JP2005309376A - Positive resist composition for liquid immersion exposure and method for forming pattern by using same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a positive resist composition suitable for liquid immersion exposure and improved in such problems as collapse of a resist pattern due to post exposure delay between steps of exposure and PEB (post exposure bake), deterioration in the profile and production of scum during liquid immersion exposure, and to provide a method for forming a pattern by using the composition. <P>SOLUTION: The positive resist composition for liquid immersion exposure comprises: (A) a resin having a monocyclic or polycyclic alicyclic hydrocarbon structure and having the solubility with an alkali developing solution which increases by the effect of an acid; (B) a compound which generates an acid by irradiation with actinic rays or radiation; (C) a nitrogen-containing compound having no hydroxyl group; and (D) solvent. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a positive 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 also in a lithography process for other photo applications, and a pattern forming method using the same. It is. In particular, the present invention relates to a positive 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 wavelength of the exposure light source has been shortened and the projection lens has a high numerical aperture (high NA). At present, an exposure machine with NA 0.84 using an ArF excimer laser having a wavelength of 193 nm as a light source has been developed. ing. 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
Where 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 F ₂ excimer laser having a wavelength of 157 nm as a light source has been studied for higher resolution by further shortening the wavelength. Lens materials and resists used in the exposure apparatus for shorter wavelength have been studied. Because the materials used in the process are very limited, it is very difficult to stabilize the manufacturing cost and quality of the apparatus and materials, and the exposure apparatus and resist that have sufficient performance and stability within the required period are not in time. The possibility is coming 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 image exposure pattern of a semiconductor element include Patent Document 1 (Japanese Patent Publication No. 57-153433), Patent Document 2 (Japanese Patent Laid-Open No. 7-220990), and Patent Document 3 ( Japanese Patent Publication No. 63-49893), but a resist suitable for the immersion exposure technique is not discussed.
Patent Document 4 (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.
Recent progress of immersion exposure technology is reported in Non-Patent Document 1 (SPIE Proc 4688, 11 (2002)), Non-Patent Document 2 (J. Vac. Sci. Tecnol. B, 17 (1999)), and the like. In the case of using an ArF excimer laser as a light source, pure water (refractive index at 193 nm: 1.44) is considered to be most promising as an immersion liquid in terms of handling safety, transmittance at 193 nm, and refractive index. .
When an F ₂ excimer laser is used as a light source, a solution containing fluorine has been studied from the balance between transmittance and refractive index at 157 nm. However, a sufficient product has not yet been seen in terms of environmental safety and refractive index. It has not been issued. From the degree of immersion effect and the degree of completeness of the resist, the immersion exposure technique is considered to be installed in the ArF exposure machine earliest.

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. 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 during exposure, and the generated acid is used as a reaction catalyst in post-exposure baking (PEB). In this image forming method, the alkali-insoluble group is changed to an alkali-soluble group, and the exposed portion is removed by alkali development.
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. It is expected that the penetration into the resist film will affect the chemical reaction (acid-catalyzed deprotection reaction, development reaction) caused in the resist during or after exposure. But I still do n’t know.

  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 a major problem at the beginning of the development of chemically amplified positive resists. Exposure to PEB (PED: PostExposuretimeDelay) caused an environmental loss of the exposed area caused by a very small amount of basic contamination from the environment at several ppb level. Although it seems to be very similar to life, the influence and mechanism of immersion exposure on the resist have not been clarified yet.

  For example, when a chemically amplified resist that does not have a problem with lithography in normal exposure is subjected to immersion exposure, the resist pattern collapses, profile deterioration, and scum occur, and improvement is necessary. Further, if the wafer is moved quickly during the immersion, the followability of the immersion liquid is poor, so that there is a problem that a portion between the lens and the resist on the wafer is not filled with the immersion liquid.

  Very recently, as resist compositions used for immersion exposure, for example, Patent Document 5 (International Publication No. 2004-068242 pamphlet), Patent Document 6 (International Publication No. 2004-074937 pamphlet) and the like have been introduced. began. However, further performance improvement is required.

Japanese Patent Publication No.57-153433 JP-A-7-220990 Japanese Examined Patent Publication No. 63-49893 JP-A-10-303114 International Publication No. 2004-068242 Pamphlet International Publication No. 2004-074937 Pamphlet Proc. SPIE, 2002, Vol. 4688, p. 11 J.Vac.Sci.Tecnol.B, 17 (1999)

  An object of the present invention is to solve the problems of the prior art as described above, in the liquid immersion exposure, the liquid in which the resist pattern collapses due to the placement between the exposure and the PEB, the profile is deteriorated, and the occurrence of scum is improved. It is an object of the present invention to provide a positive resist composition suitable for immersion exposure and a pattern forming method using the same.

  The present invention is a positive resist composition for immersion exposure having the following constitution and a pattern forming method using the same, whereby the above object of the present invention is achieved.

一般式（Ｉ）において、
Ｒ₁〜Ｒ₃は、各々独立にアルキル基またはシクロアルキル基を表す。但し、Ｒ₂またはＲ₃の少なくとも一方はシクロアルキル基であるか、または互いに結合して環を形成する。
３．（Ａ）成分の樹脂が、一般式（１Ａ）で表される繰り返し単位を含有することを特徴とする上記１．または２．に記載の液浸露光用ポジ型レジスト組成物。

式（Ｉ）中、
Ｒ_xは水素原子またはメチル基を表す。
Ｒ_yは炭素数１〜６のアルキル基を表す。
４．（Ｃ）成分の含窒素化合物が酸素原子を含まないことを特徴とする上記１．〜３．のいずれかに記載の液浸露光用ポジ型レジスト組成物。
５．（Ｃ）成分の含窒素化合物の分子量が、１００以上であることを特徴とする上記１．〜４．のいずれかに記載の液浸露光用ポジ型レジスト組成物。
６．（Ａ）成分の樹脂が、フッ素原子を含有することを特徴とする上記１．〜５．のいずれかに記載の液浸露光用ポジ型レジスト組成物。
７．さらに、（Ｆ１）フッ素系ノニオン界面活性剤を含有すること特徴とする上記１．〜６．のいずれかに記載の液浸露光用ポジ型レジスト組成物。
８．さらに、固形分濃度が２．０〜６．０（Ｆ１）フッ素系ノニオン界面活性剤を含有すること特徴とする上記１．〜７．のいずれかに記載の液浸露光用ポジ型レジスト組成物。
９．上記１．〜４．のいずれかに記載のレジスト組成物によりレジスト膜を形成し、該レジスト膜を液浸露光し、現像する工程を含むことを特徴とするパターン形成方法。 1. (A) a resin having a monocyclic or polycyclic alicyclic hydrocarbon structure, which increases the solubility in an alkaline developer 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 exposure, comprising a nitrogen-containing compound containing no hydroxyl group and (D) a solvent.
2. The resin of the component (A) contains a repeating unit having a group represented by the general formula (I). A positive resist composition for immersion exposure as described in 1. above.

In general formula (I):
R _{1 to} R ₃ each independently represents an alkyl group or a cycloalkyl group. However, at least one of R _{2 and} R ₃ is a cycloalkyl group or is bonded to each other to form a ring.
3. The resin of the component (A) contains a repeating unit represented by the general formula (1A). Or 2. A positive resist composition for immersion exposure as described in 1. above.

In formula (I),
R _x represents a hydrogen atom or a methyl group.
R _y represents an alkyl group having 1 to 6 carbon atoms.
4). (1) The nitrogen-containing compound as component (C) does not contain an oxygen atom. ~ 3. The positive resist composition for immersion exposure according to any one of the above.
5). The molecular weight of the nitrogen-containing compound as component (C) is 100 or more. ~ 4. The positive resist composition for immersion exposure according to any one of the above.
6). (1) The resin as component (A) contains a fluorine atom. ~ 5. The positive resist composition for immersion exposure according to any one of the above.
7). Further, (F1) a fluorine-based nonionic surfactant is contained. ~ 6. The positive resist composition for immersion exposure according to any one of the above.
8). Furthermore, the solid content concentration of 2.0 to 6.0 (F1) contains a fluorine-based nonionic surfactant. ~ 7. The positive resist composition for immersion exposure according to any one of the above.
9. Above 1. ~ 4. A pattern forming method comprising the steps of: forming a resist film from the resist composition according to any one of the above; and subjecting the resist film to immersion exposure and development.

  INDUSTRIAL APPLICABILITY According to the present invention, a positive resist composition suitable for immersion exposure improved in resist pattern collapse, profile deterioration, and scum generation due to placement between exposure and PEB during immersion exposure, and use thereof A pattern forming method can be provided.

