JP2007326903A - Resin, positive-type resist composition comprising the resin, protecting film-forming composition comprising the resin, pattern-forming method using the positive-type resist composition, and pattern-forming method using the protecting film-forming composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin suitably employable for a positive-type resist composition that is improved in defective development, and exhibits a good follow-up property to water and good line edge roughness on immersion exposure, a positive-type resist composition comprising the resin, a protecting film-forming composition comprising the resin, a pattern-forming method using the positive-type resist composition, and a pattern-forming method using the protecting film-forming composition. <P>SOLUTION: The resin has at least either one of a fluorine atom and a silicon atom, and a -CONHSO<SB>2</SB>- group. The positive-type resist composition comprises the resin. The protecting film-forming composition comprises the resin. The pattern-forming method comprises using the positive-type resist composition. The pattern-forming method comprises using the protecting film-forming composition. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  Positive resist compositions are used in semiconductor manufacturing processes such as ICs, circuit boards such as liquid crystals and thermal heads, and lithography processes for other photo applications. The present invention uses a resin that can be used in such a positive resist composition, a positive resist composition containing the resin, a protective film-forming composition containing the resin, and the positive resist composition. The present invention relates to a pattern forming method and a pattern forming method using the protective film forming composition. In particular, a resin that can be used for a positive resist composition for immersion exposure 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 positive resist containing the resin The present invention relates to a composition, a protective film forming composition containing the resin, a pattern forming method using the positive resist composition, and a pattern forming method using the protective film forming composition.

With the miniaturization of semiconductor elements, the exposure light source has become shorter in wavelength and the projection lens has a higher numerical aperture (high NA). Currently, an exposure machine with NA 0.84 using an ArF excimer laser having a 193 nm wavelength 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 pattern of a semiconductor element are introduced in Patent Document 1 (Japanese Patent Laid-Open No. 57-153433), Patent Document 2 (Japanese Patent Laid-Open No. 7-220990), and the like. Yes.
Recent progress in immersion exposure technology is described in Non-Patent Document 1 (SPIE Proc 4688, 11 (2002)), Non-Patent Document 2 (J. Vac. Sci. Tecnol. B 17 (1999)), Non-Patent Document 3 (SPIE Proc 3999, 2 (2000)), Patent Document 3 (Japanese Patent Laid-Open No. 10-303114), and the like. In the case of using an ArF excimer laser as a light source, pure water (refractive index of 1.44 at 193 nm) 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. Explaining by taking a positive chemical amplification image forming method as an example, the acid generator in the exposed area is decomposed by exposure to generate an acid upon exposure, and the generated acid is reacted as a reaction catalyst by post exposure baking (PEB). Is used to change an alkali-insoluble group to an alkali-soluble group, and an exposed portion is removed by alkali development.
Although resists for ArF excimer laser (wavelength 193 nm) using this chemical amplification mechanism are becoming mainstream at present, improvement in the number of development defects during development has been desired.

In addition, when a chemically amplified resist is applied to immersion exposure, the resist layer comes into contact with the immersion liquid at the time of exposure, so that the resist layer is altered and components that adversely affect the immersion liquid are leached from the resist layer. Has been pointed out. Patent Document 4 (International Publication WO 2004-068242 Pamphlet) describes an example in which resist performance changes by immersing a resist for ArF exposure in water before and after exposure, and points to a problem in immersion exposure. .
In the immersion exposure process, when exposure is performed using a scanning immersion exposure machine, the exposure speed decreases unless the immersion liquid moves following the movement of the lens. Concerned about giving. When the immersion liquid is water, it is desirable that the resist film be a hydrophobic film with good water followability. On the other hand, if the resist film surface is hydrophobized, the line edge roughness deteriorates. There was also an adverse effect on performance, and improvements were desired.

JP-A-57-153433 JP-A-7-220990 JP-A-10-303114 International Publication WO 2004-068242 Pamphlet Proc. SPIE, 2002, Vol. 4688, p. 11 J.Vac.Sci.Tecnol.B 17 (1999) Proc. SPIE, 2000, Vol. 3999, p. 2

  An object of the present invention is to provide a resin that can be suitably used for a positive resist composition with improved development defects, a positive resist composition containing the resin, a protective film-forming composition containing the resin, and the positive resist composition. It is providing the pattern formation method using a type resist composition, and the pattern formation method using this protective film formation composition. Further, in immersion exposure, a resin that can be suitably used for a positive resist composition having good followability to water and good line edge roughness, a positive resist composition containing the resin, and containing the resin A protective film forming composition, a pattern forming method using the positive resist composition, and a pattern forming method using the protective film forming composition.

  The present invention is as follows, and the above object is achieved by the present invention.

(1) A resin having at least one of a fluorine atom and a silicon atom and a —CONHSO ₂ — group.

(2) The resin according to (1), which is selected from the following resin (a) and resin (b).
(A) A resin having a repeating unit (x) having at least one of a fluorine atom and a silicon atom and a repeating unit (y) having a —CONHSO ₂ — group.
(B) A resin having a repeating unit (xy) having at least one of a fluorine atom and a silicon atom and a —CONHSO ₂ — group.

  (3) The resin according to (2), wherein the repeating unit (y) of the resin (a) further has at least one of a fluorine atom and a silicon atom.

  (4) The resin according to (1), which has a repeating unit represented by the following general formula (Ax) and a repeating unit represented by the following general formula (Ay).

In general formulas (Ax) and (Ay),
Rz represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.
Rax represents an organic group having at least one of a fluorine atom and a silicon atom.
Ray represents an organic group.

  (5) (A) A positive resist composition comprising the resin according to any one of (1) to (4).

(6) A protective film forming composition for forming a protective film provided on a resist film,
(A) A protective film-forming composition comprising the resin according to any one of (1) to (4) and (S) a solvent that does not corrode the resist film.

  (7) A pattern forming method comprising a step of forming a resist film with the positive resist composition according to (5), exposing and developing.

  (8) A pattern forming method comprising forming a resist film, forming a protective film on the resist film with the protective film forming composition described in (6), immersion exposure, and developing.

  (9) A compound represented by the following general formula (Ay2).

In the general formula (Ay2),
Rz represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.
Ray ₂ represents an organic group having at least one silicon atom.

The preferred embodiments of the present invention will be further described below.
(10) (A) The resin according to any one of (1) to (4),
(B) a resin whose solubility in an alkaline developer is increased by the action of an acid;
(C) A positive resist composition as described in (5), which contains a compound capable of generating an acid upon irradiation with actinic rays or radiation, and (D) a solvent.

  (11) The positive resist composition as described in (10) above, wherein the resin (B) has a repeating unit having an alicyclic hydrocarbon group substituted with a hydroxyl group or a cyano group.

  (12) The positive resist composition as described in any one of (5), (10), and (11), wherein a receding contact angle with respect to a water film upon film formation is 70 ° or more.

  (13) The protective film-forming composition as described in (6), wherein the solvent (S) contains either an aliphatic hydrocarbon solvent or a fluorine-based solvent.

  (14) The protective film-forming composition as described in (6) or (13) above, wherein a receding contact angle with respect to the water film upon film formation is 70 ° or more.

  (15) A pattern forming method comprising: forming a resist film from the positive resist composition as described in any one of (10) to (12) above, and exposing and developing the resist film.

  (16) A pattern formed by forming a resist film, forming a protective film on the resist film with the protective film-forming composition as described in (13) or (14) above, immersion exposure, and developing Forming method.

  (17) The pattern forming method as described in any one of (7), (8), (15) and (16) above, wherein immersion exposure is performed through pure water.

  According to the present invention, a resin that can be suitably used for a positive resist composition with improved development defects, a positive resist composition containing the resin, a protective film forming composition containing the resin, and the positive resist A pattern forming method using the composition and a pattern forming method using the protective film forming composition can be provided. Further, in immersion exposure, a resin that can be suitably used for a positive resist composition having good followability to water and good line edge roughness, a positive resist composition containing the resin, and containing the resin A protective film forming composition, a pattern forming method using the positive resist composition, and a pattern forming method using the protective film forming composition can be provided.

Hereinafter, the best mode for carrying out the present invention will be described.
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) one at least one of the fluorine atom and a silicon atom, -CONHSO ₂ - one and at least one of the resin fluorine atom and a silicon atom and a group, -CONHSO ₂ - resin having a group ( The “resin (A)”) may have any structure as long as it is a resin having at least one of a fluorine atom and a silicon atom and a —CONHSO ₂ — group, but the fluorine atom and the silicon atom a repeating unit having at least either one of the (x), -CONHSO ₂ - is preferably a resin having a repeating unit (y) having a group. Furthermore, it is more preferable that the repeating unit (y) has at least one of a fluorine atom and a silicon atom.

When the repeating unit (x) is a repeating unit having a fluorine atom, the partial structure having a fluorine atom includes an alkyl group having 1 to 10 carbon atoms (preferably 1 to 4 carbon atoms) having a fluorine atom, a fluorine atom A cycloalkyl group having 3 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms having a fluorine atom.
The alkyl group having a fluorine atom is a linear or branched alkyl group substituted with at least one fluorine atom, and may further have another substituent.
The cycloalkyl group having at least one fluorine atom is a monocyclic or polycyclic cycloalkyl group substituted with at least one fluorine atom, and may further have another substituent.
Examples of the aryl group having at least one fluorine atom include those in which at least one fluorine atom is substituted on an aryl group such as a phenyl group or a naphthyl group, and may further have other substituents.

  Specific examples of the alkyl group having a fluorine atom, the cycloalkyl group having a fluorine atom, or the aryl group having a fluorine atom include groups represented by the following general formulas (F2) to (F4). .

In general formulas (F2) to (F4),
R _{57 to} R ₆₈ each independently represents a hydrogen atom, a fluorine atom or an alkyl group. However, at least one of R _{57 to} R ₆₁ represents a fluorine atom or an alkyl group (preferably having 1 to 4 carbon atoms) in which at least one hydrogen atom is substituted with a fluorine atom, and R _{62 to} R ₆₄ Among them, at least one represents a fluorine atom or an alkyl group (preferably having 1 to 4 carbon atoms) in which at least one hydrogen atom is substituted with a fluorine atom, and at least one of R _{65 to} R ₆₈ is fluorine. It represents an alkyl group (preferably having 1 to 4 carbon atoms) in which an atom or at least one hydrogen atom is substituted with a fluorine atom.

R _{57 to} R ₆₁ and R _{65 to} R ₆₇ are preferably all fluorine atoms.
R ₆₂ , R ₆₃ and R ₆₈ are preferably an alkyl group (preferably having 1 to 4 carbon atoms) in which at least one hydrogen atom is substituted with a fluorine atom, and preferably a perfluoroalkyl group having 1 to 4 carbon atoms. Further preferred. R ₆₂ and R ₆₃ may be connected to each other to form a ring.

Specific examples of the group represented by the general formula (F2) include a p-fluorophenyl group, a pentafluorophenyl group, and a 3,5-di (trifluoromethyl) phenyl group.
Specific examples of the group represented by the general formula (F3) include trifluoroethyl group, pentafluoropropyl group, pentafluoroethyl group, heptafluorobutyl group, hexafluoroisopropyl group, heptafluoroisopropyl group, hexafluoro (2 -Methyl) isopropyl group, nonafluorobutyl group, octafluoroisobutyl group, nonafluorohexyl group, nonafluoro-t-butyl group, perfluoroisopentyl group, perfluorooctyl group, perfluoro (trimethyl) hexyl group, 2,2 1,3,3-tetrafluorocyclobutyl group, perfluorocyclohexyl group and the like. Hexafluoroisopropyl group, heptafluoroisopropyl group, hexafluoro (2-methyl) isopropyl group, octafluoroisobutyl group, nonafluoro-t-butyl group and perfluoroisopentyl group are preferable, and hexafluoroisopropyl group and heptafluoroisopropyl group are preferable. Further preferred.
Specific examples of the group represented by the general formula (F4) include, for example, —C (CF ₃ ) ₂ OH, —C (C ₂ F ₅ ) ₂ OH, —C (CF ₃ ) (CH ₃ ) OH, -CH (CF ₃₎ OH and the like, -C (CF _{3) 2} OH is preferred.

When the repeating unit (x) is a repeating unit having a silicon atom, the partial structure having a silicon atom is preferably an alkylsilyl structure (preferably a trialkylsilyl group) or a cyclic siloxane structure.
Specific examples include groups represented by the following general formulas (CS-1) to (CS-3).

