JP2000267287A - Positive photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a pattern profile with high sensitivity and high resolution when ArF excimer laser light is used as the exposure light source by incorporating a compd. which produces an acid by irradiation of active rays or irradiation and a specified resin having a group which decomposes by the effect of an acid to increase the solubility in an alkali developer. SOLUTION: This compsn. contains (A) a compd. which produces an acid by irradiation of active rays or radiation and (B) a resin having a group which decomposes by the effect of an acid to increase the solubility in an alkali developer. The resin contains at least one structure expressed by formulae I, II and III. In formulae I to III, each of R1 to R5 may be same or different from others and is a hydrogen atom, straight-chain, branched or cyclic alkyl group or the like which may have substituents, X is a single bond or divalent coupling group, Y is an oxygen atom, sulfur atom, -NH-, -N(OH)- or -N(alkyl)-, and (n) is an integer 1 to 3.

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

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

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

Since these systems mainly use a resin having a low absorption in the 248 nm region and having a poly (hydroxystyrene) basic skeleton as a main component, a high sensitivity is obtained when a KrF excimer laser is used as an exposure light source. A high-resolution and good pattern can be formed, and it can be a good system as compared with the conventional naphthoquinonediazide / novolak resin system. However, even shorter wavelength light sources, such as ArF
When an excimer laser (193 nm) is used as an exposure light source, the compound having an aromatic group is essentially 193 nm.
The above-mentioned chemical amplification system was not sufficient because of the large absorption in the nm region. In addition, J. Vac. Sci. Technol., B9, 3357 (1991) describes the use of poly (meth) acrylate as a polymer having a small absorption in the wavelength region of 193 nm. However, there is a problem that the resistance to dry etching performed in the above 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). In recent years, the use of this polymer has been vigorously studied. More specifically,
-39665, 5-80515, 5-2652
No. 12, No. 5-297591, No. 5-346668
Nos. 6-289615, 6-324494, 7-49568, 7-185046, 7-19
Nos. 1463, 7-199467 and 7-23451
No. 1, No. 7-252324, No. 8-259626, and the like. However, these polymers do not always have sufficient dry etching resistance, and some of them require many steps for synthesis.

In addition, when an alicyclic group is introduced for imparting dry etching resistance, there is a problem that the adhesion to the substrate is reduced and the film is peeled off in the pattern after development. As a method for solving this problem, EP0856773 describes a resin containing a structural unit having a γ-butyrolactone structure. When this is used, the adhesion is improved, but the acid decomposability is low due to the use of the secondary carboxylic acid ester, so that the sensitivity is low and the resolution is not sufficient. In addition, the introduction of alicyclic groups increases the hydrophobicity of the resist film, thereby increasing the number of development defects.

[0011]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a positive photosensitive composition suitable for use with an exposure light source having a wavelength of 250 nm or less, particularly 220 nm or less. In particular, it is an object of the present invention to provide a positive photosensitive composition which gives good sensitivity, resolution, adhesion and a resist pattern when an exposure light source having a wavelength of 220 nm or less is used, and further exhibits sufficient dry etching resistance.

[0012]

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

[0013]

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In the formulas (I) to (III), R ₁ and R ₂ are the same or different and each represent a hydrogen atom or a linear, branched or cyclic alkyl group which may have a substituent. ₁ and R ₂ may combine to form a monocyclic or polycyclic ring. Further, the ring may have an oxygen atom, a sulfur atom, a nitrogen atom, a ketone, an ester, an imide, or an amide as a linking group. R
_{3 to} R ₅ are the same or different and each represent a hydrogen atom, an optionally substituted straight-chain, branched, or cyclic alkyl group or an alkoxy group, and two or all of R _{3 to} R ₅ May combine to form a monocyclic or polycyclic ring which may have an oxygen atom, a sulfur atom, a nitrogen atom, a ketone or an ester as a linking group. X represents a single bond or a divalent bonding group, and X may be bonded to either or both of R ₁ and R ₂ to form a monocyclic or polycyclic ring. Y is an oxygen atom, a sulfur atom, -NH-, -N (OH)-or -N (alkyl)
Represents-. n represents an integer of 1 to 3.

(2) (A) a compound which generates an acid upon irradiation with actinic rays or radiation, (B) a resin having a group which is decomposed by the action of an acid to increase the solubility in an alkaline developer, and C) a molecular weight of 3 having a group that is decomposed by the action of an acid and increases the solubility in an alkali developer
The resin (B) and / or the low molecular compound (C) has a structure represented by the general formula (I), (II) or (III) described in the above (1). A positive photosensitive composition comprising at least one. (3) (D) The resin having a group that decomposes under the action of an acid and increases the solubility in an alkali developer is selected from among the repeating structural units having the structure of the general formula (I), (II) or (III) The positive photosensitive composition according to the above (1) or (2), which is a resin containing at least one of the repeating units having a monocyclic or polycyclic alicyclic hydrocarbon moiety.

(4) The positive electrode according to any of (1) to (3) above, wherein the monocyclic or polycyclic alicyclic hydrocarbon moiety is an adamantane residue which may be substituted. -Type photosensitive composition. (5) (1) wherein the resin having a group which is decomposed by the action of an acid to increase solubility in an alkaline developer contains a structure represented by the general formula (a). The positive photosensitive composition according to any one of (1) to (4).

[0017]

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(Wherein, R _{1 to} R ₅ and n have the same meanings as in the general formula (I), and R ₁₅ represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group or a haloalkyl group.)

(6) (B) The resin having a group which is decomposed by the action of an acid to increase the solubility in an alkaline developer contains a structure represented by the general formula (b): The positive photosensitive composition according to any one of the above (1) to (5).

[0020]

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(Where R₁~ R_Five, N is the general formula (I)
Synonymous with R₁₅Is hydrogen, halogen, cyano
Represents a group, an alkyl group or a haloalkyl group. Note that R in the general formulas (a) and (b)₁₅For details, see General
R in formula (IV) ₁₅Has the same meaning as described above.

(7) (A) a compound capable of generating an acid upon irradiation with actinic rays or radiation; (C) a compound having a molecular weight of not more than 3000 having a group capable of decomposing by the action of an acid to increase the solubility in an alkaline developer. A molecular compound, and (E)
The low-molecular-weight compound (C) contains a resin that is insoluble in water and soluble in an alkali developing solution,
A positive photosensitive composition comprising at least one of the structures represented by (II) or (III). (8) (1) to (7), wherein R ₁ and R ₂ in the repeating structural unit having the structure of the general formula (I), (II) or (III) are substituents other than a hydrogen atom. The positive photosensitive composition according to any one of the above.

