JPH10312060A - Positive resist composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain good sensitivity and good resolution and sufficient resistance to dry etching and intimate contact with a substrate by using a resin and a polyfunctional enol ether each specified in structure. SOLUTION: This composition comprises a compound to be allowed to produce an acid by irradiation with activated rays or radiation, a resin having polycyclic alicyclic groups and carboxylic groups and the compound having at least 2 groups each represented by the formula in which each of R1 -R3 is, independently, an H atom or an optionally substituted alkyl or cycloalkyl group, and any 2 of them may combine with each other to form a cyclic structure comprising 3-8C and hetero atoms; and Z is an O or S atom or a -SO2 - or -NH- group, thus permitting the resist composition to be high in sensitivity and resolution and transmittance of light in the case of using an exposure light in the far ultraviolet wavelength region of <=220 nm.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive resist composition used in the process of manufacturing semiconductors such as ICs, the manufacture of circuit boards such as liquid crystals and thermal heads, and other photofabrication processes. More specifically, the present invention relates to a positive resist composition suitable for using far ultraviolet rays of 220 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. For example, US Pat. No. 3,666,473, US Pat. No. 4,115,128 and US Pat. No. 4,173,470 as “Novolak-type phenol resin / naphthoquinonediazide-substituted compound”
As the most typical composition, "Novolak resin composed of cresol-formaldehyde / trihydroxybenzophenone-1,2-naphthoquinonediazidesulfonic acid ester" is exemplified by Thompson "Introduction to Microlithography" (LFThompson "Intr
oduction to Microlithography ") (ACS Publishing, N
o. 2, 19, p112-121). In such a positive photoresist consisting essentially of a novolak resin and a quinonediazide compound, the novolak resin gives high resistance to plasma etching, and the naphthoquinonediazide compound acts as a dissolution inhibitor. Then, naphthoquinonediazide has the property of losing its dissolution inhibiting ability by generating carboxylic acid upon irradiation with light, and increasing the alkali solubility of the novolak resin.

[0003] From this point of view, many positive photoresists containing a novolak resin and a naphthoquinonediazide-based photosensitive material have been developed and put into practical use.
Sufficient results have been achieved in line width processing down to about 2 μm. However, the degree of integration of integrated circuits has been increasing more and more, and in the manufacture of semiconductor substrates such as VLSIs, processing of ultrafine patterns having a line width of half a micron or less has been required.

[0004] As one of means for miniaturizing a pattern, it is known to shorten the wavelength of an exposure light source used for 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 the mass production process of 256 Mbit DRAM, adoption 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.

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
-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.

These systems mainly use a resin having a low absorption in the 248 nm region and having poly (hydroxystyrene) as a main skeleton, so that 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 a large absorption in the 193 nm region. Did not. As a polymer having a small absorption in the 193 nm region, use of poly (meth) acrylate is described in J. Vac. Sci.
Technol., B9, 3357 (1991). However, this polymer has a problem 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. The polymers having an alicyclic group shown therein include 193n
Since it is necessary to reduce the absorption in the m region, a carboxyl group is used instead of a phenolic OH group as a group that imparts solubility to an alkaline developer. However, since the carboxyl group has a high solubility in a developing solution, in a developing solution (for example, a 2.38% tetramethylammonium hydroxide aqueous solution) used for a conventional resist material, unexposed portions are dissolved during development, and There was a problem of reduction. In order to improve this, it is necessary to dilute the developer to lower the concentration or to reduce the content of the carboxyl group in the polymer. When the developer concentration is reduced, the reproducibility of development becomes a problem, and when the content of the carboxyl group in the polymer is reduced, the hydrophobicity of the polymer increases, and the problem that the adhesion to the substrate is deteriorated occurs. Was.

[0011]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a positive resist composition suitable for use with an exposure light source having a wavelength of 220 nm or less, particularly an ArF excimer laser beam (193 nm). Gives good sensitivity and resolution when using an exposure light source of 220 nm or less,
Further, it has sufficient dry etching resistance and good adhesion to the substrate, and is also suitable for a developer (for example, a 2.38% aqueous solution of tetramethylammonium hydroxide) used for a conventional resist. An object of the present invention is to provide a positive resist composition exhibiting developability.

[0012]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies while paying attention to the above characteristics, and as a result, the object of the present invention is to provide a resin having a specific structure and a polyfunctional enol ether compound having a specific structure as follows. The present inventors have found that the use of the compound is excellently achieved, and arrived at the present invention. That is, the present invention has the following configuration. (1) (A) a compound which generates an acid upon irradiation with actinic rays or radiation, (B) a resin having a polycyclic alicyclic group and a carboxyl group, and (C) a compound represented by the following general formula (I) Positive resist composition comprising a compound having at least two groups represented by the formula:

[0013]

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In the formula (I), R _{1 to} R ₃ may be the same or different, and may have a hydrogen atom or a substituent.
Represents an alkyl group or a cycloalkyl group. Also, R _1-
Two of R ₃ may combine to form a ring structure composed of 3 to 8 carbon atoms and hetero atoms. Z is an oxygen atom,
Sulfur atom, -SO ₂ - shows or -NH-. (2) The resin of the component (B) is represented by the following general formula (II) or (II)
The positive resist composition according to the above (1), which has at least one of the repeating structural units having a polycyclic alicyclic group represented by (I) or (IV).

