JP2002221795A - Positive type photoresist composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a chemically-sensitized positive type photoresist composition with both its developing faulty performance and line edge roughness simultaneously-improved. SOLUTION: The positive type photoresist composition is provided with (A) a compound generating acid by irradiation of an active light ray or a radial ray and (B) a resin insoluble or hardly soluble for alkali, dissolved by action of acid to increase its solubility in an alkali developer. It is characterized in that the resin of (B) comprises a mixture of at least two types of resins (B1) and (B2) to satisfy the following formula: 9.9>=(B1M)/(B2M)>=1.3 where: (B1M) = dispersity of (B1): Mw (B2M) = dispersity of (B2): Mn.

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 EP 29,139. The chemically amplified positive resist composition generates an acid in the exposed area by irradiation with radiation such as far 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.

The above chemically amplified positive resist composition comprises an alkali-soluble resin, a compound that generates an acid upon exposure to radiation (photoacid generator), and a compound that inhibits dissolution of the alkali-soluble resin having an acid-decomposable group. A three-component system, a two-component system composed of a resin having a group which becomes alkali-soluble by being decomposed by reaction with an acid, and a resin having a group which becomes alkali-soluble by being decomposed by a reaction with an acid; It can be broadly classified into a hybrid system comprising a low molecular weight dissolution inhibiting compound having an acid-decomposable group and a photoacid generator.

[0004]

There are two types of resins (acid-decomposable resins) which are decomposed by the action of an acid used in the above-described chemically amplified positive resist composition and have increased solubility in an alkali developing solution. Various techniques for improving the performance by mixing as described above are known. In addition, for a single resin, a technique that focuses on the degree of dispersion of the resin is also known. However, even if such a technique is used, there are problems in development defect performance and line edge roughness performance.
Accordingly, an object of the present invention is to provide a chemically sensitized positive photoresist composition which has improved development defect performance and line edge roughness simultaneously.

[0005]

Means for Solving the Problems In view of the present situation, the present inventors have made intensive studies and as a result, have achieved the above object by using a positive photoresist composition having at least two resins having different degrees of dispersion. Thus, the present invention has been completed. That is, the positive photoresist composition according to the present invention has the following constitution.

(1) (A) a compound which generates an acid upon irradiation with actinic rays or radiation; (B) it is insoluble or hardly soluble in alkali, decomposes by the action of an acid, and has a solubility in an alkali developing solution. In the positive resist composition containing a resin that increases the dispersibility, the resin (B) is composed of a mixture of at least two kinds of resins (B1) and (B2), and the respective dispersities Mw / Mn are (B1M) And (B2
M), 9.9 ≧ (B1M) / (B2M) ≧
1.3. A positive photoresist composition which satisfies 1.3.

(2) The resin as described in (1) above, wherein at least one of the resins (B1) and (B2) contains a repeating unit represented by the following general formulas (IV) and (V). A positive photoresist composition.

[0008]

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In the above formula, L represents a hydrogen atom, a linear, branched or cyclic alkyl group which may be substituted, or an aralkyl group which may be substituted. Z is a linear, branched or cyclic alkyl group which may be substituted;
Or an aralkyl group which may be substituted. Also Z
And L may combine to form a 5- or 6-membered ring.

(3) The resin of (1) or (2), wherein both the resins (B1) and (B2) contain repeating units represented by the following general formulas (IV) and (V). 4. The positive photoresist composition according to item 1.

[0011]

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In the above general formula, L represents a hydrogen atom, an optionally substituted linear, branched or cyclic alkyl group, or an optionally substituted aralkyl group. Z is a linear, branched or cyclic alkyl group which may be substituted;
Or an aralkyl group which may be substituted. Also Z
And L may combine to form a 5- or 6-membered ring.

[0013]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. [1] (B) Resin which is insoluble or hardly soluble in alkali, decomposes by the action of an acid, and increases the solubility in an alkali developer. The resin (B) used in the present invention is alkali-soluble. On the other hand, it is a resin that is insoluble or hardly soluble, decomposes under the action of an acid, and increases the solubility in an alkaline developer. Such a resin that is insoluble or hardly soluble in alkali, decomposes by the action of an acid, and increases the solubility in an alkali developer, has a repeating unit corresponding to hydroxystyrene, and is reacted by the action of an acid. A resin that decomposes and increases solubility in alkali is preferably used. Here, the hydroxystyrene may be any of o-, m-, or p-hydroxystyrene, and may be partially hydrogenated. Further, it may have a substituent other than a hydroxyl group. Examples of such a substituent include an alkyl group, an alkoxy group, an aralkyl group, and an aryl group. Examples of the resin having a group (hereinafter, referred to as an “acid-decomposable group”) that is decomposed by the action of an acid and increases the solubility in an alkaline developer, which is used in the positive chemically amplified resist of the present invention, , A resin having an acid-decomposable group in the main chain or side chain of the resin, or in both the main chain and the side chain.
Among them, a resin having a group which can be decomposed by an acid in a side chain is more preferable.

The acid-decomposable group is preferably -C
OOA ⁰ and —O—B ⁰ groups. Examples of the group containing these are the groups represented by —R ⁰ —COOA ⁰ and —Ar—O—B ⁰ . Here, A ⁰ is -C (R ⁰¹ ) (R
^{02) (R 03), -} Si (R 01) ( indicating the R ⁰²⁾ (R ^{0 3)} or ^{-C (R 04) (R 05} ) -O-R 06 group. B ⁰ is
A ⁰ or —CO—OA ⁰ represents a group. R ⁰¹ , R ⁰² , R ⁰³ ,
R ⁰⁴ and R ⁰⁵ are the same or different and represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group, and R ⁰⁶ represents an alkyl group or an aryl group. However, at least two of R ^{01 to} R ⁰³ are groups other than a hydrogen atom, and two of R ^{01 to} R ⁰³ and R ^{04 to} R ⁰⁶
Two groups may combine to form a ring. R ⁰ represents a divalent aliphatic or aromatic hydrocarbon group which may have a substituent, and -Ar- represents a divalent aromatic group which may have a monocyclic or polycyclic substituent. Represents a group.