(9) (F) It is characterized by containing a fluorine-based and / or silicon-based surfactant.
The positive photosensitive composition according to any one of (7). (10) The positive photosensitive composition according to any one of (1) to (7), wherein far-ultraviolet light of 250 nm or less is used as an exposure light source. (11) The positive photosensitive composition according to any one of (1) to (7), wherein a far ultraviolet light having a wavelength of 220 nm or less is used as an exposure light source.

[0024]

BEST MODE FOR CARRYING OUT THE INVENTION (B) The above general formulas (I) to (I)
A resin having a structure represented by (III) and a group which is decomposed by the action of an acid to increase the solubility in an alkaline developer (also referred to as an acid-decomposable group): In the present invention, the resin represented by the general formula (I) ) To (III) can be bonded to any place in the base resin. That is, the groups represented by the general formulas (I) to (III) and the acid-decomposable group may be bonded to different repeating units in the base resin, or may be bonded to the same repeating unit. And the case where both cases coexist in the resin. Further, the case where the structure represented by the general formulas (I) to (III) contains an acid-decomposable group is also included.

The alkyl group of R ₁ , R ₂ and R _{3 to} R _{5 in} the above general formula (I), (II) or (III) may have a substituent, and may be a straight-chain, branched or cyclic alkyl group. Preferably an alkyl group having 1 to 12 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, a cyclopropyl group And a cyclopentyl group. R ₁ and R ₂ may combine to form a monocyclic or polycyclic ring, in which an oxygen atom, a sulfur atom, a nitrogen atom,
It may have a ketone, ester, imide, or amide as a linking group. As the ring structure, a ring forming a 5- to 8-membered ring or a polycyclic structure having two or more 5- to 8-membered rings,
Specific examples include a cyclohexane ring, a cyclopentane ring, a tetrahydropyran ring, a piperidine ring, a tetrahydropyrrole ring, a cyclohexanone ring, and a butyrolactone ring. The alkoxy group of R _{3 to} R ₅ preferably has 1 to 8 carbon atoms, for example, a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, a propoxy group, a hydroxypropoxy group, a butoxy group. Two or all of R _{3 to} R ₅ may combine to form a monocyclic or polycyclic ring, and the ring has an oxygen atom, a sulfur atom, a nitrogen atom, a ketone, or an ester as a linking group. You may. Examples of the ring structure include the same ring structures as described for R ₁ and R ₂ above. R _{1 to} R ₅ may have a substituent, and examples of the substituent include an alkyl group,
Examples thereof include an alkenyl group, an alkoxyl group, an acyloxy group, and a halogen.

X represents a single bond or a divalent linking group. 2
As the valent linking group, for example, an oxygen atom, a sulfur atom,-
NH— represents a divalent organic group or the like. Examples of the divalent organic group include a linear, branched, or cyclic alkylene group, alkenylene group, -COO- group, -CO- group, and-
SO ₂ — group, —SO ₂ NH— group, —CONH— group, —CO
NHSO ₂ -group, -N (alkyl group)-group (alkyl group preferably represents 1 to 8 carbon atoms, for example, methyl, ethyl, propyl, butyl, octyl), -COS
-Groups or linking groups containing two or more of these groups. In X, the alkylene group preferably has 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. . As the cyclic alkylene group, preferably may have a substituent,
5 carbon atoms such as cyclopentylene and cyclohexylene
To 8 items. Alkenylene groups include
Preferably an ethenylene group which may have a substituent,
Those having 2 to 6 carbon atoms such as a propenylene group and a butenylene group are exemplified.

Y is an oxygen atom, a sulfur atom, -N (OH)
-, -N (alkyl)-(The alkyl group preferably has 1 to 8 carbon atoms, for example, represents methyl, ethyl, propyl, butyl, octyl.) Among them, an oxygen atom and a sulfur atom are preferable. n represents an integer of 1 to 3.

In the resin according to the present invention, general formulas (I) to (I)
As the repeating structural unit having a group represented by the general formula (III), any repeating unit having a group represented by the general formulas (I) to (III) can be used. Preferred are repeating structural units represented by the following general formulas (IV) to (IV). Among them, a repeating structural unit represented by the general formula (IV) is preferable.

[0029]

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In the formulas (IV) to (VI), R ₁₅ , R ₁₆ , R ₁₈
R ₂₀ is the same or different and represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group or a haloalkyl group. R ₁₇ is a cyano group, —CO—OR ₂₇ or —CO—
Represents NR ₂₈ R ₂₉ . X _{1 to} X ₃ are the same or different and are each a single bond or may have a substituent; a divalent alkylene group, alkenylene group or cycloalkylene group, —CO—, —SO ₂ —, -O-CO-R ₃₀ -,
-CO-O-R ₃₁ -, or -CO-NR ₃₂ -R ₃₃ - represents a. R ₂₇ 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 solubility in an alkaline developer. R ₂₈ , R ₂₉ and R ₃₂ are the same or different and each represent a hydrogen atom, an alkyl group, a cycloalkyl group or an alkenyl group which may have a substituent. R ₂₈ and R ₂₉ may combine to form a ring. R
_{30 to} R ₃₁ and R ₃₃ are the same or different and represent a single bond or a divalent alkylene group, an alkenylene group or a cycloalkylene group;
A divalent group may be formed together with an ester group, an amide group, a urethane group or a ureide group. Y represents a structure represented by the above general formulas (I) to (III).

The alkyl group of R _{27 to} R ₂₉ and R ₃₂ includes:
Preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, which may have a substituent,
Examples thereof include those having 1 to 8 carbon atoms such as a hexyl group, a 2-ethylhexyl group and an octyl group. The cycloalkyl group preferably has 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group and a cyclohexyl group, which may have a substituent. The alkenyl group preferably may have a substituent,
Examples thereof include those having 2 to 6 carbon atoms such as vinyl group, propenyl group, allyl group, butenyl group, pentenyl group, hexenyl group and cyclohexenyl group.

The position of the bond between the linking group X and the ring structure in the structure represented by the general formula (I), (II) or (III) may be any position in the ring structure.

The alkyl group represented by R ₁₅ , R ₁₆ and R _{18 to} R ₂₀ is preferably a methyl group, an ethyl group, a propyl group, an n-butyl group or a sec-butyl group which may have a substituent. And those having 1 to 4 carbon atoms. 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, a fluoroethyl group, a chloroethyl group, a bromoethyl group and the like can be mentioned.

The alkylene group represented by X _{1 to} X ₃ 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. Individual ones. The alkenylene group preferably has 2 to 6 carbon atoms such as an ethenylene group, a propenylene group and a butenylene group which may have a substituent. As the cycloalkylene group, preferably may have a substituent,
5 carbon atoms such as cyclopentylene and cyclohexylene
To 8 items.