[0015]

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In the formulas (II) to (IV), R ₄ , R ₅ , R ₇
R ₉ may be the same or different and represents a hydrogen atom, a halogen atom, a cyano group, or an optionally substituted alkyl group or haloalkyl group. R ₆ is a cyano group, —C
O-OR ₁₀ or -CO-N (R ₁₁₎ represents the (R _12). X
_{1 to} X ₃ may be the same or different, and represent a single bond, a divalent alkylene group which may have a substituent, an alkenylene group or a cycloalkylene group, or -O-, -SO
_{2 -, - O-CO-} R 13 -, - CO-O-R 14 -, - C
_{O-N (R 15) -R} 16 - represents a. R ₁₀ represents a hydrogen atom, an alkyl group, a cycloalkyl group or an alkenyl group which may have a substituent, or a group which is decomposed by the action of an acid to increase the solubility in an alkaline developer.
R ₁₁ , R ₁₂ and R ₁₅ may be the same or different and represent a hydrogen atom, an alkyl group, a cycloalkyl group or an alkenyl group which may have a substituent. R ₁₁ and R ₁₂ may combine to form a ring. R ₁₃ , R ₁₄ and R ₁₆ may be the same or different, and represent a single bond or an ether group;
It represents a divalent alkylene group, alkenylene group or cycloalkylene group which may have an ester group, an amide group, a urethane group or a ureide group. Y represents a polycyclic alicyclic group. (3) The resin of the component (B) is represented by the following general formulas (V) and (V).
The positive resist composition according to (1) or (2), which has at least one of the repeating structural units having a carboxyl group represented by (I) or (VII).

[0017]

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In the formulas (V) to (VII), R ₁₇ , R ₁₈ , R _20-
R ₂₂ may be the same or different and represents a hydrogen atom, a halogen atom, a cyano group, or an optionally substituted alkyl group or haloalkyl group. R ₁₉ is a cyano group, -C
O-OR ₂₃ or -CO-N (R ₂₄₎ represents the (R _25). X
_{4 to} X ₆ may be the same or different and are a single bond, a divalent alkylene group which may have a substituent, an alkenylene group or a cycloalkylene group, or -O-, -SO
_{2 -, - O-CO-} R 26 -, - CO-O-R 27 -, - C
_{O-N (R 28) -R} 29 - represents a. R ₂₃ represents a hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group or an alkenyl group, or a group which is decomposed by the action of an acid to increase the solubility in an alkaline developer. R ₂₄ ,
R ₂₅ and R ₂₈ may be the same or different, and represent a hydrogen atom,
Represents an alkyl group, a cycloalkyl group or an alkenyl group which may have a substituent. R ₂₄ and R ₂₅ may combine to form a ring. R ₂₆ , R ₂₇ and R ₂₉ may be the same or different and may have a single bond or an ether group, an ester group, an amide group, a urethane group or a ureide group, a divalent alkylene group or an alkenylene group Alternatively, it represents a cycloalkylene group.

(4) Any one of the above (1) to (3), wherein the resin as the component (B) has a group which is decomposed by the action of an acid to increase the solubility in an alkaline developer. A positive resist composition according to any one of the above. (5) The group which decomposes by the action of an acid in the resin of the component (B) to increase the solubility in an alkaline developer is a group represented by the following general formula (VIII) or (IX). The positive resist composition according to any one of the above (2) to (4).

[0020]

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In the formulas (VIII) and (IX), R _{30 to} R ₃₂ may be the same or different, and may be a hydrogen atom or a substituted or unsubstituted alkyl, cycloalkyl or alkenyl group. , An acyl group or an alkoxycarbonyl group. R ₃₃ is an alkyl group which may have a substituent,
Represents a cycloalkyl group or an alkenyl group. However, at least two of R _{30 to} R _{32 in} the formula (VIII) are groups other than a hydrogen atom. Also, 2 of R _{30 to} R _{32 in} the formula (VIII)
Or two of R ₃₀ , R ₃₁ , and R ₃₃ in formula (IX) may combine to form a ring structure composed of 3 to 8 carbon atoms and hetero atoms.

(6) The positive resist composition as described in any of (1) to (5) above, wherein the resin as the component (B) has a hydroxyl group. (7) The compound of component (C) is a compound represented by the following formula (X):
The positive resist composition according to any one of (6).

[0023]

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In the formula (X), R _{1 to} R ₃ and Z have the same meanings as those described in the above (1). R represents a m-valent alkylene group, a m-valent cycloalkylene group which may contain a hetero atom, or a m-valent group obtained by combining two or more of these groups, and further, these groups are ether groups , An ester group, an amide group, a urethane group or a ureide group may form a divalent or higher valent linking group. m represents an integer of 2 or more. (8) The resin of the component (B) and the compound of the component (C) are crosslinked by heat at the time of forming a coating film and insolubilized in an alkali developer, and the resin of the component (B) is crosslinked with the compound of the component (C). The positive resist composition according to any one of the above (1) to (7), wherein the product is decomposed by an acid generated upon irradiation with actinic rays or radiation to improve solubility in an alkali developing solution. . (9) The positive resist composition as described in any one of (1) to (8) above, wherein far ultraviolet light having a wavelength of 220 nm or less is used as an exposure light source.

