JP5037402B2 - Positive photosensitive resin composition and pattern forming method using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a positive photosensitive resin composition nearly free from a fall of a resist pattern and deterioration of a profile thereof not only in usual exposure (dry exposure) but also in immersion exposure, and to provide a pattern forming method using the positive photosensitive resin composition. <P>SOLUTION: The positive photosensitive resin composition contains (A) a resin which includes an acid decomposition recurring unit represented by general formula (Ia) and/or (Ib) and whose dissolution rate in an alkali developer is increased by an action of acid and (B) a compound generating acid by irradiation with an active ray or a radiation. In general formula (Ia) and (Ib), Xa<SB>1</SB>denotes a hydrogen atom, an alkyl group, a hydroxymethyl group, a trifluoromethyl group, a cyano group or a halogen atom, Ry<SB>1</SB>denotes an alkyl group or a cycloalkyl group, Ra denotes an alkyl group or a cycloalkyl group, l denotes an integer of 2 to 3, m denotes an integer of 1 to 8 and n denotes an integer of 4 to 8. When a plurality of Ra are arranged, they may be equal to or different from each other and may be bonded to form a ring. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a positive photosensitive resin composition used in a semiconductor manufacturing process such as an IC, a circuit board such as a liquid crystal or a thermal head, and other photofabrication processes, and a pattern forming method using the same. It is. More specifically, the present invention relates to a positive photosensitive resin composition suitable for use as an exposure light source such as far ultraviolet light of 250 nm or less, preferably 220 nm or less, and an irradiation source using an electron beam, and a pattern forming method using the same. .

  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.
As a technique for increasing the resolving power in an optical microscope, a so-called immersion method in which a space between a projection lens and a sample is filled with a liquid having a high refractive index (hereinafter also referred to as “immersion liquid”) has been known.
This “immersion effect” is expressed as follows when λ ₀ is the wavelength of 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. Can be expressed in terms of resolution and depth of focus.

(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 transfer of a fine image pattern of a semiconductor element are introduced in Patent Document 1, Patent Document 2, and the like.

Recent progress in immersion exposure technology is reported in Non-Patent Documents 1 to 3, Patent Document 3, 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 most promising as an immersion liquid from the viewpoint of handling safety, transmittance and refractive index at 193 nm.
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.

  It is pointed out that when 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. Patent Document 4 describes an example in which resist performance is changed by immersing a resist for ArF exposure in water before and after exposure, and points out a problem in immersion exposure.

Patent Documents 5 and 6 describe examples of resist resins having a tertiary cycloalkyl ester type acid-decomposable group. However, in these resins, the acid-decomposable part is insufficiently hydrophobic, and there is a problem in pattern collapse.
JP-A-57-153433 JP-A-7-220990 JP-A-10-303114 International Publication No. 2004/068242 Pamphlet International Publication No. 2005/016982 Pamphlet JP 2005-97533 A 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 use a positive photosensitive resin composition with less resist pattern collapse and profile deterioration not only in normal exposure (dry exposure) but also in immersion exposure, and the positive photosensitive resin composition. A pattern forming method.

This invention is the positive photosensitive resin composition of the following structure, and the pattern formation method using this positive photosensitive resin composition, Thereby, the said objective of this invention is achieved.
(1) (A) a resin containing an acid-decomposable repeating unit represented by the following general formula (Ia) and / or (Ib), which increases the dissolution rate in an alkali developer by the action of an acid, and (B) activity A positive photosensitive resin composition comprising a compound capable of generating an acid upon irradiation with light or radiation.

In general formulas (Ia) and (Ib):
Xa ₁ represents a hydrogen atom, an alkyl group, a hydroxymethyl group, a trifluoromethyl group, a cyano group or a halogen atom.
Ry ₁ represents an alkyl group or a cycloalkyl group.
Ra represents an alkyl group or a cycloalkyl group. When there are a plurality of Ras, they may be the same as or different from each other, and may be bonded to each other to form a ring.
l represents an integer of 1 to 3.
m represents an integer of 1 to 8.
n represents an integer of 3 to 8.

(2) The positive photosensitive resin composition as described in (1), wherein the resin of the component (A) further contains a repeating unit having a lactone structure.
(3) The positive photosensitive resin composition as described in (1) or (2), wherein the resin as the component (A) further contains a repeating unit having a cyano group.

(4) The positive photosensitive resin composition according to any one of (1) to (3), wherein the positive photosensitive resin composition further contains (C) a hydrophobic resin.
(5) A resist film is formed using the positive photosensitive composition according to any one of (1) to (4), and then the resist film is subjected to immersion exposure and developed. Pattern forming method.
(6) The pattern forming method as described in (7), wherein immersion exposure is performed through pure water as the immersion liquid.

  According to the present invention, it is possible to provide a positive photosensitive resin composition that is particularly suitable for liquid immersion exposure because the resist pattern collapse and profile deterioration are improved.

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

(A) Acid-decomposable resin The resin component (A) contained in the positive photosensitive resin composition of the present invention is a resin whose solubility in an alkaline developer is increased by the action of an acid, and the main chain or side of the resin Resin (hereinafter referred to as “acid-decomposable resin”) having a group (hereinafter also referred to as “acid-decomposable group”) that is decomposed by the action of an acid to generate an alkali-soluble group in both the main chain and the side chain. , Also referred to as “acid-decomposable resin (A)” or “resin (A)”).

The resin (A) includes a repeating unit represented by the following general formula (Ia) and / or (Ib) as a repeating unit having an acid-decomposable group (hereinafter also referred to as “acid-decomposable repeating unit”). .

In general formulas (Ia) and (Ib):
Xa ₁ represents a hydrogen atom, an alkyl group, a hydroxymethyl group, a trifluoromethyl group, a cyano group or a halogen atom.
Ry ₁ represents an alkyl group or a cycloalkyl group.
Ra represents an alkyl group or a cycloalkyl group. When there are a plurality of Ras, they may be the same or different from each other, and may be bonded to each other to form a ring.

l represents an integer of 1 to 3.
m represents an integer of 1 to 8.
n represents an integer of 3 to 8.

Inclusion of the acid-decomposable repeating units represented by the general formulas (Ia) and (Ib) of the present invention is effective in improving the resist pattern collapse and profile deterioration. The reason for this is not clear, but it is presumed that the hydrophobicity of the entire pattern is improved because the acid-decomposable unit is hydrophobic, and the swelling of the pattern during development is suppressed.
Specific examples of the acid-decomposable repeating units represented by the general formulas (Ia) and (Ib) are shown below, but the present invention is not limited thereto.

The resin (A) of the present invention can contain an acid-decomposable repeating unit other than the repeating units represented by the general formulas (Ia) and (Ib).
Although it does not specifically limit as acid-decomposable repeating units other than general formula (Ia) and (Ib), The repeating unit which has the partial structure shown by general formula (pI)-general formula (pIV) is preferable.

In general formulas (pI) to (pIV),
R _{12 to} R ₁₆ each independently represents a linear or branched alkyl group or cycloalkyl group having 1 to 4 carbon atoms, provided that at least one of R _{12 to} R ₁₄ , or R ₁₅ , Any of R ₁₆ is preferably 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, provided that at least one of R _{17 to} R ₂₁ is cyclo An alkyl group is preferred. 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, provided that at least one of R _{22 to} R ₂₅ is cyclo An alkyl group is preferred. R ₂₃ and R ₂₄ may be bonded to each other to form a ring.

  The structures represented by the general formulas (pI) to (pIV) 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)-(pIV).

As the repeating unit having an alkali-soluble group protected by the structure represented by the general formulas (pI) to (pIV), a repeating unit represented by the following general formula (III-1) is preferable.

Here, 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 or a combination of an ester group and an alkylene group is preferred.
Rp ₁ represents any group of the above formulas (pI) to (pV).
Specific examples of the repeating unit represented by formula (III-1) are shown below.

The resin (A) of the present invention preferably further contains a repeating unit having a lactone structure.
As the lactone group, any group can be used as long as it contains a lactone structure, but it is preferably a group containing a 5- to 7-membered ring lactone structure, and a bicyclo structure in the 5- to 7-membered ring lactone structure, Those in which other ring structures are condensed to form a spiro structure are preferred. It is more preferable to include a repeating unit having a group having a lactone structure represented by any of the following general formulas (LC1-1) to (LC1-16). 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). By using a specific lactone structure, line edge roughness, Development defects are improved.

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. A halogen atom, a hydroxyl group, a cyano group, an acid-decomposable group, etc., more preferably an alkyl group having 1 to 4 carbon atoms, a cyano group, and an acid-decomposable functional group. When n ₂ 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.

