thereof can be contained. As these (D) surfactants, for example, JP-A-62-36663,
JP-A-61-226746, JP-A-61-226745, JP-A-62-170
950, JP-A-63-34540, JP-A-7-230165, JP-A-8
-62834, JP-A-9-54432 and JP-A-9-5988, and the following commercially available surfactants can be used as they are. As commercially available surfactants that can be used, for example, F-top EF301, EF303, (manufactured by Shin-Akita Chemical Co., Ltd.), Florad FC430, 431 (Sumitomo 3M)
Co., Ltd.), Mega Fuck F171, F173, F176, F189, R08
(Dai Nippon Ink Co., Ltd.), Surflon S-382, SC10
1, 102, 103, 104, 105, 106 (manufactured by Asahi Glass Co., Ltd.) and other fluorine-based and / or silicon-based surfactants. Also, polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can be used as a silicon-based surfactant. Among these surfactants, surfactants having both fluorine atoms and silicon atoms are particularly excellent in terms of improvement of development defects.

(D) The amount of the surfactant is usually 0.01 to 2 parts by weight, preferably 0.01 to 1 part by weight, per 100 parts by weight of the solids in the composition of the present invention. It is. These surfactants can be used alone or in combination of two or more.

The positive photosensitive resin composition of the present invention has a molecular weight of 2,000 or less, if necessary, has a group which can be decomposed by the action of an acid, and the alkali solubility is increased by the action of an acid. A low molecular acid decomposable dissolution inhibiting compound may be included. For example, Proc. SPIE, 2724, 355 (1996),
-15865, USP5310619, USP-5329912, J.Photopol
ym. Sci., Tech., Vol. 10, No. 3, 511 (1997)), a cholic acid derivative containing an acid-decomposable group, a dehydrocholic acid derivative, a deoxycholic acid derivative, a lithocholic acid derivative, ursocol Alicyclic compounds such as acid derivatives and abietic acid derivatives, and aromatic compounds such as naphthalene derivatives containing an acid-decomposable group can be used as the low-molecular acid-decomposable compounds. Further, a low-molecular acid-decomposable dissolution inhibiting compound described in JP-A-6-51519 can be used in an addition range that does not deteriorate the transmittance at 220 nm, and a 1,2-naphthoquinonediazide compound can also be used. When the low-molecular acid-decomposable dissolution inhibiting compound is used in the photosensitive resin composition of the present invention, the content thereof is usually 1 to 50% by weight, based on the total weight (solid content) of the photosensitive resin composition. It is preferably used in the range of 3 to 40% by weight, more preferably 5 to 30% by weight. The addition of these low-molecular acid-decomposable dissolution inhibiting compounds not only further improves the development defects, but also improves the dry etching resistance.

The positive photosensitive resin composition of the present invention may further contain, if necessary, a compound capable of accelerating dissolution in a developer.
Antihalation agent, plasticizer, surfactant, photosensitizer,
It may contain an adhesion aid, a crosslinking agent, a photobase generator, and the like.

Examples of the compound capable of accelerating dissolution in a developer which can be used in the present invention include compounds having two or more phenolic hydroxyl groups described in JP-A-3-206458,
Naphthols such as naphthol or carboxyl group
Or more, a carboxylic acid anhydride, a sulfonamide compound or a sulfonylimide compound having a molecular weight of 100 or more.
And 0 or less low molecular weight compounds. The compounding amount of these dissolution promoting compounds may be determined based on the total weight of the composition.
(Solid content), preferably 30% by weight or less, more preferably 20% by weight or less.

As a suitable antihalation agent, a compound that efficiently absorbs the irradiated radiation is preferable, and substituted benzenes such as fluorene, 9-fluorenone, and benzophenone; anthracene, anthracene-9-methanol, and anthracene-9-carboxy. And polycyclic aromatic compounds such as ethyl, phenanthrene, perylene, and azylene. Among them, polycyclic aromatic compounds are particularly preferred. These antihalation agents exhibit the effect of improving the standing wave by reducing the reflected light from the substrate and reducing the effect of multiple reflection in the resist film.

For the purpose of improving the coating property of the photosensitive resin composition of the present invention or improving the developing property, a nonionic surfactant can be used in combination. As nonionic surfactants that can be used in combination, polyoxyethylene lauryl ether,
Examples thereof include polyoxyethylene stearyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, polyoxyethylene sorbitan monostearate, and sorbitan monolaurate.