The alkyl group preferably has 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group and a t-butyl group. Preferred are those having 3 to 10 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclohexyl group and adamantyl group, and alkenyl groups having 2 to 2 carbon atoms such as vinyl group, propenyl group, allyl group and butenyl group. Preferably, the aryl group has 6 to 1 carbon atoms such as phenyl, xylyl, toluyl, cumenyl, naphthyl and anthracenyl.
Four are preferred. Further, as these substituents, a hydroxyl group, a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, the above-mentioned alkyl group, methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group, Alkoxy groups such as n-butoxy group, isobutoxy group, sec-butoxy group, t-butoxy group, alkoxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group, benzyl group, phenethyl group, aralkyl groups such as cumyl group, aralkyloxy Groups, formyl group, acetyl group, butyryl group, benzoyl group, cyanyl group, acyl group such as valeryl group, acyloxy group such as butyryloxy group, the above alkenyl group, vinyloxy group, propenyloxy group, allyloxy group, butenyloxy group, etc. Alkenyloxy group, above Aryl group, an aryloxy group such as phenoxy group, and an aryloxycarbonyl group such as benzoyloxy group.

An acid-decomposable group (—COOA ⁰ or —O—
B ⁰ ) is preferably a silyl ether group, a cumyl ester group, an acetal group, a tetrahydropyranyl ether group, an enol ether group, an enol ester group, a tertiary alkyl ether group, a tertiary alkyl ester group, or a tertiary alkyl ester group. And the like. More preferred are a tertiary alkyl ester group, a tertiary alkyl carbonate group, a cumyl ester group, an acetal group, and a tetrahydropyranyl ether group. Particularly preferred is an acetal group.

Next, when the group decomposable by these acids is bonded as a side chain, the base resin has a repeating unit corresponding to the above-mentioned hydroxystyrene and has -OH or -COOH, preferably- It is an alkali-soluble resin having a ^R0- COOH or -Ar-OH group.
For example, an alkali-soluble resin described below can be used.

From the viewpoint of achieving a rectangular profile, an alkali-soluble resin having a high transmittance to far ultraviolet light or excimer laser light is preferable. Preferably, the transmittance at a wavelength of 248 nm with a thickness of 1 μm is 20 to 90%. From such a viewpoint, a particularly preferred alkali-soluble resin is o
-, M-, p-poly (hydroxystyrene) and copolymers thereof, hydrogenated poly (hydroxystyrene), halogen- or alkyl-substituted poly (hydroxystyrene), partially O-alkylated poly (hydroxystyrene) or O-acylated product, styrene-hydroxystyrene copolymer, α-methylstyrene-hydroxystyrene copolymer and hydrogenated novolak resin.

The resin having an acid-decomposable group used in the present invention is disclosed in EP 254853, JP-A-2-25.
No. 850, No. 3-223860, No. 4-251259
As described in No. 2, the alkali-soluble resin is reacted with a precursor of an acid-decomposable group, or an alkali-soluble resin monomer having an acid-decomposable group bonded thereto is copolymerized with various monomers. Can be obtained.

Specific examples (1) to (18) of the resin (B) used in the present invention, which are insoluble or hardly soluble in alkali, decompose by the action of an acid, and increase the solubility in an alkali developer. ) Is shown below, but the present invention is not limited to these.

(1): pt-butoxystyrene / p-
Hydroxystyrene copolymer, (2): p- (t-butoxycarbonyloxy) styrene / p-hydroxystyrene copolymer, (3): p- (t-butoxycarbonylmethyloxy)
Styrene / p-hydroxystyrene copolymer, (4): 4- (t-butoxycarbonylmethyloxy)
-3-methylstyrene / 4-hydroxy-3-methylstyrene copolymer, (5): p- (t-butoxycarbonylmethyloxy)
Styrene / p-hydroxystyrene (10% hydrogenated) copolymer, (6): m- (t-butoxycarbonylmethyloxy)
Styrene / m-hydroxystyrene copolymer, (7): o- (t-butoxycarbonylmethyloxy)
Styrene / o-hydroxystyrene copolymer, (8): p- (cumyloxycarbonylmethyloxy)
Styrene / p-hydroxystyrene copolymer,

(9): p- (t-butoxycarbonylmethyloxy) styrene / p-hydroxystyrene / styrene copolymer, (10): pt-butoxystyrene / p-hydroxystyrene / fumaronitrile copolymer, (11): p-hydroxystyrene / t-butyl methacrylate copolymer, (12): styrene / p-hydroxystyrene / t-butyl methacrylate copolymer (13): p-hydroxystyrene / t-butyl acrylate copolymer (14): styrene / p-hydroxystyrene / t-butyl acrylate copolymer (15): p- (t-butoxycarbonylmethyloxy) styrene / p-hydroxystyrene / N-methylmaleimide copolymer, 16): p-hydroxystyrene / t-butyl acrylate / p- ( (t-butoxycarbonyloxy) styrene copolymer, (17): p-hydroxystyrene / t-butyl acrylate / p- (t-butoxycarbonylmethyloxy)
Styrene copolymer,

(18): p-hydroxystyrene / t-
Butyl acrylate / p-acetoxystyrene copolymer (see the following structural formula).

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In the present invention, it is decomposed by the action of an acid,
As the resin (B) that increases the solubility in an alkali developer, a resin containing a repeating structural unit represented by the following general formula (IV) or (V) is preferable. This allows
The effects of the present invention become more remarkable.

