JP2001201860A - Positive photoresist composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive resist composition having high sensitivity and high resolving power in the production of a semiconductor device, having a rectangular shape, ensuring low edge roughness of a line pattern and causing a small size shift, in pattern transfer to a lower layer in an oxygen plasma etching step. SOLUTION: The positive photoresist composition contains a high molecular compound, having repeating units with a specified structure and repeating units containing a group which is decomposed by an acid and can generate an acid group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive photoresist composition used 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 the density and integration of semiconductor devices and the like, the line width and spacing of patterns have become extremely small.
Since dry etching has been adopted for substrate etching, high resolution and high dry etching resistance have been demanded for photoresists, and the majority of positive photoresists are nowadays. Was. In particular, among the positive photoresists, they have excellent sensitivity, resolution and dry etching resistance. For example, JC Strieta, Kodak Microelectronics Seminar Proceedings, No. 11
6 (1976) (JC Strieter, Kodak Micro ele
ctronics Seminar Proceedings, 116 (1976)
And the like, alkali-developable positive photoresists based on alkali-soluble novolak resins are the mainstream of current processes.

However, in recent years, multifunctional electronic devices have been
As the sophistication increases, there is a strong demand for finer patterns to achieve higher densities 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 planarization film by O ₂ 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. Polysiloxane containing an image-forming portion transparent to ArF excimer laser light is disclosed in, for example, JP-A-8-16.
0623, JP-A-10-324748, JP-A-11-6
0733 and JP-A-11-60734.
However, these resists have insufficient resolution power for processing ultra-fine patterns, rectangularity of patterns, and poor edge roughness of line patterns, and furthermore,
When used as an upper layer resist of a two-layer resist, there has been a problem that a dimension shift becomes large when transferring a pattern to a lower layer in the next oxygen plasma process.

[0009]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a positive resist composition which has high sensitivity and high resolution and provides a photoresist having a rectangular shape in the manufacture of semiconductor devices. It is. Another object of the present invention is to provide a positive resist composition having a small edge roughness of a line pattern. Edge roughness refers to the fact that the top and bottom edges of a resist line pattern fluctuate irregularly in the direction perpendicular to the line direction due to the characteristics of the resist. It means that it looks uneven. Still another object of the present invention is to provide a positive resist composition having a small dimensional shift when transferring a pattern to a lower layer in an oxygen plasma etching step.

[0010]

Means for Solving the Problems As a result of intensive studies on the resist composition in a positive-type chemical amplification system, the present inventors have found that the use of an acid-decomposable resin copolymerized with a specific repeating unit enables the present invention to be used. I found that my goal was achieved. That is, the above object is achieved by using a positive photoresist composition containing the following acid-decomposable resin. (1) A positive type comprising a polymer compound having a repeating unit represented by the general formula (I) and a repeating unit having a group capable of decomposing with an acid to generate an acid group. Photoresist composition.

[0011]

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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. M represents a single bond or a divalent linking group. R ′ and R ″ may be the same or different and include a hydrogen atom, a trialkylmethylsilyl group, a trialkylmethylsilylmethyl group, a trichlorosilyl group, a trialkoxysilyl group, a dialkoxymethylsilyl group, —CO—
A group (A represents -OH, -OB, or -NHB group; B represents a linear or branched alkyl group.)
Represents R 'and R''are an alkylene group, -CO-O-CO
-Or -CO-NR '''-CO- linked via any atomic group, or R' and R '' are integrally alkylene group, -CO-O-CO-, or- CO-N
It may constitute any atomic group of R ′ ″ — CO— and thereby constitute a ring structure. (R ′ ″ represents a hydrogen atom, a hydroxyl group, a linear or branched alkyl group, or —O—SO ₂ —R ″ ″. R ″ ″ represents an alkyl group or a trihalomethyl group. 2. The method according to claim 1, wherein the repeating unit having a group capable of decomposing with an acid to generate an acid group is any one of the following general formulas (IIa) and (IIb): Positive photoresist composition.

[0013]

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Y represents a hydrogen atom or a group selected from 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 generating a carboxylic acid by decomposition with an acid.

[0015]

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X¹And X^TwoIs independently an oxygen atom,
Sulfur atom, -NH-, -NHSO _TwoGroup selected from-
Represents L¹And L^TwoAre each independently a single bond or divalent
Represents a linking group. A¹Represents -Q or -COOQ
Is X¹Is an oxygen atom and L¹When A represents a single bond,¹
Represents Q. A^TwoRepresents a hydrogen atom, a cyano group, a hydroxyl group, -C
OOH, -COOR ', -CO-NH-R' ', substituted
Alkyl group which may be substituted, cyclic carbon which may be substituted
Represents a hydride group, an alkoxy group, or —COOQ.
(R ′ and R ″ each independently have a substituent
Represents a good alkyl group. ) Q is decomposed by hydrogen atom or acid
Represents a group capable of generating a carboxylic acid. (3) Q in the general formulas (IIa) and (IIb) is decomposed with an acid to
Represents a group capable of generating rubonic acid,
The above is a generic term including partial hydrogen
The positive photoresist composition according to (2). (4) The polymer compound is represented by the general formula (III)
(1) to (1), which have a repeating unit.
Positive photoresist composition according to any of (3).
object.

