JP2001290276A - Positive resist composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive resist composition excellent in sensitivity and resolving power, ensuring excellent resolving power and pattern profile even if time passes considerably until after-heating after exposure and having small density dependency in microphotofabrication using far ultraviolet light, particularly ArF excimer laser light. SOLUTION: The positive resist composition contains two or more photo-acid generating agents each with a specified structure and a polymer having repeating structural units with different specified structures and also having a group which is decomposed by the action of an acid.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive resist composition capable of using far ultraviolet rays as an exposure light source for an ultra microlithography process such as the production of an ultra LSI and a high capacity microchip and other photofabrication processes. From a different point of view, the present invention relates to a positive resist composition capable of forming a high-definition pattern by using light having a wavelength of 220 nm or less, 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 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, also 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 its 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.

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 as described above for improving it have been studied in various ways, but there are still many insufficient points with the above techniques,
Improvement is desired.

As described above, various resins containing an acid-decomposable group in a chemically amplified photoresist for ArF exposure have been studied, but there is still room for improvement. That is, sufficient sensitivity and resolution to radiation having a wavelength of 193 nm are required. Further, there is a demand for a chemically amplified photoresist that can obtain excellent resolution and pattern profile even after a considerable time has elapsed from exposure to post-heating, that is, has high process tolerance. 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. In other words, the device has a pattern where the lines are dense,
In addition, there are isolated lines. Therefore, it is important to resolve various lines with high reproducibility. However, it is not always easy to reproduce various lines due to optical factors, and at present, the solution by a 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 It is an object of the present invention to solve the problem of the performance improvement technology inherent in microphotofabrication using far ultraviolet light, particularly ArF excimer laser light. To provide a positive resist composition which has excellent sensitivity and resolution, and which can obtain excellent resolution and pattern profile even after a considerable time elapses from post-exposure to post-heating, and has excellent process tolerance. It is in. Another object of the present invention is to provide a positive resist composition capable of obtaining a resist pattern with little dependency on density.

[0009]

Means for Solving the Problems The present inventors have intensively studied constituent materials of a resist composition in a positive-type chemical amplification system and found that a specific combination of a photoacid generator and a specific acid-decomposable resin were used. As a result, it was found that the object of the present invention was achieved, and the present invention was achieved. That is, the above object is achieved by the following constitutions.

[0010] (1) (A) a cationic portion is composed of iodonium or sulfonium, anionic portion R ^F SO ₃ ^-
(In the formula, R ^F is a fluorine-substituted alkyl group having 1 to 10 carbon atoms.) And (B) a resin having an alicyclic hydrocarbon structure having 6 or more carbon atoms and having a dissolution rate in an alkali developing solution increased by the action of an acid. A positive resist composition characterized in that at least one pair of photoacid generators having a difference in the number of carbon atoms of R ^{F in} the anion portion in the range of 2 to 8 is present in the kind of photoacid generator.

[0011] (2) (A) a cationic portion is composed of iodonium or sulfonium, anionic portion R ^F SO ₃ ^-
(In the formula, R ^F is a fluorine-substituted alkyl group having 1 to 10 carbon atoms.) (B) a resin (B) containing a repeating structural unit represented by the following general formulas (I ′) and (II ′), and having a dissolution rate in an alkali developing solution increased by the action of an acid (B) -1) or at least one of the repeating structural units represented by the following general formulas (Ia ″) and (Ib ″) and the following general formula (II ″)
And a resin (B-2) having a repeating structural unit represented by the formula (1) and having a dissolution rate in an alkali developing solution increased by the action of an acid. A positive resist composition wherein at least one pair of photoacid generators having a difference in the number of carbon atoms of R ^{F in} the anion portion in the range of 2 to 8 is present.

[0012]

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In the above general formulas (I ') and (II'): R
₀₁ independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ₀₂ represents an alkyl group having 1 to 4 carbon atoms.
W represents a single bond or a single or a combination of two or more groups selected from the group consisting of an alkylene group, an ether group, a thioether group, a carbonyl group, and an ester group.
Ra, Rb, Rc, Rd, Re, and Rf in Lc each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. However, any one of Ra to Rf represents a single bond or an alkylene group having 1 to 4 carbon atoms, and is bonded to W.
m and n each independently represent an integer of 0 to 3, and m + n is an integer of 2 to 6.

[0014]

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In the formula (Ia ″): R ′ ₁ and R ′ ₂ each independently represent a hydrogen atom, a cyano group, a hydroxyl group, —COOH, —CO
_{OR '5, -CO-NH-} R' 6, -CO-NH-SO 2 -
R ′ _{6 represents} an optionally substituted alkyl group, an optionally substituted alkoxy group or an optionally substituted cyclic hydrocarbon group, or the following —Y group. Where R '
₅ represents an alkyl group which may have a substituent, a cyclic hydrocarbon group which may have a substituent, or the following -Y group. R ′ ₆ represents an alkyl group which may have a substituent or a cyclic hydrocarbon group which may have a substituent. X
It represents an oxygen atom, a sulfur atom, -NH -, - NHSO ₂ - or an -NHSO ₂ NH-. A represents a single bond or a divalent linking group. -Y group:

[0016]

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(In the —Y group, R ′ _{21 to} R ′ ₃₀ each independently represent a hydrogen atom or an alkyl group which may have a substituent. A and b are 1 or 2.) In (Ib ″): Z ₂ represents —O— or —N (R ′ ₃ ) —, wherein R ′ ₃ is a hydrogen atom, a hydroxyl group, or —OSO
Representing a ₂ -R _'4. R ₄ ′ is an alkyl group, a haloalkyl group,
Represents 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. Represents an atomic group for forming an alicyclic structure which may have a substituent and contains two carbon atoms (CC).

(3) Among a pair of photoacid generators having a difference in the number of carbon atoms of R ^{F in} the anion portion in the range of 2 to 8, as a photo acid generator having a relatively large number of carbon atoms of R ^F Is selected from the group of photoacid generators in which R ^F in the anion portion is a linear fluorine-substituted alkyl group having a carbon number in the range of 4 to 10, and a photo acid generator in which R ^F has a relatively small number of carbon atoms. (1) or (2) above, wherein the agent is selected from the group of photoacid generators in which R ^F in the anion portion is a linear fluorine-substituted alkyl group having 1 to 5 carbon atoms. 4. The positive resist composition according to item 1. (4) The cation moiety of the photoacid generator has the following general formula (I):
The positive resist composition according to any one of the above (1) to (3), which is represented by (II) or (III).

[0019]

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In the above general formulas (I) to (III): R _{1 to} R ₃₇
Are the same or different and are a hydrogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a hydroxyl group, a halogen atom, or -S-
Represents an _R38 group. R ₃₈ represents a linear, branched or cyclic alkyl group or aryl group. Further, R _{1 to} R ₁₅ , R
Two or more of R _{16 to} R ₂₇ and R _{28 to} R ₃₇ are bonded to each other and selected from a single bond, carbon, oxygen, sulfur, and nitrogen;
Species or a ring containing two or more species may be formed.

(5) The repeating structural unit represented by the general formula (II ") is a repeating structural unit represented by the following general formula (II" -A) or (II "-B) The positive resist composition according to any one of the above (1) to (4), wherein

[0022]

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In the general formulas (II "-A) and (II" -B):
R _'13 ~R' ₁₆ are each independently a hydrogen atom, a halogen atom, a cyano group, -COOH, -COOR '(the ₅ R' ₅ are as defined above), is decomposed by the action of an acid group, - C (=
O) -X-A-R ' 17, or may have a substituent represents an alkyl group or a cyclic hydrocarbon group. Also, R '
_l3 to R _'16 may form at least two members to ring out of. Here, X and A have the same meanings as above. R _{'17 is, -COOH, -COOR' 5, -CN} ,
A hydroxyl group, an optionally substituted alkoxy group, -C
_{O-NH-R '6,} -CO-NH-SO 2 -R' 6 (R '5,
R _'6 each represents a are as defined above) or above -Y groups. n is 0 or 1.

(6) The positive resist composition as described in any of (1) to (5) above, further comprising a nitrogen-containing basic compound. (7) The positive resist composition according to any one of (1) to (6), further comprising a fluorine-based and / or silicon-based surfactant. (8) The positive resist composition as described in any one of (1) to (7) above, wherein active light or radiation having a wavelength of 220 nm or less is irradiated.