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 alkaline developer (also referred to as acid-decomposable resin (A))
The resin used for the chemically amplified resist film for immersion exposure according to the present invention is a resin (acid-decomposable resin) that is decomposed by the action of an acid and increases the solubility in an alkali developer, and the main chain or side chain of the resin. Alternatively, it is a resin having a group (hereinafter also referred to as “acid-decomposable group”) that decomposes by the action of an acid to generate an alkali-soluble group in both the main chain and the side chain. The resin of the present invention can be suitably used particularly for ArF immersion exposure.
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 contained in the positive resist composition for immersion exposure of the present invention includes a group represented by the following general formula (I) as a group (acid-decomposable group) that decomposes by the action of an acid to generate an alkali-soluble group. It is preferable that it is resin to have.

In general formula (I):
R _{1 to} R ₃ each independently represents an alkyl group or a cycloalkyl group. However, at least one of R _{2 and} R ₃ is a cycloalkyl group or is bonded to each other to form a ring.

As the alkyl group for R _{1 to} R ₃ , an alkyl group having 1 to 8 carbon atoms is preferable, and examples thereof include a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a 2-hexyl group, and an octyl group. Groups and the like.

The cycloalkyl group of R _{1 to} R ₃ may be monocyclic or polycyclic, and specifically includes 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.
Preferred examples of the cycloalkyl group represented by R _{1 to} R ₃ 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, and a cycloheptyl group. , Cyclooctyl 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. A part of the hydrocarbon in the cycloalkyl group may be substituted with a hetero atom such as an oxygen atom.

The alkyl group and cycloalkyl group in R _{1 to} R ₃ may have a substituent. Examples of the substituent include an alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, a cyano group, and an ester 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, more preferably a methyl group, an ethyl group, a propyl group or 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. The alkyl group and alkoxy group may further have a substituent. Examples of the substituent that the alkyl group and alkoxy group may have include a hydroxyl group, a halogen atom, and an alkoxy group.

However, at least one of R _{2 and} R ₃ is a cycloalkyl group or is bonded to each other to form a ring. When R ₂ and R ₃ are bonded to each other to form a ring, they may be through a hetero atom such as an oxygen atom.

  The repeating unit having a group represented by the general formula (I) may be any repeating unit, but a repeating unit represented by the following general formula (pA) is preferable.

In general formula (pA), R represents a hydrogen atom, a halogen atom, or a substituted or unsubstituted linear or branched alkyl group having 1 to 4 carbon atoms. A plurality of R may be the same or different.
A is a single bond, a group selected from the group consisting of an alkylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a sulfonamide group, a urethane group, or a urea group, or a combination of two or more groups. Represents. The alkylene group may have a substituent.
R < ₁ > -R < ₃ > is synonymous with R < ₁ > -R < ₃ > in general formula (I).

  The repeating unit represented by the general formula (pA) is most preferably a repeating unit of 2-alkyl-2-adamantyl (meth) acrylate and dialkyl (1-adamantyl) methyl (meth) acrylate.

  Specific examples of the repeating unit represented by the general formula (pA) are shown below.

  In the acid-decomposable resin (A), the content of the repeating unit having a group represented by the general formula (I) is preferably 10 to 60 mol%, more preferably 10 to 50 mol% in all repeating structural units. is there.

The acid-decomposable resin (A) may have only the group represented by the general formula (I) as an acid-decomposable group, or may have other acid-decomposable groups in combination. .
Examples of other acid-decomposable groups that the acid-decomposable resin (A) may have include, for example, —O—C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), —O—C (R ₃₆ ). (R ₃₇ ) (OR ₃₉ ), —O—C (═O) —O—C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), —O—C (R ₀₁ ) (R ₀₂ ) (OR ₃₉ ) , —O—C (R ₀₁ ) (R ₀₂ ) —C (═O) —O—C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ) and the like.
In the formula, R _{36 to} R ₃₉ each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. R ₃₆ and R ₃₇ , R ₃₆ and R ₃₉ may be bonded to each other to form a ring.
R _{01 and} R ₀₂ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
Note that —C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ) means a group in which each group represented by R _{36 to} R ₃₈ is bonded to a carbon atom with a single bond. The same shall apply hereinafter.

  The acid-decomposable resin (A) is a repeating unit having an acid-decomposable group including a repeating unit having an acid-decomposable group represented by the general formula (I) and a repeating unit having another acid-decomposable group. The total amount is preferably 10 to 70 mol%, more preferably 20 to 65 mol%, still more preferably 25 to 50 mol% in all repeating units.

  The acid-decomposable resin (A) preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure, and includes an alicyclic hydrocarbon represented by the following general formula (pI) to general formula (pVI). It preferably contains at least one selected from the group consisting of repeating units having a partial structure and a repeating unit represented by the following general formula (II-AB).

  First, the partial structure containing the alicyclic hydrocarbon shown by general formula (pI)-general formula (pVI) is demonstrated.

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.

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 structures represented by the general formulas (pI) to (pVI) in the resin can be used for protecting alkali-soluble groups. Examples of the alkali-soluble group include various groups known in this technical field.

  Specific examples include a carboxylic acid group, a sulfonic acid group, a phenol group, and a thiol group, and a carboxylic acid group and a sulfonic acid group are preferable.

  As the alkali-soluble group protected by the structure represented by the general formulas (pI) to (pVI) in the above resin, the hydrogen atom of the carboxyl group is preferably substituted with the structure represented by the general formula (pI) to (pVI). Structure.

  Specific examples of the repeating unit having a structure in which the hydrogen atom of the carboxyl group is substituted with the structure represented by the general formulas (pI) to (pVI) include, for example, the repeating unit represented by the general formula (pA). The thing similar to a specific example can be mentioned.

  More preferably, the resin of component (A) contains a repeating unit having a group represented by the general formula (1A).

In formula (IA),
R _x represents a hydrogen atom or a methyl group.
R _y represents an alkyl group having 1 to 6 carbon atoms. The alkyl group having 1 to 6 carbon atoms of R _y may be linear or branched, may be unsubstituted, and may further have a substituent. Examples of the substituent that may have include an alkoxy group having 1 to 4 carbon atoms, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an acyl group, an acyloxy group, a cyano group, a hydroxyl group, a carboxy group, An alkoxycarbonyl group, a nitro group, etc. can be mentioned.

  Examples of the repeating unit represented by the formula (IA) include 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, and 2-propyl-2-adamantyl (meth) acrylate. , Repeating units derived from 2-isopropyl-2-adamantyl (meth) acrylate, 2-butyl-2-adamantyl (meth) acrylate, 2- (3-methoxypropyl) -2-adamantyl (meth) acrylate, and the like. . Preferably, repeating units derived from 2-methyl-2-adamantyl (meth) acrylate and 2-ethyl-2-adamantyl (meth) acrylate are used.

  Next, the repeating unit having an alicyclic structure represented by the general formula (II-AB) will be described.

In formula (II-AB):
R ₁₁ ′ and R ₁₂ ′ each independently represents a hydrogen atom, a cyano group, a halogen atom or an alkyl group.
Z ′ represents an atomic group for forming an alicyclic structure containing two bonded carbon atoms (C—C).

  Moreover, it is preferable that the repeating unit represented by the said general formula (II-AB) is a repeating unit represented by the following general formula (II-A) or general formula (II-B).

In formulas (II-A) and (II-B):
R ₁₃ ′ to R ₁₆ ′ each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, —COOH, —COOR ₅ , a group that decomposes by the action of an acid, —C (═O) —XA ′. —R ₁₇ ′ represents an alkyl group or a cyclic hydrocarbon group.
Wherein, R ₅ represents an alkyl group, cyclic hydrocarbon group, or -Y group shown below.
X represents an oxygen atom, a sulfur atom, -NH -, - NHSO ₂ - or an -NHSO ₂ NH-.
A ′ represents a single bond or a divalent linking group.
Further, at least two of R ₁₃ ′ to R ₁₆ ′ may be bonded to form a ring. n represents 0 or 1.
R ₁₇ ′ represents —COOH, —COOR ₅ , —CN, a hydroxyl group, an alkoxy group, —CO—NH—R ₆ , —CO—NH—SO ₂ —R ₆ or the following —Y group.
R ₆ represents an alkyl group or a cyclic hydrocarbon group.

  The -Y group;

In the —Y group, R ₂₁ ′ to R ₃₀ ′ each independently represents a hydrogen atom or an alkyl group. a and b represent 1 or 2.

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.

In the general formula (II-AB), R ₁₁ ′ and R ₁₂ ′ each independently represent a hydrogen atom, a cyano group, a halogen atom, or an alkyl group.
Z ′ represents an atomic group for forming an alicyclic structure containing two bonded carbon atoms (C—C).

