JP2001188349A - Photoresist composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive photoresist composition having high resolving power in the production of a semiconductor device, giving a photoresist having a rectangular shape and ensuring low edge roughness of a line pattern. SOLUTION: The positive photoresist composition contains a resin containing repeating units including a specified structure and having solubility to an alkali developing solution increased by the action of an acid, a compound which generated the acid when irradiated with active light or radiation, an organic solvent which dissolves the above components, an organic basic compound and at least one selected from a fluorine- and/or silicon-containing surfactant and a nonionic surfactant.

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, a terpolymer composed of maleic anhydride-unsaturated carboxylic acid t-butyl ester-allyltrimethylsilane is disclosed in JP-A-5-11.
No. 450 is disclosed. Although this resist has excellent resolution for processing ultra-fine patterns,
There is a problem that the rectangularity of the line pattern and the edge roughness of the line pattern are poor. 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.

[0009]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a positive photoresist composition which has a high resolution and provides a photoresist having a rectangular shape in the manufacture of semiconductor devices. Another object of the present invention is to provide a positive photoresist composition having a small edge roughness of a line pattern.

[0010]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies on a resist composition in a positive-type chemical amplification system and found that an acid-decomposable resin copolymerized with a specific repeating unit and a specific additive were used. Have achieved the object of the present invention. That is, the present invention is the following positive photoresist composition. (1) (A) A side chain containing a repeating unit having a partial structure represented by the following general formula (I) and a group capable of decomposing by the action of an acid to increase the solubility in an alkali developing solution. (B) a compound that generates an acid upon irradiation with actinic rays or radiation (C) an organic solvent that dissolves the above (A) and (B) (D) an organic basic compound (E) fluorine Positive photoresist composition comprising at least one surfactant selected from the group consisting of a surfactant, a silicon surfactant, and a nonionic surfactant, represented by the general formula (I):

[0011]

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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. (2) The positive photoresist composition according to claim 1, wherein the repeating unit containing the partial structure represented by the general formula (I) is represented by the following general formula (Ia). General formula (Ia)

[0013]

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In the formula (Ia), 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.

(3) In the general formula (I), n is 1
The positive photoresist composition according to the above (1), wherein (4) The positive photoresist composition as described in any of (1) to (3) above, wherein the component (B) is a compound that generates an organic sulfonic acid upon irradiation with actinic rays or radiation. object.

(5) The compound capable of generating an organic sulfonic acid upon irradiation with actinic rays or radiation is the following (B)
The positive photoresist composition according to the above (4), which is a compound belonging to any of the group consisting of 1) to (B6). (B1) Sulfonium salt compound having an organic sulfonic acid anion as a counter anion (B2) Iodonium salt compound having an organic sulfonic acid anion as a counter anion (B3) Organic disulfone derivative compound (B4) Imino sulfonate derivative compound (B5) Diazodisulfone derivative Compound (B6) diazoketosulfone derivative compound

In the present invention, the rectangularity and line edge roughness of a pattern are improved by using an organic basic compound and a specific surfactant together with a silicon-containing acid-decomposable resin having a specific repeating unit. . Although the mechanism is not clear, the organic basic compound and the specific surfactant cooperate to work, and the acid-decomposable group decomposition rate of the acid-decomposable resin in the area corresponding to the line side wall and the edge portion, and It is presumed that the resulting developer solubility was controlled.

Further, in the present invention, the silicon-containing acid-decomposable resin (A) having the specific repeating unit contains a repeating unit represented by at least one of the following general formulas (IIa) and (IIb): Is preferred. General formula (IIa)

[0019]

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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)

[0021]

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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, or —COO
Q (wherein 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.

Further, in the present invention, the silicon-containing acid-decomposable resin (A) having the specific repeating unit preferably contains a repeating unit represented by the following general formula (III). General formula (III)

[0024]

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The formula (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 represents an alkyl group or a trihalomethyl group.

[0026]

First, the resin (A) of the present invention will be described. In the partial structure (I) and the repeating unit (Ia) containing the partial structure, R ^{1 to} R ³ each independently represent an alkyl group, a haloalkyl group, a halogen atom, an alkoxy group, a trialkylsilyl group, a trialkylsilyloxy group. Represents a group selected from groups. 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. Examples of the haloalkyl group include 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-alkyl 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 edge roughness is further improved.