The repeating unit having a group having a lactone structure represented by any of the general formulas (LC1-1) to (LC1-16) is represented by the following general formula (IV).

In general formula (IV), R ₁ represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. Preferable substituents that the alkyl group of R ₁ may have include a hydroxyl group and a halogen atom.
Examples of the halogen atom for R ₁ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. R ₁ is preferably a hydrogen atom or a methyl group.

A _b is an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, a single bond, an ether group, an ester group, a carbonyl group, a carboxyl group, or a divalent group obtained by combining these. Represents. A single bond and a linking group represented by -A _b1 -CO _2- are preferred.
A _b1 is a linear, branched alkylene group, monocyclic or polycyclic cycloalkylene group, preferably a methylene group, an ethylene group, a cyclohexyl group, an adamantyl group, or a norbornyl group.
R ₂ represents a group represented by any one of the general formulas (LC1-1) to (LC1-16).

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

The most preferred repeating unit having a lactone group includes the following repeating units. By selecting the optimum lactone structure, the pattern profile and the density dependence become good.

The resin (A) of the present invention preferably contains a repeating unit containing an organic group having a polar group, particularly 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 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 general formula (VIIa), it is more preferable that two members out of R _{2c to} R _4c are a hydroxyl group and the remaining is a hydrogen atom.
Examples of the repeating unit having groups represented by general formulas (VIIa) to (VIId) include the repeating units represented by the following general formulas (AIIa) to (AIId).

In general formulas (AIIa) to (AIId),
R _1c represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.
R _2c to R _4c have the same meanings as R _2c to R _4c in formulas (VIIa) ~ (VIIc).
Although the specific example of the repeating unit which has a structure represented by general formula (AIIa)-(AIId) is given to the following, this invention is not limited to these.

The resin (A) of the present invention may further contain 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 resin (A) of the present invention preferably further contains a repeating unit having an alkali-soluble group, and more preferably has a repeating unit having a carboxyl group. By containing this, the resolution in contact hole applications increases. The repeating unit having a carboxyl group includes a repeating unit in which a carboxyl group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid or methacrylic acid, or a carboxyl group in the main chain of the resin through a linking group. Either a repeating unit that is bonded, or a polymerization initiator or chain transfer agent having an alkali-soluble group is introduced at the end of the polymer chain at the time of polymerization, and the linking group is a monocyclic or polycyclic hydrocarbon. You may have a structure. Particularly preferred are repeating units of acrylic acid or methacrylic acid.

The resin (A) of the present invention may further contain a repeating unit having 1 to 3 groups represented by the general formula (F1). This improves line edge roughness performance.

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.
Rx represents a hydrogen atom or an organic group (preferably an acid-decomposable protecting group, an alkyl group, a cycloalkyl group, an acyl group, or an alkoxycarbonyl group).

The alkyl group of R _{50 to} R ₅₅ may be substituted with a halogen atom such as a fluorine atom, a cyano group, etc., preferably an alkyl group having 1 to 3 carbon atoms, such as a methyl group or a trifluoromethyl group. be able to.
R _{50 to} R ₅₅ are preferably all fluorine atoms.

  Examples of the organic group represented by Rx include an acid-decomposable protective group and an optionally substituted alkyl group, cycloalkyl group, acyl group, alkylcarbonyl group, alkoxycarbonyl group, alkoxycarbonylmethyl group, alkoxymethyl group. , 1-alkoxyethyl group is preferable.

The repeating unit having a group represented by the general formula (F1) is preferably a repeating unit represented by the following general formula (F2).

In general formula (F2),
Rx represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. Preferable substituents that the alkyl group of Rx may have include a hydroxyl group and a halogen atom.
Fa represents a single bond or a linear or branched alkylene group (preferably a single bond).

Fb represents a monocyclic or polycyclic hydrocarbon group. As the cyclic hydrocarbon group, a cyclopentyl group, a cyclohexyl group, and a norbornyl group are preferable.
Fc represents a single bond or a linear or branched alkylene group (preferably a single bond or a methylene group).
F ₁ represents a group represented by the general formula (F1).
P ₁ represents an integer of 1 to 3.
Specific examples of the repeating unit having a group represented by formula (F1) are shown below, but the present invention is not limited thereto.

  The resin (A) of the present invention may further contain 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, and cyclohexyl (meth) acrylate.

In addition to the above repeating structural units, the resin (A) of the present invention further has dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and general required characteristics of resist, resolving power, heat resistance, Various repeating structural units can be contained for the purpose of adjusting sensitivity and the like.
Examples of such repeating structural units include, but are not limited to, repeating structural units corresponding to the following monomers.

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

As such a monomer, for example, a compound having one addition polymerizable unsaturated bond selected from acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, etc. Etc.
In addition, any addition-polymerizable unsaturated compound that can be copolymerized with monomers corresponding to the above various repeating structural units may be copolymerized.

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

  In the resin (A), the content of the repeating unit having a partial structure containing the alicyclic hydrocarbon represented by the general formulas (Ia) and (Ib) is preferably 20 to 70 mol% in all the repeating structural units, More preferably, it is 20-50 mol%, More preferably, it is 25-40 mol%.

  In the acid-decomposable resin (A), the content of the repeating unit having a lactone ring is preferably 10 to 70 mol%, more preferably 20 to 60 mol%, still more preferably 25 to 40 mol% in all repeating structural units. It is.

In the acid-decomposable resin (A), the content of the repeating unit having an organic group having a polar group is preferably 1 to 40 mol%, more preferably 5 to 30 mol%, still more preferably 5 in all repeating structural units. ~ 20 mol%.
When the positive photosensitive resin 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 resin (A) of the present invention is preferably one in which all the repeating units are composed of (meth) acrylate repeating units. In this case, all of the repeating units may be methacrylate repeating units, all of the repeating units may be acrylate repeating units, and all of the repeating units may be any mixture of methacrylate repeating units / acrylate repeating units, It is preferable that the acrylate repeating unit is 50 mol% or less of the entire repeating unit.

  Resin (A) includes at least a (meth) acrylate repeating unit having a lactone ring, a (meth) acrylate repeating unit having an organic group substituted with at least one of a hydroxyl group and a cyano group, and an acid-decomposable group It is preferable that it is a copolymer which has three types of repeating units of the (meth) acrylate type repeating unit which has this.

  The resin (A) of 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 the solvent used in the photosensitive resin composition of the present invention. Thereby, generation | occurrence | production of the particle at the time of a preservation | save 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 initiators include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2'-azobis (2-methylpropionate) and the like. 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.

  For purification, the same method as that for the resin (C) described later can be used. The liquid-liquid extraction method for removing residual monomers and oligomer components by combining water washing and an appropriate solvent, only those having a specific molecular weight or less. A purification method in a solution state such as ultrafiltration to extract and remove the residual monomer by coagulating the resin in the poor solvent by dropping the resin solution into the poor solvent, A usual method such as a purification method in a solid state, such as washing the filtered resin slurry with a poor solvent, can be applied.

  The weight average molecular weight of the resin (A) according to the present invention is preferably 1,000 to 200,000, more preferably 3,000 to 20,000, most preferably 5, as a polystyrene conversion value by GPC method. 000 to 15,000. 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 1 to 5, preferably 1 to 3, more preferably 1.2 to 3.0, particularly preferably 1.2 to 2.0. . The smaller the degree of dispersion, the better the resolution and the resist shape, the smoother the side wall of the resist pattern, and the better the roughness.

In the positive photosensitive resin composition of the present invention, the blending ratio of the resin (A) in the entire composition is preferably 50 to 99.5 mass%, more preferably 60 to 99 mass% in the total solid content. %. Moreover, in the positive photosensitive resin composition of the present invention, the blending ratio of all resins including the hydrophobic resin (C) described later is preferably 50 to 99.9% by mass in the total solid content. More preferably, it is 60-99.0 mass%.
In the present invention, the resin (A) may be used alone or in combination.

  From the viewpoint of compatibility with the hydrophobic resin (C) described later, the resin (A) of the present invention contains fluorine when the positive photosensitive resin composition of the present invention contains the hydrophobic resin (C). It is preferable not to contain an atom and a silicon atom.

(B) Photoacid generator The photosensitive resin composition of this invention contains the compound (henceforth an "acid generator") which generate | occur | produces an acid by irradiation of actinic light or a radiation.
As an acid generator, photo-initiator of photocation polymerization, photo-initiator of photo-radical polymerization, photo-decoloring agent of dyes, photo-discoloring agent, or irradiation with actinic ray or radiation used for micro-resist etc. Known compounds that generate acids and mixtures thereof can be appropriately selected and used.

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

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

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

Preferred compounds among the acid generators include compounds represented by the following general formulas (ZI), (ZII), and (ZIII).

