JPH11109628A - Positive photosensitive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a positive photosensitive compsn. which imparts satisfactory sensitivity and resolution at the time of using a light source of <=220 nm for exposure and has satisfactory dry etching resistance, adhesion to a substrate and developability by using an acid decomposable resin having specified alicyclic groups. SOLUTION: A photosensitive compsn. contains a compd. which generates an acid by irradiating active light beams or radiation and a resin having polycyclic alicyclic groups represented by formulae I-III, etc. and groups which are decomposed by the action of the acid and increase solubility in an alkali developer. In the formulae I-III, R is an H atom, a linear or branched alkyl group which may have a substituent, a cycloalkyl, alkenyl or acyl group, X is a single bond, a divalent alkylene, alkenylene or cycloalkylene group which may have an ether, ester, amido, urethane or ureido group and Me is a methyl group. It is preferable that the resin further has carboxyl groups.

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. 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 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.

[0007] Examples of such a combination include a combination of a compound that generates an acid by photolysis with an acetal or an O, N-acetal compound (JP-A-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 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.
1672,66 (1992), and the use of this polymer has recently 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 in synthesis. In addition, the polymers having an alicyclic group shown in these publications are required to reduce the absorption in the 193 nm region.
A carboxyl group is used instead of the H group. 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.

[0012]

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). 220nm
When the following exposure light source is used, good sensitivity and resolution are provided, and furthermore, sufficient dry etching resistance, good adhesion to the substrate, and good adhesion to the substrate are obtained. (38% tetramethylammonium hydroxide aqueous solution) is to provide a positive resist composition exhibiting good developability.

[0013]

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 has been successfully achieved by using an acid-decomposable resin having the following 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 polycyclic compound represented by the following general formula (I), (II), (III) or (IV) A positive photosensitive composition comprising a resin having at least one alicyclic group of a type and a group which is decomposed by the action of an acid to increase solubility in an alkaline developer.

[0015]

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In the general formulas (I) to (IV), R is a hydrogen atom,
Represents a linear or branched alkyl group, cycloalkyl group, alkenyl group, or acyl group which may have a substituent. X represents a single bond or a divalent alkylene group, alkenylene group, or cycloalkylene group which may have an ether group, an ester group, an amide group, a urethane group, or a ureido group. Me represents a methyl group. 2. The resin (B) is decomposed by the action of an acid with at least one of the repeating structural units having a polycyclic alicyclic group represented by the general formula (V), (VI) or (VII). 3. The positive photosensitive composition as described in 1 above, wherein the resin has a group that increases the solubility in an alkaline developer.

[0017]

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In the general formulas (V) to (VII), R₁~ R_Two,
R_Four~ R₆May be the same or different, a hydrogen atom,
Halogen atom, cyano group, alkyl group or haloalkyl
Represents a group. R_ThreeIs a cyano group, -CO-OR₇, -CO-
NR₈R₉Represents X₁~ X _ThreeAre the same but different
May be a single bond or may have a substituent 2
Valent alkylene group, alkenylene group, cycloalkylene
Group, or -O-, -SO_Two-, -O-CO-R
_Ten-, -CO-OR₁₁-, -CO-NR₁₂-R₁₃-
Represent. R₇Represents a hydrogen atom or an optionally substituted
Kill group, cycloalkyl group, alkenyl group, or acid
Represents a group that is decomposed by the action of R₈~ R₉, R₁₂Is each
Hydrogen atom, an alkyl group which may have a substituent,
Represents a chloroalkyl group or an alkenyl group. Also R₈, R₉
May combine to form a ring. R_Ten~ R₁₁, R₁₃Is simply
Bond or ether group, ester group, amide group, urethane
A divalent alkylene group which may have a urein group,
Represents an alkenylene group or a cycloalkylene group. Y is billed
Item 1. Polycyclic type represented by general formulas (I) to (IV) described in item 1.
Represents an alicyclic group.

(3) The resin of the component (B) is combined with at least one of the repeating structural units represented by the general formulas (V), (VI) and (VII) according to claim 2 by the action of an acid. It has a group that decomposes to increase the solubility in an alkali developer, and further has a polycyclic alicyclic group different from the general formulas (V), (VI) and (VII). VIII),
3. The positive photosensitive composition as described in 1 or 2 above, which is a resin having at least one of the repeating structural units represented by (IX) or (X).

[0020]

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In the general formulas (VIII) to (X), R₁₄~ R_Fifteen,
R₁₇~ R₁₉May be the same or different, a hydrogen atom,
Halogen atom, cyano group, alkyl group or haloalkyl
Represents a group. R₁₆Is a cyano group, -CO-OR₇, -CO-
NR₈R₉Represents X_Four~ X ₆Are the same but different
May be a single bond or may have a substituent 2
Valent alkylene group, alkenylene group, cycloalkylene
Group, or -O-, -SO_Two-, -O-CO-R
_Ten-, -CO-OR₁₁-, -CO-NR₁₂-R₁₃-
Represent. R₇~ R₁₃Is the same as in claim 2.
You. P is a polycyclic alicyclic ring different from the general formulas (I) to (IV)
Represents a formula group.

(4) The resin of the component (B) comprises at least one of the repeating structural units represented by the general formulas (V), (VI) and (VII) and the resin represented by the general formula (VIII), (IX) or Having at least one repeating structural unit represented by (X) and at least one repeating structural unit represented by the following general formula (XI), (XII) or (XIII);
4. The positive photosensitive composition as described in any one of the above items 1 to 3, which is a resin which is decomposed by the action of an acid to increase solubility in an alkaline developer.

