TW202022488A - Resist pattern forming method - Google Patents

Abstract

To provide a resist pattern forming method by which generation of a defect in an unexposed portion of a resist film can be reduced and a resist pattern having a good profile can be formed. The resist pattern forming method includes: a step of forming a resist film on a support by using a resist composition; a step of exposing the resist film; and a step of developing the exposed resist film with an alkali developer solution containing a nonionic surfactant to form a resist pattern. The resist composition comprises a base material component and a compound (B1) represented by general formula (b1-1) as an acid generator component. In the formula, R0101 represents a polycyclic aliphatic hydrocarbon group; R102 is a fluorine atom or the like; Y101 represents a single bond or the like; V101 represents a single bond or the like; m represents an integer of 1 or more; and M'm+ represents an m-valent onium cation.

Description

Formation method of resist pattern

The present invention relates to an invention of a method for forming a resist pattern.

In the lithographic etching technology, generally used, for example, on a substrate to form a resist film formed of a resist material, and use radiation such as light and electrons to form a mask of a specific pattern to apply the resist The film is selectively exposed, subjected to a development process, and the like, and steps such as forming a resist pattern of a specific shape on the aforementioned resist film are performed. The resist material whose exposed part changes to the characteristic of dissolving in the developer is called positive type, and the resist material whose characteristic of changing the exposed part to insoluble in the developer is called negative type. In recent years, in the manufacture of semiconductor elements or liquid crystal display elements, with the advancement of photolithography technology, the miniaturization of patterns has been rapidly progressed. The method of miniaturizing the pattern is generally performed by shortening the wavelength (higher energy) of the exposure light source. Specifically, in the past, ultraviolet rays represented by g-line and i-line were used, but now KrF excimer lasers or ArF excimer lasers are used for mass production of semiconductor devices. In addition, researches on electron beams, EUV (extreme ultraviolet), or X-rays, which have shorter wavelengths (higher energy) than these excimer lasers, have already begun. For resist materials, lithographic etching characteristics such as sensitivity to these exposure light sources and reproducible resolution of fine-sized patterns are sought. The resist material that meets these requirements currently uses a chemically amplified resist containing a base material component that changes the solubility of an alkali developer through the action of acid, and an acid generator component that generates acid through exposure.剂组合物。 Agent composition.

One of the methods to improve resolution is known as the lithography of exposure (immersion exposure) between the objective lens of the exposure machine and the sample through a liquid (wetting medium) with a higher refractive index than air The etching method is a so-called immersion lithography method (Liquid Immersion Lithography. Hereinafter, also referred to as "immersion exposure"). During the immersion exposure process, even if the light source with the same exposure wavelength is used, the same high resolution can be achieved as the case of using a light source of shorter wavelength or the case of using a high NA lens. In addition, it will not cause the depth of focus width to decrease. . In addition, the immersion exposure can be performed using an existing exposure device. Therefore, immersion exposure can achieve low cost, high resolution, and form a resist pattern with excellent focal depth of field width, so it has been widely used in recent years. Immersion exposure is effective when forming a so-called pattern shape. In addition, it can also be used in combination with super-analysis techniques such as phase shift method and anamorphic illumination method. At present, the immersion exposure technology has been actively researched on the technology that mainly uses ArF excimer laser as the light source. However, the infiltration medium is still water as the main research object. In the resist composition used for this immersion exposure, it has been proposed to add a compound containing a fluorine atom. For example, Patent Document 1 discloses that the fluorine atom-containing compound added to the resist composition is a fluorine atom-containing structural unit and a fluorine-containing polymer compound having a (meth)acrylic acid-derived structural unit. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] JP 2011-13569 A

[Problems to be solved by the invention]

In the above-mentioned immersion exposure, a resist material that has characteristics corresponding to the immersion exposure technology in addition to the usual lithographic etching characteristics (sensitivity, resolution, etching resistance, etc.) is still sought. For example: in the immersion exposure, when the resist film is brought into contact with the immersion solvent, the substance in the resist film will dissolve out of the immersion solvent (material dissolution). The elution of the substance will cause the deterioration of the resist layer and the change of the refractive index of the wetting solvent, which will cause deterioration of the lithographic etching characteristics. The amount of the substance eluted is affected by the surface characteristics of the resist film (such as hydrophilicity, hydrophobicity, etc.). For example, when the hydrophobicity of the resist film surface is increased, the elution of the substance can be reduced.

As mentioned above, when the hydrophobicity of the surface of the resist film is increased, it should be possible to reduce the elution of the substance or improve the water followability, etc., so as to solve the unique problems of the immersion exposure technology. However, even when the resist film is only hydrophobized, it still has an adverse effect on the lithographic etching characteristics. For example, when the hydrophobicity of the resist film is increased, there will be a problem that defects (Defect) are likely to occur on the resist film after alkali development. In particular, when the pattern is formed using an alkali development process, defects are likely to occur in the unexposed part of the resist film. The term "defect" here refers to, for example, the use of KLA Danker's surface defect observation device (trade name "KLA") to observe all the defects found when the pattern is observed directly above the developed resist pattern . The missing phenomenon can include, for example: scum (resist residue), foam, waste and other foreign matter or precipitation after development is attached to the surface of the resist pattern, or the bridging between circuit patterns and contact hole pattern The hole of the burial is buried, such as the lack of the shape of the pattern, or the stain of the pattern. The resist composition described in Patent Document 1 mentioned above can improve the water repellency of the resist film during exposure due to the presence of a fluorine-containing polymer compound during exposure, and can improve the water repellency of the resist film during development by forming a hydrophilic group. The hydrophilicity of the resist film reduces defects. However, these conventional resist compositions described in Patent Document 1 still have problems such as inability to sufficiently exhibit the effect of reducing defects due to differences in the types of developers used. In view of the above situation, the present invention aims to provide a resist pattern forming method that can reduce the occurrence of defects in the unexposed portion of the resist film and can form a resist pattern with a good shape. [Solving the problem]

However, in the formation of the resist pattern, if the hydrophobicity of the surface of the resist film is increased, it will be difficult for the alkali developer to wet the resist film, etc. The analytical point of view is also one of the problems. Regarding this point, when considering the purpose of improving the wettability of the alkali developer to the resist film, methods such as adding a surfactant to the alkali developer are also considered. However, in the resist film with improved resolution, the unexposed part of the resist film after development still has the problem that defects with a size of 0.1 μm or more are likely to occur. As a result of research, the inventors found that when an acid generator having a specific structure is used in a resist composition, the above-mentioned problems can be solved, and the present invention has been completed.

That is, one aspect of the present invention is a method for forming a resist pattern, which includes the step (i) of forming a resist film on a support using a resist composition, and the step of exposing the aforementioned resist film ( ii), and the step (iii) of forming a resist pattern by developing the exposed resist film using an alkali developer containing a nonionic surfactant; and, the resist composition contains: The base material component (A) that changes the solubility of the alkaline developer due to the action of acid and the acid generator component (B) that generates acid through exposure. The aforementioned acid generator component (B) contains the following Compound (B1) represented by formula (b1-1).

[式中，R₀ ¹⁰¹ 為多環式脂肪族烴基；其中，多環式脂肪族烴基的氫原子亦可被取代基所取代；R¹⁰² 為氟原子或碳數1～5之氟化烷基；Y¹⁰¹ 為單鍵，或含有氧原子的2價之連結基；V¹⁰¹ 為單鍵、伸烷基或氟化伸烷基；m為1以上之整數，且M’^{m ＋} 為m價之鎓陽離子]。 [發明之效果]

[In the formula, R ₀ ¹⁰¹ is a polycyclic aliphatic hydrocarbon group; among them, the hydrogen atom of the polycyclic aliphatic hydrocarbon group may also be substituted by a substituent; R ¹⁰² is a fluorine atom or a fluorinated alkyl group with 1 to 5 carbon atoms ; Y ¹⁰¹ is a single bond, or a divalent linking group containing an oxygen atom of a; V ¹⁰¹ is a single bond, an alkylene group or fluorinated alkylene group; m is an integer of 1 or more, and m ^{'m +} m is the valence of Onium cation]. [Effect of invention]

According to the resist pattern forming method of the present invention, the occurrence of defects in the unexposed portion of the resist film can be reduced, and a resist pattern with a good shape can be formed.

[Forms for carrying out the invention]

In this specification and the scope of the patent application, "aliphatic" is a concept that is relative to aromatics, and is defined as meaning a group, compound, etc. that do not have aromaticity. "Alkyl", when not particularly limited, is a monovalent saturated hydrocarbon group including linear, branched, and cyclic. The same applies to the alkyl group in the alkoxy group. The "alkylene group", when not particularly limited, includes a linear, branched, and cyclic divalent saturated hydrocarbon group. The "halogenated alkyl group" is a group obtained by substituting a part or all of the hydrogen atoms of an alkyl group with halogen atoms. Examples of the halogen atom include fluorine atom, chlorine atom, bromine atom, and iodine atom. "Fluorinated alkyl group" or "fluorinated alkylene group" refers to a group in which part or all of the hydrogen atoms of an alkyl group or alkylene group are substituted with fluorine atoms. "Structural unit" means a monomer unit (monomer unit) constituting a polymer compound (resin, polymer, copolymer). When it is described as "substitutable" or "substitutable", it includes the case where the hydrogen atom (-H) is replaced by a monovalent group, and the methylene group (-CH ₂ -) is divalent The situation where the group is substituted and so on. "Exposure" refers to the entire concept of radiation exposure.

"Structural unit derived from acrylate" means a structural unit formed by cracking the ethylenic double bond of acrylate. "Acrylate" is a compound obtained by replacing the hydrogen atom at the carboxyl terminal of acrylic acid (CH ₂ =CH-COOH) with an organic group. In the acrylate, the hydrogen atom bonded to the carbon atom at the α position may be replaced by a substituent. The substituent (R ^α0 ) that replaces the hydrogen atom bonded to the carbon atom at the α position is an atom or a group other than a hydrogen atom, and examples thereof include alkyl groups with 1 to 5 carbons, and halogenated groups with 1 to 5 carbons. Alkyl etc. And also comprising a substituent group ^(R α0) containing itaconic acid are ester-bonded substituent of the substituent group, or substituent ^(R α0) or the hydroxyalkyl group is a hydroxyl group is modified to give the substituted Alpha hydroxy acrylate. In addition, the carbon atom at the α-position of acrylate means the carbon atom to which the carbonyl group of acrylic acid is bonded, unless it is particularly limited. Hereinafter, the acrylate obtained by replacing the hydrogen atom bonded to the carbon atom at the α-position with a substituent is sometimes referred to as α-substituted acrylate. In addition, acrylate and α-substituted acrylate are also collectively referred to as "(α-substituted) acrylate".

"A structural unit derived from acrylamide" means a structural unit formed by cracking the ethylenic double bond of acrylamide. In acrylamide, the hydrogen atom bonded to the carbon atom at the α-position may be substituted by a substituent, or one or both of the hydrogen atoms in the amine group of the acrylamide may be substituted by a substituent. In addition, the carbon atom at the α-position of acrylamide means the carbon atom to which the carbonyl group of acrylamide is bonded, unless it is particularly limited. Substituents that replace the hydrogen atom bonded to the carbon atom at the α-position of acrylamide, for example, are the same as the α-substituted acrylates listed as the substituent at the α-position (substituent (R ^α0 )) content.

"Structural unit derived from hydroxystyrene" means a structural unit formed by cracking the ethylenic double bond of hydroxystyrene. "A structural unit derived from a hydroxystyrene derivative" means a structural unit formed by cracking the ethylenic double bond of a hydroxystyrene derivative. "Hydroxystyrene derivatives" are those obtained by substituting a hydrogen atom at the α position of hydroxystyrene by other substituents such as alkyl groups and halogenated alkyl groups, and the concept of these derivatives. Examples of these derivatives include: hydroxystyrene in which the hydrogen atom at the α-position may be substituted by a substituent, and the hydrogen atom in the hydroxyl group of the hydroxystyrene is substituted by an organic group; The benzene ring of styrene is bonded with substituents other than the hydroxyl group. In addition, the α-position (carbon atom at the α-position) means the carbon atom bonded to the benzene ring when it is not particularly limited. Substituents substituting the hydrogen atom at the α-position of hydroxystyrene are, for example, the same as those listed as the substituent at the α-position in the aforementioned α-substituted acrylate.

"Structural unit derived from ethylene benzoic acid or ethylene benzoic acid derivatives" means a structural unit formed by cracking the ethylenic double bonds of ethylene benzoic acid or ethylene benzoic acid derivatives. "Ethylene benzoic acid derivative" refers to the concept of a hydrogen atom in the α position of ethylene benzoic acid replaced by an alkyl group, a halogenated alkyl group and other substituents, and the concept of these derivatives. Examples of these derivatives include: vinyl benzoic acid in which the hydrogen atom at the α-position may be substituted by a substituent, wherein the hydrogen atom in the carboxyl group of the benzoic acid is replaced by an organic group; The benzene ring of benzoic acid is bonded with substituents other than hydroxyl and carboxyl groups. In addition, the α-position (carbon atom at the α-position) means the carbon atom bonded to the benzene ring when it is not particularly limited.

"Styrenic derivative" refers to the concept that includes a hydrogen atom at the α-position of styrene replaced by other substituents such as alkyl and halogenated alkyl, and the concept of these derivatives. Examples of these derivatives include those having a substituent bonded to the benzene ring of hydroxystyrene in which the hydrogen atom at the α-position may be substituted by a substituent. In addition, the α-position (carbon atom at the α-position) means the carbon atom bonded to the benzene ring when it is not particularly limited. "Structural unit derived from styrene" and "structural unit derived from styrene derivative" refer to a structural unit formed by cracking the ethylenic double bond of styrene or a styrene derivative.

The above-mentioned alkyl group as the substituent at the α position is preferably a linear or branched alkyl group. Specifically, examples include: alkyl groups with 1 to 5 carbon atoms (methyl, ethyl, propyl , Isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl) and so on. In addition, the halogenated alkyl group as the substituent at the α-position can be specifically exemplified by the substitution of a part or all of the hydrogen atoms of the aforementioned "alkyl group as the substituent at the α-position" by halogen atoms Base etc. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is particularly preferred. In addition, the hydroxyalkyl group as the substituent at the α-position, specifically, includes a group obtained by substituting a part or all of the hydrogen atoms of the above-mentioned "alkyl group as the substituent at the α-position" by a hydroxyl group Wait. The number of hydroxyl groups in the hydroxyalkyl group is preferably 1 to 5, and 1 is the most preferred.

In this specification and the scope of the patent application, there are asymmetric carbons based on the differences in the structure represented by the chemical formulas, so there may be enantiomers or diastereomers. In this case, a chemical formula represents the isomers. These isomers may be used singly or as a mixture.

[Method of forming resist pattern] One aspect of the present invention is a method for forming a resist pattern, which has: a step (i) of forming a resist film on a support using a resist composition, and a step (ii) of exposing the aforementioned resist film , And the step (iii) of developing the resist film after exposure using an alkali developer containing a non-ionic surfactant to form a resist pattern. The aforementioned resist composition uses a base component (A) that changes the solubility to an alkali developer through the action of acid, and an acid generator component (B) that generates acid through exposure. The acid generator component (B) here includes the compound (B1) described later. One of the embodiments of the resist pattern forming method is, for example, the resist pattern forming method performed in the following manner.

Step (i): First, the specific resist composition described later is coated on the support using a spin coater or the like, and then at 80 to 150°C, preferably 100 to 150°C (more preferably over 100°C, 150°C or less Under the temperature condition of ), a baking (Post Apply Bake (PAB)) treatment is applied for 40 to 120 seconds, preferably 60 to 120 seconds, to form a resist film.

Step (ii): Next, for example, an exposure device or the like performs selective exposure such as exposure of the resist film via a mask (mask pattern) forming a specific pattern. Subsequently, for example, at a temperature of 80-150°C, preferably 90-130°C, for 40-120 seconds, preferably 60-100 seconds (Post Exposure Bake) (PEB)) processing.

Step (iii): Next, the above-mentioned exposed resist film is developed using an alkali developer containing a nonionic surfactant to form a resist pattern.

After the development treatment, washing treatment is preferably performed. The washing treatment is preferably water washing using pure water. After the development process or the washing process, the drying process is performed. Moreover, depending on the situation, the baking treatment (post-baking) may be performed after the above-mentioned development treatment. In this way, the resist pattern can be formed.

The support is not particularly limited, and conventionally known materials can be used, such as substrates for electronic parts, or those with specific wiring patterns formed thereon. More specifically, metal substrates such as silicon wafers, copper, chromium, iron, and aluminum, or glass substrates can be cited. For wiring pattern materials, for example, copper, aluminum, nickel, gold, etc. can be used. In addition, the support may also be one provided with an inorganic and/or organic film on the above-mentioned substrate. Examples of inorganic films include inorganic anti-reflective films (inorganic BARC). The organic film includes, for example, an organic anti-reflection film (organic BARC), or an organic film used as a lower organic film in the multilayer resist method. Among them, the multilayer resist method means that at least one layer of organic film (lower layer organic film) and at least one layer of resist film (upper layer resist film) are provided on a substrate, and then the resist pattern formed on the upper layer resist film is used. The pattern is used as a mask to pattern the underlying organic film. According to this method, a pattern with a high aspect ratio can be formed. That is, the multilayer resist method can ensure the required thickness of the underlying organic film, so that the resist film can be thinned to form a fine pattern with a high aspect ratio. In the multilayer resist method, basically, it can be divided into a method with a two-layer structure (two-layer resist method) such as an upper resist film and a lower organic film, and a method between the upper resist film and the lower organic film. A method of a multilayer structure with three or more layers (three-layer resist method) with one or more intermediate layers (metal thin films, etc.).

The wavelength used for exposure is not particularly limited. For example, ArF excimer laser, KrF excimer laser, F ₂ excimer laser, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electronics) Line), X-ray, soft X-ray, etc.

The exposure method of the resist film may be normal exposure (dry exposure) performed in an inert gas such as air or nitrogen, or may be immersion exposure (Liquid Immersion Lithography). The immersion exposure involves filling a solvent (wetting medium) with a refractive index larger than that of air between the resist film and the lens at the lowest position of the exposure device in advance, and then performing exposure in this state (immersion exposure ) The exposure method. The wetting medium is preferably a solvent having a refractive index larger than that of air and a refractive index smaller than that of the exposed resist film. The refractive index of the solvent is not particularly limited as long as it is within the aforementioned range. Solvents that have a higher refractive index than air and a lower refractive index than the aforementioned resist film, such as water, fluorine-based inert liquids, silicon-based solvents, and hydrocarbon-based solvents. Specific examples of fluorine-based inert liquids include: C ₃ HCl ₂ F ₅ , C ₄ F ₉ OCH ₃ , C ₄ F ₉ OC ₂ H ₅ , C ₅ H ₃ F ₇ and other fluorine-based compounds as the main component For liquids, the boiling point is preferably 70-180°C, preferably 80-160°C. When the fluorine-based inert liquid has a boiling point in the above-mentioned range, it is preferable that the medium used for wetting can be removed by a simple method after the exposure is completed. The fluorine-based inert liquid is particularly preferably a perfluoroalkyl compound obtained by substituting all hydrogen atoms of an alkyl group with fluorine atoms. Specific examples of perfluoroalkyl compounds include perfluoroalkyl ether compounds and perfluoroalkylamine compounds. In addition, specifically, the aforementioned perfluoroalkyl ether compound includes perfluoro(2-butyl-tetrahydrofuran) (boiling point 102°C) and the like, and the aforementioned perfluoroalkylamine compound includes, for example, perfluorotributylamine ( Boiling point 174℃) and so on. As the infiltration medium, water is preferred from the viewpoints of cost, safety, environmental issues, and universality.

In the above step (iii), the developer is an alkaline developer containing a nonionic surfactant. For example, a 0.1-10% by mass tetramethylammonium hydroxide (TMAH) aqueous solution containing a nonionic surfactant can be used as the developer. In addition, a well-known nonionic surfactant may be added to the nonionic surfactant contained in the alkali developer. Specifically, examples include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene octyl ether, polyoxyethylene oleyl ether, etc. Polyoxyethylene allyl ethers such as oxyethylene nonphenol ether; sorbitol monolaurate, sorbitol monopalmitate, sorbitol monostearate, sorbitol monooleate, sorbitol Sorbitol fatty acid esters such as sugar alcohol trioleate and sorbitol tristearate; and polyoxyethylene sorbitol monolaurate, polyoxyethylene sorbitol monopalmitate, polyoxyethylene Polyoxyethylene sorbitan fatty acid esters such as sorbitol monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, etc.; acetylene glycol, acetylene glycol The oxyethylene adducts and other acetylenes.

The addition amount of the nonionic surfactant is generally preferably 0.001 to 5 mass%, preferably 0.005 to 2 mass%, and more preferably 0.01 to 0.5 mass% relative to the total amount of the developer.

The development treatment can be carried out using known development methods, such as: immersing the support in the developer for a specific time (dipping method), and covering the surface of the support by the surface tension of the developer and maintaining it in a static state for a specific time Method (puddle method), the method of spraying the developer on the surface of the support (spray method), the developer is sprayed from the developer that scans at a specific speed, and the nozzle is continuously applied to the support that rotates at a specific speed The above method (Dynamic dispense method) and so on.

The washing treatment (washing treatment) using the washing liquid can be carried out in accordance with a known washing method. The method of the washing treatment includes, for example, a method of continuously applying the washing liquid on a support rotating at a specific speed (spin coating method), a method of immersing the support in the washing liquid for a specific time (dipping method), The method of spraying the washing liquid on the surface of the support (spray method), etc.

(Resist composition) In the above-mentioned resist pattern forming method of this embodiment, step (i) is to use a specific resist composition.

The resist composition in this embodiment contains the base component (A) (hereinafter, also referred to as "component (A)") that changes the solubility to the alkaline developer through the action of acid, and The acid generator component (B) that generates acid by exposure (hereinafter also referred to as "(B) component"), and the aforementioned (B) component contains the compound (B1) represented by the general formula (b1-1) described later (Hereinafter, also referred to as "(B1) component"). When the resist composition is used to form a resist film, and the resist film is selectively exposed, an acid is generated in the exposed part, and the solubility of component (A) in the alkaline developer is made by the action of the acid At the same time, in the unexposed part, the solubility of the component (A) to the alkali developer has not changed, so there will be a difference in the solubility of the developer between the exposed part and the unexposed part. Therefore, when the resist film is developed, a resist pattern can be formed.

For example: when component (A) is used as a base component (A-1) (hereinafter also referred to as "(A-1) component") that is poorly soluble in alkaline developer and has increased polarity through the action of acid, When an acid is generated by exposure, the exposed part of the resist film changes from being poorly soluble to alkali developing solution, while the unexposed part of the resist film is still poorly soluble in alkali without change. Therefore, when developing through alkali , Then a positive resist pattern can be formed. On the other hand, when the (A) component uses the base component (A-2) (hereinafter, also referred to as "(A-2) component") that is soluble in alkaline developer, and the crosslinking agent component is added, it is exposed to When an acid is generated, the effect of the acid causes the cross-linking between the component (A-2) and the cross-linking agent component. As a result, the solubility to the alkali developer will be reduced. Therefore, while the exposed part of the resist film becomes poorly soluble in alkali developing solution, the unexposed part of the resist film is still soluble in alkali developing solution without change. Therefore, negative resistance can be formed during alkali development. Dosage pattern.