In general formula (ZI):
R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represents an organic group.
The carbon number of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is generally 1-30, preferably 1-20.

Two of R _{201 to} R ₂₀₃ may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. The two of the group formed by bonding of the R ₂₀₁ to R _203, there can be mentioned an alkylene group (e.g., butylene, pentylene).

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

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

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

  The aliphatic moiety in the aliphatic sulfonate anion may be an alkyl group or a cycloalkyl group, preferably an alkyl group having 1 to 30 carbon atoms and a cycloalkyl group having 3 to 30 carbon atoms such as methyl. Group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group , Tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group and the like.

The aromatic group in the aromatic sulfonate anion is preferably an aryl group having 6 to 14 carbon atoms, such as a phenyl group, a tolyl group, and a naphthyl group.
The alkyl group, cycloalkyl group and aryl group in the aliphatic sulfonate anion and aromatic sulfonate anion may have a substituent. Examples of the substituent of the alkyl group, cycloalkyl group, and aryl group in the aliphatic sulfonate anion and aromatic sulfonate anion include, for example, a nitro group, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), carboxyl group , Hydroxyl group, amino group, cyano group, alkoxy group (preferably having 1 to 15 carbon atoms), cycloalkyl group (preferably having 3 to 15 carbon atoms), aryl group (preferably having 6 to 14 carbon atoms), alkoxycarbonyl group ( Preferably 2 to 7 carbon atoms, acyl group (preferably 2 to 12 carbon atoms), alkoxycarbonyloxy group (preferably 2 to 7 carbon atoms), alkylthio group (preferably 1 to 15 carbon atoms), alkylsulfonyl group (Preferably having 1 to 15 carbon atoms), alkyliminosulfonyl group (preferably having 2 to 15 carbon atoms), aryl Ruoxysulfonyl group (preferably having 6 to 20 carbon atoms), alkylaryloxysulfonyl group (preferably having 7 to 20 carbon atoms), cycloalkylaryloxysulfonyl group (preferably having 10 to 20 carbon atoms), alkyloxyalkyloxy group (Preferably having 5 to 20 carbon atoms), a cycloalkylalkyloxyalkyloxy group (preferably having 8 to 20 carbon atoms), and the like. About the aryl group and ring structure which each group has, an alkyl group (preferably C1-C15) can further be mentioned as a substituent.

Examples of the aliphatic moiety in the aliphatic carboxylate anion include the same alkyl group and cycloalkyl group as in the aliphatic sulfonate anion.
Examples of the aromatic group in the aromatic carboxylate anion include the same aryl group as in the aromatic sulfonate anion.

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

The alkyl group, cycloalkyl group, aryl group and aralkyl group in the aliphatic carboxylate anion, aromatic carboxylate anion and aralkylcarboxylate anion may have a substituent. Examples of the substituent of the alkyl group, cycloalkyl group, aryl group and aralkyl group in the aliphatic carboxylate anion, aromatic carboxylate anion and aralkylcarboxylate anion include, for example, the same halogen atom and alkyl as in the aromatic sulfonate anion Group, cycloalkyl group, alkoxy group, alkylthio group and the like.
Examples of the sulfonylimide anion include saccharin anion.

  The alkyl group in the bis (alkylsulfonyl) imide anion and tris (alkylsulfonyl) methyl anion is preferably an alkyl group having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, An isobutyl group, a sec-butyl group, a pentyl group, a neopentyl group, and the like can be given. Examples of substituents for these alkyl groups include halogen atoms, alkyl groups substituted with halogen atoms, alkoxy groups, alkylthio groups, alkyloxysulfonyl groups, aryloxysulfonyl groups, cycloalkylaryloxysulfonyl groups, and the like. Alkyl groups substituted with fluorine atoms are preferred.

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

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

Examples of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ include the corresponding groups in the compounds (ZI-1), (ZI-2) and (ZI-3) described later.
In addition, the compound which has two or more structures represented by general formula (ZI) may be sufficient. For example, the general formula at least one of R ₂₀₁ to R ₂₀₃ of a compound represented by (ZI), at least one coupling structure of R ₂₀₁ to R ₂₀₃ of another compound represented by formula (ZI) It may be a compound.

More preferable (ZI) components include compounds (ZI-1), (ZI-2), and (ZI-3) described below.
The compound (ZI-1) is at least one of the aryl groups R ₂₀₁ to R ₂₀₃ in formula (ZI), arylsulfonium compounds, namely, compounds containing an 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 with the remaining being 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 a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom or the like. Examples of the aryl group having a heterocyclic structure include a pyrrole residue (a group formed by losing one hydrogen atom from pyrrole) and a furan residue (a group formed by losing one hydrogen atom from furan). Groups), thiophene residues (groups formed by the loss of one hydrogen atom from thiophene), indole residues (groups formed by the loss of one hydrogen atom from indole), benzofuran residues ( A group formed by losing one hydrogen atom from benzofuran), a benzothiophene residue (a group formed by losing one hydrogen atom from benzothiophene), and the like. 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 or cycloalkyl group that the arylsulfonium compound has as necessary is preferably a linear or branched alkyl group having 1 to 15 carbon atoms and a cycloalkyl group having 3 to 15 carbon atoms, such as a methyl group, Examples thereof include an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, 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, more preferably carbon. These are an alkyl group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms. The substituent may be substituted with any one of the three R _{201 to} R ₂₀₃ , or may be substituted with all three. When R _{201 to} R ₂₀₃ are an aryl group, the substituent is preferably substituted at the p-position of the aryl group.

Next, the compound (ZI-2) will be described.
Compound (ZI-2) is a compound in which R _{201 to} R ₂₀₃ in formula (ZI) each independently represents an organic group having no 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 no aromatic ring having 1 to 20 carbon atoms organic group.

R _{201 to} R ₂₀₃ are each independently preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, more preferably a linear or branched 2-oxoalkyl group, 2-oxocycloalkyl group, alkoxy group. A carbonylmethyl group, particularly preferably a linear or branched 2-oxoalkyl group.

The alkyl group and cycloalkyl group of R ₂₀₁ to R _203, preferably a linear or branched alkyl group having 1 to 10 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, pentyl group), carbon Examples thereof include cycloalkyl groups of several 3 to 10 (cyclopentyl group, cyclohexyl group, norbornyl group). More preferred examples of the alkyl group include a 2-oxoalkyl group and an alkoxycarbonylmethyl group. More preferred examples of the cycloalkyl group include a 2-oxocycloalkyl group.

The 2-oxoalkyl group may be either linear or branched, and a group having> C = O at the 2-position of the above alkyl group is preferable.
The 2-oxocycloalkyl group is preferably a group having> C═O at the 2-position of the cycloalkyl group.

The alkoxy group in the alkoxycarbonylmethyl group is preferably an alkoxy group having 1 to 5 carbon atoms (methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy group).
R _{201 to} R ₂₀₃ may be further substituted with a halogen atom, an alkoxy group (for example, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group.

Next, the compound (ZI-3) will be described.
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.
R _x and R _y each independently represents an alkyl group, a cycloalkyl group, an allyl group or a vinyl group.

Any two or more of R _{1c to} R _5c , R _6c and R _7c , and R _x and R _y may be bonded to each other to form a ring structure, and this ring structure includes an oxygen atom and a sulfur atom. , An ester bond and an amide bond may be included. Examples of the group formed by combining any two or more of R _{1c to} R _5c , R _6c and R _7c , and R _x and R _y include a butylene group and a pentylene group.
Zc ⁻ represents a non-nucleophilic anion, and examples thereof include the same non-nucleophilic anion as Z ^{− in} formula (ZI).

The alkyl group as R _{1c to} R _7c may be either linear or branched, for example, an alkyl group having 1 to 20 carbon atoms, preferably a linear or branched alkyl group having 1 to 12 carbon atoms ( Examples thereof include a methyl group, an ethyl group, a linear or branched propyl group, a linear or branched butyl group, and a linear or branched pentyl group. Examples of the cycloalkyl group include cyclohexane having 3 to 8 carbon atoms. An alkyl group (for example, a cyclopentyl group, a cyclohexyl group) can be mentioned.

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

_Examples of the alkyl group and cycloalkyl group as R _x and R _y include the same alkyl group and cycloalkyl group as in R _{1c to} R _7c , such as a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxy group. A carbonylmethyl group is more preferred.
Examples of the 2-oxoalkyl group and 2-oxocycloalkyl group include a group having> C═O at the 2-position of the alkyl group or cycloalkyl group as R _{1c to} R _7c .

