JPH11231538A - Positive photosensitive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the positive photosensitive composition adapted to the use of an exposure light source in the wavelength region of a specified wavelength or lower by incorporating an acid generating compound and a resin having at least one kind of specified univalent polycyclic alicyclic group and a group to be decomposed by an acid and to be increased in solubility in an alkaline developing solution. SOLUTION: The positive photosensitive composition contains the compound to be allowed to generate an acid by irradiation with active light or radiation and the resin having at least one kind of univalent polyalicyclic group represented by the formula and a group to be decomposed by an acid and to be increased in solubility in the alkaline developing solution, thus permitting the obtained by positive photosensitive composition to be adapted to use of the exposure light source in the wavelength region of <=25 nm, especially, <=220 nm. In the formula, each of R1 -R4 is an alkyl, cycloalkyl, acyloxy, or hydroxy group or the like; and R is -R5 -CO-X1 -A1 -R6 or -R5 -CO-X1 -A2 -R7 or R5 -CO- NHSO2 -X2 -A-R7 or -COOY.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive photosensitive composition used in a process for producing semiconductors such as ICs, a circuit substrate for liquid crystals and thermal heads, and other photofabrication processes. . More specifically, the present invention relates to a positive-type photosensitive composition suitable for using far ultraviolet rays having a wavelength of 250 nm or less as an exposure light source.

[0002]

2. Description of the Related Art Positive photoresist compositions include:
In general, a composition containing an alkali-soluble resin and a naphthoquinonediazide compound as a photosensitive material is used. However, integrated circuits are increasing their integration density, and ultra LS
In the production of semiconductor substrates such as I, it has become necessary to process an ultrafine pattern having a line width of half a micron or less.

[0003] As one of means for miniaturizing a pattern, it is known to shorten the wavelength of an exposure light source used in forming a resist pattern. This means Rayleigh's equation representing the resolution (line width) R of the optical system, R = k · λ / NA (where λ is the wavelength of the exposure light source, NA is the numerical aperture of the lens,
k is a process constant). From this equation, it can be seen that in order to achieve higher resolution, that is, to reduce the value of R, it is sufficient to shorten the wavelength λ of the exposure light source. For example, in the manufacture of a DRAM having a degree of integration of up to 64 Mbits, the i-line (365 nm) of a high-pressure mercury lamp has been used as a light source until now. In a mass production process of a 256 Mbit DRAM, use of a KrF excimer laser (248 nm) as an exposure light source instead of i-line is being studied. Further, for the purpose of manufacturing a DRAM having an integration degree of 1 Gbit or more, a light source having a shorter wavelength has been studied.
It is considered that the use of rF excimer laser (193 nm), F ₂ excimer laser (157 nm), X-rays, electron beams, etc. is effective (Takumi Ueno et al., “Short Wavelength Photoresist Material-Fine Processing for ULSI” − ”, Bunshin Publishing, 1988).

When a conventional resist composed of a novolak and a naphthoquinonediazide compound is used for lithography pattern formation using deep ultraviolet light or excimer laser light,
Because of the strong absorption of novolak and naphthoquinonediazide in the far ultraviolet region, light hardly reaches the bottom of the resist, and only a low-sensitivity, tapered pattern can be obtained.

One of the means for solving such a problem is as follows.
It is a chemically amplified resist composition described in U.S. Pat. No. 4,491,628 and European Patent No. 249,139. The chemically amplified positive resist composition generates an acid in the exposed area by irradiation with radiation such as deep ultraviolet light, and the reaction using the acid as a catalyst dissolves the active radiation irradiated area and the non-irradiated area in the developing solution. It is a pattern forming material that changes the properties and forms a pattern on a substrate.

Examples of such a combination include a combination of a compound capable of generating an acid by photolysis with an acetal or an O, N-acetal compound (Japanese Patent Application Laid-Open No. 48-89003), a combination of an orthoester or an amide acetal compound ( JP-A-5120714), a combination with a polymer having an acetal or ketal group in the main chain (JP-A-53-1)
No. 33429), a combination with an enol ether compound (Japanese Patent Application Laid-Open No. 55-12959), a combination with an N-acyliminocarbonate compound (Japanese Patent Application Laid-Open No. 55-126236).
), A combination with a polymer having an orthoester group in the main chain (JP-A-56-17345), a combination with a tertiary alkyl ester compound (JP-A-60-3625),
Combination with a silyl ester compound (JP-A-60-102)
No. 47) and a combination with a silyl ether compound (JP-A-60-37549, JP-A-60-12446).
And the like. These have high photosensitivity because the quantum yield exceeds 1 in principle.

[0007] Similarly, as a system which is decomposed by heating in the presence of an acid and solubilized in an alkali, for example, JP-A-59-59
-45439, JP-A-60-3625, JP-A-62
JP-A-229242, JP-A-63-27829, JP-A-63-36240, JP-A-63-250642, JP-A-5-181279, Polym.Eng.Sce., Vol. 23, 1012
Page (1983); ACS. Sym. 242, 11 (1984); Semicondu
ctor World 1987, November, p. 91; Macromolecules, 21,
Vol., P. 1475 (1988); SPIE, vol. 920, p. 42 (1988), etc., and a compound capable of generating an acid upon exposure to a tertiary or secondary carbon (for example, t-butyl, 2-cyclohexenyl). )
And JP-A-4-219775, JP-A-5-249682, and JP-A-6-219572.
Combination systems with acetal compounds described in JP-A-65332 and JP-A-4-21258 and JP-A-6-65.
No. 333, etc., in combination with a t-butyl ether compound.

Since these systems mainly use a resin having a low absorption in the 248 nm region and having a poly (hydroxystyrene) basic skeleton as a main component, a high sensitivity is obtained when a KrF excimer laser is used as an exposure light source. A high-resolution and good pattern can be formed, and it can be a good system as compared with the conventional naphthoquinonediazide / novolak resin system.

However, when a light source having a shorter wavelength, for example, an ArF excimer laser (193 nm) is used as an exposure light source, the compound having an aromatic group essentially exhibits large absorption in the 193 nm region. The system was not enough. Further, as a polymer having a small absorption in a wavelength region of 193 nm, use of poly (meth) acrylate is described in J. Vac. Sci. Technol., B9, 3357 (1991).
However, this polymer has a problem in that resistance to dry etching generally performed in a semiconductor manufacturing process is lower than that of a conventional phenol resin having an aromatic group.

On the other hand, the polymer having an alicyclic group has the same dry etching resistance as an aromatic group and has a small absorption in the 193 nm region, Proc. Of SPIE,
1672, 66 (1992). In recent years, the use of this polymer has been vigorously studied. More specifically,
-39665, 5-80515, 5-2652
No. 12, No. 5-297591, No. 5-346668
Nos. 6-289615, 6-324494, 7-49568, 7-185046, 7-19
Nos. 1463, 7-199467 and 7-23451
No. 1, No. 7-252324, No. 8-259626, and the like. However, these polymers do not always have sufficient dry etching resistance, and some of them require many steps for synthesis. Further, a positive photosensitive composition using a polymer having such a resin has a problem of deterioration in developability. That is, development residues and development defects occurred. Further, there is room for improvement in adhesion to the substrate.