A photosensitizer may be added to improve the rate of acid generation by exposure. Suitable photosensitizers include benzophenone, p, p'-tetramethyldiaminobenzophenone, 2-chlorothioxanthone, anthrone, 9-ethoxyanthracene, pyrene, phenothiazine, benzyl, benzoflavin, acetophenone, phenanthrene, benzoquinone, anthraquinone, , 2
-Naphthoquinone and the like, but are not limited thereto. These photosensitizers can also be used as the antihalation agent.

After the photosensitive resin composition of the present invention is dissolved in a solvent capable of dissolving each of the above-mentioned components, it is usually prepared, for example, with a pore size of 0.05.
It is prepared as a solution by filtering with a filter of about μm to 0.2 μm. Examples of the solvent used herein include ethylene glycol monoethyl ether acetate, cyclohexanone, 2-heptanone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether acetate, and propylene glycol monoethyl ether acetate. -Methyl methoxypropionate, ethyl 3-ethoxypropionate, methyl β-methoxyisobutyrate, ethyl butyrate, propyl butyrate, methyl isobutyl ketone, ethyl acetate, isoamyl acetate, ethyl lactate, toluene, xylene, cyclohexyl acetate, diacetone alcohol, N -Methylpyrrolidone, N, N-dimethylformamide, γ-butyrolactone, N, N-dimethylacetamide and the like. It is. These solvents are used alone or in combination. The choice of the solvent is important because it affects the solubility in the photosensitive resin composition of the present invention, the applicability to a substrate, the storage stability, and the like. Further, since the water contained in the solvent affects these performances, it is preferable that the water content is small.

Further, the photosensitive resin composition of the present invention contains one or more metal impurities such as metals and impurity components such as chlorine ions.
It is preferable to reduce it to 00 ppb or less. The presence of many of these impurities is not preferable because it causes operation failure, defects, and reduced yield in manufacturing a semiconductor device.

After the photosensitive resin composition of the present invention is applied on a substrate by an appropriate application method such as a spinner or a coater, the substrate is pre-baked (pre-exposure heating) and passed through a predetermined mask.
A good resist pattern can be obtained by exposing with exposure light having a wavelength of nm or less, performing PEB (bake after exposure), and developing. The substrate used here may be a substrate usually used in a semiconductor device or other manufacturing apparatus, and examples thereof include a silicon substrate, a glass substrate, and a non-magnetic ceramic substrate. If necessary, additional layers such as a silicon oxide layer, a metal layer for wiring, an interlayer insulating film, a magnetic film, an antireflection film layer, and the like may be present on these substrates. , A circuit or the like may be built. Further, these substrates may be subjected to a hydrophobic treatment according to a conventional method in order to enhance the adhesion of the resist film. Suitable hydrophobizing agents include, for example, 1,1,1,3,3,3-hexamethyldisilazane (HMDS).

The thickness of the resist applied on the substrate is preferably in the range of about 0.1 to 10 μm. In the case of ArF exposure, the thickness is preferably about 0.1 to 1.5 μm. The resist film applied on the substrate is heated at a temperature of about 60 to 160 ° C. for about 3 hours.
Prebaking is preferably performed for 0 to 300 seconds. If the pre-baking temperature is low and the time is short, the amount of residual solvent in the resist film becomes relatively large, and adverse effects such as deterioration of adhesion are caused, which is not preferable. On the other hand, if the prebaking temperature is high and the time is long, adverse effects such as decomposition of components such as the binder and the photoacid generator of the photosensitive resin composition are not preferred.

[0066] Commercially available UV exposure apparatus as the resist film to expose a device prebaked, X-rays exposure apparatus, an electron beam exposure apparatus, KrF excimer exposure apparatus, ArF excimer exposure system, F ₂ excimer exposure apparatus or the like is used, Particularly, in the present invention, an apparatus using an ArF excimer laser as an exposure light source is preferable. The post-exposure bake is performed for the purpose of causing the elimination of the protecting group using an acid as a catalyst, for eliminating the standing wave, and for diffusing an acid generator or the like into the film. This post-exposure bake can be performed in the same manner as the previous pre-bake. For example, the baking temperature is about 60-160C, preferably about 90-150C.

