JP2001125269A - Chemical amplification type resist composition, method for preparing the same and pattern forming method using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a chemical amplification type resist composition containing an acid generating agent and an acid decomposable resin, having suitability to coating, shelf stability and high sensitivity and excellent in the stability of its sensitivity. SOLUTION: A resist solution containing an acid generating agent and an acid decomposable resin is filtered with a filter containing polyethylene, nylon or polysulfone as a material to obtain the objective chemical amplification type resist composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a chemically amplified resist composition containing an acid generator and an acid-decomposable resin having high sensitivity and excellent sensitivity stability as well as coating properties and storage stability. The present invention relates to a method for preparing the resist composition and a method for forming a pattern using the resist composition.

[0002]

2. Description of the Related Art In recent years, 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 less than half a micron is required. It has become. In order to satisfy the need, the wavelength used in an exposure apparatus used for photolithography is becoming shorter and shorter, and now it is considered to use excimer laser light (XeCl, KrF, ArF, etc.) having a short wavelength among far ultraviolet rays. Up to now.
A chemically amplified resist is used for forming a pattern in lithography in this wavelength region.

In general, chemically amplified resists can be broadly classified into three types: so-called two-component, 2.5-component and three-component resists. The two-component system combines a compound that generates an acid by photolysis (hereinafter referred to as a photoacid generator) and a binder resin. The binder resin is a resin having in its molecule a group (also referred to as an acid-decomposable group) that decomposes under the action of an acid to increase the solubility of the resin in an alkaline developer. The 2.5-component system further contains a low-molecular compound having an acid-decomposable group in such a two-component system. The three-component system contains a photoacid generator, an alkali-soluble resin, and the above low molecular compound.

The above-mentioned chemically amplified resist is suitable for a photoresist for irradiating ultraviolet rays or far ultraviolet rays, but among them, it is necessary to further meet the required characteristics in use. In particular, ultrafine processing is not always successful unless a resist composition in which each component in the composition is completely dissolved in a solvent and maintains stable quality under ordinary storage conditions. JP-A-11-2
JP-A-31539 discloses that a resist solution containing a polymer containing a structural unit containing an alicyclic hydrocarbon group capable of reacting with an acid to be eliminated, an acid generator and a solvent forms a solid having a diameter of 0.1 μm or more. It is described that fine processing was made possible by not including it.

[0005]

However, as described in the art, good sensitivity cannot be obtained simply by not containing solids having a diameter of 0.1 μm or more, and the obtained sensitivity cannot be obtained. Depending on the product, the sensitivity varies greatly,
It turned out that sufficient performance was not obtained. Accordingly, it is an object of the present invention to provide a chemically amplified resist composition containing an acid generator and an acid-decomposable resin which has high sensitivity and excellent sensitivity stability as well as coating properties and storage stability. It is in.

[0006]

According to the prior art,
The inventors further studied various factors in order to derive optimal resist characteristics from the resist material, and as a result, by filtering the resist composition with a filter of a specific material, with good coating properties and storage stability, It has been found that excellent sensitivity and sensitivity stability can be obtained. That is, the present invention includes the following (1) to (3).

(1) A chemically amplified resist composition obtained by filtering a resist solution containing an acid generator and an acid-decomposable resin using a filter containing polyethylene, nylon or polysulfone as a material. object. (2) A method for preparing a chemically amplified resist composition, comprising filtering a resist solution containing an acid generator and an acid-decomposable resin using a filter containing polyethylene, nylon or polysulfone as a material. (3) A pattern forming method, comprising a step of applying the chemically amplified resist composition according to the above (1) on a substrate and a step of exposing the composition to actinic light.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The filter used to filter the resist composition of the present invention is selected from those used in the resist field, and specifically, the material of the filter is polyethylene,
Those containing nylon or polysulfone are used. More specifically, micro guard manufactured by Millipore,
Microguard Plus, Microguard Minichem-
D, Microgard Minichem-D PR, Millipore Obturizer DEV / DEV-C, Millipore Obturizer 16/14, Ultipore N66 manufactured by Pall Corporation, Posidyne, Nylon Falcon, and the like. Also,
The pore diameter of the filter can be the one confirmed by the following method. In other words, PSL standard particles (polystyrene latex beads, particle size 0.100μ
m) is dispersed and continuously flowed at a constant flow rate to the primary side of the filter by a tube pump, and the challenge concentration is measured by a particle counter. Those that can capture 90% or more can be used as a filter having a pore diameter of 0.1 μm.

Hereinafter, a resist composition containing an acid generator and an acid-decomposable resin used in the present invention will be described in detail.

The acid generator (A) 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, 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.

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. En.
g., 18,387 (1974), TS Bal et al, Polymer, 21, 42.
3 (1980) and the like diazonium salts, U.S. Pat.No. 4,069,0
No. 55, 4,069, 056, Re 27,992, JP-A-3-14014
Ammonium salts described in No. 0, etc., DC Necker et al, M
acromolecules, 17, 2468 (1984), CS Wen et al, Te
h, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (19
88), U.S. Pat.Nos. 4,069,055 and 4,069,056, phosphonium salts described in JV Crivello et al, Macromorec
ules, 10 (6), 1307 (1977), Chem. & Eng. News, Nov. 2
8, p31 (1988), European Patent No. 104,143, U.S. Patent No. 339,
No. 049, No. 410,201, JP-A-2-150,848, JP-A 2-2
Iodonium salts described in No. 96,514, JV Crivello
et al, Polymer J. 17, 73 (1985), JV Crivello et
al. J. Org.Chem., 43, 3055 (1978), WR Watt et a
l, J. Polymer Sci., Polymer Chem. Ed., 22, 1789 (198
4), JV Crivello et al, Polymer Bull., 14, 279 (1
985), JV Crivello et al, Macromorecules, 14 (5),
1141 (1981), JVCrivello et al, J. Polymer Sci.,
Polymer Chem. Ed., 17, 2877 (1979), European Patent No. 370,
693, 161,811, 410,201, 339,049, 23
No. 3,567, No. 297,443, No. 297,442, U.S. Pat.
2,114, 4,933,377, 4,760,013, 4,734,444
No. 2,833,827, Dokoku Patent No. 2,904,626, No. 3,604,
No.580, 3,604,581, JP-A-7-28237, sulfonium salts described in JP-A-8-27102, etc., JVCrivello et al, Mac
romorecules, 10 (6), 1307 (1977), JV Crivello et
al, J. Polymer Sci., Polymer Chem. Ed., 17, 1047 (1
979) etc., CS Wen et al, Te
h, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1
Onium salts such as arsonium salts described in 988), etc.

US 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
Organohalogen compounds described in JP-A-63-298339, K. Meier et al, J. Rad.Curing, 13 (4), 26 (198
6), TP Gill et al, Inorg. Chem., 19, 3007 (198
0), D. Astruc, Acc. Chem. Res., 19 (12), 377 (1896),
Organometallic / organic halides described in JP-A-2-14145, S. Hayase et al, J. Polymer Sci., 25, 753 (198
7), E. Reichmanis et al, J. Pholymer Sci., Polymer
Chem. Ed., 23, 1 (1985), QQ Zhu et al, J. Photoch.
em., 36, 85, 39, 317 (1987), B. Amit et al, Tetrahe
dron Lett., (24) 2205 (1973), DHR Barton et al,
J. Chem Soc., 3571 (1965), PM Collins et al, J.
Chem. Soc., PerkinI, 1695 (1975), M. Rudinstein et a
l, Tetrahedron Lett., (17), 1445 (1975), JW Walke
r et al J. Am. Chem. Soc., 110, 7170 (1988), SC B
usman et al, J. Imaging Technol., 11 (4), 191 (198
5), HM Houlihan et al, Macormolecules, 21, 2001 (1
988), PM Collinsetal, J. Chem. Soc., Chem. Commu
n., 532 (1972), S. Hayase et al, Macromolecules, 18,
1799 (1985), E. Reichman et al, J. Electrochem. So
c., Solid State Sci.Technol., 130 (6), FM Houliha
n et al, Macromolcules, 21, 2001 (1988), European Patent No.
0290,750, 046,083, 156,535, 271,851
No. 0,388,343, U.S. Pat.Nos. 3,901,710, 4,181,
No. 531, JP-A-60-198538, a photoacid generator having an o-nitrobenzyl-type protecting group described in JP-A-53-133022, etc.
M. TUNOOKA et al, Polymer Preprints Japan, 35 (8),
G. Berner et al, J. Rad. Curing, 13 (4), WJ Mijs
et al, Coating Technol., 55 (697), 45 (1983), Akzo,
H. Adachi et al, Polymer Preprints, Japan, 37 (3),
European Patent Nos. 0199,672, 84515, 044,115, 61
No. 8,564, No. 0101,122, U.S. Pat.No. 4,371,605, No. 4,
431,774, JP-A-64-18143, JP-A-2-245756, JP-A-3-140109, etc. 61-166544, disulfone compounds described in JP-A-2-71270, JP-A-3-103854, JP-A-3-103856, JP-A-4-2109
And diazoketosulfone and diazodisulfone compounds described in No. 60 and the like.

A group generating an acid by the light;
Alternatively, a compound having a compound introduced into the main chain or side chain of a polymer, for example, ME Woodhouse et al, J. Am. Ch.
em. Soc., 104, 5586 (1982), SP Pappas et al, J. I.
maging Sci., 30 (5), 218 (1986), S. Kondo et al, Mak
romol. Chem., Rapid Commun., 9, 625 (1988), Y. Yama
da et al, Makromol.Chem., 152, 153, 163 (1972);
V. Crivello et al, J. Polymer Sci., Polymer Chem.
Ed., 17, 3845 (1979), U.S. Patent No. 3,849,137, Dokoku Patent No. 3,914,407, JP-A-63-26653, JP-A-55-164824,
JP-A-62-69263, JP-A-63-146038, JP-A-63-1634
Compounds described in JP-A No. 52, JP-A-62-153853, JP-A-63-146029 and the like can be used.

Further, VNR Pillai, Synthesis, (1),
1 (1980), A. Abad et al, Tetrahedron Lett., (47) 4
555 (1971), DHR Barton et al, J. Chem. Soc.,
(C), 329 (1970), U.S. Pat.No. 3,779,778, European Patent No. 12
Compounds that generate an acid by light described in 6,712 and the like can also be used.

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

[0016]

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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
Is shown. Y represents a chlorine atom or a bromine atom. Specific examples include the following compounds, but the present invention is not limited thereto.

[0018]

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[0019]

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[0020]

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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).

[0022]

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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, it is an aryl group having 6 to 14 carbon atoms, an alkyl group having 1 to 8 carbon atoms, or a substituted derivative thereof. Preferred substituents include an aryl group, an alkoxy group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms, a nitro group,
A carboxyl group, a hydroxy group and a halogen atom, and an alkyl group is an alkoxy group having 1 to 8 carbon atoms, a carboxyl group and an alkoxycarbonyl group.

[0025] Z ^{chromatography} represents a counter anion, for example BF ₄ ^over,
AsF ₆ ^over, PF ₆ ^over, SbF ₆ ^over, SiF ₆ ^2-, ClO ₄ ^over,
CF ₃ SO ₃ ^over perfluoroalkanesulfonic acid anion such as, 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 via a single bond or a substituent.

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

[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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The above onium salts represented by the general formulas (PAG3) and (PAG4) are known, for example, JW Knapcz
yk et al, J. Am. Chem. Soc., 91, 145 (1969), AL
Maycok et al, J. Org.Chem., 35, 2532, (1970), E.
Goethas et al, Bull.Soc.Chem.Belg., 73, 546, (19
64), HM Leicester, J. Ame. Chem. Soc., 51, 3587.
(1929), JV Crivello et al, J. Polym. Chem. Ed.,
18, 2677 (1980); U.S. Pat.Nos. 2,807,648 and 4,2
No. 47,473, JP-A-53-101,331 and the like.