[0011]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a positive photosensitive composition suitable for use with an exposure light source having a wavelength of 250 nm or less, particularly 220 nm or less. In particular, it is an object of the present invention to provide a positive photosensitive composition having excellent developability, that is, having no development residue or development defect and having excellent adhesion to a substrate when an exposure light source having a wavelength of 220 nm or less is used.

[0012]

Means for Solving the Problems The inventors of the present invention have made intensive studies while paying attention to the above-mentioned characteristics, and as a result, the object of the present invention has been successfully achieved by using the following resin having a specific alicyclic group. And reached the present invention. That is, the present invention has the following configuration. (1) (A) a compound capable of generating an acid upon irradiation with actinic rays or radiation, and (B) a compound represented by the following general formula (I)
A positive-type photosensitive resin comprising a resin having at least one of a polyvalent alicyclic group having a valency and a group which is decomposed by the action of an acid to increase solubility in an alkaline developer. Composition.

[0013]

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In the formula (I), R _{1 to} R ₄ may be the same or different and may have a substituent, and may be an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, an alkoxy group, an acyloxy group. Represents a group or a hydroxyl group. R is -R
₅ -CO-X ₁ -A ₁ -R ₆ , -R ₅ -CO-X ₁ -A
_{2 -R 7, -R 5 -CO-} NHSO 2 -X 2 -A-R 7
Or represents -COOY. R ₅ represents a single bond, an alkylene group or a cycloalkylene group which may have a substituent. X ₁ represents an oxygen atom, a sulfur atom, or —NH—. X ₂ represents a single bond or —NH—. A is selected from the group consisting of a single bond, an alkylene group which may have a substituent, 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. Represents a single or a combination of two or more groups. A ₁ represents a single or a combination of two or more groups selected from the group consisting of an alkylene group which may have a substituent, an ether group, a thioether group, a carbonyl group, and an ester group. A ₂ is an alkylene group which may have a substituent, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a sulfonamide group, a urethane group, or a urea group alone or Represents a combination of two or more groups, provided that at least one is a sulfonamide group,
It is selected from a urethane group or a urea group. R ₆ is-
COOH, -COOY, -CN, a hydroxyl group, or -CO-
It represents a NH-SO ₂ -R _30. R ₇ is a hydrogen atom, —CO
OH, -CN, a hydroxyl _{group, -CO-NH-R 30,} -CO-
_{NH-SO 2 -R 30, -COOR} 35, -Y, which may have a substituent, an alkyl group, a cycloalkyl group or an alkoxy group. R ₃₀ ; an alkyl group or a cycloalkyl group which may have a substituent; R ₃₅ ; an alkyl group or a cycloalkyl group which may have a substituent, or -Y Y is a group shown below. .

[0015]

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R₁₉~ R₂₆Can be the same or different,
The hydrogen atom and the alkyl group which may have a substituent
You. a and b each represent 1 or 2. l, m, n, p are
May be the same or different and represent 0 or an integer of 1 to 5
You. Here, when l, m, n, and p are 2 or more,
R₁~ R_FourMay be the same or different, of which
Two R₁~ R_FourIs substituted on the same carbon atom,
A carbonyl group (＝ O) or a thiocarbonyl group
(= S), and two Rs₁~ R_FourBut next
When substituting on adjacent carbon atoms, the two are bonded to each other.
And may represent a double bond between the carbon atoms. Ma
R₁~ R _FourIs substituted two or more times,
Two R₁~ R_FourMay combine with each other to form a ring
No. Of a monovalent polycyclic alicyclic group represented by the general formula (I)
The position of the bond is a position other than R in the hydrocarbon polycyclic structure.
Any position may be used.

(2) The resin as the component (B) is composed of a repeating structural unit represented by the following general formula (II) and a group which is decomposed by the action of an acid to increase the solubility in an alkaline developer. The positive photosensitive composition according to the above (1), which is a resin having the same.

[0018]

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In the formula (II), R ₀ represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group or a haloalkyl group. A is selected from the group consisting of a single bond, an alkylene group which may have a substituent, 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. Represents a single or a combination of two or more groups. Z is the above (1)
Represents a monovalent polycyclic alicyclic group represented by the general formula (I).

(3) The resin of the component (B) is the resin of the above (2)
And a repeating structural unit represented by the general formula (II),
Having a repeating structural unit represented by the following general formula (III),
The positive photosensitive composition according to the above (1) or (2), which is a resin which is decomposed by the action of an acid to increase the solubility in an alkaline developer.

[0021]

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In the formula (III), R ₀ and A have the same meanings as those described in the above (2). Z ′ is represented by the following general formula (Ia)
And a monovalent polycyclic alicyclic group represented by the general formula (I
The position of the bond of the monovalent polycyclic alicyclic group represented by -a) may be any position other than G in the hydrocarbon polycyclic structure.

[0023]

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In the formula (Ia), R _{1 to} R ₅ , l, m,
n and p have the same meanings as those described in the above (1). G
Represents a group which is decomposed by the action of an acid to increase the solubility in an alkaline developer. (4) The positive photosensitive composition as described in any of (1) to (3) above, wherein a deep ultraviolet light having a wavelength of 250 nm or less is used as an exposure light source. (5) The positive photosensitive composition as described in (4) above, wherein a far ultraviolet light having a wavelength of 220 nm or less is used as an exposure light source.

In the present invention, as the resin used in the positive photosensitive composition, an acid-decomposable group-containing resin having a polycyclic alicyclic group having a specific structure bonded to a group having a specific structure is used. As a result, as described above, developability and adhesion were significantly improved.