Examples of the alkylene group, alkenylene group and cycloalkylene group represented by R _{30 to} R ₃₁ and R ₃₃ include the same groups as those described above. , A urethane group and a ureido group together form a divalent group. As the ring and R ₂₈ and R ₂₉ form together with the bond to the nitrogen atom, preferably one to form a 5- to 8-membered ring, in particular pyrrolidine, piperidine, piperazine and the like.

R ₂₇ represents a group (acid-decomposable group) which is decomposed by the action of an acid to increase the solubility in an alkaline developer. Here, in the resin according to the present invention, the acid-decomposable group may be included in the structure of the group represented by the general formulas (I) to (III), or may be included in the general formulas (I) to (III). It may be contained in the repeating structural unit having the group shown (as R ₂₇ ), may be contained in another repeating structural unit, 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 elimination of a carbon cation by the action of an acid. Preferred are groups represented by the following formulas (XIII) and (XIV). Thereby, the stability over time becomes excellent.

[0037]

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Here, R _{47 to} R ₄₉ may be the same or different and each represents a hydrogen atom or an alkyl group, a cycloalkyl group or an alkenyl group which may have a substituent. However, among R _{47 to} R _{49 in} the formula (XIII),
At least one is a group other than a hydrogen atom. R ₅₀ represents an alkyl group, a cycloalkyl group or an alkenyl group which may have a substituent. Further, R _{47 to} R ₄₉ of the formula (XIII)
Or two of R _{47 to} R ₄₈ and R ₅₀ of the formula (XIV)
Two groups may combine to form a ring structure consisting of 3 to 8 carbon atoms or heteroatoms. Specific examples of such a ring include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a 1-cyclohexenyl group, a 2-tetrahydrofuranyl group, a 2-tetrahydropyranyl group, and the like. Z _{1 and} Z ₂ may be the same or different and represent an oxygen atom or a sulfur atom. Here, as the alkyl group, cycloalkyl group, and alkenyl group,
Preferred are the same as those described for R ₂₇ above.

Further, as the further substituent in each of the above-described substituents, preferably, a hydroxyl group, a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, an amide group, a sulfonamide group, R ₂₇ Alkyl group, methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group, alkoxy group such as butoxy group, methoxycarbonyl group, alkoxycarbonyl group such as ethoxycarbonyl group, formyl group, acetyl group,
Examples include an acyl group such as a benzoyl group, an acetoxy group, an acyloxy group such as a butyryloxy group, and a carboxy group.

In the resin according to the present invention, a repeating structural unit having an alicyclic group represented by any of the above formulas (I) to (III) (preferably a repeating structure represented by any of the formulas (IV) to (VI)) Unit) content, dry etching resistance,
The content is adjusted by the balance with alkali developability and the like, but is preferably 20 mol% or more, more preferably 30 to 80 mol%, and still more preferably 40 to 70 mol%, based on all repeating units. . The general formula (I
Specific examples of repeating structural units represented by V) to (VI) (a
1) to (a61), but the present invention is not limited thereto.

[0041]

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[0042]

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[0043]

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[0044]

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Among them, as the preferred structural unit of the present invention, those having the following structure linked by a tertiary ester group are excellent in acid decomposability, and are particularly preferable in terms of sensitivity.

[0046]

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(Wherein, R _{1 to} R ₅ , Y, n, and R ₁₅ have the same meanings as described above.)

Further, those having a structure of the above general formula (a) in which an ester linking group is bonded to a lactone have high hydrophilicity due to a synergistic effect of adjacent oxygen atoms, and have a high sensitivity, a good adhesion to a substrate, and a reduced development defect. It is preferred in that respect. Further, those having the structure of the above general formula (b) in which the ester linking group is bonded to the α-position of the lactone, the lactone is decomposed by the alkali developer to generate carboxylic acid, and the dissolution rate of the exposed part is increased. It is particularly preferable in terms of sensitivity, substrate adhesion, development defect reduction, and resolution.

(C) a molecular weight of 300 having a group which is decomposed by the action of an acid to increase the solubility in an alkaline developer
0 or less low molecular weight compound: When combined with an alkali-soluble resin, the acid-decomposable dissolution inhibiting compound (C) used in the present invention is a group represented by any of the general formulas (I) to (III). Is a low molecular weight compound having a molecular weight of 3,000 or less which may further contain an acid-decomposable group. When combined with the resin of the present invention, if it contains an acid-decomposable group, a molecular weight of 3, which may or may not contain a group represented by the general formula (I) to (III).
It is a low molecular compound of 000 or less. In particular, Proceeding of SPIE, 272 in order not to lower the transmittance below 220 nm.
Alicyclic or aliphatic compounds such as the cholic acid derivatives described in 4,355 (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 based on the solid content of the whole photosensitive composition.
, Preferably 5 to 40% by weight, more preferably 1 to 40% by weight.
It is in the range of 0 to 35% by weight. Specific examples of low molecular weight compounds having a molecular weight of 3000 or less having groups represented by the general formulas (I) to (III) and a group which is decomposed by the action of an acid to increase the solubility in an alkaline developer. Examples will be given, but the present invention is not limited to these.

[0050]

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(D) The resin having a group which is decomposed by the action of an acid and increases the solubility in an alkaline developer is a repeating structural unit having the structure of the above formula (I), (II) or (III). A resin containing at least one of the above and a repeating unit having a monocyclic or polycyclic alicyclic hydrocarbon moiety: a group which is decomposed by the action of an acid to increase the solubility in an alkaline developer in the present invention. Is a resin having at least one of the repeating structural units having the structure of the above general formula (I), (II) or (III) and a monocyclic or polycyclic alicyclic hydrocarbon moiety for improving dry etching resistance. The object of the present invention can be achieved even with a resin containing a repeating unit having the formula: Resin (D)
The structural unit having a monocyclic or polycyclic alicyclic group in the above is preferably a structural unit having an alicyclic group represented by the general formula (VII), (VIII) or (IX).

[0052]

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In the formulas (VII) to (IX), R₃₅, R₃₆, R₃₈~ R
₄₀Are the same or different and are a hydrogen atom, a halogen atom,
Represents a cyano group, an alkyl group or a haloalkyl group. R
₃₇Is a cyano group, -CO-OR₄₇Or -CO-NR₄₈
R₄₉Represents X_Four~ X₆Are the same or different
Divalent alkyl, which may be
A len group, alkenylene group or cycloalkylene group,
-OO, -SO_Two-, -O-CO-R₅₀-, -CO-O
-R₅₁-Or -CO-NR ₅₂-R₅₃Represents-. R
₄₇Is a hydrogen atom, an optionally substituted alkyl group
Group, cycloalkyl group or alkenyl group, or acid
Decomposes to increase solubility in alkaline developer
Represents a group to be formed. R₄₈, R₄₉, R₅₂Are the same or different
Thus, a hydrogen atom, an alkyl which may have a substituent,
A cycloalkyl group or an alkenyl group. Ma
R₄₈And R₄₉May combine with each other to form a ring. R₅₀~ R
₅₁, R₅₃Are the same or different and are a single bond or divalent
Alkylene group, alkenylene group or cycloalkyl
And ether groups, ester groups,
And amide, urethane and ureido groups
May form a divalent group. A is a monocyclic or polycyclic
Represents an alicyclic group.

