JP2002131913A - Positive photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive resist composition having improved line edge roughness and excellent in sensitivity, resolving power, resist shape and density dependence when deep UV, particularly ArF excimer laser light is used as a light source for exposure. SOLUTION: The positive type photosensitive resin composition contains a polymer having a cycloaliphatic hydrocarbon skeleton and made alkali-soluble by decomposition based on the action of an acid, a compound which generates the acid when irradiated with active light or radiation, a compound of formula (I) or (II) (in the formula (I), R1 and R2 are mutually the same or different and each H, a 1-4C alkyl or phenyl which may have a substituent and in the formulae (I) and (II), R3 and R4 are mutually the same or different and each a halogen, a 1-4C alkyl or trifluoromethyl and (l) and (m) are each an integer of 0-3) and a fluorine- and/or silicon-containing surfactant.

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 chemically amplified photosensitive resin composition suitably used for fine processing of a semiconductor element using light energy rays having a short wavelength such as far ultraviolet rays, X-rays, and electron beams, and particularly relates to an ArF excimer. The present invention relates to a positive chemically amplified photosensitive resin composition suitably used for fine processing of a semiconductor element using a laser.

[0002]

2. Description of the Related Art In recent years, high integration of semiconductor integrated circuits has progressed, and LSIs and VLSIs have been put into practical use, and the minimum pattern width of integrated circuits has reached a sub-half micron area.
Further miniaturization is 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.
In a mass production process of a 256 Mbit DRAM, a KrF excimer laser (248 nm) is put to practical use as an exposure light source instead of i-line, and a D having an integration degree of 1 Gbit or more.
Shorter wavelength light sources are being studied for the manufacture of RAMs, such as ArF excimer laser (193 nm), F ₂
The use of excimer laser (157 nm), X-rays, and electron beams is considered to be effective (Takumi Ueno et al., "Short Wavelength Photoresist Materials-Fine Processing for ULSI", Bunshin Publishing, 1988). .

A chemically amplified resist composition generates an acid in an exposed portion by irradiation with radiation such as deep ultraviolet light, and a reaction using the acid as a catalyst causes a reaction between a portion irradiated with active radiation and a portion not irradiated with a developing solution. A material that forms a pattern on a substrate by changing its solubility. Chemically amplified resists have the advantage that they have high sensitivity and resolution, and can form an image with a compound that generates an acid by a small amount of radiation (hereinafter, referred to as a “photoacid generator”).

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. Thus, a resist containing an alicyclic hydrocarbon group instead of an aromatic ring shows the same dry etching resistance as an aromatic group,
Proc. SPIE, 1672,66 (1992)
In recent years, the use of this polymer has been energetically studied.

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 [5.2.1.0 ^2.6 ]
A decanediyl group, a norbornanediyl group, a norbornanedimethyl group and an adamantanediyl group are disclosed, and JP-A-7-199467 discloses a tricyclodecanyl group, a dicyclopentenyl group, a dicyclopentenyloxyethyl group, a norbornyl group, a cyclohexyl group. 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. Further, JP-A-9-230595, JP-A-9-244247, JP-A-10-10739, 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.

[0008] However, even with the above-mentioned techniques, the photoresist composition for exposure to far ultraviolet rays has many insufficiencies in line edge roughness performance, and there is a need for improvement. Here, the line edge roughness refers to the line pattern of the resist and the edge of the interface between the substrate and the edge of the resist that fluctuate irregularly in the direction perpendicular to the line direction due to the characteristics of the resist. The edge looks uneven. The unevenness is transferred by an etching process using a resist as a mask, and lowers the yield because the electrical characteristics are deteriorated. In particular, as the resist pattern size becomes smaller than quarter micron, there is an increasing demand for improvement in line edge roughness, but no guideline for improvement has been disclosed so far. Furthermore, with the miniaturization of semiconductor devices, there is an increasing demand for improvement in the pattern dependency. Furthermore, in lithography using chemically amplified resists for deep ultraviolet exposure, there is an increasing demand for photoresists that are highly dependent on dense and sparse patterns (pattern formation in dense and sparse parts of patterns). . However, a means for improving the dependency on the density pattern has not been disclosed so far in a chemically amplified resist for deep ultraviolet exposure. It is the only method disclosed in JP-A-11-160876 that an orthoester compound is added to a chemically amplified resist composition for a KrF excimer laser to improve the dense / dense pattern dependency.
To the extent disclosed in the issue.

[0009]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to improve the line edge roughness, the coarse / dense dependency of the pattern, and further prevent the reflection when deep ultraviolet light, particularly ArF excimer laser light, is used as the exposure light source. When a substrate having a film is used, it is an object to provide a positive photosensitive resin composition for deep ultraviolet exposure which is excellent in resolution and resist shape.

[0010]

Means for Solving the Problems The present inventors diligently studied constituent materials of a resist composition in a positive-type chemical amplification system. As a result, they have a cyclic aliphatic hydrocarbon skeleton, and are decomposed by the action of an acid. The above object is achieved by a composition containing an alkali-soluble polymer, a compound generating an acid upon irradiation with actinic rays or radiation, a specific low-molecular compound, and a fluorine-based and / or silicon-based surfactant. This led to the present invention.

That is, the above objects are achieved by the following constitutions (1) to (4) of the present invention. (1) (A) a polymer having a cyclic aliphatic hydrocarbon skeleton and being decomposed by the action of an acid to become alkali-soluble, (B) a compound capable of generating an acid upon irradiation with actinic rays or radiation,
A positive photosensitive resin composition comprising (C) a compound represented by the following general formula (I) or (II), and (D) a fluorine-based and / or silicon-based surfactant.