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

[0043]

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Where 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.

[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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[0050]

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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 0.1% based on the total weight of the resist composition (excluding the coating solvent).
It is used in the range of 001 to 40% by weight, preferably 0.1 to 40%.
It is used in the range of 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.

Next, the acid-decomposable resin that can be used in the present invention will be described in detail. Such acid-decomposable resins include:
The following resin (B-1), (B-2) or (B-3) is mentioned. In particular, the following resin (B-1) or (B-2) is preferable for the positive photoresist composition for deep ultraviolet exposure.

(B-1) having at least one of the repeating units represented by the following general formulas (Ia) and (Ib) and a repeating unit represented by the following general formula (II),
And a polymer having a group that decomposes under the action of an acid (hereinafter abbreviated as “resin (B-1)”)

[0054]

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In the formula (Ia): R ¹ and R ² are each independently
Hydrogen atom, cyano group, hydroxyl group, -COOH, -COOR
⁵ represents a ^{-CO-NH-R 6, -CO} -NH-SO 2 -R 6, which may be substituted, an alkyl group, an alkoxy group or a cyclic hydrocarbon group, or the following -Y group. X represents an oxygen atom, a sulfur atom, -NH -, - NHSO ₂ - or -NH
Represents SO ₂ NH—. Here, R ⁵ represents an optionally substituted alkyl group, cyclic hydrocarbon group or the following —Y group. R ⁶ represents an alkyl group or a cyclic hydrocarbon group which may have a substituent. A represents a single bond or a divalent linking group. A —Y group;

[0056]

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(In the —Y group, R ^{21 to} R ³⁰ are each independently
Represents a hydrogen atom or an alkyl group which may have a substituent. a and b represent 1 or 2, respectively. In formula (Ib): Z ² represents —O— or —N (R ³ ) —. Here, R ³ is a hydrogen atom, a hydroxyl group or —OSO ₂ —R
Represents ⁴ . R ⁴ represents an alkyl group, a haloalkyl group, a cycloalkyl group or a camphor residue. In the formula (II), R ¹¹ and R ¹² each independently represent a hydrogen atom, a cyano group, a halogen atom, or an alkyl group which may have a substituent. Z represents two bonded carbon atoms (C
-C) and represents an atomic group for forming an alicyclic structure which may have a substituent.

(B-2) The following general formulas (III) and (IV)
(Abbreviated as "resin (B-2)").

[0059]

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In the above general formulas (III) and (IV), R ³¹ is
Represents a hydrogen atom or a methyl group. R ³² represents an alkyl group having 1 to 4 carbon atoms. W represents a single bond, an alkylene group, an ether group, a thioether group, a carbonyl group, or an ester group, or a single or a combination of two or more groups. Ra, Rb, Rc, Rd, and Re each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
m and n each independently represent an integer of 0 to 3, and m + n is 2 or more and 6 or less.

(B-3) A resin having a structural unit containing a group represented by the following general formula (X) and decomposed by the action of an acid to increase the solubility in an alkali developing solution (hereinafter referred to as “resin (B -3) ").

[0062]

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In the general formula (X), R⁵¹, R⁵²Is the same
May be different, a hydrogen atom, an alkyl having 1 to 4 carbon atoms
R⁵³, R⁵⁴May be the same or different
And a hydrogen atom, which may have a substituent,
Represents a cyclic or cyclic alkyl group; ⁵⁵May have a substituent
It may have a good linear, branched or cyclic alkyl group or substituent.
Aryl groups and aralkyl groups which may have
You. m represents an integer of 1 to 20, and n represents an integer of 0 to 5.
You.

In particular, among the above resins (B-3), having the structural units represented by the following general formulas (XI), (XII) and (XIII), they are decomposed by the action of an acid, A resin having increased solubility in a liquid (hereinafter, abbreviated as “resin (B-3) ′”) is preferable.

[0065]

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In the formulas (XI) to (XIII), R ⁶¹ represents a hydrogen atom or a methyl group, R ⁶² represents a group not decomposed by the action of an acid, R ⁶³ represents a hydrogen atom, a halogen atom, an alkyl group,
Represents an aryl group, an alkoxy group, an acyl group or an acyloxy group. n represents an integer of 1 to 3. W represents a group represented by the general formula (X).

First, the resin (B-1) will be described. In the general formula (Ia), R ¹ and R ² each independently represent a hydrogen atom, a cyano group, a hydroxyl group, —COOH, —C
^{OOR 5, -CO-NH-R} 6, -CO-NH-SO 2
—R ⁶ represents an optionally substituted alkyl group, alkoxy group or cyclic hydrocarbon group, or the above-mentioned —Y group.
Wherein, R ⁵ may have a substituent, an alkyl group, cyclic hydrocarbon group or the -Y group. R ⁶ represents an alkyl group or a cyclic hydrocarbon group which may have a substituent. In the -Y group, R ²¹ to R ³⁰ each independently represent a hydrogen atom or an optionally substituted alkyl group, a and b each represents 1 or 2. X is
Oxygen atom, sulfur atom, -NH -, - NHSO ₂ - or -
NHSO represents a ₂ NH-. A represents a single bond or a divalent linking group.

In the formula (Ib), Z ² represents —O— or —N (R ³ ) —. Here, R ³ represents a hydrogen atom, a hydroxyl group, or —OSO ₂ —R ⁴ . R ⁴ represents an alkyl group, a haloalkyl group, a cycloalkyl group or a camphor residue.

The above R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ^{21 to} R
The alkyl group in ³⁰ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, more preferably a linear or branched alkyl group having 1 to 6 carbon atoms, further preferably methyl Group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, s
an ec-butyl group and a t-butyl group. The above R ¹ , R ² ,
Examples of the cyclic hydrocarbon group for R ⁵ and R ⁶ include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a 2-methyl-2-adamantyl group, a norbornyl group, a boronyl group, an isobornyl group, a tricyclodecanyl group, Examples include a dicyclopentenyl group, a nobornane epoxy group, a menthyl group, an isomenthyl group, a neomenthyl group, and a tetracyclododecanyl group. Examples of the alkoxy group in R ¹ and R ² include a methoxy group,
C1-C1 such as ethoxy, propoxy and butoxy groups
Four things can be mentioned. Examples of the haloalkyl group for R ⁴ include a trifluoromethyl group, a nanofluorobutyl group, a pentadecafluorooctyl group, and a trichloromethyl group. Examples of the cycloalkyl group for R ⁴ include a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.

Further substituents of the above-mentioned alkyl group, cyclic hydrocarbon group and alkoxy group include a hydroxyl group, a halogen atom, a carboxyl group, an alkoxy group, an acyl group, a cyano group and an acyloxy group. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. As the alkoxy group,
Examples thereof include those having 1 to 4 carbon atoms such as methoxy group, ethoxy group, propoxy group and butoxy group. Examples of the acyl group include formyl group and acetyl group. Examples of the acyloxy group include acetoxy group. Can be mentioned.

The divalent linking group represented by A in the general formulas (Ia) and (Ib) includes an alkylene group, a substituted alkylene group, an ether group, a thioether group, a carbonyl group,
Examples thereof include a single group selected from the group consisting of an ester group, an amide group, a sulfonamide group, a urethane group, and a urea group, or a combination of two or more groups. Examples of the alkylene group and substituted alkylene group in A include groups represented by the following formula.

-[C (Rx) (Ry)] r-

In the formula, Rx and Ry represent a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, or an alkoxy group, and they may be the same or different. As the alkyl group, a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group is preferable, and a methyl group, an ethyl group, and a propyl group are more preferable.
Selected from isopropyl groups. Examples of the substituent of the substituted alkyl group include a hydroxyl group, a halogen atom and an alkoxy group. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. r represents an integer of 1 to 10.

Specific examples of the repeating unit represented by the general formula (Ia) include the following [I-1] to [I-65], but the present invention is not limited to these specific examples. Absent.

[0075]

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[0076]

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[0077]

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[0078]

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[0079]

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[0080]

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Specific examples of the repeating unit represented by formula (Ib) include the following [I'-1] to [I'-7], but the present invention is limited to these specific examples. Not something.

[0082]

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[0083]

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In the above general formula (II), R ¹¹ , R
Each ¹² independently represents a hydrogen atom, a cyano group, a halogen atom, or an alkyl group which may have a substituent.
Z represents an atomic group containing two bonded carbon atoms (C-C) and forming an alicyclic structure which may have a substituent.

Examples of the halogen atom in R ¹¹ and R ¹² include a chlorine atom, a bromine atom, a fluorine atom and an iodine atom. The alkyl group for R ¹¹ and R ¹² is preferably a straight-chain or branched alkyl group having 1 to 10 carbon atoms, more preferably a straight-chain or branched alkyl group having 1 to 6 carbon atoms. More preferably methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group,
t-butyl group.

Further substituents on the alkyl groups R ¹¹ and R ¹² include a hydroxyl group, a halogen atom, a carboxyl group, an alkoxy group, an acyl group, a cyano group and an acyloxy group. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom and an iodine atom, and examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group. And formyl group as acyl group,
An acetyl group and the like can be mentioned, and an acyloxy group can be an acetoxy group and the like.

The atomic group for forming the alicyclic structure of Z is an atomic group for forming a repeating unit of an alicyclic hydrocarbon which may have a substituent on the resin. An atomic group for forming a bridged alicyclic structure forming a repeating unit of the alicyclic hydrocarbon is preferable. Examples of the skeleton of the formed alicyclic hydrocarbon include those represented by the following structures.

[0088]

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[0089]

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Preferred bridged alicyclic hydrocarbon skeletons include (5), (6), (7),
(9), (10), (13), (14), (15),
(23), (28), (36), (37), (42),
(47).

The alicyclic hydrocarbon skeleton may have a substituent. Examples of such a substituent include R ^{13 to} R ¹⁶ in the following general formula (II-A) or (II-B). Among the repeating units having a bridged alicyclic hydrocarbon, a repeating unit represented by the following general formula (II-A) or (II-B) is more preferable.

[0092]

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Formula (II-A) or (II-B)
In, R¹³~ R¹⁶Is independently a hydrogen atom, a halo
Gen atom, cyano group, -COOH, -COOR^Five(R^FiveIs
An alkyl group or a cyclic hydrocarbon which may have a substituent
A group or the same -Y group as in the above general formula (I).
), A group decomposed by the action of an acid, -C (= O) -X-
AR¹⁷Or an alkyl group which may have a substituent
Or a cyclic hydrocarbon group. n represents 0 or 1. X
Represents an oxygen atom, a sulfur atom, -NH-, -NHSO _Two-Again
Is -NHSO_TwoRepresents NH-. R¹⁷Is -COOH,-
COOR^Five, -CN, a hydroxyl group and a substituent
Alkoxy group, -CO-NH-R⁶, -CO-NH-
SO_Two-R⁶(R^Five, R⁶Is the same as defined above)
Represents a -Y group in the general formula (Ia). A is a single bond or divalent
Represents a linking group.

In the resin (B-1), the acid-decomposable group is
The above -C (= O) -XA-R ¹ , -C (= O) -X-
It may be contained in AR ² or as a substituent of Z in the general formula (II). As the structure of the acid-decomposable group,
—C (＝ O) —X ¹ —R ⁰ . In the formula, R ⁰ represents a tertiary alkyl group such as a t-butyl group and a t-amyl group;
Alkoxy such as 1-alkoxyethyl group such as isobornyl group, 1-ethoxyethyl group, 1-butoxyethyl group, 1-isobutoxyethyl group and 1-cyclohexyloxyethyl group, 1-methoxymethyl group and 1-ethoxymethyl group Methyl group, 3-oxoalkyl group, tetrahydropyranyl group, tetrahydrofuranyl group, trialkylsilyl ester group, 3-oxocyclohexyl ester group, 2-
Methyl-2-adamantyl group, mevalonic lactone residue, 2- (γ-butyrolactonyloxycarbonyl)-
Examples thereof include a 2-propyl group. X ¹ has the same meaning as X described above.

