TW201736386A - Processing liquid, pattern forming method and method for manufacturing electronic device - Google Patents

Abstract

Provided are: a processing liquid which enables the formation of a pattern that has excellent etching resistance and etching roughness; a pattern forming method; and a method for manufacturing an electronic device. A processing liquid which contains (1) a compound having a silicon atom and a group that produces an interaction with a polar group and (2) a solvent, and which is used for a resist film that is obtained from an active light sensitive or radiation sensitive composition and/or a resist pattern that is obtained from this resist film, or alternatively used for the formation of a resist pattern; a pattern forming method which uses this processing liquid; and a method for manufacturing an electronic device, which comprises this pattern forming method.

Description

Processing liquid, pattern forming method, and method of manufacturing electronic component

The present invention relates to a processing liquid, a pattern forming method, and a method of manufacturing an electronic component. More specifically, the present invention relates to a process for forming a semiconductor such as an IC, a process for manufacturing a circuit substrate such as a liquid crystal or a thermal head, and a process for forming a lithography process such as a photolithography process, a pattern forming method, and the like. A method of manufacturing an electronic component including the pattern forming method.

In the manufacturing process of a semiconductor element such as an IC (Integrated Circuit) or an LSI (Large Scale Integrated Circuit), microfabrication is performed by using a lithography method of a resist composition. In recent years, with the high integration of integrated circuits, it has been demanded to form ultrafine patterns of submicron regions or quarter micrometer regions. Accordingly, the exposure wavelength also tends to be short-wavelength from the g-ray to the i-ray, and further to the KrF excimer laser light. Further, in addition to excimer laser light, lithography using electron beams or X-rays or EUV light (Extreme Ultra Violet) has been developed. In this lithography method, after the film is formed by the resist composition, the obtained film is developed by a developing solution, or the developed film is washed with a rinse liquid. For example, Patent Document 1 describes a method of forming a resist pattern by developing a developing solution in which tetraisocyanate decane is dissolved in n-butyl acetate. [Prior Art Document [Patent Literature]

[Patent Document 1]: JP-A-2015-31923

In recent years, various electronic devices have been required to be highly functional, and it is required to produce finer wiring. Further, it is required to further improve the etching resistance of the pattern and further reduce the roughness (etching roughness) after etching.

Therefore, the present invention has been made in view of the above circumstances, and an object of the invention is to provide a processing liquid, a pattern forming method, and a method of manufacturing an electronic component which are capable of forming a pattern excellent in etching resistance and etching roughness.

As a result of intensive studies on the above-mentioned problems, the inventors of the present invention have found that a resist film or a resist pattern is treated or formed using a treatment liquid containing a compound having a ruthenium atom and a group that forms an interaction with a polar group. The resist pattern can thereby solve the above problems. In other words, the inventors of the present invention have found that the above problems can be solved by the following constitution.

<1> A treatment liquid for use in at least one of a resist film obtained from a sensitizing ray-sensitive or radiation-sensitive composition and a resist pattern obtained from the resist film, or for forming an anti-resistance The etching solution is used, and the treatment liquid comprises: (1) a compound having a group that interacts with a ruthenium atom and a polar group; and (2) a solvent. <2> The treatment liquid according to <1>, wherein the compound of the above (1) is an ionic compound. <3> The treatment liquid according to <1> or <2>, wherein the compound having the interaction with the polar group of the compound of the above (1) is a group which forms an ionic bond with the polar group. The treatment liquid according to any one of <1> to <3>, wherein the compound having the interaction with the polar group of the compound of the above (1) is an acidic group or a basic group. The treatment liquid according to any one of <1> to <4> wherein the compound having the interaction with the polar group of the compound of the above (1) has a pKa of 8 for the counter salt. The above basic group. The treatment liquid according to any one of <1> to <5> wherein the solvent of the above (2) contains an organic solvent. The treatment liquid according to any one of <1> to <6> wherein the compound of the above (1) is represented by the following formula (1-1).

[Chemical Formula 1]

In the formula (1-1), A ^- represents an organic acid anion, and the cation X ⁺ represents a nitrogen cation, a sulfur cation or an iodide cation. Rx represents an alkyl group, a cycloalkyl group, an aryl group, an arylalkyl group or a heterocyclic group. When there are a plurality of Rx, the plurality of Rx may be the same or different. Further, when a plurality of Rx are present, a plurality of Rx may be bonded to each other to form a ring, and the ring formed may have a nitrogen atom, an oxygen atom or a sulfur atom as a ring member. L represents a single bond or a divalent linking group. n represents 3 in the case where X ⁺ is a nitrogen cation, 2 in the case where X ⁺ is a sulfur cation, and 1 in the case where X ⁺ is an iodine cation. Ry represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an arylalkyl group or a heterocyclic group. B ¹ represents a group containing a halogen atom. <8> The treatment liquid according to <7>, wherein the above B ¹ has a sesquiterpene alkoxy structure. The treatment liquid according to any one of the above-mentioned items (1), wherein the content of the compound of the above (1) is 1% by mass or more based on the total mass of the treatment liquid. The solvent of the above (2) is a hydrocarbon solvent having 7 or more carbon atoms or a ketone solvent having 7 or more carbon atoms, in the treatment liquid according to any one of the above aspects. <11> The treatment liquid according to any one of <1> to <10> wherein the treatment liquid is used as a rinse liquid. <12> A pattern forming method comprising: a resist film forming process for forming a resist film using a sensitizing ray-sensitive or radiation-sensitive linear composition; an exposure process for exposing the resist film; a developing process for developing the exposed resist film by the liquid; and a rinsing process for rinsing the developed resist film with a rinsing liquid, and satisfying at least the following (a) to (c) One of the conditions: (a) Between the exposure process and the development process described above, the process of bringing the treatment liquid described in any one of <1> to <10> into contact with the exposed resist film. (b) The developer solution includes the treatment liquid according to any one of <1> to <10>. (c) The rinse liquid contains the treatment liquid according to any one of <1> to <10>. <13> A method of producing an electronic component, comprising the pattern forming method according to <12>. [Effect of the invention]

According to the present invention, it is possible to provide a treatment liquid, a pattern formation method, and a method of producing an electronic component which can form a pattern excellent in etching resistance and etching roughness.

Hereinafter, an example of a mode for carrying out the present invention will be described. In the labeling of the group and the atomic group in the present specification, it is not explicitly shown that both the group having no substituent and the group having a substituent are contained in the case of substitution and unsubstitution. For example, it is not expressly stated that the substituted or unsubstituted "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). In the present specification, "actinic ray" or "radiation" means, for example, a bright line spectrum of a mercury lamp, a far ultraviolet ray represented by an excimer laser, an extreme ultraviolet ray (EUV light), an X-ray, an electron beam, an ion beam, or the like. Bunch and so on. In the present invention, "light" means actinic rays or radiation. In addition, the term "exposure" in the present specification refers to exposure including not only a mercury lamp, a far-ultraviolet light represented by a quasi-molecular laser, X-rays, or extreme ultraviolet rays (EUV light), but also includes use. Drawing of particle beams such as electron beams and ion beams. In the present specification, the term "(meth)acrylate" means "at least one of acrylate and methacrylate." In addition, "(meth)acrylic acid" means "at least one of acrylic acid and methacrylic acid". The numerical range expressed by "~" in the present specification means a range including the numerical values described before and after "~" as the lower limit and the upper limit. In the present specification, the weight average molecular weight of the resin is a polystyrene equivalent value measured by a GPC (gel permeation chromatography) method. GPC can be used according to the method of using HLC-8120 (manufactured by TOSOH CORPORATION), using TSK gel Multipore HXL-M (manufactured by TOSOH CORPORATION, 7.8 mm ID × 30.0 cm) as a column, and using THF (tetrahydrofuran) as a solution.

<Processing liquid> The processing liquid of the present invention is used for at least one of a resist film obtained from a sensitizing ray-sensitive or radiation-sensitive composition and a resist pattern obtained from the resist film, or for forming The resist pattern is used, and the treatment liquid contains: (1) a compound having a ruthenium atom and a group that forms an interaction with a polar group; and (2) a solvent.

The details of the reason why the above problem can be solved by the present invention are not clear, but the inventors of the present invention presume as follows. The treatment liquid of the present invention contains (1) a compound having a ruthenium atom and a group which forms an interaction with a polar group (also referred to as "compound (1)"). The treatment liquid is used for at least one of the resist film and the resist pattern, or a resist pattern is formed using the treatment liquid, whereby polar groups and compounds existing in the resist film or the resist pattern are present ( 1) Form an interaction. As a result, it is considered that a coating film of the compound (1) can be formed on the resist film or the resist pattern. Further, the compound (1) is a compound containing a ruthenium atom, and the resist film or the resist pattern of the coating film in which the compound (1) is formed is etched by O _{2 as} compared with the case where the compound (1) is not formed. The film resist film or resist pattern can take a good etching selectivity and is therefore considered to be associated with optimization of etch resistance. In addition, the polar group existing in the resist film or the resist pattern forms an interaction with the compound (1), and therefore it is considered that the coating film of the above compound (1) can be uniformly formed, and is optimized to the etching roughness. .

The treatment liquid of the present invention is used for at least one of a resist film and a resist pattern obtained from a resist film, or for forming a resist pattern. The use of the treatment liquid for the resist film means that the treatment liquid is brought into contact with the resist film. As a form in which the treatment liquid is used for the resist film, for example, a pre-rinsing process for washing the surface of the resist film with a treatment liquid, or the like can be given. When pre-flushing is performed between the exposure process and the development process using the treatment liquid, the polar group existing in the exposed portion or the unexposed portion interacts with the compound (1) in the pre-rinsing liquid, thereby being exposed or unexposed at the exposure portion A coating film based on the compound (1) is formed on the upper surface of the portion. When the resist film having the coating film is developed using a developing solution, a coating film based on the compound (1) remains on the surface of the resist pattern. Further, the timing of bringing the treatment liquid into contact with the resist film may be either before or after exposure.

The use of the treatment liquid in the resist pattern obtained by developing the resist film means that the treatment liquid is brought into contact with the resist pattern, and examples thereof include a case where the treatment liquid is contained in the rinse liquid and rinsed. When the resist pattern is used for rinsing after the development of the resist pattern, the coating film based on the compound (1) can be formed on the resist pattern.

The treatment liquid of the present invention may be a user for forming a resist pattern. In this case, for example, a case where the treatment liquid of the present invention is contained in the developer, and the resist film is developed using the developer to form a resist pattern. When development is carried out using the treatment liquid of the present invention, the polar group present in the exposed portion or the unexposed portion during development interacts with the compound (1) in the treatment liquid, whereby the compound (1) can be formed on the resist pattern. The film is coated.

Further, the treatment liquid of the present invention is a coating film (preferably, a film thickness of 5 nm or less) for forming a compound (1) on a resist film or a resist pattern as described above, and a so-called shrinkage agent. Or different fillers.

[Compound (1)] (1) A compound (compound (1)) having a ruthenium atom and a group which forms an interaction with a polar group will be described. The compound (1) is not particularly limited as long as it has a ruthenium atom and a group which forms an interaction with a polar group. For example, a decane-based compound (-SiR ² -: R ² is an organic group) or a siloxane-based compound (-SiR ² -O-: R ² is an organic group) can be given.

The compound (1) has a group having a resist film or a compound contained in the resist pattern which forms an interaction with a polar group. The polar group may, for example, be a carboxyl group, an alcoholic hydroxyl group, a phenolic hydroxyl group or a sulfonic acid group, and is preferably a carboxyl group, an alcoholic hydroxyl group or a phenolic hydroxyl group, more preferably a carboxyl group or a phenolic hydroxyl group.

Further, in the present invention, the treatment liquid containing the compound (1) is used for a resist film or a resist pattern, or a resist pattern is formed by the treatment liquid, and therefore, in a short time (for example, usual rinsing time) It is preferred to form an interaction uniformly within 10 seconds to 30 seconds, and therefore, as an interaction, an ionic bond is preferred. As the group which the compound (1) has an interaction with a polar group, a group which forms an ionic bond with a polar group is preferable, an acidic group or a basic group is more preferable, and a basic group is further preferably a relative A basic group having a pKa of 8 or more is particularly preferred, and a basic group having a pKa of 9 or more is preferred. pKa was calculated by ACD/LABs pKaDB ((Version 8.0) Fujitsu Limited). Specific examples of the group which the compound (1) forms an interaction with a polar group include a group containing an alkylcation salt structure, and a group containing an alkylammonium salt structure is preferred.

The compound (1) is typically a compound containing a group having a ruthenium atom, and examples of the group having a ruthenium atom include, for example, a trimethylcarbinyl group, a triethylmethane group, and a triphenylcarbenyl group. Tricyclohexylcarbenyl, tris(trimethylformamoxy)carbenyl, tris(trimethylformamidinyl)carboxyalkyl, methylbis(trimethylformamido)carboxyalkyl, A Bis(trimethylformamoxy)carbenyl, dimethyl(trimethylformanyl)carboxyalkyl, dimethyl(trimethylformamoxy)carbenyl or have a decane The group of the bond. Examples of the group having a siloxane chain include a group having a linear polyoxyalkylene structure, a group having a cyclic polyoxyalkylene structure, and the like, and the group having a sesquiterpene structure is Preferably. The group having a sesquiterpene oxide structure may, for example, be a cage type, a ladder type or a random sesquiterpene alkane structure, and is preferably a group shown below. In the following structural formula, R and R ¹ each independently represent a monovalent substituent. * indicates a bond.

[Chemical Formula 2]

The group having a ruthenium atom is preferably a group having a sesquioxane structure having a high Si ratio per unit volume, whereby excellent etch resistance can be found. Examples of the sesquiterpene oxide structure include a cage sesquiterpene oxide structure, a ladder sesquiterpene oxide structure (LADDER-TYPE sesquiterpene oxide structure), a random sesquiterpene alkane structure, and the like. . Among them, a cage sesquiterpene structure is preferred. Here, the cage sesquiterpene structure is a sesquiterpene structure having a cage skeleton. The cage sesquiterpene structure may be a completely caged sesquiterpene structure or an incomplete cage sesquiterpene structure, but a fully caged sesquiterpene structure is preferred. Further, the ladder type sesquiterpene oxide structure is a sesquiterpene oxide structure having a ladder-like skeleton. Further, the structure of the random sesquiterpene oxide is a structure of a sesquiterpene oxide having an irregular skeleton.

The cage sesquiterpene structure is preferably a oxoxane structure represented by the following formula (S).

[Chemical Formula 3]

In the above formula (S), R represents a monovalent substituent. There are a plurality of R which may be the same or different. The monovalent substituent represented by R is not particularly limited, and specific examples thereof include a halogen atom, a hydroxyl group, a nitro group, a carboxyl group, an alkoxy group, an amine group, a fluorenyl group, and a blocked fluorenyl group (for example, a fluorene group). Block (protected) fluorenyl), fluorenyl, fluorenylene, phosphino, phosphinyl, germyl, vinyl, hydrocarbyl group having a hetero atom, group containing a (meth)acryl group And a group containing an epoxy group or the like. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the hetero atom which may have a hydrocarbon group of a hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, and a phosphorus atom. Examples of the hydrocarbon group which may have a hetero atom include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group obtained by combining the same. The aliphatic hydrocarbon group may be any of a linear chain, a branched chain, and a cyclic chain. The aliphatic hydrocarbon group may be any of a linear chain, a branched chain, and a cyclic chain. Specific examples of the aliphatic hydrocarbon group include a linear or branched alkyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, still more preferably 1 carbon atom). ～10), a linear or branched alkenyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, still more preferably 2 to 10 carbon atoms), or a linear chain or A branched alkynyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, still more preferably 2 to 10 carbon atoms). As the hydrocarbon group having a hetero atom, an alkoxy group is particularly preferable. The aromatic hydrocarbon group may, for example, be an aromatic hydrocarbon group having 6 to 18 carbon atoms such as a phenyl group, a tolyl group, a xylyl group or a naphthyl group (preferably having 6 to 15 carbon atoms, more preferably a carbon number). 6 to 12) and so on.

The compound (1) is preferably an ionic compound, and is more preferably represented by the following formula (1-1).

[Chemical Formula 4]

In the formula (1-1), A ^- represents an organic acid anion, and the cation X ⁺ represents a nitrogen cation, a sulfur cation or an iodine cation. Rx represents an alkyl group, a cycloalkyl group, an aryl group, an arylalkyl group or a heterocyclic group. When there are a plurality of Rx, the plurality of Rx may be the same or different. Further, when a plurality of Rx are present, a plurality of Rx may be bonded to each other to form a ring, and the ring formed may have a nitrogen atom, an oxygen atom or a sulfur atom as a ring member. L represents a single bond or a divalent linking group. n represents 3 when X ⁺ is a nitrogen cation, 2 when X ⁺ is a sulfur cation, and 1 when X ⁺ is an iodine cation. Ry represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an arylalkyl group or a heterocyclic group. B ¹ represents a group containing a halogen atom.

In the above formula (1-1), the conjugate base structure of the organic acid anion A ^- is not particularly limited, and examples thereof include a carboxylic acid group, a sulfonic acid group, a hydroxyl group, a decyl group, a quinone imine group, and a sulfonylamino group. Sulfonimide group, methylene compound (malonic acid derivative, acetoacetic acid derivative, cyanoacetic acid derivative, malononitrile derivative, cyclopentadiene derivative, bissulfonyl methane derivative, etc.) A conjugated base structure such as a nitrogen-containing aromatic compound (imidazole derivative, an anthracene derivative, an isocyanuric acid derivative, etc.), wherein a carboxylic acid group or a sulfonic acid group is preferred, and a carboxylic acid group is particularly preferred. The organic acid anion A ^- is not particularly limited, and a carboxylic acid anion or a sulfonic acid anion is preferred, and a carboxylic acid anion is particularly preferred.

X ⁺ represents a nitrogen cation, a sulfur cation or an iodide cation, and preferably represents a nitrogen cation or a sulfur cation, and more preferably a nitrogen cation.

The divalent linking group of L may, for example, be an alkyl group (preferably having 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, such as a methylene group, an ethyl group, a stretching group or a stretching group). a butyl group or the like, a cycloalkyl group (preferably having 6 to 12 carbon atoms, more preferably 6 to 9 carbon atoms, such as a cyclopentyl group, a cyclohexylene group, an adenantyl group, etc.) or an aryl group. (preferably having 6 to 12 carbon atoms, more preferably 6 to 9 carbon atoms, such as a phenyl group, a phenylene group or a naphthyl group), or an alkenyl group (preferably having 2 to 6 carbon atoms). More preferably, the carbon number is 2 to 4, such as a vinyl group, a propenyl group, a butenyl group, etc., -COO-, -OCO-, -CO-, -O-, -S-, -SO- And -SO ₂ - and a group obtained by combining the two or more groups, an alkyl group, a cycloalkyl group, an aryl group or a combination of two or more of these groups is preferred. The alkyl group, the cycloalkyl group or the aryl group is more preferred, and the alkyl group is further preferred. The divalent linking group of L may have a substituent. Examples of the substituent which the divalent linking group of L may have include an alkoxy group (preferably having 1 to 15 carbon atoms), an alkylthio group (preferably having 1 to 15 carbon atoms), and an alkyl group. a carbonylamino group (preferably having 1 to 15 carbon atoms), a hydroxyl group, an alkyl group (preferably having 1 to 15 carbon atoms), a cycloalkyl group (preferably having 3 to 15 carbon atoms), and an aryl group (compared Preferably, the carbon number is 6 to 14), a halogen atom, a fluorenyl group (preferably having 2 to 15 carbon atoms), a decyloxy group (preferably having 2 to 15 carbon atoms), and an alkoxycarbonyl group (preferably carbon). Atomic number 2 to 15), cyano group and nitro group.

As the alkyl group of Rx, preferred are methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, pentyl, hexyl, 2-ethylhexyl, octyl or dodecyl groups. The linear or branched alkyl group having 1 or more and 20 or less carbon atoms is preferably an alkyl group having 5 to 10 carbon atoms, and more preferably an alkyl group having 6 to 8 carbon atoms.