In the positive resist composition of the present invention, a compound having at least two groups represented by the general formula (I) of the component (c) of the present invention (for example, polyvalent) Enol ether compound)
The component (B) undergoes an addition reaction with a carboxyl group (and a hydroxy group) in the resin to cause crosslinking by an acetal group.
As a result, the unexposed portion is insoluble in the alkali developing solution while maintaining the adhesion to the substrate, and does not cause over-development (film reduction) due to a carboxyl group. Further, in the exposed area, the acetal cross-linked part is decomposed by the generated acid together with an acid-decomposable group introduced as necessary, and shows sufficient developability with an alkali developing solution. Therefore, a large dissolution discrimination is obtained. Attempts to form a positive image by forming a crosslink using a thermal addition reaction of such an enol ether group and a carboxyl group and then decomposing the same are described in JP-A-6-148889 and JP-A-6-230574. However, the system used there is 220 nm
The following absorption, especially ArF excimer laser light (193
nm), and the dry etching resistance was not sufficient. In the present invention, this problem can be solved satisfactorily, and a positive resist composition having a small absorption for far ultraviolet rays having a wavelength of 220 nm or less (particularly, ArF excimer laser light) and having excellent dry etching resistance can be provided.

[0026]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the compounds used in the present invention will be described in detail. [1] Resin as Component (B) The resin as the component (B) is a resin having a polycyclic alicyclic group and a carboxyl group. The structural unit having a polycyclic alicyclic group in the resin of the component (B) preferably has a polycyclic alicyclic group represented by the general formula (II), (III) or (IV). It is a repeating structural unit. In the resin of the component (B), the carboxyl group is represented by the above general formula (II) or (III)
Alternatively, it may be contained in the repeating structural unit represented by (IV), or may be contained in another repeating structural unit other than them. Further, it may be contained in a plurality of positions among the substitution positions of these carboxyl groups. As the structural unit having a carboxyl group, a repeating structural unit represented by the general formula (V), (VI) or (VII) is preferable.

The resin of the component (B) has a hydroxy group and / or
Alternatively, it preferably has 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. Thereby, discrimination in solubility in an alkali developing solution can be further increased. Similarly, the hydroxy group and the acid-decomposable group may be contained in the repeating structural units represented by the above general formulas (II) to (VII), or may be contained in another repeating structural unit different from them. Is also good. Furthermore, it may be included in a plurality of locations among these replacement locations.

R in the general formulas (II) to (VII)_Four,
R_Five, R₇~ R₉, R₁₇, R₁₈, R ₂₀~ R_{twenty two}The alkyl of
The group is preferably a methyl group which may have a substituent.
, Ethyl, propyl, n-butyl, sec-
Those having 1 to 4 carbon atoms such as a butyl group are exemplified.
As the haloalkyl group, preferably a fluorine atom, chlorine
Atom or bromine atom substituted alkyl having 1 to 4 carbon atoms
Groups such as fluoromethyl, chloromethyl, bromo
Methyl group, fluoroethyl group, chloroethyl group, bromo
And an ethyl group.

The alkyl group of R _{10 to} R ₁₂ , R ₁₅ , R _{23 to} R ₂₅ and R ₂₈ is preferably a methyl group, an ethyl group, a propyl group or an n-butyl group which may have a substituent. , S
ec-butyl group, hexyl group, 2-ethylhexyl group,
Examples thereof include those having 1 to 8 carbon atoms such as an octyl group. As the cycloalkyl group, preferably a cyclopropyl group optionally having a substituent, a cyclopentyl group,
A monocyclic type having 3 to 8 carbon atoms such as a cyclohexyl group,
Polycyclic ones such as an adamantyl group, a norbornyl group, an isobornyl group, a dicyclopentyl group, a σ-pinel group, and a tricyclodecanyl group are exemplified. Examples of the alkenyl group preferably include those having 2 to 6 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. Can be R ₁₁ and R ₁₂ , or R ₂₄ and R ₂₅ may be bonded to each other to form a ring together with the nitrogen atom. Such rings include pyrrolidine, piperidine,
A 5- to 8-membered ring such as piperazine is preferred.

The alkylene group for X _{1 to} X ₆ is preferably an alkylene group having 1 to 8 carbon atoms such as an optionally substituted methylene group, ethylene group, propylene group, butylene group, hexylene group and octylene group. One. Examples of the alkenylene group preferably include those having 2 to 6 carbon atoms such as an ethenylene group, a propenylene group, and a butenylene group which may have a substituent. Examples of the cycloalkylene group preferably include those having 5 to 8 carbon atoms such as a cyclopentylene group and a cyclohexylene group which may have a substituent.

Examples of the alkylene group, alkenylene group, and cycloalkylene group represented by R ₁₃ , R ₁₄ , R ₁₆ , R ₂₆ , R ₂₇ , and R ₂₉ include the groups represented by X _{1 to} X _6. Further, those in which these form a divalent group together with at least one of an ether group, an ester group, an amide group, a urethane group and a ureido group are also included.

The acid-decomposable group and the acid-decomposable groups of R ₁₀ and R ₂₃ preferably introduced into the resin of the component (B) of the present invention are decomposed by the action of an acid to increase the solubility in an alkali developer. These are groups that increase, for example, groups that form an acid by hydrolysis under the action of an acid, and groups that form an acid by the removal of a carbon cation under the action of an acid. As the acid-decomposable group,
Preferred is a group represented by the above general formula (VIII) or (IX).

The alkyl group of R _{30 to} R _{33 in} the general formulas (VIII) to (IX) is preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, which may have a substituent.
Those having 1 to 8 carbon atoms such as sec-butyl group, hexyl group, 2-ethylhexyl group and octyl group are exemplified. Examples of the cycloalkyl group preferably include those having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group which may have a substituent. Examples of the alkenyl group preferably include those having 2 to 6 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. Can be

Preferred acyl groups for R _{30 to} R ₃₂ include those having 1 to 10 carbon atoms such as formyl group, acetyl group, propanoyl group, butanoyl group and octanoyl group. Preferred alkoxycarbonyl groups include those having 1 to 8 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group and a butoxycarbonyl group. R in the formula (VIII)
Any two of ₃₀ to R _32, and R _30, R ₃₁ in formula (IX),
Any two of R ₃₃ may combine to form a ring. Preferred rings include 3- to 8-membered rings that may contain a heteroatom such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a tetrahydrofuranyl group, and a tetrahydropyranyl group. These rings may further have a substituent.

