JP2001142210A - Positive photoresist composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive photoresist composition which ensures improved edge roughness of a resist pattern, deposits no insoluble matter in the prepara tion of a resist solution or after storage, is excellent in dependency on density and can reduce a sensitivity change after storage. SOLUTION: The positive photoresist composition contains a resin containing specified silicon-containing repeating units and having solubility to an alkali developing solution increased by the action of an acid, a compound which generates the acid when irradiated with active light or radiation and a specified solvent.

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

[0002]

2. Description of the Related Art As a pattern forming method for manufacturing electronic components such as a semiconductor device, a magnetic bubble memory, and an integrated circuit, a method utilizing a photoresist which is sensitive to ultraviolet light or visible light has been widely used. Have been. There are two types of photoresist: a negative type, in which the irradiated part is insoluble in the developer by light irradiation, and a positive type, in which the exposed part is solubilized.The negative type has higher sensitivity than the positive type and is necessary for wet etching. Until recently, photoresists occupied the mainstream because of their excellent adhesion to substrates and chemical resistance.

However, with the increase in density and integration of semiconductor devices and the like, the line width and spacing of patterns have become extremely small.
In addition, since dry etching has been adopted for etching the substrate, photoresists have been desired to have high resolution and high dry etching resistance,
At present, positive photoresists occupy the majority. Further, in recent years, as electronic devices have become multifunctional and sophisticated, there has been a strong demand for finer patterns to achieve higher density and higher integration.

That is, since the vertical dimension of the integrated circuit is not much reduced as compared with the horizontal dimension of the integrated circuit, the ratio of the height to the width of the resist pattern has to be increased. For this reason, it has become more difficult to suppress the dimensional change of the resist pattern on a wafer having a complicated step structure as the pattern becomes finer. Further, in various types of exposure methods, there is a problem with the reduction of the minimum size. For example,
In light exposure, the interference effect of reflected light due to the step of the substrate has a great effect on dimensional accuracy, whereas in electron beam exposure, the proximity effect caused by backscattering of electrons causes the fine resist pattern The height to width ratio can no longer be increased.

It has been found that many of these problems are eliminated by using a multilayer resist system. For a description of multilayer resist systems, see Solid State Technology, 74 (1981) [Solid State Technolog
y, 74 (1981)], but many other studies on this system have been published. Generally, a multilayer resist method includes a three-layer resist method and a two-layer resist method. In the three-layer resist method, an organic flattening film is applied on a stepped substrate, an inorganic intermediate layer and a resist are stacked thereon, and the resist is patterned. Then, the inorganic intermediate layer is dry-etched using the resist as a mask. This is a method of patterning an organic flattening film by O2 RIE (reactive ion etching) using the inorganic intermediate layer as a mask. Basically, this method has been studied from an early stage because conventional techniques can be used, but the process is very complicated, or the organic film, the inorganic film, and the organic film have different three-layer physical properties. The problem is that cracks and pinholes are likely to occur in the intermediate layer due to the overlapping of the objects.

In contrast to the three-layer resist method, the two-layer resist method uses a resist having both properties of the resist and the inorganic intermediate layer in the three-layer resist method, that is, a resist having oxygen plasma resistance. In addition, the generation of cracks and pinholes is suppressed, and the process is simplified because the number of layers is reduced from three to two. However, in the three-layer resist method, a conventional resist can be used as the upper resist, whereas in the two-layer resist method, there is a problem that a new resist having oxygen plasma resistance has to be developed.

[0007] From the above background, it has excellent oxygen plasma resistance which can be used as an upper layer resist such as a two-layer resist method.
There has been a demand for the development of a high-sensitivity, high-resolution positive photoresist, in particular, an alkali developing type resist that can be used without changing the current process.

Further, in the manufacture of VLSI, which requires processing of an ultrafine pattern having a line width of half a micron or less, the wavelength used by an exposure apparatus used for lithography has been shortened, and now a KrF excimer laser beam is used. The use of ArF excimer laser light has been studied. In such short wavelength optical lithography, a resist generally called a chemically amplified type is used. In particular, when an ArF excimer laser beam is used, it is not appropriate to introduce a phenol structure into a binder resin, which is a main component of the resist, from the viewpoint of optical transparency of the film. In general, a resin polymer containing, as an image-forming portion, a structure capable of decomposing with an acid to generate a carboxylic acid, such as an ester, a 1-alkyladamantyl ester, or a THP-protected carboxylic acid, is used as a binder.

As an example of a Si-containing resist containing an image-forming portion transparent to ArF excimer laser light, maleic anhydride-unsaturated carboxylic acid t-butyl ester-
A terpolymer comprising allyltrimethylsilane is disclosed in JP-A-5-11450. This resist has excellent resolution for processing ultra-fine patterns, but has roughness (unevenness) on the edges of the resist pattern.
Was occurring. Here, the edge roughness refers to the top and bottom edges of a resist line pattern that fluctuate irregularly in a direction perpendicular to the line direction due to the characteristics of the resist. Means that the edge looks uneven. Further, during the preparation of the resist solution, it is poorly compatible with the photoacid generator, causing turbidity, or insoluble matter is precipitated with time, resulting in a problem with time stability.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to provide a positive photoresist composition having improved edge roughness of a resist pattern in the manufacture of a semiconductor device. Another object of the present invention is to provide a positive photoresist composition which does not cause precipitation of insoluble matter during preparation of a resist solution or after storage over time. Still another object of the present invention is to provide a positive photoresist composition having excellent dependency on density. Still another object of the present invention is to provide a positive photoresist composition which can reduce sensitivity fluctuation after storage over time.

[0011]

Means for Solving the Problems As a result of intensive studies on the resist composition in the positive-type chemical amplification system, the present inventors have found that the use of an acid-decomposable resin obtained by copolymerizing a specific repeating unit and a specific solvent. It has been found that the object of the present invention can be achieved. That is, the present invention is the following positive photoresist composition. (1) (A) containing a repeating unit represented by the following general formula (I) and a repeating unit represented by at least one of the following general formulas (IIa) and (IIb), and A resin whose solubility in an alkali developer increases,
A positive photoresist composition comprising (B) a compound that generates an acid upon irradiation with actinic rays or radiation, and (C) a solvent containing heptanone. General formula (I)

[0012]

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In the formula (I), R ^{1 to} R ³ each independently represent an alkyl group, a haloalkyl group, a halogen atom, an alkoxy group, a trialkylsilyl group or a trialkylsilyloxy group. n represents 0 or 1. General formula (IIa)

[0014]

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In the formula (IIa), Y is a hydrogen atom, a methyl group,
Represents a group selected from a cyano group and a chlorine atom. L represents a single bond or a divalent linking group. Q represents a hydrogen atom or a group capable of decomposing with an acid to generate a carboxylic acid. General formula (IIb)

[0016]

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In the formula (IIb), X ¹ and X ² each independently represent a group selected from an oxygen atom, a sulfur atom, —NH— and —NHSO ₂ —. L ¹ and L ² each independently represent a single bond or a divalent linking group. A ¹ is -Q or -C
OOQ is represented, and when X ¹ is an oxygen atom and L ¹ represents a single bond, A ¹ represents -Q. A ² is a hydrogen atom, a cyano group,
Hydroxyl group, -COOH, -COOR ', -CO-NH-
R '', an optionally substituted alkyl group, an optionally substituted cyclic hydrocarbon group, an alkoxy group, -Q or -C
OOQ (here, R ′ and R ″ each independently represent an alkyl group which may have a substituent). Q represents a group capable of decomposing with an acid to generate a carboxylic acid. (2) The positive photoresist composition as described in (1) above, wherein the resin (A) further contains a repeating structural unit represented by the following general formula (III). General formula (III)

[0018]

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In the formula (III), Z represents an oxygen atom or NR ³ . R ³ represents a hydrogen atom, a hydroxyl group, a linear or branched alkyl group, or —O—SO ₂ —R ⁴ . R ⁴ represents an alkyl group or a trihalomethyl group. (3) The positive type as described in the above (1) or (2), wherein the solvent (C) contains at least one of propylene glycol monoalkyl ether, alkyl lactate and alkoxyalkyl propionate. Photoresist composition. (4) The mixed solvent of (C) further comprises γ-butyrolactone,
The positive photoresist composition according to any one of the above (1) to (3), comprising at least one of ethylene carbonate and propylene carbonate. (5) The positive photoresist composition as described in any of (1) to (4) above, which comprises at least one of (D) a fluorine-based and / or silicon-based surfactant. (6) The positive photoresist composition as described in any of (1) to (5) above, which further comprises (E) an organic basic compound.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the compounds used in the present invention will be described in detail. The resin (A) of the present invention will be described. The resin (A) is a resin containing a repeating structural unit represented by the general formula (I) and at least one of the repeating structural units represented by the general formulas (IIa) and (IIb). is there. The resin (A) preferably contains a repeating structural unit represented by the above general formula (III). By containing this, the density dependency is further improved. In the repeating structural unit (I), R ^{1 to} R ³ each independently represent a group selected from an alkyl group, a haloalkyl group, a halogen atom, an alkoxy group, a trialkylsilyl group, and a trialkylsilyloxy group. The alkyl group is preferably a straight-chain or branched alkyl group having 1 to 10 carbon atoms, more preferably a straight-chain or branched alkyl group having 1 to 6 carbon atoms, still more preferably a methyl group, an ethyl group, n-propyl group, i
-Propyl group, n-butyl group, i-butyl group, s-butyl group and t-butyl group. As the haloalkyl group,
A chloromethyl group, a bromomethyl group, and an iodomethyl group.