The cycloalkyl group of Rx may be a monocyclic type or a polycyclic type, a cycloalkyl group having 3 to 15 carbon atoms is preferred, and a cycloalkyl group having 3 to 10 carbon atoms is more preferred, and the number of carbon atoms is 3 to 3. A cycloalkyl group of 6 is further preferred. Specific examples of the cycloalkyl group of Rx include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a decahydronaphthyl group, a cyclodecyl group, and a 1-adamantane. Base, 2-adamantyl, 1-norbornyl and 2-norinyl. The cycloalkyl group of Rx is preferably a cyclopropyl group, a cyclopentyl group or a cyclohexyl group.

The aryl group of Rx may, for example, be an aryl group having 6 to 18 carbon atoms such as a phenyl group or a naphthyl group, and more preferably an aryl group having 6 to 10 carbon atoms.

The aralkyl group of Rx is preferably an aralkyl group having 6 to 20 carbon atoms, more preferably an aralkyl group having 7 to 12 carbon atoms. Specific examples of the aralkyl group of Rx include a benzyl group, a phenethyl group, a naphthylmethyl group, and a naphthylethyl group.

The heterocyclic group of Rx is preferably a heterocyclic group having 2 to 20 carbon atoms, and more preferably a heterocyclic group having 2 to 12 carbon atoms. Specific examples of the heterocyclic group of Rx include a triazolyl group, an imidazolyl group, a pyrrolyl group, a pyridyl group, a pyrazinyl group, a tetrahydrofuranyl group, a tetrahydropyranyl group, a tetrahydrothiophenyl group, a piperidinyl group, and a piperidine group. Azinyl, furyl, pyranyl, chromanyl group, and the like.

The alkyl group, the cycloalkyl group, the aryl group, the arylalkyl group and the heterocyclic group as Rx may further have a substituent. Specific examples and preferred examples of the substituent which the alkyl group, the cycloalkyl group, the aryl group, the arylalkyl group and the heterocyclic group of Rx have may further include a substituent which may have a divalent linking group as L. The specific examples and preferred examples of the substituents described above are the same groups.

When there are a plurality of Rx, the plurality of Rx may be the same or different. When a plurality of Rx are present, a plurality of Rx may be bonded to each other to form a ring, and the ring formed may have a nitrogen atom, an oxygen atom or a sulfur atom as a ring member. Examples of the ring to be formed include a cycloalkane ring such as a cyclopentane ring, a cyclohexane ring, an adamantane ring, a norbornene ring, and a norbornane ring, an imidazole ring, a piperidine ring, and a tetrahydrothiophene ring. Heterocyclic rings such as tetrahydrothiopyran ring and dibenzothiophene ring. The ring may have a substituent, and examples of the substituent which may be contained include a specific example of the substituent which the substituent of the divalent linking group of L may have.

B ¹ represents a group containing a halogen atom. It is preferred that B ¹ has a sesquiterpene alkoxy structure. Further, B ^{1 is} preferably a group represented by the following formula (a) or (b).

[Chemical Formula 5]

In the above formula (a), R represents a monovalent organic group. There are a plurality of Rs which may be the same or different. Specific examples and preferred embodiments of R are the same as R in the above formula (S). * indicates a bond.

[Chemical Formula 6]

In the above formula (b), R _b represents a hydrocarbon group which may have a hetero atom. Specific examples and preferred embodiments of the hydrocarbon group which may have a hetero atom are the same as those in the above formula (S). * indicates a bond.

The compound (1) can be purified by filtration through a filter, reprecipitation, recrystallization, or the like. Further, it may be purified by column chromatography as needed. Further, a compound which is a raw material of the compound (1) or a treatment liquid containing the compound (1) can be filtered by a filter. As the filter, a filter made of polytetrafluoroethylene, polyethylene or nylon having a pore size of 0.1 μm or less, more preferably 0.05 μm or less, further preferably 0.03 μm or less is preferable.

The compound (1) to be contained in the treatment liquid of the present invention may be one type or two or more types may be used in combination. The content of the compound (1) is not particularly limited, and is preferably 1% by mass or more, more preferably 1 to 40% by mass, even more preferably 1 to 20% by mass, based on the total mass of the treatment liquid.

Specific examples of the compound (1) include the following structures, but the present invention is not limited thereto. In the following structural formula, Et represents an ethyl group, tBu represents a third butyl group, C5 represents an n-pentyl group, and C8 represents an n-octyl group.

[Chemical Formula 7]

[Chemical Formula 8]

[Chemical Formula 9]

[(2) Solvent] The solvent (also referred to as "solvent (2)") contained in the treatment liquid of the present invention will be described. The solvent (2) is preferably water or an organic solvent. The organic solvent is selected from the group consisting of an organic solvent containing at least one of a hydrocarbon solvent, a ketone solvent, an ester solvent, an alcohol solvent, a guanamine solvent, an ether solvent, a fluorine atom, and a ruthenium atom. At least one organic solvent is preferable, and a hydrocarbon solvent, an ester solvent or a ketone solvent is preferable, and a hydrocarbon solvent having 5 or more carbon atoms or a carbon number of 5 is considered from the viewpoint of suppressing penetration into the resist film. The above ketone solvent is more preferable, and a hydrocarbon solvent having 7 or more carbon atoms or a ketone solvent having 7 or more carbon atoms is particularly preferable.

The ester solvent is a solvent having an ester bond in a molecule. The ketone solvent is a solvent having a ketone group in the molecule. The alcohol solvent is a solvent having an alcoholic hydroxyl group in the molecule. The amide-based solvent is a solvent having a guanamine group in the molecule. The ether solvent is a solvent having an ether bond in the molecule. Among these, a solvent having a plurality of the above functional groups in one molecule is also present, and in this case, it is considered to correspond to any solvent type containing a functional group which the solvent has. For example, diethylene glycol monomethyl ether is regarded as any solvent corresponding to the alcohol solvent or the ether solvent in the above classification. Further, the hydrocarbon solvent is a hydrocarbon solvent having no substituent.

Examples of the hydrocarbon-based solvent include aliphatic hydrocarbon solvents such as pentane, hexane, octane, decane, decane, dodecane, undecane, and hexadecane; toluene, xylene, and ethylbenzene; , propylbenzene, 1-methylpropylbenzene, 2-methylpropylbenzene, dimethylbenzene, diethylbenzene, ethylmethylbenzene, trimethylbenzene, ethyldimethylbenzene, two An aromatic hydrocarbon solvent such as propylbenzene; 2,2,4-trimethylpentane, 2,2,3-trimethylhexane, isohexane, isoheptane, isooctane, isodecane, iso a branched aliphatic hydrocarbon solvent such as dodecane, isoundecane, isohexadecane, isotetradecane, isopentadecane, limonene, isopropylcyclopentane or t-butylcyclohexane; An unsaturated hydrocarbon solvent such as octene, decene, decene, undecene, dodecene or hexadecene. The unsaturated hydrocarbon solvent may have a plurality of double bonds and triple bonds, and may exist at any position of the hydrocarbon chain. It is also possible to mix cis (Cis) and trans (trans) bodies having a double bond. Further, the hydrocarbon solvent may be a mixture of compounds having the same number of carbon atoms and different structures. For example, when decane is used as the aliphatic hydrocarbon solvent, 2-methyl decane, 2,2-dimethyloctane, 4-ethyl octane, and different compounds having the same number of carbon atoms and different structures are used. The decane or the like may be contained in an aliphatic hydrocarbon solvent. Further, the compound having the same number of carbon atoms and different structures may be contained alone or in a plurality of kinds as described above. The hydrocarbon solvent is preferably a carbon number of 5 or more, more preferably 7 or more, and still more preferably 10 or more. For example, decane, undecane, isodecane, isododecane, isoundecane, isohexadecane, isotetradecane, isopentadecane are preferred, particularly preferably decane, undecane . The treatment liquid of the present invention contains at least one of decane and undecane, which is particularly preferable. By containing a branched aliphatic hydrocarbon solvent having 10 or more carbon atoms, good pattern collapse characteristics and good bridging characteristics can be achieved. The upper limit of the number of carbon atoms of the hydrocarbon-based solvent is not particularly limited, and examples thereof include 16 or less, preferably 14 or less, and more preferably 12 or less. Thereby, the drying efficiency at the time of spin drying can be improved, and the occurrence of defects in the wafer surface can be suppressed.

Examples of the ester solvent include methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, isopropyl acetate, and amyl acetate (pentyl acetate). ), isoamyl acetate (isopentyl acetate), 3-methylbutyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, acetic acid Isohexyl ester, heptyl acetate, octyl acetate, ethyl methoxyacetate, ethyl ethoxyacetate, propylene glycol monomethyl ether acetate (PGMEA; alias 1-methoxy-2-ethoxypropane) , ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate , diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, 2-methoxybutyl Acetyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3- Methoxybutyl acetate, Glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2 -Methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3- Methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, propylene glycol diacetate Ester, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, pyruvic acid Ester, propyl pyruvate, butyl pyruvate, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, butyl propionate, Amyl propionate, hexyl propionate, heptyl propionate, butyl butyrate, isobutyl butyrate, amyl butyrate, hexyl butyrate, isobutyl isobutyrate, propyl valerate, valeric acid Isopropyl ester, butyl valerate, amyl valerate, ethyl hexanoate, propyl hexanoate, butyl hexanoate, isobutyl hexanoate Ester, methyl heptanoate, ethyl heptanoate, propyl heptanoate, cyclohexyl acetate, cycloheptyl acetate, 2-ethylhexyl acetate, cyclopentyl propionate, methyl 2-hydroxypropionate, 2 -ethyl hydroxypropionate, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, propyl-3-methoxy Propionate and the like. Among these, butyl acetate, amyl acetate, isoamyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, and propyl propionate are used. Esters, ethyl propionate, heptyl propionate, and butyl butyrate are preferred, and butyl acetate and isoamyl acetate are particularly preferred.

Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone, 4-heptanone, 1-hexanone, and 2-hexanone. , diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetamidine acetone, acetone acetone, ionone, diacetone Diacetonyl alcohol, acetamethanol, acetophenone, methylnaphthyl ketone, isophorone, propylene carbonate, γ-butyrolactone, etc., wherein diisobutyl ketone is preferred . Further, the ketone solvent may be a ketone solvent having a branched alkyl group. The ketone solvent having a branched alkyl group is a solvent having a branched alkyl group and a ketone group in the molecule, and is a cyclic aliphatic ketone solvent having a branched alkyl group or an acyclic aliphatic ketone having a branched alkyl group. A solvent is preferred. Examples of the cyclic aliphatic ketone solvent having a branched alkyl group include 2-isopropylcyclohexanone, 3-isopropylcyclohexanone, 4-isopropylcyclohexanone, and 2-isopropyl group. Cycloheptanone, 3-isopropylcycloheptanone, 4-isopropylcycloheptanone, 2-isopropylcyclooctene ketone. Examples of the acyclic aliphatic ketone solvent having a branched alkyl group include diisohexyl ketone, methyl isoamyl ketone, ethyl isoamyl ketone, propyl isoamyl ketone, and diisoamyl ketone. , methyl isobutyl ketone, ethyl isobutyl ketone, propyl isobutyl ketone, diisobutyl ketone, diisopropyl ketone, ethyl isopropyl ketone, methyl isopropyl ketone, etc. Jia is diisobutyl ketone.

Examples of the alcohol-based solvent include methanol, ethanol, 1-propanol, isopropanol, 1-butanol, 2-butanol, 3-methyl-1-butanol, tert-butanol, and 1-pentyl. Alcohol, 2-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol, 2-hexanol, 2-heptanol, 2-octanol, 3-hexanol, 3-glycol Alcohol, 3-octanol, 4-octanol, 3-methyl-3-pentanol, cyclopentanol, 2,3-dimethyl-2-butanol, 3,3-dimethyl-2-butan Alcohol, 2-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-2-pentanol, 3-methyl-3-pentanol, 4-methyl-2-pentyl Alcohol, 4-methyl-3-pentanol, cyclohexanol, 5-methyl-2-hexanol, 4-methyl-2-hexanol, 4,5-dimethyl-2-hexanol, 6 -methyl-2-heptanol, 7-methyl-2-octanol, 8-methyl-2-nonanol, 9-methyl-2-nonanol, 3-methoxy-1-butanol, etc. Alcohol (monovalent alcohol), or alcoholic solvent such as ethylene glycol, diethylene glycol or triethylene glycol, or ethylene glycol monomethyl ether or propylene glycol monomethyl ether (PGME; alias 1-methoxy-2) -propanol), diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxymethyl butanol, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol single Ether, propylene glycol A glycol ether solvent containing a hydroxyl group such as propyl ether, propylene glycol monobutyl ether or propylene glycol monophenyl ether. Among these, a glycol ether solvent is preferred.

Examples of the ether solvent include, in addition to the glycol ether solvent containing a hydroxyl group, propylene glycol dimethyl ether, propylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, diethylene glycol dimethyl ether, a glycol ether solvent which does not contain a hydroxyl group such as diethylene glycol diethyl ether, an aromatic ether solvent such as anisole or phenethyl ether, dioxane, tetrahydrofuran, tetrahydropyran, perfluoro-2-butyltetrahydrofuran, Perfluorotetrahydrofuran, 1,4-dioxane, and the like. Further, examples thereof include cyclopentyl isopropyl ether, cyclopentane second butyl ether, cyclopentyl third butyl ether, cyclohexyl isopropyl ether, cyclohexyl second butyl ether, and cyclohexyl third butyl. a cyclic aliphatic ether solvent having a branched alkyl group such as a hydroxy ether; an acyclic aliphatic group having a linear alkyl group such as di-n-propyl ether, di-n-butyl ether, di-n-pentyl ether or di-n-hexyl ether; Ether solvent; diisohexyl ether, methyl isoamyl ether, ethyl isoamyl ether, propyl isoamyl ether, diisoamyl ether, methyl isobutyl ether, ethyl isobutyl ether, An acyclic aliphatic ether solvent having a branched alkyl group such as propyl isobutyl ether, diisobutyl ether, diisopropyl ether, ethyl isopropyl ether or methyl isopropyl ether. In particular, from the viewpoint of in-plane uniformity of the wafer, an acyclic aliphatic ether solvent having 8 to 12 carbon atoms is preferred, and an acyclic compound having a branched alkyl group having 8 to 12 carbon atoms is more preferred. An aliphatic ether solvent. Particularly preferred is diisobutyl ether, diisoamyl ether or diisohexyl ether.

The organic solvent containing at least one of a fluorine atom and a ruthenium atom is preferably a hydrocarbon solvent or an ether solvent containing at least one of a fluorine atom and a ruthenium atom. The organic solvent containing at least one of a fluorine atom and a ruthenium atom is preferably an organic solvent containing a fluorine atom. Examples of the organic solvent containing at least one of a fluorine atom and a ruthenium atom include hydrofluoroether, perfluorocarbon, and hydrofluorocarbon, and at least one selected from the group consisting of these is preferably selected from the group consisting of perfluorofluoride. At least one of carbon and hydrofluorocarbon is more preferred.

(Hexafluoroether) The hydrofluoroether (HFE) is not particularly limited, and is preferably a compound represented by the following formula 1. Formula 1 R1-O-R2 In Formula 1, R1 represents an alkyl group having 1 to 12 carbon atoms or a fluoroalkyl group, and R2 represents a perfluoroalkyl group having 1 to 12 carbon atoms or a fluoroalkyl group. R1 and R2 are preferably a perfluoroalkyl group or a fluoroalkyl group having 3 to 12 carbon atoms.

Specific examples of the hydrofluoroether include methyl perfluoroisobutyl ether, methyl perfluorobutyl ether, and HFE-347pc-f (CF ₃ CH ₂ OCF ₂ CHF ₂ ). Specific examples of the product include ASAHIKLIN AE-3000 (ASAHI GLASS CO., LTD.), NOVEC HFE-7100 (Sumitomo 3M Limited), and NOVEC HFE-7200 (Sumitomo 3M Limited). The hydrofluoroether may be used singly or in combination of two or more.

(Perfluorocarbon) Perfluorocarbon (PFC) is a perfluorinated alkyl compound, whether it is linear, branched or cyclic. The range of the number of carbon atoms of the perfluorocarbon is preferably from 3 to 12. If the number of carbon atoms is small, the volatility is too high, and the temperature uniformity in the wafer surface is deteriorated. On the other hand, when the number of carbon atoms is large, the volatility is too low. Therefore, even if spin drying after rinsing, the solvent does not volatilize but remains, and it is difficult to obtain the original purpose of rinsing.

Specific examples of the perfluorocarbon include perfluorobutane, perfluoropentane, perfluorohexane, perfluoroheptane, perfluorooctane, perfluorodecane, perfluorodecane, and the like. Specific examples of the product include FLUORINERT FC-770 (Sumitomo 3M Limited), FLUTEC (Rhone‐Poulenc S. A.), GALDEN (Ausimont Co., Ltd.), and ALFOOD (ASAHI GLASS CO., LTD.). The perfluorocarbon may be used alone or in combination of two or more.

(HFC) Hydrofluorocarbon (HFC) is a compound in which a part of hydrogen atoms in a hydrocarbon is a fluorine atom, and at least one or more fluorine atoms are present in the compound molecule regardless of whether it is linear, branched or cyclic. . The range of the number of carbon atoms of the hydrofluorocarbon is preferably from 3 to 12.

Specific examples of the hydrofluorocarbon include HFC-52-13p (CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CHF ₂ ), HFC-569sf (CF ₃ CF ₂ CF ₂ CF ₂ CH ₂ CH ₃ ), and HFC. -43-10mee, 1,1,1,3,3-pentafluorobutane, octafluorocyclopentane, 2,3-dihydrodecafluoropentane, and the like. Specific examples of the product include VERTREL (Du Pont-Mitsui Fluorochemicals Co., Ltd.), SOLKANE 365mfc (Solvay Japan, Ltd.), ASAHIKLIN AC-2000 (ASAHI GLASS CO., LTD.), and ASAHIKLIN AC-4000 ( ASAHI GLASS CO., LTD.), ASAHIKLIN AC-6000 (ASAHI GLASS CO., LTD.), and the like. The hydrofluorocarbon may be used alone or in combination of two or more.

As the amide-based solvent, for example, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide can be used. , hexamethyl phosphoric triamide, 1,3-dimethyl-2-imidazolidinone, and the like.

The content of the solvent (2) is preferably from 99 to 60% by mass, more preferably from 99 to 70% by mass, even more preferably from 99 to 80% by mass, based on the total mass of the treatment liquid of the present invention.

[Antioxidant] The treatment liquid of the present invention preferably contains an antioxidant. Thereby, it is possible to suppress the generation of the oxidizing agent over time, and it is possible to further reduce the content of the oxidizing agent. The content of the antioxidant is not particularly limited, and is preferably 0.0001 to 1% by mass, more preferably 0.0001 to 0.1% by mass, and even more preferably 0.0001 to 0.01% by mass, based on the total mass of the treatment liquid. When the amount is 0.0001% by mass or more, a more excellent oxidation resistance effect can be obtained, and when it is 1% by mass or less, the development residue can be suppressed.

<Pattern forming method> The pattern forming method of the present invention has, in order, a resist film forming process for forming a resist film using a sensitizing ray-sensitive or radiation-sensitive composition; and an exposure process for exposing the resist film a developing process for developing the exposed resist film using a developing solution; and a rinsing process for rinsing the developed resist film with a rinsing liquid, and satisfying the following (a) to (c) At least one condition. (a) A process for bringing the treatment liquid of the present invention into contact with the exposed resist film between the exposure process and the development process. (b) The above developing solution contains the treatment liquid of the present invention. (c) The above rinse liquid contains the treatment liquid of the present invention.