In each of the above substituents, a further preferred substituent is a hydroxyl group, a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, an amide group,
A sulfonamide group, the above R _{10 to} R ₁₂ , R ₁₅ , R ₂₃ to
The alkyl group, methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group, butoxy group and the like having 1 to 1 carbon atoms described for R ₂₅ and R ₂₈
Eight alkoxy groups such as an alkoxy group, a methoxycarbonyl group and an ethoxycarbonyl group, an acyl group such as a formyl group, an acetyl group and a benzoyl group, an acyloxy group such as an acetoxy group and a butyryloxy group, and a carboxy group.

The polycyclic alicyclic group contained in the resin of the component (B) is preferably an alicyclic group such as bicyclo, tricyclo, tetracyclo or the like having 5 or more carbon atoms which may have a substituent. Group, preferably a polycyclic alicyclic group having 6 to 30 carbon atoms which may have a substituent, more preferably 7 to 25 carbon atoms which may have a substituent. Represent.
Preferred substituents of the polycyclic alicyclic group include a hydroxyl group, a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, an amide group, a sulfonamide group, the above R _{10 to} R ₁₂ , Alkyl groups having 1 to 8 carbon atoms, such as alkyl groups, methoxy groups, ethoxy groups, hydroxyethoxy groups, propoxy groups, hydroxypropoxy groups, butoxy groups, and methoxycarbonyl described for R ₁₅ , R _{23 to} R ₂₅ , and R _28. Groups, an alkoxycarbonyl group such as an ethoxycarbonyl group, an acyl group such as a formyl group, an acetyl group, and a benzoyl group; an acyloxy group such as an acetoxy group and a butyryloxy group; and a carboxy group.

Representative structures of the polycyclic alicyclic moiety in the above polycyclic alicyclic groups include, for example, those shown below.

[0038]

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[0039]

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The content of the structural unit having the alicyclic group (preferably, the repeating structural unit represented by any one of the general formulas (II) to (IV)) in the resin of the present invention is determined by the resistance to dry etching and alkali development. Although it is adjusted by the balance with the properties and the like, it is preferably contained in an amount of 20 mol% or more based on all the repeating structural units. The content is more preferably 30 to 1
The range is from 00 mol%, more preferably from 40 to 90 mol%, and even more preferably from 45 to 75 mol%.

Specific examples of the repeating structural units represented by formulas (II) to (IV) are shown below, but the present invention is not limited thereto.

[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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The content of the repeating structural unit having a carboxyl group (preferably the repeating structural units represented by formulas (V) to (VII)) in the resin according to the present invention is the same as that of the compound of component (C). In accordance with the content, alkali developability, substrate adhesion, is prepared from the viewpoint of performance such as sensitivity, but preferably 10 to 10 for all repeating structural units.
It is used in a range of 70 mol%, more preferably 20 to 60 mol%, and still more preferably 30 to 50 mol%. Here, the content of the repeating structural unit having a carboxyl group is determined by the general formulas (V) to (VII) having a carboxyl group.
Is the amount of all the carboxyl group-containing repeating structural units in the resin including the repeating structural unit represented by Specific examples (b1) to (b18) of the repeating structural units represented by formulas (V) to (VII) are shown below, but the present invention is not limited thereto.

[0049]

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[0050]

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The content of the repeating structural unit having an acid-decomposable group in the resin according to the present invention is adjusted according to the properties such as alkali developability, substrate adhesion and sensitivity.
It is preferably in the range of 0 to 70 mol%, more preferably 10 to 60 mol%, and still more preferably 20 to 50 mol%, based on all repeating structural units. Here, the content of the repeating structural unit having an acid-decomposable group is determined by the total amount of the acid-decomposable groups in the resin including the repeating structural units represented by the general formulas (II) to (VII). It is the amount of the repeating unit containing a functional group. Specific examples (c1) to (c30) of the repeating structural unit having an acid-decomposable group are shown below, but 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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For the purpose of improving the performance of the resin of the component (B) of the present invention, other polymerizable monomers are 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, acrylates 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 esters, for example, alkyl (alkyl having preferably 1 to 10 carbon atoms) 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.,
Dialkyl itaconate (eg, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, etc.); dialkyl esters of maleic acid or fumaric acid (eg, dimethyl maleate) rate,
Dibutyl fumarate), 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 these, 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.

The resin of the component (B) of the present invention is synthesized by radical, cationic or anionic polymerization of an unsaturated monomer 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 molecular weight of the resin of the component (B) of the present invention is 2,000 or more by weight average (Mw: polystyrene standard).
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, the amount of the resin added to the photosensitive composition is 5 to the total solid content.
It is 0 to 99.7% by weight, preferably 70 to 99% by weight.

[2] A compound having at least two groups represented by the general formula (I) of the component (C) The compound of the component (C) has at least two enol ether groups represented by the general formula (I). Compounds. The alkyl group represented by R _{1 to} R _{3 in} the general formula (I) is preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a hexyl group, which may have a substituent. Those having 1 to 8 carbon atoms such as 2-ethylhexyl group and octyl group are exemplified. Examples of the cycloalkyl group preferably include those having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group which may have a substituent. Also, any two of R _{1 to} R ₃ may combine to form a ring. Such a ring is preferably a 3- to 8-membered ring which may contain a hetero atom such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a dihydrofuranyl group, a dihydropyranyl group. Can be These rings may further have a substituent.

