JPH10232495A - Positive photosensitive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To ensure satisfactory sensitivity and resolution, to give a resist pattern and to attain sufficiently high dry etching resistance by incorporating a compd. generating an acid when irradiated with active light and a resin having a specified monovalent polycyclic alicyclic group and a group increasing solubility in an alkali developer. SOLUTION: This photosensitive compsn. contains a compd. generating an acid when irradiated with active light or radiation and a resin having at least one of monovalent polycyclic alicyclic groups represented by formulae I-III and a group increasing solubility in an alkali developer when decomposed by the action of the acid. In the formulae I-III, each of R1 -R5 is alkyl which may have a substituent, cycloalkyl which may have a substituent, alkenyl which may have a substituent, alkynyl which may have a substituent, halogen, cyano,- R6 -O-R7 ,-R6 -CO-O-R9 , -R10 -CO-NR11 R12 or -R13 -O-CO-R14 and each of (l), (m), (n), (p) and (q) is 0 or an integer of 1-5.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

2. Description of the Related Art Positive photoresist compositions include:
In general, a composition containing an alkali-soluble resin and a naphthoquinonediazide compound as a photosensitive material is used. For example, US Pat. No. 3,666,473, US Pat. No. 4,115,128 and US Pat. No. 4,173,470 as “Novolak-type phenol resin / naphthoquinonediazide-substituted compound”
As the most typical composition, "Novolak resin composed of cresol-formaldehyde / trihydroxybenzophenone-1,2-naphthoquinonediazidesulfonic acid ester" is exemplified by Thompson "Introduction to Microlithography" (LFThompson "Intr
oduction to Microlithography ") (ACS Publishing, N
o. 2, 19, p112-121). In such a positive photoresist consisting essentially of a novolak resin and a quinonediazide compound, the novolak resin gives high resistance to plasma etching, and the naphthoquinonediazide compound acts as a dissolution inhibitor. Then, naphthoquinonediazide has the property of losing its dissolution inhibiting ability by generating carboxylic acid upon irradiation with light, and increasing the alkali solubility of the novolak resin.

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

[0004] As one of means for miniaturizing a pattern, it is known to shorten the wavelength of an exposure light source used for forming a resist pattern. This means Rayleigh's equation representing the resolution (line width) R of the optical system, R = k · λ / NA (where λ is the wavelength of the exposure light source, NA is the numerical aperture of the lens,
k is a process constant). From this equation, it can be seen that in order to achieve higher resolution, that is, to reduce the value of R, it is sufficient to shorten the wavelength λ of the exposure light source. For example, in the manufacture of a DRAM having a degree of integration of up to 64 Mbits, the i-line (365 nm) of a high-pressure mercury lamp has been used as a light source until now. In a mass production process of a 256 Mbit DRAM, use of a KrF excimer laser (248 nm) as an exposure light source instead of i-line is being studied. Further, for the purpose of manufacturing a DRAM having an integration degree of 1 Gbit or more, a light source having a shorter wavelength has been studied.
It is considered that the use of rF excimer laser (193 nm), F ₂ excimer laser (157 nm), X-rays, electron beams, etc. is effective (Takumi Ueno et al., “Short Wavelength Photoresist Material-Fine Processing for ULSI” − ”, Bunshin Publishing, 1988).

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

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

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

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

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

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

On the other hand, the polymer having an alicyclic group has the same dry etching resistance as an aromatic group and has a small absorption in the 193 nm region.
1672, 66 (1992). 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.

[0012]

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 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.

[0013]

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

[0014]

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In the formulas (I) to (III), R₁~ R_FiveIs the same
May be different and may have a substituent.
Alkyl group, cycloalkyl group, alkenyl group or
Rukinyl group, halogen atom, cyano group, -R₆-OR
₇Group, -R₈-CO-OR ₉Group, -R_Ten-CO-NR
₁₁R₁₂Group or -R₁₃-O-CO-R₁₄Represents a group. R₇,
R₉May be the same or different; a hydrogen atom, a substituent
Which may have an alkyl group or a cycloalkyl group
Or decompose by the action of an alkenyl group or an acid
Represents a group that increases the solubility in a potash developer. R₁₁~
R₁₂, R₁₄May be the same or different, a hydrogen atom,
An alkyl group or a cycloalkyl, which may have a substituent;
R or alkenyl group;₁₁And R₁₂Is linked to a ring
May be formed. R₆, R₈, R_Ten, R₁₃Is the same
May be different, have a single bond or a substituent
Alkylene group, alkenylene group, or cycloalkyl
Represents a loalkylene group. l, m, n, p, q are the same
They may be different and represent 0 or an integer of 1 to 5. here
In the case where l, m, n, p or q is 2 or more,
R₁~ R_FiveMay be the same or different, and the two
R₁~ R_FiveIs substituted on the same carbon atom,
Carbonyl group (＝ O) or thiocarbonyl group (=
S) may be represented by two R₁~ R_FiveBut adjacent
When two carbon atoms are substituted on the same carbon atom
Alternatively, a double bond between those carbon atoms may be represented. Ma
R₁~ R_FiveIs substituted two or more times,
Two R₁~ R_FiveMay combine with each other to form a ring
No. A monovalent compound represented by the general formula (I), (II) or (III)
The position of the bond of the polycyclic alicyclic group is
It may be at any position in the ring structure.

(2) The resin of the component (B) is decomposed by the action of an acid with at least one of the repeating structural units represented by the following general formulas (IV), (V) or (VI), and alkali development is performed. The positive photosensitive composition according to the above (1), which is a resin having a group that increases solubility in a liquid.

[0017]

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In the formulas (IV) to (VI), R_Fifteen, R₁₆, R₁₈~
R₂₀May be the same or different; a hydrogen atom, a halogen atom
, A cyano group, an alkyl group or a haloalkyl group.
R₁₇Is a cyano group, -CO-OR₂₇Or -CO-NR₂₈
R₂₉Represents X₁~ X_ThreeMay be the same or different.
Divalent alkyl, which may be a bond or may have a substituent
Kylene group, alkenylene group or cycloalkylene
Group, -O-, -SO_Two-, -O-CO-R₃₀-, -CO
-OR₃₁-Or -CO-NR ₃₂-R₃₃Represents-. R
₂₇Is a hydrogen atom, an optionally substituted alkyl group
Group, cycloalkyl or alkenyl group, or acid
Decomposes by action to increase solubility in alkaline developer
Represents a group to be formed. R₂₈, R₂₉, R₃₂Are the same but different
Hydrogen atom, which may have a substituent,
A cycloalkyl group or an alkenyl group. Also
R₂₈And R₂₉May combine to form a ring. R₃₀~
R₃₁, R₃₃May be the same or different, may be a single bond or
Is a divalent alkylene group, alkenylene group or cycloalkyl
Represents a alkylene group, and these groups further include an ether group,
Stele group, amide group, urethane group or ureide group
Both may form a divalent group. Y is the above (1)
Polycyclic alicyclic represented by the general formulas (I) to (III) described above
Represents a group.