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

[0030]

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The repeating unit preferably used in the present invention
In (IIa), Y is a hydrogen atom, a methyl group, a cyano group,
Represents a group selected from chlorine atoms. L is a single bond or 2
Represents a valent 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 decomposed from the resin by the acid generated from the component (B) upon exposure to light.
It is a group that generates a -COOH group upon leaving. Specific examples of such a group include a tertiary alkyl group such as a t-butyl group and a t-amyl group, an isobornyl group, a 1-ethoxyethyl group, a 1-butoxyethyl group, a 1-isobutoxyethyl group, 1-alkoxyethyl group such as cyclohexyloxyethyl group, alkoxymethyl group such as 1-methoxymethyl group, 1-ethoxymethyl group, tetrahydropyranyl group, tetrahydrofurfuryl group, trialkylsilyl group, 3-oxocyclohexyl group , A 2-methyl-adamantyl group, a mevalonic lactone residue, and a 2- (γ-butyrolactonyloxycarbonyl) -2-propyl group.

In the repeating unit (IIb) preferably used in the present invention, 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.

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, or -COO
Represents Q. (R ′ and R ″ each independently represent an alkyl group which may have a substituent.) A ² , R ′ and R ″
Is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, more preferably a linear or branched alkyl group having 1 to 6 carbon atoms, still more preferably a methyl group or an ethyl group , 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, an n-butoxy group, an i- Butoxy, s-butoxy and t-butoxy groups, among which methoxy and ethoxy groups are particularly preferred. Similarly, Q is the same group as Q in the repeating unit (IIa). Examples of the further substituent of the above alkyl group and alkoxy group 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. Groups, nobornane epoxy group, menthyl group, isomenthyl group, neomenthyl group, tetracyclododecanyl group and the like. The bond forming the ring of these cyclic hydrocarbon groups may have an ester bond or a carbonyl bond. Further substituents of the cyclic hydrocarbon group include a hydroxyl group, a halogen atom, a carboxyl group, an alkoxy group, an acyl group, a cyano group, an acyloxy group and the like. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. As the alkoxy group, a methoxy group, an ethoxy group,
Examples thereof include those having 1 to 4 carbon atoms such as a propoxy group and a butoxy group. Examples of the acyl group include a formyl group and an acetyl group. Examples of the acyloxy group 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.

[0037]

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[0038]

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

[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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The repeating unit preferably used in the present invention
In (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 . 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.

[0046]

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[0047]

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

Methacrylamides, for example, methacrylamide, N-alkyl methacrylamide (alkyl having 1 to 10 carbon atoms, for example, methyl, ethyl, t-butyl, ethylhexyl, hydroxyethyl, cyclohexyl) Groups, etc.), N, N-dialkylmethacrylamide (an alkyl group 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) of the present invention, the repeating unit represented by the general formula (I), and if necessary, at least one of the repeating units (IIa) and (IIb), the general formula (III) The content of the repeating unit represented by) is as follows: the resistance of the desired resist to oxygen plasma etching, sensitivity, prevention of pattern cracking, substrate adhesion,
It can be appropriately set in consideration of the resist profile, and the resolution, heat resistance, and the like, which are necessary requirements of a general resist. Generally, in the resin (A) of the present invention, the content of the repeating unit represented by the general formula (I) is as follows:
10 to 90 mol%, preferably 15 to 70 mol%, more preferably 20 to 5 mol%, based on all repeating units.
0 mol%.

When at least one of the repeating units (IIa) and (IIb) is contained, the content is 5 to 50 mol%, preferably 10 to 40 mol%, based on all repeating units. %. When the repeating unit (III) is contained, the content is 10% with respect to all repeating units.
To 90 mol%, preferably 15 to 70 mol%, more preferably 20 to 60 mol%.

In the resin (A) of the present invention, the compound represented by the general formula (II)
In the case where a repeating unit represented by a), (IIb) and / or (III) is contained, in addition to the monomer corresponding to the repeating unit represented by the general formula (I), a compound represented by the general formula (IIa) And (II
b) is obtained by copolymerizing a monomer corresponding to at least one of the repeating units and / or a monomer corresponding to the repeating unit represented by the general formula (III) in the presence of a polymerization catalyst. . Alternatively, a monomer corresponding to the repeating unit represented by the general formula (I) may be added to the monomer represented by the general formula (IIa)
Or a maleic anhydride is further copolymerized with a monomer corresponding to the repeating unit represented by the general formula (I). There is also a method in which a repeating unit derived from maleic anhydride of the obtained copolymer is partially subjected to ring-opening esterification with an alcohol or hydrolysis under basic or acidic conditions to synthesize.

