JP2000258913A - Positive radiation sensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a chemically amplified positive photoresist compsn. having adaptability for a halftone phase difference shift mask (resistance against side lobe light) by incorporating at least one kind of specified acetal compd. SOLUTION: This compsn. contains a polymer which is decomposed by the effect of an acid to increase its solubility with an alkali developer, a compd. which produces an acid by irradiation of active rays or radiation, and at least one kind of acetal compd. expressed by formula I or formula II. In formulae, each of R1 and R2 is independently a straight-chain, branched or cyclic 1-12C alkyl group which may have substituents or 7-18C aralkyl group which may have substituents. The total amt. of the acetal compds. is preferably >=0.1 pts.wt. and <100 pts.wt. to the total weight of the polymer.

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 for manufacturing semiconductor integrated circuit devices, masks for manufacturing integrated circuits, printed wiring boards, liquid crystal panels, and the like.

[0002]

2. Description of the Related Art As a positive photoresist composition, there is a chemically amplified resist composition described in U.S. Pat. No. 4,491,628 and European Patent No. 29,139. The chemically amplified positive resist composition produces an acid in the exposed area by irradiation with radiation such as deep ultraviolet light, and the acid-catalyzed reaction causes the active and non-irradiated parts of the active radiation to dissolve in the developing solution. Is a pattern forming material for forming a pattern on a substrate by changing the pattern.

Examples of such a combination include a combination of a compound that generates an acid by photolysis and an acetal or an O, N-acetal compound (Japanese Patent Laid-Open No. 48-89003), a combination of an orthoester or an amide acetal compound ( JP-A-5120714), a combination with a polymer having an acetal or ketal group in the main chain (JP-A-5-120714).
3-133429), a combination with an enol ether compound (JP-A-55-12995), a combination with an N-acyliminocarbonate compound (JP-A-55-126236).
Gazette), a combination with a polymer having an orthoester group in the main chain (JP-A-56-17345), a combination with a tertiary alkyl ester compound (JP-A-60-3625), and a combination with a silyl ester compound (JP-A-60-
10247 gazette) and a combination with a silyl ether compound (JP-A-60-37549, JP-A-60-121)
446 gazette) and the like. These have high photosensitivity because the quantum yield exceeds 1 in principle.

Similarly, systems which are stable under aging at room temperature but are decomposed by heating in the presence of an acid to solubilize in alkali are disclosed in, for example, JP-A-59-45439 and JP-A-60-3625. JP-A-62-229242, JP-A-63-27829, JP-A-63-362
40, JP-A-63-250642, Polym.Eng.
Sce., 23, 12 (1983); ACS. Sym. 242, 11 (198
4); Semiconductor World 1987, November, p. 91; M
acromolecules, 21, 21475 (1988); SPIE, 920, 42
Page (1988) and the like, a combination system of a compound generating an acid upon exposure to light and an ester or carbonate compound of a tertiary or secondary carbon (eg, t-butyl, 2-cyclohexenyl). . These systems also have high sensitivity,
In addition, since the absorption in the Deep-UV region is smaller than that of the naphthoquinonediazide / novolak resin system, it can be an effective system for shortening the wavelength of the light source.

Japanese Patent Application Laid-Open No. Hei 2-19847 discloses poly (p
(Hydroxystyrene) is disclosed which contains a resin in which the phenolic hydroxyl group of the compound is completely or partially protected by a tetrahydropyranyl group. Japanese Patent Application Laid-Open No. 219957/1992 also discloses a photoresist composition characterized by containing a resin in which 20 to 70% of the phenolic hydroxyl groups of poly (p-hydroxystyrene) are substituted with acetal groups. Have been. Further, JP-A-5-24968
JP-A No. 2 also discloses a photoresist composition using a similar acetal-protected resin.

Further, JP-A-8-123032 discloses a photoresist composition using a terpolymer containing a group substituted with an acetal group. Further, Japanese Patent Application Laid-Open
-113667, JP-A-6-266112, JP-A-6-289608, JP-A-7-209
No. 868 discloses a photoresist composition comprising a hydroxystyrene and a (meth) acrylate copolymer. Also, JP-A-9-297396 discloses that
It contains a polymer having a group decomposable by an acid, a radiation-sensitive acid generator, a compound obtained by acetalizing a hydrogen atom of a phenolic hydroxyl group in a compound having a molecular weight of less than 1000 having a phenolic hydroxyl group, and an acid diffusion controlling material. A radiation-sensitive resin composition is described. It is described that this composition is excellent in resolving power, cross-sectional shape and focus tolerance of a contact hole.

On the other hand, various attempts have been made to further increase the resolving power by a super-resolution technique such as an exposure technique or a mask technique. Various super-resolution techniques have been studied for the light source plane, the mask plane, the pupil plane, and the image plane. On the light source surface, there is a technique for improving the resolving power by forming a light source called a modified irradiation method, that is, a shape different from a conventional circular shape. On the mask surface, a technique has been reported in which a phase is also controlled using a phase shift mask, that is, a phase difference is given to light transmitted through the mask, and a high resolution is obtained by making good use of the interference (for example, Tokuhisa Ito) : Stepper optics (1) to (4), optical technology contact, vo
l.27, No.12, 762 (1988), vol.28, No.1,59 (1990), vo
l.28, No.2, 108 (1990), vol.28, No.3, 165 (1990),
JP-A-58-173744, JP-A-62-50811,
Nos. 62-67514, JP-A-1-147458, 1-283925, and 221451.).