Examples of the developer of the photosensitive resin composition of the present invention include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, and aqueous ammonia; and primary amines such as ethylamine and n-propylamine. , Secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcoholamines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide (TMAH), water Quaternary ammonium salts such as tetraethylammonium oxide (TEAH), trimethylhydroxymethylammonium hydroxide, triethylhydroxymethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, pyrrole, piperi Emissions, 1,8-diazabicyclo -
An aqueous alkaline solution such as a cyclic amine such as [5.4.0] -7-undecene, 1,5-diazabicyclo- [4.3.0] -5-nonane can be used.

Further, an appropriate amount of a hydrophilic organic solvent such as alcohols or ketones, a nonionic or anionic surfactant, a cationic surfactant or an antifoaming agent may be added to the alkaline aqueous solution. Can be used. These additives may be used to improve the performance of the resist, increase the adhesion to the substrate, reduce the amount of developer used, or reduce defects caused by bubbles during development. Added to the aqueous solution.

[0069]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.

Synthesis Example 1 (Synthesis of Polymer a-1) 800 g of phenol and 150 g of toluene were charged into a 2.5 L reactor equipped with a reflux condenser and a Liebig condenser.
The mixture was heated to 170 ° C and 250 g of toluene was distilled off.
It was dehydrated to 0 ppm. Next, the inside of the system was cooled to 80 ° C, and after adding 19 g of boron trifluoride-phenol complex, while controlling the reaction temperature to 80 ° C, the water concentration was 20 ppm.
-185 g of vinyl norbornene was gradually added dropwise over 1.5 hours. After completion of the dropwise addition, the reaction was continued at 80 ° C for 40 minutes.
The temperature was raised to 0 ° C., and the mixture was further heated and stirred for 2.5 hours. After completion of the reaction, 40 g of a magnesium compound `` KW-1000 '' (trade name, manufactured by Kyowa Chemical Industry Co., Ltd.) was added, the mixture was stirred for 60 minutes to deactivate the catalyst, and then reacted using filter paper covered with Celite. The liquid was filtered. The obtained transparent filtrate was distilled under reduced pressure at 230 ° C. to obtain 270 g of a polymer A ′.

100 g of this polymer A ′ was added to t-butyl alcohol
A solution dissolved in 200 g and 3.5 g of a nickel catalyst having diatomaceous earth as a carrier were placed in an autoclave having an internal volume of 1 L, replaced several times with nitrogen, and then replaced several times with hydrogen.
The temperature was elevated while stirring as m ^2, and held at 200 ° C. 10 hours. After cooling, the catalyst was removed from the reaction solution by filtration, and the filtrate was dropped into 10 times by weight of water to precipitate a polymer.
This precipitated polymer was collected and dried under reduced pressure at 50 ° C, 82 g.
The polymer A ″ was obtained. The weight average molecular weight of the polymer A ″ was 4210, and the hydrogenation ratio of the phenol nucleus was calculated by IR and NMR to be 93%.

Next, 53 g of polymer A "and 1,1 were added to a three-necked flask.
Add 300 g of 2-cyclohexanedicarboxylic anhydride to THF300
Then, 20 g of sodium hydride was slowly added dropwise, and reacted at 40 ° C. for 6 hours. After the reaction, crystallized in water,
After removing unreacted components, the mixture was filtered and dried under reduced pressure at 50 ° C. to obtain a polymer.
53 g of A '''was obtained. The weight average molecular weight of the polymer A ′ ″ was 5,480. Further, a mixture of 20 g of the polymer A ′ ″ and 23 ml of thionyl chloride was refluxed for 1 hour. Excess thionyl chloride was removed, the solid obtained was dissolved in 90 ml of THF, 8.7 g of potassium-t-butoxide were added slowly, the reaction mixture was refluxed for 6 hours, cooled and poured into water. The resulting solid was collected by filtration, washed with water and dried under reduced pressure. The purified product was recrystallized from n-hexane to obtain a polymer (a-1) of the present invention. The weight average molecular weight of the polymer (a-1) was 5,940, and the degree of dispersion was 3.0.

Synthesis Example 2 (Synthesis of Polymer a-10) The polymer (a-10) of the present invention was prepared in the same manner as in Synthesis Example 1 except that 5-vinylnorbornene in Synthesis Example 1 was changed to 4-vinylcyclohexene. ). The weight average molecular weight of the polymer (a-10) was 7,990, and the degree of dispersion was 3.0.

