JP2001042533A - Positive type photoresist composition for exposure with far ultraviolet ray - Google Patents

Abstract

PROBLEM TO BE SOLVED: To ensure superior uniformity in coating in the surface of a substrate by incorporating a resin containing one of specified groups each containing an alicyclic hydrocarbon structure and a solvent containing one of solvents including propylene glycol monomethyl ether propionate. SOLUTION: This positive photoresist composition contains a compound which generates an acid when irradiated with active light or radiation, a resin containing at least one of groups of formulae I and II each containing an alicyclic hydrocarbon structure and a solvent containing at least one of solvents including propylene glycol monomethyl ether propionate. In the formulae I and II, R1 is methyl, ethyl or the like, ZA is an atomic group required to form an alicyclic hydrocarbon group together with C, R2 and R3 are each 1-4C alkyl and ZB is a di- or trivalent alicyclic hydrocarbon group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive photoresist composition used in an ultra microlithography process such as the production of an ultra LSI or a high-capacity micro chip, and other photofabrication processes. More specifically, the present invention relates to a positive photoresist composition capable of forming a highly fine pattern by using light having a wavelength of 250 nm, particularly a deep ultraviolet region including excimer laser light.

[0002]

2. Description of the Related Art In recent years, the degree of integration of integrated circuits has been increasing more and more, and in the manufacture of semiconductor substrates such as ultra LSIs, processing of ultrafine patterns having a line width of less than half a micron is required. It has become In order to meet this need, the wavelength of an exposure apparatus used for photolithography is becoming shorter and shorter, and now excimer laser light (XeCl, KrF, ArF, etc.) having a short wavelength among far ultraviolet rays is used.
The use of is being considered. A chemically amplified resist is used for forming a pattern in lithography in this wavelength region.

In general, chemically amplified resists can be broadly classified into three types: so-called two-component, 2.5-component and three-component resists. The two-component system combines a compound that generates an acid by photolysis (hereinafter referred to as a photoacid generator) and a binder resin. The binder resin is a resin having in its molecule a group (also referred to as an acid-decomposable group) that decomposes under the action of an acid to increase the solubility of the resin in an alkaline developer. The 2.5-component system further contains a low-molecular compound having an acid-decomposable group in such a two-component system. The three-component system contains a photoacid generator, an alkali-soluble resin, and the above low molecular compound.

The above-mentioned chemically amplified resist is suitable for a photoresist for irradiating ultraviolet rays or far ultraviolet rays, but among them, it is necessary to further meet the required characteristics in use. For example,
When using 248 nm light of a KrF excimer laser, a hydroxystyrene-based polymer having a low light absorption is particularly used.
There has been proposed a resist composition using a polymer having an acetal group or a ketal group introduced as a protective group. JP-A-2-141636, JP-A-2-19847, JP-A-4-219775, JP-A-5-281745 and the like are examples thereof. In addition, similar compositions using a t-butoxycarbonyloxy group or a p-tetrahydropyranyloxy group as an acid-decomposable group are disclosed in JP-A-2-209977, JP-A-3-206458, JP-A-2-19847, and the like. Proposed. These are suitable when using KrF excimer laser light of 248 nm,
When an ArF excimer laser is used as the light source, the sensitivity is low because the absorbance is still essentially too high. Further, there are other disadvantages associated therewith, such as deterioration of resolution, deterioration of focus tolerance, deterioration of pattern profile, and the like, and many points still need improvement.

As a photoresist composition for an ArF light source, a resin having an alicyclic hydrocarbon moiety introduced therein for the purpose of imparting dry etching resistance has been proposed. As such a resin, a monomer having a carboxylic acid moiety such as acrylic acid or methacrylic acid or a monomer having a hydroxyl group or a cyano group in a molecule is copolymerized with a monomer having an alicyclic hydrocarbon group. Resin.

On the other hand, besides the method of introducing an alicyclic hydrocarbon moiety into the side chain of the acrylate monomer, a method of imparting dry etching resistance utilizing an alicyclic hydrocarbon moiety as a polymer main chain has also been studied. I have.

Further, Japanese Patent Application Laid-Open No. 9-73173 and
JP-A-90637 and JP-A-10-161313 each disclose an alkali-soluble group protected by a structure containing an alicyclic group, and a structural unit which is made to be alkali-soluble when the alkali-soluble group is eliminated by an acid. A resist material using an acid-sensitive compound is described. JP-A-11-1
JP 09632 describes that a resin containing a polar group-containing alicyclic functional group and an acid-decomposable group is used for a radiation-sensitive material.

[0008] Even in the above-mentioned techniques, in a photoresist composition (particularly, a photoresist for exposure to far ultraviolet rays), an improvement due to a resin containing an acid-decomposable group still exists, and an aliphatic compound is simultaneously contained in a molecule. There are still many insufficient points such as improvement in adhesion to a substrate caused by containing a cyclic hydrocarbon group, and improvement is desired.

The next important requirement to be met is coatability. In recent years, the size of wafers has been increasing with the integration of LSIs and the like. As the size becomes larger, there is a problem that the spin coating uniformity in the substrate surface is deteriorated, and the residual wetness is generated, and the industrial value is reduced.

On the other hand, as described above, various resins containing acid-decomposable groups in a chemically amplified photoresist for deep ultraviolet exposure have been studied, but there is still room for improvement due to the hydrophobicity of the resin. There was. That is, when the chemically amplified photoresist is stored in a liquid state, the compatibility between the resin and the photoacid generator is poor, particles are generated in the liquid, and the resist performance is deteriorated. Still present (deterioration of storage stability of resist solution).

JP-A-10-254139 discloses an acid-decomposable group-containing resin having an alicyclic skeleton, a radiation-sensitive acid generator, a linear ketone, a cyclic ketone, a propylene glycol monoalkyl ether acetate, A resin composition containing a solvent comprising a mixture with at least one selected from the group of alkyl 2-hydroxypropionates is described. This system also has the above-mentioned problems such as poor storage stability, and improvement by a similar approach is being studied.