The alkoxy group is a linear or branched alkoxy group having 1 to 6 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propyloxy group, an i-propyloxy group, an n-butoxy group, i-butoxy group, s
-Butoxy group and t-butoxy group, particularly preferred are methoxy and ethoxy groups.

The alkyl group of the trialkylsilyl is a linear or branched alkyl group having 1 to 6 carbon atoms, more preferably a methyl group, an ethyl group, an n-propyl group, or an i-type group.
-Propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, and most preferred is a methyl group. The alkyl group of the trialkylsilyloxy group is a linear or branched alkyl group having 1 to 6 carbon atoms, more preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, i-butyl group, s
-Butyl group and t-butyl group, and among them, the most preferred is a methyl group. n represents 0 or 1, and is preferably 1. Thereby, the roughness (irregularity) of the edge of the line is improved.

In the repeating unit (IIa), Y represents a group selected from a hydrogen atom, a methyl group, a cyano group and a chlorine atom. L represents a single bond or a divalent linking group. Q represents a hydrogen atom or a group capable of decomposing with an acid to generate a carboxylic acid. The group capable of decomposing with an acid to generate a carboxylic acid is a group capable of decomposing / separating from a resin by an acid generated from the component (B) upon exposure to generate a —COOH group. Specific examples of such a group include t-
Butyl group, tertiary alkyl group such as t-amyl group, isobornyl group, 1-ethoxyethyl group, 1-butoxyethyl group, 1-isobutoxyethyl group, 1-alkoxyethyl group such as 1-cyclohexyloxyethyl group, Alkoxymethyl groups such as 1-methoxymethyl group and 1-ethoxymethyl group, tetrahydropyranyl group, tetrahydrofurfuryl group, trialkylsilyl group, 3-oxocyclohexyl group, 2-methyl-adamantyl group, mevalonic lactone residue And a 2- (γ-butyrolactonyloxycarbonyl) -2-propyl group.

The following are specific examples of the repeating unit represented by the above general formula (I), but the present invention is not limited to these specific examples.

[0025]

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In the repeating unit (IIb), X ¹ and X ² each independently represent an oxygen atom, a sulfur atom, -NH-, -N
Represents a group selected from HSO ₂ —. L ¹ and L ² each independently represent a single bond or a divalent linking group.

Specific examples of the divalent linking group in L ¹ and L ² include an alkylene group, a substituted alkylene group, an ether group, a thioether group, a carbonyl group, an ester group,
A single group selected from the group consisting of an amide group, a sulfonamide group, a urethane group, and a urea group, or a combination of two or more groups may be used. Examples of the alkylene group and substituted alkylene group in L ¹ and L ² include groups represented by the following formulas. -[C (Ra) (Rb)] r- wherein Ra and Rb represent a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, or an alkoxy group;
Both may be the same or different. As the alkyl group, a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group is preferable, and a methyl group, an ethyl group, a propyl group, and an isopropyl group are more preferable. As the substituent of the substituted alkyl group,
Examples include a hydroxyl group, a halogen atom and an alkoxy group. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. r represents an integer of 1 to 10.

A ² represents a hydrogen atom, a cyano group, a hydroxyl group, -C
OOH, -COOR ', -CO-NH-R ", an optionally substituted alkyl group, an alkoxy group, -Q or -C
OOQ. (R ′ and R ″ each independently represent an alkyl group which may have a substituent.) The alkyl group in A ² , R ′ and R ″ is a straight-chain having 1 to 10 carbon atoms. A chain or branched alkyl group is preferred,
More preferably, it is a linear or branched alkyl group having 1 to 6 carbon atoms, and further preferably, a methyl group, an ethyl group, or an n-
Propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group and t-butyl group. Similarly, the alkoxy group is a linear or branched alkoxy group having 1 to 6 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propyloxy group, an i-propyloxy group,
n-butoxy group, i-butoxy group, s-butoxy group, t
-Butoxy groups, especially preferred are methoxy and ethoxy groups. Similarly, Q is Q of repeating unit (IIa)
And the same groups as mentioned above.

Further substituents of the above-mentioned alkyl groups and alkoxy groups include halogen atoms such as fluorine, chlorine, bromine and iodine, and alkoxy groups such as methoxy, ethoxy, propoxy and butoxy. Examples of the cyclic hydrocarbon group for A ² include cyclopropyl, cyclopentyl, cyclohexyl, adamantyl, 2-methyl-2-adamantyl, norbornyl, boronyl, isobornyl, tricyclodecanyl, and dicyclopentenyl. Group,
Nobornane epoxy group, menthyl group, isomenthyl group,
Examples include a neomenthyl group and a tetracyclododecanyl group. The bond forming the ring of these cyclic hydrocarbon groups may have an ester bond or a carbonyl bond. As a further substituent of the cyclic hydrocarbon group,
Examples thereof include a hydroxyl group, a halogen atom, a carboxyl group, an alkoxy group, an acyl group, a cyano group, and an acyloxy group. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom.
Examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Examples of the acyl group include a formyl group and an acetyl group. Examples thereof include an acetoxy group.

Specific examples of the repeating unit represented by the above general formula (IIa) include the following, but the present invention is not limited to these specific examples.

[0031]

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[0032]

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Specific examples of the repeating unit represented by the above general formula (IIb) include the following, but the present invention is not limited to these specific examples.

[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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In the repeating unit (III), Z represents an oxygen atom, NR ³ . R ³ represents a hydrogen atom, a hydroxyl group, a linear or branched alkyl group, or —O—SO ₂ —R ⁴
Represents R ⁴ represents an alkyl group or a trihalomethyl group.
The alkyl group of R ³ and R ⁴ is preferably a straight-chain or branched alkyl group having 1 to 10 carbon atoms, more preferably a straight-chain or branched alkyl group having 1 to 6 carbon atoms, and further preferably methyl Group, ethyl group, n-propyl group, i-
Propyl group, n-butyl group, i-butyl group, s-butyl group and t-butyl group. Specific examples of the repeating unit represented by the general formula (III) include the following, but the present invention is not limited to these specific examples.

[0040]

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[0041]

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In the resin according to the present invention, the following monomers may be further copolymerized to give a repeating unit constituting the resin as long as the effects of the present invention can be effectively obtained. However, it is not limited to the following monomers. Thereby, the performance required for the resin, particularly (1) solubility in a coating solvent, (2) film forming property (glass transition point), (3) alkali developability, and (4) film loss (hydrophobicity, alkali (Selection of a soluble group), (5) adhesion of the unexposed portion to the substrate, and (6) dry etching resistance can be finely adjusted. Examples of such a comonomer include acrylates, methacrylates,
Examples thereof include compounds having one addition-polymerizable unsaturated bond selected from acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, and the like.

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

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

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

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

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

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

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

Dialkyl itaconates (eg, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, etc.); acrylic acid, methacrylic acid, crotonic acid, itaconic acid, acrylonitrile, methacrylonitrile and the like.

In the resin (A) according to the present invention, the repeating unit represented by the general formula (I), and at least one of the repeating units (IIa) and (IIb), and a component which is preferably copolymerized are used. The content of the repeating unit represented by the general formula (III) depends on the desired resist of oxygen plasma etching, the sensitivity, the prevention of pattern cracking, the substrate adhesion, the resist profile, and the requirements of general resist. Can be appropriately set in consideration of the resolution, heat resistance, and the like. Generally, in the resin (A) of the present invention, the content of the repeating unit represented by the general formula (I) is 10 to 9 with respect to all the repeating units.
0 mol%, preferably 15 to 70 mol%, more preferably 20 to 50 mol%. Also repeat unit
The content of at least one of the repeating units (IIa) and (IIb) is from 5 to 50 mol%, preferably from 10 to 40 mol%, based on all repeating units. Repeat unit
The content of (III) is usually 10
To 90 mol%, preferably 15 to 70 mol%, more preferably 20 to 60 mol%.

In the resin (A) of the present invention, a monomer corresponding to the repeating unit represented by the general formula (I) or a monomer corresponding to at least one of the repeating units represented by the general formulas (IIa) and (IIb) Monomer and, if necessary, formula (III)
Can be obtained by copolymerizing a monomer corresponding to the repeating unit represented by the formula in the presence of a polymerization catalyst. Alternatively,
A monomer corresponding to the repeating unit represented by the general formula (I) is further copolymerized with a monomer corresponding to the repeating unit of the general formula (IIa) and maleic anhydride, or After copolymerizing maleic anhydride to the monomer corresponding to the repeating unit represented, partially repeat the repeating units derived from maleic anhydride of these obtained copolymers,
There is also a method of synthesizing by ring-opening esterification with an alcohol or hydrolysis under basic or acidic conditions.