In general formulas (CS-1) to (CS-3),
R _{12 to} R ₂₆ each independently represents a linear or branched alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms.
L _{3 to} L ₅ each independently represents a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group, an arylene group, an ether group, a thioether group, a carbonyl group, a carbonyloxy group, an amide group, a urethane group, and a urea group. A combination is mentioned.

  The resin (A) is preferably a resin having at least one selected from the group of repeating units represented by the following general formulas (CI) to (C-IV).

In the general formulas (CI) to (C-IV),
R _{1 to} R ₃ each independently represents a hydrogen atom, a fluorine atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched fluorinated alkyl group having 1 to 4 carbon atoms. Represents a group.
W _{1 to} W ₂ represent an organic group having at least one of a fluorine atom and a silicon atom.
R _{4 to} R ₇ are each independently a hydrogen atom, a fluorine atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched fluorinated alkyl group having 1 to 4 carbon atoms. Represents a group. However, at least one of R _{4 to} R ₇ represents a fluorine atom. R ₄ and R ₅ or R ₆ and R ₇
May form a ring.
R ₈ represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms.
R ₉ represents a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched fluorinated alkyl group having 1 to 4 carbon atoms.
L < ₁ > -L < ₂ > represents a single bond or a bivalent coupling group, and the same thing as said L < ₃ > -L < ₅ > is mentioned.
Q represents a monocyclic or polycyclic cyclic aliphatic group.

  The general formula (CI) is more preferably the following general formulas (C-Ia) to (C-Id).

In the general formulas (C-1a) to (C-1d),
R _{10 to} R ₁₁ represent a hydrogen atom, a fluorine atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched fluorinated alkyl group having 1 to 4 carbon atoms.
W _{3 to} W ₆ represent an organic group having at least one of a fluorine atom and a silicon atom.

When W _{1 to} W ₆ are organic groups having a fluorine atom, they are fluorinated, straight chain, branched alkyl group or cycloalkyl group having 1 to 20 carbon atoms, or fluorinated having 1 to 20 carbon atoms. It is preferably a linear, branched, or cyclic alkyl ether group.

Examples of the fluorinated alkyl group for W _{1 to} W ₆ include trifluoroethyl group, pentafluoropropyl group, hexafluoroisopropyl group, hexafluoro (2-methyl) isopropyl group, heptafluorobutyl group, heptafluoroisopropyl group, octafluoro Examples thereof include an isobutyl group, a nonafluorohexyl group, a nonafluoro-t-butyl group, a perfluoroisopentyl group, a perfluorooctyl group, and a perfluoro (trimethyl) hexyl group.

When W _{1 to} W ₆ are an organic group having a silicon atom, a trialkylsilyl group or a cyclic siloxane substituted with an alkyl group having 1 to 6 carbon atoms is preferable. Specific examples include groups represented by the above general formulas (CS-1) to (CS-3).

Specific examples of the repeating unit represented by the general formula (CI) are shown below. In specific examples, X represents a hydrogen atom, —CH ₃ , —F, or —CF ₃ .

  The resin (A) preferably has a repeating unit represented by the following general formula (Ax) and a repeating unit represented by the following general formula (Ay).

In general formulas (Ax) and (Ay),
Rz represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.
Rax represents an organic group having at least one of a fluorine atom and a silicon atom.
Ray represents an organic group.
m represents an integer of 0 to 80.
n represents an integer of 10 to 100.

Examples of the organic group having a fluorine atom of Rax include an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, and an aryl group having a fluorine atom as described above.
Examples of the organic group having a silicon atom of Rax include the same alkylsilyl structure and cyclic siloxane structure as described above.
Examples of the organic group for Ray include an optionally substituted alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, aryl group, and aralkyl group. Ray preferably has at least one of a fluorine atom and a silicon atom.

  A resin having a repeating unit represented by the general formula (Ax) and a repeating unit represented by the general formula (Ay) is a novel compound.

  Specific examples of the repeating unit represented by the general formula (Ax) include those similar to the specific examples of the repeating unit represented by the general formula (C-1).

Specific examples of the repeating unit represented by the general formula (Ay) are shown below, but the present invention is not limited thereto. In specific examples, X represents a hydrogen atom, —CH ₃ , —F, or —CF ₃ .

  The repeating unit represented by the general formula (Ay) can be formed of a compound represented by the following general formula (Ay2).

In the general formula (Ay2),
Rz represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.
Ray ₂ represents an organic group having at least one silicon atom.

  The compound represented by the general formula (Ay2) is a novel compound.

  Resin (A) has a repeating unit represented by the following general formula (Az) in addition to the repeating unit represented by the general formula (Ax) and the repeating unit represented by the general formula (Ay). It may be.

In general formula (Az):
R _{1 to} R ₃ each independently represents a hydrogen atom, a fluorine atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched fluorinated alkyl group having 1 to 4 carbon atoms. Represents a group.
Ra represents an organic group.
L ₁ represents a single bond or a divalent linking group.

In the general formula (Az), examples of the organic group represented by Ra include an alkyl group (preferably having 1 to 10 carbon atoms), a cycloalkyl group (preferably having 3 to 10 carbon atoms), and an aryl group (preferably having a carbon number). 6-10) alone, a group combining two or more of these, a group having a lactone structure, a carboxyl group, and the like. Examples of the group having a lactone structure of Ra include a group having a lactone structure which will be described later in the resin of the component (B).
Examples of the divalent linking group for L ₁ include a carbonyloxy group, an alkylene group, a cycloalkylene group, an arylene group, and an ether group.

  Specific examples of the resin (A) are shown below, but the present invention is not limited thereto.

  When resin (A) has a silicon atom, it is preferable that content of a silicon atom is 2-50 mass% with respect to the molecular weight of resin (A), and it is more preferable that it is 2-30 mass%. Moreover, it is preferable that the repeating unit which has a silicon atom is 10-100 mass% in resin (A), and it is more preferable that it is 20-100 mass%.

When resin (A) has a fluorine atom, it is preferable that content of a fluorine atom is 5-80 mass% with respect to the molecular weight of resin (A), and it is more preferable that it is 10-80 mass%. Moreover, it is preferable that the repeating unit which has a fluorine atom is 10-100 mass% in resin (A), and it is more preferable that it is 30-100 mass%. The repeating unit having a —CONHSO ₂ — group is preferably 10 to 90% by mass, more preferably 10 to 50% by mass, and further preferably 10 to 30% by mass in the resin (A). preferable.

Resin (A) can be synthesized according to a conventional method (for example, radical polymerization). For example, as a general synthesis method, a monomer polymerization method in which a monomer species and an initiator are dissolved in a solvent and the polymerization is performed by heating, and a solution of the monomer species and the initiator is dropped into the heating solvent over 1 to 10 hours. And a dropping polymerization method to be added. Examples of the reaction solvent include ethers such as tetrahydrofuran, 1,4-dioxane, diisopropyl ether, ketones such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate, amide solvents such as dimethylformamide and dimethylacetamide, Examples thereof include a solvent that dissolves a resist composition such as propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and cyclohexanone.
The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon. As a polymerization initiator, a commercially available radical initiator (azo initiator, peroxide, etc.) is used to initiate the polymerization. As the radical initiator, an azo initiator is preferable, and an azo initiator having an ester group, a cyano group, or a carboxyl group is preferable. Preferred examples of the initiator include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2′-azobis (2-methylpropionate) and the like. A chain transfer agent such as a thiol compound may be used in combination with the polymerization initiator. 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 5 to 50% by mass, preferably 20 to 50% by mass. The reaction temperature is usually 10 ° C to 150 ° C, preferably 30 ° C to 120 ° C, more preferably 60-100 ° C.
After completion of the reaction, the mixture is allowed to cool to room temperature and purified. Purification can be accomplished by a liquid-liquid extraction method that removes residual monomers and oligomer components by combining water and an appropriate solvent, and a purification method in a solution state such as ultrafiltration that extracts and removes only those having a specific molecular weight or less. , Reprecipitation method that removes residual monomer by coagulating resin in poor solvent by dripping resin solution into poor solvent and purification in solid state such as washing filtered resin slurry with poor solvent A normal method such as a method can be applied. For example, the resin is precipitated as a solid by contacting a solvent (poor solvent) in which the resin is hardly soluble or insoluble in a volume amount of 10 times or less, preferably 10 to 5 times that of the reaction solution.

  The solvent (precipitation or reprecipitation solvent) used in the precipitation or reprecipitation operation from the polymer solution may be a poor solvent of the polymer. For example, hydrocarbon (pentane, hexane, Aliphatic hydrocarbons such as heptane and octane; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; aromatic hydrocarbons such as benzene, toluene and xylene), halogenated hydrocarbons (methylene chloride, chloroform, carbon tetrachloride, etc.) Halogenated aliphatic hydrocarbons; halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene), nitro compounds (nitromethane, nitroethane, etc.), nitriles (acetonitrile, benzonitrile, etc.), ethers (diethyl ether, diisopropyl ether, dimethoxyethane) Chain A Cyclic ethers such as tetrahydrofuran and dioxane), ketones (acetone, methyl ethyl ketone, diisobutyl ketone, etc.), esters (ethyl acetate, butyl acetate, etc.), carbonates (dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, etc.), alcohols ( (Methanol, ethanol, propanol, isopropyl alcohol, butanol, etc.), carboxylic acid (acetic acid, etc.), water, a mixed solvent containing these solvents, and the like. Among these, as a precipitation or reprecipitation solvent, a solvent containing at least an alcohol (particularly methanol or the like) or water is preferable. In such a solvent containing at least hydrocarbon, the ratio of alcohol (particularly methanol) and other solvent (for example, ester such as ethyl acetate, ethers such as tetrahydrofuran) is, for example, the former / the latter (volume ratio). 25 ° C.) = 10/90 to 99/1, preferably the former / the latter (volume ratio; 25 ° C.) = 30/70 to 98/2, more preferably the former / the latter (volume ratio; 25 ° C.) = 50 / It is about 50 to 97/3.

  The amount of the precipitation or reprecipitation solvent used can be appropriately selected in consideration of efficiency, yield, and the like, but generally 100 to 10000 parts by mass, preferably 200 to 2000 parts by mass with respect to 100 parts by mass of the polymer solution, More preferably, it is 300-1000 mass parts.

  The nozzle diameter at the time of supplying the polymer solution to the precipitation or reprecipitation solvent (poor solvent) is preferably 4 mmφ or less (for example, 0.2 to 4 mmφ). Moreover, the supply speed (dropping speed) of the polymer solution into the poor solvent is, for example, about 0.1 to 10 m / second, preferably about 0.3 to 5 m / second, as the linear speed.

  The precipitation or reprecipitation operation is preferably performed with stirring. As a stirring blade used for stirring, for example, a desk turbine, a fan turbine (including a paddle), a curved blade turbine, an arrow blade turbine, a fiddler type, a bull margin type, an angled blade fan turbine, a propeller, a multistage type, an anchor type (or Horseshoe type), gate type, double ribbon, screw, etc. can be used. Stirring is preferably further performed for 10 minutes or more, particularly 20 minutes or more after the supply of the polymer solution. When the stirring time is short, the monomer content in the polymer particles may not be sufficiently reduced. Further, the polymer solution and the poor solvent can be mixed and stirred using a line mixer instead of the stirring blade.

  The temperature for precipitation or reprecipitation can be appropriately selected in consideration of efficiency and operability, but is usually about 0 to 50 ° C., preferably around room temperature (for example, about 20 to 35 ° C.). The precipitation or reprecipitation operation can be performed by a known method such as a batch method or a continuous method using a conventional mixing vessel such as a stirring tank.

  The precipitated or re-precipitated particulate polymer is usually subjected to conventional solid-liquid separation such as filtration and centrifugation, and dried before use. Filtration is performed using a solvent-resistant filter medium, preferably under pressure. Drying is performed at a temperature of about 30 to 100 ° C., preferably about 30 to 50 ° C. under normal pressure or reduced pressure (preferably under reduced pressure).

In addition, once the resin is precipitated and separated, it may be dissolved again in a solvent, and the resin may be brought into contact with a hardly soluble or insoluble solvent.
That is, after completion of the radical polymerization reaction, a solvent in which the polymer is hardly soluble or insoluble is brought into contact, the resin is precipitated (step a), the resin is separated from the solution (step b), and the resin solution A is dissolved again in the solvent. (Step c), and then contact the resin solution A with a solvent in which the resin is hardly soluble or insoluble in a volume amount less than 10 times that of the resin solution A (preferably 5 times or less volume). This may be a method including precipitating a resin solid (step d) and separating the precipitated resin (step e).
The solvent used in the preparation of the resin solution A can be the same solvent as the solvent that dissolves the monomer in the polymerization reaction, and may be the same as or different from the solvent used in the polymerization reaction.

