JP2000338676A - Positive photoresist composition for exposure with far ultraviolet ray - Google Patents

Abstract

PROBLEM TO BE SOLVED: To ensure superior sensitivity, resolving power, dry etching resistance and adhesion to a substrate and to prevent the occurrence of development defects and scum by incorporating a compound which generates an acid when irradiated, a compound which has specified repeating units, is decomposed by the action of the acid and increases its solubility to an alkali developing solution and a surfactant. SOLUTION: This positive photoresist composition contains a compound which generates an acid when irradiated with active light or radiation, a compound which has repeating units of the formula, is decomposed by the action of the acid and increases its solubility to an alkali developing solution and a fluorine-containing surfactant and/or a silicon-containing surfactant. In the formula, R1 is H, a halogen or a 1-4C linear or a branched alkyl and R2-R4 are each H or hydroxy but at least one of R2-R4 is hydroxy.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive photoresist composition for deep ultraviolet exposure used in an ultra microlithography process such as the production of an ultra LSI or a high-capacity microchip and other photofabrication processes. It is. More specifically, the present invention relates to a positive photoresist composition for deep ultraviolet exposure which can form a high-definition pattern by using light having a wavelength of not more than 250 nm, particularly a deep ultraviolet region including excimer laser light.

[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 meet 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. As a photoresist composition for an ArF light source, a resin having an alicyclic hydrocarbon moiety introduced therein for the purpose of imparting dry etching resistance has been proposed. However, such a phenomenon that the development with an aqueous solution of tetramethylammonium hydroxide (hereinafter referred to as TMAH), which has been widely used as a resist developing solution in the past, becomes difficult, and the resist is peeled off from the substrate during the development. Can be seen. In response to such a resist hydrophobization, measures such as mixing an organic solvent such as isopropyl alcohol with a developing solution have been studied, and although tentative results have been obtained, the swelling of the resist film and the process become complicated. This does not necessarily mean that the problem has been solved. In the approach of improving the resist, many measures have been taken to supplement various hydrophobic alicyclic hydrocarbon sites by introducing a hydrophilic group.

JP-A-10-10739 discloses an energy-sensitive resist containing a polymer obtained by polymerizing a monomer having an alicyclic structure such as a norbornene ring in the main chain, maleic anhydride, and a monomer having a carboxyl group. Materials are disclosed. JP-A-10-111569 discloses a radiation-sensitive resin composition containing a resin having an alicyclic skeleton in the main chain and a radiation-sensitive acid generator. JP-A-11-109632 describes that a resin containing a polar group-containing alicyclic functional group and an acid-decomposable group is used for a radiation-sensitive material.

A resin containing an acid-decomposable group used for a photoresist for exposure to far ultraviolet rays generally contains an aliphatic cyclic hydrocarbon group in the molecule at the same time. For this reason, the resin becomes hydrophobic, and there is a problem caused by the hydrophobicity. Various means for improving the above have been studied, but the above techniques still have many unsatisfactory points (especially in terms of developability), and improvements are desired.

That is, the above-mentioned far ultraviolet ray, short wavelength light source,
For example, even in a technique using an ArF excimer laser (193 nm) as an exposure light source, there is still room for improvement in developability. Specifically, there are problems such as generation of development defects and generation of scum (development residue). In addition, there is room for improvement in the problem of dependency on density. Since various patterns are included as a tendency of recent devices, resists are required to have various performances. One of them is dependency on density. That is, the device has a portion where lines are dense, a pattern having a wider space than the lines, and an isolated line. Therefore, it is important to resolve various lines with high reproducibility. But,
It is not always easy to reproduce various lines due to optical factors, and at present the solution by resist is not clear. In particular, in the above-mentioned resist system containing an alicyclic group, the performance difference between the isolated pattern and the dense pattern is remarkable, and improvement is desired.

[0008]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to solve the problem of the performance improvement technology inherent in microphotofabrication using far ultraviolet light, particularly ArF excimer laser light. Specifically, it is an object of the present invention to provide a positive photoresist composition which is excellent in sensitivity, resolution, dry etching resistance, and adhesion to a substrate, and further eliminates problems of development defects and scum during development. is there. It is a further object of the present invention to provide a positive photoresist composition for deep ultraviolet exposure, which has excellent dependency on density.

[0009]

Means for Solving the Problems The present inventors have conducted intensive studies on the constituent materials of a resist composition in a positive-type chemical amplification system, and as a result, by using a specific acid-decomposable resin and a specific additive, the present invention has been developed. Knowing that the object of the invention is achieved, the present invention has been achieved. That is, the above object is achieved by the following constitutions.

(1) (A) a compound capable of generating an acid upon irradiation with actinic rays or radiation; (B) a compound having a repeating unit represented by the following general formula (I) and decomposed by the action of an acid to form an alkali A positive photoresist composition for deep ultraviolet light exposure, comprising: a resin having increased solubility in water; and (C) a fluorine-based and / or silicon-based surfactant.

[0011]

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In the formula (I), R ₁ represents a hydrogen atom, a halogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms. R _{2 to} R ₄ each independently represent a hydrogen atom or a hydroxyl group. However, at least one of R _{2 to} R ₄ represents a hydroxyl group.