[0025]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the compounds used in the positive resist composition of the present invention and the method of using the composition will be described in detail.

[0026] [1] The photoacid generator present invention that generates an acid upon irradiation of (A) an actinic ray or radiation, a cation portion is composed of iodonium or sulfonium, anionic part R ^F SO ₃ ^- (in the formula, R ^F
Represents a fluorine-substituted alkyl group having 1 to 10 carbon atoms), and a plurality of types of photoacid generators selected from sulfonic acid salts composed of anions represented by the following formulas are used. R ^F
The fluorine-substituted alkyl group represented by may be linear, branched, or cyclic. Preferable R ^F is a fluorine-substituted linear alkyl group represented by CF ₃ (CF ₂ ) y, wherein y is an integer of 0 to 9.

In the present invention, the difference in the number of carbon atoms of R ^F is 2 to 8, preferably 3 to 7 in the above-mentioned plural kinds of photoacid generators.
Is present in at least one pair of photoacid generators. For example, when the number of carbon atoms of R ^F are three photoacid generator are used are each 3,4,5, photoacid generator difference in the number of carbon atoms in R ^F is in the range of 2 to 8 pair Exists and meets the above conditions. When three kinds of photoacid generators each having 2, 6, and 8 carbon atoms of R ^F are used, there are three pairs, and the above condition is satisfied. In the plurality of types of photoacid generators, the ratio of the paired photoacid generators is 50 to 100.
Mol%, more preferably 70 to 1 mol%.
00 mol%.

The positive resist composition of the present invention comprises a plurality of photoacid generators satisfying the above conditions together with the above-mentioned specific resin (B-1) or polymer (B-2) described in detail (B). By containing it, in micro photo-fabrication using ArF excimer laser light, excellent resolution and pattern profile can be obtained even when a considerable amount of time elapses after exposure to post-heating after exposure. Results.

In a preferred embodiment, R ^F of the anion moiety
The at least a pair of photoacid generator difference in the number of carbon atoms is in the range of 2-8, R ^F photoacid generator carbon number of R ^F is relatively large is a C4-10 a linear fluorine-substituted alkyl group (hereinafter, this photoacid generator may be abbreviated as "photoacid generator A1"), and the photoacid generator carbon number of R ^F is relatively small R ^F is a linear fluorine-substituted alkyl group having 1 to 5 carbon atoms (hereinafter, this photoacid generator may be abbreviated as “photoacid generator A2”). Also, the molar ratio of the photoacid generator A1 to the photoacid generator A2 (A1
/ A2) is 90/10 to 10/90, especially 80/2
It is preferably 0 to 20/80.

The cation moiety of the photoacid generator is preferably represented by the above general formulas (I) to (III). General formula (I)
In (III), as the linear or branched alkyl group for R _{1 to} R ₃₈ , a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, which may have a substituent, t
Examples thereof include those having 1 to 4 carbon atoms such as -butyl group. The cyclic alkyl group may have a substituent,
Those having 3 to 8 carbon atoms such as cyclopropyl group, cyclopentyl group and cyclohexyl group are exemplified. R ₁ ~
Examples of the linear or branched alkoxy group for R ₃₇ include:
Methoxy, ethoxy, hydroxyethoxy, propoxy, n-butoxy, isobutoxy, sec-
Those having 1 to 4 carbon atoms such as a butoxy group and a t-butoxy group are exemplified. As the cyclic alkoxy group, a cyclopentyloxy group, for example, a cyclopentyloxy group,
A cyclohexyloxy group; Examples of the halogen atom for R _{1 to} R ₃₇ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the aryl group for R ₃₈ include those having 6 to 14 carbon atoms which may have a substituent such as a phenyl group, a tolyl group, a methoxyphenyl group, and a naphthyl group. Preferred as these substituents are alkoxy groups having 1 to 4 carbon atoms, halogen atoms (fluorine atom, chlorine atom, iodine atom), aryl groups having 6 to 10 carbon atoms, and alkenyl groups having 2 to 6 carbon atoms. , A cyano group, a hydroxy group, a carboxy group, an alkoxycarbonyl group, a nitro group and the like.

Further, R _{1 to} R ₁₅ , R _{16 to} R ₂₇ , R _{28 to} R
Of _37, two or more of formed by combining a single bond, carbon, oxygen, one selected sulfur, and nitrogen or 2
Examples of the ring containing more than one kind include a furan ring, a dihydrofuran ring, a pyran ring, a trihydropyran ring, a thiophene ring, a pyrrole ring, and the like.

Photoacid generator A usable in the present invention
Specific examples (A1-1) to (A1-64) of No. 1 are shown below.

[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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Photoacid generator A usable in the present invention
Specific examples (A2-1) to (A2-58) of No. 2 are shown below.

[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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Among them, the photoacid generator A1 is CF
Compounds that generate ₃ (CF ₂ ) ₃ SO ₃ H and CF ₃ (CF ₂ ) ₇ SO ₃ H are preferred, and the photoacid generator A2 is CF ₃ S
Compounds that generate O ₃ H and CF ₃ (CF ₂ ) ₃ SO ₃ H are preferred. Preferred combinations of the photoacid generators A1 and A2 (photoacid generators A1 / A2, represented by the generated acid) include CF ₃ (CF ₂ ) ₃ SO ₃ H / CF ₃ SO ₃ H, CF
₃ (CF ₂ ) ₇ SO ₃ H / CF ₃ SO ₃ H, CF ₃ (CF ₂ ) ₇
SO ₃ H / CF ₃ (CF ₂ ) ₃ SO ₃ H.

The amount of the photoacid generator (A) is usually in the range of 0.001 to 40% by weight, preferably 0.01 to 20% by weight, more preferably 0.01 to 20% by weight, based on the solid content in the composition. Preferably, it is used in the range of 0.1 to 5% by weight. When the addition amount of the photoacid generator is less than 0.001% by weight, the sensitivity is lowered. When the addition amount is more than 40% by weight, the light absorption of the resist becomes too high, and the deterioration of the profile and the process (particularly baking) ) The margin is undesirably narrow.

In the positive resist composition of the present invention, a photoacid generator other than the compounds specified above can be used in combination. Examples of the photoacid generator that can be used in combination include a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization,
Known light (eg, ultraviolet light having a wavelength of 400 to 200 nm, far ultraviolet light, particularly preferably g-line, h-line, i-line)
X-rays, KrF excimer laser light), ArF excimer laser light, electron beams, X-rays, compounds generating an acid by a molecular beam or an ion beam, and mixtures thereof can be appropriately selected and used.

Examples of other photoacid generators that can be used in combination include onium salts such as diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenonium salts, and arsonium salts; Organic halides, photoacid generators having an o-nitrobenzyl-type protecting group, compounds that generate sulfonic acid upon photolysis represented by iminosulfonate, disulfone compounds, diazoketosulfones, diazodisulfone compounds, and the like. be able to. In addition, a group in which an acid is generated by these lights or a compound in which a compound is introduced into a main chain or a side chain of a polymer can be used in combination.

Further, VNRPillai, Synthesis, (1), 1 (198
0), A. Abad etal, Tetrahedron Lett., (47) 4555 (1971),
The compounds described in DHR Barton et al., J. Chem. Soc., (C), 329 (1970), U.S. Pat. No. 3,779,778, and EP 126,712, which can generate an acid by light can also be used in combination. Among the compounds capable of decomposing upon irradiation with actinic rays or radiation to generate an acid, particularly effective compounds include the following general formula (PAG3), general formula (PAG4), general formula (PAG6) or general formula (PAG6). PAG7).

[0054]

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In the general formulas (PAG3) and (PAG4), A
r ¹ and Ar ² are the same or different and 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 are
The same or different, substituted or unsubstituted alkyl group,
Indicates an 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 are 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 for the aryl group, and a substituent for the alkyl group. Carbon number 1
To 8 alkoxy groups, carboxyl groups, and alkoxycarbonyl groups.

