JP2002072481A - Positive type photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive type photosensitive resin composition which does not cause the problem of development defects and has excellent line edge roughness, resist shape, sensitivity and resolving power when deep UV, particularly ArF excimer laser light, is used as the light source for exposure. SOLUTION: The positive type photosensitive resin composition contains (A) a polymer having a cycloaliphatic hydrocarbon skeleton and made alkali- soluble by decomposition under the action of an acid, (B) a compound which generates the acid when irradiated with active light or radiation, (C) a 4-20C aliphatic (di)carboxylic acid having at least 4 fluorine atoms in one molecule and a molecular weight of <=1,000, (D) a nitrogen-containing basic compound and (E) 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 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.
It is a positive photosensitive resin composition suitably 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.

[0003] For this reason, the demand for photolithography technology for forming fine patterns has become increasingly 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, a DRA with a degree of integration of up to 64 Mbits
To date, the production of M has been based on the i-line (365 n
m) has been used as a light source. 256 Mbit DR
In the mass production process of AM, a KrF excimer laser (248 nm) has been put to practical use as an exposure light source instead of i-line, and a shorter wavelength light source has been studied for the purpose of manufacturing a DRAM having an integration degree of 1 Gbit or more. ArF excimer laser (193 nm), F ₂ excimer laser (1
It is considered that the use of X-rays and electron beams is effective (Takashi Ueno et al., "Short Wavelength Photoresist Material-UL
Microfabrication for SI-", Bunshin Publishing, 1988
Year).

In particular, an ArF excimer laser is positioned as a next-generation exposure technique, and development of a resist having high sensitivity, high resolution, and excellent dry etching resistance for ArF excimer laser exposure is desired.

As a conventional resist material for i-line and KrF excimer laser exposure, a resist containing an aromatic polymer is widely used in order to obtain high dry etching resistance. For example, a novolak resin resist or polyvinyl phenol is used. A 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 the transparency of the resist 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, it is found that a resist containing an alicyclic hydrocarbon group instead of an aromatic ring exhibits the same dry etching resistance as an aromatic group, and has a small absorption at 193 nm, Proc. SPIE, 1672, 66 ( 1992), and the use of this polymer has been energetically studied in recent years.

Originally, attempts to apply a polymer containing an alicyclic hydrocarbon group to a resist have been made for a long time. For example, JP-A-60-195542, JP-A-1-174743, JP-A-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 by an acid-decomposable group, and is disclosed in JP-A-4-39665 and 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-7-25
No. 2324 and JP-A-9-221526 disclose 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] .
1.02.6] decane dimethylene group, tricyclo [5.2.1.0]
2.6] decanediyl, norbornanediyl, norbornanedimethyl, adamantanediyl,
JP-A-7-199467 discloses a compound in which a tricyclodecanyl group, a dicyclopentenyl group, a dicyclopentenyloxyethyl group, a norbornyl group, and a cyclohexyl group are linked to a side chain of a polymer.

Japanese Patent Application Laid-Open No. 9-325498 discloses a polymer having a cyclohexane and isobornyl skeleton in the main chain. Further, Japanese Patent Application Laid-Open Nos. 9-230595, 9-244247, 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.

Apart from the resist performance as described above, the generation of defects (voids) due to the lithography process is one of the major factors for lowering the yield, and has recently become a particularly important problem.

For example, it is said that development defects are generally caused by bubbles at the time of liquid replenishment and microbubbles due to dissolved gas in the developer, which cause defects (Hirano et al .; The 42nd JSAP. 27p-ZW-9 (1996)), as the wafer becomes larger in diameter and the discharge amount of the developer increases, it is more important to take measures against bubbles. As a measure against these bubbles, improvement on the equipment to discharge the developing solution softly
(See Science Forum Publishing Co., ULSI Manufacturing Contamination Control Technology, 41 (1992)), and attempts to reduce bubbles by adding a degassing mechanism for dissolved gases have not been made to a satisfactory level.

In order to reduce development defects, a nonionic surfactant is added to the developing solution to improve the wettability of the developing solution and promote bubble desorption. Attempts have been made to improve affinity by optimizing the type and amount of activator (Tasushima et al .; No. 42
Annual Meeting of the Japan Society of Applied Physics, 27p-ZW-7 (1996)).

However, in order to reduce development defects of a chemically amplified resist for ArF using a non-aromatic polymer, these methods are not only sufficient, but may even have an adverse effect. Up to now, there has been no guideline for improvement on how to reduce development defects. In addition, if the affinity of the resist is improved to reduce development defects, the residual film ratio and the profile tend to deteriorate, and it is extremely difficult to achieve both.

Furthermore, 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.Ph
otopolym.Sci.Tech.Vol.8.No.4,561 (1995), Jpn.J.App
As reported in l.Phys. 33, 7023 (1994), etc., as the exposure time from exposure to heat treatment (PEB) becomes longer,
The generated acid is diffused, and the acid on the surface of the resist is deactivated due to basic impurities in the atmosphere, resulting in changes in sensitivity, profile and line width of the resist pattern after development. Was.