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(2) The positive photosensitive resin composition according to the above (1), further comprising (E) a nitrogen-containing basic compound as an acid scavenger. (3) The above-mentioned (3), further comprising a low-molecular acid-decomposable compound having a molecular weight of 2000 or less, having a group decomposable by the action of an acid, and having an alkali solubility increased by the action of an acid. The positive photosensitive resin composition according to 1) or (2). (4) The positive photosensitive resin composition according to any one of (1) to (3) above, wherein the actinic ray is deep ultraviolet light having a wavelength of 220 nm or less.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the compounds used in the present invention will be described in detail. First, as the polymer having a cyclic aliphatic hydrocarbon skeleton structure in the present invention, which is decomposed by the action of an acid and becomes alkali-soluble (polymer (A)), a conventionally known polymer can be used. Specific examples of the polymer include a group having a cyclic aliphatic hydrocarbon skeleton unit in a main chain represented by the following (a-1) to (a-15) and decomposing by the action of an acid ( A polymer having a cyclic aliphatic hydrocarbon skeleton in the side chain or a repeating unit represented by the following (b-1) to (b-8), and an acid-decomposable group Polymers may be mentioned. In addition, the following (a-
1) to (a-15), structural units having a cyclic aliphatic hydrocarbon skeleton structure such as structural units represented by (b-1) to (b-8) are essential for the polymer according to the present invention. However, structural units represented by the following (c-1) to (c-4) may be contained as a copolymer component. still,
The polymer (A) preferably has no aromatic group from the viewpoint of transparency to exposure light. A polymer having a cyclic aliphatic hydrocarbon skeleton in both the main chain and the side chain may be used.

[0014]

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[0015]

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[0016]

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In the structural units represented by (a-1) to (a-15) and (b-1) to (b-8), A and B each independently represent a hydrogen atom,
Hydroxyl group, carboxyl group, alkoxycarbonyl group, substituted or unsubstituted alkyl group having 1 to 10 carbon atoms,
Represents an alkoxy group or an alkenyl group, and A and B may combine to form a ring; X and Y each independently represent a group decomposed by the action of an acid. Formulas (b-1) to (b-8), (c-
In 1) to (c-4), R represents a hydrogen atom, a methyl group or other alkyl group having 1 to 3 carbon atoms. Z represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, an alkoxycarbonyl group, or a group decomposed by the action of an acid. )

In the above, examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group and a butoxycarbonyl group. 1 carbon
~ 10 alkyl groups may be substituted,
A straight-chain, branched or cyclic alkyl group is mentioned, and specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, t-butyl group, cyclopentyl group,
Examples include a cyclohexyl group, a hydroxymethyl group, and a hydroxyethyl group. Examples of the alkoxy group having 1 to 10 carbon atoms include a methoxy group, an ethoxy group, an n-butoxy group, a t-butoxy group, a propoxy group and an isopropoxy group. Examples of the alkenyl group having 2 to 10 carbon atoms include an allyl group, a vinyl group, and a 2-propenyl group. As a ring formed by bonding A and B, A and B are bonded to form -C (= O) -OC (= O)-, -C (= O) -NH-C (= O _{) -, -CH 2 -C (=} O) -O-C (= O) -, or the like formed to a include those made with the ring.

The group decomposed by the action of an acid includes-
A (CH ₂ ) _n —COORa group or — (CH ₂ ) _n —
OCORb groups. Here, Ra has 2 to 2 carbon atoms.
Represents 20 hydrocarbon groups, and the hydrocarbon groups include:
Examples include a t-butyl group, a norbornyl group, and a cyclodecanyl group. Rb is a tetrahydrofuranyl group,
Represents an alkoxyethyl group such as a tetrahydropyranyl group, an ethoxyethyl group, an isopropylethyl group, a lactone group, or a cyclohexyloxyethyl group. n represents 0 or 1.

Further substituents in the above groups include:
Examples include a halogen atom, a cyano group, and a nitro group. In the present invention, the cyclic aliphatic hydrocarbon skeleton contained in the polymer (A) preferably has a bridged structure. Thereby, the image performance (registration profile, defocus latitude, etc.) is improved. Examples of the repeating unit having such a bridged cyclic aliphatic hydrocarbon skeleton include (a-2), (a-5), (a-7) to (a-14), (b-1) to (b-1). b-3) and (b-
5) to repeating units represented by (b-8).

The polymer (A) comprising the structural units represented by the above formulas (a-1) to (a-6) can be prepared, for example, by subjecting a cyclic olefin to an organic solvent or a non-organic solvent in the presence of a metathesis catalyst. By ring-opening polymerization followed by hydrogenation. Ring-opening (co) polymerization is described, for example, by WLTruett.
J. Am. Chem. Soc., 82, 2337 (1960), A. Pacreau; Macromo
l. Chem., 188, 2585 (1987), JP-A-51-31800, JP-A-1-
It can be easily polymerized by the synthesis methods described in 197460, JP-A-2-42094, EP-0789278 and the like. Examples of the metathesis catalyst used here include, for example, edited by the Society of Polymer Science, Polymer Synthesis and Reaction (1), Kyoritsu Shuppan, p375-381 (1992), and JP-A-49-779.
No. 99, specifically, a catalyst system comprising a halogen compound of a transition metal such as tungsten and / or molybdenum and an organoaluminum compound or a combination thereof with a third component.