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 that generate an acid upon irradiation with actinic rays or radiation used in the present invention include, for example, SI Schlesinger, Photogr. Sci. Eng., 18, 38
7 (1974), diazonium salts described in TSBal et al, Polymer, 21, 423 (1980), U.S. Pat.Nos. 4,069,055 and 4,06
9,056, the same Re 27,992, ammonium salts described in JP-A-3-140140, etc., DCNecker et al, Macromolecule
s, 17, 2468 (1984), CSWenet al, Teh, Proc. Conf.Ra.
d. Curing ASIA, p478 Tokyo, Oct (1988), US Patent 4,0
69,055, the phosphonium salt described in 4,069,056 and the like,
JVCrivello et al, Macromorecules, 10 (6), 1307 (19
77), Chem. & Eng. News, Nov. 28, p31 (1988), European Patent No. 104,143, U.S. Patent Nos. 339,049, 410,201.
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No. 34,444, No. 2,833,827, Dokoku Patent No. 2,904,626, No.
3,604,580 and 3,604,581, JP-A-7-28237
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V. Crivello et al, Macromorecules, 10 (6), 1307 (197
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echnol., 130 (6), FMHoulihan et al, Macromolcules, 2
1,2001 (1988), European Patent Nos. 0290,750 and 046,083,
No. 156,535, No. 271,851, No. 0,388,343, U.S. Pat.No. 3,901,710, No. 4,181,531, JP-A-60-198538,
A photoacid generator having a 0-nitrobenzyl-type protecting group described in JP-A-53-133022 and the like, M. TUNOOKA et al, Polymer P
reprints Japan, 35 (8), G. Berner et al., J. Rad. Curing,
13 (4), WJ Mijs et al, Coating Technol., 55 (697),
45 (1983), Akzo, H. Adachi et al, Polymer Preprints,
Japan, 37 (3), European Patent Nos. 0199,672, 84515, 04
No. 4,115, No. 618,564, No. 0101,122, U.S. Pat.
Nos. 1,605, 4,431,774, JP-A-64-18143, JP-A-2
Compounds which generate sulfonic acid by photolysis, such as iminosulfonates described in JP-A-245756 and JP-A-3-140109, JP-A-61-166544, JP-A-2-71270
Compounds described in JP-A-3-10385
And diazoketosulfone and diazodisulfone compounds described in JP-A Nos. 4,103,856 and 4-210960.

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 particularly effectively used are described below. (1) The following general formula (PAG) substituted with a trihalomethyl group
The oxazole derivative represented by 1) or the general formula (PA)
An S-triazine derivative represented by G2).

[0067]

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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.

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[0070]

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

[0073]

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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.

[0076] 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.

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[0090]

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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).

[0094]

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

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

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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 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. Specific examples of these substituents include the same as those described in the above (PAG-7). 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.

Examples of such a compound include the following (B1)
To (B6). These (B1) ~
The compound of (B6) is a compound represented by the aforementioned general formula (PAG-1)
It corresponds to a compound which generates an organic sulfonic acid among the compounds represented by (PAG-8). (B1) Sulfonium salt compound having an organic sulfonic acid anion as a counter anion (B2) Iodonium salt compound having an organic sulfonic acid anion as a counter anion (B3) Organic disulfone derivative compound (B4) Imino sulfonate derivative compound (B5) Diazodisulfone derivative Compound (B6) diazoketosulfone derivative compound

As the photoacid generator, an organic sulfonic acid is generated by irradiation with actinic rays or radiation (B-3)
The compound (B-6) is preferable because the resolution of the resist pattern is improved, and the compounds (B-3) to (B-6) that generate a fluorinated organic sulfonic acid have high sensitivity and are particularly preferable.

The amount of the photoacid generator (B) to be used 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
(D) It contains an organic basic compound. Examples of the organic basic compound include compounds having the following structures.

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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.

