JP2006065211A - Chemically amplified resist composition for immersion process, and method of forming pattern using same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a chemically amplified resist composition for an immersion process that is improved in a profile shape and line edge roughness LER in immersion exposure, and to provide a method of forming a pattern that uses the same. <P>SOLUTION: The chemically amplified resist composition contains a resin which contains a specified recurring unit having a ring system in a side-chain, and whose dissolution rate to an alkali developing solution is increased by acidic action, a compound generating acid by the irradiation of active light or radiation, and a solvent. Also, the method of forming the pattern is provided which uses the resist composition. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  TECHNICAL FIELD The present invention relates to a chemically amplified resist composition used in a semiconductor manufacturing process such as an IC, a circuit board such as a liquid crystal or a thermal head, and a lithography process for other photo applications, and a pattern forming method using the same. Is. In particular, the present invention relates to a chemically amplified resist composition suitable for exposure with an immersion projection exposure apparatus using far ultraviolet light having a wavelength of 300 nm or less as a light source and a pattern forming method using the same.

With the miniaturization of semiconductor elements, the exposure light source has become shorter and the projection lens has a higher numerical aperture (high NA). Currently, an NA 0.84 exposure machine using an ArF excimer laser having a wavelength of 193 nm as a light source has been developed. Has been. These can be expressed by the following equations as is generally well known.
(Resolving power) = k ₁ · (λ / NA)
(Depth of focus) = ± k ₂ · λ / NA ²
Here, λ is the wavelength of the exposure light source, NA is the numerical aperture of the projection lens, and k ₁ and k ₂ are coefficients related to the process.

  An exposure machine using a F2 excimer laser having a wavelength of 157 nm as a light source has been studied for higher resolution by further shortening the wavelength. Because the materials to be used are very limited, it is very difficult to stabilize the manufacturing cost and quality of the equipment and materials, and it is possible that the exposure apparatus and resist having sufficient performance and stability will not be in time within the required period. Sex has come out.

As a technique for increasing the resolving power in an optical microscope, a so-called immersion method in which a high refractive index liquid (hereinafter also referred to as “immersion liquid”) is filled between a projection lens and a sample is known.
This “immersion effect” means that when λ ₀ is the wavelength of the exposure light in the air, n is the refractive index of the immersion liquid with respect to air, θ is the convergence angle of the light beam, and NA ₀ = sin θ. The above-described resolving power and depth of focus can be expressed by the following equations.
(Resolving power) = k ₁ · (λ ₀ / n) / NA ₀
(Depth of focus) = ± k ₂ · (λ ₀ / n) / NA ₀ ²
That is, the immersion effect is equivalent to using an exposure wavelength having a wavelength of 1 / n. In other words, in the case of a projection optical system with the same NA, the depth of focus can be increased n times by immersion. This is effective for all pattern shapes, and can be combined with a super-resolution technique such as a phase shift method and a modified illumination method which are currently being studied.

Examples of apparatuses in which this effect is applied to the transfer of a fine pattern of a semiconductor element include Patent Document 1 (Japanese Patent Publication No. 63-49893) and Patent Document 2 (Japanese Patent Laid-Open No. 6-124873). There is no discussion of resists suitable for exposure techniques.
Patent Document 3 (Japanese Patent Laid-Open No. 10-303114) points out that the refractive index control of the immersion liquid is important because the change in the refractive index of the immersion liquid causes deterioration of the projected image due to the wavefront aberration of the exposure machine. Disclosed is a water to which the temperature coefficient of the refractive index of the immersion liquid is controlled within a certain range and, as a suitable immersion liquid, an additive that lowers the surface tension or increases the surface activity is added. Has been. However, the disclosure of additives and the resist suitable for the immersion exposure technique are not discussed.

Since the resist for KrF excimer laser (248 nm), an image forming method called chemical amplification has been used as an image forming method for a resist in order to compensate for sensitivity reduction due to light absorption. Explaining by taking a positive chemical amplification image forming method as an example, the acid generator in the exposed area is decomposed by exposure to generate an acid upon exposure, and the generated acid is reacted as a reaction catalyst by post exposure baking (PEB). Is used to change an alkali-insoluble group to an alkali-soluble group, and an exposed portion is removed by alkali development.

When a chemically amplified resist is applied to the immersion exposure technique, the acid on the resist surface generated during exposure moves to the immersion liquid, and the acid concentration on the exposed portion surface changes. This is the surface of the exposed area caused by a very small amount of basic contamination of several ppb level from the environment during exposure-PEB placement (PED: Post Exposure time Delay), which was a major problem at the beginning of the development of chemically amplified positive resists. Although it is thought that it is very similar to acid deactivation, the influence and mechanism of immersion exposure on the resist have not been clarified yet.
In immersion exposure, the resist film and the optical lens are filled with an immersion liquid (also referred to as an immersion liquid) and exposed through a photomask to transfer the photomask pattern to the resist film. The penetration of the solution into the resist film is expected to affect a chemical reaction (acid-catalyzed deprotection reaction, development reaction) caused in the resist during or after exposure. However, the extent and mechanism of the effect is still unknown.

  For example, when a chemically amplified resist that does not have a problem with lithography in normal exposure is subjected to immersion exposure, the variation in line width (PEB temperature dependence) due to a change in heating temperature after development increases, and improvement is necessary. It was. In addition, if the wafer is moved quickly during exposure, the followability of the immersion liquid is poor, and there is a problem that a portion between the lens and the resist on the wafer is not filled with the immersion liquid.

Japanese Examined Patent Publication No. 63-49893 JP-A-6-124873 JP-A-10-303114

  An object of the present invention is to provide a chemically amplified resist composition for an immersion process with improved profile shape and line edge roughness (LER) at the time of immersion exposure in view of the problems of the prior art as described above, and the same. Another object of the present invention is to provide a pattern forming method using the above.

  The present invention is a chemically amplified resist composition for an immersion process having the following constitution and a pattern forming method using the same, thereby achieving the object of the present invention.

(1) (A) Resin containing a repeating unit represented by any one of formulas (A-1-1) to (A-1-3), whose dissolution rate in an alkaline developer is increased by the action of an acid ,
(B) a compound that generates an acid upon irradiation with actinic rays or radiation,
(C) A positive resist composition for immersion process containing a solvent.

R ₁ represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group or an alkoxy group.
L ₁ and L ₂ represent a single bond or a divalent linking group.
A ₁ represents an alicyclic group which may have a lactone structure.
J represents a fluorine atom or a substituent having a fluorine atom.
p represents an integer of 1 to 3.

(2) The resin (A) further includes a repeating unit (A-2) having a lactone structure represented by the general formula (A-2) and a repeating unit represented by the general formula (A-3) (A- 3) It contains a repeating unit (A-4) represented by the general formula (A-4) and having a group capable of decomposing by the action of an acid, for the immersion process according to (1) above Positive resist composition.

R _{2 to} R ₄ each independently represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group or an alkoxy group.
L ₃ represents a single bond or a divalent linking group.
B represents a ring having a lactone structure.
K represents a fluorine atom, a chlorine atom, a hydroxyl group, a cyano group, an alkyl group having no fluorine atom, or an alkoxy group.
q represents an integer of 1 to 3.
ADG represents an acid-decomposable group.

(3) The resin (A) has at least one group represented by the following general formula (Z) as J in the general formulas (A-1-1) to (A-1-3). The positive resist composition for immersion process according to (1) or (2) above.

R _{50 to} R ₅₅ each independently represents a hydrogen atom, a fluorine atom or an alkyl group.
However, at least one of R _{50 to} R ₅₅ represents a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. R ₄₀ represents a hydrogen atom, an alkyl group, a cycloalkyl group or an acyl group.

Preferred embodiments can further include the following configurations.
(4) In the above (2) or (3), the group represented by the acid-decomposable group as ADG in the general formula (A-4) is a group represented by the general formula (pI) The positive resist composition for immersion process as described.

R ₁₁ represents methyl, ethyl, n-propyl, isopropyl group, n-butyl group, isobutyl group or sec-butyl group, and Z represents an atom necessary for forming an alicyclic hydrocarbon group together with a carbon atom. Represents a group.

(5) In the above (2) or (3), the group represented by the acid-decomposable group as ADG in the general formula (A-4) is a group represented by the general formula (pII) The positive resist composition for immersion process as described.

R _{12 to} R ₁₄ each independently represents an alkyl group (preferably having 1 to 4 carbon atoms) or an alicyclic hydrocarbon group. However, at least one of R _{12 to} R ₁₄ represents an alicyclic hydrocarbon group.

(6) The ring containing the lactone structure represented by B in the repeating unit represented by the general formula (A-2) is a group represented by any one of the following general formulas (B-1) to (B-3). The positive resist composition for immersion process as described in (2) or (3) above, wherein

In General Formulas (B-1) to (B-3), R _{1b to} R _6b each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an alkenyl group. Two of R _{1b to} R _6b may combine to form a ring.

(7) The above characterized in that the ring containing the lactone structure represented by B in the repeating unit represented by the general formula (A-2) is a group represented by the following general formula (B-4) ( A positive resist composition for immersion process as described in 2) or (3).

R _7b and R _8b each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group or an alkenyl group.

(8) including a step of forming a resist film with the chemical amplification resist composition for immersion process according to any one of (1) to (7), performing immersion exposure on the resist film, and developing the resist film. A characteristic pattern forming method.

  INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a chemically amplified resist composition for an immersion process with improved profile shape and line edge roughness (LER) during immersion exposure, and a pattern forming method using the same.

Hereinafter, the present invention will be described in detail.
In addition, in the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what does not have a substituent and what has a substituent. . For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

(A) Resin that decomposes by the action of an acid and increases the solubility in an alkali developer The resin (A) used in the chemically amplified resist composition for the immersion process of the present invention is decomposed by the action of an acid and developed by alkali Resin (acid-decomposable resin) with increased solubility in liquid, a group that decomposes by the action of an acid on the main chain or side chain of the resin or both the main chain and side chain to produce an alkali-soluble group , Also referred to as “acid-decomposable group”).
Examples of the alkali-soluble group include a carboxyl group, a hydroxyl group, and a sulfonic acid group.
A preferred group that can be decomposed with an acid is a group in which the hydrogen atom of the —COOH group is substituted with a group capable of leaving with an acid.
The acid-decomposable group is preferably a cumyl ester group, an enol ester group, an acetal ester group, a tertiary alkyl ester group or the like. More preferably, it is a tertiary alkyl ester group.

  The resin (A) contains at least one repeating unit represented by any one of the general formulas (A-1-1) to (A-1-3).