[0056] Z ^- represents a counter anion, for example BF ₄ ^{-,
_{AsF 6 -, PF 6 -,}} SbF 6 -, SiF 6 2-, ClO 4 -,
Alkanesulfonic acid which may be substituted, perfluoroalkanesulfonic acid, benzenesulfonic acid which may be substituted, naphthalenesulfonic acid, anthracenesulfonic acid,
Examples include but are not limited to camphor sulfonic acid. Preferred are alkanesulfonic acid, perfluoroalkanesulfonic acid, alkyl-substituted benzenesulfonic acid, and pentafluorobenzenesulfonic acid. Two of R ²⁰³ , R ²⁰⁴ , and R ²⁰⁵ and Ar ¹ , Ar ²
May be bonded via each single bond or a substituent.

In the general formulas (PAG6) and (PAG7), R
²⁰⁶ represents a substituted or unsubstituted alkyl group or aryl group. A represents a substituted or unsubstituted alkylene group, alkenylene group, or arylene group. R represents a linear, branched or cyclic alkyl group, or an optionally substituted aryl group. Specific examples thereof include the following compounds, but are not limited thereto.

[0058]

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[0059]

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In the present invention, the photoacid generator to be used in combination is preferably one represented by the above formula (PAG-7). These photoacid generators that can be used in combination are used in an amount of 5% by weight or less, preferably 2% by weight or less, based on the solid content in the composition.

[2] (B) A resin having an alicyclic hydrocarbon structure having 6 or more carbon atoms and having a dissolution rate in an alkali developing solution increased by the action of an acid having 6 or more carbon atoms contained in the resin (B) May be contained in the main chain and / or side chain of the resin. The alicyclic hydrocarbon structure having 6 or more carbon atoms is preferably a bridged alicyclic hydrocarbon structure. Specific examples thereof include those similar to the specific examples of the skeleton of the alicyclic hydrocarbon represented by Z in the general formula (II '') described later.
As the resin of (B), the following resin (B-1) or (B
-2) is preferred.

[2-] (B) Resin (B-1) whose dissolution rate in an alkali developing solution is increased by the action of an acid
(Hereinafter also referred to as “acid-decomposable resin”). General formula (I ′) representing a repeating structural unit of an acid-decomposable resin
And (II ′), R ₀₁ , R ₀₂ and Ra to Rf alkyl groups having 1 to 4 carbon atoms include a methyl group, an ethyl group,
Examples thereof include a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a t-butyl group. In the general formula (II ′) showing the repeating structural unit of the acid-decomposable resin, the alkylene group of W is X, in the following general formulas (III′-a) to (III′-d):
It represents the same group as the alkylene group represented by Z ₀ , R ₁₁ and R ₁₃ . Further, as described above, Ra to Ra of the general formula (II ′)
Any one of Rf is a single bond or an alkylene having 1 to 4 carbon atoms, and is bonded to W.

Specific examples (a1) to (a20) of the repeating structural unit represented by the general formula (II ') are described below.

[0064]

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[0065]

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The acid-decomposable resin has the following general formula (III'-a):
It may contain a repeating structural unit represented by (III'-d).

[0067]

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In the above general formulas (III′-a) to (III′-d): R
₁ represents a hydrogen atom or a methyl group. R _{3 to} R ₁₀ each independently represent a hydrogen atom or an alkyl group which may have a substituent. R represents a hydrogen atom or an optionally substituted alkyl group, cyclic alkyl group, aryl group or aralkyl group. m represents an integer of 1 to 10. X is a single bond, an alkylene group which may have a substituent, a cyclic alkylene group which may have a substituent, an arylene group which may have a substituent, an ether group, a thioether group, or a carbonyl Group, ester group, amide group,
It represents a sulfonamide group, a urethane group, a urea group, or a divalent group that is not decomposed by the action of an acid combining these. 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 ₁₁ represents a single bond, an alkylene group, an arylene group, or a divalent group obtained by combining these. R ₁₂ is an alkyl group which may have a substituent, a cyclic alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl which may have a substituent. Represents a group. R ₁₃ represents an alkylene group, an arylene group, or a divalent group obtained by combining them. R ₁₄ is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cyclic alkyl group, or a substituted or unsubstituted substituent. It represents a good alkenyl group, an aryl group which may have a substituent or an aralkyl group which may have a substituent. A represents any of the functional groups shown below.

[0069]

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[0070] the general formula (III'-a) ~ in (III'-d), the alkyl group of _{R 3 ~R 10, R, R} 12, R 1 4 is
It may be linear or branched, and may have a substituent. The linear or branched alkyl group preferably has 1 to 12 carbon atoms, more preferably has 1 to 10 carbon atoms, and specifically includes a methyl group, an ethyl group, a propyl group, an isopropyl group, Preferable examples include n-butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, and decyl group. R,
The cyclic alkyl group of R ₁₂ and R ₁₄ has 3 to 3 carbon atoms.
0, specifically, a cyclopropyl group,
Cyclopentyl, cyclohexyl, adamantyl, norbornyl, boronyl, tricyclodecanyl, dicyclopentenyl, nobornane epoxy, menthyl, isomenthyl, neomenthyl, tetracyclododecanyl, steroid residues, etc. Can be mentioned.

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 ₀ 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 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. X
Examples of the cyclic alkylene group include those in which the above-mentioned cyclic alkyl group is divalent. X, Z ₀ , R ₁₁ , R ₁₃
Examples of the alkylene group in include groups represented by the following formula. -[C (Rf) (Rg)] r- In the above formula, Rf and Rg 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, 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.

[0074]

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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 specific examples of the structure of the side chain in the formula (III′-b), the structure of the side chain except for X is shown below, but is not limited thereto.

[0077]

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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 it should not be construed that the invention is limited thereto.

[0079]

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[0080]

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[0081]

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Hereinafter, specific examples of the monomer corresponding to the repeating structural unit represented by the general formula (III′-d) will be shown, but it should not be construed that the invention is limited thereto.

[0083]

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[0084]

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[0085]

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In formula (III′-b), R _{3 to} R ₁₀ are preferably a hydrogen atom or a methyl group. As R,
A hydrogen atom and an alkyl group having 1 to 4 carbon atoms are preferred. m
Is preferably 1 to 6. In the general formula (III′-c),
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.
Preferred as ₁₂ are an alkyl group having 1 to 10 carbon atoms such as a methyl group and an ethyl group, a cyclic alkyl group such as 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 (III′-d), R ₁₃ is preferably an alkylene group having 1 to 4 carbon atoms. R ₁₄
May have a substituent, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a neopentyl group, an alkyl group having 1 to 8 carbon atoms such as an octyl group,
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 general formulas (III′-a) to (III′-d),
The repeating structural units represented by the general formulas (III′-b) and (III′-d) are preferred.

[2-] (B) The above general formula (Ia ″)
And at least one of the repeating structural units represented by the general formula (Ib ″) and the repeating structural unit represented by the general formula (II ″), and the dissolution rate in an alkali developer by the action of an acid is Increasing resin (B-2) (hereinafter abbreviated as “resin according to the present invention”)

In the general formula (Ia ″), R ′ ₁ ,
R _'2 each independently represents a hydrogen atom, a cyano group, a hydroxyl group, -
_{COOH, -COOR '5, -CO-} NH-R' 6, -C
_{O-NH-SO 2 -R '} 6, optionally substituted alkyl group, an optionally substituted alkoxy group or an optionally substituted cyclic hydrocarbon group, or represents the group -Y. Here, R _'5 is an optionally substituted alkyl group, or cyclic optionally substituted hydrocarbon group or the -Y group. R ′ ₆ represents an alkyl group which may have a substituent or a cyclic hydrocarbon group which may have a substituent. In the -Y group, R _'21 ~R' ₃₀ each independently represent a hydrogen atom or an optionally substituted alkyl group, a, b is 1 or 2. X is an oxygen atom,
Sulfur atom, -NH -, - NHSO ₂ - or -NHSO ₂
Represents NH-. A represents a single bond or a divalent linking group.