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

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

Particularly preferred specific examples are 1,5-diazabicyclo [4.3.0] -5-nonene, 1,8-diazabicyclo [5.4.0] -7-undecene (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
It contains the surfactant (E). That is, it contains at least one surfactant of a fluorine-based surfactant, a silicon-based surfactant, a surfactant containing both a fluorine atom and a silicon atom, 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,
JP-A-61-226746, JP-A-61-226745, JP-A-62-170
950, JP-A-63-34540, JP-A-7-230165, JP-A-8
-62834, JP-A-9-54432 and JP-A-9-5988, and the following commercially available surfactants can be used as they are. As commercially available surfactants that can be used, for example, F-top EF301, EF303, (manufactured by Shin-Akita Chemical Co., Ltd.), Florad FC430, 431 (Sumitomo 3M)
Co., Ltd.), Mega Fuck 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, polyoxyethylene oleyl ether, and polyoxyethylene. 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. (E)
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
It contains a solvent that dissolves the above components (A) and (B). Examples of the solvent include propylene glycol monomethyl ether acetate, propylene glycol monoalkyl ether acetates such as propylene glycol monoethyl ether acetate, methyl lactate, alkyl lactates such as ethyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether and the like. Ethylene glycol monoalkyl ethers such as propylene glycol monoalkyl ethers, ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; -Heptanone, γ-butyrolactone, methoxyp Methyl acid, ethyl ethoxypropionate alkoxypropionic acid alkyls such as methyl pyruvate, pyruvate alkyl esters such as ethyl pyruvate, N- methylpyrrolidone, N, N
-Applied using at least one solvent selected from dimethylacetamide, dimethylsulfoxide and the like.

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.

The 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 0.4 to 1.5 μm. The above composition is applied to a substrate (eg, such as used in the manufacture of precision integrated circuit devices).
A good resist pattern can be obtained by applying a suitable coating method such as a spinner, a coater or the like on a silicon / silicon dioxide coating), exposing through a predetermined mask, baking and developing. Here, the exposure light is preferably 250 nm or less, more preferably 22 nm or less.
It is far ultraviolet light having a wavelength of 0 nm or less. Specifically, Kr
F excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (157
nm), X-rays, electron beams 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 resist composition film pattern 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 film 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.

[0133]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto. Synthesis Example 1 (Synthesis of Resin (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 was stabilized, a polymerization initiator V-65 manufactured by Wako Pure Chemical Industries, Ltd. was added at 10 mol% of the total number of 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, and hexane was added little by little to precipitate a polymer. After the polymer precipitated in the lower layer was dissolved again in acetone, it was poured into a large amount of hexane to precipitate a white powder. After recovering the white polymer by filtration, drying under reduced pressure was performed to obtain a resin (1). As a result of GPC measurement, the molecular weight of the obtained resin (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
Met.

Synthesis Examples 2 to 18 (Synthesis of Resins (2) to (18)) Resins (2) to (18) were synthesized by the same synthesis method as in Synthesis Example 1. The molar ratio and weight average molecular weight of each repeating unit of the resins (1) to 18 are shown in the following structural formula and Table 1.

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Example 1 2 g of resin (1) as an acid-decomposable resin (A) component, 0.12 g of triphenylsulfonium-2,4,6-triisopropylphenylsulfonate as a compound component generating an acid upon exposure, 0.012 g of DBU and 0.003 g of the following surfactant W-1 were dissolved in 19.2 g of propylene glycol monomethyl ether acetate, and the solution was microfiltered with a 0.1 μm membrane filter. FHi-028 on silicon wafer
D resist (a resist for i-line, manufactured by Fujifilm Ohlin Co.) was applied using a coater CDS-650 manufactured by Canon, and baked at 90 ° 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 silicon-containing resist composition prepared above was applied thereon, baked at 90 ° C. for 90 seconds, and applied to a thickness of 0.20 μm.

The wafer thus obtained was exposed to an ArF excimer laser stepper while loading a resolving power mask thereon while changing the exposure amount and focus. Then, after heating in a clean room at 120 ° C. for 90 seconds, tetramethylammonium hydroxide developer (2.38%) was used for 60 minutes.
After developing for 2 seconds, rinsing with distilled water and drying were performed to obtain a pattern. When observed with a scanning electron microscope, it was 0.15 μm
Were resolved (line resolution). The rectangularity of the cross section was evaluated as A. The roughness was evaluated as A.