[0025]

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[In the above formula, L represents a hydrogen atom, an optionally substituted linear, branched or cyclic alkyl group, or an optionally substituted aralkyl group. Z represents a linear, branched or cyclic alkyl group which may be substituted, or an aralkyl group which may be substituted. Further, Z and L may combine to form a 5- or 6-membered ring. ]

The alkyl group in L and Z in the general formula (IV) includes methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, cyclopentyl, hexyl Group, cyclohexyl group, octyl group, dodecyl group, etc.
Straight-chain, branched or cyclic ones.

Preferred substituents which the alkyl groups of L and Z may have are an alkyl group, an alkoxy group, a hydroxyl group,
Halogen atom, nitro group, acyl group, acyloxy group,
Acylamino group, a sulfonylamino group, an alkylthio group, an arylthio group, an aralkylthio group, a thiophenecarbonyloxy group, a thiophenemethylcarbonyloxy group, and a heterocyclic residue such as a pyrrolidone residue.
Preferably, it has 12 or less carbon atoms.

Examples of the alkyl group having a substituent include a cyclohexylethyl group, an alkylcarbonyloxymethyl group, an alkylcarbonyloxyethyl group, an arylcarbonyloxyethyl group, an aralkylcarbonyloxyethyl group, an alkyloxymethyl group, an aryloxymethyl group, Aralkyloxymethyl group, alkyloxyethyl group, aryloxyethyl group, aralkyloxyethyl group, alkylthiomethyl group, arylthiomethyl group, aralkylthiomethyl group, alkylthioethyl group,
An arylthioethyl group, an aralkylthioethyl group and the like can be mentioned.

The alkyl in these groups is not particularly limited, but may be any of a chain, a ring and a branch, and may further have a substituent such as the above-mentioned alkyl group and alkoxy group. Examples of the alkylcarbonyloxyethyl group include a cyclohexylcarbonyloxyethyl group, t-
Butylcyclohexylcarbonyloxyethyl group, n-
A butylcyclohexylcarbonyloxyethyl group and the like can be mentioned.

The aryl is also not particularly limited, but generally includes those having 6 to 14 carbon atoms such as phenyl group, xylyl group, toluyl group, cumenyl group, naphthyl group and anthracenyl group. It may have a substituent such as an alkoxy group. Examples of the aryloxyethyl group include a phenyloxyethyl group and a cyclohexylphenyloxyethyl group.
The aralkyl is not particularly limited, but examples thereof include a benzyl group. Examples of the aralkylcarbonyloxyethyl group include a benzylcarbonyloxyethyl group.

The aralkyl group of L and Z in the general formula (IV) includes, for example, a substituted or unsubstituted benzyl group,
Examples thereof include those having 7 to 15 carbon atoms, such as a substituted or unsubstituted phenethyl group. Preferred substituents on the aralkyl group include an alkoxy group, a hydroxyl group, a halogen atom, a nitro group, an acyl group, an acylamino group, a sulfonylamino group, an alkylthio group, an arylthio group, an aralkylthio group, and the like. Examples thereof include an alkoxybenzyl group, a hydroxybenzyl group, and a phenylthiophenethyl group. The range of the carbon number of the substituent which the aralkyl group as L or Z may have is preferably 12 or less.

As described above, the introduction of a bulky group such as a phenyl group or a cyclohexyl group at the terminal of the substituted alkyl group or the substituted aralkyl group can further improve the edge roughness.

5 or 6 formed by combining L and Z with each other
Examples of the member ring include a tetrahydropyran ring and a tetrahydrofuran ring.

The ratio of the repeating structural unit represented by the general formula (IV) to the repeating structural unit represented by the general formula (V) in the resin is preferably from 1/99 to 60/40, more preferably It is 5/95 to 50/50, more preferably 10/90 to 40/60.

The resin containing the repeating structural units represented by the general formulas (IV) and (V) may include structural units derived from other monomers. Other monomers include hydrogenated hydroxystyrene; halogen, alkoxy or alkyl-substituted hydroxystyrene; styrene; halogen, alkoxy, acyloxy or alkyl-substituted styrene; maleic anhydride; acrylic acid derivative; methacrylic acid derivative; Examples include, but are not limited to:
The ratio between the structural units of the general formulas (IV) and (V) and the structural units of the other monomers is represented by a molar ratio of [(IV) +
(V)] / [other monomer components] = 100/0 to 50 /
50, preferably 100/0 to 60/40, and more preferably 100/0 to 70/30.

Specific examples of the resin containing a repeating structural unit represented by the above general formulas (IV) and (V) include:
The following are mentioned.

[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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In the above specific examples, Me is a methyl group, E
t is an ethyl group, n-Bu is an n-butyl group, iso-Bu
Represents an isobutyl group, and t-Bu represents a t-butyl group.

When an acetal group is used as an acid-decomposable group, a polyhydroxy compound is added at the synthesis stage to adjust the alkali dissolution rate and improve heat resistance to introduce a cross-linking site connecting the polymer main chain with a polyfunctional acetal group. May be. The amount of the polyhydroxy compound to be added is 0.01 to 5 mol%, more preferably 0.05 to 4 mol%, based on the amount of hydroxyl groups in the resin. Examples of the polyhydroxy compound include those having 2 to 6 phenolic hydroxyl groups or alcoholic hydroxyl groups, preferably 2 to 4 hydroxyl groups, and more preferably 2 to 4 hydroxyl groups.
Or three. Specific examples of the polyhydroxy compound are shown below, but the invention is not limited thereto.

[0050]

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In the present invention, the content of the repeating unit having an acid-decomposable group in the resin (B) is preferably from 5 to 50 mol%, more preferably from 10 to 40 mol%, based on all repeating units. It is. In the present invention, (B)
The content of the repeating unit corresponding to hydroxystyrene in the resin is preferably from 5 to 95 mol%, more preferably from 10 to 85 mol%, based on all repeating units.