Examples of the halogen atom in R ₁₁ ′ and R ₁₂ ′ include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom.

The alkyl group in R ₁₁ ′, R ₁₂ ′, and R ₂₁ ′ to R ₃₀ ′ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms. It is a linear or branched alkyl group, more preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, or a t-butyl group.

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

  The atomic group for forming the alicyclic structure of Z ′ is an atomic group that forms a repeating unit of an alicyclic hydrocarbon which may have a substituent in a resin, and among them, a bridged type alicyclic group. An atomic group for forming a bridged alicyclic structure forming a cyclic hydrocarbon repeating unit is preferred.

Examples of the skeleton of the alicyclic hydrocarbon formed include the same alicyclic hydrocarbon groups as R _{11 to} R _{25 in} the general formulas (pI) to (pVI).

The alicyclic hydrocarbon skeleton may have a substituent. Examples of such a substituent include R ₁₃ ′ to R ₁₆ ′ in the general formula (II-A) or (II-B).

  Among the repeating units having the bridged alicyclic hydrocarbon, the repeating unit represented by the general formula (II-A) or (II-B) is more preferable.

In the repeating unit represented by the general formula (II-AB), the acid-decomposable group may be contained in the aforementioned —C (═O) —XA′—R ₁₇ ′, or Z ′ forms. It may be included as a substituent that the alicyclic structure has.

The structure of the acid-decomposable group is represented by —C (═O) —X ₁ —R ₀ .
In the formula, R ₀ is a tertiary alkyl group such as t-butyl group or t-amyl group, isobornyl group, 1-ethoxyethyl group, 1-butoxyethyl group, 1-isobutoxyethyl group, 1-cyclohexyloxy. 1-alkoxyethyl group such as ethyl group, 1-methoxymethyl group, alkoxymethyl group such as 1-ethoxymethyl group, 3-oxoalkyl group, tetrahydropyranyl group, tetrahydrofuranyl group, trialkylsilyl ester group, 3- An oxocyclohexyl ester group, a 2-methyl-2-adamantyl group, a mevalonic lactone residue and the like can be mentioned. X ₁ has the same meaning as X above.

Examples of the halogen atom in R ₁₃ ′ to R ₁₆ ′ include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom.

The alkyl group in R ₅ , R ₆ and R ₁₃ ′ to R ₁₆ ′ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, more preferably a linear chain having 1 to 6 carbon atoms. Or a branched alkyl group, more preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, or a t-butyl group.

Examples of the cyclic hydrocarbon group in R ₅ , R ₆ and R ₁₃ ′ to R ₁₆ ′ include a cyclic alkyl group and a bridged hydrocarbon group, such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, 2- List methyl-2-adamantyl group, norbornyl group, boronyl group, isobornyl group, tricyclodecanyl group, dicyclopentenyl group, nobornane epoxy group, menthyl group, isomenthyl group, neomenthyl group, tetracyclododecanyl group, etc. Can do.

Examples of the ring formed by combining at least two of R ₁₃ ′ to R ₁₆ ′ include rings having 5 to 12 carbon atoms such as cyclopentene, cyclohexene, cycloheptane, and cyclooctane.

Examples of the alkoxy group for R ₁₇ ′ 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 further substituents in the alkyl group, cyclic hydrocarbon group, and alkoxy group include a hydroxyl group, a halogen atom, a carboxyl group, an alkoxy group, an acyl group, a cyano group, an acyloxy group, an alkyl group, and a cyclic hydrocarbon group. Can do. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group. Examples of the acyl group include a formyl group and an acetyl group. Examples thereof include an acetoxy group.

  Examples of the alkyl group and cyclic hydrocarbon group include those listed above.

  The divalent linking group for A ′ is one or two selected from the group consisting of an alkylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a sulfonamide group, a urethane group, and a urea group. Combinations of the above groups can be mentioned.

Various substituents of R ₁₃ ′ to R ₁₆ ′ in the general formula (II-A) or the general formula (II-B) are atomic groups for forming an alicyclic structure in the general formula (II-AB). Or it becomes a substituent of atomic group Z for forming a bridged alicyclic structure.

  Specific examples of the repeating unit represented by the general formula (II-A) or the general formula (II-B) include the following, but the present invention is not limited to these specific examples.

  In the acid-decomposable resin (A), the content of the repeating unit having a partial structure containing the alicyclic hydrocarbon represented by the general formulas (pI) to (pVI) is 20 to 70 mol% in all repeating structural units. Is more preferable, more preferably 24-65 mol%, still more preferably 28-60 mol%.

  In the acid-decomposable resin (A), the content of the repeating unit represented by the general formula (II-AB) is preferably from 10 to 60 mol%, more preferably from 15 to 55 mol%, more preferably from all repeating structural units. Preferably it is 20-50 mol%.

  In the acid-decomposable resin (A) having a monocyclic or polycyclic alicyclic hydrocarbon structure, the acid-decomposable group represented by the general formula (I) and other acid-decomposable groups are represented by the above general formula ( pI) to a repeating unit having a partial structure containing an alicyclic hydrocarbon represented by formula (pVI), a repeating unit represented by formula (II-AB), and other copolymerization components as described later Any of the repeating units may have.

  Moreover, it is preferable that acid-decomposable resin (A) has a lactone group, More preferably, it represents with either the following general formula (Lc) or the following general formula (III-1)-(III-5). It has a repeating unit having a group having a lactone structure, and the group having a lactone structure may be directly bonded to the main chain.

In general formula (Lc), Ra ₁ , Rb ₁ , Rc ₁ , Rd ₁ , and Re ₁ each independently represent a hydrogen atom or an alkyl group. m and n each independently represents an integer of 0 to 3, and m + n is 2 or more and 6 or less.

In the general formulas (III-1) to (III-5), R _{1b to} R _5b each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylsulfonylimino group, or an alkenyl group. Represents. Two of R _{1b to} R _5b may combine to form a ring.

R _{1 to} Re ₁ alkyl groups in general formula (Lc) and R _{1b to} R _5b alkyl groups, alkoxy groups, alkoxycarbonyl groups, alkyls in general formulas (III-1) to (III-5) Examples of the alkyl group in the sulfonylimino group include linear and branched alkyl groups, which may have a substituent.

  Preferred substituents include an alkoxy group having 1 to 4 carbon atoms, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), an acyl group having 2 to 5 carbon atoms, an acyloxy group having 2 to 5 carbon atoms, and cyano. A group, a hydroxyl group, a carboxy group, an alkoxycarbonyl group having 2 to 5 carbon atoms, a nitro group, and the like.

As the repeating unit having a group having a lactone structure represented by the general formula (Lc) or any one of the general formulas (III-1) to (III-5), the above general formula (II-A) or (II- B) wherein at least one of R ₁₃ ′ to R ₁₆ ′ has a group represented by general formula (Lc) or general formula (III-1) to (III-5) (for example, R in —COOR ₅ ) ₅ represents a group represented by the general formula (Lc) or the general formulas (III-1) to (III-5)), or a repeating unit represented by the following general formula (AI).

In general formula (AI), R _b0 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. As a preferable substituent which the alkyl group of R _b0 may have, as a preferable substituent which the alkyl group as R _1b in the general formulas (III-1) to (III-5) may have. What was illustrated previously is mentioned.

Examples of the halogen atom for R _b0 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. R _b0 is preferably a hydrogen atom.

  A ′ represents a single bond, an ether group, an ester group, a carbonyl group, an alkylene group, or a divalent group obtained by combining these.

B ₂ represents a group represented by general formula (Lc) or any one of general formulas (III-1) to (III-5).

  Specific examples of the repeating unit having a group having a lactone structure are shown below, but the present invention is not limited thereto.

  The acid-decomposable resin (A) may contain a repeating unit having a group represented by the following general formula (IV).

In the general formula _{(IV), R 2 c~R 4} c represents a hydrogen atom or a hydroxyl group independently. However, at least one of R ₂ c to R ₄ c represents a hydroxyl group.

  The group represented by the general formula (IV) is preferably a dihydroxy body or a monohydroxy body, and more preferably a dihydroxy body.

As the repeating unit having a group represented by the general formula (IV), at least one of R ₁₃ ′ to R ₁₆ ′ in the general formula (II-A) or (II-B) is represented by the general formula (IV ) (For example, R _{5 in} —COOR ₅ represents a group represented by the general formula (IV)), or a repeating unit represented by the following general formula (AII). it can.