[0023]

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In the general formulas (XI) to (XIII), R _{20 to} R ₂₁ ,
R _{23 to} R ₂₅ may be the same or different, and represent a hydrogen atom,
Represents a halogen atom, a cyano group, an alkyl group or a haloalkyl group, and R ₂₂ represents a cyano group, a carboxyl group, -CO-
OR ₇ represents —CO—NR ₈ R ₉ . X _{7 to} X ₉ may be the same or different and are a single bond or a divalent alkylene group or alkenylene group which may have a substituent;
Cycloalkylene group or _{-O, -, - SO 2 -} , -
_{O-CO-R 10 -,} - CO-O-R 11 -, - CO-NR
₁₂ -R ₁₃ - represents a. Definition of R ₇ to R ₁₃ are the same as in claim 2. B represents a group which is decomposed by the action of an acid to increase solubility in an alkaline developer.

(5) The positive photosensitive composition as described in any one of (1) to (4) above, wherein the resin as the component (B) further has a carboxyl group.

(6) The resin of the component (B) further comprises a carboxyl group represented by the following general formula (XIV), (XV) or (XVI)
6. The positive photosensitive composition as described in 5 above, comprising at least one of the repeating structural units represented by

[0027]

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In the general formulas (XIV) to (XVI), R _{26 to} R ₂₇ , R
_{29 to} R ₃₁ may be the same or different and represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group or a haloalkyl group, and R ₂₈ represents a cyano group, a carboxyl group, —CO—O
R _7, represents the -CO-NR ₈ R _9. X _{10 to} X ₁₂ may be the same or different and are a single bond or a divalent alkylene group, alkenylene group, cycloalkylene group which may have a substituent, or —O—, —SO ₂ -, -O
_{-CO-R 10 -, - CO} -O-R 11 -, - CO-NR 12
Represents -R < ₁₃ >-. Definition of R ₇ to R ₁₃ are the same as in claim 2.

(7) It contains a low molecular weight acid-decomposable dissolution inhibiting compound having a molecular weight of 3,000 or less, which has a group decomposable by the action of an acid and whose solubility in an alkaline developer is increased by the action of an acid. 7. The positive photosensitive composition as described in any one of the above items 1 to 6, wherein

(8) The positive photosensitive composition as described in any one of (1) to (7) above, wherein far-ultraviolet light having a wavelength of 250 nm or less is used as an exposure light source.

(9) The positive photosensitive 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.

[0032]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the compounds used in the present invention will be described in detail. (B) a group that decomposes by the action of an acid and a polycyclic alicyclic group represented by the above general formulas (I) to (III) to increase solubility in an alkaline developer (acid decomposition) In the present invention, the polycyclic alicyclic group of the general formulas (I) to (III) and the acid-decomposable group are bonded to any position in the base resin. be able to. That is, the above general formulas (I) to
(III) the polycyclic alicyclic group and the acid-decomposable group may be bonded to different repeating units in the base resin, may be bonded to the same repeating unit, or both of them. The case includes the case where the compound is present in the resin. Examples of the repeating structural unit having a group represented by the general formula (I) to the general formula (III) in the resin according to the present invention include those having a group represented by the general formula (I) to the general formula (III). Any one can be used as long as it has the general formula (I
It is a repeating structural unit represented by V) to (IV).

R, R _{7 to} R ₉ , R ₁₂ in the above general formula
The alkyl group preferably has a carbon atom such as a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group and an octyl group which may have a substituent. Examples of the number 1 to 8 are given. 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 As the acyl group for R, a formyl group, an acetyl group,
Those having 1 to 5 carbon atoms such as a propyl group are exemplified.

R _{1 to} R ₂ , R _{4 to} R ₆ , R _{14 to} R ₁₅ , R
_As the alkyl group of _{17 to} R ₂₁ , R _{23 to} R ₂₇ , and R _{29 to} R _31, a methyl group, an ethyl group, a propyl group, an n-butyl group, and a sec-butyl which may have a substituent are preferable. Examples thereof include those having 1 to 4 carbon atoms such as a group. As the haloalkyl group, preferably a fluorine atom, a chlorine atom, an alkyl group having 1 to 4 carbon atoms substituted by a bromine atom, for example, a fluoromethyl group, a chloromethyl group, a bromomethyl group,
Examples thereof include a fluoroethyl group, a chloroethyl group, and a bromoethyl group.

The alkylene group for X _{1 to} X ₁₂ is preferably an alkylene group having 1 to 8 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group and an octylene group which may have a substituent. 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. The alkylene group, alkenylene group, and cycloalkylene group represented by R _{10 to} R ₁₁ , R ₁₃ , and X include the groups described above which may have an ether group, an ester group, an amide group, a urethane group, or a ureido group. Can be R ₇
And B represent 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 is represented by the general formula (V)
It may be contained in any of the repeating structural units represented by (XVI), or may be contained in a plurality of these positions. 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 removal of a carbon cation by the action of an acid. Preferred are groups represented by the following formulas (XVII) to (XVIII). Thereby, the stability over time becomes excellent.