The weight average molecular weight of the resin according to the present invention is G
It is preferably from 1,000 to 200,000 in terms of polystyrene according to the PC method. When the weight average molecular weight is less than 1,000, heat resistance and dry etching resistance are deteriorated, so that it is not preferable. When the weight average molecular weight exceeds 200,000, the developability is deteriorated and the viscosity becomes extremely high, so that the film forming property is deteriorated. And so on, which produces very unfavorable results.

In the positive photoresist composition of the present invention, the compounding amount of the resin (A) according to the present invention in the entire composition is preferably 40 to 99.99% by weight, and more preferably the total solid content of the resist. 50-99.97% by weight.

Next, the compound (B) which generates an acid upon irradiation with actinic rays or radiation will be described. Examples of the compound used in the present invention, which decomposes upon irradiation with actinic rays or radiation to generate an acid, include a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization, a photobleaching agent for dyes, and a photodiscoloration agent. Agents or known light used for micro resists (ultraviolet rays of 400 to 200 nm, far ultraviolet rays, particularly preferably g-rays, i-rays, KrF excimer laser light, A
A compound capable of generating an acid by rF excimer laser light, electron beam, X-ray, molecular beam or ion beam, and a mixture thereof can be appropriately selected and used. Examples of the compound used in the present invention, which decomposes upon irradiation with actinic rays or radiation to generate an acid, include a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization, a photobleaching agent for dyes, and a photodiscoloration agent. 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 ,
Compounds that generate an acid by X-rays, molecular beams or ion beams 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, SI Schlesinger, Photogr. Sci. Eng., 18, 38.
7 (1974), TSBetal, Polymer, 21,423 (1980) and the like diazonium salts, U.S. Pat.Nos. 4,069,055 and 4,069,0
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68 (1984), CSwen et al., Teh, Proc. Conf. Rad. Curing AS
IA, p478 Tokyo, Oct (1988), U.S. Pat.No. 4,069,055,
4,069,056, etc., phosphonium salts, JVCrivell
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No. 2, U.S. Pat.Nos. 4,371,605 and 4,431,774,
Compounds that generate sulfonic acid upon photolysis, such as iminosulfonate described in JP-A-64-18143, JP-A-2-245756, JP-A-3-140109, etc. Disulfone compounds described in JP-A-2-71270, JP-A-3-103854, JP-A-3-103856 and JP-A-3-103856.
And diazoketosulfone and diazodisulfone compounds described in JP-A-210960.

Further, a group that generates an acid by these lights,
Alternatively, a compound having a compound introduced into the main chain or side chain of a polymer, for example, ME Woodhouse etal, J. Am. Che.
m. Soc., 104, 5586 (1982), SPPappas etal, J. Imagi
ng Sci., 30 (5), 218 (1986), S. Kondo et al., Makromol. C
hem., Rapid Commun., 9, 625 (1988), Y. Yamadaetal, Mak
romol. Chem., 152, 153, 163 (1972), JVCrivello eta
l, J. PolymerSci., Polymer Chem. Ed., 17, 3845 (197
9), U.S. Patent No. 3,849,137, Dokoku Patent No. 3914407, JP-A-63-26653, JP-A-55-164824, JP-A-62-69263
No., JP-A-63-146038, JP-A-63-163452, JP-A-62-163452
Compounds described in JP-A-153853 and JP-A-63-146029 can be used.

Further, VNRPillai, Synthesis, (1), 1 (19
80), A. Abad et al, Tetrahedron Lett., (47) 4555 (197
1), DHR Barton et al, J. Chem. Soc., (C), 329 (197
0), compounds which generate an acid by light described in US Pat. No. 3,779,778 and European Patent No. 126,712 can also be used.

Among the compounds capable of decomposing upon irradiation with actinic rays or radiation to generate an acid, those which are used particularly effectively 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).

[0060]

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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.

[0062]

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[0063]

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[0064]

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

[0066]

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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, it is an aryl group having 6 to 14 carbon atoms, an alkyl group having 1 to 8 carbon atoms, or a substituted derivative thereof. Preferred substituents include an aryl group, 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, and an alkyl group is an alkoxy group having 1 to 8 carbon atoms, a carboxyl group and an alkoxycarbonyl group.

[0069] 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.

[0072]

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[0073]

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[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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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 Leicest
er, J. Ame.Chem. Soc., 51, 3587 (1929), JVCrivello
et al., J. Polym. Chem. Ed., 18, 2677 (1980), U.S. Pat.
Nos. 2,807,648 and 4,247,473, JP-A-53-101,331
And the like.

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

[0087]

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

[0089]

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[0090]

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[0091]

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[0092]

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[0093]

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[0094]

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

[0096]

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Here, R ²¹ and R ²² are each independently
It represents an alkyl group which may have a substituent, a cycloalkyl group, or an aryl group which may have a substituent. Here, the alkyl group is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, and more preferably a linear or branched alkyl group having 1 to 12 carbon atoms. As the cycloalkyl group, a cyclopentyl group or a cyclohexyl group is preferable. As the aryl group, an aryl group which may have a substituent having 6 to 10 carbon atoms is preferable. Here, as a substituent, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, n
Alkyl such as -butyl group, i-butyl group, s-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, nonyl group, decyl group and dodecyl group Groups, a methoxy group, an ethoxy group, a propoxy group, an alkoxy group such as a butoxy group, a halogen atom, a nitro group, and an acetyl group.

Specific examples of the diazodisulfone derivative compound include the following compounds. Bis (methylsulfonyl) diazomethane, bis (ethylsulfonyl) diazomethane, bis (propylsulfonyl) diazomethane,
Bis (1-methylpropylsulfonyl) diazomethane,
Bis (butylsulfonyl) diazomethane, bis (1-methylbutylsulfonyl) diazomethane, bis (heptylsulfonyl) diazomethane, bis (octylsulfonyl) diazomethane, bis (nonylsulfonyl) diazomethane, bis (decylsulfonyl) diazomethane, bis (dodecylsulfonyl) Diazomethane, bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (benzylsulfonyl) diazomethane, bis (2-chlorobenzylsulfonyl) diazomethane, bis (4-chlorobenzylsulfonyl) diazomethane, bis (phenylsulfonyl) Diazomethane, bis (4-methoxyphenylsulfonyl)
Diazomethane, bis (2-methylphenylsulfonyl)
Diazomethane, bis (3-methylphenylsulfonyl)
Diazomethane, bis (4-methylphenylsulfonyl)
Diazomethane, bis (2,4-dimethylphenylsulfonyl) diazomethane, bis (2,5-dimethylphenylsulfonyl) diazomethane, bis (3,4-dimethylphenylsulfonyl) diazomethane, bis (2,4,6-
Trimethylphenylsulfonyl) diazomethane, bis (4-fluorophenylsulfonyl) diazomethane, bis (2,4-difluorophenylsulfonyl) diazomethane, bis (2,4,6-trifluorophenylsulfonyl) diazomethane, bis (4-nitrophenylsulfonyl) ) Diazomethane

(5) A diazoketosulfone derivative compound represented by the following general formula (PAG8). (PAG8)

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Here, R ²¹ and R ²² have the same meanings as in the above (PAG7). Specific examples of the diazoketosulfone derivative compound include the following compounds.

Methylsulfonyl-benzoyldiazomethane, ethylsulfonyl-benzoyldiazomethane,
Methylsulfonyl-4-bromobenzoyldiazomethane, ethylsulfonyl-4-bromobenzoyldiazomethane, phenylsulfonyl-benzoyldiazomethane, phenylsulfonyl-2-methylphenyldiazomethane, phenylsulfonyl-3-methylphenyldiazomethane, phenylsulfonyl- 4-methylphenyldiazomethane, phenylsulfonyl-3-methoxyphenyldiazomethane, phenylsulfonyl-4-methoxyphenyldiazomethane, phenylsulfonyl-3
-Chlorobenzoyldiazomethane, phenylsulfonyl-4-chlorophenyldiazomethane, tolylsulfonyl-3-chlorobenzoyldiazomethane, tolylsulfonyl-4-chlorophenyldiazomethane, phenylsulfonyl-4-fluorophenyldiazomethane,
Tolylsulfonyl-4-fluorophenyldiazomethane

Among the above, compounds which decompose upon irradiation with actinic rays or radiation to generate organic sulfonic acids can be suitably used. Here, the organic sulfonic acid is a sulfonic acid having an organic group, and the organic group is
Examples thereof include an alkyl group which may have a substituent, a phenyl group which may have a substituent, and a naphthyl group which may have a substituent. The substituent may have 1 carbon atom
To 12 linear or branched alkyl groups, 1 to 6 carbon atoms
And halogen atoms such as fluorine, chlorine, bromine and iodine. As the organic group, specifically,
Methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, n-
Amyl group, i-amyl group, t-amyl group, s-amyl group, n-hexyl group, n-pentyl group, n-octyl group, 2-ethylhexyl group, nonyl group, decyl group, dodecyl group and other alkyl groups , A substituted alkyl group such as a chloromethyl group, a dichloromethyl group, a trichloromethyl group, a chloroethyl group, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a perfluorobutyl group, a perfluorooctyl group, a phenyl group, a tosyl group, Substituted phenyl groups such as dimethylphenyl group, trimethylphenyl group, methoxyphenyl group, ethoxyphenyl group, chlorophenyl group, bromophenyl group, iodophenyl group, fluorophenyl group, pentafluorophenyl group, naphthyl group, methylnaphthyl group, methoxynaphthyl Group, chlorophenyl group, bromonaphthyl And a substituted naphthyl group such as Yodonafuchiru group. Among these organic groups, a group having a fluorine atom is particularly preferable.