(2) The positive photoresist composition for deep ultraviolet exposure according to the above (1), further comprising a nitrogen-containing basic compound. (3) The nitrogen-containing basic compound is 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, and hindered piperidines The positive photoresist composition for deep ultraviolet exposure according to the above (2), which is at least one compound selected from hindered amines having a skeleton.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the compounds used in the present invention will be described in detail. (A) Compound that generates an acid upon irradiation with actinic rays or radiation (photoacid generator) The photoacid generator used in the present invention is a compound that generates an acid upon irradiation with actinic rays or radiation. As the compound used in the present invention, which decomposes upon irradiation with actinic rays or radiation to generate an acid, a photoinitiator for photocationic polymerization,
Known light (400 to 200 nm ultraviolet light, far ultraviolet light, particularly preferably g-line, h-ray) used in photoinitiators of photoradical polymerization, photodecolorants of dyes, photochromic agents, micro resists and the like. Ray, i-ray, KrF excimer laser light), ArF excimer laser light, an electron beam, an X-ray, a compound generating an acid by a molecular beam or an ion beam, and a mixture thereof can be appropriately selected and used.

Further, examples of other compounds which generate an acid upon irradiation with actinic rays or radiation used in the present invention include, for example, SISchlesinger, Photogr. Sci. Eng., 18, 3
87 (1974), TSBetal, Polymer, 21,423 (1980) and the like diazonium salts, U.S. Pat.Nos. 4,069,055 and 4,06
No. 9,056, Re 27,992, ammonium salts described in JP-A-3-140140, DC Necker et al., Macromolecules, 1,
7,2468 (1984), CSwen et al, Teh, Proc.Conf.Rad.Curin
g ASIA, p478 Tokyo, Oct (1988), U.S. Pat.No. 4,069,055
No. 4,069,056, etc.
vello etal, Macromorecules, 10 (6), 1307 (1977), Chem.
& Eng.News, Nov. 28, p31 (1988), EP 104,143,
U.S. Patent Nos. 339,049 and 410,201, JP-A-2-150,84
No. 8, iodonium salts described in JP-A-2-296,514 etc.,
JVCrivello etal, Polymer J. 17, 73 (1985), JVCriv
ello etal. J. Org. Chem., 43, 3055 (1978), WRWatt eta
l, J. Polymer Sci., Polymer Chem. Ed., 22, 1789 (1984),
JVCrivello etal, Polymer Bull., 14,279 (1985), JV
Crivello etal, Macromorecules, 14 (5), 1141 (1981), J.
V. Crivello etal, J. PolymerSci., Polymer Chem. Ed., 17,
2877 (1979), European Patent Nos. 370,693, 161,811, 4
No. 10,201, No. 339,049, No. 233,567, No. 297,443,
No. 297,442, U.S. Pat.Nos. 3,902,114 and 4,933,377,
No. 4,760,013, No. 4,734,444, No. 2,833,827, Dokoku Patent No. 2,904,626, No. 3,604,580, No. 3,604,581,
Sulfonium salts described in JP-A-7-28237 and JP-A-8-27102, JVCrivello et al., Macromorecule
s, 10 (6), 1307 (1977), JVCrivello etal, J. PolymerSc
Selenonium salts described in i., Polymer Chem.Ed., 17, 1047 (1979), etc., CSWen et al., Teh, Proc. Conf. Rad. Curing AS
Onium salts such as arsonium salts described in IA, p478 Tokyo, Oct (1988), U.S. Pat.No. 3,905,815, JP-B-46-4605
No., JP-A-48-36281, JP-A-55-32070, JP-A-60-2
39736, JP-A-61-169835, JP-A-61-169837, JP-A-62-58241, JP-A-62-212401, JP-A-63-70243
Nos., Organohalogen compounds described in JP-A-63-298339, K. Meier et al, J. Rad. Curing, 13 (4), 26 (1986), T.
P. Gill et al, Inorg.Chem., 19, 3007 (1980), D. Astruc, A
cc.Chem.Res., 19 (12), 377 (1896), organometallic / organic halides described in JP-A-2-14145, etc., S. Hayase et al.
J. Polymer Sci., 25, 753 (1987), E. Reichmanis et al., J. Ph
olymer Sci., Polymer Chem. Ed., 23, 1 (1985), QQZhu et.
al, J. Photochem., 36, 85, 39, 317 (1987), B. Amit etal, Te
trahedron Lett., (24) 2205 (1973), DHR Barton etal,
J. Chem Soc., 3571 (1965), PM Collins et al., J. Chem. So
C., PerkinI, 1695 (1975), M. Rudinstein et al, Tetrahedro
n Lett., (17), 1445 (1975), JWWalkeretal J. Am. Chem. S
oc., 110, 7170 (1988), SCBusman et al., J. Imaging Techn.
ol., 11 (4), 191 (1985), HM Houlihan et al, Macormolecul
es, 21, 2001 (1988), PMCollinsetal, J. Chem. Soc., Che
m.Commun., 532 (1972), S.Hayase etal, Macromolecules, 1
8,1799 (1985), E. Reichman et al., J. Electrochem. Soc., So
lid State Sci.Technol., 130 (6), FMHoulihan etal, Ma
cromolcules, 21, 2001 (1988), EP 0290,750,
046,083, 156,535, 271,851, 0,388,343
No. 3,901,710, 4,181,531, U.S. Pat.
-198538, JP-A-53-133022, etc., a photoacid generator having a 0-nitrobenzyl-type protecting group, M. TUNOOKA et al., P.
olymer Preprints Japan, 35 (8), G. Berner et al., J. Rad. C
uring, 13 (4), WJMijs etal, CoatingTechnol., 55 (69
7), 45 (1983), Akzo, H. Adachi et al, Polymer Preprints, J
apan, 37 (3), European Patent Nos. 0199,672, 84515, 044,
No. 115, No. 618,564, No. 0101,122, U.S. Pat.No. 4,371,
605, 4,431,774, JP-A-64-18143, JP-A 2-2
Compounds which generate sulfonic acid upon photolysis, such as iminosulfonates described in JP-A-45756, JP-A-3-140109 and the like, described in JP-A-61-166544, JP-A-2-71270 and the like. Disulfone compound, JP-A-3-103854
And diazoketosulfone and diazodisulfone compounds described in JP-A Nos. 3-103856 and 4-210960.