Examples of the halogen atom for R ^{13 to} R ¹⁶ include a chlorine atom, a bromine atom, a fluorine atom and an iodine atom.

The alkyl group represented by R ^{13 to} R ¹⁶ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, more preferably a linear or branched alkyl group having 1 to 6 carbon atoms. And more preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group and a t-butyl group.

The cyclic hydrocarbon group represented by R ^{13 to} R ¹⁶ is, for example, a cyclic alkyl group or a bridged hydrocarbon group such as cyclopropyl group, cyclopentyl group, cyclohexyl group, adamantyl group, 2-methyl-2-adamantyl. Group, norbornyl group, boronyl group, isobornyl group,
Examples include a tricyclodecanyl group, a dicyclopentenyl group, a nobornane epoxy group, a menthyl group, an isomenthyl group, a neomenthyl group, and a tetracyclododecanyl group. The ring formed by combining at least two of the above R ^{13 to} R ¹⁶ includes cyclopentene, cyclohexene, cycloheptane, cyclooctane and the like having 5 to 1 carbon atoms.
And 2 rings.

As the alkoxy group for R ¹⁷ ,
Examples thereof include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group.

Further substituents in the above alkyl group, cyclic hydrocarbon group and alkoxy group include a hydroxyl group, a halogen atom, a carboxyl group, an alkoxy group, an acyl group, a cyano group and an acyloxy group. As the halogen atom, a chlorine atom, a bromine atom, a fluorine atom,
And iodine atoms. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Examples of the acyl group include a formyl group and an acetyl group. Examples thereof include an acetoxy group.

Examples of the divalent linking group of A include a single bond, an alkylene group, a substituted alkylene group, an ether group, a thioether group, and a carbonyl group, similarly to the divalent linking group of A in formula (Ia). , An ester group, an amide group,
A single one selected from the group consisting of a sulfonamide group, a urethane group, and a urea group, or a combination of two or more groups is exemplified. As the alkylene group and the substituted alkylene group in the above A, 2 of A in the general formula (Ia)
Examples are the same as those of the valent linking group.

In the resin (B-1), the group which decomposes under the action of an acid is a repeating unit represented by the general formula (Ia), a repeating unit represented by the general formula (Ib) or a repeating unit represented by the general formula (II) And at least one of the repeating units of the copolymer component described below.

The above formula (II-A) or (II
The various substituents of R ^{13 to} R ¹⁶ in —B) may be an atomic group for forming an alicyclic structure in the above general formula (II) or an atomic group Z for forming a bridged alicyclic structure. It also serves as a substituent.

The formula (II-A) or the formula (II
-B) As specific examples of the repeating unit represented by the following [II]
-1] to [II-166], but the present invention is not limited to these specific examples.

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[0115]

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[0120]

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The resin (B-1) comprises at least one of the repeating units represented by the general formulas (Ia) and (Ib), and the resin represented by the general formula (II) (the general formula (II-A),
A repeating unit represented by the general formula (II-B):
In addition to including one or more of each, for the purpose of adjusting dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and resolution, heat resistance, sensitivity, and other general requirements of resist, It can be a copolymer containing repeating units of various monomers.
Preferred copolymerization components include the following general formula (IV ′):
And a repeating unit represented by (V ′).

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Here, in the formula, Z is an oxygen atom, -NH-,-
^{N (-R 40) -, -} N (-OSO 2 R 40) - represents, R
⁴⁰ also has the same meaning as the above (substituted) alkyl group and (substituted) cyclic hydrocarbon group. The general formulas (IV ′) and (V
') The following [IV'
-9] to [IV'-16], [V'-9] to [V'-1]
6], but is not limited to these specific examples.

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[0125]

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The resin (B-1) may be copolymerized with the following monomers to give a repeating unit constituting the resin, as long as the effects of the present invention can be effectively obtained. Good, but not limited to the following monomers.
Thereby, the performance required for the resin, particularly (1) solubility in a coating solvent, (2) film forming property (glass transition point), (3) alkali developability, and (4) film loss (hydrophobicity, alkali (Selection of a soluble group), (5) adhesion of the unexposed portion to the substrate, and (6) dry etching resistance can be finely adjusted. As such a comonomer, for example,
Examples thereof include compounds having one addition-polymerizable unsaturated bond selected from acrylates, methacrylates, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, and the like.

Specifically, for example, acrylates such as alkyl (the alkyl group has 1 to 1 carbon atoms)
Acrylates (for example, methyl acrylate, ethyl acrylate, propyl acrylate, amyl acrylate, cyclohexyl acrylate, ethylhexyl acrylate, octyl acrylate, acrylate-
t-octyl, chloroethyl acrylate, 2-hydroxyethyl acrylate 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate, Tetrahydrofurfuryl 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, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate,
Benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate,
5-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, etc.);

Acrylamides, for example, acrylamide, N-alkylacrylamide, (alkyl group having 1 to 10 carbon atoms, for example, methyl group, ethyl group, propyl group, butyl group, t-butyl group, heptyl group, octyl Group, cyclohexyl group, hydroxyethyl group, etc.), N, N-dialkylacrylamide (alkyl group having 1 to 10 carbon atoms, for example, methyl group, ethyl group, butyl group, isobutyl group, ethylhexyl group, Cyclohexyl group, etc.), N-
Hydroxyethyl-N-methylacrylamide, N-2
-Acetamidoethyl-N-acetylacrylamide and the like;

Methacrylamides, for example, methacrylamide, N-alkyl methacrylamide (alkyl having 1 to 10 carbon atoms, for example, methyl, ethyl, t-butyl, ethylhexyl, hydroxyethyl, cyclohexyl) Groups, etc.), N, N-dialkylmethacrylamide (an alkyl group includes an ethyl group, a propyl group, a butyl group, etc.), N-hydroxyethyl-N-methylmethacrylamide and the like;

Allyl compounds such as allyl esters (eg, allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate), allyloxy Ethanol, 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-ethyl Butyl 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 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, Vinyl acetoacetate, vinyl lactate, vinyl-β-phenylbutyrate, vinylcyclohexylcarboxylate and the like;

Dialkyl itaconates (eg, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, etc.); acrylic acid, methacrylic acid, crotonic acid, itaconic acid, acrylonitrile, methacrylonitrile and the like.

In the resin (B-1), the compound represented by the general formula (Ia)
And / or the repeating unit represented by the general formula (Ib); and the general formula (II) (the general formula (II-A) or the general formula (II-
The content of the repeating unit represented by the formula (B) also includes the desired resist dry etching resistance, sensitivity, pattern cracking prevention, substrate adhesion, resist profile, and resolution which is a necessary requirement of general resists. , Heat resistance, etc., and can be set as appropriate.
Generally, the content of the repeating unit represented by the general formula (Ia) and / or the general formula (Ib) in the resin (B-1) and the content of the repeating unit represented by the general formula (II) are as follows: The content is suitably at least 25 mol%, preferably at least 30 mol%, more preferably at least 35 mol%, based on all monomer repeating units of the resin.

Further, in the resin (B-1), the content of the repeating unit (general formula (IV ′) or general formula (V ′)) derived from the above-mentioned preferable comonomer in the resin is not limited. Can be appropriately set according to the performance of the resist, but generally, the repeating unit represented by the general formula (Ia) and / or the general formula (Ib) and the repeating unit represented by the general formula (II) To the total number of moles
It is preferably at most 90 mol%, more preferably at most 90 mol%, even more preferably at most 80 mol%. In addition, the content of the repeating unit based on the monomer of the further copolymerization component in the resin can also be appropriately set according to the desired resist performance. In general, the general formula (Ia) and the general formula (Ia) And / or 99 mol% or less, more preferably 9 mol%, based on the total number of moles of the repeating unit represented by the general formula (Ib) and the repeating unit represented by the general formula (II).
0 mol% or less, more preferably 80 mol% or less. When the amount of the repeating unit based on the monomer of the further copolymer component exceeds 99 mol%, the effect of the present invention is not sufficiently exhibited, so that it is not preferable.

In the resin (B-1), the group decomposed by the action of an acid is represented by a repeating unit represented by the general formula (Ia) and / or the general formula (Ib) or a group represented by the general formula (II) The repeating unit may be contained in any of the repeating units based on the monomers of the copolymerization component, but the content of the repeating unit containing a group that is decomposed by the action of an acid may be contained in the entire resin. 8 to 60 mol% in the repeating unit
Is suitable, preferably 10 to 55 mol%, more preferably 12 to 50 mol%.

The resin (B-1) is obtained by combining a monomer corresponding to the repeating unit represented by the general formula (II) and maleic anhydride with a monomer of the copolymer component when the copolymer component is used. Copolymerize, copolymerize in the presence of a polymerization catalyst, and subject the repeating units derived from maleic anhydride of the resulting copolymer to ring-opening esterification or hydrolysis with alcohols under basic or acidic conditions. Alternatively, it can also be synthesized by a method of converting the carboxylic acid site generated thereafter into a desired substituent.

The resin (B-1) has a weight average molecular weight of GP
According to the method C, as polystyrene conversion value, preferably 1,
000-200,000. Weight average molecular weight is 1,
If it is less than 000, heat resistance and dry etching resistance are deteriorated, so that it is not preferable. If it exceeds 200,000, developability is deteriorated, and the viscosity becomes extremely high, so that film forming property is deteriorated. Occurs.

In the positive photoresist composition for deep ultraviolet exposure according to the present invention, the amount of the resin (B-1) in the entire composition is from 40 to 99.99% by weight based on the total solid content of the resist.
Is more preferable, and more preferably 50 to 99.97% by weight.

Next, the action of the acid on the alkali developing solution
The resin (B-2) whose dissolution rate increases is described in detail.
You. General formula showing a repeating structural unit of resin (B-2)
In (III) and (IV), R ³², Ra to Rd have 1 carbon atom
Examples of the alkyl group of (1) to (4) are a methyl group, an ethyl group,
Pill group, isopropyl group, n-butyl group, isobutyl
Group, sec-butyl group, t-butyl group and the like.
it can. General showing repeating structural unit of resin (B-2)
In the formula (IV), the alkylene group of W includes the following
X, Z, R₁₁, R₁₃Group similar to the alkylene group represented by
Represents

The resin (B-2) has the general formula (Va)
It may contain a repeating structural unit represented by (Vd).

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In the general formulas (Va) to (Vd),
The alkyl groups of R _{3 to} R ₁₀ , R, R ₁₂ and R ₁₄ are linear,
It may be branched or may have a substituent. The linear or branched alkyl group preferably has 1 to 12 carbon atoms, and more preferably has 1 carbon atom.
And specifically, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, pentyl, hexyl, heptyl, octyl And a nonyl group and a decyl group. Examples of the cyclic alkyl group represented by R, R ₁₂ and R ₁₄ include those having 3 to 30 carbon atoms, and specifically, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a norbornyl group, a boronyl group, Examples thereof include a tricyclodecanyl group, a dicyclopentenyl group, a nobornane epoxy group, a menthyl group, an isomenthyl group, a neomenthyl group, a tetracyclododecanyl group, and a steroid residue.