[Resist Film Formation Process] The resist film formation process is a process of forming a resist film (photosensitive ray or radiation sensitive film) using a sensitizing ray-sensitive or radiation-sensitive composition, for example, by the following The method is carried out. Further, the resist composition will be described later. In order to form a resist film on a substrate using a resist composition, each component described later is dissolved in a solvent to prepare a sensitizing ray-sensitive or radiation-sensitive composition, which is filtered by a filter as needed, and then applied to the substrate. on. As the filter, a filter made of polytetrafluoroethylene, polyethylene or nylon having a pore size of 0.1 μm or less, more preferably 0.05 μm or less, further preferably 0.03 μm or less is preferable.

The sensitizing ray-sensitive or radiation-sensitive composition is applied to a substrate (for example, ruthenium or ruthenium dioxide coating) for producing integrated circuit elements by a suitable coating method such as a spin coater. Thereafter, it is dried to form a resist film. Various undercoat films (inorganic film, organic film, antireflection film) may be formed in the lower layer of the resist film as needed.

As the drying method, a method of heating and drying is generally used. The heating can be performed by a mechanism provided on a usual exposure/developer, or by a heating plate or the like. The heating temperature is preferably 80 to 150 ° C, more preferably 80 to 140 ° C, and still more preferably 80 to 130 ° C. The heating time is preferably from 30 to 1,000 seconds, more preferably from 60 to 800 seconds, and further preferably from 60 to 600 seconds.

The film thickness of the resist film is generally 200 nm or less, preferably 100 nm or less. For example, in order to analyze a 1:1 line and space pattern having a line width of 20 nm or less, the thickness of the formed resist film is preferably 50 nm or less. When the film thickness is 50 nm or less, when the developing process described later is applied, pattern collapse is less likely to occur, and more excellent analytical performance can be obtained. As the range of the film thickness, a range of 15 nm to 45 nm is more preferable. When the film thickness is 15 nm or more, sufficient etching resistance can be obtained. As the range of the film thickness, 15 nm to 40 nm is further preferable. When the film thickness is within this range, the etching resistance and the more excellent analytical performance can be simultaneously satisfied.

Further, in the pattern forming method of the present invention, an upper layer film (top coat layer) may be formed on the upper layer of the resist film. It is preferable that the top coat layer is not mixed with the resist film, and it can be uniformly applied to the upper layer of the resist film.

[Composition for forming an upper layer film] The composition for forming an upper layer film (a composition for forming a top coat layer) will be described. It is preferable that the top coat layer is not mixed with the resist film, and it can be uniformly applied to the upper layer of the resist film. The top coat layer is not particularly limited, and a conventionally known top coat layer can be formed by a conventionally known method. For example, the top coat layer can be formed in accordance with paragraphs 0072 to 0082 of JP-A-2014-059543. For example, it is preferred to form a top coat layer containing a basic compound as described in JP-A-2013-61648 on a resist film. Specific examples of the basic compound which may be contained in the top coat layer are the same as those in the photosensitive ray-sensitive or radiation-sensitive composition. Further, the top coat layer preferably contains a compound containing at least one group or bond selected from the group consisting of an ether bond, a thioether bond, a hydroxyl group, a thiol group, a carbonyl bond, and an ester bond.

Further, it is preferred that the top coat contains a resin. The resin which can be contained in the top coat layer is not particularly limited, and the same hydrophobic resin which can be contained in the resist composition can be used. For the hydrophobic resin, refer to <0017> to <0023> of the Japanese Patent Publication No. 2013-61647 (corresponding to <0017> to <0023> of US Published Patent Publication No. 2013/244438) and JP-A-2014-56194 The contents of <0016> to <0165> of the Japanese Patent Publication, the contents of which are incorporated herein by reference. The top coat layer preferably contains a resin containing a repeating unit having an aromatic ring. By containing a repeating unit having an aromatic ring, especially in the case of electron beam or EUV exposure, the efficiency of secondary electron generation and the acid-generating efficiency of a compound derived from an actinic ray or a radiation-generating acid become high, and can be expected at the time of pattern formation. High sensitivity and high resolution. When used in ArF immersion exposure, it is preferable that the resin does not substantially have an aromatic group from the viewpoint of transparency to ArF light.

The weight average molecular weight of the resin is preferably from 3,000 to 100,000, further preferably from 3,000 to 30,000, most preferably from 5,000 to 20,000. The blending amount of the resin in the top coat layer-forming composition is preferably from 50 to 99.9% by mass, more preferably from 70 to 99.7% by mass, even more preferably from 80 to 99.5% by mass, based on the total solid content.

When the top coat layer contains a plurality of resins, it is preferred to contain at least one resin (XA) having a fluorine atom and/or a ruthenium atom. The top coat layer contains at least one resin having a fluorine atom and/or a ruthenium atom (XA), and a resin having a fluorine atom and/or a ruthenium atom content lower than that of the resin (XA). (XB) is better. Thereby, when the top coat film is formed, since the resin (XA) is biased on the surface of the top coat film, performance such as development characteristics or liquid immersion followability can be improved.

The content of the resin (XA) is preferably from 0.01 to 30% by mass, more preferably from 0.1 to 10% by mass, even more preferably from 0.1 to 8% by mass, based on the total solid content of the top coat composition. 0.1 to 5 mass% is particularly preferred. The content of the resin (XB) is preferably 50.0 to 99.9% by mass based on the total solid content contained in the top coat composition, more preferably 60 to 99.9% by mass, and still more preferably 70 to 99.9% by mass. 80 to 99.9% by mass is particularly preferred.

The fluorine atom contained in the resin (XA) is preferably from 5 to 80% by mass, more preferably from 10 to 80% by mass, based on the weight average molecular weight of the resin (XA). The amount of the ruthenium atom contained in the resin (XA) is preferably from 2 to 50% by mass, more preferably from 2 to 30% by mass, based on the weight average molecular weight of the resin (XA).

The resin (XB) is preferably a form in which a fluorine atom and a ruthenium atom are not substantially present. In this case, specifically, a total content of a repeating unit having a fluorine atom and a repeating unit having a ruthenium atom is relative to the resin ( All repeating units in XB) are preferably 0 to 20 mol%, more preferably 0 to 10 mol%, more preferably 0 to 5 mol%, and most preferably 0 to 3 mol%. It is 0% by mole, that is, no fluorine atom or germanium atom.

The blending amount of the resin in the entire top coat composition is preferably from 50 to 99.9% by mass, more preferably from 60 to 99.0% by mass, based on the total solid content.

Also, the top coat layer may contain an acid generator and a crosslinking agent. Specific examples of these components and preferred examples are as described above.

The top coat layer is typically formed of a top coat forming composition. In the top coat layer-forming composition, it is preferred to dissolve each component in a solvent (top coat solvent) and filter it by a filter. As the filter, a filter made of polytetrafluoroethylene, polyethylene or nylon having a pore size of 0.1 μm or less, more preferably 0.05 μm or less, further preferably 0.03 μm or less is preferable. In addition, the filter may be used by connecting a plurality of types in series or in parallel. Moreover, the composition may be subjected to multiple filtrations, and the plurality of filtration processes may be a cyclic filtration process. Further, the composition may be subjected to a degassing treatment or the like before and after the filter is filtered. The top coat layer forming composition of the present invention is preferably free from impurities such as metals. The content of the metal component contained in the materials is preferably 10 ppm or less, more preferably 5 ppm or less, further preferably 1 ppm or less, and substantially no (below the detection limit of the measuring device). Further, the compound (1) of the present invention may be added to the top coat solvent.

When the exposure described later is immersion exposure, the top coat layer is disposed between the resist film and the liquid immersion liquid, and also functions as a layer in which the resist film does not directly contact the liquid immersion liquid. In this case, as a top coat layer (a composition for forming a top coat layer), it has preferable characteristics, such as coating suitability to a resist film, transparency to radiation, especially to 193 nm, and liquid immersion liquid (compared to Jia is water) is difficult to dissolve. Further, it is preferable that the top coat layer is not mixed with the resist film and can be uniformly applied to the surface of the resist film. Further, in order to uniformly apply the composition for forming a top coat layer to the surface of the resist film without dissolving the resist film, it is preferred that the top coat layer-forming composition contains a solvent which does not dissolve the resist film. Further, as a solvent in which the resist film is not dissolved, a solvent different from the component containing the developing solution (organic developing solution) containing an organic solvent is further preferable.

The coating method of the top coat layer forming composition is not particularly limited, and a conventionally known spin coating method, spray method, roll coating method, dipping method, or the like can be used.

The film thickness of the top coat layer is not particularly limited, and is usually from 5 nm to 300 nm, preferably from 10 nm to 300 nm, more preferably from 20 nm to 200 nm, even more preferably from 30 nm to 100 nm, from the viewpoint of transparency to the exposure light source. The thickness is formed. After the top coat is formed, the substrate is heated (PB) as needed. From the standpoint of analyticity, the refractive index of the top coat layer is preferably close to the refractive index of the resist film. It is preferred that the top coat is insoluble in the liquid immersion liquid, and that it is more soluble in water. The receding contact angle of the top coat layer is preferably from 50 to 100 degrees, preferably from 80 to 100 degrees, from the viewpoint of the followability of the liquid immersion liquid, and the back contact angle (23 ° C) of the top coat layer is preferably from 50 to 100 degrees. . In liquid immersion exposure, the liquid immersion liquid needs to follow the high-speed scanning of the exposure head on the wafer to form the movement of the exposure pattern to move on the wafer, so the liquid immersion liquid phase is very important for the contact angle of the top coating layer in the dynamic state. In order to obtain better resist performance, a receding contact angle having the above range is preferable.

When the top coat is peeled off, an organic developer may be used, or a release agent may be additionally used. As the release agent, a solvent having less penetration into the resist film is preferred. From the viewpoint of simultaneously performing development of the resist film and peeling of the top coat layer, it is preferable to peel off the top coat layer with the organic developer. The organic developing solution used for the peeling is not particularly limited as long as it is a low-exposure portion capable of dissolving and removing the resist film.

The dissolution rate of the top coat layer to the organic developer is preferably from 1 to 300 nm/sec, more preferably from 10 to 100 nm/sec, from the viewpoint of being peeled off by the organic developer. Here, the dissolution rate of the top coat layer to the organic developer solution is the film thickness reduction rate when the top coat layer is formed after the top coat layer is formed, and the speed at which the butyl acetate is immersed in 23 ° C in the present invention. . The dissolution rate of the top coat layer to the organic developer is set to 1 nm/sec second or more, preferably 10 nm/sec or more, thereby reducing the occurrence of development defects after development of the resist film. . Further, by setting it to 300 nm/sec or less, preferably 100 nm/sec, it is possible to have a line edge of a pattern after developing the resist film due to the influence of unevenness in exposure unevenness during immersion exposure. The roughness becomes more effective. The top coat layer can be removed using other known developing solutions such as an aqueous alkali solution or the like. Specific examples of the aqueous alkali solution that can be used include an aqueous solution of tetramethylammonium hydroxide.

In the pattern forming method of the present invention, there may be a process of applying a pre-wet solvent to the resist film. Thereby, the coating property of the composition for forming an upper layer film is improved, and liquid eliminating can be achieved. The pre-wetting solvent is not particularly limited as long as it has a low solubility in the resist film, and one or more selected from the group consisting of an alcohol solvent, a fluorine solvent, an ether solvent, a hydrocarbon solvent, and an ester solvent may be used. The compound film is pre-wet solvent.

These solvents may be used singly or in combination of plural kinds. By mixing the solvent other than the above, the solubility in the resist film, the solubility in the resin in the composition for forming an upper layer film, the elution property from the resist film, and the like can be appropriately adjusted.

[Exposure Process] The exposure process is a process of exposing the resist film, and can be performed, for example, by the following method. The irradiated film formed as described above is irradiated through a prescribed mask of illuminating rays or radiation. Further, the irradiation by the electron beam is usually performed without drawing a mask (straight drawing). The actinic ray or radiation is not particularly limited, and is, for example, KrF excimer laser light, ArF excimer laser light, extreme ultraviolet ray (EUV, Extreme Ultra Violet), electron beam (EB, Electron Beam), etc., extreme ultraviolet ray or electron beam. It is especially good. The exposure can be a liquid immersion exposure.

[Roasting] In the pattern forming method of the present invention, it is preferred to perform baking (heating) after exposure after development. The reaction of the exposed portion is promoted by baking, and the sensitivity and pattern shape are further improved. The heating temperature is preferably 80 to 150 ° C, more preferably 80 to 140 ° C, and still more preferably 80 to 130 ° C. The heating time is preferably from 30 to 1,000 seconds, more preferably from 60 to 800 seconds, and further preferably from 60 to 600 seconds. The heating can be performed by a mechanism provided on a usual exposure/developer, or by a heating plate or the like.

[Pre-flushing process] The pattern forming method of the present invention may have a process (pre-flushing process) for bringing the treatment liquid of the present invention into contact with the exposed resist film between the exposure process and the development process. As a method of bringing the treatment liquid into contact with the resist film, for example, a method of ejecting the treatment liquid onto the substrate having the resist film by the shower head; and having a resist in the tank filled with the treatment liquid can be applied. a method in which a substrate of a film is immersed for a certain period of time (dip method); a method in which a treatment liquid is deposited on a surface of a substrate having a resist film by a surface tension and allowed to stand for a certain period of time (puddle method) a method of spraying a treatment liquid onto a surface of a substrate having a resist film (spray method); and scanning a developer discharge nozzle at a constant speed on a substrate having a resist film rotated at a constant speed A method of continuously discharging a treatment liquid (dynamic dispense method) or the like. The time for bringing the treatment liquid into contact with the resist film is not particularly limited, but is usually 1 to 300 seconds, preferably 1 to 120 seconds. The temperature of the treatment liquid is not particularly limited, and is preferably 0 to 50 ° C, more preferably 15 to 35 ° C.

[Developing Process] The developing process is a process of developing the exposed resist film using a developing solution.

As the developing method, for example, a method of immersing the substrate in a tank filled with a developing solution for a certain period of time (dipping method), and a surface tension to deposit the developer on the surface of the substrate and allowing it to stand for a certain period of time can be applied. Method for developing (liquid coating method); method for spraying a developer onto a surface of a substrate (spray method); method for continuously ejecting a developer while ejecting a developer at a constant speed on a substrate rotating at a constant speed (dynamic allocation method) and so on. Further, after the development process, a process of stopping development while replacing with another solvent can be performed. The development time is not particularly limited as long as the resin in the exposed portion or the unexposed portion is sufficiently dissolved, and is usually 10 to 300 seconds, preferably 10 to 120 seconds. The temperature of the developer is preferably 0 to 50 ° C, more preferably 15 to 35 ° C.

(Developing Solution) The developing solution may be an alkali developing solution or a developing solution (organic developing solution) containing an organic solvent.

- alkali developing solution - as the alkali developing solution, for example, inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, and aqueous ammonia; primary amines such as ethylamine and n-propylamine; Secondary amines such as ethylamine and di-n-butylamine; tertiary amines such as triethylamine and methyldiethylamine; alcoholamines such as dimethylethanolamine and triethanolamine; tetramethylammonium hydroxide and tetraethylamine Ammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctyl ammonium hydroxide, ethyltrimethylammonium hydroxide, butyl Tetraalkylammonium hydroxide such as trimethylammonium hydroxide, methyltripentylammonium hydroxide or dibutyldipentylammonium hydroxide; dimethylbis(2-hydroxyethyl)ammonium hydroxide, trimethyl A quaternary ammonium salt such as phenylphenylammonium hydroxide, trimethylbenzylammonium hydroxide or triethylbenzylammonium hydroxide; or an aqueous alkaline solution such as a cyclic amine such as pyrrole or piperidine. An appropriate amount of an alcohol or a surfactant may be added to the above aqueous alkaline solution for use. 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. As the alkali developing solution, an aqueous solution of tetramethylammonium hydroxide (2.38 mass%) is particularly preferred.

- Organic developing solution - Next, the organic solvent contained in the organic developing solution will be described.

The vapor pressure of the organic solvent (the entire vapor pressure in the case of a mixed solvent) is preferably 5 kPa or less at 20 ° C, more preferably 3 kPa or less, and particularly preferably 2 kPa or less. By setting the vapor pressure of the organic solvent to 5 kPa or less, evaporation of the developer on the substrate or in the developing cup can be suppressed, and temperature uniformity in the wafer surface can be improved, and as a result, dimensional uniformity in the wafer surface becomes uniform. good. Various organic solvents can be widely used as the organic solvent to be used in the organic developing solution. For example, an ester solvent, a ketone solvent, an alcohol solvent, a guanamine solvent, an ether solvent, or a hydrocarbon solvent can be used. Specific examples of the organic solvents are the same as those described in the solvent (2) contained in the treatment liquid.

In the case where EUV light and EB are used in the above-mentioned exposure process, the organic solvent contained in the organic developer has a carbon number of 7 or more (7 to 14 is considered) from the viewpoint of suppressing swelling of the resist film. Preferably, 7 to 12 is more preferable, 7 to 10 is further preferred, and an ester solvent having 2 or less hetero atoms is preferable. The hetero atom of the ester solvent is an atom other than a carbon atom or a hydrogen atom, and examples thereof include an oxygen atom, a nitrogen atom, and a sulfur atom. It is preferred that the number of hetero atoms is 2 or less.

Preferable examples of the ester solvent having 7 or more carbon atoms and 2 or less hetero atoms include amyl acetate, isoamyl acetate, and 2-methylbutyl acetate. Ester, 1-methylbutyl acetate, hexyl acetate, amyl propionate, hexyl propionate, butyl propionate, isobutyl isobutyrate, heptyl propionate, butyl butyrate, etc., using acetic acid Isoamyl acetate is particularly preferred.

When EUV light and EB are used in the above-mentioned exposure process, the organic solvent contained in the organic developing solution may be used in place of the ester solvent having 7 or more carbon atoms and 2 or less hetero atoms, and the above-mentioned ester solvent and the above-mentioned ester solvent. A mixed solvent of a hydrocarbon solvent or a mixed solvent of the above ketone solvent and the above hydrocarbon solvent. In this case as well, the swelling of the resist film can be effectively suppressed. When an ester solvent and a hydrocarbon solvent are used in combination, isoamyl acetate is preferably used as the ester solvent. Further, as the hydrocarbon-based solvent, a saturated hydrocarbon solvent (for example, octane, decane, decane, dodecane, undecane, hexadecane or the like) is used from the viewpoint of adjusting the solubility of the resist film. good. When a ketone solvent and a hydrocarbon solvent are used in combination, 2-heptanone is preferably used as the ketone solvent. Further, as the hydrocarbon-based solvent, a saturated hydrocarbon solvent (for example, octane, decane, decane, dodecane, undecane, hexadecane or the like) is used from the viewpoint of adjusting the solubility of the resist film. good. In the case of using the above mixed solvent, the content of the hydrocarbon-based solvent depends on the solvent solubility of the resist film, and therefore is not particularly limited, and may be appropriately adjusted to determine the required amount.

The above organic solvent may be used in combination of a plurality of kinds, or may be used by mixing a solvent other than the above or water. However, in order to sufficiently exhibit the effects of the present invention, the water content of the entire developing solution is preferably less than 10% by mass, and it is more preferable that the water content is substantially not contained. The concentration of the organic solvent (total of a plurality of kinds) in the developer is preferably 50% by mass or more, more preferably 50 to 100% by mass, still more preferably 85 to 100% by mass or more, still more preferably 90%. 100% by mass, particularly preferably 95 to 100% by mass. It is preferably the case where it consists essentially only of an organic solvent. Further, in the case where it is substantially composed only of an organic solvent, a trace amount of a surfactant, an antioxidant, a stabilizer, an antifoaming agent, or the like may be contained.

It is also preferred that the developer contains an antioxidant. Thereby, the generation of the oxidizing agent can be suppressed, and the content of the oxidizing agent can be further reduced. As the antioxidant, a known one can be used, and when it is used for a semiconductor, it is preferred to use an amine-based antioxidant or a phenol-based antioxidant.

The content of the antioxidant is not particularly limited, but is preferably 0.0001 to 1% by mass based on the total mass of the developer, more preferably 0.0001 to 0.1% by mass, and still more preferably 0.0001 to 0.01% by mass. When it is 0.0001% by mass or more, a more excellent oxidation resistance effect can be obtained, and when it is 1% by mass or less, the development residue can be suppressed.

