JP2000010286A - Positive type photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a positive type photosensitive resin compsn. excellent in resolving power to far UV by incorporating at least a polymer contg. structural units having an alicyclic hydrocarbon skeleton, a photo-acid generating agent, a nitrogen-contg. basic compd., a specified dissolution inhibitor and a fluorine- and/or silicon-contg. surfactant. SOLUTION: This photosensitive resin compsn. contains a polymer which has a cycloaliphatic hydrocarbon skeleton and is made alkali-soluble when decomposed by the action of an acid, a low molecular acid decomposable compd. of formula I having a mol.wt. of <=3,000, having a group decomposable by the action of the acid and increasing its alkali solubility under the action of the acid, a compd. which generates the acid under active rays of light, a nitrogen-contg. basic compd. and a fluorine- and/or silicon-contg. surfactant. In the formula I, Z is one of groups of formulae II or a group formed by combining one or more such groups, R1 is a group which is decomposed by the action of an acid, R2 is H, hydroxyl, a 1-4C alkyl or the like and (n) and (m) are each 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, 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). .

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-A-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 pattern profile, the resolution, the dry etching resistance, and does not cause a problem of a development defect 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 an alicyclic hydrocarbon skeleton structural unit, a photoacid generator, The present invention has been found to achieve the above object by containing at least a nitrogen-containing basic compound, a specific dissolution inhibitor having a molecular weight of 3000 or less, and a fluorine-based and / or silicon-based surfactant. That is, the configuration of the present invention is shown below. (1) (A) a polymer having a cyclic aliphatic hydrocarbon skeleton and decomposed by the action of an acid to become alkali-soluble, and (B) a group having a molecular weight of 3000 or less and decomposable by the action of an acid. A low-molecular acid-decomposable compound having a partial structure represented by the general formula (I), wherein the alkali solubility is increased by the action of an acid; (C) a compound capable of generating an acid by actinic light; (D) a nitrogen-containing compound. A positive photosensitive resin composition comprising a basic compound and (E) a fluorine-based and / or silicon-based surfactant.

[0012]

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In the general formula (I), Z is

[0014]

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Or a group obtained by combining one or more of these groups. R ₁ represents a group decomposed by the action of an acid. R
₂ represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group. n and m each represent 1 or 2. (2) The positive photosensitive resin composition according to the above (1), 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, in the present invention, (A) having a cyclic aliphatic hydrocarbon skeleton structure, as a polymer that is decomposed by the action of an acid and becomes alkali-soluble, a conventionally known polymer can be used. As a specific example, for example, a group having a cyclic aliphatic hydrocarbon skeleton unit in the main chain represented by the following (a-1) to (a-15) and decomposing by the action of an acid (acid-decomposable group) The following (b-1) having a polymer having a cyclic aliphatic hydrocarbon skeleton in the side chain
And a polymer having an acid-decomposable group and a repeating unit represented by (b-7). In addition, the following (a-1)-(a-
15), structural units having a cyclic aliphatic hydrocarbon skeleton structure such as structural units represented by (b-1) to (b-7) are indispensable for the polymer according to the present invention, the following ( The structural units represented by c-1) to (c-4) may be included as copolymer components.

[0017]

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[0018]

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[0019]

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In the structural units represented by (a-1) to (a-15) and (b-1) to (b-7), 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-7), (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 ₁ 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.

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 are triethylaluminum, triisobutylaluminum, trihexylaluminum, diethylaluminum 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 with the tungsten or molybdenum compound at a ratio of 5 mol or less to 1 mol. 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 ° C.
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 consisting of the structural units represented by the above formulas (a-7) to (a-15) can be used, for example, in the presence of an effective amount of a free radical polymerization initiator in the presence of a radical (C) of a cyclic aliphatic hydrocarbon monomer. 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-7) 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 hydrocarbon skeleton is preferably at least 10 mol%, more preferably at least 20 mol%, even more preferably at least 30 mol% of all the structural units. In the polymer (A), the content of the structural unit having an acid-decomposable group is from 10 to 90 mol%, preferably from 15 to 85 mol%, more preferably from 20 to 90 mol% of all the structural units.
~ 80 mol%. In the polymer used in the present invention, the content of other copolymer components such as the units represented by (c-1) to (c-4) is 3 to 60 in the repeating units of all monomers.
Mol% is preferable, more preferably 5 to 55 mol%, and still more preferably 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
When the molecular weight is less than 0, dry etching resistance, heat resistance, and adhesion to a substrate are insufficient, and when the molecular weight exceeds 100,000, the resist sensitivity decreases, which is not preferable. Further, the molecular weight distribution (Mw / Mn) is preferably 1.0 to 6.0, more preferably 1.0 to 4.0.
Image performance (resist profile, defocus latitude, etc.) is improved. The weight average molecular weight and molecular weight distribution (Mw / Mn) of the polymerization (A) were determined by gel permeation chromatography equipped with a refractive index detector.
It is measured as a polystyrene equivalent.