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-5-249662, and JP-A-5-127369. No., JP-A-5-289322, JP-A-5-249683
No., JP-A-5-289340, JP-A-5-232706, JP-A-5-25
No. 7282, JP-A-6-242605, JP-A-6-242606, JP-A-6-242606
6-266100, JP-A-6-266110, JP-A-6-317902, JP-A-7-120929, JP-A7-146-558, JP-A-7-319163
No., JP-A-7-508840, JP-A-7-333844, JP-A-7-21
No. 9217, JP-A 7-92678, JP-A 7-28247, JP-A 8-
No. 22120, JP-A-8-110638, JP-A-8-123030, JP-A-9-274312, JP-A-9-66871, JP-A-9-292708,
JP-A-9-325496, JP-T-Hei 7-508840, USP5525453,
Many of the basic compounds described in US Pat. No. 5,629,134 and US Pat. No. 5,667,938 have been disclosed and are well known.

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 a non-aromatic polymer, although it is effective against a change in sensitivity or a change in profile or line width of a resist pattern after development, the result is that the development defect is extremely inferior. Was.

On the other hand, for the purpose of improving the sensitivity and the shape of the resist pattern, it is known to add a carboxylic acid compound to a chemically amplified resist composition for excimer laser light for KrF as disclosed in JP-A-7-92679 and JP-A-5-181279.
No. 6,086,045. Japanese Patent Application Laid-Open No. 9-6001 discloses that an amine and a carboxylic acid compound are added,
It has been known to have excellent resolution and to improve the stability over time between exposure and PEB.

However, a strongly basic and low boiling point amine (eg, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine) and an aromatic carboxylic acid (eg, disclosed in Japanese Patent Application Laid-Open No. 9-6001) are preferred. When salicylic acid, nitrobenzoic acid, and phthalic acid) are added to a chemically amplified resist for ArF using a non-aromatic polymer having a cyclic aliphatic hydrocarbon skeleton, KrF using a non-aromatic polymer is surely added. As in the case of the chemically amplified resist composition for excimer laser light for use, although the effect on the storage stability with time between exposure and PEB is seen, the development defects are extremely poor, and countermeasures are desired. Was. In addition, amines having a low boiling point tend to evaporate during PEB, so that the effect of adding amines is not exhibited at all, or amines used in semiconductor manufacturing such as hot plates are contaminated with amines. Had a problem.

Japanese Patent Application Laid-Open No. 2000-66402 discloses an ArF resist in which a benzenecarboxylic acid derivative is added to an alicyclic acrylic resin, and a device for improving the adhesion to a substrate and the dry etching resistance has been devised. I have. However, there is a problem that the profile becomes tapered when these carboxylic acids are added.

In the conventional resist composition as described above,
Further, the performance of line edge roughness is insufficient and needs to be improved. Line edge roughness means that the edge of the interface between the resist line pattern and the substrate fluctuates irregularly in the direction perpendicular to the line direction due to the characteristics of the resist. It says that it 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 less than quarter micron,
There is an increasing demand for improvement in line edge roughness, but no guideline for improvement has been disclosed so far.

[0023]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a method for using a deep ultraviolet ray, particularly an ArF excimer laser beam, as an exposure light source to obtain a line edge roughness, a resist shape,
An object of the present invention is to provide a positive photosensitive resin composition which is excellent in sensitivity and resolution and does not cause a problem of development defects.

[0024]

Means for Solving the Problems The present inventors have intensively studied a positive photosensitive resin composition which does not cause a problem of development defects. For example, polymers having a cyclic aliphatic hydrocarbon skeleton disclosed in JP-A-11-338150 and JP-A-2000-47385, which are decomposed by the action of an acid and become alkali-soluble, irradiation with actinic rays or radiation , A compound having a molecular weight of 1,000 or less, a cyclic aliphatic organic carboxylic acid, an organic carboxylic acid having a naphthalene skeleton, at least one carboxylic acid derivative selected from carboxylic anhydrides, a nitrogen-containing basic compound, and a fluorine-based compound And / or the positive photosensitive resin composition containing a silicon-based surfactant could solve the problem of development defects.

The present inventors have further studied the constituent materials of the resist composition in the positive-type chemical amplification system.
(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; (C) a molecule in one molecule An aliphatic carboxylic acid or aliphatic dicarboxylic acid having at least 4 fluorine atoms, having 4 to 20 carbon atoms and a molecular weight of 1000 or less, (D) a nitrogen-containing basic compound,
And (E) a positive photosensitive resin composition which is excellent in resist shape, sensitivity, resolution, and line edge roughness and does not cause a problem of development defect can be obtained by combining a fluorine-based and / or silicon-based surfactant. The inventors have found that the present invention has been achieved.

That is, the present invention is an invention having the following constitutions (1) to (3) and achieves the above object. (1) (A) a polymer having a cyclic aliphatic hydrocarbon skeleton and decomposed by the action of an acid to become alkali-soluble, (B) a compound capable of generating an acid by irradiation with actinic rays or radiation, and (C) An aliphatic carboxylic acid or an aliphatic dicarboxylic acid having at least 4 fluorine atoms in one molecule, having 4 to 20 carbon atoms and a molecular weight of 1000 or less, (D) a nitrogen-containing basic compound, and (E) a fluorine-based compound And / or a silicon-based surfactant.

(2) 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 the above (1), wherein (3) The positive photosensitive resin composition as described in any of (1) and (2) above, wherein the actinic ray is exposed to far ultraviolet light having a wavelength of 220 nm or less.