The developer may contain a basic compound, and specifically, the same as the basic compound which may be contained in the resist composition.

The developer may contain a surfactant. By the developer containing the surfactant, the wettability of the resist film is improved, and the development is performed more efficiently. As the surfactant, the same surfactant as that which can be contained in the resist composition can be used. When the developer contains a surfactant, the content of the surfactant is preferably 0.001 to 5% by mass, more preferably 0.005 to 2% by mass, still more preferably 0.01 to 0.5% by mass, based on the total mass of the developer.

As the developing method, for example, a method of immersing the substrate in a tank filled with a developing solution for a certain period of time (dipping method), and a surface tension to deposit the developer on the surface of the substrate and allowing it to stand for a certain period of time can be applied. Method for developing (liquid coating method); method for spraying a developer onto a surface of a substrate (spray method); method for continuously ejecting a developer while ejecting a developer at a constant speed on a substrate rotating at a constant speed (dynamic allocation method) and so on. Further, after the development process, a process of stopping development while replacing it with another solvent can be performed. The development time is not particularly limited and is usually from 10 to 300 seconds, preferably from 20 to 120 seconds. The temperature of the developer is preferably 0 to 50 ° C, more preferably 15 to 35 ° C.

As the developing solution used in the developing process, both development using a developing solution containing an organic solvent and development by an alkali developing solution can be performed (so-called double development can be performed).

In the pattern forming method of the present invention, the developer may contain the treatment liquid of the present invention, and in this case, the treatment liquid is preferably a developer.

[Reling Process] The rinsing process is a process of cleaning (rinsing) using a rinsing liquid after the developing process.

During the rinsing process, the developed wafer is cleaned using a rinsing liquid. The method of the cleaning treatment is not particularly limited. For example, it can be applied to a method of continuously ejecting a rinse liquid on a substrate rotating at a constant speed (rotary discharge method), and a method of immersing a substrate in a tank filled with a rinse liquid for a certain period of time (dipping method) A method of spraying a rinse liquid on a surface of a substrate (spraying method) or the like, wherein the cleaning treatment is performed by a rotary discharge method, and after the cleaning, the substrate is rotated at a number of revolutions of 2000 rpm to 4000 rpm to remove the rinse liquid from the substrate. The rinsing time is not particularly limited, but is preferably from 10 seconds to 300 seconds, more preferably from 10 seconds to 180 seconds, and most preferably from 20 seconds to 120 seconds. The temperature of the rinse liquid is preferably 0 to 50 ° C, more preferably 15 to 35 ° C.

Further, after the development treatment or the rinsing treatment, the treatment of removing the developer or the rinsing liquid adhering to the pattern by the supercritical fluid can be performed. Further, after the development treatment or the rinsing treatment or the treatment based on the supercritical fluid, the heat treatment can be performed in order to remove the solvent remaining in the pattern. The heating temperature is not particularly limited as long as it can obtain a favorable resist pattern, but is usually 40 to 160 °C. The heating temperature is preferably from 50 to 150 ° C, and most preferably from 50 to 110 ° C. The heating time is not particularly limited as long as a good resist pattern can be obtained, but it is usually 15 to 300 seconds, preferably 15 to 180 seconds.

(Rinsing liquid) As the rinsing liquid, a rinsing liquid containing an organic solvent is preferably used, and the organic solvent is selected from the group consisting of a hydrocarbon solvent, a ketone solvent, an ester solvent, an alcohol solvent, a guanamine solvent, and an ether solvent. At least one organic solvent in the group is preferred. The organic solvent contained in the rinsing liquid is preferably at least one selected from the group consisting of a hydrocarbon solvent, an ether solvent, and a ketone solvent, and is preferably at least one selected from the group consisting of a hydrocarbon solvent and an ether solvent. As the organic solvent contained in the rinse liquid, an ether solvent can be suitably used. Specific examples of the organic solvents are the same as those described in the solvent (2) contained in the treatment liquid.

The vapor pressure of the rinse liquid is preferably 0.05 kPa or more and 5 kPa or less at 20 ° C, more preferably 0.1 kPa or more and 5 kPa or less, and most preferably 0.12 kPa or more and 3 kPa or less. When the rinsing liquid is a mixed solvent of a plurality of kinds of solvents, the overall vapor pressure is preferably in the above range. By setting the vapor pressure of the rinse liquid to 0.05 kPa or more and 5 kPa or less, the temperature uniformity in the wafer surface is improved, and the swelling due to the penetration of the rinse liquid can be suppressed, and the dimensional uniformity in the wafer surface becomes uniform. good. The organic solvent contained in the rinse liquid may be one type or two or more types. When two or more types are contained, for example, a mixed solvent of undecane and diisobutyl ketone may be mentioned.

The rinse solution may contain a surfactant. The rinse liquid contains a surfactant, whereby the wettability to the resist film is improved, the rinsing property is improved, and the tendency of foreign matter generation can be suppressed. As the surfactant, the same surfactant as that used in the sensitizing ray-sensitive or radiation-sensitive composition described later can be used. The rinse liquid contains a surfactant, and the content of the surfactant is preferably 0.001 to 5% by mass, more preferably 0.005 to 2% by mass, still more preferably 0.01 to 0.5% by mass based on the total mass of the rinsing liquid. .

The rinse solution may contain an antioxidant. The antioxidant which may contain the rinsing liquid is the same as the antioxidant which the developing solution may contain.

When the rinsing liquid contains an antioxidant, the content of the antioxidant is not particularly limited, and is preferably 0.0001 to 1% by mass, more preferably 0.0001 to 0.1% by mass, and 0.0001 to 0.01% by mass, based on the total mass of the rinsing liquid. Further preferred.

In the pattern forming method of the present invention, it is preferred that the rinse liquid contains the treatment liquid of the present invention, and it is more preferable to use the treatment liquid as the rinse liquid.

[Photosensitized ray-sensitive or radiation-sensitive composition] The sensitizing ray-sensitive or radiation-sensitive composition used in the pattern forming method of the present invention is typically a resist composition, preferably a chemically amplified resist. Composition. The sensitizing ray-sensitive or radiation-sensitive composition is preferably a photosensitive ray-sensitive or radiation-sensitive composition for developing an organic solvent using a developing solution containing an organic solvent and/or for developing an alkali using an alkali developing solution. Here, the term "organic solvent development" means use for at least a process of developing using a developer containing an organic solvent. The term "alkali development" refers to the use of at least a process for developing using an alkali developer. The sensitizing ray-sensitive or radiation-sensitive composition may be either a positive resist composition or a negative resist composition. The sensitizing ray-sensitive or radiation-sensitive composition is preferably an electron beam or an extreme ultraviolet ray. Hereinafter, each component contained in the sensitizing ray-sensitive or radiation-sensitive composition will be described.

<Resin (A)> The photosensitive ray-sensitive or radiation-sensitive composition contains a resin (A). The resin (A) has at least (i) a repeating unit containing a group which generates a carboxyl group by decomposition of an acid (further, may contain a repeating unit having a phenolic hydroxyl group), or at least (ii) a phenolic hydroxyl group. Repeat unit. Further, when it has a repeating unit containing a group which decomposes by an action of an acid to form a carboxyl group, the solubility of the alkali developing solution by the action of an acid increases, and the solubility in an organic solvent decreases.

A repeating unit having a phenolic hydroxyl group which the resin (A) can have will be described. The repeating unit having a phenolic hydroxyl group may, for example, be a repeating unit represented by the following formula (I) or (I-1).

[Chemical Formula 10]

In the general formula (I) and the general formula (I-1), R ₄₁ , R ₄₂ and R ₄₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. Wherein R ₄₂ may be bonded to Ar ₄ to form a ring, and R _{42 in this case} represents a single bond or an alkylene group. X ₄ represents a single bond, -COO- or -CONR ₆₄ -, and R ₆₄ represents a hydrogen atom or an alkyl group. L ₄ represents a single bond or a divalent linking group. Ar ₄ represents an (n+1)-valent aromatic ring group, and when it is bonded to R ₄₂ to form a ring, it represents an (n+2)-valent aromatic ring group. n represents an integer of 1 to 5.

The alkyl group of R ₄₁ , R ₄₂ and R ₄₃ in the formula (I) and the formula (I-1) is preferably a methyl group, an ethyl group, a propyl group or an isopropyl group which may have a substituent. Further, an alkyl group having 20 or less carbon atoms, such as a group, n-butyl group, a second butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group or a dodecyl group, may more preferably have an alkyl group having 8 or less carbon atoms. An alkyl group having 3 or less carbon atoms can be particularly preferably mentioned.

The cycloalkyl group of R ₄₁ , R ₄₂ and R ₄₃ in the formula (I) and the formula (I-1) may be a monocyclic type or a polycyclic type. Preferably, a cycloalkyl group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group or a cyclohexyl group which may have a substituent and a monocyclic type may be mentioned. The halogen atom of R ₄₁ , R ₄₂ and R ₄₃ in the general formula (I) and the general formula (I-1) may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and a fluorine atom is particularly preferred. General formula (I) and formula (I-1) in the R _41, R _42, the alkyl group contained in the alkoxycarbonyl group R _43, with the above-described R _41, R _42, R ₄₃ are alkoxy of The same is preferred.

Preferred examples of the above-mentioned respective groups include an alkyl group, a cycloalkyl group, an aryl group, an amine group, a decylamino group, a ureido group, a urethane group, a hydroxyl group, a carboxyl group, and a halogen atom. An alkoxy group, a thioether group, a decyl group, a decyloxy group, an alkoxycarbonyl group, a cyano group, a nitro group or the like, and the number of carbon atoms of the substituent is preferably 8 or less.

Ar ₄ represents an (n+1)-valent aromatic ring group. When the n is 1, the divalent aromatic ring group may have a substituent, and examples thereof include a stretching group such as a phenyl group, a tolylene group, a naphthyl group, and a fluorenyl group. Or an aromatic ring group containing a heterocyclic ring such as thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole or thiazole. example.

Specific examples of the (n+1)-valent aromatic ring group when n is an integer of 2 or more are preferably (n-1) arbitrary from the above specific examples of the divalent aromatic ring group. a group formed by a hydrogen atom. The (n+1)-valent aromatic ring group may further have a substituent.

The alkyl group, the cycloalkyl group, the alkoxycarbonyl group, the alkylene group and the (n+1)-valent aromatic ring group may have a substituent, and examples thereof include R ₄₁ and R in the formula (I). _42. An alkyl group as defined in R ₄₃ ; an alkoxy group such as a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, a hydroxypropoxy group or a butoxy group; an aryl group such as a phenyl group or the like. The alkyl group of R ₆₄ in -CONR ₆₄ - (R ₆₄ represents a hydrogen atom or an alkyl group) represented by X ₄ is preferably a methyl group, an ethyl group, a propyl group or an isopropyl group which may have a substituent. An alkyl group having 20 or less carbon atoms, such as a group, n-butyl group, a second butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group or a dodecyl group, may furthermore be an alkyl group having 8 or less carbon atoms. As X ₄ , a single bond, -COO-, -CONH- is preferable, and a single bond or -COO- is more preferable.

When L ₄ represents a divalent linking group, an alkyl group is preferred as a divalent linking group. Examples of the alkylene group in L ₄ include a methylene group which may have a substituent, an exoethyl group, a propyl group, a butyl group, a hexyl group, and an exenyl group. The number of carbon atoms is 1 to 8 By. As Ar ₄ , an aromatic ring group having 6 to 18 carbon atoms which may have a substituent is more preferable, and a benzene ring group, a naphthalene ring group, and a biphenylene ring group are particularly preferable. The repeating unit represented by the formula (I) is preferably a hydroxystyrene structure. That is, it is preferred that Ar ₄ is a benzene ring group.

The repeating unit having a phenolic hydroxyl group which the resin (A) has is preferably a repeating unit represented by the following formula (p1).

[Chemical Formula 11]

R in the formula (p1) represents a hydrogen atom, a halogen atom or an alkyl group which may have a straight chain or a branch of 1 to 4 carbon atoms. Each of the plurality of Rs may be the same or different. As R in the formula (p1), a hydrogen atom is particularly preferred.

In the general formula (p1), Ar represents an aromatic ring, and examples thereof include an aromatic hydrocarbon ring having a substituent of 6 to 18 carbon atoms such as a benzene ring, a naphthalene ring, an anthracene ring, an anthracene ring, and a phenanthrene ring, or Containing, for example, a thiophene ring, a furan ring, a pyrrole ring, a benzothiophene ring, a benzofuran ring, a benzopyrrole ring, a triazine ring, an imidazole ring, a benzimidazole ring, a triazole ring, a thiadiazole ring, a thiazole ring, etc. A heterocyclic aromatic ring heterocyclic ring. Among them, the benzene ring is the best.

m in the formula (p1) represents an integer of 1 to 5, preferably 1.

Hereinafter, a specific example in which the resin (A) may have a repeating unit having a phenolic hydroxyl group is shown, but the present invention is not limited thereto. Where a represents 1 or 2. Further, as a specific example of the repeating unit having a phenolic hydroxyl group which the resin (A) can have, a specific example described in <0177> to <0178> of JP-A-2014-232309 can be incorporated, and the content can be incorporated. In the specification of the present application.

[Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 14]

The content of the repeating unit having a phenolic hydroxyl group is preferably 0 to 50 mol%, more preferably 0 to 45 mol%, still more preferably 0 to 40 mol%, based on all the repeating units in the resin (A). %.

Next, a description will be given of a repeating unit which the resin (A) has a group which decomposes by an action of an acid to generate a carboxyl group. The repeating unit having a group which decomposes by the action of an acid to form a carboxyl group is a repeating unit having a group in which a hydrogen atom of a carboxyl group is substituted with a group which is decomposed by an action of an acid.

Examples of the group which is liberated by the action of an acid include -C(R ₃₆ )(R ₃₇ )(R ₃₈ ), -C(R ₃₆ )(R ₃₇ )(OR ₃₉ ), -C(R ₀₁ ) (R ₀₂ ) (OR ₃₉ ) and so on. In the formula, R ₃₆ to R ₃₉ each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. R ₃₆ and R ₃₇ may be bonded to each other to form a ring. R ₀₁ and R ₀₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an arylalkyl group or an alkenyl group.

As a repeating unit having a group which generates a carboxyl group by decomposition by an acid, a repeating unit represented by the following formula (AI) is preferred.

[Chemical Formula 15]

In the formula (AI), Xa ₁ represents a hydrogen atom or an alkyl group which may have a substituent. T represents a single bond or a divalent linking group. Rx ₁ to Rx ₃ each independently represent an alkyl group (straight chain or branched) or a cycloalkyl group (monocyclic or polycyclic). However, when all of Rx ₁ to Rx ₃ are an alkyl group (straight chain or branched), it is preferred that at least two of Rx ₁ to Rx ₃ are a methyl group. Two of Rx ₁ to Rx ₃ may be bonded to form a cycloalkyl group (monocyclic or polycyclic).

The alkyl group which may have a substituent represented by Xa ₁ may, for example, be a group represented by a methyl group or -CH ₂ -R ₁₁ . R ₁₁ represents a halogen atom (such as a fluorine atom), a hydroxyl group or a monovalent organic group, and examples thereof include an alkyl group having 5 or less carbon atoms and a fluorenyl group having 5 or less carbon atoms, and preferably having 3 or less carbon atoms. The alkyl group is further preferably a methyl group. In one aspect, Xa _{1 is} preferably a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group. Examples of the divalent linking group of T include an alkylene group, a —COO—Rt— group, and an —O—Rt— group. In the formula, Rt represents an alkylene group or a cycloalkyl group. T is preferably a single bond, an extended aryl group or a -COO-Rt- group, and a single bond or an extended aryl group is more preferred. As the aryl group, a aryl group having 6 to 10 carbon atoms is preferred, and a phenyl group is more preferred. Rt is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a -CH ₂ - group, a -(CH ₂ ) ₂ - group or a -(CH ₂ ) ₃ - group.

The alkyl group of Rx ₁ to Rx ₃ is preferably a group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a tributyl group. a cycloalkyl group of Rx ₁ to Rx _{3 ,} a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, a cyclopentylene group, a tetracyclodecyl group, a tetracyclododecyl group or an adamantyl group. An alkyl group is preferred. a cycloalkyl group formed by bonding two of Rx ₁ to Rx ₃ , a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, a norbornyl group, a tetracyclodecyl group, a tetracyclododecyl group, or the like. A polycyclic cycloalkyl group such as an adamantyl group is preferred. A monocyclic cycloalkyl group having 5 to 6 carbon atoms is particularly preferred. In the cycloalkyl group formed by bonding two of Rx ₁ to Rx ₃ , for example, one of the methylene groups constituting the ring may be substituted with a hetero atom such as an oxygen atom or a group having a hetero atom such as a carbonyl group. The repeating unit represented by the formula (AI) is preferably, for example, a state in which Rx ₁ is a methyl group or an ethyl group and Rx ₂ and Rx _{3 are} bonded to each other to form the above cycloalkyl group.

Each of the above groups may have a substituent. Examples of the substituent include an alkyl group (having 1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (having 1 to 4 carbon atoms), a carboxyl group, and an alkoxy group. A carbonyl group (having 2 to 6 carbon atoms) or the like is preferred, and a carbon number of 8 or less is preferred.

The repeating unit represented by the formula (AI) is preferably an acid-decomposable tertiary alkyl (meth)acrylate-based repeating unit (Xa ₁ represents a hydrogen atom or a methyl group, and T represents a repeating unit of a single bond) . More preferably Rx ₁ ~ Rx ₃ each independently represents a repeating unit of a linear or branched alkyl group, and further preferably Rx ₁ ~ Rx ₃ each independently represents a linear alkyl group of the repeating unit.

Specific examples of the repeating unit having a group in which a carboxyl group is decomposed by the action of an acid are shown below, but the present invention is not limited thereto. In a specific example, Rx represents a hydrogen atom, CH ₃ , CF ₃ or CH ₂ OH. Rxa and Rxb each represent an alkyl group having 1 to 4 carbon atoms. Z represents a substituent having a polar group, and is independent when a plurality of them are present. p represents 0 or a positive integer. The substituent containing a polar group represented by Z may, for example, be a linear or branched alkyl group having a hydroxyl group, a cyano group, an amine group, an alkylguanamine group or a sulfonylamino group, or a cycloalkyl group. It is an alkyl group having a hydroxyl group. As the branched alkyl group, isopropyl is particularly preferred. Further, as a specific example of the repeating unit having a group in which a carboxyl group is decomposed by the action of an acid, a specific example described in <0227> to <0233> of JP-A-2014-232309 can be used. Can be incorporated into the specification of this application.

[Chemical Formula 16]

[Chemical Formula 17]

The resin (A) preferably contains a repeating unit represented by the following formula (5) or (6), and more preferably a repeating unit represented by the formula (6).

[Chemical Formula 18]

In the general formulae (5) and (6), R ₄₁ , R ₄₂ and R ₄₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₄₂ may be bonded to L ₄ to form a ring, and R _{42 in this case} represents an alkylene group. L ₄ represents a single bond or a divalent linking group, and when it forms a ring with R ₄₂ , it represents a trivalent linking group. R ₄₄ and R ₄₅ represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, a fluorenyl group or a heterocyclic group. M ₄ represents a single bond or a divalent linking group. Q ₄ represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group. At least two of Q ₄ , M ₄ and R ₄₄ may be bonded to form a ring. Rx ₁ to Rx ₃ each independently represent an alkyl group (straight chain or branched) or a cycloalkyl group (monocyclic or polycyclic). However, when all of Rx ₁ to Rx ₃ are an alkyl group (straight chain or branched), at least two of Rx ₁ to Rx ₃ are preferably a methyl group. Two of Rx ₁ to Rx ₃ may be bonded to form a cycloalkyl group (monocyclic or polycyclic). The meanings of R ₄₄ and R ₄₅ are the same as those of R ₃ in the following general formula (3), and the preferred ranges are also the same. Same formula ₃ M M (3) in the meaning of the ₄ described later, and preferred ranges are also the same. In the same Q Q ₃ of the general formula (3) Meaning ₄ described later, and the preferred ranges are also the same. Examples of the ring formed by bonding at least two of Q ₄ , M ₄ and R ₄₄ include a ring formed by bonding at least two of Q ₃ , M ₃ and R ₃ , and a preferred range is also the same.