[0012]

As described above, the prior art of the conventional photoresist composition does not respond to the recent required performance, and in particular, the uniformity of coating on the substrate surface and the storage stability of the resist solution. However, further improvement was desired. Therefore, an object of the present invention is to provide a method for producing deep ultraviolet light,
It is an object of the present invention to solve the problems of the technology for improving the performance of microphotofabrication using excimer laser light. Specifically, a positive resist for exposure to far ultraviolet light having excellent coating uniformity within a substrate surface. It is to provide a composition. A further object of the present invention is to provide a positive resist composition for exposure to far ultraviolet light, which has excellent storage stability of a resist solution.

[0013]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies on constituent materials of a resist composition in a positive-type chemical amplification system, and have found that a specific acid-decomposable resin and a specific mixed solvent are used. Knowing that the purpose of the invention is achieved,
The present invention has been reached. That is, the above object is achieved by the following constitutions.

(1) (a) a compound capable of generating an acid upon irradiation with actinic rays or radiation; and (b) a compound having an alicyclic hydrocarbon structure represented by the following general formulas (I) and (II): A resin containing at least one group selected from the group and having increased solubility in alkali due to the action of an acid; and (c) a resin selected from the group consisting of (1) propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether propionate. A positive-working photoresist composition for deep ultraviolet exposure, comprising: a solvent containing at least one solvent.

[0015]

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In the general formulas (I) and (II), R ₁ is a methyl group, an ethyl group, an n-propyl group, an isopropyl group,
represents an n-butyl group, an isobutyl group or a sec-butyl group, and Z _A represents an atomic group necessary for forming an alicyclic hydrocarbon group together with a carbon atom. R _{2 to} R ₃ each independently represent a linear or branched alkyl group having 1 to 4 carbon atoms, and Z _B represents a divalent or trivalent alicyclic hydrocarbon group. a and b each independently represent 1 or 2. (2) The solvent of (c) further comprises (2) a solvent containing at least one solvent selected from the group consisting of ethyl lactate, propylene glycol monomethyl ether and ethoxyethyl propionate. The positive photoresist composition for deep ultraviolet exposure according to the above (1). (3) The solvent according to (1), wherein the solvent (c) further contains (3) a solvent containing at least one solvent selected from the group consisting of γ-butyrolactone, ethylene carbonate and propylene carbonate. Or (2)
4. The positive photoresist composition for deep ultraviolet exposure according to item 1. (4) The far ultraviolet ray according to any one of (1) to (3), wherein the resin (b) further contains a repeating unit having a group represented by the following general formula (III). Positive photoresist composition for exposure.

[0017]

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In the general formula (III), Ra to Re each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
m and n each independently represent an integer of 0 to 3, and m + n
Is 2 or more and 6 or less.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the compounds used in the present invention will be described in detail. <(A) Compound that generates an acid upon irradiation with actinic rays or radiation (photoacid generator)> The (a) photoacid generator used in the present invention is a compound which generates an acid upon irradiation with actinic rays or radiation. is there. As the photoacid generator used in the present invention, a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization, a photodecolorant for dyes, a photochromic agent, or a microresist is used. Known light (400 to 200
nm ultraviolet light, far ultraviolet light, particularly preferably g-line, h
Ray, i-ray, KrF excimer laser light), ArF excimer laser light, an electron beam, an X-ray, a compound generating an acid by a molecular beam or an ion beam, and a mixture thereof can be appropriately selected and used.

Other photoacid generators used in the present invention include, for example, onium salts such as diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenonium salts and arsonium salts.
Organic halogen compound, organic metal / organic halide, o
A photoacid generator having a nitrobenzyl-type protecting group; a compound represented by photolysis such as iminosulfonate that generates sulfonic acid; a disulfone compound; a diazoketosulfone; and a diazodisulfone compound.
Further, a group in which an acid is generated by such light or a compound in which a compound is introduced into a main chain or a side chain of a polymer can be used.

Further, VNRPillai, Synthesis, (1), 1 (198
0), A. Abad etal, Tetrahedron Lett., (47) 4555 (1971),
Compounds that generate an acid by light described in DHR Barton et al., J. Chem. Soc., (C), 329 (1970), U.S. Pat. No. 3,779,778, and EP 126,712 can also be used.

Among the compounds which decompose upon irradiation with an electron beam to generate an acid, those which are particularly effectively used will be described below. (1) The following general formula (PAG) substituted with a trihalomethyl group
The oxazole derivative represented by 1) or the general formula (PA)
An S-triazine derivative represented by G2).

[0023]

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In the formula, R ²⁰¹ is a substituted or unsubstituted aryl group or alkenyl group, and R ²⁰² is a substituted or unsubstituted aryl group, alkenyl group, alkyl group, —C (Y) ₃
Show Y represents a chlorine atom or a bromine atom. Specific examples include the following compounds, but the present invention is not limited thereto.

[0025]

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

[0027]

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Here, the formulas Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aryl group. R ²⁰³ , R ²⁰⁴ , R
²⁰⁵ is each independently a substituted or unsubstituted alkyl group,
Indicates an aryl group.

Z- represents a counter anion such as BF_Four ^-,
AsF₆ ^-, PF₆ ^-, SbF₆ ^-, SiF₆ ^2-, ClO_Four ^-,
CF_ThreeSO_Three ^-Perfluoroalkanesulfonic acid ani
On, pentafluorobenzenesulfonate anion, na
Condensed polynuclear aromatics such as phthalene-1-sulfonic acid anion
Sulfonic acid anion, anthraquinone sulfonic acid ani
And sulfonic acid group-containing dyes.
It is not limited to these.

Further, two of R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ and Ar ¹ and Ar ² may be bonded through a single bond or a substituent.

Specific examples include the following compounds, but are not limited thereto.

[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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The above onium salts represented by the general formulas (PAG3) and (PAG4) are known, for example, JWKnapczyk
etal, J. Am. Chem. Soc., 91, 145 (1969), ALMaycok eta
l, J. Org. Chem., 35, 2532, (1970), E. Goethas et al., Bul
l.Soc.Chem.Belg., 73,546, (1964), HM Leicester, J. Am
e.Chem.Soc., 51,3587 (1929), JVCrivello etal, J.Pol
18, 2677 (1980), U.S. Pat. Nos. 2,807,648 and 4,247,473, and JP-A-53-101,331.