(3) The resin of the component (B) is as described in the above (2).
And at least one of the repeating structural units represented by the general formula (IV), (V) or (VI) and the repeating structural unit represented by the following general formula (VII), (VIII) or (IX) (1) or (2), which is a resin having at least one of which is decomposed by the action of an acid to increase solubility in an alkaline developer. Composition.

[0020]

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In the formulas (VII) to (IX), R_{twenty one}, R_{twenty two}, R_{twenty four}~
R₂₆May be the same or different; a hydrogen atom, a halogen atom
, A cyano group, an alkyl group or a haloalkyl group.
R_{twenty three}Is a cyano group, -CO-OR₂₇Or -CO-NR₂₈
R₂₉Represents X_Four~ X₆May be the same or different.
Divalent alkyl, which may be a bond or may have a substituent
Kylene group, alkenylene group or cycloalkylene
Group, -O-, -SO_Two-, -O-CO-R₃₀-, -CO
-OR₃₁-Or -CO-NR ₃₂-R₃₃Represents-. R
₂₇Is a hydrogen atom, an optionally substituted alkyl group
Group, cycloalkyl or alkenyl group, or acid
Decomposes by action to increase solubility in alkaline developer
Represents a group to be formed. R₂₈, R₂₉, R₃₂Are the same but different
Hydrogen atom, which may have a substituent,
A cycloalkyl group or an alkenyl group. Also
R₂₈And R₂₉May combine to form a ring. R₃₀~
R₃₁, R₃₃May be the same or different, may be a single bond or
Is a divalent alkylene group, alkenylene group or cycloalkyl
Represents a alkylene group, and these groups further include an ether group,
Stele group, amide group, urethane group or ureide group
Both may form a divalent group. B is due to the action of acid
Decomposes to increase solubility in alkaline developer
Represents

(4) The resin of component (B) further has a carboxyl group.
The positive photosensitive composition according to any one of the above. (5) The resin as the component (B) further comprises at least one of the repeating structural units having a carboxyl group and represented by the following general formula (X), (XI) or (XII). The positive photosensitive composition according to the above (4).

[0023]

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In the general formulas (X) to (XII), R ₃₄ , R ₃₅ , R
₃₇ to R ₃₉ may be the same or different, represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group or a haloalkyl group. R ₃₆ represents a cyano group, a carboxyl group, —CO—OR ₄₀
Or an -CO-NR ₄₁ R _42. X _{7 to} X ₉ may be the same or different and may have a single bond or a substituent;
Divalent alkylene group, alkenylene group or cycloalkylene _{group, -O -, - SO 2 -} , - O-CO-R
_{43 -, - CO-O-} R 44 - or -CO-NR ₄₅ -R ₄₆ -
Represents R ₄₀ represents an alkyl group, a cycloalkyl group, or an alkenyl group which may have a substituent. R ₄₁ , R
₄₂ and R ₄₅ may be the same or different and represent a hydrogen atom, an alkyl group, a cycloalkyl group or an alkenyl group which may have a substituent, wherein R ₄₁ and R ₄₂ are bonded to form a ring; May be. R ₄₃ , R ₄₄ and R ₄₆ may be the same or different and represent a single bond, a divalent alkylene group, an alkenylene group, or a cycloalkylene group.
A divalent group may be formed together with an ether group, an ester group, an amide group, a urethane group or a ureide group.

(6) It contains a low molecular weight acid-decomposable dissolution inhibiting compound having a molecular weight of 3,000 or less, which has a group decomposable by the action of an acid and whose solubility in an alkaline developer is increased by the action of an acid. (1) to (5), wherein
The positive photosensitive composition according to any one of the above. (7) The positive photosensitive composition as described in any of (1) to (6) above, wherein a deep ultraviolet light having a wavelength of 250 nm or less is used as an exposure light source. (8) The positive photosensitive composition as described in (7) above, wherein far-ultraviolet light having a wavelength of 220 nm or less is used as an exposure light source.

[0026]

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

In the above formula, R _{1 to} R ₅ , R ₇ , R
_9, the alkyl group of _{R 11, R 12, R 14} , R 27 ~R 29, R 32, preferably may have a substituent, a methyl group, an ethyl group, a propyl group, n- butyl group , Sec-
Examples thereof include those having 1 to 8 carbon atoms such as a butyl group, 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 has 2 to 6 carbon atoms such as a vinyl group, a propenyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, and a cyclohexenyl group which may have a substituent. No. R ₁ ~
The alkynyl group for R ₅ is preferably an acetyl group,
Those having 2 to 4 carbon atoms such as a propargyl group are exemplified.

[0028] Here, l, m, n, when p or q is 2 or more, each plurality of R ₁ to R ₅ may also be different from be the same, each plurality R ₁ to R ₅ Two of R _{1 to} R ₅
Are substituted on the same carbon atom, two of them may represent a carbonyl group (＝ O) or a thiocarbonyl group (＝ S). Furthermore, two R ₁ out of each of the plurality of R _{1 to} R _5.
When R ₅ substitutes on an adjacent carbon atom,
May bond together to represent a double bond between those carbon atoms. Here, it is preferable that the formed double bond between carbon atoms does not form a conjugated double bond between carbon and carbon. When two or more of R _{1 to} R ₅ are substituted, the two R _{1 to} R ₅ may be bonded to each other to form a ring. Such a ring preferably contains a hetero atom such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a tetrahydrofuranyl group, a tetrahydropyranyl group, or the like.
And a membered ring. These rings may further have a substituent. The position of the bond of the monovalent polycyclic alicyclic group represented by the general formula (I), (II) or (III) may be at any position in the hydrocarbon polycyclic structure.

The alkyl group represented by R ₁₅ , R ₁₆ , R ₁₈ -R ₂₂ and R ₂₄ -R ₂₆ is preferably an optionally substituted methyl group, ethyl group, propyl group, n-butyl group. Group,
Those having 1 to 4 carbon atoms such as a sec-butyl group are exemplified. 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,
Bromomethyl group, fluoroethyl group, chloroethyl group,
A bromoethyl group;

The alkylene group represented by R ₆ , R ₈ , R ₁₀ , R ₁₃ and X _{1 to} X ₆ is preferably an optionally substituted methylene group, ethylene group, propylene group, butylene group, Examples thereof include those having 1 to 8 carbon atoms such as a hexylene group and an octylene group. 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. Examples of the cycloalkylene group preferably include those having 5 to 8 carbon atoms such as a cyclopentylene group and a cyclohexylene group which may have a substituent.