[0054] R ₃₅ to R _40, the details of the substituents _{R 47 ~R 53, X 4 ~X} 6, R 15 in the general formula (IV) ~ (VI)
_{~R 20, R 27 ~R 33,} X 1 ~X 3 in the above formula, preferred groups are also synonymous.

The monocyclic alicyclic group represented by A includes:
An alicyclic group such as cyclopropane, cyclobutane, cyclopentane, cyclohexane or the like having 3 or more carbon atoms which may have a substituent, preferably an alicyclic group having 3 to 8 carbon atoms which may have a substituent Represents a formula group. The polycyclic alicyclic group represented by A is preferably an alicyclic group which may have a substituent and has 5 or more carbon atoms, such as bicyclo, tricyclo, tetracyclo, and the like. Represents 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. As preferred substituents of the polycyclic alicyclic group,
A hydroxyl group, a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, an amide group, a sulfonamide group, an alkyl group described above for R ₄₇ , a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, Hydroxypropoxy group, butoxy group, etc.
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.

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

[0057]

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[0058]

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The content of the alicyclic group-containing structural unit (preferably, a repeating structural unit represented by any of the general formulas (VII) to (IX)) in the resin of the present invention depends on dry etching resistance, 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 repeating structural units. The content is more preferably 30 to 8
The range is 0 mol%, more preferably 35 to 70 mol%, and still more preferably 40 to 60 mol%.

Use of a repeating unit having a structure of the general formula (I), (II) or (III) and a repeating unit having a monocyclic or polycyclic alicyclic hydrocarbon moiety in the resin (D). The ratio is preferably 80:20 to 2
0:80, more preferably 70:30 to 30: 7.
0. Further, the repeating structural unit having the structure of the general formula (I), (II) or (III) may have a monocyclic or polycyclic alicyclic hydrocarbon moiety.

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

[0062]

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[0063]

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[0064]

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[0065]

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[0066]

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[0067]

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[0068]

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[0069]

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(E) A resin insoluble in water and soluble in an alkaline developer: does not contain an acid-decomposable group in the positive photoresist composition of the present invention, and is insoluble in water and soluble in an alkaline developer. Resin (hereinafter, simply referred to as an alkali-soluble resin), whereby the sensitivity is improved. The alkali-soluble resin not containing an acid-decomposable group is preferably a resin having a repeating structural unit having a carboxyl group (preferably a structure represented by the following general formulas (XV) to (XVII)). For adjusting alkali solubility, these may be copolymerized with the monomers described below (other polymerizable monomers). Further, in order to improve dry etching resistance, structural units having an alicyclic group represented by the general formulas (VII), (VIII) and (IX) may be copolymerized. Alternatively, both may be performed. In the present invention, novolak resins and polyhydroxystyrene derivatives can also be used, but since these have large absorption for light of 250 nm or less, they may be partially hydrogenated or used, or 30% by weight of the total resin amount. It is preferred to use the following amounts.

The positive photoresist composition of the present invention may have at least one of the repeating structural units represented by the following general formulas (X), (XI) and (XII).

[0072]

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In the formulas (X) to (XII), R₅₅, R₅₆, R₅₈~ R
₆₀Are the same or different and are a hydrogen atom, a halogen atom,
Represents a cyano group, an alkyl group or a haloalkyl group. R
₅₇Is a cyano group, -CO-OR₆₇Or -CO-NR₆₈
R₆₉Represents X₇~ X₉Are the same or different
Divalent alkyl, which may be
A len group, alkenylene group or cycloalkylene group,
-OO, -SO_Two-, -O-CO-R₇₀-, -CO-O
-R₇₁-Or -CO-NR ₇₂-R₇₃Represents-. R
₆₇Is a hydrogen atom, an optionally substituted alkyl group
Group, cycloalkyl group or alkenyl group, or acid
Decomposes to increase solubility in alkaline developer
Represents a group to be formed. R₆₈, R₆₉, R₇₂Are the same or different
Thus, a hydrogen atom, an alkyl which may have a substituent,
A cycloalkyl group or an alkenyl group. Ma
R₆₈And R₆₉May combine with each other to form a ring. R₇₀~ R
₇₁, R₇₃Are the same or different and are a single bond or divalent
Alkylene group, alkenylene group or cycloalkyl
And ether groups, ester groups,
And amide, urethane and ureido groups
May form a divalent group. B is separated by the action of an acid.
Groups that increase solubility in alkaline developers
The details thereof are described in the general formulas (IV) to (VI).₂₇
Has the same meaning as the acid-decomposable group.

[0074] R ₅₅ to R _60, the R ₆₇ to R _73, details of the substituents of X ₇ ~X _9, R ₁₅ in the general formula (IV) ~ (VI)
_{~R 20, R 27 ~R 33,} X 1 ~X 3 in the above formula, preferred groups are also synonymous.

The general formula in the resin according to the present invention
The content of the repeating structural units represented by (X) to (XII) is
It is adjusted by the performance such as alkali developability and substrate adhesion, but is preferably in the range of 0 to 80 mol%, more preferably 0 to 70 mol%, and still more preferably 0 to 60 mol%, based on all repeating units. Used in. The general formula below
Specific examples of the repeating structural units represented by (X) to (XII) are shown below, but the present invention is not limited thereto.

[0076]

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[0077]

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[0078]

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[0079]

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The resin according to the present invention may further contain a carboxyl group. The carboxyl group may be contained in a repeating structural unit having a group represented by the above general formulas (IV) to (IX), or may be contained in a repeating structural unit having an acid-decomposable group and in a low molecular compound (C). And it may be contained in another repeating structural unit different from them. Further, it may be contained in a plurality of positions among the substitution positions of these carboxyl groups. As the repeating structural unit having a carboxyl group, repeating structural units represented by formulas (XV) to (XVII) are preferable.