  The weight average molecular weight of the resin (A) according to the present invention is preferably 2000 to 100,000, more preferably 1000 to 50,000, and still more preferably 3000 to 15000 as a polystyrene conversion value by the GPC method. The degree of dispersion (molecular weight distribution) is usually 1 to 5, preferably 1 to 3, more preferably 1.2 to 2.2.

  The resin (A) of the present invention preferably has a residual monomer amount of 0 to 5% by mass, and more preferably 0 to 1% by mass.

Resin (A) can be suitably used in a positive resist composition. In that case, the positive resist composition preferably also contains the following components (B) to (D).
(B) a resin whose solubility in an alkaline developer is increased by the action of an acid;
(C) a compound that generates an acid upon irradiation with actinic rays or radiation, and (D) a solvent.

  The addition amount of the resin (A) in the positive resist composition is preferably 0.1 to 5% by mass, more preferably 0.2 to 3%, based on the total solid content of the positive resist composition. It is 0.0 mass%, More preferably, it is 0.3-2.0 mass%.

The resin (A) can also be used as a protective film forming composition for forming a protective film provided on the resist film. In that case, the resist film is used by dissolving in a solvent (S) that does not corrode.
80-100 mass% is preferable with respect to the total solid, and, as for the addition amount of resin (A) in a protective film formation composition, 95-100 mass% is more preferable.

  When the resin (A) is used for semiconductor applications, it should be understood that there are few impurities such as metals, and the residual monomer and oligomer components are not more than predetermined values, for example, 0.1% by mass or the like by HPLC. Thus, not only the sensitivity, resolution, process stability, pattern shape and the like as a resist can be further improved, but also a resist having no temporal change such as foreign matter in liquid or sensitivity can be obtained.

[1] Positive resist composition (B) Resin whose solubility in an alkaline developer is increased by the action of acid When the positive resist composition of the present invention is irradiated with ArF excimer laser light, the resin as component (B) Is preferably a resin that has a monocyclic or polycyclic alicyclic hydrocarbon structure, decomposes by the action of an acid, and increases the solubility in an alkaline developer.

  As a resin that has a monocyclic or polycyclic alicyclic hydrocarbon structure, decomposes by the action of an acid, and increases its solubility in an alkaline developer (hereinafter also referred to as “alicyclic hydrocarbon-based acid-decomposable resin”) , At least selected from the group consisting of repeating units having a partial structure containing an alicyclic hydrocarbon represented by the following general formula (pI) to general formula (pV) and repeating units represented by the following general formula (II-AB) A resin having one kind is preferred.

In the general formulas (pI) to (pV),
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.
Z represents an atomic group necessary for forming a cycloalkyl group together with a carbon atom.
R _{12 to} R ₁₆ each independently represents a linear or branched alkyl group or cycloalkyl group having 1 to 4 carbon atoms. However, at least one of R _{12 to} R ₁₄ , or any of R ₁₅ and R ₁₆ represents a cycloalkyl 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 a cycloalkyl group. However, at least one of R _{17 to} R ₂₁ represents a cycloalkyl group. Further, either R ₁₉ or R ₂₁ represents a linear or branched alkyl group or cycloalkyl 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 a cycloalkyl group. However, at least one of R _{22 to} R ₂₅ represents a cycloalkyl group. R ₂₃ and R ₂₄ may be bonded to each other to form a ring.

In general 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).

  The general formula (II-AB) is more preferably the following general formula (II-AB1) or general formula (II-AB2).

In the general formulas (II-AB1) and (II-AB2),
R ₁₃ ′ to R ₁₆ ′ each independently represents a hydrogen atom, a halogen atom, 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 cycloalkyl group. At least two of R ₁₃ ′ to R ₁₆ ′ may combine to form a ring.
Here, R ₅ represents an alkyl group, a cycloalkyl group, or a group having a lactone structure.
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.
R ₁₇ ′ represents —COOH, —COOR ₅ , —CN, a hydroxyl group, an alkoxy group, —CO—NH—R ₆ , —CO—NH—SO ₂ —R ₆ or a group having a lactone structure.
R ₆ represents an alkyl group or a cycloalkyl group.
n represents 0 or 1.

Examples of the linear or branched alkyl group having 1 to 4 carbon atoms in the general formulas (pI) to (pV) and R _{12 to} R ₂₅ include a methyl group and an ethyl group. .

The cycloalkyl group represented by R _{12 to} R ₂₅ or the cycloalkyl group formed by Z and the 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 cycloalkyl groups may have a substituent.

  Preferred cycloalkyl groups include adamantyl group, noradamantyl group, decalin residue, tricyclodecanyl group, tetracyclododecanyl group, norbornyl group, cedrol group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, A cyclodecanyl group and a cyclododecanyl group can be mentioned. More preferable examples include an adamantyl group, norbornyl group, cyclohexyl group, cyclopentyl group, tetracyclododecanyl group, and tricyclodecanyl group.

  As further substituents of these alkyl groups and cycloalkyl groups, alkyl groups (1 to 4 carbon atoms), halogen atoms, hydroxyl groups, alkoxy groups (1 to 4 carbon atoms), carboxyl groups, alkoxycarbonyl groups (carbon numbers) 2-6). 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 (pV) 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 structure in which a hydrogen atom of a carboxylic acid group, a sulfonic acid group, a phenol group, or a thiol group is substituted with a structure represented by the general formulas (pI) to (PV), preferably a carboxylic acid Group, the hydrogen atom of a sulfonic acid group is the structure substituted by the structure represented by general formula (pI)-(PV).

  As the repeating unit having an alkali-soluble group protected by the structure represented by the general formulas (pI) to (pV), a repeating unit represented by the following general formula (pA) is preferable.

In the general formula (pA),
R represents a hydrogen atom, a halogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms. A plurality of R may be the same or different.
A represents a single bond, 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. A single bond is preferable.
Rp ₁ represents any one of the general formulas (pI) to (pV).

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

  Hereinafter, although the specific example of the repeating unit shown by general formula (pA) is shown, this invention is not limited to this.

Examples of the halogen atom in the general formula (II-AB), R ₁₁ ′, and R ₁₂ ′ include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom.
Examples of the alkyl group for R ₁₁ ′ and R ₁₂ ′ include linear or branched alkyl groups having 1 to 10 carbon atoms.
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 the resin, and in particular, a bridged alicyclic ring An atomic group for forming a bridged alicyclic structure forming a repeating unit of the formula hydrocarbon is preferred.

Examples of the skeleton of the alicyclic hydrocarbon formed include those similar to the cycloalkyl groups of R _{12 to} R _{25 in} the general formulas (pI) to (pV).

The alicyclic hydrocarbon skeleton may have a substituent. Examples of such a substituent include R ₁₃ ′ to R ₁₆ ′ in the general formula (II-AB1) or (II-AB2).

In the alicyclic hydrocarbon-based acid-decomposable resin according to the present invention, the group decomposed by the action of an acid has a partial structure containing the alicyclic hydrocarbon represented by the general formula (pI) to the general formula (pV). It can be contained in at least one kind of repeating unit among the repeating unit having, the repeating unit represented by formula (II-AB), and the repeating unit of the copolymerization component described later.
One acid-decomposable repeating unit may be used, but it is preferable to use two or more acid-decomposable repeating units having different numbers of carbon atoms in the acid leaving group. Thereby, the balance between the resolution and the exposure latitude is improved.

Various substituents of R ₁₃ ′ to R ₁₆ ′ in the general formula (II-AB1) or the general formula (II-AB2) are atomic groups or groups for forming an alicyclic structure in the general formula (II-AB). It can also be a substituent of the atomic group Z ′ for forming a bridged alicyclic structure.

  Specific examples of the repeating unit represented by the general formula (II-AB1) or (II-AB2) include the following specific examples, but the present invention is not limited to these specific examples.

The alicyclic hydrocarbon-based acid-decomposable resin of the present invention preferably has a group having a lactone structure. As the group having a lactone structure, any group having a lactone structure can be used, but a group having a 5- to 7-membered ring lactone structure is preferable. A structure in which another ring structure is condensed to form a structure or a spiro structure is preferable. A group having a lactone structure represented by any one of the following general formulas (LC1-1) to (LC1-16) is more preferable. Further, a group having a lactone structure may be directly bonded to the main chain. Preferred lactone structures are (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), (LC1-14), and a specific lactone structure is used. This improves line edge roughness and development defects.

The lactone structure moiety may or may not have a substituent (Rb ₂ ). Preferred substituents (Rb ₂ ) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, and a carboxyl group. , Halogen atom, hydroxyl group, cyano group, acid-decomposable group and the like. n2 represents an integer of 0 to 4. When n2 is 2 or more, a plurality of Rb ₂ may be the same or different, and a plurality of Rb ₂ may be bonded to form a ring.

As the repeating unit having a group having a lactone structure represented by any of the general formulas (LC1-1) to (LC1-16), R _{13 in the} general formula (II-AB1) or (II-AB2) may be used. A group having a group represented by general formula (LC1-1) to (LC1-16) at least one of 'to R ₁₆ ' (for example, R _{5 of} -COOR ₅ is represented by formula (LC1-1) to ( And 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. Preferable substituents that the alkyl group for R _b0 may have include a hydroxyl group and a halogen atom.
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 or a methyl group.
Ab represents a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a divalent group obtained by combining these. To express.
Ab is preferably a single bond or a linking group represented by —Ab ₁ —CO ₂ —. Ab ₁ is a linear or branched alkylene group, a monocyclic or polycyclic cycloalkylene group, preferably a methylene group, an ethylene group, a cyclohexyl residue (a group in which one hydrogen atom has been removed from the cyclohexyl group, The same shall apply hereinafter), adamantyl residue and norbornyl residue.
V represents a group having a lactone structure represented by any one of the general formulas (LC1-1) to (LC1-16).

  The repeating unit having a group having a lactone structure usually has an optical isomer, but any optical isomer may be used. One optical isomer may be used alone, or a plurality of optical isomers may be mixed and used. When one kind of optical isomer is mainly used, the optical purity (ee) thereof is preferably 90 or more, more preferably 95 or more.

  The content of the repeating unit having a group having a lactone structure is preferably from 15 to 60 mol%, more preferably from 20 to 50 mol%, still more preferably from 30 to 50 mol%, based on all repeating units in the polymer.

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

  Examples of the repeating unit having a group having a particularly preferable lactone structure include the following repeating units. By selecting the optimum lactone structure, the pattern profile and the density dependence become good.

  The alicyclic hydrocarbon-based acid-decomposable resin of the present invention preferably has a repeating unit having an alicyclic hydrocarbon structure substituted with a polar group. This improves the substrate adhesion and developer compatibility. The alicyclic hydrocarbon structure of the alicyclic hydrocarbon structure substituted with a polar group is preferably an adamantyl group, a diamantyl group, or a norbornane group. The polar group is preferably a hydroxyl group or a cyano group. As the alicyclic hydrocarbon structure substituted with a preferable polar group, partial structures represented by the following general formulas (VIIa) to (VIId) are preferable.

In general formulas (VIIa) to (VIIc),
R _{2c to} R _4c each independently represents a hydrogen atom, a hydroxyl group or a cyano group. However, at least one of R _{2c to} R _4c represents a hydroxyl group or a cyano group. Preferably, one or two of R _{2c to} R _4c are a hydroxyl group and the rest are hydrogen atoms. In (VIIa), more preferably, two of R _{2c to} R _4c are hydroxyl groups and the rest are hydrogen atoms.

As the repeating unit having a group represented by general formulas (VIIa) to (VIId), at least one of R ₁₃ ′ to R ₁₆ ′ in general formula (II-AB1) or (II-AB2) is generally Those having a group represented by formulas (VIIa) to (VIId) (for example, R _{5 in} —COOR ₅ represents a group represented by general formulas (VIIa) to (VIId)), or the following general formula (AIIa) The repeating unit etc. which are represented by-(AIId) can be mentioned.

In the general formulas (AIIa) to (AIIb),
R _1c represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.
R ₂ c to R ₃ c is a general formula (VIIa) ~ same meanings as in R ₂ c to R ₃ c in (VIIc).