[0036]

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Where R₃₂~ R₃₄Are the same
May have a hydrogen atom or a substituent,
Alkyl, cycloalkyl, or alk
Represents a nyl group. Provided that R of the formula (XVII)₃₂~ R₃₄Of which,
At least one is a group other than a hydrogen atom. R₃₅Is a substituent
An alkyl group or a cycloalkyl group which may have
Represents an alkenyl group. Further, R of the formula (XVII)₃₂~ R₃₄of
And R of the formula (XVIII)₃₂~ R₃₃, R₃₅Within
Two to three carbon atoms or heteroatoms
It may form a ring structure consisting of: Z1 and Z2 are the same
May be different, and oxygen or sulfur atoms
You. Where alkyl, cycloalkyl, alkenyl
As the group, R, R₇~ R₉, R₁₂And
Similar ones are preferred. In addition, each substituent described in detail above
As the further substituent, preferably a hydroxyl group, a halogen atom
Atom (fluorine, chlorine, bromine, iodine), nitro group,
Ano group, amide group, sulfonamide group, R₁~ R_Two, R
_Four~ R₆, R₁₄~ R_Fifteen, R₁₇~ R_{twenty one}, R _{twenty three}~ R₂₇, R₂₉
~ R₃₁Alkyl group, methoxy group, ethoxy group, hydro
Xyethoxy, propoxy, hydroxypropoxy
Group, alkoxy group such as butoxy group, methoxycarbonyl
, Alkoxycarbonyl groups such as ethoxycarbonyl group
Acyl such as a group, formyl group, acetyl group, benzoyl group
Acyloxy such as a group, acetoxy group and butyryloxy group
And carboxy groups.

The polycyclic alicyclic group represented by P in the general formulas (VIII) to (X) is preferably a bicyclo or tricyclo having 5 or more carbon atoms which may have a substituent. Alicyclic groups such as tetracyclo, more preferably 6 to 30 carbon atoms which may have a substituent, and further preferably 7 to 25 carbon atoms which may have a substituent; Represents an alicyclic group of 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, and the above R _{1 to} R ₂ , R _{4 to} R ₆ , R ₁₄ to
R ₁₅ , R _{17 to} R ₂₁ , R _{23 to} R ₂₇ , and alkoxy groups such as the alkyl group, methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group and butoxy group described for R _{29 to} R _31. And alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group; acyl groups such as formyl group, acetyl group and benzoyl group; acyloxy groups such as acetoxy group and butyryloxy group; and carboxy group.

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

[0040]

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[0041]

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The repeating structural unit having an alicyclic group of the above general formulas (I) to (IV) in the resin according to the present invention (preferably the repeating structural unit represented by the general formulas (V) to (VII)) Is adjusted by the balance of adhesion to the substrate, alkali developability, dry etching resistance, etc., but is preferably contained in an amount of 10 mol% or more based on all repeating units. More preferably 15 to 50 mol%,
More preferably, it is used in the range of 20 to 45 mol%. The total content of the repeating structural unit having an alicyclic group, which is a combination of the general formulas (VIII) to (X), is preferably at least 40 mol%, more preferably at least 50 mol%, and still more preferably at least 50 mol%. It is used in the range of 90 mol%.

The content of the above-mentioned repeating structural unit having an acid-decomposable group (preferably the repeating structural units represented by formulas (XI) to (XIII)) in the resin according to the present invention depends on the alkali developability and the substrate. It is adjusted by the performance such as adhesion, but preferably 5 to 60 for all the repeating units.
Mol%, more preferably in the range of 10 to 50 mol%, and even more preferably 15 to 40 mol%. Here, the content of the acid-decomposable group-containing repeating structural unit is determined by the amount of all acids in the resin included in the repeating structural units represented by the general formulas (V) to (X) and (XIV) to (XVI). This is the amount of the repeating structural unit containing a decomposable group.

Further, in the resin according to the present invention, the carboxyl group may be contained in any of the repeating structural units represented by the general formulas (V) to (XVI). It may be included in a plurality of places. The content of the repeating structural unit having a carboxyl group (preferably, the repeating structural unit represented by any of formulas (XIV) to (XVI)) is adjusted depending on performance such as alkali developability, substrate adhesion, and sensitivity. However, it is preferably used in the range of 0 to 50 mol%, more preferably 0 to 40 mol%, and still more preferably 0 to 20 mol%, based on all repeating units. Here, the content of the carboxyl group-containing repeating structural unit is the amount of all the carboxyl group-containing repeating structural units in the resin included in the repeating structural units represented by the general formulas (V) to (XIII).

Specific examples (a1) to (a31) of the repeating structural units represented by formulas (V) to (VII),
Specific examples of repeating structural units represented by I) to (X) (d
1) to (d42), specific examples (b1) to (b30) of the repeating structural units represented by general formulas (XI) to (XIII), and general formula (XI
Specific examples of repeating structural units represented by V) to (XVI) (c1)
To (c18), but the present invention is not limited thereto.

[0046]

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[0047]

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[0048]

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[0049]

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[0051]

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[0052]

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[0053]

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[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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[0060]

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[0061]

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[0062]

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[0063]

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[0064]

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The resin of the component (B) having the repeating structural unit according to the present invention will be further described. (B) In order to improve the performance of the resin of the component,
Further, other polymerizable monomers may be copolymerized within a range that does not significantly impair the permeability of less than m and the dry etching resistance. 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 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, for example, styrene, alkyl styrene (for example, 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), 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.