(3) Disulfone derivatives represented by the following formula (PAG5) or iminosulfonate derivatives represented by the following formula (PAG6).

[0041]

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Where Ar^Three, Ar^FourAre each independently substituted
Or an unsubstituted aryl group. R ²⁰⁶Is replaced or
It represents an unsubstituted alkyl group or aryl group. A is a substitution
Or unsubstituted alkylene, alkenylene, arylene
Shows a substituent group. Specific examples include the compounds shown below.
However, the present invention is not limited to these.

[0043]

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[0044]

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[0045]

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

[0047]

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Here, R represents a linear, branched or cyclic alkyl group or an optionally substituted aryl group. Specific examples include the following compounds, but are not limited thereto.

[0049]

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The amount of the photoacid generator to be added is generally in the range of 0.001 to 40% by weight, preferably 0.01 to 20% by weight, more preferably 0.01 to 20% by weight, based on the solids in the composition. Is used in the range of 0.1 to 5% by weight. When the addition amount of the photoacid generator is less than 0.001% by weight, the sensitivity is lowered. When the addition amount is more than 40% by weight, the light absorption of the resist becomes too high, and the profile deteriorates,
The process (especially baking) margin is unfavorably reduced.

<Resin which decomposes under the action of (b) acid to increase its solubility in alkali> The resin used in the composition of the present invention which decomposes under the action of (b) acid and increases its solubility in alkali (hereinafter referred to as "resin") , Simply referred to as “(b) alkali-soluble resin”) is a compound represented by the above general formula (I) or (I)
A group containing an alicyclic hydrocarbon structure represented by I) is included as a partial structure.

In the general formulas (I) and (II), R ₂
The alkyl group for R _{3 to} R ₃ represents a linear or branched alkyl group having 1 to 4 carbon atoms, which may be substituted or unsubstituted. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group,
ec-butyl group, t-butyl group and the like. Also,
Further substituents of the above alkyl group include those having 1 to 4 carbon atoms.
And an alkoxy group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), an acyl group, an acyloxy group, a cyano group, a hydroxyl group, a carboxy group, an alkoxycarbonyl group, and a nitro group.

The alicyclic hydrocarbon group formed by Z _A and a carbon atom or the divalent or trivalent alicyclic hydrocarbon group of Z _B may be monocyclic or polycyclic. In particular,
Examples thereof include a group having a monocyclo, bicyclo, tricyclo, tetracyclo structure or the like having 5 or more carbon atoms. The number of carbon atoms is preferably 6 to 30, especially 7 to 25.
Are preferred. These alicyclic hydrocarbon groups may have a substituent. Hereinafter, structural examples of the alicyclic portion of the group containing the alicyclic hydrocarbon structure will be described.

[0054]

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[0055]

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[0056]

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In the present invention, preferred examples of the alicyclic moiety include an adamantyl group, a noradamantyl group, a decalin residue, a tricyclodecanyl group, a tetracyclododecanyl group, a norbornyl group, a cedrol group, and a cyclohexyl group. , Cycloheptyl group, cyclooctyl group,
Examples thereof include a cyclodecanyl group and a cyclododecanyl group. More preferred are an adamantyl group, a decalin residue, a norbornyl group, a cedrol group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecanyl group, and a cyclododecanyl group. Particularly, an adamantyl group is preferable.

Examples of the substituent of these alicyclic hydrocarbon groups include an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group and an alkoxycarbonyl group. As the alkyl group, a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group is preferable, and a methyl group, an ethyl group, a propyl group, and an isopropyl group are more preferable. Examples of the substituent of the substituted alkyl group include a hydroxyl group, a halogen atom and an alkoxy group. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group.

As the repeating unit having the structure represented by the general formulas (I) and (II) constituting the above (ii) alkali-soluble resin, a repeating unit represented by the following general formula (pA) is preferable.

[0060]

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In the general formula (pA), R represents a hydrogen atom, a halogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 4 carbon atoms, or a cyano group. Multiple R
May be the same or different. A ′ is a single bond, an alkylene group, a substituted alkylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group,
It represents a single or a combination of two or more groups selected from the group consisting of a sulfonamide group, a urethane group, and a urea group. Ra represents any one of the above formulas (I) and (II). Hereinafter, specific examples of the monomer corresponding to the repeating unit represented by the general formula (pA) are shown.

[0062]

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[0063]

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(B) The alkali-soluble resin includes, in addition to the repeating unit having at least one group selected from the group of groups having an alicyclic hydrocarbon structure represented by the general formulas (I) and (II), Other repeating units may be included. As such another repeating unit, the general formula (III)
And preferably a repeating unit represented by the following general formula (AI). By including this, not only the effect of the present invention becomes more remarkable, but also the sensitivity is remarkably improved. In the general formula (III), preferred Ra to Re are a hydrogen atom and a methyl group, and the preferred value of m is 0 or 1, and the preferred value of n is 1, 2, 3.

[0065]

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In the general formula (AI), R and A ′ have the same meanings as in the above general formula (pA). B represents a group represented by the general formula (III). Preferred examples of A 'include a single bond, an alkylene group having 1 to 10 carbon atoms, an ether group, a carbonyl group, and an ester group, or a divalent group obtained by combining two or more of these groups. Preferred structures as the divalent group in which two or more are combined include those having the following structures.

[0067]

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In the above formula, Ra, Rb, and r1 have the same meanings as described below. m is a number from 1 to 3. The (b) alkali-soluble resin in the present invention may further contain other copolymer components in addition to the repeating unit having a group represented by the general formula (III) as another copolymer component. Examples of such a copolymer component include repeating units represented by the following general formulas (III-a) to (III-d). Thereby, the sensitivity is improved.