R ₁ represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group or an alkoxy group.
L ₁ and L ₂ represent a single bond or a divalent linking group.
A ₁ represents an alicyclic group which may have a lactone structure.
J represents a fluorine atom or a substituent having a fluorine atom.
p represents an integer of 1 to 3.

The alkyl group as R ₁ preferably has 1 to 5 carbon atoms, and examples thereof include a propyl group, an ethyl group, and a methyl group.
The alkoxy group as R ₁ preferably has 1 to 5 carbon atoms, and examples thereof include a propoxy group, an ethoxy group, and a methoxy group.

The divalent linking group of L ₁ preferably has 5 or less carbon atoms, more preferably 3 or less carbon atoms, and represents an ester group, a carbonyl group, an alkylene group, or a divalent group obtained by combining these.
The divalent linking group of L ₂ preferably has 5 or less carbon atoms, more preferably 3 or less carbon atoms, and represents an ester group, a carbonyl group, an alkylene group, or a divalent group obtained by combining these.

The alicyclic group (alicyclic hydrocarbon group) in the alicyclic group which may have a lactone structure of A ₁ may be monocyclic or polycyclic. Specific examples include groups having a monocyclo, bicyclo, tricyclo, tetracyclo structure or the like having 5 or more carbon atoms. The carbon number is preferably 6-30, and particularly preferably 7-25.

  Specific examples of the alicyclic group include, for example, an adamantyl group, a noradamantyl group, a decalin residue, a tricyclodecanyl group, a tetracyclododecanyl group, a norbornyl group, a cedrol group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, A cyclodecanyl group and a cyclododecanyl group can be mentioned. More preferable examples include an adamantyl group, a decalin residue, a norbornyl group, a cedrol group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecanyl group, and a cyclododecanyl group.

A ₁ may be an alicyclic group having a lactone structure, and examples of the alicyclic group having a lactone structure include those obtained by adding a lactone structure to the alicyclic group. Examples include groups represented by general formulas (B-1) to (B-3) as B in the repeating unit represented by A-2).

The substituent having a fluorine atom as J is, for example, an organic group substituted with at least one fluorine atom, and preferably has 15 or less carbon atoms, more preferably 1 to 10 carbon atoms. 1-15 are preferable and, as for the number of fluorine atoms, 3-10 are more preferable.
Examples of the organic group include an alkyl group, a cycloalkyl group, an alkoxy group, and an alkoxycarbonyl group.
Organic groups such as an alkyl group, a cycloalkyl group, an alkoxy group, and an alkoxycarbonyl group may have other substituents (a hydroxyl group, a halogen atom, an alkoxy group, and the like) in addition to a fluorine atom.

  In particular, as a substituent having a fluorine atom of J, a group represented by the following general formula (Z) is preferable.

R _{50 to} R ₅₅ each independently represents a hydrogen atom, a fluorine atom or an alkyl group (preferably having 1 to 5 carbon atoms). However, at least one of R _{50 to} R ₅₅ represents a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. R ₄₀ represents a hydrogen atom, an alkyl group, a cycloalkyl group or an acyl group.
The alkyl group, cycloalkyl group or acyl group as R ₄₀ preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms.

An alicyclic group optionally having a lactone structure represented by A ₁ in general formulas (A-1-1) and (A-1-2), or a benzene ring in general formula (A-1-3) In addition to the fluorine atom represented by J or a substituent having a fluorine atom, may have another substituent not having a fluorine atom, and the other substituent preferably has 5 carbon atoms. Examples thereof include a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, a carboxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, and an alkoxycarbonyl group. These organic groups may be further substituted with a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group or an alkoxy group.

  Specific examples of the repeating unit represented by any one of the general formulas (A-1-1) to (A-1-3) are shown below, but are not limited thereto.

The resin (A) further includes a repeating unit (A-2) having a lactone structure represented by the general formula (A-2), a repeating unit (A-3) represented by the general formula (A-3),
It is preferable to contain the repeating unit (A-4) represented by general formula (A-4), which has a group that decomposes by the action of an acid.

R _{2 to} R ₄ each independently represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group or an alkoxy group.
The details of the alkyl or alkoxy group R ₂ to R _4, the same as the alkyl or alkoxy group as R ₁ in the general formula (A-1-1).

The side chain group via the ester group in the general formulas (A-2) to (A-4) does not have a fluorine atom. That is, a group represented by L ₃ and a group represented by B in the general formula (A-2), an adamantyl group in the general formula (A-3), and a group represented by ADG in the general formula (A-4) Has no fluorine atom.

Details of the divalent linking group of L _{3 in} the general formula (A-2) are the same as those of the divalent linking group as L ₂ in the general formula (A-1-2).
B in the general formula (A-2) represents a ring having a lactone structure.

As the ring containing the lactone structure represented by B in the repeating unit represented by the general formula (A-2), as A ₁ in the general formulas (A-1-1) and (A-1-2), Are those in which a lactone structure is added to the alicyclic group described above, and groups represented by any of the following general formulas (B-1) to (B-3) are particularly preferable.

In General Formulas (B-1) to (B-3), R _{1b to} R _6b each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an alkenyl group. Two of R _{1b to} R _6b may combine to form a ring.

  Moreover, it is preferable that the ring which has the lactone structure represented by B in the repeating unit represented by general formula (A-2) is group represented by the following general formula (B-4).

R _7b and R _8b each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group or an alkenyl group.

The alkyl group, cycloalkyl group or alkenyl group as R _{1b to} R _8b preferably has 15 or less carbon atoms, more preferably 10 or less.

  Specific examples of the repeating unit represented by formula (A-2) are shown below, but are not limited thereto.

In General Formula (A-3), K represents a chlorine atom, a hydroxyl group, a cyano group, or an alkyl group or alkoxy group that does not contain a fluorine atom, and a hydroxyl group is preferable.
The alkyl group containing no fluorine atom as K preferably has 1 to 5 carbon atoms, and examples thereof include a propyl group, an ethyl group, and a methyl group.
The alkoxy group containing no fluorine atom as K preferably has 1 to 5 carbon atoms,
It may have an external substituent, and examples of such a substituent include the alicyclic group represented by A ₁ in the general formulas (A-1-1) and (A-1-2). The same as those mentioned as the substituent which may be included.
q represents an integer of 1 to 3.

  Specific examples of the repeating unit represented by the general formula (A-3) are shown below, but are not limited thereto.

ADG in the general formula (A-4) represents an acid-decomposable group.
The acid-decomposable group as ADG is a group that generates a carboxy group, which is an alkali-soluble group, in the repeating unit as a result of elimination by the action of an acid in the repeating unit represented by formula (A-4).

  Examples of the acid-decomposable group of ADG include groups having an alicyclic hydrocarbon group represented by the following general formula (pI) to general formula (pVI).

In the formula, R ₁₁ represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a sec-butyl group, and Z forms an alicyclic hydrocarbon group together with a carbon atom. Represents the atomic group necessary to do.
R _{12 to} R ₁₆ each independently represents a linear or branched alkyl group or alicyclic hydrocarbon group having 1 to 4 carbon atoms, provided that at least one of R _{12 to} R ₁₄ , or Either R ₁₅ or R ₁₆ represents an alicyclic hydrocarbon group.
R _{17 to} R ₂₁ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or an alicyclic hydrocarbon group, provided that at least one of R _{17 to} R ₂₁ Represents an alicyclic hydrocarbon group. Further, either R ₁₉ or R ₂₁ represents a linear or branched alkyl group or alicyclic hydrocarbon group having 1 to 4 carbon atoms.
R _{22 to} R ₂₅ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or an alicyclic hydrocarbon group, provided that at least one of R _{22 to} R ₂₅ Represents an alicyclic hydrocarbon group. R ₂₃ and R ₂₄ may be bonded to each other to form a ring.

In the general formulas (pI) to (pVI), the alkyl group in R _{12 to} R ₂₅ represents a linear or branched alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a t-butyl group.

  In addition, examples of the substituent that each alkyl group may have include an alkoxy group having 1 to 4 carbon atoms, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), acyl group, acyloxy group, cyano. Group, hydroxyl group, carboxy group, alkoxycarbonyl group, nitro group and the like.

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

  Preferred examples of the alicyclic hydrocarbon group include an adamantyl group, a noradamantyl group, a decalin residue, a tricyclodecanyl group, a tetracyclododecanyl group, a norbornyl group, a cedrol group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Group, cyclodecanyl group, and cyclododecanyl group. More preferred are an adamantyl group, a decalin residue, a norbornyl group, a cedrol group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecanyl group, and a cyclododecanyl group.

  Examples of the substituent for these alicyclic hydrocarbon groups include an alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group, and an alkoxycarbonyl group. The alkyl group is preferably a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group, and more preferably selected from the group consisting of a methyl group, an ethyl group, a propyl group, and an isopropyl 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 substituent that the alkyl group, alkoxy group, alkoxycarbonyl group and the like may further have include a hydroxyl group, a halogen atom, and an alkoxy group.

  The group represented by the acid-decomposable group as ADG is particularly preferably a group represented by the general formula (pI) or (pII).

R ₁₁ represents methyl, ethyl, n-propyl, isopropyl group, n-butyl group, isobutyl group or sec-butyl group, and Z represents an atom necessary for forming an alicyclic hydrocarbon group together with a carbon atom. Represents a group.

R _{12 to} R ₁₄ each independently represents an alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group. However, at least one of R _{12 to} R ₁₄ represents an alicyclic hydrocarbon group.

  Specific examples of the repeating unit represented by formula (A-4) are shown below, but are not limited thereto.

Resin (A) adjusts dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and resolution, heat resistance, sensitivity, etc., which are general required characteristics of resist, in addition to the above repeating structural units. For this purpose, various repeating structural units can be contained.

  Examples of such repeating structural units include, but are not limited to, repeating structural units corresponding to the following monomers.

Thereby, performance required for the alicyclic hydrocarbon-based acid-decomposable resin, in particular,
(1) Solubility in coating solvent,
(2) Film formability (glass transition point),
(3) Alkali developability,
(4) Membrane slip (hydrophobic, alkali-soluble group selection),
(5) Adhesion of unexposed part to substrate,
(6) Dry etching resistance,
Etc. can be finely adjusted.

  As such a monomer, for example, a compound having one addition polymerizable unsaturated bond selected from acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, etc. Etc.

  In addition, any addition-polymerizable unsaturated compound that can be copolymerized with monomers corresponding to the above various repeating structural units may be copolymerized.

  In alicyclic hydrocarbon-based acid-decomposable resins, the molar ratio of each repeating structural unit is the resist's dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and resolution that is a general required performance of resists. In order to adjust heat resistance, sensitivity, etc., it is set appropriately.

