JP2005213215A - Fluorine-containing polymerizable monomer, fluorine-containing macromolecular compound, resist material using the same and method for forming pattern - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fluorine-containing acrylate compound of a new fluorine-containing polymerizable monomer; to provide a macromolecular compound and a resist material using the compound; and to provide a method for forming a pattern. <P>SOLUTION: The fluorine-containing acrylate compound is represented by general formula (1) (wherein, R<SP>1</SP>is one functional group of a hydrogen atom, a methyl group and a trifluoromethyl group; R<SP>2</SP>is a hydrogen atom or a 1-25C straight chain, branched or cyclic alkyl group which may contain a fluorine atom, an oxygen atom, a nitrogen atom, a sulfur atom or a carbonyl bond as a part thereof; R<SP>3</SP>to R<SP>14</SP>are each a hydrogen atom, a 1-25C straight chain, branched or cyclic alkyl group which may contain a fluorine atom, an oxygen atom, a nitrogen atom, a sulfur atom or a hydroxy group as a part thereof; R<SP>3</SP>and R<SP>5</SP>, R<SP>7</SP>and R<SP>9</SP>, or two of R<SP>11</SP>to R<SP>14</SP>may form a ring as a 1-25C alkylene group by bonding each other, and a part thereof may contain an oxygen atom, a sulfur atom or a nitrogen atom; l is 0 or 1; and m and n are each an arbitrary integer of 0-4). <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a fluorine-containing acrylate compound which is a novel fluorine-containing polymerizable monomer, a fluorine-containing polymer compound polymerized or copolymerized using the same, a resist material, and a pattern forming method, and has been actively studied recently. The present invention relates to a chemically amplified resist material and a pattern forming method.

In recent years, with the higher integration and higher speed of LSI, pattern rule miniaturization has been demanded. As one of means for miniaturization, the short wavelength of an exposure light source used for resist pattern formation. Is known. Up to now, high-pressure mercury lamp i-line (365 nm) is used to manufacture semiconductor devices with a degree of integration up to 64 Mbit, and KrF excimer laser light (248 nm) is used instead of i-line to manufacture semiconductor elements with a density of 256 Mbit or higher. It has been adopted as an exposure light source. Furthermore, for the purpose of manufacturing semiconductors with a degree of integration of 1 Gbit or more, the use of ArF excimer laser light (193 nm), which is a light source with a shorter wavelength, and further use of F ₂ excimer laser light (157 nm) have been studied in recent years.

In ArF excimer laser lithography (193 nm), processing with a design rule of 0.13 μm or less is expected, but novolak and polyvinylphenol (aromatic) resins used for KrF excimer laser light are 193 nm. Since it has very strong absorption in the vicinity, it cannot be used as a base resin for ArF resist. Therefore, acrylic resins and cycloolefin resins into which a cyclic compound is introduced in order to secure etching resistance have been examined in order to improve the transparency, instead of the aromatic type to the aliphatic type (Patent Documents 1 to 4). Regarding F ₂ laser lithography (157 nm), miniaturization of 0.10 μm or less is expected, but it becomes increasingly difficult to ensure transparency, and base polymers for KrF and ArF have strong absorption and cannot be used. know.

  To date, copolymerization of tbutyl trifluoromethacrylate and 5- (2-hydroxy-2,2-bistrifluoromethyl) ethyl-2-norbornene as a polymer for F2 resist, tbutyl trifluoromethacrylate and 3- Copolymerization with (2-hydroxy-2,2-bistrifluoromethyl) methylstyrene has been reported, but the absorbance is about 3, which is not sufficient for pattern formation with a normal film thickness, and the transmittance is further increased. It was necessary to improve (Non-Patent Document 1). Recently, a highly transparent resin having an absorbance of 1 or less and excellent substrate adhesion has been proposed, but the low dissolution rate in the exposed area is a drawback, and studies to overcome this are underway. (Non-Patent Document 2).

Until now, there has been little discussion about the performance of the glass transition temperature (Tg) of the polymer compound constituting the resist. Recently, in resist patterning made of a polymer having a low glass transition temperature (Tg), the diffusion rate of the acid generated from the photoacid generator is high, so that the formed pattern collapses or the pattern size is smaller than the mask pattern. It has been found that defects such as becoming smaller occur. Further, the baking temperature during patterning must be set lower than the glass transition temperature (Tg), but in the case of a resist having a glass transition temperature (Tg) lower than the normal baking temperature (120 to 130 ° C.), It took time and effort to change and readjust the patterning process conditions such as the bake temperature. Despite these problems, there has been almost no molecular design focused on increasing the glass transition temperature (Tg) so far, and the high glass transition temperature (Tg) is high. Since there were no molecules that had transparency, high etching resistance, high adhesion to the substrate, and film-forming properties, it was highly desirable to create new monomers or polymer compounds that satisfy all these functions. It was.
JP-A-9-73173 Japanese Patent Laid-Open No. 10-10739 Japanese Patent Laid-Open No. 9-230595 International Publication No. 97/33198 Proc. SPIE. 4345, pp. 273-284, 2001. (SPIE 2001 lecture number 4345-31 Polymer design for 157-nm chemically amplified resists) Proc. SPIE. 4690, pp. 76-83, 2002. (SPIE 2002 lecture number 4690-09 Synthesis of novel fluoropolymers for 157 nm photo-sensitives by cyclo-polymerization)

  An object of the present invention is to provide a fluorine-containing acrylate compound that is a novel fluorine-containing polymerizable monomer, a polymer compound using the same, a resist material, and a pattern forming method.