[0069]

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In the above formula, R₁Has the same meaning as R described above.
R_Five~ R₁₂Each independently has a hydrogen atom or a substituent
Represents an optionally substituted alkyl group. R represents a hydrogen atom or
Is an alkyl group which may have a substituent,
Represents a kill group, an aryl group or an aralkyl group. m is 1
Represents an integer of 10 to 10. X has a single bond or a substituent
An alkylene group, a cyclic alkylene group,
-Ene group, ether group, thioether group,
Bonyl group, ester group, amide group, sulfonamide
Group, a urethane group, or a urea group.
Germany or a combination of at least two of these groups
And represents a divalent group that is not decomposed by the action of an acid. Z
Is a single bond, an ether group, an ester group, an amide group,
Represents a kylene group or a divalent group obtained by combining them.
R₁₃Is a single bond, an alkylene group, an arylene group, or
It represents a divalent group obtained by combining these. R_FifteenIs an archille
Group, arylene group, or divalent
Represents a group. R₁₄Is an alkyl which may have a substituent
Group, cyclic alkyl group, aryl group or aralkyl group
You. R ₁₆Represents a hydrogen atom or a substituent
Good, alkyl group, cyclic alkyl group, alkenyl group,
Represents a reel group or an aralkyl group. A is the official
Represents any functional group.

[0071]

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Examples of the alkyl group of R _{5 to} R ₁₂ , R, R ₁₄ and R ₁₆ include a linear or branched alkyl group, which may have a substituent. As the linear or branched alkyl group, a linear or branched alkyl group having 1 to 12 carbon atoms is preferable, and a linear or branched alkyl group having 1 to 10 carbon atoms is more preferable. More preferably methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group,
t-butyl group, pentyl group, hexyl group, heptyl group,
An octyl group, a nonyl group, and a decyl group. R, R _14, R
_Examples of the cyclic alkyl group of ₁₆ include those having 3 to 30 carbon atoms, and specifically, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a norbornyl group, a boronyl group, a tricyclodecanyl group , Dicyclopentenyl group, nobornane epoxy group, menthyl group, isomenthyl group, neomenthyl group, tetracyclododecanyl group, steroid residue and the like.

The aryl group represented by R, R ₁₄ and R ₁₆ includes those having 6 to 20 carbon atoms, and may have a substituent. Specific examples include a phenyl group, a tolyl group, and a naphthyl group. Examples of the aralkyl group represented by R, R ₁₄ and R ₁₆ include those having 7 to 20 carbon atoms, such as a benzyl group, a phenethyl group and a cumyl group which may have a substituent. The alkenyl group for R ₁₆ has 2 carbon atoms.
To 6 alkenyl groups, specifically, a vinyl group, a propenyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, a cyclopentenyl group, a cyclohexenyl group, a 3-oxocyclohexenyl group, and a 3-oxo group. A cyclopentenyl group, a 3-oxoindenyl group and the like. Among these, the cyclic alkenyl group may contain an oxygen atom.

As the linking group X, an alkylene group, a cyclic alkylene group, an arylene group or an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a sulfonamide group, a urethane group which may have a substituent. A group selected from the group consisting of urea groups, or a combination of at least two or more of these groups;
Examples include divalent groups that do not decompose under the action of an acid. Z
Represents a single bond, an ether group, an ester group, an amide group, an alkylene group, or a divalent group obtained by combining these.
R ₁₃ represents a single bond, an alkylene group, an arylene group, or a divalent group obtained by combining these. R ₁₅ represents an alkylene group, an arylene group, or a divalent group obtained by combining them. Examples of the arylene group in X, R ₁₃ and R ₁₅ include those having 6 to 10 carbon atoms, which may have a substituent. Specifically, phenylene group, tolylene group,
And a naphthylene group. Examples of the cyclic alkylene group for X include those in which the above-mentioned cyclic alkyl group is divalent. Examples of the alkylene group for X, Z, R ₁₃ , R ₁₅ , and A ′ include groups represented by the following formula. -[C (Ra) (Rb)] r1 wherein Ra and Rb represent a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, or an alkoxy group;
Both may be the same or different. As the alkyl group, a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group is preferable, and a methyl group, an ethyl group, a propyl group, and an isopropyl group are more preferable. As the substituent of the substituted alkyl group,
Examples include a hydroxyl group, a halogen atom and an alkoxy group. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. r1 represents an integer of 1 to 10. Specific examples of the linking group X are shown below, but the content of the present invention is not limited thereto.

[0075]

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Further substituents in the above alkyl group, cyclic alkyl group, alkenyl group, aryl group, aralkyl group, alkylene group, cyclic alkylene group, and arylene group include carboxyl group, acyloxy group, cyano group,
Alkyl group, substituted alkyl group, halogen atom, hydroxyl group,
Examples include an alkoxy group, an acetylamide group, an alkoxycarbonyl group, and an acyl group. Here, examples of the alkyl group include lower alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a cyclopropyl group, a cyclobutyl group, and a cyclopentyl group. Examples of the substituent of the substituted alkyl group include a hydroxyl group, a halogen atom and an alkoxy group. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group. Examples of the acyloxy group include an acetoxy group. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom.

Hereinafter, specific examples of the structure of the terminal except X are shown below as specific examples of the structure of the side chain in the general formula (III-b), but the present invention is not limited thereto. .

[0078]

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Hereinafter, specific examples of the monomer corresponding to the repeating structural unit represented by the general formula (III-c) will be shown, but the present invention is not limited thereto.

[0080]

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[0081]

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[0082]

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Hereinafter, specific examples of the repeating structural unit represented by formula (III-d) will be shown, but the present invention is not limited thereto.

[0084]

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[0085]

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[0086]

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In the general formula (III-b), R _{5 to} R ₁₂ are preferably a hydrogen atom or a methyl group. R is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. m is
1-6 are preferred. In the general formula (III-c), R ₁₃ is preferably a single bond, an alkylene group such as a methylene group, an ethylene group, a propylene group, or a butylene group, and R ₁₄ is a group having 1 carbon atom such as a methyl group or an ethyl group. Preferred are 10 to 10 alkyl groups, cyclopropyl groups, cyclohexyl groups, cyclic alkyl groups such as camphor residues, naphthyl groups, and naphthylmethyl groups. Z is preferably a single bond, an ether bond, an ester bond, an alkylene group having 1 to 6 carbon atoms, or a combination thereof, and more preferably a single bond or an ester bond. In the general formula (III-d), R ₁₅ is preferably an alkylene group having 1 to 4 carbon atoms. As R ₁₆ , an alkyl group having 1 to 8 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a neopentyl group, an octyl group, which may have a substituent;
Cyclohexyl group, adamantyl group, norbornyl group,
Boronyl, isobornyl, menthyl, morpholino, 4-oxocyclohexyl, and optionally substituted phenyl, toluyl, mesityl, naphthyl, and camphor residues are preferred. As these further substituents, a halogen atom such as a fluorine atom, an alkoxy group having 1 to 4 carbon atoms and the like are preferable.