The repeating structural units having the groups represented by the general formulas (I) to (IV) (preferably the repeating structural units of the general formulas (V) to (VII)) and the general formulas (I) to (IV) Repeating structural units having different general formulas (VIII) to (X) and repeating structural units having an acid-decomposable group (preferably, general formulas (XI) to (X))
(XIII), if necessary, a repeating structural unit having a carboxyl group (preferably a repeating structural unit represented by any one of formulas (VIV) to (XVI)) or other polymerizable monomer. Component (B) of the present invention
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 molecular weight of the resin as the component (B) according to the present invention is 2,000 in weight average (Mw: polystyrene standard).
As mentioned above, it is preferably in the range of 3,000 to 1,000,000, more preferably in the range of 5,000 to 200,000, and still more preferably in the range of 20,000 to 100,000. In this case, developability etc. decrease,
The balance is adjusted to a preferable range by these balances. Further, the degree of dispersion (Mw / Mn) is preferably from 1.0 to 5.
0, more preferably 1.0 to 3.0, and the smaller the
Heat resistance and image performance (pattern profile, defocus latitude, etc.) are improved. In the present invention, the amount of the resin added in the photosensitive composition is 50 to 99.7% by weight, preferably 70 to 99% by weight, based on the total solid content.

[Photoacid Generator] The photoacid generator 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 to generate an acid upon being decomposed by irradiation with actinic rays or radiation,
Known light (400 to 200 n) used for a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization, a photodecolorant for dyes, a photochromic agent, or a micro resist.
m ultraviolet rays, far ultraviolet rays, particularly preferably g-rays, h-rays,
Compounds that generate an acid by i-ray, KrF excimer laser light), ArF excimer laser light, electron beam, X-ray, molecular beam or ion beam, and mixtures thereof can be appropriately selected and used.

Further, other compounds which generate an acid upon irradiation with actinic rays or radiation used in the present invention 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 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 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 particularly effectively used will be 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).

[0078]

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In the formula, R ²⁰¹ is a substituted or unsubstituted aryl group or alkenyl group, and R ²⁰² is a substituted or unsubstituted aryl group, alkenyl group, alkyl group, —C (Y) ₃
Show Y represents a chlorine atom or a bromine atom. Specific examples include the following compounds, but the present invention is not limited thereto.

[0080]

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[0081]

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[0082]

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

[0084]

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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.

[0087] 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.

[0090]

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[0091]

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[0092]

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[0093]

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[0094]

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[0095]

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[0096]

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[0097]

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[0098]

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[0099]

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[0100]

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The above-mentioned 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).

[0103]

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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.

[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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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.

[Other Components Used in the Photosensitive Composition of 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, and a surfactant. Agents, photosensitizers, organic basic compounds, compounds that promote 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 general formulas (XVII) and (XVIII). In particular, Proceeding of SPIE, 2724, 355 (1
Alicyclic or aliphatic compounds such as the cholic acid derivatives described in 996) are preferred. In the present invention, when an acid-decomposable dissolution inhibiting compound is used, its addition amount is 3 to 50% by weight based on the total weight of the photosensitive composition (excluding the solvent).
, Preferably 5 to 40% by weight, more preferably 1 to 40% by weight.
It is in the range of 0 to 35% by weight.

Examples of the compound capable of accelerating dissolution in a developer usable in the present invention include 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 the compound has a carboxy group, an alicyclic or aliphatic compound is preferable for the same reason as described above. The preferable addition amount of these dissolution promoting compounds is 2 to 50% by weight, more preferably 5 to 30% by weight, based on the resin of the present invention. An addition amount exceeding 50% by weight is not preferable because new development defects such as development residue deterioration and pattern deformation during development occur.

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).

[0117]

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

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 for 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.

Examples of the developer for the photosensitive composition of the present invention include:
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.

[0126]

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 Raw Material Monomer of Structural Example (a1))] 413.7 g (0.36 mol) of LiAlH was dispersed in 300 ml of dehydrated THF.
A solution of 5 g (0.060 mol) of 200 ml of dehydrated THF was added over 1 hour at room temperature with stirring. Thereafter, the reaction was continued at room temperature for 5 hours. Add 10 ion-exchanged water to the reaction mixture.
After treating the excess LiAlH4 by adding a little at a time, the reaction mixture was poured into 2 L of ion-exchanged water with stirring. The precipitated solid was separated by filtration, washed sufficiently with water, and dried at 40 ° C. under reduced pressure. 22.4 g of a white powder was obtained.
The powder was confirmed to be a compound having the following structure (A) by MR measurement. Compound (A) 19.7 g (0.050
Mol), 9.2 g (0.060 mol) of methacrylic anhydride
Was dissolved in 170 ml of THF. 7.3 g (0.060 mol) of N, N-dimethylaminopyridine was added to this solution.
A 30 ml solution of MF was added with stirring at room temperature. The mixture was further heated under reflux for 5 hours while stirring. After cooling, the reaction solution was poured into 2 L of ion-exchanged water with vigorous stirring, and extracted with 300 ml of ethyl acetate. The ethyl acetate solution was washed with water, dried over magnesium sulfate, and concentrated under reduced pressure. Purified by column chromatography (filler: silica gel, eluent: hexane / ethyl acetate = 1/2) to obtain a white powder 1
4.8 g were obtained. By NMR measurement, it was confirmed that this powder was the raw material monomer of Structural Example (a1) of the present invention.

[0128]

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[Synthesis Example 2 (Synthesis of Raw Material Monomer of Structural Example (a2))] In place of cholic acid of Synthesis Example 1, 23.6 g (0.060 mol) of deoxycholic acid was used. In the same manner as in Example 1, 15.1 g of a white powder was obtained. N
By MR measurement, it was confirmed that this powder was the raw material monomer of Structural Example (a2) of the present invention.