  The content of the repeating unit having an alicyclic hydrocarbon structure substituted with a polar group is preferably 5 to 40 mol%, more preferably 5 to 30 mol%, still more preferably 10 to 25 mol, based on all repeating units in the polymer. %.

  Specific examples of the repeating unit having an alicyclic hydrocarbon structure substituted with a polar group are given below, but the present invention is not limited thereto.

  The alicyclic hydrocarbon-based acid-decomposable resin of the present invention may have a repeating unit represented by the following general formula (VIII).

In the above general formula (VIII),
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 of R ₄₁ and R ₄₂ may be substituted with a halogen atom (preferably a fluorine atom) or the like.

  Examples of the repeating unit represented by the general formula (VIII) include the following specific examples, but the present invention is not limited thereto.

  The alicyclic hydrocarbon-based acid-decomposable resin of the present invention preferably has a repeating unit having an alkali-soluble group. As an alkali-soluble group, a carboxyl group, a sulfonamide group, a sulfonylimide group, a bisulsulfonylimide group, an aliphatic alcohol substituted with an electron-attracting group at the α-position (preferably a structure represented by the following general formula (F1)) It is more preferable to have a repeating unit having a carboxyl group.

In general formula (F1),
R _{50 to} R ₅₅ each independently represents a hydrogen atom, a fluorine atom or an alkyl group. However, at least one of R _{50 to} R ₅₅ represents a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. All of R _{50 to} R ₅₅ are preferably fluorine atoms.

  By having a repeating unit having an alkali-soluble group, the resolution in contact hole applications is increased. The repeating unit having an alkali-soluble group includes a repeating unit in which an alkali-soluble group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid or methacrylic acid, or an alkali in the main chain of the resin through a linking group. Either a repeating unit to which a soluble group is bonded, or a polymerization initiator or chain transfer agent having an alkali-soluble group is used at the time of polymerization and introduced at the end of the polymer chain, and the linking group is monocyclic or polycyclic. It may have a cyclic hydrocarbon structure. Particularly preferred are repeating units of acrylic acid or methacrylic acid.

  As for content of the repeating unit which has an alkali-soluble group, 1-20 mol% is preferable with respect to all the repeating units in a polymer, More preferably, it is 3-15 mol%, More preferably, it is 5-10 mol%.

  Specific examples of the repeating unit having an alkali-soluble group are shown below, but the present invention is not limited thereto.

  The alicyclic hydrocarbon-based acid-decomposable resin of the present invention may further have a repeating unit having an alicyclic hydrocarbon structure and not exhibiting acid decomposability. This can reduce the elution of low molecular components from the resist film to the immersion liquid during immersion exposure. Examples of such a repeating unit include 1-adamantyl (meth) acrylate, tricyclodecanyl (meth) acrylate, cyclohexyl (meth) acrylate, and the like.

  In addition to the above repeating structural units, the alicyclic hydrocarbon-based acid-decomposable resin of the present invention has a dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and resolving power that is a general necessary characteristic of a resist. Various repeating structural units can be contained for the purpose of adjusting heat resistance, sensitivity, and the like.

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

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

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

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

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

Preferred embodiments of the alicyclic hydrocarbon-based acid-decomposable resin of the present invention include the following.
(1) What has a repeating unit which has a partial structure containing the alicyclic hydrocarbon represented by said general formula (pI)-(pV) (side chain type).
Preferably, those having a (meth) acrylate-based repeating unit having a structure represented by general formulas (pI) to (pV).
(2) One having a repeating unit represented by the general formula (II-AB) (main chain type).
However, in (2), the following are further exemplified.
(3) Those having a repeating unit represented by formula (II-AB), a maleic anhydride derivative and a (meth) acrylate structure (hybrid type).

  In the alicyclic hydrocarbon-based acid-decomposable resin, the content of the repeating unit having an acid-decomposable group is preferably 10 to 60 mol%, more preferably 20 to 50 mol%, still more preferably 25 in all repeating structural units. -40 mol%.

  In the alicyclic hydrocarbon-based acid-decomposable resin, the content of the repeating unit having a partial structure containing the alicyclic hydrocarbon represented by the general formulas (pI) to (pV) is 20 to 70 in all the repeating structural units. The mol% is preferable, more preferably 20 to 50 mol%, still more preferably 25 to 40 mol%.

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

  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. ) To 99 p% with respect to the total number of moles of the repeating structural unit having a partial structure containing an alicyclic hydrocarbon represented by (pV) and the repeating unit represented by the general formula (II-AB). The following is preferable, More preferably, it is 90 mol% or less, More preferably, it is 80 mol% or less.

  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 alicyclic hydrocarbon-based acid-decomposable resin used in the present invention is preferably one in which all of the repeating units are composed of (meth) acrylate-based repeating units. In this case, all of the repeating units may be methacrylate-based, all of the repeating units may be acrylate-based, or methacrylate / acrylate-based mixed, but the acrylate-based repeating unit is 50 mol% or less of the total repeating units. It is preferable. More preferably, the repeating unit having a partial structure containing an alicyclic hydrocarbon represented by the general formulas (pI) to (pV) is 20 to 50 mol%, the repeating unit having a lactone structure is 20 to 50 mol%, and is substituted with a polar group. It is a ternary copolymer containing 5 to 30 mol% of repeating units having an alicyclic hydrocarbon structure, or a quaternary copolymer containing 0 to 20 mol% of other repeating units.
Particularly preferable alicyclic hydrocarbon-based acid-decomposable resins include 20 to 50 mol% of repeating units having an acid-decomposable group represented by the following general formulas (ARA-1) to (ARA-5), and a general formula (ARL- 1) to (ARL-6), a fatty acid substituted with 20 to 50 mol% of a repeating unit having a group having a lactone structure represented by formula (ARH-1) to (ARH-3) A terpolymer having 5-30 mol% of repeating units having a cyclic hydrocarbon structure, or a carboxyl group, or a repeating unit containing a structure represented by the general formula (F1), having an alicyclic hydrocarbon structure. And a quaternary copolymer containing 5 to 20 mol% of repeating units that do not exhibit acid decomposability.
In the formula, Rxy ₁ represents a hydrogen atom or a methyl group, and Rxa ₁ and Rxb ₁ represent a methyl group or an ethyl group.

The alicyclic hydrocarbon-based acid-decomposable resin used in the present invention can be synthesized according to a conventional method (for example, radical polymerization). For example, as a general synthesis method, a monomer polymerization method in which a monomer species and an initiator are dissolved in a solvent and the polymerization is performed by heating, and a solution of the monomer species and the initiator is dropped into the heating solvent over 1 to 10 hours. The dropping polymerization method is added, and the dropping polymerization method is preferable. Examples of the reaction solvent include ethers such as tetrahydrofuran, 1,4-dioxane, diisopropyl ether, ketones such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate, amide solvents such as dimethylformamide and dimethylacetamide, Furthermore, the solvent which melt | dissolves the composition of this invention like the below-mentioned propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and cyclohexanone is mentioned. More preferably, the polymerization is performed using the same solvent as that used in the resist composition of the present invention. Thereby, the generation of particles during storage can be suppressed.
The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon. As a polymerization initiator, a commercially available radical initiator (azo initiator, peroxide, etc.) is used to initiate the polymerization. As the radical initiator, an azo initiator is preferable, and an azo initiator having an ester group, a cyano group, or a carboxyl group is preferable. Preferred examples of the initiator include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2′-azobis (2-methylpropionate) and the like. A chain transfer agent such as a thiol compound may be used in combination with the polymerization initiator. 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 5 to 50% by mass, preferably 10 to 30% by mass. The reaction temperature is usually 10 ° C to 150 ° C, preferably 30 ° C to 120 ° C, more preferably 60-100 ° C.

The weight average molecular weight of the resin according to the present invention is preferably 1,000 to 200,000, more preferably 3,000 to 20,000, and particularly preferably 5,000 to 15 in terms of polystyrene by GPC method. , 000. By setting the weight average molecular weight to 1,000 to 200,000, deterioration of heat resistance and dry etching resistance can be prevented, developability is deteriorated, and viscosity is increased, resulting in deterioration of film forming property. Can be prevented.
The degree of dispersion (molecular weight distribution) is usually from 1 to 5, preferably from 1 to 3, more preferably from 1 to 2. The smaller the degree of dispersion (molecular weight distribution), the better the resolution and the resist shape, the smoother the sidewall of the resist pattern, and the better the roughness.

In the positive resist composition of the present invention, the blending amount of all the resins according to the present invention in the entire composition is preferably 60 to 99% by mass, more preferably 80 to 98% by mass in the total solid content.
In the present invention, the resins may be used alone or in combination.

(C) Compound that generates acid upon irradiation with actinic ray or radiation The positive resist composition of the present invention comprises a compound that generates acid upon irradiation with actinic ray or radiation (hereinafter also referred to as “photoacid generator”). contains.
Examples of such photoacid generators include photoinitiators for photocationic polymerization, photoinitiators for photoradical polymerization, photodecolorants for dyes, photochromic agents, actinic rays used in microresists, etc. Known compounds that generate an acid upon irradiation with radiation 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.

  Among the compounds that generate an acid upon irradiation with actinic rays or radiation, compounds represented by the following general formulas (ZI), (ZII), and (ZIII) can be exemplified.

In general formula (ZI):
R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represents an organic group.
X ⁻ represents a non-nucleophilic anion, preferably sulfonate anion, carboxylate anion, bis (alkylsulfonyl) amide anion, tris (alkylsulfonyl) methide anion, BF ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ^{— and the} like. Preferably, it is an organic anion containing a carbon atom.

  Preferred organic anions include organic anions represented by the following general formulas (AN1) to (AN4).

In general formulas (AN1) to (AN2),
Rc ₁ represents an organic group.
Examples of the organic group in Rc ₁ include those having 1 to 30 carbon atoms, and preferably an alkyl group, an aryl group, or a plurality of which may be substituted is a single bond, —O—, —CO ₂ —, _{-S -, - SO 3 -,} - SO 2 N (Rd 1) - can be exemplified linked group a linking group such as.
Rd ₁ represents a hydrogen atom or an alkyl group, and may form a ring structure with the bonded alkyl group or aryl group.
More preferred as the organic group for Rc ₁ is an alkyl group substituted at the 1-position with a fluorine atom or a fluoroalkyl group, or a phenyl group substituted with a fluorine atom or a fluoroalkyl group. By having a fluorine atom or a fluoroalkyl group, the acidity of the acid generated by light irradiation is increased and the sensitivity is improved. When Rc ₁ has 5 or more carbon atoms, it is preferable that at least one carbon atom has a hydrogen atom, not all hydrogen atoms are substituted with fluorine atoms, and the number of hydrogen atoms is fluorine. More preferably than atoms. By not having a perfluoroalkyl group having 5 or more carbon atoms, ecotoxicity is reduced.
A particularly preferred embodiment of Rc ₁ is a group represented by the following general formula.

In the above general formula,
Rc ₆ is substituted with a perfluoroalkylene group having 4 or less carbon atoms, more preferably 2 to 4, more preferably 2 to 3, or 1 to 4 fluorine atoms and / or 1 to 3 fluoroalkyl groups. Represents a substituted phenylene group.
Ax represents a single bond or a divalent linking group (preferably —O—, —CO ₂ —, —S—, —SO ₃ —, —SO ₂ N (Rd ₁ ) —). Rd ₁ represents a hydrogen atom or an alkyl group, and may combine with Rc ₇ to form a ring structure.
Rc ₇ represents a hydrogen atom, a fluorine atom, may be substituted linear or branched alkyl group, a monocyclic or polycyclic cycloalkyl group, or an optionally substituted aryl group. The optionally substituted alkyl group, cycloalkyl group and aryl group preferably do not contain a fluorine atom as a substituent.

In general formulas (AN3) and (AN4),
Rc ₃ , Rc ₄ and Rc ₅ each independently represents an organic group.
Preferred examples of the organic group for Rc ₃ , Rc ₄ and Rc ₅ include the same organic groups as those for Rc ₁ .
Rc ₃ and Rc ₄ may combine to form a ring.
Examples of the group formed by combining Rc ₃ and Rc ₄ include an alkylene group, a cycloalkylene group, and an arylene group. A perfluoroalkylene group having 2 to 4 carbon atoms is preferred. By combining Rc ₃ and Rc ₄ to form a ring, the acidity of the acid generated by light irradiation is increased, and the sensitivity is improved, which is preferable.