[0017]

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Z represents an oxygen atom or a group represented by ＮN—R ³ . R ³ is a hydrogen atom, a hydroxyl group, an alkyl group, a group represented by —OSO ₂ —R ⁴ or —SO ₂ —R ⁴ , or any of these. R ⁴ represents an alkyl group or a trihalomethyl group. The alkyl group generically referred to as R ³ and R ⁴ may be linear or may have a branch. (5) (A) the polymer compound according to any of the above (1) to (4), (B) a compound which generates an acid upon irradiation with actinic rays or radiation, and (C) the above (A) and A positive photoresist composition comprising at least an organic solvent for dissolving (B). (6) The positive photoresist composition as described in (5) above, which further comprises (D) an organic basic compound. (7) The positive photoresist composition as described in (6) above, which further comprises (E) a surfactant.

[0019]

DESCRIPTION OF THE PREFERRED EMBODIMENTS First, the polymer (A) used in the positive photoresist composition of the present invention will be described. In the repeating 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-
A butyl group, an i-butyl group, an s-butyl group and a t-butyl group. The alkoxy group is a linear or branched alkyl 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 group. Groups, s-butoxy groups and t-butoxy groups, among which methoxy and ethoxy groups are particularly preferred. The alkyl group of the trialkylsilyl group is a linear or branched alkyl group having 1 to 6 carbon atoms, more preferably a methyl group, an ethyl group, or an n-
A propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group and a t-butyl group, among which the 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,
n-propyl group, i-propyl group, n-butyl group, i-
A butyl group, an s-butyl group, and a t-butyl group are the most preferable, and the most preferable is a methyl group. M represents a single bond or a divalent linking group. Examples of the divalent linking group in M include an alkylene group, a substituted alkylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a sulfonamide group, a urethane group, and a urea group. Alternatively, a combination of two or more groups is exemplified.

Examples of the alkylene group and substituted alkylene group in M 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. Preferred as M are a single bond, a methylene group, an ethylene group, and a propylene group. R ′ and R ″ may be the same or different and include a hydrogen atom, a trialkylmethylsilyl group, a trialkylmethylsilylmethyl group, a trichlorosilyl group,
Trialkoxysilyl group, dialkoxymethylsilyl group, -CO-A group (A is -OH, -OB, or -N
Represents an HB group. Here, B represents a linear or branched alkyl group. ). R 'and R''are an alkylene group,
A ring may be formed via -CO-O-CO-, -CO-NR '"-CO-, or the like. R ′ and R ″ are both an alkylene group, —CO—O—CO—, —CO—N
R ′ ″ — CO— or the like may be formed to form a ring structure. (R ′ ″ represents a hydrogen atom, a hydroxyl group, a linear or branched alkyl group, or —O—SO ₂ —R ″ ″. R ″ ″ represents an alkyl group or a trihalomethyl group. Here, the alkyl groups of the trialkylmethylsilyl group and the trialkylmethylsilylmethyl group are respectively the same as those of R ¹ to
The same examples as the specific examples of the alkyl group generically referred to by R ³ can be given. The alkyl groups of B, R ′ ″ and R ″ ″ are the same in the range of the alkyl groups generically referred to by R ^{1 to} R ³ . Specific examples of the repeating unit represented by the general formula (I) include the following. The present invention is not limited to these specific examples.

[0021]

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[0022]

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[0023]

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[0024]

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The repeating unit having a group capable of decomposing with an acid to generate an acid group includes an olefinically unsaturated bond copolymerizable with the general formula (I), and an acid group decomposing with an acid to generate an acid group. It is derived from a monomer having both groups capable of being reacted. Such a repeating unit is preferably, for example, at least one selected from the repeating units (IIa) and (IIb). In the repeating unit (IIa),
Y is a hydrogen atom. Or Y is 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. Examples of the divalent linking group in L include an alkylene group, a substituted alkylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group,
A single or a combination of two or more groups selected from the group consisting of a sulfonamide group, a urethane group, and a urea group may be mentioned.

Examples of the alkylene group and substituted alkylene group in L include a group represented by the following formula. -[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, and they 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. Examples of the substituent of the substituted alkyl group include a hydroxyl group, a halogen atom and an alkoxy group. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. r represents an integer of 1 to 10. 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. Specifically, tertiary alkyl groups such as t-butyl group and t-amyl group, isobornyl group, 1-ethoxyethyl group, 1-butoxyethyl group, 1-isobutoxyethyl group, 1-cyclohexyloxyethyl group, etc. 1-alkoxymethyl group such as 1-alkoxyethyl group, 1-methoxymethyl group, 1-ethoxymethyl group, tetrahydropyranyl group, tetrahydrofurfuryl group, trialkylsilyl group, 3-oxocyclohexyl group, 2-methyl-adamantyl Group, a mevalonic lactone residue, a 2- (γ-butyrolactonyloxycarbonyl) -2-propyl group, and the like.