[0081]

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In the formulas (XV) to (XVII), R₇₅, R₇₆, R₇₈~ R
₈₀Are the same or different and are a hydrogen atom, a halogen atom,
Represents a cyano group, an alkyl group or a haloalkyl group. R
₇₇Is a cyano group, -CO-OR₈₇Or -CO-NR₈₈
R₈₉Represents X_Ten~ X₁₂Are the same or different
Divalent alkyl, which may be
A len group, alkenylene group or cycloalkylene group,
-OO, -SO_Two-, -O-CO-R₉₀-, -CO-O
-R₉₁-Or -CO-NR ₉₂-R₉₃Represents-. R
₈₇Is a hydrogen atom, an optionally substituted alkyl group
Group, cycloalkyl group or alkenyl group, or acid
Decomposes to increase solubility in alkaline developer
Represents a group to be formed. R₈₈, R₈₉, R₉₂Are the same or different
Thus, a hydrogen atom, an alkyl which may have a substituent,
A cycloalkyl group or an alkenyl group. Ma
R₈₈And R₈₉May combine with each other to form a ring. R₉₀~ R
₉₁, R₉₃Are the same or different and are a single bond or divalent
Alkylene group, alkenylene group or cycloalkyl
And ether groups, ester groups,
And amide, urethane and ureido groups
May form a divalent group.

[0083] R ₇₅ to R _80, the details of the substituents _{R 87 ~R 93, X 10 ~X} 12, R 15 in the general formula (IV) ~ (VI)
_{~R 20, R 27 ~R 33,} X 1 ~X 3 in the above formula, preferred groups are also synonymous.

The repeating structural unit having a carboxyl group in the resin according to the present invention (preferably represented by the general formula (X)
The content of (V) to (XVII) represented by the repeating structural unit) is adjusted by alkali developability, substrate adhesion, and performance such as sensitivity, but is preferably 0 to 0 for all repeating units.
The range is 60 mol%, more preferably 0 to 40 mol%, and still more preferably 0 to 20 mol%. Here, the content of the carboxyl group-containing repeating structural unit includes the repeating structural unit having the carboxyl group-containing group represented by the general formulas (IV) to (IX), the low molecular compound (C), and the carboxyl group. Is the amount of all the carboxyl group-containing repeating structural units in the resin, including the acid-decomposable group-containing repeating structural units containing. The general formula (X
Specific examples of the repeating structural units represented by V) to (XVII) are shown below, but the present invention is not limited thereto.

[0085]

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[0086]

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(Other Polymerizable Monomers) For the purpose of improving the performance of the resin according to the present invention, another polymerizable monomer is further added within a range that does not significantly impair the transmittance of the resin of 220 nm or less and the dry etching resistance. It may be copolymerized.
Copolymerizable monomers that can be used include those shown below. For example, acrylic esters,
It is a compound having one addition-polymerizable unsaturated bond selected from acrylamides, methacrylic esters, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, crotonic esters and the like.

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 such as alkyl (preferably having 1 to 10 carbon atoms in the alkyl group) methacrylate (eg, 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
Arylarylamides (for example, aryl groups include phenyl groups), 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 such as 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 itaconates (eg, dimethyl itaconate, diethyl itaconate, dibutyl itaconate); 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.

A repeating structural unit having a group represented by any one of the general formulas (I) to (III) (preferably the general formulas (IV) to (IX)
A repeating structural unit having an acid-decomposable group (preferably a repeating structural unit represented by any of the general formulas (X) to (XII)), and a repeating structural unit having a carboxyl group as necessary (preferably Is the general formula (XV)
The resin according to the present invention containing (the repeating structural unit represented by (XVII)) or another polymerizable monomer is synthesized by radical, cation, or anion 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 according to the present invention is 2,000 or more by weight average (Mw: polystyrene standard), preferably 3,000 to 1,000,000, more preferably 3,000 to 200,000, and Preferably 4,000
The range is from 0 to 100,000. The larger the value, the higher the heat resistance and the like, while the lower the developability and the like. Also, the degree of dispersion (Mw
/ Mn) is preferably from 1.0 to 5.0, more preferably from 1.0 to 3.0, and the smaller the ratio, the better the heat resistance and image performance (pattern profile, defocus latitude, etc.). In the present invention, the addition amount of the above resin in the photosensitive composition is 50 to 9 with respect to the total solid content.
It is 9.7% by weight, preferably 70 to 99% by weight.

(F) Fluorine and / or silicon surfactant: Next, (F) the fluorine surfactant and the silicon surfactant contained in the positive photosensitive resin composition of the present invention will be described. . The photosensitive resin composition of the present invention may contain one or both of a fluorine-based surfactant and a silicon-based surfactant. Examples of these (F) surfactants include JP-A-62-36663, JP-A-61-226746, JP-A-61-226745, and JP-A-62-17095.
No. 0, JP-A-63-34540, JP-A-7-230165, JP-A-8-6
No. 2,834, JP-A-9-54432, JP-A-9-5988, and the following commercially available surfactants can be used as they are. As commercially available surfactants that can be used, for example, F-top EF301, EF303, (manufactured by Shin-Akita Kasei Co., Ltd.), Florado FC430, 431 (Sumitomo 3M Co., Ltd.)
), Megafac F171, F173, F176, F189, R08 (Dai Nippon Ink Co., Ltd.), Surflon S-382, SC101, 102,
Fluorinated surfactants such as 103, 104, 105, and 106 (manufactured by Asahi Glass Co., Ltd.) and silicon-based surfactants can be exemplified. Also, polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can be used as a silicon-based surfactant. The amount of the surfactant is usually 0.01% by weight to 2% by weight, preferably 0.01% by weight to 1% by weight, based on 100% by weight of the solids in the composition of the present invention. These surfactants can be used alone or in combination of two or more.

(A) Compound that generates an acid upon irradiation with actinic rays or radiation: The photoacid generator used in the present invention includes:
A compound that generates an acid upon irradiation with actinic rays or radiation. Examples of the compound used in the present invention, which decomposes upon irradiation with actinic rays or radiation to generate an acid, include a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization, a photobleaching agent for dyes, and a photodiscoloration agent. Or known light used in micro-resists (ultraviolet rays of 400 to 200 nm, far ultraviolet rays, particularly preferably g-line, h-line, i-line, K-line).
rF excimer laser light), an ArF excimer laser light, an electron beam, an X-ray, a molecular beam or a compound capable of generating an acid by an ion beam, and a mixture thereof can be appropriately selected and used.

Examples of other compounds that generate an acid upon irradiation with actinic rays or radiation used in the present invention include, for example, onium salts such as diazonium salts, phosphonium salts, iodonium salts, sulfonium salts, and arsonium salts, and organic halogen compounds. Compounds, organometallic / organic halides, photoacid generators having o-nitrobenzyl-type protecting groups,
Examples thereof include compounds that generate sulfonic acid upon photodecomposition represented by iminosulfonate and the like, disulfone compounds, diazoketosulfones, diazodisulfone compounds, and the like.

Further, a group that generates an acid by these lights,
Alternatively, a compound having a compound introduced into the main chain or side chain of a polymer, for example, U.S. Pat.No. 3,849,137, German Patent No. 3
914407, JP-A-63-26653, JP-A-55-164824, JP-A-62-69263, JP-A-63-146038, JP-A-63-163452
And compounds described in JP-A-62-153853, JP-A-63-146029 and the like can be used.