The resist composition has the ability to generate acid through exposure. In addition to component (B), component (A) can also generate acid through exposure. When the component (A) generates acid through exposure, the component (A) is "the substrate component that generates acid through exposure and changes the solubility of the developer through the action of the acid." When the component (A) is a substrate component that generates acid through exposure and changes the solubility of the developer through the action of the acid, the component (A1) described below is to generate acid through exposure, and through the acid A polymer compound that changes the solubility of the developer is preferred. Examples of these polymer compounds include resins having structural units that generate acid through exposure. As for the monomer deriving the structural unit that generates acid by exposure, a known monomer can be used.

＜(A) Ingredients＞ In this embodiment, the component (A) of the resist composition is a substrate component that changes the solubility of the developer through the action of acid. In the present invention, the "substrate component" is an organic compound having film-forming ability, and it is preferable to use an organic compound with a molecular weight of 500 or more. When the molecular weight of the organic compound is 500 or more, the film forming ability can be improved. In addition, it is easy to form a resist pattern of about nanometer. Organic compounds used as substrate components can be roughly divided into non-polymers and polymers. Non-polymers are usually those with a molecular weight of 500 or more but less than 4000. Hereinafter, when it is referred to as a "low molecular compound", it means a non-polymer with a molecular weight of 500 or more and less than 4000. The polymer is usually one with a molecular weight of 1,000 or more. Hereinafter, when referred to as "resin", "polymer compound" or "polymer", it means a polymer having a molecular weight of 1,000 or more. The molecular weight of the polymer is the weight average molecular weight converted from polystyrene using GPC (Gel Permeation Chromatography).

In this embodiment, when the resist composition is the "negative resist composition for alkali development process" that forms a negative resist pattern in the alkali development process, as described above, the component (A-2) is used With cross-linking agent ingredients. (A-2) Among the components, it is preferable to use a resin that is soluble in an alkali developer (hereinafter, also referred to as "alkali-soluble resin"). Alkali-soluble resins, such as those disclosed in JP 2000-206694 No. 2000-206694, have an alkyl ester of α-(hydroxyalkyl)acrylic acid or α-(hydroxyalkyl)acrylic acid (preferably an alkane having 1 to 5 carbon atoms). Esters) selected at least one derived structural unit resin; U.S. Patent No. 6,694,325 discloses an acrylic resin having a sulfonamide group bonded to the carbon atom at the α position and the hydrogen atom can be replaced by a substituent or Polycyclic olefin resin; U.S. Patent No. 6,694,325, JP 2005-336452, JP 2006-317803, which contain fluorinated alcohols and hydrogen atoms bonded to the carbon atoms at the α position may be substituted by substituents Substituted acrylic resins; the polycyclic olefin resins with fluorinated alcohols disclosed in JP 2006-259582, etc., are preferred because they can form a good resist pattern with less swelling. In addition, the aforementioned α-(hydroxyalkyl)acrylic acid refers to acrylic acid in which the hydrogen atom bonded to the carbon atom at the α position can be substituted by a substituent, and includes a hydrogen atom bonded to the carbon atom at the α position of the carboxyl group. The acrylic acid means one or both of the α-hydroxyalkyl acrylic acid bonded with a hydroxyalkyl group (preferably a hydroxyalkyl group with 1 to 5 carbons) to the carbon atom at the α position. The cross-linking agent component is easy to form a good resist pattern with less swelling. Use amine-based cross-linking agents such as acetylene urea with methylol or alkoxymethyl, or melamine-based cross-linking agents, etc. Better. The addition amount of the crosslinking agent component is preferably 1-50 parts by mass relative to 100 parts by mass of the alkali-soluble resin.

When the resist composition in this embodiment is a "positive resist composition for alkaline development process" that forms a positive resist pattern in the alkaline development process, it uses the component (A-1) as described above . The component (A) preferably uses the component (A-1) described above.

The (A) component of the resist composition in this embodiment may be used alone or in combination of two or more. When the component (A) is the component (A-1), the component (A-1) should preferably contain the resin component (A1) (hereinafter, also referred to as "(A1) component").

・(A1) Component (A1) is a resin component, which preferably contains a polymer compound having a structural unit (a1) containing an acid-decomposable group that increases polarity by the action of acid. (A1) component, in addition to structural units (A1), having also comprising: the lactone-containing cyclic group containing -SO ₂ - group or the cyclic carbon containing cyclic group of the ester constituent unit (a2) By. In addition, the component (A1), in addition to the structural unit (a1), may also be a structural unit (a3) containing an aliphatic hydrocarbon group containing a polar group (wherein, it corresponds to the structural unit (a1) or the structural unit (a2) Except for those). In addition, the component (A1) may have a structural unit other than the structural unit (a1), the structural unit (a2), and the structural unit (a3).

≪Structural unit (a1)≫ Structural unit (a1) is a structural unit containing an acid-decomposable group that increases polarity through the action of acid. The "acid-decomposable group" is an acid-decomposable group that bonds at least a part of the structure of the acid-decomposable group to form a crack through the action of acid. The acid-decomposable group whose polarity increases through the action of acid includes, for example, a group that decomposes through the action of acid to generate a polar group. Examples of polar groups include carboxyl groups, hydroxyl groups, amino groups, and sulfonic acid groups (-SO ₃ H). Among these, a polar group containing -OH in the structure (hereinafter, also referred to as "OH-containing polar group") is preferred, a carboxyl group or a hydroxyl group is preferred, and a carboxyl group is particularly preferred. Specifically, the acid-decomposable group includes a group in which the aforementioned polar group is protected by an acid-dissociable group (for example, a hydrogen atom of an OH-containing polar group, a group protected by an acid-dissociable group).

The "acid-dissociable group" here refers to: (i) The bond between the acid-dissociable group and the atom adjacent to the acid-dissociable group forms a cracked acid-dissociable group through the action of acid , Or (ii) After a part of the bond is formed and cracked by the action of acid, the bond between the acid dissociable group and the adjacent atom of the acid dissociable group is formed through the decarbonation reaction The base of cracking, wait for both. The acid dissociable group constituting the acid dissociable group must have a lower polar group than the polar group generated by dissociation of the acid dissociable group. Thus, when the acid dissociable group is dissociated by the action of acid, A polar group with higher polarity than the acid dissociable group is generated, and the polarity is increased. As a result, the polarity of the entire component (A1) will increase. As a result of the increase in polarity, the solubility to the developer is relatively changed. When the developer is an alkaline developer, the solubility is increased, and when the developer is an organic developer, the solubility is reduced.

As the acid dissociable group, for example, the acid dissociable group proposed so far as the base resin for the chemically amplified resist composition can be used. The acid dissociable groups of base resins proposed as chemically amplified resist compositions, specifically, include: "acetal type acid dissociable groups" and "tertiary alkyl ester type acid dissociable groups" described below "Tertiary alkoxycarbonyl acid dissociable group", "tertiary alkoxycarbonyl acid dissociable group, etc.

Acetal acid dissociable group: Among the aforementioned polar groups, the acid-dissociable group that protects the carboxyl or hydroxyl group includes, for example, the acid-dissociable group represented by the following general formula (a1-r-1) (hereinafter, also referred to as "acetal acid-dissociable group基") etc.

[式中，Ra’¹ 、Ra’² 為氫原子或烷基；Ra’³ 為烴基，且Ra’³ 可與Ra’¹ 、Ra’² 之任一者鍵結而形成環]。

[In the formula, Ra' ¹ and Ra' ² are hydrogen atoms or alkyl groups; Ra' ³ is a hydrocarbon group, and Ra' ³ may be bonded to any of Ra' ¹ and Ra' ² to form a ring].

In the formula (a1-r-1), at least one of Ra' ¹ and Ra' ² is preferably a hydrogen atom, and both of them are preferably hydrogen atoms. When Ra' ¹ or Ra' ² is an alkyl group, for example, the alkyl group has the same content as the alkyl group exemplified as the substituent that can be bonded to the carbon atom at the α position in the description of the α-substituted acrylate. An alkyl group with 1 to 5 carbon atoms is preferred. Specifically, a linear or branched alkyl group is preferably exemplified. More specifically, examples include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, etc., and Methyl or ethyl is preferred, and methyl is particularly preferred.

Of formula (a1-r-1) of, Ra ^'3 hydrocarbon group, the alkyl group may be of straight-chain or branched, or cyclic hydrocarbon group of. The linear alkyl group preferably has 1 to 5 carbon atoms, preferably 1 to 4 carbon atoms, and more preferably 1 or 2 carbon atoms. Specifically, examples thereof include methyl, ethyl, n-propyl, n-butyl, n-pentyl, and the like. Among these, methyl, ethyl or n-butyl is preferred, and methyl or ethyl is preferred.

The branched alkyl group preferably has a carbon number of 3-10, and preferably has a carbon number of 3-5. Specifically, examples include isopropyl, isobutyl, tert-butyl, isopentyl, neopentyl, 1,1-diethylpropyl, 2,2-dimethylbutyl, etc., Isopropyl is preferred.

When Ra' ³ is a cyclic hydrocarbon group, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and it may be a polycyclic group or a monocyclic group. The aliphatic hydrocarbon group of the monocyclic group is preferably a group obtained by removing one hydrogen atom from a monocyclic alkane. The monocyclic alkane is preferably one having 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane. The aliphatic hydrocarbon group of the polycyclic group is preferably a group obtained by removing one hydrogen atom from a polycyclic alkane. The polycyclic alkane is preferably a carbon number of 7-12. Specifically, examples include : Adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc.

When the cyclic hydrocarbon group of Ra' ³ is an aromatic hydrocarbon group, the aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring. The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons, and it may be monocyclic or polycyclic. The carbon number of the aromatic ring is preferably 5-30, preferably 5-20, more preferably 6-15, and particularly preferably 6-12. Aromatic rings, specifically, include: aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, phenanthrene, etc.; aromatic heterocycles in which part of the carbon atoms constituting the aforementioned aromatic hydrocarbon ring is substituted by heteroatoms Wait. Examples of heteroatoms in the aromatic heterocycle include oxygen atoms, sulfur atoms, and nitrogen atoms. Specific examples of the aromatic heterocyclic ring include a pyridine ring and a thiophene ring. Specifically, the aromatic hydrocarbon group in Ra' ³ includes: a group (aryl group or heteroaryl group) obtained by removing one hydrogen atom from the aforementioned aromatic hydrocarbon ring or aromatic heterocyclic ring; The above aromatic compound of the aromatic ring (for example, biphenyl, fluorine, etc.) is obtained by removing one hydrogen atom; one of the hydrogen atoms of the aforementioned aromatic hydrocarbon ring or aromatic heterocyclic ring is substituted by an alkylene group (E.g., aralkyl groups such as benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc.) and the like. The number of carbon atoms of the alkylene group bonded to the aforementioned aromatic hydrocarbon ring or aromatic heterocyclic ring is preferably 1 to 4, preferably 1 to 2 carbons, and particularly preferably 1 carbon.

The cyclic hydrocarbon group in Ra' ³ may have a substituent. Examples of the substituent include -R ^P1 , -R ^P2 -OR ^P1 , -R ^P2 -CO-R ^P1 , -R ^P2 -CO-OR ^P1 , -R ^P2 -O-CO-R ^P1 , -R ^P2 -OH, -R ^P2 -CN or -R ^P2 -COOH (hereinafter, these substituents are collectively referred to as "Ra ⁰⁵ ") and the like. Among them, R ^P1 is a monovalent chain saturated hydrocarbon group having 1 to 10 carbons, a monovalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbons, or a monovalent aromatic hydrocarbon group having 6 to 30 carbons. In addition, R ^P2 is a single bond, a divalent chain saturated hydrocarbon group with 1 to 10 carbons, a divalent aliphatic cyclic saturated hydrocarbon group with 3 to 20 carbons, or a divalent aromatic hydrocarbon group with 6 to 30 carbons . Among them, part or all of the hydrogen atoms of the chain saturated hydrocarbon groups, aliphatic cyclic saturated hydrocarbon groups, and aromatic hydrocarbon groups of R ^P1 and R ^P2 may be substituted by fluorine atoms. The aliphatic cyclic hydrocarbon group may have one or more of the above-mentioned substituents alone, or may have one or more of the above-mentioned substituents of plural kinds. Examples of the monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and decyl. A monovalent aliphatic cyclic saturated hydrocarbon group with 3 to 20 carbons, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclodecyl Monocyclic aliphatic saturated hydrocarbon groups such as alkyl groups; bicyclo[2.2.2]heptyl, tricyclo[5.2.1. 0 ^2,6 ]decyl, tricyclo[3.3.1. 1 ^3,7 ]decyl , Tetracyclic [6.2.1. 1 ^{3,6.0 2,7} ] dodecyl, adamantyl and other polycyclic aliphatic saturated hydrocarbon groups. The monovalent aromatic hydrocarbon group having 6 to 30 carbon atoms includes, for example, a group obtained by removing one hydrogen atom from an aromatic hydrocarbon ring such as benzene, biphenyl, pyrene, naphthalene, anthracene, and phenanthrene.

When Ra' ³ is bonded to any one of Ra' ¹ and Ra' ² to form a ring, the cyclic group is preferably a 4- to 7-membered ring, and more preferably a 4- to 6-membered ring. Specific examples of the cyclic group include tetrahydropyranyl and tetrahydrofuranyl.

Tertiary alkyl ester type acid dissociable group: Among the above-mentioned polar groups, the acid dissociable group that protects the carboxyl group includes, for example, an acid dissociable group represented by the following general formula (a1-r-2). In addition, among the acid dissociable groups represented by the following formula (a1-r-2), those composed of an alkyl group are hereinafter also referred to as "tertiary alkyl ester type acid dissociable groups" for simplicity.

[式中，Ra’⁴ ～Ra’⁶ 各別為烴基，且Ra’⁵ 、Ra’⁶ 可相互鍵結而形成環]。

[In the formula, Ra' ⁴ to Ra' ^{6 are} each a hydrocarbon group, and Ra' ⁵ and Ra' ⁶ may be bonded to each other to form a ring].

The hydrocarbon group of Ra' ⁴ includes, for example, a linear or branched alkyl group, a chain or cyclic alkenyl group, or a cyclic hydrocarbon group. The linear or branched alkyl group and cyclic hydrocarbon group in Ra' ⁴ (monocyclic aliphatic hydrocarbon group, polycyclic aliphatic hydrocarbon group, aromatic hydrocarbon group), for example: and the aforementioned Ra' ³ is the same content. The chain or cyclic alkenyl group in Ra' ⁴ is preferably an alkenyl group having 2 to 10 carbon atoms. The hydrocarbon group in Ra' ⁵ and Ra' ⁶ , for example, has the same content as the aforementioned Ra' ³ .

When Ra' ⁵ and Ra' ⁶ are bonded to each other to form a ring, the group represented by the following general formula (a1-r2-1), the group represented by the following general formula (a1-r2-2), and the following general The group represented by the formula (a1-r2-3) is a preferable example. On the other hand, when Ra' ⁴ to Ra' ^{6 are} not bonded to each other but are independent hydrocarbon groups, a group represented by the following general formula (a1-r2-4) is preferably exemplified.

[式(a1-r2-1)中，Ra’¹⁰ 為碳數1～10之烷基，或下述通式(a1-r2-r1)所表示之基。Ra’¹¹ 為與Ra’¹⁰ 鍵結之碳原子共同形成脂肪族環式基之基；式(a1-r2-2)中，Ya為碳原子；Xa為與Ya共同形成環狀烴基之基；該環狀之烴基所具有的氫原子之一部份或全部可被取代。Ra⁰¹ ～Ra⁰³ 各別獨立為氫原子、碳數1～10的1價之鏈狀飽和烴基或碳數3～20的1價之脂肪族環狀飽和烴基。該鏈狀飽和烴基及脂肪族環狀飽和烴基所具有的氫原子之一部份或全部可被取代。Ra⁰¹ ～Ra⁰³ 之2個以上可相互鍵結而形成環狀結構。式(a1-r2-3)中，Yaa為碳原子；Xaa為與Yaa共同形成脂肪族環式基之基。Ra⁰⁴ 為可具有取代基的芳香族烴基。式(a1-r2-4)中，Ra’¹² 及Ra’¹³ 各別獨立為碳數1～10的1價之鏈狀飽和烴基或氫原子。該鏈狀飽和烴基所具有的氫原子之一部份或全部可被取代。Ra’¹⁴ 為可具有取代基之烴基。＊表示鍵結鍵(以下相同)]。

[In the formula (a1-r2-1), Ra' ¹⁰ is an alkyl group having 1 to 10 carbon atoms, or a group represented by the following general formula (a1-r2-r1). Ra' ¹¹ is a group that forms an aliphatic cyclic group together with the carbon atom bonded to Ra'¹⁰; in formula (a1-r2-2), Ya is a carbon atom; Xa is a group that forms a cyclic hydrocarbon group together with Ya; Part or all of the hydrogen atoms of the cyclic hydrocarbon group may be substituted. Ra ⁰¹ to Ra ^{03 are} each independently a hydrogen atom, a monovalent chain saturated hydrocarbon group with 1 to 10 carbons, or a monovalent aliphatic cyclic saturated hydrocarbon group with 3 to 20 carbons. Part or all of the hydrogen atoms of the chain saturated hydrocarbon group and the aliphatic cyclic saturated hydrocarbon group may be substituted. Two or more of Ra ⁰¹ to Ra ⁰³ may be bonded to each other to form a ring structure. In the formula (a1-r2-3), Yaa is a carbon atom; Xaa is a group that forms an aliphatic cyclic group together with Yaa. Ra ⁰⁴ is an aromatic hydrocarbon group which may have a substituent. In the formula (a1-r2-4), Ra' ¹² and Ra' ^{13 are} each independently a monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom. Part or all of the hydrogen atoms of the chain saturated hydrocarbon group may be substituted. Ra' ¹⁴ is a hydrocarbon group which may have a substituent. ＊ indicates the bonding key (the same below)].

[式中，Ya⁰ 為四級碳原子。Ra⁰³¹ 、Ra⁰³² 及Ra⁰³³ ，為各別獨立之可具有取代基之烴基。其中，Ra⁰³¹ 、Ra⁰³² 及Ra⁰³³ 中之1個以上，為具有至少一個極性基的烴基]。

[In the formula, Ya ⁰ is a quaternary carbon atom. Ra ⁰³¹ , Ra ⁰³² and Ra ⁰³³ are independent hydrocarbon groups which may have substituents. Among them, one or more of Ra ⁰³¹ , Ra ^032, and Ra ⁰³³ is a hydrocarbon group having at least one polar group].

In the above formula (a1-r2-1), the alkyl group with 1 to 10 carbon atoms of Ra' ¹⁰ is defined by the linear or branched alkyl group of Ra' ³ in the formula (a1-r-1) The base of enumeration is better. Ra' ¹⁰ is preferably an alkyl group with 1 to 5 carbon atoms.

In the aforementioned formula (a1-r2-r1), Ya ⁰ is a quaternary carbon atom. That is, the number of adjacent carbon atoms to which Ya ⁰ (carbon atom) is bonded is four.

In the aforementioned formula (a1-r2-r1), Ra ⁰³¹ , Ra ⁰³² and Ra ⁰³³ are each independently a hydrocarbon group which may have a substituent. The hydrocarbyl groups in Ra ⁰³¹ , Ra ^032, and Ra ⁰³³ are independently linear or branched alkyl groups, chain or cyclic alkenyl groups, or cyclic hydrocarbon groups.

In Ra ⁰³¹ , Ra ⁰³² and Ra ⁰³³ , the linear alkyl group preferably has 1 to 5 carbon atoms, preferably 1 to 4, and more preferably 1 or 2. Specifically, examples thereof include methyl, ethyl, n-propyl, n-butyl, n-pentyl, and the like. Among these, methyl, ethyl or n-butyl is preferred, and methyl or ethyl is preferred. In Ra ⁰³¹ , Ra ⁰³² and Ra ⁰³³ , the branched alkyl group preferably has a carbon number of 3-10, more preferably 3-5. Specifically, examples include isopropyl, isobutyl, tert-butyl, isopentyl, neopentyl, 1,1-diethylpropyl, 2,2-dimethylbutyl, etc., Isopropyl is preferred. Among Ra ⁰³¹ , Ra ⁰³² and Ra ⁰³³ , the chain or cyclic alkenyl group is preferably an alkenyl group with 2-10 carbon atoms.

In Ra ⁰³¹ , Ra ^032, and Ra ⁰³³ , the cyclic hydrocarbon group may be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a polycyclic group, or a monocyclic group. The aliphatic hydrocarbon group of the monocyclic group is preferably a group obtained by removing one hydrogen atom from a monocyclic alkane. The monocyclic alkane is preferably one having 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane. The aliphatic hydrocarbon group of the polycyclic group is preferably a group obtained by removing one hydrogen atom from a polycyclic alkane. The polycyclic alkane is preferably a carbon number of 7-12. Specifically, examples include : Adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc.

In Ra ⁰³¹ , Ra ^032, and Ra ⁰³³ , the aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring. The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons, and it may be monocyclic or polycyclic. The carbon number of the aromatic ring is preferably 5-30, preferably 5-20, more preferably 6-15, and particularly preferably 6-12. Aromatic rings, specifically, include: aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, phenanthrene, etc.; aromatic heterocycles in which part of the carbon atoms constituting the aforementioned aromatic hydrocarbon ring is substituted by heteroatoms Wait. Examples of heteroatoms in the aromatic heterocycle include oxygen atoms, sulfur atoms, and nitrogen atoms. Specific examples of the aromatic heterocyclic ring include a pyridine ring and a thiophene ring. Specifically, the aromatic hydrocarbon group includes a group (aryl group or heteroaryl group) obtained by removing one hydrogen atom from the aforementioned aromatic hydrocarbon ring or aromatic heterocyclic ring; and a group containing two or more aromatic rings Aromatic compounds (such as biphenyl, stilbene, etc.) obtained by removing one hydrogen atom; a group obtained by substituting one of the hydrogen atoms of the aforementioned aromatic hydrocarbon ring or aromatic heterocyclic ring with an alkylene group (may Examples include aralkyl groups such as benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc.). The number of carbon atoms of the alkylene group bonded to the aforementioned aromatic hydrocarbon ring or aromatic heterocyclic ring is preferably 1 to 4, preferably 1 to 2, and particularly preferably 1.

When the hydrocarbon group represented by Ra ⁰³¹ , Ra ^032, and Ra ⁰³³ is substituted, the substituent includes, for example, a hydroxyl group, a carboxyl group, a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), and an alkoxy group (methoxy group). , Ethoxy, propoxy, butoxy, etc.), alkyloxycarbonyl, etc.

Among the above, among Ra ⁰³¹ , Ra ^032, and Ra ⁰³³ , the hydrocarbon group that may have a substituent is preferably a linear or branched alkyl group that may have a substituent, and a linear alkyl group is more preferred.

Among them, one or more of Ra ⁰³¹ , Ra ^032, and Ra ⁰³³ is a hydrocarbon group having at least a polar group. The "hydrocarbon group having a polar group" includes either one in which the methylidene group (-CH ₂ -) constituting the hydrocarbyl group is substituted by a polar group, or at least one hydrogen atom constituting the hydrocarbyl group is substituted with a polar group. The "hydrocarbon group having a polar group" is preferably a functional group represented by the following general formula (a1-p1).

[式中，Ra⁰⁷ 表示碳數2～12的2價之烴基。Ra⁰⁸ 表示含有雜原子的2價之連結基。Ra⁰⁶ 表示碳數1～12的1價之烴基。n_p0 為1～6之整數]。

[In the formula, Ra ⁰⁷ represents a divalent hydrocarbon group having 2-12 carbon atoms. Ra ⁰⁸ represents a divalent linking group containing a heteroatom. Ra ⁰⁶ represents a monovalent hydrocarbon group having 1 to 12 carbon atoms. n _p0 is an integer of 1 to 6].