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. 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, an amide group, a sulfonamide group,
A single or a combination of two or more groups selected from the group consisting of urethane groups and urea groups may be mentioned. L ¹ above
Examples of the alkylene group and substituted alkylene group for L ² 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, and 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. Examples of the substituent of the substituted alkyl group include a hydroxyl group, a halogen atom and an alkoxy group. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group. Examples of the 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,-
COOH, —COOR ¹¹ , —CO—NH—R ¹² , an alkyl group, an alkoxy group, a cyclic hydrocarbon group, or —COOQ
Represents In the case of an alkyl group, an alkoxy group, or a cyclic hydrocarbon group, it may have a substituent. (Note that R ¹¹ , R
Each of ¹² independently represents an alkyl group which may have a substituent. A ² is an alkyl group generically referred to, and a breakdown of A ² is —C
The following ranges are preferable as OOR ¹¹ , —CO—NH—R ¹² , and the alkyl group collectively referred to by R ¹¹ and R ¹² . That is, a linear or branched alkyl group having 1 to 10 carbon atoms is preferable, a linear or branched alkyl group having 1 to 6 carbon atoms is more preferable, and a methyl group, an ethyl group, and an n-propyl group are more preferable. , 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 alkyl 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 a repeating unit (I
The same groups as Q in Ia) can be mentioned. 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 a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group,
2-methyl-2-adamantyl group, norbornyl group, boronyl group, isobornyl group, tricyclodecanyl group, dicyclopentenyl group, nobornane epoxy group, menthyl group, isomenthyl group, neomenthyl group, tetracyclododecanyl group, etc. Can be mentioned. 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. 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 general formula (IIa) include the following, but the present invention is not limited to these specific examples.

[0029]

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[0030]

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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.

[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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In the repeating unit (III), Z represents an oxygen atom or ＮN—R ³ . R ³ represents a hydrogen atom, a hydroxyl group, a linear or branched alkyl group, or —OS
Represents O ₂ —R ⁴ or —SO ₂ —R ⁴ . R ⁴ represents an alkyl group or a trihalomethyl group. As the alkyl group for R ⁴ , a linear or branched alkyl group having 1 to 10 carbon atoms is preferable, a linear or branched alkyl group having 1 to 6 carbon atoms is more preferable, and a methyl group, an ethyl group is more preferable. 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. The present invention is not limited to these specific examples.

[0039]

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[0040]

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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 within a range where 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)
10 are preferred) acrylates (eg, methyl acrylate, ethyl acrylate, propyl acrylate,
Amyl acrylate, cyclohexyl acrylate, ethyl hexyl acrylate, octyl acrylate, tert-octyl acrylate, chloroethyl acrylate, 2-hydroxyethyl acrylate 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane Monoacrylate, pentaerythritol monoacrylate, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, etc.);

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

Acrylamides, for example, acrylamide, N-alkylacrylamide, 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 (the alkyl group 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.

The polymer compound used in the present invention may have a desired resistance to oxygen plasma etching of a resist, sensitivity, prevention of pattern cracking, substrate adhesion, a resist profile, and a resolution required for a general resist. It can be appropriately set in consideration of heat resistance and the like.
In general, the content of the repeating unit represented by the general formula (I) in the polymer compound used in the present invention is calculated as follows:
To 90 mol%, preferably 15 to 70 mol%, and more preferably 20 to 50 mol%. Further, the content of the repeating unit having a group capable of decomposing with an acid to generate an acid group, preferably the content of at least one of the repeating units (IIa) and (IIb) is the total repeating unit 5 to 50 mol%, preferably 10 to 4
0 mol%. The content of the repeating unit (III) is from 10 to 90 mol%, preferably from 15 to 70 mol%, more preferably from 20 to 60 mol%, based on all repeating units.

The polymer compound used in the present invention comprises a monomer corresponding to the repeating unit represented by the general formula (I), an olefinically unsaturated bond copolymerizable with the general formula (I), and an acid. It is obtained by copolymerizing a monomer having both groups capable of decomposing to generate an acid group in the presence of a polymerization catalyst. Block polymerization, graft polymerization, or random polymerization may be used. Either regular polymerization or irregular polymerization may be used. For example, in the case of a polymer compound containing a repeating unit represented by the general formula (I) and at least any one of the general formulas (IIa) and (IIb), the polymer represented by the general formula (I) And a monomer corresponding to at least one of the repeating units of the general formulas (IIa) and (IIb) in the presence of a polymerization catalyst. When a radical polymerization initiator is used as the polymerization catalyst, from the viewpoint of copolymerizability, at least a monomer corresponding to the repeating unit represented by the general formula (I) and at least one of the general formulas (IIa) and (IIb) Maleic anhydride is further copolymerized with the monomer corresponding to one of the repeating units, and the repeating unit derived from maleic anhydride in the obtained copolymer is opened with an alcohol under basic or acidic conditions. A method in which cyclic esterification or hydrolysis is carried out, and then the generated carboxylic acid moiety is converted into a desired substituent can also be applied. Further, a polymer containing a repeating unit represented by the general formula (I), at least one of the repeating units represented by the general formulas (IIa) and (IIb), and a repeating unit represented by the general formula (III) In the case of a compound, a monomer corresponding to the repeating unit represented by the general formula (I),
A monomer corresponding to at least one of the repeating units of the general formulas (IIa) and (IIb) and a monomer corresponding to the repeating unit represented by the general formula (III) are copolymerized in the presence of a polymerization catalyst. It is obtained by doing. Alternatively, a monomer corresponding to the repeating unit represented by the general formula (I) may be further copolymerized with a monomer corresponding to the repeating unit of the general formula (IIa) and maleic anhydride, or After copolymerizing maleic anhydride with a monomer corresponding to the repeating unit represented by (I), the repeating units derived from maleic anhydride in these resulting copolymers are partially converted to basic or acidic groups. There is also a method of synthesizing by ring-opening esterification with an alcohol or hydrolysis under conditions.

The weight average molecular weight of the polymer compound used in the present invention can be calculated as a polystyrene equivalent value by the GPC method.
Preferably it is 1,000-200,000. When the weight-average molecular weight is less than 1,000, heat resistance and dry etching resistance are deteriorated.
If it is more than 000, the development property is deteriorated and the viscosity becomes extremely high, so that the film-forming property is deteriorated. In the positive photoresist composition of the present invention, the amount of the polymer compound contained therein in the entire composition is preferably from 40 to 99.99% by weight, more preferably from 50 to 99.97% by weight, based on the total resist solids. % By weight. Hereinafter, specific examples will be described, but the scope of the resin according to the present invention is not limited thereto.