In the resin (A), the repeating unit represented by any one of the general formulas (A-1-1) to (A-1-3) is, as a total amount, based on all the repeating units constituting the resin (A). In general, it is 1 to 50 mol%, preferably 3 to 40 mol%, more preferably 5 to 30 mol%.
In the resin (A), the repeating unit represented by the general formula (A-2) is usually 3 to 60 mol%, preferably 5 to 50 mol%, based on all repeating units constituting the resin (A). More preferably, it is 10-40 mol%.
In the resin (A), the repeating unit represented by the general formula (A-3) is usually 3 to 60 mol%, preferably 5 to 50 mol%, based on all repeating units constituting the resin (A). More preferably, it is 10-40 mol%.
In the resin (A), the repeating unit represented by the general formula (A-4) is usually 3 to 60 mol%, preferably 5 to 50 mol%, based on all repeating units constituting the resin (A). More preferably, it is 10-40 mol%.

The resin (A) can be synthesized according to a conventional method (for example, radical polymerization). For example, as a general synthesis method, monomer species are charged into a reaction vessel in a batch or in the course of reaction, and if necessary, a reaction solvent such as ethers such as tetrahydrofuran, 1,4-dioxane, diisopropyl ether, methyl ethyl ketone, A ketone such as methyl isobutyl ketone, an ester solvent such as ethyl acetate, and further dissolved in a solvent for dissolving the composition of the present invention such as propylene glycol monomethyl ether acetate described later, and then nitrogen, argon, etc. Polymerization is started using a commercially available radical initiator (such as an azo-based initiator or peroxide) under an inert gas atmosphere as necessary. If desired, an initiator is added or added in portions, and after completion of the reaction, it is put into a solvent and a desired polymer is recovered by a method such as powder or solid recovery. The concentration of the reaction is usually 20% by mass or more, preferably 3
It is 0 mass% or more, More preferably, it is 40 mass% or more. The reaction temperature is usually from 10 ° C to 150 ° C, preferably from 30 ° C to 120 ° C, more preferably from 50 to 100 ° C.

  Each of the above repeating structural units may be used alone or in combination. In the present invention, the resins may be used alone or in combination.

  The weight average molecular weight of the alicyclic hydrocarbon-based acid-decomposable resin of the present invention is preferably 1,000 to 200,000 as a polystyrene conversion value by gas permeation chromatography (GPC) method, more preferably 3000 to 200,000. 20000. By making the weight average molecular weight 1,000 or more, heat resistance and dry etching resistance can be improved, and by making the weight average molecular weight 200,000 or less, developability can be improved. In addition, the viscosity is lowered and the film forming property can be improved.

  The molecular weight distribution (Mw / Mn, also referred to as dispersity) is usually 1 to 5, preferably 1 to 4, more preferably 1 to 3. The molecular weight distribution is preferably 5 or less from the viewpoint of resolution, resist shape, resist pattern side wall, roughness, and the like.

  In the chemically amplified resist composition for immersion process according to the present invention, the blending amount of the alicyclic hydrocarbon-based acid-decomposable resin is preferably 40 to 99.99% by mass, more preferably 50 to 50%, based on the total solid content of the resist. It is 99.97 mass%.

(B) Compound that generates acid upon irradiation with actinic ray or radiation Compound that generates acid upon irradiation with actinic ray or radiation (hereinafter referred to as “acid generation”) used in the chemically amplified resist composition for immersion process of the present invention. The “agent” may be referred to below.
The acid generator used in the present invention can be selected from compounds generally used as an acid generator.
That is, it generates an acid upon irradiation with actinic rays or radiation used for photoinitiators of photocationic polymerization, photoinitiators of photoradical polymerization, photodecolorants of dyes, photochromic agents, or microresists. Known compounds and mixtures thereof can be appropriately selected and used.

  Examples thereof include diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imide sulfonates, oxime sulfonates, diazodisulfones, disulfones, and o-nitrobenzyl sulfonates.

  Further, a group that generates an acid upon irradiation with these actinic rays or radiation, or a compound in which a compound is introduced into the main chain or side chain of the polymer, for example, US Pat. No. 3,849,137, German Patent No. 3914407. JP, 63-26653, JP, 55-164824, JP, 62-69263, JP, 63-146038, JP, 63-163452, JP, 62-153853, The compounds described in JP-A 63-146029 can be used.

  Furthermore, compounds capable of generating an acid by light described in US Pat. No. 3,779,778, European Patent 126,712 and the like can also be used.

  Preferred examples of the acid generator include compounds represented by the following general formula (ZI), (ZII) or (ZIII).

In the above general formula (ZI), R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represents an organic group.
X ⁻ represents a non-nucleophilic anion.
The carbon number of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is generally 1-30, preferably 1-20.
Two of R _{201 to} R ₂₀₃ may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group.

The two of the group formed by bonding of the R ₂₀₁ to R _203, there can be mentioned an alkylene group (e.g., butylene, pentylene).

Specific examples of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ include corresponding groups in the compounds (ZI-1), (ZI-2) and (ZI-3) described later.

In addition, the compound which has two or more structures represented by general formula (ZI) may be sufficient. For example, the general formula at least one of R ₂₀₁ to R ₂₀₃ of a compound represented by (ZI) is, at least one bond with structure of R ₂₀₁ to R ₂₀₃ of another compound represented by formula (ZI) It may be a compound.

  More preferable (ZI) components include compounds (ZI-1), (ZI-2), and (ZI-3) described below.

The compound (ZI-1) is at least one of the aryl groups R ₂₀₁ to R ₂₀₃ in formula (ZI), arylsulfonium compound, i.e., a compound having arylsulfonium as a cation.

In the arylsulfonium compound, all of R _{201 to} R ₂₀₃ may be an aryl group, or a part of R _{201 to} R ₂₀₃ may be an aryl group, and the rest may be an alkyl group or a cycloalkyl group.

  Examples of the arylsulfonium compound include triarylsulfonium compounds, diarylalkylsulfonium compounds, aryldialkylsulfonium compounds, diarylcycloalkylsulfonium compounds, aryldicycloalkylsulfonium compounds, and the like.

  The aryl group of the arylsulfonium compound is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. When the arylsulfonium compound has two or more aryl groups, the two or more aryl groups may be the same or different.

The alkyl group that the arylsulfonium compound has as necessary is preferably a linear or branched alkyl group having 1 to 15 carbon atoms, such as a methyl group, an ethyl group, a propyl group, n
-A butyl group, a sec-butyl group, a t-butyl group, etc. can be mentioned.

  The cycloalkyl group that the arylsulfonium compound has as necessary is preferably a cycloalkyl group having 3 to 15 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, and a cyclohexyl group.

The aryl group, alkyl group, and cycloalkyl group of R _{201 to} R ₂₀₃ are an alkyl group (for example, having 1 to 15 carbon atoms), a cycloalkyl group (for example, having 3 to 15 carbon atoms), an aryl group (for example, having 6 to 6 carbon atoms) 14), an alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, a phenylthio group or the like may be used as a substituent. Preferred substituents are linear or branched alkyl groups having 1 to 12 carbon atoms, cycloalkyl groups having 3 to 12 carbon atoms, and alkoxy groups having 1 to 12 carbon atoms, most preferably alkyl having 1 to 4 carbon atoms. Group, an alkoxy group having 1 to 4 carbon atoms. The substituent may be substituted with any one of the three R _{201 to} R ₂₀₃ , or may be substituted with all three. When R _{201 to} R ₂₀₃ are an aryl group, the substituent is preferably substituted at the p-position of the aryl group.

Examples of the non-nucleophilic anion as X ⁻ include a sulfonate anion, a carboxylate anion, a sulfonylimide anion, a bis (alkylsulfonyl) imide anion, and a tris (alkylsulfonyl) methyl anion.

  A non-nucleophilic anion is an anion that has an extremely low ability to cause a nucleophilic reaction, and is an anion that can suppress degradation over time due to an intramolecular nucleophilic reaction. This improves the temporal stability of the resist.

  Examples of the sulfonate anion include an aliphatic sulfonate anion, an aromatic sulfonate anion, and a camphor sulfonate anion.

  Examples of the carboxylate anion include an aliphatic carboxylate anion, an aromatic carboxylate anion, and an aralkylcarboxylate anion.

  Examples of the aliphatic group in the aliphatic sulfonate anion include, for example, an alkyl group having 1 to 30 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, sec- Butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl And an eicosyl group and a cycloalkyl group having 3 to 30 carbon atoms, specifically, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a norbornyl group, a boronyl group, and the like.

  The aromatic group in the aromatic sulfonate anion is preferably an aryl group having 6 to 14 carbon atoms, such as a phenyl group, a tolyl group, and a naphthyl group.

  The alkyl group, cycloalkyl group, and aryl group in the aliphatic sulfonate anion and aromatic sulfonate anion may have a substituent.

Examples of such substituents include nitro groups, halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, iodine atoms), carboxyl groups, hydroxyl groups, amino groups, cyano groups, and alkoxy groups (preferably having 1 to 5 carbon atoms). ), A cycloalkyl group (preferably 3 to 15 carbon atoms), an aryl group (preferably 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably 2 to 7 carbon atoms), an acyl group (preferably 2 to 12 carbon atoms). ), An alkoxycarbonyloxy group (preferably having 2 to 7 carbon atoms), an alkylthio group (preferably having 1 to 15 carbon atoms), and the like. About the aryl group and ring structure which each group has, an alkyl group (preferably C1-C15) can further be mentioned as a substituent.

  Examples of the aliphatic group in the aliphatic carboxylate anion include those similar to the aliphatic group in the aliphatic sulfonate anion.

  Examples of the aromatic group in the aromatic carboxylate anion include the same aromatic groups as in the aromatic sulfonate anion.

  The aralkyl group in the aralkyl carboxylate anion is preferably an aralkyl group having 6 to 12 carbon atoms, such as a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, and a naphthylmethyl group.

  The aliphatic group, aromatic group and aralkyl group in the aliphatic carboxylate anion, aromatic carboxylate anion and aralkylcarboxylate anion may have a substituent. Examples of the substituent include aliphatic sulfonic acid The same halogen atom, alkyl group, cycloalkyl group, alkoxy group, alkylthio group and the like as in the anion can be exemplified.

  Examples of the sulfonylimide anion include saccharin anion.

  The alkyl group in the bis (alkylsulfonyl) imide anion and tris (alkylsulfonyl) methyl anion is preferably an alkyl group having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, An isobutyl group, a sec-butyl group, a pentyl group, a neopentyl group, and the like can be given. These alkyl groups may have a substituent, and examples of the substituent include a halogen atom, an alkyl group substituted with a halogen atom, an alkoxy group, an alkylthio group, and the like, which are substituted with a fluorine atom. Alkyl groups are preferred.