In the present invention, general formulas (III-a) to (III-a)
Among (III-d), repeating units represented by formulas (III-b) and (III-d) are preferable.

(B) In addition to the above, the alkali-soluble resin controls dry etching resistance, suitability for a standard developing solution, substrate adhesion, resist profile, and resolution, heat resistance, sensitivity, and the like, which are general requirements for resists. It can be used as a copolymer with various monomer repeating units for the purpose.

Examples of such a repeating unit include, but are not limited to, repeating units corresponding to the following monomers. Thereby, the performance required for the resin, particularly (1) solubility in a coating solvent, (2) film forming property (glass transition point), (3)
Alkali developability, (4) film loss (hydrophilic / hydrophobic, alkali-soluble group selection), (5) adhesion of unexposed portion to substrate,
(6) Fine adjustment of dry etching resistance becomes possible.
Examples of such a copolymerizable monomer include, for example, an acrylate, a methacrylate, an acrylamide, a methacrylamide, an allyl compound, a vinyl ether, and an addition-polymerizable unsaturated bond selected from vinyl esters. And the like.

Specifically, for example, acrylates such as alkyl (the alkyl group has 1 to 1 carbon atoms)
Acrylates (for example, methyl acrylate, ethyl acrylate, propyl acrylate, amyl acrylate, cyclohexyl acrylate, ethylhexyl acrylate, octyl acrylate, acrylate-
t-octyl, chloroethyl acrylate, 2-hydroxyethyl acrylate 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate, Tetrahydrofurfuryl acrylate, etc.);

Methacrylic esters such as alkyl (preferably having 1 to 10 carbon atoms in the alkyl group) methacrylate (eg, methyl methacrylate,
Ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate,
Benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate,
5-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, etc.);

Acrylamides, for example, acrylamide, N-alkylacrylamide, (where the alkyl group has 1 to 10 carbon atoms, for example, methyl, ethyl, propyl, butyl, t-butyl, heptyl, octyl Group, cyclohexyl group, hydroxyethyl group, etc.), N, N-dialkylacrylamide (alkyl group having 1 to 10 carbon atoms, for example, methyl group, ethyl group, butyl group, isobutyl group, ethylhexyl group, Cyclohexyl group, etc.), N-hydroxyethyl-N-methylacrylamide, N-2-
Acetamidoethyl-N-acetylacrylamide and the like;

Methacrylamides, for example, methacrylamide, N-alkyl methacrylamide (alkyl having 1 to 10 carbon atoms, for example, methyl, ethyl, t-butyl, ethylhexyl, hydroxyethyl, cyclohexyl) Groups, etc.), N, N-dialkylmethacrylamide (an alkyl group such as an ethyl group, a propyl group, a butyl group, etc.), N-hydroxyethyl-N-methylmethacrylamide and the like;

Allyl compounds such as allyl esters (eg, allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, etc.), allyloxy Ethanol, etc .;

Vinyl ethers such as alkyl vinyl ethers (eg, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethyl Butyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, etc.);

Vinyl esters such as vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxy acetate, vinyl butoxy acetate, Vinyl acetoacetate, vinyl lactate, vinyl-β-phenylbutyrate, vinylcyclohexylcarboxylate and the like;

Dialkyl itaconates (eg, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, etc.); dialkyl esters of fumaric acid (eg, dibutyl fumarate, etc.) or monoalkyl esters; other acrylic acid, methacrylic acid, croton Acid, itaconic acid, maleic anhydride, maleimide, acrylonitrile,
Examples thereof include methacrylonitrile and maleilenitrile. In addition, any addition-polymerizable unsaturated compound copolymerizable with the above various repeating units may be used.

(B) In the alkali-soluble resin, the molar ratio of each repeating unit structure is determined by the acid value, the dry etching resistance of the resist, the suitability for a standard developer, the substrate adhesion, the dependence of the resist profile on the density of the resist, and the dependence on the resist. It is appropriately set to adjust generally required resolution, heat resistance, sensitivity, and the like.

(B) In the alkali-soluble resin, the content of the repeating unit having a partial structure represented by the general formulas (I) and (II) is 10 to 85 mol% in all the repeating units.
, Preferably 20 to 80 mol%, more preferably 30 to 75 mol%. Further, (b) the content of the repeating unit represented by the general formula (III) in the alkali-soluble resin is usually from 10 to 65 mol%, preferably from 20 to 60 mol%, based on all monomer repeating units. , More preferably 3
0 to 55 mol%. The content of the repeating units represented by formulas (III-a) to (III-d) in (b) the alkali-soluble resin is usually 0.1% in all monomer repeating units.
05 mol% to 25 mol%, preferably 0.1 to 2 mol%.
0 mol%, and more preferably 0.2 to 16 mol%.

The content of the repeating unit based on the monomer of the additional copolymer component in the resin can be appropriately set according to the desired resist properties. It is preferably at most 80 mol%, more preferably at least 70 mol%, based on the total number of moles of the repeating units containing a group containing the alicyclic hydrocarbon structure represented by (I) and (II) as a partial structure. Or less, more preferably 60 mol% or less.

(B) The weight average molecular weight Mw of the alkali-soluble resin is preferably in the range of 1,000 to 1,000 by gel permeation chromatography based on polystyrene standards.
1,000,000, more preferably 1,500 to 50
000, more preferably 2,000 to 200,00.
0, particularly preferably in the range of 2,500 to 100,000, and the larger the weight average molecular weight, the higher the heat resistance and the like, while the lower the developability and the like. .

The (b) alkali-soluble resin used in the present invention can be synthesized according to a conventional method, for example, by a radical polymerization method.