Preferred examples of the above substituents and rings include a hydroxyl group, a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, an amide group, a sulfonamide group, and the above R _{1 to} R ₃ . The alkyl group described by the way,
A methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, a hydroxypropoxy group, an alkoxy group having 1 to 8 carbon atoms such as a butoxy group, a methoxycarbonyl group,
Examples include an alkoxycarbonyl group such as an ethoxycarbonyl group, an acyl group such as a formyl group and an acetyl group, and an acyloxy group such as an acetoxy group and a butyryloxy group.

The compound having at least two enol ether groups represented by the general formula (I) includes two or more enol ether groups represented by the general formula (I).
Compounds linked by a linking group of valence or higher can be mentioned. Examples of the linking structure (linking group) include a polyvalent alkylene group, a polyvalent cycloalkylene group, and a polyvalent group formed by combining two or more of these, which may have a substituent. , These may contain heteroatoms. These linking groups may further form a divalent or higher linking group together with an ether group, an ester group, an amide group, a urethane group, or a ureido group. As the compound having at least two enol ether groups represented by the general formula (I), the compound represented by the general formula (X) is preferable. The number (m) of the group represented by the general formula (I) contained in the compound having at least two enol ether groups represented by the general formula (I) is preferably 2 to 8, more preferably 2 ~ 5. As the alkylene group,
An m-valent group having 1 to 8 carbon atoms such as an ethylene group, a propylene group, a butylene group, and a hexylene group is preferred. Examples of the cycloalkylene group include m-valent cycloalkylenes having 5 to 20 carbon atoms, such as cyclopentylene, cyclohexylene, cyclooctylene, adamantylene, and tricyclodecaneylene groups. Groups are preferred. Examples of the hetero atom include an oxygen atom, a sulfur atom, a nitrogen atom and the like.

Preferred substituents of the above linking group include a hydroxyl group, a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, an amide group, a sulfonamide group, and the above R _{1 to} R ₃ . Alkoxy groups having 1 to 8 carbon atoms such as alkyl group, methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group, butoxy group, alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group, formyl group , An acyl group such as an acetyl group, and an acyloxy group such as an acetoxy group and a butyryloxy group. Among these, from the viewpoint of imparting dry etching resistance, particularly m
Those having a valent cycloalkylene group are preferred.

In the present invention, the content of the compound of the component (C) in the composition is adjusted according to the carboxyl group (and the hydroxy group) in the resin of the component (B), and further, alkali developability, substrate adhesion It is prepared from the viewpoint of performance such as properties and sensitivity. Preferably 3 to 6 with respect to the solid content of the whole composition.
It is used in an amount of 0% by weight, more preferably 5 to 50% by weight, further preferably 10 to 40% by weight.

Specific examples of the compound of the component (C) are shown below, but the present invention is not limited thereto.

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[0072]

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[0073]

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[0074]

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[0075]

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The photoacid generator (A) used in the present invention is a compound that generates an acid upon irradiation with actinic rays or radiation. As the compound used in the present invention, which decomposes upon irradiation with actinic rays or radiation to generate an acid, a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization,
Known light (eg, ultraviolet light having a wavelength of 400 to 200 nm, far ultraviolet light, particularly preferably g-line, h-line, i-line)
X-rays, KrF excimer laser light), ArF excimer laser light, electron beams, X-rays, compounds generating an acid by a molecular beam or an ion beam, and mixtures thereof can be appropriately selected and used.

Other compounds used in the present invention that generate an acid upon irradiation with actinic rays or radiation include, for example, SI Schlesinger, Photogr. Sci. Eng., 18, 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 a photoacid generator having a 0-nitrobenzyl-type protecting group described in JP-A-53-133022, etc.
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 capable of generating 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).

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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.

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[0084]

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[0085]

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

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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.

[0090] 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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[0101]

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[0102]

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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).

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In the formula, Ar^Three, Ar^FourAre each independently substituted
Or an unsubstituted aryl group. R ²⁰⁶Is replaced or
Indicates 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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[0109]

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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 composition of the present invention may further contain, if necessary, an acid-decomposable dissolution inhibiting compound, a dye, a plasticizer, a surfactant, a photosensitizer, and an organic compound. It may contain a basic compound, a compound that promotes solubility in a developer, and the like. The acid-decomposable dissolution inhibiting compound used in the present invention includes, for example, at least one acid-decomposable group represented by the above general formulas (VIII) and (IX).
It is a low molecular compound having a molecular weight of 3,000 or less.
In particular, Procee
Alicyclic or aliphatic compounds such as the cholic acid derivatives described in ding of SPIE, 2724, 355 (1996) are preferred.
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, more preferably 5 to 40% by weight based on the total weight of the composition (excluding the solvent). Ranges from 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 a phenol compound having a molecular weight of 1,000 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).

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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 can be used alone or in combination of two or more. The amount of the nitrogen-containing basic compound to be used is generally 0.001-10 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 the above components and applied on a support. As the solvent used here, ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, γ-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate , Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate,
Ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N, N-dimethylformamide, 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, 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 manufacture 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, it is preferable to perform a heat treatment for drying and forming a coating film after the application. By this heat treatment, the resin of the component (B) and the compound of the component (C) form a crosslinked structure. Here, the heating temperature is preferably 80 ° C. or more, more preferably 100 ° C. or more, and still more preferably 120 to 160 ° C., and the heating time is preferably 30 seconds or more, more preferably 1 minute or more, and further preferably 1 minute to 10 minutes. The exposure light is preferably a far ultraviolet ray having a wavelength of 250 nm or less, more preferably 220 nm or less. Specifically, a KrF excimer laser (248 nm) and an ArF excimer laser (19
3 nm), F ₂ excimer laser (157 nm), X
Line, 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.