The weight average molecular weight (Mw) of the resin having an acid-decomposable group is preferably in the range of 2,000 to 300,000. If it is less than 2,000, the film is greatly reduced due to the development of the unexposed portion, and if it exceeds 300,000, the dissolution rate of the resin itself in alkali becomes slow and the sensitivity is lowered. Here, the weight average molecular weight is defined as a polystyrene equivalent value of gel permeation chromatography.

The resins (B1) and (B1) of the present invention
2), but at the time of mixing, when the respective dispersities Mw / Mn are (B1M) and (B2M), 9.9 ≧ (B1M) / (B2
M) ≧ 1.3, preferably 7.0 ≧ (B1M) / (B2
M) It is necessary to satisfy ≧ 1.3.

To satisfy this, for example, a mixture of a monodispersed resin and a non-monodispersed resin, a mixture of a narrower resin and a slightly wider resin in a monodispersion, a mixture of a polydisperse resin with a wider resin, and the like are given. Conceivable. Among the above, it is preferable to mix a monodispersed resin and a resin that is not.

The monodispersed resin can be synthesized by a living polymerization method such as anionic ribink polymerization, cationic living polymerization, and radical living polymerization. The polydispersed resin can be synthesized by ordinary radical polymerization or the like. further,
In these polymerization methods, the degree of dispersion can be adjusted by adjusting the amount of the initiator and the polymerization temperature.

In the present invention, the monodispersed resin refers to a resin having a degree of dispersion Mw / Mn of 1.0 or more and 1.5 or less.

By mixing the two kinds of resins satisfying the above conditions, development defects, line edge roughness, and density dependency can be improved.
In the case of (B1M) / (B2M) <1.3, deterioration of development defect capability was confirmed, and in the case of (B1M) / (B2M)> 9.9, remarkable deterioration of line edge roughness was confirmed.

The resin (B1) and the resin (B2) in the above resin
Is preferably 1/99 to 99/1, more preferably 5/95 to 95/5, and even more preferably 10/90 to 90/10.

The amount of the resin (B) to be added is usually in the range of 0.001 to 99% by weight, preferably 0.01 to 90% by weight, more preferably 0.01 to 90% by weight, based on the solid content in the composition. Is used in the range of 0.1 to 80% by weight.

The composition comprises at least two of the above-mentioned resins.
The method is characterized in that the seeds are mixed, but a resin may be further mixed. When more resins are mixed, it is necessary that at least one of them has a different dispersity from the other three. Even if the structure is different, it is considered only in the dispersity and is included in the above mixing ratio. I just want to. For example, when four types of resins are mixed, when one type has a dispersity of 1.1, the remaining three types are included in the above composition ratio.
0, 2.5, 2.8, etc. If the dispersities of all the resins are different, the resins farthest apart are compared with each other as a reference to determine whether or not the resins are included in the above composition ratio.

[2] (A) Compound that Generates Acid by Irradiation with Actinic Ray or Radiation (Photoacid Generator) The (A) photoacid generator used in the present invention is a compound which generates an acid by irradiation with actinic ray or radiation. It is a compound that is generated. 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 (ultraviolet light of 400 to 200 nm, far ultraviolet light, particularly preferably g-ray, h-ray, i-ray, KrF excimer laser light), ArF excimer laser light, electron beam, X-ray, molecular beam or ion beam And a mixture thereof can be appropriately selected and used.

Examples of other photoacid generators used in the present invention include 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 above-mentioned photoacid generators, those 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).

[0065]

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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.

[0067]

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

[0069]

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Here, the formulas Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aryl group. Preferred substituents include an alkyl group, a haloalkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a nitro group, a carboxyl group, an alkoxycarbonyl group, a hydroxy group, a mercapto group, and a halogen atom. R ²⁰³ ,
R ²⁰⁴ and R ²⁰⁵ each independently represent a substituted or unsubstituted alkyl group or aryl group. Preferably, the carbon number is 6 to
They are a 14 aryl group, an alkyl group having 1 to 8 carbon atoms, and substituted derivatives thereof. Preferred substituents are an alkoxy group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms, a nitro group, a carboxyl group, a hydroxy group and a halogen atom for the aryl group, and a substituent for the alkyl group. It is an alkoxy group having 1 to 8 carbon atoms, a carboxyl group, or an alkoxycarbonyl group.

[0071] Z ^- represents a counter anion, for example BF ₄ ^{-,
_{AsF 6 -, PF 6 -,}} SbF 6 -, SiF 6 2-, ClO 4 -,
Alkanesulfonic acid which may be substituted, perfluoroalkanesulfonic acid, benzenesulfonic acid which may be substituted, naphthalenesulfonic acid, anthracenesulfonic acid,
Examples include but are not limited to camphorsulfonic acid anion, saccharin anion, and the like. Preferred are anions of alkanesulfonic acid, perfluoroalkanesulfonic acid, alkyl-substituted benzenesulfonic acid, pentafluorobenzenesulfonic acid, and saccharin anion.

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

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

[0074]

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[0075]

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[0076]

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[0077]

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[0078]

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[0079]

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[0080]

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[0081]

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[0082]

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[0083]

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[0084]

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[0085]

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[0086]

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[0087]

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[0088]

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[0089]

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The above-mentioned onium salts represented by the general formulas (PAG3) and (PAG4) are known, for example, JWKnapczyk
etal, J. Am. Chem. Soc., 91, 145 (1969), AL Maycok
etal, J. Org. Chem., 35, 2532, (1970), E. Goethas etal,
Bull. Soc. Chem. Belg., 73, 546, (1964), HMLei
cester, J. Ame.Chem. Soc., 51, 3587 (1929), JV
Crivello et al., J. Polym.Chem.Ed., 18,2677 (1980), U.S. Patent Nos. 2,807,648 and 4,247,473, JP-A-53-473.
It can be synthesized by the method described in JP-A-101,331 and the like.