Further, as described in Japanese Patent Application Laid-Open No. 8-15851, a resist exposure method using a halftone type phase shift mask attracts particular attention as a practical technique for improving the spatial image and contrast of a projected image. However, in the light intensity distribution of the exposure light reaching the resist, a so-called sub-peak occurs in addition to the main peak, and the resist portion that should not be exposed is exposed,
In particular, the higher the coherence degree (σ), the larger the sub-peak. When such a sub-peak occurs, unevenness due to the sub-peak is formed in the resist after exposure and development in the positive resist, which is not preferable. In the above-described conventional resist material technology, unevenness after development due to these subpeaks (side lobe light) occurs, and therefore, improvement thereof has been desired.

[0009]

When the super-resolution technique is used, the resolution is improved, but other resist characteristics may be reduced. Therefore, when the super-resolution technique is used, for example, how to design a positive photoresist material, for example, has little knowledge in the past. An object of the present invention is to provide a chemically amplified positive type which exhibits high sensitivity, high resolution, and good halftone phase difference shift mask (side lobe light resistance) which has conventionally been incompatible, particularly in the manufacture of semiconductor devices and the like. It is to provide a photoresist composition.

[0010]

Means for Solving the Problems In view of the above situation, the present inventors have conducted intensive studies and have found that a binder having an acid-decomposable group, a compound capable of generating an acid upon irradiation with actinic rays or radiation, and an acetal having a specific structure. By using a positive photoresist composition containing at least a compound,
The inventors have found that the object of the present invention is achieved, and have completed the present invention. That is, the positive radiation-sensitive resin composition according to the present invention has the following constitution. (1) (a) a polymer which is decomposed by the action of an acid to increase the solubility in an alkali developer, (b) a compound which generates an acid upon irradiation with actinic rays or radiation, and (c)
A positive-type radiation-sensitive resin composition comprising at least one of the atal compounds represented by the following general formula (A) or (B).

[0011]

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In the formula (A) or (B), R ₁ and R ₂ each independently represent a linear, branched or cyclic C ₁ -C 12
Represents an alkyl group which may have one or more substituents, or an aralkyl group which may have one or more substituents having 7 to 18 carbon atoms. (2) The polymer (a) is obtained by reacting an alkali-soluble polymer having a hydroxyl group with a vinyl ether compound represented by the following general formula (C) and an alcohol compound represented by the following general formula (D) under an acid catalyst. The positive-type radiation-sensitive resin composition according to the above (1), which is a polymer to be obtained.

[0013]

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In the formula (C) or (D), R ₃ or R ₄ each independently represents a linear, branched or cyclic alkyl group which may have a substituent having 1 to 12 carbon atoms; Carbon number 6-1
An aromatic group which may have 8 substituents or 7 carbon atoms
Represents an aralkyl group which may have from 18 to 18 substituents.

(3) The above (1), wherein the total amount of the attar compound of (c) is not less than 0.1 part by weight and less than 100 parts by weight based on the total weight of the polymer of (a). Or the positive-type radiation-sensitive resin composition according to (2).

[0016]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. (C) Acetal compound The component (c) in the present invention is a compound represented by the general formula (A) and / or the general formula (B). R ₁ and R ₂ are each independently a straight-chain, branched, or cyclic C ₁ -C 1
12 unsubstituted or optionally substituted alkyl groups,
Alternatively, it is an aralkyl group having 7 to 18 carbon atoms which may be unsubstituted or have a substituent.

Linear, branched or cyclic C 1 -C 12
Examples of the alkyl group include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, and a cyclopropyl group. And an alkyl group such as a cyclopentyl group, a cyclohexyl group and a 1-adamantylethyl group. Further substituents of these alkyl groups include a hydroxyl group, fluorine, chlorine, bromine, a halogen atom such as iodine, an amino group, a nitro group, a cyano group, a carbonyl group, an ester group, an alkoxy group, and a hetero atom. And a substituent having a cycloalkyl group, an aryloxy group, and a sulfonyl group. Here, the carbonyl group is preferably an alkyl-substituted carbonyl group or an aromatic-substituted carbonyl group, the ester group is preferably an alkyl-substituted ester group or an aromatic-substituted ester group, and the alkoxy group is preferably a methoxy group, an ethoxy group, or a propoxy group. And a t-butoxy group and the like.
Examples of the cycloalkyl group include a cyclohexyl group,
Examples thereof include an adamantyl group, a cyclopentyl group, and a cyclopropyl group. Examples of the group containing a hetero atom include an oxolanyl group. As the aryloxy group,
Examples include a phenoxy group, and the aryl group may have a substituent. Examples of the substituent having a sulfonyl group include an alkylsulfonyl group such as a methylsulfonyl group and an ethylsulfonyl group, and an arylsulfonyl group such as a phenylsulfonyl group. Examples of the aralkyl group include a benzyl group, a phenethyl group, a benzhydryl group, and a naphthylmethyl group. These aralkyl groups can have, as substituents, those described for further substituents of the alkyl group.

As a method for synthesizing the acetal compound,
It can be synthesized by dissolving a vinyl ether compound and a corresponding alcohol compound in an appropriate solvent and reacting in the presence of an acid catalyst. Here, p-
Toluenesulfonic acid, p-toluenesulfonic acid pyridinium salt and the like can be used. The reaction may involve an acetal exchange reaction and may be obtained as a mixture of a plurality of acetal compounds. However, a single substance or a mixture can be suitably used for the purpose of the present invention. The vinyl ether compound and the alcohol compound can be represented by the general formulas (C) and (D), respectively. Hereinafter, examples of the (c) acetal compound suitably used in the present invention will be described. In the following specific examples, Me represents a methyl group, t-Bu represents a t-butyl group, and iso-Bu represents an isobutyl group.