[0052]

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[0053]

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[0054]

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[0055]

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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. Or known light used for microresist or the like (ultraviolet light of 400 to 200 nm, far ultraviolet light, particularly preferably g-line, i-line, KrF excimer laser light,
A compound capable of generating an acid by an ArF excimer laser beam, an electron beam, an X-ray, a molecular beam or an ion beam, and a mixture thereof can be appropriately selected and used. Among them, a compound that is decomposed by irradiation with actinic rays or radiation to generate an organic sulfonic acid can be suitably used. Such compounds include the following. (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) Iminosulfonate derivative compound (B5) Diazodisulfone derivative Compound (B6) Diazoketosulfone derivative compound These are exemplified below.

Other compounds used in the present invention that generate an acid upon irradiation with actinic rays or radiation include, for example, SISchlesinger, Photogr. Sci. Eng., 18, 3
87 (1974), TSBetal, Polymer, 21,423 (1980) and the like diazonium salts, U.S. Pat.Nos. 4,069,055 and 4,06
No. 9,056, Re 27,992, ammonium salts described in JP-A-3-140140, DC Necker et al., Macromolecules, 1,
7,2468 (1984), CSwen et al, Teh, Proc.Conf.Rad.Curin
g ASIA, p478 Tokyo, Oct (1988), U.S. Pat.No. 4,069,055
No. 4,069,056, etc.
vello etal, Macromorecules, 10 (6), 1307 (1977), Chem.
& Eng.News, Nov. 28, p31 (1988), EP 104,143,
U.S. Patent Nos. 339,049 and 410,201, JP-A-2-150,84
No. 8, iodonium salts described in JP-A-2-296,514 etc.,
JVCrivello etal, Polymer J. 17, 73 (1985), JVCriv
ello etal. J. Org. Chem., 43, 3055 (1978), WRWatt eta
l, J. Polymer Sci., Polymer Chem. Ed., 22, 1789 (1984),
JVCrivello etal, Polymer Bull., 14,279 (1985), JV
Crivello etal, Macromorecules, 14 (5), 1141 (1981), J.
V. Crivello etal, J. PolymerSci., Polymer Chem. Ed., 17,
2877 (1979), European Patent Nos. 370,693, 161,811, 4
No. 10,201, No. 339,049, No. 233,567, No. 297,443,
No. 297,442, U.S. Pat.Nos. 3,902,114 and 4,933,377,
No. 4,760,013, No. 4,734,444, No. 2,833,827, Dokoku Patent No. 2,904,626, No. 3,604,580, No. 3,604,581,
Sulfonium salts described in JP-A-7-28237 and JP-A-8-27102, JVCrivello et al., Macromorecule
s, 10 (6), 1307 (1977), JVCrivello etal, J. PolymerSc
Selenonium salts described in i., Polymer Chem.Ed., 17, 1047 (1979), etc., CSWen et al., Teh, Proc. Conf. Rad. Curing AS
Onium salts such as arsonium salts described in IA, p478 Tokyo, Oct (1988), U.S. Pat.No. 3,905,815, JP-B-46-4605
No., JP-A-48-36281, JP-A-55-32070, JP-A-60-2
39736, JP-A-61-169835, JP-A-61-169837, JP-A-62-58241, JP-A-62-212401, JP-A-63-70243
Nos., Organohalogen compounds described in JP-A-63-298339, K. Meier et al, J. Rad. Curing, 13 (4), 26 (1986), T.
P. Gill et al, Inorg.Chem., 19, 3007 (1980), D. Astruc, A
cc.Chem.Res., 19 (12), 377 (1896), organometallic / organic halides described in JP-A-2-14145, etc., S. Hayase et al.
J. Polymer Sci., 25, 753 (1987), E. Reichmanis et al., J. Ph
olymer Sci., Polymer Chem. Ed., 23, 1 (1985), QQZhu et.
al, J. Photochem., 36, 85, 39, 317 (1987), B. Amit etal, Te
trahedron Lett., (24) 2205 (1973), DHR Barton etal,
J. Chem Soc., 3571 (1965), PM Collins et al., J. Chem. So
C., PerkinI, 1695 (1975), M. Rudinstein et al, Tetrahedro
n Lett., (17), 1445 (1975), JWWalkeretal J. Am. Chem. So
c., 110,7170 (1988), SCBusman et al, J.Imaging Techno
l., 11 (4), 191 (1985), HM Houlihan et al, Macormolecule
s, 21, 2001 (1988), PM Collinsetal, J. Chem. Soc., Chem.
Commun., 532 (1972), S. Hayase et al, Macromolecules, 18,
1799 (1985), E. Reichman et al., J. Electrochem. Soc., Soli
d State Sci.Technol., 130 (6), FMHoulihan et al, Macr
omolcules, 21, 2001 (1988), EP 0290,750, 0
No. 46,083, No. 156,535, No. 271,851, No. 0,388,343,
U.S. Pat.Nos. 3,901,710, 4,181,531, JP-A-60-19
No. 8538, JP-A-53-133022, etc., a photoacid generator having a 0-nitrobenzyl-type protecting group, M. TUNOOKA etal, Pol
ymer Preprints Japan, 35 (8), G. Berner et al., J. Rad. Cur
ing, 13 (4), WJMijs etal, CoatingTechnol., 55 (697), 4
5 (1983), Akzo, H. Adachi et al, Polymer Preprints, Japa
n, 37 (3), European Patent Nos. 0199,672, 84515, 044,115
No. 618,564, No. 0101,122, U.S. Pat.No. 4,371,605
No. 4,431,774, JP-A-64-18143, JP-A 2-2457
No. 56, iminosulfone described in JP-A-3-140109 and the like
Compounds that generate sulfonic acid upon photolysis, such as those disclosed in JP-A-61-166544, JP-A-2-71270, JP-A-3-103854,
Examples thereof include diazoketosulfone and diazodisulfone compounds described in JP-A-3-103856 and JP-A-210960.