In the formula (Ib ″), Z ₂ represents —O— or —N (R ′ ₃ ) —, wherein R ′ ₃ is a hydrogen atom,
Hydroxyl or an -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 ,
As the alkyl group for R ′ _{21 to} R ′ ₃₀ ,
Preferred are 10 linear or branched alkyl groups,
More preferably, it is a linear or branched alkyl group having 1 to 6 carbon atoms, and still 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, a t-group. -A butyl group. As the _{R '1, R' 2,} R cyclic hydrocarbon group in _'5, R' _6, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, 2-methyl-2-adamantyl group, norbornyl group, bornyl Group, isobornyl group, tricyclodecanyl group, dicyclopentenyl group,
Nobornane epoxy group, menthyl group, isomenthyl group,
Examples include a neomenthyl group and a tetracyclododecanyl group. Examples of the alkoxy group in R ′ ₁ and R ′ ₂ include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group. The haloalkyl group represented by R _'4 can be exemplified trifluoromethyl, nano-fluoro butyl group, pentadecafluorooctyl group, a trichloromethyl group and the like. The cycloalkyl groups represented by R _'4, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.

Further substituents of 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, an acyloxy group and the like. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. 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.

The divalent linking group in the above 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 (R _a ) (R _b )] _r-wherein R _a and R _b represent a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, 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. r represents an integer of 1 to 10.

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

[0095]

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[0096]

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[0097]

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[0098]

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[0099]

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[0100]

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As specific examples of the repeating structural unit represented by the above general formula (Ib ″), the following [I′-1] to [I′-7]
However, the present invention is not limited to these specific examples.

[0102]

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[0103]

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In the 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 linear or branched alkyl group having 1 to 10 carbon atoms, more preferably 1 to 10 carbon atoms.
It is six linear or branched alkyl groups, 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.

[0106] As further substituents of the alkyl group of the R _'11, R' ₁₂ may be a hydroxyl group, a halogen atom, a carboxyl group, an alkoxy group, an acyl group, a cyano group, 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. Examples of the acyl group include a formyl group and an acetyl group, and examples of the acyloxy group include an acetoxy group.

The atomic group for forming the alicyclic structure of Z in the general formula (II ″) forms a repeating structural unit of an alicyclic hydrocarbon which may have a substituent on the resin. An atomic group is preferable, and among them, an atomic group for forming a bridged alicyclic structure forming a repeating structural unit of a bridged alicyclic hydrocarbon is preferable. Examples of the skeleton of the formed alicyclic hydrocarbon include those represented by the following structures.

[0108]

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[0109]

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

The alicyclic hydrocarbon skeleton has a substituent.
It may be. As such a substituent, the above general
R ′ in the formula (II ″ -A) or (II ″ -B)₁₃~ R '₁₆
Can be mentioned. The bridged alicyclic hydrocarbon is
Among the repeating structural units having the general formula (II "-
A) or a repeating structural unit represented by (II "-B)
Is more preferred. Formula (II "-A) or (I
In I ″ -B), R ′₁₃~ R '₁₆Are each independently water
Element atom, halogen atom, cyano group, -COOH, -CO
OR '_Five(R '_FiveIs an alkyl which may have a substituent
Group, a cyclic hydrocarbon group which may have a substituent or the above
Represents the same -Y group as in formula (Ia ")), an acid
-C (= O) -XA-R '
₁₇Or an alkyl group which may have a substituent or
Represents a cyclic hydrocarbon group. n represents 0 or 1. X is an acid
Element atom, sulfur atom, -NH-, -NHSO_Two-Or -N
HSO_TwoRepresents NH-. R '₁₇Is -COOH, -CO
OR '_Five, -CN, a hydroxyl group, may have a substituent
Alkoxy group, -CO-NH-R '₆, -CO-NH-
SO_Two-R '₆(R ' _Five, R '₆Is as defined above) or
Represents a -Y group in the above general formula (Ia ").
Or a divalent linking group.

In the resin according to the present invention, the acid-decomposable group includes the above-mentioned —C (＝ O) —XA—R ′ ₁ , —C (＝ O)
—XA—R ′ ₂ , or a compound represented by the general formula (II ″):
May be included as a substituent of Z. The structure of the acid-decomposable group is represented by —C (＝ O) —X ₁ —R ₀ . In the formula, R ₀ represents 3 such as t-butyl group and t-amyl group.
Primary alkyl group, isobornyl group, 1-ethoxyethyl group, 1-butoxyethyl group, 1-isobutoxyethyl group, 1-alkoxyethyl group such as 1-cyclohexyloxyethyl group, 1-methoxymethyl group, 1-ethoxymethyl Alkoxymethyl 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.

[0113] As the halogen atom in the R _'13 ~R' _16, it may be mentioned a chlorine atom, a bromine atom, a fluorine atom, an iodine atom.

[0114] Examples of the alkyl group for R _'13 ~R' _16, a linear or branched alkyl group having 1 to 10 carbon atoms, more preferably straight-chain or branched having 1 to 6 carbon atoms Alkyl group, more preferably methyl group, ethyl group, propyl group, isopropyl group, n-
A butyl group, an isobutyl group, a sec-butyl group and a t-butyl group.

Examples of the cyclic hydrocarbon group for R ′ _{13 to} R ′ ₁₆ include a cyclic alkyl group and a bridged hydrocarbon, and include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group and a 2-methyl-2 group. -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 is preferably a ring having 5 to 5 carbon atoms such as cyclopentene, cyclohexene, cycloheptane and cyclooctane.
Twelve rings.

[0116] The alkoxy group in the above R _'17, a methoxy group, an ethoxy group, a propoxy group, may be mentioned those having 1 to 4 carbon atoms or 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, an acyloxy group and the like. 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 represented by 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 represented by A in formula (Ia ″). Group, ester group, 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. Examples of the alkylene group and substituted alkylene group in A include those similar to the divalent linking group of A in formula (Ia ″).

In the resin according to the present invention, the group decomposed by the action of an acid may be a repeating structural unit represented by the general formula (Ia ″), a repeating structural unit represented by the general formula (Ib ″), It can be contained in at least one of the repeating structural units represented by (II ″) and the repeating structural units of the copolymer component described below.

The various substituents of R ′ _{13 to} R ′ _{16 in} the general formula (II ″ -A) or (II ″ -B) form the alicyclic structure in the general formula (II ″). Or a substituent of the atomic group Z for forming a bridged alicyclic structure.

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

[0122]

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[0123]

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[0124]

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[0125]

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[0126]

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[0127]

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[0128]

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[0129]

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[0130]

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[0131]

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[0132]

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[0133]

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[0134]

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[0135]

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[0136]

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[0137]

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[0138]

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The resin according to the present invention comprises a structural unit of at least one of the repeating structural units represented by the general formula (Ia ″) and the general formula (Ib ″), and the general formula (II ″) (the general formula (II) "-A) and one or more of the repeating structural units represented by the general formula (II" -B), as well as dry etching resistance, suitability for a standard developer, substrate adhesion, and resist. For the purpose of adjusting the profile and the general requirements of the resist, such as resolution, heat resistance, sensitivity, etc., the copolymer can be a copolymer containing repeating structural units of various monomers. Is a repeating structural unit represented by the following general formulas (IV ′) and (V ′).

[0140]

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In the formula, Z represents an oxygen atom, —NH—, —
N (-R '₅₀)-, -N (-OSO_Two R '₅₀)-
R '₅₀Is also the same as the above (substituted) alkyl group, (substituted) ring
Hydrocarbon groups have meaning. The general formula (IV ′),
Specific examples of the repeating structural unit represented by (V ′) are as follows:
[IV'-9] to [IV'-16], [V'-9] to [V'-
16], but are not limited to these specific examples.
Not.

[0142]

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[0143]

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In the resin (B), those having no aromatic ring and no carbon-carbon multiple bond are most preferred. This increases the transparency to light having a wavelength of 220 nm or less, and improves the pattern profile. The acid-decomposable resin (B-1) as the component (B) or the resin (B-2) according to the present invention may contain, in addition to the above-mentioned repeating structural units, dry etching resistance, standard developer suitability, substrate adhesion, and resist. Various recurring structural units can be contained for the purpose of adjusting the profile, and the resolution, heat resistance, sensitivity, and the like, which are general necessary characteristics of the resist. As the other repeating structural unit, a (meth) acrylate containing an alicyclic hydrocarbon group having a hydroxyl group and a carbonyl group is preferable. Particularly preferably, 3-hydroxy-1-adamantane (meth) acrylate, 3,5-dihydroxy-1-
Adamantane (meth) acrylate is mentioned.