[0028]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the compounds used in the present invention will be described in detail. First, as the polymer (A) having a cyclic aliphatic hydrocarbon skeleton structure and decomposed by the action of an acid to become alkali-soluble in the present invention, 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) Also called)
Or a polymer having an acid-decomposable group and a repeating unit represented by the following (b-1) to (b-7) having a cyclic aliphatic hydrocarbon skeleton in a side chain. . Incidentally, a polymer having no benzene ring is preferable from the viewpoint of transparency to ArF light.

Further, the following (a-1) to (a-15),
Structural units having a cyclic aliphatic hydrocarbon skeleton structure, such as the structural units represented by (b-1) to (b-7), are indispensable for the polymer according to the present invention. ) To (c-
The structural unit represented by 4) may be included as a copolymer component.

[0030]

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[0031]

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[0032]

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The above (a-1) to (a-15), (b-
In the structural units represented by 1) to (b-7), A, B
Each independently represents a hydrogen atom, a hydroxyl group, a carboxyl group, an alkoxycarbonyl group, a substituted or unsubstituted alkyl group, alkoxy group or alkenyl group having 1 to 10 carbon atoms, wherein A and B are bonded to each other to form a ring; May be formed. X,
Y represents a group which is independently decomposed by the action of an acid.

The formulas (b-1) to (b-7), (c-
In 1) to (c-4), R represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms such as a methyl group. 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.

As the alkyl group having 1 to 10 carbon atoms,
Examples thereof include a linear, branched or cyclic alkyl group which may be substituted. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a t-butyl group, a cyclopentyl group, and a cyclohexyl group. Group, hydroxymethyl group, hydroxyethyl group and the like.

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.

The ring formed by combining A and B includes:
Bonded A and B -C (= O) -O- C (= O) -, -C (= O) -NH-C (= O) -, -CH 2 -C (= O) -O —C (＝ O) —, and the like to form a ring.

The group decomposed by the action of an acid includes-
A (CH ₂ ) n-COORa group or — (CH ₂ ) n—O
CORb group. Here, Ra has 2 to 2 carbon atoms.
Represents 0 hydrocarbon groups, and the hydrocarbon groups include t
-Butyl group, norbornyl group, cyclodecanyl group and the like. Rb represents an alkoxyethyl group such as a tetrahydrofuranyl group, a tetrahydropyranyl group, an ethoxyethyl group, an isopropylethyl group, a lactone group, or a cyclohexyloxyethyl group. 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; Macrom.
ol.Chem., 188, 2585 (1987), JP-A-51-31800,
It can be easily polymerized by the synthesis method described in JP-A 1-197460, JP-A-2-42094, EP 0789278 and the like. Examples of the metathesis catalyst used herein include, for example, Polymer Synthesis and Reaction (1), edited by The Society of Polymer Science, Kyoritsu Shuppan pp. 375-381 (1992), compounds described in JP-A-49-77999, 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 and a third component Can be mentioned.

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 the 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.

The third component for improving the polymerization activity of the catalyst includes water, hydrogen peroxide, an oxygen-containing organic compound,
A nitrogen-containing organic compound, a halogen-containing organic compound, a phosphorus-containing organic compound, a sulfur-containing organic compound, a metal-containing organic compound, and a tungsten or molybdenum compound 1
It is used in a proportion of 5 mol or less per 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.degree. 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.

As the heterogeneous catalyst, for example, palladium,
Examples include solid catalysts in which a noble metal catalyst such as platinum, nickel, ruthenium, and rhodium is supported on a carrier such as carbon, silica, alumina, and titania. Examples of the homogeneous catalyst include, for example, nickel / triethylaluminum naphthenate, nickel acetylacetonate / triethylaluminum, cobalt / n-butyllithium octoate, titanocene dichloride / diethylaluminum monochloride, rhodium acetate, and chlorotris (triphenylphosphine) rhodium. Rhodium catalyst can be mentioned.

Among these catalysts, heterogeneous catalysts are advantageous because they have high reaction activity, can easily remove 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 prepared, 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 and dicumyl peroxide. 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.
% By weight. The polymerization temperature can be varied over a wide range, usually from room temperature to 250 ° C, preferably from 40 to 200 ° C,
More preferably, the polymerization is carried out in the range of 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 carry out distillation and purification under reduced pressure 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.

In the polymer (A), the content of the structural unit having a cyclic aliphatic skeleton is preferably at least 10 mol%, more preferably at least 20 mol%, even more preferably at least 30 mol% of the total structural units. is there.

In the polymer (A), the content of the structural unit having an acid-decomposable group is from 10 to 90 mol% of all the structural units.
, Preferably 15 to 85 mol%, more preferably 20 to 80 mol%.

In the polymer used in the present invention, (c)
The content of other copolymer components such as the units represented by -1) to (c-4) is preferably 3 to 60 mol%, more preferably 5 to 55 mol%, based on 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.

The weight average molecular weight and molecular weight distribution (Mw / Mn) of the polymerization (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 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 other polymers as required, 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 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.

Next, the compound (B) contained in the positive photosensitive resin composition of the present invention, which decomposes upon irradiation with actinic rays to generate an acid (hereinafter also referred to as "(B) photoacid generator") ) Will be described.