[0129]

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 (Synthesis of Compound Example (d5))] NaH (content 6)
(0%) was dispersed in 200 ml of N, N-dimethylacetamide, and 48.0 g of 2,2-bis (4-hydroxycyclohexyl) propane was added thereto.
(0.20 mol) was added at room temperature, and 42.6 g (0.40 mol) of 2-chloroethyl vinyl ether was further added to 30
Dropped over minutes. Thereafter, the mixture was heated and stirred at 100 ° C. for 5 hours. After cooling, the reaction mixture was poured into 1.5 L of water and extracted with 500 ml of ethyl acetate. The extract was washed with water and dried over sodium sulfate. The dried ethyl acetate solution was concentrated and purified by column chromatography (filler: silica gel, eluent: hexane / ethyl acetate = 4/1) to obtain 39.7 g of a colorless liquid. By NMR measurement, it was confirmed that this solid was Compound Example (d5) of the present invention.

[Synthesis Example 2 (Synthesis of Compound Example (d35))]
Instead of 2,2-bis (4-hydroxycyclohexyl) propane of Synthesis Example 1, 39.2 g of bis (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane
(0.20 mol), and 34.2 g of a colorless liquid was obtained in the same manner as in Synthesis Example 1 except for the above. By NMR measurement, it was confirmed that this solid was a compound example (d35) of the present invention.

[Synthesis Example 3 (Synthesis of Compound Example (d39))]
In place of 2,2-bis (4-hydroxycyclohexyl) propane of Synthesis Example 1, 33.6 g (0.20 mol) of 1,3-dihydroxyadamantane was used, and the others were the same as in Synthesis Example 1 to produce a colorless liquid 31.5 g were obtained. NM
By R measurement, it was confirmed that this liquid was a compound example (d39) of the present invention.

[Synthesis Example 4 (Synthesis of Compound Example (d20))]
44.5 g (0.20 mol) of isophorone diisocyanate was dissolved in 200 ml of dioxane, and 35.2 g (0.40 mol) of 2-hydroxyethyl vinyl ether was added. Further, 0.2 g of dibutyltin dilauryl ester was added as a catalyst, and the mixture was heated and stirred at 100 ° C. for 5 hours. After cooling, the reaction mixture was poured into 1.5 L of water and extracted with 500 ml of ethyl acetate. Wash the extract with water,
It was dried over sodium sulfate. The dried ethyl acetate solution was concentrated and purified by column chromatography (filler: silica gel, eluent: hexane / ethyl acetate = 3/1) to obtain 48.6 g of a white solid. By NMR measurement,
This solid was confirmed to be a compound example (d20) of the present invention.

[Synthesis Example 5 (Synthesis of Compound Example (d31))]
36.4 g of 5-norbornene-2,3-dicarboxylic acid
(0.20 mol) and 54.5 g (0.40 mol) of 2-hydroxyethyl vinyl sulfone were dissolved in 300 ml of THF. To this solution is added dicyclohexylcarbodiimide 8
A solution of 2.5 g of THF in 100 ml was added dropwise over 1 hour. After stirring at room temperature for 3 hours and further at 50 ° C. for 3 hours, the precipitated solid was filtered. The THF solution of the filtrate was concentrated and purified by column chromatography (filler: silica gel, eluent: hexane / ethyl acetate = 4/1) to obtain 52.4 g of a white solid. By NMR measurement,
This solid was confirmed to be a compound example (d31) of the present invention.

[Synthesis Example 6 (Synthesis of Resin (p-1))] 13.2 g (0.060 mol) of tricyclodecanyl methacrylate / 3.4 g (0.040 mol) of methacrylic acid were added to 1-
Dissolved in 60 ml of methoxy-2-propanol, and the polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.) at 70 ° C under a nitrogen stream and stirring. V-65) 50 mg were added. Two hours and four hours after the start of the reaction, 50 mg of the same initiator was added. After further reacting for 3 hours, the temperature was raised to 90 ° C., and stirring was continued for 1 hour. After allowing the reaction solution to cool, it was poured into 1 L of ion-exchanged water with vigorous stirring to precipitate a polymer. The obtained polymer was dried at 40 ° C. under reduced pressure to obtain 13.9 g of a resin (p-1). When the molecular weight was measured by GPC, the weight average (Mw: in terms of polystyrene) was 3
2.4 × 10 ³ (dispersion degree (Mw / Mn) 2.7).

[Synthesis Example 7 (Synthesis of Resin (p-2) of the Present Invention)] Instead of tricyclodecanyl methacrylate in Synthesis Example 6, 13.2 g of 1-adamantane methacrylate was used.
(0.060 mol), and otherwise the same as in Synthesis Example 6, to obtain 14.7 g of resin (p-2). When the molecular weight was measured by GPC, the weight average (Mw: in terms of polystyrene) was 35.3 × 10 ³ (dispersion degree (Mw / Mn) 2.
8).