Examples of other such repeating structural units include, but are not limited to, repeating structural units corresponding to the following monomers. Thereby, the performance required for the acid-decomposable resin, especially,
(1) solubility in a coating solvent, (2) film forming property (glass transition point), (3) alkali developability, (4) film slippage (hydrophobicity, alkali-soluble group selection), (5) unexposed part Fine adjustments such as adhesion to the substrate and (6) dry etching resistance can be made. 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 acrylates having 1 to 10 carbon atoms in the alkyl group): methyl acrylate, ethyl acrylate, propyl acrylate,
Amyl acrylate, cyclohexyl acrylate, ethyl hexyl acrylate, octyl acrylate, tert-octyl acrylate, 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.

Methacrylates (preferably alkyl methacrylates 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 (eg, 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 barate, vinyl caproate, vinyl chloride acetate, 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 the monomer corresponding to the above-mentioned various repeating structural units, it may be copolymerized.

In the acid-decomposable resin (B-1), the molar ratio of each repeating structural unit depends on the dry etching resistance of the resist, the suitability for a standard developer, the substrate adhesion, the resist profile, and the general required performance of the resist. Are appropriately set in order to adjust the resolution, heat resistance, sensitivity and the like.

The content of the repeating structural unit represented by formula (I ') in (B-1) in the acid-decomposable resin is preferably from 30 to 80 mol%, more preferably from 32 to 80 mol%, of all repeating structural units. 75 mol%, more preferably 35 to 7
0 mol%. In the acid-decomposable resin (B-1), the content of the repeating structural unit represented by the general formula (II ′) is as follows:
In all repeating structural units, 30 to 70 mol% is preferable,
More preferably, it is in the range of 32 to 68 mol%, and still more preferably, 35 to
~ 65 mol%. In the acid-decomposable resin (B-1), the content of the repeating structural units represented by the general formulas (III′-a) to (III′-d) is preferably 0 to 20 mol% in all the repeating structural units. , More preferably 0 to 18 mol%, still more preferably 0 to 16 mol%.

The content of the repeating structural unit based on the monomer of the further copolymerization component in the resin (B-1) is also as follows.
Although it can be appropriately set according to the desired resist properties, it is generally 99 mol% or less based on the total number of moles of the repeating structural units represented by the general formulas (I ′) and (II ′). Is more preferably 90 mol% or less, further preferably 80 mol% or less.

Further, in the acid-decomposable resin (B-1), the group decomposed by the action of an acid is a repeating structural unit represented by the general formula (I ′) and / or the general formula (II ′), Although it may be contained in any of the repeating structural units based on the monomers of the copolymerization component, the content of the repeating structural unit containing a group that is decomposed by the action of an acid,
10 to 90 mol% of all the repeating structural units of the resin is suitable, preferably 20 to 80 mol%, more preferably 3 to 80 mol%.
0-70 mol%.

The molecular weight of the acid-decomposable resin (B-1) as described above is a weight average (Mw: a value in terms of polystyrene by a GPC method), and is preferably from 1,000 to 1,000,000.
0, more preferably from 1,500 to 500,000, still more preferably from 2,000 to 200,000, and still more preferably from 2,500 to 100,000. In this case, developability etc. decrease,
The balance is adjusted to a preferable range by these balances. The acid-decomposable resin 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 acid-decomposable resin (B-1) in the entire resist composition is preferably 40 to 99.99% by weight based on the total solid content,
More preferably, it is 50 to 99.97% by weight.

Preferred specific examples of the combination of the repeating structural units of the acid-decomposable resin (B-1) as the component (B), Resin 1 to Resin 16, are shown below.

[0163]

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[0164]

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[0165]

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[0166]

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[0167]

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In the resin (B-2) according to the present invention, the repeating structural unit represented by the general formula (Ia ″) and / or the general formula (Ib ″), and the general formula (II ″) (the general formula (I
The content of the repeating structural unit represented by I "-A) and the general formula (II" -B) is determined by the desired resist dry etching resistance, sensitivity, pattern cracking prevention, substrate adhesion, and resist profile. Further, it can be appropriately set in consideration of the resolving power, heat resistance, and the like, which are necessary requirements of general resists. In general, the repeating unit represented by the general formula (Ia ″) and / or the general formula (Ib ″) in the resin (B-2) according to the present invention, and the repeating unit represented by the general formula (II ″) The content of the structural unit is suitably at least 25 mol%, preferably at least 30 mol%, more preferably at least 35 mol%, based on all monomer repeating structural units of the resin.

Further, in the resin (B-2) according to the present invention, in the resin represented by the repeating structural unit (general formula (IV ′) or general formula (V ′)) derived from the above-mentioned preferable copolymerizable monomer, The content can also be appropriately set according to the desired dist performance, but generally, the repeating structural unit represented by the general formula (Ia ″) and / or the general formula (Ib ″) and the general formula ( 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 II ″). The content of the repeating structural unit based on the monomer of the polymerization component in the resin (B-2) can also be appropriately set according to the desired dist performance, but generally, the general formula (Ia ″) And / or represented by the general formula (Ib ″) It is preferably at most 99 mol%, more preferably at most 90 mol%, even more preferably at most 80 mol%, based on the total moles of the repeating structural units and the repeating structural units represented by the general formula (II "). is there. If the amount of the repeating structural unit based on the monomer of the further copolymer component exceeds 99 mol%, the effect of the present invention is not sufficiently exhibited, which is not preferable.

In the resin (B-2) according to the present invention, the group decomposed by the action of an acid is represented by the general formula (Ia ″):
And / or a repeating structural unit represented by the general formula (Ib ″), a repeating structural unit represented by the general formula (II ″), or a repeating structural unit based on a monomer of a copolymer component. The content of the repeating structural unit containing a group that is decomposed by the action of an acid is suitably 8 to 60 mol%, preferably 10 to 55 mol%, of all the repeating structural units in the resin. More preferably, 12
~ 50 mol%.

The resin (B-2) according to the present invention comprises a monomer corresponding to the repeating structural unit represented by the general formula (II "), maleic anhydride, and a copolymerization component when a copolymerization component is used. The component monomers are copolymerized and copolymerized in the presence of a polymerization catalyst, and the repeating structural unit derived from maleic anhydride in the obtained copolymer is ring-opened with an alcohol under basic or acidic conditions. It can also be synthesized by a method of esterifying or hydrolyzing and then converting the carboxylic acid moiety generated thereafter to a desired substituent.

The weight average molecular weight of the resin (B-2) according to the present invention is preferably from 1,000 to 200,000 in terms of polystyrene by the GPC method. When the weight average molecular weight is less than 1,000, heat resistance and dry etching resistance are deteriorated, so that it is not preferable.
If the molecular weight exceeds 000, the developing property is deteriorated, and the viscosity becomes extremely high, so that the film forming property is deteriorated.

In the positive photoresist composition for exposure to far ultraviolet rays of the present invention, the amount of the resin (B-2) according to the present invention in the entire composition is from 40 to 9 in the total solid content of the resist.
9.99% by weight is preferable, and more preferably 50 to 9% by weight.
9.97% by weight.

Preferred specific examples of the combination of the repeating structural units of the resin (B-2) according to the present invention, which is the component (B), Resins 21 to 33 are shown below.

[0175]

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[0176]

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[0177]

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[0178]

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[3] Fluorine and / or Silicon Surfactant The positive resist composition of the present invention preferably contains a fluorine and / or silicon 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 resist composition of the present invention contains the above surfactant, the sensitivity, when using an exposure light source of 250 nm or less, particularly 220 nm or less,
A resist pattern having excellent 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
No., JP-A-61-226746, JP-A-61-226745, JP-A-62
-170950, JP-A-63-34540, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, and JP-A-9-5988 can include surfactants. The following commercially available surfactants can be used as they are. As commercially available surfactants that can be used, for example, F-top EF301, EF303, (manufactured by Shin-Akita Kasei Co., Ltd.), Florad FC430, 431 (manufactured by Sumitomo 3M Limited), Megafac F171, F173, F176, F189, R08
(Dai Nippon Ink Co., Ltd.), Surflon S-382, SC10
1, 102, 103, 104, 105, and 106 (manufactured by Asahi Glass Co., Ltd.), and a fluorinated surfactant such as Troysol S-366 (manufactured by Troy Chemical Co., Ltd.) or a silicon-based surfactant. 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 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.