[Synthesis Example 3 (Synthesis of Raw Material Monomer of Structural Example (a3))] In place of cholic acid of Synthesis Example 1, 23.6 g (0.060 mol) of chemodeoxycholic acid was used. 13.7 g of a white powder was obtained in the same manner as in Example 1. According to NMR measurement, this powder was found to have a structural example (a
It was confirmed to be the starting monomer of 3).

[Synthesis Example 4 (Synthesis of Starting Monomer of Structural Example (a5))] Synthesis Example 1 In place of cholic acid, 22.6 g (0.060 mol) of lysocholic acid was used. Similarly, 14.3 g of a white powder was obtained. By NMR measurement, it was confirmed that this powder was the raw material monomer of Structural Example (a5) of the present invention.

[Synthesis Example 5 (Synthesis of Starting Monomer of Structural Example (a7))] 19.7 g (0.050 mol) of the above compound (A) and 7.8 g of 2-isocyanatoethyl methacrylate
(0.050 mol) in 200 ml of dioxane,
After adding 0.1 g of dibutyltin dilaurate as a catalyst, the mixture was heated and stirred at 90 ° C. for 5 hours. After cooling down,
The reaction solution was poured into 2 L of ion-exchanged water with vigorous stirring to precipitate a viscous solid. The precipitated viscous solid was separated by decantation, washed with water, and then purified by column chromatography (filler: silica gel, eluent: ethyl acetate) to obtain 20.7 g of a white powder. By NMR measurement, it was confirmed that this powder was the raw material monomer of Structural Example (a7) of the present invention.

[Synthesis Example 6 (Synthesis of Starting Monomer of Structural Example (a15))] 5.9 g (0.060 mol) of maleic anhydride was dissolved in 200 ml of THF, and 14.2 g of pyridine was obtained.
Was added, 19.7 g (0.050 mol) of the above compound (A) was added, and the mixture was heated under reflux for 5 hours. After cooling, the reaction solution was poured into 2 L of ion-exchanged water with vigorous stirring to precipitate a viscous solid. The precipitated viscous solid was separated by decantation, washed with water, and then subjected to column chromatography (filler: silica gel, eluent: hexane / ethyl acetate = 1/1).
Purification was performed in 2) to obtain 15.8 g of a white powder. By NMR measurement, it was confirmed that this powder was the raw material monomer of Structural Example (a15) of the present invention.

[Synthesis Example 7 (Synthesis of Raw Material Monomer of Structural Example (b7))] 15.4 g (0.10 mol) of methacrylic anhydride, 8.6 g of 3-hydroxy-3-methylbutenol
(0.10 mol) was dissolved in 200 ml of THF. 12.3 g of N, N-dimethylaminopyridine was added to this solution.
(0.10 mol) of DMF (50 ml) was added with stirring at room temperature. The mixture was further heated under reflux for 5 hours while stirring. After cooling, the reaction solution was poured into 3 L of ion-exchanged water with vigorous stirring, and extracted with 300 ml of ethyl acetate. The ethyl acetate solution was washed with water, dried over magnesium sulfate, and concentrated under reduced pressure. Purified by vacuum distillation, 11.4 g of colorless liquid
I got By NMR measurement, it was confirmed that this liquid was the raw material monomer of Structural Example (b7) of the present invention.

[Synthesis Example 8 (Synthesis of Starting Monomer of Structural Example (b15))] 17.2 g (0.20 mol) of methacrylic acid and 25.2 g (0.30 mol) of dihydropyran were added to T
It was dissolved in 200 ml of HF. This solution was used as a catalyst in 2-
Add 0.1 g of ethylhexyl phosphate and add 50 g
The mixture was heated and stirred at 8 ° C. for 8 hours. After neutralizing the catalyst with triethylamine, the mixture was purified by distillation under reduced pressure to give a colorless liquid.
5 g were obtained. By NMR measurement, it was confirmed that this liquid was the raw material monomer of Structural Example (b15) of the present invention.

[Synthesis Example 9 (Synthesis of Starting Monomer of Structural Example (b18))] In place of dihydropyran of Synthesis Example 8, 21.6 (0.30 mol) of ethyl vinyl ether was used. 24.5 g of a colorless liquid in the same manner as
I got By NMR measurement, it was confirmed that this liquid was the starting monomer of the structural example (b18) of the present invention.

[Synthesis Example 10 (Synthesis of Raw Material Monomer of Structural Example (b20))] 17.2 g (0.20 mol) of methacrylic acid and 24.9 g of 2-methoxyethoxymethyl chloride
(0.20 mol) was dissolved in 200 ml of DMAc. 20.3 g of triethylamine was added, and the mixture was heated and stirred at 90 ° C. for 7 hours. After standing to cool, the reaction solution was mixed with
The mixture was charged with vigorous stirring and extracted with 300 ml of ethyl acetate. The ethyl acetate solution was washed with water, dried over magnesium sulfate, and concentrated under reduced pressure. Purification by column chromatography (filler: silica gel, eluent: hexane / ethyl acetate = 3/1) gave 13.4 g of a colorless liquid. According to NMR measurement, this liquid was found to be a structural example (b2
It was confirmed to be the starting monomer of 0).

[Synthesis Example 11 (Synthesis of Resin Consisting of Structural Example (a1) / (d28))] Structural Example (a7) / (d28) of the Present Invention
13.9 g (0.030 mol) /
32.2 g (0.070 mol) of 1-methoxy-2-propanol / N, N-dimethylacetamide (1/1)
Dissolved in 160 ml, and at 70 ° C. under a nitrogen stream and stirring, polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd .; trade name V-6)
5) 100 mg was added. Two hours and four hours after the start of the reaction, 100 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 a structural example (a1) / (d28)
43.7 g of a resin (B) composed of (30/70) was obtained. G
When the molecular weight was measured by PC, it was 17.8 × 103 in weight average (Mw: converted to polystyrene).