[0019]

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[0020]

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[0021]

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[0022]

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[0023]

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The acetal compound (c), which is an essential component of the present invention, preferably accounts for 0.1 to less than 100 parts by weight based on 100 parts by weight of the solid content of the polymer (a). More preferably, it is 1 part by weight or more and less than 50 parts by weight, and more preferably 2 parts by weight or more and less than 30 parts by weight. If the amount exceeds 100 parts by weight, the heat resistance of the resist tends to decrease, which is not preferable. If the amount is less than 0.1 part by weight, the effect of the present invention may not be exhibited.

(A) A polymer which is decomposed by the action of an acid to increase the solubility in an alkali developing solution (also referred to as an acid-decomposable polymer). The acid-decomposable polymer is a polymer that is decomposed by an acid generated from a photoacid generator upon irradiation with actinic rays or radiation and solubilized in an alkali developer. The acid-decomposable polymer is a polymer in which the alkali-soluble group in the base polymer having an alkali-soluble group is protected by a group capable of decomposing by an action of an acid. As the alkali-soluble group, a phenolic hydroxyl group and a carboxylic acid group are preferable. As the protecting group for these alkali-soluble groups, an acetal group, a ketal group, a t-butyl ester group, a t-butoxycarbonyl group and the like are preferable, an acetal group and a t-butyl ester group are more preferable, and an acetal group is particularly preferable for sensitivity and exposure. Stability of sensitivity fluctuation and dimensional fluctuation with respect to the subsequent withdrawal time (PE
It is preferable from the viewpoint of D).

The backbone polymer is preferably a hydroxystyrene, and a copolymer with an acid-decomposable (meth) acrylate such as t-butyl acrylate or t-butyl methacrylate can also be used. In addition, a non-acid-decomposable group can be introduced for the purpose of adjusting the alkali solubility of the trunk polymer. As a method for introducing a non-acid-decomposable group, a method by copolymerization with styrenes, (meth) acrylic esters, (meth) acrylic amides, or substitution of a hydroxyl group of hydroxystyrene with non-acid-decomposable compounds The method of protecting with a group is preferred. As a substituent of the non-acid-decomposable group, an acetyl group, a mesyl group, a toluenesulfonyl group and the like are preferable, but not limited thereto. Hereinafter, a polymer represented by the general formula (E) is preferable as the acid-decomposable polymer.

[0027]

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In the formula (E), R ₃ represents a hydrogen atom or a methyl group, and each of a plurality of R ₃ may be the same or different. R ₄ is a linear, branched or cyclic C 1 -C 1
An alkyl group optionally having two substituents, having 6 carbon atoms
Represents an aromatic group which may have from 18 to 18 substituents or an aralkyl group which may have from 7 to 18 carbon atoms; Here, specific examples of the alkyl group and the aralkyl group are the same as those described for R ₁ and R ₂ in the general formula (A) or (B). Examples of the aromatic group include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring. On these aromatic rings, those described in the above further substituents of the alkyl group can be present as substituents. R ₅ is a linear, branched C1-4 alkyl groups (e.g. methyl group carbon, ethyl group, propyl group, butyl group, sec- butyl group, t
-Butyl group), an acetyl group, a mesyl group, a tosyl group and the like are preferable, and an acetyl group is more preferable.

R ₆ is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, an aromatic group which may have a substituent having 6 to 12 carbon atoms or a carbon atom having 7 carbon atoms. ~ 18
Represents an aralkyl group which may have one or more substituents. R
₇ and R ₈ are each independently a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms,
It represents an aromatic group which may have 12 substituents or an aralkyl group which may have 7 to 18 carbon atoms. Specific examples of the alkyl group, the aromatic group, and the aralkyl group in R _{6 to} R ₈ are those represented by the general formula (A) or (B).
Examples of the examples described in ₁ , R ₂ and examples of the above R ₃ and R ₄ which fall within the range of the number of carbon atoms can be given.

A, b, c, d, and e each independently represent mol% of each monomer unit, and 0 <a / (a + b) <0.
6, and more preferably 0.05 <a / (a + b) <0.5. 0 ≦ c / (a + b + c) <0.3 is preferable, and 0 ≦ c / (a + b + c) <0.2 is more preferable.
0 ≦ d / (a + b + d) <0.4 is preferable, and 0 ≦ d /
(A + b + d) <0.3 is more preferable. 0 ≦ e / (a
+ B + e) <0.4, and 0 ≦ e / (a + b +
e) <0.3 is more preferred.

Preferred examples of the acid-decomposable polymer are shown below. However, “i-Bu” is an isobutyl group, and “n-Bu”
Represents an n-butyl group, and “Et” represents an ethyl group.

[0032]

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[0033]

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[0034]

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[0035]

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The weight average molecular weight of the polymer (a) was determined by gel permeation chromatography (GP
C), it can be measured as a polystyrene-equivalent molecular weight (Mw), preferably from 2,000 to 200,0
00, more preferably 4,000 to 50,000, particularly preferably 8,000 to 30,000. If the molecular weight exceeds 200,000, the solubility tends to be poor and the resolving power tends to decrease. Further, the polymer (a) may be used in combination of two or more kinds.