[0026]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the compounds used in the present invention will be described in detail. (B) a group (also referred to as an acid-decomposable group) which is decomposed by the action of an acid to increase the solubility in an alkaline developer with the polycyclic alicyclic group represented by the general formula (I). In the present invention, the polycyclic alicyclic group of the general formula (I) and the acid-decomposable group can be bonded to any position in the base resin. That is, the polycyclic alicyclic group and the acid-decomposable group of the general formula (I) may be bonded to different repeating units in the base resin, or may be bonded to the same repeating unit. And the case where both cases coexist in the resin. The monovalent polycyclic alicyclic group represented by the general formula (I) has various optical isomers, and any of the optical isomers is included in the general formula (I) in the present invention. You. A stereoisomer in which the 3-position steroid skeleton proton is oriented in the axial direction is preferable from the viewpoint of alkali developability. As the repeating structural unit having a group represented by general formula (I) in the resin according to the present invention, any repeating unit having a group represented by general formula (I) can be used, Preferably, the compound represented by the general formula (II)
Is a repeating structural unit represented by

R _{1 to} R ₄ , R ₇ , R
_As the alkyl group of _{19 to} R ₂₆ , R ₃₀ , R ₃₅ , and R ₀ , a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, which may preferably have a substituent, Examples thereof include those having 1 to 8 carbon atoms such as a hexyl group, a 2-ethylhexyl group and an octyl group. R _{1 to} R ₄ ,
As the cycloalkyl group for R ₇ , R ₃₀ and R ₃₅ , a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a 2-methyl-2-adamantyl group, which may optionally have a substituent, Examples include a norbornyl group, a boronyl group, an isobornyl group, a tricyclodecanyl group, a dicyclopentenyl group, a nobornane epoxy group, a menthyl group, an isomenthyl group, a neomenthyl group, and a tetracyclododecanyl group. R ₁
As the alkoxy group for R ₄ and R ₇ , a methoxy group, an ethoxy group, a propoxy group, which may have a substituent,
Examples thereof include those having 1 to 4 carbon atoms such as a butoxy group. R
The acyloxy group of _{1 to} R ₄ may have a substituent and may have 1 to 1 carbon atoms such as an acetoxy group and a butyryloxy group.
There are four.

Here, when l, m, n or p is 2 or more,
If multiple R₁~ R_FourMay be the same or different
And a plurality of R₁~ R_FourR of two of₁~ R
_FourAre substituted on the same carbon atom,
Represents a bonyl group (＝ O) or a thiocarbonyl group (＝ S)
May be. Furthermore, a plurality of R₁~ R_FourR of two of
₁~ R_FourIs substituted on an adjacent carbon atom.
Two bonds to each other and shows the double bond between those carbon atoms.
You may. Where the double bond between the formed carbon atoms
Preferably does not form a conjugated double bond between carbon and carbon.
Good. Also, R₁~ R_FourReplaces two or more of each
In the case, two of them R₁~ R _FourAre bonded to each other to form a ring
It may be formed. Such a ring is preferably
Chloropropyl group, cyclopentyl group, cyclohexyl
Group, cycloheptyl group, tetrahydrofuranyl group, tet
May contain heteroatoms such as lahydropyranyl groups
A 3- to 8-membered ring is exemplified. These rings further have a substituent.
You may have. Monovalent polycycle represented by the general formula (I)
The position of the bond of the type alicyclic group depends on the hydrocarbon polycyclic structure.
Any position other than the position of R during construction may be preferable,
Are positions 3, 7, and 12 of the steroid skeleton.

The haloalkyl group represented by R ₀ preferably has 1 carbon atom substituted by a fluorine atom, a chlorine atom or a bromine atom.
And 4 to 4 alkyl groups such as a fluoromethyl group, a chloromethyl group, a bromomethyl group, a fluoroethyl group, a chloroethyl group, and a bromoethyl group. In the present invention, as the halogen atom, a fluorine atom, a chlorine atom,
Bromine atoms and the like can be mentioned. _{R 5, A, A 1,} A
_{As the} alkylene group optionally having ₂ substituents,
The groups shown below can be exemplified. -[C (R _a ) (R _b )] _r-wherein R _a and R _b each represent a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, or an alkoxy group; The alkyl group is preferably a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group and a butyl group, and more preferably selected from the group consisting of a methyl group, an ethyl group, a propyl group and an isopropyl group. Represents a substituent. 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. r represents an integer of 1 to 10. As the cycloalkylene group for R ₅ , preferably those having 5 to 8 carbon atoms, such as a cyclopentylene group and a cyclohexylene group, which may have a substituent, may be mentioned.

A ₂ contains at least one group selected from the group consisting of a sulfonamide group, a urethane group and a ureido group, and an alkylene group, a substituted alkylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a sulfoneamide group. A divalent group may be formed with a divalent group selected from the group consisting of an amide group, a urethane group, and a urea group alone or in combination of two or more groups. In the general formula (I), l, m, n, and p represent 0 or an integer of 1 to 5, preferably 0 or an integer of 1 to 2.

G in the general formula (III) represents a group (acid-decomposable group) which is decomposed by the action of an acid to increase the solubility in an alkaline developer. Here, in the resin according to the present invention, the acid-decomposable group may be included in the structure of the group represented by the general formula (I), or a repeating structural unit having the group represented by the general formula (I) May be contained in the compound, may be contained in another repeating structural unit, or may be contained in a plurality of places among these places. Examples of the acid-decomposable group include a group which is hydrolyzed by the action of an acid to form an acid, and a group which forms an acid by the elimination of a carbon cation by the action of an acid. Preferably, the following general formula (XII
These are groups represented by (I) and (XIV). Thereby, the stability over time becomes excellent.

[0032]

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Here, R _{47 to} R ₄₉ may be the same or different and represent a hydrogen atom or an alkyl group, a cycloalkyl group or an alkenyl group which may have a substituent. However, among R _{47 to} R _{49 in} the formula (XIII),
At least one is a group other than a hydrogen atom. R ₅₀ represents an alkyl group, a cycloalkyl group or an alkenyl group which may have a substituent. Further, R _{47 to} R ₄₉ of the formula (XIII)
Or two of R _{47 to} R ₄₈ and R ₅₀ of the formula (XIV)
Two groups may combine to form a ring structure composed of 3 to 8 carbon atoms and hetero atoms. Specific examples of such a ring include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a 1-cyclohexenyl group, a 2-tetrahydrofuranyl group, a 2-tetrahydropyranyl group, and the like. Z _{1 and} Z ₂ may be the same or different and represent an oxygen atom or a sulfur atom. Here, as the alkyl group and the cycloalkyl group, the above R _{1 to} R ₄
The same ones as shown in are preferred. The alkenyl group preferably has 2 to 2 carbon atoms such as a vinyl group, a propenyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, and a cyclohexenyl group which may have a substituent.
There are six. As the acid-decomposable group, preferred is -C (= O) -OR (where R is a trialkylsilyl group such as a trimethylsilyl group, a t-butyldimethylsilyl group, a diisopropylmethylsilyl group, or 3). -Oxocyclohexyl group).

Further, as the further substituent in each of the above-mentioned substituents, preferably, a hydroxyl group, a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, an amide group, a sulfonamide group, R ₁ alkyl group to R _5,
Methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group, alkoxy group such as butoxy group, methoxycarbonyl group, alkoxycarbonyl group such as ethoxycarbonyl group, formyl group, acetyl group, acyl group such as benzoyl group, Examples include an acyloxy group such as an acetoxy group and a butyryloxy group, and a carboxy group.