In general formula (AII), R ₁ c represents a hydrogen atom or a methyl group.
R ₂ c to R ₄ c each independently represents a hydrogen atom or a hydroxyl group. However, at least one of R ₂ c to R ₄ c represents a hydroxyl group. _{Two of} R ₂ c to R ₄ c are preferably hydroxyl groups.

  Although the specific example of the repeating unit which has a structure represented by general formula (AII) below is given, it is not limited to these.

  The acid-decomposable resin (A) may contain a repeating unit represented by the following general formula (V).

In the general formula (V), Z ₂ represents —O— or —N (R ₄₁ ) —. R ₄₁ represents a hydrogen atom, a hydroxyl group, an alkyl group, or —OSO ₂ —R ₄₂ . R ₄₂ represents an alkyl group, a cycloalkyl group or a camphor residue. The alkyl group, cycloalkyl group, and camphor residue of R ₄₁ and R ₄₂ may be substituted with a halogen atom (preferably a fluorine atom).

  Examples of the repeating unit represented by the general formula (V) include, but are not limited to, the following specific examples.

  The resin (A) of the present invention preferably contains a fluorine atom. The fluorine atom may be contained in the repeating unit represented by each general formula described above, or may be contained in the following other repeating unit.

  The number of fluorine atoms is preferably 3 or more and 21 or less, more preferably 6 or more and 18 or less, per repeating unit contained.

  The other repeating unit having a fluorine atom preferably contains at least one selected from the group of the following general formulas (II) and (IV to IX). More preferably, it contains at least one repeating unit selected from the group of the following general formulas (IV to IX).

X ₁ represents an oxygen atom or a sulfur atom.
X ₂ represents a methylene group, an oxygen atom or a sulfur atom.
Rx represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, an alkyl group, or a -L ₃ -CRa. L ₃ represents an alkylene _{group, -CH 2 O -, - CH} 2 O (C = O) - represents, Ra represents a hydroxyl group, a lactone group, a fluoroalkyl group.
Rf, Rf ₁ and Rf ₂ each independently represents a group having at least one fluorine atom. Rf ₁ and Rf ₂ may be connected to each other to form a ring having — (CF ₂ ) n ₁ —. n ₁ represents an integer of 1 or more.
j represents an integer of 1 to 3.

In the general formula (II), R _{x1 to} R _x3 each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, an alkyl group, or —L ₃ —C (R _f1 ) (R _f2 ) Ra. Represent.
R _f1 and R _f2 each independently represent a hydrogen atom, a fluorine atom or an alkyl group. However, at least one of R _f1 and R _f2 is a fluorine atom or a fluoroalkyl group.
Ra represents a hydrogen atom or a hydroxyl group.
L ₃ represents a single bond, an alkylene group, —CH ₂ —O— or —CH ₂ —COO—.
R ₁ and R _m each independently represents a hydrogen atom or an alkyl group.
Z ₁ represents a single bond, an alkylene group, a cycloalkylene group, or an arylene group.
L ₁ represents a single bond or a divalent linking group.
n and q each independently represents 0 or 1.
r represents an integer of 0-6.
Y represents a hydrogen atom or an organic group.

In the general formula (II),
The alkyl group represented by R _{x1 to} R _x3 may have a substituent and is preferably an alkyl group having 1 to 8 carbon atoms. For example, a methyl group, an ethyl group, a propyl group, an n-butyl group, sec- Examples thereof include a butyl group and a t-butyl group. The alkyl group represented by R _{x1 to} R _x3 is preferably an alkyl group substituted with a fluorine atom, and the carbon number thereof is 1 to 8, preferably 1 or 2, and more preferably 1 carbon. A perfluoroalkyl group in which all hydrogen atoms of the alkyl group are substituted with fluorine atoms is preferred.
In the case where R _{x1 to} R _x3 are groups represented by -L ₃ -C (R _f1 ) (R _f2 ) Ra;
_Examples of the alkyl group for R _f1 and R _f2 include the same alkyl groups as R _{x1 to} R _x3 .
The alkylene group of L ₃ is preferably a linear or branched alkylene group having 1 to 8 carbon atoms, and examples thereof include a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and an octylene group. .
As the alkyl group for R ₁ and R _m , an alkyl group having 1 to 3 carbon atoms is preferable, and specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a fluoroalkyl group. Of the groups, a methyl group is most preferred. As the fluoroalkyl group, those having 1 to 4 carbon atoms are preferable. Specifically, a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a nonafluorobutyl group, etc. However, a trifluoromethyl group is most preferable.
Examples of the alkylene group for Z ₁ include the same as the divalent alkylene group for L ₃ .
The cycloalkylene group for Z ₁ may have a substituent and may be monocyclic or polycyclic. Examples of the substituent include a hydroxyl group, an alkyl group, an alkoxy group, a halogen atom, and a cyano group. The monocyclic type preferably has 3 to 8 carbon atoms, and examples thereof include a cyclopropylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, and a cyclooctylene group. The polycyclic type has 6 to 20 carbon atoms, such as adamantyl residue, norbornyl residue, isobornyl residue, camphanyl residue, dicyclopentyl residue, α-pinel residue, tricyclodecanyl residue. Preferred examples include a group, a tetocyclododecyl residue, an androstanyl residue, and the like. Moreover, the carbon atom in said monocyclic or polycyclic cycloalkyl group may be substituted by a hetero atom such as an oxygen atom. As the substituent of the cycloalkylene group, a fluorine atom is preferable. As the cycloalkylene group substituted with a fluorine atom (a cycloalkylene group in which at least one hydrogen atom is substituted with a fluorine atom), for example, a perfluorocyclopropylene group Perfluorocyclopentylene group, perfluorocyclohexylene group, perfluorocycloheptylene group, perfluorocyclooctylene group and the like.
As the arylene group for Z _1, an arylene group having 4 to 20 carbon atoms is preferable, and examples thereof include a phenylene group, a tolylene group, and a naphthylene group.
Examples of the divalent linking group of L ₁ include an alkylene group, a cycloalkylene group, an alkenylene group, an arylene group, —O—, —S—, —O—R _22a —, —O—C (═O) —. R _22b —, —C (═O) —O—R _22c —, —C (═O) —N (R _22d ) —R _22e — and the like can be mentioned. R _22a , R _22b , R _22c and R _{22e each} may have a single bond or an ether group, an ester group, an amide group, a urethane group or a ureido group, a divalent alkylene group, a cycloalkylene group, an alkenylene. Represents a group or an arylene group. R _22d is a hydrogen atom or an alkyl group (preferably having 1 to 5 carbon atoms), a cycloalkyl group (preferably having 3 to 10 carbon atoms), an aralkyl group (preferably having 7 to 10 carbon atoms), or an aryl group (preferably carbon). Equations 6 to 10) are expressed.

The organic group for Y includes both acid-decomposable and non-acid-decomposable ones, and preferably has 1 to 30 carbon atoms. Examples of the acid-decomposable organic group for Y include -C (R _11a ) (R _12a ) (R _13a ), -C (R _14a ) (R _15a ) (OR _16a ), -Xa-COO-C ( R _11a ) (R _12a ) (R _13a ) and the like.
R _{11a to} R _13a and R _16a each independently represents an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group or an aryl group.
R _14a and R _15a each independently represents a hydrogen atom or an alkyl group.
Two of R _11a , R _12a , and R _13a and two of R _14a , R _15a , and R _16a may be bonded to form a ring.
Xa represents a single bond, an alkylene group, a cycloalkylene group, an alkenylene group or an arylene group.
As the alkyl group for R _{11a to} R _13a , R _14a , R _15a and R _16a , an alkyl group having 1 to 8 carbon atoms which may have a substituent is preferable, and examples thereof include a methyl group, an ethyl group, Propyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group, fluoroalkyl group (monofluoromethyl group, difluoromethyl group, trifluoromethyl group, pentafluoroethyl group, etc.) be able to. Of the fluoroalkyl groups, a trifluoromethyl group is most preferred.
The cycloalkyl group for R _{11a to} R _13a and R _16a may have a substituent, and may be monocyclic or polycyclic. The monocyclic type is preferably a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclobutyl group, and a cyclooctyl group. As the polycyclic type, a cycloalkyl group having 6 to 20 carbon atoms is preferable. For example, an adamantyl group, norbornyl group, isobornyl group, camphanyl group, dicyclopentyl group, α-pinel group, tricyclodecanyl group, tetocyclo A dodecyl group, an androstanyl group, etc. can be mentioned. A part of carbon atoms in the cycloalkyl group may be substituted with a hetero atom such as an oxygen atom.