  Examples of other non-nucleophilic anions include fluorinated phosphorus, fluorinated boron, and fluorinated antimony.

Examples of the non-nucleophilic anion of X ⁻ include an aliphatic sulfonate anion in which the α-position of the sulfonic acid is substituted with a fluorine atom, an aromatic sulfonate anion substituted with a fluorine atom or a group having a fluorine atom, and an alkyl group. A bis (alkylsulfonyl) imide anion substituted with a fluorine atom and a tris (alkylsulfonyl) methide anion wherein an alkyl group is substituted with a fluorine atom are preferred. The non-nucleophilic anion is particularly preferably a perfluoroaliphatic sulfonic acid anion having 4 to 8 carbon atoms, an aromatic sulfonic acid anion having a fluorine atom, most preferably a nonafluorobutanesulfonic acid anion, a perfluorooctanesulfonic acid anion, It is a pentafluorobenzenesulfonic acid anion and 3,5-bis (trifluoromethyl) benzenesulfonic acid anion.

Next, the compound (ZI-2) will be described.
Compound (ZI-2) is a compound in the case where R _{201 to} R ₂₀₃ in formula (ZI) each independently represents an organic group not containing an aromatic ring. Here, the aromatic ring includes an aromatic ring containing a hetero atom.

The organic group having no aromatic ring as R ₂₀₁ to R ₂₀₃ generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.

R _{201 to} R ₂₀₃ are each independently preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, more preferably a linear, branched, cyclic 2-oxoalkyl group, or an alkoxycarbonylmethyl group, most preferably Is a linear, branched 2-oxoalkyl group.

The alkyl group as R _{201 to} R ₂₀₃ may be either linear or branched, and is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, or a propyl group. Butyl group, pentyl group and the like. More preferable examples of the alkyl group include a 2-linear or branched oxoalkyl group and an alkoxycarbonylmethyl group.

The cycloalkyl group as R ₂₀₁ to R ₂₀₃ is preferably a cycloalkyl group having 3 to 10 carbon atoms, e.g., cyclopentyl, cyclohexyl group and a norbornyl group. More preferred examples of the cycloalkyl group include a 2-oxocycloalkyl group.

  The 2-oxoalkyl group may be linear, branched or cyclic, and preferably includes a group having> C═O at the 2-position of the above alkyl group or cycloalkyl group.

  The alkoxy group in the alkoxycarbonylmethyl group is preferably an alkyl group having 1 to 5 carbon atoms (methyl group, ethyl group, propyl group, butyl group, pentyl group).

R _{201 to} R ₂₀₃ may be further substituted with a halogen atom, an alkoxy group (for example, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group.

  The compound (ZI-3) is a compound represented by the following general formula (ZI-3), and is a compound having a phenacylsulfonium salt structure.

R _{1c to} R _5c each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group or a halogen atom.
R _6c and R _7c represent a hydrogen atom, an alkyl group, or a cycloalkyl group.
Rx and Ry each independently represents an alkyl group, a cycloalkyl group, an allyl group or a vinyl group.

Any two or more of R _{1c to} R _5c , and R _x and R _y may be bonded to each other to form a ring structure, and this ring structure includes an oxygen atom, a sulfur atom, an ester bond, and an amide bond. May be included.

Zc ⁻ represents a non-nucleophilic anion, and examples thereof include the same as the non-nucleophilic anion of X ^{− in} formula (ZI).

The alkyl group as R _{1c to} R _7c is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, such as a methyl group, an ethyl group, a linear or branched propyl group, a linear or branched butyl group, A linear or branched pentyl group can be exemplified.

The cycloalkyl group as R _{1c to} R _7c is preferably a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof include a cyclopentyl group and a cyclohexyl group.

The alkoxy group as R _{1c to} R _{5c may} be linear, branched or cyclic, for example, an alkoxy group having 1 to 10 carbon atoms, preferably a linear or branched alkoxy group having 1 to 5 carbon atoms. (For example, methoxy group, ethoxy group, linear or branched propoxy group, linear or branched butoxy group, linear or branched pentoxy group), C3-C8 cyclic alkoxy group (for example, cyclopentyloxy group, cyclohexyloxy group) ).

Preferably, any one of R _{1c to} R _5c is a linear or branched alkyl group, a cycloalkyl group, or a linear, branched or cyclic alkoxy group, and more preferably the sum of the carbon number of R _{1c to} R _5c is 2 ~ 15. Thereby, solvent solubility improves more and generation | occurrence | production of a particle is suppressed at the time of a preservation | save.

_Examples of the alkyl group and cycloalkyl group as R _x and R _y include the same alkyl groups and cycloalkyl groups as R _{1c to} R _{7c, such} as a 2-oxoalkyl group and a 2-oxocycloalkyl group. An alkoxycarbonylmethyl group is more preferable.

Examples of the 2-oxoalkyl group and 2-oxocycloalkyl group include a group having> C═O at the 2-position of the alkyl group or cycloalkyl group as R _{1c to} R _7c .

Examples of the alkoxy group in the alkoxycarbonylmethyl group include the same alkoxy groups as R _{1c to} R _5c .

Examples of the group formed by combining any two or more of R _{1c to} R _5c and R _x and R _y include a butylene group and a pentylene group.

R _x and R _y are preferably an alkyl group having 4 or more carbon atoms, more preferably 6 or more, and still more preferably 8 or more.

In formula (ZII) and (ZIII), R ₂₀₄ ~R ₂₀₇ each independently represents an aryl group, an alkyl group or a cycloalkyl group.

Phenyl group and a naphthyl group are preferred as the aryl group of R ₂₀₄ to R _207, more preferably a phenyl group.

The alkyl group as R ₂₀₄ to R ₂₀₇ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group.

The cycloalkyl group as R ₂₀₄ to R ₂₀₇ is preferably a cycloalkyl group having 3 to 10 carbons, e.g., cyclopentyl, cyclohexyl group and a norbornyl group.

The R ₂₀₄ to R ₂₀₇ are substituents which may have, for example, an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms), an aryl group (e.g., 6 carbon atoms 15), alkoxy groups (for example, having 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, phenylthio groups and the like.

X ⁻ represents a non-nucleophilic anion, and examples thereof include the same non-nucleophilic anion as X ^{− in} formula (ZI).

  Preferred examples of the acid generator include compounds represented by the following general formula (ZIV), (ZV), or (ZVI).

In general formulas (ZIV) to (ZVI), Ar ₃ and Ar ₄ each independently represents an aryl group.

R ₂₀₆ , R ₂₀₇ and R _{208 each} represents an alkyl group, a cycloalkyl group or an aryl group.
A represents an alkylene group, an alkenylene group or an arylene group.

  Among the acid generators, compounds represented by the general formulas (ZI) to (ZIII) are more preferable.

  Among the compounds that generate an acid upon irradiation with actinic rays or radiation, examples of particularly preferable compounds are listed below.

An acid generator can be used individually by 1 type or in combination of 2 or more types.
The content of the acid generator in the chemically amplified resist composition for immersion process is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, based on the total solid content of the resist composition. More preferably, it is 1-7 mass%.

(C) Solvent The chemical amplification resist composition for immersion process of the present invention is used by dissolving each component in a predetermined solvent.
Examples of solvents that can be used include ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, γ-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, ethylene glycol monoethyl ether. Acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N, N- Examples include dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, methoxybutanol, and tetrahydrofuran. Rukoto can.

In this invention, you may use the mixed solvent which mixed the solvent which has a hydroxyl group in a structure, and the solvent which does not have a hydroxyl group as a solvent.
Examples of the solvent having a hydroxyl group include ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethyl lactate, and the like. Propylene glycol monomethyl ether and ethyl lactate are preferred.
Examples of the solvent having no hydroxyl group include propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, butyl acetate, N-methylpyrrolidone, N, N-dimethylacetamide, dimethyl sulfoxide. Among these, propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, and butyl acetate are preferable, propylene glycol monomethyl ether acetate, ethyl ethoxypropionate 2-heptanone is more preferable.
The mixing ratio (mass) of the solvent having a hydroxyl group and the solvent having no hydroxyl group is preferably 1/99 to 99/1, more preferably 10/90 to 90/10, and even more preferably 20/80 to 60. / 40. A mixed solvent containing 50% by mass or more of a solvent having no hydroxyl group is particularly preferable from the viewpoint of coating uniformity.

  In the chemically amplified resist composition for immersion process of the present invention, the content of the solvent is preferably 80 to 98% by mass, more preferably 85 to 95% by mass in the total composition. .

(D) Fluorine and / or silicon-based surfactant The chemically amplified resist composition for immersion process of the present invention has a concentration of 1000 ppm or more, preferably 2000 ppm or more, more preferably 3000 ppm, based on the total amount of the composition. Fluorine-based and / or silicon-based surfactants (fluorine-based surfactants, silicon-based surfactants, surfactants having both fluorine and silicon atoms) at the above concentrations, particularly preferably at a concentration of 3000 to 10,000 ppm. contains.

The surfactant is preferable from the viewpoint of good sensitivity, good resolution, improved adhesion, reduction of development defects, and the like when using an exposure light source of 193 nm.
Examples of the fluorine-based and / or silicon-based surfactant include, for example, JP-A No. 62-36663, JP-A No. 61-226746, JP-A No. 61-226745, JP-A No. 62-170950, JP 63-34540 A, JP 7-230165 A, JP 8-62834 A, JP 9-54432 A, JP 9-5988 A, JP 2002-277862 A, US Patent Nos. 5,405,720, 5,360,692, 5,529,881, 5,296,330, 5,436,098, 5,576,143, 5,294,511, 5,824,451 Surfactant can be mentioned, The following commercially available surfactant can also be used as it is.
Examples of commercially available surfactants that can be used include F-top EF301, EF303 (manufactured by Shin-Akita Kasei Co., Ltd.), Florard FC430, 431 (manufactured by Sumitomo 3M Co., Ltd.), MegaFuck F171, F173, F176, F189, R08 (Dainippon Ink Chemical Co., Ltd.), Surflon S-382, SC101, 102, 103, 104, 105, 106 (Asahi Glass Co., Ltd.), Troisol S-366 (Troy Chemical Co., Ltd.), etc. Fluorine type surfactant or silicon type surfactant can be mentioned. Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.