Examples of the photoacid generator (B) used in the present invention include photoinitiators for photocationic polymerization, photoinitiators for photoradical polymerization, photodecolorants for dyes, photochromic agents, or UV light, deep UV light, KrF excimer laser light, ArF excimer laser light, electron beam, X-ray, molecular beam, ion beam, etc. A well-known photo-acid generator and its mixture are appropriately selected for micro-photoresist. 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, No. 15, 3055 (1978) and -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 triphenyliodonium hexafluoroantimonate. Examples thereof include sulfonium naphthalene sulfonate, triphenylsulfonyumcamphorsulfonium, (4-methoxyphenyl) phenyliodonium trifluoromethanesulfonate, and bis (t-butylphenyl) iodonium trifluoromethanesulfonate.

Also, 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.,
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 (B) which decomposes upon irradiation with actinic rays to generate an acid is usually 0.00% based on the total weight (solid content) of the positive photosensitive resin composition.
It is 1 to 40% by weight, preferably 0.01 to 20% by weight, more preferably 0.1 to 5% by weight. (B) 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 deterioration and the process margin, especially the bake margin become narrow. Not preferred.

Next, (C) an aliphatic carboxylic acid having at least 4 fluorine atoms in one molecule, having 4 to 20 carbon atoms and a molecular weight of 1000 or less contained in one molecule of the positive photosensitive resin composition of the present invention. The acid and the aliphatic dicarboxylic acid will be described.

As the aliphatic carboxylic acid having at least 4 fluorine atoms in one molecule, having 4 to 20 carbon atoms and having a molecular weight of 1000 or less, preferably used is the following general formula (I): Or an aliphatic carboxylic acid represented by the general formula (II).

R ¹ —COOH (I) R ² —O—R ³ —COOH (II)

In the general formula (I), R ¹ has at least four fluorine atoms which may be substituted,
Represents a fluoroalkyl group having 3 to 19 carbon atoms. In the general formula (II), R ² represents an optionally substituted alkyl group or an optionally substituted fluoroalkyl group. R ³ represents an optionally substituted alkylene group or an optionally substituted fluoroalkylene group. R2 and R3 have at least 4 fluorine atoms in total and 3 to 19 carbon atoms.

Examples of the fluoroalkyl group as R ¹ in the general formula (I), the alkyl group and the fluoroalkyl group as R ² in the general formula (II), the alkylene group and the fluoroalkylene group as R ³ are as follows. And compounds (C-1) to (C-18) of Examples.

Specific examples of the aliphatic carboxylic acid having at least 4 fluorine atoms in one molecule, having 4 to 20 carbon atoms, and having a molecular weight of 1000 or less, used in the present invention include:
The following (C-1) to (C-18) are mentioned.

[0076]

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[0077]

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[0078]

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The molecule of the present invention has at least 4 fluorine atoms in one molecule, has 4 to 20 carbon atoms and has a molecular weight of 1000
The following aliphatic carboxylic acids can be used alone or in combination of two or more. Several types having different carbon numbers may be combined. As these compounds, reagents can be used as they are, or commercially available products (for example, Krytox, manufactured by DuPont) can also be used.

The aliphatic dicarboxylic acid having at least four fluorine atoms in one molecule, having 4 to 20 carbon atoms and having a molecular weight of 1,000 or less used in the present invention includes, for example, those represented by the following general formula (III): The aliphatic dicarboxylic acids represented may be mentioned.

HOOC-R ⁴ —COOH (III)

In the general formula (III), R ⁴ represents an optionally substituted fluoroalkylene group having at least 4 fluorine atoms and having 2 to 18 carbon atoms.

Specific examples of the aliphatic dicarboxylic acid having at least 4 fluorine atoms in one molecule, having 4 to 20 carbon atoms and having a molecular weight of 1,000 or less used in the present invention include the following (C-19) (C-23).

[0084]

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The molecule of the present invention has at least 4 fluorine atoms in one molecule, has 4 to 20 carbon atoms and has a molecular weight of 1000
The following aliphatic dicarboxylic acids can be used alone or in combination of two or more.

The positive photosensitive resin composition of the present invention contains (C)
By blending an aliphatic carboxylic acid or aliphatic dicarboxylic acid having at least 4 fluorine atoms in one molecule, having 4 to 20 carbon atoms and a molecular weight of 1000 or less, development defects are significantly reduced, and line edge An effect that roughness is improved is exhibited.

(C) The molecular weight of the aliphatic carboxylic acid or aliphatic dicarboxylic acid is 1,000 or less, and
Is preferable, and 150-700 is more preferable. When the molecular weight exceeds 1,000, the above effects cannot be exhibited.

The amount of the aliphatic carboxylic acid and aliphatic dicarboxylic acid (C) is usually 0.001 to 15% by weight, preferably 0.1 to 15% by weight, based on the positive photosensitive resin composition (solid content) of the present invention. 01 to 10% by weight. If the amount is less than 0.001% by weight, the effect of addition cannot be sufficiently obtained. On the other hand, if it exceeds 15% by weight, the residual film ratio decreases, which is not preferable.