The content of the repeating structural unit having an alicyclic group represented by the general formula (I) (preferably, the repeating structural unit represented by the general formula (II)) in the resin according to the present invention is as follows. The content is adjusted by the balance between dry etching properties, alkali developability, and the like, but is preferably 20 mol% or more, more preferably 30 to 80 mol%, and still more preferably 40 to 6 mol% based on all repeating units.
The range is 5 mol%.

The content of the repeating structural unit having an acid-decomposable group in the resin according to the present invention is adjusted by the performance such as alkali developability and substrate adhesion. 5 to 80 mol%, more preferably 10 to 70 mol%, and still more preferably 20
It is used in the range of ６０60 mol%. Here, the content of the acid-decomposable group-containing repeating structural unit is determined by the general formula (I)
Is the amount of all the acid-decomposable group-containing repeating structural units in the resin including the acid-decomposable group contained in the repeating structural unit having the group represented by Specific examples (II-1) to (II-80) of the repeating structural unit represented by the general formula (II) are shown below, but the present invention is not limited thereto.

[0037]

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[0038]

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[0039]

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[0041]

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[0047]

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[0051]

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[0052]

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Examples of the repeating unit having an acid-decomposable group include specific examples (III-1) to (III-80) of the repeating structural unit represented by the general formula (III), and Specific examples (b1) to (b4) of the repeating structural unit having
2) is shown, but the present invention is not limited to this.

[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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[0070]

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[0071]

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[0074]

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[0075]

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In order to improve the performance of the resin of the component (B) of the present invention, another polymerizable monomer is further copolymerized within a range that does not significantly impair the transmittance of the resin of 220 nm or less and the dry etching resistance. May be. Copolymerizable monomers that can be used include those shown below. For example, it has one addition-polymerizable unsaturated bond selected from acrylates, acrylamides, methacrylates, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, crotonates, and the like. Compound.

Specifically, for example, acrylic esters such as alkyl (the alkyl group has 1 to 1 carbon atoms)
Acrylates (eg, methyl acrylate, ethyl acrylate, propyl acrylate, t-butyl acrylate, amyl acrylate, cyclohexyl acrylate, ethylhexyl acrylate, octyl acrylate, tert-octyl acrylate) , Chloroethyl acrylate, 2-hydroxyethyl acrylate 2,2
-Dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, glycidyl acrylate, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, etc.)
Aryl acrylates (eg phenyl acrylate,
Hydroxyphenyl acrylate, etc.);

Methacrylic acid 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, t-butyl methacrylate,
Amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate,
Chlorbenzyl methacrylate, octyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, glycidyl methacrylate , Furfuryl methacrylate, tetrahydrofurfuryl methacrylate, etc.),
Aryl methacrylates (for example, phenyl methacrylate, hydroxyphenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, etc.); acrylamides, for example, acrylamide, N-alkylacrylamide, (where the alkyl group has 1 to 1 carbon atoms)
Ten compounds, for example, methyl, ethyl, propyl, butyl, t-butyl, heptyl, octyl, cyclohexyl, benzyl, hydroxyethyl, benzyl and the like. ), N-arylacrylamide (for example, phenyl group, tolyl group, nitrophenyl group, naphthyl group, cyanophenyl group, hydroxyphenyl group, carboxyphenyl group, etc.), N, N-dialkylacrylamide ( As the alkyl group, those having 1 to 10 carbon atoms, for example,
Examples include a methyl group, an ethyl group, a butyl group, an isobutyl group, an ethylhexyl group, and a cyclohexyl group. ), N, N
-Aryl acrylamide (an aryl group includes, for example, a phenyl group), N-methyl-N-phenylacrylamide, N-hydroxyethyl-N-methylacrylamide, N-2-acetamidoethyl-N-acetylacrylamide and the like; Methacrylamides, for example, methacrylamide, N-alkyl methacrylamide (an alkyl group having 1 to 10 carbon atoms, for example, a methyl group, an ethyl group, a t-butyl group, an ethylhexyl group, a hydroxyethyl group, a cyclohexyl Group, etc.), N-aryl methacrylamide (an aryl group includes a phenyl group, a hydroxyphenyl group, a carboxyphenyl group, etc.), N, N-dialkylmethacrylamide (an alkyl group includes an ethyl group, Propyl group, butyl group ), N, N-diarylmethacrylamide (the aryl group includes a phenyl group and the like), N-hydroxyethyl-N-methylmethacrylamide, N-methyl-N-phenylmethacrylamide, N- Ethyl-N-phenylmethacrylamide and the like; allyl compounds, for example, allyl esters (for example, allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate) , Allyl lactate, etc.), allyloxyethanol, 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-ethylbutyl 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 aryl ethers (for example, vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-
2,4-dichlorophenyl ether, vinyl naphthyl ether, vinyl anthranyl 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,
Vinylphenyl acetate, vinyl acetoacetate,
Vinyl lactate, vinyl-β-phenylbutyrate,
Vinyl cyclohexyl carboxylate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate, and the like;

Styrenes such as styrene, alkyl styrene (eg, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl Styrene, trifluoromethylstyrene, ethoxymethylstyrene, acetoxymethylstyrene, etc., alkoxystyrene (eg, methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene, etc.), halogen styrene (eg, chlorostyrene, dichlorostyrene) , Trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluors Ren, trifluoromethyl styrene, 2
-Bromo-4-trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene, etc., hydroxystyrene (e.g., 4-hydroxystyrene, 3-
Hydroxystyrene, 2-hydroxystyrene, 4-hydroxy-3-methylstyrene, 4-hydroxy-3,
5-dimethylstyrene, 4-hydroxy-3-methoxystyrene, 4-hydroxy-3- (2-hydroxybenzyl) styrene, etc.), carboxystyrene; crotonic esters such as alkyl crotonates (e.g.,
Butyl crotonate, hexyl crotonate, glycerin monocrotonate, etc.); dialkyl itaconates (eg, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, etc.); dialkyl esters of maleic acid or fumaric acid (eg, dimethyl maleate) rate,
Dibutyl fumarate), acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic anhydride, maleimide, acrylonitrile, methacrylonitrile, maleilenitrile, and the like. In addition, generally, any addition-polymerizable unsaturated compound that can be copolymerized may be used.

Among them, monomers having a carboxyl group such as carboxystyrene, N- (carboxyphenyl) acrylamide, N- (carboxyphenyl) methacrylamide, hydroxystyrene, N- (hydroxyphenyl) acrylamide, N- ( Monomers having a phenolic hydroxyl group, such as (hydroxyphenyl) methacrylamide, hydroxyphenyl acrylate, and hydroxyphenyl methacrylate, and monomers that improve alkali solubility, such as maleimide, are preferred as the copolymerization component. The content of the other polymerizable monomer in the resin in the present invention is preferably 50 mol% or less, more preferably 30 mol% or less, based on all repeating units.