Examples of the alkoxy group in the alkoxycarbonylmethyl group include the same alkoxy groups as in R _{1c to} R _5c .
R _x and R _y are preferably an alkyl group or cycloalkyl group having 4 or more carbon atoms, more preferably 6 or more, and still more preferably 8 or more alkyl groups or cycloalkyl groups.

In general formulas (ZII) and (ZIII),
R ₂₀₄ to R ₂₀₇ each independently represents an aryl group, an alkyl group or a cycloalkyl group.
Phenyl group and a naphthyl group are preferred as the aryl group of R ₂₀₄ to R _207, more preferably a phenyl group. Aryl group R ₂₀₄ to R ₂₀₇ represents an oxygen atom, a nitrogen atom, may be an aryl group having a heterocyclic structure having a sulfur atom and the like. Examples of the aryl group having a heterocyclic structure include a pyrrole residue (a group formed by losing one hydrogen atom from pyrrole) and a furan residue (a group formed by losing one hydrogen atom from furan). Groups), thiophene residues (groups formed by the loss of one hydrogen atom from thiophene), indole residues (groups formed by the loss of one hydrogen atom from indole), benzofuran residues ( A group formed by losing one hydrogen atom from benzofuran), a benzothiophene residue (a group formed by losing one hydrogen atom from benzothiophene), and the like.

The alkyl group and cycloalkyl group in R ₂₀₄ to R _207, preferably a linear or branched alkyl group having 1 to 10 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, pentyl group), carbon Examples thereof include cycloalkyl groups of several 3 to 10 (cyclopentyl group, cyclohexyl group, norbornyl group).

Aryl group, alkyl group of R ₂₀₄ to R _207, cycloalkyl groups may have a substituent. Aryl group, alkyl group of R ₂₀₄ to R _207, the cycloalkyl group substituent which may be possessed by, 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 (for example, having 6 to 15 carbon atoms), an alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, and a phenylthio group.
Z ⁻ represents a non-nucleophilic anion, and examples thereof include the same as the non-nucleophilic anion of Z ^{− in} formula (ZI).

Examples of the acid generator further include compounds represented by the following general formulas (ZIV), (ZV), and (ZVI).

In general formulas (ZIV) to (ZVI),
Ar ₃ and Ar ₄ each independently represents an aryl group.
R ₂₀₈ , R ₂₀₉ and R ₂₁₀ each independently represents an alkyl group, a cycloalkyl group or an aryl group.
A represents an alkylene group, an alkenylene group or an arylene group.
Among the acid generators, compounds represented by the general formulas (ZI) to (ZIII) are more preferable.

Further, the acid generator is preferably a compound that generates an acid having one sulfonic acid group or imide group, more preferably a compound that generates monovalent perfluoroalkanesulfonic acid, or a monovalent fluorine atom or fluorine atom. A compound that generates an aromatic sulfonic acid substituted with a group containing fluorinated acid, or a compound that generates a monovalent fluorine atom or imide acid substituted with a group containing a fluorine atom, and even more preferably, It is a sulfonium salt of a substituted alkanesulfonic acid, a fluorine-substituted benzenesulfonic acid, a fluorine-substituted imide acid or a fluorine-substituted methide acid. The acid generator that can be used is particularly preferably a fluorinated substituted alkane sulfonic acid, a fluorinated substituted benzene sulfonic acid or a fluorinated substituted imido acid whose pKa of the generated acid is pKa = -1 or less, and the sensitivity is improved. .
Among acid generators, particularly preferred examples are given below.

An acid generator can be used individually by 1 type or in combination of 2 or more types.
The content of the acid generator in the photosensitive resin composition is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, based on the total solid content of the photosensitive resin composition. Preferably it is 1-7 mass%.

(C) Hydrophobic resin (HP)
When exposing the photosensitive film | membrane which consists of the photosensitive composition of this invention through an immersion medium, (C) hydrophobic resin (HP) can be further added as needed.
“Hydrophobic resin” refers to a resin that, when added to the photosensitive film, contributes to an improvement in the contact angle of water on the surface of the photosensitive film. The hydrophobic resin may be any resin as long as the receding contact angle of the surface is improved by addition, but it is a resin having at least one of fluorine atoms and silicon atoms and being unevenly distributed on the surface of the photosensitive film. Is preferred.

The photosensitive advancing contact angle is preferably adjusted to 70 ° to 120 °, and more preferably 75 ° to 100 °. The receding contact angle is preferably adjusted to 60 ° to 100 °, more preferably 70 ° to 90 °.
The addition amount of the hydrophobic resin (HP) can be adjusted as appropriate so that the receding contact angle of the photosensitive film falls within the above range, but is 0.1 to 10% by mass based on the total solid content of the photosensitive composition. It is preferably 0.1 to 5% by mass.

It is preferable to contribute to improving the receding contact angle with a smaller addition amount, and the glass transition point (Tg) of the resin is preferably in the range of 50 ° C to 200 ° C.
Further, the hydrophobic resin (HP) is preferably a solid at room temperature (25 ° C.).
The advancing contact angle and receding contact angle defined here are advancing and receding contact angles measured by the expansion and contraction method. Specifically, 36 μL of a positive photosensitive resin composition prepared on a silicon wafer is obtained with a syringe. After forming the water droplet, the liquid was discharged or sucked at a speed of 6 μL / sec, and the contact angle during discharge / suction showed a stable value.
Hydrophobic resins are often ubiquitous at the interface, but unlike the surfactant (E), it is not always necessary to have a hydrophilic group in the molecule, contributing to uniform mixing of polar / nonpolar substances. You don't have to.

(C) The hydrophobic resin (HP) will be described in detail below.
The photosensitive resin composition of the present invention contains a hydrophobic resin (hereinafter, also referred to as “hydrophobic resin (HP)” or “resin (HP)”) as a component (C) resin to make the surface hydrophobic. Can do.
Such a hydrophobic resin (HP) can be used without particular limitation, but a resin having at least one of a fluorine atom and a silicon atom is preferable. The fluorine atom or silicon atom in the resin (HP) may be contained in the main chain of the resin or may be substituted with a side chain.

The resin (HP) may be unnecessary or soluble in the alkali developer, but is preferably alkali-soluble. “Soluble in alkaline developer” means that the amount of the hydrophobic resin film dissolved in a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 23 ° C. is 50 nm or more in 30 seconds from the start of development. Say. In order to be soluble in an alkali developer, it is necessary that the photosensitive resin film has an alkali-soluble group in the development step. The alkali-soluble group may be previously contained in the resin, or may be generated by the action of an acid between the exposure and development steps, or may react with an alkali developer to generate an alkali-soluble group. .
Further, the hydrophobic resin (HP) can be suitably used as a top coat.
First, a hydrophobic resin (HP) having no fluorine atom or silicon atom will be described in detail below.

The resin (HP) is preferably a resin having a repeating unit selected from the following general formulas (CI) to (C-III).

In the formulas (CI) to (C-III),
R ₁ each independently represents a hydrogen atom or a methyl group.
Each R ₂ independently represents a hydrocarbon group having one or more —CH ₃ partial structures (ie, methyl groups).
P ₁ represents a single bond or alkylene, ether, or a linking group having two or more thereof.
P ₂ represents a linking group selected from —O—, —NR— (R is a hydrogen atom or alkyl), and —NHSO ₂ —.
n represents an integer of 1 to 4. When n is 2 or more, a plurality of R ₂ may be the same or different.
These repeating units may be one or a plurality of repeating units may be combined.

In the formulas (CI) to (C-III), as the hydrocarbon group having one or more —CH ₃ partial structures (that is, methyl groups) of R ₂ , alkyl having one or more —CH ₃ partial structures Groups, alkyloxy groups, alkyl-substituted cycloalkyl groups, alkenyl groups, alkyl-substituted alkenyl groups, alkyl-substituted cycloalkenyl groups, alkyl-substituted aryl groups, and alkyl-substituted aralkyl groups, and alkyl groups and alkyl-substituted cycloalkyl groups are preferred. Hydrocarbon group having one or more -CH ₃ partial structure R ₂ more preferably has a -CH ₃ partial structures of two or more.

The alkyl group having at least one —CH ₃ partial structure in R ₂ is preferably a branched alkyl group having 3 to 20 carbon atoms. Specific examples of preferable alkyl groups include isopropyl group, isobutyl group, t-butyl group, 3-pentyl group, 2-methyl-3-butyl group, 3-hexyl group, 2-methyl-3-pentyl group, 3-methyl-4-hexyl group, 3,5-dimethyl-4-pentyl group, isooctyl group, 2,4,4-trimethylpentyl group, 2-ethylhexyl group, 2,6-dimethylheptyl group, 1,5- Examples thereof include a dimethyl-3-heptyl group and 2,3,5,7-tetramethyl-4-heptyl group. More preferably, an isobutyl group, a t-butyl group, a 2-methyl-3-butyl group, a 2-methyl-3-pentyl group, a 3-methyl-4-hexyl group, a 3,5-dimethyl-4-pentyl group, 2,4,4-trimethylpentyl group, 2-ethylhexyl group, 2,6-dimethylheptyl group, 1,5-dimethyl-3-heptyl group, 2,3,5,7-tetramethyl-4-heptyl group is there.