Examples of the alkylene group, alkenylene group and cycloalkylene group represented by R _{30 to} R ₃₁ and R ₃₃ include the same groups as those described above, and further include those groups, ether groups, ester groups, and amide groups. , A urethane group and a ureido group together form a divalent group. The ring formed by R ₁₁ and R ₁₂ or R ₂₈ and R ₂₉ together with the nitrogen atom is preferably a ring which forms a 5- to 8-membered ring, and specific examples include pyrrolidine, piperidine, and piperazine. No.

R ₇ , R ₉ , R ₂₇ and B represent groups (acid-decomposable groups) which are 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) (as R ₇ or R ₉ ), may be contained in the repeating unit (as R ₂₇₎ having a group represented by (I) ~ (III), may be included in more other repeating structural units, more of these locations May be included in the location. Examples of the acid-decomposable group include a group which is hydrolyzed by the action of an acid to form an acid, and a group which forms an acid by the elimination of a carbon cation by the action of an acid. Preferably, the following general formula (XI
II) and (XIV). Thereby, the stability over time becomes excellent.

[0033]

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Where R₄₇~ R₄₉Are the same
May have a hydrogen atom or a substituent.
Alkyl, cycloalkyl or alky!
Represents a phenyl group. However, R in the formula (XIII)₄₇~ R₄₉Of which
At least one is a group other than a hydrogen atom. R₅₀Is replaced
Alkyl group and cycloalkyl group which may have a group
Or an alkenyl group. In addition, R of the formula (XIII)₄₇~ R₄₉
Or R of formula (XIV)₄₇~ R₄₈, R₅₀2 of
Three groups are bonded to form 3-8 carbon atoms,
May be formed. As such a ring
Physically, cyclopropyl, cyclopentyl, cyclo
Hexyl group, cycloheptyl group, 1-cyclohexenyl
Group, 2-tetrahydrofuranyl group, 2-tetrahydropi
Ranyl group and the like. Z₁~ Z_TwoAre the same but different
And may represent an oxygen atom or a sulfur atom. Here
As the alkyl group, cycloalkyl group, and alkenyl group,
R above₁~ R _FiveThe same ones as shown in are preferred.
In the general formulas (I) to (III), l, m, n, p, and q are 0 or
Represents an integer of 1 to 5, preferably 0 or an integer of 1 to 2
Is shown.

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

In the resin according to the present invention, a repeating structural unit having an alicyclic group represented by any one of the above general formulas (I) to (III) (preferably, a repeating structure represented by the general 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 65 mol%, based on all repeating units. .

In the resin according to the present invention, the content of the repeating structural unit having an acid-decomposable group (preferably, the repeating structural unit represented by any one of formulas (VII) to (IX)) is selected from the group consisting of alkali developability, It is adjusted depending on the performance such as substrate adhesion, but it is preferably used in the range of 5 to 80 mol%, more preferably 10 to 70 mol%, and still more preferably 20 to 60 mol%, based on all repeating units. . Here, the content of the acid-decomposable group-containing repeating structural unit is the total content of the resin including the acid-decomposable group contained in the repeating structural unit having a group represented by the above general formulas (I) to (III). Of the acid-decomposable group-containing repeating structural unit. Specific examples (a1) to (a33) of the repeating structural units represented by the general formulas (IV) to (VI) and specific examples (a1) to (a33) of the repeating structural units represented by the general formulas (VII) to (XI) ( b1) to (b30) are shown, but the present invention is not limited thereto.

[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[2] Repeating Structural Unit Having Carboxyl Group In the resin according to the present invention, the carboxyl group may be contained in the repeating structural unit having a group represented by the above general formulas (I) to (III), It may be contained in a repeating structural unit having an acid-decomposable group, or may be contained in another repeating structural unit. 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, the repeating structural units represented by the above general formulas (X) to (XII) are preferable.

In the general formulas (X) to (XII), R ₃₄ ,
The alkyl group of R ₃₅ and R _{37 to} R ₃₉ preferably has 1 carbon atom such as a methyl group, an ethyl group, a propyl group, an n-butyl group, and a sec-butyl group which may have a substituent.
To four. As the haloalkyl group,
Preferable examples include an alkyl group having 1 to 4 carbon atoms substituted by a fluorine atom, a chlorine atom and a bromine atom, such as a fluoromethyl group, a chloromethyl group, a bromomethyl group, a fluoroethyl group, a chloroethyl group, and a bromoethyl group.

As the alkyl group of R _{40 to} R ₄₂ and R ₄₅ ,
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. As 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 alkylene group of X _{7 to} X ₉ 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. Preferred examples of the alkylene group, alkenylene group, and cycloalkylene group represented by R _{43 to} R ₄₄ and R ₄₆ include the same as the preferred examples of X _{7 to} X ₉ described above, and further, an ether group, an ester group, At least one of an amide group, a urethane group and a ureido group
One in which one and two together form a divalent group.

As further substituents of the above-mentioned substituents, preferably, a hydroxyl group, a halogen atom (fluorine,
Chlorine, bromine, iodine), nitro group, cyano group, amide group, sulfonamide group, alkyl group of R _{1 to} R ₅ , methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group, butoxy group, etc. Examples include an alkoxycarbonyl group such as an alkoxy group, a methoxycarbonyl group and an ethoxycarbonyl group, an acyl group such as a formyl group, an acetyl group and a benzoyl group, an acyloxy group such as an acetoxy group and a butyryloxy group, and a carboxy group.

The content of the above-mentioned repeating structural unit having a carboxyl group (preferably the repeating structural units represented by formulas (X) to (XII)) in the resin according to the present invention depends on the alkali developability and the substrate adhesion. Although it is adjusted by the performance such as sensitivity, it is preferably in the range of 0 to 60 mol%, more preferably 0 to 40 mol%, and still more preferably 0 to 20 mol%, based on all repeating units. Here, the content of the carboxyl group-containing repeating structural unit is determined by the general formulas (I) to (II) containing a carboxyl group.
It is the amount of all the carboxyl group-containing repeating structural units in the resin, including the repeating structural unit having the group represented by I) and the acid-decomposable group-containing repeating structural unit having a carboxyl group. Specific examples (c1) to (c18) of the repeating structural units represented by formulas (X) to (XII) are shown below, but the present invention is not limited thereto.

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[0057]

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[3] Resin of Component (B) of the Present Invention Having the Recurring Structural Unit In order to improve the performance of the resin of component (B) of the present invention,
Other polymerizable monomers may be further copolymerized within a range that does not significantly impair the transmittance of the resin at 220 nm or less and the dry etching resistance. Copolymerizable monomers that can be used include those shown below. For example, it has one addition-polymerizable unsaturated bond selected from acrylates, acrylamides, methacrylates, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, crotonates, and the like. Compound.