The polymer (a) used in the present invention is:
It can be obtained by subjecting a part of the phenolic hydroxyl group of the trunk polymer having a phenolic hydroxyl group to an acetalization reaction using a corresponding vinyl ether compound and an acid catalyst. For example, an acetal group can be introduced by the methods described in JP-A-5-249682, JP-A-8-123032, and JP-A-10-221854. Also,
A desired acetal group can be introduced using the acetal exchange reaction of S. Malik described in J. Photopolym. Sci. Tech., 11 (3) 431 (1998). This method comprises reacting a resin having a phenolic hydroxyl group with a vinyl ether compound represented by the general formula (C) and an alcohol compound represented by the general formula (D) in the presence of an acid catalyst, as shown in the following reaction formula. By doing so, only R ₃ and R ₄ or R ₄ can be introduced as an acetal group as shown in the following general formula (F).

[0038]

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In the present invention, the amount of the polymer (a) added to the composition is preferably from 40 to 99% by weight, more preferably from 60 to 99% by weight, based on the total weight of the solid content of the composition. 97% by weight. In the present invention, an alkali-soluble resin containing no acid-decomposable group can be used in the positive-type radiation-sensitive resin composition, whereby the sensitivity is improved. Alkali-soluble resin containing no acid-decomposable group (hereinafter simply referred to as alkali-soluble resin)
Is a resin soluble in alkali, and preferably includes polyhydroxystyrene, novolak resin and derivatives thereof. A copolymer resin containing a p-hydroxystyrene unit can also be used as long as it is alkali-soluble. Among them, poly (p-hydroxystyrene),
Poly (p- / m-hydroxystyrene) copolymer, poly (p- / o-hydroxystyrene) copolymer, poly (p-
(Hydroxystyrene / styrene) copolymer is preferably used. Further, poly (alkyl-substituted hydroxystyrene) such as poly (4-hydroxy-3-methylstyrene) and poly (4-hydroxy-3,5-dimethylstyrene)
Resins and resins in which some of the phenolic hydroxyl groups of the resins are alkylated or acetylated are also preferably used as long as they are alkali-soluble.

Further, when a part of the phenol nucleus (30 mol% or less of the total phenol nucleus) of the above resin is hydrogenated, the transparency of the resin is improved, and the sensitivity, the resolution and the rectangular formation of the profile are improved. preferable. In the present invention,
The amount of the alkali-soluble resin not containing the acid-decomposable group in the composition is preferably 2 to 60% by weight, more preferably 5 to 30% by weight, based on the total weight of the solid content of the composition. %.

(B) Compound that generates an acid upon irradiation with actinic rays or radiation (also referred to as a photoacid generator) The photoacid generator used in the present invention includes a photoinitiator for photocationic polymerization and a photoradical polymerization. Known photoinitiators, photodecolorants of dyes, photochromic agents, or known light (ultraviolet light of 400 to 200 nm, far ultraviolet light, particularly preferably g-line, h-line, X-rays, KrF excimer laser light), ArF excimer laser light, electron beams, X-rays, compounds generating an acid by a molecular beam or an ion beam, and mixtures thereof can be appropriately selected and used.

Other compounds used in the present invention that generate an acid upon irradiation with actinic rays or radiation include, for example, diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenonium salts, arsonium salts and the like. Onium salts, organic halogen compounds, organometallic / organic halides, photoacid generators having o-nitrobenzyl-type protecting groups, iminosulfone-
And the like, a compound which generates sulfonic acid by photolysis, such as diazotosulfone, diazoketosulfone, and 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 capable of decomposing upon irradiation with actinic rays or radiation to generate an acid, those particularly effectively used are 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).

[0045]

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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.

[0047]

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

[0049]

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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, for example, BF ₄ ⁻ ,
_{^{AsF 6 -, PF 6 -,}} SbF 6 -, SiF 6 2-, ClO 4 -,
CF ₃ SO ₃ ^-, etc. perfluoroalkane sulfonate anion, pentafluorobenzenesulfonic acid anion, condensed polynuclear aromatic sulfonic acid anion such as naphthalene-1-sulfonic acid anion, anthraquinone sulfonic acid anion, a sulfonic acid group-containing dyes Examples include, but are not limited to:

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.

[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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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, JA
me.Chem.Soc., 51,3587 (1929), JVCrivello etal, J.Po
Chem. Ed., 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).

[0061]

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Where Ar^Three, Ar^FourAre each independently substituted
Or an unsubstituted aryl group. R ²⁰⁶Is replaced or
Indicates 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.

[0063]

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[0064]

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[0065]

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

[0067]

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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.

[0069]

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The amount of the compound which decomposes upon irradiation with actinic rays or radiation to generate an acid is usually in the range of 0.001 to 40% by weight based on the solid content in the composition, and is preferably used. Is used in the range of 0.01 to 20% by weight, more preferably 0.1 to 5% by weight. If the amount of the compound that decomposes upon irradiation with actinic rays or radiation to generate an acid 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 high. This is not preferable because the profile is deteriorated and the process (especially baking) margin is narrowed.

(Other Components Used in the Present Invention) The positive-type radiation-sensitive resin composition of the present invention may further contain, if necessary, an acid-decomposable dissolution-promoting compound, a dye, a plasticizer, a surfactant, A sensitizer, an organic basic compound, a compound that promotes solubility in a developer, and the like can be contained. In the positive radiation-sensitive resin composition of the present invention, a fluorine-based and / or silicon-based surfactant (fluorine-based surfactant, silicon-based surfactant and surfactant containing both fluorine atom and silicon atom) Can be contained.
As these surfactants, for example, JP-A-62-36663,
JP-A-61-226746, JP-A-61-226745, JP-A-62-170
950, JP-A-63-34540, JP-A-7-230165, JP-A-8
-62834, JP-A-9-54432 and JP-A-9-5988, and the following commercially available surfactants can be used as they are.