The alkyl group of R ₄₁ to R ₄₃ in the formula (5) is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group or a second butyl group which may have a substituent. An alkyl group having 20 or less carbon atoms such as a hexyl group, a 2-ethylhexyl group, an octyl group or a dodecyl group is more preferably an alkyl group having 8 or less carbon atoms, and particularly preferably a carbon atom number of 3 The following alkyl groups. The alkyl group contained in the alkoxycarbonyl group is preferably the same as the alkyl group in the above R ₄₁ to R ₄₃ . The cycloalkyl group may be a monocyclic type or a polycyclic type. Preferably, a cycloalkyl group having 3 to 10 carbon atoms such as a cyclopropyl group, a cyclopentyl group or a cyclohexyl group which may have a substituent and a monocyclic type may be mentioned. The halogen atom may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and a fluorine atom is particularly preferred.

Examples of the substituent in each of the above groups include an alkyl group, a cycloalkyl group, an aryl group, an amine group, a decylamino group, a ureido group, a urethane group, a hydroxyl group, a carboxyl group, a halogen atom, and an alkoxy group. The substituent, the thiol group, the fluorenyl group, the decyloxy group, the alkoxycarbonyl group, the cyano group, the nitro group and the like, and the number of carbon atoms of the substituent is preferably 8 or less.

Further, when R ₄₂ is an alkylene group and forms a ring with L ₄ , examples of the alkylene group include a methylene group, an exoethyl group, a propyl group, a butyl group, a hexyl group, and a decyl group. An alkyl group having 1 to 8 carbon atoms. The alkylene group having 1 to 4 carbon atoms is more preferable, and the alkylene group having 1 to 2 carbon atoms is particularly preferable. It is particularly preferable that the ring formed by bonding R ₄₂ and L ₄ is a 5- or 6-membered ring.

R ₄₁ and R ₄₃ are more preferably a hydrogen atom, an alkyl group or a halogen atom, and a hydrogen atom, a methyl group, an ethyl group, a trifluoromethyl group (-CF ₃ ), a hydroxymethyl group (-CH ₂ -OH), or a chlorine atom. A methyl group (-CH ₂ -Cl) or a fluorine atom (-F) is particularly preferred. R ₄₂ is preferably a hydrogen atom, an alkyl group, a halogen atom or an alkyl group (forming a ring with L ₄ ), a hydrogen atom, a methyl group, an ethyl group, a trifluoromethyl group (-CF ₃ ) or a hydroxymethyl group ( -CH ₂ -OH), chloromethyl (-CH ₂ -Cl), a fluorine atom (-F), a methylene group (forming a ring with L ₄ ), and an ethyl group (forming a ring with L ₄ ) are particularly preferred.

Examples of the divalent linking group represented by L ₄ include an alkylene group, a divalent aromatic ring group, -COO-L ₁ -, -OL ₁ -, and a combination of two or more of these groups. Mission and so on. Here, L ₁ represents an alkyl group, a cycloalkyl group, a divalent aromatic ring group, a group in which an alkyl group and a divalent aromatic ring group are combined. L ₄ is a single bond, a group represented by -COO-L ₁ - or a divalent aromatic ring group is preferred, and a divalent aromatic ring group (extended aryl group) is more preferable. L ₁ is preferably an alkylene group having 1 to 5 carbon atoms, and more preferably a methylene group or a propyl group. As the divalent aromatic ring group, 1,4-phenylene, 1,3-phenylene, 1,2-phenylene, 1,4-naphthyl is preferred, 1,4-phenylene For better. The trivalent linking group represented by L ₄ when L ₄ and R _{42 are} bonded to each other to form a ring is preferably one by one selected from the above specific examples of the divalent linking group represented by L ₄ . a group of hydrogen atoms.

Specific examples of the repeating unit represented by the general formula (5) can be referred to the specific examples described in <0270> to <0272> of JP-A-2014-232309, and the contents can be incorporated in the specification of the present application. However, the invention is not limited thereto.

Further, the resin (A) may contain a repeating unit represented by the following formula (BZ).

[Chemical Formula 19]

In the formula (BZ), AR represents an aryl group. Rn represents an alkyl group, a cycloalkyl group or an aryl group. Rn and AR may be bonded to each other to form a non-aromatic ring. R ₁ represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.

With respect to formulas (BZ) in AR, Rn, R _1, may be invoked <0101> ~ matter <0122> as described in the Japanese Patent Publication Laid-Open No. 2012-208447, the contents of which can be incorporated in the present specification, the present The invention is not limited to this. Specific examples of the repeating unit represented by the general formula (BZ) can be referred to the specific examples described in <0123> to <0131> of JP-A-2012-208447, and the contents can be incorporated in the specification of the present application. However, the invention is not limited thereto.

The content of the repeating unit having a group which generates a carboxyl group by decomposition by an acid is preferably from 20 to 90 mol%, more preferably from 25 to 80 mol%, based on all the repeating units in the resin (A). Further preferably, it is 30 to 70 mol%.

It is preferred that the resin (A) further contains a repeating unit having a lactone group. As the lactone group, any group may be used as long as it contains a lactone structure, preferably a group having a 5- to 7-membered ring lactone structure, and a double-ring structure and a snail in a 5- to 7-membered ring lactone structure. It is preferred that the form of the ring structure is fused to other ring structures. It is further preferred to include a repeating unit having a group having a lactone structure represented by any one of the following general formulae (LC1-1) to (LC1-17). Further, a group having a lactone structure may be directly bonded to the main chain. Preferred lactone structures are those represented by the formulae (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), and (LC1-14). group.

[Chemical Formula 20]

The lactone moiety may or may not have a substituent (Rb ₂ ). Preferred examples of the substituent (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, and 1 carbon atom. ～8 alkoxycarbonyl group, carboxyl group, halogen atom, hydroxyl group, cyano group, acid-decomposable group, and the like. N2 represents an integer of 0 to 4. When n2 is 2 or more, a plurality of Rb ₂ may be the same or different, and a plurality of Rb ₂ may be bonded to each other to form a ring.

Examples of the repeating unit having a group having a lactone structure represented by any one of the formulae (LC1-1) to (LC1-17) include a repeating unit represented by the following formula (AI). .

[Chemical Formula 21]

In the general formula (AI), Rb ₀ represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms. The alkyl group as Rb ₀ may have a preferred substituent, and examples thereof include a hydroxyl group and a halogen atom. Examples of the halogen atom of Rb ₀ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. It is preferred that Rb ₀ is a hydrogen atom or a methyl group. Ab represents a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group or a divalent group obtained by combining these. A single bond, a link represented by -Ab ₁ -CO ₂ - is preferred. Ab ₁ is a linear, branched alkyl, monocyclic or polycyclic cycloalkyl group, preferably a methylene group, an ethyl group, a cyclohexylene group, an adamantyl group, or a fluorenyl group. V represents a group represented by any one of the formulae (LC1-1) to (LC1-17).

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

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

[Chemical Formula 22]

[Chemical Formula 23]

The content of the repeating unit having a lactone group is preferably from 1 to 30 mol%, more preferably from 5 to 25 mol%, still more preferably from 5 to 20 mol%, based on all the repeating units in the resin (A). %. The resin (A) may further have a repeating unit containing an organic group having a polar group, and in particular, may further have a repeating unit having an alicyclic hydrocarbon structure substituted with a polar group. Thereby, the substrate adhesion and the developer affinity are improved. As the alicyclic hydrocarbon structure of the polar group-substituted alicyclic hydrocarbon structure, adamantyl group, diamantyl group or norbornyl group is preferred. As the polar group, a hydroxyl group or a cyano group is more preferable. Specific examples of the repeating unit having a polar group are given below, but the present invention is not limited thereto.

[Chemical Formula 24]

When the resin (A) has a repeating unit containing an organic group having a polar group, the content thereof is preferably from 1 to 30 mol%, more preferably from 5 to 25 mol%, based on all the repeating units in the resin (A). % is further preferably 5 to 20 mol%.

The resin (A) may further contain a repeating unit having a group (photoacid generating group) which generates an acid by irradiation with actinic rays or radiation as a repeating unit other than the above. In this case, it is considered that the repeating unit having a photoacid generating group corresponds to a compound (B) which generates an acid by irradiation with actinic rays or radiation which will be described later. As such a repeating unit, for example, a repeating unit represented by the following formula (4) can be given.

[Chemical Formula 25]

R ⁴¹ represents a hydrogen atom or a methyl group. L ⁴¹ represents a single bond or a divalent linking group. L ⁴² represents a divalent linking group. R ⁴⁰ represents a structural site in which an acid is generated in a side chain by decomposition of actinic rays or radiation.

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

In addition, examples of the repeating unit represented by the formula (4) include repeating units described in paragraphs <0094> to <0105> of JP-A-2014-041327.

When the resin (A) contains a repeating unit having a photoacid generating group, the content of the repeating unit having a photoacid generating group is preferably from 1 to 40 mol%, more preferably from 1 to 40 mol% of all the repeating units in the resin (A). It is 5 to 35 mol%, and more preferably 5 to 30 mol%.

The resin (A) can be synthesized in accordance with a conventional method such as radical polymerization. For example, as a general synthesis method, a polymerization method in which polymerization is carried out by dissolving a monomer type and an initiator in a solvent and heating is carried out; and a monomer is added dropwise to the heating solvent for 1 to 10 hours. The dropwise addition polymerization method of the type and the initiator solution is preferred, and the dropwise addition polymerization method is preferred. Examples of the reaction solvent include ethers such as tetrahydrofuran, 1,4-dioxane and diisopropyl ether; ketones such as methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate; and dimethylformamidine; A guanamine solvent such as an amine or dimethylacetamide; a solvent such as propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether or cyclohexanone to dissolve the resist composition of the present invention. It is preferred to carry out polymerization using the same solvent as that used in the resist composition of the present invention. Thereby, it is possible to suppress generation of partial parts during storage.

The polymerization is preferably carried out under an inert gas atmosphere such as nitrogen or argon. As a polymerization initiator, polymerization is initiated using a commercially available radical initiator (azo initiator, peroxide, etc.). As the radical initiator, an azo initiator is preferred, and an azo initiator having an ester group, a cyano group or a carboxyl group is more preferred. Preferred examples of the initiator include azobisisobutyronitrile, azobisdimethylvaleronitrile, and dimethyl-2,2'-azobis(2-methylpropionate). The initiator is added in an additional or divided amount as needed, and after completion of the reaction, it is introduced into a solvent, and the desired polymer is recovered by a method such as recovery of powder or solid component. The concentration of the reaction is 5 to 50% by mass, preferably 10 to 30% by mass. The reaction temperature is usually from 10 ° C to 150 ° C, preferably from 30 ° C to 120 ° C, and more preferably from 60 to 100 ° C. For the purification, the following general method can be applied: a liquid-liquid extraction method in which residual monomers or oligomer components are removed by washing with water or a suitable solvent; and a method of purifying in a solution state by ultrafiltration such as extraction and removal of only a specific molecular weight or less. Or a reprecipitation method in which the resin is solidified in a poor solvent by dropping the resin solution in a poor solvent, thereby removing residual monomers or the like; or cleaning the filtered resin slurry or the like in a solid state by using a poor solvent. The following purification methods.

The weight average molecular weight of the resin (A) is preferably from 1,000 to 200,000, more preferably from 3,000 to 20,000, most preferably from 5,000 to 15,000, as a polystyrene equivalent value measured by a GPC method. By setting the weight average molecular weight to 1,000 to 200,000, deterioration of heat resistance and dry etching resistance can be prevented, and deterioration of developability or viscosity can be prevented, and film formability can be deteriorated. Another preferred form of the weight average molecular weight of the resin (A) is 3,000 to 9,500 in terms of a polystyrene equivalent value measured by a GPC method. By setting the weight average molecular weight to 3,000 to 9,500, it is possible to particularly suppress the resist residue (hereinafter referred to as "scum"), and it is possible to form a more favorable pattern. The resin having a degree of dispersion (molecular weight distribution) of usually 1 to 5, preferably 1 to 3, more preferably 1.2 to 3.0, particularly preferably 1.2 to 2.0 is used. The smaller the degree of dispersion, the more excellent the resolution and the resist shape, and the smoothness of the side walls of the resist pattern and the excellent roughness.

In the sensitizing ray-sensitive or radiation-sensitive composition, the content of the resin (A) is preferably from 50 to 99.9% by mass, more preferably from 60 to 99.0% by mass, based on the total solid content. Further, in the sensitizing ray-sensitive or radiation-sensitive composition, the resin (A) may be used singly or in combination of plural kinds.

Further, the resin (A) may contain a repeating unit represented by the following formula (VI).

[Chemical Formula 26]

In the formula (VI), R ₆₁ , R ₆₂ and R ₆₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. Wherein R ₆₂ may be bonded to Ar ₆ to form a ring, and R _{62 in this case} represents a single bond or an alkylene group. X ₆ represents a single bond, -COO- or -CONR ₆₄ -. R ₆₄ represents a hydrogen atom or an alkyl group. L ₆ represents a single bond or an alkyl group. Ar ₆ represents an (n+1)-valent aromatic ring group, and when it is bonded to R ₆₂ to form a ring, it represents an (n+2)-valent aromatic ring group. When n ≥ 2, Y ₂ each independently represents a hydrogen atom or a group which is detached by the action of an acid. Among them, at least one of Y ₂ represents a group which is detached by the action of an acid. n represents an integer of 1 to 4. As the group Y ₂ which is detached by the action of an acid, the structure represented by the following formula (VI-A) is more preferable.

[Chemical Formula 27]

Here, L ₁ and L ₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group obtained by combining an alkyl group and an aryl group. M represents a single bond or a divalent linking group. Q represents an alkyl group, a cycloalkyl group which may contain a hetero atom, an aryl group which may contain a hetero atom, an amine group, an ammonium group, a thiol group, a cyano group or an aldehyde group. At least two of Q, M, and L ₁ may be bonded to form a ring (preferably a 5-member or a 6-membered ring).

The repeating unit represented by the above formula (VI) is preferably a repeating unit represented by the following formula (3).

[Chemical Formula 28]

In the formula (3), Ar ₃ represents an aromatic ring group. R ₃ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, a fluorenyl group or a heterocyclic group. M ₃ represents a single bond or a divalent linking group. Q ₃ represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group. At least two of Q ₃ , M ₃ and R ₃ may be bonded to form a ring.

The aromatic ring group represented by Ar ₃ is the same as Ar ₆ in the above formula (VI) when n in the above formula (VI) is 1, more preferably a phenyl group or a naphthyl group, and still more preferably Stretch phenyl.

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

[Chemical Formula 29]

The above-mentioned repeating unit having an acid-decomposable group may be one type or two or more types may be used in combination.

The content of the repeating unit having an acid-decomposable group in the resin (A) (total when it contains a plurality of kinds) is 5 mol% or more and 90 mol% or less based on all the repeating units in the above resin (A) Preferably, it is more preferably 5 mol% or more and 80 mol% or less, more preferably 5 mol% or more and 75 mol% or less, and more preferably 10 mol% or more and 70 mol% or less. 10 mol% or more and 65 mol% or less are optimal.

The resin (A) may contain a repeating unit represented by the following formula (V-1) or the following formula (V-2).

[Chemical Formula 30]

In the formula, R ₆ and R ₇ each independently represent a hydrogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an alkoxy group, a decyloxy group, a cyano group or a nitro group. An amine group, a halogen atom, an ester group (-OCOR or -COOR: R is an alkyl group having 1 to 6 carbon atoms or a fluorinated alkyl group) or a carboxyl group. n ₃ represents an integer of 0-6. n ₄ represents an integer of 0 to 4. X ₄ is a methylene group, an oxygen atom or a sulfur atom. Specific examples of the repeating unit represented by the general formula (V-1) or (V-2) are shown below, but are not limited thereto.

[Chemical Formula 31]

[Repeating unit (b) having a halogen atom in a side chain] The resin (A) may further have a repeating unit (b) having a halogen atom in a side chain. The repeating unit (b) having a ruthenium atom in the side chain is not particularly limited as long as it has a ruthenium atom in the side chain, and examples thereof include a (meth) acrylate-based repeating unit having a ruthenium atom and a ruthenium atom. Vinyl repeating unit or the like. The repeating unit (b) having a deuterium atom is preferably a repeating unit in which the polar group does not have a structure (acid-decomposable group) which is decomposed and desorbed by the action of an acid.

The repeating unit (b) having a ruthenium atom in a side chain is typically a repeating unit having a group having a ruthenium atom in a side chain, as a group having a ruthenium atom, and is described in the compound (1) The same.

The repeating unit having a ruthenium atom is preferably represented by the following formula (I).

[Chemical Formula 32]

In the above formula (I), L represents a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group, a -COO-Rt- group, and an -O-Rt- group. In the formula, Rt represents an alkylene group or a cycloalkyl group. It is preferred that L is a single bond or a -COO-Rt- group. Rt is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a -CH ₂ - group, a -(CH ₂ ) ₂ - group or a -(CH ₂ ) ₃ - group. In the above formula (I), X represents a hydrogen atom or an organic group. The organic group may, for example, be an alkyl group which may have a substituent such as a fluorine atom or a hydroxyl group, and a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group is preferred. In the above formula (I), A represents a group containing a ruthenium atom. Among them, a group represented by the above formula (a) or (b) is preferred. When A in the above formula (I) is a group represented by the above formula (a), the above formula (I) is represented by the following formula (Ia).

[Chemical Formula 33]

The resin (A) may have a repeating unit containing a ruthenium atom, or may have two or more repeating units containing a ruthenium atom. The content of the repeating unit containing a halogen atom is preferably from 1 to 30 mol%, more preferably from 1 to 20 mol%, and further preferably from 1 to 10 mol%, based on all the repeating units of the resin (A). .

Further, in the specification of the present application, a repeating unit having a structure in which a deuterium atom and a polar group are decomposed and desorbed by an action of an acid (the acid-decomposable group) is set to be suitable for a repeating unit having a deuterium atom, It is also applicable to repeating units having an acid-decomposable group.

Further, the resin (A) may have a repeating unit other than the above, and may have a repeating unit having the following structure, for example.

[Chemical Formula 34]

[(B) Compounds which generate acid by actinic rays or radiation] The sensitizing ray-sensitive or radiation-sensitive composition contains a compound which generates an acid by actinic rays or radiation (also referred to as "photoacid generator" PAG: Photo Acid Generator" or "Compound (B)") is preferred. The photoacid generator may be in the form of a low molecular compound or may be in a form incorporated into a part of the polymer. Further, the form of the low molecular compound and the form incorporated into a part of the polymer may be used in combination. When the photoacid generator is in the form of a low molecular compound, the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, and still more preferably 1,000 or less. When the photoacid generator is in the form of being incorporated into a part of the polymer, it may be incorporated into a part of the resin (A) or may be incorporated into a resin different from the resin (A). For the purpose of adjusting the cross-sectional shape of the pattern, the number of fluorine atoms possessed by the acid generator can be appropriately adjusted. By adjusting the fluorine atoms, it is possible to control the surface bias of the acid generator in the resist film. The more fluorine atoms the acid generator has, the more it is present on the surface. In the present invention, the photoacid generator is preferably in the form of a low molecular compound. The photoacid generator is not particularly limited as long as it is known, and an organic acid such as a sulfonic acid or a bis(alkylsulfonate) is produced by irradiation with actinic rays or radiation, preferably electron beam or extreme ultraviolet rays. A compound of at least any one of quinonemine or tris(alkylsulfonyl)methide is preferred. The photoacid generator may more preferably be a compound represented by the following formulas (ZI), (ZII) or (ZIII).