The aryl group represented by R, R ₁₂ and R ₁₄ includes those having 6 to 20 carbon atoms, and may have a substituent. Specific examples include a phenyl group, a tolyl group, and a naphthyl group. Examples of the aralkyl group represented by R, R ₁₂ and R ₁₄ include those having 7 to 20 carbon atoms and may have a substituent. Specifically, a benzyl group, a phenethyl group,
And a cumyl group. Examples of the alkenyl group for R ₁₄ include an alkenyl group having 2 to 6 carbon atoms, specifically, a vinyl group, a propenyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, a cyclopentenyl group, a cyclohexenyl group, 3-oxocyclohexenyl group, 3-
An oxocyclopentenyl group, a 3-oxoindenyl group and the like can be mentioned. Among these, the cyclic alkenyl group may contain an oxygen atom.

As the linking group X, an alkylene group, a cyclic alkylene group, an arylene group or an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a sulfonamide group, a urethane group which may have a substituent. A group selected from the group consisting of urea groups, or a combination of at least two or more of these groups;
Examples include divalent groups that do not decompose under the action of an acid.

Z is a single bond, an ether group, an ester group,
An amide group, an alkylene group, or a combination thereof
Represents a valence group. R ₁₁ represents a single bond, an alkylene group, an arylene group, or a divalent group obtained by combining these. R
₁₃ represents an alkylene group, an arylene group, or a divalent group obtained by combining them. In X, R ₁₁ and R ₁₃ , examples of the arylene group include those having 6 to 10 carbon atoms, which may have a substituent. Specific examples include a phenylene group, a tolylene group, and a naphthylene group. Examples of the cyclic alkylene group for X include those in which the above-mentioned cyclic alkyl group is divalent. Examples of the alkylene group in X, Z, R ₁₁ and R ₁₃ include groups represented by the following formulas.

-[C (Rf) (Rg)] r- In the above formula, Rf and Rg each represent a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, or an alkoxy group. You may. As the alkyl group, a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group is preferable, and a methyl group, an ethyl group, a propyl group, and an isopropyl group are more preferable. Examples of the substituent of the substituted alkyl group include a hydroxyl group, a halogen atom and an alkoxy group. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. r is an integer of 1 to 10. Specific examples of the linking group X are shown below, but the content of the present invention is not limited thereto.

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Further substituents in the above alkyl group, cyclic alkyl group, alkenyl group, aryl group, aralkyl group, alkylene group, cyclic alkylene group and arylene group include carboxyl group, acyloxy group, cyano group,
Alkyl group, substituted alkyl group, halogen atom, hydroxyl group,
Examples include an alkoxy group, an acetylamide group, an alkoxycarbonyl group, and an acyl group. Here, examples of the alkyl group include lower alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a cyclopropyl group, a cyclobutyl group, and a cyclopentyl group. Examples of the substituent of the substituted alkyl group include a hydroxyl group, a halogen atom and an alkoxy group. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group. Examples of the acyloxy group include an acetoxy group. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom.

Hereinafter, as a specific example of the structure of the side chain in the general formula (Vb), the structure of the side chain except for X is shown below, but is not limited thereto.

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Hereinafter, specific examples of the monomer corresponding to the repeating structural unit represented by formula (Vc) will be shown, but the invention is not limited thereto.

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Hereinafter, specific examples of the repeating structural unit represented by the general formula (Vd) will be shown, but it should not be construed that the invention is limited thereto.

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In formula (Vb), R _{3 to} R ₁₀ are preferably a hydrogen atom or a methyl group. R is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. m is
1-6 are preferred. In the general formula (Vc), R ₁₁ is preferably a single bond, an alkylene group such as a methylene group, an ethylene group, a propylene group, or a butylene group, and R ₁₂ is a group having 1 carbon atom such as a methyl group or an ethyl group. And a cyclic alkyl group such as an alkyl group, a cyclopropyl group, a cyclohexyl group, and a camphor residue, a naphthyl group, and a naphthylmethyl group. Z is preferably a single bond, an ether bond, an ester bond, an alkylene group having 1 to 6 carbon atoms, or a combination thereof, and more preferably a single bond or an ester bond.

In the general formula (Vd), R ₁₃ is
An alkylene group having 1 to 4 carbon atoms is preferred. As R ₁₄ , a methyl group, an ethyl group, which may have a substituent,
An alkyl group having 1 to 8 carbon atoms such as a propyl group, an isopropyl group, a butyl group, a neopentyl group, an octyl group, a cyclohexyl group, an adamantyl group, a norbornyl group, a boronyl group, an isobornyl group, a menthyl group, a morpholino group,
-Oxocyclohexyl group, phenyl group, toluyl group, mesityl group, naphthyl group and camphor residue which may have a substituent are preferable. As these further substituents, a halogen atom such as a fluorine atom, an alkoxy group having 1 to 4 carbon atoms and the like are preferable.

Of the general formulas (Va) to (Vd), the repeating structural units represented by the general formulas (Vb) and (Vd) are preferable.

The resin (B-2) may contain, in addition to the above-mentioned repeating structural units, dry etching resistance, suitability for a standard developing solution, substrate adhesion, a resist profile, and resolution, heat resistance which are general necessary characteristics of a resist. Various repeating structural units can be contained for the purpose of adjusting the sensitivity and the like.

Examples of such a repeating structural unit include repeating structural units corresponding to the following monomers, but are not limited thereto. Thereby, the performance required for the resin (B-2), in particular, (1) solubility in a coating solvent, (2) film forming property (glass transition point), (3) alkali developability, (4) film sliding (Selection of hydrophilic / hydrophobic, alkali-soluble groups), (5) adhesion of the unexposed portion to the substrate, and (6) resistance to dry etching can be finely adjusted. As such a monomer, for example, a compound having one addition-polymerizable unsaturated bond selected from acrylates, methacrylates, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, and the like And the like.

Specifically, the following monomers can be mentioned. Acrylic esters (preferably alkyl acrylate having an alkyl group having 1 to 10 carbon atoms): methyl acrylate, ethyl acrylate, propyl acrylate, amyl acrylate, cyclohexyl acrylate, ethylhexyl acrylate, octyl acrylate, acrylic Acid-t-octyl, chloroethyl acrylate, 2-hydroxyethyl acrylate 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate,
Trimethylolpropane monoacrylate, pentaerythritol monoacrylate, benzyl acrylate,
Methoxybenzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate and the like.

Methacrylic acid esters (preferably alkyl methacrylate having an alkyl group having 1 to 10 carbon atoms): methyl methacrylate, ethyl methacrylate,
Propyl methacrylate, isopropyl methacrylate, amyl methacrylate, hexyl methacrylate,
Cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monomethacrylate, penta Erythritol monomethacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate and the like.

Acrylamides: acrylamide, N-
Alkyl acrylamide (the alkyl group has 1 carbon atom
And 10 such as methyl, ethyl, propyl, butyl, t-butyl, heptyl, octyl, cyclohexyl, and hydroxyethyl. ), N, N-dialkylacrylamide (alkyl group having 1 to 10 carbon atoms, for example, methyl group, ethyl group, butyl group, isobutyl group, ethylhexyl group,
A cyclohexyl group, etc.), N-hydroxyethyl-
N-methylacrylamide, N-2-acetamidoethyl-N-acetylacrylamide and the like.

Methacrylamides: methacrylamide,
N-alkyl methacrylamide (an alkyl group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group,
Butyl group, ethylhexyl group, hydroxyethyl group, cyclohexyl group, etc.), N, N-dialkylmethacrylamide (alkyl group includes ethyl group, propyl group, butyl group, etc.), N-hydroxyethyl-N-
Methyl methacrylamide and the like.

Allyl compounds: allyl esters (eg, allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, etc.), allyloxyethanol etc.

Vinyl ethers: alkyl vinyl ethers (for example, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether,
-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 and the like.

Vinyl esters: vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxy acetate, vinyl butoxy acetate, vinyl Acetoacetate, vinyl lactate, vinyl-β-phenylbutyrate, vinylcyclohexylcarboxylate and the like.

Dialkyl itaconates: dimethyl itaconate, diethyl itaconate, dibutyl itaconate and the like. Dialkyl esters or monoalkyl esters of fumaric acid; dibutyl fumarate;

Others crotonic acid, itaconic acid, maleic anhydride, maleimide, acrylonitrile, methacrylonitrile, maleilenitrile and the like.

In addition, as long as it is an addition-polymerizable unsaturated compound copolymerizable with a monomer corresponding to the above-mentioned various repeating structural units, it may be copolymerized.

In the resin (B-2), the molar ratio of each repeating structural unit depends on the dry etching resistance of the resist, suitability for a standard developer, substrate adhesion, resist profile, and the like.
Further, it is appropriately set in order to adjust resolution, heat resistance, sensitivity and the like, which are general required properties of the resist.

The content of the repeating structural unit represented by formula (III) in the resin (B-2) is preferably from 30 to 80 mol%, more preferably from 32 to 80 mol%, of all the repeating structural units.
-75 mol%, more preferably 35-70 mol%. In the resin (B-2), the content of the repeating structural unit represented by the general formula (IV) is such that
It is preferably 30 to 70 mol%, more preferably 32 to 6 mol%.
It is 8 mol%, more preferably 35 to 65 mol%. In the resin (B-2), the content of the repeating structural units represented by the general formulas (Va) to (Vd) is preferably 0 to 20% by mole, more preferably 0 to 20% by mole of all the repeating structural units. １８18 mol%, more preferably 0-16 mol%.

The content of the repeating structural unit based on the monomer of the further copolymer component in the resin can be appropriately set according to the desired resist properties. It is preferably at most 99 mol%, more preferably at most 90 mol%, further preferably at most 80 mol%, based on the total number of moles of the repeating structural units represented by (III) and (IV).

The molecular weight of the resin (B-2) is as follows:
Weight average (Mw: polystyrene equivalent value by GPC method)
In the range of preferably from 1,000 to 1,000,000, more preferably from 1,500 to 500,000, further preferably from 2,000 to 200,000, and still more preferably from 2,500 to 100,000. Yes, the bigger,
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. The resin (B-2) used in the present invention can be synthesized according to a conventional method (for example, radical polymerization).

In the positive resist composition of the present invention,
The compounding amount of the resin (B-2) in the whole resist composition is preferably from 40 to 99.99% by weight, more preferably from 50 to 99.97% by weight, based on the total solid content.

Preferred specific examples of the combination of the repeating structural units of the resin (B-2) are shown below.

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[0183]

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[0184]

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Next, the resin (B-3) having a group represented by the general formula (X), which is decomposed by the action of an acid and has increased solubility in an alkali developing solution, will be described. As the alkyl group of R ⁵¹ and R ⁵² in the general formula (X),
Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group,
Examples thereof include an alkyl group having 1 to 4 carbon atoms such as a t-butyl group. R ⁵³ and R ⁵⁴ may be the same or different and represent a hydrogen atom or a linear, branched or cyclic alkyl group which may have a substituent. The straight-chain alkyl group preferably has 1 to 30 carbon atoms, and more preferably 1 to 20 carbon atoms. For example, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl Group, n-heptyl group, n-octyl group, n-nonyl group, n-decanyl group and the like. The branched alkyl group preferably has 1 to 30 carbon atoms, and more preferably has 1 to 20 carbon atoms. For example, i-propyl group, i-butyl group, t-butyl group, i-propyl group
-Pentyl group, t-pentyl group, i-hexyl group, t-
Examples include a hexyl group, an i-heptyl group, a t-heptyl group, an i-octyl group, a t-octyl group, an i-nonyl group, and a t-decanoyl group. The cyclic alkyl group preferably has 3 to 30 carbon atoms, more preferably 3 to 20 carbon atoms, for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group,
Examples thereof include a cyclooctyl group, a cyclononyl group, and a cyclodecanoyl group.