[0139]

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[Synthesis Example 12 (Synthesis of resin (p-1) of the present invention by methoxymethyl protection of resin (B))] 18.5 g of the resin (B) obtained in the above synthesis example was dissolved in 200 ml of DMF. 1.3 g of methoxymethyl chloride (0.0 g
16 mol) and then 2.2 g of triethylamine.
(0.022 mol), and the mixture was stirred at room temperature for 5 hours.
Thereafter, the mixture was poured into 2 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 18.7 g of the resin (p-1) of the present invention having the following structure. When the molecular weight was measured by GPC, it was 18.5 × 10 ³ in weight average (Mw: in terms of polystyrene).

[0141]

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Synthesis Example 13 (Synthesis of resin (p-2) of the present invention by 1-ethoxyethyl protection of resin (B)) 18.5 g of resin (B) obtained in the above synthesis example was treated with dioxane 200
of ethyl vinyl ether.
(0.017 mol) and 0.36 g (0.0017 mol) of mono-2-ethylhexyl phosphate were added, and the mixture was stirred at room temperature for 20 hours. Thereafter, the mixture was poured into 2 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 19.0 g of the resin (p-2) of the present invention having the following structure. The molecular weight measured by GPC was 18.9 × 10 ³ in weight average (Mw: in terms of polystyrene).

[0143]

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[Synthesis Example 14 (Synthesis of Resin (p-3) of the Invention by Protecting Resin (B) with t-butyl)] 18.5 g of the resin (B) obtained in the above Synthesis Example was replaced with t-butanol. 200ml
, 4.0 g of pyridine was added thereto, and 2.0 g (0.025 mol) of acetyl chloride was further added thereto, followed by stirring at room temperature for 7 hours. Thereafter, the mixture was poured into 2 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 18.2 g of the resin (p-3) of the present invention having the following structure.
When the molecular weight was measured by GPC, the weight average (Mw:
It was 18.4 × 10 ³ in terms of polystyrene.

[0145]

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[Synthesis Example 15 (Structural Example (a1) / (b1) /
(Synthesis of Resin (p-4) of the Present Invention Consisting of (d28))] 18.5 g (0.040 mol) / 4 of each of the starting monomers of structural example (a1) / (b1) / (d28) of the present invention 0.3 g (0.03
0 mol) /13.8 g (0.030 mol) was dissolved in 160 ml of 1-methoxy-2-propanol / N, N-dimethylacetamide (1/1).
At 70 ° C., 100 mg of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) (V-65, manufactured by Wako Pure Chemical Industries, Ltd.) was added. Two hours and four hours after the start of the reaction, 100 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 a structural example (a1) /
34.7 g of the resin (p-4) of the present invention comprising (b1) / (d28) (40/30/30) was obtained. When the molecular weight was measured by GPC, it was 24.6 × 10 ³ in weight average (Mw: in terms of polystyrene).

[Synthesis Examples 16 to 23 (Synthesis of the Resin of the Present Invention Having the Structural Unit)] In the same manner as in Synthesis Examples 11 to 15, using the starting monomers of the repeating structural units shown in Table 1 below, Was synthesized. Table 1 shows the structural units used, the molar ratio of the raw material monomers charged therein, and the weight average molecular weight of the produced resin.

[0148]

[Table 1]

Example 1 Measurement of Optical Density 1.0 g of the resin of the present invention obtained in the above synthesis example and 0.03 g of triphenylsulfonium triflate salt were mixed with 4.5 g of propylene glycol monomethyl ether acetate.
And filtered through a 0.2 μm Teflon filter. The composition was uniformly applied on a quartz glass substrate by a spin coater, and dried by heating on a hot plate at 100 ° C. for 90 seconds to form a 1 μm resist film. When the optical absorption of the obtained film was measured with an ultraviolet spectrophotometer,
The optical density at 93 nm was as shown in Table 2.

[0150]

[Table 2]

From the results shown in Table 2, the measured optical density of the resin of the present invention was smaller than that of the poly (hydroxystyrene) (weight average molecular weight 15.1 × 10 ⁻³ ) of the comparative example, and was 193n.
It turns out that it has sufficient transmittance | permeability with respect to m light.

Example 2 Measurement of Dry Etching Resistance 1.0 g of the resin of the present invention obtained in the above Synthesis Example was dissolved in 4.5 g of propylene glycol monomethyl ether acetate, and the solution was filtered through a 0.2 μm Teflon filter. . The composition was uniformly applied on a silicon substrate by a spin coater, and dried by heating on a hot plate at 100 ° C. for 90 seconds to form a 0.7 μm resist film. The resulting film using a ULVAC Ltd. reactive ion etching apparatus (CSE-1110) _{to, CF 4 / O 2 (8} /
When the etching rate for the gas of 2) was measured,
As shown in Table 3 (etching conditions: Power
= 500W, Pressure = 4.6Pa, Gas
(Flow Rate = 10 sccm).

[0153]

[Table 3]

From the results in Table 3, it can be seen that the etching rate of the resin of the present invention is smaller than the value of poly (methyl methacrylate) (weight average molecular weight: 35.5 × 10 ⁻³ ) of the comparative example, and that the resin of the present invention has sufficient dry etching resistance. I understand.