Further, as long as the effects of the present invention are not impaired,
A carboxylic acid other than the present invention, for example, an aliphatic carboxylic acid or an aromatic carboxylic acid containing no fluorine atom may be mixed. However, addition of a polymer having a carboxyl group, for example, an oligomer such as a styrene-acrylic acid copolymer, a styrene-methacrylic acid copolymer, or a carboxyl group-substituted norbornene polymer is not preferable because it deteriorates the resist profile.

Next, the nitrogen-containing basic compound (D) preferably used in the positive photosensitive resin composition of the present invention will be described. As the nitrogen-containing basic compound, an organic amine, a basic ammonium salt, a sulfonium salt, or the like is used, and any compound may be used as long as it does not deteriorate sublimation or resist performance. If the amine is liquid at room temperature, the one having a boiling point of 150 ° C. or higher is preferable. If the amine is a solid amine, the melting point is 100 ° C.
The above are preferred.

For example, JP-A-63-149640, JP-A-5-24966
No. 2, JP-A-5-127369, JP-A-5-289322, JP-A 5-2
No. 49683, JP-A-5-289340, JP-A-5-232706, JP-A-5-257282, JP-A-6-242605, JP-A-6-242606,
JP-A-6-266100, JP-A-6-266110, JP-A-6-317902
No., JP-A-7-120929, JP-A-7-146558, JP-A-7-31
No. 9163, JP-A-7-508840, JP-A-7-333844, JP-A
7-219217, JP-A-7-92678, JP-A-7-28247, JP-A-8-22120, JP-A-8-110638, JP-A-8-123030,
JP-A-9-274312, JP-A-9-66871, JP-A-9-292708
No., JP-A-9-325496, JP-T-Hei 7-508840, USP5525453
Basic compounds described in US Pat. No. 5,629,134, 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.

The basic compound (D) can be used alone or in combination of two or more.

In the present invention, the weight ratio of the polymer (A) to the nitrogen-containing basic compound (D) in the composition ((A) / (D)) is in the range of 500 to 20,000. And more preferably 1000 to 150
00 range. By setting this ratio, in addition to reducing development defects, developability and line width reproducibility are improved, and uniformity of the coating film thickness is improved.

The content of (D) the nitrogen-containing basic compound is usually 0.03 to the positive photosensitive resin composition (solid content).
It is from 0.01 to 10% by weight, preferably from 0.01 to 5% by weight. If the amount is less than 0.001% by weight, the effect cannot be sufficiently obtained.
On the other hand, if it exceeds 10% by weight, the sensitivity tends to decrease and the developability of the non-exposed area tends to deteriorate significantly.

Next, (E) a fluorine-based surfactant and a silicon-based surfactant preferably contained in the positive photosensitive resin composition of the present invention will be described. The positive photosensitive resin composition of the present invention can contain either or both of a fluorine-based surfactant and a silicon-based surfactant.

Examples of these surfactants (E) include, for example, JP-A-61-226745, JP-A-61-226746, and JP-A-62-366.
No. 57, JP 62-36663, JP 62-170950, JP 6
3-34540, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, JP-A-2000-122289, U.S. Patent 5,405,720, U.S. Patent 5,360,692, US Patent 552988
No. 1, U.S. Patent No. 5,296,330, U.S. Patent No. 5,436,098, U.S. Patent No. 5,576,143, U.S. Patent No. 5,945,511, and surfactants described in U.S. Patent No. 5,824,451, and the following commercially available surfactants can be used as they are. it can.

Examples of commercially available surfactants that can be used include, for example, F-Top EF301 and EF303 (manufactured by Shin-Akita Chemical Co., Ltd.), Florado FC430 and 431 (manufactured by Sumitomo 3M Limited), Megafac F171, F173, and F176. F189, R08 (manufactured by Dainippon Ink and Chemicals, Inc.), Surflon S-382, SC101, 102, 103, 1
04, 105, 106 (manufactured by Asahi Glass Co., Ltd.), Troysol S-36
6 (manufactured by Troy Chemical Co., Ltd.) or a silicon-based surfactant. In addition, polysiloxane polymer KP-341 (manufactured by 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 particularly excellent in improving development defects. The amount of the surfactant (E) is usually 0.01% by weight to 2% by weight, preferably 0.01% by weight to 1% by weight, based on the solid content of the composition of the present invention. These surfactants can be used alone or in combination of two or more.

It is not clear why the positive photosensitive resin composition of the present invention is specifically superior against the above-mentioned development defects, but (A) it has a cyclic aliphatic hydrocarbon skeleton and A polymer which is decomposed by action to become alkali-soluble, (B) a compound which generates an acid upon irradiation with actinic rays or radiation, and (C) which has at least 4 fluorine atoms in one molecule and has 4 to 4 carbon atoms 20 and molecular weight 100
0 or less aliphatic carboxylic acid, or aliphatic dicarboxylic acid,
Furthermore, it is considered that the expression occurred by combining (D) a nitrogen-containing basic compound and a specific (E) surfactant. For example, in the case of a combination of (D) a nitrogen-containing basic compound and a surfactant other than the present invention, for example, a combination of a nonionic surfactant and the like, development defects are not eliminated.
Further, when the aliphatic carboxylic acid or aliphatic dicarboxylic acid (C) of the present invention is replaced with an aliphatic carboxylic acid having no fluorine atom, development defects are not sufficiently reduced and the line edge roughness can be satisfied. It cannot be improved to the level.