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

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

Vinyl ethers such as alkyl vinyl ethers (eg, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether,
Ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, Tetrahydrofurfuryl vinyl ether, etc.), vinyl aryl ethers (for example, vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-
2,4-dichlorophenyl ether, vinyl naphthyl ether, vinyl anthranyl ether, etc.); vinyl esters such as vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valate, vinyl caproate, Vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxy acetate, vinyl butoxy acetate,
Vinylphenyl acetate, vinyl acetoacetate,
Vinyl lactate, vinyl-β-phenylbutyrate,
Vinyl cyclohexyl carboxylate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate, and the like;

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

Among 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 (VI)
Repeating structural unit), a repeating structural unit having an acid-decomposable group (preferably, a repeating structural unit represented by any one of formulas (VII) to (IX)), and a repeating structural unit having a carboxyl group as needed (preferably a general formula (VII)). The resin of the component (B) of the present invention containing (X) to (XII) or another polymerizable monomer contains a radical, cation, or anion of an unsaturated monomer corresponding to each structure. It is synthesized by polymerization. More specifically, each monomer is blended based on the preferred composition described above, a polymerization catalyst is added at a monomer concentration of about 10 to 40% by weight in an appropriate solvent, and the mixture is heated and polymerized as needed.

The molecular weight of the resin of the component (B) of the present invention is 2,000 or more by weight average (Mw: polystyrene standard).
Preferably from 3,000 to 1,000,000, more preferably from 5,000 to 200,000, even more preferably from 2 to
It is in the range of 0000 to 100,000.
While the heat resistance and the like are improved, the developability and the like are lowered, and the balance is adjusted to a preferable range by these balances. Further, the degree of dispersion (Mw / Mn) is preferably 1.0 to 5.0, more preferably 1.0 to 3.0.
Image performance (pattern profile, defocus latitude, etc.) is improved. In the present invention, the amount of the resin added to the photosensitive composition is 5 to the total solid content.
It is 0 to 99.7% by weight, preferably 70 to 99% by weight.

The photoacid generator used in the present invention is a compound which generates an acid upon irradiation with actinic rays or radiation.
Examples of the compound used in the present invention that decomposes upon irradiation with actinic rays or radiation to generate an acid include a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization, a photobleaching agent for dyes, and a photochromic Known light (ultraviolet light of 400 to 200 nm, far ultraviolet light, particularly preferably g-ray, h-ray, i-ray, KrF excimer laser light), ArF excimer laser light, electron beam , An X-ray, a molecular beam or an ion beam to generate an acid and a mixture thereof can be appropriately selected and used.

Other compounds that generate an acid upon irradiation with actinic rays or radiation used in the present invention include, for example, SI Schlesinger, Photogr. Sci. Eng., 18, 3
87 (1974), TSBetal, Polymer, 21,423 (1980) and the like diazonium salts, U.S. Pat.Nos. 4,069,055 and 4,06
Ammonium salts described in 9,056, Re 27,992, Japanese Patent Application No. 3-140,140, etc., DC Necker et al., Macromolecules, 1
7,2468 (1984), CSWenetal, Teh, Proc.Conf.Rad.Curing
ASIA, p478 Tokyo, Oct (1988), U.S. Pat.No. 4,069,055
No. 4,069,056, etc.
vello etal, Macromorecules, 10 (6), 1307 (1977), Chem.
& Eng.News, Nov. 28, p31 (1988), EP 104,143,
U.S. Patent Nos. 339,049 and 410,201, JP-A-2-150,84
No. 8, iodonium salts described in JP-A-2-296,514 etc.,
JVCrivello etal, Polymer J. 17, 73 (1985), JVCrive
llo etal. J. Org. Chem., 43, 3055 (1978), WRWatt eta
l, J. Polymer Sci., Polymer Chem. Ed., 22, 1789 (1984),
JVCrivello etal, Polymer Bull., 14,279 (1985), JV
Crivello etal, Macromorecules, 14 (5), 1141 (1981), J.
V. Crivello etal, J. PolymerSci., Polymer Chem. Ed., 17,
2877 (1979), European Patent Nos. 370,693 and 3,902,114
233,567, 297,443, 297,442, U.S. Pat.
No. 33,377, No. 161,811, No. 410,201, No. 339,049,
No. 4,760,013, No. 4,734,444, No. 2,833,827, Dokoku Patent No. 2,904,626, No. 3,604,580, No. 3,604,581,
Sulfonium salts described in JP-A-7-28237 and JP-A-8-27102, JVCrivello et al., Macromorecule
s, 10 (6), 1307 (1977), JVCrivello etal, J. PolymerSc
Selenonium salts described in i., Polymer Chem.Ed., 17, 1047 (1979), etc., CSWen et al., Teh, Proc. Conf. Rad. Curing AS
Onium salts such as arsonium salts described in IA, p478 Tokyo, Oct (1988), U.S. Pat.No. 3,905,815, JP-B-46-4605
No., JP-A-48-36281, JP-A-55-32070, JP-A-60-2
39736, JP-A-61-169835, JP-A-61-169837, JP-A-62-58241, JP-A-62-212401, JP-A-63-70243
Nos., Organohalogen compounds described in JP-A-63-298339, K. Meier et al, J. Rad. Curing, 13 (4), 26 (1986), T.
P. Gill et al, Inorg.Chem., 19, 3007 (1980), D. Astruc, A
Chem. Res., 19 (12), 377 (1896), organometallic / organic halides described in JP-A-2-14145, etc., S. Hayase eta
l, J. Polymer Sci., 25, 753 (1987), E. Reichmanis et al., J.
Pholymer Sci., Polymer Chem. Ed., 23, 1 (1985), QQZhu
etal, J. Photochem., 36, 85, 39, 317 (1987), B. Amit etal,
Tetrahedron Lett., (24) 2205 (1973), DHR Barton eta
l, J. Chem Soc., 3571 (1965), PM Collins et al., J. Chem.
SoC., PerkinI, 1695 (1975), M. Rudinstein et al, Tetrahed
ron Lett., (17), 1445 (1975), JWWalker etal J. Am. Che
m.Soc., 110, 7170 (1988), SCBusman et al., J. Imaging Te
chnol., 11 (4), 191 (1985), HMHoulihan et al, Macormole
cules, 21, 2001 (1988), PM Collins et al., J. Chem. Soc.,
Chem. Commun., 532 (1972), S. Hayase et al, Macromolecule
s, 18, 1799 (1985), E. Reichmanis et al., J. Electrochem. So
c., Solid State Sci. Technol., 130 (6), FMHoulihan et.
al, Macromolcules, 21, 2001 (1988), EP 0290,750
Nos. 046,083, 156,535, 271,851, 0,38
No. 3,343, U.S. Pat.Nos. 3,901,710, 4,181,531, JP-A-60-198538, and a photoacid generator having a 0-nitrobenzyl-type protecting group described in JP-A-53-133022, etc.
etal, Polymer Preprints Japan, 35 (8), G. Berner etal,
J.Rad.Curing, 13 (4), WJMijs etal, Coating Techno
l., 55 (697), 45 (1983), Akzo, H. Adachi et al, Polymer Pr
eprints, Japan, 37 (3), European Patent Nos. 0199,672 and 84515
No. 199,672, No. 044,115, No. 0101,122, U.S. Pat.No. 618,564, No. 4,371,605, No. 4,431,774, JP-A-64-18143, JP-A-2-245756, and Japanese Patent Application No. 3- Compounds that generate sulfonic acid upon photolysis, such as iminosulfonate described in 140109 and the like, JP-A-61-166544,
Disulfone compounds described in JP-A-2-71270,
Examples thereof include diazoketosulfone and diazodisulfone compounds described in JP-A-3-103854, JP-A-3-103856, JP-A-4-210960 and the like.