In addition to the known surfactants described above, surfactants are derived from fluoroaliphatic compounds produced by the telomerization method (also referred to as the telomer method) or the oligomerization method (also referred to as the oligomer method). A surfactant using a polymer having a fluoroaliphatic group can be used. The fluoroaliphatic compound can be synthesized by the method described in JP-A-2002-90991.
As the polymer having a fluoroaliphatic group, a copolymer of a monomer having a fluoroaliphatic group and (poly (oxyalkylene)) acrylate and / or (poly (oxyalkylene)) methacrylate is preferable and distributed irregularly. Or may be block copolymerized. Examples of the poly (oxyalkylene) group include a poly (oxyethylene) group, a poly (oxypropylene) group, a poly (oxybutylene) group, and the like, and a poly (oxyethylene, oxypropylene, and oxyethylene group). A unit having different chain lengths in the same chain length, such as a block link) or poly (block link of oxyethylene and oxypropylene) may be used. Furthermore, a copolymer of a monomer having a fluoroaliphatic group and (poly (oxyalkylene)) acrylate (or methacrylate) is not only a binary copolymer but also a monomer having two or more different fluoroaliphatic groups, Further, it may be a ternary or higher copolymer obtained by simultaneously copolymerizing two or more different (poly (oxyalkylene)) acrylates (or methacrylates).

Examples of commercially available surfactants include Megafac F178, F-470, F-473, F-475, F-476, and F-472 (Dainippon Ink Chemical Co., Ltd.). Further, a copolymer of an acrylate (or methacrylate) having a C ₆ F ₁₃ group and (poly (oxyalkylene)) acrylate (or methacrylate), an acrylate (or methacrylate) having a C ₆ F ₁₃ group and (poly (oxy) (Ethylene)) acrylate (or methacrylate) and (poly (oxypropylene)) acrylate (or methacrylate) copolymer, acrylate (or methacrylate) and (poly (oxyalkylene)) acrylate having C ₈ F ₁₇ groups (or Copolymer of acrylate (or methacrylate), (poly (oxyethylene)) acrylate (or methacrylate), and (poly (oxypropylene)) acrylate (or methacrylate) having a C ₈ F ₁₇ group List union It can be.

  These surfactants may be used alone or in several combinations.

In the present invention, other surfactants other than fluorine-based and / or silicon-based surfactants may be used in combination.
Examples of other surfactants other than fluorine and / or silicon surfactants include polyoxyethylene such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, and the like. Alkyl ethers, polyoxyethylene alkyl allyl ethers such as polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate Sorbitan fatty acid esters such as sorbitan monooleate, sorbitan trioleate, sorbitan tristearate, polyoxyethylene Nonionics such as polyoxyethylene sorbitan fatty acid esters such as sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate Surfactant etc. can be mentioned.

(E) Basic compound It is preferable that the chemically amplified resist composition for immersion process of the present invention further contains a basic compound. As the basic compound, for example, a nitrogen-containing basic compound, a basic ammonium salt, a basic sulfonium salt, a basic iodonium salt, or the like may be used as long as it does not deteriorate sublimation or resist performance.

  The basic compound is a component having an action of controlling a diffusion phenomenon in a resist film of an acid generated from an acid generator by exposure and suppressing an undesirable chemical reaction in a non-exposed region. By blending such a basic compound, the storage stability of the chemically amplified resist composition for immersion process that can control the diffusion phenomenon in the resist film of the acid generated from the acid generator by exposure is improved, In addition, the resolution as a resist is further improved, and a change in the line width of the resist pattern due to fluctuations in the holding time (PED) from exposure to development processing can be suppressed, and a composition having excellent process stability can be obtained. .

  Examples of the nitrogen-containing basic compound include primary, secondary and tertiary aliphatic amines, aromatic amines, heterocyclic amines, nitrogen-containing compounds having a carboxy group, and compounds having a sulfonyl group. Examples thereof include nitrogen compounds, nitrogen-containing compounds having a hydroxyl group, nitrogen-containing compounds having a hydroxyphenyl group, alcoholic nitrogen-containing compounds, amide derivatives, imide derivatives, and nitrogen-containing compounds having a cyano group.

  As aliphatic amines, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, pentylamine, tert-amylamine, cyclopentylamine, hexylamine, cyclohexylamine, Heptylamine, octylamine, nonylamine, decylamine, dodecylamine, cetylamine, methylenediamine, ethylenediamine, tetraethylenepentamine, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di -Sec-butylamine, dipentylamine, dicyclopentylamine, dihexylamine, dicyclohexylamine, diheptylamine , Dioctylamine, dinonylamine, didecylamine, didodecylamine, dicetylamine, N, N-dimethylmethylenediamine, N, N-dimethylethylenediamine, N, N-dimethyltetraethylenepentamine, trimethylamine, triethylamine, tri-n-propylamine , Triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tripentylamine, tricyclopentylamine, trihexylamine, tricyclohexylamine, triheptylamine, trioctylamine, trinonylamine, tri Decylamine, tridodecylamine, tricetylamine, N, N, N ′, N′-tetramethylmethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, , N, N ', N'- tetramethyl-tetraethylenepentamine, dimethylethylamine, methylethylpropylamine, benzylamine, phenethylamine, benzyldimethylamine, and the like.

Aromatic amines and heterocyclic amines include aniline derivatives such as aniline, N-methylaniline, N-ethylaniline, N-propylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, ethylaniline,
Propylaniline, trimethylaniline, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2,4-dinitroaniline, 2,6-dinitroaniline, 3,5-dinitroaniline, N, N-dimethyltoluidine, etc.) , Diphenyl (p-tolyl) amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, pyrrole derivatives (eg pyrrole, 2H-pyrrole, 1-methylpyrrole, 2,4-dimethylpyrrole, 2,5- Dimethylpyrrole, N-methylpyrrole, etc.), oxazole derivatives (eg oxazole, isoxazole etc.), thiazole derivatives (eg thiazole, isothiazole etc.), imidazole derivatives (eg imidazole, 4-methylimidazole, -Methyl-2-phenylimidazole, etc.), pyrazole derivatives, furazane derivatives, pyrroline derivatives (eg pyrroline, 2-methyl-1-pyrroline etc.), pyrrolidine derivatives (eg pyrrolidine, N-methylpyrrolidine, pyrrolidinone, N-methylpyrrolidone etc.) ),

Imidazoline derivatives, imidazolidine derivatives, pyridine derivatives (eg pyridine, methylpyridine, ethylpyridine, propylpyridine, butylpyridine, 4- (1-butylpentyl) pyridine, dimethylpyridine, trimethylpyridine, triethylpyridine, phenylpyridine, 3-methyl 2-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 1-methyl-2-pyridone, 4-pyrrolidinopyridine, 1-methyl-4-phenylpyridine 2- (1-ethylpropyl) pyridine, aminopyridine, dimethylaminopyridine, etc.), pyridazine derivatives, pyrimidine derivatives, pyrazine derivatives, pyrazoline derivatives, pyrazolidine derivatives, Lysine derivative, piperazine derivative, morpholine derivative, indole derivative, isoindole derivative, 1H-indazole derivative, indoline derivative, quinoline derivative (eg quinoline, 3-quinolinecarbonitrile, etc.), isoquinoline derivative, cinnoline derivative, quinazoline derivative, quinoxaline derivative, Examples include phthalazine derivatives, purine derivatives, pteridine derivatives, carbazole derivatives, phenanthridine derivatives, acridine derivatives, phenazine derivatives, 1,10-phenanthroline derivatives, adenine derivatives, adenosine derivatives, guanine derivatives, guanosine derivatives, uracil derivatives, uridine derivatives, etc. Is done.

  Examples of the nitrogen-containing compound having a carboxy group include aminobenzoic acid, indolecarboxylic acid, amino acid derivatives (for example, nicotinic acid, alanine, arginine, aspartic acid, glutamic acid, glycine, histidine, isoleucine, glycylleucine, leucine, methionine, phenylalanine. , Threonine, lysine, 3-aminopyrazine-2-carboxylic acid, methoxyalanine) and the like.

  Examples of the nitrogen-containing compound having a sulfonyl group include 3-pyridinesulfonic acid and pyridinium p-toluenesulfonate.

Examples of the nitrogen-containing compound having a hydroxyl group include 2-hydroxypyridine, aminocresol, 2,4-quinolinediol, 3-indolemethanol hydrate, monoethanolamine, diethanolamine, triethanolamine, N-ethyldiethanolamine, N, N- Diethylethanolamine, triisopropanolamine, 2,2′-iminodiethanol, 2-aminoethanol, 3-amino-1-propanol, 4-amino-1-butanol, 4- (2-hydroxyethyl) morpholine, 2- ( 2-hydroxyethyl) pyridine, 1- (2-hydroxyethyl) piperazine, 1- [2- (2-hydroxyethoxy) ethyl] piperazine, piperidineethanol, 1- (2-hydroxyethyl) pyrrolidine, 1- (2- Hydroxyethyl ) -2-pyrrolidinone, 3-piperidino-1,2-propanediol, 3-pyrrolidino-1,2-propanediol, 8-hydroxyeurolidine, 3-quinuclidinol, 3-tropanol, 1-methyl-2 -Pyrrolidine ethanol, 1-aziridine ethanol, N- (2-hydroxyethyl) phthalimide, N- (2-hydroxyethyl) isonicotinamide and the like are exemplified.

  Examples of amide derivatives include formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide and the like.

  Examples of imide derivatives include phthalimide, succinimide, maleimide and the like.