The alkyl group having one —CH ₃ partial structure in R ₂ is preferably a linear alkyl group having 1 to 20 carbon atoms. Specific examples of preferred alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and nonyl groups.

Examples of the alkyloxy group having at least one —CH ₃ partial structure in R ₂ include groups in which an ether group is bonded to an alkyl group having at least two —CH ₃ partial structures.

The cycloalkyl group in R ₂ 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. 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. More preferably, they are a norbornyl group, a cyclopentyl group, and a cyclohexyl group.

The alkenyl group in R ₂ is preferably a linear or branched alkenyl group having 1 to 20 carbon atoms, and more preferably a branched alkenyl group.
The aryl group in R ₂ is preferably an aryl group having 6 to 20 carbon atoms, and examples thereof include a phenyl group and a naphthyl group, and a phenyl group is preferable.
The aralkyl group in R ₂ is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, and a naphthylmethyl group.

Specific examples of the hydrocarbon group having at least two —CH ₃ partial structures in R ₂ of the general formulas (CI) to (C-II) include an isopropyl group, an isobutyl group, t- Butyl group, 3-pentyl group, 2-methyl-3-butyl group, 3-hexyl group, 2,3-dimethyl-2-butyl group, 2-methyl-3-pentyl group, 3-methyl-4-hexyl group 3,5-dimethyl-4-pentyl group, isooctyl group, 2,4,4-trimethylpentyl group, 2-ethylhexyl group, 2,6-dimethylheptyl group, 1,5-dimethyl-3-heptyl group, 2 , 3,5,7-tetramethyl-4-heptyl group, 3,5-dimethylcyclohexyl group, 4-isopropylcyclohexyl group, 4-tbutylcyclohexyl group, isobornyl group and the like. More preferably, an isobutyl group, a t-butyl group, a 2-methyl-3-butyl group, a 2,3-dimethyl-2-butyl group, a 2-methyl-3-pentyl group, a 3-methyl-4-hexyl group, 3,5-dimethyl-4-pentyl group, 2,4,4-trimethylpentyl group, 2-ethylhexyl group, 2,6-dimethylheptyl group, 1,5-dimethyl-3-heptyl group, 2,3,5 , 7-tetramethyl-4-heptyl group, 3,5-dimethylcyclohexyl group, 4-isopropylcyclohexyl group, 4-tbutylcyclohexyl group and isobornyl group.

Specific examples of the hydrocarbon group having at least two —CH ₃ partial structures in R ₂ of the general formula (C-III) include an isobutyl group, a t-butyl group, a 3-pentyl group, 2 , 3-dimethylbutyl group, 2-methyl-3-butyl group, 3-hexyl group, 2-methyl-3-pentyl group, 3-methyl-4-hexyl group, 3,5-dimethyl-4-pentyl group, Isooctyl group, 2,4,4-trimethylpentyl group, 2-ethylhexyl group, 2,6-dimethylheptyl group, 1,5-dimethyl-3-heptyl group, 2,3,5,7-tetramethyl-4- Examples include heptyl group, 3,5-dimethylcyclohexyl group, 4-isopropylcyclohexyl group, 4-tbutylcyclohexyl group and the like. More preferably, it has more preferably 5 to 20 carbon atoms, and 2-methyl-3-butyl group, 2-methyl-3-pentyl group, 3-methyl-4-hexyl group, 3,5-dimethyl-4. -Pentyl group, 2,4,4-trimethylpentyl group, 2-ethylhexyl group, 2,6-dimethylheptyl group, 1,5-dimethyl-3-heptyl group, 2,3,5,7-tetramethyl-4 -Heptyl group, 2,6-dimethylheptyl group, 3,5-dimethylcyclohexyl group, 4-isopropylcyclohexyl group, 4-tbutylcyclohexyl group.

As for the total content rate of the repeating unit chosen from general formula (CI)-(C-III), 50-100 mol% is preferable with respect to all the repeating units in hydrophobic resin (HP), More preferably, 80- It is 100 mol%, More preferably, it is 90-100 mol%.
Preferable specific examples of the repeating unit represented by formula (CI) are listed below. Note that the present invention is not limited to this.

Preferred specific examples of the repeating unit represented by formula (C-II) are shown below. Note that the present invention is not limited to this.

In general formula (C-III), when P ₂ is an oxygen atom, the carbon atom directly connected to the oxygen atom is preferably secondary or tertiary.
Specific preferred examples of the repeating unit represented by formula (C-III) are shown below. Note that the present invention is not limited to this. In specific examples, Rx represents a hydrogen atom or a methyl group, and Rxa, Rxb, and Rxc each represents an alkyl group having 1 to 4 carbon atoms.

Specific examples of the resin (HP) are shown below. The following table shows the molar ratio of repeating units in each resin (corresponding to each repeating unit in order from the left), the weight average molecular weight, and the degree of dispersion.

Next, a hydrophobic resin (HP) having at least one of a fluorine atom and a silicon atom will be described.
The fluorine atom or silicon atom in the resin (HP) may be contained in the main chain of the resin or may be substituted with a side chain.
The resin (HP) is preferably a resin having, as a partial structure having a fluorine atom, an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom.

The alkyl group having a fluorine atom (preferably having 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms) is a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, It may have a substituent.
The cycloalkyl group having a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may further have another substituent.

Examples of the aryl group having a fluorine atom include those in which at least one hydrogen atom of an aryl group such as a phenyl group or a naphthyl group is substituted with a fluorine atom, and may further have another substituent.
A general formula of an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom is shown below, but the present invention is not limited thereto.

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 , R _{62 to} R ₆₄ and R _{65 to} R ₆₈ is a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom (preferably having a carbon number of 1 ~ 4). 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 trifluoromethyl 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.

Hereinafter, the specific example of the repeating unit containing group represented by general formula (F2)-(F4) is shown.
In the formula, X1 represents a hydrogen atom, —CH ₃ , —F, or —CF ₃ .
X2 is, -F, or represents a -CF _3.

  When resin (HP) has a fluorine atom, it is preferable that the content rate of a fluorine atom is 5-80 mass% with respect to the molecular weight of resin (HP), and it is more preferable that it is 10-80 mass%. Moreover, it is preferable that the repeating unit containing a fluorine atom is 10-100 mass% in resin (HP), and it is more preferable that it is 30-100 mass%.

In the resin (HP), the partial structure having a silicon atom is preferably a resin having an alkylsilyl structure (preferably a trialkylsilyl group) or a cyclic siloxane structure.
Specific examples of the alkylsilyl structure or the cyclic siloxane structure 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 (preferably having 1 to 20 carbon atoms) or a cycloalkyl group (preferably having 3 to 20 carbon atoms).
L _{3 to} L ₅ each independently represents a single bond or a divalent linking group. As the divalent linking group, an alkylene group, a phenyl group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a urethane group, or a urea group is used alone or in combination of two or more groups. Combinations are listed.
n represents an integer of 1 to 5.

Hereinafter, the specific example of the repeating unit containing group represented by general formula (CS-1)-(CS-3) is shown.
In the formula, X ₁ represents a hydrogen atom, —CH ₃ , —F, or —CF ₃ .

Specific examples of the hydrophobic resin (HP) containing at least one of a fluorine atom and a silicon atom are shown below. The following table shows the molar ratio of repeating units in each resin (corresponding to each repeating unit in order from the left), the weight average molecular weight, and the degree of dispersion.

  Furthermore, the resin (HP) may contain at least one group selected from the following groups (x) to (z).

(X) an alkali-soluble group,
(Y) a group that decomposes by the action of an alkali developer and increases the solubility in the alkali developer;
(Z) A group that decomposes by the action of an acid.

  (X) Alkali-soluble groups include phenolic hydroxyl groups, carboxylic acid groups, fluorinated alcohol groups, sulfonic acid groups, sulfonamido groups, sulfonylimide groups, (alkylsulfonyl) (alkylcarbonyl) methylene groups, (alkylsulfonyl) ( Alkylcarbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, tris (alkylsulfonyl) And a group having a methylene group.

  Preferred alkali-soluble groups include fluorinated alcohol groups (preferably hexafluoroisopropanol), sulfonimide groups, and bis (carbonyl) methylene groups.