Further, a group 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, MEWoodhouse et al., J. Am. Chem.
Soc., 104, 5586 (1982), SPPappas etal, J. Imaging Sc
i., 30 (5), 218 (1986), S. Kondoetal, Makromol.Chem., Rap
id Commun., 9,625 (1988), Y.Yamadaetal, Makromol.Che
m., 152, 153, 163 (1972), JVCrivello etal, J. PolymerS
ci., Polymer Chem. Ed., 17, 3845 (1979), U.S. Pat.
49,137, Dokoku Patent 3914407, JP-A-63-26653, JP-A-55-164824, JP-A-62-69263, JP-A-63-146038
JP-A-63-163452, JP-A-62-153853, JP-A-63-163452
Compounds described in JP-A-146029 can be used.

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

Among the compounds capable of decomposing upon irradiation with actinic rays or radiation to generate an acid, those which are particularly effectively used are described below. (1) The following general formula (PAG) substituted with a trihalomethyl group
The oxazole derivative represented by 1) or the general formula (PA)
An S-triazine derivative represented by G2).

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In the formula, R ²⁰¹ 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.

[0073]

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[0074]

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[0075]

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

[0077]

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Here, the formulas Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aryl group. Preferred substituents include an alkyl group, a haloalkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a nitro group, a carboxyl group, an alkoxycarbonyl group, a hydroxy group, a mercapto group, and a halogen atom.

R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ each independently represent a substituted or unsubstituted alkyl group or aryl group. Preferably, an aryl group having 6 to 14 carbon atoms, 1 to 8 carbon atoms
And substituted derivatives thereof. Preferred substituents are those having 1 to 8 carbon atoms for the aryl group.
And an alkyl group having 1 to 8 carbon atoms, a nitro group, a carboxyl group, a hydroxy group and a halogen atom. The alkyl group is an alkoxy group having 1 to 8 carbon atoms, a carboxyl group or an alkoxycarbonyl group. is there.

[0080] Z ^- represents a counter anion, for example BF ₄ ^{-,
_{AsF 6 -, PF 6 -,}} SbF 6 -, SiF 6 2-, ClO 4 -,
CF ₃ SO ₃ ^-, etc. perfluoroalkane sulfonate anion, pentafluorobenzenesulfonic acid anion, condensed polynuclear aromatic sulfonic acid anion such as naphthalene-1-sulfonic acid anion, anthraquinone sulfonic acid anion, a sulfonic acid group-containing dyes Examples include, but are not limited to:

Further, two of R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ and Ar ¹ and Ar ² may be bonded through a single bond or a substituent.

Specific examples include the following compounds, but are not limited thereto.

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[0084]

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[0085]

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[0086]

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[0087]

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[0088]

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[0089]

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[0090]

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[0091]

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[0092]

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[0093]

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

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

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In the formula, Ar^Three, Ar^FourAre each independently substituted
Or an unsubstituted aryl group. R ²⁰⁶Is replaced or
Indicates an unsubstituted alkyl group or aryl group. A is a substitution
Or unsubstituted alkylene, alkenylene, arylene
Shows a substituent group. Specific examples include the compounds shown below.
However, the present invention is not limited to these.

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[0101]

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[0102]

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[0103]

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The amount of the compound capable of decomposing upon irradiation with actinic rays or radiation to generate an acid is usually 0.03% based on the total weight of the photosensitive composition (excluding the coating solvent).
It is used in the range of 0.01 to 40% by weight, preferably 0.0
It is used in an amount of 1 to 20% by weight, more preferably 0.1 to 5% by weight. If the amount of the compound that decomposes upon irradiation with actinic rays or radiation to generate an acid is less than 0.001% by weight, the sensitivity is low, and if the amount is more than 40% by weight, the light absorption of the resist is high. This is not preferable because the profile is deteriorated and the process (especially baking) margin is narrowed.

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

The compound capable of accelerating dissolution in a developer that can be used in the present invention includes two or more phenolic OH groups.
Alternatively, it is a low-molecular compound having at least one carboxy group and a molecular weight of 1,000 or less. When the compound has a carboxy group, an alicyclic or aliphatic compound is preferable for the same reason as described above. The preferable addition amount of these dissolution promoting compounds is 2 to 50% by weight, more preferably 5 to 30% by weight, based on the resin of the present invention. An addition amount exceeding 50% by weight is not preferable because new development defects such as development residue deterioration and pattern deformation during development occur.

Such phenol compounds having a molecular weight of 1,000 or less can be prepared by those skilled in the art by referring to the methods described in, for example, JP-A-4-122938, JP-A-2-28531, US Pat. No. 4,916,210, and EP 219294. It can be easily synthesized at Specific examples of the phenol compound are shown below, but the compounds that can be used in the present invention are not limited to these.

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

Preferred organic basic compounds that can be used in the present invention are compounds that are more basic than phenol. Among them, a nitrogen-containing basic compound is preferable. Preferred chemical environments include the structures of the following formulas (A) to (E).