  Specific examples of nitrogen-containing compounds having a cyano group include 3- (diethylamino) propiononitrile, N, N-bis (2-hydroxyethyl) -3-aminopropiononitrile, N, N-bis (2- Acetoxyethyl) -3-aminopropiononitrile, N, N-bis (2-formyloxyethyl) -3-aminopropiononitrile, N, N-bis (2-methoxyethyl) -3-aminopropiononitrile, N, N-bis [2- (methoxymethoxy) ethyl] -3-aminopropiononitrile, methyl N- (2-cyanoethyl) -N- (2-methoxyethyl) -3-aminopropionate, N- (2 -Cyanoethyl) -N- (2-hydroxyethyl) -3-aminopropionic acid methyl, N- (2-acetoxyethyl) -N- (2-cyanoethyl) Methyl 3-aminopropionate, N- (2-cyanoethyl) -N-ethyl-3-aminopropiononitrile, N- (2-cyanoethyl) -N- (2-hydroxyethyl) -3-aminopropiononitrile, N- (2-acetoxyethyl) -N- (2-cyanoethyl) -3-aminopropiononitrile, N- (2-cyanoethyl) -N- (2-formyloxyethyl) -3-aminopropiononitrile, N -(2-cyanoethyl) -N- (2-methoxyethyl) -3-aminopropiononitrile, N (2-cyanoethyl) -N- [2- (methoxymethoxy) ethyl] -3-aminopropiononitrile, N -(2-cyanoethyl) -N- (3-hydroxy-1-propyl) -3-aminopropiononitrile, N- (3-acetoxy-1-propionitrile ) -N- (2-cyanoethyl) -3-aminopropiononitrile, N- (2-cyanoethyl) -N- (3-formyloxy-1-propyl) -3-aminopropiononitrile, N- (2- Cyanoethyl) -N-tetrahydrofurfuryl-3-aminopropiononitrile,

N, N-bis (2-cyanoethyl) -3-aminopropiononitrile, diethylaminoacetonitrile, N, N-bis (2-hydroxyethyl) aminoacetonitrile, N, N-bis (2-acetoxyethyl) aminoacetonitrile, N , N-bis (2-formyloxyethyl) aminoacetonitrile, N, N-bis (2-methoxyethyl) aminoacetonitrile, N, N-bis [2- (methoxymethoxy) ethyl] aminoacetonitrile, N-cyanomethyl-N -(2-methoxyethyl) -3-aminopropionic acid methyl, N-cyanomethyl-N- (2-hydroxyethyl) -3-aminopropionic acid methyl, N- (2-acetoxyethyl) -N-cyanomethyl-3- Methyl aminopropionate, N-cyanomethyl-N- (2-hydroxy Til) aminoacetonitrile, N- (2-acetoxyethyl) -N- (cyanomethyl) aminoacetonitrile, N-cyanomethyl-N- (2-formyloxyethyl) aminoacetonitrile, N-cyanomethyl-N- (2-methoxyethyl) Aminoacetonitrile, N-cyanomethyl-N- [2- (methoxymethoxy) ethyl] aminoacetonitrile, N- (cyanomethyl) -N- (3-hydroxy-1-propyl) aminoacetonitrile, N- (3-acetoxy-1- Propyl) -N- (cyanomethyl) aminoacetonitrile, N-cyanomethyl-N- (3-formyloxy-1-propyl) aminoacetonitrile, N, N-bis (cyanomethyl) aminoacetonitrile, 1-pyrrolidinepropiononitrile, 1- Piperidine propiono Tolyl, 4-morpholine propiononitrile, 1-pyrrolidine acetonitrile, 1-piperidine acetonitrile,

4-morpholine acetonitrile, cyanomethyl 3-diethylaminopropionate, N, N
-Cyanomethyl bis (2-hydroxyethyl) -3-aminopropionate, cyanomethyl N, N-bis (2-acetoxyethyl) -3-aminopropionate, N, N-bis (2-formyloxyethyl) -3- Cyanomethyl aminopropionate, cyanomethyl N, N-bis (2-methoxyethyl) -3-aminopropionate, cyanomethyl N, N-bis [2- (methoxymethoxy) ethyl] -3-aminopropionate, 3-diethylaminopropion Acid (2-cyanoethyl), N, N-bis (2-hydroxyethyl) -3-aminopropionic acid (2-cyanoethyl), N, N-bis (2-acetoxyethyl) -3-aminopropionic acid (2- Cyanoethyl), N, N-bis (2-formyloxyethyl) -3-aminopropionic acid (2-sia Ethyl), N, N-bis (2-methoxyethyl) -3-aminopropionic acid (2-cyanoethyl), N, N-bis [2- (methoxymethoxy) ethyl] -3-aminopropionic acid (2-cyanoethyl) ), Cyanomethyl 1-pyrrolidinepropionate, cyanomethyl 1-piperidinepropionate, cyanomethyl 4-morpholinepropionate, 1-pyrrolidinepropionic acid (2-cyanoethyl), 1-piperidinepropionic acid (2-cyanoethyl), 4-morpholinepropionic acid (2-cyanoethyl) is exemplified.

  As the nitrogen-containing basic compound, 1,5-diazabicyclo [4.3.0] -5-nonene, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,4-diazabicyclo [ 2.2.2] Octane, 4-dimethylaminopyridine, 1-naphthylamine, piperidines, hexamethylenetetramine, imidazoles, hydroxypyridines, pyridines, anilines, hydroxyalkylanilines, 4,4′-diaminodiphenyl ether , Pyridinium p-toluenesulfonate, 2,4,6-trimethylpyridinium p-toluenesulfonate, tetramethylammonium p-toluenesulfonate, tetrabutylammonium lactate, triethylamine, tributylamine, tripentylamine, tri-n-octylami , Tri-i-octylamine, tris (ethylhexyl) amine, tridecylamine, tridodecylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, Tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine, cyclohexyldimethylamine, methyldicyclohexylamine, ethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, Tetramethylenediamine, hexamethylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 4,4′-diaminobenzophenone, 4,4′-diaminodiphenylamine,

2,2-bis (4-aminophenyl) propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane, 2- (4-aminophenyl) -2- (3-hydroxyphenyl) propane 2- (4-aminophenyl) -2- (4-hydroxyphenyl) propane, 1,4-bis [1- (4-aminophenyl) -1-methylethyl] benzene, 1,3-bis [1- (4-Aminophenyl) -1-methylethyl] benzene, bis (2-dimethylaminoethyl) ether, bis (2-diethylaminoethyl) ether, N, N, N ′, N′-tetrakis (2-hydroxypropyl) Tri (cyclo) alkylamines such as ethylenediamine and tricyclohexylamine, aniline, N-methylaniline, N, N-dimethylaniline, 2-methylamine Aromatic amines such as phosphorus, 3-methylaniline, 4-methylaniline, 4-nitroaniline, diphenylamine, triphenylamine, naphthylamine, 2,6-diisopropylaniline, polyethyleneimine, polyallylamine, 2-dimethylaminoethylacrylamide Nt-butoxycarbonyldi-n-octylamine, Nt-butoxycarbonyldi-n-nonylamine, Nt-butoxycarbonyldi-n-decylamine,

Nt-butoxycarbonyldicyclohexylamine, Nt-butoxycarbonyl-1
Adamantylamine, Nt-butoxycarbonyl-N-methyl-1-adamantylamine, N, N-di-t-butoxycarbonyl-1-adamantylamine, N, N-di-t-butoxycarbonyl-N-methyl -1-adamantylamine, Nt-butoxycarbonyl-4,4′-diaminodiphenylmethane, N, N′-di-t-butoxycarbonylhexamethylenediamine, N, N, N′N′-tetra-t-butoxy Carbonylhexamethylenediamine, N, N′-di-t-butoxycarbonyl-1,7-diaminoheptane, N, N′-di-t-butoxycarbonyl-1,8-diaminooctane, N, N′-di- t-butoxycarbonyl-1,9-diaminononane, N, N′-di-t-butoxycarbonyl-1,10-diaminodecane, N, N′- -t- butoxycarbonylamino-1,12-diamino dodecane, N, N'-di -t- butoxycarbonylamino-4,4'-diaminodiphenylmethane, N-t-butoxycarbonyl-benzimidazole,

Nt-butoxycarbonyl-2-methylbenzimidazole, Nt-butoxycarbonyl-2-phenylbenzimidazole, formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N -Dimethylacetamide, propionamide, benzamide, pyrrolidone, N-methylpyrrolidone, urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3- Imidazoles such as diphenylurea, tri-n-butylthiourea, imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, benzimidazole, 2-phenylbenzimidazole, pyridine, 2-methylpyridine, 4-methylpi Gin, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, 2-methyl-4-phenylpyridine, nicotine, nicotinic acid, nicotinamide, quinoline, 4-hydroxyquinoline, 8-oxy Pyridines such as quinoline and acridine, piperazine, piperazines such as 1- (2-hydroxyethyl) piperazine, pyrazine, pyrazole, pyridazine, quinosaline, purine, pyrrolidine, piperidine, 3-piperidino-1,2-propanediol, morpholine 4-methylmorpholine, 1,4-dimethylpiperazine and the like.

  Among these, 1,5-diazabicyclo [4.3.0] -5-nonene, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,4-diazabicyclo [2.2.2] Octane, 4-dimethylaminopyridine, 1-naphthylamine, piperidine, 4-hydroxypiperidine, 2,2,6,6-tetramethyl-4-hydroxypiperidine, hexamethylenetetramine, imidazoles, hydroxypyridines, pyridines, 4 , 4'-diaminodiphenyl ether, triethylamine, tributylamine, tripentylamine, tri-n-octylamine, tris (ethylhexyl) amine, tridodecylamine, N, N-di-hydroxyethylaniline, N-hydroxyethyl-N- Nitrogen-containing basic compounds such as ethylaniline are particularly preferred. Yes.

The chemically amplified resist composition for immersion process of the present invention can further use a basic ammonium salt as the basic compound. Specific examples of the basic ammonium salt include the following compounds, but are not limited thereto.
Specifically, ammonium hydroxide, ammonium triflate, ammonium pentaflate, ammonium heptaflate, ammonium nonaflate, ammonium undecaflate, ammonium tridecaflate, ammonium pentadecaflate, ammonium methylcarboxylate, ammonium ethylcarboxylate, Ammonium propyl carboxylate, ammonium butyl carboxylate, ammonium heptyl carboxylate, ammonium hexyl carboxylate, ammonium octyl carboxylate, ammonium nonyl carboxylate, ammonium decyl carboxylate, ammonium undecyl carboxylate, ammonium dodecadecyl carboxylate, ammonium salt Decyl carboxylate, ammonium tetradecyl carboxylate, ammonium pentadecyl carboxylate, ammonium hexadecyl carboxylate, ammonium heptadecyl carboxylate, ammonium octadecyl carboxylate and the like.

  Specific examples of ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, and tetraheptyl. Ammonium hydroxide, methyltrioctylammonium hydroxide, tetraoctylammonium hydroxide, didecyldimethylammonium hydroxide, tetrakisdecylammonium hydroxide, dodecyltrimethylammonium hydroxide, dodecylethyldimethylammonium hydroxide, didodecyldimethylammonium hydroxide, Tridodecylmethylammonium hydro Sid, myristyl trimethyl ammonium hydroxide, dimethyl tetradecyl ammonium hydroxide, hexadecyltrimethylammonium hydroxide, octadecyltrimethylammonium hydroxide,

Dimethyldioctadecylammonium hydroxide, tetraoctadecylammonium hydroxide, diallyldimethylammonium hydroxide, (2-chloroethyl) -trimethylammonium hydroxide, (2-bromoethyl) trimethylammonium hydroxide, (3-bromopropyl) -trimethylammonium hydroxy (3-bromopropyl) triethylammonium hydroxide, glycidyltrimethylammonium hydroxide, choline hydroxide, (R)-(+)-(3-chloro-2-hydroxypropyl) trimethylammonium hydroxide, (S)- (−)-(3-Chloro-2-hydroxypropyl) -trimethylammonium hydroxide, (3-chloro-2-hydroxypropyl) -trimethylan Nium hydroxide, (2-aminoethyl) -trimethylammonium hydroxide, hexamethonium hydroxide, decamethonium hydroxide, 1-azoniapropellan hydroxide, petronium hydroxide, 2-chloro-1,3-dimethyl Examples include 2-imidazolinium hydroxide and 3-ethyl-2-methyl-2-thiazolinium hydroxide.