A repeating structural unit having a group represented by the general formula (I) (preferably a repeating structural unit of the general formula (II)) and a repeating structural unit having an acid-decomposable group (preferably a repeating unit of the general formula (III)) Component (B) of the present invention containing another polymerizable monomer)
Is synthesized by radical, cationic or anionic polymerization of unsaturated monomers corresponding to each structure. More specifically, each monomer is blended based on the preferred composition described above, a polymerization catalyst is added at a monomer concentration of about 10 to 40% by weight in an appropriate solvent, and the mixture is heated and polymerized as needed.

The resin of the component (B) of the present invention has a weight average molecular weight (Mw: polystyrene standard) of 2,000 or more.
Preferably from 3,000 to 1,000,000, more preferably from 5,000 to 200,000, even more preferably from 2 to
It is in the range of 0000 to 100,000.
While the heat resistance and the like are improved, the developability and the like are lowered, and the balance is adjusted to a preferable range by these balances. Further, the degree of dispersion (Mw / Mn) is preferably 1.0 to 5.0, more preferably 1.0 to 3.0.
Image performance (pattern profile, defocus latitude, etc.) is improved. In the present invention, (B)
The resin is added in the photosensitive composition in an amount of 50 to 99.7% by weight, preferably 70 to 99% by weight, based on the total solid content.

The photoacid generator used in the present invention is a compound which generates an acid upon irradiation with actinic rays or radiation.
Examples of the compound used in the present invention that 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 photochromic 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 , An X-ray, a molecular beam or an ion beam to generate an acid and a mixture thereof can be appropriately selected and used.

Further, examples of other compounds used in the present invention which 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
Ammonium salts described in 9,056, Re 27,992, Japanese Patent Application No. 3-140,140, etc., DC Necker et al., Macromolecules, 1
7,2468 (1984), CSWenetal, Teh, Proc.Conf.Rad.Curing
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), JVCrive
llo 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 and 3,902,114
233,567, 297,443, 297,442, U.S. Pat.
No. 33,377, No. 161,811, No. 410,201, No. 339,049,
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
Chem. Res., 19 (12), 377 (1896), organometallic / organic halides described in JP-A-2-14145, etc., S. Hayase eta
l, J. Polymer Sci., 25, 753 (1987), E. Reichmanis et al., J.
Pholymer Sci., Polymer Chem. Ed., 23, 1 (1985), QQZhu
etal, J. Photochem., 36, 85, 39, 317 (1987), B. Amit etal,
Tetrahedron Lett., (24) 2205 (1973), DHR Barton eta
l, J. Chem Soc., 3571 (1965), PM Collins et al., J. Chem.
SoC., PerkinI, 1695 (1975), M. Rudinstein et al, Tetrahed
ron Lett., (17), 1445 (1975), JWWalker etal J. Am. Che
m.Soc., 110, 7170 (1988), SCBusman et al., J. Imaging Te
chnol., 11 (4), 191 (1985), HMHoulihan et al, Macormole
cules, 21, 2001 (1988), PM Collins et al., J. Chem. Soc.,
Chem. Commun., 532 (1972), S. Hayase et al, Macromolecule
s, 18, 1799 (1985), E. Reichmanis et al., J. Electrochem. So
c., Solid State Sci. Technol., 130 (6), FMHoulihan et.
al, Macromolcules, 21, 2001 (1988), EP 0290,750
Nos. 046,083, 156,535, 271,851, 0,38
No. 3,343, U.S. Pat.Nos. 3,901,710, 4,181,531, JP-A-60-198538, and photoacid generators having a 0-nitrobenzyl-type protecting group described in JP-A-53-133022, M. TUNOOKA
etal, Polymer Preprints Japan, 35 (8), G. Berner etal,
J.Rad.Curing, 13 (4), WJMijs etal, Coating Techno
l., 55 (697), 45 (1983), Akzo, H. Adachi et al, Polymer Pr
eprints, Japan, 37 (3), European Patent Nos. 0199,672 and 84515
No. 199,672, No. 044,115, No. 0101,122, U.S. Pat.No. 618,564, No. 4,371,605, No. 4,431,774, JP-A-64-18143, JP-A-2-245756, and Japanese Patent Application No. 3- Compounds that generate sulfonic acid upon photolysis, such as iminosulfonate described in 140109 and the like, JP-A-61-166544,
Disulfone compounds described in JP-A-2-71270,
Examples thereof include diazoketosulfone and diazodisulfone compounds described in JP-A-3-103854, JP-A-3-103856, JP-A-4-210960 and the like.

Further, a group which 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, MEWoodhouse et al., J. Am. Chem.
Soc., 104, 5586 (1982), SPPappas etal, J. Imaging Sc
i., 30 (5), 218 (1986), S. Kondoetal, Makromol.Chem., Rap
id Commun., 9,625 (1988), Y.Yamadaetal, Makromol.Che
m., 152, 153, 163 (1972), JVCrivello etal, J. PolymerS
ci., Polymer Chem. Ed., 17, 3845 (1979), U.S. Pat.
49,137, Dokoku Patent 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-63-163452
Compounds described in JP-A-146029 can be used.

Further, VNRPillai, Synthesis, (1), 1 (198
0), A. Abad etal, Tetrahedron Lett., (47) 4555 (1971),
Compounds that generate an acid by light described in DHR Barton et al., J. Chem. Soc., (C), 329 (1970), U.S. Pat. No. 3,779,778, and EP 126,712 can also be used.

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

[0089]

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In the formula, R ²⁰¹ represents a substituted or unsubstituted aryl group or alkenyl group, and R ²⁰² represents 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.

[0091]

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[0092]

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[0093]

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

[0095]

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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, an aryl group having 6 to 14 carbon atoms, 1 to 8 carbon atoms
And substituted derivatives thereof. Preferred substituents are those having 1 to 8 carbon atoms for the aryl group.
And an alkyl group having 1 to 8 carbon atoms, a nitro group, a carboxyl group, a hydroxy group and a halogen atom. The alkyl group is an alkoxy group having 1 to 8 carbon atoms, a carboxyl group or an alkoxycarbonyl group. is there.

[0098] 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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[0102]

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[0103]

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[0104]

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[0105]

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[0106]

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[0107]

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[0108]

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[0109]

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[0110]

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[0111]

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The 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).

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In the formula, 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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[0117]

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[0118]

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[0119]

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[0120]

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The amount of the compound capable of decomposing upon irradiation with actinic rays or radiation to generate an acid is usually 0.03% based on the total weight of the photosensitive composition (excluding the coating solvent).
It is used in the range of 0.01 to 40% by weight, preferably 0.0
It is used in an amount of 1 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.