The rectangularity of the cross section was compared by a three-step evaluation as follows. That is, the angle between the substrate and the side wall of the resist pattern was measured, and the angle between 80 ° and 90 ° was A
Evaluated, those with 70 ° or more and less than 80 ° were evaluated as B, and those with less than 70 ° were evaluated as C. The roughness was visually evaluated by observing the size of the roughness (irregularity) at the line edge portion in the 0.15 μm line and space pattern with an SEM. Evaluation was made in three stages of A, B, and C in order from the best one, and A was given when little roughness (roughness) was seen at the line edge, and B was given when little roughness (roughness) was seen at the line edge. Samples in which roughness (roughness) was clearly seen at the line edge were designated C.

(Examples 2 to 4) Positive-type photo resists were prepared in exactly the same manner as in Example 1 except that the resist compositions in Table 1 were used instead of the resist compositions in Example 1. The resist composition was adjusted, and exposed and developed in the same manner as in Example 1. The obtained performance is shown in Table-C.

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.

(Comparative Example 1) Example 1 was the same as Example 1 except that the following organic basic compounds and / or fluorine-based, silicon-based or nonionic-based surfactants were omitted as shown in Table-B. A positive photoresist composition was prepared in exactly the same manner, and exposed and developed in the same manner as in Example 1. Table D shows the obtained performance. (Comparative Examples 2 to 12) In the same manner as in Comparative Example 1, the compositions having the formulations shown in Table-B were evaluated. Table D shows the results.
It was shown to.

[0143]

[Table 1]

[0144]

[Table 2]

[0145]

[Table 3]

[0146]

[Table 4]

[0147]

[Table 5]

[0148]

[Table 6]

[0149]

[Table 7]

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

[0151]

According to the present invention, it is possible to provide a positive resist composition which provides a photoresist having a high resolution and a rectangular shape in the manufacture of a semiconductor device, and further has a low edge roughness of a line pattern. A positive resist composition can be provided.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03F 7/004 501 G03F 7/004 501 7/075 521 7/075 521 H01L 21/027 H01L 21/30 502R F-term (reference) 2H025 AA02 AA03 AB16 AC08 AD03 BE00 BE07 BE10 BF30 BG00 CB10 CB14 CB41 CC03 CC04 CC20 4J002 BD122 BG041 BG051 BG071 BH021 BQ001 CH052 CP032 EB106 ER026 EU026 EU076 EU136R03 EU03 EU306 EU03 EU206 EU076 EU136 EU3 6 AP16P BA03R BA04R BA05R BA06Q BA06R BA11Q BA11R BA15R BA16R BA40R BA51R BA58R BA72P BA72Q BA77P BA80P BA82P BC04Q BC04R BC07R BC53Q BC53R CA01 CA04 CA05 DA28 DA61

Claims (5)

[Claims] (A) A side chain comprising a repeating unit having a partial structure represented by the following general formula (I) and a group capable of decomposing by the action of an acid to increase the solubility in an alkali developing solution. (B) a compound that generates an acid upon irradiation with actinic rays or radiation (C) an organic solvent that dissolves the above (A) and (B) (D) an organic basic compound (E ) Positive photoresist composition characterized by containing at least one surfactant selected from a fluorine-based surfactant, a silicon-based surfactant, and a nonionic surfactant, general formula (I) Formula 1 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. 2. The positive photoresist composition according to claim 1, wherein the repeating unit containing the partial structure represented by the general formula (I) is represented by the following general formula (Ia). object. Formula (Ia) In the formula (Ia), 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. 3. The positive photoresist composition according to claim 1, wherein n in the general formula (I) is 1. 4. The positive photoresist composition according to claim 1, wherein the component (B) is a compound that generates an organic sulfonic acid upon irradiation with actinic rays or radiation. . 5. The compound capable of generating an organic sulfonic acid upon irradiation with actinic rays or radiation includes the following compounds (B1) to (B1):
The positive photoresist composition according to claim 4, which is a compound belonging to any of the group consisting of (B6). (B1) Sulfonium salt compound having an organic sulfonic acid anion as a counter anion (B2) Iodonium salt compound having an organic sulfonic acid anion as a counter anion (B3) Organic disulfone derivative compound (B4) Imino sulfonate derivative compound (B5) Diazodisulfone derivative Compound (B6) diazoketosulfone derivative compound