Further, compounds capable of generating an acid by light described in US Pat. No. 3,779,778 and European Patent 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).

[0101]

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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.

[0103]

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[0104]

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[0105]

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

[0107]

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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.

[0110] 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.

[0113]

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[0114]

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[0115]

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[0116]

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[0117]

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[0118]

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[0119]

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[0120]

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[0121]

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[0122]

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The onium salts represented by the general formulas (PAG3) and (PAG4) are known and described, for example, in US Pat.
Nos. 2,807,648 and 4,247,473, JP-A-53-101,331
And the like.

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

[0125]

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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.

[0127]

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[0128]

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[0129]

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[0130]

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[0131]

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[0132]

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

[0134]

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Here, R represents a linear, branched or cyclic alkyl group or an optionally substituted aryl group. Specific examples include the following compounds, but are not limited thereto.

[0136]

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The amount of the compound which decomposes upon irradiation with actinic rays or radiation to generate an acid is usually in the range of 0.001 to 40% by weight based on the solid content in the composition, and is preferably used. Is used in the range of 0.01 to 20% by weight, more preferably 0.1 to 5% by weight. If the amount of the compound that decomposes upon irradiation with actinic rays or radiation to generate an acid is less than 0.001% by weight, the sensitivity 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 Present Invention) The positive photosensitive composition of the present invention may further contain, if necessary, an acid-decomposable dissolution accelerating compound, a dye, a plasticizer, a surfactant, and a photosensitizer. , An organic basic compound, a compound that promotes solubility in a developer, and the like. Examples of the compound that promotes dissolution in a developer that can be used in the present invention include:
Two or more phenolic OH groups or one carboxy group
It is a low-molecular compound having 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 5 with respect to the resin of the present invention.
0% by weight, and more preferably 5 to 30% by weight. 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 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).

[0142]

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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,
N-aminomorpholine, N- (2-aminoethyl) morpholine, 1,5-diazabicyclo [4,3,0] non-5-ene, 1,8-diazabicyclo [5,4,0]
Examples include, but are not limited to, undec-7-ene and 2,4,5-triphenylimidazole.

These nitrogen-containing basic compounds are used alone or in combination of two or more. The amount of the nitrogen-containing basic compound used is based on the solid content of the photosensitive resin composition.
Usually 0.001 to 10% by weight, preferably 0.01 to 5%
% By weight. If the amount is less than 0.001% by weight, the effect of the addition of the nitrogen-containing basic compound cannot be obtained. On the other hand, if it exceeds 10% by weight, the sensitivity tends to decrease and the developability of the unexposed portion tends to deteriorate.

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

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

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

In the present invention, a surfactant other than the above-mentioned (F) fluorine-based and / or silicon-based surfactant may be added. Specifically, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether, polyoxyethylene nonyl phenol ether and the like Polyoxyethylene alkyl allyl ethers, 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,
Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate, and the like. The amount of these surfactants is usually 2% by weight or less, preferably 1% by weight or less, based on 100% by weight of the solid content 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) which is 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.

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.

[0151]

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)]
25 g of γ-crotonolactone was dissolved in 500 ml of isopropyl alcohol, and this solution was placed in a photoreactor made of quartz and irradiated with light using a low-pressure mercury lamp (6 W made by USHIO) for 80 hours. The reaction solution was filtered, and then isopropyl alcohol was distilled off to obtain a crude product. This was purified by distillation under reduced pressure to obtain 31 g of an alcohol. 9.3 g (64.6 mmol) of the obtained alcohol compound was dissolved in 100 ml of THF, and triethylamine 1
2.8 g (129.2 mmol) and 0.7 g of dimethylaminopyridine were added. To this solution, 10.1 g (96.9 mmol) of methacrylic acid chloride was added dropwise over 30 minutes under ice cooling, and the mixture was stirred for 2 hours under ice cooling and at room temperature for 3 hours. Water was added to the reaction solution, and the mixture was stirred for a while, then, ethyl acetate was added, and the mixture was separated. The organic phase was washed with water, Brine, dried and concentrated to obtain a crude product. This was purified by column chromatography to obtain 2.7 g of the desired product.

[Synthesis Example 2 (Synthesis of Raw Material Monomer of Structural Example (a2))] A raw material monomer of Structural Example a2 was prepared in the same manner as in Synthetic Example 1 except that methacrylic chloride in Synthetic Example 1 was changed to acrylic acid chloride. Obtained.

[Synthesis Example 3 (Synthesis of Raw Material Monomer of Structural Example (a3))] Structural Example a3 was performed in the same manner as in Synthetic Example 1 except that isopropanol in Synthetic Example 1 was changed to cyclohexanol.
Was obtained. Similarly, a tertiary alcohol was obtained by photoreacting the α, β-unsaturated carbonyl compound with a secondary alcohol. This was reacted with the corresponding carboxylic acid chloride, carboxylic anhydride and isocyanate to obtain the raw material monomers of structural examples a4 to a36.

[Synthesis Example 4 (Synthesis of Raw Material Monomer of Structural Example (a39))] α-bromo-γ-butyrolactone 19.8
g and 25 g of 2-hydroxyisobutyric acid were dissolved in 80 ml of methyl isobutyl ketone.
6 g were added. The reaction was carried out at room temperature for 10 hours, and the precipitated powder was filtered. The filtrate was washed with a 5% aqueous sodium hydrogen carbonate solution, then with distilled water and saturated saline, dried and concentrated to obtain 11.7 g of a crude product. This was dissolved in 100 ml of tetrahydrofuran, and triethylamine was added thereto.
7 g and 0.1 g of N, N-dimethylaminopyridine were added. To this solution, 9.8 g of methacrylic acid chloride was added dropwise over 30 minutes, and reacted at room temperature for 20 hours. 100 ml of distilled water was added to the reaction solution, stirred for 30 minutes, extracted with ethyl acetate, the organic phase was washed with water, dried and concentrated to obtain a crude product. This was purified by column chromatography to obtain 7.2 g of the desired product.

[Synthesis Example 5 (Synthesis of Raw Material Monomer of Structural Example (a41))] Under ice cooling, 9 g of sodium borohydride was dissolved in 80 ml of methanol, and α-acetyl-γ-
15 g of butyrolactone was added dropwise over 30 minutes. After reacting at room temperature for 5 hours, 4.5 g of sodium borohydride
Was added, and the mixture was further reacted for 5 hours. 100m of water
and hydrochloric acid was added until the solution became slightly acidic. The solution was concentrated, and ethyl acetate was added thereto. Insoluble matter was removed by filtration, and the mixture was concentrated to obtain a crude product. This was purified by column chromatography to give alcohol 1
0.5 g was obtained. 3 g of the alcohol was dissolved in 50 ml of tetrahydrofuran, and 2.3 g of triethylamine and 0.05 g of N, N-dimethylaminopyridine were added thereto.
Was added. To this solution, 2.4 g of methacrylic acid chloride was added dropwise over 30 minutes, and reacted at room temperature for 2 hours. 100 ml of distilled water was added to the reaction solution, stirred for 30 minutes, extracted with ethyl acetate, the organic phase was washed with water, dried and concentrated to obtain a crude product. This was purified by column chromatography to obtain 3.9 g of the desired product.