A group which generates an acid by the light;
Alternatively, a compound having a compound introduced into a main chain or a side chain of a polymer, for example, MEWoodhouse et al., J. Am. Chem.
c., 104, 5586 (1982), SPPappas etal, J. Imaging Sci.,
30 (5), 218 (1986), S. Kondoetal, Makromol.Chem., Rapid
Commun., 9,625 (1988), Y.Yamadaetal, Makromol.Chem., 1
52,153,163 (1972), JVCrivello etal, J. PolymerSci.,
Polymer Chem.Ed., 17,3845 (1979), U.S. Pat.
No. 7, Dokoku Patent No. 3914407, JP-A-63-26653, JP-A-55
-164824, JP-A-62-69263, JP-A-63-146038, JP-A-63-163452, JP-A-62-153853, JP-A-63-14602
Compounds described in No. 9 and the like can be used.

Further, VNRPillai, Synthesis, (1), 1 (19
80), A. Abad et al, Tetrahedron Lett., (47) 4555 (197
1), DHR Barton et al, J. Chem. Soc., (C), 329 (197
0), compounds which generate an acid by light described in US Pat. No. 3,779,778 and European Patent No. 126,712 can also be used.

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

[0019]

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

[0021]

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[0022]

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[0023]

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

[0025]

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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.

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

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

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

[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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[0041]

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[0042]

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[0043]

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

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

[0046]

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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.

[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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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% by weight.
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, (B) a resin having a repeating unit represented by the above general formula (I) and decomposed by the action of an acid to increase the solubility in alkali will be described. In the general formula (I), the alkyl group for R ₁ is a linear or branched one having 1 to 4 carbon atoms. Specifically, methyl, ethyl, n-propyl, isopropyl, n
-Butyl, isobutyl, sec-butyl, t-butyl and the like. The alkyl group may be substituted, and as the substituent, an alkoxy group having 1 to 4 carbon atoms,
Halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), acyl group, acyloxy group, cyano group, hydroxyl group, carboxy group, alkoxycarbonyl group,
Examples thereof include a nitro group. Examples of the halogen atom for R ₁ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

In the general formula (I), as described above, at least one of R _{2 to} R ₄ is a hydroxyl group, preferably a dihydroxy form or a monohydroxy form, more preferably a monohydroxy form. .

The resin according to the present invention contains a group which is decomposed by the action of an acid (also referred to as an acid-decomposable group). As such an acid-decomposable group, those conventionally used in this field can be used. Examples of the acid-decomposable group include-
Examples thereof include those represented by C (= O) -X ₁ -R ₀ .
In the formula, R ₀ represents a tertiary alkyl group such as t-butyl group, t-amyl group, isobornyl group, 1-ethoxyethyl group, 1-butoxyethyl group, 1-isobutoxyethyl group, 1-cyclohexyloxy 1-alkoxyethyl group such as ethyl group, 1-methoxymethyl group, alkoxymethyl group such as 1-ethoxymethyl group, tetrahydropyranyl group, tetrahydrofuranyl group, trialkylsilyl ester group, 3-oxocyclohexyl ester group and the like. Can be mentioned. X1 is an oxygen atom, a sulfur atom, -NH
-, - NHSO ₂ - or an -NHSO ₂ NH-. Further, a group in which an alkali-soluble group is protected by a group represented by the following general formula (II) or a group represented by the following general formulas (pI) to (pVI) is also exemplified. In the present invention, the acid-decomposable group is preferably a group represented by the following general formula (II) or a group represented by the following general formulas (pI) to (pVI) in which an alkali-soluble group is protected.

[0058]

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In the general formula (II), Ra is a hydrogen atom and has 1 carbon atom.
Represents up to 4 alkyl groups. However, when m = 0 or 2,
Ra represents an alkyl group having 1 to 4 carbon atoms. Rb ~ Re
Each independently represents a hydrogen atom or an alkyl group which may have a substituent. m represents an integer of 0 to 2, and n is
Represents an integer of 1 to 3. m + n is 2 or more and 6 or less.