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Further preferred compounds are nitrogen-containing basic compounds having two or more nitrogen atoms having different chemical environments in one molecule, and particularly preferred is a ring structure containing a substituted or unsubstituted amino group and a nitrogen atom. Or a compound having an alkylamino group. Preferred specific examples include substituted or unsubstituted guanidine, substituted or unsubstituted aminopyridine, substituted or unsubstituted aminoalkylpyridine, substituted or unsubstituted aminopyrrolidine, substituted or unsubstituted indazol,
Substituted or unsubstituted pyrazole, substituted or unsubstituted pyrazine, substituted or unsubstituted pyrimidine, substituted or unsubstituted purine, substituted or unsubstituted imidazoline, substituted or unsubstituted pyrazoline, substituted or unsubstituted piperazine, substituted Or, unsubstituted aminomorpholine, substituted or unsubstituted aminoalkylmorpholine and the like can be mentioned. Preferred substituents are an amino group,
An aminoalkyl group, an alkylamino group, an aminoaryl group, an arylamino group, an alkyl group, an alkoxy group, an acyl group, an acyloxy group, an aryl group, an aryloxy group, a nitro group, a hydroxyl group, and a cyano group. As particularly preferred compounds, guanidine, 1,1-dimethylguanidine, 1,1,3,3-tetramethylguanidine, 2-
Aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2-diethylaminopyridine, 2- (aminomethyl) pyridine, 2-amino-3-methylpyridine, 2-amino -4-methylpyridine, 2-amino-5
-Methylpyridine, 2-amino-6-methylpyridine,
3-aminoethylpyridine, 4-aminoethylpyridine, 3-aminopyrrolidine, piperazine, N- (2-aminoethyl) piperazine, N- (2-aminoethyl) piperidine, 4-amino-2,2,6,6 -Tetramethylpiperidine, 4-piperidinopiperidine, 2-iminopiperidine, 1- (2-aminoethyl) pyrrolidine, pyrazole, 3-amino-5-methylpyrazole, 5-amino-3-methyl-1-p- Tolylpyrazole, pyrazine, 2- (aminomethyl) -5-methylpyrazine, pyrimidine, 2,4-diaminopyrimidine, 4,6-dihydroxypyrimidine, 2-pyrazoline, 3-pyrazoline,
Examples include, but are not limited to, N-aminomorpholine and N- (2-aminoethyl) morpholine.

These nitrogen-containing basic compounds can be used alone or in combination of two or more. The amount of the nitrogen-containing basic compound to be used is generally 0.001-10 parts by weight, preferably 0.01-5 parts by weight, per 100 parts by weight of the photosensitive resin composition (excluding the solvent). When the amount is less than 0.001 part by weight, the effect of the addition of the nitrogen-containing basic compound cannot be obtained.
On the other hand, if it exceeds 10 parts by weight, the sensitivity tends to decrease and the developability of the unexposed part tends to deteriorate.

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

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

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

A surfactant may be added to the above solvent. Specifically, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether,
Polyoxyethylene alkyl allyl ethers such as polyoxyethylene nonylphenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, Sorbitan fatty acid esters such as sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate Surfactants such as polyoxyethylene sorbitan fatty acid esters such as acrylates and the like, F-top EF301, E 303, EF352 (manufactured by Shin Akita Kasei Co., Ltd.), Megafac F171, F173 (manufactured by Dainippon Ink Co., Ltd.), Flora - de FC430, FC43
1 (manufactured by Sumitomo 3M Limited), Asahi Guard AG71
0, Surflon S-382, SC101, SC102,
Fluorinated surfactants such as SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), and acrylic or methacrylic (co) polymerized polyflow No. 75, no. 95 (manufactured by Kyoeisha Yushi Kagaku Kogyo KK) and the like. The amount of these surfactants is usually 2 parts by weight or less, preferably 1 part by weight or less, per 100 parts by weight of the solids in the composition of the present invention. These surfactants may be added alone or in some combination.

The above-mentioned photosensitive composition is applied on a substrate (eg, silicon / silicon dioxide coating) 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 of 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.

[0119]

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))] 15.4 g (0.10 mol) of methacrylic anhydride and 28.5 g (0.10 mol) of the following compound (1) in 200 ml of tetrahydrofuran (THF) Was dissolved. N,
A solution of 12.3 g (0.10 mol) of N-dimethylaminopyridine in 50 ml of DMF was added at room temperature with stirring. The mixture was further heated under reflux for 5 hours while stirring. After cooling, the reaction solution was poured into 3 L of ion-exchanged water with vigorous stirring.
Extracted with 300 ml of ethyl acetate. The ethyl acetate solution was washed with water, dried over magnesium sulfate, and concentrated under reduced pressure. Column chromatography (filler: silica gel,
Eluent: hexane / ethyl acetate = 4/1)
21.7 g of a colorless liquid were obtained. By NMR measurement, it was confirmed that this liquid was the raw material monomer of Structural Example (a1) of the present invention.

[0120]

Embedded image

[Synthesis Example 2 (Synthesis of Raw Material Monomer of Structural Example (a4))] In place of compound (1) of Synthesis Example 1, 38.8 g of the following compound (2) (3β-cholesterol) (0.
10 mol), and 27.2 g of a colorless liquid was obtained in the same manner as in Synthesis Example 1 except for the above. By NMR measurement, it was confirmed that this liquid was the raw material monomer of Structural Example (a4) of the present invention.

[0122]

Embedded image

[Synthesis Example 3 (Synthesis of Raw Material Monomer of Structural Example (a7))] In place of compound (1) of Synthesis Example 1, 37.7 g (0.10) of the following compound (3) (deoxycholic acid)
Mol), and the others were the same as in Synthesis Example 1 to obtain 25.4 g of a white powder. By NMR measurement, it was confirmed that this liquid was a raw material monomer of Structural Example (a7) of the present invention.

[0124]

Embedded image

Synthesis Example 4 (Synthesis of Starting Monomer of Structural Example (a10)) The following compound (4) (17α-ethynyltestosterone) was used in place of compound (1) of Synthesis Example 1.
0 g (0.10 mol) was used, and the other conditions were the same as in Synthesis Example 1 to obtain 20.5 g of a white powder. By NMR measurement, it was confirmed that this liquid was the raw material monomer of Structural Example (a10) of the present invention.

[0126]

Embedded image

[Synthesis Example 5 (Synthesis of Raw Material Monomer of Structural Example (a8))] The following compound (5) (lysocholic acid) 18.8
g (0.050 mol) and 7.8 g (0.050 mol) of 2-isocyanatoethyl methacrylate in dioxane 20.
After dissolving in 0 ml, 0.1 g of dibutyltin dilaurate was added as a catalyst, and the mixture was heated and stirred at 90 ° C. for 5 hours. After cooling, the reaction solution was poured into 3 L of ion-exchanged water with vigorous stirring to precipitate a viscous solid. The precipitated viscous solid was separated by decantation, washed with water, and then purified by column chromatography (filler: silica gel, eluent: ethyl acetate) to obtain 19.7 g of a white powder. NM
By R measurement, it was confirmed that this powder was the raw material monomer of Structural Example (a8) of the present invention.