  Examples of the repeating unit having an alkali-soluble group (x) include 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 a main group of the resin via a linking group. It is preferable to use a repeating unit in which an alkali-soluble group is bonded to the chain, and further introduce a polymerization initiator or chain transfer agent having an alkali-soluble group at the end of the polymer chain at the time of polymerization.

  The content of the repeating unit having an alkali-soluble group (x) is preferably from 1 to 50 mol%, more preferably from 3 to 35 mol%, still more preferably from 5 to 20 mol, based on all repeating units in the hydrophobic resin (HP). %.

Specific examples of the repeating unit having an alkali-soluble group (x) are shown below.

(Y) Examples of the group that decomposes by the action of an alkali developer and increases the solubility in the alkali developer include a group having a lactone structure, an acid anhydride, an acid imide group, and the like, and preferably a lactone group It is.
The repeating unit having a group (y) that is decomposed by the action of an alkali developer and increases the solubility in the alkali developer includes a resin via a linking group such as a repeating unit of an acrylate ester or a methacrylate ester. A polymerization initiator or chain transfer agent having a repeating unit in which an alkali-soluble group is bonded to the main chain or a group (y) that increases solubility in an alkaline developer is introduced at the end of the polymer chain during polymerization. Both are preferable.

The content of the repeating unit having a group (y) whose solubility in an alkali developer is increased is preferably 1 to 40 mol%, more preferably 3 to 30 mol, based on all repeating units in the hydrophobic resin (HP). %, More preferably 5 to 15 mol%.
Specific examples of the repeating unit having a group (y) that increases the solubility in an alkali developer include those similar to the lactone structure exemplified in the resin (A) and the structure represented by the general formula (VIII). Can be mentioned.

(Z) Examples of the group capable of decomposing by the action of an acid include the same acid-decomposable groups as mentioned for the resin (A). When the fluorine-containing compound (HP) is a resin, (z) the repeating unit containing a group capable of decomposing by the action of an acid is the same as the repeating unit containing an acid-decomposable group mentioned in the resin (A). can give. When the fluorine-containing compound (HP) is a resin, the content of the repeating unit having a group (z) that decomposes by the action of an acid is preferably 1 to 80 mol% with respect to all the repeating units in the hydrophobic resin (HP). More preferably, it is 10-80 mol%, More preferably, it is 20-60 mol%.
Furthermore, the resin (HP) may have a repeating unit represented by the following general formula (III).

In general formula (III):
R ₄ represents a group having an alkyl group, a cycloalkyl group, an alkenyl group, or a cycloalkenyl group.
L ₆ represents a single bond or a divalent linking group.
In general formula (III), the alkyl group represented by R ₄ is preferably a linear or branched alkyl group having 3 to 20 carbon atoms.
The cycloalkyl group is preferably a cycloalkyl group having 3 to 20 carbon atoms.
The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms.
The cycloalkenyl group is preferably a cycloalkenyl group having 3 to 20 carbon atoms.
The divalent linking group of L ₆ is preferably an alkylene group (preferably having 1 to 5 carbon atoms) or an oxy group.

The weight average molecular weight of the resin (HP) in terms of standard polystyrene is preferably 1,000 to 100,000, more preferably 1,000 to 50,000, and still more preferably 2,000 to 15,000.
As with the acid-decomposable resin (A), the resin (HP) preferably has 0 to 10% by mass of residual monomer and oligomer components, and more preferably has few impurities such as metals. 0-5 mass% and 0-1 mass% are still more preferable. Thereby, a resist having no change over time such as foreign matter in liquid or sensitivity can be obtained. The molecular weight distribution (Mw / Mn, also referred to as dispersity) is preferably 1 to 5, more preferably 1 to 3, in terms of resolution, resist shape, resist pattern side wall, roughness, and the like.

  As the resin (HP), various commercially available products can be used, or they 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 the solvent used in the photosensitive resin composition of the present invention. Thereby, generation | occurrence | production of the particle at the time of a preservation | save can be suppressed.

  The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon. As the polymerization initiator, a commercially available radical initiator (azo initiator, peroxide, etc.) can be used to start the polymerization, and a chain transfer agent can be used if necessary. 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. The concentration of the reaction is usually 5 to 50% by mass, preferably 30 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 for the polymer, and may be a hydrocarbon, halogenated hydrocarbon, nitro, depending on the type of polymer. A compound, ether, ketone, ester, carbonate, alcohol, carboxylic acid, water, a mixed solvent containing these solvents, and the like can be appropriately selected for use. Among these, as a precipitation or reprecipitation solvent, a solvent containing at least an alcohol (particularly methanol or the like) or water is preferable.

  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 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 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).

  The resin may be once deposited and separated, and then 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 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 resin content of the component (C) is preferably 0.1 to 20% by mass, more preferably based on the solid content of the positive photosensitive resin composition (total solid content constituting the resist film). It is 0.1-10 mass%, More preferably, it is 0.1-5 mass%.

  In addition to the component (A), the component (B), and the component (C), the positive photosensitive resin composition of the present invention includes (D) a solvent, (E) a basic compound, (F ) Surfactant, (G) carboxylic acid onium salt, (H) other additives can be added.

(D) Solvent Examples of the solvent that can be used in preparing the positive resist composition by dissolving the above components include, for example, alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate ester, Examples thereof include organic solvents such as alkyl alkoxypropionates, cyclic lactones having 4 to 10 carbon atoms, monoketone compounds having 4 to 10 carbon atoms, which may contain a ring, alkylene carbonate, alkyl alkoxyacetates, and alkyl pyruvates. .

  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-he Sen-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.
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 an organic 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. Particularly preferred are propylene glycol monomethyl ether and ethyl lactate.

  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 particularly preferred, and propylene glycol monomethyl ether acetate, ethyl ethoxypropionate. 2-heptanone is most preferred.

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.
The solvent is preferably a mixed solvent of two or more containing propylene glycol monomethyl ether acetate.

(E) Basic compound The positive photosensitive resin composition of the present invention is a basic compound for reducing the change in performance over time from exposure to heating or for controlling the diffusibility of the acid generated by exposure in the film. It is preferable to contain.

Examples of basic compounds include nitrogen-containing basic compounds and onium salt compounds. Preferable nitrogen-containing basic compound structures include compounds having partial structures represented by the following general formulas (A) to (E).

In general formula (A),
R ^250, R ²⁵¹ and R ²⁵² are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group or an aryl group having 6 to 20 carbon atoms having 3 to 20 carbon atoms, and R ²⁵⁰ R ²⁵¹ may combine with each other to form a ring. These may have a substituent. Examples of the alkyl group and cycloalkyl group having a substituent include an aminoalkyl group having 1 to 20 carbon atoms, an aminocycloalkyl group having 3 to 20 carbon atoms, and 1 to 1 carbon atoms. A 20 hydroxyalkyl group or a C 3-20 hydroxycycloalkyl group is preferred.
These may contain an oxygen atom, a sulfur atom, or a nitrogen atom in the alkyl chain.

In general formula (E),
R ²⁵³ , R ²⁵⁴ , R ²⁵⁵ and R ²⁵⁶ each independently represent an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms.

  Preferable compounds include guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, and piperidine, and may have a substituent. More preferable compounds include compounds having an imidazole structure, a diazabicyclo structure, an onium hydroxide structure, an onium carboxylate structure, a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, a hydroxyl group and / or Or the aniline derivative which has an ether bond etc. can be mentioned.

  Examples of the compound having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole, and 2-phenylbenzimidazole. Examples of the compound having a diazabicyclo structure include 1,4-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4,3,0] non-5-ene, and 1,8-diazabicyclo [5,4,0. ] Undec-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, tris (methoxyethoxyethyl) amine, N-phenyldiethanolamine and the like. Examples of aniline derivatives having a hydroxyl group and / or an ether bond include N, N-bis (hydroxyethyl) aniline.

Preferred examples of the basic compound further include an amine compound having a phenoxy group and an ammonium salt compound having a phenoxy group.
As the amine compound, a primary, secondary or tertiary amine compound can be used, and an amine compound in which at least one alkyl group is bonded to a nitrogen atom is preferable. The amine compound is more preferably a tertiary amine compound. As long as at least one alkyl group (preferably having 1 to 20 carbon atoms) is bonded to a nitrogen atom, the amine compound has an cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group (preferably having 3 to 20 carbon atoms). Preferably C6-C12) may be bonded to a nitrogen atom.

The amine compound preferably has an oxygen atom in the alkyl chain and an oxyalkylene group is formed. The number of oxyalkylene groups is one or more in the molecule, preferably 3 to 9, and more preferably 4 to 6. Among the oxyalkylene groups, an oxyethylene group (—CH ₂ CH ₂ O—) or an oxypropylene group (—CH (CH ₃ ) CH ₂ O— or —CH ₂ CH ₂ CH ₂ O—) is preferable, and more preferably oxy Ethylene group.