[4] Organic Basic Compound The preferred organic basic compound that can be used in the present invention is a compound that is more basic than phenol. Among them, a nitrogen-containing basic compound having a structure represented by the following (A) to (E) is preferable. By using the nitrogen-containing basic compound, the performance change is small even with the lapse of time from exposure to post-heating.

[0183]

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Here, R²⁵⁰, R²⁵¹And R²⁵²Are each
Independently, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms,
1-6 aminoalkyl groups, hydroxy having 1-6 carbon atoms
Alkyl group or substituted or unsubstituted 6 to 20 carbon atoms
An aryl group, where R ²⁵¹And R²⁵²Are connected to each other
To form a ring.

[0185]

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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). 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 amino Examples include morpholine, substituted or unsubstituted aminoalkyl morpholine, and the like, and include mono, di, trialkylamine, substituted or unsubstituted aniline, substituted or unsubstituted piperidine, mono and diethanolamine, and the like. Preferred substituents are an amino group, aminoalkyl group, alkylamino group, aminoaryl group, arylamino group, alkyl group, alkoxy group, acyl group, acyloxy group, aryl group, aryloxy group, nitro group, hydroxyl group, cyano group It is.

Preferred 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, 2-amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-5-methylpyridine, 2-amino-6
-Methylpyridine, 3-aminoethylpyridine, 4-aminoethylpyridine, 3-aminopyrrolidine, piperazine, N- (2-aminoethyl) piperazine, N- (2-
Aminoethyl) piperidine, 4-amino-2,2,6,
6-tetramethylpiperidine, 4-piperidinopiperidine, 2-iminopiperidine, 1- (2-aminoethyl)
Pyrrolidine, pyrazole, 3-amino-5-methylpyrazole, 5-amino-3-methyl-1-p-tolylpyrazole, pyrazine, 2- (aminomethyl) -5-methylpyrazine, pyrimidine, 2,4-diaminopyrimidine ,
4,6-dihydroxypyrimidine, 2-pyrazoline, 3
-Pyrazolin, N-aminomorpholine, N- (2-aminoethyl) morpholine, 1,5-diazabicyclo [4,3,0] non-5-ene, 1,8-diazabicyclo [5,4,0] Undec-7-ene, 2,4,5-triphenylimidazole, tri (n-butyl) amine,
Tri (n-octyl) amine, N-phenyldiethanolamine, N-hydroxyethylpiperidine, 2,6-
Diisopropylaniline, N-cyclohexyl-N'-
Examples include, but are not limited to, morpholinoethylthiourea, N-hydroxyethylmorpholine, and the like.

Of these, particularly preferred compounds include 1,5-diazabicyclo [4.3.0] non-5-
Ene, 1,8-diazabicyclo [5.4.0] undec-7-ene, 2,4,5-triphenylimidazole,
Tri (n-butyl) amine, tri (n-octyl) amine, N-phenyldiethanolamine, N-hydroxyethylpiperidine, 2,6-diisopropylaniline,
N-cyclohexyl-N'-morpholinoethylthiourea and N-hydroxyethylmorpholine. 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 usually 0.001 to 10% by weight, based on the solid content of the composition,
Preferably it is 0.01 to 5% by weight. If the amount is less than 0.001% by weight, the effect of the addition of the nitrogen-containing basic compound cannot be obtained. On the other hand, if it exceeds 10% by weight, the sensitivity tends to decrease and the developability of the unexposed portion tends to deteriorate.

[5] Other Additives, Preparation Method of Positive Resist Composition, Usage Method, etc. An acid-decomposable dissolution inhibitor can be added to the positive resist composition of the present invention. Thereby, the contrast and the resolution are improved, and the pattern profile is made rectangular. Examples of the acid-decomposable dissolution inhibitor include compounds containing an acid-decomposable group, decomposed by the action of an acid, and increased in solubility in an alkali developing solution. Compounds containing no group are preferred, and compounds having a monocyclic or polycyclic hydrocarbon structure are more preferred. Thereby, dry etching resistance is improved. Specific examples of the monocyclic or polycyclic hydrocarbon structure include a monocyclic cycloalkane structure, an adamantane structure, a norbornane structure, and a steroid structure, and more preferably an adamantane structure and a steroid structure. As the acid-decomposable group contained in the acid-decomposable dissolution inhibitor, a group obtained by protecting a carboxylic acid with a group capable of leaving with an acid is preferable. Examples of such an acid-decomposable group include t-butyl ester and t-amyl. Tertiary alkyl ester groups such as esters,
Examples thereof include linear or cyclic acetal ester groups such as 1-alkoxyethyl ester and 2-tetrahydropyranyl ester. Preferably it is a tertiary alkyl ester group. The amount of the acid-decomposable dissolution inhibitor used in the positive resist composition of the present invention is usually 1 to 30% by weight, preferably 5 to 20% by weight, based on the solid content of the composition.

The positive resist composition of the present invention may further contain, if necessary, a dye, a plasticizer, a sensitizer, a compound which promotes solubility in a developing solution, and the like.

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

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, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, methoxypropionic acid Examples thereof include methyl, 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 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 coated on a substrate (eg, 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
It is light having a wavelength of from nm to 250 nm, more preferably 220 nm or less. Specifically, a KrF excimer laser (248 nm) and an ArF excimer laser (193n)
m), F ₂ excimer laser (157 nm), X-ray, electron beam and the like.

Examples of the developer 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.

[0197]

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 Photoacid Generator as Component (A)] The sulfonium salt of the photoacid generator A1 or the photoacid generator A2 is, for example, substituted or unsubstituted phenylsulfoxide with an aryl Grignard reagent such as arylmagnesium bromide. And the resulting triarylsulfonium halide is subjected to salt exchange with the corresponding sulfonic acid, or the substituted or unsubstituted phenylsulfoxide and the corresponding aromatic compound are treated with methanesulfonic acid / diphosphorus pentoxide or aluminum chloride. It can be synthesized by a method of condensation and salt exchange using an acid catalyst, and a method of condensation and salt exchange between a diaryliodonium salt and a diaryl sulfide using a catalyst such as copper acetate. On the other hand, the photoacid generator A1
Alternatively, the iodonium salt of the photoacid generator A2 can be synthesized by reacting an aromatic compound with periodate and subjecting the obtained iodonium salt to salt exchange with the corresponding sulfonic acid. The sulfonic acid or sulfonic acid salt used for the salt exchange can be obtained by using a commercially available sulfonic acid as it is, or by hydrolyzing a sulfonic acid halide. Hereinafter, two examples of the synthesis of the photoacid generator as the component (A) will be described. Other photoacid generators used in Tables 3 and 4 below may be prepared in the same manner or in the above-described general method. A product synthesized by the method or a commercially available product was used. The following photoacid generators were manufactured by Midori Kagaku Co., Ltd. Triphenylsulfonium perfluoro-n-butanesulfonate: (A1-1), (A2-4) Triphenylsulfonium trifluoromethanesulfonate: (A2-1) bis (t-butylphenyliodonium) perfluoro-
n-butanesulfonate: (A1-49)

Synthesis Example 1 (Synthesis of triphenylsulfonium perfluoro-n-octanesulfonate (A1-3)) 50 g of diphenylsulfoxide was dissolved in 800 ml of benzene, 200 g of aluminum chloride was added thereto, and the mixture was refluxed for 24 hours. The reaction solution was slowly poured into 2 L of water, and 400 ml of concentrated hydrochloric acid was added thereto.
1 was added and heated at 70 ° C. for 10 minutes. The aqueous solution was washed with 500 ml of ethyl acetate, filtered, and a solution prepared by dissolving 200 g of ammonium iodide in 400 ml of water was added. The precipitated powder was collected by filtration, washed with water, washed with ethyl acetate, and dried to remove triphenylsulfonium iodide.
0 g was obtained. Triphenylsulfonium iodide 1
7.6 g was dissolved in 1000 ml of methanol, and 12.5 g of silver oxide was added to this solution, followed by stirring at room temperature for 4 hours.
The solution was filtered, and to this was added 25 g of a solution of perfluoro-n-octanesulfonic acid in methanol. The reaction solution was concentrated, and the precipitated oil was dissolved in ethyl acetate, washed with water, dried and concentrated to obtain 20.5 g of the desired product.