[0128]

Embedded image

[Synthesis Example 6 (Synthesis of Raw Material Monomer of Structural Example (a22))] 9.8 g (0.10 mol) of maleic anhydride was dissolved in 200 ml of THF, and 23.8 g of pyridine was added. 1) 28.5 g (0.10 mol) was added, and the mixture was heated under reflux for 5 hours. After cooling, the reaction solution was poured into 3 L of ion-exchanged water with vigorous stirring to precipitate a viscous solid. The precipitated viscous solid was separated by decantation and washed with water, and then purified by column chromatography (filler: silica gel, eluent: hexane / ethyl acetate = 1/1) to obtain 23.8 g of a white powder. By NMR measurement, it was confirmed that this powder was the raw material monomer of Structural Example (a22) of the present invention.

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

[Synthesis Example 8 (Synthesis of Raw Material Monomer of Structural Example (b15))] 17.2 g (0.20 mol) of methacrylic acid,
25.2 g (0.30 mol) of dihydropyran was added to THF2
Dissolved in 00 ml. To this solution was added 0.1 g of 2-ethylhexyl phosphate as a catalyst, and the mixture was heated and stirred at 50 ° C. for 8 hours. After neutralizing the catalyst with triethylamine, purification was performed by distillation under reduced pressure to obtain 26.5 g of a colorless liquid. By NMR measurement, it was confirmed that this liquid was the raw material monomer of Structural Example (b15) of the present invention.

[Synthesis Example 9 (Synthesis of Starting Monomer of Structural Example (b18))] In place of dihydropyran of Synthesis Example 8, 21.6 (0.30 mol) of ethyl vinyl ether was used.
Otherwise, in the same manner as in Synthesis Example 7, 24.5 g of a colorless liquid was obtained. According to NMR measurement, this liquid was found to be a structural example of the present invention (b1
It was confirmed to be the starting monomer of 8).

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

[Synthesis Example 11 (Synthesis of Resin of the Present Invention Consisting of Structural Example (a7) / (b7) / Acrylonitrile)] The starting monomer of Structural Example (a7) / (b7) obtained in the above Synthetic Example was used. 20.0 g (0.045 mol) /4.31 g each
(0.025 mol), and 1.59 g of acrylonitrile
(0.030 mol) was dissolved in 60 ml of 1-methoxy-2-propanol, and the polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) (Wako Pure Chemical Industries, Ltd.) was added at 70 ° C. under a nitrogen stream and stirring. (Product name: V-65, manufactured by Yakuhin Kogyo Co., Ltd.)
100 mg was added. Two hours and four hours after the start of the reaction, 100 mg of the same initiator was added. After further reacting for 3 hours, the temperature was raised to 90 ° C., and stirring was continued for 1 hour. After allowing the reaction solution to cool, it was poured into 1 L of ion-exchanged water with vigorous stirring to precipitate a polymer. The obtained polymer was dried at 40 ° C. under reduced pressure to obtain a resin (p-1) 2 of the present invention.
1.9 g were obtained. When the molecular weight was measured by GPC,
28.7 × 10 in weight average (Mw: in terms of polystyrene)
³ (dispersion degree (Mw / Mn) 2.6).

[Synthesis Example 12 (Structure example (a1) / (b15) /
Synthesis of Resin of the Present Invention Consisting of (c2))] The starting monomers of Structural Examples (a1) / (b15) obtained in the above Synthesis Examples were each 1
7.7 g (0.050 mol) /5.96 g (0.035
Mol), and 1.29 g (0.015 mol) of methacrylic acid were dissolved in 60 ml of 1-methoxy-2-propanol, followed by reaction and post-treatment in the same manner as in Synthesis Example 11 to obtain the resin (p-2) of the present invention. ) 22.6 g were obtained. When the molecular weight was measured by GPC, the weight average (Mw: in terms of polystyrene) was 32.5 × 10 ³ , and the degree of dispersion (Mw / Mn) was 2.
8).

[Synthesis Examples 13 to 30 (Resin of the present invention (p-
3) Synthesis of (p-20))] In the same manner as in Synthesis Examples 11 and 12, the resin of the present invention was synthesized using the raw material monomers of the repeating structural units shown in Table 1 below. 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.

[0137]

[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.

[0139]

[Table 2]

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

Example 2 (Measurement of Dry Etching Resistance) 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 filtered with 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).

[0142]

[Table 3]

From the results shown in Table 3, it can be seen that the etching rate of the resin of the present invention is sufficiently smaller than the values of the poly (methyl methacrylate) and the polymer (1) of the comparative example, and that the resin has a sufficient dry etching resistance.

Example 3 (Evaluation of image) 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. Apply uniformly on a silicon substrate that has been treated with hexamethyldisilazane by a spin coater,
Heat and dry on a hot plate for 0 seconds, 0.4 μm
Was formed. For this resist film, K
rF excimer laser stepper (NA = 0.42;
(248 nm) and heated on a hot plate at 110 ° C. for 60 seconds immediately after exposure. Further, the film was immersed and developed in a 2.0% 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.

[0145]

[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) A mask having a pattern drawn with chrome on a quartz plate was adhered to the 0.4 μm resist film obtained in Example 3, and
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 and developed in a 2.0% aqueous solution of tetramethylammonium hydroxide at 23 ° C. for 60 seconds.
After rinsing with pure water for 2 seconds, it was dried. As a result, Table 5
With the sensitivity and resolution shown in (1), a favorable positive pattern was formed in which only the exposed portions of the resist film were dissolved and removed. The sensitivity, resolution and pattern shape were evaluated in the same manner as described above.

[0148]

[Table 5]

From the results shown in Table 5, it can be seen that the resist using the resin of the present invention shows good sensitivity and resolution to ArF excimer laser light and forms a good positive pattern.

[0150]

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 and good dry etching resistance. 250 nm or less,
Further, when far ultraviolet light (especially ArF excimer laser light) having a wavelength of 220 nm or less is used as an exposure light source, it exhibits high sensitivity, high resolution, and a good pattern profile, and is effectively used for forming a fine pattern required for semiconductor device production. It is possible.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI H01L 21/027 H01L 21/30 502R

Claims (8)