Examples of commercially available surfactants that can be used include F-Top EF301 and EF303 (manufactured by Shin-Akita Kasei Co., Ltd.), Florado FC430 and 431 (manufactured by Sumitomo 3M Limited), Megafac F171, F173, and F176. F189, R08 (Dainippon Ink Co., Ltd.)
Manufactured), Surflon S-382, SC101, 102, 103, 104, 10
5, 106 (manufactured by Asahi Glass Co., Ltd.) or a fluorine-based surfactant 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. The amount of the surfactant is 100% solids in the composition of the present invention.
It is usually 0.01% to 2% by weight, preferably 0.01% to 1% by weight, based on% by weight. These surfactants can be used alone or in combination of two or more.

An organic basic compound can be used in the composition of the present invention. This is preferable because the storage stability is improved and the line width change due to PED is reduced. Preferred organic basic compounds that can be used in the present invention are compounds that are more basic than phenol. Among them, a nitrogen-containing basic compound is preferable. Preferred chemical environments include the structures of the following formulas (A) to (E).

[0074]

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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.

[0076]

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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 cyclic compounds or nitrogen-containing basic compounds having two or more nitrogen atoms having different chemical environments in one molecule. . The nitrogen-containing cyclic compound more preferably has a polycyclic structure. Preferred specific examples of the nitrogen-containing polycyclic compound include a compound represented by the following general formula (F).

[0078]

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In the formula (F), Y and Z each independently represent a linear, branched or cyclic alkylene group which may contain a hetero atom and may be substituted. Here, examples of the hetero atom include a nitrogen atom, a sulfur atom, and an oxygen atom. The alkylene group preferably has 2 to 10 carbon atoms, and more preferably has 2 to 5 carbon atoms. Examples of the substituent of the alkylene group include an alkyl group having 1 to 6 carbon atoms, an aryl group, an alkenyl group, a halogen atom, and a halogen-substituted alkyl group. Further, specific examples of the compound represented by the general formula (F) include the following compounds.

[0080]

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Of the above, 1,8-diazabicyclo [5.4.0] undec-7-ene and 1,5-diazabicyclo [4.3.0] non-5-ene are particularly preferred.

The nitrogen-containing basic compound having two or more nitrogen atoms having different chemical environments in one molecule is particularly preferably a compound containing both a substituted or unsubstituted amino group and a ring structure containing a nitrogen atom. Or a compound having an alkylamino group. As particularly preferred compounds, guanidine, 1,1-dimethylguanidine, 1,1,3,
3, -tetramethylguanidine, 2-aminopyridine,
3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2-
Diethylaminopyridine, 2- (aminomethyl) pyridine, 2-amino-3-methylpyridine, 2-amino-4
-Methylpyridine, 2-amino-5-methylpyridine,
2-amino-6-methylpyridine, 3-aminoethylpyridine, 4-aminoethylpyridine, 3-aminopyrrolidine, piperazine, N- (2-aminoethyl) piperazine, N- (2-aminoethyl) piperidine, 4- Amino-2,2,6,6-tetramethylpiperidine, 4-piperidinopiperidine, 2-iminopiperidine, 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-pyrazolin, N-aminomorpholine, N- (2-aminoethyl) morpholine, trimethylimidazole, triphenylimidazole, methyldiphenylimidazole, and the like, but are not limited thereto.

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 from 0.001 to 10 parts by weight, preferably from 0.01 to 10 parts by weight, per 100 parts by weight of the composition (excluding the solvent).
1 to 5 parts by weight. If the amount is less than 0.001 part by weight, the above effects cannot be obtained. On the other hand, if it exceeds 10 parts by weight, the sensitivity tends to decrease and the developability of the unexposed part tends to deteriorate.

The compound capable of accelerating dissolution in a developer that can be used in the present invention includes two or more phenolic OH groups.
Alternatively, it is a low-molecular compound having at least one carboxy group and a molecular weight of 1,000 or less. When it has a carboxy group, an alicyclic or aliphatic compound is preferable for the same reason as described above.
The preferable addition amount of these dissolution promoting compounds is 2 to 50% by weight, more preferably 5 to 30% by weight, based on the polymer in the present invention. An addition amount exceeding 50% by weight is not preferable because new development defects such as development residue deterioration and pattern deformation during development occur.

Such a phenol compound having a molecular weight of 1000 or less can be prepared by those skilled in the art by referring to the methods described in, for example, JP-A-4-122938, JP-A-2-28531, US Pat. No. 4,916,210, and EP 219294. It can be easily synthesized at Specific examples of the phenol compound are shown below, but the compounds that can be used in the present invention are not limited to these.

Resorcin, phloroglucin, 2, 3, 4
-Trihydroxybenzophenone, 2,3,4,4'-
Tetrahydroxybenzophenone, 2,3,4,3 ',
4 ', 5'-hexahydroxybenzophenone, acetone-pyrogallol condensation resin, fluoroglucoside,
4,2 ', 4'-biphenyltetrol, 4,4'-thiobis (1,3-dihydroxy) benzene, 2,2',
4,4'-tetrahydroxydiphenyl ether, 2,
2 ', 4,4'-tetrahydroxydiphenylsulfoxide, 2,2', 4,4'-tetrahydroxydiphenylsulfone, tris (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) Cyclohexane, 4,4- (α-methylbenzylidene) bisphenol, α, α ′, α ″ -tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene,
α, α ', α "-tris (4-hydroxyphenyl)-
1-ethyl-4-isopropylbenzene, 1,2,2-
Tris (hydroxyphenyl) propane, 1,1,2-
Tris (3,5-dimethyl-4-hydroxyphenyl)
Propane, 2,2,5,5-tetrakis (4-hydroxyphenyl) hexane, 1,2-tetrakis (4-hydroxyphenyl) ethane, 1,1,3-tris (hydroxyphenyl) butane, para [α, α , Α ', α'-tetrakis (4-hydroxyphenyl)]-xylene.