Specific examples of the above-mentioned tungsten and molybdenum compounds include molybdenum pentachloride, tungsten hexachloride and tungsten oxytetrachloride, and examples of the organic aluminum compounds include triethylaluminum, triisobutylaluminum, trihexylaluminum, and diethylaluminum monochloride. Ride,
Di-n-butylaluminum monochloride, ethylaluminum sesquichloride, diethylaluminum monobutoxide and triethylaluminum-water (molar ratio 1: 0.5). In performing ring-opening polymerization, the use ratio of the organoaluminum compound to 1 mol of the tungsten or molybdenum compound is preferably 0.5 mol or more. Water, hydrogen peroxide, oxygen-containing organic compounds, nitrogen-containing organic compounds, halogen-containing organic compounds, phosphorus-containing organic compounds, sulfur-containing organic compounds, metal-containing organic Compounds are used in combination at a ratio of 5 mol or less to 1 mol of the tungsten or molybdenum compound.
The use ratio of the catalyst to the monomer depends on the kind thereof, but is usually used in a ratio of 0.1 to 20 mol per 100 mol of the monomer.

The polymerization temperature in the ring-opening (co) polymerization is -40.degree.
To + 150 ° C., preferably in an inert gas atmosphere. Examples of the solvent used include aliphatic hydrocarbons such as pentane, hexane, heptane and octane; alicyclic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as benzene, toluene and xylene; methylene chloride; 1-dichloroethane, 1,2-dichloroethylene, 1-chloropropane, 1-chlorobutane, 1-chloropentane, chlorobenzene, bromobenzene, o-
Halogenated hydrocarbons such as dichlorobenzene and m-dichlorobenzene; and ether compounds such as diethyl ether and tetrahydrofuran.

By hydrogenating the polymer obtained by such ring-opening (co) polymerization, the polymer (A) used in the present invention is obtained. As a catalyst used in the hydrogenation reaction, a heterogeneous catalyst or a homogeneous catalyst used in a usual hydrogenation reaction of an olefinic compound can be used. Examples of the heterogeneous catalyst include a solid catalyst in which a noble metal catalyst such as palladium, platinum, nickel, ruthenium, and rhodium is supported on a carrier such as carbon, silica, alumina, and titania. As the homogeneous catalyst, for example, nickel naphthenate / triethylaluminum, nickel acetylacetonate / triethylaluminum, cobalt octenoate / n-butyllithium,
Rhodium catalysts such as titanocene dichloride / diethylaluminum monochloride, rhodium acetate and chlorotris (triphenylphosphine) rhodium can be mentioned. Of these catalysts, heterogeneous catalysts are advantageous because they have high reaction activity, facilitate removal of the catalyst after the reaction, and do not discolor the resulting polymer.

The hydrogenation reaction is carried out under a hydrogen gas atmosphere at normal pressure to 300 atm, preferably 3 to 200 atm.
It can be carried out at 200 ° C, preferably at 20 to 180 ° C. The hydrogenation rate is usually at least 50%, preferably at least 70%, more preferably at least 80%. If the hydrogenation rate is less than 50%, the thermal stability and the aging stability of the resist are undesirably deteriorated.

The polymer composed of the structural units represented by the above formulas (a-7) to (a-15) can be prepared, for example, by reacting a radical (C) of a cyclic aliphatic hydrocarbon monomer in the presence of an effective amount of a free radical polymerization initiator. It can be synthesized by (co) polymerization. Specifically, J. Macromol.Sci.Chem.A-5 (3) 491 (1971), A-5 (8) 1
339 (1971), Polym. Lett. Vol. 2,469 (1964), USP3143533
No., USP3261815, USP3510461, USP3793501, USP3
The compound can be synthesized by the method described in JP-A-703501 and JP-A-2-46045. Preferred initiators used for radical (co) polymerization include 2,2'-azobis (2-methylpropanenitrile), benzoyl peroxide, dicumyl peroxide and the like. The concentration of the initiator is usually from 0.01 to 10% by weight, preferably from 0.1 to 5% by weight, based on the total weight of the monomers. The polymerization temperature can be varied over a wide range, usually from room temperature to 250
The polymerization is carried out in a temperature range of preferably from 40 to 200 ° C, more preferably from 60 to 160 ° C.

The polymerization or copolymerization is preferably carried out in an organic solvent. A solvent that dissolves the monomer at a predetermined temperature and also dissolves the produced polymer is preferable. Preferred solvents vary depending on the type of monomers to be copolymerized, but are, for example, aromatic hydrocarbons such as toluene; aliphatics such as ethyl acetate;
Aromatic esters; and aliphatic ethers such as tetrahydrofuran. After the reaction for a predetermined time, it is preferable to perform distillation under reduced pressure and purification for the purpose of separating the obtained polymer from unreacted monomer components, solvents and the like.

Polymers having the structural units (b-1) to (b-8), or copolymer components (c-1) to (c-4)
Can be synthesized by radical (co) polymerization in the presence of an effective amount of a free radical initiator. Polymer (A)
In the above, the content of the structural unit having a cyclic aliphatic skeleton is preferably at least 10 mol% of all the structural units, and more preferably 2 mol% or more.
It is at least 0 mol%, more preferably at least 30 mol%.
In the polymer (A), the content of the structural unit having an acid-decomposable group is 10 to 90 mol%, preferably 15 to 85 mol%, more preferably 20 to 80 mol% of all the structural units. It is. Further, in the polymer used in the present invention, (c)
The content of other copolymerization components such as the units represented by -1) to (c-4) is preferably 3 to 60 mol%, more preferably 5 to 55 mol%, of the repeating units of all monomers. More preferably, it is 10 to 50 mol%.