The aryl group of R _{11a to} R _13a and R _16a may have a substituent, and is preferably an aryl group having 6 to 10 carbon atoms. For example, a phenyl group, a tolyl group, a dimethylphenyl group, 2, A 4,6-trimethylphenyl group, a naphthyl group, an anthryl group, a 9,10-dimethoxyanthryl group, etc. can be mentioned.
The aralkyl group of R _{11a to} R _13a and R _16a may have a substituent and is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, and a naphthylmethyl group. Can do.
The alkenyl group of R _{11a to} R _13a and R _16a may have a substituent, and is preferably an alkenyl group having 2 to 8 carbon atoms, such as a vinyl group, an allyl group, a butenyl group, or a cyclohexenyl group. Etc.
The substituents that R _{11a to} R _13a , R _14a , R _15a , and R _16a may have include an alkyl group, a cycloalkyl group, an aryl group, an amino group, an amide group, a ureido group, a urethane group, and a hydroxy group. Carboxy group, halogen atom, alkoxy group, thioether group, acyl group, acyloxy group, alkoxycarbonyl group, cyano group, nitro group and the like.

  Preferred examples of the acid-decomposable group for Y include a t-butyl group, a t-amyl group, a 1-alkyl-1-cyclohexyl group, a 2-alkyl-2-adamantyl group, a 2-adamantyl-2-propyl group, Tertiary alkyl groups such as 2- (4-methylcyclohexyl) -2-propyl group, acetal groups such as 1-alkoxy-1-ethoxy group, 1-alkoxy-1-methoxy group and tetrahydropyranyl group, t-alkyl Preferred examples include a carbonyl group and a t-alkylcarbonylmethyl group.

  The non-acid-decomposable organic group of Y is an organic group that is not decomposed by the action of an acid, for example, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group that is not decomposed by the action of an acid. , Alkoxy groups, alkoxycarbonyl groups, amide groups, cyano groups, and the like. The alkyl group is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a hexyl group, or a 2-ethylhexyl group. And octyl group. The cycloalkyl group preferably has 3 to 10 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclohexyl group, and an adamantyl group. The aryl group is preferably an aryl group having 6 to 14 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthracenyl group. The aralkyl group is preferably an aralkyl group having 6 to 12 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, and a cumyl group. The alkoxy group in the alkoxy group and the alkoxycarbonyl group is preferably an alkoxy group having 1 to 5 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, and an isobutoxy group.

  Hereinafter, although the specific example of the repeating unit represented by general formula (II) is given, it is not limited to these.

In the general formulas (IV) to (IX), examples of the alkyl group include the same alkyl groups as Rx _{1 to} Rx ₃ in the general formula (II), and examples of the alkylene group include the general formula (II). It includes the same ones as divalent alkylene group as L ₁ in).
The lactone group preferably has a lactone structure represented by any one of the following general formula (Lc) or the following general formulas (V-1) to (V-5).
As the fluoroalkyl group, those having 1 to 4 carbon atoms are preferable, and specifically, a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a nonafluorobutyl group, Hexafluoroisopropyl group, nonafluoro-t-butyl group, trifluoroisopropyl group and the like can be mentioned.
n1 is an integer greater than or equal to ₁ , Preferably it is 3-6.

  Specific examples of the repeating unit represented by formula (IV) are shown below, but the present invention is not limited to these.

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

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

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

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

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

  The resin of the present invention preferably has a lactone group, more preferably a group having a lactone structure represented by any of the following general formula (Lc) or the following general formulas (V-1) to (V-5). A group having a lactone structure may be directly bonded to the main chain.

In general formula (Lc), Ra ₁ , Rb ₁ , Rc ₁ , Rd ₁ , and Re ₁ each independently represent a hydrogen atom or an alkyl group that may have a substituent. m and n each independently represents an integer of 0 to 3, and m + n is 2 or more and 6 or less.

In the general formulas (V-1) to (V-5), R _{1b to} R _5b each independently represent a hydrogen atom or an optionally substituted alkyl group, cycloalkyl group, alkoxy group, alkoxy group. A carbonyl group, an alkylsulfonylimino group or an alkenyl group is represented. Two of R _{1b to} R _5b may combine to form a ring.

R _{1 to} Re ₁ alkyl groups in general formula (Lc) and R _{1b to} R _5b alkyl groups, alkoxy groups, alkoxycarbonyl groups, alkyl groups in general formulas (V-1) to (V-5) Examples of the alkyl group in the sulfonylimino group include linear and branched alkyl groups, which may have a substituent.

As the repeating unit containing these fluorine atoms, a commercially available one can be used, and it can also be synthesized by a usual method.
For example, the following monomer (IV-a) can be synthesized by esterifying the following compound (a). Compound (a) can also be synthesized from the following compound (b) obtained by Diels-Alder reaction of furan and trifluoromethylacrylic acid.

  In the resin of the present invention, the content of the repeating unit containing a fluorine atom as described above is usually 5 to 100 mol%, preferably 7 to 80 mol%, more preferably 10 to 30 in the resin (A). The mol% is more preferably 20% to 30 mol%, most preferably 25 mol% to 30 mol%.

  In addition to the above repeating structural units, the acid-decomposable resin (A) has dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and general required properties of resist, resolving power, heat resistance, sensitivity. Various repeating structural units can be contained for the purpose of adjusting the above.

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

Thereby, the performance required for the resin of component (A), 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) Fine adjustment such as dry etching resistance can be performed.

  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 the acid-decomposable resin (A), the molar ratio of each repeating structural unit is the resist dry etching resistance, the standard developer suitability, the substrate adhesion, the resist profile, and the general required performance of the resist, resolving power and heat resistance. It is appropriately set to adjust the property, sensitivity, etc.

  In addition, the content of the repeating structural unit based on the monomer of the further copolymer component in the resin can also be appropriately set according to the performance of the desired resist. 99 mol% with respect to the total number of moles of the repeating structural unit having a partial structure containing the alicyclic hydrocarbon represented by (pVI) and the repeating unit represented by the above general formula (II-AB) The following is preferable, More preferably, it is 90 mol% or less, More preferably, it is 80 mol% or less.

In particular, the content of the above-described repeating unit having a group having a lactone structure and the repeating unit having a group represented by the general formula (IV) (hydroxyadamantane structure) is as follows.
The total number of moles of the repeating structural unit having a partial structure containing an alicyclic hydrocarbon represented by the general formulas (pI) to (pVI) and the repeating unit represented by the general formula (II-AB) for,
The content of the repeating unit having a group having a lactone structure is preferably 1 to 70 mol%, more preferably 10 to 70 mol%,
Content of the repeating unit which has group represented by general formula (IV) becomes like this. Preferably it is 1-70 mol%, More preferably, it is 1-50 mol%.

  When the composition of the present invention is for ArF exposure, the resin preferably has no aromatic group from the viewpoint of transparency to ArF light.

The acid-decomposable 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 the composition of the present invention such as propylene glycol monomethyl ether acetate described below are dissolved in a solvent that dissolves uniformly and then nitrogen, argon, etc. Polymerization is started using a commercially available radical initiator (azo initiator, peroxide, etc.) as necessary under an inert gas atmosphere. 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 30% by mass or more, and more preferably 40% by 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 acid-decomposable resin (A) is preferably 1,000 to 200,000, more preferably 3000 to 20000 as a polystyrene-converted value by a gas permeation chromatography (GPC) method. 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 positive resist composition of the present invention, the compounding amount of the acid-decomposable resin is preferably 40 to 99.99% by mass, more preferably 50 to 99.97% by mass, based on the total solid content of the resist.

(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 generator”) used in the positive resist composition for immersion exposure of the present invention. Will be described 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 compounds among the acid generators include compounds represented by the following general formulas (ZI), (ZII), and (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 (Z1-1), (Z1-2) and (Z1-3) 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 examples of the (ZI) component include compounds (Z1-1), (Z1-2), and (Z1-3) described below.

Compound (Z1-1) 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, an n-butyl group, sec- Examples thereof include a butyl group and a t-butyl group.

  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 having a remarkably low ability to cause a nucleophilic reaction, and is an anion capable of suppressing degradation with 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 sulfonate anion having 4 to 8 carbon atoms, an aromatic sulfonate anion having a fluorine atom, most preferably a nonafluorobutane sulfonate anion, a perfluorooctane sulfonate anion, It is a pentafluorobenzenesulfonic acid anion and 3,5-bis (trifluoromethyl) benzenesulfonic acid anion.

Next, the compound (Z1-2) will be described.
The compound (Z1-2) is a compound when R _{201 to} R ₂₀₃ in the general 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.

Two members out of R _{201 to} R ₂₀₃ may combine 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).