In formula (ZI), the carbon number of the organic group as R _201, R ₂₀₂ and R ₂₀₃ is generally from 1 to 30, preferably 1 to 20.
It is also possible to form the two members ring structure of the R ₂₀₁ to R _203, an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. The two of the group formed by bonding of the R ₂₀₁ to R _203, there can be mentioned an alkylene group (e.g., butylene, pentylene).
Specific examples of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ include corresponding groups in the compounds (ZI-1), (ZI-2) and (ZI-3) described later.

In addition, the compound which has two or more structures represented by general formula (Z1) 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.

  Further preferred examples of the component (Z1) include compounds (ZI-1), (ZI-2), and (ZI-3) described below.

The compound (ZI-1) is at least one of the aryl groups R ₂₀₁ to R ₂₀₃ in formula (ZI), arylsulfonium compound, i.e., a compound having arylsulfonium as a cation.
In the arylsulfonium compound, all of R _{201 to} R ₂₀₃ may be an aryl group, or a part of R _{201 to} R ₂₀₃ may be an aryl group, and the rest may be an alkyl group or a cycloalkyl group.
Examples of the arylsulfonium compound include triarylsulfonium compounds, diarylalkylsulfonium compounds, aryldialkylsulfonium compounds, diarylcycloalkylsulfonium compounds, and aryldicycloalkylsulfonium compounds.
The aryl group of the arylsulfonium compound is preferably an aryl group such as a phenyl group or a naphthyl group, or a heteroaryl group such as an indole residue or a pyrrole residue, more preferably a phenyl group or an indole residue. 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.
Aryl group, alkyl group of R ₂₀₁ to R _203, cycloalkyl group, an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms), an aryl group (for example, 6 to 14 carbon atoms) , An alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, or a phenylthio group may be substituted. Preferred substituents are linear or branched alkyl groups having 1 to 12 carbon atoms, cycloalkyl groups having 3 to 12 carbon atoms, and linear, branched or cyclic alkoxy groups having 1 to 12 carbon atoms, particularly preferably. They are a C1-C4 alkyl group and a C1-C4 alkoxy group. 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.

Next, the compound (ZI-2) will be described.
Compound (ZI-2) is a compound in the case where R _{201 to} R ₂₀₃ in formula (ZI) each independently represents an organic group not containing an aromatic ring. Here, the aromatic ring includes an aromatic ring containing a hetero atom.
The organic group having no aromatic ring as R ₂₀₁ to R ₂₀₃ generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
R _{201 to} R ₂₀₃ are 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, and particularly preferably a linear group. A branched 2-oxoalkyl group.

The alkyl group as R ₂₀₁ to R ₂₀₃ may be linear, it may be either branched, preferably a straight-chain or branched alkyl group (e.g., methyl group having 1 to 10 carbon atoms, an ethyl group, a propyl Group, butyl group, pentyl group). The alkyl group as R ₂₀₁ to R ₂₀₃ is a straight-chain or branched 2-oxoalkyl group is preferably an alkoxycarbonyl methyl group.
The cycloalkyl group as R ₂₀₁ to R ₂₀₃ is preferably, and a cycloalkyl group having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl, norbornyl). The cycloalkyl group as R ₂₀₁ to R ₂₀₃ is preferably a cyclic 2-oxoalkyl group.
The 2-oxoalkyl group as R _{201 to} R ₂₀₃ may be linear, branched or cyclic, and preferably a group having> C═O at the 2-position of the above alkyl group or cycloalkyl group Can be mentioned.
The alkoxy group in the alkoxycarbonylmethyl group as R ₂₀₁ to R _203, preferably may be mentioned alkoxy groups having 1 to 5 carbon atoms (a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group).
R _{201 to} R ₂₀₃ may be further substituted with a halogen atom, an alkoxy group (eg, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group.

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

In general formula (ZI-3),
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 each independently represents 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 _7c, and R _x and R _y may be bonded to each other to form a ring structure, the ring structure may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond May be included. Examples of the group formed by combining any two or more of R _{1c to} R _7c and R _x and R _y include a butylene group and a pentylene group.
X ⁻ represents a non-nucleophilic anion, and examples thereof include the same non-nucleophilic anion as X ^{− in} formula (ZI).

The alkyl group as R _{1c to} R _7c may be linear or branched, for example, a linear or branched alkyl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms. Examples thereof include linear and branched alkyl groups (for example, methyl group, ethyl group, linear or branched propyl group, linear or branched butyl group, linear or branched pentyl group).
Preferable examples of the cycloalkyl group as R _{1c to} R _7c include a cycloalkyl group having 3 to 8 carbon atoms (for example, 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 carbon numbers 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 as R _x and R _y include the same alkyl groups as R _{1c to} R _7c . The alkyl group as R _x and R _y is preferably a linear or branched 2-oxoalkyl group or an alkoxycarbonylmethyl group.
The cycloalkyl group as R _x and R _y may be the same as the cycloalkyl group as R _1c to R _7c. The cycloalkyl group as R _x and R _y is preferably a cyclic 2-oxoalkyl group.
Examples of the linear, branched, or cyclic 2-oxoalkyl 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 .
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 the general formulas (ZII) and (ZIII),
R ₂₀₄ to R ₂₀₇ each independently represents an aryl group, an alkyl group or a cycloalkyl group.
The aryl group of R ₂₀₄ to R _207, a phenyl group, a naphthyl group, more preferably a phenyl group.
The alkyl group as R ₂₀₄ to R ₂₀₇ may be linear, it may be either branched, preferably a straight-chain or branched alkyl group (e.g., methyl group having 1 to 10 carbon atoms, an ethyl group, a propyl Group, butyl group, pentyl group).
The cycloalkyl group as R ₂₀₄ to R ₂₀₇ is preferably, and a cycloalkyl group having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl, norbornyl).
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).

  Among the compounds that generate an acid upon irradiation with actinic rays or radiation, compounds represented by the following general formulas (ZIV), (ZV), and (ZVI) can be further exemplified.

In the general formulas (ZIV) to (ZVI),
Ar ₃ and Ar ₄ each independently represents an aryl group.
R ₂₀₆ represents an alkyl group, a cycloalkyl group or an aryl group.
R ₂₀₇ and R ₂₀₈ each independently represents an alkyl group, a cycloalkyl group, an aryl group, or an electron-withdrawing group. R ₂₀₇ is preferably an aryl group. R ₂₀₈ is preferably an electron-withdrawing group, more preferably a cyano group or a fluoroalkyl group.
A represents an alkylene group, an alkenylene group or an arylene group.

Of the compounds that generate an acid upon irradiation with actinic rays or radiation, more preferred are compounds represented by general formulas (ZI) to (ZIII), and even more preferred are compounds represented by general formula (ZI). And particularly preferred are compounds represented by the general formulas (ZI-1) to (ZI-3).
Furthermore, the compound which generate | occur | produces the acid represented by the following general formula (AC1)-(AC3) by irradiation of actinic light or a radiation is preferable.

  That is, as a particularly preferable mode of the photoacid generator, in the compound represented by the general formula (ZI), X- is an anion selected from the general formulas (AN1), (AN3), and (AN4). It is a compound which is.

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

A photo-acid generator can be used individually by 1 type or in combination of 2 or more types. When two or more types are used in combination, it is preferable to combine two types of compounds that generate two types of organic acids that differ in the total number of atoms excluding hydrogen atoms by two or more.
The content of the photoacid generator in the composition is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, and still more preferably 1 based on the total solid content of the positive resist composition. -7% by mass.

(D) Solvent Solvents that can be used in preparing the positive resist composition by dissolving each component include, for example, alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate ester, alkoxy Examples thereof include organic solvents such as alkyl propionate, cyclic lactones having 4 to 10 carbon atoms, monoketone compounds having 4 to 10 carbon atoms, which may contain a ring, alkylene carbonate, alkyl alkoxyacetate, and alkyl pyruvate.

Examples of the alkylene glycol monoalkyl ether carboxylate include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl Preferred examples include ether propionate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate.
Preferred examples of the alkylene glycol monoalkyl ether include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether, and ethylene glycol monoethyl ether.

Preferred examples of the alkyl lactate include methyl lactate, ethyl lactate, propyl lactate and butyl lactate.
Preferable examples of the alkyl alkoxypropionate include ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, and ethyl 3-methoxypropionate.

  Examples of the cyclic lactone having 4 to 10 carbon atoms include β-propiolactone, β-butyrolactone, γ-butyrolactone, α-methyl-γ-butyrolactone, β-methyl-γ-butyrolactone, γ-valerolactone, γ- Caprolactone, γ-octanoic lactone, and α-hydroxy-γ-butyrolactone are preferred.

  Examples of the monoketone compound having 4 to 10 carbon atoms which may contain a ring include 2-butanone, 3-methylbutanone, pinacolone, 2-pentanone, 3-pentanone, 3-methyl-2-pentanone, 4- Methyl-2-pentanone, 2-methyl-3-pentanone, 4,4-dimethyl-2-pentanone, 2,4-dimethyl-3-pentanone, 2,2,4,4-tetramethyl-3-pentanone, 2 -Hexanone, 3-hexanone, 5-methyl-3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-methyl-3-heptanone, 5-methyl-3-heptanone, 2,6-dimethyl-4 -Heptanone, 2-octanone, 3-octanone, 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 3-decanone, 4-decanone, 5- Xen-2-one, 3-penten-2-one, cyclopentanone, 2-methylcyclopentanone, 3-methylcyclopentanone, 2,2-dimethylcyclopentanone, 2,4,4-trimethylcyclopenta Non, cyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, 4-ethylcyclohexanone, 2,2-dimethylcyclohexanone, 2,6-dimethylcyclohexanone, 2,2,6-trimethylcyclohexanone, cycloheptanone, 2-methylcyclo Preferred are heptanone and 3-methylcycloheptanone.

Preferred examples of the alkylene carbonate include propylene carbonate, vinylene carbonate, ethylene carbonate, and butylene carbonate.
Examples of the alkyl alkoxyacetate include 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2- (2-ethoxyethoxy) ethyl acetate, 3-methoxy-3-methylbutyl acetate, and 1-methoxy-acetate. 2-propyl is preferred.
Preferred examples of the alkyl pyruvate include methyl pyruvate, ethyl pyruvate, and propyl pyruvate.

As a solvent which can be preferably used, a solvent having a boiling point of 130 ° C. or higher under normal temperature and normal pressure can be mentioned. Specifically, cyclopentanone, γ-butyrolactone, cyclohexanone, ethyl lactate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, ethyl pyruvate, 2-ethoxyethyl acetate, acetic acid -2- (2-ethoxyethoxy) ethyl and propylene carbonate are mentioned. A particularly preferred solvent is propylene glycol monomethyl ether acetate.
In the present invention, the above solvents may be used alone or in combination of two or more.

In this invention, you may use the mixed solvent which mixed the solvent which contains a hydroxyl group in a structure, and the solvent which does not contain a hydroxyl group as a solvent.
Examples of the solvent containing 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. And propylene glycol monomethyl ether is more preferred.
Examples of the solvent not containing a hydroxyl group include propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, butyl acetate, N-methylpyrrolidone, N, N-dimethylacetamide, dimethyl sulfoxide and the like. Among these, propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, and butyl acetate are more preferable, and propylene glycol monomethyl ether acetate and cyclohexanone are particularly preferable.
The mixing ratio (mass) of the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group is 1/99 to 99/1, preferably 10/90 to 90/10, more preferably 20/80 to 60/40. . A mixed solvent containing 50% by mass or more of a solvent not containing a hydroxyl group is particularly preferred from the viewpoint of coating uniformity.

(E) Basic compound The positive resist composition of the present invention preferably contains (E) a basic compound in order to reduce a change in performance over time from exposure to heating.
Preferred examples of the basic compound include compounds having structures represented by the following formulas (A) to (E).

In the general formulas (A) to (E),
R ²⁰⁰ , R ²⁰¹ and R ²⁰² may be the same or different and are a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms. Here, R ²⁰¹ and R ²⁰² 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 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, Or a C1-C20 cyanoalkyl group is preferable.
R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ may be the same or different and each represents an alkyl group having 1 to 20 carbon atoms.
The alkyl groups in these general formulas (A) to (E) are more preferably unsubstituted.

  Preferred compounds include substituted or unsubstituted guanidine, substituted or unsubstituted aminopyrrolidine, substituted or unsubstituted pyrazole, substituted or unsubstituted pyrazoline, substituted or unsubstituted piperazine, substituted or unsubstituted aminomorpholine, substituted or An unsubstituted aminoalkylmorpholine, a substituted or unsubstituted piperidine can be mentioned, and more preferable compounds are imidazole structure, diazabicyclo structure, onium hydroxide structure, onium carboxylate structure, trialkylamine structure, aniline structure or pyridine. Examples thereof include a compound having a structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, and an aniline derivative having a hydroxyl group and / or an ether bond.