The positive photosensitive resin composition of the present invention has a molecular weight of 2,000 or less, if necessary, has a group which can be decomposed by the action of an acid, and the alkali solubility is increased by the action of an acid. A low molecular acid decomposable compound may be included.

For example, Proc. SPIE, 2724, 355 (1996), JP-A-8-15865, USP5310619, USP-5372912, J. Photo
polym.Sci., Tech., Vol. 10, No. 3, 511 (1997)), containing an acid-decomposable group, a cholic acid derivative, a dehydrocholic acid derivative, a deoxycholic acid derivative, a lithocholic acid derivative, ursocol Alicyclic compounds such as acid derivatives and abietic acid derivatives, and aromatic compounds such as naphthalene derivatives containing an acid-decomposable group can be used as the low-molecular acid-decomposable compounds.

Further, low-molecular acid-decomposable dissolution inhibiting compounds described in JP-A-6-51519 can also be used in an addition range which does not deteriorate the transmittance at 220 nm.
A 2-naphthoquinonediazide compound can also be used.

When the low-molecular acid-decomposable dissolution inhibiting compound is used in the positive photosensitive resin composition of the present invention, its content is based on the total weight (solid content) of the positive photosensitive resin composition. Usually, it is used in the range of 1 to 50% by weight, preferably 3 to 40% by weight, more preferably 5 to 30% by weight. The addition of these low-molecular acid-decomposable dissolution inhibiting compounds not only further improves the development defects, but also improves the dry etching resistance.

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

Examples of the compound which promotes 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
Compounds having at least one carboxylic acid anhydride, a carboxylic anhydride, a sulfonamide compound, a sulfonylimide compound, etc.
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 which 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 coatability of the positive photosensitive resin composition of the present invention and improving the developability, a nonionic surfactant can be used in combination. As nonionic surfactants that can be used in combination, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, polyoxyethylene sorbitan mono Stearate,
Sorbitan monolaurate and the like.

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.

The positive-type photosensitive resin composition of the present invention is prepared as a solution by dissolving the above components in a solvent that dissolves the above components, and usually filtering through a filter having a pore size of about 0.05 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. These solvents are used alone or in combination.

The choice of the solvent is important because it affects the solubility in the positive 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, in the positive photosensitive resin composition of the present invention, it is preferable to reduce metal impurities such as metals and impurity components such as chloride ions to 100 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.

The positive photosensitive resin composition of the present invention is applied onto a substrate by a suitable application method such as a spinner or a coater, and prebaked (pre-exposure heating), and exposed to light having a wavelength of 220 nm or less through a predetermined mask. Exposure, PEB (post-exposure bake), and development can provide a good resist pattern.

The substrate used here may be any substrate commonly used in semiconductor devices and other manufacturing equipment, and examples 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) and the like can be mentioned.

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 about 60
It is preferred to pre-bake at a temperature of １６０160 ° C. for about 30 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.

[0117] 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 carried out 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 positive photosensitive resin composition of the present invention include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate and aqueous ammonia, and ethylamine and n-propylamine. Primary amines, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide (TMAH ), Quaternary ammonium salts such as tetraethylammonium hydroxide (TEAH), trimethylhydroxymethylammonium hydroxide, triethylhydroxymethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, pyrrole Use of an alkaline aqueous solution such as cyclic amines such as piperidine, 1,8-diazabicyclo- [5.4.0] -7-undecene, and 1,5-diazabicyclo- [4.3.0] -5-nonane. Can be.

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.

[0121]

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) 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)

[0123]

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Synthesis Example 2 (Synthesis of Polymer B) A copolymer of adamantyl methacrylate and t-butyl acrylate (repeated structural units are described below) was prepared by the method described in JP-A-7-2.
The compound was synthesized according to the method described in No. 34511, the first example.

[0125]

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Synthesis Example 3 (Synthesis of acid-decomposable low molecular weight compound a) A mixture of 122.7 g (0.3 mol) of cholic acid and 120 ml of thionyl chloride was refluxed for 1 hour. Excess thionyl chloride was removed, the resulting solid was dissolved in 150 ml of tetrahydrofuran, 40 g (0.35 mol) of potassium tert-bucitoxide was gradually added, and the reaction mixture was added to 6 parts.
After refluxing for an hour, the mixture was cooled and poured into water. The resulting solid was collected by filtration, washed with water and dried under reduced pressure. The crude product was recrystallized from n-hexane to give cholic acid with a yield of 70%.
As a result, t-butyl (the following formula) was obtained.

[0127]

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Examples 1 to 5 and Comparative Examples 1 to 5 (Preparation of Positive-Type Photosensitive Resin Composition) In preparing the photosensitive resin component, the following components were synthesized, namely, synthesized in Synthesis Examples 1 and 2. Polymers A and B, triphenylsulfonium triflate (PAG-1) as photoacid generator, acid-decomposable low-molecular compound (compound a) synthesized in Synthesis Example 3, aliphatic carboxylic acid and aliphatic dicarboxylic acid of the present invention Each component of an acid, a nitrogen-containing basic compound, a surfactant, and a solvent was used. The respective components were mixed so that the solid content concentration became about 12% by weight, and filtered with a 0.1 μm microfilter to prepare a positive photosensitive resin composition.