In the aforementioned formula (a1-p1), Ra ⁰⁷ represents a divalent hydrocarbon group having 2 to 12 carbon atoms. The carbon number of Ra ⁰⁷ is 2-12, and the carbon number is preferably 2-8, preferably the carbon number is 2-6, more preferably the carbon number is 2 to 4, and particularly preferably the carbon number is 2. The hydrocarbon group in Ra ⁰⁷ is preferably a chain or cyclic aliphatic hydrocarbon group, and a chain hydrocarbon group is preferable. Ra ⁰⁷ , for example: ethylene, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, Heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, decane-1,10-diyl, undecane-1,11-diyl , Dodecane-1,12-diyl and other linear alkanediyl groups; propane-1,2-diyl, 1-methylbutane-1,3-diyl, 2-methylpropane-1 ,3-diyl, pentane-1,4-diyl, 2-methylbutane-1,4-diyl and other branched chain alkanediyl groups; cyclobutane-1,3-diyl, ring Cycloalkanediyl such as pentane-1,3-diyl, cyclohexane-1,4-diyl, cyclooctane-1,5-diyl; norbornane-1,4-diyl, Polycyclic divalent alicyclic hydrocarbon groups such as norbornane-2,5-diyl, adamantane-1,5-diyl, and adamantane-2,6-diyl. Among the above, an alkanediyl group is preferred, and a linear alkanediyl group is preferred.

In the aforementioned formula (a1-p1), Ra ⁰⁸ represents a heteroatom-containing divalent linking group. Ra ⁰⁸ , such as: -O-, -C(=O)-O-, -C(=O)-, -OC(=O)-O-, -C(=O)-NH-,- NH-, -NH-C(=NH)-(H may be substituted by substituents such as alkyl and acyl), -S-, -S(=O) ₂ -, -S(=O) _2- O-etc. Among these, in terms of the solubility of the developer, -O-, -C(=O)-O-, -C(=O)-, -OC(=O)-O- are preferred, -O- and -C(=O)- are particularly preferred.

In the aforementioned formula (a1-p1), Ra ⁰⁶ represents a monovalent hydrocarbon group having 1 to 12 carbon atoms. The carbon number of Ra ⁰⁶ is 1-12. From the viewpoint of the solubility to the developer, the carbon number is preferably 1-8, preferably the carbon number is 1 to 5, and more preferably the carbon number is 1 to 3. Carbon number 1 or 2 is particularly preferred, and 1 is the best.

The hydrocarbyl group in Ra ⁰⁶ includes, for example, a chain hydrocarbyl group or a cyclic hydrocarbyl group, or a chain and a cyclic hydrocarbyl group. Chain hydrocarbon groups, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl Yl, 2-ethylhexyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, etc.

The cyclic hydrocarbon group may be an alicyclic hydrocarbon group or an aromatic hydrocarbon group. The alicyclic hydrocarbon group can be either monocyclic or polycyclic. The monocyclic alicyclic hydrocarbon group may include, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methyl Cycloalkyl groups such as cyclohexyl, dimethylcyclohexyl, cycloheptyl, cyclooctyl, cycloheptyl, and cyclodecyl. Polycyclic alicyclic hydrocarbon groups, such as decahydronaphthyl, adamantyl, 2-alkyladamantan-2-yl, 1-(adamantan-1-yl)alkan-1-yl, Norbornyl, methylnorbornyl, isobornyl, etc. Aromatic hydrocarbon groups, such as phenyl, naphthyl, anthracenyl, p-methylphenyl, p-tert-butylphenyl, p-adamantylphenyl, tolyl, xylyl, isopropyl Phenyl, mesityl, biphenyl, phenanthryl, 2,6-diethylphenyl, 2-methyl-6-ethylphenyl, etc.

Ra ⁰⁶ , from the viewpoint of solubility to the developer, a chain hydrocarbon group is preferred, an alkyl group is preferred, and a linear alkyl group is more preferred.

In the aforementioned formula (a1-p1), n _p0 is an integer of 1 to 6, preferably an integer of 1 to 3, preferably 1 or 2, and even more preferably 1.

The following are specific examples of the hydrocarbon group having at least a polar group. In the following formula, * is the bonding bond of the quaternary carbon atom (Ya ⁰ ) bonding.

In the aforementioned formula (a1-r2-r1), in Ra ⁰³¹ , Ra ⁰³² and Ra ⁰³³ , the number of hydrocarbon groups having at least a polar group is one or more, but it can be considered when the resist pattern is formed. The solubility of the liquid is determined appropriately, for example, one or two of Ra ⁰³¹ , Ra ^032, and Ra ⁰³³ is preferred, and one is particularly preferred.

The aforementioned hydrocarbon group having at least a polar group may have a substituent other than the polar group. Examples of the substituent include halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, etc.), halogenated alkyl groups having 1 to 5 carbon atoms, and the like.

In the formula (a1-r2-1), Ra' ¹¹ (an aliphatic cyclic group formed by the carbon atom bonded to Ra' ¹⁰ ) is a monocyclic ring of Ra' ³ in the formula (a1-r-1) The groups exemplified for the aliphatic hydrocarbon group of the formula group or the polycyclic group are preferred.

In the formula (a1-r2-2), Xa and Ya together form a cyclic hydrocarbon group, such as the cyclic monovalent hydrocarbon group (aliphatic) in Ra' ³ in the aforementioned formula (a1-r-1) Group hydrocarbon group) and the like obtained by removing one or more hydrogen atoms. Xa and Ya together form a cyclic hydrocarbon group, which may have a substituent. Examples of the substituent include the same content as the substituent that the cyclic hydrocarbon group in Ra' ³ may have. In the formula (a1-r2-2), among Ra ⁰¹ to Ra ⁰³ , a monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, Hexyl, heptyl, octyl, decyl, etc. Among Ra ⁰¹ to Ra ⁰³ , monovalent aliphatic cyclic saturated hydrocarbon groups with 3 to 20 carbon atoms include, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, Monocyclic aliphatic saturated hydrocarbon groups such as cyclodecyl and cyclododecyl; bicyclo[2.2.2]heptyl, tricyclo[5.2.1. 0 ^2,6 ]decyl, tricyclo[3.3.1. 1 ^3,7] decyl group, tetracyclo [6.2.1. 1 ^3,6 0 ^2,7] dodecyl group, adamantyl group and the like polycyclic aliphatic saturated hydrocarbon group and the like. Among Ra ⁰¹ to Ra ⁰³ , from the viewpoint of easy synthesis of monomeric compounds derived from the structural unit (a1), hydrogen atoms and monovalent chain saturated hydrocarbon groups with 1 to 10 carbon atoms are preferred. Among them, hydrogen atoms are used. , Methyl and ethyl are preferred, and hydrogen atom is particularly preferred.

The chain saturated hydrocarbon groups represented by Ra ⁰¹ to Ra ⁰³ or the substituents of the aliphatic cyclic saturated hydrocarbon groups include, for example, the same groups as the above Ra ⁰⁵ .

Two or more of Ra ⁰¹ to Ra ⁰³ are bonded to each other to form a carbon-carbon double bond-containing group, such as cyclopentenyl, cyclohexenyl, methylcyclopentenyl, Methylcyclohexenyl, cyclopentylene vinyl, cyclohexylene vinyl, etc. Among these, from the viewpoint of easy synthesis of monomer compounds derived from the structural unit (a1), cyclopentenyl, cyclohexenyl, and cyclopentylene vinyl are preferred.

In formula (a1-r2-3), the aliphatic cyclic group formed by Xaa and Yaa together is a monocyclic group or polycyclic aliphatic hydrocarbon group of Ra' ³ in formula (a1-r-1) The listed base is better. In the formula (a1-r2-3), the aromatic hydrocarbon group in Ra ⁰⁴ includes, for example, a group obtained by removing one or more hydrogen atoms from an aromatic hydrocarbon ring having 5 to 30 carbon atoms. Among them, Ra ^{04 is} preferably a group obtained by removing more than one hydrogen atom from an aromatic hydrocarbon ring with 6 to 15 carbon atoms, and a group obtained by removing more than one hydrogen atom from benzene, naphthalene, anthracene or phenanthrene Preferably, the group obtained by removing more than one hydrogen atom from benzene, naphthalene or anthracene is more preferable, and the group obtained by removing more than one hydrogen atom from benzene or naphthalene is particularly preferable, and it is removed from benzene. One or more hydrogen atoms is the best group.

The substituents that Ra ⁰⁴ in the formula (a1-r2-3) may have include, for example, methyl, ethyl, propyl, hydroxyl, carboxyl, halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), alkane Oxy groups (methoxy, ethoxy, propoxy, butoxy, etc.), alkyloxycarbonyl, etc.

In the formula (a1-r2-4), Ra' ¹² and Ra' ^{13 are} each independently a monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom. In Ra' ¹² and Ra' ¹³ , the monovalent chain saturated hydrocarbon group having 1 to 10 carbons, for example, the monovalent chain saturated hydrocarbon group having 1 to 10 carbons in the above Ra ⁰¹ to Ra ⁰³ is The same content. Part or all of the hydrogen atoms of the chain saturated hydrocarbon group may be substituted. Among Ra' ¹² and Ra' ¹³ , a hydrogen atom and an alkyl group with 1 to 5 carbon atoms are preferred, an alkyl group with 1 to 5 carbon atoms is preferred, methyl and ethyl are more preferred, and methyl is preferred. The base is particularly good. When the chain saturated hydrocarbon groups represented by Ra' ¹² and Ra' ¹³ are substituted, examples of the substituent include the same groups as the aforementioned Ra ⁰⁵ .

In the formula (a1-r2-4), Ra ' 14 is a substituent group of a hydrocarbon group. Ra ^'14 in the hydrocarbon group include such as: the straight-chain or branched alkyl, or cyclic hydrocarbon group of.

The straight-chain alkyl group in Ra' ¹⁴ preferably has 1 to 5 carbon atoms, preferably 1 to 4, and more preferably 1 or 2. Specifically, examples thereof include methyl, ethyl, n-propyl, n-butyl, n-pentyl, and the like. Among these, methyl, ethyl or n-butyl is preferred, and methyl or ethyl is preferred.

Ra 'in the alkyl chain of ¹⁴ to 10 carbon atoms, preferably 3 ~ to 5 ~ 3 preferred. Specifically, examples include isopropyl, isobutyl, tert-butyl, isopentyl, neopentyl, 1,1-diethylpropyl, 2,2-dimethylbutyl, etc., Isopropyl is preferred.

When Ra' ¹⁴ is a cyclic hydrocarbon group, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and it may be a polycyclic group or a monocyclic group. The aliphatic hydrocarbon group of the monocyclic group is preferably a group obtained by removing one hydrogen atom from a monocyclic alkane. The monocyclic alkane is preferably one having 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane. The aliphatic hydrocarbon group of the polycyclic group is preferably a group obtained by removing one hydrogen atom from a polycyclic alkane. The polycyclic alkane is preferably a carbon number of 7-12. Specifically, examples include : Adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc.

Ra ^'14 in the aromatic hydrocarbon group include such as: and Ra ⁰⁴ are the same as the aromatic hydrocarbon content. Among them, Ra' ^{14 is} preferably a group obtained by removing more than one hydrogen atom from an aromatic hydrocarbon ring with 6 to 15 carbon atoms, and it is obtained by removing more than one hydrogen atom from benzene, naphthalene, anthracene or phenanthrene The group is preferred, the group obtained by removing more than one hydrogen atom from benzene, naphthalene or anthracene is more preferable, the group obtained by removing more than one hydrogen atom from naphthalene or anthracene is particularly preferable, and one group is removed from naphthalene The group derived from the above hydrogen atom is the best. The substituents that Ra' ¹⁴ may have and the substituents that Ra ⁰⁴ may have are the same.

When Ra' ¹⁴ in the formula (a1-r2-4) is a naphthyl group, its bonding position to the tertiary carbon atom in the aforementioned formula (a1-r2-4) can be the 1-position or 2-position of the naphthyl group Either one is fine. When Ra' ¹⁴ in the formula (a1-r2-4) is an anthracene group, the position where it is bonded to the tertiary carbon atom in the aforementioned formula (a1-r2-4) can be the 1-position or 2-position of the anthracene group Or any of 9 people.

Specific examples of the group represented by the aforementioned formula (a1-r2-1) are as follows, for example.

Specific examples of the group represented by the aforementioned formula (a1-r2-2) are as follows, for example.

Specific examples of the group represented by the aforementioned formula (a1-r2-3) are as follows, for example.

Specific examples of the group represented by the aforementioned formula (a1-r2-4) are as follows, for example.

Tertiary alkyloxycarbonyl acid dissociable group: The acid dissociable group for protecting the hydroxyl group in the polar group includes, for example, the acid dissociable group represented by the following general formula (a1-r-3) (hereinafter, for simplicity, also referred to as "tertiary alkyl Oxycarbonyl acid dissociable group") etc.

[式中，Ra’⁷ ～Ra’⁹ 各別為烷基]。

[In the formula, Ra' ⁷ to Ra' ^{9 are} each an alkyl group].

In the formula (a1-r-3), Ra' ⁷ to Ra' ⁹ are each preferably an alkyl group having 1 to 5 carbon atoms, and preferably an alkyl group having 1 to 3 carbon atoms. In addition, the total carbon number of each alkyl group is preferably 3-7, more preferably 3-5 carbons, and most preferably 3-4 carbons.

The structural unit (a1) includes, for example, a structural unit derived from an acrylate whose hydrogen atom bonded to a carbon atom at the α position can be substituted by a substituent, a structural unit derived from acrylamide, and a hydroxystyrene Or a structural unit in which at least part of the hydrogen atom in the hydroxyl group of the structural unit derived from a hydroxystyrene derivative is protected by a substituent containing the aforementioned acid-decomposable group, derived from vinyl benzoic acid or a vinyl benzoic acid derivative The structural unit of -C(=O)-OH has at least a part of the hydrogen atom protected by the substituent containing the aforementioned acid-decomposable group, etc.

The structural unit (a1), among the above, is preferably a structural unit derived from an acrylate in which a hydrogen atom bonded to a carbon atom at the α position can be substituted by a substituent. Preferable specific examples of the structural unit (a1) include structural units represented by the following general formula (a1-1) or (a1-2).

[式中，R為氫原子、碳數1～5之烷基或碳數1～5之鹵化烷基；Va¹ 為可具有醚鍵結的2價之烴基；n_a1 為0～2之整數；Ra¹ 為上述通式(a1-r-1)或(a1-r-2)所表示之酸解離性基。Wa¹ 為n_a2 ＋1價之烴基，n_a2 為1～3之整數，Ra² 為上述通式(a1-r-1)或(a1-r-3)所表示之酸解離性基]。

[In the formula, R is a hydrogen atom, an alkyl group with 1 to 5 carbons or a halogenated alkyl group with 1 to 5 carbons; Va ¹ is a divalent hydrocarbon group which may have ether linkages; n _a1 is an integer of 0 to 2 ; Ra ¹ is an acid dissociable group represented by the general formula (a1-r-1) or (a1-r-2). ¹ is a WA n _a2 +1 valence of hydrocarbon, n _a2 is an integer of 1 to 3, Ra ² is represented by the above general formula the acid dissociable group (a1-r-1) or (a1-r-3)] .

In the aforementioned formula (a1-1), the alkyl group having 1 to 5 carbon atoms in R is preferably a linear or branched alkyl group having 1 to 5 carbon atoms. Specifically, examples include: methyl , Ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, etc. The halogenated alkyl group having 1 to 5 carbon atoms is a group obtained by substituting a part or all of the hydrogen atoms of the aforementioned alkyl group having 1 to 5 carbon atoms by halogen atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is particularly preferred. R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms. For ease of industrial acquisition, a hydrogen atom or a methyl group is most preferred.

In the aforementioned formula (a1-1), the divalent hydrocarbon group in Va ¹ may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

The aliphatic hydrocarbon group that is the divalent hydrocarbon group in Va ¹ may be saturated or unsaturated, and saturated is generally preferred. More specifically, the aliphatic hydrocarbon group includes a linear or branched aliphatic hydrocarbon group, or an aliphatic hydrocarbon group containing a ring in the structure.

The aforementioned linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms. The straight-chain aliphatic hydrocarbon group is preferably a straight-chain alkylene group. Specifically, examples include: methylidene [-CH ₂ -], ethylidene [-(CH ₂ ) ₂ -], Methyl [-(CH ₂ ) ₃ -], tetramethylene [-(CH ₂ ) ₄ -], pentamethyl [-(CH ₂ ) ₅ -], etc. The aforementioned branched aliphatic hydrocarbon group preferably has 2 to 10 carbons, preferably 3 to 6 carbons, more preferably 3 or 4 carbons, and most preferably 3 carbons. The branched aliphatic hydrocarbon group is preferably a branched alkylene group, specifically, for example: -CH(CH ₃ )-, -CH(CH ₂ CH ₃ )-, -C(CH ₃ ) ₂ -, -C(CH ₃ )(CH ₂ CH ₃ )-, -C(CH ₃ )(CH ₂ CH ₂ CH ₃ )-, -C(CH ₂ CH ₃ ) ₂ -and other alkylene groups; -CH(CH ₃ )CH ₂ -, -CH(CH ₃ )CH(CH ₃ )-, -C(CH ₃ ) ₂ CH ₂ -, -CH(CH ₂ CH ₃ )CH ₂ -, -C(CH ₂ CH ₃ ) ₂ -CH ₂ -and other alkyl ethylene groups; -CH(CH ₃ )CH ₂ CH ₂ -, -CH ₂ CH(CH ₃ )CH ₂ -and other alkyl ethylene groups; -CH( CH ₃ )CH ₂ CH ₂ CH ₂ -, -CH ₂ CH(CH ₃ )CH ₂ CH ₂ -and other alkylene groups such as tetramethyl group and the like. The alkyl group in the alkylene group is preferably a straight-chain alkyl group with 1 to 5 carbon atoms.

The aliphatic hydrocarbon group containing a ring in the aforementioned structure includes, for example, an alicyclic hydrocarbon group (a group obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring), an alicyclic hydrocarbon group bonded to a linear or branched aliphatic A group derived from the terminal of a group hydrocarbon group, a group derived from an alicyclic hydrocarbon group between a linear or branched aliphatic hydrocarbon group, etc. The aforementioned straight-chain or branched aliphatic hydrocarbon group is, for example, the same as the aforementioned straight-chain aliphatic hydrocarbon group or the aforementioned branched aliphatic hydrocarbon group. The aforementioned alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms. The aforementioned alicyclic hydrocarbon group may be polycyclic or monocyclic. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a monocyclic alkane. The monocyclic alkane preferably has a carbon number of 3 to 6, and specific examples include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a polycyclic alkane. The polycyclic alkane preferably has 7 to 12 carbon atoms. Specifically, examples include: Adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc.

The aromatic hydrocarbon group which is a divalent hydrocarbon group in Va ¹ is a hydrocarbon group having an aromatic ring. The aromatic hydrocarbon group preferably has a carbon number of 3-30, preferably 5-30, more preferably 5-20, particularly preferably 6-15, and most preferably 6-12. However, the carbon number is one that does not include the carbon number in the substituent. Specifically, the aromatic ring possessed by the aromatic hydrocarbon group includes: aromatic hydrocarbon rings such as benzene, biphenyl, pyrene, naphthalene, anthracene, phenanthrene, etc.; part of the carbon atoms constituting the aforementioned aromatic hydrocarbon ring Aromatic heterocycles etc. which are substituted by heteroatoms. Examples of heteroatoms in the aromatic heterocycle include oxygen atoms, sulfur atoms, and nitrogen atoms. Specifically, the aromatic hydrocarbon group includes: a group obtained by removing two hydrogen atoms from the aforementioned aromatic hydrocarbon ring (arylene group); a group obtained by removing one hydrogen atom from the aforementioned aromatic hydrocarbon ring ( A group derived from the substitution of one of the hydrogen atoms of an aryl group by an alkylene group (e.g., benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl , 2-naphthylethyl, etc., the aryl group in the aralkyl group is obtained by removing one hydrogen atom), etc. The carbon number of the aforementioned alkylene (alkane chain in the aralkyl group) is preferably 1 to 4, preferably 1 to 2, and particularly preferably 1.

In the aforementioned formula (a1-1), Ra ¹ is an acid dissociable group represented by the aforementioned formula (a1-r-1) or (a1-r-2).

In the formula (a1-2), Wa in the n _a2 +1 monovalent hydrocarbon group of ^1, may be an aromatic hydrocarbon group may also be an aliphatic hydrocarbon group. The aliphatic hydrocarbon group means a hydrocarbon group that does not have aromaticity, and it may be saturated or unsaturated, and saturated is generally preferred. The aforementioned aliphatic hydrocarbon groups include, for example, linear or branched aliphatic hydrocarbon groups, aliphatic hydrocarbon groups containing rings in the structure, or a combination of linear or branched aliphatic hydrocarbon groups and aliphatic hydrocarbon groups containing rings in the structure And get the base and so on. The aforementioned n _a2 + 1 valence is preferably 2 to 4 valences, and 2 or 3 valences are more preferred.

In the aforementioned formula (a1-2), Ra ² is an acid dissociable group represented by the aforementioned general formula (a1-r-1) or (a1-r-3).

The following are specific examples of the structural unit represented by the aforementioned formula (a1-1). In the following formulae, R ^α represents a hydrogen atom, a methyl group or a trifluoromethyl group.

The following are specific examples of the structural unit represented by the aforementioned formula (a1-2).

(A1) The structural unit (a1) possessed by the component may be one type or two or more types. The structural unit (a1) is preferably the structural unit represented by the aforementioned formula (a1-1). Among these, the structural unit (a1) is particularly preferable to contain a structural unit represented by the following general formula (a1-1-1).

[式中，Ra¹ ”為通式(a1-r2-1)所表示之酸解離性基]。

[In the formula, Ra ¹ "is an acid dissociable group represented by the general formula (a1-r2-1)].

In the formula (a1-1-1), R, Va ¹ and n _a1, as in the above formula (a1-1) R, Va ¹ and n _a1 is the same as the contents. The description of the acid dissociable group represented by the general formula (a1-r2-1) is as described above.

(A1) The ratio of the structural unit (a1) in the component, relative to the total (100 mol%) of the total structural units constituting the component (A1), is preferably 5 to 80 mol%, and 10 to 75 mol% % Is better, more preferably 20-60 mol%. When the ratio of the structural unit (a1) is more than the lower limit of the aforementioned preferable range, the sensitivity, resolution, and roughness of lithographic etching characteristics can be improved. On the other hand, when it is below the upper limit of the aforementioned preferred range, it is easy to achieve a balance with other structural units, and various lithographic etching characteristics can be made better.

≪Structural unit (a2)≫ (A1), in addition to the structural unit (a1), it may contain: lactone-containing cyclic group, -SO ₂ --containing cyclic group or carbonate-containing cyclic group The structural unit (a2) (except those equivalent to the structural unit (a1)) is preferred. The structural unit (a2) contains lactone-containing cyclic group, -SO ₂ --containing cyclic group or carbonate-containing cyclic group, when component (A1) is used to form a resist film, it is useful for improving the resist film Effective for the adhesion of the substrate. In addition, when it has the structural unit (a2), it has the effects of appropriately adjusting the diffusion length of the acid, improving the adhesion of the resist film to the substrate, appropriately adjusting the solubility during development, and improving the etching resistance. It can make the lithographic etching characteristics more favorable.