[Chemical Formula 35]

In the above formula (ZI), R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represent an organic group. The organic group of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ has a carbon number of usually 1 to 30, preferably 1 to 20. Further, two of R ₂₀₁ to R ₂₀₃ may be bonded to each other to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, a guanamine bond or a carbonyl group. Examples of the group formed by bonding two of R ₂₀₁ to R ₂₀₃ include an alkylene group (for example, a butyl group and a pentyl group). Z ^- represents a non-nucleophilic anion (an anion having a significantly lower ability to cause a nucleophilic reaction).

Examples of the non-nucleophilic anion include a sulfonic acid anion (an aliphatic sulfonate anion, an aromatic sulfonate anion, a camphorsulfonate anion, etc.), a carboxylic acid anion (an aliphatic carboxylic acid anion, an aromatic carboxylic acid anion, and the like). An aralkylcarboxylic acid anion or the like), a sulfonyl quinone imine anion, a bis(alkylsulfonyl) quinone imine anion, a tris(alkylsulfonyl) methide anion, or the like.

The aliphatic moiety in the aliphatic sulfonic acid anion and the aliphatic carboxylic acid anion may be an alkyl group or a cycloalkyl group, and preferably a linear or branched alkyl group having 1 to 30 carbon atoms and a carbon atom are mentioned. A number of 3 to 30 cycloalkyl groups.

The aromatic group in the aromatic sulfonic acid anion and the aromatic carboxylic acid anion is preferably an aryl group having 6 to 14 carbon atoms, and examples thereof include a phenyl group, a tolyl group, and a naphthyl group.

The alkyl group, the cycloalkyl group and the aryl group mentioned above may have a substituent. Specific examples thereof include a halogen atom such as a nitro group or a fluorine atom, a carboxyl group, a hydroxyl group, an amine group, a cyano group, an alkoxy group (preferably having 1 to 15 carbon atoms), and a cycloalkyl group (preferably carbon). The atomic number is 3 to 15), the aryl group (preferably having 6 to 14 carbon atoms), the alkoxycarbonyl group (preferably having 2 to 7 carbon atoms), and the fluorenyl group (preferably having 2 to 12 carbon atoms). An alkoxycarbonyloxy group (preferably having 2 to 7 carbon atoms), an alkylthio group (preferably having 1 to 15 carbon atoms), an alkylsulfonyl group (preferably having 1 to 15 carbon atoms). An alkyl sulfoximine sulfonyl group (preferably having 1 to 15 carbon atoms), an aryloxysulfonyl group (preferably having 6 to 20 carbon atoms), or an alkylaryloxysulfonyl group (compared to Preferably, the carbon number is 7 to 20), the cycloalkylaryloxysulfonyl group (preferably having 10 to 20 carbon atoms), the alkoxyalkoxy group (preferably having 5 to 20 carbon atoms), and a ring. An alkyl alkoxy alkoxy group (preferably having 8 to 20 carbon atoms) or the like. The aryl group and the ring structure of each group may further include an alkyl group (preferably having 1 to 15 carbon atoms) as a substituent.

The aralkyl group in the aralkyl carboxylate anion is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, and a naphthyl group. Butyl and the like.

Examples of the sulfonyl quinone imine anion include a saccharin anion.

The alkyl group in the bis(alkylsulfonyl)phosphonium anion and the tris(alkylsulfonyl)methide anion is preferably an alkyl group having 1 to 5 carbon atoms. Examples of the substituent of the alkyl group include a halogen atom, an alkyl group substituted with a halogen atom, an alkoxy group, an alkylthio group, an alkoxysulfonyl group, an aryloxysulfonyl group, and a cycloalkylaryloxy group. A sulfonyl group or the like, a fluorine atom or an alkyl group substituted with a fluorine atom is preferred. Further, the alkyl groups in the bis(alkylsulfonyl) quinone imine anion may be bonded to each other to form a ring structure. Thereby, the acid strength increases.

Examples of the other non-nucleophilic anion include phosphorus fluoride (for example, PF ₆ ^- ), boron fluoride (for example, BF ₄ ^- ), and cesium fluoride (for example, SbF ₆ ^- ).

As a non-nucleophilic anion, an aliphatic sulfonate anion having at least the α position of the sulfonic acid substituted by a fluorine atom, an aromatic sulfonic acid anion substituted with a fluorine atom or a group having a fluorine atom, and a double substituted with an alkyl group via a fluorine atom A (alkylsulfonyl) quinone imine anion and a tri(alkylsulfonyl)methide anion having an alkyl group substituted with a fluorine atom are preferred. The non-nucleophilic anion is more preferably a perfluoroaliphatic sulfonic acid anion (further preferably having 4 to 8 carbon atoms), a benzenesulfonic acid anion having a fluorine atom, and still more preferably a nonafluorobutanesulfonic acid anion. Perfluorooctanesulfonate anion, pentafluorobenzenesulfonate anion, 3,5-bis(trifluoromethyl)benzenesulfonate anion.

From the viewpoint of acid strength, the sensitivity is improved when the pKa of the generated acid is -1 or less, which is preferable.

Further, examples of the non-nucleophilic anion include an anion represented by the following formula (AN1).

[Chemical Formula 36]

In the formula, Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. R ¹ and R ² each independently represent a hydrogen atom, a fluorine atom or an alkyl group, and when a plurality of R ¹ and R ^{2 are present, they} may be the same or different. L represents a divalent linking group, and L may be the same or different when there are a plurality of plural. A represents a cyclic organic group. x represents an integer of 1 to 20, y represents an integer of 0 to 10, and z represents an integer of 0 to 10.

The general formula (AN1) will be described in further detail. The alkyl group in the alkyl group substituted with a fluorine atom of Xf preferably has 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms. Further, an alkyl group substituted with a fluorine atom of Xf is preferably a perfluoroalkyl group. Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. Specific examples of Xf include a fluorine atom, CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , CH ₂ CF ₃ , CH ₂ CH ₂ CF ₃ , CH ₂ C ₂ F ₅ , and CH. ₂ CH ₂ C ₂ F ₅ , CH ₂ C ₃ F ₇ , CH ₂ CH ₂ C ₃ F ₇ , CH ₂ C ₄ F ₉ , CH ₂ CH ₂ C ₄ F ₉ , wherein a fluorine atom and CF ₃ are preferred. . Both Xf are particularly excellent for fluorine atoms.

The alkyl group of R ¹ and R ² may have a substituent (preferably a fluorine atom), and those having 1 to 4 carbon atoms are preferred. More preferably, it is a perfluoroalkyl group having 1 to 4 carbon atoms. Specific examples of the alkyl group having a substituent of R ¹ and R ² include CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , C ₅ F ₁₁ , C ₆ F ₁₃ , and C _{7 .} F ₁₅ , C ₈ F ₁₇ , CH ₂ CF ₃ , CH ₂ CH ₂ CF ₃ , CH ₂ C ₂ F ₅ , CH ₂ CH ₂ C ₂ F ₅ , CH ₂ C ₃ F ₇ , CH ₂ CH ₂ C ₃ F _7. CH ₂ C ₄ F ₉ , CH ₂ CH ₂ C ₄ F ₉ , wherein CF ₃ is preferred. R ¹ and R ^{2 are} preferably a fluorine atom or CF ₃ .

x is preferably from 1 to 10, more preferably from 1 to 5. y is preferably 0 to 4, and 0 is more preferred. z is preferably 0 to 5, and more preferably 0 to 3. The divalent linking group of L is not particularly limited, and examples thereof include -COO-, -OCO-, -CO-, -O-, -S-, -SO-, -SO ₂ -, alkylene, and extens. A cycloalkyl group, an alkenyl group, or a linking group obtained by a plurality of such linkages, and a linking group having a total carbon number of 12 or less are preferred. Among them, -COO-, -OCO-, -CO-, -O- are preferred, and -COO-, -OCO- is more preferred.

The cyclic organic group of A is not particularly limited as long as it has a cyclic structure, and examples thereof include an alicyclic group, an aryl group, and a heterocyclic group (including not only aromatics but also having no Aromatic) and so on. As the alicyclic group, it may be a monocyclic ring or a polycyclic ring, a cyclopentyl group such as a cyclopentyl group, a cyclohexyl group or a cyclooctyl group, a cycloalkyl group, a decyl group, a tricyclodecyl group, a tetracyclodecyl group, or a tetracyl group. A polycyclic cycloalkyl group such as a cyclododecyl group or an adamantyl group is preferred. Among them, from the viewpoint of suppressing the diffusibility in the film in the post-exposure heating process and improving the MEEF (mask error enhancement factor), a thiol group, a tricyclodecyl group, a tetracyclodecane An alicyclic group having a high volume structure having 7 or more carbon atoms such as a tetracyclododecyl group or an adamantyl group is preferred. Examples of the aryl group include a benzene ring, a naphthalene ring, a phenanthrene ring, and an anthracene ring. Examples of the heterocyclic group include those derived from a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Among them, those derived from a furan ring, a thiophene ring, and a pyridine ring are preferred.

Further, the lactone structure may be mentioned as a cyclic organic group, and a lactone structure represented by the above formula (LC1-1) to (LC1-17) may be mentioned as a specific example.

The cyclic organic group may have a substituent, and examples of the substituent include an alkyl group (which may be any of a straight chain, a branch, and a ring, preferably having 1 to 12 carbon atoms), and a naphthenic ring. a group (which may be any of a monocyclic, polycyclic, or spiro ring, preferably having 3 to 20 carbon atoms), an aryl group (preferably having 6 to 14 carbon atoms), a hydroxyl group, an alkoxy group, and an ester group. , amidino group, urethane group, ureido group, thioether group, sulfonylamino group, sulfonate group, and the like. Further, the carbon constituting the cyclic organic group (the carbon contributing to the formation of the ring) may be a carbonyl carbon.

_Examples of the organic group of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ include an aryl group, an alkyl group, and a cycloalkyl group. It is preferred that at least one of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is an aryl group, and all three are aryl groups. The aryl group may be a heteroaryl group such as a hydrazine residue or a pyrrole residue, in addition to a phenyl group or a naphthyl group. The alkyl group and the cycloalkyl group of R ₂₀₁ to R ₂₀₃ are preferably a linear or branched alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms. As the alkyl group, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group or the like can be more preferably mentioned. As the cycloalkyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group or the like can be more preferably mentioned. These groups may further have a substituent. Examples of the substituent include a halogen atom such as a nitro group or a fluorine atom, a carboxyl group, a hydroxyl group, an amine group, a cyano group, an alkoxy group (preferably having 1 to 15 carbon atoms), and a cycloalkyl group (preferably carbon). The atomic number is 3 to 15), the aryl group (preferably having 6 to 14 carbon atoms), the alkoxycarbonyl group (preferably having 2 to 7 carbon atoms), and the fluorenyl group (preferably having 2 to 12 carbon atoms). And an alkoxycarbonyloxy group (preferably having 2 to 7 carbon atoms), but is not limited thereto.

Preferred examples of the anion represented by the formula (AN1) include the followings. In the following examples, A represents a cyclic organic group. SO ₃ -CF ₂ -CH ₂ -OCO-A, SO ₃ -CF ₂ -CHF-CH ₂ -OCO-A, SO ₃ -CF ₂ -COO-A, SO ₃ -CF ₂ -CF ₂ -CH ₂ - A, SO ₃ -CF ₂ -CH(CF ₃ )-OCO-A

In the general formulae (ZII) and (ZIII), R ₂₀₄ to R ₂₀₇ each independently represent an aryl group, an alkyl group or a cycloalkyl group.

The aryl group, the alkyl group or the cycloalkyl group of R ₂₀₄ to R ₂₀₇ is the same as the aryl group described as the aryl group, the alkyl group or the cycloalkyl group of R ₂₀₁ to R ₂₀₃ in the compound (ZI). The aryl group, the alkyl group or the cycloalkyl group of R ₂₀₄ to R ₂₀₇ may have a substituent. The substituent may also be an aryl group, an alkyl group or a cycloalkyl group of R ₂₀₁ to R ₂₀₃ in the compound (ZI).

Z ^- represents a non-nucleophilic anion, and is the same as the non-nucleophilic anion of Z ^- in the general formula (ZI).

In the present invention, the photoacid generator is generated by irradiation with an electron beam or extreme ultraviolet rays in a volume of 130 Å ³ or more from the viewpoint of suppressing diffusion of an acid generated by exposure to a non-exposed portion and improving the resolution. acid compound (more preferably a sulfonic acid) it is preferred, (more preferably a sulfonic acid) compound to produce the volume size than 190Å ³ is more preferably an acid, to produce a volume size of 270Å ³ or more acids (more preferably acid) is further preferred compound of the generated volume size than 400Å ³ acid (more preferably sulfonic acid) the compound is particularly preferred. However, the sensitivity or solubility in a coating solvent consideration the volume is 2000Å ³ or less is preferred, 1500Å ³ or less is further preferred. The value of the above volume was determined using "WinMOPAC" manufactured by Fujitsu Limited. That is, the chemical structure of the acid involved in each case is first input, and then the structure is taken as the initial structure and the most stable solid shape of each acid is determined by using the molecular force field calculation of the MM3 method, and then, for the most The stable three-dimensional shape is calculated using the molecular orbital calculation of the PM3 method, whereby the "accessible volume" of each acid can be calculated.

As a photo-acid generator, the <0368>-<0377> section of JP-A-2014-41328, and the <0240>-<0262> section of JP-A-2013-228681 (corresponding US Patent Application Publication) <0339> of the specification of 2015/004533, the contents of which are incorporated herein. Further, as a preferable specific example, the following compounds are mentioned, but it is not limited to these.

[Chemical Formula 37]

[Chemical Formula 38]

[Chemical Formula 39]

[Chemical Formula 40]

The photoacid generator may be used alone or in combination of two or more. The content of the photoacid generator in the sensitizing ray-sensitive or radiation-sensitive linear composition is preferably from 0.1 to 50% by mass, more preferably from 5 to 50% by mass, based on the total solid content of the composition, further preferably. It is 8 to 40% by mass. In particular, in order to achieve both high sensitivity and high resolution in electron beam or extreme ultraviolet light exposure, the content of the photoacid generator is preferably higher, more preferably 10 to 40% by mass, most preferably 10 to 35. quality%.

(C) Solvent The photosensitive ray-sensitive or radiation-sensitive composition used in the present invention preferably contains a solvent (also referred to as "resist solvent"). The solvent may contain isomers (compounds having the same number of atoms and different structures). Further, the isomer may contain only one kind, and may also contain plural kinds. The solvent contains (M1) propylene glycol monoalkyl ether carboxylate and is selected from (M2) propylene glycol monoalkyl ether, lactate, acetate, alkoxypropionate, chain ketone, cyclic ketone, lactone At least one of at least one of the groups consisting of alkylene carbonates is preferred. Further, the solvent may further contain components other than the components (M1) and (M2).

The component (M1) is preferably at least one selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, and propylene glycol monoethyl ether acetate, and propylene glycol monomethyl ether acetate Ester is especially good.

As the component (M2), the following are preferred. As the propylene glycol monoalkyl ether, propylene glycol monomethyl ether or propylene glycol monoethyl ether is preferred. As the lactate, ethyl lactate, butyl lactate or propyl lactate is preferred. As acetate, methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, isoamyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate or acetic acid 3- Methoxybutyl ester is preferred. Butyl butyrate is also preferred. As the alkoxypropionate, methyl 3-methoxypropionate (MMP) or ethyl 3-ethoxypropionate (EEP) is preferred. As a chain ketone, 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, phenyl Acetone, methyl ethyl ketone, methyl isobutyl ketone, acetamidine acetone, acetone acetone, ionone, diacetone alcohol, acetamethanol, acetophenone, methylnaphthyl ketone or methyl amyl ketone. As the cyclic ketone, methylcyclohexanone, isophorone or cyclohexanone is preferred. As the lactone, γ-butyrolactone is preferred. As the alkylene carbonate, propyl carbonate is preferred.

As component (M2), propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate, methyl amyl ketone, cyclohexanone, butyl acetate, amyl acetate, γ-butyrolactone or Propyl carbonate is more preferred.

In addition to the above components, an ester solvent having 7 or more carbon atoms (7 to 14 is preferred, 7 to 12 is more preferred, 7 to 10 is more preferred) and the number of hetero atoms is 2 or less is preferably used.

Preferable examples of the ester solvent having 7 or more carbon atoms and 2 or less hetero atoms include pentyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, and hexyl acetate. Amyl propionate, hexyl propionate, butyl propionate, isobutyl isobutyrate, heptyl propionate, butyl butyrate, etc., are particularly preferably used with isoamyl acetate.

As the component (M2), it is preferred to use a flash point (hereinafter, also referred to as fp) of 37 ° C or higher. As such a component (M2), propylene glycol monomethyl ether (fp: 47 ° C), ethyl lactate (fp: 53 ° C), ethyl 3-ethoxypropionate (fp: 49 ° C), methyl amyl ketone (fp: 42 ° C), cyclohexanone (fp: 44 ° C), amyl acetate (fp: 45 ° C), methyl 2-hydroxyisobutyrate (fp: 45 ° C), γ-butyrolactone (fp: 101 ° C) or propyl carbonate (fp: 132 ° C) is preferred. Among these, propylene glycol monoethyl ether, ethyl lactate, amyl acetate or cyclohexanone is further preferred, and propylene glycol monoethyl ether or ethyl lactate is particularly preferred. In addition, "flash point" here means the value as described in the reagent catalogue of the Tokyo Chemical Industry Co., Ltd. or Sigma-Aldrich company.

The solvent-containing component (M1) is preferred. The solvent is preferably a composition solvent consisting essentially only of the component (M1) or a mixture of the component (M1) and other components. In the latter case, both the solvent-containing component (M1) and the component (M2) are further preferable.

The mass ratio of the component (M1) to the component (M2) is preferably in the range of 100:0 to 15:85, more preferably in the range of 100:0 to 40:60, and in the range of 100:0 to 60:40. The scope is further preferred. That is, the solvent is composed only of the component (M1) or both the component (M1) and the component (M2), and the mass ratios are preferably as follows. That is, in the latter case, the mass ratio of the component (M1) to the component (M2) is preferably 15/85 or more, more preferably 40/60 or more, and still more preferably 60/40 or more. According to this configuration, the number of development defects can be further reduced

Further, when the solvent contains both the component (M1) and the component (M2), the mass ratio of the component (M1) to the component (M2) is, for example, 99/1 or less.

As described above, the solvent may further contain components other than the components (M1) and (M2). In this case, the content of the components other than the components (M1) and (M2) is preferably in the range of 5 mass% to 30 mass% with respect to the total amount of the solvent.

The content of the solvent in the sensitizing ray-sensitive or radiation-sensitive composition is preferably such that the solid content concentration of all the components is from 0.5 to 30% by mass, more preferably from 1 to 20% by mass. In this case, the coatability of the sensitizing ray or the radiation sensitive composition can be further improved. For the purpose of adjusting the thickness of the resist film to be formed, the solid content concentration of the sensitizing ray or the radiation sensitive composition can be appropriately adjusted.

(E) Basic compound In order to reduce the change in performance caused by the elapse of time from exposure to heating, it is preferred that the sensitizing ray-sensitive or radiation-sensitive composition contains (E) a basic compound. The basic compound is preferably a compound having a structure represented by the following general formulae (A) to (E).

[Chemical Formula 41]

In the general formulae (A) and (E), R ²⁰⁰ , R ²⁰¹ and R ²⁰² may be the same or different and each represent a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), or a cycloalkyl group (preferably The carbon number is 3 to 20) or the aryl group (preferably having 6 to 20 carbon atoms), and R ²⁰¹ and R ²⁰² may be bonded to each other to form a ring.

The alkyl group is preferably an alkyl group having a substituent, an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms or a cyanoalkyl group having 1 to 20 carbon atoms. . R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ may be the same or different and each represent an alkyl group having 1 to 20 carbon atoms. The alkyl group in the above formulae (A) and (E) is preferably unsubstituted.