(Image Evaluation Method) A positive type photosensitive resin composition was prepared using a spin coater and manufactured by Brewer Science.
DUV-30 was applied on a 6-inch silicon wafer coated with 500 nm, and heated and dried on a hot plate at 120 ° C. for 90 seconds to form a 0.40 μm resist film. This resist film was pattern-exposed with ArF excimer laser light (NA = 0.60) through a mask, and immediately after exposure, heated on a hot plate at 110 ° C. for 90 seconds, immediately after which 2.38% by weight of tetramethylammonium hydroxide was exposed. After developing with an aqueous solution, followed by rinsing with pure water,
Spin drying was performed to obtain a resist pattern.

The sensitivity was shown by an exposure amount for reproducing a mask size of 0.18 μm. The resolving power indicates a limit resolving power at a minimum exposure amount for reproducing a mask size of 0.18 μm. As for the profile, a line pattern of 0.18 μm was observed with a scanning electron microscope. Those having a rectangular shape are represented by Δ, and those having a tapered shape are represented by X. A slightly tapered shape is represented by a triangle. Line edge roughness is
In the range of 5 μm in the longitudinal direction edge of the 0.18 μm line pattern obtained by the minimum exposure amount that reproduces the 0.18 μm line pattern on the mask, the distance from the reference line where the edge should be, to Hitachi, Ltd. S-
Measured 50 points according to 8840, found standard deviation,
3σ was calculated. The smaller the value, the better the performance.

The development defects were evaluated as follows. (1) Number of Development Defects-I An antireflection film (DUV-30 manufactured by BrewerScience) was formed on a silicon substrate treated with hexamethyldisilazane by 60 nm.
And cured at 190 ° C. On this antireflection film, a positive photosensitive resin composition was uniformly applied by a spin coater, and heated and dried on a hot plate at 120 ° C. for 90 seconds to form a 0.40 μm resist film. This resist film was exposed to ArF excimer laser light through a mask, and immediately after exposure, heated at 110 ° C. for 90 seconds on a hot plate. Furthermore, 2.38% by weight
Developed with a tetramethylammonium hydroxide aqueous solution at a concentration of 23 ° C. for 60 seconds, rinsed with pure water for 30 seconds, and dried. The number of development defects of the sample on which the contact hole pattern was formed was measured using a KLA2112 machine (manufactured by KLA Tencor Co., Ltd.) (Threshold 12, Pixcel Size = 0.39).

(2) Number of Developing Defects-II In (1) Number of Developing Defects-I, the number of development defects was measured in the same manner as for the sample heated, developed, rinsed and dried except that no exposure was performed.

The symbols used in the following examples and comparative examples are as follows. C-1, C-3, C-11, C-1
8, C-19 is the carboxylic acid compound of the present invention exemplified above. C′-1, C′-2 and C′-3 are comparative compounds described below.

[0134]

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PAG-1: triphenylsulfonium triflate N-1: 1,5-diazabicyclo [4.3.0] -5
Nonene N-2: 1.8-diazabicyclo [5.4.0] -7-
Undecene

W-1: Megafac F-176 (a fluorosurfactant manufactured by Dainippon Ink and Chemicals, Inc.) W-2: Megafac R-08 (fluorine and silicon manufactured by Dainippon Ink and Chemicals, Inc.) W-3: Polysiloxane polymer KP-341 (Silicon surfactant manufactured by Shin-Etsu Chemical Co., Ltd.) W-4: Polyoxyethylene nonyl phenyl ether

S-1: Propylene glycol monomethyl ether acetate S-2: Propylene glycol monomethyl ether S-3: Ethyl lactate S-4: Ethoxyethyl propionate S-5: Gamma-butyrolactone

Composition of Positive Photosensitive Resin Composition of Example 1: Polymer A 98.38 parts by weight Photoacid generator (PAG-1) 1.0 Carboxylic acid (C-1) of the present invention 0.50 Nitrogen-containing basic compound ( N-1) 0.10 Surfactant (W-1) 0.02 Solvent (S-1) 733.33

Composition of Positive Photosensitive Resin Composition of Example 2: Polymer A 91.88 parts by weight Photoacid generator (PAG-1) 2.0 Carboxylic acid (C-3) of the present invention 1.0 Nitrogen-containing basic compound ( N-2) 0.10 Acid-decomposable low molecular weight compound a 5.0 Surfactant (W-2) 0.02 Solvent (S-1) 513.33 (S-2) 220.00

Composition of Positive Photosensitive Resin Composition of Example 3: Polymer A 90.88 parts by weight Photoacid generator (PAG-1) 2.0 Carboxylic acid (C-11) of the present invention 2.0 Nitrogen-containing basic compound ( N-1) 0.10 Acid-decomposable low molecular weight compound a 5.0 Surfactant (W-3) 0.02 Solvent (S-3) 660.00 (S-5) 73.33

Composition of Positive Photosensitive Resin Composition of Example 4: Polymer B 93.88 parts by weight Photoacid generator (PAG-1) 1.0 Carboxylic acid (C-18) of the present invention 5.0 Nitrogen-containing basic compound ( N-1) 0.10 Surfactant (W-1) 0.02 Solvent (S-1) 733.33