"Lactone-containing cyclic group" means a cyclic group containing a ring (lactone ring) containing -O-C(=O)- in its ring skeleton. The lactone ring is counted as one ring. When it is only the lactone ring, it is called a monocyclic group. When there are other ring structures, no matter its structure, it is called a polycyclic group. The lactone-containing cyclic group may be a monocyclic group or a polycyclic group. The lactone-containing cyclic group in the structural unit (a2) is not particularly limited, and any components can be used. Specifically, for example, groups represented by the following general formulas (a2-r-1) to (a2-r-7), and the like.

[式中，Ra’²¹ 各別獨立為氫原子、烷基、烷氧基、鹵素原子、鹵化烷基、羥基、-COOR”、-OC(=O)R”、羥烷基或氰基；R”為氫原子、烷基、含內酯之環式基、含碳酸酯之環式基，或含-SO₂ -之環式基；A”為可含有氧原子(-O-)或硫原子(-S-)的碳數1～5之伸烷基、氧原子或硫原子，n’為0～2之整數，m’為0或1]。

[In the formula, Ra' ^{21 are} each independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, -COOR", -OC(=O)R", a hydroxyalkyl group or a cyano group; R" is a hydrogen atom, an alkyl group, a lactone-containing cyclic group, a carbonate-containing cyclic group, or a -SO ₂ --containing cyclic group; A" is an oxygen atom (-O-) or sulfur The atom (-S-) has an alkylene group with 1 to 5 carbon atoms, an oxygen atom or a sulfur atom, n'is an integer of 0 to 2, and m'is 0 or 1].

In the aforementioned general formulas (a2-r-1) to (a2-r-7), the alkyl group in Ra' ²¹ is preferably an alkyl group with 1 to 6 carbon atoms. The alkyl group is preferably linear or branched. Specifically, examples thereof include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, and hexyl. Among these, methyl or ethyl is preferred, and methyl is particularly preferred. The alkoxy group in Ra' ²¹ is preferably an alkoxy group with 1 to 6 carbon atoms. The alkoxy group is preferably linear or branched. Specifically, for example, in the aforementioned Ra' ²¹ , an alkyl group as an alkyl group, a group formed by linking an oxygen atom (-O-), and the like are exemplified. The halogen atom in Ra' ²¹ can be exemplified by fluorine atom, chlorine atom, bromine atom, iodine atom, etc., and fluorine atom is preferred. Ra ^'21 In the halogenated alkyl group include such as: the Ra' a part of the hydrogen atoms in the alkyl group of ²¹ or all of the preceding groups substituted by a halogen atom and the like. The halogenated alkyl group is preferably a fluorinated alkyl group, particularly a perfluoroalkyl group.

In Ra' ²¹ -COOR" and -OC(=O)R", any R" is a hydrogen atom, an alkyl group, a lactone-containing cyclic group, a carbonate-containing cyclic group, or a- The cyclic group of SO ₂ -. The alkyl group in R" may be linear, branched, or cyclic, and the carbon number is preferably 1-15. When R" is a linear or branched alkyl group, it preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and particularly preferably methyl or ethyl. R" is cyclic In the case of an alkyl group, the carbon number is preferably 3-15, more preferably 4-12, and most preferably 5-10. Specifically, examples include: groups obtained by removing one or more hydrogen atoms from a monocyclic alkane that may be substituted by a fluorine atom or a fluorinated alkyl group, or unsubstituted; from a bicyclic alkane, a tricyclic chain Polycyclic alkanes such as alkanes and tetracyclic alkanes are groups obtained by removing one or more hydrogen atoms. More specifically, examples include: radicals obtained by removing one or more hydrogen atoms from monocyclic alkanes such as cyclopentane and cyclohexane; radicals obtained from adamantane, norbornane, isobornane, and tricyclodecane Polycyclic alkanes such as alkanes and tetracyclododecane are groups obtained by removing one or more hydrogen atoms. The lactone-containing cyclic group in R" has the same content as the groups represented by the aforementioned general formulas (a2-r-1) to (a2-r-7). The carbonate-containing ring in R" The formula group has the same content as the carbonate-containing cyclic group described below, and specifically, the groups represented by (ax3-r-1) to (ax3-r-3) and the like can be mentioned. The cyclic group containing -SO ₂ -in R" has the same content as the cyclic group containing -SO ₂ -described later. Specifically, examples include: general formulas (a5-r-1) to (a5) -R-4) The groups respectively represented by the groups, etc. The hydroxyalkyl group in Ra' ²¹ preferably has 1 to 6 carbon atoms, specifically, for example: at least one hydrogen in the alkyl group in Ra' ²¹ Atoms are substituted by hydroxyl groups, etc.

In the aforementioned general formulas (a2-r-2), (a2-r-3), (a2-r-5), the alkylene group having 1 to 5 carbon atoms in A" is linear or branched The alkylene group is preferably, such as: methylene, ethylidene, n-propylene group, isopropylidene, etc. When the alkylene group contains an oxygen atom or a sulfur atom, specific examples are as follows: Groups derived from -O- or -S- interposed between the end of the alkyl group or the carbon atoms, etc., for example: -O-CH ₂ -, -CH ₂ -O-CH ₂ -, -S-CH ₂ -, -CH ₂ -S-CH ₂ -etc. A" is preferably an alkylene having 1 to 5 carbon atoms or -O-, preferably an alkylene having 1 to 5 carbon atoms, and most preferably a methylene group good.

The following are specific examples of groups represented by the general formulas (a2-r-1) to (a2-r-7).

"Containing -SO ₂ - the cyclic group" means, contained in the cyclic skeleton containing -SO ₂ - meaning of cyclic ring group, specifically, -SO ₂ - sulfur atom (S) is formed A cyclic group that is a part of the cyclic skeleton of a cyclic group. It is counted in the way that the ring containing -SO ₂ -in its ring skeleton is regarded as a ring. When only this ring is called a monocyclic group, when there are other ring structures, no matter what the structure is, it is called a polycyclic ring.式基。 Formula base. The cyclic group containing -SO ₂ -may be a monocyclic group or a polycyclic group. The cyclic group containing -SO ₂ -, especially the cyclic group containing -O-SO ₂ -in the ring skeleton, that is, the -OS- in -O-SO ₂ -forms part of the ring skeleton The cyclic group of the sultone ring is preferred. More specifically, the -SO ₂ --containing cyclic group includes groups represented by the following general formulas (a5-r-1) to (a5-r-4).

[式中，Ra’⁵¹ 各別獨立為氫原子、烷基、烷氧基、鹵素原子、鹵化烷基、羥基、-COOR”、-OC(=O)R”、羥烷基或氰基；R”為氫原子、烷基、含內酯之環式基、含碳酸酯之環式基，或含-SO₂ -之環式基；A”為可含有氧原子或硫原子的碳數1～5之伸烷基、氧原子或硫原子，n’為0～2之整數]

[In the formula, Ra' ^{51 are} each independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, -COOR", -OC(=O)R", a hydroxyalkyl group or a cyano group; R "is a hydrogen atom, an alkyl group, the lactone-containing cyclic group, the cyclic group containing carbonate, or an -SO ₂ - group of cyclic; a" carbon atoms which may contain an oxygen atom or a sulfur atom ～5 alkylene, oxygen atom or sulfur atom, n'is an integer of 0-2]

In the aforementioned general formulas (a5-r-1) to (a5-r-2), A" and the aforementioned general formulas (a2-r-2), (a2-r-3), (a2-r-5) The "A" is the same content. Ra ^'51 in the alkyl group, alkoxy group, halogen atom, halogenated alkyl group, -COOR ", - OC (= O) R", a hydroxyl group, respectively, with the general formula (a2-r-1) ~ ( The contents listed in the description of Ra' ²¹ in a2-r-7) are the same. The following are specific examples of groups represented by the general formulas (a5-r-1) to (a5-r-4). The "Ac" in the formula means acetyl group.

"Carbonate-containing cyclic group" means a cyclic group containing a -O-C(=O)-O- ring (carbonate ring) in its ring skeleton. The carbonate ring is counted as one ring. When it is only a carbonate ring, it is called a monocyclic group. When there are other ring structures, it is called a polycyclic group regardless of the structure. The carbonate-containing cyclic group may be a monocyclic group or a polycyclic group. The cyclic group containing a carbonate ring is not particularly limited, and any component can be used. Specifically, for example, groups represented by the following general formulas (ax3-r-1) to (ax3-r-3) and the like can be cited.

[式中，Ra’^x31 各別獨立為氫原子、烷基、烷氧基、鹵素原子、鹵化烷基、羥基、-COOR”、-OC(=O)R”、羥烷基或氰基；R”為氫原子、烷基、含內酯之環式基、含碳酸酯之環式基，或含-SO₂ -之環式基；A”為可含有氧原子或硫原子的碳數1～5之伸烷基、氧原子或硫原子，p’為0～3之整數，q’為0或1]。

[In the formula, Ra' ^{x31 are} each independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, -COOR", -OC(=O)R", a hydroxyalkyl group or a cyano group; R "is a hydrogen atom, an alkyl group, the lactone-containing cyclic group, the cyclic group containing carbonate, or an -SO ₂ - group of cyclic; a" carbon atoms which may contain an oxygen atom or a sulfur atom ~5 alkylene, oxygen atom or sulfur atom, p'is an integer of 0 to 3, q'is 0 or 1].

In the aforementioned general formulas (ax3-r-2) to (ax3-r-3), A" and the aforementioned general formulas (a2-r-2), (a2-r-3), (a2-r-5) The "A" is the same content. The alkyl group, alkoxy group, halogen atom, halogenated alkyl group, -COOR", -OC(=O)R", and hydroxyalkyl group in Ra' ³¹ are respectively the same as the aforementioned general formulas (a2-r-1)～( The contents listed in the description of Ra' ²¹ in a2-r-7) are the same. The following are specific examples of groups represented by the general formulas (ax3-r-1) to (ax3-r-3).

In the structural unit (a2), a structural unit derived from an acrylate in which a hydrogen atom bonded to a carbon atom at the α position can be substituted by a substituent is preferred. This structural unit (a2) is preferably a structural unit represented by the following general formula (a2-1).

[式中，R為氫原子、碳數1～5之烷基或碳數1～5之鹵化烷基。Ya²¹ 為單鍵或2價之連結基；La²¹ 為-O-、      -COO-、-CON(R’)-、-OCO-、-CONHCO-或-CONHCS-，R’表示氫原子或甲基。但，La²¹ 為-O-時，Ya²¹ 不為-CO-。Ra²¹ 為含內酯之環式基、含碳酸酯之環式基，或含-SO₂ -之環式基]。

[In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbons, or a halogenated alkyl group having 1 to 5 carbons. Ya ²¹ is a single bond or a bivalent linking group; La ²¹ is -O-, -COO-, -CON(R')-, -OCO-, -CONHCO- or -CONHCS-, R'represents a hydrogen atom or a base. However, when La ²¹ is -O-, Ya ^{21 is} not -CO-. Ra ²¹ is a cyclic group containing lactone, a cyclic group containing carbonate, or a cyclic group containing -SO ₂ -].

In the aforementioned formula (a2-1), R has the same content as described above. R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms. In terms of ease of industrial availability, a hydrogen atom or a methyl group is particularly preferred.

In the aforementioned formula (a2-1), the divalent linking group of Ya ²¹ is not particularly limited, and it is preferably a bivalent hydrocarbon group which may have a substituent, a divalent linking group containing a heteroatom, etc. Exemplify. In Ya ²¹ , the description of the divalent hydrocarbon group that may have a substituent, the divalent linking group containing a heteroatom, etc. are respectively the same as the divalent substituent of the Ya ^x1 in the above general formula (a10-1) The description of the hydrocarbon group and the heteroatom-containing divalent linking group are the same. Ya ^{21 is} preferably a single bond, an ester bond [-C(=O)-O-], an ether bond (-O-), a linear or branched alkylene group, or a combination of these.

In the aforementioned formula (a2-1), Ra ²¹ is a lactone-containing cyclic group, -SO ₂ --containing cyclic group, or a carbonate-containing cyclic group. The lactone-containing cyclic group, -SO ₂ --containing cyclic group, and carbonate-containing cyclic group in Ra ²¹ are respectively represented by the aforementioned general formulas (a2-r-1) to (a2-r-7) Each of the groups represented by the formulas (a5-r-1)～(a5-r-4), the groups represented by the formulas (ax3-r-1)～(ax3-r-3) Do not indicate the basis for better exemplified content. Among them, the lactone-containing cyclic group or the -SO ₂ -containing cyclic group is preferred, and the aforementioned general formulas (a2-r-1), (a2-r-2), (a2-r-6 The groups represented by) or (a5-r-1) are preferred. Specifically, according to the aforementioned chemical formulas (r-lc-1-1) ~ (r-lc-1-7), (r-lc-2-1) ~ (r-lc-2-18), (r- Any group represented by lc-6-1), (r-sl-1-1), and (r-sl-1-18) is preferred.

(A1) The structural unit (a2) possessed by the component may be one type or two or more types. When the component (A1) has the structural unit (a2), the ratio of the structural unit (a2) relative to the total of the total structural units (100 mol%) constituting the component (A1) is preferably 20 to 70 mol%. 40-60 mol% is preferred. When the ratio of the structural unit (a2) is above the preferred lower limit, sufficient effects can be obtained when the structural unit (a2) is contained. When the ratio is below the upper limit, the balance with other structural units can be easily achieved, and the Various lithography etching characteristics are better.

≪Structural unit (a3)≫ (A1) Ingredients, in addition to the structural unit (a1), a structural unit (a3) containing an aliphatic hydrocarbon group containing a polar group (except those equivalent to the structural unit (a1) and the structural unit (a2)) Better. (A1) When the component has a structural unit (a3), it has the effects of appropriately adjusting the diffusion length of the acid, improving the adhesion of the resist film to the substrate, appropriately adjusting the solubility during development, and improving the etching resistance. , And can make the lithography etching characteristics better.

Examples of the polar groups include hydroxyl groups, cyano groups, carboxyl groups, and hydroxyalkyl groups in which a part of the hydrogen atoms of the alkyl groups are substituted with fluorine atoms. The hydroxyl group is particularly preferred. The aliphatic hydrocarbon group includes, for example, a linear or branched hydrocarbon group having 1 to 10 carbon atoms (preferably an alkylene group), or a cyclic aliphatic hydrocarbon group (cyclic group). The cyclic group may be a monocyclic group or a polycyclic group. For example, among the resins that can be used in the resist composition for ArF excimer lasers, the most proposed components are appropriately selected and used. . The cyclic group is preferably a polycyclic group, and the carbon number is preferably 7-30. Among them, it is a structural unit derived from an aliphatic polycyclic acrylate containing a hydroxyl group, a cyano group, a carboxyl group, or a part of the hydrogen atom containing an alkyl group by a fluorine atom. For better. Examples of the polycyclic group include groups obtained by removing two or more hydrogen atoms from bicyclic alkane, tricyclic alkane, tetracyclic alkane, and the like. Specifically, examples thereof include groups obtained by removing two or more hydrogen atoms from polycyclic alkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. Among these polycyclic groups, two or more hydrogen atoms are removed from adamantane, two or more hydrogen atoms are removed from norbornane, and two are removed from tetracyclododecane. A base derived from more than one hydrogen atom is industrially preferred.

The structural unit (a3) is not particularly limited as long as it contains a polar group-containing aliphatic hydrocarbon group, and any component can be used. The structural unit (a3) is preferably a structural unit derived from an acrylate in which a hydrogen atom bonded to a carbon atom at the α position can be substituted by a substituent, and a structural unit containing an aliphatic hydrocarbon group containing a polar group is preferred. The structural unit (a3), when the hydrocarbon group in the polar group-containing aliphatic hydrocarbon group is a linear or branched hydrocarbon group having 1 to 10 carbon atoms, a structural unit derived from hydroxyethyl acrylic acid is preferred. In addition, the structural unit (a3), when the hydrocarbon group in the polar group-containing aliphatic hydrocarbon group is a polycyclic group, is represented by the structural unit represented by the following formula (a3-1) and the formula (a3-2) The structural unit and the structural unit represented by formula (a3-3) are preferred examples.

[式中，R與前述為相同內容，j為1～3之整數，k為1～3之整數，t’為1～3之整數，l為1～5之整數，s為1～3之整數]。

[In the formula, R is the same as the above, j is an integer of 1 to 3, k is an integer of 1 to 3, t'is an integer of 1 to 3, l is an integer of 1 to 5, and s is an integer of 1 to 3. Integer].

In the formula (a3-1), j is preferably 1 or 2, and more preferably 1. When j is 2, the hydroxyl group is preferably bonded to the 3-position and 5-position of the adamantyl group. When j is 1, the hydroxyl group is preferably bonded to the 3-position of the adamantyl group. j is preferably 1, and the hydroxyl group is particularly preferably bonded to the 3 position of the adamantyl group.

In formula (a3-2), k is preferably 1. The cyano group is preferably bonded to the 5 or 6 position of the norbornyl group.

In the formula (a3-3), t'is preferably 1. l is preferably 1. s is preferably 1. These are preferably those bonded to the carboxyl end of acrylic acid with 2-norbornyl or 3-norbornyl. The fluorinated alkanol is preferably bonded to the 5 or 6 position of the norbornyl group.

(A1) The structural unit (a3) possessed by the component may be one type or two or more types. When the component (A1) has a structural unit (a3), relative to the total of the total structural units constituting the component (A1), 1-40 mol% is preferred, 10-30 mol% is preferred, and 20 ~30 mol% is better. When the ratio of the structural unit (a3) is more than the lower limit of the aforementioned preferable range, sufficient effects can be obtained when the structural unit (a3) is contained, and when the ratio is less than the upper limit of the aforementioned preferable range, it can be easily obtained with The balance of other structural units can make various lithography etching characteristics better.

≪Other structural units≫ The component (A1) may have structural units other than the above-mentioned structural unit (a1), structural unit (a2), and structural unit (a3). Other structural units include, for example, the structural unit (a10) containing a hydroxystyrene skeleton, the structural unit (a9) represented by the general formula (a9-1), and the structural unit derived from styrene (wherein, equivalent to Structural units (except for a10)), structural units (a4) containing non-acid dissociable aliphatic cyclic groups, etc.

≪Structural unit containing hydroxystyrene skeleton (a10)≫ (A1) In addition to the structural unit (a1), the component (A1) preferably has a structural unit (a10) containing a hydroxystyrene skeleton. The structural unit (a10) is preferably exemplified by the structural unit represented by the following general formula (a10-1).

[式中，R為氫原子、碳數1～5之烷基或碳數1～5之鹵化烷基；Ya^x1 為單鍵或2價之連結基。Wa^x1 為(n_ax1 ＋1)價之芳香族烴基。n_ax1 為1～3之整數]。

[In the formula, R is a hydrogen atom, an alkyl group with 1 to 5 carbons or a halogenated alkyl group with 1 to 5 carbons; Ya ^x1 is a single bond or a divalent linking group. Wa ^x1 is an aromatic hydrocarbon group with (n _ax1 +1) valence. n _ax1 is an integer of 1 to 3].

In the aforementioned formula (a10-1), R is a hydrogen atom, an alkyl group with 1 to 5 carbons, or a halogenated alkyl group with 1 to 5 carbons; The C1-C5 alkyl group of R is preferably a C1-C5 linear or branched chain alkyl group. Specifically, examples include methyl, ethyl, propyl, isopropyl Base, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, etc. The halogenated alkyl group having 1 to 5 carbon atoms of R is a group obtained by substituting a part or all of the hydrogen atoms of the aforementioned alkyl group having 1 to 5 carbon atoms by halogen atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is particularly preferred. R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms. For ease of industrial acquisition, a hydrogen atom or a methyl group is most preferred.

In the aforementioned formula (a10-1), Ya ^x1 is a single bond or a divalent linking group. The divalent linking group in Ya ^x1 is preferably exemplified by, for example, a divalent hydrocarbon group which may have a substituent and a divalent linking group containing a heteroatom.

・An optionally substituted divalent hydrocarbon group: When Ya ^x1 is an optionally substituted divalent hydrocarbon group, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

・・The aliphatic hydrocarbon group in Ya ^x1 This aliphatic hydrocarbon group refers to a hydrocarbon group that is not aromatic. The aliphatic hydrocarbon group may be saturated or unsaturated, and saturated is usually preferred. The aforementioned aliphatic hydrocarbon group includes, for example, a linear or branched aliphatic hydrocarbon group, or an aliphatic hydrocarbon group containing a ring in the structure.

・・・Straight-chain or branched aliphatic hydrocarbon group The straight-chain aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and more preferably 1 to 4 carbon atoms , The best carbon number is 1～3. The straight-chain aliphatic hydrocarbon group is preferably a straight-chain alkylene group. Specifically, examples include: methylidene [-CH ₂ -], ethylidene [-(CH ₂ ) ₂ -], Methyl [-(CH ₂ ) ₃ -], tetramethylene [-(CH ₂ ) ₄ -], pentamethyl [-(CH ₂ ) ₅ -], etc. The branched aliphatic hydrocarbon group preferably has a carbon number of 2-10, preferably a carbon number of 3-6, more preferably a carbon number of 3 or 4, and a carbon number of 3 is the most preferred. The branched aliphatic hydrocarbon group is preferably a branched alkylene group, specifically, for example: -CH(CH ₃ )-, -CH(CH ₂ CH ₃ )-, -C(CH ₃ ) ₂ -, -C(CH ₃ )(CH ₂ CH ₃ )-, -C(CH ₃ )(CH ₂ CH ₂ CH ₃ )-, -C(CH ₂ CH ₃ ) ₂ -and other alkylene groups; -CH(CH ₃ )CH ₂ -, -CH(CH ₃ )CH(CH ₃ )-, -C(CH ₃ ) ₂ CH ₂ -, -CH(CH ₂ CH ₃ )CH ₂ -, -C(CH ₂ CH ₃ ) ₂ -CH ₂ -and other alkyl ethylene groups; -CH(CH ₃ )CH ₂ CH ₂ -, -CH ₂ CH(CH ₃ )CH ₂ -and other alkyl ethylene groups; -CH( CH ₃ )CH ₂ CH ₂ CH ₂ -, -CH ₂ CH(CH ₃ )CH ₂ CH ₂ -and other alkylene groups such as tetramethyl group and the like. The alkyl group in the alkylene group is preferably a straight-chain alkyl group with 1 to 5 carbon atoms.

The aforementioned linear or branched aliphatic hydrocarbon group may or may not have a substituent. Examples of the substituent include a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms substituted by a fluorine atom, and a carbonyl group.

・・・Aliphatic hydrocarbon group with ring in the structure The aliphatic hydrocarbon group containing a ring in the structure includes, for example, a cyclic aliphatic hydrocarbon group (a group obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring) that may contain a heteroatom-containing substituent in the ring structure, the aforementioned ring A group in which a linear or branched aliphatic hydrocarbon group is bonded to the terminal of a linear or branched aliphatic hydrocarbon group, a group in which the aforementioned cyclic aliphatic hydrocarbon group is interposed between a linear or branched aliphatic hydrocarbon group, etc. The aforementioned linear or branched aliphatic hydrocarbon group has the same content as the aforementioned. The cycloaliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, and preferably 3 to 12 carbon atoms. The cyclic aliphatic hydrocarbon group may be a polycyclic group or a monocyclic group. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a monocyclic alkane. The monocyclic alkane is preferably one having 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a polycyclic alkane. The polycyclic alkane is preferably a carbon number of 7-12. Specifically, examples include : Adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc.