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-type 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 as follows.
It is preferably at most 30 parts by weight, more preferably at most 20 parts by weight, particularly preferably at most 10 parts by weight, per 100 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 alicyclic polymer of the present invention, such as poly-p-hydroxyethylene and hydrogenated poly-p-. Hydroxyethylene,
Novolak resins and the like can be mentioned.

Next, the (B) low-molecular acid-decomposable compound (also referred to as a dissolution inhibitor) contained in the positive photosensitive resin composition of the present invention will be described. Examples of the acid-decomposable group R ₁ in the general formula (I) include groups represented by the following formula.

[0036]

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In the above formula, R_Three, R_FourIs, independently of each other, hydrogen
Represents an atom or a methyl group. R_FiveIs -OR₆, -COOR₆
Or a substituted or unsubstituted alkyl having 2 to 16 carbon atoms
R represents a group_FourAnd R_FiveAre bonded to each other to form a ring
Good. m represents 0 or 1. R₆Has 2 to 16 carbon atoms
Represents a substituted or unsubstituted alkyl group. Where charcoal
A substituted or unsubstituted alkyl group having 2 to 16 prime numbers
Methyl, ethyl, propyl, isopropyl
Group, butyl group, isobutyl group, t-butyl group, pentyl
Group, hexyl group, hexyl group substituted with cyclohexyl group,
Phenoxy-substituted hexyl and phenethyl-substituted
Xyl groups and the like. R _FourAnd R_FiveAre connected to each other
The ring to be formed is a tetrahydropyran ring,
Lofran ring and the like.

Examples of the alkyl group having 1 to 4 carbon atoms for R ₂ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group and a t-butyl group. Further, as the alkoxy group having 1 to 4 carbon atoms,
Examples include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, and a t-butoxy group. The dissolution inhibitor used in the present invention can be synthesized by synthesizing a phenol compound having a structure represented by the general formula (II) and protecting a hydroxyl group with an acid-decomposable group.

[0039]

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In the above general formula (II), Z, R ₂ ,
n and m have the same meanings as those in the general formula (I). In order to synthesize a phenol compound having a partial structure represented by the general formula (II), 4-vinylcyclohexene, 5-vinylnorborna-2-ene, 3a, 4,7,7a-tetrahydroindene are used in the presence of an acidic catalyst. , Dicyclopentadiene, α-pinene, β-pinene, limonene or a mixture thereof with a compound selected from naphthols and dihydroxynaphthalene. As the acidic catalyst to be used, boron trifluoride, boron trifluoride ether, boron trifluoride complex, aluminum trichloride, aluminum compounds such as diethylaluminum monochloride, iron chloride, titanium tetrachloride, sulfuric acid,
Hydrogen fluoride, trifluoromethanesulfonic acid, p-toluenesulfonic acid and the like are used. The amount of the acidic catalyst used depends on the catalyst used, but the amount of the unsaturated cyclic hydrocarbon compound
0.1 to 20 parts by weight is preferable for 100 parts by weight.

The method for synthesizing a phenol compound having a partial structure represented by the general formula (II) can be carried out with or without using a solvent. When a solvent is used, any solvent may be used as long as it does not inhibit the reaction, and specific examples thereof include aromatic hydrocarbon compounds such as benzene, toluene, and xylene. Reaction temperature is 10 ° C
~ 200 ° C is preferred.