Suitable dyes include oil dyes and basic dyes. Specifically, Oil Yellow # 101, Oil Yellow # 103, Oil Pink # 312, Oil Green BG, Oil Blue BOS, Oil Blue # 60
3. Oil black BY, oil black BS, oil black T-505 (all manufactured by Orient Chemical Co., Ltd.), crystal violet (CI42555), methyl violet (CI42535), rhodamine B
(CI45170B), malachite green (CI42
000), methylene blue (CI52015) and the like.

In order to improve the acid generation rate by exposure, a photosensitizer as described below can be further added. Examples of suitable photosensitizers include benzophenone, p, p'-tetramethyldiaminobenzophenone,
p, p'-tetraethylethylaminobenzophenone,
2-chlorothioxanthone, anthrone, 9-ethoxyanthracene, anthracene, pyrene, perylene, phenothiazine, benzyl, acridine orange, benzoflavin, setoflavin-T, 9,10-diphenylanthracene, 9-fluorenone, acetophenone, phenanthrene, 2-nitro Fluorene, 5-nitroacenaphthene, benzoquinone, 2-chloro-4-nitroaniline, N-acetyl-p-nitroaniline, p-nitroaniline, N-acetyl-4-nitro-1-naphthylamine, picramide, anthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone 1,2-benzanthraquinone, 3-methyl-1,3-diaza-
1,9-benzanthrone, dibenzalacetone, 1,
2-naphthoquinone, 3,3′-carbonyl-bis (5,
7-dimethoxycarbonylcoumarin) and coronene, but are not limited thereto. These photosensitizers can also be used as a light absorbing agent for far ultraviolet light as a light source. In this case, the light absorbing agent exerts the effect of improving the standing wave by reducing the reflected light from the substrate and reducing the influence of multiple reflection in the resist film.

The photosensitive composition of the present invention is dissolved in a solvent capable of dissolving each of the above components, and coated on a support. As the solvent used here, ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, γ-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate , Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate,
Ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N, N-dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, tetrahydrofuran and the like are preferable, and these solvents are used alone or in combination.

In the present invention, a surfactant other than the above-mentioned fluorine-based and / or silicon-based surfactants can be added. Specifically, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether,
Polyoxyethylene alkyl ethers such as polyoxyethylene cetyl ether and polyoxyethylene oleyl ether; polyoxyethylene alkyl allyl ethers such as polyoxyethylene octyl phenol ether and polyoxyethylene nonyl phenol ether; polyoxyethylene / polyoxypropylene block copolymer Sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan fatty acid esters such as sorbitan tristearate,
Polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, etc. Nonionic surfactants and the like. The amount of these surfactants is
Per 100% by weight of solids in the composition of the present invention,
It is at most 2% by weight, preferably at most 1% by weight. These surfactants may be added alone or in some combination.

The above composition is applied on a substrate (eg, silicon / silicon dioxide coating) to be used for the production of precision integrated circuit devices by an appropriate application method such as a spinner, a coater, etc., and then prebaked. By exposing through a mask, performing post-baking and developing, a good resist pattern can be obtained. Here, the exposure light is preferably far ultraviolet light having a wavelength of 250 nm or less. Specifically, a KrF excimer laser (248n
m), an ArF excimer laser (193 nm), an F ₂ excimer laser (157 nm), X-rays, an electron beam, and the like.

Examples of the developer for the photosensitive composition of the present invention include:
Sodium hydroxide, potassium hydroxide, sodium carbonate,
Inorganic alkalis such as sodium silicate, sodium metasilicate and aqueous ammonia, primary amines such as ethylamine and n-propylamine, secondary amines such as diethylamine and di-n-butylamine, and triethylamine and methyldiethylamine Use alkaline aqueous solutions such as triamines, alcoholamines such as dimethylethanolamine and triethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, and cyclic amines such as pyrrole and pichelidine. be able to. Further, an appropriate amount of an alcohol or a surfactant may be added to the above alkaline aqueous solution.

[0093]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples. Synthesis Example 1 32.4 g (0.2 mol) of p-acetoxystyrene was dissolved in 120 ml of butyl acetate, and the mixture was stirred under a nitrogen stream.
At 3 ° C., azobisisobutylnitrile (AIBN) 0.
033 g was added three times every 3 hours, and finally, stirring was continued for another 6 hours to carry out a polymerization reaction. The reaction solution was poured into 1200 ml of hexane to precipitate a white resin. After drying the obtained resin, it was dissolved in 150 ml of methanol. To this was added an aqueous solution of 7.7 g (0.19 mol) of sodium hydroxide / 50 ml of water, and the mixture was hydrolyzed by heating under reflux for 3 hours. Thereafter, 200 ml of water was added for dilution, and neutralized with hydrochloric acid to precipitate a white resin. This resin was separated by filtration, washed with water and dried. Further, the resultant was dissolved in 200 ml of tetrahydrofuran and dropped and reprecipitated in 5 L of ultrapure water with vigorous stirring. This reprecipitation operation was repeated three times. The obtained resin is dried in a vacuum dryer for 120 minutes.
C., dried for 12 hours, poly (p-hydroxystyrene)
[Resin R-1] was obtained. The weight average molecular weight of the obtained resin was 13,000.