The cycloaliphatic hydrocarbon group may or may not have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, and a carbonyl group. The aforementioned alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably methyl, ethyl, propyl, n-butyl, and tert-butyl. The aforementioned alkoxy group as a substituent is preferably an alkoxy group with 1 to 5 carbon atoms, methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, tert -Butoxy is preferred, methoxy and ethoxy are the most preferred. The aforementioned halogen atom as the substituent includes, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and a fluorine atom is preferred. The halogenated alkyl group as the substituent includes, for example, a group obtained by substituting part or all of the hydrogen atoms of the alkyl group with the halogen atom. In the cyclic aliphatic hydrocarbon group, part of the carbon atoms constituting the ring structure may be substituted by a substituent containing a heteroatom. The heteroatom-containing substituent is preferably -O-, -C(=O)-O-, -S-, -S(=O) ₂ -, -S(=O) ₂ -O-.

・・The aromatic hydrocarbon group in Ya ^x1 The aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring. The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons, and it may be monocyclic or polycyclic. The carbon number of the aromatic ring is preferably 5-30, preferably 5-20, more preferably 6-15, and particularly preferably 6-12. However, the carbon number is one that does not include the carbon number in the substituent. Aromatic rings, specifically, include: aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, phenanthrene, etc.; aromatic heterocycles in which part of the carbon atoms constituting the aforementioned aromatic hydrocarbon ring is substituted by heteroatoms Wait. Examples of heteroatoms in the aromatic heterocycle include oxygen atoms, sulfur atoms, and nitrogen atoms. Specific examples of the aromatic heterocyclic ring include a pyridine ring and a thiophene ring. Specifically, the aromatic hydrocarbon group includes: a group obtained by removing two hydrogen atoms from the aforementioned aromatic hydrocarbon ring or aromatic heterocyclic ring (arylene group or heteroarylene group); A ring of aromatic compounds (for example: biphenyl, fen, etc.) is a group obtained by removing two hydrogen atoms; a group obtained by removing one hydrogen atom from the aforementioned aromatic hydrocarbon ring or aromatic heterocyclic ring (aryl or heteroaromatic (For example, benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, The aryl group in the aralkyl group such as 2-naphthylethyl group is obtained by removing one more hydrogen atom). The carbon number of the alkylene group bonded to the aryl or heteroaryl group is preferably 1 to 4, preferably 1 to 2 carbons, and particularly preferably 1 carbon.

In the aforementioned aromatic hydrocarbon group, the hydrogen atom of the aromatic hydrocarbon group may be substituted with a substituent. For example: the hydrogen atom bonded to the aromatic ring in the aromatic hydrocarbon group can be replaced by a substituent. Examples of the substituent include alkyl groups, alkoxy groups, halogen atoms, halogenated alkyl groups, and hydroxyl groups. The aforementioned alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably methyl, ethyl, propyl, n-butyl, and tert-butyl. The alkoxy group, halogen atom, and halogenated alkyl group as the aforementioned substituents are, for example, exemplified as substituents that replace the hydrogen atom of the aforementioned cyclic aliphatic hydrocarbon group.

・Divalent linking group containing heteroatoms: When Ya ^x1 is a divalent linking group containing heteroatoms, the preferred linking group includes: -O-, -C(=O)-O- , -C(=O)-, -OC(=O)-O-, -C(=O)-NH-, -NH-, -NH-C(=NH)-(H can be alkyl, 醯Substituents such as groups), -S-, -S(=O) ₂ -, -S(=O) ₂ -O-, general formula -Y ²¹ -OY ²² -, -Y ²¹ -O-, -Y ²¹ -C(=O)-O-, -C(=O)-OY ²¹ -, -[Y ²¹ -C(=O)-O] _m” -Y ²² -, -Y ²¹ -OC( =O)-Y ²² -or -Y ²¹ -S(=O) ₂ -OY ²² -represents a group [wherein, Y ²¹ and Y ^{22 are} each independently an optionally substituted divalent hydrocarbon group, O Is an oxygen atom, m" is an integer of 0 to 3] and the like. The aforementioned heteroatom-containing divalent linking group is -C(=O)-NH-, -C(=O)-NH-C(=O)-, -NH-, -NH-C(=NH)- In case, the H may be substituted by substituents such as alkyl and acyl groups. The substituent (alkyl group, acyl group, etc.) preferably has a carbon number of 1-10, more preferably 1-8, and particularly preferably 1-5. General formula -Y ²¹ -OY ²² -, -Y ²¹ -O-, -Y ²¹ -C(=O)-O-, -C(=O)-OY ²¹ -, -(Y ²¹ -C(=O )-O] _m” -Y ²² -, -Y ²¹ -OC(=O)-Y ²² -or -Y ²¹ -S(=O) ₂ -OY ²² -, Y ²¹ and Y ^{22 are} independently A divalent hydrocarbon group that may have a substituent. The divalent hydrocarbon group is, for example, the same as those listed in the description of the divalent linking group (the divalent hydrocarbon group that may have a substituent). Y ²¹ is Straight-chain aliphatic hydrocarbon groups are preferred, and straight-chain alkylene groups are preferred, straight-chain alkylene groups with 1 to 5 carbon atoms are more preferred, and methylidene or ethylidene groups are particularly preferred. 。 Y ^{22 is} preferably a straight-chain or branched aliphatic hydrocarbon group, preferably a methylidene, an ethylene group or an alkylene group. The alkyl group in the alkylene group has 1 to 5 carbon atoms. The straight-chain alkyl group is preferred, the straight-chain alkyl group with 1 to 3 carbon atoms is preferred, and the methyl group is the most preferred. Formula -[Y ²¹ -C(=O)-O] _m" In the group represented by -Y ²² -, m" is an integer from 0 to 3, preferably an integer from 0 to 2, preferably 0 or 1, and particularly preferably 1. That is, the formula -[Y ²¹ The group represented by -C(=O)-O] _m" -Y ²² -is particularly preferably the group represented by the formula -Y ²¹ -C(=O)-OY ²² -. Among these are the formula _{- (CH 2) a '-C} (= O) -O- (CH 2) b' - preferably the group represented. In this formula, a'is an integer of 1-10, preferably an integer of 1-8, more preferably an integer of 1-5, more preferably 1 or 2, and most preferably 1. b'is an integer of 1-10, preferably an integer of 1-8, preferably an integer of 1-5, more preferably 1 or 2, and most preferably 1.

Ya ^{x1 is} a single bond, ester bond [-C(=O)-O-], ether bond (-O-), -C(=O)-NH-, linear or branched alkylene A base or a combination of these is preferred, and among them, a single bond is particularly preferred.

In the aforementioned formula (a10-1), Wa ^x1 is an aromatic hydrocarbon group having a valence of (n _ax1 + 1). The aromatic hydrocarbon group in Wa ^x1 includes, for example, a group obtained by removing (n _ax1 +1) hydrogen atoms from an aromatic ring. The aromatic ring here is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons, and it may be monocyclic or polycyclic. The carbon number of the aromatic ring is preferably 5-30, preferably 5-20, more preferably 6-15, and particularly preferably 6-12. Aromatic rings, specifically, include: aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, phenanthrene, etc.; aromatic heterocycles in which part of the carbon atoms constituting the aforementioned aromatic hydrocarbon ring is substituted by heteroatoms Wait. Examples of heteroatoms in the aromatic heterocycle include oxygen atoms, sulfur atoms, and nitrogen atoms. Specific examples of the aromatic heterocyclic ring include a pyridine ring and a thiophene ring.

In the aforementioned formula (a10-1), n _ax1 is an integer of 1 to 3, preferably 1 or 2, and more preferably 1.

The following are specific examples of the structural unit represented by the aforementioned general formula (a10-1). In the following formula, R ^α represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

(A1) The structural unit (a10) possessed by the component may be one type or two or more types. (A1) The proportion of the structural unit (a10) in the component, relative to the total (100 mol%) of the total structural units constituting the component (A1), is for example 0 to 80 mol%, and 10 to 80 mol% % Is better, preferably 20 to 70 mol%, and particularly preferably 30 to 60 mol%. When the ratio of the structural unit (a10) is more than the lower limit of the aforementioned preferable range, the sensitivity, resolution, and roughness of lithographic etching characteristics can be improved. On the other hand, when it is below the upper limit of the aforementioned preferred range, it is easy to achieve a balance with other structural units, and various lithographic etching characteristics can be made better.

Structural unit (a9): The structural unit (a9) is a structural unit represented by the following general formula (a9-1).

[式中，R為氫原子、碳數1～5之烷基或碳數1～5之鹵化烷基；Ya⁹¹ 為單鍵或2價之連結基。Ya⁹² 為2價之連結基。R⁹¹ 為可具有取代基之烴基]。

[In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbons, or a halogenated alkyl group having 1 to 5 carbons; Ya ⁹¹ is a single bond or a divalent linking group. Ya ⁹² is the link base of 2 valence. R ⁹¹ is a hydrocarbon group which may have a substituent].

In the foregoing formula (a9-1), R is the same as the foregoing. R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms. In terms of ease of industrial availability, a hydrogen atom or a methyl group is particularly preferred.

In the aforementioned formula (a9-1), the divalent linking group in Ya ⁹¹ is the same as the divalent linking group in Ya ^x1 in the above general formula (a10-1). Among them, Ya ^{91 is} preferably a single bond.

In the aforementioned formula (a9-1), the divalent linking group in Ya ⁹² has the same content as the divalent linking group of Ya ^x1 in the general formula (a10-1). Among the divalent linking groups in Ya ⁹² , the divalent hydrocarbon group which may have a substituent is preferably a linear or branched aliphatic hydrocarbon group. In addition, among the divalent linking groups in Ya ⁹² , the divalent linking groups containing heteroatoms include: -O-, -C(=O)-O-, -C(=O)-,- OC(=O)-O-, -C(=O)-NH-, -NH-, -NH-C(=NH)-(H can be substituted by substituents such as alkyl and acyl),- S-, -S(=O) ₂ -, -S(=O) ₂ -O-, -C(=S)-, general formula -Y ²¹ -OY ²² -, -Y ²¹ -O-, -Y ^{21 -C (= O) -O-,} -C (= O) -O - Y 21, [Y 21 -C (= O) -O] m '-Y 22 - or -Y ²¹ -OC (= O) A group represented by -Y ^22- [In the formula, Y ²¹ and Y ^{22 are} each independently an optionally substituted divalent hydrocarbon group, O is an oxygen atom, and m'is an integer of 0 to 3] and the like. Among them, -C(=O)- and -C(=S)- are better.

In the aforementioned formula (a9-1), the hydrocarbon group in R ⁹¹ includes, for example, an alkyl group, a monovalent alicyclic hydrocarbon group, an aryl group, and an aralkyl group. The alkyl group in R ⁹¹ preferably has 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms, and more preferably 1 to 4 carbon atoms. It can be linear or branched. . Specifically, for example, methyl, ethyl, propyl, butyl, hexyl, octyl, etc. are preferable examples. The monovalent alicyclic hydrocarbon group in R ⁹¹ preferably has 3 to 20 carbon atoms, preferably 3 to 12 carbon atoms, and it may be polycyclic or monocyclic. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a monocyclic alkane. The monocyclic alkane is preferably one having 3 to 6 carbon atoms, and specific examples thereof include cyclobutane, cyclopentane, and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a polycyclic alkane, and the polycyclic alkane is preferably one with 7 to 12 carbon atoms. Specifically, it can be exemplified Such as: adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc. The aryl group in R ⁹¹ preferably has 6 to 18 carbons, preferably 6 to 10 carbons. Specifically, phenyl is particularly preferred. R ⁹¹ in the aralkyl, the alkylene group of carbon number 1 to 8 of the above-described "aryl group R ⁹¹ in the" aralkyl group bonded to give it better to 6 carbon atoms, alkyl of 1 to extend and The aralkyl group obtained by bonding the aforementioned "aryl group in R ⁹¹ " is preferred, and the aralkyl group obtained by bonding an alkylene group with 1 to 4 carbon atoms to the aforementioned "aryl group in R ⁹¹ " is Especially good. The hydrocarbyl group in R ⁹¹ is preferably one in which part or all of the hydrogen atoms in the hydrocarbyl group are substituted by fluorine atoms, and it is preferable that 30-100% of the hydrogen atoms in the hydrocarbyl group are substituted by fluorine atoms. Among them, a perfluoroalkyl group in which all hydrogen atoms in the above-mentioned alkyl group are replaced by fluorine atoms is particularly preferred.

The hydrocarbon group in R ⁹¹ may have a substituent. Examples of the substituent include a halogen atom, a pendant oxygen (oxo) group (=O), a hydroxyl group (-OH), an amino group (-NH ₂ ), -SO ₂ -NH ₂ and the like. In addition, part of the carbon atoms constituting the hydrocarbon group may be substituted with a substituent containing a heteroatom. The substituents containing heteroatoms, for example: -O-, -NH-, -N=, -C(=O)-O-, -S-, -S(=O) ₂ -, -S(=O ) ₂ -O- etc. In R ⁹¹ , the hydrocarbon group having a substituent includes, for example, the lactone-containing cyclic group represented by the aforementioned general formulas (a2-r-1) to (a2-r-7).

In addition, in R ⁹¹ , the hydrocarbon group having a substituent includes, for example, the -SO ₂ -containing cyclic group represented by the aforementioned general formulas (a5-r-1) to (a5-r-4); The substituted aryl group, monovalent heterocyclic group, etc. represented by the above chemical formula.

Among the structural units (a9), a structural unit represented by the following general formula (a9-1-1) is preferred.

[式中，R與前述為相同之內容，Ya⁹¹ 為單鍵或2價之連結基，R⁹¹ 為可具有取代基之烴基，R⁹² 為氧原子或硫原子]。

[In the formula, R is the same as the above, Ya ⁹¹ is a single bond or a divalent linking group, R ⁹¹ is an optionally substituted hydrocarbon group, and R ⁹² is an oxygen atom or a sulfur atom].

In the general formula (a9-1-1), the description of Ya ⁹¹ , R ⁹¹ and R is the same as the above. In addition, R ⁹² is an oxygen atom or a sulfur atom.

The following are specific examples of the structural unit represented by the aforementioned formula (a9-1) or general formula (a9-1-1). In the following formula, R ^α represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

(A1) The structural unit (a9) contained in the component may be one type or two or more types. When the component (A1) has a structural unit (a9), the ratio of the structural unit (a9) relative to the total structural unit (100 mol%) of the component (A1) is preferably 1-40 mol%. It is preferably 3-30 mol%, more preferably 5-25 mol%, and particularly preferably 10-20 mol%. When the ratio of the structural unit (a9) is above the lower limit of the aforementioned preferable range, for example, it is possible to appropriately adjust the diffusion length of the acid, improve the adhesion of the resist film to the substrate, and appropriately adjust the solubility during development. , The effect of improving the etching resistance, etc., when it is below the upper limit of the above-mentioned preferred range, the balance with other structural units can be easily achieved, and various lithographic etching characteristics can be made better.

Structural unit (a4): The structural unit (a4) is a structural unit containing a non-acid dissociable cyclic group. When the component (A1) has the structural unit (a4), the dry etching resistance of the formed photosensitive resin pattern can be improved. In addition, the hydrophobicity of (A1) component can be improved. The "non-acid dissociable cyclic group" in the structural unit (a4), when an acid is generated from the component (B) described later by exposure, will not be dissociated even if it is subjected to the action of the acid, but will remain in the The cyclic group in the structural unit.

The structural unit (a4) is preferably a structural unit derived from an acrylic ester containing a non-acid dissociable aliphatic cyclic group. The cyclic group can be exemplified by the same exemplification as exemplified in the aforementioned structural unit (a1), and it can be used conventionally known as ArF excimer lasers and KrF excimer lasers (preferably It is the group of resin component of resist composition such as ArF excimer laser. In particular, when at least one selected from tricyclodecyl, adamantyl, tetracyclododecyl, isobornyl, and norbornyl, it is preferred from the viewpoint of easy industrial availability. These polycyclic groups may have a linear or branched alkyl group having 1 to 5 carbon atoms as a substituent.

Specific examples of the structural unit (a4) include those having a structure represented by the following general formulas (a4-1) to (a4-7).

[式中，R^α 表示氫原子、甲基或三氟甲基]。

[In the formula, R ^α represents a hydrogen atom, a methyl group, or a trifluoromethyl group].

(A1) The structural unit (a4) contained in the component may be one type or two or more types. (A1) When the component contains the structural unit (a4), the ratio of the structural unit (a4) relative to the total of the total structural units constituting the component (A1) is preferably 1-30 mol%, and 10-20 mol% Ear% is better.

The (A1) component contained in the resist composition may be used alone or in combination of two or more. The component (A1) preferably contains a polymer compound (A1-1) (hereinafter, also referred to as "(A1-1) component") having the structural unit (a1). The preferred (A1-1) component includes, for example, a polymer compound having a repeating structure of the structural unit (a1) and the structural unit (a2). In addition to the combination of the above two types of structural units, the third or more structural units can be combined with the above-described structural units appropriately according to the desired effect. The third structural unit is preferably structural unit (a3) or the like.

The (A1) component can dissolve the monomers that derive each structural unit in the polymerization solvent, and then dissolve, for example, azobisisobutyronitrile (AIBN), dimethyl azobisisobutyrate (such as V-601, etc.) It is prepared by adding other free radical polymerization initiators to it and conducting polymerization reaction. Or, the component (A1) can combine the monomer of the derivatized structural unit (a1) and the precursor monomer of the structural unit other than the derivatized structural unit (a1) (a monomer with a protected functional group). , Dissolved in the polymerization solvent, and then added the above-mentioned free radical polymerization initiator to the polymerization reaction, followed by the deprotection reaction. In addition, during polymerization, a chain transfer agent such as HS-CH ₂ -CH ₂ -CH ₂ -C(CF ₃ ) ₂ -OH can be used in combination to introduce a -C(CF ₃ ) ₂ -OH group at the end. In this way, the copolymer produced by introducing the "hydroxyalkyl group obtained by replacing part of the hydrogen atoms of the alkyl group with fluorine atoms" can effectively reduce development defects or reduce LER (line roughness: line sidewall The uneven unevenness).

(A1) The weight average molecular weight (Mw) of the component (GPC conversion standard for polystyrene) is not particularly limited. Generally, 1000～50,000 is better, and 2000～30,000 is better. Good, more preferably 3000 to 20000. (A1) When the Mw of the component is below the preferred upper limit of the range, when used as a resist, it has sufficient solubility in the resist solvent, and when it is above the preferred lower limit of the range, it has good solubility. The dry etching resistance or the cross-sectional shape of the resist pattern. (A1) The degree of dispersion (Mw/Mn) of the components is not particularly limited. Generally, 1.0-4.0 is preferred, 1.0-3.0 is preferred, and 1.1-2.0 is particularly preferred. In addition, Mn represents the number average molecular weight.

・(A2) Ingredients In the resist composition of this embodiment, the (A) component may be combined with a base component that does not correspond to the aforementioned (A1) component that changes the solubility of the developer through the action of acid (hereinafter, also referred to as " (A2) Ingredients"). The component (A2) is not particularly limited, and it can be arbitrarily selected and used from many components conventionally known as substrate components for chemically amplified resist compositions. (A2) Ingredients, one type of high molecular compound or low molecular compound can be used alone, or two or more types can be used in combination.

(A) The ratio of (A1) component in component (A) is preferably 25% by mass or more, preferably 50% by mass or more, and more preferably 75% by mass or more relative to the total mass of (A) components. It can be 100% by mass. When the ratio is 25% by mass or more, it is easy to form a resist pattern with various excellent lithographic etching characteristics such as high sensitivity, resolution, and roughness improvement.

In the resist composition of this embodiment, the content of component (A) can be adjusted appropriately according to the thickness of the resist film to be formed.

＜(B) Ingredients＞ The (B) component of the resist composition in this embodiment contains the compound (B1) represented by the following general formula (b1-1) (hereinafter, also referred to as "(B1) component").

[式中，R₀ ¹⁰¹ 為多環式脂肪族烴基；其中，多環式脂肪族烴基的氫原子亦可被取代基所取代；R¹⁰² 為氟原子或碳數1～5之氟化烷基；Y¹⁰¹ 為單鍵，或含有氧原子的2價之連結基；V¹⁰¹ 為單鍵、伸烷基或氟化伸烷基；m為1以上之整數，且M’^{m ＋} 為m價之鎓陽離子]。

[In the formula, R ₀ ¹⁰¹ is a polycyclic aliphatic hydrocarbon group; among them, the hydrogen atom of the polycyclic aliphatic hydrocarbon group may also be substituted by a substituent; R ¹⁰² is a fluorine atom or a fluorinated alkyl group with 1 to 5 carbon atoms ; Y ¹⁰¹ is a single bond, or a divalent linking group containing an oxygen atom of a; V ¹⁰¹ is a single bond, an alkylene group or fluorinated alkylene group; m is an integer of 1 or more, and m ^{'m +} m is the valence of Onium cation].

{Anion portion} In the formula (b1-1), R ₀ ¹⁰¹ is a polycyclic aliphatic hydrocarbon group. Among them, the hydrogen atom of the polycyclic aliphatic hydrocarbon group may be substituted by a substituent.

The polycyclic aliphatic hydrocarbon group is preferably a group obtained by removing one hydrogen atom from a polycyclic alkane, and the polycyclic alkane is preferably one having 7-30 carbons. Among them, the polycyclic alkane may include, for example, adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, and other polycyclic alkane having a cross-linked ring system with a polycyclic skeleton; Condensed ring systems such as a cyclic group having a cholesterol skeleton and a polycyclic alkane having a polycyclic skeleton, etc. Among them, polycyclic alkanes having a crosslinked ring system with a polycyclic skeleton are preferred. Preferred specific examples of the polycyclic aliphatic hydrocarbon group include adamantyl group and the like.

When the hydrogen atom of the polycyclic aliphatic hydrocarbon group is substituted, the substituent includes, for example, a hydroxyl group, a carboxyl group, a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), alkoxy (methoxy, ethoxy) Group, propoxy group, butoxy group, etc.), alkyloxycarbonyl group and the like. Among the substituents, it is easier to suppress the occurrence of defects in the unexposed portion of the resist film, and the hydroxyl group is preferred. The plural hydrogen atoms of the polycyclic aliphatic hydrocarbon group may be independently substituted with the above-mentioned substituents and the like.

In the formula (b1-1), Y ¹⁰¹ is a single bond or a divalent linking group containing an oxygen atom. When Y ¹⁰¹ is a divalent linking group containing an oxygen atom, the Y ¹⁰¹ may contain atoms other than the oxygen atom. Atoms other than oxygen atoms, such as carbon atoms, hydrogen atoms, sulfur atoms, and nitrogen atoms. The divalent linking group containing an oxygen atom, for example, an oxygen atom (ether bond: -O-), an ester bond (-C(=O)-O-), an oxycarbonyl group (-OC(=O) -), amide bond (-C(=O)-NH-), carbonyl group (-C(=O)-), carbonate bond (-OC(=O)-O-) and other non-hydrocarbon systems The linking group containing oxygen atoms; the combination of the non-hydrocarbon linking group containing oxygen atoms and alkylene groups. In this combination, a sulfonyl group (-SO ₂ -) can be connected. The divalent linking group containing an oxygen atom is, for example, a linking group represented by the following general formulas (y-al-1) to (y-al-7).

[式中，V’¹⁰¹ 為單鍵或碳數1～5之伸烷基，V’¹⁰² 為碳數1～30的2價之飽和烴基]。

[In the formula, ^V'101 is a single bond or an alkylene group having 1 to 5 carbons, and ^V'102 is a divalent saturated hydrocarbon group having 1 to 30 carbons].