Further, a group that generates an acid by these lights,
Alternatively, a compound having a compound introduced into a main chain or a side chain of a polymer, for example, MEWoodhouse et al., J. Am. Chem.
c., 104, 5586 (1982), SPPappas etal, J. Imaging Sci.,
30 (5), 218 (1986), S. Kondoetal, Makromol.Chem., Rapid
Commun., 9,625 (1988), Y.Yamadaetal, Makromol.Chem., 1
52,153,163 (1972), JVCrivello etal, J. PolymerSci.,
Polymer Chem.Ed., 17,3845 (1979), U.S. Pat.
No. 7, Dokoku Patent No. 3914407, JP-A-63-26653, JP-A-55
-164824, JP-A-62-69263, JP-A-63-146038, JP-A-63-163452, JP-A-62-153853, JP-A-63-14602
Compounds described in No. 9 and the like 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 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).

[0061]

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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.

[0063]

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[0064]

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[0065]

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

[0067]

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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.

[0070] 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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[0074]

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[0076]

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[0077]

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[0078]

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[0081]

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[0082]

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[0083]

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[0084]

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[0085]

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

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

[0088]

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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.

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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)

[0097]

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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 the substituent, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-
Alkyl groups 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, dodecyl group Methoxy group, ethoxy group, propoxy group, butoxy group, etc., halogen atom, nitro group, acetyl group and the like. 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

(4) A diazoketosulfone derivative represented by the following general formula (PAG8)

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[0102] wherein R ^21, R ²² has the same meaning as R ^21, R ²² above (PAG7). Specific examples of the diazoketosulfone derivative compound include the following compounds. Methylsulfonyl-benzoyl-diazomethane, ethylsulfonyl-benzoyl-diazomethane, methylsulfonyl-4-bromobenzoyl-diazomethane, ethylsulfonyl-4-bromobenzoyl-diazomethane, phenylsulfonyl-benzoyl-diazomethane, phenylsulfonyl-2-methylphenyl-diazomethane Phenylsulfonyl-3-methylphenyl-diazomethane, phenylsulfonyl-4-methylphenyl-diazomethane, phenylsulfonyl-3-methoxyphenyl-diazomethane, phenylsulfonyl-4-methoxyphenyl-diazomethane, phenylsulfonyl-3-chlorobenzoyl-diazomethane Phenylsulfonyl-4-chlorophenyl-diazomethane, tolylsulfonyl-3-chlorobenzoyl- Azometan, tolylsulfonyl - 4
-Chlorophenyl-diazomethane, phenylsulfonyl-4-fluorophenyl-diazomethane, tolylsulfonyl-4-fluorophenyl-diazomethane In each of the above (PAG1) to (PAG8),
A compound that generates a fluorinated organic sulfonic acid upon irradiation with actinic rays or radiation is particularly preferred because of its good sensitivity and good line pattern edge roughness. The amount of the compound capable of decomposing upon irradiation with actinic rays or radiation to generate an acid is generally used in the range of 0.001 to 40% by weight based on the total weight of the resist composition (excluding the coating solvent). , Preferably 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 is low, and if the amount is more than 40% by weight, the light absorption of the resist is high. This is not preferable because the profile is deteriorated and the process (especially baking) margin is narrowed.

The positive photoresist composition for deep ultraviolet exposure according to the present invention comprises (E) at least one of a fluorine-based surfactant, a silicon-based surfactant, and a surfactant containing both a fluorine atom and a silicon atom. It is preferable to contain a surfactant. The positive photoresist composition for deep ultraviolet exposure of the present invention contains the above acid-decomposable resin and the above surfactant, so that the thickness is 250 nm or less, particularly 220 nm.
When the following exposure light source is used, not only a resist pattern with less development defects and scum can be obtained, but also line width reproducibility is excellent. As these surfactants, for example, JP-A-62-36663, JP-A-61-226746, JP-A-61-226746
226745, JP-A-62-170950, JP-A-63-34540, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432,
Examples can include surfactants described in JP-A-9-5988,
The following commercially available surfactants can be used as they are.
As commercially available surfactants that can be used, for example, F-top
EF301, EF303, (Shin-Akita Chemical Co., Ltd.), Florard FC43
0, 431 (manufactured by Sumitomo 3M Limited), Mega Fuck F171, F1
Fluorinated surfactants such as 73, F176, F189, R08 (manufactured by Dainippon Ink Co., Ltd.), Surflon S-382, SC101, 102, 103, 104, 105, 106 (manufactured by Asahi Glass Co., Ltd.) or silicon-based surfactants Surfactants can be mentioned. Also, polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can be used as a silicon-based surfactant.