The basic compound can be used alone or in combination of two or more, and it is more preferable to use two or more.
The amount of the basic compound used is generally 0.001 to 10% by mass, preferably 0.01 to 5% by mass, based on the solid content of the chemically amplified resist composition for immersion process, as a total amount.

(F) A dissolution inhibiting compound having a molecular weight of 3000 or less, which decomposes by the action of an acid and increases the solubility in an alkaline developer. The chemically amplified resist composition for immersion process of the present invention is decomposed by the action of an acid. It is preferable to contain a dissolution inhibiting compound having a molecular weight of 3000 or less (hereinafter also referred to as “dissolution inhibiting compound”) that increases the solubility in an alkali developer.
As a dissolution inhibiting compound, it contains an acid-decomposable group such as a cholic acid derivative containing an acid-decomposable group described in Proceeding of SPIE, 2724, 355 (1996) in order not to lower the permeability below 220 nm. Preferred are alicyclic or aliphatic compounds. Examples of the acid-decomposable group and alicyclic structure are the same as those described for the resin as the component (A).
The molecular weight of the dissolution inhibiting compound in the present invention is 3000 or less, preferably 300 to 3000, and more preferably 500 to 2500.

  The addition amount of the dissolution inhibiting compound is preferably 1 to 30% by mass, more preferably 2 to 20% by mass, based on the solid content of the chemically amplified resist composition for immersion process.

  Specific examples of the dissolution inhibiting compound are shown below, but are not limited thereto.

(G) Alkali-soluble resin The chemically amplified resist composition for an immersion process of the present invention can further contain a resin soluble in an alkali developer, thereby improving the sensitivity.
In the present invention, a novolak resin having a molecular weight of about 1000 to 20000 and a polyhydroxystyrene derivative having a molecular weight of about 3000 to 50000 can be used as such a resin, since these have a large absorption with respect to light of 250 nm or less. It is preferable to use a partly hydrogenated amount or 30% by mass or less of the total resin amount.
A resin having a carboxyl group as an alkali-soluble group can also be used. The resin having a carboxyl group preferably has a monocyclic or polycyclic alicyclic hydrocarbon group in order to improve dry etching resistance. Specifically, a methacrylic acid ester and (meth) acrylic acid copolymer having an alicyclic hydrocarbon structure that does not exhibit acid decomposability, or a (meth) acrylic acid ester having an alicyclic hydrocarbon group having a carboxyl group at the terminal And the like.
The addition amount of such an alkali-soluble resin is usually 30% by mass or less based on the total amount of the resin including the acid-decomposable resin.

(H) Carboxylic acid onium salt The chemical amplification resist composition for immersion process of the present invention may contain a carboxylic acid onium salt.
Examples of carboxylic acid onium salts in the present invention include carboxylic acid sulfonium salts, carboxylic acid iodonium salts, and carboxylic acid ammonium salts. In particular, as the carboxylic acid onium salt, an iodonium salt and a sulfonium salt are preferable. Furthermore, in the carboxylic acid onium salt of the present invention, it is preferable that the carboxylate residue does not contain an aromatic group or a carbon-carbon double bond. As a particularly preferable anion moiety, a linear, branched, monocyclic or polycyclic alkylcarboxylic acid anion having 1 to 30 carbon atoms is preferable. More preferably, an anion of a carboxylic acid in which some or all of these alkyl groups are fluorine-substituted is preferable. The alkyl chain may contain an oxygen atom. This ensures transparency with respect to light of 220 nm or less, improves sensitivity and resolution, and improves density dependency and exposure margin.

  Fluoro-substituted carboxylic acid anions include fluoroacetic acid, difluoroacetic acid, trifluoroacetic acid, pentafluoropropionic acid, heptafluorobutyric acid, nonafluoropentanoic acid, perfluorododecanoic acid, perfluorotridecanoic acid, perfluorocyclohexanecarboxylic acid, 2 , 2-bistrifluoromethylpropionic acid anion and the like.

  These carboxylic acid onium salts can be synthesized by reacting sulfonium hydroxide, iodonium hydroxide, ammonium hydroxide and carboxylic acid with silver oxide in a suitable solvent.

  The content of the carboxylic acid onium salt in the composition is usually 0.1 to 20% by mass, preferably 0.5 to 10% by mass, more preferably 1 to 7% by mass, based on the total solid content of the composition. It is.

(I) Other Additives The chemical amplification resist composition for immersion process of the present invention may further contain dyes, plasticizers, photosensitizers, and compounds that promote solubility in a developer (for example, as necessary) , A phenol compound having a molecular weight of 1000 or less, an alicyclic compound having a carboxyl group, or an aliphatic compound).

Such phenol compounds having a molecular weight of 1000 or less can be obtained by referring to, for example, the methods described in JP-A-4-1222938, JP-A-2-28531, US Pat. No. 4,916,210, European Patent 219294, etc. It can be easily synthesized by those skilled in the art.
Specific examples of alicyclic or aliphatic compounds having a carboxyl group include carboxylic acid derivatives having a steroid structure such as cholic acid, deoxycholic acid, lithocholic acid, adamantane carboxylic acid derivatives, adamantane dicarboxylic acid, cyclohexane carboxylic acid, cyclohexane Examples thereof include, but are not limited to, dicarboxylic acids.

(J) Pattern Forming Method The chemical amplification resist composition for immersion process according to the present invention is prepared by dissolving each component in a predetermined solvent, preferably the mixed solvent, and applying the solution onto a predetermined support as follows. Use.
That is, a chemical amplification resist composition for immersion process is applied to a substrate (eg, silicon / silicon dioxide coating) used for manufacturing a precision integrated circuit element by an appropriate coating method such as a spinner or a coater. It is applied with a thickness (usually 50 to 500 nm). It is also preferable to provide an antireflection film on the substrate and form a resist film thereon.

After the application, the resist applied by spin or baking is dried to form a resist film, and then exposed (immersion exposure) through an immersion liquid through a mask for pattern formation. For example, the exposure is performed in a state where the space between the resist film and the optical lens is filled with the immersion liquid. The exposure amount can be set as appropriate, but is usually 1 to 100 mJ / cm ² . After exposure, preferably spin or / and bake, develop and rinse to obtain a good pattern.
Baking is preferably performed after exposure, and the baking temperature is usually 30 to 300 ° C. The time from the exposure to the baking process should be short.
Here, as the exposure light, it is possible to list far ultraviolet rays having a wavelength of preferably 250 nm or less, more preferably 220 nm or less. Specific examples include KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (157 nm), X-rays, and the like, and ArF excimer laser (193 nm) is more preferable.

Examples of the substrate include ordinary BareSi substrates and SOG substrates, and examples of the antireflection film include inorganic film types such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon, and α-silicon, and light absorption. An organic film type composed of an agent and a polymer material can be used.
Examples of the organic antireflection film include a condensate of a diphenylamine derivative and a formaldehyde-modified melamine resin described in JP-B-7-69611, an alkali-soluble resin, a light absorber, and maleic anhydride copolymer described in US Pat. No. 5,294,680. A reaction product of a coalescence and a diamine type light absorbing agent, a resin binder described in JP-A-6-186863 and a methylolmelamine thermal crosslinking agent, a carboxylic acid group, an epoxy group and a light-absorbing group described in JP-A-6-118656. An acrylic resin-type antireflection film in the same molecule, a composition comprising methylol melamine and a benzophenone-based light absorber described in JP-A-8-7115, and a low-molecular light absorber added to a polyvinyl alcohol resin described in JP-A-8-179509 And the like.
As the organic antireflection film, DUV30 series manufactured by Brewer Science, DUV-40 series, ARC25, AC-2, AC-3, AR19, AR20 manufactured by Shipley, ARC29A manufactured by Nissan Chemical Co., etc. can be used. .

  The change in performance observed when the resist is applied to pattern formation by immersion exposure is considered to be derived from the fact that the resist surface is in contact with the immersion liquid.

Hereinafter, the immersion liquid used for the immersion exposure will be described.
The immersion liquid is preferably a liquid that is transparent to the exposure wavelength and has a refractive index temperature coefficient as small as possible so as to minimize distortion of the optical image projected onto the resist. In the case of an ArF excimer laser (wavelength: 193 nm), it is preferable to use water from the viewpoints of availability and ease of handling in addition to the above-described viewpoints.
When water is used as the immersion liquid, the surface tension of the water is decreased and the surface activity is increased, so that the resist layer on the wafer is not dissolved and the influence on the optical coating on the lower surface of the lens element can be ignored. An additive (liquid) may be added in a small proportion. The additive is preferably an aliphatic alcohol having a refractive index substantially equal to that of water, and specifically includes methyl alcohol, ethyl alcohol, isopropyl alcohol and the like. By adding an alcohol having a refractive index substantially equal to that of water, even if the alcohol component in water evaporates and the content concentration changes, an advantage that the change in the refractive index of the entire liquid can be extremely small can be obtained. On the other hand, when an opaque substance or impurities whose refractive index is significantly different from that of water are mixed with respect to 193 nm light, the optical image projected on the resist is distorted. Therefore, distilled water is preferable as the water to be used. Further, pure water filtered through an ion exchange filter or the like may be used.
The electrical resistance of water is desirably 18.3 M ohm · cm or more, and the TOC (organic concentration) is desirably 20 ppb or less. Moreover, it is desirable to have deaerated.
Lithography performance can be improved by increasing the refractive index of the immersion liquid.
From such a viewpoint, an additive that increases the refractive index may be added to water, or heavy water (D ₂ O) may be used instead of water.