In the positive photoresist composition for deep ultraviolet exposure according to the present invention, (b) the amount of the alkali-soluble resin added to the whole composition is from 40 to 99.
It is preferably 99% by weight, more preferably 50 to 99.9.
7% by weight.

The composition of the present invention comprises, together with (a) the photoacid generator and (b) the alkali-soluble resin, (c)
(1) A solvent containing at least one solvent selected from the group consisting of propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether propionate (hereinafter also referred to as the solvent of (1)).
In the present invention, in addition to the solvent (1), (2) a solvent containing at least one solvent selected from the group consisting of ethyl lactate, propylene glycol monomethyl ether and ethoxyethyl propionate (hereinafter referred to as (2) (3) γ-butyrolactone, a solvent containing at least one solvent selected from the group consisting of ethylene carbonate and propylene carbonate (hereinafter, referred to as
(Also referred to as the solvent of (3)). This improves the storage stability of the resist solution in addition to the coating uniformity. The weight ratio of the solvent (1) to the solvent (2) [(1) :( 2)] is 90:10 to 15: 8.
5, preferably 80:20 to 20:80,
More preferably, it is 70:30 to 25:75. (3)
The weight ratio of the solvent used is 1 to 20 with respect to the total weight of the solvent.
%, Preferably 3 to 15. This addition further improves the storage stability.

Preferred combinations of the solvents in the present invention are propylene glycol monomethyl ether acetate / γ-butyrolactone, propylene glycol monomethyl ether acetate / ethylene carbonate, propylene glycol monomethyl ether acetate / propylene carbonate, propylene glycol monomethyl ether acetate / ethyl lactate / γ-butyrolactone. Butyrolactone,
Propylene glycol monomethyl ether acetate /
Ethyl lactate / ethylene carbonate, propylene glycol monomethyl ether acetate / ethyl lactate / propylene carbonate, propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether / γ-butyrolactone, propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether / ethylene carbonate, propylene glycol monomethyl Ether acetate / propylene glycol monomethyl ether / propylene carbonate.

The solid content of (a) the photoacid generator and (b) the alkali-soluble resin is converted into a solid concentration in the solvent described above.
It is preferable to dissolve 3 to 25%, more preferably 5 to 5%.
-22%, more preferably 7-20%.

The positive resist composition of the present invention may further contain an acid-decomposable dissolution inhibiting compound, a dye, a plasticizer,
A surfactant, a photosensitizer, an organic basic compound, and a compound that promotes solubility in a developer can be contained.

The positive photoresist composition of the present invention may contain a fluorine-based and / or silicon-based surfactant. In the positive photoresist composition of the present invention,
Any one of a fluorine-based surfactant, a silicon-based surfactant, and a surfactant containing both a fluorine atom and a silicon atom, or two or more thereof can be contained. As these surfactants, for example, JP-A-62-36663,
No. 61-226746, JP-A-61-226745, JP-A-62-170950
No., JP-A-63-34540, JP-A-7-230165, JP-A-8-62
No. 834, 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, (Shin-Akita Kasei
Co., Ltd.), Florado FC430, 431 (Sumitomo 3M Limited)
), Megafac F171, F173, F176, F189, R08 (Dai Nippon Ink Co., Ltd.), Surflon S-382, SC101, 102,
Fluorinated surfactants such as 103, 104, 105, and 106 (manufactured by Asahi Glass Co., Ltd.) and silicon-based surfactants can be exemplified. Also, polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can be used as a silicon-based surfactant.

The amount of the surfactant is usually 0.001 to 2% by weight, preferably 0.01 to 1% by weight, based on the solid content in the composition of the present invention. These surfactants may be added alone or in some combination. As the surfactant that can be used in addition to the above, specifically,
Polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkyl allyl such as polyoxyethylene octyl phenol ether and polyoxyethylene nonyl phenol ether Ethers, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan fatty acid esters such as sorbitan tristearate, poly Oxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, Polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, it may be mentioned nonionic surfactants of polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan tristearate and the like. The amount of these other surfactants is usually 2 parts by weight or less, preferably 1 part by weight or less, per 100 parts by weight of the solids in the composition of the present invention.

Examples of the organic basic compound that can be used in the present invention include a nitrogen-containing basic compound having the following structure.

[0112]

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Here, R ²⁵⁰ , R ²⁵¹ and R ²⁵² are the same or different and are a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aminoalkyl group having 1 to 6 carbon atoms, a hydroxyalkyl having 1 to 6 carbon atoms. Or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, wherein R ²⁵¹ and R ²⁵² may be bonded to each other to form a ring.

[0114]

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Wherein R ²⁵³ , R ²⁵⁴ , R ²⁵⁵ and R ²⁵⁶
Are the same or different and represent an alkyl group having 1 to 6 carbon atoms.) Further preferred compounds are nitrogen-containing basic compounds having two or more nitrogen atoms having different chemical environments in one molecule,
Particularly preferred are compounds containing both a substituted or unsubstituted amino group and a ring structure containing a nitrogen atom, or compounds having an alkylamino group. Preferred specific examples include substituted or unsubstituted guanidine, substituted or unsubstituted aminopyridine, substituted or unsubstituted aminoalkylpyridine, substituted or unsubstituted aminopyrrolidine, substituted or unsubstituted indazol, substituted or unsubstituted Pyrazole, substituted or unsubstituted pyrazine,
Substituted or unsubstituted pyrimidine, substituted or unsubstituted purine, substituted or unsubstituted imidazoline, substituted or unsubstituted pyrazoline, substituted or unsubstituted piperazine, substituted or unsubstituted aminomorpholine, substituted or unsubstituted amino And alkyl morpholine. Preferred substituents are an amino group, an aminoalkyl group, an alkylamino group, an aminoaryl group, an arylamino group, an alkyl group, an alkoxy group, an acyl group, an acyloxy group, an aryl group, an aryloxy group, a nitro group,
A hydroxyl group and a cyano group.