R ⁵⁵ represents a linear, branched or cyclic alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent. The linear or branched alkyl group represented by R ⁵⁵ preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms,
For example, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, t-pentyl, n- Hexyl group, i-hexyl group, t-hexyl group, n-heptyl group, i-heptyl group, t-heptyl group, n-octyl group, i-octyl group, t-octyl group, n-nonyl group, i- Nonyl group, t-nonyl group, n-
Decanyl group, i-decanyl group, t-decanyl group, n-undecyl group, i-undecyl group, n-dodecyl group, i-
Dodecyl group, n-tridecyl group, i-tridecyl group, n
-Tetradecyl group, i-tetradecyl group, n-pentadecyl group, i-pentadecyl group, n-hexadecyl group, i
-Hexadecyl group, n-heptadecyl group, i-heptadecyl group, n-octadecyl group, i-octadecyl group, n
-Nonadecyl group, i-nonadecyl group and the like.

The cyclic alkyl group represented by R ⁵⁵ preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and has a substituent even when forming a ring with up to 20 carbon atoms. For example, for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecanyl group, cycloundecyl group, cyclododecyl group, cyclotridecyl group, cyclotridecyl group , Cyclotetradecyl group, cyclopentadecyl group,
Cyclohexadecyl group, cycloheptadecyl group, cyclooctadecyl group, cyclononadecyl group, 4-cyclohexylcyclohexyl group, 4-n-hexylcyclohexyl group, pentanylcyclohexyl group, hexyloxycyclohexyl group, pentanyloxycyclohexyl group, etc. Can be. Substituted cyclic alkyl groups other than those listed here can also be used within the above range.

The aryl group represented by R ⁵⁵ preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and includes, for example, a phenyl group, a 4-methylphenyl group and a 3-methylphenyl group.
Methylphenyl group, 2-methylphenyl group, 4-ethylphenyl group, 3-ethylphenyl group, 2-ethylphenyl group, 4-n-propylphenyl group, 3-n-propylphenyl group, 2-n-propylphenyl Group, 4-i-propylphenyl group, 3-i-propylphenyl group, 2-
i-propylphenyl group, 4-cyclopropylphenyl group, 3-cyclopropylphenyl group, 2-cyclopropylphenyl group, 4-n-butylphenyl group, 3-n-butylphenyl group, 2-n-butylphenyl group , 4-i-
Butylphenyl group, 3-i-butylphenyl group, 2-i
-Butylphenyl group, 4-t-butylphenyl group, 3-
t-butylphenyl group, 2-t-butylphenyl group, 4
-Cyclobutylphenyl group, 3-cyclobutylphenyl group, 2-cyclobutylphenyl group, 4-cyclopentylphenyl group, 4-cyclohexylphenyl group, 4-cycloheptenylphenyl group, 4-cyclooctanylphenyl group, 2-cyclobutylphenyl group, Cyclopentylphenyl group, 2-cyclohexylphenyl group, 2-cycloheptenylphenyl group, 2
-Cyclooctanylphenyl group, 3-cyclopentylphenyl group, 3-cyclohexylphenyl group, 3-cycloheptenylphenyl group, 3-cyclooctanylphenyl group, 4-cyclopentyloxyphenyl group, 4-cyclohexyloxyphenyl group, 4 -Cycloheptenyloxyphenyl group, 4-cyclooctanyloxyphenyl group, 2-cyclopentyloxyphenyl group, 2-cyclohexyloxyphenyl group, 2-cycloheptenyloxyphenyl group, 2-cyclooctanyloxyphenyl group, 3 -Cyclopentyloxyphenyl group, 3-cyclohexyloxyphenyl group, 3-cycloheptenyloxyphenyl group, 3-cyclooctanyloxyphenyl group, 4-n-pentylphenyl group, 4-n-hexylphenyl group, 4-n -Hep Nirufeniru group, 4-n-octanyl phenyl group, 2-n-pentyl phenyl group, 2
-N-hexylphenyl group, 2-n-heptenylphenyl group, 2-n-octanylphenyl group, 3-n-pentylphenyl group, 3-n-hexylphenyl group, 3-n-
Heptenylphenyl group, 3-n-octanylphenyl group, 2,6-di-isopropylphenyl group, 2,3-di-isopropylphenyl group, 2,4-di-isopropylphenyl group, 3,4-di- Isopropylphenyl group,
3,6-di-t-butylphenyl group, 2,3-di-t-
Butylphenyl group, 2,4-di-t-butylphenyl group, 3,4-di-t-butylphenyl group, 2,6-di-
n-butylphenyl group, 2,3-di-n-butylphenyl group, 2,4-di-n-butylphenyl group, 3,4-di-n-butylphenyl group, 2,6-di-i- Butylphenyl group, 2,3-di-i-butylphenyl group, 2,4-
Di-i-butylphenyl group, 3,4-di-i-butylphenyl group, 2,6-di-t-amylphenyl group, 2,3
-Di-t-amylphenyl group, 2,4-di-t-amylphenyl group, 3,4-di-t-amylphenyl group, 2,
6-di-i-amylphenyl group, 2,3-di-i-amylphenyl group, 2,4-di-i-amylphenyl group,
3,4-di-i-amylphenyl group, 2,6-di-n-
Pentylphenyl group, 2,3-di-n-pentylphenyl group, 2,4-di-n-pentylphenyl group, 3,4-
Di-n-pentylphenyl group, 4-adamantylphenyl group, 2-adamantylphenyl group, 4-isobornylphenyl group, 3-isobornylphenyl group, 2-isoboronylphenyl group, 4-cyclopentyloxyphenyl group , 4-cyclohexyloxyphenyl group, 4-cycloheptenyloxyphenyl group, 4-cyclooctanyloxyphenyl group, 2-cyclopentyloxyphenyl group, 2-cyclohexyloxyphenyl group, 2-cycloheptenyloxyphenyl group, 2 -Cyclooctanyloxyphenyl group, 3-cyclopentyloxyphenyl group, 3-cyclohexyloxyphenyl group, 3-cycloheptenyloxyphenyl group, 3-cyclooctanyloxyphenyl group, 4-n-pentyloxyphenyl group,
4-n-hexyloxyphenyl group, 4-n-heptenyloxyphenyl group, 4-n-octanyloxyphenyl group, 2-n-pentyloxyphenyl group, 2-n-hexyloxyphenyl group, 2-n -Heptenyloxyphenyl group, 2-n-octanyloxyphenyl group, 3-
n-pentyloxyphenyl group, 3-n-hexyloxyphenyl group, 3-n-heptenyloxyphenyl group,
3-n-octanyloxyphenyl group, 2,6-di-isopropyloxyphenyl group, 2,3-di-isopropyloxyphenyl group, 2,4-di-isopropyloxyphenyl group, 3,4-di-isopropyl Oxyphenyl group, 2,6-di-t-butyloxyphenyl group, 2,3
-Di-t-butyloxyphenyl group, 2,4-di-t-
Butyloxyphenyl group, 3,4-di-t-butyloxyphenyl group, 2,6-di-n-butyloxyphenyl group, 2,3-di-n-butyloxyphenyl group, 2,4
-Di-n-butyloxyphenyl group, 3,4-di-n-
Butyloxyphenyl group, 2,6-di-i-butyloxyphenyl group, 2,3-di-i-butyloxyphenyl group, 2,4-di-i-butyloxyphenyl group, 3,4
-Di-i-butyloxyphenyl group, 2,6-di-t-
Amyloxyphenyl group, 2,3-di-t-amyloxyphenyl group, 2,4-di-t-amyloxyphenyl group, 3,4-di-t-amyloxyphenyl group, 2,6
-Di-i-amyloxyphenyl group, 2,3-di-i-
Amyloxyphenyl group, 2,4-di-i-amyloxyphenyl group, 3,4-di-i-amyloxyphenyl group, 2,6-di-n-pentyloxyphenyl group, 2,
3-di-n-pentyloxyphenyl group, 2,4-di-
n-pentyloxyphenyl group, 3,4-di-n-pentyloxyphenyl group, 4-adamantyloxyphenyl group, 3-adamantyloxyphenyl group, 2-adamantyloxyphenyl group, 4-isobornyloxyphenyl group, Examples thereof include a 3-isoboronyloxyphenyl group and a 2-isoboronyloxyphenyl group, and these may be further substituted within the above range, and are not limited to substituents other than the above examples.