Examples of the compound having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole, and the like. As the compound having a diazabicyclo structure, 1,4-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4,3,0] non-5-ene, 1,8-diazabicyclo [5,4,0 ] Undecar 7-ene. Examples of the compound having an onium hydroxide structure include triarylsulfonium hydroxide, phenacylsulfonium hydroxide, sulfonium hydroxide having a 2-oxoalkyl group, specifically triphenylsulfonium hydroxide, tris (t-butylphenyl) sulfonium. Examples thereof include hydroxide, bis (t-butylphenyl) iodonium hydroxide, phenacylthiophenium hydroxide, and 2-oxopropylthiophenium hydroxide. The compound having an onium carboxylate structure is a compound having an onium hydroxide structure in which the anion moiety is converted to a carboxylate, and examples thereof include acetate, adamantane-1-carboxylate, and perfluoroalkylcarboxylate. Examples of the compound having a trialkylamine structure include tri (n-butyl) amine and tri (n-octyl) amine. Examples of aniline compounds include 2,6-diisopropylaniline and N, N-dimethylaniline. Examples of the alkylamine derivative having a hydroxyl group and / or an ether bond include ethanolamine, diethanolamine, triethanolamine, and tris (methoxyethoxyethyl) amine. Examples of aniline derivatives having a hydroxyl group and / or an ether bond include N, N-bis (hydroxyethyl) aniline.
These basic compounds are used alone or in combination of two or more.

  The usage-amount of a basic compound is 0.001-10 mass% normally on the basis of solid content of a positive resist composition, Preferably it is 0.01-5 mass%.

  The use ratio of the acid generator and the basic compound in the composition is preferably acid generator / 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 / basic compound (molar ratio) is more preferably 5.0 to 200, still more preferably 7.0 to 150.

(F) Surfactant The positive resist composition of the present invention preferably further contains (F) a surfactant, and is a fluorine-based and / or silicon-based surfactant (fluorine-based surfactant, silicon-based interface). It is more preferable to contain any one or two or more of an activator and a surfactant having both a fluorine atom and a silicon atom.

When the positive resist composition of the present invention contains the surfactant (F), a resist having good sensitivity and resolution and less adhesion and development defects when using an exposure light source of 250 nm or less, particularly 220 nm or less. A pattern can be given.
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, 4430 (manufactured by Sumitomo 3M Co., Ltd.), MegaFuck F171, F173, F176, F189 , F113, F110, F177, F120, R08 (Dainippon Ink Chemical Co., Ltd.), Surflon S-382, SC101, 102, 103, 104, 105, 106 (Asahi Glass Co., Ltd.), Troisol S-366 (Manufactured by Troy Chemical Co., Ltd.), GF-300, GF-150 (manufactured by Toagosei Chemical Co., Ltd.), Surflon S-393 (manufactured by Seimi Chemical Co., Ltd.), F-top EF121, EF122A, EF122B, RF122C, EF125M , EF135M, EF351, 352, EF801, EF802, EF 01 (manufactured by Gemco), PF636, PF656, PF6320, PF6520 (manufactured by OMNOVA), FTX-204D, 208G, 218G, 230G, 204D, 208D, 212D, 218, 222D (manufactured by Neos) 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 ₃ F ₇ group and (poly (oxy) And a copolymer of (ethylene)) acrylate (or methacrylate) and (poly (oxypropylene)) acrylate (or methacrylate).

  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.

  (F) The usage-amount of surfactant becomes like this. Preferably it is 0.01-10 mass% with respect to positive resist composition whole quantity (except a solvent), More preferably, it is 0.1-5 mass%.

(G) Carboxylic acid onium salt The positive resist composition in the present invention may contain (G) a carboxylic acid onium salt. Examples of the carboxylic acid onium salt include a carboxylic acid sulfonium salt, a carboxylic acid iodonium salt, and a carboxylic acid ammonium salt. In particular, the (G) carboxylic acid onium salt is preferably an iodonium salt or a sulfonium salt. Furthermore, it is preferable that the carboxylate residue of the (G) carboxylic acid onium salt of the present invention 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 (G) 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.

  (G) 0.1-20 mass% is suitable for the content in the composition of carboxylic acid onium salt with respect to the total solid of a composition, Preferably it is 0.5-10 mass%, More preferably, it is 1 -7% by mass.

Other Additives The positive resist composition of the present invention further promotes solubility in dyes, plasticizers, photosensitizers, light absorbers, alkali-soluble resins, dissolution inhibitors and developers as necessary. A compound (for example, a phenol compound having a molecular weight of 1000 or less, an alicyclic compound having a carboxyl group, or an aliphatic compound) and the like can be contained.

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.

[Physical properties of resist composition]
The positive resist composition of the present invention is preferably used at a film thickness of 30 to 250 nm, more preferably at a film thickness of 30 to 200 nm, from the viewpoint of improving resolution. Such a film thickness can be obtained by setting the solid content concentration in the positive resist composition to an appropriate range to give an appropriate viscosity and improving the coating property and film forming property.
The total solid content concentration in the positive resist composition is generally 1 to 10% by mass, more preferably 1 to 8.0% by mass, and still more preferably 1.0 to 6.0% by mass.

[Pattern formation method]
The positive resist composition of the present invention is used by dissolving the above components in a predetermined solvent, preferably the above mixed solvent, filtering the solution, and then applying the solution on a predetermined support as follows. The filter used for filter filtration is preferably made of polytetrafluoroethylene, polyethylene, or nylon of 0.1 microns or less, more preferably 0.05 microns or less, and still more preferably 0.03 microns or less.

For example, a positive resist composition is coated on a substrate (eg, silicon / silicon dioxide coating) used for manufacturing a precision integrated circuit element by an appropriate coating method such as a spinner or a coater, and dried to form a resist film. Form.
The resist film is irradiated with actinic rays or radiation through a predetermined mask, preferably baked (heated), developed and rinsed. Thereby, a good pattern can be obtained.

Examples of the actinic ray or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, X-ray, electron beam, etc., but preferably far ultraviolet light having a wavelength of 250 nm or less, more preferably 220 nm or less. Specifically, KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (157 nm), X-ray, electron beam, etc., ArF excimer laser and F ₂ excimer laser are preferable.

  In the present invention, a commercially available inorganic or organic antireflection film can be formed below the resist film as necessary.

As the antireflection film, any of an inorganic film type such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon, and amorphous silicon, and an organic film type made of a light absorber and a polymer material can be used. The former requires equipment such as a vacuum deposition apparatus, a CVD apparatus, and a sputtering apparatus for film formation. Examples of the organic antireflection film include a condensate of a diphenylamine derivative and a formaldehyde-modified melamine resin described in JP-B-7-69611, an alkali-soluble resin, a light absorber, and maleic anhydride copolymer described in US Pat. No. 5,294,680. A reaction product of a coalescence and a diamine type light absorbing agent, a resin binder described in JP-A-6-186863 and a methylolmelamine thermal crosslinking agent, a carboxylic acid group, an epoxy group and a light-absorbing group described in JP-A-6-118656. An acrylic resin-type antireflection film in the same molecule, a composition comprising methylol melamine and a benzophenone-based light absorber described in JP-A-8-87115, and a low-molecular light absorber added to a polyvinyl alcohol resin described in JP-A-8-179509 And the like.

  In addition, as the organic antireflection film, commercially available organic antireflection films such as DUV30 series, DUV-40 series manufactured by Brewer Science, and AR-2, AR-3, AR-5 manufactured by Shipley may be used. it can.

In the development step, an alkaline developer is used as follows. As an alkaline developer of the resist composition, inorganic hydroxides such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, primary amines such as ethylamine and n-propylamine, Secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide and the like Alkaline aqueous solutions such as quaternary ammonium salts, cyclic amines such as pyrrole and pihelidine can be used.
Furthermore, alcohols and surfactants can be added in appropriate amounts to the alkaline developer.
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.
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.
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.

  Exposure (immersion exposure) may be performed by filling a liquid (immersion medium) having a higher refractive index than air between the resist film and the lens during irradiation with actinic rays or radiation. Thereby, resolution can be improved. As the immersion medium to be used, any liquid can be used as long as it has a higher refractive index than air, but pure water is preferred. Further, an overcoat layer may be further provided on the photosensitive film so that the immersion medium and the photosensitive film do not come into direct contact with each other during the immersion exposure. Thereby, the elution of the composition from the photosensitive film to the immersion medium is suppressed, and development defects are reduced.

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.
Further, a medium having a refractive index of 1.5 or more can be used in that the refractive index can be further improved. This medium may be an aqueous solution or an organic solvent.

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 MQcm or more, the TOC (organic substance concentration) is desirably 20 ppb or less, and deaeration treatment is desirably performed.
Moreover, it is possible to improve lithography performance by increasing the refractive index of the immersion liquid. From such a viewpoint, an additive for increasing the refractive index may be added to water, or heavy water (D ₂ O) may be used instead of water.

In order to prevent the resist film from coming into direct contact with the immersion liquid between the resist film made of the positive resist composition of the present invention and the immersion liquid, an immersion liquid hardly soluble film (“protective film” or “topcoat”) is used. 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. From the viewpoint of contaminating the optical lens when impurities are eluted from the top coat into the immersion liquid, it is preferable that the residual monomer component of the polymer contained in the top coat is small.

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 top coat and the immersion liquid. In the case of using water as the immersion liquid in an ArF excimer laser (wavelength: 193 nm), the top coat for ArF immersion exposure is preferably close to the refractive index of the immersion liquid. From the viewpoint of making the refractive index close to the immersion liquid, it is preferable to have fluorine atoms in the topcoat. A thin film is more preferable from the viewpoint of transparency and refractive index.

  It is preferred that the top coat is not mixed with the resist and further not mixed with the immersion liquid. From this viewpoint, when the immersion liquid is water, the topcoat solvent is preferably a resist solvent hardly soluble and water-insoluble medium. Furthermore, when the immersion liquid is an organic solvent, the topcoat may be water-soluble or water-insoluble.

  When the resist composition of the present invention is used as a resist film, the receding contact angle of water with respect to the resist film is preferably 65 ° or more, and more preferably 70 ° or more. Here, the receding contact angle is the receding contact angle when the resist film is tilted and the liquid droplet starts to fall under normal temperature and normal pressure. In general, the receding contact angle is substantially correlated with the falling angle, and a film having a higher receding contact angle and a smaller falling angle indicates better water repelling.

[2] Protective film forming composition (S) Solvent The protective film forming composition of the present invention is prepared by dissolving the resin (A) in a solvent that does not corrode the resist film.

Here, “does not corrode the resist film” means that a positive resist composition is applied on a silicon wafer and dried to form a resist film, which is then immersed in a solvent (S) at 23 ° C. for 1 minute and dried. When the film thickness is measured, it means the property that the film thickness does not decrease.
As a solvent that does not corrode the resist film, a solvent whose solubility parameter is about 2 to 5 larger than that of the resist solvent is preferable, the solubility parameter is 2.5 to 5, preferably 3 to 5, and more preferably 3.5 to 5. Things are good.

The solvent is preferably a solvent having a boiling point of 100 ° C to 200 ° C.
In the present invention, one kind of solvent may be used, or another solvent may be mixed and used.

The solvent used in the protective film-forming composition of the present invention is preferably used by mixing a plurality of solvents as a mixed solvent, thereby further improving the effects of the present invention. The mixed solvent is not particularly limited, but is a non-polar solvent such as a hydrocarbon solvent, a halogenated hydrocarbon solvent, a fluorine solvent, an alcohol solvent, an ether solvent, a nitrogen-containing solvent, an ester solvent, A mixed solvent to which a polar solvent such as a ketone solvent is added is preferable.
Examples of the hydrocarbon solvent include aromatic hydrocarbon solvents and aliphatic hydrocarbon solvents. Examples of the aromatic hydrocarbon solvent include toluene, ethylbenzene, amylbenzene, isopropylbenzene, xylene, cyclohexylbenzene, naphthalene, dimethylnaphthalene, cymene, tetralin, biphenyl, mesitylene and the like. Aliphatic hydrocarbon solvents include hexane, heptane, octane, nonane, decane, dodecane, cyclohexane, methylcyclohexane, ethylcyclohexane, p-menthane, decalin, isooctane, isododecane, cyclohexene, cyclopentane, dipentene, isopar E, isopar G, Isopar H, Isopar L, Isopar M (manufactured by Kokura Kosan Co., Ltd.), turpentine oil, decahydronaphthalene, limonene, benzine, Kyowasol C-800, shellsol, isosol, ligroin (manufactured by Gordo Kogyo Co., Ltd.) ) And the like. When the exposure light source is ArF exposure, an aliphatic hydrocarbon solvent is preferable from the viewpoint of 193 transparency.
Examples of the halogenated hydrocarbon solvent include methylene chloride, hexyl chloride, chlorobenzene, bromobenzene and the like.
Fluorine solvents include 1,4-difluorobenzene, 1,1,2,2-tetrachlorodifluoroethane, tetrafluoropropanol, ethyl trifluoroacetoacetate, perfluoroheptane, hexafluoroisopropanol, perfluorobutylethanol, pentafluoro Examples include propanol, hexafluorobenzene, perfluorobutyltetrahydrofuran, perfluoropolyethers, and fluorophenols.