Preferred specific compounds include guanidine, 1,1-dimethylguanidine, 1,1,3,3,-
Tetramethylguanidine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2-diethylaminopyridine, 2- (aminomethyl) pyridine,
-Amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-5-methylpyridine, 2-amino-6-methylpyridine, 3-aminoethylpyridine, 4-aminoethylpyridine, 3-amino Pyrrolidine, piperazine, N- (2-aminoethyl) piperazine, N- (2-aminoethyl) piperidine, 4-amino-2,2,6,6-tetramethylpiperidine, 4-piperidinopiperidine, 2-imino Piperidine, 1- (2-
Aminoethyl) pyrrolidine, pyrazole, 3-amino-
5-methylpyrazole, 5-amino-3-methyl-1-
p-tolylpyrazole, pyrazine, 2- (aminomethyl) -5-methylpyrazine, pyrimidine, 2,4-diaminopyrimidine, 4,6-dihydroxypyrimidine,
-Pyrazoline, 3-pyrazoline, N-aminomorpholine, N- (2-aminoethyl) morpholine, 1,5-
Diazabicyclo [4,3,0] non-5-ene, 1,8
-Diazabicyclo [5,4,0] undec-7-ene,
3,4,5-triphenylimidazole, N-methylmorpholine, N-ethylmorpholine, N-hydroxyethylmorpholine, N-benzylmorpholine, cyclohexylmorpholinoethylthiourea (CHMETU), etc.
Grade morpholine derivatives, hindered amines described in JP-A-11-52575 (for example, [0005]
, Etc.) and the like, but is not limited thereto.

Particularly preferred specific examples are 1,5-diazabicyclo [4.3.0] -5-nonene, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,4-diazabicyclo [2 .2.2] octane, 4-dimethylaminopyridine,
Hexamethylenetetramine, 4,4-dimethylimidazoline, pyrroles, pyrazoles, imidazoles, pyridazines, pyrimidines, tertiary morpholines such as CHMETU, bis (1,2,2,6,6-pentamethyl-
Hindered amines such as (4-piperidyl) sebagate and the like can be mentioned. Among them, 1,5-diazabicyclo [4,3,0] non-5-ene, 1,8-diazabicyclo [5,4,0] undec-7-ene, 1,4-diazabicyclo [2,2,2] Octane, 4-dimethylaminopyridine, hexamethylenetetramine, CHMET
U, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebagate is preferred.

These nitrogen-containing basic compounds are used alone or in combination of two or more. The amount of the nitrogen-containing basic compound to be used is generally 0.001 to 10% by weight, preferably 0.01 to 5% by weight, based on the solid content of the entire photosensitive resin composition. If the amount is less than 0.001% by weight, the effect of the addition of the nitrogen-containing basic compound cannot be obtained. On the other hand, if it exceeds 10% by weight, the sensitivity tends to decrease and the developability of the unexposed portion tends to deteriorate.

The positive resist composition of the present invention is applied on a substrate to form a thin film. The thickness of this coating film is preferably from 0.2 to 1.2 μm. In the present invention,
If necessary, a commercially available inorganic or organic antireflection film can be used.

As the antireflection film, an inorganic film type such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon and α-silicon, and an organic film type comprising a light absorbing agent and a polymer material can be used. The former requires equipment such as a vacuum deposition apparatus, a CVD apparatus, and a sputtering apparatus for film formation. As the organic antireflection film, for example, Japanese Patent Publication No. 7-69
611, a condensate of a formaldehyde-modified melamine resin with a diphenylamine derivative, an alkali-soluble resin,
A light absorbing agent or a reaction product of a maleic anhydride copolymer and a diamine type light absorbing agent described in US Pat. No. 5,294,680;
JP-A-6-118631, containing a resin binder and a methylolmelamine-based thermal crosslinking agent;
Acrylic resin type antireflection coating having a carboxylic acid group, an epoxy group and a light absorbing group in the same molecule as described in 18656, one comprising a methylolmelamine and a benzophenone-based light absorbing agent described in JP-A-8-87115, and described in JP-A-8-179509. Examples thereof include those obtained by adding a low-molecular-weight light absorbing agent to a polyvinyl alcohol resin. Also, as an organic anti-reflection film,
DUV30 series manufactured by Brewer Science,
DUV-40 series, Shipley's AC-2, AC
-3 can also be used.

The resist solution is applied on a substrate (eg, a silicon / silicon dioxide coating) used for manufacturing precision integrated circuit devices (on a substrate provided with the above antireflection film if necessary), a spinner, a coater, and the like. After coating by an appropriate coating method such as that described above, exposure through a predetermined mask, baking and development can provide a good resist pattern. Here, the exposure light is preferably 150
It is light having a wavelength of nm to 250 nm. Specifically, Kr
F excimer laser (248 nm), ArF excimer laser (193 nm), F2 excimer laser (157
nm), X-rays, electron beams and the like.

Examples of the developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia.
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, tetraethylammonium hydroxide and the like An alkaline aqueous solution such as a quaternary ammonium salt, a cyclic amine such as pyrrole, or pyrhelidine can be used. Further, an appropriate amount of an alcohol or a surfactant may be added to the above alkaline aqueous solution.

[0123]

(Synthesis of resin)

Synthesis Example (1) Synthesis of Resin 1 1-hydroxy-4-methyl-4-adamantyl methacrylate and methacrylate of γ-dimethyl-α-hydroxybutyrolactone were charged at a ratio of 47/53, and N, N
-Dimethylacetamide / Titrahydrofuran = 8/2
To prepare 100 mL of a solution having a solid content of 20%. To this solution, 1 mol% of Wako Pure Chemical Industries V-65 and 3 mol% of mercaptoethanol were added, and this was added dropwise to 10 mL of N, N-dimethylacetamide heated to 60 ° C. over 2 hours under a nitrogen atmosphere. After completion of the dropwise addition, the reaction solution was heated for 2 hours, 1 mol% of V-65 was added again, and the mixture was stirred for 2 hours. After the completion of the reaction, the reaction solution was cooled to room temperature, and white powder precipitated and crystallized in 3 L of a distilled water / methanol = 5 / l solution was recovered. The polymer composition ratio determined from C ¹³ NMR was 49/51. The weight average molecular weight in terms of standard polystyrene determined by GPC measurement was 7,600. Resins 2 to 40 having the composition ratios and molecular weights shown in the following table were synthesized in the same manner as in the above Synthesis Examples. (Repeating unit 1, 2
Is the order from the left of the structural formula) In the resin in the table, the resin with a hyphen (for example, 2
-1, 2-2) means that the composition of the resin is represented by 2, but the composition ratio and molecular weight of each are different.