The aralkyl group represented by R ⁵⁵ preferably has 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, and includes, for example, phenylethyl, 4-methylphenylethyl, 3-methylphenylethyl, 2-methylphenylethyl group, 4-ethylphenylethyl group, 3-ethylphenylethyl group, 2-ethylphenylethyl group,
-N-propylphenylethyl group, 3-n-propylphenylethyl group, 2-n-propylphenylethyl group,
4-i-propylphenylethyl group, 3-i-propylphenylethyl group, 2-i-propylphenylethyl group, 4-cyclopropylphenylethyl group, 3-cyclopropylphenylethyl group, 2-cyclopropylphenylethyl group , 4-n-butylphenylethyl group, 3-n
-Butylphenylethyl group, 2-n-butylphenylethyl group, 4-i-butylphenylethyl group, 3-i-butylphenylethyl group, 2-i-butylphenylethyl group, 4-t-butylphenylethyl group A 3-t-butylphenylethyl group, a 2-t-butylphenylethyl group,
4-cyclobutylphenylethyl group, 3-cyclobutylphenylethyl group, 2-cyclobutylphenylethyl group, 4-cyclopentylphenylethyl group, 4-cyclohexylphenylethyl group, 4-cycloheptenylphenylethyl group, 4-cyclo Octanylphenylethyl group, 2-cyclopentylphenylethyl group, 2-cyclohexylphenylethyl group, 2-cycloheptenylphenylethyl group, 2-cyclooctanylphenylethyl group, 3-cyclopentylphenylethyl group, 3-cyclohexylphenylethyl Group, 3-cycloheptenylphenylethyl group, 3-cyclooctanylphenylethyl group, 4-cyclopentyloxyphenylethyl group, 4-
Cyclohexyloxyphenylethyl group, 4-cycloheptenyloxyphenylethyl group, 4-cyclooctanyloxyphenylethyl group, 2-cyclopentyloxyphenylethyl group, 2-cyclohexyloxyphenylethyl group, 2-cycloheptenyloxyphenylethyl Group, 2-cyclooctanyloxyphenylethyl group, 3
-Cyclopentyloxyphenylethyl group, 3-cyclohexyloxyphenylethyl group, 3-cycloheptenyloxyphenylethyl group, 3-cyclooctanyloxyphenylethyl group, 4-n-pentylphenylethyl group, 4-n-hexylphenyl Ethyl group, 4-n-heptenylphenylethyl group, 4-n-octanylphenylethyl group, 2-n-pentylphenylethyl group, 2-n
-Hexylphenylethyl group, 2-n-heptenylphenylethyl group, 2-n-octanylphenylethyl group,
3-n-pentylphenylethyl group, 3-n-hexylphenylethyl group, 3-n-heptenylphenylethyl group, 3-n-octanylphenylethyl group, 2,6-di-isopropylphenylethyl group, 2 2,3-di-isopropylphenylethyl group, 2,4-di-isopropylphenylethyl group, 3,4-di-isopropylphenylethyl group, 2,6-di-t-butylphenylethyl group,
2,3-di-t-butylphenylethyl group, 2,4-di-t-butylphenylethyl group, 3,4-di-t-butylphenylethyl group, 2,6-di-n-butylphenylethyl Group, 2,3-di-n-butylphenylethyl group,
2,4-di-n-butylphenylethyl group, 3,4-di-n-butylphenylethyl group, 2,6-di-i-butylphenylethyl group, 2,3-di-i-butylphenylethyl group Group, 2,4-di-i-butylphenylethyl group,
3,4-di-i-butylphenylethyl group, 2,6-di-t-amylphenylethyl group, 2,3-di-t-amylphenylethyl group, 2,4-di-t-amylphenylethyl group Group, 3,4-di-t-amylphenylethyl group,
2,6-di-i-amylphenylethyl group, 2,3-di-i-amylphenylethyl group, 2,4-di-i-amylphenylethyl group, 3,4-di-i-amylphenylethyl group Group, 2,6-di-n-pentylphenylethyl group, 2,3-di-n-pentylphenylethyl group, 2,
4-di-n-pentylphenylethyl group, 3,4-di-
n-pentylphenylethyl group, 4-adamantylphenylethyl group, 3-adamantylphenylethyl group, 2
-Adamantyl phenylethyl group, 4-isobornylphenylethyl group, 3-isobornylphenylethyl group,
2-isoboronylphenylethyl group, 4-cyclopentyloxyphenylethyl group, 4-cyclohexyloxyphenylethyl group, 4-cycloheptenyloxyphenylethyl group, 4-cyclooctanyloxyphenylethyl group, 2-cyclopentyloxyphenyl Ethyl group, 2
-Cyclohexyloxyphenylethyl group, 2-cycloheptenyloxyphenylethyl group, 2-cyclooctanyloxyphenylethyl group, 3-cyclopentyloxyphenylethyl group, 3-cyclohexyloxyphenylethyl group, 3-cycloheptenyloxyphenyl Ethyl group, 3-cyclooctanyloxyphenylethyl group,
4-n-pentyloxyphenylethyl group, 4-n-hexyloxyphenylethyl group, 4-n-heptenyloxyphenylethyl group, 4-n-octanyloxyphenylethyl group, 2-n-pentyloxyphenyl Ethyl group, 2-n-hexyloxyphenylethyl group, 2-n
-Heptenyloxyphenylethyl group, 2-n-octenyloxyphenylethyl group, 3-n-pentyloxyphenylethyl group, 3-n-hexyloxyphenylethyl group, 3-n-heptenyloxyphenylethyl group,
3-n-octanyloxyphenylethyl group, 2,6-
Diisopropyloxyphenylethyl group, 2,3-di-isopropyloxyphenylethyl group, 2,4-di-
Isopropyloxyphenylethyl group, 3,4-diisopropyloxyphenylethyl group, 2,6-di-t-
Butyloxyphenylethyl group, 2,3-di-t-butyloxyphenylethyl group, 2,4-di-t-butyloxyphenylethyl group, 3,4-di-t-butyloxyphenylethyl group, 2, 6-di-n-butyloxyphenylethyl group, 2,3-di-n-butyloxyphenylethyl group, 2,4-di-n-butyloxyphenylethyl group, 3,4-di-n-butyloxy Phenylethyl group, 2,6-di-i-butyloxyphenylethyl group,
2,3-di-i-butyloxyphenylethyl group, 2,
4-di-i-butyloxyphenylethyl group, 3,4-
Di-i-butyloxyphenylethyl group, 2,6-di-
t-amyloxyphenylethyl group, 2,3-di-t-
Amyloxyphenylethyl group, 2,4-di-t-amyloxyphenylethyl group, 3,4-di-t-amyloxyphenylethyl group, 2,6-di-i-amyloxyphenylethyl group, 2, 3-di-i-amyloxyphenylethyl group, 2,4-di-i-amyloxyphenylethyl group, 3,4-di-i-amyloxyphenylethyl group, 2,6-di-n-pentyloxy Phenylethyl group, 2,3-di-n-pentyloxyphenylethyl group, 2,4-di-n-pentyloxyphenylethyl group, 3,4-di-n-pentyloxyphenylethyl group, 4-adamantyloxy Phenylethyl group, 3-adamantyloxyphenylethyl group, 2-adamantyloxyphenylethyl group, 4-isobornyloxyphenylethyl group, 3-iso B sulfonyloxy phenylethyl group, 2-isobornyl-oxy-phenylethyl group, or the alkyl is a methyl group, propyl group, and replaced with a butyl group and the like.

Further, further substituents of the above groups include a hydroxyl group, a halogen atom (fluorine, chlorine, bromine, iodine),
Nitro group, cyano group, the above alkyl group, methoxy group,
Ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, alkoxycarbonyl group such as t-butoxy group, methoxycarbonyl group, alkoxycarbonyl group such as ethoxycarbonyl group, benzyl Groups, phenethyl groups, aralkyl groups such as cumyl groups, aralkyloxy groups,
Formyl group, acetyl group, butyryl group, benzoyl group,
Acyl groups such as cyanamyl group and valeryl group; acyloxy groups such as butyryloxy group; alkenyl groups such as alkenyl group, vinyloxy group, propenyloxy group, allyloxy group and butenyloxy group; aryl groups such as the above aryl group and phenoxy group; Examples include an aryloxycarbonyl group such as an oxy group and a benzoyloxy group.

The substituent of R ⁵⁵ is preferably
It is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. These substituents may further have a substituent.

Specific examples of the group represented by formula (X) are shown below, but it should not be construed that the invention is limited thereto.

[0194]

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[0195]

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A resin having a group represented by the general formula (X) in the present invention, which is decomposed by the action of an acid to increase solubility in an alkali developing solution (hereinafter, a resin having a group represented by the general formula (X) The resin has a structure in which an acid-decomposable group represented by the general formula (X) is introduced into a compound having a molecular weight distribution obtained by polymerizing a monomer, and becomes alkali-soluble by the action of an acid. A compound. The resin having a group represented by the general formula (X) is a resin having a group represented by the general formula (X) in the main chain or side chain of the resin, or in both the main chain and the side chain. Among them, a resin having a group represented by the general formula (X) in a side chain is more preferable. Next, when the group represented by the general formula (X) is bonded as a side chain, the base resin includes -OH or-
COOH, preferably -R ⁵⁰ -COOH or -Ar
It is an alkali-soluble resin having an -OH group. For example,
An alkali-soluble resin not containing an acid-decomposable group described below can be used. Here, -R ⁵⁰ - represents an aliphatic or aromatic hydrocarbon divalent or more which may have a substituent, -Ar- may have a monocyclic or polycyclic substituent divalent It represents the above aromatic group.

In the present invention, a preferable base resin is an alkali-soluble resin having a phenolic hydroxyl group. The alkali-soluble resin having a phenolic hydroxyl group used in the present invention is o-, m- or p-hydroxystyrene (these are collectively referred to as hydroxystyrene), or o-, m- or p-hydroxy-α-. A copolymer containing at least 30 mol%, preferably 50 mol% or more of a repeating unit corresponding to methylstyrene (collectively referred to as hydroxy-α-methylstyrene) or a homopolymer thereof, or a benzene nucleus of the unit Is preferably a partially hydrogenated resin, and more preferably a p-hydroxystyrene homopolymer. As monomers other than hydroxystyrene and hydroxy-α-methylstyrene for preparing the copolymer by copolymerization, acrylates, methacrylates, acrylamides, methacrylamides, acrylonitrile, methacrylonitrile, Maleic anhydride, styrene, α-methylstyrene, acetoxystyrene, alkoxystyrenes are preferred, styrene,
Acetoxystyrene and t-butoxystyrene are more preferred.

In the present invention, the content of the repeating unit (structural unit) having a group represented by the general formula (X) in such a resin is from 5 mol% to 50 mol% based on all repeating units. Preferably, more preferably, 5 mol% or more.
30 mol%.

In the present invention, the resin having a group represented by formula (X) may contain other acid-decomposable groups in addition to the group represented by formula (X).

The resin containing the group represented by the general formula (X) is prepared by synthesizing a corresponding vinyl ether and reacting the resin with a phenolic hydroxyl group-containing alkali-soluble resin dissolved in an appropriate solvent such as tetrahydrofuran by a known method. Can be obtained at The reaction is usually carried out in the presence of an acidic catalyst, preferably an acidic ion exchange resin, a salt such as hydrochloric acid, p-toluenesulfonic acid or pyridinium tosylate. The corresponding vinyl ether can be synthesized from an active material such as chloroethyl vinyl ether by a method such as nucleophilic substitution reaction,
It can be synthesized using a mercury or palladium catalyst. Alternatively, it can be synthesized by acetal exchange using the corresponding alcohol and vinyl ether. In this case, the alcohol to be introduced has a substituent to be introduced, the vinyl ether is mixed with a relatively unstable vinyl ether such as t-butyl vinyl ether, and the reaction is carried out in the presence of an acid such as p-toluenesulfonic acid or pyridinium tosylate. .

The weight average molecular weight of the resin containing the group represented by the general formula (X) is preferably from 3,000 to 80,000, more preferably from 5,000 to 50,000. The range of the molecular weight distribution (Mw / Mn) is from 1.01 to 4.0, preferably from 1.05 to 3.00. In order to obtain a polymer having such a molecular weight distribution, it is preferable to use a technique such as anionic polymerization or radical polymerization.

Specific examples of the structure of the resin containing the group represented by the general formula (X) are shown below, but the present invention is not limited thereto.

[0203]

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[0204]

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[0205]

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[0206]

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[0207]

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[0208]

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In the resin containing the group represented by the general formula (X), a polyhydroxy compound is added in the synthesis stage to adjust the alkali dissolution rate and improve the heat resistance, and the polymer main chain is linked by a polyfunctional acetal group. Cross-linking sites may be introduced. The addition amount of the polyhydroxy compound is 0.01 to 10 mol%, preferably 0.05 to 8 mol%, more preferably 0.1 to 5 m, based on the number of hydroxyl groups of the resin.
ol%. Examples of the polyhydroxy compound include those having 2 to 6 phenolic hydroxyl groups or alcoholic hydroxyl groups, preferably 2 to 4 hydroxyl groups, and more preferably 2 or 3 hydroxyl groups. is there. Specific examples are shown below, but the present invention is not limited to these.

[0210]

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Next, the above general formulas (XI) and (XII)
And a resin (B-3) ′ having a group represented by the general formula (XIII), which is decomposed by the action of an acid and has increased solubility in an alkali developing solution. R ⁶¹ represents a hydrogen atom or a methyl group. The group incapable of decomposing under the action of acid in the R ⁶² (also referred to as acid-stable group), a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an alkyloxy group (provided that, -O- third
Lower alkyl), an acyl group, a cycloalkyloxy group, an alkenyloxy group, an aryloxy group, an alkylcarbonyloxy group, an alkylamidomethyloxy group,
Examples thereof include an alkylamide group, an arylamidomethyl group, and an arylamido group. As the acid stabilizer, preferably an acyl group, an alkylcarbonyloxy group, an alkyloxy group, a cycloalkyloxy group, an aryloxy group,
An alkylamidooxy group, an alkylamido group, more preferably an acyl group, an alkylcarbonyloxy group,
An alkyloxy group, a cycloalkyloxy group, and an aryloxy group.

[0212] In the acid-stable group of R ^62, the alkyl group, methyl group, ethyl group, propyl group, n- butyl group, sec- butyl group, 1 such carbon number of t- butyl group
The cycloalkyl group is preferably a group having 3 to 10 carbon atoms such as a cyclopropyl group, a cyclobutyl group, a cyclohexyl group, or an adamantyl group. The alkenyl group is preferably a vinyl group, a propenyl group, or an allyl group. And a butenyl group having 2 to 4 carbon atoms are preferable, and as the alkenyl group, a vinyl group, a propenyl group,
Those having 2 to 4 carbon atoms such as an allyl group and a butenyl group are preferable. As the aryl group, a phenyl group, a xylyl group,
Those having 6 to 14 carbon atoms such as a toluyl group, a cumenyl group, a naphthyl group and an anthracenyl group are preferred. Examples of the alkoxy group include a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, a hydroxypropoxy group, n
An alkoxy group having 1 to 4 carbon atoms such as -butoxy group, isobutoxy group and sec-butoxy group is preferred.