  As the ammonium salt compound, a primary, secondary, tertiary, or quaternary ammonium salt compound can be used, and an ammonium salt compound in which at least one alkyl group is bonded to a nitrogen atom is preferable. As long as at least one alkyl group (preferably having 1 to 20 carbon atoms) is bonded to a nitrogen atom, the ammonium salt compound has a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group in addition to the alkyl group. (Preferably having 6 to 12 carbon atoms) may be bonded to a nitrogen atom.

The ammonium salt compound preferably has an oxygen atom in the alkyl chain and an oxyalkylene group is formed. The number of oxyalkylene groups is one or more in the molecule, preferably 3 to 9, and more preferably 4 to 6. Among the oxyalkylene groups, an oxyethylene group (—CH ₂ CH ₂ O—) or an oxypropylene group (—CH (CH ₃ ) CH ₂ O— or —CH ₂ CH ₂ CH ₂ O—) is preferable, and more preferably oxy Ethylene group.

  Examples of the anion of the ammonium salt compound include halogen atoms, sulfonates, borates, and phosphates. Among them, halogen atoms and sulfonates are preferable. As the halogen atom, chloride, bromide, and iodide are particularly preferable. As the sulfonate, an organic sulfonate having 1 to 20 carbon atoms is particularly preferable. Examples of the organic sulfonate include alkyl sulfonates having 1 to 20 carbon atoms and aryl sulfonates. The alkyl group of the alkyl sulfonate may have a substituent, and examples of the substituent include fluorine, chlorine, bromine, alkoxy groups, acyl groups, and aryl groups. Specific examples of the alkyl sulfonate include methane sulfonate, ethane sulfonate, butane sulfonate, hexane sulfonate, octane sulfonate, benzyl sulfonate, trifluoromethane sulfonate, pentafluoroethane sulfonate, and nonafluorobutane sulfonate. Examples of the aryl group of the aryl sulfonate include a benzene ring, a naphthalene ring, and an anthracene ring. The benzene ring, naphthalene ring and anthracene ring may have a substituent, and the substituent is preferably a linear or branched alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms. Specific examples of the linear or branched alkyl group and cycloalkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, t-butyl, n-hexyl, cyclohexyl and the like. Examples of the other substituent include an alkoxy group having 1 to 6 carbon atoms, a halogen atom, cyano, nitro, an acyl group, and an acyloxy group.

  The amine compound having a phenoxy group and the ammonium salt compound having a phenoxy group are those having a phenoxy group at the terminal opposite to the nitrogen atom of the alkyl group of the amine compound or ammonium salt compound. The phenoxy group may have a substituent. Examples of the substituent of the phenoxy group include an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, a carboxyl group, a carboxylic acid ester group, a sulfonic acid ester group, an aryl group, an aralkyl group, an acyloxy group, and an aryloxy group. Etc. The substitution position of the substituent may be any of the 2-6 positions. The number of substituents may be any in the range of 1 to 5.

It is preferable to have at least one oxyalkylene group between the phenoxy group and the nitrogen atom. The number of oxyalkylene groups is one or more in the molecule, preferably 3 to 9, and more preferably 4 to 6. Among the oxyalkylene groups, an oxyethylene group (—CH ₂ CH ₂ O—) or an oxypropylene group (—CH (CH ₃ ) CH ₂ O— or —CH ₂ CH ₂ CH ₂ O—) is preferable, and more preferably oxy Ethylene group.

  The amine compound having a phenoxy group is prepared by reacting a primary or secondary amine having a phenoxy group with a haloalkyl ether by heating, and then adding an aqueous solution of a strong base such as sodium hydroxide, potassium hydroxide or tetraalkylammonium. It can be obtained by extraction with an organic solvent such as ethyl acetate or chloroform. Alternatively, after reacting by heating a primary or secondary amine and a haloalkyl ether having a phenoxy group at the end, an aqueous solution of a strong base such as sodium hydroxide, potassium hydroxide, or tetraalkylammonium is added, and then ethyl acetate, It can be obtained by extraction with an organic solvent such as chloroform.

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 photosensitive composition, Preferably it is 0.01-5 mass%. In order to obtain a sufficient addition effect, 0.001% by mass or more is preferable, and 10% by mass or less is preferable in terms of sensitivity and developability of the non-exposed area.

(F) Surfactant The positive photosensitive resin 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 It is more preferable to contain any one of a system surfactant, a surfactant having both a fluorine atom and a silicon atom, or two or more thereof.

  When the positive photosensitive resin composition of the present invention contains the surfactant (F), adhesion and development defects can be obtained with good sensitivity and resolution when using an exposure light source of 250 nm or less, particularly 220 nm or less. A small resist pattern can be provided.

  Examples of the fluorine-based and / or silicon-based surfactant include, for example, JP-A No. 62-36663, JP-A No. 61-226746, JP-A No. 61-226745, JP-A No. 62-170950, JP 63-34540 A, JP 7-230165 A, JP 8-62834 A, JP 9-54432 A, JP 9-5988 A, JP 2002-277862 A, US Patent Nos. 5,405,720, 5,360,692, 5,529,881, 5,296,330, 5,436,098, 5,576,143, 5,294,511, 5,824,451 Surfactant can be mentioned, The following commercially available surfactant can also be used as it is.

Examples of commercially available surfactants that can be used include F-top EF301, EF303 (manufactured by Shin-Akita Kasei Co., Ltd.), Florard FC430, 431, 4430 (manufactured by Sumitomo 3M Co., Ltd.),
Megafuck F171, F173, F176, F189, F113, F110, F177, F120, R08 (manufactured by Dainippon Ink and Chemicals), 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 Co., Ltd.), Surflon S-393 (manufactured by Seimi Chemical Co., Ltd.), Ftop EF121, EF122A, EF122B, RF122C, EF125M, EF135M, EF351, 352, EF801, EF802, EF601 (manufactured by Gemco), PF636, PF656, PF6320, PF6520 (manufactured by OMNOVA), FTX-204D, 208, 230G, 204 , Mention may be made of 208D, 212D, the fluorine-based surfactant or silicone-based surfactants such as 218D and 222D ((KK) Neos). 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 amount of the surfactant used is preferably 0.0001 to 2% by mass, more preferably 0.001 to 1% by mass, based on the total amount of the positive photosensitive resin composition (excluding the solvent). .

(G) Carboxylic acid onium salt The positive photosensitive resin composition in this invention may contain (G) 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 (H) 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.

  Fluorine-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.

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

(H) Other additives The positive photosensitive resin composition of the present invention may further contain dyes, plasticizers, photosensitizers, light absorbers, alkali-soluble resins, dissolution inhibitors and developers as necessary. A compound that promotes solubility (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.

(I) Pattern Forming Method The positive photosensitive resin composition of the present invention is preferably used at a film thickness of 30 to 500 nm, more preferably at a film thickness of 30 to 250 nm, from the viewpoint of improving resolution. Even more preferably, the film thickness is 30 to 200 nm. Such a film thickness can be obtained by setting the solid content concentration in the positive photosensitive resin 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 photosensitive resin 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. .

  The positive photosensitive resin composition of the present invention is used by dissolving the above components in a predetermined organic solvent, preferably the 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 having a pore size of 0.1 μm or less, more preferably 0.05 μm or less, and still more preferably 0.03 μm or less.

  For example, a positive photosensitive resin composition is coated on a substrate (eg, silicon / silicon dioxide coating) used for the manufacture of precision integrated circuit elements by an appropriate coating method such as a spinner or a coater, dried, and exposed to light. Forming a conductive film. In addition, you may coat a well-known antireflection film beforehand.

  The photosensitive 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., preferably 250 nm or less, more preferably 220 nm or less, particularly preferably 1 to 1. Far ultraviolet light having a wavelength of 200 nm, 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, F ₂ Excimer laser, EUV (13 nm), and electron beam are preferable.

Before forming the resist film, an antireflection film may be coated on the substrate in advance.
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. In addition, as the organic antireflection film, commercially available organic antireflection films such as DUV30 series, DUV-40 series manufactured by Brewer Science, AR-2, AR-3, AR-5 manufactured by Shipley, etc. 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.
The development process or the rinsing process may be performed by forming a paddle or may be performed by a paddleless process.
In the case of immersion exposure, a rinsing step may be performed before and after exposure.