[Synthesis Example 8 (Synthesis of Resin (p-3) of the Present Invention)] 11.0 g of tricyclodecanyl methacrylate
(0.050 mol) / t-butyl methacrylate 2.8
g (0.020 mol) /2.6 g of methacrylic acid (0.0
30 mol) in 1 ml of 1-methoxy-2-propanol
In the same manner as in Synthesis Example 6 except for the resin (p-3)
14.3 g were obtained. When the molecular weight was measured by GPC, the weight average (Mw: in terms of polystyrene) was 37.1 ×.
10 ³ (dispersion degree (Mw / Mn) 2.8).

[Synthesis Examples 9 to 19 (Synthesis of Resin of the Present Invention)] Resins of the present invention shown in Table 1 below were synthesized in the same manner as in Synthesis Examples 6 to 8. Table 1 shows the molar ratios of the monomers used and the weight average molecular weight of the produced resin.

[0138]

[Table 1]

[0139]

Embedded image

[0140]

Embedded image

Example 1 (Measurement of Thermal Crosslinkability and Optical Density) In Table 2 below, 1.0 g of the resin as the component (B), 0.35 g of the compound as the component (c) and triphenylsulfonium trif A 0.01 g rate was dissolved in 6.0 g of propylene glycol monomethyl ether acetate, and the solution was filtered through a 0.2 μm Teflon filter. It is applied uniformly on a quartz glass substrate by a spin coater, and heated on a hot plate at 130 ° C. for 2 minutes.
A 1 μm resist film was formed. In order to confirm the crosslinkability of the obtained film, it was immersed in a 2.38% aqueous solution of tetramethylammonium hydroxide for 1 minute. In each case, the film loss was 5% or less, and it was found that the crosslinkability was sufficient. When the optical absorption per 1 μm of these films obtained above was measured by an ultraviolet spectrophotometer, the optical density at 193 nm was as shown in Table 2 below.

[0142]

[Table 2]

From the results shown in Table 2, it is found that the measured optical density of the resin of the present invention is smaller than that of the poly (hydroxystyrene) of the comparative example, and that the resin of the present invention has a sufficient transmittance to light of 193 nm.

[Example 2 (Measurement of dry etching resistance)] The composition of the present invention shown in Example 1 was uniformly applied on a silicon substrate in the same manner as in Example 1 to obtain a composition.
Heat on a hot plate at 0 ° C for 2 minutes,
m of the resist film was formed. The obtained membrane is ULVAC
Reactive Ion Etching Equipment (CSE-111)
0), the etching rate for CF ₄ / O ₂ (8/2) gas was measured. The result was as shown in Table 3 below (etching conditions: Power = 500 W, P
response = 4.6 Pa, GasFlow Rat
e = 10 sccm).

[0145]

[Table 3]

From the results shown in Table 3, it can be seen that the etching rate of the composition of the present invention is smaller than the value obtained when poly (methyl methacrylate) of the comparative example is used, and that the composition has a sufficient dry etching resistance.

Example 3 (Evaluation of Image) 1.0 g of the resin (B), 0.35 g of the compound (C) and 0.01 g of triphenylsulfonium triflate of the present invention shown in Table 4 below were mixed with propylene. It was dissolved in 6.0 g of glycol monomethyl ether acetate and filtered through a 0.2 μm Teflon filter. The solution was uniformly coated on a hexamethyldisilazane-treated silicon substrate by a spin coater, and dried by heating on a hot plate at 130 ° C. for 2 minutes to form a 0.4 μm resist film. A mask having a pattern drawn with chromium on a quartz plate is adhered to the resist film, and an ArF excimer laser beam (193) is used.
nm). Immediately after exposure, heating was performed on a hot plate at 110 ° C. for 60 seconds. Further, the solution is treated with a 2.38% aqueous solution of tetramethylammonium hydroxide at 23 ° C. for 60
After immersion development for 2 seconds, rinsing with pure water for 30 seconds, and drying. The shape of the resulting pattern was observed with a scanning electron microscope, and a rectangular one was determined to be good. Further, the sensitivity was defined as an exposure amount for reproducing a 0.35 μm mask pattern. The resolution was defined as a critical resolution at an exposure amount for reproducing a 0.35 μm mask pattern. The results of the pattern shape, sensitivity, and resolution are shown in Table 4 below.

[0148]

[Table 4]

From the results shown in Table 4, the resist using the resin and the compound of the present invention has high sensitivity and good resolution.
Also, it can be seen that the pattern shape is good. In addition, it can be developed brilliantly with a developer (concentration of tetramethylammonium hydroxide solution) of a concentration conventionally used,
There was no occurrence of film thinning and deterioration of adhesion, and a good pattern shape and excellent sensitivity and resolution were obtained.

[0150]

As is apparent from the above description, the positive resist composition of the present invention has a high transmittance for far ultraviolet light of 220 nm or less and a good dry etching resistance. . Furthermore, when far-ultraviolet light (especially ArF excimer laser light) having a wavelength of 220 nm or less is used as an exposure light source, it exhibits high sensitivity, high resolution, and a good pattern profile, and is effectively used for forming a fine pattern required for semiconductor device manufacturing. It can be used.