[Synthesis Example 6 (Synthesis of methyl-2-adamantyl methacrylate (b1))] 30 g of 2-methyl-2-adamantanol, 36 g of triethylamine, N, N
-4 g of dimethylaminopyridine was added to tetrahydrofuran 3
Then, 29 g of methacrylic acid chloride was added dropwise to this solution over 30 minutes under ice cooling. The temperature was raised to room temperature, and the reaction was allowed to proceed overnight. Distilled water 5 under ice-cooling
After adding 00 ml, the mixture was extracted with ethyl acetate, and the organic phase was dried and concentrated to obtain a crude product. This was purified by column chromatography to obtain 17 g of the desired product.

[Synthesis Example 7 (Cedrol acrylate (b)
Synthesis of 5))] (+)-Cedrol (manufactured by LANCASTER) 25 g was dissolved in THF 200 ml, and triethylamine 22.8 g and N, N-dimethylaminopyridine 1 g were added thereto. 15.2 g of acrylic acid chloride was added to this solution under ice cooling.
Was added dropwise over 30 minutes, and the mixture was stirred at room temperature for 2 days. 100 ml of distilled water was added to this solution under ice-cooling, and the mixture was stirred for 30 minutes.
300 ml of ethyl acetate was added. After liquid separation and removal of the aqueous phase, the organic phase was washed with water, dried and concentrated to obtain a crude product. This was purified by column chromatography to obtain 18.2 g of the desired product (raw material monomer of Structural Example b5).

[Synthesis Example 8 (Synthesis of Polymer (P1) of the Present Invention)] 10 g of the starting monomer of Structural Example a3 and a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical; V-65) 0.50 g and 0.15 g of mercaptoacetic acid were added to 30 m of N, N-dimethylacetamide.
and heated at 60 ° C. under a stream of nitrogen to obtain N,
It was added dropwise to 10 ml of N-dimethylacetamide over 4 hours. Two hours after the completion of the dropwise addition, 0.50 g of V-65 was added, and a heating reaction was performed for another two hours. After allowing the reaction solution to cool, it was poured into 1 L of ion-exchanged water, and the precipitated powder was collected by filtration. This powder was dissolved in 100 ml of THF,
The homopolymer (P1) of Structural Example a3 was obtained by charging the precipitated powder into L and collecting the precipitated powder by filtration. (Weight average molecular weight 730
0, dispersity 2.8)

Synthesis Example 9 (Synthesis of Polymer (P2) of the Present Invention) 1.2 g of the starting monomer of Structural Example a1 and 1.36 g of the starting monomer of Structural Example b1, 2,2′-azobis (2,4-dimethyl) (Valeronitrile) 0.16 g and mercaptoacetic acid 0.043 g were dissolved in N, N-dimethylacetamide 8.2 g, and THF 1.4 g was added thereto. This solution was heated at 60 ° C. under a nitrogen stream and added dropwise to 2 g of N, N-dimethylacetamide over 4 hours. Two hours after the completion of the dropwise addition, 0.16 g of 2,2'-azobis (2,4-dimethylvaleronitrile) was added, and the mixture was further heated and reacted for 2 hours. After allowing the reaction solution to cool, it was poured into 1 L of ion-exchanged water, and the precipitated powder was collected by filtration. This powder is added to THF100
The resin (P2) of the present invention was obtained by dissolving the resulting solution in 1 ml of hexane, adding the solution to 1 L of hexane, and filtering the precipitated powder.
(Weight average molecular weight 6500, dispersity 2.0)

Thereafter, in the same manner as in Synthesis Examples 8 and 9, the resins P3 to P25 of the present invention were synthesized using the raw material monomers of the repeating structural units shown in Table 1. 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.

[0161]

[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.

[0163]

[Table 2]

From the results shown in Table 2, it can be seen 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 has a sufficient transmittance to light of 193 nm.

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).

[0166]

[Table 3]

Polymer (1): Copolymer of tricyclodecanyl methacrylate / tetrahydropyranyl methacrylate / methacrylic acid = 50/30/20 (molar ratio) (weight average molecular weight 32500, dispersity 2.7) Polymer (2) ): 2-methyladamantyl methacrylate / methacrylic acid (±) -mevalonic lactone ester (synthesized by the method described in JP-A-9-90637) From the results in Table 3, the etching rate of the resin of the present invention is comparative example. Poly (methyl methacrylate) and polymer (1)
It can be seen that the film has a sufficiently small dry etching resistance.

Example 3 (Evaluation of Image) 1.0 g of the resin of the present invention obtained in the above synthesis example, 0.03 g of triphenylsulfonium triflate salt, and 1.5
-Diazabicyclo [4,3,0] non-5-ene 0.0
04 g was dissolved in 4.5 g of propylene glycol monomethyl ether acetate and filtered with a 0.2 μm Teflon filter. It was uniformly applied on a silicon substrate that had been subjected to hexamethyldisilazane treatment by a spin coater, and was dried by heating on a hot plate at 100 ° C. for 90 seconds to form a 0.4 μm resist film. This resist film was subjected to pattern exposure using a KrF excimer laser stepper (NA = 0.42; 248 nm), and immediately after exposure, heated at 110 ° C. for 60 seconds on a hot plate. 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. Here, as for the pattern shape, the obtained pattern was observed with a scanning electron microscope, and a rectangular shape was determined to be good. Here, 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. As a result, at the sensitivity and resolution shown in Table 4, a favorable positive pattern in which only the exposed portions of the resist film were dissolved and removed was formed.

[0169]

[Table 4]

From the results shown in Table 4, the resist using the resin of the present invention has high sensitivity and good resolution. Also, it can be seen that the pattern shape is good.

Example 4 (Evaluation of Image) On the 0.4 μm resist film obtained in Example 3, a mask having a pattern drawn with chromium on a quartz plate was adhered.
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. As a result, at the sensitivity and resolution shown in Table 5, a good positive pattern was formed in which only the exposed portions of the resist film were dissolved and removed.
Further, the photosensitive resin composition prepared in Example 3 was uniformly applied to a hexamethyldisilazane-treated silicon substrate by a spin coater, and heated and dried on a hot plate at 120 ° C. for 90 seconds. A 0.50 μm resist film was formed. This resist film is exposed to ArF excimer laser light through a mask.
Heated on hot plate at 0 ° C. for 90 seconds. Further 2.
The film was developed with a 38% by weight aqueous solution of tetramethylammonium hydroxide at 23 ° C. for 60 seconds, rinsed with pure water for 30 seconds, and dried. The sample on which the contact hole pattern thus obtained was formed was subjected to KLA.
The number of development defects (number of development defects-I) shown in Table 5 was measured using a 2112 machine (manufactured by KLA Tencor Corporation) (Thres).
hold12, Pixcel Size = 0.39).