The amount of the surfactant is usually 0.001 to 2% by weight, preferably 0.01 to 1% by weight, based on the solid content in the composition of the present invention. These surfactants can be used alone or in combination of two or more.

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, an organic basic compound, a compound that promotes solubility in a developer, and the like can be contained.

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

[0106]

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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. Group 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.

[0108]

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In the above formula (E), 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, and particularly preferred is a ring structure containing a substituted or unsubstituted amino group and a nitrogen atom. Or a compound having an alkylamino group. Preferred specific examples are substituted or unsubstituted guanidine,
Substituted or unsubstituted aminopyridine, substituted or unsubstituted aminoalkylpyridine, substituted or unsubstituted aminopyrrolidine, substituted or unsubstituted indazole, 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 aminoalkylmorpholine, etc. Is mentioned. Preferred substituents are an amino group, aminoalkyl group, alkylamino group, aminoaryl group, arylamino group, alkyl group, alkoxy group, acyl group, acyloxy group, aryl group, aryloxy group, nitro group, hydroxyl group, cyano group It is. Particularly preferred compounds include guanidine, 1,1-dimethylguanidine, 1,1,3,3-tetramethylguanidine,
-Aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2-diethylaminopyridine, 2- (aminomethyl) pyridine, 2-amino-3-methylpyridine, 2- Amino-4-methylpyridine, 2-amino-5
-Methylpyridine, 2-amino-6-methylpyridine,
3-aminoethylpyridine, 4-aminoethylpyridine, 3-aminopyrrolidine, piperazine, N- (2-aminoethyl) piperazine, N- (2-aminoethyl) piperidine, 4-amino-2,2,6,6 -Tetramethylpiperidine, 4-piperidinopiperidine, 2-iminopiperidine, 1- (2-aminoethyl) pyrrolidine, pyrazole, 3-amino-5-methylpyrazole, 5-amino-3-methyl-1-p- Tolylpyrazole, pyrazine, 2- (aminomethyl) -5-methylpyrazine, pyrimidine, 2,4-diaminopyrimidine, 4,6-dihydroxypyrimidine, 2-pyrazoline, 3-pyrazoline,
Examples include, but are not limited to, N-aminomorpholine, N- (2-aminoethyl) morpholin and the like.

These nitrogen-containing basic compounds are used alone or in combination of two or more. The amount of the nitrogen-containing basic compound to be used is the photosensitive resin composition (excluding the solvent) 1
The amount is usually 0.001 to 10 parts by weight, preferably 0.01 to 5 parts by weight, based on 00 parts by weight. If the amount is less than 0.001 part by weight, the above effects cannot be obtained. On the other hand, if it exceeds 10 parts by weight, the sensitivity tends to decrease and the developability of the unexposed part tends to deteriorate.

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

Among the above, preferred solvents are 2-
Heptanone, γ-butyrolactone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, methoxypropionic acid Examples thereof include methyl, ethyl ethoxypropionate, N-methylpyrrolidone, and tetrahydrofuran.

Examples of the other surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; Polyoxyethylene alkyl allyl ethers such as oxyethylene octyl phenol ether, polyoxyethylene nonyl phenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate Fatty acid esters such as sorbitan trioleate, sorbitan tristearate, polyoxyethylene sorbitan monolaurate Nonionic surfactants such as polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan tristearate, etc. Can be mentioned. The amount of these surfactants is usually 2 parts by weight or less, preferably 1 part by weight or less, per 100 parts by weight of the solids in the composition of the present invention. These surfactants may be added alone or in some combination.

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 method of forming a pattern 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. 2 obtained
The layer resist is then subjected to a pattern forming step. As a first step, first, a pattern forming process is performed on the second layer, that is, the film of the upper photoresist composition. Mask alignment is performed as necessary, and high-energy rays are irradiated through the mask, so that the irradiated portion of the photoresist composition becomes soluble in an aqueous alkaline solution and developed with an aqueous alkaline solution to form a pattern.

Next, the organic polymer film is etched as a second step. This operation is performed by oxygen plasma etching using the above-described 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. 2 including the resist film of the present invention
The etching treatment by the layer film resist method is completed by a stripping operation of 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. Alternatively, peeling can be performed by a process such as plasma etching without using a solvent.

[0119]

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 1-1) (Synthesis of Resin (1-1))> Structural formula is the same as resin 1-1 already shown as an example of a copolymer resin containing a repeating unit represented by formula (I). Resin (1)
-1) was synthesized as follows. 55.2 g of cyclopentadienyltrimethylsilane, 46 g of allyltrimethylsilane and 300 ml of toluene were charged in an autoclave under nitrogen and heated to 120 ° C. After reacting for 10 hours, toluene was distilled off, and the residue was purified by silica gel column chromatography to obtain an intermediate olefin. Yield 32%. This intermediate olefin 25.2
g, maleic anhydride 9.8 g, methyl acrylate 4.3
g was added to 40 g of dry THF, and then heated to 65 ° C. under a nitrogen stream. When the reaction temperature stabilizes, Wako Pure Chemical Industries, Ltd.
Initiator V-65 was added to 10 moles of the total number of moles of the monomer.
1% was added to start the reaction. After reacting for 6 hours, the reaction mixture was diluted twice with THF, and then poured into 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. Hexane /
After washing with acetone (8/2) and drying, acetone 1
And 10 g of t-butanol and 12.2 g of 4-dimethylaminopyridine were added thereto.
The reaction was carried out at 6 ° 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 (1-1). The obtained resin (1-
As a result of GPC measurement, the molecular weight of 1) was 3600 in weight average using polystyrene as a standard sample, and the molecular weight was 10
The content of the components of 00 or less was 4% in terms of the area ratio of GPC. Resins (1-2) to (1-8) were obtained in the same manner as described above. The structure (molar ratio) and weight average molecular weight of each repeating unit of the resins (1-1) to (1-8) are as described above.