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

[0092]

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In the formula, Ar ³ and Ar ⁴ each independently represent a substituted or unsubstituted aryl group. R ²⁰⁶ represents a substituted or unsubstituted alkyl group or aryl group. A represents a substituted or unsubstituted alkylene group, alkenylene group, or arylene group. Specific examples include the following compounds, but are not limited thereto.

[0094]

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[0095]

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[0096]

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

[0098]

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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.

[0100]

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The compound (A) that generates an acid upon irradiation with actinic rays or radiation is preferably at least one of a compound having a sulfonium salt structure and a compound having a diazodisulfone structure, and more preferably a compound having a diazodisulfone structure. It is preferable to use both a compound having a structure and a compound having a diazodisulfone structure.
Thereby, the effect of the present invention becomes more remarkable.

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 solid content 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.

In the composition of the present invention, a compound capable of generating a carboxylic acid upon irradiation with actinic rays or radiation (carboxylic acid generating compound) can be used. Thereby, the stability at the time of storage is further improved, the line width change due to PED is further reduced, and the density dependency is further improved. Examples of the carboxylic acid generating compound include an onium salt having a cation (preferably a triphenylsulfonium cation) exemplified in the photoacid generator and an anion of carboxylic acid. Specific examples include diphenyliodonium carboxylate, triphenylsulfonium carboxylate, diphenyliodonium benzenecarboxylate, triphenylsulfoniumbenzenecarboxylate, and those in which a substituent is introduced. Among them, triphenylsulfonium carboxylate and triphenylsulfonium-substituted benzenecarboxylate are more preferred. The amount of the carboxylic acid generating compound to be added in the composition of the present invention is usually 0.01 to 40% by weight, preferably 0.01 to 20% by weight, based on the total solid content of the composition.

An organic basic compound can be used in the composition of the present invention. This is preferable because the stability during storage is further improved and the line width change due to PED is further 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).

[0105]

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

[0107]

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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.

[0109]

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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. 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 amino Morpholine, substituted or unsubstituted aminoalkylmorpholine and the like. Preferred substituents are an amino group, aminoalkyl group, alkylamino group, aminoaryl group, arylamino group, alkyl group, alkoxy group, acyl group, acyloxy group, aryl group, aryloxy group, nitro group, hydroxyl group, cyano group It is.

Particularly preferred compounds are 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, 2-pyrazoline, 3
-Pyrazoline, N-aminomorpholine, N- (2-aminoethyl) morpholine, trimethylimidazole,
Examples include, but are not limited to, triphenylimidazole, methyldiphenylimidazole, and the like.

These nitrogen-containing basic compounds may be 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 0.03% by weight, based on the solid content of the whole composition in the composition of the present invention.
1 to 5% by weight. If the amount is less than 0.001% by weight, the above effects 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 chemical amplification type positive resist composition of the present invention may further have a solubility in a surfactant, an acid-decomposable dissolution inhibiting compound, a dye, a pigment, a plasticizer, a photosensitizer and a developing solution, if necessary. A compound having two or more phenolic OH groups to be promoted can be contained.

The positive resist composition of the present invention preferably contains a surfactant. Specifically, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether, polyoxyethylene nonyl phenol ether and the like Sorbitan such as polyoxyethylene alkyl allyl ethers, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate Fatty acid esters, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopal Te - door, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate,
Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan tristearate, EFTOP EF301, EF30
3, EF352 (manufactured by Shin-Akita Kasei Co., Ltd.), Megafac F171, F173, F176, F189, R08 (manufactured by Dainippon Ink Co., Ltd.), Florad FC430, FC4
31 (manufactured by Sumitomo 3M Limited), Asahi Guard AG7
10, Surflon S-382, SC101, SC10
2, SC103, SC104, SC105, SC106
(Asahi Glass Co., Ltd.) and other fluorine-based surfactants, organosiloxane polymer KP341 (Shin-Etsu Chemical Co., Ltd.)
No.) or an acrylic or methacrylic (co) polymerized polyflow No. 75, no. 95 (manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.) and Troysol S-366 (manufactured by Troy Chemical Co., Ltd.). Among these surfactants, a fluorine-based or silicon-based surfactant is preferable in terms of coating properties and reduction of development defects.

The amount of the surfactant is usually 0.01% by weight to 2% by weight, preferably 0.01% by weight to 1% by weight, based on the solid content of the whole composition in the composition of the present invention. is there. These surfactants can be used alone or in combination of two or more.

Examples of the acid-decomposable dissolution inhibiting compound which can be used in the positive resist composition of the present invention include, for example, those disclosed in
And low-molecular acid-decomposable dissolution inhibiting compounds described in JP-A-134415 and JP-A-6-51519.

Further, by adding a spectral sensitizer as described below and sensitizing the photoacid generator to be used in a longer wavelength region than the deep ultraviolet where the photoacid generator used has no absorption, the chemically amplified positive resist of the present invention is obtained. Can be made sensitive to i or g rays. Suitable spectral sensitizers include, specifically, benzophenone, p, p'-tetramethyldiaminobenzophenone, p, p'-tetraethylethylaminobenzophenone, 2-chlorothioxanthone, anthrone, 9-ethoxyanthracene, anthracene, pyrene , Perylene,
Phenothiazine, benzyl, acridine orange, benzoflavin, cetoflavin-T, 9,10-diphenylanthracene, 9-fluorenone, acetophenone, phenanthrene, 2-nitrofluorene, 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-
Benzuansuraquinone, 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.