  The compound (Z1-3) is a compound represented by the following general formula (Z1-3), 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 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), (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 carbon atoms, 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 formulas (ZIV), (ZV), and (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 are an alkyl group, a cycloalkyl group or an aryl group, and these are the same as the alkyl group, cycloalkyl group or aryl group as R _{204 to} R ₂₀₇ .
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 positive resist composition for immersion exposure 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) Nitrogen-containing compound not containing hydroxyl group The positive resist composition for immersion exposure of the present invention further contains a nitrogen-containing compound not containing a hydroxyl group, which is a basic compound.
The nitrogen-containing compound not containing a hydroxyl group is a component having an action of controlling a phenomenon of diffusion of an acid generated from an acid generator upon exposure in a resist film and suppressing an undesirable chemical reaction in a non-exposed region. The nitrogen-containing compound that does not contain a hydroxyl group preferably has an aromatic group. Moreover, it is also preferable that the nitrogen-containing compound which does not contain a hydroxyl group has a C2-C10 alkyl group. Furthermore, the nitrogen-containing compound not containing a hydroxyl group preferably has a fluorine atom.
Also, by incorporating such a nitrogen-containing compound that does not contain a phenolic hydroxyl group, a positive resist composition for immersion exposure that can control the diffusion phenomenon of an acid generated from an acid generator upon exposure in a resist film by exposure. Storage stability is improved, resolution as a resist is further improved, and changes in resist pattern line width due to fluctuations in holding time (PED) from exposure to development processing can be suppressed, making process stability extremely high. An excellent composition is obtained.

  As the nitrogen-containing compound not containing a hydroxyl group, those having a molecular weight of 150 to 1000, more preferably 250 to 1000, and still more preferably 300 to 1000 are used. Examples include substituted or unsubstituted primary, secondary, and tertiary aliphatic amines, aromatic amines, heterocyclic amines, amide derivatives, imide derivatives, and nitrogen-containing compounds having a cyano group. It is done. Of these, aliphatic amines, aromatic amines, and heterocyclic amines are preferable. Preferred substituents that may be present are an amino group, an alkyl group, an alkoxy group, an acyl group, an acyloxy group, an aryl group, an aryloxy group, a nitro group, a cyano group, an ester group, and a lactone group.

  As aliphatic amines, diisobutylamine, di-sec-butylamine, dipentylamine, dicyclopentylamine, dihexylamine, dicyclohexylamine, diheptylamine, N, N-dimethylmethylenediamine, N, N-dimethylethylenediamine, N, N -Dimethyltetraethylenepentamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tripentylamine, tricyclopentylamine, trihexylamine, tricyclohexylamine, Triheptylamine, trioctylamine, trinonylamine, tridecylamine, tridodecylamine, tricetylamine, N, N, N ′, N′-tetramethylmethylenediamine, N, N, ', N'-tetramethylethylenediamine, N, N, N', N'-tetramethyltetraethylenepentamine, dimethylethylamine, methylethylpropylamine, benzylamine, phenethylamine, benzyldimethylamine, 1,5-diazabicyclo [4 .3.0] -5-nonene, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,4-diazabicyclo [2.2.2] octane, hexamethylenetetramine, 4,4'- Diaminodiphenyl ether, 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, 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, tri (cyclo) alkylamines such as tricyclohexylamine, morpholine, 4-methylmorpholine 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 -Dimethylpyro , 2,5-dimethylpyrrole, N-methylpyrrole, etc.), oxazole derivatives (eg oxazole, isoxazole etc.), thiazole derivatives (eg thiazole, isothiazole etc.), imidazole derivatives (eg imidazole, 4-methylimidazole, 4 -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, piperidine derivatives, Piperazine derivatives, morpholine derivatives, indole derivatives, isoindole derivatives, 1H-indazole derivatives, indoline derivatives, quinoline derivatives (eg quinoline, 3-quinolinecarbonitrile) Etc.), isoquinoline derivatives, cinnoline derivatives, quinazoline derivatives, quinoxaline derivatives, 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., diphenylamine, triphenylamine, naphthylamine, 2,6-diisopropylaniline, nicotine, nicotinamide, quinoline, 8-oxyquinoline, acridine and other pyridines, piperazine Piperazines such as pyrazine, pyrazole, pyridazine, quinosaline, purine, pyrrolidine, piperidine, 1,4-dimethylpiperazine, N, N, N ′, Examples thereof include N′-tetrabutylbenzidine, tris [4- (dimethylamino) phenyl] methane-4,4′-methylenebis (2,6-diisopropylaniline) and the like.

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

  Examples of the imide derivative 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-acetoxyethyl) -3-aminopropiononitrile, N, N-bis (2- Formyloxyethyl) -3-aminopropiononitrile, N, N-bis (2-methoxyethyl) -3-aminopropiononitrile, N, N-bis [2- (methoxymethoxy) ethyl] -3-aminopropi Ononitrile, methyl N- (2-cyanoethyl) -N- (2-methoxyethyl) -3-aminopropionate, methyl N- (2-acetoxyethyl) -N- (2-cyanoethyl) -3-aminopropionate N- (2-cyanoethyl) -N-ethyl-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- (3-acetoxy-1-propyl) -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, diethylaminoacetononitrile 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, methyl N-cyanomethyl-N- (2-methoxyethyl) -3-aminopropionate, methyl N- (2-acetoxyethyl) -N-cyanomethyl-3-aminopropionate 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- (3-acetoxy-1-propyl) -N- (cyanomethyl) aminoacetonitrile, N-cyanomethyl-N- (3-formyloxy-1-propyl) aminoacetonitrile, N, N-bis (cyanomethyl) Aminoacetonitrile, 1-pyrrolidinepropiononitrile, 1-piperidinepropiononitrile, 4-morpholinepropiononitrile, 1-pyrrolidineacetonitrile, 1-piperidineacetonitrile, 4-morpholineacetonitrile, cyanomethyl 3-diethylaminopropionate, N, N- Cyanomethyl bis (2-acetoxyethyl) -3-aminopropionate, cyanomethyl N, N-bis (2-formyloxyethyl) -3-aminopropionate, N, N-bis (2-methoxyethyl) -3-amino Cyanomethyl lopionate, N, N-bis [2- (methoxymethoxy) ethyl] -3-aminopropionate cyanomethyl, 3-diethylaminopropionic acid (2-cyanoethyl), N, N-bis (2-acetoxyethyl) -3 -Aminopropionic acid (2-cyanoethyl), N, N-bis (2-formyloxyethyl) -3-aminopropionic acid (2-cyanoethyl), N, N-bis (2-methoxyethyl) -3-aminopropion Acid (2-cyanoethyl), N, N-bis [2- (methoxymethoxy) ethyl] -3-aminopropionic acid (2-cyanoethyl), cyanomethyl 1-pyrrolidinepropionate, cyanomethyl 1-piperidinepropionate, 4-morpholine Cyanomethyl propionate, 1-pyrrolidine propionic acid (2-cyanoethyl 1-piperidine propionic acid (2-cyanoethyl) 4-morpholin-propionic acid (2-cyanoethyl) are exemplified.

  Other nitrogen-containing compounds not containing a hydroxyl group are preferably polyethyleneimine, polyallylamine, 2-dimethylaminoethylacrylamide polymer, 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, NN′N′-tetra-t-butoxycarbonylhexamethylenediamine, 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′-di-t-butoxycarbonyl-1,12-diaminododecane, N, N′-di-t-butoxycarbonyl-4,4′-diaminodiphenylmethane, Nt-butoxycarbonylbenzimidazole, Nt- Butoxycarbonyl-2-methylbenzimidazole, Nt-butoxycarbonyl-2-phenylbenzimidazole, pyrrolide N-methylpyrrolidone, urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, tri-n-butylthiourea , 6-poly (N, N′-diethylamino) styrene 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, hexamethylenetetramine, imidazoles, pyridines, 4,4′-diaminodiphenyl ether, triethylamine, tributylamine, tripentylamine, tri-n-octylamine, tris ( Nitrogen-containing compounds that do not contain a hydroxyl group, such as ethylhexyl) amine and tridodecylamine, are particularly preferred.

In the composition of the present invention, performance fluctuations due to aging after irradiation with actinic rays or radiation and heat treatment (pattern T-top shape formation, sensitivity fluctuations, pattern line width fluctuations, etc.) and performance fluctuations over time after application Furthermore, in addition to nitrogen-containing compounds that do not contain hydroxyl groups, other organic basic compounds are also included in addition to nitrogen-containing compounds that do not contain hydroxyl groups for the purpose of preventing excessive diffusion (degradation of resolution) of acids during heat treatment after irradiation with actinic rays or radiation. Can be used. The organic basic compound is, for example, an organic basic compound containing basic nitrogen, and a compound having a pKa value of 4 or more of the conjugate acid is preferably used.
Specifically, the structures of the following formulas (A) to (E) can be exemplified.