As the halogen atom for R ⁶³ ,
Fluorine, chlorine, bromine and iodine are preferred. As the alkyl group, methyl, ethyl, propyl, n-butyl, sec.
Those having 1 to 8 carbon atoms such as -butyl, t-butyl, hexyl, octyl and the like are preferable. As the aryl group, those having 6 to 14 carbon atoms such as phenyl, xylyl, toluyl, cumenyl, naphthyl, anthracenyl and the like are preferable. Are preferred. As the alkoxy group, those having 1 to 4 carbon atoms such as methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy, n-butoxy, isobutoxy, sec-butoxy, t-butoxy and the like are preferable.As the acyl group, Preferred are those having 1 to 7 carbon atoms such as formyl, acetyl, propanoyl, butanoyl and benzoyl. As the acyloxy group, acetoxy,
Those having 2 to 7 carbon atoms, such as propnoyloxy, butanoyloxy and benzoyloxy, are preferred.

The substituent W in the general formula (XI) is the same as the general formula (X), and the general formula (X) is as described above.

Specific examples of the structural unit represented by the general formula (XI) are shown below, but the present invention is not limited thereto.

[0216]

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[0219]

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[0218]

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[0219]

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[0220]

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[0221]

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When the resin contains the structural unit represented by the general formula (XII), the resin is decomposed by the action of an acid, and the solubility in an alkali developing solution can be controlled. Further, by introducing this structural unit, a profile excellent in rectangularity can be achieved. Further, it is effective for adjusting the amount of the structural unit represented by the general formula (XI).

Specific examples of the polymerizable monomer having the structural unit represented by formula (XII) include, but are not limited to, the following.

[0224]

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[0225]

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Formula (XII) or (XIII)
Can be obtained by reacting a phenolic resin or a monomer thereof with an acid anhydride in the presence of a base, or with a corresponding halide in the presence of a base.

In the present invention, it is decomposed by the action of an acid,
The resin having a group that increases the solubility in an alkali developer is represented by the general formula (XI), the general formula (XII) or the general formula (XIII)
Other monomer units may be contained as a copolymer component in addition to the structural unit represented by

In the present invention, general formula (XI) and general formula (XI
It is preferable that the ratio of the structural units represented by I) and the general formula (XIII) satisfies the following conditions. 0.10 <(XI) / (XI) + (XII) + (XIII) <0.
25 0.01 <(XII) / (XI) + (XII) + (XIII) <0.
15 (XI)> (XII) 0.5 <(XI) / (XI) + (XII) <0.85 (wherein (XI), (XII) and (XIII) are each represented by the general formula (X
I) represents the mole fraction of the structural unit containing the groups represented by the general formulas (XII) and (XIII). When the resin of the present invention satisfies the above conditions, the rectangularity of the profile is improved, and in particular, development defects are further improved.

The repeating structural units represented by the general formula (XI), (XII) or (XIII), or the repeating structural units derived from other polymerizable monomers may be used alone or in combination of two or more. It may be present inside. Further, the resin contained in the positive photosensitive composition of the present invention is suitable so that an alkali-soluble group, for example, a phenolic hydroxyl group or a carboxyl group can be introduced in order to maintain good developability in an alkali developing solution. Other polymerizable monomers may be copolymerized.

The molecular weight of the resin having a repeating structural unit of the above general formula (XI), (XII) or (XIII) synthesized by the above method has a weight average (Mw: polystyrene standard) of 2, 000 or more, preferably 3,000
0 to 200,000, more preferably 5,000
~ 70,000. Also, the degree of dispersion (Mw / Mn)
Is preferably 1.0 to 4.0, more preferably 1.0 to 4.0.
-3.5, particularly preferably 1.0-3.0, and the smaller the degree of dispersion, the better the heat resistance and image forming properties (pattern profile, defocus latitude, etc.). The content of the resin having a repeating structural unit of the general formula (XI), (XII) or (XIII) in the positive photosensitive composition (excluding the coating solvent) is preferably 50 to 99% by weight,
More preferably, it is 70 to 97% by weight. General formula (X
Specific examples of the resin having a repeating structural unit represented by I), general formula (XII) or general formula (XIII) are shown below, but the present invention is not limited thereto.

[0231]

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[0232]

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[0233]

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[0234]

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[0235]

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[0236]

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[0237]

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[0238]

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[0239]

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[0240]

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[0241]

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[0242]

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[0243]

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[0244]

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In the present invention, another resin having an acid-decomposable group may be used in combination. Decomposed by other acids used in the chemically amplified resist of the present invention,
Examples of the resin having a group that increases the solubility in an alkali developer include a resin having an acid-decomposable group in the main chain or side chain of the resin, or in both the main chain and the side chain.
Among them, a resin having a group which can be decomposed by an acid in a side chain is more preferable. A preferred group capable of being decomposed by an acid is -CO
OA ⁰ and —O—B ⁰ groups. Examples of the groups containing these groups include groups represented by —R ⁰ —COOA ⁰ or —Ar—O—B ⁰ . Here, A ⁰ is -C (R ⁰¹ )
^{(R 02) (R 03)} , - showing the ^{Si (R 01) (R 02} ) (R 0 3) or ^{-C (R 04) (R 05} ) -O-R 06 group. B ⁰ is
-A ⁰ or -CO-O-A ⁰ group (R ^0, R ⁰¹ ~
R ⁰⁶ and Ar have the same meanings as described below.

The acid-decomposable group is preferably a silyl ether group, a cumyl ester group, an acetal group, a tetrahydropyranyl ether group, a tetrahydropyranyl ester group, an enol ether group, an enol ester group,
And a tertiary alkyl ester group and a tertiary alkyl carbonate group. More preferred are a tertiary alkyl ester group, a tertiary alkyl carbonate group, a cumyl ester group, an acetal group, and a tetrahydropyranyl ether group.

Next, when the group decomposable with an acid is bonded as a side chain, the base resin may be a group containing -OH or -COOH in the side chain, preferably -R ⁰ -CO
It is an alkali-soluble resin having an OH group or an -Ar-OH group. For example, an alkali-soluble resin described below can be used.

The alkali dissolution rate of these alkali-soluble resins was measured (at 23 ° C.) using 0.261N tetramethylammonium hydroxide (TMAH).
A / sec or more is preferable. Particularly preferably 330A
/ Sec or more (A is angstroms). From the viewpoint of achieving a rectangular profile, an alkali-soluble resin having a high transmittance to far ultraviolet light or excimer laser light is preferable. Preferably, the transmittance at a wavelength of 248 nm with a thickness of 1 μm is 20 to 90%. From this perspective,
Particularly preferred alkali-soluble resins are o-, m-, p-
Poly (hydroxystyrene) and copolymers thereof, hydrogenated poly (hydroxystyrene), halogen- or alkyl-substituted poly (hydroxystyrene), part of poly (hydroxystyrene), O-alkylated or O-acylated product, styrene -Hydroxystyrene copolymer, α
-Methylstyrene-hydroxystyrene copolymer and hydrogenated novolak resin.

The resin having an acid-decomposable group used in the present invention may be prepared by reacting an alkali-soluble resin with a precursor of an acid-decomposable group, or an alkali-soluble resin having an acid-decomposable group bonded thereto. It can be obtained by copolymerizing a monomer with various monomers.

The positive resist composition of the present invention is applied to a support by dissolving the above components in a solvent capable of dissolving the above components. 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, lactic acid Ethyl, 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.

Among the above, preferred solvents are 2-
Heptanone, γ-butyrolactone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate , N-methylpyrrolidone and tetrahydrofuran.

The solid content of the (A) photoacid generator and (B) the resin is preferably 3 to 25%, more preferably 5 to 22%, further preferably 5 to 22%, as the solid concentration in the solvent. Is 7 to 20%.

The positive photoresist composition of the present invention comprises
It is preferable to contain a fluorine-based and / or silicon-based surfactant. Examples of the fluorine-based and / or silicon-based surfactant include a fluorine-based surfactant, a silicon-based surfactant, and at least one type of surfactant containing both a fluorine atom and a silicon atom. When the positive photoresist composition of the present invention contains the acid-decomposable resin and the surfactant, when using an exposure light source of 250 nm or less, particularly 220 nm or less, sensitivity, resolution,
A resist pattern with excellent substrate adhesion and dry etching resistance, and with less development defects and scum can be obtained.

As these surfactants, for example, those described in
No. 62-36663, JP-A-61-226746, JP-A-61-226745,
JP-A-62-170950, JP-A-63-34540, JP-A-7-23016
No. 5, JP-A-8-62834, JP-A-9-54432, JP-A-9-598
The surfactant described in No. 8 can be used, and the following commercially available surfactant can be used as it is. Commercially available surfactants that can be used, for example, F-top EF301, EF3
03, (Shin-Akita Chemical Co., Ltd.), Florado FC430, 431 (Sumitomo 3M), MegaFac F171, F173, F176, F
189, R08 (Dainippon Ink Co., Ltd.), Surflon S-38
2, SC101, 102, 103, 104, 105, 106 (Asahi Glass Co., Ltd.)
) Or a silicon-based surfactant. In addition, polysiloxane polymer KP
-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.

The amount of the surfactant is usually 0.001 to 2% by weight, preferably 0.01 to 1% by weight, based on the solid content in the composition of the present invention. These surfactants can be used alone or in combination of two or more.

Examples of the other surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; Polyoxyethylene alkyl allyl ethers such as oxyethylene octyl phenol ether, polyoxyethylene nonyl phenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate Fatty acid esters such as sorbitan trioleate, sorbitan tristearate, polyoxyethylene sorbitan monolaurate Nonionic surfactants such as polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan tristearate, etc. Can be mentioned. 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.

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.

[0258]

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Here, R ²⁵⁰ , R ²⁵¹ and R ²⁵² are the same or different and are a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aminoalkyl group having 1 to 6 carbon atoms, a hydroxyalkyl having 1 to 6 carbon atoms. Or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, wherein R ²⁵¹ and R ²⁵² may be bonded to each other to form a ring.

[0260]

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Wherein R ²⁵³ , R ²⁵⁴ , R ²⁵⁵ and R ²⁵⁶
Is the same or different and represents an alkyl group having 1 to 6 carbon atoms. Further preferred compounds are nitrogen-containing basic compounds having two or more nitrogen atoms having different chemical environments in one molecule,
Particularly preferred are compounds containing both a substituted or unsubstituted amino group and a ring structure containing a nitrogen atom, or compounds 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 amino And alkyl morpholine. 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.

Preferred specific compounds include guanidine, 1,1-dimethylguanidine, 1,1,3,3,-
Tetramethylguanidine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2-diethylaminopyridine, 2- (aminomethyl) pyridine,
-Amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-5-methylpyridine, 2-amino-6-methylpyridine, 3-aminoethylpyridine, 4-aminoethylpyridine, 3-amino Pyrrolidine, piperazine, N- (2-aminoethyl) piperazine, N- (2-aminoethyl) piperidine, 4-amino-2,2,6,6-tetramethylpiperidine, 4-piperidinopiperidine, 2-imino Piperidine, 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,
-Pyrazoline, 3-pyrazoline, N-aminomorpholine, N- (2-aminoethyl) morpholine, 1,5-
Diazabicyclo [4,3,0] non-5-ene, 1,8
-Diazabicyclo [5,4,0] undec-7-ene,
3,4,5-triphenylimidazole, N-methylmorpholine, N-ethylmorpholine, N-hydroxyethylmorpholine, N-benzylmorpholine, cyclohexylmorpholinoethylthiourea (CHMETU), etc.
Grade morpholine derivatives, hindered amines described in JP-A-11-52575 (for example, [0005]
, Etc.) and the like, but is not limited thereto.