Synthesis Example 3 (Synthesis of Polymer a-11) 20 g of Polymer A ″ ′ obtained in Synthesis Example 1 was dissolved in 80 g of THF, and 5.2 g of 3,4-dihydro-2H-pyran was used as a reaction reagent. React
The solid was coagulated with hexane to obtain a polymer (a-11) of the present invention. The weight average molecular weight of the polymer (a-11) was 5,640, and the degree of dispersion was 3.0.

Synthesis Example 4 (Synthesis of Polymer a-23) The reaction was carried out in the same manner as in Synthesis Example 1 except that the phenol as a starting material in Synthesis Example 1 was changed to α-naphthol, and the polymer of the present invention (a -23). The weight average molecular weight of the polymer (a-23) was 4310, and the degree of dispersion was 2.3.

Synthesis Example 5 (Synthesis of acid-decomposable low molecular weight compound a) A mixture of 122.7 g (0.3 mol) of cholic acid and 120 ml of thionyl chloride was refluxed for 1 hour. Excess thionyl chloride was removed, the resulting solid was dissolved in 150 ml of tetrahydrofuran, 40 g (0.35 mol) of potassium tert-bucitoxide was gradually added, and the reaction mixture was added to 6 parts.
After refluxing for an hour, the mixture was cooled and poured into water. The resulting solid was collected by filtration, washed with water and dried under reduced pressure. The crude product was recrystallized from n-hexane to give cholic acid with a yield of 70%.
As a result, t-butyl (the following formula) was obtained.

[0077]

Embedded image

Synthesis Example 6 Synthesis of Polymer (b-1): Comparative Example According to the method described in Synthesis Example 1 disclosed in JP-A-9-325498, 1-cyclohexyl-3-carboxylic acid and t-butyl methacrylate Was obtained.

Synthesis Example 7 Synthesis of Polymer (b-2): Comparative Example According to the method described in Synthesis Example 6 disclosed in JP-A-9-325498, a copolymer of norbornene dicarboxylic acid, t-butyl methacrylate and methyl acrylate was used. A polymer was obtained.

Examples 1-4, Comparative Examples 1-4 (Preparation of photosensitive resin composition) In preparing the photosensitive resin component, the components described in Table 1 were synthesized, that is, synthesized in Synthesis Examples 1-4. Polymers (a-1), (a-10), (a-11), (a-23), or the polymers (b-1), (b-2), light synthesized in Synthesis Examples 6 and 7 Triphenylsulfonium triflate (PAG-
1) The components of the acid-decomposable low-molecular compound a synthesized in Synthesis Example 5, a nitrogen-containing basic compound, a surfactant, and a solvent were used. The dotted line in Table 1 means that the component was not used. After mixing the components, the mixture was filtered through a 0.1 μm Teflon filter to prepare a photosensitive resin composition. The amounts of each component are as follows. Polymer 9.0g Photoacid generator 0.10g Acid-decomposable low molecular weight compound a 1.0g Nitrogen-containing basic compound 0.01g Surfactant 0.003g Solvent 55.12g

[0081]

[Table 1]

PAG-1: triphenylsulfonium triflate N-1,1,5-diazabicyclo [4.3.0] -5-nonene N-2: 1,8-diazabicyclo [5.4.0] -7-undecene N- 3: 1,4-diazabicyclo [2.2.2] octane W-1: Megafac F176 (manufactured by Dainippon Ink Co., Ltd.) (fluorinated surfactant) W-2: Megafac R08 (Dainippon Ink Co., Ltd.) S-1: propylene glycol monomethyl ether acetate S-2: ethyl lactate

The photosensitive resin composition thus prepared was evaluated for the number of development defects, resist image performance, and dry etching resistance by the following methods. Table 2 shows the evaluation results of the development defects, Table 3 shows the evaluation results of the image performance, and Table 4 shows the evaluation results of the dry etching resistance.

(Method of Evaluating Development Defects) (1) Number of Development Defects-I The photosensitive resin composition was uniformly applied to a hexamethyldisilazane-treated silicon substrate by a spin coater.
Heat and dry on a hot plate at 140 ° C for 90 seconds.
A 0 μm resist film was formed. The resist film is exposed to ArF excimer laser light through a mask,
Immediately after exposure, heating was performed on a hot plate at 140 ° C. for 90 seconds. The film was further developed with a 2.38% aqueous solution of tetramethylammonium hydroxide at 23 ° C. for 60 seconds, rinsed with pure water for 30 seconds, and dried. The sample on which the pattern thus obtained was formed was measured for the number of development defects using a KLA2112 machine manufactured by KLA Tencor Co., Ltd. (Threshold 12, Pixel Size = 0.
39). (2) Number of Development Defects-II In the above (1) Number of Development Defects-I, the number of development defects was measured in the same manner as for the heated, developed, rinsed, and dried samples except that no exposure was performed.