[5] Other Components Used in the Present Invention The positive photosensitive composition of the present invention may further contain, if necessary, an acid-decomposable dissolution inhibiting compound, a dye, a plasticizer, a surfactant, and a photosensitizer. It may contain a sensitizer, an organic basic compound, a compound that promotes solubility in a developer, and the like. The acid-decomposable dissolution inhibiting compound used in the present invention is, for example, a low-molecular-weight compound having a molecular weight of 3,000 or less and having at least one acid-decomposable group represented by the above general formulas (XIII) and (XIV). Particularly, an alicyclic or aliphatic compound such as a cholic acid derivative described in Proceeding of SPIE, 2724, 355 (1996) is preferable so as not to lower the transmittance at 220 nm or less. In the present invention, when an acid-decomposable dissolution inhibiting compound is used, its addition amount is 3 to 50% by weight, preferably 5 to 40% by weight, based on the total weight of the photosensitive composition (excluding the solvent). More preferably, it is in the range of 10 to 35% by weight.

The compound capable of accelerating dissolution in a developer that can be used in the present invention includes two or more phenolic OH groups.
Alternatively, it is a low-molecular compound having at least one carboxy group and a molecular weight of 1,000 or less. When it has a carboxy group, an alicyclic or aliphatic compound is preferable for the same reason as described above.
The preferred addition amount of these dissolution promoting compounds is 2 to 50% by weight based on the resin of the present invention, and more preferably 5 to
３０30% by weight. With an addition amount exceeding 50% by weight,
It is not preferable because a new defect that development residue is deteriorated and a pattern is deformed during development is generated.

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

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

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).

[0128]

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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 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 aminoalkylmorpholine and the like can be mentioned. 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. As particularly preferred compounds, guanidine, 1,1-dimethylguanidine, 1,1,3,3-tetramethylguanidine, 2-
Aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2-diethylaminopyridine, 2- (aminomethyl) pyridine, 2-amino-3-methylpyridine, 2-amino -4-methylpyridine, 2-amino-5
-Methylpyridine, 2-amino-6-methylpyridine,
3-aminoethylpyridine, 4-aminoethylpyridine, 3-aminopyrrolidine, piperazine, N- (2-aminoethyl) piperazine, N- (2-aminoethyl) piperidine, 4-amino-2,2,6,6 -Tetramethylpiperidine, 4-piperidinopiperidine, 2-iminopiperidine, 1- (2-aminoethyl) pyrrolidine, pyrazole, 3-amino-5-methylpyrazole, 5-amino-3-methyl-1-p- Tolylpyrazole, pyrazine, 2- (aminomethyl) -5-methylpyrazine, pyrimidine, 2,4-diaminopyrimidine, 4,6-dihydroxypyrimidine, 2-pyrazoline, 3-pyrazoline,
Examples include, but are not limited to, N-aminomorpholine and N- (2-aminoethyl) morpholine.

These nitrogen-containing basic compounds are used alone or in combination of two or more. The amount of the nitrogen-containing basic compound to be used is generally 0.001-10 parts by weight, preferably 0.01-5 parts by weight, per 100 parts by weight of the photosensitive resin composition (excluding the solvent). When the amount is less than 0.001 part by weight, the effect of the addition of the nitrogen-containing basic compound 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.

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

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

The photosensitive composition of the present invention is dissolved in a solvent capable of dissolving each of the above components and applied 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.

A surfactant may be added to the above solvents. Specifically, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether,
Polyoxyethylene alkyl allyl ethers such as polyoxyethylene nonylphenol 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, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate Surfactants such as polyoxyethylene sorbitan fatty acid esters such as acrylates and the like, F-top EF301, E 303, EF352 (manufactured by Shin Akita Kasei Co., Ltd.), Megafac F171, F173 (manufactured by Dainippon Ink Co., Ltd.), Flora - de FC430, FC43
1 (manufactured by Sumitomo 3M Limited), Asahi Guard AG71
0, Surflon S-382, SC101, SC102,
Fluorinated surfactants such as SC103, SC104, SC105 and SC106 (manufactured by Asahi Glass Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), and acrylic or methacrylic (co) polymerized polyflow No. 75, no. 95 (manufactured by Kyoeisha Yushi Kagaku Kogyo KK) and the like. 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 above-mentioned photosensitive composition is applied on a substrate (eg, silicon / silicon dioxide coating) to be used in the production of precision integrated circuit devices by an appropriate application method such as a spinner or a coater, and then passed through a predetermined mask. By exposing, baking and developing, a good resist pattern can be obtained. Here, the exposure light is preferably 25
It is a far ultraviolet ray having a wavelength of 0 nm or less, more preferably 220 nm or less. Specifically, a KrF excimer laser (248 nm) and an ArF excimer laser (193n)
m), F ₂ excimer laser (157 nm), X-ray, electron beam and the like.

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

[0137]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the contents of the present invention are not limited thereto. (Synthesis example) (1) Monomer (M-3) corresponding to repeating unit [II-34]
Synthesis of 4) 75 g of deoxycholic acid and 1 L of dimethylformamide were charged into a 2 L three-necked flask, and stirred and dissolved at room temperature. To this, 19.2 g of triethylamine was added, and ethoxymethyl chloride was further added dropwise. After completion of the dropwise addition, the mixture was stirred for 3 hours to terminate the reaction. After completion of the reaction, the solvent was distilled off under reduced pressure, followed by extraction with ethyl acetate / water. The obtained ethyl acetate solution was dehydrated and then concentrated again to obtain 70 g of ethoxymethyl protected deoxycholic acid. The obtained protective body was dissolved again in 2 L of THF, and added to a 3 L three-necked flask together with 100 g of triphenylphosphine. After 27 g of acrylic acid was further added, 66 g of diethyl azobiscarboxylate was added dropwise. After completion of the dropwise addition, the mixture was stirred for 16 hours. The obtained reaction mixture was concentrated, and the ethyl acetate layer extracted with ethyl acetate / aqueous sodium bicarbonate solution was filtered, concentrated, dissolved again in acetone, and hydrolyzed with hydrochloric acid. After completion of the reaction, the reaction solution was neutralized and concentrated, and purified by silica gel column chromatography to obtain 45 g of a target monomer a having the following structure.

[0138]

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The monomer a obtained above is reacted with thionyl chloride in a conventional manner, and then reacted with glycine. The reaction product obtained is purified by silica gel column chromatography to obtain the desired repeating unit. (II-34)
A monomer (M-34) corresponding to was synthesized. (2) A monomer (M-5) corresponding to the repeating unit [II-51]
Synthesis of 1) The following monomer b was synthesized in the same manner as in Synthesis Example (1), except that chenocholic acid was used instead of deoxycholic acid in Synthesis Example (1).

[0140]

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The monomer b obtained above was reacted with thionyl chloride in a conventional manner, and then reacted with pantoyl lactone. The reaction mixture obtained was purified by silica gel column chromatography, and the desired repeating unit [II- 51] (M-51) was synthesized. (3) A monomer (M-1) corresponding to the repeating unit [II-12]
Synthesis of 2) The following monomer c was synthesized in the same manner as in Synthesis Example (1), except that cholic acid was used instead of deoxycholic acid in Synthesis Example (1).