V '2 of the monovalent saturated hydrocarbon group ^102, extends carbon number of alkyl group having 1 to 30 is preferable, and an alkylene group having a carbon number of 1 to 10 is preferred to extend 1 to 5 carbon atoms of the alkyl group is more good.

V ^'101 and V' ¹⁰² in the alkylene may be straight-chain alkylene it may, the alkylene chain may also be branched, again preferably straight chain alkylene of. V ^'101 and V' ¹⁰² in the alkylene group, specific examples thereof include such as: Methyl extension _{[-CH 2 -]; - CH} (CH 3) -, - CH (CH 2 CH 3) -, - C(CH ₃ ) ₂ -, -C(CH ₃ )(CH ₂ CH ₃ )-, -C(CH ₃ )(CH ₂ CH ₂ CH ₃ )-, -C(CH ₂ CH ₃ ) ₂ -etc. Alkyl ethylene; ethylene [-CH ₂ CH ₂ -]; -CH(CH ₃ )CH ₂ -, -CH(CH ₃ )CH(CH ₃ )-, -C(CH ₃ ) ₂ CH _2- , -CH(CH ₂ CH ₃ )CH ₂ -, etc. alkyl ethylene; trimethyl (n-propylene) [-CH ₂ CH ₂ CH ₂ -]; -CH(CH ₃ )CH ₂ CH ₂ -, -CH ₂ CH(CH ₃ )CH ₂ -and other alkyl trimethylidene; tetramethylidene [-CH ₂ CH ₂ CH ₂ CH ₂ -]; -CH(CH ₃ )CH ₂ CH ₂ CH ₂ -, -CH ₂ CH(CH ₃ )CH ₂ CH ₂ -such as alkyltetramethylene; pentamethyl [-CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -] and so on.

Y ^{101 is} preferably a divalent linking group containing an ester bond, or a divalent linking group containing an ether bond.

In the formula (b1-1), V ¹⁰¹ is a single bond, an alkylene group or a fluorinated alkylene group. The alkylene group and fluorinated alkylene group in V ¹⁰¹ preferably have 1 to 4 carbon atoms. V ¹⁰¹ In the fluorinated alkylene group, for example: V ¹⁰¹ in the alkylene group, one hydrogen atom is partially or completely substituted by fluorine atoms of the group. Among them, V ^{101 is} preferably a single bond or a fluorinated alkylene group having 1 to 4 carbon atoms, and a fluorinated alkylene group having 1 to 4 carbon atoms is preferred.

In the formula (b1-1), R ¹⁰² is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. Among them, a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms is preferred, and a fluorine atom is preferred.

(b1-1) Specific examples of the anion portion of the component include, for example, anions represented by the following formulas (an-b-1) to (an-b-3).

{} In the cation portion of formula (b1-1), m is an integer of 1 or more, and M ^{'m +} m is the valence of the cation, again sulfonium cation, iodonium cation of the preferred embodiment illustrated, for example, by the following general formula (CA -1)～(ca-4) Organic cations, etc. respectively represented.

[式中，R²⁰¹ ～R²⁰⁷ 及R²¹¹ ～R²¹² 各別獨立表示可具有取代基的芳基、可具有取代基的烷基，或可具有取代基的烯基。R²⁰¹ ～R²⁰³ 、R²⁰⁶ ～R²⁰⁷ 、R²¹¹ ～R²¹² 可各別相互鍵結並與式中的硫原子共同形成環。R²⁰⁸ ～R²⁰⁹ 表示各別獨立之氫原子或碳數1～5之烷基，或相互鍵結並與式中的硫原子共同形成環。R²¹⁰ 為可具有取代基的芳基、可具有取代基的烷基、可具有取代基的烯基，或可具有取代基的含-SO₂ -之環式基。L²⁰¹ 表示-C(=O)-或-C(=O)-O-。複數個Y²⁰¹ 各別獨立表示伸芳基、伸烷基或伸烯基。x為1或2。W²⁰¹ 表示(x＋1)價之連結基]。

[In the formula, R ²⁰¹ to R ²⁰⁷ and R ²¹¹ to R ²¹² each independently represent an optionally substituted aryl group, an optionally substituted alkyl group, or an optionally substituted alkenyl group. R ²⁰¹ to R ²⁰³ , R ²⁰⁶ to R ²⁰⁷ , and R ²¹¹ to R ²¹² may be individually bonded to each other and form a ring with the sulfur atom in the formula. R ²⁰⁸ to R ²⁰⁹ represent independent hydrogen atoms or alkyl groups with 1 to 5 carbon atoms, or they are bonded to each other and form a ring with the sulfur atom in the formula. R ²¹⁰ is an optionally substituted aryl group, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted -SO ₂ -containing cyclic group. L ²⁰¹ represents -C(=O)- or -C(=O)-O-. A plurality of Y ²⁰¹ each independently represents an arylene group, an alkylene group or an alkenylene group. x is 1 or 2. W ²⁰¹ represents the link base of (x+1) valence].

The aryl groups in R ²⁰¹ to R ²⁰⁷ and R ²¹¹ to R ²¹² include, for example, aryl groups with 6 to 20 carbon atoms, and phenyl and naphthyl are preferred. The alkyl group in R ²⁰¹ to R ²⁰⁷ and R ²¹¹ to R ²¹² is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms. The alkenyl groups in R ²⁰¹ to R ²⁰⁷ and R ²¹¹ to R ²¹² preferably have 2 to 10 carbon atoms. The substituents that R ²⁰¹ to R ²⁰⁷ and R ²¹¹ to R ²¹² may have include, for example, alkyl groups, halogen atoms, halogenated alkyl groups, carbonyl groups, cyano groups, amino groups, aryl groups, and the following general formula (ca-r -1) ~ (ca-r-7) the base and so on.

[式中，R’²⁰¹ 各別獨立為氫原子、可具有取代基之環式基、可具有取代基之鏈狀烷基，或可具有取代基之鏈狀烯基]。

[Wherein, R ^'201 independently of each other a hydrogen atom, a cyclic group may have a substituent group, the group may have a substituent of an alkyl chain, or a chain substituent groups of the alkenyl group].

^R'201 is a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent.

Cyclic groups that may have substituents: The cyclic group is preferably a cyclic hydrocarbon group, and the cyclic hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group. An aliphatic hydrocarbon group means a hydrocarbon group that is not aromatic. In addition, the aliphatic hydrocarbon group may be saturated or unsaturated, and saturated ones are generally preferred.

R ^'201 in the aromatic hydrocarbon group, an aromatic hydrocarbon group having rings. The carbon number of the aromatic hydrocarbon group is preferably 3-30, preferably 5-30, more preferably 5-20, particularly preferably 6-15, and most preferably 6-10. Wherein, the carbon number is one that does not include the carbon number in the substituent. R ^'201 in the aromatic hydrocarbon group has an aromatic ring, specific examples thereof include such as: benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or an aromatic ring constituting the plurality of portion of one of the carbon atoms is heteroaryl Aromatic heterocyclic ring derived from atom substitution. Examples of heteroatoms in the aromatic heterocycle include oxygen atoms, sulfur atoms, and nitrogen atoms. R 'is an aromatic hydrocarbon group of ^201, specifically, include such as: the aromatic ring is removed by a hydrogen atom to give the group (aryl group: include such as: phenyl, naphthyl, etc.), the aromatic ring One of the hydrogen atoms is substituted by an alkylene group (e.g., benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2- Aralkyl groups such as naphthylethyl, etc.). The carbon number of the aforementioned alkylene (alkane chain in the aralkyl group) is preferably 1 to 4, preferably 1 to 2, and particularly preferably 1.

R ^'201 in the cyclic aliphatic hydrocarbon group include such as: aliphatic hydrocarbon group containing a ring of the structure. The aliphatic hydrocarbon group containing the ring in the structure, for example, alicyclic hydrocarbon group (a group obtained by removing one hydrogen atom from an aliphatic hydrocarbon ring), an alicyclic hydrocarbon group is bonded to a linear or branched aliphatic A group derived from the terminal of a group hydrocarbon group, a group derived from an alicyclic hydrocarbon group between a linear or branched aliphatic hydrocarbon group, etc. The aforementioned alicyclic hydrocarbon group preferably has a carbon number of 3-20, preferably 3-12. The aforementioned alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a monocyclic alkane. The monocyclic alkane is preferably one having 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing more than one hydrogen atom from a polycyclic alkane, and the polycyclic alkane preferably has 7-30 carbon atoms. Among them, the polycyclic alkane is a polycyclic alkane with a cross-linked ring system such as adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc.; with cholesterol A polycyclic alkane having a polycyclic skeleton of a condensed ring system such as a cyclic group of the skeleton is preferable.

Chain alkyl group may have a substituent group of: R 'alkyl chain of ^201, may be any linear or branched chain of one. The linear alkyl group preferably has a carbon number of 1-20, preferably 1-15, and most preferably 1-10. Specifically, examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl Group, isotridecyl, tetradecyl, pentadecyl, hexadecyl, isohexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, two Undecyl, behenyl, etc. The branched alkyl group preferably has a carbon number of 3-20, preferably 3-15, and most preferably 3-10. Specifically, examples include: 1-methylethyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, etc.

Chain alkenyl group may have a substituent group of: R 'chain alkenyl group of ^201, may be any linear or branched chain of one can, again preferably 2 to 10 carbon atoms, 2 to 5 Preferably, 2 to 4 are more preferable, and 3 is particularly preferable. Linear alkenyl, for example: vinyl, propenyl (allyl), butynyl, etc. Examples of the branched alkenyl group include 1-methylvinyl, 2-methylvinyl, 1-methylpropenyl, and 2-methylpropenyl. Among the above-mentioned chain alkenyl groups, linear alkenyl groups are preferred, vinyl and propenyl are preferred, and vinyl is particularly preferred.

R 'chain alkyl or alkenyl substituent group ²⁰¹ of the group may include: an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, the above-described R' are the cyclic group ²⁰¹ Wait.

環、氧硫

環、噻蒽環、啡噁噻環、四氫噻吩鎓環、四氫硫代吡喃鎓環等。When R ²⁰¹ ～R ²⁰³ , R ²⁰⁶ ～R ²⁰⁷ , R ²¹¹ ～R ²¹² are bonded to each other and form a ring with the sulfur atom in the formula, they can be interposed by heteroatoms such as sulfur atom, oxygen atom, nitrogen atom, etc. , Or carbonyl, -SO-, -SO ₂ -, -SO ₃ -, -COO-, -CONH- or -N(R _N )- (the _RN is an alkyl group with 1 to 5 carbons), etc. The base is bonded. The formed ring is a ring formed by including a sulfur atom in the ring skeleton in the formula, and contains a sulfur atom. A 3-10 membered ring is preferred, and a 5-7 membered ring is particularly preferred. Specific examples of the ring formed, for example: thiophene ring, thiazole ring, benzothiophene ring, thianthene ring, benzothiophene ring, dibenzothiophene ring, 9H-sulfur

Ring, oxygen sulfur

Ring, thianthracene ring, phenanthrene ring, tetrahydrothiophenium ring, tetrahydrothiopyrylium ring, etc.

R ²⁰⁸ to R ²⁰⁹ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. When the alkyl group is an alkyl group, they may be formed by bonding to each other ring.

R ²¹⁰ is an optionally substituted aryl group, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted -SO ₂ -containing cyclic group. The aryl group in R ²¹⁰ includes, for example, unsubstituted aryl groups with 6 to 20 carbon atoms, etc., and phenyl and naphthyl are preferred. The alkyl group in R ²¹⁰ is preferably a chain or cyclic alkyl group with 1-30 carbon atoms. The alkenyl group in R ²¹⁰ preferably has 2 to 10 carbon atoms. R ²¹⁰ may be the group having a substituent -SO ₂ - cyclic group, with "containing -SO ₂ - many cyclic group" preferably, in the formula (a5-r-1) is a group represented by the more good.

Y ²⁰¹ each independently represents an arylene group, an alkylene group or an alkenylene group. The aryl group in Y ²⁰¹ includes, for example, a group obtained by removing one hydrogen atom from the aryl group in R ²¹⁰ . ²⁰¹ of the Y in the alkylene, alkenylene group may include: by the R 'alkyl chain, alkenyl chain ²⁰¹ is illustrated removal of the group a group derived from the hydrogen atom and the like.

In the aforementioned formula (ca-4), x is 1 or 2. W ²⁰¹ is (x+1) valence, that is, the linking base of divalent or trivalent. The divalent linking group in W ²⁰¹ is preferably a divalent hydrocarbon group that may have a substituent, and examples thereof include the same divalent substituent that may have a substituent as Ya ²¹ in the above general formula (a2-1) The hydrocarbon group. The divalent linking group in W ²⁰¹ may be linear, branched, or cyclic, and cyclic is preferred. Among them, a group obtained by combining two carbonyl groups at both ends of the aryl group is preferred. The arylene group may be exemplified by phenylene, naphthylene, etc., and phenylene is particularly preferred. W ²⁰¹ of the trivalent linking group include such as: derived by removing one hydrogen atom from the aforementioned group of W ²⁰¹ of the divalent linking group, the divalent linking group of the bonded and then the divalent linking group And get the base and so on. The trivalent linking group in W ²⁰¹ is preferably a group obtained by bonding two carbonyl groups with an aryl group.

Preferred cations represented by the aforementioned formula (ca-1), specifically, include the following chemical formulas (ca-1-1)～(ca-1-78), (ca-1-101)～( ca-1-149) cations, etc. respectively expressed. In the following chemical formula, g1 represents the number of repetitions, and g1 is an integer of 1-5. g2 represents the number of repetitions, and g2 is an integer from 0 to 20. g3 represents the number of repetitions, and g3 is an integer from 0 to 20.

[式中，R”²⁰¹ 為氫原子或取代基。該取代基，可列舉如：上述R²⁰¹ ～R²⁰⁷ 及R²¹¹ ～R²¹² 可具有的取代基中所列舉的烷基、鹵素原子、鹵化烷基、羰基、氰基、胺基、芳基、通式(ca-r-1)～(ca-r-7)所各別表示之基等]。

[In the formula, R" ²⁰¹ is a hydrogen atom or a substituent. Examples of the substituent include alkyl groups, halogen atoms, and halogenated groups as mentioned in the substituents that R ²⁰¹ to R ²⁰⁷ and R ²¹¹ to R ²¹² may have. Alkyl group, carbonyl group, cyano group, amino group, aryl group, groups represented by the general formulas (ca-r-1) to (ca-r-7), etc.].

Preferred cations represented by the aforementioned formula (ca-2), specifically, cations represented by the following formulas (ca-2-1)～(ca-2-2), diphenylidium Cation, bis(4-tert-butylphenyl) iodonium cation, etc.

Preferable cations represented by the aforementioned formula (ca-3) include, specifically, cations represented by the following formulas (ca-3-1) to (ca-3-7), and the like.

Preferable cations represented by the aforementioned formula (ca-4), specifically, cations represented by the following formulas (ca-4-1) to (ca-4-2), etc.

Among the above, the cation part ((M ^{m +} ) _1/m ) is preferably the cation represented by the general formula (ca-1), and the chemical formula (ca-1-1)～(ca-1-78) The cations represented by (ca-1-101)～(ca-1-149) are preferred.

(B1) Among the above components, the compound (B11) represented by the following formula (b1-1-1) is more preferable.

[式中，R₀ ²⁰¹ 為具有羥基的多環式脂肪族烴基。R¹⁰² 為氟原子或碳數1～5之氟化烷基。V₀ ¹⁰¹ 為碳數1～4之氟化伸烷基。m為1以上之整數，且M’^{m ＋} 為m價之鎓陽離子]。

[In the formula, R ₀ ²⁰¹ is a polycyclic aliphatic hydrocarbon group having a hydroxyl group. R ¹⁰² is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. V ₀ ¹⁰¹ is a fluorinated alkylene group having 1 to 4 carbon atoms. m is an integer of 1 or more, and M ^{'m +} is an onium cation of valence m].

In the formula (b1-1-1), R ₀ ²⁰¹ is a polycyclic aliphatic hydrocarbon group having a hydroxyl group. The plural hydrogen atoms in the polycyclic aliphatic hydrocarbon group can be taken by the hydroxyl group. The polycyclic aliphatic hydrocarbon group has, for example, the same content as that described in R ₀ ¹⁰¹ in the formula (b1-1).

In the formula (b1-1-1), R ¹⁰² is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms, which is the same as the content explained in the formula (b1-1). In the formula (b1-1-1), V ₀ ¹⁰¹ is a fluorinated alkylene group having 1 to 4 carbon atoms. The fluorinated alkylene group in V ₀ ¹⁰¹ , for example: a part or all of the hydrogen atoms of the alkylene group are substituted by fluorine atoms. Among them, a group obtained by replacing part of the hydrogen atoms of the alkylene group with fluorine atoms is preferred. In the fluorinated alkylene group of V ₀ ¹⁰¹ , the number of fluorine atoms is preferably 1 to 6, preferably 1 to 3, and more preferably 2 or 3.

In the formula (b1-1-1), M ^{'m + content} in the formula (b1-1) described the same as the contents.

In this embodiment, the preferred specific examples of the component (B1) of the resist composition are as follows; however, it is not limited to this content.

The (B1) component of the resist composition in this embodiment may be used alone or in combination of two or more.

The content of the (B1) component of the resist composition in this embodiment is preferably 50 parts by mass or less, preferably 1-40 parts by mass, and 5-30 parts by mass relative to 100 parts by mass of the (A) component Servings are better. (B1) When the content of the component is above the above lower limit, in the formation of the resist pattern, the sensitivity, resolution performance, LWR (Line Wise Roughness), shape and other lithographic etching characteristics can be reduced, or more effective It suppresses the occurrence of defects in the unexposed part of the resist film. (B1) When the content of the component is below the above upper limit, when each component is dissolved in an organic solvent, a uniform solution can be easily prepared, and the storage stability of the resist composition can be improved.

In the resist composition, the ratio of the above-mentioned (B1) component is, for example, 50% by mass or more, preferably 70% by mass in the total acid generator component (B) that acts on component (A) to generate acid Above, more preferably 95% by mass or more. In addition, it may be 100% by mass. (B1) When the ratio of the components is more than the lower limit of the aforementioned preferable range, the occurrence of defects in the unexposed part of the resist film can be further reduced.

＜Optional ingredients＞ The resist composition in this embodiment may further contain components (optional components) other than the above-mentioned (A) component and (B1) component. The optional components include (B2) component, (D) component, (E) component, (F) component, (S) component, etc. as shown below.

≪(B2) Ingredients≫ The resist composition in the present embodiment may contain acid generator components other than the above-mentioned (B1) component (hereinafter, also referred to as "(B2) component") without impairing the effect of the present invention. (B2) The ingredients are not particularly limited, and the acid generators that have been proposed so far as chemically amplified resist compositions can be used. These acid generators include, for example, onium salt-based acid generators such as iodonium salt or sulfonium salt, oxime sulfonate-based acid generators; dialkyl or bisarylsulfonyl diazomethanes, poly( Diazomethane acid generators such as bissulfonyl) diazomethanes; nitrobenzyl sulfonate acid generators, iminosulfonate acid generators, diazonium acid generators, etc. Ingredients.

Onium salt-based acid generators, for example: the compound represented by the following general formula (b-1) (hereinafter, also referred to as "(b-1) component"), the compound represented by the general formula (b-2) ( Hereinafter, it is also referred to as "(b-2) component") or a compound represented by general formula (b-3) (hereinafter, also referred to as "(b-3) component"), etc. In addition, the component (b-1) does not contain a compound corresponding to the component (B1).

[式中，R¹⁰¹ 、R¹⁰⁴ ～R¹⁰⁸ 各別獨立為可具有取代基的環式基、可具有取代基的鏈狀之烷基，或可具有取代基的鏈狀之烯基。R¹⁰⁴ 、R¹⁰⁵ 可相互鍵結而形成環。R¹⁰² 為氟原子或碳數1～5之氟化烷基；Y¹⁰¹ 為單鍵，或含有氧原子的2價之連結基；V¹⁰¹ ～V¹⁰³ 各別獨立為單鍵、伸烷基或氟化伸烷基。L¹⁰¹ ～L¹⁰² 各別獨立為單鍵或氧原子。L¹⁰³ ～L¹⁰⁵ 各別獨立為單鍵、-CO-或-SO₂ -。m為1以上之整數，且M’^{m ＋} 為m價之鎓陽離子]。

[In the formula, R ¹⁰¹ , R ¹⁰⁴ to R ^{108 are} each independently a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent. R ¹⁰⁴ and R ¹⁰⁵ may be bonded to each other to form a ring. R ¹⁰² is a fluorine atom or a fluorinated alkyl group with 1 to 5 carbon atoms; Y ¹⁰¹ is a single bond or a divalent linking group containing an oxygen atom; V ¹⁰¹ to V ^{103 are} each independently a single bond, alkylene group or Fluorinated alkylene. L ¹⁰¹ to L ^{102 are} each independently a single bond or an oxygen atom. L ¹⁰³ to L ^{105 are} each independently a single bond, -CO- or -SO ₂ -. m is an integer of 1 or more, and M ^{'m +} is an onium cation of valence m].

{Anion part} ・In formula (b-1) of the anion part of component (b-1), R ¹⁰¹ is a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or may have a substituent The chain of alkenyl.

Cyclic groups that may have substituents: The cyclic group is preferably a cyclic hydrocarbon group, and the cyclic hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group. An aliphatic hydrocarbon group means a hydrocarbon group that is not aromatic. In addition, the aliphatic hydrocarbon group may be saturated or unsaturated, and saturated ones are generally preferred.

The aromatic hydrocarbon group in R ¹⁰¹ is a hydrocarbon group having an aromatic ring. The carbon number of the aromatic hydrocarbon group is preferably 3-30, preferably 5-30, more preferably 5-20, particularly preferably 6-15, and 6- 12 is the best. Wherein, the carbon number is one that does not include the carbon number in the substituent. The aromatic ring possessed by the aromatic hydrocarbon group in R ¹⁰¹ , specifically, can be exemplified as: benzene, sulphur, naphthalene, anthracene, phenanthrene, biphenyl, or a part of the carbon atoms constituting these aromatic rings are heteroatoms Aromatic heterocyclic ring derived from substitution. Examples of heteroatoms in the aromatic heterocycle include oxygen atoms, sulfur atoms, and nitrogen atoms. The aromatic ring of the aromatic hydrocarbon group in R ¹⁰¹ , from the viewpoint of compatibility with component (A), is preferably one that does not contain heteroatoms, and it is also benzene, fen, naphthalene, anthracene, phenanthrene, biphenyl, etc. Aromatic ring is preferred. Specifically, the aromatic hydrocarbon group in R ¹⁰¹ includes a group obtained by removing one hydrogen atom from the aforementioned aromatic ring (aryl group: exemplified by phenyl, naphthyl, etc.), and hydrogen of the aforementioned aromatic ring One of the atoms is substituted by alkylene group (e.g., benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthalene Aralkyl, etc.), etc. The carbon number of the aforementioned alkylene (alkane chain in the aralkyl group) is preferably 1 to 4, preferably 1 to 2 carbons, and particularly preferably 1 carbon.