Example 3 Evaluation of Substrate Adhesion 4.5 g of propylene glycol monomethyl ether acetate was prepared by adding 1.0 g of the resin of the present invention obtained in the above synthesis example and 0.03 g of triphenylsulfonium triflate salt.
And filtered through a 0.2 μm Teflon filter. Apply uniformly on a silicon substrate that has been treated with hexamethyldisilazane by a spin coater,
Heat and dry on a hot plate for 0 seconds, 0.4 μm
Was formed. As a comparative example, a resist film of a comparative example was formed in the same manner as above except that the resin of the following comparative example was used instead of the resin of the present invention. These resist films were subjected to pattern exposure using a KrF excimer laser stepper (NA = 0.42; 248 nm), and heated on a hot plate at 110 ° C. for 60 seconds immediately after exposure. The film was further immersed and developed in a 2.38% aqueous solution of tetramethylammonium hydroxide at 23 ° C. for 60 seconds, rinsed with pure water for 30 seconds, and dried. Table 4 shows the results of observing the obtained pattern with a scanning electron microscope and examining the state of the pattern.

[0156]

[Table 4]

[0157]

Embedded image

From the results shown in Table 4, it can be seen that the resist using the resin of the present invention did not collapse the pattern as seen in the resin of the comparative example, did not over-develop, and dissolved only the exposed portion to the bottom and did not The exposed portion was not dissolved, and a good rectangular pattern shape was obtained.

Example 4 Image Evaluation-1 Pattern Shape, Resolution and Sensitivity of Resist Film-1 The 0.4 μm resist film obtained in Example 3 was
KrF excimer laser stepper (NA = 0.4
2; 248 nm) and heated on a hot plate at 110 ° C. for 60 seconds immediately after exposure.
The film was further immersed and developed in a 2.38% aqueous solution of tetramethylammonium hydroxide at 23 ° C. for 60 seconds, rinsed with pure water for 30 seconds, and dried. As a result, the obtained pattern shape was observed with a scanning electron microscope, and a rectangular shape was evaluated as good. The sensitivity was defined as an exposure amount that reproduced a 0.35 μm mask pattern. Resolution is 0.35
It was defined as the limit resolution at the exposure dose for reproducing a μm mask pattern. Table 5 shows the results of the pattern profile, sensitivity, and resolution.

[0160]

[Table 5]

From the results shown in Table 5, it can be seen that the resist using the resin of the present invention has high sensitivity, good resolution, and good pattern shape, reflecting the high transmittance. In addition, good development is performed with a 2.38% aqueous solution of tetramethylammonium hydroxide, which is a standard developer, and a good pattern shape and excellent sensitivity and resolution can be obtained without causing a decrease in film thickness or a decrease in adhesion. You can see that.

Example 5 Image Evaluation-2 Sensitivity, Resolution and Pattern Shape of Resist Film-2 A pattern was drawn on a quartz plate on a 0.4 μm resist film obtained in Example 3 with chromium on a quartz plate. Attach the mask, A
Irradiation with rF excimer laser light (193 nm) was performed.
Immediately after exposure, heating was performed on a hot plate at 110 ° C. for 60 seconds. Further, the film was immersed in a 2.38% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 60 seconds,
After rinsing with pure water for 0 second, it was dried. The obtained pattern shape was observed with a scanning electron microscope, and a rectangular shape was determined as good. The sensitivity was defined as an exposure amount that reproduced a 0.35 μm mask pattern. Resolution is 0.35μ
m is defined as the limit resolution at the exposure dose for reproducing the mask pattern of m. These pattern profiles,
Table 6 shows the results of the sensitivity and resolution. A good positive pattern having the sensitivity and resolution shown in Table 6 and having only the exposed portions of the resist film dissolved and removed was formed.

[0163]

[Table 6]

From the results shown in Table 6, it can be seen that the resist using the resin of the present invention exhibited good sensitivity and resolution to ArF excimer laser light and formed a good positive pattern.

[0165]

As is apparent from the above description, the resist using the resin of the present invention has a high transmittance to far ultraviolet light of 220 nm or less, a dry etching resistance, and a resistance to the Si substrate. Good adhesion. Also 250nm
Hereinafter, when far ultraviolet light (especially ArF excimer laser light) of 220 nm or less is used as an exposure light source, high sensitivity,
It shows high resolution and a good pattern profile, and can be effectively used for forming a fine pattern necessary for manufacturing a semiconductor device.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03F 7/033 G03F 7/033 H01L 21/027 C08F 20/10 // C08F 20/10 20/54 20/54 22/40 22 / 40 28/02 28/02 C08L 27/00 C08L 27/00 29/10 29/10 33/14 33/14 33/24 33/24 35/00 35/00 41/00 41/00 H01L 21/30 502R

Claims (9)