Synthesis Example 2 35.25 g (0.2 mol) of p-tert-butoxystyrene monomer and 5.21 g (0.05 mol) of styrene monomer, which were dehydrated and purified by distillation according to a conventional method, were dissolved in 100 ml of tetrahydrofuran. . Azobisisobutylnitrile (AIB) at 83 ° C under a nitrogen stream and stirring
N) 0.033 g was added three times every three hours, and finally, stirring was continued for another six hours to carry out a polymerization reaction.
The reaction solution was poured into 1200 ml of hexane to precipitate a white resin. After drying the obtained resin, it was dissolved in 150 ml of tetrahydrofuran. To this is added 4N hydrochloric acid,
After hydrolysis by heating under reflux for 6 hours, 5 L
The resin was separated by filtration, washed with water and dried. Further dissolved in 200 ml of tetrahydrofuran,
The solution was dropped and reprecipitated in L ultrapure water with vigorous stirring.
This reprecipitation operation was repeated three times. The obtained resin was dried in a vacuum drier at 120 ° C. for 12 hours to obtain a poly (p-hydroxystyrene / styrene) copolymer [Resin R-2]. The weight average molecular weight of the obtained resin was 11,000.

Synthesis Example 3 40 g (0.33 mol) of p-hydroxystyrene 10.7 g (0.08 mol) of tert-butyl acrylate was dissolved in 50 g of dioxane, and 8 g of azobisisobutylnitrile (AIBN) was obtained.
And heated and stirred at 60 ° C. for 8 hours under a nitrogen stream. The reaction solution was poured into 1200 ml of hexane to precipitate a white resin. The resulting resin was dried, dissolved in acetone, dropped into 5 L of ultrapure water with vigorous stirring, and reprecipitated. This reprecipitation operation was repeated three times. The obtained resin was dried in a vacuum dryer at 120 ° C. for 12 hours, and the poly (p
-Hydroxystyrene / tert-butyl acrylate) copolymer [Resin R-3]. The weight average molecular weight of the obtained resin was 21,000.

Synthesis Example 4 Poly (p-hydroxystyrene) 24 g of Nippon Soda Co., Ltd. (molecular weight: 8,000) was dissolved in 100 ml of dioxane, followed by bubbling with nitrogen for 30 minutes. To this solution was added di-tert-butyl-dicarbonate 13.1.
g of triethylamine was added dropwise while stirring. After completion of the dropwise addition, the reaction solution was stirred for 5 hours. This reaction solution was dropped into a 1% by weight aqueous ammonia solution to precipitate a polymer. The obtained resin is dried and dissolved in acetone.
The solution was dropped and reprecipitated in L ultrapure water with vigorous stirring.
This reprecipitation operation was repeated three times. The obtained resin was dried in a vacuum dryer at 120 ° C. for 12 hours to obtain a poly (p-hydroxystyrene / p-tert-butoxycarbonyloxystyrene) copolymer [Resin R-4]. The weight average molecular weight of the obtained resin was 8,300.

Synthesis Example 5 Poly (p-hydroxystyrene) 70 g of Nippon Soda Co., Ltd. (molecular weight: 8,000) was dissolved in 320 g of propylene glycol methyl ether acetate (PGMEA), and p-toluenesulfonic acid pyridinium salt 0.35 was further dissolved.
g was added and dissolved by heating at 60 ° C. This mixture is heated at 60 ° C.
The pressure was reduced to 20 mmHg, and about 40 g of the solvent was distilled off together with the water remaining in the system. After cooling to 20 ° C., 18.9 g of benzyl alcohol was added and dissolved. Then te
17.5 g of rt-butyl vinyl ether was added, and stirring was continued at 20 ° C. for 5 hours. Further, 5.5 g of pyridine was added, followed by 5.9 g of acetic anhydride, and added at 20 ° C. for 1 hour and 30 hours.
For a minute. 280 ml of ethyl acetate was added to the reaction mixture, and 140 ml of water and 12 ml of acetone were further added to perform an extraction operation. After repeating the washing operation three times,
Distillation was performed at 60 ° C. and 20 mmHg to remove water in the system. Further, the obtained resin solution was diluted with acetone and precipitated in a large amount of hexane to obtain a white resin. This operation was repeated three times, and the obtained resin was dried in a vacuum drier for 40 minutes.
The resultant was dried by heating at 24 ° C. for 24 hours to obtain a poly (p-hydroxystyrene / p- (1-benzyloxyethoxy) styrene / p-acetoxystyrene) copolymer [Resin R-5]. The weight average molecular weight was 8,400.

Synthesis Example 6 The same operation as in Synthesis Example 5 was performed except that 70 g of poly (p-hydroxystyrene) [alkali-soluble resin R-1] was used, and 22.0 g of phenethyl alcohol was used instead of benzyl alcohol. Then, poly (p-hydroxystyrene / p- (1-phenoxyethoxy) styrene /
(p-acetoxystyrene) copolymer [Resin R-6] was obtained. The weight average molecular weight was 13,800.

Synthesis Example 7 70 g of poly (p-hydroxystyrene / styrene) [alkali-soluble resin R-2] was dissolved in 320 g of PGMEA, and 0.35 g of pyridinium p-toluenesulfonate was added, followed by heating to 60 ° C. for dissolution. . The mixture was reduced in pressure to 60 mm and 20 mmHg, and about 40 g of the solvent was distilled off together with the water remaining in the system. The mixture was cooled to 20 ° C., and 8.7 g of ethyl vinyl ether was added. Thereafter, stirring was continued at 20 ° C. for 5 hours. After adding 0.3 g of triethylamine, 280 ml of ethyl acetate was added to the reaction mixture.
Was added, and 140 ml of water and 12 ml of acetone were further added to perform an extraction operation. After the water washing operation was repeated three times, the water in the system was removed by distillation at 60 ° C. and 20 mmHg to remove poly (p-hydroxystyrene / p- (1-ethoxyethoxy) styrene / styrene) copolymer [ Resin R-7] was obtained. The weight average molecular weight was 12,600.