The cyclic aliphatic hydrocarbon group in R ¹⁰¹ includes, for example, an aliphatic hydrocarbon group containing a ring in the structure. The aliphatic hydrocarbon group containing the ring in the structure, for example, alicyclic hydrocarbon group (a group obtained by removing one hydrogen atom from an aliphatic hydrocarbon ring), an alicyclic hydrocarbon group is bonded to a linear or branched aliphatic A group derived from the terminal of a group hydrocarbon group, a group derived from an alicyclic hydrocarbon group between a linear or branched aliphatic hydrocarbon group, etc. The aforementioned alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms. The aforementioned alicyclic hydrocarbon group includes, for example, a monocyclic alicyclic hydrocarbon group, etc., and it is preferably a group obtained by removing one or more hydrogen atoms from a monocyclic alkane. The monocyclic alkane is preferably one having 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane.

Among them, the cyclic aliphatic hydrocarbon group in R ¹⁰¹ is preferably obtained by removing more than one hydrogen atom from a monocyclic alkane or polycyclic alkane, and it is obtained by removing one hydrogen atom from a monocyclic alkane. The group is preferable, and the group obtained by removing one hydrogen atom from cyclopentane or cyclohexane is particularly preferable.

A straight-chain aliphatic hydrocarbon group that can be bonded to an alicyclic hydrocarbon group, preferably having 1 to 10 carbons, preferably 1 to 6 carbons, more preferably 1 to 4 carbons, and 1 ~3 is the best. The straight-chain aliphatic hydrocarbon group is preferably a straight-chain alkylene group. Specifically, examples include: methylidene [-CH ₂ -], ethylidene [-(CH ₂ ) ₂ -], Methyl [-(CH ₂ ) ₃ -], tetramethylene [-(CH ₂ ) ₄ -], pentamethyl [-(CH ₂ ) ₅ -], etc. A branched aliphatic hydrocarbon group that can be bonded to an alicyclic hydrocarbon group, preferably with a carbon number of 2-10, preferably a carbon number of 3-6, more preferably a carbon number of 3 or 4, and a carbon number of 3 optimal. The branched aliphatic hydrocarbon group is preferably a branched alkylene group, specifically, for example: -CH(CH ₃ )-, -CH(CH ₂ CH ₃ )-, -C(CH ₃ ) _2- , -C(CH ₃ )(CH ₂ CH ₃ )-, -C(CH ₃ )(CH ₂ CH ₂ CH ₃ )-, -C(CH ₂ CH ₃ ) ₂ -etc. alkylene; -CH(CH ₃ )CH ₂ -, -CH(CH ₃ )CH(CH ₃ )-, -C(CH ₃ ) ₂ CH ₂ -, -CH(CH ₂ CH ₃ )CH ₂ -, -C(CH ₂ CH ₃ ) ₂ -CH ₂ -and other alkylene groups; -CH(CH ₃ )CH ₂ CH ₂ -, -CH ₂ CH(CH ₃ )CH ₂ -and other alkyl groups; -CH( CH ₃ )CH ₂ CH ₂ CH ₂ -, -CH ₂ CH(CH ₃ )CH ₂ CH ₂ -and other alkylene groups such as tetramethyl group and the like. The alkyl group in the alkylene group is preferably a straight-chain alkyl group with 1 to 5 carbon atoms.

Examples of the substituents in the cyclic group of R ¹⁰¹ include alkyl groups, alkoxy groups, halogen atoms, halogenated alkyl groups, hydroxyl groups, nitro groups, carbonyl groups, and the like. As the alkyl group as the substituent, an alkyl group having 1 to 5 carbon atoms is preferred, and methyl, ethyl, propyl, n-butyl, and tert-butyl are preferred. As the alkoxy group of the substituent, an alkoxy group having 1 to 5 carbon atoms is preferred, and methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, tert- Butoxy is preferred, and methoxy and ethoxy are the most preferred. The halogen atom of the substituent includes, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and a fluorine atom is preferred. As the halogenated alkyl group of the substituent, for example, an alkyl group having 1 to 5 carbon atoms, such as a part or all of hydrogen atoms such as methyl, ethyl, propyl, n-butyl, tert-butyl, etc. Substitution by the aforementioned halogen atom, etc. The carbonyl group as a substituent is a group substituted for the methylene group (-CH ₂ -) constituting the cyclic hydrocarbon group. Among them, the substituent in the cyclic group of R ¹⁰¹ is preferably an alkyl group, a halogen atom, a halogenated alkyl group, etc., from the viewpoint of compatibility with component (A), and an alkyl group is preferred.

The chain alkyl group which may have a substituent: The chain alkyl group of R ¹⁰¹ may be either linear or branched. The linear alkyl group preferably has 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms, and most preferably 1 to 10 carbon atoms. Specifically, examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl Group, isotridecyl, tetradecyl, pentadecyl, hexadecyl, isohexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, two Undecyl, behenyl, etc. The branched alkyl group preferably has 3 to 20 carbons, preferably 3 to 15 carbons, and most preferably 3 to 10 carbons. Specifically, examples include: 1-methylethyl, 1,1-dimethylethyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methyl Butyl, 3-methylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl Base etc.

The chain-like alkenyl group which may have a substituent: The chain-like alkenyl group of R ¹⁰¹ can be either linear or branched, and preferably has a carbon number of 2 to 10, and a carbon number of 2 to 5 is preferred, carbon number 2 to 4 is more preferred, and carbon number 3 is particularly preferred. Linear alkenyl, for example: vinyl, propenyl (allyl), butynyl, etc. Examples of the branched alkenyl group include 1-methylvinyl, 2-methylvinyl, 1-methylpropenyl, and 2-methylpropenyl. Among the above-mentioned chain alkenyl groups, linear alkenyl groups are preferred, vinyl and propenyl are preferred, and vinyl is particularly preferred.

The substituents in the chain alkyl or alkenyl group of R ¹⁰¹ include, for example, alkoxy, halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), halogenated alkyl group, hydroxyl group, carbonyl group, nitro group , Amine group, cyclic group in the above R ¹⁰¹ , etc. Wherein chain alkyl or alkenyl group of R ¹⁰¹ substituents, and on the (A) ingredient and the like compatibility viewpoint, again a halogen atom, a halogenated alkyl group, R ¹⁰¹ in the above-described cyclic group enumerated yl Etc. are preferable, and the groups exemplified in the cyclic group in R ¹⁰¹ above are preferable.

Among the above, R ¹⁰¹ is preferably a cyclic group which may have a substituent, and preferably a cyclic hydrocarbon group which may have a substituent. More specifically, examples include groups obtained by removing one or more hydrogen atoms from phenyl, naphthyl, and polycyclic alkanes; the aforementioned general formulas (a2-r-1), (a2-r-3) ～(a2-r-7) The lactone-containing cyclic group separately represented; The aforementioned general formulas (a5-r-1)～(a5-r-4) respectively represent the -SO ₂ -containing cyclic formula The base is better.

In the aforementioned formula (b-1), Y ¹⁰¹ is a single bond or a divalent linking group containing an oxygen atom. When Y ¹⁰¹ is a divalent linking group containing an oxygen atom, the Y ¹⁰¹ may contain atoms other than the oxygen atom. Atoms other than oxygen atoms, such as carbon atoms, hydrogen atoms, sulfur atoms, and nitrogen atoms. Examples of the divalent linking group containing an oxygen atom include linking groups represented by the general formulas (y-al-1) to (y-al-8). Y ^{101 is} preferably a divalent linking group containing ester linkage, or a divalent linking group containing ether linkage, and is represented by the above general formulas (y-al-1) ~ (y-al-5) respectively The linking base is better.

In the aforementioned formula (b-1), V ¹⁰¹ is a single bond, an alkylene group or a fluorinated alkylene group. The alkylene group and fluorinated alkylene group in V ¹⁰¹ preferably have 1 to 4 carbon atoms. V ¹⁰¹ In the fluorinated alkylene group, for example: V ¹⁰¹ in the alkylene group, one hydrogen atom is partially or completely substituted by fluorine atoms of the group. Among them, V ^{101 is} preferably a single bond or a fluorinated alkylene group with 1 to 4 carbon atoms.

In the aforementioned formula (b-1), R ¹⁰² is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. R ^{102 is} preferably a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms, and preferably a fluorine atom.

(b-1) Specific examples of the anion part of the component, for example, when Y ¹⁰¹ is a single bond, fluorinated alkyl sulfonic acids such as trifluoromethanesulfonate anion or perfluorobutanesulfonate anion Ester anion; when Y ¹⁰¹ is a divalent linking group containing an oxygen atom, examples include anions represented by any of the following formulas (an1) to (an3).

[式中，R”¹⁰¹ 為可具有取代基的脂肪族環式基、上述化學式(r-hr-1)～(r-hr-6)各別表示之1價之雜環式基，或可具有取代基的鏈狀之烷基。R”¹⁰² 為可具有取代基的脂肪族環式基、前述通式(a2-r-1)、(a2-r-3)～(a2-r-7)各別表示之含內酯之環式基，或前述通式(a5-r-1)～(a5-r-4)各別表示之含-SO₂ -之環式基。R”¹⁰³ 為可具有取代基的芳香族環式基、可具有取代基的脂肪族環式基，或可具有取代基的鏈狀之烯基。V”¹⁰¹ 為碳數1～4之伸烷基，或碳數1～4之氟化伸烷基。R¹⁰² 為氟原子或碳數1～5之氟化烷基。v”各別獨立為0～3之整數，q”各別獨立為1～20之整數，n”為0或1]。

[In the formula, R" ¹⁰¹ is an aliphatic cyclic group which may have a substituent, a monovalent heterocyclic group represented by the above chemical formulas (r-hr-1) to (r-hr-6), or A chain-like alkyl group having substituents. R" ¹⁰² is an aliphatic cyclic group which may have substituents, the aforementioned general formulas (a2-r-1), (a2-r-3) to (a2-r-7) ) The lactone-containing cyclic group represented separately, or the -SO ₂ -containing cyclic group represented by the aforementioned general formulas (a5-r-1) to (a5-r-4). R" ¹⁰³ is an optionally substituted aromatic cyclic group, an optionally substituted aliphatic cyclic group, or an optionally substituted chain alkenyl group. V" ¹⁰¹ is an alkylene group having 1 to 4 carbons Group, or a fluorinated alkylene group with 1 to 4 carbon atoms. R ¹⁰² is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. v" is independently an integer of 0 to 3, q" is independently an integer of 1 to 20, and n" is 0 or 1].

The aliphatic cyclic group which may have a substituent of R" ¹⁰¹ , R " ¹⁰² and R" ¹⁰³ is preferably a group exemplified as a cyclic aliphatic hydrocarbon group in R ¹⁰¹ in the aforementioned formula (b-1). The substituent has the same content as the substituent of the substitutable cycloaliphatic hydrocarbon group in R ¹⁰¹ in the aforementioned formula (b-1).

The aromatic cyclic group which may have a substituent in R" ¹⁰³ is preferably the group exemplified as the aromatic hydrocarbon group in the cyclic hydrocarbon group in R ¹⁰¹ in the aforementioned formula (b-1). The aforementioned substituents are as follows: The substituents that can replace the aromatic hydrocarbon group in R ¹⁰¹ in the aforementioned formula (b-1) have the same content.

The chain alkyl group which may have a substituent in R" ¹⁰¹ is preferably a group exemplified as the chain alkyl group in R ¹⁰¹ in the aforementioned formula (b-1). R" ¹⁰³ may have a substituent The chain-like alkenyl group of is preferably the group exemplified as the chain-like alkenyl group in R ¹⁰¹ in the aforementioned formula (b-1).

・In the anion part formula (b-2) of the component (b-2), R ¹⁰⁴ and R ¹⁰⁵ are independent cyclic groups that may have substituents, chain alkyl groups that may have substituents, or A chain-like alkenyl group with substituents, respectively, and R ¹⁰¹ in the aforementioned formula (b-1), a cyclic group that may have a substituent, a chain-like alkyl group that may have a substituent, or a substituted The chain alkenyl group of the group has the same content. In addition, R ¹⁰⁴ and R ¹⁰⁵ may be bonded to each other to form a ring. R ¹⁰⁴ and R ¹⁰⁵ are preferably a chain alkyl group which may have a substituent, and preferably a linear or branched alkyl group, or a linear or branched fluorinated alkyl group. The carbon number of the chain alkyl group is preferably from 1 to 10, more preferably from 1 to 7, and particularly preferably from 1 to 3. When the carbon number of the chain alkyl group of R ¹⁰⁴ and R ¹⁰⁵ is within the above-mentioned carbon number range, for reasons such as good solubility in the solvent for the resist, the smaller the better. In addition, in the chain alkyl group of R ¹⁰⁴ and R ¹⁰⁵ , the greater the number of hydrogen atoms substituted by fluorine atoms, the stronger the acid strength, which is more preferable. The ratio of fluorine atoms in the aforementioned chain alkyl group, that is, the fluorination rate, is preferably 70-100%, more preferably 90-100%, and most preferably a perfluoroalkyl group in which all hydrogen atoms are replaced by fluorine atoms. In the formula (b-2), V ¹⁰² and V ^{103 are} each independently a single bond, an alkylene group, or a fluorinated alkylene group, which respectively have the same content as V ¹⁰¹ in the formula (b-1). In formula (b-2), L ¹⁰¹ and L ^{102 are} each independently a single bond or an oxygen atom.

・In the anion part formula (b-3) of the component (b-3), R ¹⁰⁶ to R ¹⁰⁸ are independently cyclic groups that may have substituents, chain alkyl groups that may have substituents, or A chain-like alkenyl group with substituents, respectively, and R ¹⁰¹ in the aforementioned formula (b-1), a cyclic group that may have a substituent, a chain-like alkyl group that may have a substituent, or a substituted The chain alkenyl group of the group has the same content. L ¹⁰³ to L ^{105 are} each independently a single bond, -CO- or -SO ₂ -.

{} Cationic unit of formula (b-1), (b -2) and (b-3), m is an integer of 1 or more, and M ^{'m +} m is the valence of the cation, again sulfonium cation, iodonium cation For preferred examples, for example, organic cations represented by the above formulas (ca-1-1) to (ca-1-78), (ca-1-101) to (ca-1-149), and the like.

Further, the formula (b-1), in the (b-2) and ^{(b-3) M 'm} +, but also include such as: diphenyl iodonium cation, bis (4-tert- butylphenyl) iodonium Cations, cations represented by the above formulas (ca-3-1) to (ca-3-6), cations represented by the above formulas (ca-4-1) to (ca-4-2), etc.

Among the above, the cation part [(M' ^{m +} ) _1/m ] is in the formula (ca-1-1)～(ca-1-78), (ca-1-101)～(ca-1-149 ) The organic cations separately expressed are preferably organic cations expressed separately.

In the resist composition of this embodiment, the component (B2) may be used alone or in combination of two or more. When the resist composition contains component (B2), the content of component (B2) in the resist composition relative to 100 parts by mass of (A) component is preferably 50 parts by mass or less, and 1-40 parts by mass Preferably, it is more preferably 5-30 parts by mass. In addition, when the resist composition contains component (B2), the content of component (B2) in the total acid generator component (B) component that acts on component (A) to generate acid in the resist composition, for example It is 50% by mass or less, preferably 30% by mass or less, and more preferably 0% by mass or more and 5% by mass or less. (B2) When the content of the component is within the above range, pattern formation can be sufficiently performed.

≪(D) Ingredients≫ In addition to the (A) component and (B) component, the resist composition in this embodiment may further contain an acid diffusion control agent component (hereinafter, also referred to as "(D) component") (D) component. In the agent composition, one has an inhibitor (acid diffusion control agent) function that traps acid generated by exposure. (D) Components, such as: nitrogen-containing organic compounds (D1) (hereinafter also referred to as "(D1) component"), which is not equivalent to the (D1) component, but can be decomposed by exposure to lose acid diffusion control Photodisintegratable base (D2) (hereinafter, also referred to as "(D2) component")) etc. In the case of a resist composition containing the component (D), the contrast between the exposed part and the unexposed part of the resist film can be improved when the resist pattern is formed.

・(D1) Ingredients (D1) The component is an alkali component and a nitrogen-containing organic compound component that functions as an acid diffusion control agent in the resist composition.

The component (D1) is not particularly limited as long as it functions as an acid diffusion control agent, and examples include aliphatic amines and aromatic amines.

Among the aliphatic amines, secondary aliphatic amines or tertiary aliphatic amines are preferred. The aliphatic amine is an amine having one or more aliphatic groups, and the aliphatic group preferably has 1-12 carbon atoms. Aliphatic amines, include such as: ammonia NH _3, at least one hydrogen atom is 12 or less carbon atoms of alkyl or hydroxyalkyl substituted to give the amine (alkylamine or alkanolamine) or a cyclic amine. Specific examples of alkylamines and alkanolamines include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, and n-decylamine; diethylamine, di- n-propylamine, di-n-heptylamine, di-n-octylamine, dicyclohexylamine and other dialkylamines; trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri- n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine, tri-n-dodecylamine, etc. Trialkanolamine; diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, di-n-octanolamine, tri-n-octanolamine and other alkanolamines. Among these, trialkylamine having 5 to 10 carbon atoms is more preferred, and tri-n-pentylamine or tri-n-octylamine is particularly preferred.

Cyclic amines include, for example, heterocyclic compounds containing a nitrogen atom as a hetero atom. The heterocyclic compound may be monocyclic (aliphatic monocyclic amine) or polycyclic (aliphatic polycyclic amine). Specific examples of aliphatic monocyclic amines include piperidine and piperazine. The aliphatic polycyclic amine preferably has 6 to 10 carbon atoms. Specifically, examples include: 1,5-diazabicyclo[4.3.0]-5-nonene, 1,8-diaza Heterobicyclo[5.4.0]-7-undecene, hexamethyltetraamine, 1,4-diazabicyclo[2.2.2]octane, etc.

Other aliphatic amines include, for example, tris(2-methoxymethoxyethyl)amine, tris{2-(2-methoxyethoxy)ethyl}amine, tris{2-(2- Methoxyethoxymethoxy)ethyl)amine, tris{2-(1-methoxyethoxy)ethyl)amine, tris{2-(1-ethoxyethoxy)ethyl }Amine, tris{2-(1-ethoxypropoxy)ethyl}amine, tris[2-{2-(2-hydroxyethoxy)ethoxy}ethyl]amine, triethanolamine triethyl Acid esters, etc., and triethanolamine triacetate is preferred.

Aromatic amines include, for example, 4-dimethylaminopyridine, pyrrole, indole, pyrazole, imidazole or their derivatives, tribenzylamine, aniline compounds, N-tert-butoxycarbonylpyrrolidine, etc. .

(D1) The component may be used alone or in combination of two or more. (D1) Among the above components, aromatic amines are preferred, and aniline compounds are preferred. Examples of the aniline compound include 2,6-diisopropylaniline, N,N-dimethylaniline, N,N-dibutylaniline, and N,N-dihexylaniline.

・(D2) Ingredients The component (D2) is not particularly limited as long as it is a component that decomposes through exposure and loses acid diffusion controllability. It is also a compound represented by the following general formula (d2-1) (hereinafter also referred to as "(D2-1) component"), the compound represented by the following general formula (d2-2) (hereinafter also referred to as "(d2-2) component") and the following general formula (d2-3) One or more compounds selected from the group of the compound (hereinafter also referred to as "(d2-3) component") are preferred. The components (d2-1) to (d2-3), in the exposed part of the resist film, do not act as an inhibitor that loses acid diffusion controllability (alkaline) due to decomposition. It acts as an inhibitor in the exposed part.

[式中，Rd¹ ～Rd⁴ 為可具有取代基的環式基、可具有取代基的鏈狀之烷基，或可具有取代基的鏈狀之烯基。其中，通式(d2-2)中之Rd² 中，S原子鄰接的碳原子上，為不鍵結氟原子者。Yd¹ 為單鍵或2價之連結基；m為1以上之整數，且M’^{m ＋} 各別獨立為m價之鎓陽離子]。

[In the formula, Rd ¹ to Rd ⁴ are a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent. Among them, in Rd ² in the general formula (d2-2), the carbon atom adjacent to the S atom is not bonded with a fluorine atom. YD ¹ is a single bond or the divalent linking group; m is an integer of 1 or more, and M ^{'m +} m are independently of the monovalent cation].

{(d2-1) component} ・In the anion formula (d2-1), Rd ¹ is a cyclic group that may have a substituent, a chain alkyl that may have a substituent, or a chain that may have a substituent The alkenyl group has the same content as R ¹⁰¹ in the aforementioned formula (b-1). Among these, Rd ¹ is preferably an aromatic hydrocarbon group which may have a substituent, an aliphatic cyclic group which may have a substituent, or a chain alkyl group which may have a substituent. The substituents that these groups may have include, for example, a hydroxyl group, a pendant oxo group, an alkyl group, an aryl group, a fluorine atom, a fluorinated alkyl group, and the above general formulas (a2-r-1) to ( a2-r-7) The lactone-containing cyclic group, ether linkage, ester linkage, or a combination of these separately represented. In the case of ether or ester bonding as a substituent, an alkylene group may be intervened in the chain. In this case, the substituents are represented by the above formulas (y-al-1) to (y-al-5). Do not indicate the link base is better. The aforementioned aromatic hydrocarbon group is preferably exemplified by a phenyl group, a naphthyl group, and a polycyclic structure containing a bicyclooctane skeleton (e.g., a polycyclic structure formed by a bicyclic octane skeleton and other ring structures) . The aforementioned aliphatic cyclic group is preferably a group obtained by removing one or more hydrogen atoms from a polycyclic alkane such as adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc. . The aforementioned chain alkyl group preferably has a carbon number of 1-10. Specifically, examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and nonyl , Decyl and other linear alkyl groups; 1-methylethyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methyl Branched chains of butyl, 1-ethylbutyl, 2-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, etc.的alkyl etc.

When the aforementioned chain alkyl group is a fluorinated alkyl group having a fluorine atom or a fluorinated alkyl group as a substituent, the carbon number of the fluorinated alkyl group is preferably from 1 to 11, preferably from 1 to 8, and 1 to 4 are more preferable. The fluorinated alkyl group may contain atoms other than fluorine atoms. Atoms other than fluorine atoms, such as oxygen atoms, sulfur atoms, and nitrogen atoms. Rd ^{1 is} preferably a fluorinated alkyl group in which part or all of the hydrogen atoms constituting the linear alkyl group are replaced by fluorine atoms, and all the hydrogen atoms constituting the linear alkyl group are replaced by fluorine atoms The obtained fluorinated alkyl group (linear perfluoroalkyl group) is particularly preferred.

The following are preferred specific examples of the anion part of the component (d2-1).

Cationic the unit of formula (d2-1), M ^{'m +} is an onium cation of valence m. M ^{'m +} of the cation, a cationic (ca-4) with the general formula (ca-1) represented by the ~ same respective content provider of the preferred embodiment is illustrated, again the general formula (ca-1) represented by The cations are preferred, and the cations represented by the aforementioned formulas (ca-1-1) to (ca-1-78) and (ca-1-101) to (ca-1-149) are more preferred. (d2-1) The component may be used alone or in combination of two or more.

{(d2-2) Ingredient} ・In the anion formula (d2-2), Rd ² is a cyclic group that may have a substituent, a chain alkyl that may have a substituent, or a chain that may have a substituent Examples of the alkenyl group include the same content as R ¹⁰¹ in the aforementioned formula (b-1). Among them, in Rd ² , the carbon atom adjacent to the S atom is not bonded to a fluorine atom (not substituted with fluorine). In this way, the anion of the (d2-2) component can form a moderately weak acid anion, and the inhibitory ability of the (D2) component can be improved. Rd ² is preferably a chain alkyl group which may have a substituent or an aliphatic cyclic group which may have a substituent. The chain-like alkyl group preferably has 1-10 carbon atoms, preferably 3-10. An aliphatic cyclic group, a group obtained by removing more than one hydrogen atom from adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc. (which may have substituents); A group obtained by removing one or more hydrogen atoms from camphor or the like is preferred. The hydrocarbon group of Rd ² may have a substituent. The substituent may be substituted with the hydrocarbon group (aromatic hydrocarbon group, aliphatic cyclic group, chain alkyl group) in Rd ¹ of the aforementioned formula (d2-1), for example The base is the same content.