Examples of the compound having two or more phenolic OH groups which promote the solubility in a developing solution include polyhydroxy compounds. Preferably, the polyhydroxy compound includes phenols, resorcin, phloroglucin, phloroglucid, 2, 3,4-trihydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, α, α ′, α ″ -tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene, tris ( 4-hydroxyphenyl) methane, tris (4-hydroxyphenyl) ethane, and 1,1′-bis (4-hydroxyphenyl) cyclohexane.

The chemically amplified positive resist composition of the present invention is prepared by dissolving each of the above-mentioned components in a solvent for dissolving and coating the solution on a support. Examples of usable solvents include ethylene dichloride, cyclohexanone and cyclohexanone. Pentanone, 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,
Dimethyl sulfoxide, N-methylpyrrolidone, tetrahydrofuran and the like are preferable, and these solvents are used alone or in combination.

The above-mentioned chemically amplified positive resist composition is applied onto a substrate (eg, silicon / silicon dioxide coating) used for the production of precision integrated circuit devices by an appropriate application method such as a spinner or a coater. A good resist pattern can be obtained by exposing through a mask, baking and developing.

Examples of the developing solution of the chemically amplified positive resist composition of the present invention include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium phosphate, 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; dimethylethanolamine;
Alcoholamines such as triethanolamine, amides such as formamide and acetamide, tetramethylammonium hydroxide, trimethyl (2-hydroxyethyl) ammonium hydroxide, tetraethylammonium hydroxide, tributylmethylammonium hydroxide, tetraethanolammonium hydroxide , Methyltriethanol ammonium hydroxide,
Quaternary ammonium salts such as benzylmethyldiethanolammonium hydroxide, benzyldimethylethanolammonium hydroxide, benzyltriethanolammonium hydroxide, tetrapropylammonium hydroxide and tetrabutylammonium hydroxide, and alkalis such as cyclic amines such as pyrrole and piperidine And the like.

[0123]

The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. (1) (Synthesis Example of Resin) Resin can be synthesized by acetalization using either a method using vinyl ether or an acetal exchange method using alcohol and alkyl vinyl ether. For efficient and stable synthesis, the following dehydration azeotropic method can be preferably used. However, these synthesizing methods are merely examples, and the present invention is not limited thereto.

Synthesis Example 1 (Synthesis of Resin B-1) VP15000 (1800 g) manufactured by Nippon Soda and propylene glycol monomethyl ether acetate (PGME)
A) (8200 g) was dissolved in a flask and distilled under reduced pressure to distill off water and PGMEA azeotropically. After confirming that the water content was sufficiently low, a solution of pyridinium-p-toluenesulfonate (9.0 g) dissolved in cyclohexaneethanol (576.2 g) was added to the reaction solution, and t-butyl vinyl ether was further added. (450.2
g) was added and stirred at room temperature for 5 hours. Thereto, pyridine (142.2 g) and acetic anhydride (153.2 g) were added, and the mixture was stirred at room temperature for 2 hours. Water (3.6 liters) and ethyl acetate (7.2 liters) were added to the reaction solution, and the mixture was separated.
After washing with water, ethyl acetate, water,
The azeotropic PGMEA was distilled off to obtain a substituted alkali-soluble resin B-1 (30% PGMEA solution) according to the present invention. The obtained resin had a weight average molecular weight of 17,0.
00 and the degree of dispersion (Mw / Mn) was 1.08. The protection rate was 20% for the acetalized hydroxystyrene unit and 10% for the acetoxystyrene unit.

Also, the charged amounts of t-butyl vinyl ether, cyclohexaneethanol, acetic anhydride, and pyridine were adjusted, and the following resins B-1HHH, B-1HH,
B-1H, B-1L, B-1LL, and B-1LLL were obtained.

[0126]

[Table 1]

Synthesis Example 2 (Synthesis of Resin B-2) A p-acetoxystyrene monomer (or pt-butoxystyrene monomer) was polymerized using dimethyl 2,2′-azobisisobutyrate (AIBN) as an initiator. Further deprotection with hydrochloric acid or the like gave R-1. The obtained R-1 had a weight average molecular weight of 17,000 and a degree of dispersion (Mw / Mn).
1.6. R-1 (1800 g) and propylene glycol monomethyl ether acetate (PGMEA)
(8200 g) was dissolved in the flask, and distilled under reduced pressure to distill off water and PGMEA azeotropically. After confirming that the water content was sufficiently low, cyclohexaneethanol (5
76.2 g) and a solution of pyridinium-p-toluenesulfonate (9.0 g) dissolved therein was added to the reaction solution, and t-butyl vinyl ether (450.2 g) was further added.
Was added and stirred at room temperature for 5 hours. Thereto, pyridine (142.2 g) and acetic anhydride (153.2 g) were added, and the mixture was stirred at room temperature for 2 hours. Water (3.6 liters) and ethyl acetate (7.2 liters) were added to the reaction solution, and the mixture was separated.
After washing with water, ethyl acetate, water,
The azeotropic PGMEA was distilled off to obtain a resin B-2. The obtained resin had a weight average molecular weight of 17,000 and a degree of dispersion (Mw).
/ Mn) was 1.6. The protection rate was 20% for the acetalized hydroxystyrene unit and 10% for the acetoxystyrene unit.

Further, the amounts of t-butyl vinyl ether, cyclohexaneethanol, acetic anhydride, and pyridine were adjusted, and the following resins B-2HHH, B-2HH,
B-2H, B-2L, B-2LL, and B-2LLL were obtained.