[0142]

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The monomer c obtained above was reacted with thionyl chloride by a conventional method, and then reacted with 2-cyanoethanol. The resulting reaction mixture was purified by silica gel column chromatography, and the desired repeating unit [II -12)
A monomer (M-12) corresponding to was synthesized. (4) A monomer (M-7) corresponding to the repeating unit [II-71]
Synthesis of 1) The following monomer d was synthesized in the same manner as in Synthesis Example (1) except that cholic acid was used instead of deoxycholic acid in Synthesis Example (1).

[0144]

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The monomer d obtained above was reacted with thionyl chloride in a conventional manner, and then reacted with ethanolamine. The resulting reaction mixture was purified by silica gel column chromatography, and the desired repeating unit [II-71 ] (M-71) was synthesized.

(5) Synthesis of Monomer (M-38) Corresponding to Repeating Unit [II-38] Monomer a obtained above was reacted with thionyl chloride by a conventional method.
The reaction mixture obtained by reacting with methanesulfonylamide was purified by silica gel column chromatography to synthesize a monomer (M-38) corresponding to the intended repeating unit [II-38].

(6) Synthesis of Monomer (M'-77) Corresponding to Repeating Unit [III-77] The monomer d obtained in Synthesis Example (4) and an excess of triethylene glycol methyl vinyl ether were prepared by a conventional method. The reaction mixture obtained by reacting under an acid catalyst according to the above is neutralized with triethylamine, washed with aqueous sodium bicarbonate, and further distilled off under reduced pressure to obtain the desired repeating unit [III-77].
A monomer (M'-77) corresponding to was obtained. (7) A monomer (M'-3) corresponding to the repeating unit [III-35]
Synthesis of 5) The monomer (M-34) obtained in Synthesis Example (1) was dispersed in t-butanol, and acetyl chloride was added dropwise over 1 hour. After the reaction solution after completion of the dropwise addition was stirred for 10 hours, the obtained reaction mixture was crystallized in distilled water, and the precipitated solid was taken out by decantation. The solid thus obtained was purified by silica gel column chromatography to obtain a monomer (M'-35) corresponding to the intended repeating unit [III-35].

(8) Synthesis of Resin A The above monomer (M-34) 20.1 g, monomer (M'-35) 2
A solution prepared by dissolving 2.4 g, 2.0 g of ethyl acrylate, and 1.25 g of V-65 manufactured by Wako Pure Chemical Industries in 180 g of THF was dropped in a reaction vessel containing 20 g of THF heated to 50 ° C. under a nitrogen stream over 2 hours. did. After the addition, the mixture was stirred for 6 hours. The reaction solution was allowed to cool to room temperature, and crystallized in 5 L of water. The precipitated powder was collected by filtration to recover 44 g of Resin A. The weight average molecular weight of the obtained resin A was measured in terms of standard polystyrene using GPC.
It was 0.

(9) Synthesis of Resin B 17.2 g of the above monomer (M-51) and monomer (M'-35) 2
2.4 g, 2.2 g of acrylic acid, V-65 manufactured by Wako Pure Chemical Industries, Ltd.
A solution obtained by dissolving 1.25 g in 170 g of THF was dropped into a reaction vessel containing 20 g of THF heated at 50 ° C. over 2 hours under a nitrogen stream. After the addition, the mixture was stirred for 6 hours. The reaction solution was allowed to cool to room temperature, and crystallized in 5 L of water.
The precipitated powder was collected by filtration to recover 42 g of Resin B. When the weight average molecular weight of the obtained resin B was measured by GPC using standard polystyrene conversion, it was 10,400.

(10) Synthesis of Resin C The above monomer (M-12) (15.5 g) and monomer (M'-77) 2
4.8 g, acrylic acid 2.5 g, V-65 manufactured by Wako Pure Chemical Industries, Ltd.
A solution obtained by dissolving 1.25 g in 170 g of THF was dropped into a reaction vessel containing 20 g of THF heated at 50 ° C. over 2 hours under a nitrogen stream. After the addition, the mixture was stirred for 6 hours. The reaction solution was allowed to cool to room temperature, and crystallized in 5 L of water.
The precipitated powder was collected by filtration to recover 41 g of Resin C. It was 11,400 when the weight average molecular weight of the obtained resin C was measured in terms of standard polystyrene using GPC.

(11) Synthesis of Resin D The above monomer (M-71) (14.1 g) and monomer (M'-77) 2
4.8 g, acrylic acid 2.4 g, V-65 manufactured by Wako Pure Chemical Industries, Ltd.
A solution obtained by dissolving 1.25 g in 170 g of THF was dropped into a reaction vessel containing 20 g of THF heated at 50 ° C. over 2 hours under a nitrogen stream. After the addition, the mixture was stirred for 6 hours. The reaction solution was allowed to cool to room temperature, and crystallized in 5 L of water.
The precipitated powder was collected by filtration, and 40 g of Resin D was recovered. It was 10,100 when the weight average molecular weight of the obtained resin D was measured in terms of standard polystyrene using GPC.

(12) Synthesis of Resin E 18.3 g of the above monomer (M-38) and monomer (M'-35) 2
2.4 g, 1.0 g of ethyl acrylate, 1.2 g of acrylic acid, 1.25 g of V-65 manufactured by Wako Pure Chemical Industries, Ltd. in THF
The solution dissolved in 160 g was dropped into a reaction vessel containing 20 g of THF heated at 50 ° C. over 2 hours under a nitrogen stream. After the addition, the mixture was stirred for 6 hours. The reaction solution was allowed to cool to room temperature, and crystallized in 5 L of water. The precipitated powder was collected by filtration, and 41 g of Resin E was recovered. It was 10,600 when the weight average molecular weight of the obtained resin E was measured in terms of standard polystyrene using GPC.

Examples and Comparative Examples 1.2 g (as shown in Table 1) of each of the resins synthesized in the above synthesis examples and 0.25 g of triphenylsulfonium triflate were mixed at a solid content of 16% by weight. After dissolving in propylene glycol monoethyl ether acetate, the solution was filtered through a 0.1 μm microfilter to prepare a positive photoresist composition solution.

(Evaluation Test) The obtained positive photoresist composition solution was applied on a silicon wafer using a spin coater and dried at 120 ° C. for 90 seconds to form a 1.0 μm positive photoresist film. It was exposed to ArF excimer laser (193 nm). A heat treatment after the exposure was performed at 130 ° C. for 90 seconds, developed with a 2.38% aqueous solution of tetramethylammonium hydroxide, and rinsed with distilled water to obtain a resist pattern profile.