Composition of Positive Photosensitive Resin Composition of Example 5: Polymer A 87.88 parts by weight Photoacid generator (PAG-1) 1.5 Carboxylic acid (C-19) of the present invention 0.5 Nitrogen-containing basic compound ( N-1) 0.10 Acid-decomposable low molecular weight compound a 10 Surfactant (W-3) 0.02 Solvent (S-3) 513.33 (S-4) 220.00

Composition of Positive Photosensitive Resin Composition of Comparative Example 1: Polymer A 98.88 parts by weight Photoacid generator (PAG-1) 1.0 Nitrogen-containing basic compound (N-1) 0.10 Surfactant (W- 1) 0.02 solvent (S-1) 733.33

Composition of Positive Photosensitive Resin Composition of Comparative Example 2: Polymer A 91.70 parts by weight Photoacid generator (PAG-1) 2.0 Carboxylic acid (C-3) of the present invention 1.0 Nitrogen-containing basic compound ( N-2) 0.10 Acid-decomposable low molecular weight compound a 5.0 Surfactant (W-4) 0.20 Solvent (S-1) 513.33 (S-2) 220.00

Composition of Positive Photosensitive Resin Composition of Comparative Example 3: Polymer A 90.88 parts by weight Photoacid generator (PAG-1) 2.0 Carboxylic acid (C′-1) 2.0 Nitrogen-containing basic compound (N- 1) 0.10 Acid-decomposable low molecular weight compound a 5.0 Surfactant (W-3) 0.02 Solvent (S-3) 660.00 (S-5) 73.33

Composition of the positive photosensitive resin composition of Comparative Example 4: Polymer B 93.88 parts by weight Photoacid generator (PAG-1) 1.0 Carboxylic acid (C′-2) 5.0 Nitrogen-containing basic compound (N- 1) 0.10 Surfactant (W-1) 0.02 Solvent (S-1) 733.33

Composition of Positive Photosensitive Resin Composition of Comparative Example 5: Polymer A 87.88 parts by weight Photoacid generator (PAG-1) 1.5 Carboxylic acid (C′-3) 0.5 Nitrogen-containing basic compound (N- 1) 0.10 Acid-decomposable low molecular weight compound a 10 Surfactant (W-3) 0.02 Solvent (S-3) 513.33 (S-4) 220.00

[0148]

[Table 1]

[0149]

[Table 2]

As shown in Tables 1 and 2, the positive photosensitive resin composition of the present invention has very few development defects, and shows satisfactory results in line edge roughness, shape and the like. On the other hand, Comparative Example 1 containing no (C) carboxylic acid is inferior in development defects and line edge roughness. In addition, when a surfactant not specified in the present invention was used even when the carboxylic acid of the present invention was used (Comparative Example 2), similarly, development defects and line edge roughness were poor.
When a carboxylic acid having a fluorine atom in its molecular structure but having a short carbon number is used (Comparative Example 3), the development defects and the line edge roughness are inferior to those of the examples of the present invention.
When the aromatic carboxylic acid having a fluorine atom was used (Comparative Example 4), the development defect and the profile were inferior. When an aliphatic carboxylic acid having no fluorine atom was used (Comparative Example 5), the development defect, profile, and line edge roughness were slightly inferior to Examples of the present invention.

[0151]

The positive photosensitive resin composition according to the present invention comprises (A) a polymer having a cyclic aliphatic hydrocarbon skeleton, which is decomposed by the action of an acid to become alkali-soluble, and (B) an actinic ray. Or a compound that generates an acid upon irradiation with radiation,
(C) at least four fluorine atoms in one molecule,
By combining an aliphatic carboxylic acid or aliphatic dicarboxylic acid having a carbon number of 4 to 20 and a molecular weight of 1,000 or less, (D) a nitrogen-containing basic compound and (E) a fluorine-based and / or silicon-based surfactant, a resist is obtained. Shape, sensitivity,
The resolution and line edge roughness are excellent, and development defects can be reduced.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03F 7/004 501 G03F 7/004 501 504 504 H01L 21/027 H01L 21/30 502R F-term (Reference) 2H025 AA01 AA02 AA04 AB15 AB16 AC04 AC05 AC06 AC08 AD03 BE00 BE10 BG00 CC04 CC20 FA03 FA12 FA17 4J002 BG071 BK001 CE001 EF037 EF067 EN048 EN068 EN136 EN138 EU048 EU068 EV248 EV296 EW176 FD319 GP03

Claims (3)

[Claims] (A) having a cyclic aliphatic hydrocarbon skeleton,
A polymer that is decomposed by the action of an acid and becomes alkali-soluble,
(B) a compound which generates an acid upon irradiation with actinic rays or radiation, (C) an aliphatic carboxylic acid or fat having at least 4 fluorine atoms in one molecule, having 4 to 20 carbon atoms and a molecular weight of 1000 or less A positive photosensitive resin composition comprising an aromatic dicarboxylic acid, (D) a nitrogen-containing basic compound, and (E) a fluorine-based and / or silicon-based surfactant. 2. The method according to claim 1, wherein the molecular weight is 2,000 or less.
The positive photosensitive resin composition according to claim 1, further comprising a low-molecular acid-decomposable compound having a group that can be decomposed by the action of an acid and having an alkali solubility increased by the action of the acid. 3. The positive photosensitive resin composition according to claim 1, wherein the actinic ray is exposed to far ultraviolet light having a wavelength of 220 nm or less.