[0129]

[Table 2]

Synthesis Example 3 (Synthesis of Resin B-3) VP15000 (100 g) manufactured by Nippon Soda and propylene glycol monomethyl ether acetate (PGMEA)
(400 g) was dissolved in a flask and distilled under reduced pressure.
Water and PGMEA were azeotropically distilled off. After confirming that the water content was sufficiently low, ethyl vinyl ether (25.0) was used.
g) and p-toluenesulfonic acid (0.02 g),
Stirred at room temperature for 1 hour. Triethylamine (0.03 g) was added to the reaction solution to stop the reaction, and water (400 m
l) and ethyl acetate (800 ml) were added, liquid-separated, washed with water, and then distilled under reduced pressure to remove ethyl acetate, water and azeotropic PGMEA, thereby obtaining an alkali-soluble resin having a substituent according to the present invention. B-3 (30% PGMEA solution)
I got The obtained resin had a weight average molecular weight of 17,00.
0 and the degree of dispersion (Mw / Mn) was 1.08. The protection rate was 30% for acetalized hydroxystyrene units.

Further, the charged amount of ethyl vinyl ether was adjusted, and the resins B-3HH, B-3H, and B-3 shown below were adjusted.
L and B-3LL were obtained.

[0132]

[Table 3]

Synthesis Example-4 (Synthesis of Resin B-4) A p-acetoxystyrene monomer (or pt-butoxystyrene monomer) was polymerized using dimethyl 2,2′-azobisisobutyrate (AIBN) as an initiator. Further deprotection with hydrochloric acid or the like gave R-1. The obtained R-1 had a weight average molecular weight of 17,000 and a degree of dispersion (Mw / Mh).
1.6. R-1 (100 g) and propylene glycol monomethyl ether acetate (PGMEA)
(400 g) was dissolved in a flask and distilled under reduced pressure.
Water and PGMEA were azeotropically distilled off. After confirming that the water content was sufficiently low, ethyl vinyl ether (25.0) was used.
g) and p-toluenesulfonic acid (0.02 g) were added, and the mixture was stirred at room temperature for 1 hour. Triethylamine (0.03 g) was added to the reaction solution to stop the reaction, and water (400
m1) and ethyl acetate (800 ml) were added, the layers were separated, washed with water, and then distilled under reduced pressure to remove ethyl acetate, water, and an azeotropic PGMEA, thereby obtaining a resin B-4. The obtained resin had a weight average molecular weight of 17,000 and a dispersity (Mw /
Mn) was 1.6. The protection rate was 30% for acetalized hydroxystyrene units.

Further, the charge amount of ethyl vinyl ethyl was adjusted, and the following resins B-4HH, B-4H, B-4
L and B-4LL were obtained.

[0135]

[Table 4]

Synthesis Example 5 (Synthesis of Resin B-5) A p-acetoxystyrene monomer (or pt-butoxystyrene monomer) and a cyclohexyl acrylate monomer were converted to dimethyl 2,2′-azobisisobutyrate (AIB).
Polymerization using N) as an initiator and further deprotection with hydrochloric acid or the like gave p-hydroxystyrene / cyclohexyl acrylate copolymer (90/10) R-2. Resin R-
2 (100 g) and propylene glycol monomethyl ether acetate (PGMEA) (400 g) were dissolved in a flask, and distilled under reduced pressure to distill azeotropically water and PGMEA. After confirming that the water content was sufficiently low, ethyl vinyl ether (25.0 g) and p-toluenesulfonic acid (0.02 g) were added, and the mixture was stirred at room temperature for 1 hour.
Triethylamine (0.03 g) was added to the reaction solution to stop the reaction, and water (400 ml) and ethyl acetate (800 ml) were added.
l) was added thereto, and the mixture was separated, washed with water, and then distilled under reduced pressure to remove ethyl acetate, water and an azeotropic PGMEA, thereby obtaining an alkali-soluble resin B-5 having a substituent according to the present invention.
(30% PGMEA solution) was obtained. The obtained resin had a weight average molecular weight of 13,000 and a dispersity (Mw / Mn) of 1.
71. The protection rate was 20% for the acetalized hydroxystyrene unit and 10% for the cyclohexyl acrylate unit.

Further, the charged amount of ethyl vinyl ether was adjusted, and the following resins B-5HH, B-5H, B-5
L and B-5LL were obtained.

[0138]

[Table 5]

Synthesis Example 6 (Synthesis of Resin B-6) A p-acetoxystyrene monomer (or pt-butoxystyrene monomer) and a t-butyl acrylate monomer were converted to dimethyl 2,2′-azobisisobutyrate (AIBN).
Was used as an initiator, followed by deprotection with hydrochloric acid or the like to obtain a p-hydroxystyrene / t-butyl acrylate copolymer (60/40) B-6. The resulting resin had a weight average molecular weight of 14,000 and a dispersity (Mw / M
n) 1.65.

Similarly, the following resin B-6
H and B-6L were obtained.

[0141]

[Table 6]

Synthesis Example 7 (Synthesis of Resin B-7) A p-acetoxystyrene monomer (or pt-butoxystyrene monomer) and a t-butyl acrylate monomer were polymerized using sec-butyllithium as an initiator. Deprotected with hydrochloric acid or the like, p-hydroxystyrene / t-butyl acrylate copolymer (60/40) B
-7 was obtained. The obtained resin had a weight average molecular weight of 13,0.
00 and the degree of dispersion (Mw / Mn) was 1.12.

Similarly, the following resin B-7
H and B-7L were obtained.

[0144]

[Table 7]

Synthesis Example 8 (Synthesis of Resins B-8 and B-9) The same method as the synthesis method of Resin B-2 was performed, and the following Resins B-8 and B-9 differing only in the degree of dispersion were prepared. Obtained.