The polymer (A) 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. Further, if unreacted monomer remains, it is not preferable because dry etching resistance is deteriorated and transmittance of the resist film is lowered. The amount of unreacted monomer is 2% by weight or less, preferably 1% by weight or less in the polymer. The weight average molecular weight and the molecular weight distribution (Mw / Mn) of the polymer (A) 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 (A) 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 (A).
The content of the other polymer is preferably 30 parts by weight or less, more preferably 20 parts by weight, per 100 parts by weight of the polymer (A).
It is at most 10 parts by weight, more preferably at most 10 parts by weight, particularly preferably at most 5 parts by weight.

The other polymer which can be contained in the positive photosensitive resin composition of the present invention may be any polymer which is compatible with the alicyclic polymer of the present invention, such as poly-p-hydroxyethylene, hydrogenated Poly p-hydroxyethylene,
Novolak resins and the like can be mentioned.

Preferred specific examples of the polymer having a cyclic aliphatic hydrocarbon skeleton used in the present invention are shown below, but the present invention is not limited thereto.

[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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Next, the compound (hereinafter also referred to as "(B) photoacid generator") contained in the positive photosensitive resin composition of the present invention which decomposes upon irradiation with actinic rays to generate an acid will be described. I do. Examples of the photoacid generator (B) used in the present invention include a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization, a photodecolorant for dyes, a photochromic agent, or ultraviolet light.
Appropriately select well-known photoacid generators and their mixtures in microphotoresist generating acid by far ultraviolet rays, KrF excimer laser light, ArF excimer laser light, electron beam, X-ray, molecular beam, ion beam, etc. Can be used. In the present invention, the actinic ray is used in a broad concept including radiation as described above.

The photoacid generator (B) 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 (B) photoacid generators include, for example, triphenylsulfonium salt derivatives described in J. Org. Chem. Vol. 43, N0.15, 3055 (1978); -1
84090 and other onium salts described in JP-A-11-184091
(Sulfonium salt, iodonium salt, phosphonium salt,
Diazonium salts, ammonium salts) can also be used. Specific examples of onium salts include diphenyliodonium triflate, diphenyliodonium pyrene sulfonate, diphenyliodonium dodecylbenzenesulfonate, triphenylsulfonium triflate,
Triphenylsulfonium hexafluoroantimonate, diphenyliodonium hexafluoroantimonate, triphenylsulfonium naphthalene sulfonate, triphenylsulfonyum camphorsulfonium, (4-methoxyphenyl) phenyliodonium trifluoromethanesulfonate, bis (t-butylphenyl) iodonium trifluoro Romethanesulfonate,
Examples include triphenylsulfonium hexafluorophosphate, (4-methoxyphenyl) diphenylsulfonium trifluoromethanesulfonate, and triphenylsulfonium nonafluorobutanesulfonate.

Further, JP-A-3-103854, 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.,
The sulfonium salts described in Vol. 7, No. 3, 423 (1994) can also be suitably used, and they are used alone or in combination of two or more. Of these photoacid generators, onium salts are particularly good in terms of resist sensitivity and resolution,
It is preferably used.

The content of the photoacid generator (B) is usually 0.001 to 40% by weight, preferably 0.01 to 20% by weight, based on the total weight (solid content) of the photosensitive resin composition. %, More preferably 0.1 to 15% by weight, particularly preferably 0.5 to 10% by weight. (B) If the amount of the photoacid generator is less than 0.001% by weight, the sensitivity may be lowered. If the amount 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 increased. May be narrow, which is not preferable.

Next, the compound (C) represented by the general formula (I) or (II) contained in the positive photosensitive resin composition of the present invention will be described. In the general formula (I), R ₁ and R ₂ represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group which may have a substituent. C 1-4
Examples of the alkyl group include a methyl group, an ethyl group,
A straight-chain or branched propyl group, a straight-chain or branched butyl group and the like can be mentioned. As the substituent that the phenyl group may have,
Examples thereof include an alkyl group, a fluoroalkyl group, an alkoxy group, an acyl group, a halogen atom, and a hydroxyl group, and preferably have 4 or less carbon atoms. R ₁ and R ₂ are preferably a hydrogen atom, a methyl group or a phenyl group.

R ₃ and R _{4 each} represent a halogen atom, a carbon number of 1 to
4 represents an alkyl group or a trifluoromethyl group.
When l and m are 2 or 3, a plurality of R ₃ and R ₄ may be the same or different. R ₃ and R ₄ are preferably a methyl group or a trifluoromethyl group. l and m are preferably 1.

Specific examples of the compound represented by the general formula (I) include the following compounds (C-1) to (C-5), and specific examples of the compound represented by the general formula (II) Examples thereof include the following compounds (C-6) and (C-7), but are not limited thereto.

[0050]

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[0051]

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In the present invention, the amount of the compound (C) to be added is usually 0.001 based on the solid content in the composition.
Used in a range of from 40 to 40% by weight, preferably from 0.01 to 40% by weight.
It is used in an amount of 20% by weight, more preferably 0.05 to 15% by weight. When the addition amount of the compound (C) of the present invention is
If less than 0.001% by weight, line edge roughness,
There is a case where the effect of improving the density dependency is not sufficiently effective. On the other hand, if the addition amount is more than 40% by weight, the profile of the resist may be deteriorated or the process margin may be narrowed, which is not preferable. The method for synthesizing the compound (C) is known, and a commercially available method can be used.