In order to prevent the resist film from coming into direct contact with the immersion liquid between the resist film made of the chemically amplified resist for immersion process of the present invention and the immersion liquid, an immersion liquid hardly soluble film (hereinafter referred to as “top coat”). May also be provided. The necessary functions for the top coat are suitability for application to the upper layer of the resist, radiation, especially transparency to 193 nm, and poor immersion liquid solubility. It is preferable that the top coat is not mixed with the resist and can be uniformly applied to the resist upper layer.
From the viewpoint of 193 nm transparency, the topcoat is preferably a polymer that does not contain an aromatic, and specifically, a hydrocarbon polymer, an acrylate polymer, a polymethacrylic acid, a polyacrylic acid, a polyvinyl ether, a silicon-containing polymer, And fluorine-containing polymers.
When peeling the top coat, a developer may be used, or a separate release agent may be used. As the release agent, a solvent having a small penetration into the resist is preferable. It is preferable that the peeling process can be performed with an alkali developer in that the peeling process can be performed simultaneously with the resist development process. From the viewpoint of peeling with an alkaline developer, the topcoat is preferably acidic, but may be neutral or alkaline from the viewpoint of non-intermixability with the resist.
The resolution is improved when there is no difference in refractive index between the topcoat and the immersion liquid. When the exposure light source is an ArF excimer laser (wavelength: 193 nm), it is preferable to use water as the immersion liquid. Therefore, the top coat for the immersion process should be close to the refractive index of water (1.44). preferable. A thin film is more preferable from the viewpoint of transparency and refractive index.

Examples of the alkali developer used in the development process include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, and primary amines such as ethylamine and n-propylamine. Secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide and the like Examples include alkaline aqueous solutions such as quaternary ammonium salts, cyclic amines such as pyrrole and pihelidine.
Furthermore, alcohols and surfactants can be added in appropriate amounts to the alkaline aqueous solution.
As the rinsing liquid, pure water can be used, and an appropriate amount of a surfactant can be added.
The alkali concentration of the alkali developer is usually from 0.1 to 20% by mass.
The pH of the alkali developer is usually from 10.0 to 15.0.

  Further, after the development process or the rinsing process, a process of removing the developer or the rinsing liquid adhering to the pattern with a supercritical fluid can be performed.

  EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, the content of this invention is not limited by this.

Synthesis Example 1 (Synthesis of resin (P1))
Norbornane lactone acrylate, hydroxyadamantane methyl acrylate, 1-adamantyl-1-methylethyl methacrylate and p-hexafluoroalcohol styrene are charged at a ratio of 40/20/30/10 (molar ratio), and propylene glycol monomethyl ether acetate / propylene glycol. It melt | dissolved in monomethyl ether = 60/40 (mass ratio), and 450 g of solutions with a solid content concentration of 22 mass% were prepared.
1 mol% of Wako Pure Chemical Industries polymerization initiator V-601 was added to this solution as a polymerization initiator, and this was heated to 80 ° C. over 6 hours in a nitrogen atmosphere. Propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether = 60 / 40 (mass ratio) was added dropwise to 50 g of the mixed solution.
The reaction liquid was stirred for 2 hours after completion | finish of dripping. After completion of the reaction, the reaction solution was cooled to room temperature, crystallized in 5 L of a mixed solvent of hexane / ethyl acetate = 9/1 (mass ratio), the precipitated white powder was collected by filtration, and the target resin (P1) Was recovered.
The weight average molecular weight in terms of standard polystyrene determined by GPC measurement was 8900, and the degree of dispersion was 1.96.

Resins (P2) to (P7) were synthesized in the same manner by changing the type and amount of the monomer.
Monomer composition of each resin, weight average molecular weight, dispersity (Mw / Mn), molecular weight 10
The content of 0 or less oligomer component is described below.

[Preparation of positive resist composition]
As shown in Table 2, the resin (2 g) synthesized in the above synthesis example, the photoacid generator, the organic basic compound, and the surfactant in the amounts shown in Table 2 were blended, and the solid content was 11% by mass. After dissolving in the solvent shown in No. 2, the positive resist compositions of Examples 1 to 6 and Comparative Examples 1 and 2 were prepared by filtering with a microfilter having a pore diameter of 0.1 μm. In addition, the ratio in the case of using two or more about each component in Table 2 is a mass ratio.

The symbol of each component in Table 2 shows the following.
The symbols for the acid generator correspond to those exemplified above.
[Surfactant]
W-1: MegaFuck F176 (Dainippon Ink Chemical Co., Ltd.) (Fluorine)
W-2: Megafuck R08 (Dainippon Ink Chemical Co., Ltd.)
(Fluorine and silicone)
W-3: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.)

[Basic compounds]
1: N, N-dihydroxyethylaniline 2: N, N-dibutylaniline 3: trioctylamine 4: triphenylimidazole 5: 2,6-diisopropylaniline 6: triethylamine

〔solvent〕
S1: Propylene glycol monomethyl ether acetate S2: Propylene glycol monomethyl ether S3: γ-butyrolactone S4: Cyclohexanone S5: Butyl acetate

[Profile]
An organic antireflection film ARC29A (Nissan Chemical Co., Ltd.) was applied onto a silicon wafer and baked at 205 ° C. for 60 seconds to form a 78 nm antireflection film. The resist composition prepared thereon was applied and baked at 115 ° C. for 60 seconds to form a 150 nm resist film. The wafer thus obtained was subjected to two-beam interference exposure using the apparatus shown in FIG. 1, using water as the immersion liquid. Here, a prism that forms a 90 nm line and space pattern was used. Then, after heating at 125 ° C. for 60 seconds, development was performed with an aqueous tetramethylammonium hydroxide solution (2.38 mass%) for 60 seconds, rinsing with pure water, and spin drying to obtain a resist pattern. The line width of the resist was observed with a scanning electron microscope (S-9220 manufactured by Hitachi), and the edge roughness profile at a line width of 90 nm was observed.
In the apparatus shown in FIG. 1, 1 is a laser, 2 is an aperture, 3 is a shutter, 4, 5 and 6 are reflection mirrors, 7 is a condenser lens, 8 is a prism, 9 is an immersion liquid, 10 Denotes a wafer provided with an antireflection film and a resist film, and 11 denotes a wafer stage.
In the resist pattern cross section, the width of the central portion of the pattern at a height of 75 nm from the antireflection film was A, and the width of the bottom of the pattern in contact with the antireflection film was B. The smaller the value, the smaller the tailing.
Bottoming value (%) = [(B−A) / 2B] × 100

[Changes in line edge roughness (LER) due to wet exposure]
(Exposure condition 1: dry exposure)
An organic antireflection film ARC29A (Nissan Chemical Co., Ltd.) was applied onto a silicon wafer and baked at 205 ° C. for 60 seconds to form a 78 nm antireflection film. The resist composition prepared thereon was applied and baked at 115 ° C. for 60 seconds to form a 200 nm resist film. The obtained wafer was subjected to pattern exposure using an ArF excimer laser scanner (PAS5500 / 1100, NA0.75, manufactured by ASLM). Thereafter, heating was performed at 120 ° C. for 60 seconds, followed by development with an aqueous tetramethylammonium hydroxide solution (2.38 mass%) for 60 seconds, rinsing with pure water, and spin drying to obtain a resist pattern.

(Exposure condition 2: wet exposure)
An organic antireflection film ARC29A (Nissan Chemical Co., Ltd.) was applied onto a silicon wafer and baked at 205 ° C. for 60 seconds to form a 78 nm antireflection film. The resist composition prepared thereon was applied and baked at 115 ° C. for 60 seconds to form a 200 nm resist film. The resulting wafer was treated with pure water for 60 seconds while forming a paddle, and then subjected to pattern exposure using an ArF excimer laser scanner (PAS5500 / 1100 manufactured by ASLM, NA0.75). Further, pure water treatment was performed for 60 seconds immediately after exposure. Thereafter, the mixture was heated at 120 ° C. for 60 seconds, and then added with an aqueous tetramethylammonium hydroxide solution (2.38% by mass).
After developing for 2 seconds and rinsing with pure water, spin drying was performed to obtain a resist pattern.

About the resist pattern obtained by the said 2 types of exposure method, the line width was observed with the scanning electron microscope (Hitachi S-9220), and the edge roughness (LER) in the line width of 110 nm was observed. Edge roughness is measured by using a length-measuring scanning electron microscope (SEM) to detect line pattern edges at a plurality of positions in the measurement monitor, and the dispersion (3σ) of the variation in the detected positions is detected as line edge roughness. An index of (LER) was used.
Then, (| K2−K1 | / K1) × 100 (%) where the LER for the pattern under the exposure conditions 1 and 2 is K1 and K2, respectively, was used as an index of the LER fluctuation due to the wet exposure.

  From the results shown in Table 2, it can be seen that the positive resist composition of the present invention is excellent in pattern exposure, small in line edge roughness, and excellent in immersion exposure.

It is the schematic of a two-beam interference exposure experiment apparatus.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Laser 2 Aperture 3 Shutter 4, 5, 6 Reflection mirror 7 Condensing lens 8 Prism 9 Immersion liquid 10 Wafer having antireflection film and resist film 11 Wafer stage

Claims (4)

(A) A resin containing a repeating unit represented by any one of the general formulas (A-1-1) to (A-1-3), whose dissolution rate in an alkaline developer is increased by the action of an acid,
(B) a compound that generates an acid upon irradiation with actinic rays or radiation, and
(C) A positive resist composition for an immersion process, comprising a solvent.
R ₁ represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group or an alkoxy group.
L ₁ and L ₂ represent a single bond or a divalent linking group.
A ₁ represents an alicyclic group which may have a lactone structure.
J represents a fluorine atom or a substituent having a fluorine atom.
p represents an integer of 1 to 3. The resin (A) is further represented by the repeating unit having a lactone structure represented by the general formula (A-2), the repeating unit represented by the general formula (A-3), and the general formula (A-4). The positive resist composition for an immersion process according to claim 1, further comprising a repeating unit having a group that decomposes under the action of an acid.
R _{2 to} R ₄ each independently represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group or an alkoxy group.
L ₃ represents a single bond or a divalent linking group.
B represents a ring having a lactone structure.
K represents a chlorine atom, a hydroxyl group, a cyano group, or an alkyl group or alkoxy group having no fluorine atom.
q represents an integer of 1 to 3.
ADG represents an acid-decomposable group. The resin (A) has at least one group represented by the following general formula (Z) as J in the general formulas (A-1-1) to (A-1-3). 3. A positive resist composition for immersion process according to 1 or 2.
R _{50 to} R ₅₅ each independently represents a hydrogen atom, a fluorine atom or an alkyl group.
However, at least one of R _{50 to} R ₅₅ represents a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. R ₄₀ represents a hydrogen atom, an alkyl group, a cycloalkyl group or an acyl group.   A pattern forming method comprising the steps of: forming a resist film from the chemically amplified resist composition for immersion process according to any one of claims 1 to 3; and exposing and developing the resist film. .