[0124]

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[0125]

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[0126]

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[0127]

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[0128]

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[0129]

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[0130]

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[0131]

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[0132]

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[0133]

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[0134]

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[0135]

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[0136]

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[0137]

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[0138]

[Table 1]

[0139]

[Table 2]

Examples 1 to 52 [Preparation and Evaluation of Photosensitive Composition] 1.4 g of each of the resins shown in Tables 3 to 6 synthesized in the above Synthesis Examples and triphenylsulfonium triflate 0, a photoacid generator, were added. Of the positive resist compositions of Examples 1 to 52 after dissolving each in a solvent described in Tables 3 to 6 at a solid content of 14% by weight. Prepared. The solvents described in Tables 3 to 6 are shown below.

S1: propylene glycol monomethyl ether acetate S2: propylene glycol monomethyl ether propionate S3: ethyl lactate S4: propylene glycol monomethyl ether S5: ethoxyethyl propionate S6: γ-butyrolactone S7: ethylene carbonate S8: propylene carbonate

(Evaluation Test) The obtained positive photoresist solution was applied on a silicon wafer using a spin coater, dried at 135 ° C. for 90 seconds, and a positive photoresist film of about 0.4 μm was formed. ArF excimer laser (wavelength 193 nm, NA = 0.6 manufactured by ISI)
F stepper). The heat treatment after exposure was performed at 115 ° C. for 90 seconds, developed with a 2.38% aqueous solution of tetramethylammonium hydroxide, and rinsed with distilled water to obtain a resist pattern profile. With respect to these, the uniformity of application on the substrate surface and the storage stability of the resist composition were evaluated as follows.

[Coating Uniformity on Substrate Surface] The resist solution prepared above was coated on a 6-inch silicon wafer using a coating machine CDR-650 manufactured by Canon Inc., and was applied at 140 ° C. for 60 seconds on a vacuum suction hot plate. Dry to a film thickness of 0.5
A 00 μm resist film was obtained. The surface of the resist film was observed with an optical microscope, but no residue was observed and no occurrence of striation was observed. Further, the film thickness value of the resist is set to alpha step -100.
(Manufactured by TENVCOR) to measure 10 points. The dispersion of the measured value with respect to the target film thickness was used as an index of coating uniformity.

[Sensitivity] (Initial Relative Sensitivity) The minimum exposure amount capable of resolving a 0.15 μm pattern was defined as the sensitivity, and the relative exposure amount was defined as the sensitivity with the sensitivity of Example 1 being set to 1.

[Storage Stability of Resist Composition] (Rate of Sensitivity Variation) After storing the prepared resist solution at 30 ° C. for one month, the sensitivity was evaluated, and the rate of variation from the sensitivity before storage was calculated by the following formula. Was measured. In addition, the said sensitivity is a line width of 0.
It was defined as the exposure amount that reproduced a pattern of 18 μm. {(Exposure amount before storage) − (exposure amount after storage)} / (exposure amount before storage) × 100

(Initial Value and Increase of Particles) The number of particles immediately after the preparation of the prepared resist solution was used as the initial value of the particles, and the initial value and the resist solution were stored at 30 ° C. for one month. Thereafter, the number of particles in the liquid was measured, and the number of particles that increased before and after the storage with time was evaluated.

[0147]

[Table 3]

[0148]

[Table 4]

[0149]

[Table 5]

[0150]

[Table 6]

As is clear from the results of Tables 3 to 6, all of the positive resist compositions of the present invention are at a satisfactory level. That is, it is suitable for lithography using far ultraviolet rays such as ArF excimer laser exposure.

[0152]

The present invention can provide a positive resist composition which is suitable for far ultraviolet light, especially ArF excimer laser light, and has excellent coating uniformity on the substrate surface and excellent storage stability of the resist composition.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Toshiaki Aoi 4,000 Kawajiri, Yoshida-cho, Haibara-gun, Shizuoka Prefecture F-term in Fujisha Shin Film Co., Ltd.

Claims (4)

[Claims] (1) a compound which generates an acid upon irradiation with actinic rays or radiation, and (b) a compound represented by the following general formula (I)
And (II) a resin containing at least one group selected from the group of groups containing an alicyclic hydrocarbon structure and having increased solubility in alkali by the action of an acid; and (c) (1) A positive photoresist composition for deep ultraviolet exposure, comprising: a solvent containing at least one solvent selected from the group consisting of propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether propionate. Embedded image In the general formulas (I) and (II), R ₁ represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a sec-butyl group;
_A represents an atomic group necessary for forming an alicyclic hydrocarbon group together with a carbon atom. R _{2 to} R ₃ each independently represent a linear or branched alkyl group having 1 to 4 carbon atoms;
Z _B represents a divalent or trivalent alicyclic hydrocarbon group.
a and b each independently represent 1 or 2. 2. The solvent according to claim 3, further comprising (2) a solvent containing at least one solvent selected from the group consisting of ethyl lactate, propylene glycol monomethyl ether and ethoxyethyl propionate. The positive photoresist composition for deep ultraviolet exposure according to claim 1. 3. The solvent according to claim 3, wherein the solvent further comprises (3) a solvent containing at least one solvent selected from the group consisting of γ-butyrolactone, ethylene carbonate and propylene carbonate. 3. The positive photoresist composition for deep ultraviolet exposure according to 1 or 2. 4. The resin of [2], further comprising the following general formula (I)
The positive photoresist composition for deep-UV exposure according to any one of claims 1 to 3, further comprising a repeating unit having a group represented by II). Embedded image In the general formula (III), Ra to Re are each independently a hydrogen atom,
Represents an alkyl group having 1 to 4 carbon atoms. m and n each independently represent an integer of 0 to 3, and m + n is 2 or more and 6 or less.