Next, the fluorine-based and / or silicon-based surfactant (D) contained in the positive photosensitive resin composition of the present invention will be described. In the photosensitive resin composition of the present invention,
Any of a fluorine-based surfactant, a silicon-based surfactant, a surfactant containing a fluorine atom and a silicon atom, or two or more of these surfactants can be contained. As these surfactants, for example, JP-A-62-36663, JP-A-61-226
No. 746, JP-A-61-226745, JP-A-62-170950, JP-A-63-34540, JP-A-7-230165, JP-A-8-62834,
JP 9-54432, JP 9-5988, JP 2000-162768
No., JP-A-2000-122289, U.S. Pat.
No. 5360692, U.S. Pat.No. 5,529,881, U.S. Pat.
US Patent No. 5436098, US Patent No. 5576143, US Patent No. 5296
No. 143, US Pat. No. 5,294,511, and US Pat. No. 5,824,451. The following surfactants can be used as they are. Commercially available surfactants that can be used, for example, F-top EF301, EF3
03, (Shin-Akita Chemical Co., Ltd.), Florado FC430, 431 (Sumitomo 3M), MegaFac F171, F173, F176, F
189, R08 (Dainippon Ink Co., Ltd.), Surflon S-38
2, SC101, 102, 103, 104, 105, 106 (Asahi Glass Co., Ltd.)
And Troysol S-366 (manufactured by Troy Chemical Co., Ltd.). Also, polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can be used as a silicon-based surfactant.

(D) The amount of the surfactant is usually 0.001 to 2 parts by weight, preferably 0.003 to 0.10 parts by weight, per 100 parts by weight of the solids in the composition of the present invention.
Parts by weight. These surfactants can be used alone or in combination of two or more.

In the present invention, (D) in the composition
Weight ratio of (A) polymer to surfactant ((A) / (D))
Is preferably in the range of 500 to 20,000, more preferably in the range of 1,000 to 15,000. By adopting this ratio, developability and line width reproducibility are improved,
The uniformity of the applied film thickness is improved. It is not well understood why the positive photosensitive resin composition of the present invention is specifically superior in the line edge roughness and the pattern density dependence, but (C) it is manifested by adding a specific low molecular compound. It seems to have done.

Next, (E) an acid scavenger which can be preferably used in the positive photosensitive resin composition of the present invention will be described. Examples of the acid scavenger include organic amines, basic ammonium salts, basic sulfonium salts, and the like.
Any material that does not deteriorate sublimation or resist performance may be used.
Among these acid scavengers, organic amines are preferred because of their excellent image performance. For example, 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-A-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-7-28
No. 247, JP-A-8-22120, JP-A-8-110638, JP-A-8-
123030, JP-A-9-274312, JP-A-9-166871, JP-A-9-292708, JP-A-9-325496, JP-T-Hei 7-508840,
Basic compounds described in US Pat. No. 5,525,453, US Pat. No. 5,629,134, US Pat. No. 5,667,938 can be used.

As the acid scavenger, preferably, 1,5-
Diazabicyclo [4.3.0] -5-nonene, 1,8-
Diazabicyclo [5.4.0] -7-undecene, 1,
4-diazabicyclo [2.2.2] octane, 4-dimethylaminopyridine, 1-naphthylamine, piperidine, hexamethylenetetramine, imidazoles, hydroxypyridines, pyridines, 4,4'-diaminodiphenyl ether, pyridinium p-toluene Sulfonate, 2,4,6-trimethylpyridinium p-toluenesulfonate, tetramethylammonium p-toluenesulfonate, and tetrabutylammonium lactate, triethylamine, tributylamine and the like can be mentioned. Among these, 1,5-diazabicyclo [4.
3.0] -5-Nonene, 1,8-diazabicyclo [5.
4.0] -7-undecene, 1,4-diazabicyclo [2.2.2] octane, 4-dimethylaminopyridine, 1-naphthylamine, piperidine, hexamethylenetetramine, imidazoles, hydroxypyridines,
Pyridines, 4,4′-diaminodiphenyl ether,
Organic amines such as triethylamine and tributylamine are preferred.

The content of the acid scavenger is usually from 0.001 to 1 based on 100 parts by weight of the photosensitive resin composition (solid content).
0 parts by weight, preferably 0.001 to 5 parts by weight, more preferably 0.001 to 0.5 parts by weight. If the amount is less than 0.001 part by weight, the effect of adding the acid scavenger 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. The acid scavengers can be used alone or in combination of two or more.

The positive photosensitive resin composition of the present invention may have, if necessary, (F) a molecular weight of 2,000 or less, a group which can be decomposed by the action of an acid, and an alkali-solubility which is not affected by the action of an acid. Can be included. For example, Proc.SPIE, 2724, 355 (1996), JP-A-8-1
No. 5865, USP5310619, USP-5372912, J. Photopoly
m.Sci., Tech., Vol. 10, No. 3, 511 (1997)) containing an acid-decomposable group, cholic acid derivative, dehydrocholic acid derivative, deoxycholic acid derivative, lithocholic acid derivative, Alicyclic compounds such as ursocholic 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 0.1% based on 100 parts by weight (solid content) of the photosensitive resin composition.
It is used in the range of 5 to 50 parts by weight, preferably 0.5 to 50 parts by weight.
It is used in an amount of 40 parts by weight, more preferably 0.5 to 30 parts by weight, particularly preferably 0.5 to 20.0 parts by weight.