Synthesis Example 8 Poly (p-hydroxystyrene / tert-butyl acrylate) [Resin R-3] The same operation as in Synthesis Example 7 was carried out except that 70 g of poly (p-hydroxystyrene / p-butyl acrylate) was used. (1-ethoxyethoxy) styrene / te
rt-butyl acrylate) copolymer [Resin R-8]. The weight average molecular weight was 22,000

Synthesis Example 9 54.1 g of benzyl alcohol and 0.4 g of p-toluenesulfonic acid were dissolved in 230 g of PGMEA.
The water in the system was removed by distillation under reduced pressure at 0 ° C. and 20 mmHg. The fraction was about 18 g. After cooling to 20 ° C., 50.1 g of tert-butyl vinyl ether was added and stirred for 1 hour. After adding 0.4 g of triethylamine to the reaction mixture and stirring, 200 ml of ethyl acetate was added.
Was added, and the mixture was washed and extracted with 100 ml of water. After repeating this washing step three times, ethyl acetate was distilled off under reduced pressure.
A mixture of acetal compounds A-1 and A-2 was obtained. This mixture was isolated by silica gel column chromatography.

[0102]

Embedded image

Synthetic Example 10 Acetal compounds A-3 to A-8 were obtained in the same manner as in Synthetic Example 9 by using the alcohol compounds shown in Table 1 below instead of benzyl alcohol.

[0104]

[Table 1]

Example (Preparation and Evaluation of Radiation-Sensitive Resin Composition) Each material shown in Table 2 below was dissolved in 8 g of PGMEA, and filtered with a 0.1 μm filter to prepare a resin composition solution. (PG
The resins R-7 and R-8 obtained in the MEA solution were converted into solid contents and shown in the table.) The resin composition solution was subjected to hexamethyldisilazane treatment using a spin coater on a silicon wafer. The resist was uniformly coated on the plate, and heated and dried on a hot plate at 130 ° C. for 90 seconds to form a 0.7 μm resist film. The resist film is subjected to pattern exposure using a halftone contact hole mask having a transmittance of 6% using a KrF excimer laser stepper (NA = 0.63), and immediately on the hot plate at 110 ° C. for 90 seconds after exposure. And heated. Further, it is developed with a 2.38% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 60 seconds,
After rinsing with pure water for 30 seconds, it was dried. Here, the obtained pattern was observed with a scanning electron microscope, and the performance of the resist was evaluated as described below.

The sensitivity was determined by the minimum exposure energy (minimum exposure amount) at which a 0.23 μm contact hole on the mask gave a 0.18 μm pattern. The resolving power was represented by the limit resolving power that can be resolved with this minimum exposure amount. The side lobe (resistance) was determined by whether or not a concave portion on the surface due to the sub-peak light (side lobe light) occurred between the contact holes at the minimum exposure amount. When no concave portion was observed between the contact holes, the result was ◎, and the depth was 0.
When a concave portion of less than 1 μm was observed, the result was evaluated as ○, and the depth was 0.1
Those in which a concave portion of μm or more was recognized were represented by x.

[0107]

[Table 2]

[0108]

Embedded image

[0109]

[Table 3]

As shown in Table 3, the compositions of Examples of the present invention were excellent in all of sensitivity, resolution, and side lobe light resistance. On the other hand, the composition of the comparative example provided insufficient data particularly on the side lobe light resistance.

[0111]

According to the present invention, there is provided a chemically amplified positive photoresist composition having high resolution, high sensitivity, and excellent side lobe light resistance in exposure using a halftone mask.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Toru Fujimori 4,000 Kawajiri, Yoshida-cho, Haibara-gun, Shizuoka Pref. BE10 BG00 CB17 CB41 CB45 CB52 CC20

Claims (3)

[Claims] 1. A polymer which is decomposed by the action of an acid to increase the solubility in an alkali developer, (b) a compound which generates an acid upon irradiation with actinic rays or radiation, and (c) a compound represented by the following general formula: A positive radiation-sensitive resin composition containing at least one of the atal compounds represented by (A) or the general formula (B). Embedded image In the formula (A) or (B), R ₁ and R ₂ are each independently a linear, branched or cyclic alkyl group which may have a substituent having 1 to 12 carbon atoms, or a carbon number. Represents an aralkyl group which may have 7 to 18 substituents. 2. The polymer (a) is obtained by reacting an alkali-soluble polymer having a hydroxyl group with a vinyl ether compound represented by the following general formula (C) and an alcohol compound represented by the following general formula (D) under an acid catalyst. The positive-type radiation-sensitive resin composition according to claim 1, which is a polymer obtained by the above method. Embedded image In the formula (C) or (D), R ₃ or R ₄ is each independently a linear, branched or cyclic alkyl group which may have a substituent having 1 to 12 carbon atoms, 6 carbon atoms. Represents an aromatic group which may have from 18 to 18 substituents or an aralkyl group which may have from 7 to 18 carbon atoms; 3. The total amount of the attar compound of (c) is:
The positive-type radiation-sensitive resin composition according to claim 1 or 2, wherein the amount is 0.1 part by weight or more and less than 100 parts by weight based on the total weight of the polymer (a).