[0060]

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In the general formulas (pI) to (pVI), R ₁₁ is
Represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a sec-butyl group, and Z represents an atomic group necessary for forming an alicyclic hydrocarbon group together with a carbon atom. Represents R _{12 to} R ₁₆ each independently represent a linear or branched alkyl group or an alicyclic hydrocarbon group having 1 to 4 carbon atoms, provided that at least one of R _{12 to} R ₁₄ , or Either R ₁₅ or R ₁₆ represents an alicyclic hydrocarbon group. R _{17 to} R ₂₁ each independently represent a hydrogen atom, a linear or branched alkyl group or an alicyclic hydrocarbon group having 1 to 4 carbon atoms, provided that at least one of R _{17 to} R ₂₁ One represents an alicyclic hydrocarbon group. Also,
Either R ₁₉ or R ₂₁ represents a linear or branched alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group. R ₂₂
To R ₂₅ each independently represent a linear or branched alkyl group or an alicyclic hydrocarbon group having 1 to 4 carbon atoms, provided that at least one of R _{22 to} R ₂₅ is an alicyclic group; Represents a hydrocarbon group.

In the general formulas (pI) to (pVI), R
The alkyl group for _{12 to} R ₂₅ represents a linear or branched alkyl group having 1 to 4 carbon atoms, which may be substituted or unsubstituted. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group,
Examples include a sec-butyl group and a t-butyl group. Further, as a further substituent of the above alkyl group, one having 1 carbon atom
And 4 to 4 alkoxy groups, halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom), acyl group, acyloxy group, cyano group, hydroxyl group, carboxy group, alkoxycarbonyl group, nitro group and the like.

The alicyclic hydrocarbon group for R _{11 to} R _{25 or} the alicyclic hydrocarbon group formed by Z and a carbon atom may be monocyclic or polycyclic. Specific examples include groups having a monocyclo, bicyclo, tricyclo, tetracyclo structure or the like having 5 or more carbon atoms. The number of carbon atoms is preferably from 6 to 30, particularly preferably from 7 to 25. These alicyclic hydrocarbon groups may have a substituent. Hereinafter, structural examples of the alicyclic portion of the group containing the alicyclic hydrocarbon structure will be described.

[0064]

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[0065]

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[0066]

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In the present invention, preferred examples of the alicyclic moiety include an adamantyl group, a noradamantyl group, a decalin residue, a tricyclodecanyl group, a tetracyclododecanyl group, a norbornyl group, a cedrol group, and a cyclohexyl group. , Cycloheptyl group, cyclooctyl group,
Examples thereof include a cyclodecanyl group and a cyclododecanyl group. More preferred are an adamantyl group, a decalin residue, a norbornyl group, a cedrol group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecanyl group, and a cyclododecanyl group.

Examples of the substituent of these alicyclic hydrocarbon groups include an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group and an alkoxycarbonyl group. 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 alkali-soluble group protected by the structure represented by the general formula (II) or the general formulas (pI) to (pVI) in the above resin include various groups known in this technical field. Specific examples include a carboxylic acid group, a sulfonic acid group, a phenol group, a thiol group and the like, and preferred are a carboxylic acid group and a sulfonic acid group. As the alkali-soluble group protected by the structure represented by any of the general formulas (pI) to (pVI) in the above resin, preferably, groups represented by the following general formulas (pVII) to (pXI) are exemplified.

[0070]

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Here, R _{11 to} R ₂₅ and Z are the same as defined above. As the repeating unit having the alkali-soluble group protected by the structure represented by the general formulas (pI) to (pVI) constituting the alkali-soluble resin (ii), a repeating unit represented by the following general formula (pA) is exemplified. preferable.

[0072]

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In the general formula (pA), R represents a hydrogen atom, a halogen atom or a substituted or unsubstituted linear or branched alkyl group having 1 to 4 carbon atoms. A plurality of Rs may be the same or different. A ′ is a single bond or two selected from the group consisting of a single bond, an alkylene group, a substituted alkylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a sulfonamide group, a urethane group, and a urea group. Represents a combination of the above groups. Ra represents any one of the above formulas (pI) to (pVI). Hereinafter, specific examples of the monomer corresponding to the repeating unit represented by the general formula (pA) are shown.

[0074]

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[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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In the group represented by the general formula (II), R
a represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. However, when m = 0 or 2, Ra represents an alkyl group having 1 to 4 carbon atoms. Rb to Re each independently represent a hydrogen atom or an alkyl group which may have a substituent. m represents an integer of 0 to 2, and n represents an integer of 1 to 3. m + n
Is 2 or more and 6 or less. In the general formula (II), Ra
Represents a linear or branched alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group,
Examples include a sec-butyl group and a t-butyl group. m =
When 0 or 2, Ra represents a linear or branched alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group in Rb to Re include a linear or branched alkyl group, and may have a substituent. As the linear or branched alkyl group, a linear or branched alkyl group having 1 to 12 carbon atoms is preferable, and a linear or branched alkyl group having 1 to 10 carbon atoms is more preferable. ,
More preferably, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl It is. Further, as a further substituent of the above alkyl group, one having 1 carbon atom
And 4 to 4 alkoxy groups, halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom), acyl group, acyloxy group, cyano group, hydroxyl group, carboxy group, alkoxycarbonyl group, nitro group and the like.

In the above general formula (II), preferably,
Ra is a methyl group or an ethyl group when m = 0 or 2, and Ra is a hydrogen atom, a methyl group or an ethyl group when m = 1. Rb to Re are preferably a hydrogen atom or a methyl group. The repeating unit having a group represented by the general formula (II) is preferably a repeating unit represented by the following general formula (AI).