Preferred examples of the compound include anthracene, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine, etc., as further preferred compounds, a compound having an imidazole structure, a diazabicyclo structure, an onium hydroxide structure, an onium carboxlate structure, a trialkylamine structure, an aniline structure or a pyridine structure, having a hydroxyl group and/or an ether An alkylamine derivative of a bond, an aniline derivative having a hydroxyl group and/or an ether bond, and the like.

Examples of the compound having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole and the like. Examples of the compound having a diazabicyclo structure include 1,4-diazabicyclo[2.2.2]octane and 1,5-diazabicyclo[4.3.0]non-5-ene, 1. 8-Diazabicyclo[5.4.0]undec-7-ene. Examples of the compound having a ruthenium hydroxide structure include triarylsulfonium hydroxide, benzamidine methylhydrazine hydroxide, and barium hydroxide having a 2-oxoalkyl group. Specifically, triphenyl hydroxide is exemplified. Base, tris(t-butylphenyl)phosphonium hydroxide, bis(t-butylphenyl)phosphonium hydroxide, benzamidine methylthiophene hydroxide, 2-oxopropylthiophene hydroxide, etc. . The compound having a ruthenium carboxylate structure is one in which the anion portion of the compound having a ruthenium hydroxide structure is a carboxylic acid ester, and examples thereof include acetate, adamantane-1-carboxylate, and perfluoroalkyl carboxylate. Wait. Examples of the compound having a trialkylamine structure include tri(n-butyl)amine and tri(n-octyl)amine. Examples of the aniline compound include 2,6-diisopropylaniline, N,N-dimethylaniline, N,N-dibutylaniline, and N,N-dihexylaniline. Examples of the alkylamine derivative having a hydroxyl group and/or an ether bond include ethanolamine, diethanolamine, triethanolamine, tris(methoxyethoxyethyl)amine, and the like. Examples of the aniline derivative having a hydroxyl group and/or an ether bond include N,N-bis(hydroxyethyl)aniline.

Further preferred examples of the basic compound 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 preferred. The amine compound is preferably a tertiary amine compound. The amine compound is a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group, in addition to the alkyl group, as long as at least one alkyl group (preferably having 1 to 20 carbon atoms) is bonded to the nitrogen atom. (preferably having 6 to 12 carbon atoms) may be bonded to a nitrogen atom. Further, the amine compound preferably has an oxygen atom in the alkyl chain and an oxygen-extended alkyl group. The number of the oxygen alkyl groups is one or more in the molecule, preferably from 3 to 9, more preferably from 4 to 6. Among the oxygen alkyl groups, an oxygen-extended ethyl group (-CH ₂ CH ₂ O-) or an oxygen-extended propyl group (-CH(CH ₃ )CH ₂ O- or -CH ₂ CH ₂ CH ₂ O-) is preferred. Further, it is preferably an oxygen-extended ethyl 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 preferred. The ammonium salt compound is a cycloalkyl group (preferably having 3 to 20 carbon atoms) or a aryl group, in addition to an alkyl group, as long as at least one alkyl group (preferably having 1 to 20 carbon atoms) is bonded to the nitrogen atom. The group (preferably having 6 to 12 carbon atoms) may be bonded to the nitrogen atom. The ammonium salt compound preferably has an oxygen atom in the alkyl chain and forms an oxygen-extended alkyl group. The number of the oxygen alkyl groups is one or more in the molecule, preferably from 3 to 9, more preferably from 4 to 6. Among the oxygen alkyl groups, an oxygen-extended ethyl group (-CH ₂ CH ₂ O-) or an oxygen-extended propyl group (-CH(CH ₃ )CH ₂ O- or -CH ₂ CH ₂ CH ₂ O-) is preferred. Further, it is preferably an oxygen-extended ethyl group. The anion of the ammonium salt compound may, for example, be a halogen atom, a sulfonate, a boric acid ester or a phosphate ester. Among them, a halogen atom or a sulfonate is preferred. As the halogen atom, a chloride, a bromide or an iodide is particularly preferable, and as the sulfonate, an organic sulfonate having 1 to 20 carbon atoms is particularly preferable. The organic sulfonate may, for example, be an alkylsulfonate or an arylsulfonate having 1 to 20 carbon atoms. The alkyl group of the alkyl sulfonate may have a substituent, and examples of the substituent include a fluorine atom, a chlorine atom, a bromine atom, an alkoxy group, a decyl group, and an aryl group. Specific examples of the alkyl sulfonate include methanesulfonate, ethanesulfonate, butanesulfonate, hexanesulfonate, octanesulfonate, benzylsulfonate, and trisole. Fluoromethanesulfonate, pentafluoroethanesulfonate, nonafluorobutanesulfonate, and the like. The aryl group of the aryl sulfonate may, for example, be a benzene ring, a naphthalene ring or an anthracene ring. The benzene ring, the naphthalene ring and the anthracene ring may have a substituent, and as the substituent, a linear or branched alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms is preferable. Specific examples of the linear or branched alkyl group and the cycloalkyl group include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, a n-hexyl group, and a ring. Heji and so on. Examples of the other substituent include an alkoxy group having 1 to 6 carbon atoms, a halogen atom, a cyano group, a nitro group, a decyl group, and a decyloxy 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 the 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 carboxylate group, a sulfonate group, an aryl group, an aralkyl group, and a decyloxy group. , aryloxy and the like. The substitution position of the substituent may be any of the 2 to 6 positions. The number of substituents may be any of the range of 1 to 5.

It is preferred to have at least one oxygen-extension alkyl group between the phenoxy group and the nitrogen atom. The number of the oxygen alkyl groups is one or more in the molecule, preferably from 3 to 9, more preferably from 4 to 6. Among the oxygen alkyl groups, an oxygen-extended ethyl group (-CH ₂ CH ₂ O-) or an oxygen-extended propyl group (-CH(CH ₃ )CH ₂ O- or -CH ₂ CH ₂ CH ₂ O-) is preferred. Further, it is preferably an oxygen-extended ethyl group.

An amine compound having a phenoxy group can be added with an aqueous solution of a strong base such as sodium hydroxide, potassium hydroxide or tetraalkylammonium by heating a monomer having a phenoxy group or a secondary amine and a halogen alkyl ether. Thereafter, it is obtained by extraction with an organic solvent such as ethyl acetate or chloroform. Alternatively, it may be reacted by heating a primary or secondary amine and a halogenated alkyl ether having a phenoxy group at the terminal, and then adding an aqueous solution of a strong base such as sodium hydroxide, potassium hydroxide or tetraalkylammonium, and then using acetic acid. It is obtained by extracting an organic solvent such as ethyl ester or chloroform.

(Compound (PA) which has a proton-receptive functional group and which is decomposed by irradiation with actinic rays or radiation to cause a decrease in proton acceptor property, or a compound which is changed from proton acceptor to acid) The radiation sensitive composition may further contain a compound (hereinafter, also referred to as a compound (PA)) as a basic compound having a proton acceptor functional group and decomposing by actinic rays or radiation to generate protons. A compound whose receptor is reduced, disappears, or becomes acidic by proton acceptability.

The proton acceptor functional group refers to a functional group having a group or an electron capable of electrostatically interacting with a proton, and for example, a functional group having a macrocyclic structure such as a cyclic polyether, or having a π-inclusive The yoke does not share the functional group of the nitrogen atom of the electron pair. The nitrogen atom having an unshared electron pair which does not participate in π conjugate is, for example, a nitrogen atom having a partial structure represented by the following general formula.

[Chemical Formula 42]

Preferred partial structures of the proton acceptor functional group include crown ether, azacrown ether, first to tertiary amine, pyridine, imidazole, pyrazine structure and the like.

The compound (PA) is decomposed by irradiation with actinic rays or radiation to cause a compound having a reduced proton acceptor property, disappearing, or becoming acidic by proton acceptability. Wherein, the decrease or disappearance of proton acceptor or the change from proton acceptor to acid refers to a change in proton acceptor caused by proton addition to a proton acceptor functional group, specifically, when When a proton accepting functional group compound (PA) and a proton form a proton adduct, the equilibrium constant in the chemical equilibrium is reduced.

Specific examples of the compound (PA) include the following compounds. Further, as a specific example of the compound (PA), for example, those described in paragraphs 0421 to 0428 of JP-A-2014-41328 and paragraphs 0108 to 0116 of JP-A-2014-134686 can be used. Incorporated into this specification.

[Chemical Formula 43]

[Chemical Formula 44]

These basic compounds may be used singly or in combination of two or more.

The amount of the basic compound to be used is usually 0.001 to 10% by mass, preferably 0.01 to 5% by mass based on the solid content of the sensitizing ray-sensitive or radiation-sensitive composition.

The acid generator and the basic compound are preferably used in the composition in an acid generator/basic compound (mole ratio) = 2.5 to 300. In other words, from the viewpoint of the sensitivity and the resolution, the molar ratio is preferably 2.5 or more, and from the viewpoint of suppressing the resolution of the resist pattern which is thickened over time after the post-exposure heat treatment, 300 is considered. The following are preferred. The acid generator/basic compound (mole ratio) is more preferably 5.0 to 200, still more preferably 7.0 to 150.

As the basic compound, for example, a compound (an amine compound, a guanamine-containing compound, a urea compound, a nitrogen-containing heterocyclic compound, or the like) described in paragraphs 0140 to 0144 of JP-A-2013-11833 can be used.

<Hydrophobic Resin> The sensitizing ray-sensitive or radiation-sensitive composition may have a hydrophobic resin different from the resin (A) in addition to the above resin (A). The hydrophobic resin is preferably designed to be biased on the surface of the resist film, but unlike the surfactant, it is not necessary to have a hydrophilic group in the molecule, and it is also possible to prevent the polar/nonpolar substance from being uniformly mixed. The effect of adding a hydrophobic resin is control of a static/dynamic contact angle with respect to the surface of the resist film of water, suppression of degassing, and the like.

The hydrophobic resin is preferably one or more selected from the group consisting of a "fluorine atom", a "deuterium atom", and a "CH ₃ partial structure contained in a side chain portion of the resin". The above is further preferred. Further, the hydrophobic resin preferably contains a hydrocarbon group having 5 or more carbon atoms. These groups may be present in the main chain of the resin or may be substituted in the side chain.

When the hydrophobic resin contains a fluorine atom and/or a ruthenium atom, the above-mentioned fluorine atom and/or ruthenium atom in the hydrophobic resin may be contained in the main chain of the resin or may be contained in the side chain.

When the hydrophobic resin contains a fluorine atom, it is preferably a resin 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. An 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 by a fluorine atom, and It has a substituent other than a fluorine atom. The cycloalkyl group having a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted by a fluorine atom, and may have a substituent other than a fluorine atom. The aryl group having a fluorine atom may be one in which at least one hydrogen atom of an aryl group such as a phenyl group or a naphthyl group is substituted by a fluorine atom, and may have a substituent other than a fluorine atom. Examples of the repeating unit having a fluorine atom or a ruthenium atom are exemplified in paragraph 0519 of US 2012/0251948 A1.

Further, as described above, it is preferred that the hydrophobic resin contains a CH ₃ moiety structure in the side chain portion. Here, the hydrophobic side chain moiety in the resin having the partial structure containing CH ₃ ethyl, propyl, etc. having the partial structure are CH _3. On the other hand, a methyl group directly bonded to the main chain of the hydrophobic resin (for example, an α-methyl group having a repeating unit of a methacrylic acid structure) is biased toward the surface of the hydrophobic resin due to the influence of the main chain. The effect of the chemistry is small and is therefore considered to be the CH ₃ partial structure in the present invention.

For the hydrophobic resin, the descriptions of <0348> to <0415> of JP-A-2014-010245 can be referred to, and the contents are incorporated in the specification of the present application.

In addition, as the hydrophobic resin, those described in JP-A-2011-248019, JP-A-2010-175859, and JP-A-2012-032544 are also preferably used.

When the sensitizing ray-sensitive or radiation-sensitive composition contains a hydrophobic resin, the content of the hydrophobic resin is preferably 0.01 to 20% by mass, preferably 0.01%, based on the total solid content of the sensitizing ray-sensitive or radiation-sensitive composition. 10% by mass is more preferable, and 0.05 to 8% by mass is further more preferable, and 0.5 to 5% by mass is particularly preferable.

In the pattern forming method of the present invention, a resist film may be formed on a substrate using the above-described sensitizing ray-sensitive or radiation-sensitive composition, and a top coat layer may be formed on the resist film to form a top coat layer. . The film thickness of the resist film is preferably from 10 to 100 nm, the film thickness of the top coat layer is preferably from 10 to 200 nm, more preferably from 20 to 100 nm, and particularly preferably from 40 to 80 nm. As a method of applying a sensitizing ray-sensitive or radiation-sensitive composition to a substrate, spin coating is preferred, and the number of revolutions is preferably from 1,000 to 3,000 rpm. For example, a suitable coating using a spin coater, a coater, or the like on a substrate (for example, ruthenium/ruthenium dioxide coating) in which a sensitizing ray-sensitive or radiation-sensitive composition is used for the production of a precision integrated circuit element is used. The method is applied and dried to form a resist film. Further, a known anti-reflection film can be applied in advance. Also, it is preferred to dry the resist film before forming the top coat layer. Next, the top coat composition is applied onto the obtained resist film by the same method as the above-described method of forming the resist film, and dried to form a top coat layer. For the resist film having the top coat layer in the upper layer, it is preferable to pass through the mask to irradiate electron beam (EB), X-ray or EUV light, and to perform baking (heating) for development. Thereby a good pattern can be obtained.

Surfactant (F) The sensitizing ray-sensitive or radiation-sensitive composition may further contain a surfactant (F). By using a surfactant, when an exposure light source having a wavelength of 250 nm or less, particularly 220 nm or less is used, a pattern having less adhesion and less development defects can be formed with good sensitivity and resolution. As the surfactant, fluorine-based and/or lanthanoid surfactants are particularly preferred. Examples of the fluorine-based and/or lanthanoid surfactants include the surfactants described in <0276> of the specification of U.S. Patent Application Publication No. 2008/0248425. Further, Eftop EF301 or EF303 (manufactured by Shin-Akita Kasei Co., Ltd.); Fluorad FC430, 431 or 4430 (manufactured by Sumitomo 3M Limited); Megafac F171, F173, F176, F189, F113, F110, F177, F120 can be used. Or R08 (manufactured by DIC CORPORATION); Surflon S-382, SC101, 102, 103, 104, 105 or 106 (manufactured by ASAHI GLASS CO., LTD.); Troy Sol S-366 (manufactured by Troy Chemical Industries Inc.); GF -300 or GF-150 (manufactured by TOAGOSEI CO., LTD.), Surflon S-393 (manufactured by SEIMI CHEMICAL CO., LTD.); Eftop EF121, EF122A, EF122B, RF122C, EF125M, EF135M, EF351, EF352, EF801, EF802 or EF601 (manufactured by Gemco); PF636, PF656, PF6320 or PF6520 (manufactured by OMNOVA Solutions Inc.); or FTX-204G, 208G, 218G, 230G, 204D, 208D, 212D, 218D or 222D (manufactured by Neos Corporation). Further, a polyoxyalkylene polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as the lanthanoid surfactant.

Further, in addition to the well-known ones as shown above, the surfactant may also be used by a telomerization method (also referred to as a telomer method) or an oligomerization method (also referred to as a surfactant). The fluoroaliphatic compound produced by the oligomer method is synthesized. Specifically, a polymer having a fluoroaliphatic group derived from the fluoroaliphatic compound can be used as a surfactant. The fluoroaliphatic compound can be synthesized, for example, by the method described in JP-A-2002-90991. Further, a surfactant other than the fluorine-based and/or lanthanum-based surfactants described in <0280> of the specification of the US Patent Application Publication No. 2008/0248425 can also be used.

These surfactants may be used alone or in combination of two or more.

When the sensitizing ray-sensitive or radiation-sensitive composition contains a surfactant, the content thereof is preferably 0 to 2% by mass, more preferably 0.0001 to 2% by mass based on the total solid content of the composition, further preferably. It is 0.0005 to 1% by mass.

Other Additives (G) The sensitizing ray-sensitive or radiation-sensitive composition may further contain a dissolution inhibiting compound, a dye, a plasticizer, a photosensitizer, a light absorbing agent, and/or a compound which promotes solubility in a developing solution (for example, molecular weight a phenol compound of 1000 or less, or an alicyclic or aliphatic compound containing a carboxyl group).

The sensitizing ray-sensitive or radiation-sensitive composition may further contain a dissolution inhibiting compound. Here, the "dissolution inhibiting compound" is a compound having a molecular weight of 3,000 or less which is reduced in solubility in an organic developing solution by decomposition of an acid.

In the pattern forming method of the present invention, a non-chemically amplified resist composition can also be used. Examples of the non-chemically amplified resist composition include, for example, cutting of a main chain by irradiation with g-ray, h-ray, i-ray, KrF, ArF, EB, or EUV, and solubility due to a decrease in molecular weight. The resist material which has been changed (for example, as described in JP-A-2013-210411, JP-A No. <0025> to <0029>, <0056> or US Patent Publication No. 2015/0008211<0032> to <0036>, <0063> a resist material containing a copolymer of an α-chloroacrylate compound and an α-methylstyrene compound as a main component, etc.); accompanied by g rays, h rays, i rays, KrF, ArF, EB or EUV Hydrogen sesquioxane (HSQ), chlorine-substituted calixarene, which is produced by a decyl alcohol condensation reaction; contains a metal error that absorbs light such as g-ray, h-ray, i-ray, KrF, ArF, EB or EUV. a compound (magnesium, chromium, manganese, iron, cobalt, nickel, copper, zinc, silver, cadmium, indium, tin, antimony, cerium, zirconium, hafnium, etc., from the viewpoint of pattern formation, titanium, Zirconium, hafnium is preferred), the ligand is detached or combined with an acid generator and a resist exchange process (Japanese Laid-Open Patent Publication No. 2015-075500, <0017> to <0033>, <0037> to <0047>, Japanese Patent Laid-Open Publication No. 2012-185485, <0017> to <0032>, <0043> to <0044>, US Patent Publication No. 2012/0208125 <0042> to <0051>, <0066>, and a resist material described in JP-A-2011-253185, <0015> to <0060>. In addition, as the resist composition, the resist composition described in <0010> to <0062> and <0129> to <0165> described in JP-A-2008-83384 can be used.

The treatment liquid, the sensitizing ray-sensitive or radiation-sensitive composition of the present invention, and various materials used in the pattern forming method of the present invention (for example, a resist solvent, a developing solution, a rinsing liquid, and an antireflection film forming composition) The composition for forming a top coat layer or the like is preferably a metal-free, halogen-containing metal salt, an acid, an alkali or the like. The content of the impurities contained in the materials is preferably 1 ppm or less, more preferably 1 ppb or less, still more preferably 100 ppt or less, and particularly preferably 10 ppt or less, and substantially no (below the detection limit of the measuring device). optimal. As a method of removing impurities such as metals from various materials, for example, filtration using a filter and a purification process by distillation (especially thin film distillation, molecular distillation, etc.) can be mentioned. For example, "factory operation series" addition/distillation, July 31, 1992 issue, Chemical Industry Co., Ltd., "Chemical Handbook, September 30, 2004 issue, Asakura Bookstore, 95 pages" Page 102". The pore diameter of the filter is preferably 10 nm or less, more preferably 5 nm or less, and still more preferably 3 nm or less. As a material of the filter, a filter made of polytetrafluoroethylene, polyethylene, or nylon is preferable. The filter may also be a composite material in which the materials are combined with an ion exchange medium. The filter can also be cleaned by using an organic solvent in advance. In the filter filtration process, a plurality of filters may be connected in series or in parallel for use. When a plurality of filters are used, it is also possible to use a combination of filters having different apertures and/or materials. Moreover, various materials can be filtered in multiple times, and the process of multiple filtering can be a cyclic filtration process. Further, as a method for reducing impurities such as metals contained in various materials, a method of selecting a raw material having a small metal content as a raw material constituting various materials, and a method of filtering a raw material constituting each material may be mentioned; Teflon (registered trademark) A method in which the inside of the apparatus is lining or the like to perform distillation under the condition that contamination is suppressed as much as possible. The preferred conditions for filter filtration of the materials constituting the various materials are the same as those described above. In addition to filter filtration, it is also possible to remove impurities based on the adsorbent material, and it is also possible to use a filter filter and an adsorbent material in combination. As the adsorbent, a known adsorbent can be used. For example, an inorganic adsorbent such as tannin or zeolite, or an organic adsorbent such as activated carbon can be used.