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 other than the above,
A photosensitizer, an adhesion aid, a crosslinking agent, a photobase generator and the like can be contained.

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
Compound, carboxylic anhydride, sulfonamide compound or sulfonylimide compound, JP-A-2000-2
Low molecular weight compounds having a molecular weight of 1000 or less, such as a bridged cyclic compound having a carboxyl group described in No. 58782, and the like. The compounding amount of these dissolution promoting compounds is preferably 3 to the total weight (solid content) of the composition.
0% by weight or less, more preferably 20% by weight or less.

As a suitable antihalation agent, a compound that efficiently absorbs irradiation 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 and 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 in order to increase the rate of acid generation upon 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, tetramethyl Lensulfone and the like. These solvents are used alone or in combination. Among these solvents, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and propylene glycol monomethyl ether propionate are particularly preferable from the viewpoints of solubility in the composition, coatability on a substrate, and storage stability. It is preferable that at least one solvent selected from methyl, 3-methoxypropionate, ethyl 3-ethoxypropionate, and 2-heptanone be contained in an amount of 70% by weight or more based on the total solvent. Further, since the water contained in the solvent affects the resist performance, 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 metal or an impurity component such as chlorine ion.
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, it is prebaked (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 present invention is particularly effective for a substrate having an antireflection film. As the antireflection film used as the lower layer of the resist, any of an inorganic film type such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon, and amorphous silicon, and an organic film type including a light absorbing agent and a polymer material can be used. it can. The former requires equipment such as a vacuum deposition apparatus, a CVD apparatus, and a sputtering apparatus for film formation. As the organic antireflection film, for example, Japanese Patent Publication No. 7-6
No. 9611, consisting of a condensate of a diphenylamine derivative and a formaldehyde-modified melamine resin, an alkali-soluble resin, a light absorbing agent, and a reaction product of a maleic anhydride copolymer and a diamine type light absorbing agent described in US Pat. No. 5,294,680; No. 6,118,631 containing a resin binder and a methylolmelamine-based thermal crosslinking agent; Japanese Patent Application Laid-Open No. 6-118656, an acrylic resin type antireflection film having a carboxylic acid group, an epoxy group and a light absorbing group in the same molecule; JP-A-8-87115, comprising a methylolmelamine and a benzophenone-based light-absorbing agent;
No. 79509 in which a low molecular weight light absorbing agent is added to a polyvinyl alcohol resin. The typical thickness of the anti-reflective coating layer is from 100 nm to 3000 nm.

As an organic antireflection film, DUV30 series manufactured by Brewer Science, DUV-4
0 series, Shipley AR-2, AR-3, AR
Commercially available organic antireflection films such as -5, AR-19 and AR-25 can also be used.

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.

[0071] 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 for 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, a suitable 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.

[0074]

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.

(1) Synthesis Example 1 [Synthesis of Resin (1) (Polymer A)] Norphorene, tert-butyl acrylate, and maleic anhydride were charged into a reaction vessel at a molar ratio of 40/20/40, and methyl ethyl ketone was added. And a solution having a solid content of 60% was prepared. This was heated at 60 ° C. under a nitrogen stream. When the reaction temperature becomes stable, a radical initiator V-601 manufactured by Wako Pure Chemical Industries, Ltd.
Was added to start the reaction. After heating for 10 hours,
After diluting the reaction mixture twice with methyl ethyl ketone,
It was put into a large amount of tert-butyl methyl ether to precipitate a white powder. The precipitated powder was taken out by filtration and dried to obtain the target resin (1). G of the obtained resin (1)
When molecular weight analysis by PC was attempted, the result was 15,300 (weight average) in terms of polystyrene. From the NMR spectrum, the composition of the resin (1) was 38/17/45 in molar ratio of norbornene / t-butyl acrylate / maleic anhydride of the present invention.

(2) Synthesis Example 2 [Synthesis of Resin 1 (Polymer B)] 2-Methyl-2-adamantyl methacrylate, butyrolactone methacrylate, ratio of 40/60 (molar ratio)
, Dissolved in tetrahydrofuran, and solid content concentration 2
100 mL of a 0% solution was prepared. V-65 was added to this solution.
(Trade name, manufactured by Wako Pure Chemical Industries)
mol.
The solution was added dropwise to 10 mL of tetrahydrofuran heated to ° C.
After completion of the dropwise addition, the reaction solution was heated and stirred for 6 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and white powder crystallized and precipitated in 3 L of distilled water was recovered. The composition of the resin determined from C ¹³ NMR was 41/59 (2-methyl-2-adamantyl methacrylate / butyrolactone methacrylate) in a molar ratio. The weight average molecular weight in terms of polystyrene determined by GPC measurement was 12,700.

(3) Synthesis Example 3 [Synthesis of Resin (16) (Polymer C)] The following structure, which is obtained by reacting methacrylic acid ester of 3-oxo-1,1-dimethylbutanol with cyclopentadientadienene, Tetracyclododecene derivative (1
An equimolar mixture of -1) and maleic anhydride was dissolved in tetrahydrofuran to prepare a solution having a solid content of 50%. This was charged into a three-necked flask and heated at 60 ° C. under a nitrogen stream. When the reaction temperature was stabilized, 5 mol% of a radical initiator V-60 manufactured by Wako Pure Chemical Industries, Ltd. was added to start the reaction.
After heating for 6 hours, the reaction mixture was diluted twice with tetrahydrofuran, and then poured into a large amount of hexane to precipitate a white powder. The precipitated powder was taken out by filtration, dried, and the resin (16) as an objective was obtained.