Claims (9)

[Claims] 1. A compound which generates an acid upon irradiation with an actinic ray or radiation, (B) a resin having a polycyclic alicyclic group and a carboxyl group, and (C) a compound represented by the following general formula (I): A positive resist composition comprising a compound having at least two groups represented by the formula: Embedded image In the formula (I), R _{1 to} R ₃ may be the same or different and represent a hydrogen atom, an alkyl group or a cycloalkyl group which may have a substituent. Further, two members out of R _{1 to} R ₃ may combine to form a ring structure composed of 3 to 8 carbon atoms and hetero atoms. Z represents an oxygen atom, a sulfur atom, -SO ₂ - shows or -NH-. 2. The resin of component (B) has the following general formula (I)
The positive resist composition according to claim 1, wherein the positive resist composition has at least one of repeating structural units having a polycyclic alicyclic group represented by (I), (III) or (IV). . Embedded image In the formulas (II) to (IV), R ₄ , R ₅ , R _{7 to} R ₉ may be the same or different, and may have a hydrogen atom, a halogen atom, a cyano group, or an alkyl which may have a substituent. Represents a group or a haloalkyl group. R ₆ represents a cyano group, —CO—OR ₁₀ or —CO—N (R ₁₁ ) (R ₁₂ ). X _{1 to} X ₃ may be the same or different and are a single bond, a divalent alkylene group, alkenylene group or cycloalkylene group which may have a substituent, or —O—, —SO ₂ —, or —. O-
_{CO-R 13 -, - CO} -O-R 14 -, - CO-N
(R ₁₅ ) represents —R ₁₆ —. R ₁₀ represents a hydrogen atom, an alkyl group, a cycloalkyl group or an alkenyl group which may have a substituent, or a group which is decomposed by the action of an acid to increase the solubility in an alkaline developer. R ₁₁ ,
R ₁₂ and R ₁₅ may be the same or different and include a hydrogen atom,
Represents an alkyl group, a cycloalkyl group or an alkenyl group which may have a substituent. R ₁₁ and R ₁₂ may combine to form a ring. R ₁₃ , R ₁₄ and R ₁₆ may be the same or different and may have a single bond or an ether group, an ester group, an amide group, a urethane group or a ureide group, a divalent alkylene group or an alkenylene group Alternatively, it represents a cycloalkylene group. Y represents a polycyclic alicyclic group. 3. The resin of component (B) has at least one of repeating units having a carboxyl group represented by the following general formula (V), (VI) or (VII). The positive resist composition according to claim 1. Embedded image In the formulas (V) to (VII), R ₁₇ , R ₁₈ , R _{20 to} R ₂₂ may be the same or different, and may be a hydrogen atom, a halogen atom, a cyano group, or an alkyl which may have a substituent. Represents a group or a haloalkyl group. R ₁₉ represents a cyano group, —CO—OR ₂₃ or —CO—N (R ₂₄ ) (R ₂₅ ). X _{4 to} X ₆ may be the same or different and are a single bond, a divalent alkylene group, an alkenylene group or a cycloalkylene group which may have a substituent, or —O—, —SO ₂ —, or —. O-
_{CO-R 26 -, - CO} -O-R 27 -, - CO-N
(R ₂₈ ) represents —R ₂₉ —. R ₂₃ represents a hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group or an alkenyl group, or a group which is decomposed by the action of an acid to increase the solubility in an alkaline developer. R ₂₄ , R ₂₅ ,
R ₂₈ may be the same or different and represents a hydrogen atom, an alkyl group, a cycloalkyl group or an alkenyl group which may have a substituent. R ₂₄ and R ₂₅ may combine to form a ring. R ₂₆ , R ₂₇ and R ₂₉ may be the same or different, and represent a single bond, an ether group, an ester group,
It represents a divalent alkylene group, alkenylene group or cycloalkylene group which may have an amide group, a urethane group or a ureide group. 4. The resin according to claim 1, wherein the resin as the component (B) has a group which is decomposed by the action of an acid to increase the solubility in an alkali developing solution. Positive resist composition. 5. A group represented by the following general formula (VIII) or (IX), wherein the group which decomposes by the action of an acid in the resin of the component (B) to increase the solubility in an alkaline developer is represented by the following formula (VIII) or (IX). The positive resist composition according to any one of claims 2 to 4, wherein: Embedded image In formulas (VIII) and (IX), R _{30 to} R ₃₂ may be the same or different, and may be a hydrogen atom or a substituent, and may be an alkyl group, a cycloalkyl group, an alkenyl group, or an acyl group. Alternatively, it represents an alkoxycarbonyl group. R
₃₃ represents an alkyl group, a cycloalkyl group or an alkenyl group which may have a substituent. Where equation (VIII)
And at least two of R _{30 to} R ₃₂ are groups other than a hydrogen atom. Two of R _{30 to} R ₃₂ of the formula (VIII) or two of R ₃₀ , R ₃₁ and R ₃₃ of the formula (IX) are bonded to form 3 to 8
A ring structure consisting of carbon atoms and hetero atoms may be formed. 6. The positive resist composition according to claim 1, wherein the resin (B) has a hydroxyl group. 7. The positive resist composition according to claim 1, wherein the compound of the component (C) is a compound represented by the following general formula (X). Embedded image In the formula (X), R _{1 to} R ₃ and Z have the same meanings as those described in claim 1. R may include a heteroatom;
m-valent alkylene group, m-valent cycloalkylene group or a m-valent group obtained by combining two or more of these groups, furthermore, these groups are an ether group, an ester group,
A divalent or higher valent linking group may be formed together with at least one of an amide group, a urethane group and a ureido group. m represents an integer of 2 or more. 8. The resin of the component (B) and the compound of the component (C) are crosslinked by heat at the time of forming a coating film and become insoluble in an alkali developing solution. The positive resist composition according to any one of claims 1 to 7, wherein the crosslinked product is decomposed by an acid generated upon irradiation with actinic rays or radiation to improve solubility in an alkali developing solution. 9. The positive resist composition according to claim 1, wherein far-ultraviolet light having a wavelength of 220 nm or less is used as an exposure light source.