[0082]

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In the general formula (AI), R and A ′ have the same meanings as in the above general formula (pA). B represents a group represented by the general formula (II). A 'is preferably a single bond, an alkylene group having 1 to 10 carbon atoms, an ether group, a carbonyl group,
Ester groups may be used alone or divalent groups obtained by combining two or more of these groups. Preferred structures as the divalent group in which two or more are combined include those having the following structures.

[0084]

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In the above formula, Ra, Rb, and r1 have the same meanings as described below. m is a number from 1 to 3.

The resin according to the present invention may further contain other copolymer components other than the above-mentioned repeating unit as other copolymer components. Examples of such a copolymer component include repeating units represented by the following general formulas (III-a) to (III-d). Thereby, the hydrophilicity of the resist increases, and the adhesion and the like improve.

[0087]

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In the above formula, R₁Is as defined above. R_Five
~ R₁₂Each independently has a hydrogen atom or a substituent
Represents an alkyl group. R represents a hydrogen atom or
Alkyl group, cyclic alkyl which may have a substituent
Represents an aryl group or an aralkyl group. m is 1 to 1
Represents an integer of 0. X represents a single bond or a substituent
Alkylene group, cyclic alkylene group, aryle
Group, ether group, thioether group, carbon
Group, ester group, amide group, sulfonamide group, c
Alone selected from the group consisting of a urethane group and a urea group,
Or a combination of at least two or more of these groups
Represents a divalent group that is not decomposed by the action of an acid. Z is
Single bond, ether group, ester group, amide group, alkylene
Represents a divalent group or a divalent group obtained by combining these groups. R₁₃
Is a single bond, an alkylene group, an arylene group, or
Represents a divalent group. R₁₅Is an alkylene
Group, arylene group or divalent group combining these
Represents R₁₄Is an alkyl which may have a substituent
Group, cyclic alkyl group, aryl group or aralkyl group
You. R ₁₆Represents a hydrogen atom or a substituent
Good, alkyl group, cyclic alkyl group, alkenyl group,
Represents a reel group or an aralkyl group. A is the official
Represents any functional group.

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Examples of the alkyl group of R _{5 to} R ₁₂ , R, R ₁₄ and R ₁₆ include a linear or branched alkyl group, which may have a substituent. As the linear or branched alkyl group, a linear or branched alkyl group having 1 to 12 carbon atoms is preferable, and a linear or branched alkyl group having 1 to 10 carbon atoms is more preferable. More preferably methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group,
t-butyl group, pentyl group, hexyl group, heptyl group,
An octyl group, a nonyl group, and a decyl group. R, R _14, R
_Examples of the cyclic alkyl group of ₁₆ 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, a tricyclodecanyl group , Dicyclopentenyl group, nobornane epoxy group, menthyl group, isomenthyl group, neomenthyl group, tetracyclododecanyl group, steroid residue and the like.

The aryl group represented by R, R ₁₄ and R ₁₆ has 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 ₁₄ and R ₁₆ include those having 7 to 20 carbon atoms, such as a benzyl group, a phenethyl group and a cumyl group which may have a substituent. The alkenyl group for R ₁₆ has 2 carbon atoms.
To 6 alkenyl groups, 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, a 3-oxocyclohexenyl group, and a 3-oxo group. A cyclopentenyl group, a 3-oxoindenyl group and the like. 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
Represents a single bond, an ether group, an ester group, an amide group, an alkylene group, or a divalent group obtained by combining these.
R ₁₃ represents a single bond, an alkylene group, an arylene group, or a divalent group obtained by combining these. R ₁₅ represents an alkylene group, an arylene group, or a divalent group obtained by combining them. Examples of the arylene group in X, R ₁₃ and R ₁₅ include those having 6 to 10 carbon atoms, which may have a substituent. Specifically, phenylene group, 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 ₁₃ and R ₁₅ include groups represented by the following formulas. -[C (Ra) (Rb)] r1 wherein Ra and Rb represent a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, or an alkoxy group;
Both 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, a propyl group, and an isopropyl group are more preferable. As the substituent of the substituted alkyl group,
Examples 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. r1 represents 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.

[0093]

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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, specific examples of the structure of the terminal excluding X are shown below as specific examples of the structure of the side chain in the general formula (III-b), but the present invention is not limited thereto. .

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Hereinafter, specific examples of the monomer corresponding to the repeating structural unit represented by the general formula (III-c) will be shown, but the content of the present invention is not limited thereto.

[0098]

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[0099]

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[0100]

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Hereinafter, specific examples of the repeating structural unit represented by formula (III-d) will be shown, but the present invention is not limited thereto.

[0102]

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[0103]

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[0104]

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In formula (III-b), R _{5 to} R ₁₂ 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 (III-c), R ₁₃ 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 ₁₄ is a group having 1 carbon atom such as a methyl group or an ethyl group. Preferred are 10 to 10 alkyl groups, cyclopropyl groups, cyclohexyl groups, cyclic alkyl groups such as camphor residues, naphthyl groups, and naphthylmethyl groups. 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 (III-d), R ₁₅ is preferably an alkylene group having 1 to 4 carbon atoms. As R ₁₆ , an alkyl group having 1 to 8 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a neopentyl group, an octyl group, which may have a substituent;
Cyclohexyl group, adamantyl group, norbornyl group,
Boronyl, isobornyl, menthyl, morpholino, 4-oxocyclohexyl, and optionally substituted phenyl, toluyl, mesityl, naphthyl, and camphor residues are preferred. 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.