<Synthesis Example (2-1) (Synthesis of Resin (2-1))> Cyclopentadienyltrimethylsilane 55.2
g, allyltrimethylsilane 46 g and toluene 30
0 ml was charged into an autoclave under nitrogen,
Heated. After reacting for 10 hours, toluene was distilled off, and the residue was purified by silica gel column chromatography to obtain an intermediate olefin. Yield 32%. 25.2 g of this intermediate olefin and 9.8 g of maleic anhydride
And 12.8 g of t-butyl acrylate in dry THF
After adding to 34 g, the mixture was heated to 65 ° C. under a nitrogen stream. When the reaction temperature becomes stable, initiator V-6 manufactured by Wako Pure Chemical Industries, Ltd.
5 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, THF was added to the reaction mixture.
After diluting twice with, it was 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 then dried to obtain resin (2-1).
I got As a result of GPC measurement, the molecular weight of the obtained resin (2-1) was 3,800 in weight average using polystyrene as a standard sample, and the content of components having a molecular weight of 1,000 or less was 3% by area ratio of GPC. Resins (2-2) to (2-8) were obtained in the same manner as above. The molar ratio and weight average molecular weight of each repeating unit are as described above.

Example 1-1 2 g of resin (1-1) as an acid-decomposable polymer component, 0.12 g of triphenylsulfonium perfluorooctanesulfonate and 0.02 g of DBU as a compound component which generates an acid upon exposure to light.
12 g, the following surfactant W-1 was dissolved in 19.2 g of propylene glycol monomethyl ether acetate,
Microfiltration was performed with a 0.1 μm membrane filter to obtain a silicon-containing resist. FHi- on silicon wafer
A 028D resist (a resist for i-line, manufactured by Fujifilm Ohlin Co., Ltd.) is applied using a coater CDS-650 manufactured by Canon, and baked at 90 ° C. for 90 seconds to form a film having a thickness of 0.83 μm.
Was obtained. When this was further heated at 200 ° C. for 3 minutes, the film thickness became 0.71 μm. The silicon-containing resist 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 light while changing the exposure amount and focus by loading a resolution mask on an ArF stepper. Then 120 ° C in a clean room,
After heating for 90 seconds, the film was developed with a tetramethylammonium hydroxide developer (2.38%) for 60 seconds, rinsed with distilled water and dried to obtain a pattern. Observation with a scanning electron microscope revealed that the sensitivity was 0.15 at 33 mJ / cm ² .
μm lines / spaces were resolved. The rectangularity of the cross section 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 A was evaluated at 80 ° or more and 90 ° or less, and B was evaluated at 70 ° or more and less than 80 °.
Those less than 0 ° were evaluated as C. Further, the wafer was subjected to an etching treatment for 15 minutes under the conditions of a pressure of 20 mTorr and an applied power of 100 mW / cm ² using an etching gas of oxygen and a parallel plate type reactive ion etching apparatus manufactured by ULVAC. The results were observed with a scanning electron microscope. The dimensional shift of the 0.16 μm pattern is 0.0
It was 09 μm. The roughness was visually evaluated by observing the roughness of the line edge portion in the line and space pattern of 0.15 μm 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.

[0123]

[Table 1]

[0124]

[Table 2]

Solvent PGMEA: Propylene glycol monomethyl ether acetate EL: Ethyl lactate Organic base compound DMAP: 4-dimethylaminopyridine TPI: 2,4,5-triphenylimidazole DBU: 1,8-diazabicyclo [5.4.0] -7-
Undecene 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. (Examples 1-2 to 1-12 and 2-1 to 2-12) Instead of the acid-decomposable resin, the acid generator and the organic basic compound in Example 1-1, Table 1 (part 1) Example 1 except that the acid-decomposable resin, the acid generator, the organic basic compound, the surfactant, and the solvent shown in 2) were also used.
Adjust positive photoresist exactly as in -1,
Exposure, development, and etching were performed in the same manner as in Example 1-1. Table 2 shows the obtained performance.

[0126]

[Table 3]

<Synthesis Example (3-1) (Synthesis of the following (R1))>

[0128]

Embedded image

2-cyanoethyltrichlorosilane 18
8.5 g (1.0 mol) was dissolved in 200 g of toluene and added dropwise to 500 g of water while stirring at room temperature.
After completion of the dropwise addition, the mixture was aged by stirring at the reflux temperature of the reaction solution for 5 hours. After cooling, the acidic aqueous layer was separated from the reaction mixture, and then the organic layer was washed with 1 liter of water, and further washed twice after the aqueous layer became neutral. The organic layer was separated, filtered and toluene was stripped using an evaporator to give a colorless oil, which was crystallized in water, filtered and dried to obtain poly (2-hydroxycarbonyl). Ethyl) siloxane was obtained in a yield of 102.5 g (yield: 82%). In IR of the resulting polymer, no absorption peak in the vicinity of a cyano group-specific 2,200Cm ^-1, and the absorption peak is observed in the carboxylic acid-specific 1,650Cm ^-1, even unreacted in ¹³ C-NMR No cyano group was detected, indicating that the cyano group was quantitatively converted to a carboxylic acid under an acidic atmosphere of hydrochloric acid generated during the hydrolysis of chlorosilane. The weight average molecular weight of the obtained polymer is
6,250. Comparative Example 1 A positive photoresist was prepared in exactly the same manner as in Example 1 except that the above (R1) was used instead of the acid-decomposable polysiloxane in Example 1-1. Exposure, development, and etching were performed in the same manner as in Example 1. Table 3 shows the obtained performance.