In the present invention, an onium salt is preferable as the photoacid generator. Of these, a sulfonium salt compound and an iodonium salt compound are preferable, and specific examples thereof include a compound represented by the above general formula (PAG-3) or (PAG-4). Among the compounds represented by the general formula (PAG-3) or (PAG-4), an alkyl group which has 5 or more carbon atoms and which may have a substituent, and a cyclo which may have a substituent. Alkyl group, an alkoxy group which may have a substituent, an alkoxycarbonyl group which may have a substituent, an acyl group which may have a substituent, an acyloxy which may have a substituent Those having a group as a substituent of the phenyl group in the cation portion are preferred. As such, a photoacid generator represented by the following general formula [sI] or [sII] is particularly preferable. This can reduce the number of particles after preparing the resist composition solution and the increase in the number of particles after storage with time from the preparation.

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In the formulas [sI] and [sII], Rs1 to Rs5
Is a hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkoxy group which may have a substituent, It represents a good alkoxycarbonyl group, an acyl group which may have a substituent, an acyloxy group which may have a substituent, a nitro group, a halogen atom, a hydroxyl group, and a carboxyl group. a: 1 to 5, b: 1 to 5, l: 1 to 5, m: 0 to 5, n: 0 to 5. However, at least one of Rs1 and Rs2 has an alkyl group which has 5 or more carbon atoms and may have a substituent, a cycloalkyl group which may have a substituent, and It represents a good alkoxy group, an alkoxycarbonyl group which may have a substituent, an acyl group which may have a substituent, and an acyloxy group which may have a substituent.
When l + m + n = 1, Rs3 represents an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkoxy group which may have a substituent, Represents an optionally substituted alkoxycarbonyl group, an optionally substituted acyl group, and an optionally substituted acyloxy group. X represents R—SO ₃ , R represents an aliphatic hydrocarbon group which may have a substituent, or an aromatic hydrocarbon group which may have a substituent.

In the general formula [sI] or [sII], the alkyl group for Rs1 to Rs5 may be a methyl group, an ethyl group, a propyl group, an n-butyl group, an isobutyl group, Examples thereof include those having 1 to 25 carbon atoms such as a sec-butyl group, a t-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a t-amyl group, a decanyl group, a dodecanyl group, and a hexadecanyl group. The cycloalkyl group may have a substituent and has 3 to 25 carbon atoms such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a cyclododecanyl group, and a cyclohexadecanyl group. Things. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group,
Those having 1 to 25 carbon atoms such as c-butoxy group or t-butoxy group, pentyloxy group, t-amyloxy group, n-hexyloxy group, n-octyloxy group, n-dodecaneoxy group and the like can be mentioned. .

Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, an n-butoxycarbonyl group, an isobutoxycarbonyl group and a sec-butoxycarbonyl which may have a substituent. A group having 2 to 25 carbon atoms such as a t-butoxycarbonyl group, a pentyloxycarbonyl group, a t-amyloxycarbonyl group, an n-hexyloxycarbonyl group, an n-octyloxycarbonyl group, an n-dodecaneoxycarbonyl group, etc. One. The acyl group may have a substituent and has 1 carbon atom such as a formyl group, an acetyl group, a butyryl group, a valeryl group, a hexanoyl group, an octanoyl group, a t-butylcarbonyl group, and a t-amylcarbonyl group. To 25. Examples of the acyloxy group include an acetoxy group, an ethylyloxy group, a butyryloxy group, a t-butyryloxy group, and a t which may have a substituent.
-Amylyloxy group, n-hexanecarbonyloxy group,
Examples thereof include those having 2 to 25 carbon atoms such as an n-octanecarbonyloxy group, an n-dodecanecarbonyloxy group, and an n-hexadecanecarbonyloxy group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The substituent for these groups is preferably an alkoxy group having 1 to 4 carbon atoms, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an acyl group, an acyloxy group, a cyano group, a hydroxyl group, Carboxy group,
Examples thereof include an alkoxycarbonyl group and a nitro group. As described above, at least one of Rs1 and Rs2 has 5 or more carbon atoms, and may have an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, and a substituent. Represents an alkoxy group which may have a substituent, an alkoxycarbonyl group which may have a substituent, an acyl group which may have a substituent, and an acyloxy group which may have a substituent. Examples of the substituent having 5 or more carbon atoms include those having 5 to 25 carbon atoms in the above specific examples. When l + m + n = 1, Rs3 represents an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkoxy group which may have a substituent, or a substituent. It represents an optionally substituted alkoxycarbonyl group, an optionally substituted acyl group, and an optionally substituted acyloxy group. R3 preferably has 2 or more carbon atoms, more preferably 4 or more carbon atoms.

Among the above, alkyl groups which may have a substituent of Rs1 to Rs5 include methyl, ethyl, propyl, isopropyl, butyl, t- and the like.
A butyl group, an n-pentyl group, a t-amyl group, an n-hexyl group, an n-octyl group, and a decanyl group are preferable.As the cycloalkyl group, a cyclohexyl group, a cyclooctyl group, which may have a substituent, A cyclododecanyl group is preferable, and as the alkoxy group, a methoxy group, an ethoxy group, an isopropoxy group, an n-
Butoxy group, sec-butoxy group, t-butoxy group, pentyloxy group, t-amyloxy group, n-hexyloxy group, n-octyloxy group, n-dodecaneoxy group is preferable, and the alkoxycarbonyl group is preferably a substituent. Methoxycarbonyl group, ethoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, sec-butoxycarbonyl group, t-butoxycarbonyl group, pentyloxycarbonyl group, t-amyloxycarbonyl group, n -Hexyloxycarbonyl group, n-octyloxycarbonyl group, n-dodecaneoxycarbonyl group is preferable, and the acyl group may have a substituent, formyl group, acetyl group, butyryl group, valeryl group, hexanoyl group. , Octanoyl group, t
-Butylcarbonyl group, t-amylcarbonyl group is preferable, and the acyloxy group may have a substituent,
Acetoxy group, ethylyloxy group, butyryloxy group,
A t-butyryloxy group, a t-amylyloxy group, an n-hexanecarbonyloxy group, and an n-octanecarbonyloxy group are preferred.

The alkyl group having 5 or more carbon atoms and which may have a substituent is an n-pentyl group or a t-
Amyl, n-hexyl, n-octyl and decanyl are preferred. A cycloalkyl group having 5 or more carbon atoms, which may have a substituent, is a cyclohexyl group,
A cyclooctyl group and a cyclododecanyl group are preferred. Examples of the alkoxy group having 5 or more carbon atoms, which may have a substituent, include a pentyloxy group, a t-amyloxy group,
Hexyloxy, n-octyloxy and dodecaneoxy are preferred. An alkoxycarbonyl group having 5 or more carbon atoms, which may have a substituent, includes a pentyloxycarbonyl group, a t-amyloxycarbonyl group,
Hexyloxycarbonyl, n-octyloxycarbonyl and dodecaneoxycarbonyl are preferred. As the acyl group having 5 or more carbon atoms and which may have a substituent, a paleryl group, a hexanoyl group, an octanoyl group, and a t-amylcarbonyl group are preferable. As the acyloxy group having 5 or more carbon atoms and which may have a substituent, a t-amylyloxy group, an n-hexanecarbonyloxy group, and an n-octanecarbonyloxy group are preferable. Substituents for these groups include methoxy, ethoxy, t-butoxy, chlorine, bromine, cyano,
A hydroxyl group, a methoxycarbonyl group, an ethoxycarbonyl group, a t-butoxycarbonyl group, and a t-amyloxycarbonyl group are preferred.

The sulfonium or iodonium compound represented by the general formula [sI] or [sII] used in the present invention uses a sulfonic acid having a specific structure as described above as its counter anion, X ⁻ . Examples of the aliphatic hydrocarbon group which may have a substituent of R in the counter anion include a linear or branched alkyl group having 1 to 20 carbon atoms, or a cyclic alkyl group. R may be an aromatic group which may have a substituent. As the alkyl group for R, a methyl group, an ethyl group, a propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, which may have a substituent,
Examples thereof include those having 1 to 20 carbon atoms such as an n-octyl group, a 2-ethylhexyl group, a decyl group and a dodecyl group. The cyclic alkyl group may have a substituent,
Examples thereof include a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a cyclododecyl group, an adamantyl group, a norbornyl group, a camphor group, a tricyclodecanyl group, and a menthyl group. Examples of the aromatic group include a phenyl group and a naphthyl group which may have a substituent.