Alcohol solvents include amyl alcohol, isoamyl alcohol, hexanol, 3-heptanol, 2-ethylbutanol, 2-ethylhexanol, octanol, nonanol, neopentyl alcohol, cyclohexanol, tetrahydrofurfuryl alcohol, propylene glycol, tetrafluoropropanol , Hexafluoroisopropanol, perfluorobutylethanol, pentafluoropropanol, fluorophenol and the like.
Examples of the ether solvent include anisole, dioxane, dioxolane, dibutyl ether, tetrahydrofuran and the like.
Examples of the nitrogen-containing solvent include acetonitrile, isopropanolamine, ethylhexylamine, N-ethylmorpholine, diisopropylamine, cyclohexylamine, di-n-butylamine, tetramethylethylenediamine, and tripropylamine.
Examples of the ester solvent include ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, and γ-butyrolactone.
Examples of the ketone solvent include ethyl-n-butyl ketone, diisobutyl ketone, methyl isobutyl ketone, methyl-n-butyl ketone, cyclohexanone, 2-heptanone, and methyl ethyl ketone.

  The combination of the above-mentioned polar solvent and nonpolar solvent is not particularly limited, but in particular, there is a combination using the above hydrocarbon solvent or fluorine-containing nonpolar solvent as the nonpolar solvent and the above alcohol solvent as the polar solvent. preferable.

The protective film-forming composition of the present invention can further contain a surfactant. As the surfactant, the same surfactants as described in the above (F) can be used.
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 protective film-forming composition (excluding the solvent).
In the protective film-forming composition of the present invention, the concentration of the total solids such as the resin (A) and the surfactant is preferably 1 to 5% by mass.

  The composition for forming a protective film of the present invention forms a protective film by, for example, being applied onto a resist film, so that the immersion liquid penetrates into the resist film and the resist film components are eluted into the immersion liquid. It also has a function to prevent. The means for coating is appropriately set according to the process to be applied, and is not particularly limited, and means such as spin coating can be used.

The protective film is preferably a thin film from the viewpoint that it is preferably transparent to the exposure light source, and is usually formed with a thickness of 1 nm to 300 nm, preferably 10 nm to 150 nm. It is preferable that the exposure light transmittance of the film is 50% to 80%, more preferably 60% to 70%. The exposure light transmittance can be adjusted by adjusting the polymerization component of the resin. For example, the transmittance of ArF light can be increased by reducing the amount of aromatic rings contained in the resin.
Further, in order to prevent the immersion liquid and the lens from being contaminated by the eluate from the protective film, it is preferable that the elution amount from the protective film is small.

The refractive index of the protective film is preferably close to the refractive index of the resist film from the viewpoint of resolution. The refractive index can be adjusted by controlling the components of the protective film forming composition, particularly the resin composition and the ratio of repeating units.
The protective film-forming composition is preferably one that can be applied uniformly when forming the protective film. The applicability (coating uniformity) can be improved by appropriately selecting the type of solvent, surfactant, etc. and other additives and adjusting the amount of addition.

Like the resist composition, the protective forming composition preferably does not contain a metal.
Since the protective film-forming composition is applied onto the resist film to form a film, the protective film-forming composition is preferably not mixed with the resist film at the interface.

  The protective film preferably has a dissolution rate in an alkaline developer of greater than 50 nm / second. The dissolution rate should be measured using a 2.38 mass% tetramethylammonium aqueous solution as an alkaline developer at 23 ° C. using a resist dissolution rate analyzer (RDA790) manufactured by RISOTEC JAPAN. Can do.

  When the protective film forming composition of the present invention is used as a protective film, the receding contact angle of water with respect to the protective film is preferably 65 ° or more, more preferably 70 ° or more. Here, the receding contact angle is the receding contact angle when the protective film is tilted and the liquid droplet starts to fall under normal temperature and normal pressure. In general, the receding contact angle is substantially correlated with the falling angle, and a film having a higher receding contact angle and a smaller falling angle indicates better water repelling.

[Pattern formation method]
The protective film-forming composition of the present invention is usually used by dissolving the above components in a solvent and applying the solution on a resist film on a substrate.
That is, the resist composition is applied to an arbitrary thickness (usually 50 to 500 nm) by a suitable application method such as a spinner or a coater on a substrate used for manufacturing a precision integrated circuit element. At this time, it is also preferable to form a resist film after appropriately providing an antireflection film on the substrate. After application, the resist film is formed by drying by spinning or baking.
Further, similarly to the resist composition, a protective film-forming composition is applied onto the resist film using a spinner, a coater or the like, and dried by spinning or baking to form a protective film.
The baking temperature is preferably 60 to 100 ° C.

Next, exposure (immersion exposure) is performed 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, spinning or / and baking is performed, development and rinsing are performed to obtain a pattern. In the present invention, the protective film dissolves and peels in the developing solution in the developing step, so that it is not necessary to provide a separate peeling step.
Baking is preferably performed after exposure, and the baking temperature is usually 30 to 300 ° C. From the viewpoint of the change in the line width of the resist pattern due to fluctuations in the holding time (PED) from exposure to development processing, the time from exposure to baking is better.
Here, the exposure light is preferably far ultraviolet rays having a wavelength of 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.

  Examples of the substrate that can be used include a normal BareSi substrate, an SOG substrate, and a substrate having an antireflection film.

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

  In immersion exposure using the protective film of the present invention, the resist is not particularly limited, and can be arbitrarily selected from those usually used, and may be either positive type or negative type.

  As the resist, positive type and negative type resists having sufficient characteristics that can be applied to recent ultra-fine processing can be suitably used. In the present invention, a chemical amplification type resist, and further a positive type resist are preferably used. Can do.

  Typical examples of the chemically amplified resist include those using a so-called acid generator that generates an acid by active energy rays such as light. For example, as the negative chemically amplified resist, a three-component system of a base polymer, a photoacid generator, and a crosslinking agent is usually used. At the time of resist exposure, the acid generated by light irradiation causes a crosslinking reaction in the exposed portion, and acts to reduce the solubility in the developer. On the other hand, a positive chemically amplified resist is usually a two-component system including a base polymer having a site blocked with a protective group having a dissolution inhibiting function and a photoacid generator, a base polymer, an acid generator, There are some three-component dissolution inhibitors. Then, at the time of resist exposure, in the exposed portion, the acid generated by light irradiation acts to remove the protective group of the polymer and increase the solubility in the developer.

When the exposure light source is an ArF excimer laser (wavelength: 193 nm), a two-component system containing a resin that is solubilized in an alkaline developer by the action of an acid and a photoacid generator is preferred.
In particular, the resin that is solubilized in the alkaline developer by the action of an acid is preferably an acrylic or methacrylic resin having a monocyclic or polycyclic alicyclic hydrocarbon structure, and has a lactone residue or an adamantane residue. Is more preferable.

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

Synthesis Example 1 (Synthesis of Compound (CSMA))
In a 1 L three-necked flask, 69 g of methacrylamide, 136 g of triethylamine, and 130 mL of tetrahydrofuran were prepared and cooled on ice. To this solution, 161 g of camphor-sulfonyl chloride dissolved in 200 mL of tetrahydrofuran was added dropwise over 1.5 hours and stirred for 1 hour. After completion of the reaction, the reaction mixture was neutralized with 2 mol / L dilute hydrochloric acid and extracted twice with ethyl acetate. The oil layer was extracted with 2 mol / L sodium hydroxide aqueous solution. The aqueous layer was ice-cooled, and hydrochloric acid was added dropwise for crystallization. The precipitated white crystals were collected by filtration and washed with water to obtain 103 g of the target compound (CSMA) shown below.
¹ H-NMR (400 MHz, CDCl ₃ ) δ 0.91 (s, 3H), 1.08 (s, 3H), 1.47 (td, 1H), 2.03 (m, 4H), 2.00 (s, 3H), 2.36 (m , 2H), 3.38 (d, 1H), 3.93 (d, 1H), 5.65 (d, 1H), 5.92 (d, 1H), 8.65 (bs, 1H)

Synthesis Example 2 (Synthesis of Compound (TFSMA))
In a 300 mL Erlenmeyer flask, 133 g of pentafluorobenzenesulfonic acid chloride and 750 mL of ethyl acetate were prepared. To this solution, 122 mL of aqueous ammonia was added dropwise and stirred for 1 hour. After completion of the reaction, the reaction mixture was neutralized with 2 mol / L dilute hydrochloric acid and extracted twice with ethyl acetate. The oil layer was dried over sodium sulfate and concentrated to obtain 160 g of pentafluorobenzenesulfonamide. This was dissolved in 500 mL of N-methylpyrrolidone, 153 mL of triethylamine was added dropwise, 6 g of N, N-dimethylaminopyridine was added, and the mixture was stirred until dissolved. After ice cooling, a solution prepared by dissolving 53 mL of methacrylic acid chloride in 250 mL of N-methylpyrrolidone was added dropwise over 1.5 hours and stirred for 2 hours. After completion of the reaction, the reaction mixture was neutralized with 2 mol / L dilute hydrochloric acid and extracted twice with ethyl acetate. The oil layer was dried over sodium sulfate and concentrated, and then separated on a silica gel column (hexane: ethyl acetate = 1: 1). The compound was crystallized from hexane and recrystallized to obtain 80 g of the following compound (TFSMA) which was the target product.
¹ H-NMR (400 MHz, CDCl ₃ ) δ 1.95 (s, 3H), 5.75 (d, 1H), 5.94 (d, 1H), 9.10 (bs,
1H)
¹⁹ F-NMR (400 MHz, CDCl ₃ ) δ-135.1 (m, 2F), -142.7 (m, 1F), -158.0 (m, 2F)

  The following compound (CSTA) was synthesized in the same manner as the compound (CSMA). In addition, the following compound (TFSTA), the following compound (TSISSMA), and the following compound (TSISTA) were synthesized in the same manner as the compound (TFSMA).

Synthesis Example 3 (Synthesis of Resin (A-1))
Nonafluorohexyl methacrylate and the compound (CSMA) were charged at a ratio (molar ratio) of 70/30 and dissolved in propylene glycol monomethyl ether to prepare 450 g of a solution having a solid concentration of 22% by mass. To this solution, 5 mol% of a polymerization initiator V-601 manufactured by Wako Pure Chemical Industries, Ltd. was added, and this was added dropwise to 50 mL of cyclohexanone heated to 80 ° C. over 6 hours in a nitrogen atmosphere. After completion of dropping, the mixture was stirred for 2 hours to obtain a reaction solution. After completion of the reaction, the reaction solution was cooled to room temperature, crystallized in 10 times the amount of methanol, and the precipitated white powder was collected by filtration to obtain the following resin (A-1) as the target product.
^The repeating unit composition ratio (molar ratio) determined from ¹ H-NMR was 72/28. Moreover, the weight average molecular weight of standard polystyrene conversion calculated | required by GPC measurement was 12000, and dispersion degree was 2.1.
The following resin (A-2), the following resin (A-3) and the following resin (A-4) were synthesized in the same manner as the resin (A-1).