Synthesis Example 2 (tri (t-butylphenyl) sulfonium perfluoro-n-butanesulfonate (A1-5), (A2-8)
Synthesis of di (t-butylphenyl) sulfide (80m
mol), di (t-butylphenyl) iodonium perfluoro-n-butanesulfonate (20 mmol) and copper benzoate (4 mmol) at 130 ° C under a nitrogen stream.
For 4 hours. The reaction solution was allowed to cool, and 100 ml of ethanol was added thereto to remove a precipitate. The filtrate was concentrated, and 200 ml of ether was added thereto to precipitate a powder. The powder was collected by filtration, washed with ether, and dried to obtain the desired product.

[Acid-decomposable resin (B-component)
Synthesis of 1)] Synthesis Example 3 <Synthesis of Resin 1> 2-Ethyl-2-adamantyl methacrylate, butyrolactone methacrylate, 40 /
The mixture was charged at a ratio of 60 (molar ratio) and dissolved in tetrahydrofuran to prepare 100 mL of a solution having a solid content of 20%. To this solution was added a radical polymerization initiator V-65 (trade name,
2 mol% with respect to the total number of moles of the monomer was added thereto, 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
The molar ratio was 41/59 (2-ethyl-2-adamantyl methacrylate / butyrolactone methacrylate). The weight average molecular weight in terms of polystyrene determined by GPC measurement was 12,700.

Synthesis Examples 4 to 17 <Synthesis of Resins 2 to 16>
Resins 2 to 16 were synthesized. Table 1 shows the composition ratio, weight average molecular weight, and dispersity of the resin. Repeating unit 1 in Table 1,
2, 3 represent structural units corresponding to the above-described structural units of the respective resins from the left.

[0203]

[Table 1]

[Resin according to the present invention which is the component (B) (B
Synthesis of -2) Synthesis Example 18 <Synthesis of Resin (21)> A tetracyclododecene derivative having the following structure obtained by reacting methacrylic acid ester of 3-oxo-1,1-dimethylbutanol with cyclopentadiene ( An equimolar mixture of 1-1) and maleic anhydride was dissolved in tetrahydrofuran to prepare a solution having a solid content of 50%. This was charged into a three-necked flask and heated at 60 ° C. under a nitrogen stream. When the reaction temperature was stabilized, 5 mol% of a radical initiator V-60 manufactured by Wako Pure Chemical Industries, Ltd. was added to start the reaction. After heating for 6 hours, the reaction mixture was diluted twice with tetrahydrofuran, and then poured into a large amount of hexane to precipitate a white powder. The precipitated powder was filtered out and dried to obtain the target resin (21).

[0205]

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Synthesis Examples 19 to 27 <Synthesis of Resins (22) to (33)> Resins (22) to (33) were synthesized in the same manner as in Synthesis Example 18. Table 2 shows the molar ratio, weight average molecular weight, and dispersity of each repeating structural unit of the resins (21) to (28). The molar ratio, the weight average molecular weight and the degree of dispersion of the resins (29) to (33) are as described above.

[0207]

[Table 2]

[Synthesis of dissolution inhibitor] A Schlenk tube dried in an oven and purged with argon
℃ of dried overnight under vacuum) cholate t- butyl (2.07 g, 4.457 mmol), (distilled from CaH ₂₎ N-methylmorpholine (1.1 mL, 10 mmol) and methylene chloride ( 8 mL).

The mixture is cooled to 0 ° C. and
Distilled glutaryl dichloride (0.552 g, 4.32 g)
(4 mmol, 97 mol%) was added slowly using an airtight syringe. As the addition was over, salt precipitation began. Stir the resulting slurry and add
Warm to room temperature over a period of
Warmed for minutes.

Thereafter, the mixture was treated with methylene chloride (40
mL) and water (40 mL). The organic layer was washed four times with dilute aqueous ammonium acetate and concentrated to give a solid. This solid was freeze-dried from dioxane to obtain a powder.

[0211] This powder was dispersed in water (100 mL) and stirred for 1 hour. The powder was recovered by filtration and dried in vacuo. The yield was 1.5 g (64% yield). When this method was repeated using tetrahydrofuran (THF), the yield was 1.7 g (74% yield). The structure of the resulting oligomer is shown below. This oligomer is referred to as a dissolution inhibitor A.

[0212]

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Oligo (t-butylcholate-co-glutarate) end-capped with t-butylcholate (wherein
tBu represents a t-butyl substituent, and Y represents hydrogen or a t-Bu-co-glutarate oligomer of cholic acid in which one of the hydroxyl groups of t-butyl cholate is linked by a glutaric acid ester group. )

The number of units M per molecule is from about 5 to about 20. As mentioned above, the condensation reaction can take place at any OH group on the polycyclic compound. Therefore, the above structure is shown as an aid in explaining the reaction product, and not the actual structure of the obtained product.

Examples 1 to 20 and Comparative Examples 1 to 5 (Preparation of Positive Resist Composition Solution) Various components shown in Table 3 were used in the following amounts. Resin shown in Table 3 synthesized in the above synthesis example: 2.0 g Photoacid generator A1: described in Table 3 Photoacid generator A2: described in Table 3 Organic basic compound (amine): 0.001 g Surfactant: 0.004 g The composition of each example was dissolved in propylene glycol monomethyl ether acetate so that the solid content concentration was 14% by weight, and then filtered through a 0.1 μm microfilter. A positive resist composition solution of No. 5 was prepared. When a dissolution inhibitor (dissolution inhibitor A or t-butyl cholate) is added, the amount of addition is 0.5.
g.

Examples 21 to 42 and Comparative Examples 6 to 10 (Preparation of Positive Resist Composition Solutions) Various components shown in Table 4 were used in the following amounts. Resin shown in Table 4 synthesized in the above synthesis example: 2.0 g Photoacid generator A1: described in Table 4 Photoacid generator A2: described in Table 4 Organic basic compound (amine): 0.001 g Surfactant: 0.004 g After dissolving each composition in propylene glycol monomethyl ether acetate so that the solid content concentration of each composition becomes 14% by weight, the solution was filtered through a 0.1 μm micro filter, and Examples 21 to 39 and Comparative Examples 6 to Ten positive resist composition solutions were prepared. When the dissolution inhibitor (dissolution inhibitor A or t-butyl cholate) is added, the amount added is 0.5 g.

The organic basic compounds (amines) and surfactants used are as follows. Amine (1): 1,5-diazabicyclo [4.3.0] -5-
Nonene (2): 2,4,5-triphenylimidazole (3): tri-n-butylamine (4): N-hydroxyethylpiperidine Surfactant 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 Photoacid generator PAG-A: Bis (cyclohexylsulfonyl) diazomethane

(Evaluation Test) The obtained positive photoresist composition solution was applied on a silicon wafer by using a spin coater, dried at 140 ° C. for 90 seconds, and dried at about 0.5 μm.
Was prepared and exposed to an ArF excimer laser (193 nm). A heat treatment after the exposure was performed at 140 ° 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.

[Sensitivity]: Sensitivity was defined as the amount of exposure for reproducing a 0.18 μm line and space (1: 1) mask pattern. [Resolution]: The critical resolution at an exposure amount that reproduces a 0.18 μm line-and-space (1: 1) mask pattern when heating and developing are performed immediately after exposure is defined as resolution 1, and after 2 hours of exposure, Heating and development were performed, and the limiting resolving power at the same exposure dose as above was defined as resolving power 2. [Dependency on coarse / dense]: In a line-and-space pattern (dense pattern) having a line width of 0.18 μm and an isolated line pattern (sparse pattern), an overlapping range of the depth of focus allowing 0.18 μm ± 10% was determined. The larger this range is, the better the density dependency is. The evaluation results are shown in Tables 3 and 4.