Among the above, alkyl groups which may have a substituent for R include methyl, trifluoromethyl, ethyl, pentafluoroethyl, 2,2,2
2-trifluoroethyl group, n-propyl group, n-butyl group, nonafluorobutyl group, n-pentyl group, n-hexyl group, n-octyl group, heptadecafluorooctyl group, 2-ethylhexyl group, decyl group , Dodecyl group,
Examples of the cyclic alkyl group include a cyclopentyl group, a cyclohexyl group, and a camphor group. As the aromatic group, a phenyl group, naphthyl group, pentafluorophenyl group, p-toluyl group, p-
Fluorophenyl group, p-chlorophenyl group, p-hydroxyphenyl group, p-methoxyphenyl group, dodecylphenyl group, mesityl group, triisopropylphenyl group,
4-hydroxy-1-naphthyl group, 6-hydroxy-2
-Naphthyl group.

Among the above substituents, more preferred R
Specific examples of s1 to Rs5 include a methyl group, an ethyl group,
Propyl, isopropyl, n-butyl, t-butyl, n-pentyl, t-amyl, n-hexyl, n-octyl, cyclohexyl, methoxy,
Ethoxy, isopropoxy, n-butoxy, t-
Butoxy group, pentyloxy group, t-amyloxy group, hexyloxy group, n-octyloxy group, methoxycarbonyl group, ethoxycarbonyl group, n-butoxycarbonyl group, t-butoxycarbonyl group, t-amyloxycarbonyl group, hexyl Oxycarbonyl group, n-octyloxycarbonyl group, formyl group, acetyl group, butyryl group, hexanoyl group, octanoyl group, t-butylcarbonyl group, t-amylcarbonyl group, acetoxy group, ethylyloxy group, butyryloxy group, t-butyryloxy Group, t-amylyloxy group, n-hexanecarbonyloxy group, n-octanecarbonyloxy group, hydroxyl group, chlorine atom, bromine atom and nitro group. Specific examples of the more preferable group having 5 or more carbon atoms include an n-pentyl group, a t-amyl group, an n-hexyl group, an n-octyl group,
Decanyl group, cyclohexyl group, pentyloxy group, t
-Amyloxy group, hexyloxy group, n-octyloxy group, dodecaneoxy group, pentyloxycarbonyl group, t-amyloxycarbonyl group, hexyloxycarbonyl group, n-octyloxycarbonyl group, dodecaneoxycarbonyl group, pareryl group, A hexanoyl group, an octanoyl group, a t-amylcarbonyl group, a t-amylyloxy group, an n-hexanecarbonyloxy group, and an n-octanecarboniloxy group.

Specific examples of the more preferable sulfonic acid substituent R include a methyl group, a trifluoromethyl group, an ethyl group, a pentafluoroethyl group, a 2,2,2-trifluoroethyl group, an n-butyl group and a nonafluoro group. Butyl group, n
-Hexyl group, n-octyl group, heptadecafluorooctyl group, 2-ethylhexyl group, camphor group, phenyl group, naphthyl group, pentafluorophenyl group, p-toluyl group, p-fluorophenyl group, p-chlorophenyl group, p-methoxyphenyl group, dodecylphenyl group, mesityl group, triisopropylphenyl group, 4-hydroxy-1-naphthyl group and 6-hydroxy-2-naphthyl group.

The generated acid preferably has 1 to 30 carbon atoms. The number is more preferably 1 to 28, and still more preferably 1 to 25. If the total number of carbon atoms is less than 1, the pattern formation may be hindered such as a t-top shape, and if it exceeds 30, the development residue may be undesirably generated. The general formula [s
Specific examples of the compounds represented by I] or [sII] include the following [sI-1] to [sI-18] and [sII-
1] to [sII-20], but the present invention is not limited thereto. These compounds are used alone or in combination of two or more.

[0117]

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[0118]

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[0119]

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[0120]

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[0121]

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Represented by the general formula [sI] or [sII]
The compound is, for example, the corresponding Cl^-Salt (general formula [sI] or
Or [sII] X^-To Cl^-X) and X
^-Y ⁺(X^-Is the general formula [sI] or [sI
I], Y⁺Is H⁺, Na⁺, K⁺, NH_Four ⁺, N
(CH_Three)_Four ^-And the like. ) And the salt in aqueous solution
It can be synthesized by exchanging. In addition, the above chloride
Besides, hydroxide or methanesulfonate
A similar salt exchange is possible.

The amount of the photoacid generator (B) is usually in the range of 0.001 to 40% by weight based on the total weight of the positive photoresist composition of the present invention (excluding the coating solvent). It is preferably 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. If the amount 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.

The positive photoresist composition of the present invention comprises
It is preferable to contain the surfactant (D). Thereby, the density dependency is excellent. The component (D) contains at least one surfactant selected from a fluorine-based surfactant, a silicon-based surfactant, a surfactant containing both fluorine atoms and silicon atoms, and a nonionic surfactant. Among them, a fluorine-based surfactant, a silicon-based surfactant, and a surfactant containing both a fluorine atom and a silicon atom are particularly preferable. As these surfactants, for example, JP-A-62-36663
No., JP-A-61-226746, JP-A-61-226745, JP-A-62
-170950, JP-A-63-34540, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, and JP-A-9-5988 can include surfactants. The following commercially available surfactants can be used as they are. As commercially available surfactants that can be used, for example, F-top EF301, EF303, (manufactured by Shin-Akita Kasei Co., Ltd.), Florad FC430, 431 (manufactured by Sumitomo 3M Limited), Megafac F171, F173, F176, F189, R08
(Dai Nippon Ink Co., Ltd.), Surflon S-382, SC10
Examples thereof include fluorine-based surfactants such as 1, 102, 103, 104, 105, and 106 (manufactured by Asahi Glass Co., Ltd.) and silicon-based surfactants. Also, polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can be used as a silicon-based surfactant.

Specific examples of other surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; Ethylene octyl phenol ether, polyoxyethylene alkyl allyl ethers such as polyoxyethylene nonyl phenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, Sorbitan trioleate, sorbitan fatty acid esters such as sorbitan tristearate, polyoxyethylene sorbitan monolaurate, Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; Can be mentioned. (D)
The amount of the surfactant is usually 0.001% to 2% by weight, preferably 0.01% to 1% by weight, based on the solid content in the composition of the present invention. These surfactants may be added alone or in some combination.

The positive photoresist composition of the present invention comprises
(E) It is preferable to contain an organic basic compound. Thereby, the sensitivity fluctuation over time is reduced. Examples of the organic basic compound include compounds having the following structures.

[0127]

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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.

[0129]

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

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

Particularly preferred specific examples are 1,5-diazabicyclo [4.3.0] -5-nonene, 1,8-diazabicyclo [5.4.0] -7-undecene (DBU), 1,4- Tertiary morpholines such as diazabicyclo [2.2.2] octane, 4-dimethylaminopyridine, hexamethylenetetramine, 4,4-dimethylimidazoline, pyrroles, pyrazoles, imidazoles, pyridazines, pyrimidines, and CHMETU; Hindered amines such as bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebagate and the like can be mentioned.

Among them, 1,5-diazabicyclo [4,
3,0] non-5-ene, 1,8-diazabicyclo [5,4,0] undec-7-ene, 1,4-diazabicyclo [2,2,2] octane, 4-dimethylaminopyridine, hexamethylene Preferred are tetramine, CHMETU, and bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate.

These organic basic compounds are used alone or in combination of two or more. The amount of the organic basic compound used is usually 0.001 to 10% by weight, preferably 0.01 to 5% by weight, based on the total solid content of the resist composition.
% By weight. If the amount is less than 0.001% by weight, the effect of the addition of the organic basic compound cannot be obtained. On the other hand, 10% by weight
If it exceeds 300, the sensitivity tends to decrease and the developability of the unexposed portion tends to deteriorate.

The positive photoresist composition of the present invention comprises
Contains a specific solvent (C) that dissolves the components (A) and (B). The component (C) contains heptanone (also referred to as a solvent of (1)). Examples of heptanone include 2-heptanone, 3-heptanone, and 4-heptanone, and preferably 2-heptanone. The component (C) preferably further contains at least one of propylene glycol monoalkyl ether, alkyl lactate and alkoxyalkyl propionate (also referred to as a solvent of (2)). Thereby, the edge roughness of the resist pattern is further improved.

Preferred examples of the propylene glycol monoalkyl ether include propylene glycol monomethyl ether and propylene glycol monoethyl ether. Preferred examples of the alkyl lactate include methyl lactate and ethyl lactate. Preferred examples of the alkoxyalkyl propionate include 3-ethoxyethyl propionate, 3-methoxymethyl propionate, 3-methoxyethyl propionate, and 3-ethoxymethyl propionate.