  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 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 the positive photosensitive resin composition of the present invention, since the resin (C) contained in the resist is unevenly distributed on the surface, the contact angle (particularly the receding contact angle) of the film surface can be improved. When the resist film is formed, the receding contact angle of water with respect to the resist film is preferably 65 ° or more, and more preferably 70 ° or more. The receding contact angle of the film when only the resin (C) is dissolved and applied is preferably 70 ° to 110 °. By adjusting the addition amount of the resin (C), the receding contact angle of the resist film is adjusted to 60 ° to 80 ° for use. Here, the receding contact angle is at normal temperature and pressure. The receding contact angle is the receding contact angle when the droplet starts to drop when the resist film is tilted.

  In order to prevent the resist film from coming into direct contact with the immersion liquid between the resist film made of the positive photosensitive resin composition of the present invention and the immersion liquid, an immersion liquid hardly soluble film (hereinafter referred to as “top coat”). May also be provided. The necessary functions for the top coat are suitability for application to the upper layer of the resist, radiation, especially transparency to 193 nm, and poor immersion liquid solubility. It is preferable that the top coat is not mixed with the resist and can be uniformly applied to the resist upper layer.

  From the viewpoint of 193 nm transparency, the topcoat is preferably a polymer that does not contain an aromatic, and specifically, a hydrocarbon polymer, an acrylate polymer, a polymethacrylic acid, a polyacrylic acid, a polyvinyl ether, a silicon-containing polymer, And fluorine-containing polymers. 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.

EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, the content of this invention is not limited by this.
[Synthesis of Resin (A)]
Synthesis Example 1 Synthesis of Compound 1

  After adding 240 ml of THF to 36 g of anhydrous cerium chloride in a 500 ml three-necked flask filled with Ar gas, 48 ml of ethylmagnesium bromide (manufactured by Tokyo Chemical Industry, 39 mass% diethyl ether solution) was added at −78 ° C., and the mixture was stirred for 30 minutes. did. Thereafter, 13 ml of 2-methylcyclopentanone was added, and the mixture was stirred at 0 ° C. for 30 minutes. After adding 200 ml of a saturated aqueous ammonium chloride solution, the mixture was extracted with ethyl acetate.

  After 13 g of the obtained crude product (1-ethyl-2-methylcyclopentanol) was dissolved in 70 ml of THF under Ar atmosphere, 76 ml (1.6 M solution) of n-butyllithium was added at 0 ° C. and stirred for 15 minutes. . Furthermore, after adding 12 ml of methacrylic acid chloride and stirring for 15 minutes, 150 ml of saturated sodium hydrogen carbonate solution was added, and ethyl acetate extracted. The obtained crude product was purified by silica gel column chromatography to obtain 15 g of Compound 1.

Synthesis Example 2 Synthesis of Compound 2

After adding 40 ml of THF to 43 g of ethyl magnesium bromide (manufactured by Tokyo Chemical Industry, 39 mass% diethyl ether solution) at 0 ° C. in a 300 ml two-necked flask, cyclooctanone dissolved in 10 ml of THF was added dropwise. Further, after stirring at room temperature for 15 minutes, 80 ml of saturated aqueous ammonium chloride solution was added, and extraction was performed using ethyl acetate to obtain a compositional organism (1-ethylcyclooctanol).
The resulting compositional organism was methacrylated in the same manner as in Synthesis Example 1 to obtain Compound 2.

(Synthesis Example 3) Synthesis of P-1 Under a nitrogen stream, 43 g of cyclohexanone was placed in a three-necked flask and heated to 80 ° C. To this, 8.5 g of γ-butyrolactone methacrylate, 1.70 g of 3-hydroxyadamantyl-1-methacrylate, 12.3 g of compound 1, and initiator V-601 (manufactured by Wako Pure Chemical Industries), 4.5 mol% with respect to the monomer. A solution dissolved in 82 g of cyclohexanone was added dropwise over 6 hours. After completion of dropping, the reaction was further carried out at 80 ° C. for 2 hours. The reaction solution was allowed to cool and then added dropwise to a mixed solution of 900 ml of methanol / 100 ml of water over 20 minutes. The precipitated powder was collected by filtration and dried to obtain 20 g of Resin (P-1). The weight average molecular weight of the obtained resin was 12500 in terms of standard polystyrene, and the dispersity (Mw / Mn) was 1.72.
Other resins were synthesized using the same method. The weight average molecular weight was adjusted by changing the amount of initiator.

The components shown in the following table were dissolved in a solvent, and a solution with a solid content concentration of 5% by mass was prepared for each, and filtered through a polyethylene filter having a pore size of 0.03 μm to prepare a positive resist composition. The prepared positive resist composition was evaluated by the following method, and the results are shown in Table 4. About each component in Table 3, the ratio at the time of using multiple is a mass ratio.

[Acid generator]

[Basic compounds]
TPSA: Triphenylsulfonium acetate
DIA: 2,6-diisopropylaniline
TEA: Triethanolamine
DBA: N, N-dibutylaniline
PBI: 2-phenylbenzimidazole TMEA: Tris (methoxyethoxyethyl) amine
PEA: N-phenyldiethanolamine PBMA: 2- [2- {2- (2,2-dimethoxy-phenoxyethoxy) ethyl} -bis- (2-methoxyethyl)]-amine.

[Surfactant]
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.).

〔solvent〕
S1: Propylene glycol methyl ether acetate
S2: 2-Heptanone
S3: cyclohexanone
S4: γ-butyrolactone
S5: Propylene glycol methyl ether
S6: Ethyl lactate S7: Propylene carbonate.

[Image performance test]
(Exposure condition (1))
An organic antireflection film ARC29A (Nissan Chemical Co., Ltd.) was applied on a silicon wafer and baked at 205 ° C. for 60 seconds to form a 78 nm antireflection film. The prepared positive photosensitive resin composition was applied thereon and baked at 130 ° C. for 60 seconds to form a 250 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 130 ° 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.

(Exposure condition (2))
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 prepared positive photosensitive resin composition was applied thereon and baked at 130 ° C. for 60 seconds to form a 250 nm resist film. The obtained wafer was subjected to pattern exposure using an ArF excimer laser immersion scanner (NA 0.85). Ultra pure water was used as the immersion liquid. Thereafter, heating was performed at 130 ° 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.

Pattern collapse evaluation method:
When the exposure amount that reproduces the 85nm line and space mask pattern is set as the optimal exposure amount and the line width of the line pattern formed by further increasing the exposure amount from the optimal exposure amount is reduced, the pattern does not collapse. It was defined by the line width to be resolved. A smaller value indicates that a finer pattern is resolved without falling, and pattern falling is less likely to occur.

Exposure latitude evaluation method:
The exposure amount that reproduces the 85 nm line and space mask pattern is the optimum exposure amount, and when the exposure amount is changed, an exposure amount width that allows a pattern size of 85 nm ± 10% is obtained, and this value is divided by the optimum exposure amount. Percentages. The larger the value, the smaller the change in performance due to the change in exposure amount, and the better the exposure latitude.

Line edge roughness evaluation method:
The line edge edge roughness is measured using a length measuring scanning electron microscope (SEM) by observing an isolated pattern of 120 nm, and measuring the distance from the reference line where the edge of the line pattern should be 5 μm in the longitudinal direction. 50 points were measured with a length measuring SEM (Hitachi, Ltd. S-9260), the standard deviation was obtained, and 3σ was calculated. A smaller value indicates better performance.

  From the above evaluation results, it is clear that the resist performance in immersion exposure has been improved by the present invention.

Claims (5)

(A) comprises the following general formula (Ia) and / or (Ib) acid-decomposable repeating unit represented by tree fat dissolution rate in an alkali developer increases under the action of an acid, (B) an actinic ray or radiation A positive-type photosensitive resin composition comprising a compound that generates an acid upon irradiation and (C) a hydrophobic resin .

In general formulas (Ia) and (Ib):
Xa ₁ represents a hydrogen atom, an alkyl group, a hydroxymethyl group, a trifluoromethyl group, a cyano group or a halogen atom.
Ry ₁ represents an alkyl group or a cycloalkyl group.
Ra represents an alkyl group or a cycloalkyl group. When there are a plurality of Ras, they may be the same as or different from each other, and may be bonded to each other to form a ring.
l represents an integer of 1 to 3.
m represents an integer of 1 to 8.
n represents an integer of 3 to 8.   The positive photosensitive resin composition according to claim 1, wherein the resin of the component (A) further contains a repeating unit having a lactone structure.   The positive photosensitive resin composition according to claim 1, wherein the resin of the component (A) further contains a repeating unit having a cyano group. Using a positive photosensitive composition according to any one of claims 1 to 3, after forming a resist film, pattern forming method characterized by the resist film to immersion exposure and development. The pattern forming method according to claim 4 , wherein immersion exposure is performed through pure water as the immersion liquid.