Particularly preferred specific examples are 1,5-diazabicyclo [4.3.0] -5-nonene, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,4-diazabicyclo [2 .2.2] octane, 4-dimethylaminopyridine,
Hexamethylenetetramine, 4,4-dimethylimidazoline, pyrroles, pyrazoles, imidazoles, pyridazines, pyrimidines, tertiary morpholines such as CHMETU, bis (1,2,2,6,6-pentamethyl-
Hindered amines such as (4-piperidyl) sebagate and the like can be mentioned. By using these, the density dependency becomes excellent.

Among them, 1,5-diazabicyclo [4,
3,0] non-5-ene, 1,8-diazabicyclo [5,4,0] undec-7-ene, 1,4-diazabicyclo [2,2,2] octane, 4-dimethylaminopyridine, hexamethylene Preferred are tetramine, CHMETU, and bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate.

These nitrogen-containing basic compounds are used alone or in combination of two or more. The amount of the nitrogen-containing basic compound to be used is generally 0.001 to 10% by weight, preferably 0.01 to 5% by weight, based on the solid content of the entire photosensitive resin composition. 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.

The positive photoresist composition of the present invention may further contain an acid-decomposable dissolution inhibiting compound, a dye,
A plasticizer, a sensitizer, a compound that promotes solubility in a developer, and the like can be contained.

Such a positive resist composition of the present invention is applied on a substrate to form a thin film. The thickness of this coating film is preferably from 0.2 to 1.2 μm. In the present invention,
If necessary, a commercially available inorganic or organic antireflection film can be used.

As the antireflection film, an inorganic film type such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon and α-silicon, and an organic film type comprising a light absorbing agent and a polymer material can be used. The former requires equipment such as a vacuum deposition apparatus, a CVD apparatus, and a sputtering apparatus for film formation. As the organic antireflection film, for example, Japanese Patent Publication No. 7-69
611, a condensate of a formaldehyde-modified melamine resin with a diphenylamine derivative, an alkali-soluble resin,
A light absorbing agent or a reaction product of a maleic anhydride copolymer and a diamine type light absorbing agent described in US Pat. No. 5,294,680;
JP-A-6-118631, containing a resin binder and a methylolmelamine-based thermal crosslinking agent;
Acrylic resin type antireflection coating having a carboxylic acid group, an epoxy group and a light absorbing group in the same molecule as described in 18656, one comprising a methylolmelamine and a benzophenone-based light absorbing agent described in JP-A-8-87115, and described in JP-A-8-179509. Examples thereof include those obtained by adding a low-molecular-weight light absorbing agent to a polyvinyl alcohol resin. Also, as an organic anti-reflection film,
DUV30 series manufactured by Brewer Science,
DUV-40 series, Shipley's AC-2, AC
-3 can also be used.

The resist solution is applied on a substrate (eg, silicon / silicon dioxide coating) used for manufacturing precision integrated circuit devices (on a substrate provided with the above antireflection film if necessary), a spinner, a coater, and the like. After coating by an appropriate coating method such as that described above, exposure through a predetermined mask, baking and development can provide a good resist pattern. Here, the exposure light is preferably 150
It is light having a wavelength of nm to 250 nm. Specifically, Kr
F excimer laser (248 nm), ArF excimer laser (193 nm), F2 excimer laser (157
nm), X-rays, electron beams and the like.

Examples of the developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia;
Primary amines such as ethylamine and n-propylamine;
Secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcoholamines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide and the like An alkaline aqueous solution such as a quaternary ammonium salt, a cyclic amine such as pyrrole, or pyrhelidine can be used. Further, an appropriate amount of an alcohol or a surfactant may be added to the above alkaline aqueous solution.

[0271]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.

Example 1 (i) Synthesis Example 1 of Resin 2-Methyl-2-adamantyl methacrylate and mevalonic lactone methacrylate were charged at a ratio of 50/50 (molar ratio) and dissolved in tetrahydrofuran to obtain a solid content of 20%. A 100 mL solution was prepared. V
-65 (trade name, manufactured by Wako Pure Chemical Industries, Ltd.) was added in an amount of 2 mol% based on the total number of moles of the monomers, and this was added dropwise to 10 mL of tetrahydrofuran heated to 55 ° C over 2 hours in a nitrogen atmosphere. After completion of the dropwise addition, the reaction solution was heated and stirred for 6 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and white powder crystallized and precipitated in 3 L of distilled water was recovered. The composition of the resin determined from C ¹³ NMR was 53/47 (2-methyl-
2-adamantyl methacrylate / mevalonic lactone methacrylate). The polystyrene equivalent weight average molecular weight determined by GPC measurement was 9,660. (Ii) Production of resist 100 parts by weight of 2-methyl-2-adamantyl methacrylate / mevalonic lactone methacrylate synthesized according to Synthesis Example 1 above, 2 parts by weight of triphenylsulfonium trifluoromethanesulfonate as a photoacid generator, and a surfactant KP-341 (made by Shin-Etsu Silicone Co., Ltd.) 5
After dissolving 0 ppm and 0.15 parts by weight of diphenylamine in ethyl lactate to form a uniform solution, the solution was filtered using a polyethylene filter (manufactured by Millipore) having a pore size of 0.1 μm to prepare a photoresist composition. The obtained resist solution was spin-coated on a silicon substrate pretreated with hexamethyldisilazane, and prebaked at 130 ° C. for 60 seconds to form a 0.5 μm-thick resist film.
After exposing this resist film with an ArF excimer laser exposure device (manufactured by Nikon Corporation, NA = 0.55), the resist film was exposed at 100 ° C. for 6 hours.
Bake for 0 seconds. Next, after developing with a 2.38% by weight aqueous solution of tetramethylammonium hydroxide for 60 seconds, rinsing with ultrapure water was performed to form a pattern on the silicon substrate. The resist pattern on the substrate thus obtained was observed with a scanning electron microscope to evaluate the sensitivity of the resist. Table 1 shows the results.

Example 2 A resist solution was prepared in the same manner as in Example 1 except that the filtration was carried out using a nylon filter having a pore diameter of 0.1 μm (manufactured by Pall Corporation) in place of the polyethylene filter having a pore diameter of 0.1 μm. Thus, a pattern was formed on the silicon substrate. The resulting resist pattern on the substrate was observed with a scanning electron microscope to evaluate the sensitivity of the resist. Table 1 shows the results.

Example 3 (i) Synthesis Example 2 of Resin 2-Methyl-2-adamantyl methacrylate, butyrolactone methacrylate, ratio of 40/60 (molar ratio)
, Dissolved in tetrahydrofuran, and solid content concentration 2
100 mL of a 0% solution was prepared. V-65 was added to this solution.
(Trade name, manufactured by Wako Pure Chemical Industries)
mol.
The solution was added dropwise to 10 mL of tetrahydrofuran heated to ° C.
After completion of the dropwise addition, the reaction solution was heated and stirred for 6 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and white powder crystallized and precipitated in 3 L of distilled water was recovered. The composition of the resin determined from C ¹³ NMR was 41/59 (2-methyl-2-adamantyl methacrylate / butyrolactone methacrylate) in a molar ratio. The weight average molecular weight in terms of polystyrene determined by GPC measurement was 12,700.

(Ii) Production of resist 2-methyl-2-adamantyl methacrylate / butyrolactone methacrylate 1 synthesized according to Synthesis Example 2 above
00 parts by weight, 2 parts by weight of triphenylsulfonium trifluoromethanesulfonate as a photoacid generator, R-08 (manufactured by Dainippon Ink and Chemicals, Inc.) 50 p as a surfactant
pm and 1,5-diazabicyclo [4,3,0] -5
After dissolving 0.15 parts by weight of nonene in PGMEA (propylene glycol monoethyl ether acetate) to form a uniform solution, the solution was filtered using a polyethylene filter (manufactured by Millipore) having a pore size of 0.1 μm to remove the photoresist composition. Prepared. The obtained resist solution was spin-coated on a silicon substrate pretreated with hexamethyldisilazane, and prebaked at 130 ° C. for 60 seconds to form a film having a thickness of 0.1 μm.
A 5 μm resist film was formed. This resist film is
F excimer laser exposure apparatus (manufactured by Nikon Corporation, NA = 0.
55), and baked at 100 ° C. for 60 seconds.
Next, after developing with a 2.38% by weight aqueous solution of tetramethylammonium hydroxide for 60 seconds, rinsing with ultrapure water was performed to form a pattern on the silicon substrate. The resist pattern on the substrate thus obtained was observed with a scanning electron microscope to evaluate the sensitivity of the resist. Table 1 shows the results.

Example 4 A resist solution was prepared in the same manner as in Example 3 except that filtration was performed using a nylon filter (manufactured by Pall Corporation) having a pore size of 0.1 μm instead of a polyethylene filter having a pore size of 0.1 μm. Thus, a pattern was formed on the silicon substrate. The resulting resist pattern on the substrate was observed with a scanning electron microscope to evaluate the sensitivity of the resist. Table 1 shows the results.

Example 5 Example 3 was repeated except that the mixture was filtered using a polysulfonic acid filter (manufactured by Fuji Photo Film Co., Ltd.) having a pore size of 0.1 μm instead of a polyethylene filter having a pore size of 0.1 μm.
A resist solution was prepared in the same manner as described above, and a pattern was formed on a silicon substrate. The resulting resist pattern on the substrate was observed with a scanning electron microscope to evaluate the sensitivity of the resist. Table 1 shows the results.

Comparative Example 1 Example 1 was repeated except that the filtration was performed using a tetrafluoroethylene filter (manufactured by Millipore) having a pore size of 0.1 μm instead of the polyethylene filter having a pore size of 0.1 μm.
A resist solution was prepared in the same manner as described above, and a pattern was formed on a silicon substrate. The resulting resist pattern on the substrate was observed with a scanning electron microscope to evaluate the sensitivity of the resist. Table 1 shows the results.

Comparative Example 2 Example 3 was repeated except that the filtration was performed using a tetrafluoroethylene filter (manufactured by Millipore) having a pore size of 0.1 μm instead of the polyethylene filter having a pore size of 0.1 μm.
A resist solution was prepared in the same manner as described above, and a pattern was formed on a silicon substrate. The resulting resist pattern on the substrate was observed with a scanning electron microscope to evaluate the sensitivity of the resist. Table 1 shows the results.

[0280]

[Table 1]

The sensitivity and sensitivity stability in this example were evaluated as follows. <Sensitivity> Exposure amount when a resist pattern is formed according to the above embodiment or comparative example and a pattern with a line width of 0.15 μm is obtained according to the mask dimensions (hereinafter referred to as “optimum exposure amount”).
Was called sensitivity. In Table 1, the sensitivity was measured in Example 3.
The relative sensitivity when the optimal exposure amount of the sample was 1 was shown. The higher the value, the lower the sensitivity.

<Sensitivity Stability> The above-described optimal sensitivity measurement was performed using 10 wafers, and the sensitivity fluctuation from the average was used as a measure of sensitivity stability.

It can be seen that excellent sensitivity and sensitivity stability can be obtained when filtering with the filter of the present invention.

[0284]

According to the present invention, not only coating properties and storage stability, but also a resist composition having high sensitivity and excellent sensitivity stability can be provided. Is extremely useful as a resist for manufacturing integrated circuits.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Kazuya Uenishi 4,000 Kawajiri, Yoshida-cho, Haibara-gun, Shizuoka Pref. EA01

Claims (3)

[Claims] 1. A chemically amplified resist composition obtained by filtering a resist solution containing an acid generator and an acid-decomposable resin using a filter containing polyethylene, nylon or polysulfone as a material. . 2. A method for preparing a chemically amplified resist composition, comprising filtering a resist solution containing an acid generator and an acid-decomposable resin using a filter containing polyethylene, nylon or polysulfone as a material. . 3. A pattern forming method, comprising a step of applying the chemically amplified resist composition according to claim 1 on a substrate and a step of exposing the composition to actinic light.