[0172]

[Table 5]

Polymer (3): 2-methyl-2-adamantyl methacrylate / α-methacryloxy-γ-butyrolactone copolymer (synthesized by the method described in EP0856773A) No peeling occurred.) From the results in Table 5, the resist using the resin of the present invention was:
It can be seen that the composition exhibits good sensitivity and resolution with respect to the ArF excimer laser light and forms a good positive pattern with few development defects.

Example 5 (Evaluation of Image) To the photosensitive resin composition prepared in Example 3, 0.005 g of a surfactant shown in Table 6 was added, and no exposure was performed at the number of development defects-I of Example 4. Except for the same heating, development,
The number of development defects was measured for the rinsed and dried sample (number of development defects-II). Table 6 shows the evaluation results.

[0175]

[Table 6]

W-1: Megafac F176 (Dai Nippon Ink Co., Ltd.) (fluorine) W-2: Megafac R08 (Dai Nippon Ink Co., Ltd.)
(Fluorine and silicone type) W-3: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) (silicone type)

From the results in Table 6, it can be seen that the resin of the present invention using a fluorine-based and / or silicon-based surfactant has few development defects.

[0178]

As is apparent from the above description, the positive photosensitive composition using the resin of the present invention is particularly suitable for the photosensitive composition of 220
It has high transparency to far ultraviolet light of nm or less, good dry etching resistance, good adhesion, and few development defects. When far ultraviolet light (especially ArF excimer laser light) having a wavelength of 250 nm or less, and particularly 220 nm or less, is used as an exposure light source, a high sensitivity, a high resolution, and a good pattern profile are exhibited, and a fine pattern required for manufacturing a semiconductor device is formed. Can be used effectively.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Toshiaki Aoi 4,000 Kawajiri, Yoshida-machi, Haibara-gun, Shizuoka Prefecture F-term in Fujisha Shin Film Co., Ltd. (Reference) 2H025 AA01 AA02 AA09 AA14 AB16 AC04 AC08 AD03 BE00 BE10 CB06 CB14 CB15 CB21 CB41 CB52 CB55 CC04 FA17 4J100 AJ02P AJ09P AL08P AL39P AL41P AM21P AP01P BA02P BA03P BA05P BA06P BA11P BA15P BA16P BA38P BA51P BA53P BB01P BC03P BC04P BC07P BC09P BC12P BC26P BC53P

Claims (11)

[Claims] 1. A resin comprising (A) a compound which generates an acid upon irradiation with actinic rays or radiation, and (B) a resin having a group which is decomposed by the action of an acid to increase the solubility in an alkaline developer. A positive photosensitive composition, wherein the resin contains at least one of structures represented by the following general formulas (I), (II) and (III). Embedded image Wherein (I) ~ (III), R 1, R 2 are the same or different, a hydrogen atom, which may have a substituent, a straight-chain, branched, cyclic alkyl group, R ₁ and R ₂ may combine to form a monocyclic or polycyclic ring. Further, the ring may have an oxygen atom, a sulfur atom, a nitrogen atom, a ketone, an ester, an imide, or an amide as a linking group. R _{3 to} R
₅ is the same or different and represents a hydrogen atom, a linear or branched, cyclic alkyl group or an alkoxy group which may have a substituent, and two or all of R _{3 to} R ₅ are bonded to each other; To form a monocyclic or polycyclic ring which may have an oxygen atom, a sulfur atom, a nitrogen atom, a ketone or an ester as a linking group. X represents a single bond or a divalent bonding group, and X may be bonded to either or both of R ₁ and R ₂ to form a monocyclic or polycyclic ring. Y is an oxygen atom, a sulfur atom,-
It represents NH-, -N (OH)-or -N (alkyl)-. n represents an integer of 1 to 3. (A) a compound which generates an acid upon irradiation with actinic rays or radiation, (B) a resin having a group which is decomposed by the action of an acid to increase solubility in an alkaline developer, and (C) A) a molecular weight of 3000 having a group which is decomposed by the action of an acid and increases the solubility in an alkali developer;
The resin (B) and / or the low molecular compound (C) contains the following low molecular compound, and has at least a structure represented by the general formula (I), (II) or (III) according to claim 1. A positive-type photosensitive composition comprising one. 3. A repeating unit having a structure represented by formula (I), (II) or (III), wherein the resin having a group which decomposes under the action of an acid to increase solubility in an alkaline developer. The positive photosensitive composition according to claim 1, wherein the resin is a resin containing at least one of the above and a repeating unit having a monocyclic or polycyclic alicyclic hydrocarbon moiety. 4. The positive photosensitive composition according to claim 1, wherein the monocyclic or polycyclic alicyclic hydrocarbon moiety is an adamantane residue which may be substituted. object. 5. The resin according to claim 1, wherein (B) the resin having a group which is decomposed by the action of an acid to increase the solubility in an alkaline developer contains a structure represented by the general formula (a). Item 6. The positive photosensitive composition according to any one of Items 1 to 4. Embedded image (Wherein, R _{1 to} R ₅ and n have the same meanings as in the general formula (I),
R ₁₅ represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group or a haloalkyl group. ) 6. The resin according to claim 1, wherein (B) the resin having a group which is decomposed by the action of an acid to increase the solubility in an alkaline developer contains a structure represented by the general formula (b). Item 6. The positive photosensitive composition according to any one of Items 1 to 5. Embedded image (Wherein, R _{1 to} R ₅ and n have the same meanings as in the general formula (I),
R ₁₅ represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group or a haloalkyl group. ) 7. A compound which generates an acid upon irradiation with an actinic ray or radiation, (A) a compound which decomposes under the action of an acid,
A low-molecular compound having a molecular weight of 3,000 or less having a group that increases solubility in an alkali developer, and (E) a resin insoluble in water and soluble in an alkali developer, wherein the low-molecular compound (C) is Item 4. A positive photosensitive composition comprising at least one of the structures represented by formulas (I), (II) or (III) according to item 1. 8. The method according to claim ₁ , wherein R ₁ and R ₂ in the repeating structural unit having the structure of the general formula (I), (II) or (III) are substituents other than a hydrogen atom. The positive photosensitive composition according to any one of the above. 9. The positive photosensitive composition according to claim 1, further comprising (F) a fluorine-based and / or silicon-based surfactant. 10. 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. 11. 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.