Here, R ²⁵⁰ , R ²⁵¹ and R ²⁵² may be the same or different, and are a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 1 to 20 carbon atoms, or 6 to 20 carbon atoms. Wherein R ²⁵¹ and R ²⁵² may combine with each other to form a ring.
The alkyl group may be unsubstituted or may have a substituent. Examples of the alkyl group having a substituent include an aminoalkyl group having 1 to 6 carbon atoms and a hydroxyalkyl group having 1 to 6 carbon atoms. preferable.
R ²⁵³ , R ²⁵⁴ , R ²⁵⁵ and R ²⁵⁶ may be the same or different and each represents an alkyl group having 1 to 6 carbon atoms.

  Specific examples include substituted or unsubstituted guanidine, substituted or unsubstituted aminopyridine, substituted or unsubstituted aminoalkylpyridine, substituted or unsubstituted aminopyrrolidine, substituted or unsubstituted indazole, imidazole, substituted or unsubstituted Pyrazole, substituted or unsubstituted pyrazine, substituted or unsubstituted pyrimidine, substituted or unsubstituted purine, substituted or unsubstituted imidazoline, substituted or unsubstituted pyrazoline, substituted or unsubstituted piperazine, substituted or unsubstituted Examples include aminomorpholine and substituted or unsubstituted aminoalkylmorpholine. Preferred substituents are amino group, alkyl group, alkoxy group, acyl group, acyloxy group, aryl group, aryloxy group, nitro group, hydroxyl group and cyano group.

  Particularly preferred compounds include guanidine, 1,1-dimethylguanidine, 1,1,3,3-tetramethylguanidine, imidazole, 2-methylimidazole, 4-methylimidazole, N-methylimidazole, 2-phenylimidazole, 4 , 5-diphenylimidazole, 2,4,5-triphenylimidazole, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2-diethylaminopyridine, 2- (Aminomethyl) pyridine, 2-amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-5-methylpyridine, 2-amino-6-methylpyridine, 3-aminoethylpyridine, 4- Aminoethylpyridine,

  3-aminopyrrolidine, piperazine, N- (2-aminoethyl) piperazine, N- (2-aminoethyl) piperidine, 4-amino-2,2,6,6-tetramethylpiperidine, 4-piperidinopiperidine, 2-iminopiperidine, 1- (2-aminoethyl) pyrrolidine, pyrazole, 3-amino-5-methylpyrazole, 5-amino-3-methyl-1-p-tolylpyrazole, pyrazine, 2- (aminomethyl)- Examples include 5-methylpyrazine, pyrimidine, 2,4-diaminopyrimidine, 4,6-dihydroxypyrimidine, 2-pyrazoline, 3-pyrazoline, N-aminomorpholine, N- (2-aminoethyl) morpholine. However, the present invention is not limited to this.

A basic ammonium salt can also be used. 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 Side, myristylmethylammonium hydroxide, dimethylditetradecylammonium hydroxide, hexadecyltrimethylammonium hydroxide, octadecyltrimethylammonium hydroxide, dimethyldioctadecylammonium hydroxide, tetraoctadecylammonium hydroxide, diallyldimethylammonium hydroxide, (2 -Chloroethyl) -trimethylammonium hydroxide, (2-bromoethyl) trimethylammonium hydroxide, (3-bromopropyl) -trimethylammonium hydroxide, (3-bromopropyl) triethylammonium hydroxide, glycidyltrimethylammonium hydroxide, choline hydroxy (R)-(+)-(3-chloro-2-hydro Cypropyl) trimethylammonium hydroxide, (S)-(−)-(3-chloro-2-hydroxypropyl) -trimethylammonium hydroxide, (3-chloro-2-hydroxypropyl) -trimethylammonium hydroxide, (2- Aminoethyl) -trimethylammonium hydroxide, hexamethonium hydroxide, decamethonium hydroxide, 1-azoniapropellan hydroxide, petronium hydroxide, 2-chloro-1,3-dimethyl-2-imidazolinium hydroxy And 3-ethyl-2-methyl-2-thiazolinium hydroxide.
These organic basic compounds are used alone or in combination of two or more.

  In the present invention, the nitrogen-containing compound preferably does not contain an oxygen atom.

The nitrogen-containing compounds may be used alone or in combination of two or more, and more preferably two or more.
The amount of the nitrogen-containing compound not containing a hydroxyl group is usually 0.001 to 10% by mass, preferably 0.01 to 5% by mass, based on the solid content of the positive resist composition for immersion exposure.
The use amount of the nitrogen-containing compound as a total amount is usually 0.001 to 10% by mass, preferably 0.01 to 5% by mass, based on the solid content of the positive resist composition for immersion exposure.

  The use ratio of the acid generator and the organic basic compound in the composition is preferably acid generator / organic basic compound (molar ratio) = 2.5 to 300. In other words, the molar ratio is preferably 2.5 or more from the viewpoint of sensitivity and resolution, and is preferably 300 or less from the viewpoint of suppressing the reduction in resolution due to the thickening of the resist pattern over time until post-exposure heat treatment. The acid generator / organic basic compound (molar ratio) is more preferably 5.0 to 200, still more preferably 7.0 to 150.

(D) Organic solvent The positive resist composition for immersion exposure of the present invention is used by dissolving the above components in a predetermined organic solvent.
Examples of the organic solvent 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 -Dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, methoxybutanol, tetrahydrofuran, etc. It can be mentioned.

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 an organic 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.

(E) 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 positive resist composition for immersion exposure of the present invention is decomposed by the action of an acid to be alkaline. 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 the developer.
The dissolution-inhibiting compound contains an acid-decomposable group such as a cholic acid derivative containing an acid-decomposable group described in Proceedingof SPIE, 2724,355 (1996) so as not to lower the permeability of 220 nm or less. Alicyclic or aliphatic compounds are preferred. 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 total solid content of the positive resist composition for immersion exposure.

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

(F) Surfactant The positive resist composition for immersion exposure of the present invention preferably further contains (F) a surfactant, and is a fluorine-based and / or silicon-based surfactant (fluorine-based surfactant). , A silicon-based surfactant, a surfactant having both a fluorine atom and a silicon atom), or two or more thereof. In particular, it contains (F1) a fluorine-based or fluorine-based and silicon-based nonionic surfactant.

When the positive resist composition for immersion exposure of the present invention contains the surfactant (F), adhesion and development can be achieved with good sensitivity and resolution when using an exposure light source of 250 nm or less, particularly 220 nm or less. A resist pattern with few defects can be provided.
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, the surfactant is derived from a fluoroaliphatic compound produced by a telomerization method (also called telomer method) or an oligomerization method (also called 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.

  In the present invention, other surfactants other than fluorine-based and / or silicon-based surfactants can also be used. Specifically, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol ether, etc. Sorbitans such as polyoxyethylene alkyl allyl ethers, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate Fatty acid esters, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopal Te - DOO, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, may be mentioned polyoxyethylene sorbitan tristearate nonionic surfactants of polyoxyethylene sorbitan fatty acid esters such as such.

  These surfactants may be used alone or in several combinations.

  The amount of the surfactant used is preferably 0.0001 to 2% by mass, more preferably 0.001 to 1% by mass, based on the total amount of the positive resist composition for immersion exposure (excluding the solvent).

(G) Alkali-soluble resin The positive resist composition for immersion exposure of the present invention can further contain a resin that is 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 positive resist composition for immersion exposure 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, the (H) carboxylic acid onium salt is preferably an iodonium salt or a sulfonium salt. 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 suitably from 0.1 to 20% by weight, preferably from 0.5 to 10% by weight, more preferably from 1 to 7% by weight, based on the total solid content of the composition. %.

Other Additives In the positive resist composition for immersion exposure according to the present invention, a dye, a plasticizer, a photosensitizer, and a compound (for example, a molecular weight of 1000 or less) that further promotes solubility in a developer as necessary. A phenol compound, an alicyclic compound having a carboxyl group, or an aliphatic compound).

Such phenolic 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.

(how to use)
The positive resist composition for immersion exposure according to the present invention is used by dissolving the above components in a predetermined organic solvent, preferably the mixed solvent, and applying the solution on a predetermined support as follows.
That is, a positive resist composition for immersion exposure is formed on a substrate (eg, silicon / silicon dioxide coating) used for the manufacture of precision integrated circuit elements by an appropriate coating method such as a spinner or a coater. (Normally 50 to 500 nm).
In addition, it is preferable that the solid content density | concentration in a resist composition is 2.0-6.0 mass%.
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. Although an exposure amount can be set suitably, it is 1-100 mJ / cm < ² > normally. After exposure, preferably spin or / and bake, develop and rinse to obtain a good pattern. The baking temperature is usually 30 to 300 ° C. From the above-mentioned PED point, it is better that the time from the exposure to the baking process is short.
Here, the exposure light is 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.