Next, the hydroxyl group of the phenol compound having a partial structure represented by the general formula (II) is converted by a known method.
By protecting with an acid-decomposable group, the dissolution inhibitor used in the present invention can be obtained. The protection ratio with an acid-decomposable group is preferably 5% or more, more preferably 10% or more, and still more preferably 20% or more, based on all hydroxyl groups in the phenol compound. The molecular weight of the dissolution inhibiting compound of the present invention is 3000 or less, preferably 500 to 3
000, and more preferably 800-3000. Specific examples of the dissolution inhibitor used in the present invention include, for example, the following [II] to [I-6].
N in the following specific examples is set so that the molecular weight of each compound is 3000 or less.

[0043]

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[0044]

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These dissolution inhibitors can be used alone or in combination of two or more. The content of the dissolution inhibitor in the photosensitive resin composition of the present invention, based on the total weight (solid content) of the photosensitive resin composition, is generally used in the range of 1 to 50% by weight, preferably 3 to 50% by weight. It is used in the range of 40% by weight, more preferably 5 to 30% by weight. When the dissolution inhibiting compound of the present invention is added, development defects are further improved, and dry etching resistance and resolution are improved.

Next, (C) a compound which is decomposed by irradiation with actinic rays and generates an acid contained in the positive photosensitive resin composition of the present invention (hereinafter also referred to as "(C) photoacid generator") ) Will be described. Examples of the photoacid generator (C) 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 (C) 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 (C) photoacid generators include, for example, triphenylsulfonium salt derivatives described in 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 (C) 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. (C) If the amount of the photoacid generator is less than 0.001% by weight, the sensitivity becomes low, 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 (D) contained in the positive photosensitive resin composition of the present invention will be described.
(D) As the nitrogen-containing basic compound, 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. (D) The nitrogen-containing basic compound can be used alone or in combination of two or more.

The content of the nitrogen-containing basic compound (D) 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 of addition 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-based and / or silicon-based surfactant (E) 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, and a surfactant containing both a fluorine atom and a silicon atom, or two or more of them can be contained.
As these (E) surfactants, for example, JP-A-62-366
No. 63, JP-A-61-226746, JP-A-61-226745, JP-A-61-226745
No. 62-170950, JP-A-63-34540, JP-A-7-230165,
The surfactants described in JP-A-8-62834, JP-A-9-54432 and JP-A-9-5988 can be mentioned, 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.), Florard FC430, 431 (manufactured by Sumitomo 3M Limited), Megafac F171, F173, F176, F18
9, R08 (Dainippon Ink Co., Ltd.), Surflon S-382,
SC101, 102, 103, 104, 105, 106 (manufactured by Asahi Glass Co., Ltd.) and other fluorine-based surfactants or silicon-based surfactants. In addition, polysiloxane polymer KP-341
(Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant. Among these surfactants, surfactants having both fluorine atoms and silicon atoms are:
It is particularly excellent in improving development defects.

The amount of the surfactant (E) 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 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, for example, 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.

Further, a photosensitizer can be added in order to improve the acid generation rate 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 in which each of the above components is dissolved, usually, 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 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 a suitable 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 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.

[0065] 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, 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.

[0068]

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) The hydrogenated product of the ring-opened polymer of a norbornene derivative described in the fourth example of JP-A-9-244247 (the repeating unit of which is shown below) is described in EP 0789278. It was synthesized according to the method described in the description. (Weight average molecular weight 22000)

[0070]

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Synthesis Example 2 (Synthesis of Polymer B) JP-A-9-244247 discloses a hydrogenated product of a ring-opened polymer of a norbornene derivative described in the first example (repeated structural units are described below) in EP 0789278. It was synthesized according to the method described. (Weight average molecular weight 17000)

[0072]

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Synthesis Example 3 (Synthesis of Polymer C) A copolymer of norbornene, maleic anhydride, t-butyl acrylate and acrylic acid (repeated structural units are described below) was prepared in JP-A-10-10739, No. 7 It was synthesized according to the method described in the examples. (Weight average molecular weight 17000,
(Molar ratio of each repeating unit 50/25/25)

[0074]