[0078]

Embedded image

An attempt was made to analyze the molecular weight of the obtained resin (16) by GPC.
(Weight average). From the NMR spectrum, it was found that the molar ratio of the repeating unit of tetracyclododecene and the repeating unit of maleic anhydride in the resin 16 was 50/50.

(4) Synthesis Example 4 (Synthesis of Polymer D) In a 300 mL reaction vessel, 20 g of 2-methyl-2-adamantyl methacrylate and 3-hydroxy-1-methacrylate were added.
Adamantyl 10.1 g and α-methacryloxy-γ-
Butyrolactone was charged with 7.8 g (50:25:25 molar ratio), and 80 g of methyl isobutyl ketone was added to form a solution. Azoisobutyronitrile as a polymerization initiator was added in an amount of 2.2 mol% based on all monomers, and the mixture was heated and stirred at 85 ° C. for 8 hours. Thereafter, the reaction solution was poured into 1200 g of heptane to precipitate. Thereafter, purification was performed to obtain a copolymer having a weight average molecular weight of about 4700.

(5) Synthesis Example 5 (Synthesis of Polymer E) 4 g of 2-norbornene, 4.2 g of maleic anhydride and 20 g of 2-methyl-2-adamantyl methacrylate (25:25:50) were placed in a 300 mL reaction vessel. ).
60 g of methyl isobutyl ketone were added to form a solution.
Azoisobutyronitrile as a polymerization initiator was added in an amount of 2.2 mol% based on all monomers, and the mixture was heated and stirred at 90 ° C. for 8 hours. Thereafter, the reaction solution was poured into 1200 g of heptane to precipitate. Thereafter, purification was performed to obtain a copolymer having a weight average molecular weight of about 6,200.

(6) Synthesis Example 6 (acid-decomposable low molecular weight compound a
Synthesis of 122.7 g (0.3 mol) of cholic acid and 120 ml of thionyl chloride were 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.

[0083]

Embedded image

[Examples 1 to 5 and Comparative Examples 1 to 3] Composition of photosensitive resin composition of Example 1: A photosensitive resin composition having the following composition was mixed so that the solid content concentration was about 12%. Then, the mixture was filtered through a 0.1 μm Teflon (registered trademark) microfilter to prepare a positive photoresist. Composition of the photosensitive resin composition of Example 1: 93.32 parts by weight of polymer A obtained in Synthesis Example 1 Acid generator: (PAG-1) 1.50 Compound of the present invention: (C-2) 0.10 Surfactant: ( W-2) 0.030 Acid scavenger: (N-1) 0.05 Acid-decomposable low-molecular compound a obtained in Synthesis Example 6 5.0 Solvent: (S-1) 733.33

Composition of the photosensitive resin composition of Example 2: 98.33 parts by weight of the polymer B obtained in Synthesis Example 2 Acid generator: (PAG-1) 1.50 Compound of the present invention: (C-3) 0.10 Surface activity Agent: (W-1) 0.020 Acid scavenger: (N-2) 0.05 Solvent: (S-2) 513.33 (S-3) 220.00

Composition of the photosensitive resin composition of Example 3: 97.68 parts by weight of the polymer C obtained in Synthesis Example 3 Acid generator: (PAG-1) 1.00 (PAG-2) 1.00 Compound of the present invention: (C-5) 0.20 Surfactant: (W-1) 0.020 Acid scavenger: (N-1) 0.10 Solvent: (S-2) 513.33 (S-3) 220.00

Composition of the photosensitive resin composition of Example 4: 97.37 parts by weight of the polymer D obtained in Synthesis Example 4 Acid generator: (PAG-1) 1.50 (PAG-3) 0.50 Compound of the present invention: (C -6) 1.00 Surfactant: (W-3) 0.030 Acid scavenger: (N-3) 0.10 Solvent: (S-1) 513.33 (S-4) 220.00

Composition of the photosensitive resin composition of Example 5: Polymer E obtained in Synthesis Example 5 94.59 parts by weight Acid generator: (PAG-2) 2.00 Compound of the present invention: (C-6) 0.30 Surface activity Agent: (W-2) 0.010 Acid scavenger: (N-3) 0.10 Acid-decomposable low molecular weight compound a3.0 obtained in Synthesis Example 6 Solvent: (S-2) 696.66 (S-5) 36.67

Composition of photosensitive resin composition of Comparative Example 1: 98.42 parts by weight of polymer A obtained in Synthesis Example 1 Acid generator: (PAG-1) 1.50 Surfactant: (W-2) 0.030 Acid scavenger : (N-1) 0.05 Solvent: (S-1) 733.33

Composition of photosensitive resin composition of Comparative Example 2: 98.43 parts by weight of polymer B obtained in Synthesis Example 2 Acid generator: (PAG-1) 1.50 Surfactant: (W-1) 0.020 Acid scavenger : (N-2) 0.05 Solvent: (S-2) 513.33 (S-3) 220.00

Composition of photosensitive resin composition of Comparative Example 3: 98.37 parts by weight of polymer D obtained in Synthesis Example 4 Acid generator: (PAG-2) 1.50 Surfactant: (W-3) 0.030 Acid scavenger : (N-3) 0.10 Solvent: (S-1) 513.33 (S-4) 220.00