In the present invention, general formulas (III-a) to (III-a)
Among (III-d), repeating units represented by formulas (III-b) and (III-d) are preferable.

Preferred embodiments of the resin in the present invention are shown below. 1) A resin containing a repeating unit represented by the above general formula (I) and a repeating unit having a group represented by the above general formula (II) and decomposed by the action of an acid to increase solubility in alkali. Here, it is preferable to further include the repeating units represented by the above general formulas (III-a) to (III-d).

2) At least one of the groups having an alicyclic hydrocarbon structure represented by the above general formulas (pI) to (pVI)
A recurring unit having an alkali-soluble group protected by one and a recurring unit represented by the general formula (I),
A resin that decomposes under the action of an acid to increase solubility in alkali. Here, it is preferable to further include a repeating unit having a group represented by the following general formula (II ′).

[0109]

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Here, in the general formula (II ′), Ra ′ to R ′
e ′ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom or a methyl group.
m ′ and n ′ each independently represent an integer of 0 to 3, and m ′
+ N 'is 2 or more and 6 or less, m' is preferably 0 or 1, and n 'is preferably an integer of 1 to 3. Here, it is preferable to further include the repeating units represented by the above general formulas (III-a) to (III-d).

In addition to the above-mentioned resins, various resins may be used for the purpose of adjusting dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and resolution, heat resistance, sensitivity and the like, which are general requirements for resists. It can be used as a copolymer with various monomer repeating units.

Examples of such a repeating unit include, but are not limited to, repeating units corresponding 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, (4) film loss (hydrophilic / hydrophobic, alkali-soluble group selection), (5) adhesion of unexposed portion to substrate,
(6) Fine adjustment of dry etching resistance becomes possible.
Examples of such a copolymerizable monomer include, for example, an acrylate, a methacrylate, an acrylamide, a methacrylamide, an allyl compound, a vinyl ether, and an addition-polymerizable unsaturated bond selected from 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 acid 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 having 1 to 10 carbon atoms, for example, methyl, ethyl, propyl, butyl, t-butyl, heptyl, 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, cycloethyl) Groups, etc.), N, N-dialkylmethacrylamide (an alkyl group such as 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, etc.), 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.); dialkyl esters of fumaric acid (eg, dibutyl fumarate, etc.) or monoalkyl esters; other acrylic acid, methacrylic acid, croton Acid, itaconic acid, maleic anhydride, maleimide, acrylonitrile,
Examples thereof include methacrylonitrile and maleilenitrile. In addition, any addition-polymerizable unsaturated compound copolymerizable with the above various repeating units may be used.

In the above resin, the molar ratio of each repeating unit structure depends on the acid value, the resistance to dry etching of the resist, the suitability for a standard developing solution, the substrate adhesion, the dependency of the resist profile on the density of the resist, and the general requirements of the resist. It is set appropriately in order to adjust the resolution, heat resistance, sensitivity and the like.

In the present invention, the content of each repeating unit in the above-mentioned resin is determined by using the above-mentioned preferred embodiment as an example in the embodiment 1), wherein the resin contains the repeating unit represented by the general formula (I) The amount is from 20 to 75 mol%, preferably from 25 to 70 mol%, more preferably from 30 to 65 mol%, based on all repeating units. Further, the content of the repeating unit having a group represented by the general formula (II) is from 30 to 70 in all the repeating units.
Mol%, preferably 35 to 65 mol%, more preferably 40 to 60 mol%. In the resin, the general formula
The content of the repeating units represented by formulas (III-a) to (III-d) is usually 0.1 mol% to 30 mol% in all monomer repeating units.
Mol%, preferably 0.5 to 25 mol%, more preferably 1 to 20 mol%.

In the embodiment 2). In the resin of the present invention, the content of the repeating unit represented by the general formula (I) is 0.1 to 25 in all the repeating units.
Mol%, preferably 0.5 to 22 mol%, more preferably 1 to 20 mol%. General formulas (pI) to (p
The content of the repeating unit having an alkali-soluble group protected by the structure represented by VI) is 10% of all repeating units.
To 70 mol%, preferably 15 to 65 mol%, more preferably 20 to 60 mol%. Also, in the resin,
The content of the repeating unit represented by the general formula (II) is usually from 20 to 70 mol%, preferably from 25 to 65 mol%, more preferably from 30 to 60 mol%, based on all monomer repeating units. . Further, in the resin, the general formula (III-a) to the general formula (II
The content of the repeating unit represented by Id) is usually from 0.1 mol% to 30 mol%, preferably from 0.5 to 25 mol%, more preferably from 1 to 20 mol%, based on all monomer repeating units. %.

The content of the repeating unit based on the monomer of the additional 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%, based on the total number of moles of the repeating unit containing the functional group and the repeating unit represented by formula (I).
More preferably, it is at most 80 mol%.

The weight-average molecular weight Mw of the resin is determined by gel permeation chromatography using polystyrene standards, preferably 1,000 to 1,000,000.
0, more preferably from 1,500 to 500,000, still more preferably from 2,000 to 200,000, particularly preferably from 2,500 to 100,000. The larger the weight average molecular weight, the better the heat resistance and the like. While improving, the developability and the like decrease, and the balance is adjusted to a preferable range.

The resin used in the present invention can be synthesized according to a conventional method, for example, by a radical polymerization method.