The immersion liquid used for the immersion exposure will be described below.
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 made 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.

In order to prevent the resist film from coming into direct contact with the immersion liquid between the resist film formed by the positive resist for immersion exposure 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, so that the top coat for ArF immersion exposure is close to the refractive index of water (1.44). Is preferred. A thin film is more preferable from the viewpoint of transparency and refractive index.

In the development process, a developer is used as follows. As a developer of a positive resist composition for immersion exposure, inorganic hydroxides such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, etc. Primary amines, 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, tetraethyl Alkaline aqueous solutions such as quaternary ammonium salts such as ammonium hydroxide and cyclic amines such as pyrrole and pihelidine can be used.
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 of Resin (1) 2-Adamantyl-2-propyl methacrylate, 3,5-dihydroxy-1-adamantyl methacrylate and norbornane lactone acrylate were charged at a ratio of 40/20/40 (molar ratio), and propylene glycol monomethyl ether acetate / Dissolved in propylene glycol monomethyl ether = 60/40 to prepare 450 g of a solution having a solid content of 22%. 1 mol% of a polymerization initiator V-601 (dimethyl 2,2′-azobis (2-methylpropionate) manufactured by Wako Pure Chemical Industries, Ltd. was added to this solution, and this was added at 100 ° C. over 6 hours in a nitrogen atmosphere. The solution was added dropwise to 50 g of a mixed solution of propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether = 60/40, and the reaction solution was stirred for 2 hours after the completion of the reaction. The white powder which crystallized and broke out in 5 L of mixed medium / ethyl acetate = 9/1 was collected by filtration to recover the target resin (1-A1) Polymer composition from ¹⁸ CNMR and polymer acid value measurement Ratio (2-adamantyl-2-propyl methacrylate / 3,5-dihydroxy-1-adamantyl methacrylate / norbornane lactone acrylic (A / b / c) was determined to be 39/21/40 (molar ratio), and the weight average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement was 9700, and the degree of dispersion (Mw / Mn) Was 2.01.

  The structures of the resins (1) to (22) used in the following examples are shown.

Examples 1-20 and Comparative Examples 1-4
<Resist preparation>
The components shown in Table 1 below were dissolved in a solvent to prepare a solution having a solid content concentration of 10% by mass, and this was filtered through a 0.1 μm polyethylene filter to prepare a positive resist composition for immersion exposure. The prepared positive resist composition for immersion exposure was evaluated by the following method, and the results are shown in Table 1. The ratio when using a plurality of components is a mass ratio.

[PED evaluation]
An organic antireflection film ARC29A (Nissan Chemical Co., Ltd.) was applied on a silicon wafer and baked at 205 ° C. for 60 seconds to form a 78 nm antireflection film. The prepared positive resist composition for immersion exposure was applied thereon and baked at 120 ° C. for 60 seconds to form a 150 nm resist film. The wafer thus obtained was subjected to two-beam interference exposure (wet exposure) using the apparatus shown in FIG. 1 using pure water as the immersion liquid. The laser wavelength was 193 nm, and a prism that formed a 90 nm line and space pattern was used. Immediately after exposure, the resist pattern obtained by heating at 115 ° C. for 90 seconds, developing with an aqueous tetramethylammonium hydroxide solution (2.38 mass%) for 60 seconds, rinsing with pure water, and spin drying, and exposure Thereafter, the resist pattern obtained by performing the same operation as described above after being allowed to stand for 30 minutes was observed for pattern collapse performance, pattern profile, and scum generation evaluation using a scanning electron microscope (S-9260, manufactured by Hitachi).
Moreover, the same evaluation was performed also about the resist pattern obtained by performing exposure (dry exposure) without going through immersion liquid, and performing the same operation as the above after that.
The pattern collapse was evaluated as ○ when the 90 nm line and space pattern was formed without falling, Δ when partially collapsed, and × when all were collapsed. Further, an 80 nm line and space pattern was created, and the pattern formed without falling still was marked with ◎.
The evaluation of scum generation was evaluated based on the degree of remaining scum (development residue) in a 90 nm resist pattern. A case where the residue was not observed was evaluated as A, a portion where the residue was observed was evaluated as C, and an intermediate portion was evaluated as B.
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.

Examples 21-46
Examples 21 to 38 were carried out in the same manner as in Example 1 except that the solid concentration of the resist solution was 5% by mass, the thickness of the resist film was 100 nm, and the line and space pattern to be formed was 65 nm. Evaluation was performed in the same manner as in Example 1 and the results are shown in Table 2. In the line and space pattern, “◎” is an example in which the film did not collapse even at 60 nm.

The symbols in Tables 1 and 2 are as follows.
The acid generator corresponds to that exemplified above.

N-1: N, N-dibutylaniline N-2: N, N-dipropylaniline N-3: N-cyanoethyl-N-ethylaniline N-4: 2,6-diisopropylaniline N-5: 1, 5 -Diazabicyclo [4.3.0] -5-nonene N-6: tri-n-octylamine N-7: tris [4- (dimethylamino) phenyl] methane-4,4'-methylenebis (2,6- Diisopropylaniline)
N-8: 6-poly (N, N′-diethylamino) styrene (average molecular weight 1000)
N-9: N, N-dihydroxyethylaniline N-10: Hydroxyantipyrine N-11: 2,4,5-trisphenylimidazole N-12: Tris-2- (2-methoxy (ethoxy)) ethylamine

W-1: Megafuck F176 (manufactured by Dainippon Ink & Chemicals, Inc.)
(Fluorine)
W-2: Megafuck R08 (Dainippon Ink Chemical Co., Ltd.)
(Fluorine and silicon)
W-3: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Silicon)
W-4: Troisol S-366 (manufactured by Troy Chemical Co., Ltd.)
W-5: PF656 (manufactured by OMNOVA, fluorine-based)
W-6: PF6320 (manufactured by OMNOVA, fluorine-based)

SL-1: cyclopentanone SL-2: cyclohexanone SL-3: 2-methylcyclohexanone SL-4: propylene glycol monomethyl ether acetate SL-5: ethyl lactate SL-6: propylene glycol monomethyl ether SL-7: 2-heptanone SL-8: γ-butyrolactone SL-9: Propylene carbonate

I-1: t-butyl lithocholic acid I-2: t-butyl adamantanecarboxylate

  From the table, the positive resist composition for immersion exposure according to the present invention has improved resist pattern collapse, profile degradation, and scum generation due to the placement between exposure and PEB during immersion exposure. Is clear.

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 which has antireflection film and resist film 11 Wafer stage

Claims (9)

  (A) a resin having a monocyclic or polycyclic alicyclic hydrocarbon structure, which increases the solubility in an alkaline developer 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 exposure, comprising a nitrogen-containing compound containing no hydroxyl group and (D) a solvent. The positive resist composition for immersion exposure according to claim 1, wherein the resin of component (A) contains a repeating unit having a group represented by formula (I).

In general formula (I):
R _{1 to} R ₃ each independently represents an alkyl group or a cycloalkyl group. However, at least one of R _{2 and} R ₃ is a cycloalkyl group or is bonded to each other to form a ring. The positive resist composition for immersion exposure according to claim 1 or 2, wherein the resin of component (A) contains a repeating unit represented by the general formula (1A).

In formula (I),
R _x represents a hydrogen atom or a methyl group.
R _y represents an alkyl group having 1 to 6 carbon atoms.   The positive resist composition for immersion exposure according to any one of claims 1 to 3, wherein the nitrogen-containing compound (C) does not contain an oxygen atom.   The positive resist composition for immersion exposure according to any one of claims 1 to 4, wherein the nitrogen-containing compound (C) has a molecular weight of 100 or more.   The positive resist composition for immersion exposure according to any one of claims 1 to 5, wherein the resin of component (A) contains a fluorine atom.   The positive resist composition for immersion exposure according to any one of claims 1 to 6, further comprising (F1) a fluorine-based or fluorine-based and silicon-based nonionic surfactant.   The positive resist composition for immersion exposure according to any one of claims 1 to 7, further comprising a solid content concentration of 2.0 to 6.0 mass% in the resist composition.   A pattern forming method comprising: forming a resist film from the resist composition according to claim 1, subjecting the resist film to immersion exposure, and developing.

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