[Substrate adhesion] (minimum line width of remaining fine line):
The resist pattern profile at an exposure dose reproducing a line width of 0.40 μm was observed with a scanning electron microscope, and the line width of the thinnest remaining line was evaluated. A pattern having higher adhesion has a pattern with a finer line width remaining, while a pattern having lower adhesion cannot be adhered to a substrate interface with a smaller line width, and the pattern is peeled off.

[Development residue]: 0.4 μm as described above.
A line-and-space resist pattern profile was formed and observed with a scanning electron microscope.Evaluations where the development residue was visually observed were evaluated as x, and those where the development residue was not visually observed were evaluated as ○. .

[Number of development defects]: Bare S of 6 inches
Each resist film was applied to a thickness of 0.5 μm on the i-substrate and dried at 130 ° C. for 60 seconds on a vacuum suction hot plate. Next, a 0.35 μm contact hole pattern (Hole)
Nik through a test mask with a duty ratio = 1: 3)
After exposure with the on-stepper NSR-1505EX, post-exposure heating was performed at 130 ° C. for 90 seconds. Subsequently, after paddle development with 2.38% TMAH (aqueous solution of tetramethylammonium hydroxide) for 60 seconds, 30% with pure water.
Washed with water for 2 seconds and spin dried. The sample thus obtained was used for KLA-2112 manufactured by KLA-Tencor Corporation.
The number of development defects was measured by a machine, and the obtained primary data value was defined as the number of development defects. Table 1 shows the evaluation results.

[0158]

[Table 1]

As is evident from the results shown in Table 1, all of the comparative examples have problems in substrate adhesion, development residue, and several development defects. On the other hand, all of the positive photosensitive compositions of the present invention are at a satisfactory level. That is, ArF
It is suitable for lithography using far ultraviolet rays such as excimer laser exposure.

[0160]

The present invention is sufficiently suitable especially for light in the wavelength region of 170 nm to 220 nm, and realizes a developing property, that is, a reduction in the number of development defects and a development residue, and a positive electrode excellent in substrate adhesion. Type photosensitive composition can be provided.

Claims (5)

[Claims] (A) by irradiation with actinic rays or radiation
A compound generating an acid, and (B) a compound represented by the following general formula (I):
At least one of the monovalent polycyclic alicyclic groups
And dissolve in an alkaline developer by the action of an acid
Characterized by containing a resin having a group that increases the property
Positive photosensitive composition. Embedded imageIn the formula (I), R₁~ R_FourMay be the same or different
And an optionally substituted alkyl group or cycloalkyl group.
Alkyl group, halogen atom, cyano group, alkoxy group,
Represents a siloxy group or a hydroxyl group. R is -R_Five-CO-X
₁-A₁-R₆, -R_Five-CO-X₁-A_Two-R₇, -R_Five-CO-NHSO_Two-X_Two-AR₇Or -CO
Represents OY. R_FiveMay have a single bond or a substituent.
Represents an alkylene group or a cycloalkylene group. X₁
Represents an oxygen atom, a sulfur atom, or -NH-. X
_TwoRepresents a single bond or -NH-. A is a single bond, substituted
An alkylene group which may have a group, an ether group, a thio group
Ether group, carbonyl group, ester group, amide group,
Consisting of a rufonamide group, a urethane group, or a urea group
A single or a combination of two or more groups selected from the group
Express A₁Is an alkyl group which may have a substituent
Groups, ether groups, thioether groups, carbonyl groups,
Alone or two or more selected from the group consisting of stel groups
Represents a combination of the above groups. A_TwoHas a substituent
Alkylene group, ether group, thioether group,
Carbonyl group, ester group, amide group, sulfonami
Group, urethane group, or urea group.
Represents a single or a combination of two or more groups,
And at least one is a sulfonamide group, a urethane
Or a urea group. R₆Is -COO
H, -COOY, -CN, a hydroxyl group, or -CO-NH-
SO_Two-R₃₀Represents R₇Is a hydrogen atom, -COOH,
-CN, hydroxyl group, -CO-NH-R₃₀, -CO-NH-
SO_Two-R₃₀, -COOR₃₅, -Y, having a substituent
Alkyl, cycloalkyl or alkoxy
Represents a group. R₃₀An alkyl group or a cycle optionally having a substituent;
Loalkyl group, R₃₅An alkyl group or a substituent which may have a substituent;
A cycloalkyl group or -Y Y is a group shown below. Embedded imageR₁₉~ R₂₆May be the same or different; a hydrogen atom,
Represents an alkyl group which may have a substituent. a and b are
Each represents 1 or 2. l, m, n, p are the same but different
And may represent 0 or an integer of 1 to 5. here,
When l, m, n, and p are 2 or more, a plurality of R₁~ R_Four
May be the same or different, and two R₁~
R_FourAre substituted on the same carbon atom, the two
A carbonyl group (= O) or a thiocarbonyl group (= S)
And two more R₁~ R_FourBut the adjacent carbon source
When substituting on the offspring, the two bind to each other and
It may represent a double bond between carbon atoms. Also, R₁~ R
_FourAre each substituted by two or more, the two R₁~
R_FourMay combine with each other to form a ring. General formula
Position of a bond of the monovalent polycyclic alicyclic group represented by (I)
Is any position other than R in those hydrocarbon polycyclic structures.
May be placed. 2. The resin of the component (B) has the following general formula (II):
The positive photosensitive composition according to claim 1, wherein the resin has a repeating structural unit represented by the formula: and a group which is decomposed by the action of an acid to increase the solubility in an alkaline developer. Stuff. Embedded image In the formula (II), R ₀ represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group or a haloalkyl group. A is selected from the group consisting of a single bond, an alkylene group which may have a substituent, 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. Represents a single or a combination of two or more groups. Z represents a monovalent polycyclic alicyclic group represented by the general formula (I) according to claim 1. 3. The resin as the component (B) has a repeating structural unit represented by the general formula (II) according to claim 2 and a repeating structural unit represented by the following general formula (III), The positive photosensitive composition according to claim 1 or 2, wherein the resin is a resin which is decomposed by the action of an acid to increase the solubility in an alkaline developer. Embedded image In the formula (III), R ₀ and A have the same meanings as those in the second aspect. Z ′ represents a monovalent polycyclic alicyclic group represented by the following general formula (Ia), and a monovalent polycyclic alicyclic group represented by the general formula (Ia) The position of the bond of the formula group may be any position other than G in the hydrocarbon polycyclic structure. Embedded image In the formula (Ia), R _{1 to} R ₅ , l, m, n, and p have the same meanings as those described in claim 1. G represents a group which is decomposed by the action of an acid to increase the solubility in an alkaline developer. 4. The positive photosensitive composition according to claim 1, wherein far-ultraviolet light of 250 nm or less is used as an exposure light source. 5. The positive photosensitive composition according to claim 4, wherein far-ultraviolet light having a wavelength of 220 nm or less is used as an exposure light source.