In the positive photoresist composition for deep ultraviolet exposure according to the present invention, the amount of the acid-decomposable resin in the whole composition is preferably 40 to 99.99% by weight, more preferably in the total resist solids. Is 50-99.97% by weight
It is.

The positive photoresist composition for deep ultraviolet exposure according to the present invention contains (C) 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. By containing the acid-decomposable resin and the surfactant, the positive photoresist composition for deep ultraviolet exposure of the present invention,
When an exposure light source having a wavelength of 250 nm or less, particularly 220 nm or less is used, a resist pattern having excellent sensitivity, resolution, substrate adhesion and dry etching resistance, and having less development defects and scum can be obtained. As these surfactants, for example, JP-A-62-36663, JP-A-61-226746, JP-A-61-226745
No., JP-A-62-170950, JP-A-63-34540, JP-A-7-2
No. 30165, JP-A-8-62834, JP-A-9-54432, JP-A-9
No. -5988, and the following commercially available surfactants can be used as they are. As a commercially available surfactant that can be used, for example, F-top EF30
1, EF303, (Shin-Akita Chemical Co., Ltd.), Florard FC430, 431
(Manufactured by Sumitomo 3M Limited), Mega Fuck F171, F173, F1
76, F189, R08 (Dainippon Ink Co., Ltd.), Surflon S
-382, SC101, 102, 103, 104, 105, 106 (manufactured by Asahi Glass Co., Ltd.) and the like. Also, polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can be used as a silicon-based surfactant.

The amount of the surfactant is usually 0.001 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 surfactant 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. Examples of the nitrogen-containing basic compound include those having the following structures.

[0132]

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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.

[0134]

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Wherein R ²⁵³ , R ²⁵⁴ , R ²⁵⁵ and R ²⁵⁶
Are the same or different and represent 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 are 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 used is based on the total solid content of the resist composition.
Usually, 0.001 to 10% by weight, preferably 0.01 to 10% by weight.
5% by weight. If the amount is less than 0.001% by weight, the effect of the addition of the nitrogen-containing basic compound cannot be obtained. On the other hand, if it exceeds 10% by weight, the sensitivity tends to decrease and the developability of the unexposed portion tends to deteriorate.

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.

The photosensitive composition of the present invention is dissolved in a solvent capable of dissolving each of the above-mentioned components and coated on a support. As the solvent used here, ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, γ-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate , Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene, ethylene carbonate, propylene carbonate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate, methyl 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, ethylene carbonate, propylene carbonate, butyl acetate, methyl lactate, ethyl lactate, Examples thereof include methyl methoxypropionate, ethyl ethoxypropionate, N-methylpyrrolidone, and tetrahydrofuran.

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 film having a carboxylic acid group, an epoxy group and a light absorbing group in the same molecule as described in 18656, a film comprising a methylolmelamine and a benzophenone-based light absorbing agent described in JP-A-8-87115, and a method 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 coated on a substrate (eg, a silicon / silicon dioxide coating) used for manufacturing precision integrated circuit devices (on a substrate provided with the 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
nm-250 nm. Specifically, Kr
F excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ 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.

[0147]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples.

[Synthesis of Resin] Synthesis Example (1) Synthesis of Resin 1
Prepared at a ratio of 0/15, dissolved in N, N-dimethylacetamide / tetrahydrofuran = 5/5, and solid content concentration 20%
Was prepared. The solution was added to Wako Pure Chemical V
-65 was added to N, N-dimethylacetamide 10 heated at 60 ° C. for 3 hours in a nitrogen atmosphere.
It was added dropwise to mL. After completion of the dropwise addition, the reaction solution was heated for 3 hours, 1 mol% of V-65 was added again, and the mixture was stirred for 3 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 polymer composition ratio determined from C ¹³ NMR was 35/49/16. The weight average molecular weight in terms of standard polystyrene determined by GPC measurement was 7,800. Resins 2 to 16 having the composition ratios and molecular weights shown in the following table were synthesized in the same manner as in the above Synthesis Examples. In addition, the repeating units 1, 2, and 3 in the table represent the order from the left of the structural formula.

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[Table 1]

[Synthesis of Resin] Synthesis Example (2) Synthesis of Resin 17 2-ethyl-2-adamantyl methacrylate, butyrolactone methacrylate, and 3-hydroxyadamantyl methacrylate were charged in a ratio of 42/48/10 and N, N-
It was dissolved in dimethylacetamide / tetrahydrofuran = 5/5 to prepare 100 mL of a solution having a solid content of 20%. 2 mol% of Wako Pure Chemical V-65 was added to this solution,
This was heated to 60 ° C. over 2 hours in a nitrogen atmosphere,
The solution was added dropwise to 10 mL of N-dimethylacetamide. After completion of the dropwise addition, the reaction solution was heated for 3 hours, 1 mol% of V-65 was added again, and the mixture was stirred for 3 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 polymer composition ratio determined from C ¹³ NMR was 36/54.
/ 10. The weight average molecular weight in terms of standard polystyrene determined by GPC measurement was 9,600.
Resins 18 to 26 having the composition ratios and molecular weights shown in the following table were synthesized in the same manner as in the above Synthesis Examples. The repeating units 1, 2, 3, and 4 in the table represent the order from the left in the structural formula.