<Storage container> An organic solvent (also referred to as an "organic treatment liquid") that can be used as a treatment liquid, a developer solution, and a rinse liquid, and is used in a chemically amplified or non-chemically amplified resist film having a storage portion. It is preferable that the pattern is formed in a storage container for the organic treatment liquid. As the storage container, for example, the inner wall of the accommodating portion that is in contact with the organic treatment liquid is made of a resin different from any of polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin, or rust/metal is applied. It is preferable that the storage container for the organic processing liquid for pattern formation of the resist film formed by the metal for elution prevention is preferable. A predetermined organic solvent serving as an organic processing liquid for pattern formation of a resist film is accommodated in the accommodating portion of the storage container, and when the pattern of the resist film is formed, a person who discharges from the accommodating portion can be used.

When the storage container further has a sealing portion for sealing the storage portion, the sealing portion is also different from one or more resins selected from the group consisting of polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin. It is preferable to form a resin or a metal which has been subjected to rust prevention/metal elution prevention treatment.

Here, the sealing portion refers to a member that can block the storage portion from the outside air, and preferably includes a gasket or an O-ring.

A resin different from one or more resins selected from the group consisting of polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin is preferably a perfluoro resin.

Examples of the perfluororesin include tetrafluoroethylene resin (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resin (PFA), tetrafluoroethylene-hexafluoropropylene copolymer resin (FEP), and tetrafluoroethylene. Ethylene-ethylene copolymer resin (ETFE), chlorotrifluoroethylene-ethylene copolymer resin (ECTFE), vinylidene chloride resin (PVDF), chlorotrifluoroethylene copolymer resin (PCTFE), vinyl fluoride resin (PVF), etc. .

Examples of the particularly preferred perfluororesin include a tetrafluoroethylene resin, a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resin, and a tetrafluoroethylene-hexafluoropropylene copolymer resin.

Examples of the metal in the metal subjected to the rust preventive/metal elution prevention treatment include carbon steel, alloy steel, nickel chrome steel, nickel chrome molybdenum steel, chrome steel, chrome molybdenum steel, and manganese steel.

As the rust preventive/metal elution prevention treatment, a coating film technique is preferred.

The film coating technology is roughly divided into three types: metal coating (various plating), inorganic coating (various passivation treatment, glass, cement, ceramics, etc.) and organic coating (rustproof oil, paint, rubber, plastic).

As a preferable film-coating technique, surface treatment using an rust preventive oil, a rust preventive agent, a preservative, a chelate compound, a peelable plastic, and an lining agent is mentioned.

Among them, various chromate, nitrite, citrate, phosphate, oleic acid, dimer acid, naphthenic acid and other carboxylic acids, metal carboxylic acid soaps, sulfonates, amine salts, esters (higher fatty acid glycerin Preservatives such as esters or phosphates, chelating compounds such as ethylenediaminetetraacetic acid, gluconic acid, nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, and fluororesin lining good. Particularly preferred are phosphate treatments and fluororesin liners.

Further, although it is not directly rust-proof as compared with the direct coating treatment, as a treatment method for prolonging the rust-preventing period by the coating treatment, the "pre-treatment" before the stage involved in the rust-preventing treatment is also employed. Preferably.

As a specific example of such pretreatment, a treatment for removing various corrosion factors such as chloride or sulfate present on the metal surface by washing or polishing is preferred.

Specific examples of the storage container include the following.

・Integrated Fluoro Pure PFA composite cylinder from Entegris (liquid inner surface; PFA resin lining) ・JFE steel cylinder (liquid inner surface; zinc phosphate coating)

In addition, the storage container which can be used in the present invention is also described in JP-A-H11-021393, <0013> to <0030>, and JP-A-10-45961, <0012> to <0024>. Container.

In order to prevent malfunction of the sputum piping or various components (filters, O-rings, hoses, etc.) accompanying charging of static electricity and subsequent electrostatic discharge, a conductive compound may be added to the organic processing liquid. The conductive compound is not particularly limited, and examples thereof include methanol. The amount of addition is not particularly limited, and from the viewpoint of maintaining preferable development characteristics, 10% by mass or less is preferable, and further preferably 5% by mass or less. As the member of the sputum pipe, various pipes made of SUS (stainless steel) or polyethylene, polypropylene or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) which have been subjected to antistatic treatment can be used. As the filter or the O-ring, polyethylene, polypropylene or a fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin or the like) subjected to antistatic treatment can also be used.

Further, the developer and the rinsing liquid are generally stored in a waste liquid tank through a pipe after use. In this case, when a hydrocarbon-based solvent is used as the rinsing liquid, the resist dissolved in the developing solution is deposited, and in order to prevent adhesion to the back surface of the wafer or the side surface of the pipe, the solvent for dissolving the resist is again passed through the pipe. As a method of piping, a method of cleaning the back surface or the side surface of the substrate by washing with a solvent after washing with a rinsing liquid, or flowing the solvent of the dissolved resist without contacting the resist may be mentioned. So that it passes the piping method. The solvent to be used for the piping is not particularly limited as long as it can dissolve the resist, and examples thereof include the above-mentioned organic solvent, and propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, and propylene glycol can be used. Monopropyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol Monomethyl ether (PGME), propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-heptanone, ethyl lactate, 1-propanol, acetone, etc. . Among them, PGMEA, PGME, and cyclohexanone are preferably used.

The pattern obtained by the pattern forming method of the present invention is used as a mask, and an appropriate etching treatment, ion implantation, or the like is performed, whereby a semiconductor fine circuit, a stamping mold structure, a photomask, and the like can be manufactured.

The pattern formed by the above method can also be used for guiding pattern formation in DSA (Directed Self-Assembly) (for example, see ACS Nano Vol. 4 No. 8 pages 4815-4823). In addition, the pattern formed by the above-described method can be used, for example, as a core material of a spacer process disclosed in Japanese Laid-Open Patent Publication No. Hei No. 3-270227 and No. 2013-164509.

In addition, the process of producing a stamping die using the pattern forming method of the present invention is disclosed in, for example, Japanese Patent No. 4109085, JP-A-2008-162101, and "Nano-imprinting, technology development, and application expansion. ―Nano-imprinted substrate technology and the latest technology expansion--Editor: Hirai Yoshihiko (Frontier Publishing).

The reticle manufactured by the pattern forming method of the present invention may be a light-transmitting type mask used in an ArF excimer laser or the like, or a light-reflective type mask used in lithography of a reflection system using EUV light as a light source. cover.

The present invention also relates to a method of manufacturing an electronic component comprising the above-described pattern forming method of the present invention.

The electronic component manufactured by the method of manufacturing an electronic component of the present invention is suitably mounted on an electric and electronic device (a home appliance, an office appliance, a media-related device, an optical device, a communication device, or the like).

The present invention also relates to the above compound (1). The preferred range with respect to the compound (1) is as described. [Examples]

Hereinafter, the present invention will be further described in detail by way of examples, but the invention is not limited thereto.

[Preparation of Resist Composition] As the resin (A) in the resist composition, the following were used.

As the resin (A), the following resins (A-1) to (A-15) were used. The resins (A-1) to (A-15) were synthesized in accordance with the method described in JP-A-2013-8020. The structures of the resins (A-1) to (A-15) and the composition ratio of each repeating unit (molar ratio; sequentially corresponding from the left), weight average molecular weight (Mw), and dispersity (Mw/Mn) are shown below. (Mn is a number average molecular weight).

[Chemical Formula 45]

[Chemical Formula 46]

【Table 1】

As the photoacid generator, the following were used. [Chemical Formula 47]

As the basic compound, the following were used.

[Chemical Formula 48]

As the crosslinking agent, the following were used.

[Chemical Formula 49]

As the surfactant, the following were used. W-1: Megafac F176 (manufactured by DIC CORPORATION) (fluorine) W-2: Megafac R08 (manufactured by DIC CORPORATION) (fluorine and lanthanide) W-3: polyoxyalkylene polymer KP-341 (Shin-Etsu Chemical) Co., Ltd. (manufactured by Co., Ltd.) W-4: Troy Sol S-366 (manufactured by Troy Chemical Industries Inc.) W-5: KH-20 (manufactured by Asahi Kasei Corporation) W-6: PolyFox ^TM PF-6320 (made by OMNOVA solution inc.) (fluorine system)

As the hydrophobic resin, the following were used.

[Chemical Formula 50]

As the solvent, the following were used. SL-1: propylene glycol monomethyl ether acetate (PGMEA) SL-2: propylene glycol monomethyl ether propionate SL-3: 2-heptanone SL-4: ethyl lactate SL-5: propylene glycol monomethyl ether (PGME SL-6: cyclohexanone

The components shown in the following Table 2 were dissolved in a solvent in the composition shown in Table 2, and each was filtered with a polyethylene filter having a pore size of 0.03 μm to prepare a resist composition.

【Table 2】

[Preparation of Treatment Liquid] Compounds X-1 to X-12 were used as the compound (1) contained in the treatment liquid. Hereinafter, the structures of X-1 to X-12 are shown. In the following structural formula, Et represents an ethyl group, tBu represents a third butyl group, C5 represents an n-pentyl group, and C8 represents an n-octyl group.

[Chemical Formula 51]

[Chemical Formula 52]

X-1 to X-12 were synthesized based on the following synthesis scheme. Reaction 1) Chemistry-a European Journal Vol. 17 (2011), pp. 5019-5023, Reaction 2) Experimental Chemistry Lecture 15 (Top), page 368, Reaction 3) Journal of Physical Chemistry B 116 (2012), pp. Page 4574

[Chemical Formula 53]

As the solvent of the treatment liquid, the following were used. SL-7: n-decane SL-8: n-undecane SL-9: diisobutyl ketone SL-10: pure water SL-11: 1-butanol

The components shown in the following Table 3 were dissolved in a solvent shown in the following Table 3, and filtered through a polyethylene filter having a pore size of 0.03 μm to prepare a treatment liquid (treatment liquid containing a Si compound).

【table 3】

As the resin for the upper layer film, the following resin was used. The structure of the resin, the composition ratio of each repeating unit (mol ratio; corresponding from the left), the weight average molecular weight (Mw), and the degree of dispersion (Mw/Mn) are shown below.

[Chemical Formula 54]

【Table 4】

T-1: Polyacrylic acid JULIMAR AC-10L (manufactured by Nippon Junyaku Co., Ltd.) T-2: poly ( N-vinylpyrrolidone) Luviskol K90 (manufactured by BASF JAPAN LTD.) T-3: (vinyl alcohol) 60/vinyl acetate 40) copolymer SMR-8M (manufactured by Shin-Etsu Chemica. Co., Ltd.) T-4: pullulan PI-20 (manufactured by HAYASHIBARA CO., LTD.)

As the additive, the following were used.

[Chemical Formula 55]

[Chemical Formula 56]

As the top coat solvent, the following were used. Y1: 4-methyl-2-pentanol (MIBC) Y2: decane Y3: diisoamyl ether Y4: 1-butanol Y5: isobutyl isobutyrate Y6: isobutanol

[Preparation of a composition for forming an upper layer film] The components shown in the following Table 5 were dissolved in a solvent, and a solution having a solid concentration of 2.0% by mass was prepared, and a polyethylene filter having a pore size of 0.04 μm was used. The composition for forming an upper layer film was prepared by filtration.

【table 5】

Using the above resist composition, a resist pattern was formed by the following operation.

DR-1: 3-methylbutyl acetate DR-2: butyl acetate DR-3: 2-heptanone DR-4: 2.38 mass% aqueous solution of tetramethylammonium hydroxide DR-5: undecane DR-6 : Diisobutyl ketone DR-7: undecane / diisobutyl ketone = 30/70 (mass ratio) mixture DR-8: decane DR-9: decane / diisobutyl ketone = 15 / 85 (mass ratio) mixture DR-10: diisoamyl ether DR-11: diisoamyl ether / diisobutyl ketone = 20/80 (mass ratio) mixture DR-12: 3-methyl butyl acetate /Diisobutyl ketone = 30/70 (mass ratio) mixture DR-13: pure water

(Formation of Line and Space Pattern) An organic anti-reflection film ARC29SR (manufactured by Brewer Co., Ltd.) was applied onto a ruthenium wafer, and baked at 205 ° C for 60 seconds to form an anti-reflection film having a film thickness of 86 nm. The resist composition shown in the following Table 6 was applied thereon, and baked at 120 ° C for 60 seconds to form a resist film having a film thickness of 60 nm.

[Formation of Upper Film] The composition for forming an overlayer film shown in Table 6 was applied onto the resist film to form an upper layer film having a film thickness of 30 nm.

Next, an EUV exposure apparatus (Micro Exposure Tool, Ni0.3, Quadrupole, outer sigma 0.68, inner sigma 0.36) using an exposure mask (Exitech) was used. Patterned exposure with a line/space = 1/1 mask. After pattern exposure, baking (PEB) was carried out on a hot plate at 100 ° C for 60 seconds. Thereafter, pre-rinsing was carried out using the pre-rinsing liquid described in Table 6 (there was no pre-rinsing described as "None"), and the developing liquid described in Table 6 was stirred and developed for 30 seconds. After the development, the rinse was performed using the rinse liquid described in Table 6. Thereafter, the wafer was rotated at 2000 rpm for 30 seconds to obtain a 1:1 line and space pattern with a line width of 20 nm to 30 nm.

(Evaluation of etching resistance) The obtained resist pattern was etched by a plasma etching apparatus (Hitachi ECR plasma etching apparatus U-621), and the etching rate was determined (plasma conditions: Ar 500 ml/min, N ₂ 500 ml) /min, O ₂ 10ml/min). Further, in view of the stabilization of the plasma, the etching rate was determined from the difference between the film thickness which was etched for 10 seconds from the start of etching and the film thickness which was etched for 5 seconds from the start of etching. The etching rate is preferably 210 Å (angstrom) / sec (seconds) or less, more preferably 140 Å / sec or less, and further preferably 70 Å / sec or less. 1Å is 10 ^-10 m. (Etching speed) = {(film thickness etched by 10 seconds) - (film thickness etched by 5 seconds)}/5 The smaller the etching rate, the more excellent the etching resistance.

[Evaluation of Etching Roughness/EUV] The etching roughness was evaluated using a scanning electron microscope (S-9380II manufactured by Hitachi, Ltd.).

<etching roughness> The etching roughness is measured for any 50 points of 0.5 μm in the longitudinal direction of the line and space pattern (line: space = 1:1) with a line width of 26 nm, and the standard deviation is obtained to calculate 3σ ( Nm). The smaller the value, the better the performance.

[Table 6]

As described above, the treatment liquid and the pattern formation method according to the examples of the present invention have a result of excellent etching resistance and etching roughness with respect to the comparative example.

<Evaluation when using an electron beam (EB) irradiation device> An electron beam irradiation device (JBX6000 manufactured by JEOL Co., Ltd.; acceleration voltage 50 keV) was used instead of the EUV exposure device, and a pattern was formed by the same method as the one described earlier. . Further, the obtained pattern was evaluated in the same manner as the one described above. As a result, it was confirmed that excellent etching resistance and etching roughness can be achieved even when an electron beam (EB) irradiation apparatus is used.

<Evaluation when ArF irradiation apparatus was used> Even an ArF excimer laser immersion scanner (XM1700i, NA1.20, Dipole, Outer Sigma 0.800, Neigma 0.564, etc.) was used instead of the EUV exposure apparatus. Y is biased), and ultrapure water is used as the liquid immersion liquid, and a pattern is formed by the same method as that described previously. Even if the obtained pattern is evaluated in the same manner as described above, excellent etching resistance and etching roughness can be achieved.

The treatment liquid of the present invention is used for the non-chemically amplified resist composition described in the specification of the present application (especially including light absorption for g-ray, h-ray, i-ray, KrF, ArF, EB or EUV). a metal complex (a complex of magnesium, chromium, manganese, iron, cobalt, nickel, copper, zinc, silver, cadmium, indium, tin, antimony, cerium, zirconium, hafnium, etc., from the viewpoint of pattern formability, a resist film obtained by dissociating a complex of titanium, zirconium and hafnium, a resist material which is desorbed or used together with an acid generator and a ligand exchange process, and an anti-corrosion obtained from the resist film At least one of the etchant patterns is used for forming the resist pattern, and the same effect can be obtained. The treatment liquid of the present invention is used for forming at least one of a resist film obtained from a negative resist composition containing a crosslinking agent and a resist pattern obtained from the resist film. The same effect can be obtained by using the resist pattern.

no

no

Claims (13)

A treatment liquid for use in at least one of a resist film obtained from a sensitizing ray-sensitive or radiation-sensitive composition and a resist pattern obtained from the resist film, or for forming the resist The treatment liquid is used, and the treatment liquid comprises: (1) a compound having a ruthenium atom and a group that forms an interaction with a polar group; and (2) a solvent. The treatment liquid according to claim 1, wherein the compound of (1) is an ionic compound. The treatment liquid according to claim 1 or 2, wherein the compound having the interaction with the polar group of the compound of (1) is a group which forms an ionic bond with a polar group. The treatment liquid according to claim 1 or 2, wherein the compound having the interaction with the polar group of the compound of (1) is an acidic group or a basic group. The treatment liquid according to claim 1 or 2, wherein the compound having the interaction with the polar group of the compound (1) is a basic group having a pKa of 8 or more relative to the salt. The treatment liquid according to claim 1 or 2, wherein the solvent of the (2) comprises an organic solvent. The treatment liquid according to claim 1 or 2, wherein the compound of the above (1) is represented by the following formula (1-1): In the formula (1-1), A ^- represents an organic acid anion, the cation X ⁺ represents a nitrogen cation, a thiocation or an iodide cation; and Rx represents an alkyl group, a cycloalkyl group, an aryl group, an arylalkyl group or a heterocyclic group, Rx When there are a plurality of Rx, the plurality of Rx may be the same or different, and when there are a plurality of Rx, a plurality of Rx may be bonded to each other to form a ring, and the ring formed may also have a nitrogen atom, an oxygen atom or a sulfur atom. Ring member; L represents a single bond or a divalent linking group; n represents 3 in the case where X ⁺ is a nitrogen cation; 2 represents a case where X ⁺ is a sulfur cation; 2 represents a case where X ⁺ is an iodine cation; and Ry represents a hydrogen atom. An alkyl group, a cycloalkyl group, an aryl group, an arylalkyl group or a heterocyclic group; and B ¹ represents a group containing a halogen atom. The treatment liquid according to claim 7, wherein the B ¹ has a sesquiterpene alkoxy structure. The treatment liquid according to the first or second aspect of the invention, wherein the content of the compound of the above (1) is 1% by mass or more based on the total mass of the treatment liquid. The treatment liquid according to the above aspect of the invention, wherein the solvent of the (2) is a hydrocarbon solvent having 7 or more carbon atoms or a ketone solvent having 7 or more carbon atoms. The treatment liquid according to claim 1 or 2, wherein the treatment liquid is used as a rinse liquid. A pattern forming method, comprising: a resist film forming process for forming a resist film using a sensitizing ray-sensitive or radiation-sensitive linear composition; an exposure process for exposing the resist film; using a developer solution a developing process for developing the exposed resist film; and a rinsing process for rinsing the developed resist film with a rinsing liquid; and the pattern forming method satisfies the following (a) to ( At least one of the conditions of c): (a) between the exposure process and the development process, having the treatment liquid according to any one of items 1 to 10 of the application patent and the exposure The process of contacting the resist film; (b) the developer includes the treatment liquid according to any one of claims 1 to 10; (c) the rinse liquid comprises a patent application The treatment liquid according to any one of items 1 to 10. A method of producing an electronic component, comprising the pattern forming method according to claim 12 of the patent application.