[0220]

[Table 3]

[0221]

[Table 4]

The following are clear from the results of Tables 3 and 4. The positive resist composition of the present invention (composition of the example) has sufficient sensitivity and resolution for exposure to light having a wavelength of 193 nm, and shows little change in performance over time from exposure to post-heating. In addition, the density dependency is small. On the other hand, Comparative Example 1 using only one type of photoacid generator A1 or A2
In the cases of Comparative Examples 3 to 6, Comparative Examples 6 to 8, a change in performance over time from exposure to post-heating is observed, and the density dependency is large. Further, the sensitivity may be poor (Comparative Examples 1, 3, 6, and 8).
Although the photoacid generators A1 and A2 were used in combination, the difference in the number of carbon atoms of the fluorine-substituted alkyl group in the anion portion was 9 which is beyond the range specified in the present invention, and thus Comparative Examples 4 and 9 In this case, it is inferior to any of the above characteristics. 2 photoacid generators A2
In the case of Comparative Examples 5 and 10 in which the number of carbon atoms of the fluorine-substituted alkyl group in the anion portion is less than the range specified in the present invention as 1 in the case of using the same species, the resolution is poor, and from exposure to post-heating. , A change in performance over time is observed, and the density dependency is large.

[0223]

The positive resist composition of the present invention is suitably applied particularly to light in a far ultraviolet wavelength range of 170 to 220 nm, has excellent sensitivity and resolution, and has a long time from exposure to post-heating. There is almost no change in performance due to the process, and the process tolerance is excellent. Moreover, the dependency of the formed resist pattern on the density is small.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08F 232/04 C08F 232/04 C08K 5/02 C08K 5/02 5/16 5/16 5/36 5 / 36 C08L 33/00 C08L 33/00 35/00 35/00 45/00 45/00 83/04 83/04 101/00 101/00 G03F 7/004 503 G03F 7/004 503A H01L 21/027 C07C 381 / 12 // C07C 381/12 H01L 21/30 502R (72) Inventor Toshiaki Ao 4,000 Kawajiri, Yoshida-cho, Haibara-gun, Shizuoka Pref. BF11 BG00 CB10 CB43 CC04 CC20 FA17 4H006 AB40 AB81 4J002 BG03W BG07W BH01W BK00W CP03X EB106 ER027 EU027 EU047 EU117 EV296 FD31X GP03 4J100 AK32Q AL08P AL08Q AL83P AM43Q AM47Q AR09R ARQ BA03 R BA15R BA16R BA34R BB01Q BC09P BC09R BC12R BC53Q BC53R CA04 CA05 JA37 JA38

Claims (8)

[Claims] (A) The cation moiety is composed of iodonium or sulfonium, and the anion moiety is R ^F SO ₃ ⁻ (where R ^F is a fluorine-substituted alkyl group having 1 to 10 carbon atoms). A photoacid generator which generates an acid upon irradiation with a plurality of types of actinic rays or radiations selected from sulfonates comprising the anions shown, and (B) an alicyclic hydrocarbon structure having 6 or more carbon atoms having, contains a resin having a dissolution rate in an alkaline developer that increases under the action of an acid, in the above (a) a plurality of kinds of the photoacid generator, the anion moiety R ^F
A positive resist composition, wherein at least one pair of photoacid generators having a difference in carbon number in the range of 2 to 8 is present. 2. (A) The cation moiety is composed of iodonium or sulfonium, and the anion moiety is R ^F SO ₃ ⁻ (where R ^F is a fluorine-substituted alkyl group having 1 to 10 carbon atoms). A photoacid generator that generates an acid upon irradiation with a plurality of types of actinic rays or radiations selected from the sulfonates composed of the anions shown below, and (B) the following general formulas (I ′) and (II ′) A resin (B-1) containing a repeating structural unit represented by the formula (I) and having a dissolution rate in an alkali developing solution increased by the action of an acid, or represented by the following general formulas (Ia ") and (Ib") Contains a resin (B-2) having at least one of the repeating structural units and a repeating structural unit represented by the following general formula (II "), and having a dissolution rate in an alkali developing solution increased by the action of an acid. And the above ( A) A plurality of types of photoacid generators include an R ^F
Wherein at least a pair of photoacid generators having a difference in carbon number in the range of 2 to 8 are present. Embedded image In the above general formulas (I ′) and (II ′): R ₀₁ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R
₀₂ represents an alkyl group having 1 to 4 carbon atoms. W represents a single bond or a single or a combination of two or more groups selected from the group consisting of an alkylene group, an ether group, a thioether group, a carbonyl group, and an ester group. Ra in Lc,
Rb, Rc, Rd, Re, and Rf each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. However, Ra ~
Any one of Rf represents a single bond or an alkylene group having 1 to 4 carbon atoms, and is bonded to W. m and n each independently represent an integer of 0 to 3, and m + n is an integer of 2 to 6. Embedded image In the formula (Ia ″): R ′ ₁ and R ′ ₂ are each independently a hydrogen atom, a cyano group, a hydroxyl group, —COOH, —COOR ′ ₅ ,
_{CO-NH-R '6,} -CO-NH-SO 2 -R' 6, optionally substituted alkyl group, an optionally substituted alkoxy group or an optionally substituted cyclic hydrocarbon group, or The following -Y group is represented. Here, R ′ ₅ represents an alkyl group which may have a substituent, a cyclic hydrocarbon group which may have a substituent, or the following —Y group. R ′ ₆ represents an alkyl group which may have a substituent or a cyclic hydrocarbon group which may have a substituent. X represents an oxygen atom, a sulfur atom, -NH -, - NHSO ₂ - or -NHSO ₂ NH-
Represents A represents a single bond or a divalent linking group. -Y group: (In the —Y group, R ′ _{21 to} R ′ ₃₀ each independently represent a hydrogen atom or an alkyl group which may have a substituent. A, b
Is 1 or 2.) In the formula (Ib ″): Z ₂ represents —O— or —N (R ′ ₃ ) —, wherein R ′ ₃ is a hydrogen atom, a hydroxyl group or —OSO
Representing a ₂ -R _'4. R ₄ ′ is an alkyl group, a haloalkyl group,
Represents 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. Represents an atomic group for forming an alicyclic structure which may have a substituent and contains two carbon atoms (CC). 3. The difference in the number of carbon atoms of R ^{F in} the anion portion is 2 to 8.
Of the pair of the range of the photoacid generator include photoacid generator carbon number of R ^F is a relatively large anion portion R ^F
Is selected from the group of photoacid generators which are linear fluorine-substituted alkyl groups having a carbon number in the range of 4 to 10, and a photoacid generator having a relatively small number of carbon atoms in R ^F includes an anion moiety R
3. The positive resist composition according to claim 1, wherein ^F is selected from the group of photoacid generators having a linear fluorine-substituted alkyl group having 1 to 5 carbon atoms. 4. The positive resist composition according to claim 1, wherein the cation moiety of the photoacid generator is represented by the following general formula (I), (II) or (III). . Embedded image In the above general formulas (I) to (III), R _{1 to} R ₃₇ are the same or different and each represent a hydrogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, hydroxyl, group, a halogen atom, or an -S-R ₃₈ group. R ₃₈ represents a linear, branched or cyclic alkyl group or aryl group. R _{1 to} R ₁₅ , R _{16 to} R ₂₇ ,
One or two selected from a single bond, carbon, oxygen, sulfur, and nitrogen by combining two or more of R _{28 to} R ₃₇ ;
A ring containing at least one species may be formed. 5. The repeating structural unit represented by the general formula (II ″) is represented by the following general formula (II ″ -A) or general formula (II ″).
The positive resist composition according to claim 2, which is a repeating structural unit represented by -B). Embedded image Formula (II "-A), (II " -B) in: R _'13 ~R'
₁₆ each independently represent a hydrogen atom, a halogen atom, a cyano _{group, -COOH, -COOR '5 (R} ' 5 are as defined above), group decomposable by the action of an acid, -C (= O) - X-
Have a A-R _'17, or a substituent represents an alkyl group or a cyclic hydrocarbon group. Also, they may form a ring of at least two members to one of the R _'l3 ~R' _16. Here, X and A have the same meanings as above. R '
_17, -COOH, -COOR _'5, -CN, a hydroxyl group, an alkoxy group which may have a substituent, -CO-NH-
_{R '6, -CO-NH-} SO 2 -R' 6 (R '5, R' 6 are each as defined above) represents a or above -Y groups. n is 0
Or 1. 6. The positive resist composition according to claim 1, further comprising a nitrogen-containing basic compound. 7. The positive resist composition according to claim 1, further comprising a fluorine-based and / or silicon-based surfactant. 8. The positive resist composition according to claim 1, wherein actinic rays or radiation having a wavelength of 220 nm or less is irradiated.