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Synthesis Example 4 (Synthesis of Polymer D) A copolymer of adamantyl methacrylate and t-butyl acrylate (repeated structural units are described below) was prepared as described in JP-A-7-23.
No. 4511, synthesized according to the method described in the first example. (Weight average molecular weight 5000, molar ratio of each repeating unit 58/42)

[0076]

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Synthesis Example 5 (Synthesis of acid-decomposable low-molecular compound a) 500 m equipped with a reflux condenser and a Liebig condenser
In an L reactor, 144.2 g of α-naphthol and 70 g of toluene were charged, heated to 160 ° C., and dehydrated to 50 ppm of water in the system by azeotropic distillation with toluene, and 25 g of toluene was distilled off. Then, the system was cooled down to 100 ° C, 2 g of boron trifluoride / phenol complex was added to make it homogeneous, and then 33 g of dicyclopentadiene having a water content of 20 ppm was gradually dropped at a reaction temperature of 100 ° C over 1.5 hours. After completion of the dropwise addition, the mixture was further heated and stirred for 2.5 hours. After the completion of the reaction, toluene 60
g and 8 g of a magnesium compound “KW-1000” (trade name: manufactured by Kyowa Chemical Industry Co., Ltd.) were added, and the mixture was stirred for 30 minutes to deactivate the catalyst. Then, the reaction solution was filtered. 240 ° C of the obtained clear filtrate
Distillation under reduced pressure using a thin-film distillation apparatus with phenol resin 90
g was obtained. The softening point of the obtained phenol resin was 110 ° C., and the weight average molecular weight of the resin was 1,740 by gel permeation chromatography (hereinafter, referred to as GPC) analysis.

To a solution of this phenol resin (21.8 g) in N, N-dimethylacetamide (120 mL) were added potassium carbonate (21.2 g, 0.15 mol) and further t-butyl bromoacetate (27.1 g, 0.14 mol), and the mixture was stirred at 120 ° C. for 7 hours. did. The reaction mixture is then added to water 1.
The mixture was poured into 5 L, and extracted with ethyl acetate. After drying over magnesium sulfate, the extract was concentrated and purified by column chromatography to obtain 29 g of the desired product. This is a compound example [I-1]
(Molecular weight: 2200) was confirmed by NMR.

Synthesis Example 6 (Synthesis of acid-decomposable low molecular weight compound b) 20.3 g of the phenol resin obtained in Synthesis Example 5 was diethyl ether
Dissolved in 400 mL. 31.6 g of 3,4-dihydro-2H-pyran and a catalytic amount of hydrochloric acid were added to this solution under a nitrogen atmosphere, and the mixture was reacted under reflux for 24 hours. After completion of the reaction, a small amount of sodium hydroxide was added and the mixture was filtered. The solvent of the filtrate was distilled off, and the obtained product was purified by column chromatography and dried to obtain 14 g of the desired product. This is Compound Example [I-5] (molecular weight: 22
NMR was confirmed to be 50).

Synthesis Example 7 (Synthesis of acid-decomposable low molecular weight compound c) The procedure of Synthesis Example 5 was repeated except that β-naphthol was used instead of α-naphthol and 4-vinylcyclohexene was used instead of dicyclopentadiene. The reaction was carried out in the same manner as in 5, to obtain 67 g of a phenol resin. The softening point of the obtained phenol resin was 92 ° C., and the weight average molecular weight of the resin was 2,340 by gel permeation chromatography (hereinafter, referred to as GPC) analysis. This phenolic resin 21
g was dissolved in 400 mL of tetrahydrofuran. 14 g of potassium tert-butoxide was added to this solution under a nitrogen atmosphere, and the mixture was stirred at room temperature for 10 minutes, and then di-tert-butyl dicarbonate 29.8 g was added.
Was added. The reaction was allowed to proceed at room temperature for 3 hours, the reaction solution was poured into ice water, and the product was extracted with ethyl acetate. The ethyl acetate layer was further washed with water and dried, after which the solvent was distilled off. The obtained solid was recrystallized from diethyl ether and dried. It was confirmed by NMR that this was Compound Example [I-2] (molecular weight: 2,600).

Synthesis Example 8 (Synthesis of acid-decomposable low molecular weight compound d):
For Comparative Example 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.