Synthesis Example 4 (Synthesis of Resin (A-5))
Allyltrimethylsilane and compound (CSTA) were charged at a ratio (molar ratio) of 50/50 and dissolved in tetrahydrofuran to prepare 50 g of a solution having a solid concentration of 50% by mass. To this solution, 0.2 mol% of a polymerization initiator V-65 manufactured by Wako Pure Chemical Industries, Ltd. was added and stirred for 6 hours in a nitrogen atmosphere to obtain a reaction solution. After completion of the reaction, 15 mL of tetrahydrofuran was added and the reaction solution was cooled to room temperature. This solution was crystallized into 600 mL of a mixed solution of hexane: ethyl acetate = 9: 1 (mass ratio), and the precipitated white powder was collected by filtration to obtain the following resin (A-5) as the target product.
^The repeating unit composition ratio (molar ratio) determined from ¹ H-NMR was 50/50. Moreover, the standard polystyrene conversion weight average molecular weight calculated | required by GPC measurement was 5600, and dispersion degree was 1.5.
The following resin (A-6), the following resin (A-7), the following resin (A-8), the following resin (A-9) and the following resin (A-10) are the same as the resin (A-5). Synthesized by the method.

  The structures of the resins (A-1) to (A-10) are shown below.

  Table 1 below shows the compositions of resin (A-1) to (A-10) (repeating unit molar ratio, corresponding to each repeating unit in order from the left), Mw (weight average molecular weight), and Mw / Mn (dispersion degree). Show.

  The structure of the acid-decomposable resin (B) used in the examples is shown below.

  Table 2 below shows the composition of acid-decomposable resins (B-1) to (B-6) (repeating unit molar ratio, corresponding to each repeating unit in order from the left), Mw (weight average molecular weight), Mw / Mn (dispersion). Degree).

Examples 1 to 12 and Comparative Example 1
<Resist preparation>
The components shown in Table 3 below were dissolved in a solvent, and a solution with a solid content of 6% by mass was prepared for each, and this was filtered through a 0.1 μm polyethylene filter to prepare a positive resist solution. The prepared positive resist composition was evaluated by the following method, and the results are shown in Table 3. In addition, about each component in a table | surface, ratio when using two or more is a mass ratio.

[Evaluation]
(Normal exposure)
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 positive resist composition prepared thereon was applied and baked at 120 ° C. for 60 seconds to form a 200 nm resist film. The obtained wafer was subjected to pattern exposure using an ArF excimer laser scanner (PAS5500 / 1100, NA0.75, σo / σi = 0.85 / 0.55 manufactured by ASML). Thereafter, heating was performed at 120 ° C. for 60 seconds, followed by development with an aqueous tetramethylammonium hydroxide solution (2.38 mass%) for 30 seconds, rinsing with pure water, and spin drying to obtain a resist pattern.

(Immersion exposure)
This condition is to form a resist pattern by an immersion exposure method using pure water.
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 positive resist composition prepared thereon was applied and baked at 120 ° C. for 60 seconds to form a 200 nm resist film. The obtained wafer was subjected to pattern exposure using an ArF excimer laser immersion scanner (NA 0.75). As the immersion liquid, ultrapure water having impurities of 5 ppb or less was used. Thereafter, heating was performed at 120 ° C. for 60 seconds, followed by development with an aqueous tetramethylammonium hydroxide solution (2.38 mass%) for 30 seconds, rinsing with pure water, and spin drying to obtain a resist pattern.

[Line edge roughness]
For the range of 5 μm edge in the longitudinal direction of the line pattern, measure the distance from the reference line where the edge should be at 50 points with a length measuring SEM (S-8840, manufactured by Hitachi, Ltd.), calculate the standard deviation, and calculate 3σ did. A smaller value indicates better performance.

[Water followability]
The prepared positive resist composition was applied on a silicon wafer and baked at 130 ° C. for 60 seconds to form a 160 nm resist film. Next, as shown in FIG. 1, pure water 2 was filled between the wafer 1 coated with the obtained positive resist composition and the quartz glass substrate 3.
In this state, the quartz glass substrate 3 was moved (scanned) in parallel to the surface of the resist-coated substrate 1, and the state of the pure water 2 following it was visually observed. Gradually increase the scan speed of the quartz glass substrate 3 and evaluate the water followability by obtaining the limit scan speed at which the pure water 2 cannot follow the scan speed of the quartz glass substrate 3 and water droplets begin to remain on the receding side. went. As this limit scan speed is larger, water can follow a higher scan speed, and the water followability on the resist film is better.

[Number of development defects]
The prepared positive resist composition was uniformly coated on an 8-inch silicon substrate subjected to hexamethyldisilazane treatment by a spin coater, heated and dried on a hot plate at 120 ° C. for 60 seconds, and 0.10 μm in thickness. A resist film was formed. This resist film was heated on a hot plate at 120 ° C. for 90 seconds without exposure. Further, the resist film was developed with an aqueous 2.38 wt% tetramethylammonium hydroxide solution at 23 ° C. for 60 seconds, rinsed with pure water for 30 seconds, and then dried. The number of development defects of the sample wafer thus obtained was measured using a KLA2360 machine (manufactured by KLA Tencor).

  The abbreviations in Table 3 are shown below.

W-1: MegaFuck F176 (Dainippon Ink Chemical Co., Ltd.) (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-based)
W-4: Troisol S-366 (manufactured by Troy Chemical Co., Ltd.)
W-5: PF6320 (manufactured by OMNOVA, fluorine-based)

SL-1: Cyclohexanone SL-2: Propylene glycol monomethyl ether acetate SL-3: Ethyl lactate SL-4: Propylene glycol monomethyl ether SL-5: γ-butyrolactone SL-6: Propylene carbonate

N-1: N, N-dibutylaniline N-2: N, N-dihexylaniline N-3: 2,6-diisopropylaniline N-4: tri-n-octylamine N-5: N, N-dihydroxyethyl Aniline N-6: 2,4,5-triphenylimidazole

  From Table 3, it is apparent that the positive resist composition of the present invention has improved development defects, and has good followability to water and good line edge roughness during immersion exposure.

Examples 13-20 and Comparative Examples 2-4
<Preparation of protective film forming composition>
The components shown in Table 4 below were dissolved in a solvent to prepare a solution having a solid concentration of 1.5% by mass, and this was filtered through a polyethylene filter having a pore size of 0.1 μm to prepare a protective film forming composition.

[Creation of wafer with resist film and protective film]
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 resist described in Table 4 was applied thereon and baked at 115 ° C. for 60 seconds to form a resist film having a thickness of 200 nm. In Examples 13 to 20 and Comparative Example 4, the protective film forming composition shown in Table 4 was further applied, and baked at 90 ° C. for 60 seconds to form a protective film having a thickness of 20 nm. In Comparative Examples 2 to 3, a protective film was not formed.

[Pattern formation evaluation]
The obtained wafer was subjected to two-beam interference exposure with the apparatus of FIG. 2 using water as the immersion liquid. The wavelength of the laser 4 was 193 nm. After heating at 130 ° C. for 60 seconds, the film was developed with an aqueous tetramethylammonium hydroxide solution (2.38 mass%) for 60 seconds, rinsed with pure water, and then spin-dried. The prism 11 which forms a 90 nm line and space pattern was used, and the presence or absence of pattern formation was observed with a scanning electron microscope (Hitachi S-9260).
In the apparatus shown in FIG. 2, 4 is a laser, 5 is a diaphragm, 6 is a shutter, 7, 8 and 9 are reflection mirrors, 10 is a condenser lens, 11 is a prism, 12 is an immersion liquid, 13 Denotes a wafer provided with an antireflection film, a resist film, and a protective film (however, no protective film is provided in Comparative Examples 2 to 3), and 14 denotes a wafer stage.

[Water followability evaluation]
As shown in FIG. 1, pure water 2 was filled between the obtained wafer 1 and the quartz glass substrate 3.
In this state, the quartz glass substrate 3 was moved (scanned) in parallel to the surface of the wafer 1 and the state of the pure water 2 following it was visually observed. Gradually increase the scan speed of the quartz glass substrate 3 and evaluate the water followability by obtaining the limit scan speed at which the pure water 2 cannot follow the scan speed of the quartz glass substrate 3 and water droplets begin to remain on the receding side. went. As this limit scan speed is larger, water can follow a higher scan speed, and the water followability on the resist film is better.

  In Table 4, the resists (PR1) to (PR4) are as follows.

[Resist]
PR1: Resist composition described in Example 1 of JP-A-2000-275845, that is, 10 parts by mass of the following resin P-1 (weight average molecular weight of about 10,000), acid generator (triphenylsulfonium perfluorobutanesulfonate) ("TPS-109" manufactured by Midori Chemical Co., Ltd.)) 0.2 parts by mass, 0.015 parts by mass of basic compound (2,6-diisopropylaniline), solvent (47.5 parts by mass of propylene glycol monomethyl ether acetate and γ- A resist composition containing 2.5 parts by mass of butyrolactone).

  PR2: Resist composition described in Example 1 of JP-A No. 2003-167347, that is, 100 parts by mass of the following resin P-2 (weight average molecular weight 10,000), acid generator component (triphenylsulfonimnonafluorobutanesulfonate) ) A resist composition containing 2 parts by mass, 0.2 parts by mass of a basic compound (triethanolamine), and an organic solvent (750 parts by mass of propylene glycol monomethyl ether acetate / 30 parts by mass of γ-butyrolactone).

  PR3: Resist composition described in Example 1 of JP 2002-12622 A, that is, 80 parts by mass of the following resin P-3 (weight average molecular weight: 12200), 1 part by mass of an acid generator (PAG1), a basic compound (tri A resist composition containing 0.078 parts by mass of butylamine) and 480 parts by mass of a solvent (PGMEA: propylene glycol methyl ether acetate).

  PR4: Resist composition described in Example 1 of JP-A-2003-177538, that is, 2 g of the following resin P-4 (weight average molecular weight 10600), 38 mg of acid generator (PAG2), basic compound (1,5 -Diazabicyclo [4.3.0] -5-nonene (DBN)) 4 mg, surfactant (Megafac F176 (Dainippon Ink Co., Ltd.)) 10 g, solvent (propylene glycol monomethyl ether acetate (PGMEA) / lactic acid A resist composition containing ethyl = 70/30 and a solid content concentration of 14% by mass.

  The comparative resin (R-1) in Table 4 was synthesized according to the description in the pamphlet of WO2005 / 069076A1.

Abbreviations in Table 4 are as follows.
〔solvent〕
SL1: Isopar G (manufactured by Kokura Kosan Co., Ltd.)
SL2: cyclohexanone SL3: 2-methyl-1-propanol SL4: isopropanol [surfactant]
W-1: MegaFuck F176 (Dainippon Ink Chemical Co., Ltd.) (Fluorine)
W-2: Megafuck R08 (Dainippon Ink Chemical Co., Ltd.) (fluorine and silicon)

  From Table 4, it is clear that the pattern forming property and the water following property of the resist film can be improved by forming the protective film with the protective film forming composition of the present invention.

Schematic diagram of water followability evaluation method It is the schematic of a two-beam interference exposure experiment apparatus.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Wafer 2 Pure water 3 Quartz glass substrate 4 Laser 5 Aperture 6 Shutter 7, 8, 9 Reflection mirror 10 Condensing lens 11 Prism 12 Immersion liquid 13 Wafer having antireflection film and resist film 14 Wafer stage

Claims (9)

And one fluorine atom and at least one of the silicon atoms, -CONHSO ₂ - resin characterized by having a group. The resin according to claim 1, which is selected from the following resins (a) and resins (b).
(A) A resin having a repeating unit (x) having at least one of a fluorine atom and a silicon atom and a repeating unit (y) having a —CONHSO ₂ — group.
(B) A resin having a repeating unit (xy) having at least one of a fluorine atom and a silicon atom and a —CONHSO ₂ — group.   The resin according to claim 2, further comprising at least one of a fluorine atom and a silicon atom in the repeating unit (y) of the resin (a). The resin according to claim 1, comprising a repeating unit represented by the following general formula (Ax) and a repeating unit represented by the following general formula (Ay).

In general formulas (Ax) and (Ay),
Rz represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.
Rax represents an organic group having at least one of a fluorine atom and a silicon atom.
Ray represents an organic group.   (A) A positive resist composition comprising the resin according to claim 1. A protective film forming composition for forming a protective film provided on a resist film,
A protective film-forming composition comprising (A) the resin according to any one of claims 1 to 4 and (S) a solvent that does not corrode the resist film.   A pattern forming method comprising: forming a resist film from the positive resist composition according to claim 5; and exposing and developing the resist film. A pattern forming method comprising: forming a resist film, forming a protective film on the resist film with the protective film forming composition according to claim 6, immersion exposure, and developing. The compound represented by the following general formula (Ay2).

In the general formula (Ay2),
Rz represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.
Ray ₂ represents an organic group having at least one silicon atom.

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