The amount of the solvent (1) is usually at least 30% by weight, preferably 40% by weight, based on the total amount of the solvent.
The content is more preferably 50% by weight or more. The amount of the solvent (2) used is usually 5 to 70% by weight, preferably 10 to 60% by weight, more preferably 1 to 60% by weight based on the total solvent.
5 to 50% by weight. If the amount of the solvent (2) is less than the above range, the effect of adding the solvent is reduced, and if it exceeds 70% by weight, problems such as deterioration of coating properties may occur, which is not preferable.

In the present invention, the solvent (C) preferably further contains at least one of γ-butyrolactone, ethylene carbonate and propylene carbonate (also referred to as the solvent (3)). By adding the solvent of (3), generation of particles in the resist composition solution can be suppressed, and further generation of particles in the solution over time can be suppressed. The use weight ratio of the solvent (3) is preferably 0.1 to 25% by weight, more preferably 1 to 20% by weight, and more preferably 3 to 15% with respect to the total solvent. In the present invention, the solid content of the resist composition containing each of the above components is preferably dissolved in the mixed solvent at a solid concentration of 3 to 25% by weight, more preferably 5 to 22% by weight, and still more preferably 5 to 22% by weight. 7-2
0%.

Preferred combinations of the mixed solvent in the present invention include 2-heptanone + propylene glycol monomethyl ether, 2-heptanone + ethyl lactate,
-Heptanone + 3-ethoxyethyl propionate, 2
-Heptanone + γ-butyrolactone, 2-heptanone +
Ethylene carbonate, 2-heptanone + propylene carbonate, 2-heptanone + propylene glycol monomethyl ether + γ-butyrolactone, 2-heptanone + ethyl lactate + γ-butyrolactone, 2-heptanone + 3-ethoxyethyl propionate + γ-butyrolactone, 2-heptanone + Propylene glycol monomethyl ether + ethylene carbonate, 2-heptanone +
Ethyl lactate + ethylene carbonate, 2-heptanone +
3-ethoxyethyl propionate + ethylene carbonate, 2-heptanone + propylene glycol monomethyl ether + propylene carbonate, 2-heptanone + ethyl lactate + propylene carbonate, 2-heptanone + 3-ethoxyethyl propionate + propylene carbonate. More preferably, 2-heptanone + propylene glycol monomethyl ether + γ-butyrolactone, 2-heptanone + ethyl lactate + γ-butyrolactone, 2-heptanone + 3-ethoxyethyl propionate + γ-butyrolactone, 2-heptanone + propylene glycol monomethyl ether + ethylene Carbonate, 2-heptanone + ethyl lactate + ethylene carbonate, 2-heptanone + 3-ethoxyethyl propionate + ethylene carbonate, 2-heptanone + propylene glycol monomethyl ether + propylene carbonate, 2-heptanone + ethyl lactate + propylene carbonate, 2- Heptanone + 3-ethoxyethyl propionate + propylene carbonate.

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

Such a positive photoresist composition of the present invention is applied on a substrate to form a thin film. The thickness of this coating film is preferably from 50 nm to 1500 nm. Spinning the above composition onto a substrate (eg, a silicon / silicon dioxide coating) as used in the manufacture of precision integrated circuit devices;
After coating by an appropriate coating method such as a coater or the like, exposure is performed through a predetermined mask, baking and development are performed, whereby a good resist pattern can be obtained. Here, the exposure light is preferably far ultraviolet light having a wavelength of 250 nm or less, more preferably 220 nm or less. Specific examples include a KrF excimer laser (248 nm), an ArF excimer laser (193 nm), an F ₂ excimer laser (157 nm), an X-ray, an electron beam, and the like, and an ArF excimer laser (193 nm) is particularly preferable.

Examples of the developer for the positive photoresist composition for deep ultraviolet exposure according to the present invention include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia.
Primary amines such as ethylamine and n-propylamine;
Secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcoholamines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide and the like An alkaline aqueous solution such as a quaternary ammonium salt, a cyclic amine such as pyrrole, or pyrhelidine can be used. Further, an appropriate amount of an alcohol or a surfactant may be added to the above alkaline aqueous solution.

When the resist of the positive photoresist composition of the present invention is used as the upper resist of a two-layer resist, the lower organic polymer film is etched by oxygen plasma using the upper resist pattern as a protective mask. The upper resist has sufficient resistance to oxygen plasma. Although the oxygen plasma resistance of the positive photoresist composition of the present invention depends on the silicon content of the upper resist, the etching apparatus, and the etching conditions, the etching selectivity (the etching rate ratio between the lower resist and the upper resist) is 10%. It can be taken as a sufficiently large value of ~ 100.

In the pattern forming method using the positive photoresist composition of the present invention, first, an organic polymer film is formed on a substrate to be processed. The organic polymer film may be various known photoresists, and examples thereof include FH series and FHi series manufactured by Fujifilm Olin Co., or OiR series manufactured by Olin Co., and PFI series manufactured by Sumitomo Chemical Co., Ltd. The formation of the organic polymer film is performed by dissolving these in an appropriate solvent and applying the resulting solution by a spin coating method, a spraying method or the like. Next, a film of the positive photoresist composition of the present invention is formed on the first layer of the organic polymer film. This is performed by dissolving the resist material in an appropriate solvent in the same manner as in the first layer, and applying the resulting solution by spin coating, spraying, or the like. The obtained two-layer resist is then subjected to a pattern forming step. As a first step, a pattern forming process is first performed on the second layer, that is, the film of the upper photoresist composition. Perform mask alignment as necessary, and irradiate high-energy radiation through this mask to make the irradiated portion of the photoresist composition soluble in an alkaline aqueous solution,
The pattern is formed by developing with an alkaline aqueous solution.

Next, the organic polymer film is etched as a second step. This operation is performed by oxygen plasma etching using the film pattern of the resist composition as a mask to form a fine pattern having a high aspect ratio. I do. The etching of the organic polymer film by the oxygen plasma etching is exactly the same technique as the plasma ashing used when the resist film is peeled off after the etching of the substrate is completed by the conventional photoetching operation. This operation can be performed by, for example, a cylindrical plasma etching apparatus or a parallel flat slope plasma etching apparatus using oxygen as a reactive gas, that is, an etching gas. Further, the substrate is processed using this resist pattern as a mask. As a processing method, a dry etching method such as sputter etching, gas plasma etching, or ion beam etching can be used.

The etching treatment by the two-layer resist method including the resist film of the present invention is completed by the operation of removing the resist film. The removal of the resist layer can be carried out simply by dissolving the organic polymer material of the first layer. Since this organic polymer material is an arbitrary photoresist and has not been altered (hardened or the like) at all in the photoetching operation, an organic solvent of each known photoresist itself can be used. Or,
By a process such as plasma etching, separation can be performed without using a solvent.

[0147]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples. Synthesis Example 1 (Synthesis of photoacid generator [sI-3]) t-amylbenzene 60 g, potassium iodate 39.5
g, 81 g of acetic anhydride and 170 ml of dichloromethane were mixed, and 66.8 g of concentrated sulfuric acid was added dropwise over 2 hours while cooling in an ice bath. The reaction solution was stirred as it was for 2 hours, and then stirred at room temperature overnight to complete the reaction. After completion of the reaction, 50 ml of distilled water was added dropwise to the reaction solution while cooling in an ice bath, extraction was performed, and the organic layer was washed with water, aqueous sodium bicarbonate and water, and the obtained organic layer was concentrated to give di (t-amylphenyl). ) 40 g of iodonium sulfate was obtained. By subjecting the obtained sulfate to a salt exchange reaction with potassium heptadecafluorooctanesulfonate, the target product [sI-3] was obtained.

Synthesis Example 2 (Synthesis of photoacid generator [sI-6]) 90 g of n-octylphenyl ether, 39.5 g of potassium iodate, 81 g of acetic anhydride, 180 g of dichloromethane
66.8 g of concentrated sulfuric acid while cooling in an ice bath.
Was added dropwise over 2 hours. The reaction solution was stirred as it was for 2 hours, and then stirred at room temperature overnight to complete the reaction. After completion of the reaction, distilled water (50 mL) was added dropwise to the reaction solution while cooling in an ice bath, extraction was performed, and the organic layer was washed with water, aqueous sodium bicarbonate, and water. The obtained organic layer was concentrated, and di (n-octyloxy) was added. 45 g of phenyl) iodonium sulfate were obtained. By subjecting the obtained sulfate and potassium heptadecafluorooctanesulfonate to a salt exchange reaction, [sI-6] as an intended product was obtained.

Synthesis Example 3 (Synthesis of Photoacid Generator [sI-9]) Salt exchange of di (t-amylphenyl) iodonium sulfate obtained in Synthesis Example (1) with sodium pentafluorobenzenebenzenesulfonate. [SI-
9] was synthesized.