[Claims] (A) by irradiation with actinic rays or radiation
A compound generating an acid, and (B) a compound represented by the following general formula (I):
Of a monovalent polycyclic alicyclic group represented by (II) or (III)
At least one of them is decomposed by the action of an acid
Resin having a group that increases the solubility in the re-developing solution.
A positive photosensitive composition characterized by containing: Embedded imageIn the formulas (I) to (III), R₁~ R_FiveAre the same but different
Or an alkyl group or a silyl group which may have a substituent.
Chloroalkyl, alkenyl or alkynyl,
Halogen atom, cyano group, -R₆-OR₇Group, -R₈
-CO-OR ₉Group, -R_Ten-CO-NR₁₁R₁₂Group or
-R₁₃-O-CO-R₁₄Represents a group. R₇, R₉Is the same
May have a hydrogen atom, a substituent,
Alkyl, cycloalkyl or alk
Decomposed by the action of a carbonyl group or acid in an alkaline developer
Represents a group that increases the solubility in R₁₁~ R₁₂, R₁₄Is
May be the same or different and have a hydrogen atom or a substituent
An alkyl group, a cycloalkyl group or an
Represents a phenyl group;₁₁And R₁₂Bond to form a ring
good. R₆, R₈, R_Ten, R₁₃Are the same but different
May also have a single bond or a substituent,
Alkylene group, alkenylene group, or cycloalkylene
Represents a group. l, m, n, p and q are the same or different
And may represent 0 or an integer of 1 to 5. Where l, m,
When n, p or q is 2 or more, a plurality of R₁~ R_FiveIs
The two Rs may be the same or different.₁~ R
_FiveAre substituted on the same carbon atom,
Represents a bonyl group (＝ O) or a thiocarbonyl group (＝ S)
And two more R₁~ R_FiveIs an adjacent carbon atom
In the case of substitution on the above, the two bond to each other
It may represent a double bond between elementary atoms. Also, R₁~ R_Five
Are each substituted by two or more, the two R₁~ R
_FiveMay combine with each other to form a ring. General formula
Monovalent polycyclic fat represented by (I), (II) or (III)
The position of the bond of the cyclic group is determined in the hydrocarbon polycyclic structure.
Any position may be used. 2. The resin of component (B) has the following general formula (I)
V), of the repeating structural unit represented by (V) or (VI)
At least one of them is decomposed by the action of an acid
With a group that increases the solubility in the re-developing solution
2. The positive-type photosensitive set according to claim 1, wherein
Adult. Embedded imageIn the formulas (IV) to (VI), R_Fifteen, R₁₆, R₁₈~ R₂₀Is the same
May be different, such as hydrogen atom, halogen atom, cyano
Represents a group, an alkyl group or a haloalkyl group. R₁₇Is
Ano group, -CO-OR₂₇Or -CO-NR₂₈R₂₉The table
You. X₁~ X_ThreeMay be the same or different and are
Or a divalent alkylene which may have a substituent
Group, alkenylene group or cycloalkylene group, -O
-, -SO_Two-, -O-CO-R₃₀-, -CO-OR
₃₁-Or -CO-NR ₃₂-R₃₃Represents-. R₂₇Is hydrogen
Atom, optionally substituted alkyl group, cyclo group
By the action of an alkyl or alkenyl group or acid
Groups that decompose to increase solubility in alkaline developers
Represent. R₂₈, R₂₉, R₃₂May be the same or different, water
An atom, an optionally substituted alkyl group,
Represents a loalkyl group or an alkenyl group. Also R₂₈And R₂₉
May combine to form a ring. R₃₀~ R₃₁, R₃₃Is the same
Or a single bond or a divalent alkyl
Represents a len group, alkenylene group or cycloalkylene group.
Further, these groups are ether groups, ester groups,
Di-, urethane or ureido groups
May be formed. Y is a general formula according to claim 1
It represents a polycyclic alicyclic group represented by (I) to (III). 3. The resin according to claim 2, wherein the resin (B) is a resin.
The repeating structure represented by the general formula (IV), (V) or (VI)
At least one of the structural units, and the following general formula (VII):
Of the repeating structural units represented by (VIII) or (IX)
Having at least one, decomposed by the action of an acid
Characterized by a resin that increases solubility in re-developing solutions
The positive photosensitive composition according to claim 1 or 2, wherein Embedded imageIn the formulas (VII) to (IX), R_{twenty one}, R_{twenty two}, R_{twenty four}~ R₂₆Is the same
May be different, such as hydrogen atom, halogen atom, cyano
Represents a group, an alkyl group or a haloalkyl group. R_{twenty three}Is
Ano group, -CO-OR₂₇Or -CO-NR₂₈R₂₉The table
You. X_Four~ X₆May be the same or different and are
Or a divalent alkylene which may have a substituent
Group, alkenylene group or cycloalkylene group, -O
-, -SO_Two-, -O-CO-R₃₀-, -CO-OR
₃₁-Or -CO-NR ₃₂-R₃₃Represents-. R₂₇Is hydrogen
Atom, optionally substituted alkyl group, cyclo group
By the action of an alkyl or alkenyl group or acid
Groups that decompose to increase solubility in alkaline developers
Represent. R₂₈, R₂₉, R₃₂May be the same or different, water
An atom, an optionally substituted alkyl group,
Represents a loalkyl group or an alkenyl group. Also R₂₈And R₂₉
May combine to form a ring. R₃₀~ R₃₁, R₃₃Is the same
Or a single bond or a divalent alkyl
Represents a len group, alkenylene group or cycloalkylene group.
Further, these groups are ether groups, ester groups,
Di-, urethane or ureido groups
May be formed. B is decomposed by the action of an acid
Represents a group that increases the solubility in a potash developer. 4. The positive photosensitive composition according to claim 1, wherein the resin as the component (B) further has a carboxyl group. 5. The resin of component (B) further comprises at least one of repeating structural units having a carboxyl group and represented by the following general formula (X), (XI) or (XII). The positive photosensitive composition according to claim 4, wherein Embedded image In formulas (X) to (XII), R ₃₄ , R ₃₅ and R _{37 to} R ₃₉ may be the same or different and represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group or a haloalkyl group. R ₃₆ represents a cyano group, a carboxyl group, —CO—OR ₄₀ or —CO—
Represents NR ₄₁ R ₄₂ . X _{7 to} X ₉ may be the same or different, may be a single bond, may have a substituent, a divalent alkylene group, an alkenylene group or a cycloalkylene group,
_{-O -, - SO 2 -,} - O-CO-R 43 -, - CO-O
-R ₄₄ - or -CO-NR ₄₅ -R ₄₆ - represents a. R ₄₀ represents an alkyl group, a cycloalkyl group, or an alkenyl group which may have a substituent. R ₄₁ , R ₄₂ and R ₄₅ may be the same or different and represent a hydrogen atom, an alkyl group, a cycloalkyl group or an alkenyl group which may have a substituent, wherein R ₄₁ and R ₄₂ are A ring may be formed.
R ₄₃ , R ₄₄ , and R ₄₆ may be the same or different and represent a single bond, 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. 6. A compound having a group which can be decomposed by the action of an acid, and has an increased solubility in an alkali developer due to the action of an acid.
The positive photosensitive composition according to any one of claims 1 to 5, further comprising a low-molecular acid-decomposable dissolution inhibiting compound having a molecular weight of 3,000 or less. 7. 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. 8. The positive photosensitive composition according to claim 7, wherein far-ultraviolet light having a wavelength of 220 nm or less is used as an exposure light source.