[Claims] (1) 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):
At least one of the polycyclic alicyclic groups represented by (II), (III) or (IV) and a group which decomposes under the action of an acid to increase solubility in an alkaline developer. A positive photosensitive composition characterized by containing a resin having the same. Embedded image In the general formulas (I) to (IV), R represents a hydrogen atom, a linear or branched alkyl group, cycloalkyl group, alkenyl group, or acyl group which may have a substituent. X is a single bond, or an ether group, an ester group, an amide group,
It represents a divalent alkylene group, alkenylene group or cycloalkylene group which may have a urethane group or a ureido group. M
e represents a methyl group. 2. The resin of the component (B) is represented by the general formula (V):
Having a polycyclic alicyclic group represented by (VI) or (VII)
Action of at least one of the repeating structural units
To increase solubility in alkaline developer
2. The resin according to claim 1, wherein
The positive photosensitive composition as described in the above. Embedded imageIn the general formulas (V) to (VII), R₁~ R_Two, R_Four~ R₆Is
Same or different, hydrogen atom, halogen atom
, A cyano group, an alkyl group or a haloalkyl group.
R_ThreeIs a cyano group, -CO-OR₇, -CO-NR₈R₉
Represents X₁~ X _ThreeMay be the same or different.
Divalent alkyl which may be a bond or may have a substituent
A len group, alkenylene group, cycloalkylene group, or
Is -O-, -SO_Two-, -O-CO-R_Ten-, -CO-
OR₁₁-, -CO-NR₁₂-R₁₃Represents-. R₇Is water
A hydrogen atom, an optionally substituted alkyl group,
It is separated by the action of an alkyl group, alkenyl group, or acid.
Represents a group to be understood. R₈~ R₉, R₁₂Are hydrogen atoms,
Alkyl group optionally having a substituent, cycloalkyl
Represents an alkenyl group. Also R₈, R₉Is linked to a ring
May be formed. R_Ten~ R₁₁, R₁₃Is a single bond or d
-Tel group, ester group, amide group, urethane group, urea
Divalent alkylene group, alkenylene which may have
A cycloalkylene group. Y is as defined in claim 1
The polycyclic alicyclic groups represented by the general formulas (I) to (IV)
You. 3. The resin according to claim 2, wherein the resin (B) is a resin.
A repeating unit represented by the general formula (V), (VI) or (VII)
Decomposed by the action of acid with at least one of the structural units
Group that increases solubility in alkaline developers
Different from the general formulas (V), (VI) and (VII)
The following general formulas (VIII) and (IX) having a polycyclic alicyclic group
Or at least one of the repeating structural units represented by (X)
The resin according to claim 1, further comprising:
Is a positive photosensitive composition according to item 2. Embedded imageIn the general formulas (VIII) to (X), R₁₄~ R_Fifteen, R₁₇~ R₁₉Is
Same or different, hydrogen atom, halogen atom
, A cyano group, an alkyl group or a haloalkyl group.
R₁₆Is a cyano group, -CO-OR₇, -CO-NR₈R₉
Represents X_Four~ X ₆May be the same or different.
Divalent alkyl which may be a bond or may have a substituent
A len group, alkenylene group, cycloalkylene group, or
Is -O-, -SO_Two-, -O-CO-R_Ten-, -CO-
OR₁₁-, -CO-NR₁₂-R₁₃Represents-. R₇~ R
₁₃Is the same as in claim 2. P is a general formula
It represents a polycyclic alicyclic group different from (I) to (IV). 4. The resin of the component (B) is represented by the general formula (V):
At least one of the repeating structural units represented by (VI) or (VII), and at least one of the repeating structural units represented by general formulas (VIII), (IX) or (X); A resin having at least one of the repeating structural units represented by (XI), (XII) or (XIII), and decomposing by the action of an acid to increase solubility in an alkaline developer. The positive photosensitive composition according to claim 1, wherein: Embedded image In the general formulas (XI) to (XIII), R _{20 to} R ₂₁ and R _{23 to} R ₂₅ may be the same or different and represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group or a haloalkyl group;
R ₂₂ represents a cyano group, a carboxyl group, —CO—OR ₇ ,
Represents CO-NR ₈ R ₉ . X _{7 to} X ₉ may be the same or different, and may be a single bond or a divalent alkylene group, alkenylene group, cycloalkylene group which may have a substituent, or —O—, —SO ₂ -, -O-CO-
_{R 10 -, - CO-O} -R 11 -, - CO-NR 12 -R 13 -
Represents Definition of R ₇ to R ₁₃ are the same as in claim 2. B represents a group which is decomposed by the action of an acid to increase solubility in an alkaline developer. 5. The positive photosensitive composition according to claim 1, wherein the resin as the component (B) further has a carboxyl group. 6. The resin as the component (B) further comprises at least one of the repeating structural units having a carboxyl group and represented by the following general formula (XIV), (XV) or (XVI). The positive photosensitive composition according to claim 5, wherein Embedded image In the general formulas (XIV) to (XVI), R _{26 to} R ₂₇ and R _{29 to} R ₃₁ may be the same or different and include a hydrogen atom, a halogen atom,
A cyano group, an alkyl group or a haloalkyl group, R ₂₈
Cyano group, a carboxyl group, -CO-OR _7, -CO
It represents a -NR ₈ R _9. X _{10 to} X ₁₂ may be the same or different and are a single bond or a divalent alkylene group, alkenylene group, cycloalkylene group which may have a substituent, or —O—, —SO ₂ -, - O-CO-R 10
—, —CO—O—R ₁₁ —, and —CO—NR ₁₂ —R ₁₃ —. Definition of R ₇ to R ₁₃ are the same as in claim 2. 7. A group having a group which can be decomposed by the action of an acid, and the solubility in an alkali developer is increased by the action of an acid.
The positive photosensitive composition according to any one of claims 1 to 6, further comprising a low-molecular acid-decomposable dissolution inhibiting compound having a molecular weight of 3,000 or less. 8. The positive photosensitive composition according to claim 1, wherein far ultraviolet light having a wavelength of 250 nm or less is used as an exposure light source. 9. The positive photosensitive composition according to claim 1, wherein far-ultraviolet light having a wavelength of 220 nm or less is used as an exposure light source.