Synthesis Example 4 (Synthesis of photoacid generator [sI-5]) To 40 g of iodobenzene, 91 g of peracetic acid was slowly dropped, and the reaction solution was stirred at 30 ° C. for 2 hours. When the white powder came out, it was cooled with ice, the precipitate was collected by filtration, and 38 g of iodosobenzene diacetate was recovered. 50 g of iodosobenzene diacetate, 30 g of octylphenyl ether, 70 g of acetic anhydride, and 725 mL of glacial acetic acid thus obtained were mixed, and concentrated sulfuric acid 8 was cooled in an ice bath.
g was added dropwise over 1 hour. After 1 hour, an aqueous solution in which 31 g of NaBr was dissolved in 150 mL was added dropwise, and 42 g of a precipitated white powder, iodonium bromide salt, was recovered. The obtained iodonium bromide salt and trifluoromethanesulfonate are subjected to salt exchange to obtain the desired product [sI-
5].

Synthesis Example 5 (Synthesis of photoacid generator [sII-3]) 50 g of diphenyl sulfoxide was added to 800 m of mesitylene.
L, and 200 g of aluminum chloride was added thereto, followed by stirring at 80 ° C. for 24 hours. After the completion of the reaction, the reaction solution was slowly poured into 2 L of ice. 400 mL of concentrated hydrochloric acid was added thereto, and the mixture was heated at 70 ° C. for 10 minutes. The reaction solution was cooled to room temperature, washed with ethyl acetate, and filtered. A solution prepared by dissolving 200 g of ammonium iodide in 400 mL of distilled water was added to the filtrate. The precipitated powder was collected by filtration, washed with water, washed with ethyl acetate, dried, and treated with sulfonium iodide 72.
g was obtained. 50 g of the obtained sulfonium iodide was dissolved in 300 mL of methanol, and 31 g of silver oxide was added thereto, followed by stirring for 4 hours. After filtering the reaction solution, salt exchange was performed with potassium heptadecafluorooctanesulfonate to recover 40 g of the target substance [sII-3].

Synthesis Example 6 (Synthesis of Photoacid Generator [sII-2]) The corresponding sulfonium iodide was synthesized by using octylbenzene instead of mesitylene in Synthesis Example (5), and then synthesized. Salt exchange was performed with potassium trifluoromethanesulfonate in the same manner as in Example (5) to synthesize [sII-2] in the same manner as in Synthesis Example (5).

Synthesis Example 7 (Photoacid Generator [sII-8]) The corresponding sulfonium iodide was synthesized using octyloxybenzene instead of mesitylene in Synthesis Example (5), and then synthesized. Salt exchange with potassium nonafluorobutanesulfonate was performed in the same manner as in 5) to obtain the desired product [sII-8].

Synthesis Example 8 (Synthesis of photoacid generator [sII-14]) 50 g of diphenyl sulfoxide and 45 g of 2,6-xylenol were added to methanesulfonic acid / diphosphorus pentoxide (10 /
1) 100 mL of the solution was added. After the fever subsides, 5
Heat at 0 ° C. for 4 hours. After the completion of the reaction, the reaction solution was poured on ice. After washing this aqueous solution with toluene and filtering, an aqueous solution in which 200 g of ammonium iodide was dissolved in 400 mL of distilled water was added, and the precipitated powder was collected by filtration. The obtained residue was washed with water and dried to obtain sulfonium iodide. 50 g of the obtained sulfonium iodide was added to methanol 300 m
L, and 31 g of silver oxide was added thereto, followed by stirring for 4 hours. After the reaction solution was filtered, salt exchange was performed with potassium heptadecafluorooctanesulfonate to recover 43 g of the target product [sII-14].

[Synthesis of Resin] Synthesis Example (1) (Synthesis of Resin (1-1)) 11.4 g of trimethylallylsilane, 9.8 g of maleic anhydride, and 5.3 g of acrylonitrile were dried in THF34.
g, and then heated to 65 ° C. under a nitrogen stream. When the reaction temperature was stabilized, an initiator V-65 manufactured by Wako Pure Chemical Industries, Ltd. was added at 10 mol% of the total moles of the monomers to start the reaction. After reacting for 6 hours, the reaction mixture was diluted twice with THF, and then poured into a large amount of hexane to precipitate a white powder. Next, in order to reduce residual monomers and low molecular components, the precipitated powder was dissolved in acetone,
The polymer was precipitated by gradually adding hexane thereto. The precipitated polymer was washed with hexane / acetone (8/2) and dried, and then acetone 100m
and 10 g of t-butanol and 12.2 g of 4-dimethylaminopyridine were added thereto.
Reacted for hours.

When the temperature of the reaction solution was lowered to 20 ° C., 15 g of methyl iodide was added, and the mixture was reacted at room temperature for 6 hours.
After evaporating the solvent under reduced pressure and concentrating, the polymer was poured into 1 L of distilled water and reprecipitated. Then, drying was performed under reduced pressure to obtain a resin (1-1). As a result of GPC measurement, the molecular weight of the obtained resin (1-1) was 6600 in weight average using polystyrene as a standard sample, and the content of components having a molecular weight of 1000 or less was 4% by area ratio of GPC.

Resins (1-2) to (1) were prepared in the same manner as described above.
-4) was obtained. The molar ratio and weight average molecular weight of each repeating unit of the resins (1-1) to (1-4) are shown in the following structural formula and Table 1.

[0158]

Embedded image

Synthesis Example (5) (Synthesis of Resin (2-1)) 11.4 g of trimethylallylsilane, 9.8 g of maleic anhydride, and 6.4 g of t-butyl acrylate were dried in TH.
After adding to 34 g of F, the mixture was heated to 65 ° C. under a nitrogen stream.
When the reaction temperature becomes stable, initiator V manufactured by Wako Pure Chemical Industries, Ltd.
-65 was added in an amount of 10 mol% of the total number of moles of the monomers to start the reaction. After reacting for 6 hours, the reaction mixture is
After diluting twice with HF, throw it into a large amount of hexane,
A white powder was deposited. Next, in order to reduce residual monomers and low molecular components, the precipitated powder was dissolved in acetone, and hexane was added little by little to precipitate a polymer. The precipitated polymer was washed with hexane / acetone (8/2) and dried, and then acetone 100
and 10 g of t-butanol and 4-
12.2 g of dimethylaminopyridine was added and reacted at 80 ° C. for 6 hours. When the temperature of the reaction solution was lowered to 20 ° C., 15 g of methyl iodide was added, and the mixture was reacted at room temperature for 6 hours. After evaporating the solvent under reduced pressure and concentrating, the polymer was poured into 1 L of distilled water and reprecipitated. Then, drying was performed under reduced pressure to obtain a resin (2-1). As a result of GPC measurement, the molecular weight of the obtained resin (2-1) was 5600 in weight average using polystyrene as a standard sample, and the content of components having a molecular weight of 1000 or less was 4% by area ratio of GPC.

Resins (2-1) to (2) were prepared in the same manner as described above.
-7) was obtained. The molar ratio and weight average molecular weight of each repeating unit of the resins (2-1) to (2-7) are shown in the following structural formula and Table 1.

[0161]

Embedded image

Example: KrF exposure system As the component (A), 2 g of the resin shown in Table 1 below, 0.14 g of the photoacid generator (B) shown in Table 1 below, and ( Surfactant 0.003 g as the component (D) 0.005 g of the organic basic compound as the component (E) shown in Table 1 below was dissolved in 19.2 g of the solvent (C) shown in Table 1 and 0.1 μm Microfiltration was performed with a membrane filter of No. 3 to obtain a positive photoresist solution.

[0163]

[Table 1]

As the solvent, S1: 2-heptanone S2: ethyl lactate S3: propylene glycol monomethyl ether S4: ethoxyethyl propionate S5: γ-butyrolactone S6: ethylene carbonate S7: propylene carbonate S8: propylene glycol monomethyl ether acetate S9 ： Cyclohexanone

As the surfactant, W-1: Megafac F176 (Dainippon Ink Co., Ltd.)
(Fluorine) W-2: Megafac R08 (Dai Nippon Ink Co., Ltd.)
(Fluorine and silicone type) W-3: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) W-4: Polyoxyethylene nonylphenyl ether.

A silicon wafer was coated with an FHi-028D resist (a resist for i-line, manufactured by Fujifilm Ohlin Co., Ltd.) using a coater CDS-650 manufactured by Canon.
Baking was performed at 0 ° C. for 90 seconds to obtain a uniform film having a thickness of 0.83 μm. When this was further heated at 200 ° C. for 3 minutes, the film thickness became 0.71 μm. The above-prepared solution of the positive photoresist composition was coated thereon and baked at 135 ° C. for 90 seconds to form a film having a thickness of 0.20 μm.

The thus obtained wafer was exposed to a KrF excimer laser stepper while loading a resolving power mask thereon while changing the exposure amount and focus. Thereafter, after heating in a clean room at 125 ° C. for 90 seconds, development with a developer (NMD-W manufactured by Tokyo Applied Chemical Industry Co., Ltd.) was carried out for 60 seconds, rinsing with distilled water and drying to obtain a pattern, and using a scanning electron microscope. Observed. The treatment was performed as described above, and the edge roughness of the resist pattern, the number of generated particles, and the increased number of particles during storage over time were evaluated as follows.