The following are preferred specific examples of the anion part of the component (d2-2).

Cationic the unit of formula (d2-2), M ^{'m +} m is the valence of the cation, the formula (D2-1) in the M' ^{m +} is the same as the contents. (d2-2) The component may be used alone or in combination of two or more.

{(d2-3) Ingredients} ・In the anion part formula (d2-3), Rd ³ is a cyclic group that may have a substituent, a chain alkyl that may have a substituent, or a chain that may have a substituent Examples of the alkenyl group include: the same content as R ¹⁰¹ in the aforementioned formula (b-1), etc., and a cyclic group containing a fluorine atom, a chain alkyl group, or a chain alkenyl group Better. Among them, a fluorinated alkyl group is preferred, and the same content as the aforementioned fluorinated alkyl group of Rd ¹ is preferred.

In the formula (d2-3), Rd ⁴ is a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent. Examples thereof include: and the aforementioned R ¹⁰¹ in the formula (b-1) has the same content. Among them, an alkyl group, an alkoxy group, an alkenyl group, and a cyclic group which may have a substituent are preferred. The alkyl group in Rd ⁴ is preferably a linear or branched alkyl group having 1 to 5 carbon atoms. Specifically, examples include methyl, ethyl, propyl, isopropyl, n- Butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, etc. Part of the hydrogen atoms of the alkyl group of Rd ⁴ may be substituted by a hydroxyl group or a cyano group. The alkoxy group in Rd ⁴ is preferably an alkoxy group having 1 to 5 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms is preferred. Specifically, methoxy, ethoxy, n- Propoxy, iso-propoxy, n-butoxy, tert-butoxy, etc. Among them, methoxy and ethoxy are preferred.

The alkenyl group in Rd ⁴ , for example, has the same content as R ¹⁰¹ in the aforementioned formula (b-1), etc., and also includes vinyl, propenyl (allyl), 1-methylpropenyl, 2-methyl Propylene is preferred. When these groups further have a substituent, they may have an alkyl group having 1 to 5 carbons or a halogenated alkyl group having 1 to 5 carbons.

The cyclic group in Rd ⁴ has the same content as R ¹⁰¹ in the aforementioned formula (b-1), among which it is composed of cyclopentane, cyclohexane, adamantane, norbornane, isobornane, tri Cycloalkanes, such as cyclodecane and tetracyclododecane, are alicyclic groups obtained by removing one or more hydrogen atoms, or aromatic groups such as phenyl and naphthyl are preferred. When Rd ⁴ is an alicyclic group, since the resist composition can be dissolved in an organic solvent well, the lithographic etching characteristics can be improved.

In formula (d2-3), Yd ¹ is a single bond or a divalent linking group. The divalent linking group in Yd ¹ is not particularly limited, and examples include: bivalent hydrocarbon groups (aliphatic hydrocarbon groups, aromatic hydrocarbon groups) that may have substituents, heteroatom-containing divalent linking groups, etc. . These are the same as the divalent hydrocarbon groups that may have substituents and the divalent linking groups containing heteroatoms listed in the description of the bivalent linking group in Ya ^x1 in the above formula (a10-1). content. Yd ^{1 is} preferably a carbonyl group, an ester bond, an amide bond, an alkylene group or a combination of these. The alkylene group is preferably a linear or branched alkylene group, and a methylene group or an ethylene group is more preferred.

The following are preferred specific examples of the anion part of the component (d2-3).

Cationic the unit of formula (d2-3), M ^{'m +} is a cation of valence m, with the formula (D2-1) in the M' ^{m +} is the same as the contents. (d2-3) The component may be used alone or in combination of two or more.

For the component (D2), only one of the above components (d2-1) to (d2-3) can be used, or two or more of them can be used in combination. When the resist composition contains component (D2), the content of component (D2) in the resist composition is preferably 0.5 to 35 parts by weight, and preferably 1 to 25 parts by weight relative to 100 parts by weight of (A) Preferably, it is more preferably 2-20 parts by mass, particularly preferably 3-15 parts by mass. When the content of the component (D2) is above the preferable lower limit, it is particularly easy to obtain good lithographic etching characteristics and resist pattern shape. On the other hand, when it is below the upper limit, a balance with other components can be achieved, and various lithographic etching characteristics can be made better.

(D2) Manufacturing method of ingredients: The production method of the aforementioned (d2-1) component and (d2-2) component is not particularly limited, and it can be produced according to a known method. In addition, the manufacturing method of (d2-3) component is not particularly limited. For example, it can be prepared according to the same method described in US2012-0149916.

≪(E) Ingredients: at least one compound selected from the group of organic carboxylic acids and phosphorus oxyacids and their derivatives≫ The resist composition of this embodiment may contain organic carboxylic acid and phosphorus as optional ingredients for the purpose of preventing poor sensitivity, improving resist pattern shape, and temporal stability during processing. At least one compound (E) selected from the group of oxyacids and their derivatives (hereinafter, also referred to as "(E) component").

Organic carboxylic acids, such as acetic acid, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, hydroxybenzoic acid, salicylic acid, phthalic acid, terephthalic acid, isophthalic acid, etc. . Examples of phosphorus-containing oxygen acids include phosphoric acid, phosphonic acid, and phosphine acid. Among these, phosphonic acid is particularly preferred. Examples of phosphorus oxo acid derivatives include esters in which the hydrogen atoms of the above oxo acids are substituted with hydrocarbon groups. Examples of the aforementioned hydrocarbon groups include alkyl groups with 1 to 5 carbons and 6 to carbon atoms. 15 of aryl etc. Examples of phosphoric acid derivatives include phosphoric acid esters such as di-n-butyl phosphate and diphenyl phosphate. Examples of phosphonic acid derivatives include phosphonates such as dimethyl phosphonate, di-n-butyl phosphonate, phenyl phosphonate, diphenyl phosphonate, and dibenzyl phosphonate. Examples of the derivatives of phosphinic acid include phosphinate or phenyl phosphinate.

(E) Among the above components, organic carboxylic acids are preferred, and aromatic carboxylic acids are preferred. Specifically, examples thereof include benzoic acid, hydroxybenzoic acid, salicylic acid, phthalic acid, terephthalic acid, and isophthalic acid.

In the resist composition of this embodiment, the (E) component may be used alone or in combination of two or more. When the resist composition contains component (E), the content of component (E) is preferably 0.01-5 parts by mass, and more preferably 0.1-1.5 parts by mass relative to 100 parts by mass of (A). In the above range, a balance with other components can be achieved, and various lithographic etching characteristics can be made better.

≪(F) Ingredient: Fluorine additive ingredient≫ The resist composition in this embodiment may contain a fluorine additive component (hereinafter, also referred to as "(F) component") for the purpose of imparting water repellency to the resist film or improving lithographic etching characteristics. (F) Ingredients, for example: JP 2010-002870, JP 2010-032994, JP 2010-277043, JP 2011-13569, JP 2011-128226 can be used Fluorine-containing polymer compounds. (F) The component, more specifically, includes a polymer having a structural unit (f1) represented by the following formula (f1-1). More specifically, the polymer includes: a polymer (homopolymer) formed only by the structural unit (f1) represented by the following formula (f1-1); the structural unit (f1) is the same as the aforementioned The copolymer of the structural unit (a4); the copolymer of the structural unit (f1) and the aforementioned structural unit (a1); the structural unit (f1) and the structural unit derived from acrylic acid or methacrylic acid and the aforementioned structural unit (a1) ) Is preferred. Among them, the aforementioned structural unit (a1) copolymerized with the structural unit (f1) is a structural unit derived from 1-ethyl-1-cyclooctyl (meth)acrylate, 1-methyl-1-adamantane The structural unit derived from the base (meth)acrylate is preferred.

[式中，R與前述為相同之內容，Rf¹⁰² 及Rf¹⁰³ 各別獨立表示氫原子、鹵素原子、碳數1～5之烷基或碳數1～5之鹵化烷基；Rf¹⁰² 及Rf¹⁰³ 可為相同亦可、相異亦可。nf¹ 為0～5之整數，Rf¹⁰¹ 為含有氟原子之有機基]。

[In the formula, R is the same as the above, Rf ¹⁰² and Rf ¹⁰³ each independently represent a hydrogen atom, a halogen atom, an alkyl group with 1 to 5 carbons or a halogenated alkyl group with 1 to 5 carbons; Rf ¹⁰² and Rf ¹⁰³ may be the same or different. nf ¹ is an integer of 0-5, and Rf ¹⁰¹ is an organic group containing a fluorine atom].

In formula (f1-1), the R to which the carbon atom at the α-position is bonded is the same as described above. Furthermore, R is preferably a hydrogen atom or a methyl group. In the formula (f1-1), the halogen atoms of Rf ¹⁰² and Rf ¹⁰³ include, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and a fluorine atom is particularly preferred. The alkyl group having 1 to 5 carbon atoms of Rf ¹⁰² and Rf ¹⁰³ , for example, has the same content as the alkyl group having 1 to 5 carbon atoms of R, and preferably methyl or ethyl. The halogenated alkyl groups of Rf ¹⁰² and Rf ¹⁰³ having 1 to 5 carbon atoms, specifically, examples include groups obtained by substituting a part or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms by halogen atoms Wait. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is particularly preferred. Among them, Rf ¹⁰² and Rf ^{103 are} preferably a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 5 carbon atoms, and preferably a hydrogen atom, a fluorine atom, a methyl group, or an ethyl group.

In the formula (f1-1), nf ¹ is an integer of 0-5, preferably an integer of 0-3, and more preferably 0 or 1.

In the formula (f1-1), Rf ¹⁰¹ is an organic group containing a fluorine atom, and preferably a hydrocarbon group containing a fluorine atom. The hydrocarbon group containing a fluorine atom can be linear, branched or cyclic, and preferably has a carbon number of 1-20, preferably a carbon number of 1-15, and a carbon number of 1 to 10 is particularly good. In addition, for hydrocarbon groups containing fluorine atoms, it is preferable that more than 25% of the hydrogen atoms in the hydrocarbon group are fluorinated, and more than 50% are preferably fluorinated. When more than 60% are fluorinated, the increase The hydrophobicity of the resist film during immersion exposure is particularly good. Among them, Rf ¹⁰¹ is preferably a fluorinated hydrocarbon group with 1 to 6 carbon atoms, and is preferably trifluoromethyl, -CH ₂ -CF ₃ , -CH ₂ -CF ₂ -CF ₃ , -CH(CF ₃ ) ₂ , -CH ₂ -CH ₂ -CF ₃ and -CH ₂ -CH ₂ -CF ₂ -CF ₂ -CF ₂ -CF ₃ are particularly preferred.

(F) The weight average molecular weight (Mw) of the component (polystyrene conversion standard for gel permeation chromatography) is preferably 1,000 to 50,000, preferably 5,000 to 40,000, and most preferably 10,000 to 30,000. Below the upper limit of this range, when used as a resist, it can have sufficient solubility in the solvent for the resist. When it is above the lower limit of this range, it can have good dry etching resistance or resist pattern. The cross-sectional shape of the type. (F) The degree of dispersion (Mw/Mn) of the component is preferably 1.0-5.0, preferably 1.0-3.0, and most preferably 1.2-2.5.

In the resist composition of this embodiment, the component (F) may be used alone or in combination of two or more. When the resist composition contains component (F), the content of component (F) is usually 0.5-10 parts by mass relative to 100 parts by mass of (A) component.

≪(S) Ingredients: organic solvent ingredients≫ The resist composition in this embodiment can be prepared by dissolving the resist material in an organic solvent component (hereinafter, also referred to as "(S) component"). The (S) component may be any component that can dissolve the various components used and form a uniform solution. Any component can be appropriately selected and used from known components conventionally used as solvents for chemically amplified resist compositions. (S) Ingredients, such as lactones such as γ-butyrolactone; acetone, methyl ethyl ketone, cyclohexanone, methyl-n-pentanone, methyl isopentanone, 2-heptanone, Ketones such as ethylene carbonate and propylene carbonate; polyols such as ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol; ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol mono Acetate, or dipropylene glycol monoacetate and other ester-bonded compounds, the aforementioned polyols or the aforementioned ester-bonded compounds such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, etc. Derivatives of polyols such as compounds with ether linkages such as alkyl ethers or monophenyl ethers [Among these, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) are preferred] ; Cyclic ethers such as dioxane, or methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methoxypropionic acid Esters such as methyl ester, ethyl ethoxypropionate, etc.; anisole, ethyl benzyl ether, cresol methyl ether, diphenyl ether, dibenzyl ether, phenethyl ether, butyl phenyl ether, ethyl benzene, Aromatic organic solvents such as diethylbenzene, amylbenzene, cumene, toluene, xylene, cumene, trimethylbenzene, etc., dimethyl sulfide (DMSO), etc. In the resist composition of this embodiment, the (S) component may be used alone or in a mixed solvent of two or more. Among them, PGMEA, PGME, γ-butyrolactone, propylene carbonate, EL, and cyclohexanone are preferred. In addition, a mixed solvent obtained by mixing PGMEA and a polar solvent may also be used. The addition ratio (mass ratio) can be appropriately determined after considering the compatibility of PGMEA and the polar solvent, etc., preferably 1:9-9:1, more preferably 2:8-8:2 Within the range is better. More specifically, when EL or cyclohexanone as a polar solvent is mixed, the mass ratio of PGMEA:EL or cyclohexanone is preferably 1:9-9:1, more preferably 2:8-8:2. Moreover, when mixing PGME as a polar solvent, the mass ratio of PGMEA:PGME is preferably 1:9-9:1, more preferably 2:8-8:2, and more preferably 3:7-7:3 . In addition, a mixed solvent of PGMEA, PGME and cyclohexanone can also be used. In addition, the (S) component, for example: a mixed solvent of at least one selected from PGMEA and EL, and at least one selected from γ-butyrolactone and propylene carbonate is also preferable. In this case, the mixing ratio is based on the mass ratio of the former to the latter, preferably 60:40 to 99:1, more preferably 70:30 to 95:5. The amount of (S) component used is not particularly limited, and can be appropriately set according to the concentration that can be coated on the substrate, etc., the coating film thickness, etc. Generally speaking, the amount of (S) component used is such that the solid content concentration of the resist composition is 0.1-20% by mass, preferably 0.2-15% by mass.

In the resist composition of this embodiment, it is possible to further match the purpose and appropriately add mixed additives, such as resins added to improve the performance of the resist film, dissolution inhibitors, plasticizers, stabilizers, colorants, and Halo agents, dyes, etc.

The above-explained method for forming a resist pattern using the alkali developer containing a nonionic surfactant of this embodiment for development to form a resist pattern is due to the use of a specific resist composition, that is, the use of the above-mentioned (A ) Component and (B) component, and the aforementioned (B) component is a resist composition containing (B1) component, so it can reduce the occurrence of defects in the unexposed part of the resist film, and can form a good-shaped resist pattern type. [Example]

Hereinafter, the present invention will be described in more detail with examples, but the present invention is not limited by these examples.

＜Manufacture of resist composition＞ The components shown in Table 1 were mixed and dissolved to prepare resist compositions (1) to (5), respectively.

In Table 1, each abbreviation has the following meanings. The value in [　] is the added amount (parts by mass).

(A)-1: A polymer compound represented by the following chemical formula (A-1). The polymer compound (A)-1 can be prepared by deriving the monomer constituting the structural unit of the polymer compound by radical polymerization reaction using a specific molar ratio. The polymer compound (A)-1 had a weight average molecular weight (Mw) of 7000 and a molecular weight dispersion (Mw/Mn) of 1.68 in terms of standard polystyrene obtained by GPC measurement. The copolymer composition ratio (the ratio of each structural unit in the structural formula (mole ratio)) obtained by ¹³ C-NMR is 1/m/n/o=45/30/15/10.

(B1)-1 to (B1)-3: Acid generators formed from the following compounds (B1-1) to (B1-3).

(B2)-1: An acid generator formed from the following compound (B2-1). (B2)-2: An acid generator formed from the following compound (B2-2).

(D)-1: An acid diffusion control agent formed from a compound represented by the following chemical formula (D-1). (E)-1: A compound represented by the following chemical formula (E-1). (F)-1: A fluorine-containing polymer compound represented by the following chemical formula (F-1). The weight average molecular weight (Mw) in terms of standard polystyrene obtained by the GPC measurement was 23,000, and the molecular weight dispersion (Mw/Mn) was 1.40. (S)-1: A mixed solvent of propylene glycol monomethyl ether acetate/propylene glycol monomethyl ether (mass ratio 60/40).

＜Formation of resist pattern (1)＞ (Example 1) The organic anti-reflective film composition "ARC29A" (trade name, manufactured by Polywatt Technology Co., Ltd.) was coated on a 12-inch silicon wafer using a spin coater, and heated on a hot plate at 205°C for 60 seconds As a result of sintering and drying, an organic anti-reflective film with a thickness of 89 nm was formed. The resist composition (1) of Table 1 was coated on the anti-reflective film using Coater/Developer Lithius (manufactured by Tokyo Electronics Co., Ltd.), and pre-baked at 105°C for 60 seconds on a hot plate (PAB ) After drying, a resist film with a thickness of 150 nm is formed. Next, use ArF exposure device NSR-S609B for infiltration [manufactured by Nikon; NA (number of openings)=1.07, Dipole (in/out=0.78/0.97) with Polano, infiltration medium: water], through the penetration type phase shift Mask, selectively irradiate the aforementioned resist film with ArF excimer laser (193nm). Subsequently, PEB treatment was performed at 100°C for 60 seconds. Next, using Coater/Developer Lithius (manufactured by Tokyo Electronics Co., Ltd.), a 2.38% by mass TMAH aqueous solution (trade name: NMD-W, manufactured by Tokyo Ohka Kogyo Co., Ltd.) containing an acetylene-based active agent was used for 30 seconds at 23°C. The calcined alkali was developed, followed by washing with pure water for 30 seconds, followed by vibration drying. As a result, the exposed part of the resist film is dissolved and removed by the developer, and the unexposed part remains to form a film.

(Examples 2, 3, Comparative Examples 1, 2) Except that the resist composition (1) in Table 1 was changed to resist composition (2) to (5), the other all followed the same method as in Example 1 above to form a resist pattern. In addition, Example 2 used the resist composition (2), Example 3 used the resist composition (3), Comparative Example 1 used the resist composition (4), and Comparative Example 2 used the resist composition (5).

＜Evaluation of resist pattern (1)＞ [Assessment of defects] Using a surface defect observation device (manufactured by KLA Danker, product name: KLA-2371), the remaining film portion of the unexposed portion of the resist pattern formed by the above-mentioned <Formation of resist pattern (1)> method was measured The number of defects with 0.1μm or more. The assessment of defects is carried out according to the following assessment criteria, and the assessment results are described as "Defects" as shown in Table 2. Evaluation benchmark 〇: Less than 100 ×: more than 100

Using the resist pattern forming methods of Examples 1 to 3 of the present invention, when compared with the resist pattern forming methods of Comparative Examples 1 and 2, it was confirmed that defects of 0.1 μm or more occurred in the residual film portion of the unexposed area The situation is suppressed. Among them, the resist pattern forming method of Example 3 has a higher effect of suppressing the occurrence of defects. The effect of suppressing the occurrence of defects is the order of Example 3, Example 2, and Example 1.

＜Formation of resist pattern (2)＞ (Example 4) The organic anti-reflective film composition "ARC29A" (trade name, manufactured by Polywatt Technology Co., Ltd.) was coated on a 12-inch silicon wafer using a spin coater, and heated on a hot plate at 205°C for 60 seconds As a result of sintering and drying, an organic anti-reflective film with a thickness of 89 nm was formed. The resist composition (3) of Table 1 was coated on the anti-reflective film using Coater/Developer Lithius (manufactured by Tokyo Electron Co., Ltd.), and pre-baked at 105°C for 60 seconds on a hot plate (PAB ) After drying, a resist film with a thickness of 150 nm is formed. Next, use ArF exposure device NSR-S609B for infiltration [manufactured by Nikon; NA (number of openings)=1.07, Dipole (in/out=0.78/0.97) with Polano, infiltration medium: water], through the penetration type phase shift Mask, selectively irradiate the aforementioned resist film with ArF excimer laser (193nm). Subsequently, PEB treatment was performed at 100°C for 60 seconds. Next, using Coater/Developer Lithius (manufactured by Tokyo Electronics Co., Ltd.), a 2.38% by mass TMAH aqueous solution (trade name: NMD-W, manufactured by Tokyo Ohka Kogyo Co., Ltd.) containing an acetylene-based active agent was used for 30 seconds at 23°C. The calcined alkali was developed, followed by washing with pure water for 30 seconds, followed by vibration drying. As a result, a 1:1 line and space (LS) pattern with a line width of 65 nm and a pitch of 130 nm was formed.

(Comparative example 3) Except that the developer was changed to a 2.38% by mass TMAH aqueous solution (trade name: NMD-3, manufactured by Tokyo Ohka Kogyo Co., Ltd.), the same method as in Example 4 was followed to form an LS pattern.

＜Evaluation of resist pattern (2)＞ [Evaluation of resist pattern shape] A scanning electron microscope (trade name: SU-8000, manufactured by Hitachi High-Tech Co., Ltd.) was used to observe the cross-sectional shape of the LS pattern formed in accordance with the above-mentioned <Formation of resist pattern (2)>, and evaluate the shape. As a result, it was found that when the resist pattern forming method of Example 4 of the present invention is used, the resist pattern has a good shape with high rectangularity. On the other hand, when the alkali developer uses the resist pattern forming method of Comparative Example 3 that does not contain a nonionic surfactant, there may be analytical problems such as difficulty in wetting the resist film by the alkali developer, which makes the resist pattern Formed into a tapered shape.

From the above results, it is confirmed that when the resist pattern forming method of the embodiment of the present invention is used, the occurrence of defects in the unexposed portion of the resist film can be reduced, and a good-shaped resist pattern can be formed.

Claims (3)

A method for forming a resist pattern, which is characterized by having: a step (i) of forming a resist film on a support using a resist composition, a step (ii) of exposing the aforementioned resist film, and the step of exposing the aforementioned exposed The resist film is developed using an alkali developer containing a non-ionic surfactant to form the resist pattern forming method of step (iii); and the resist composition mentioned above contains: through the action of acid The base component (A) that changes the solubility to the alkali developer and the acid generator component (B) that generates acid through exposure, the aforementioned acid generator component (B) contains the following general formula (b1) -1) The represented compound (B1);

[In the formula, R ₀ ¹⁰¹ is a polycyclic aliphatic hydrocarbon group; among them, the hydrogen atom of the polycyclic aliphatic hydrocarbon group may also be substituted by a substituent; R ¹⁰² is a fluorine atom or a fluorinated alkyl group with 1 to 5 carbon atoms ; Y ¹⁰¹ is a single bond, or a divalent linking group containing an oxygen atom of a; V ¹⁰¹ is a single bond, an alkylene group or fluorinated alkylene group; m is an integer of 1 or more, and m ^{'m +} m is the valence of Onium cation]. The resist pattern forming method of claim 1, wherein the aforementioned V ¹⁰¹ is a fluorinated alkylene group. The resist pattern forming method of claim 1 or 2, wherein the aforementioned R ₀ ¹⁰¹ is a polycyclic aliphatic hydrocarbon group having a hydroxyl group.