[0146]

[Table 8]

(2) (Adjustment and Evaluation of Positive Resist Composition) Examples 1 to 16, Comparative Examples 1 and 2 Each component shown in Table 9 below was dissolved in a solvent shown in Table 9 to obtain a solid content of 18%. Was prepared and filtered through a 0.1 μm Teflon (registered trademark) filter to prepare a resist composition. The surfactant was added in an amount of 100 ppm to the resist solution. The protection ratio of each resin may be adjusted at the stage of synthesis, or may be adjusted by mixing two or more resins having different protection ratios.

[0148]

[Table 9]

Examples of the amine include C-1: DBN (1,5-diazabicyclo [4.3.
0] -5-Nonene C-2: represents TPI (2,4,5-triphenylimidazole).

As the surfactant, W-1; Megafac F176 (Dainippon Ink Co., Ltd.)
(Fluorine) W-2; Megafac R08 (Dainippon Ink Co., Ltd.)
(Fluorine and silicon type) W-3; Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) (silicon type) W-4; Troysol S-366 (Troy Chemical Co., Ltd.)
(Fluorine).

The photoacid generators (A-1) to (A-
3) is shown below.

[0152]

Embedded image

The dissolution inhibitor (D-1) used is shown below.

[0154]

Embedded image

The obtained positive photoresist solution was applied on a silicon wafer on which a 70 nm-thick organic BARC (DUV-42) manufactured by Nissan Chemical Co., Ltd. was formed by using a spin coater (Mark 8 manufactured by Tokyo Electron Limited). 9 at ℃
Dry for 0 seconds to form a resist film of about 0.83 μm,
And a KrF excimer laser (wavelength 248 nm, NA
= 0.60, σ = 0.50, Canon FPA-300
0EX5). After the exposure, a heat treatment was performed at 100 ° C. for 90 seconds, development with a 2.38% aqueous solution of tetramethylammonium hydroxide, rinsing with pure water, and spin drying were performed to obtain a resist pattern. For the obtained resist pattern, sensitivity, resolution, development defect performance,
The line edge roughness was evaluated by the following method.

[Sensitivity] Sensitivity represents an irradiation amount for reproducing a 0.16 μm line-and-space (1/1) mask pattern. [Resolving power] The resolving power indicates a limit resolving power at an irradiation dose for reproducing a 0.16 μm line-and-space (1/1) mask pattern.

[Number of Development Defects] Bare Si of 6 inches
Each resist film was applied to a thickness of 0.5 μm on the substrate, and dried at 140 ° C. for 60 seconds on a vacuum suction hot plate. Next, a 0.35 μm contact hole pattern (Hole)
CAN through a test mask with a duty ratio = 1: 3)
After exposure by ON FPA-3000EX5, post-exposure heating was performed at 120 ° C. for 90 seconds. Continued at 2.38
After paddle development for 60 seconds with% TMAH (tetramethylammonium hydroxide aqueous solution), the resultant was washed with pure water for 30 seconds and spin-dried. The number of development defects of the sample thus obtained was measured with a KLA-2112 machine manufactured by KLA Tencor Co., Ltd., and the obtained primary data value was defined as the number of development defects.

[Line Edge Roughness] In the range of 5 μm in the longitudinal direction of the edge of the 0.16 μm line pattern obtained by the minimum exposure which reproduces the 0.16 μm line-and-space (1/1) mask pattern, The distance from the reference line where there should be was measured at 50 points using S-8840 manufactured by Hitachi, Ltd., and the standard deviation was determined to calculate 3σ. The smaller the value, the better the performance. The results are shown in Table 10 below.

[0159]

[Table 10]

As shown in Table 10 above, it can be seen that the composition of the present invention has significantly improved development defect performance and line edge roughness as compared with Comparative Examples.

[0161]

According to the present invention, it is possible to provide a chemically sensitized positive photoresist composition having improved development defect performance and line edge roughness simultaneously.

 ──────────────────────────────────────────────────続 き Continuing on the front page F term (reference) 2H025 AA03 AA04 AB14 AB15 AB16 AC04 AC08 AD03 BE00 BE10 BG00 BJ05 CB17 CB41 CB56 CC20 FA17 4J002 AA00W AA00X BC07W BC07X BC08W BC08X BC12W BC12X BG04W BG04XBG BG04W BG04XB BG04X ES006 EU186 EU216 EV216 EV246 EV296 EV306 FD206 GP03 GQ05

Claims (3)

[Claims] (A) a compound which generates an acid upon irradiation with actinic rays or radiation; and (B) a compound which is insoluble or hardly soluble in alkali, decomposes by the action of an acid, and has a solubility in an alkali developer. In the positive resist composition containing the resin for increasing, the resin of (B) is at least (B)
1) and a mixture of two resins (B2), and their respective degrees of dispersion Mw / Mn are defined as (B1M) and (B2M).
When 9.9 ≧ (B1M) / (B2M) ≧ 1.
3. A positive photoresist composition which satisfies condition 3. 2. The positive electrode according to claim 1, wherein at least one of the resins (B1) and (B2) contains a repeating unit represented by the following general formulas (IV) and (V). -Type photoresist composition. Embedded image In the above general formula, L represents a hydrogen atom, a linear, branched or cyclic alkyl group which may be substituted, or an aralkyl group which may be substituted. Z represents a linear, branched or cyclic alkyl group which may be substituted, or an aralkyl group which may be substituted. Further, Z and L may combine to form a 5- or 6-membered ring. 3. The positive resin according to claim 1, wherein both the resin (B1) and the resin (B2) contain repeating units represented by the following general formulas (IV) and (V). -Type photoresist composition. Embedded image In the above general formula, L represents a hydrogen atom, a linear, branched or cyclic alkyl group which may be substituted, or an aralkyl group which may be substituted. Z represents a linear, branched or cyclic alkyl group which may be substituted, or an aralkyl group which may be substituted. Further, Z and L may combine to form a 5- or 6-membered ring.