[Edge Roughness]: The edge roughness was measured using a length-measuring scanning electron microscope (SEM).
The edge roughness of a line-and-space (line / space = 1/1) pattern of 0.16 μm is used to detect a line pattern edge at a plurality of positions in a measurement monitor, and the variance (3σ) of variation in the detected position is determined by the edge. It is an index of roughness, and the smaller the value, the better.

[Number of particles and increase of particles after storage over time]: The positive photoresist composition solution (coating solution) prepared as described above was prepared immediately after preparation (initial value of particles) and at 4 ° C. for one week. The number of particles in the liquid after standing (the number of particles after aging) was counted by a particle counter manufactured by Rion. Along with the initial particle value, (number of particles after aging)
(Particle initial value) The number of particles increased calculated was evaluated.

[Sensitivity variation rate]: The sensitivity (exposure amount before storage) of the positive photoresist composition solution (coating solution) prepared as described above immediately after preparation was evaluated as follows. The sensitivity (exposure amount after storage) after the solution was left at 4 ° C. for one week was evaluated, and the sensitivity fluctuation rate was evaluated by the following formula. The sensitivity is defined by the minimum exposure (mJ / cm ² ) that reproduces a 0.16 μm line-and-space (line / space = 1/1) pattern. Sensitivity fluctuation rate (%) = {(exposure amount before storage) − (exposure amount after storage)} / (exposure amount before storage) × 100

[Dependency on coarse / dense]: 0.18 μm each in a line-and-space pattern (dense pattern) and an isolated line pattern (sparse pattern) having a line width of 0.18 μm.
The overlapping range of the depth of focus allowing m ± 10% was determined.
The larger this range is, the better the density dependency is. Table 3 shows the evaluation results.

(Comparative Example) In Examples, as shown in Table 2, the following organic basic compounds and / or fluorine-based, silicon-based or nonionic-based surfactants were removed, and solvents other than the solvent according to the present invention were used. Except for using, a positive photoresist composition was prepared in exactly the same manner as in the example, and exposed and developed in the same manner as in the example. Table 4 shows the obtained performance.

[0173]

[Table 2]

[0174]

[Table 3]

[0175]

[Table 4]

As can be seen from the above results, the composition of the present invention showed excellent performance in all evaluation items.

[Examples]: ArF exposure system As the component (A), 2 g of the resin shown in Table 5 below, 0.11 g of the photoacid generator (B) shown in Table 5 below, and ( Surfactant 0.003 g as the component (D) 0.005 g of the organic basic compound as the component (E) shown in Table 5 below was dissolved in 19.2 g of the solvent (C) shown in Table 5 below. Microfiltration was performed with a 1 μm membrane filter to obtain a positive photoresist solution.

[0178]

[Table 5]

In Table 5, each solvent and each surfactant are the same as those defined in Table 1.

A silicon wafer was coated with FHi-028D resist (i-line resist, manufactured by Fujifilm Ohlin Co., Ltd.) using a coater CDS-650 manufactured by Canon Inc.
Baking was performed at 0 ° C. for 90 seconds to obtain a uniform film having a thickness of 0.83 μm. When this was further heated at 200 ° C. for 3 minutes, the film thickness became 0.71 μm. The above-prepared solution of the positive photoresist composition was coated thereon and baked at 135 ° C. for 90 seconds to form a film having a thickness of 80 nm.

The wafer thus obtained was used as an ISI A
An rF excimer laser stepper was loaded with a resolving power mask and exposed while changing the exposure amount and focus. Then, after heating in a clean room at 125 ° C. for 90 seconds, deionized water was first placed on the resist film for 60 seconds. Thereafter, it was removed and development was carried out again with FHD-5 (tetramethylammonium hydroxide developer (2.38%)) for 60 seconds. Then, it was rinsed with distilled water and dried to obtain a pattern, which was observed with a scanning electron microscope. Processing as described above, the roughness, the number of generated particles,
The number of particles increased during storage over time was evaluated.

[Edge Roughness]: The edge roughness was measured using a length-measuring scanning electron microscope (SEM).
13 μm line and space (line / space =
1 / 1.2) Perform with the edge roughness of the pattern, detect line pattern edges at a plurality of positions in the measurement monitor, and use the variance (3σ) of variation in the detected positions as an index of the edge roughness. preferable. [Number of particles and number of particles increased after storage over time]: Immediately after preparation of the positive photoresist composition solution (coating solution) prepared as described above (initial value of particles) and after standing at 4 ° C. for one week. The number of particles in the liquid (number of particles after aging) was counted by a particle counter manufactured by Rion. Along with the particle initial value, the number of particles increased by (number of particles after aging)-(particle initial value) was evaluated.

[Sensitivity variation rate]: The sensitivity (exposure amount before storage) of the positive photoresist composition solution (coating solution) prepared as described above immediately after preparation was evaluated as follows. The sensitivity (exposure amount after storage) after the solution was left at 4 ° C. for one week was evaluated, and the sensitivity fluctuation rate was evaluated by the following formula. The sensitivity is defined by the minimum exposure (mJ / cm ² ) that reproduces a 0.13 μm line-and-space (line / space = 1 / 1.2) pattern. Sensitivity fluctuation rate (%) = {(exposure amount before storage) − (exposure amount after storage)} / (exposure amount before storage) × 100

[Dependency on coarse / dense]: 0.15 μm each in a line and space pattern (dense pattern) and an isolated line pattern (sparse pattern) having a line width of 0.15 μm.
The overlapping range of the depth of focus allowing m ± 10% was determined.
The larger this range is, the better the density dependency is. Table 7 shows the evaluation results.

(Comparative Example) In Examples, as shown in Table 6, the following organic basic compounds and / or fluorine-based, silicon-based or nonionic-based surfactants were removed, and solvents other than the solvent according to the present invention were used. Except for using, a positive photoresist composition was prepared in exactly the same manner as in the example, and exposed and developed in the same manner as in the example. Table 8 shows the obtained performance.

[0186]

[Table 6]

[0187]

[Table 7]

[0188]

[Table 8]

As can be seen from the above results, the composition of the present invention showed excellent performance in all evaluation items.

[0190]

The positive photoresist composition for deep ultraviolet exposure according to the present invention can be suitably applied particularly to light in the far ultraviolet wavelength region in the range of 170 nm to 220 nm, and can improve the edge roughness of a resist pattern. Further, generation of particles of the composition solution can be prevented.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H025 AA00 AA01 AB15 AB16 AB17 AC04 AC08 AD03 BE00 BE10 BG00 CC03 CC04 CC20 FA03 FA12 FA17

Claims (6)

[Claims] (A) a recurring unit represented by the following general formula (I) and a recurring unit represented by at least one of the following general formulas (IIa) and (IIb): A positive photoresist composition comprising: a resin which increases the solubility in an alkali developing solution by action; (B) a compound which generates an acid upon irradiation with actinic rays or radiation; and (C) a solvent containing heptanone. object. General formula (I) In the formula (I), R ^{1 to} R ³ each independently represent an alkyl group,
Represents a haloalkyl group, a halogen atom, an alkoxy group, a trialkylsilyl group, or a trialkylsilyloxy group. n represents 0 or 1. General formula (IIa) In the formula (IIa), Y represents a group selected from a hydrogen atom, a methyl group, a cyano group, and a chlorine atom. L represents a single bond or a divalent linking group. Q represents a hydrogen atom or a group capable of decomposing with an acid to generate a carboxylic acid. General formula (IIb) In the formula (IIb), X ¹ and X ² are each independently an oxygen atom,
Sulfur atom, -NH -, - NHSO ₂ - represents a group selected from. L ¹ and L ² are each independently a single bond or 2
Represents a valent linking group. A ¹ represents -Q or -COOQ, and when X ¹ is an oxygen atom and L ¹ represents a single bond, A ¹
Represents -Q. A ² represents a hydrogen atom, a cyano group, a hydroxyl group,-
COOH, —COOR ′, —CO—NH—R ″, an optionally substituted alkyl group, an optionally substituted cyclic hydrocarbon group, an alkoxy group, —Q or —COOQ (here, R ′ , R '' each independently represents an alkyl group which may have a substituent.) Q represents a group capable of decomposing with an acid to generate a carboxylic acid. 2. The resin of the above (A) further comprises the following general formula (II)
The positive photoresist composition according to claim 1, comprising a repeating structural unit represented by I). General formula (III) Wherein (III), Z represents an oxygen atom or N-R ^3,. R ³ represents a hydrogen atom, a hydroxyl group, a linear or branched alkyl group, or —O—SO ₂ —R ⁴ . R ⁴ is an alkyl group,
Represents a trihalomethyl group. 3. The positive-type photo according to claim 1, wherein the solvent (C) contains at least one of propylene glycol monoalkyl ether, alkyl lactate and alkoxyalkyl propionate. Resist composition. 4. The positive-type photo-injection according to claim 1, wherein the mixed solvent of (C) further contains at least one of γ-butyrolactone, ethylene carbonate and propylene carbonate. Resist composition. 5. The positive photoresist composition according to claim 1, further comprising (D) at least one of a fluorine-based and / or a silicon-based surfactant. 6. The positive photoresist composition according to claim 1, further comprising (E) an organic basic compound.