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[Table 2]

[Examples] 1.4 g of each of the resins shown in Table 3 synthesized in the above synthesis examples, 0.18 g of a photoacid generator, and a surfactant (the amount of addition was based on the total solid content of the composition) 1% by weight) An organic basic compound 10 mg
And dissolved in propylene glycol monoethyl ether acetate at a ratio of 0.1%, and then filtered through a 0.1 μm microfilter to prepare positive photoresist composition solutions of Examples 1 to 30.

In Table 3, PAG-1 represents triphenylsulfonium triflate, and PAG-2 represents the above (PAG3-28). The resin R1 used in Comparative Examples in Table 2 is described in Example 1 of JP-A-11-109632.
The resin used in Example 1 was used.

Examples of the surfactant include: W-1: Megafac F176 (Dainippon Ink Co., Ltd.)
(Fluorine) W-2: Megafac R08 (Dai Nippon Ink Co., Ltd.)
(Fluorine and silicone type) W-3: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) W-4: Polyoxyethylene nonylphenyl ether amine 1 is 1,5-diazabicyclo [4.
3.0] -5-nonene (DBN), 2 represents bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebagate 3, and 3 represents tri-n-butylamine.

(Evaluation Test) The obtained positive photoresist composition solution was applied on a silicon wafer using a spin coater, dried at 140 ° C. for 90 seconds, and about 0.5 μm
Was prepared and exposed to an ArF excimer laser (193 nm). A heat treatment after the exposure was performed at 120 ° C. for 90 seconds, developed with a 2.38% aqueous solution of tetramethylammonium hydroxide, and rinsed with distilled water to obtain a resist pattern profile.

[Number of development defects]: Bare S of 6 inches
Each resist film was applied to a thickness of 0.5 μm on the i-substrate, and dried at 140 ° C. for 60 seconds on a vacuum suction hot plate. Next, a 0.35 μm contact hole pattern (Hole)
Nik through a test mask with a duty ratio = 1: 3)
After exposure with an on-stepper NSR-1505EX, post-exposure heating was performed at 120 ° C. for 90 seconds. Subsequently, after paddle development with 2.38% TMAH (aqueous solution of tetramethylammonium hydroxide) for 60 seconds, 30% with pure water.
Washed with water for 2 seconds and spin dried. The sample thus obtained was used for KLA-2112 manufactured by KLA-Tencor Corporation.
The number of development defects was measured by a machine, and the obtained primary data value was defined as the number of development defects.

[Generation of development residue (scum)] Line width 0.2
Evaluation was made based on the residual state of the development residue in the resist pattern of 2 μm. A case where no residue was observed was evaluated as ○, and a case where a considerable amount was observed was evaluated as ×.

[Density Dependence] In a line-and-space pattern (dense pattern) having a line width of 0.22 μm and an isolated line pattern (sparse pattern), each was 0.22 μm.
The overlapping range of the depth of focus allowing ± 10% was determined. The larger this range is, the better the density dependency is. Table 3 shows the evaluation results.

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[Table 3]

As is clear from the results in Table 3, the comparative example has problems in the number of development defects and the occurrence of scum. On the other hand, the positive photoresist composition for deep ultraviolet exposure according to the present invention is excellent in sensitivity, resolution, substrate adhesion, and dry etching resistance, and has a satisfactory level of prevention of development defects and scum. That is, it is suitable for lithography using far ultraviolet rays such as ArF excimer laser exposure. Further, the resist composition of the present invention containing a specific organic basic compound is further excellent in the density dependency.

[0168]

The positive photoresist composition for deep ultraviolet exposure according to the present invention is suitably applied particularly to light in a far ultraviolet wavelength range of 170 nm to 220 nm, and has sensitivity, resolution, and dry etching resistance. In addition, adhesion of the substrate and prevention of development defects and scum can be realized, a good resist pattern profile can be obtained, and the density dependency is excellent.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03F 7/004 503 G03F 7/004 503A 504 504 H01L 21/027 H01L 21/30 502R (72) Inventor Blue Toshiaki Ago 4,000 Kawajiri, Yoshida-cho, Haibara-gun, Shizuoka Prefecture F-term in Fujisha Shin Film Co., Ltd. EN137 EQ017 ER026 ES007 EU016 EU026 EU046 EU076 EU116 EU126 EU136 EU146 EU187 EU217 EU236 EV217 EV247 EV297 EW177 FD312 FD318 GP03

Claims (3)

[Claims] (1) A compound which generates an acid upon irradiation with actinic rays or radiation, (B) has a repeating unit represented by the following general formula (I), and is decomposed by the action of an acid to react with an alkali A positive photoresist composition for deep ultraviolet exposure, comprising: a resin having increased solubility; and (C) a fluorine-based and / or silicon-based surfactant. Embedded image In the formula (I): R ₁ is a hydrogen atom, a halogen atom or 1 to
Represents a linear or branched alkyl group having 4 carbon atoms. R _{2 to} R ₄ each independently represent a hydrogen atom or a hydroxyl group. However, at least one of R _{2 to} R ₄ represents a hydroxyl group. 2. The positive photoresist composition for deep ultraviolet exposure according to claim 1, further comprising a nitrogen-containing basic compound. 3. The nitrogen-containing basic compound is 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,
The positive photoresist composition for deep ultraviolet exposure according to claim 2, wherein the composition is at least one compound selected from hindered amines having a hindered piperidine skeleton.