[0082]

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Examples 1 to 4 and Comparative Examples 1 to 4 (Preparation of Photosensitive Resin Composition) In preparing the photosensitive resin component, the components shown in Table 1 were synthesized, that is, synthesized in Synthesis Examples 1 to 4. Polymers A, B, C, D,
Triphenylsulfonium triflate (PAG-1) as a photoacid generator, acid-decomposable low molecular weight compounds a, b, c, d synthesized in Synthesis Examples 5 to 8, nitrogen-containing basic compounds, surfactants, and solvents 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 when used are as follows. Polymers A, B, C, D 9.0 g Photoacid generator 0.10 g Acid-decomposable low molecular weight compounds a, b, c, d 1.0 g Nitrogen-containing basic compound 0.01 g Surfactant 0.003 g Solvent 55.12 g

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) Number of Development Defects-I The photosensitive resin composition was uniformly applied to a hexamethyldisilazane-treated silicon substrate by a spin coater, and was heated on a hot plate at 140 ° C. for 90 seconds. Heat drying was performed to form a 0.50 μm resist film. This resist film was exposed to ArF excimer laser light through a mask, and immediately after exposure, heated 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. KLA2112 manufactured by KLA Tencor Co., Ltd.
The number of development defects was measured by a machine (Threshold 12, Pixcel S
ize = 0.39). Developing Defect Number-II With respect to the developing defect number-I, the number of developing defects was measured in the same manner as for the heated, developed, rinsed and dried sample, 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 case of the 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 critical resolution at the exposure dose for reproducing a 0.20 μm mask pattern.

(Measurement of Dry Etching Resistance) The photosensitive compositions of the present invention of Examples in Table 1 were filtered with a Teflon filter having a pore size of 0.1 μm. The composition was uniformly coated 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. The etching rate of the obtained film with respect to CF ₄ / O ₂ (8/2) gas was measured using a reactive ion etching apparatus (CSE-1110) manufactured by ULVAC. The results are shown in Table 4 below.
Shown in

[0089]

[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

[0091]

[Table 2]

[0092]

[Table 3]

[0093]

[Table 4]

As is evident from the results in Table 2, the photosensitive resin compositions of the present invention showed very few development defects. On the other hand, Comparative Examples 1, 2, and 3, which did not use (C) a nitrogen-containing basic compound and / or (D) 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 resolution and profile. On the other hand, Comparative Examples 1 and 2, which did not contain the acid-decomposable dissolution inhibitor, were inferior in resolution and profile. Comparative Example 4 using an acid-decomposable dissolution inhibitor other than the present invention was inferior in resolution to the photosensitive resin composition of the present invention. As is clear from the results in Table 4, the photosensitive resin composition of the present invention is:
In each case, the dry etching resistance was excellent. On the other hand, Comparative Examples 1 and 2 containing no acid-decomposable dissolution inhibitor were inferior. Comparative Example 4 using an acid-decomposable dissolution inhibitor other than the present invention
Was slightly inferior in dry etching resistance to the photosensitive resin composition of the present invention. Therefore, the photosensitive resin compositions of the present invention all showed excellent results in any of the above evaluations.

[0095]

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 pattern profile especially when an ArF excimer laser beam is used as an exposure light source. Indicates the resolving power. Moreover, since it has excellent dry etching resistance, it can be effectively used for forming a fine pattern required for manufacturing a semiconductor device.

Claims (2)

[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 low molecular acid having a partial structure represented by the general formula (I), having a molecular weight of 3,000 or less, having a group decomposable by the action of an acid, and increasing alkali solubility by the action of an acid; Decomposable compounds, (C) compounds that generate acid by actinic rays
A positive photosensitive resin composition comprising (D) a nitrogen-containing basic compound and (E) a fluorine-based and / or silicon-based surfactant. Embedded image In the general formula (I), Z is Or a group obtained by combining one or more of these groups. R ₁
Represents a group decomposed by the action of an acid. R ₂ represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group. n and m each represent 1 or 2. 2. The positive photosensitive resin composition according to claim 1, wherein the actinic ray is far ultraviolet light having a wavelength of 220 nm or less.