The symbols of the compounds used in the above Examples and Comparative Examples are as follows. PAG-1: triphenylsulfonium triflate PAG-2: triphenylsulfonium nonafluorobutanesulfonate PAG-3: bis (phenylsulfonyl) diazomethane N-1: hexamethylenetetramine N-2: 1.5-diazabicyclo [4.3 .0] -5
Nonene N-3: 1.8-diazabicyclo [5.4.0] -7-
Undecene W-1: Megafac F176 (manufactured by Dainippon Ink and Chemicals, Inc.) (fluorine-based) W-2: Megafac R08 (manufactured by Dainippon Ink and Chemicals, Inc.) (fluorine and silicon-based) W-3 : Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) (silicone) S-1: propylene glycol monomethyl ether acetate S-2: ethyl lactate S-3: ethoxyethyl propionate S-4: propylene glycol Monomethyl ether S-5: Propylene carbonate Compounds (C-2), (C-3), (C-5) and (C-
6) is a compound exemplified above, which was purchased as a reagent from Tokyo Chemical Industry Co., Ltd.

(Image Evaluation Method) An anti-reflection film (Brewer Scien) was formed on a hexamethyldisilazane-treated silicon substrate.
ce DUV-30) was applied in a thickness of 60 nm and cured at 190 ° C. On the antireflection film, each of the positive photoresist solutions obtained above was uniformly applied by a spin coater (Mark 8 manufactured by Tokyo Electron Limited), and heated and dried on a hot plate at 120 ° C. for 90 seconds to obtain 0.30 μm. A μm resist film was formed. Using this resist film as a mask, A
Exposure with rF excimer laser light, immediately after exposure
Heated on a hot plate at 90 ° C. for 90 seconds. 2.3
The resist was developed with an 8% by weight aqueous solution of tetramethylammonium hydroxide at 23 ° C. for 60 seconds, rinsed with pure water for 30 seconds, and spin-dried to obtain a resist pattern.

The obtained resist pattern was evaluated for sensitivity, resolution, line edge roughness, shape, and density dependence by the following methods. [Sensitivity] The minimum exposure amount for reproducing a 0.15 μm line pattern on the mask was shown. [Resolution] The width of a line pattern that can be resolved with the minimum exposure amount that reproduces a 0.15 μm line pattern of the mask
(μm), that is, the critical resolution. [Line edge roughness] 0.15 μm in mask
5 μm in the longitudinal direction of a 0.15 μm line pattern obtained by the minimum exposure amount reproducing the line pattern
In the range of m, the distance from the reference line where the edge should be located was measured at 50 points by S-8840 manufactured by Hitachi, Ltd., the standard deviation was determined, and 3σ was calculated. The smaller the value, the better the performance. [Shape] The cross-sectional shape of the 0.15 μm line pattern obtained by the minimum exposure amount for reproducing the 0.15 μm line pattern on the mask was observed with a scanning electron microscope. A rectangular shape was indicated by ○, and a tapered shape was indicated by ×. A slightly tapered shape is indicated by a triangle. [Dependency on density] Represents the line width (μm) of a 0.15 μm isolated line at the minimum exposure amount for reproducing a 0.15 μm line pattern of a mask. The closer the line width is to 0.15 μm, the better the density dependency.

[0095]

[Table 1]

As shown in Table 1, the resist composition of the present invention showed satisfactory results in sensitivity, resolution, line edge roughness, shape, and density dependence. In particular, the line edge roughness is a remarkably good result.

[0097]

Industrial Applicability The present invention can provide a positive resist composition which is suitable for far ultraviolet light, particularly ArF excimer laser light, has improved line edge roughness, and is excellent in sensitivity, resolution, resist shape, and density dependence. .

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 33/04 C08L 33/04 45/00 45/00 G03F 7/004 501 G03F 7/004 501 504 504 H01L 21/027 H01L 21/30 502R F term (reference) 2H025 AA02 AA03 AB16 AB20 AC04 AC08 AD03 BE00 BE10 BG00 CB08 CB41 CC04 CC20 DA34 FA17 4J002 BG041 BG051 BG071 BG081 BH021 BK001 CP032 EB106 EB106 EB106 EC0347

Claims (4)

[Claims] (A) a polymer having a cyclic aliphatic hydrocarbon skeleton, which is decomposed by the action of an acid and becomes alkali-soluble;
(B) a compound that generates an acid upon irradiation with actinic rays or radiation, (C) a compound represented by the following general formula (I) or (II), and (D) a fluorine-based and / or silicon-based surfactant A positive-type photosensitive resin composition comprising: Embedded image (In the general formula (I), R ₁ and R ₂ may be the same or different, and include a hydrogen atom, an alkyl group having 1 to 4 carbon atoms,
Or a phenyl group which may have a substituent. In each of the general formulas (I) and (II), R ₃ and R ₄ may be the same or different and represent a halogen atom, an alkyl group having 1 to 4 carbon atoms or a trifluoromethyl group. l and m
Represents an integer of 0 to 3. ) 2. The positive photosensitive resin composition according to claim 1, further comprising (E) a nitrogen-containing basic compound as an acid scavenger. 3. A low molecular acid-decomposable compound having a molecular weight of 2,000 or less, having a group decomposable by the action of an acid, and having an alkali solubility increased by the action of an acid. The positive photosensitive resin composition according to claim 1. 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.