[0130]

[Table 4]

[0131]

Since the present invention has the above configuration,
It is possible to provide a positive resist composition having high sensitivity, high resolution, and giving a photoresist having a rectangular shape. A positive resist composition having a small edge roughness of a line pattern can be provided.
A positive resist composition having a small dimensional shift when transferring a pattern to a lower layer in an oxygen plasma etching step can be provided. A positive resist composition having good wettability to a developer and having few development defects can be provided.

 ──────────────────────────────────────────────────続 き Continuing on the front page F-term (reference) 2H025 AA01 AA02 AA03 AA09 AB15 AB16 AD03 BE00 BE10 BG00 CB08 CB10 CB14 CB34 CB41 CC03 CC04 CC20 4J002 BG041 BG051 BG071 BH021 BK001 BQ001 CH052 EU116 EU0 EU27 EB116 EUH47 EU216 EU237 EV216 EV286 EV296 EV306 FD206 FD312 FD318 GP03 4J100 AJ09Q AK32R AK33P AL03Q AL08Q AL34Q AL36Q AL39Q AL41Q AM37Q AM43R AM45R AM47R AR11P BA02Q BA03Q BA03R BA04Q BA05Q BA06Q BA11Q BA15Q BA16P BA16Q BA20P BA20Q BA34Q BA35P BA40Q BA53Q BA55R BA58Q BA59Q BA72P BA72Q BA77P BA85P BB01P BB18R BC04Q BC08Q BC09Q BC12Q BC53Q CA04 CA05 JA38 JA44 JA46

Claims (7)

[Claims] 1. A repeating unit represented by the general formula (I):
A positive photoresist composition comprising a polymer compound having a repeating unit having a group capable of decomposing with an acid to generate an acid group. Embedded image 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. M represents a single bond or a divalent linking group. R ′ and R ″ may be the same or different and include a hydrogen atom, a trialkylmethylsilyl group, a trialkylmethylsilylmethyl group, a trichlorosilyl group, a trialkoxysilyl group, a dialkoxymethylsilyl group, —CO—A Group (A
Represents a -OH, -OB, or -NHB group. B represents a linear or branched alkyl group. ). R '
And R ″ may be linked via an atomic group of an alkylene group, —CO—O—CO—, or —CO—NR ′ ″ — CO— to form a ring structure. R 'and R''are
May be integrated to form an atomic group of an alkylene group, -CO-O-CO-, or -CO-NR '"-CO-, thereby forming a ring structure (R"'
Represents a hydrogen atom, a hydroxyl group, a linear or branched alkyl group, or —O—SO ₂ —R ″ ″. R ″ ″ represents an alkyl group or a trihalomethyl group). 2. It can be decomposed with an acid to generate an acid group.
The repeating unit having a functional group is represented by the following general formulas (IIa) and (II
2. The method according to claim 1, which is any one of b).
Positive photoresist composition. Embedded imageY is a hydrogen atom, a methyl group, a cyano group, or a salt
Represents a group selected from elementary atoms. L is a single bond or a divalent
Represents a linking group. Q decomposes with a hydrogen atom or acid to
Represents a group capable of generating an acid. Embedded imageX¹And X^TwoIs independently an oxygen atom, a sulfur atom,
-NH-, -NHSO _TwoRepresents a group selected from-. L¹When
L^TwoRepresents a single bond or a divalent linking group independently.
You. A¹Represents -Q or -COOQ, but X¹Is an oxygen source
Child, L¹When A represents a single bond,¹Represents Q. A^Two
Represents a hydrogen atom, a cyano group, a hydroxyl group, -COOH, -COO
R ′, —CO—NH—R ″, an optionally substituted
Kill group, optionally substituted cyclic hydrocarbon group, alcohol
Represents a xy group or -COOQ. (R 'and R' 'are each
Independently represent an alkyl group which may have a substituent.
You. ) Q decomposes with a hydrogen atom or acid to generate a carboxylic acid
Represents a group that can be grown. 3. In the general formulas (IIa) and (IIb), Q represents a group capable of decomposing with an acid to generate a carboxylic acid in a polymer compound, and partially represents hydrogen. (2)
4. The positive photoresist composition according to item 1. 4. The method according to claim 1, wherein the polymer compound has a repeating unit represented by the general formula (III).
4. The positive photoresist composition according to any one of items 1 to 3, Embedded image Z represents an oxygen atom, or a = group represented by N-R ^3. R
³ is a hydrogen atom, a hydroxyl group, an alkyl group, -OSO _2-
R ⁴ or a group represented by —SO ₂ —R ⁴ , or any of these. R ⁴ represents an alkyl group or a trihalomethyl group. The alkyl group generically referred to as R ³ and R ⁴ may be linear or may have a branch. 5. (A) the polymer compound according to any one of claims 1 to 4, (B) a compound which generates an acid upon irradiation with actinic rays or radiation, and (C) the above (A) and (C) A positive photoresist composition comprising at least an organic solvent for dissolving B). 6. The positive photoresist composition according to claim 5, comprising (D) an organic basic compound. 7. The positive photoresist composition according to claim 5, further comprising (E) a surfactant.