(Image Evaluation Method) A resist film of 0.50 μm was formed in the same manner as in the above (1) Number of development defects-I.
Exposure, heating, development, rinsing and drying. Thereafter, the film thickness was measured with a film thickness meter, and the residual film ratio was measured. Further, the formed 0.20 μm line pattern was observed with a scanning electron microscope to examine the profile. Those having a rectangular shape were represented by ○, and those not being represented by △. The resolution is
It shows the limit resolution at the exposure dose that reproduces a 0.30 μm mask pattern.

(Measurement of Dry Etching Resistance) Each photosensitive resin composition in Table 1 was filtered with a Teflon filter having a pore diameter of 0.1 μm. The composition was uniformly applied on a silicon substrate by a spin coater, and dried by heating on a hot plate at 130 ° C. for 90 seconds to form a 0.70 μm resist film. ULVAC reactive ion etching system
Using (CSE-1110), the etching rate for CF ₄ / O ₂ (8/2) gas was measured. The results are shown in Table 4 below.

[0087]

[Table 2]

[0088]

[Table 3]

[0089]

[Table 4]

As is evident from the results in Table 2, the photosensitive resin compositions of the present invention had very few development defects. On the other hand, (C) a nitrogen-containing basic compound and / or (D)
Comparative Examples 1 and 2, which did not use a surfactant, had poor development defects. As is evident from the results in Table 3, the photosensitive resin compositions of the present invention were all excellent in residual film ratio, resolution, and profile. On the other hand, Comparative Examples 3 and 4 were inferior in resolution and profile. As is clear from the results in Table 4, the photosensitive resin compositions of the present invention were all excellent in dry etching resistance. On the other hand, Comparative Examples 3 and 4 were inferior.

[0091]

As is apparent from the above description, the positive photosensitive resin composition of the present invention has very few development defects, and has a good residual film ratio especially when an ArF excimer laser beam is used as an exposure light source. And the pattern profile and resolution. Moreover, since it has excellent dry etching resistance, it can be effectively used for forming a fine pattern required for manufacturing a semiconductor device.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Toshiaki Aoi 4,000 Kawajiri, Yoshida-machi, Haibara-gun, Shizuoka Prefecture F-term in Fujisha Shin Film Co., Ltd. 2H025 AA02 AA09 AB15 AB16 AC04 AC08 AD03 BE07 CB41 CC04 CC20

Claims (4)

[Claims] 1. A compound which generates an acid by actinic light, (B) a polymer having a partial structure represented by the following general formula (I), (C) a nitrogen-containing basic compound, and (D) A positive photosensitive resin composition containing a fluorine-based and / or silicon-based surfactant. Embedded image (In the general formula (I), R _{1 to} R ₄ each independently represent a hydrogen atom, a hydroxyl group, a carboxyl group, an alkyl group,
Represents an alkoxy group, a substituted alkyl group, a substituted alkoxy group, or a cyclic alkyl group. Also, R ₁ and R ₃ or R
₂ and R ₄ may combine with each other to form a ring. X is
Represents a divalent organic residue having 2 to 20 carbon atoms. R
₅ represents a hydrogen atom, an alkyl group, a substituted alkyl group, a cyclic alkyl group, a substituted cyclic alkyl group, or a group constituting a group decomposed by the action of an acid at —COOR ₅ . Z represents a group of atoms forming a cyclohexane ring or a decalin ring together with the carbon atoms. Y is Wherein R ₆ and R ₇ each independently represent a hydrogen atom or a methyl group, and n represents 1 or 2. ) 2. The positive photosensitive resin composition according to claim 1, wherein the polymer (B) has a group that is decomposed by the action of an acid. 3. A compound having a group decomposable by the action of an acid, having an alkali solubility increased by the action of an acid, and having a molecular weight of 2,000.
The positive photosensitive resin composition according to claim 1 or 2, comprising the following low molecular acid decomposable dissolution inhibiting compound. 4. The positive photosensitive resin composition according to claim 1, wherein the actinic ray is deep ultraviolet light having a wavelength of 220 nm or less.