  As a result of intensive studies to achieve the above object, the present inventors have found a novel cyclic fluorinated polymerizable monomer having a hexafluoroisopropanol structure in the vicinity of the polymerizable group. A fluorine polymer compound polymerized or copolymerized using this fluorine-containing polymerizable monomer or derivative thereof has high transparency in a wide wavelength range from the ultraviolet region to the near infrared region with a high fluorine content. In addition, it has both high adhesion to the substrate and film-forming properties due to hydroxyl groups, has high etching resistance by having a cyclic structure, and further incorporates a bulky hexafluoroisopropanol structure in the vicinity of the polymerizable group. A resist material having a high glass transition temperature (Tg) that suppresses the movement of the polymer main chain and a pattern forming method using the resist material have been found, and the present invention has been completed.

  That is, the present invention is a pattern forming method of the following 1 to 5 fluorine-containing polymerizable monomers, 6 to 8 fluorine-containing polymer compounds, 9 a resist material using this, and 10 and 11.

1: Fluorine-containing acrylate compound represented by general formula (1) (wherein R ¹ is any one functional group of a hydrogen atom, a methyl group and a trifluoromethyl group, and R ² is a hydrogen atom, carbon A linear, branched or cyclic alkyl group of 1 to 25, part of which may contain a fluorine atom, an oxygen atom, a nitrogen atom, a sulfur atom, or a carbonyl bond, R ^{3 to} R ¹⁴ are A hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 25 carbon atoms, and a part thereof may contain a fluorine atom, an oxygen atom, a nitrogen atom, a sulfur atom, or a hydroxyl group, and R ³ Two groups out of R ⁵ , R ⁷ and R ⁹ , or R ^{11 to} R ¹⁴ may be bonded to form a ring as an alkylene group having 1 to 25 carbon atoms, part of which is an oxygen atom, It may contain a sulfur atom or a nitrogen atom, l is 0 or In 1, m, n represents any integer of 0 to 4.).

2: Fluorine-containing acrylate compound represented by general formula (2) (wherein R ¹ represents any one functional group of a hydrogen atom, a methyl group, and a trifluoromethyl group. R ² represents a hydrogen atom and a carbon number) 1 to 25 linear, branched, or cyclic alkyl groups, part of which may contain a fluorine atom, an oxygen atom, a nitrogen atom, a sulfur atom, or a carbonyl bond, where n is any one of 0 to 8 Represents an integer.)

3: Fluorine-containing acrylate compound represented by general formula (3) (wherein R ¹ represents any one functional group of a hydrogen atom, a methyl group, and a trifluoromethyl group. R ² represents a hydrogen atom and a carbon number) A functional group containing 1 to 25 linear, branched or cyclic hydrocarbon groups, part of which may contain a fluorine atom, an oxygen atom, a nitrogen atom, a sulfur atom or a carbonyl bond.

4: An acid labile group in R ² of the general formulas (1) to (3) (the acid labile group is an acid leaving group, and a part thereof may include a fluorine atom, an oxygen atom, or a carbonyl bond. ) -Containing fluorine-containing acrylate compound.

5: Fluorine-containing acrylate compound represented by general formula (4) (wherein R ¹ represents any one functional group of a hydrogen atom, a methyl group, and a trifluoromethyl group).

The fluoropolymer compound of the present invention is
6: A fluorine-containing polymer compound polymerized or copolymerized using the fluorine-containing acrylate compound described in any one of 1 to 5 above.

  7: A fluorine-containing polymer compound which is a copolymer of a compound having an acid labile group and the fluorine-containing acrylate compound described in any one of 1 to 5 above.

  8: A fluorine-containing polymer compound which is a copolymer of a compound having a lactone structure and the fluorine-containing acrylate compound described in any one of 1 to 5 above.

  9: A resist material containing the polymer compound according to any one of 6 to 8 above.

  10: Using the resist material described in 9 above, applying this onto a substrate, exposing to high energy rays in a wavelength range of 1 to 300 nm through a photomask, and developing with a developer after heat treatment The pattern formation method characterized by including a process.

  11: The pattern forming method as described in 10 above, wherein the high energy beam is a KrF laser, ArF laser, F2 laser, EUV laser or X-ray.

  The fluoropolymer compound and resist material of the present invention are sensitive to high energy rays, have excellent sensitivity at wavelengths of 300 nm or less, particularly 200 nm or less, and have a bulky hexafluoroisopropanol structure in the vicinity of the polymerizable group. By using, as a base resin of the resist material, a polymer compound polymerized or copolymerized using the incorporated fluorine-containing acrylate compound represented by the general formulas (1) to (4), transparency of the resist material, adhesion, It was found that the film formability, developer permeability, etching resistance and glass transition temperature (Tg) were improved. Therefore, the resist material of the present invention can be a resist material having a small absorption especially at the exposure wavelength of excimer laser and X-ray due to these characteristics, and is high in a wide wavelength region from the ultraviolet region to the near infrared region. Provided is a resist material that has transparency, high adhesion to a substrate, film formability, high etching resistance, and high glass transition temperature (Tg). Furthermore, a fine pattern that is perpendicular to the substrate can be easily formed by the pattern forming method of the present invention, and the resist material of the present invention is suitable as a fine pattern forming material for manufacturing VLSI.

  The present invention will be described in detail below. By reducing the number of carbonyl groups and carbon-carbon double bonds from the structure of the monomer or polymer compound and incorporating a hexafluoroisopropanol structure, transmittance, resin substrate adhesion and film formability, developer It has been found that the permeability can be improved at the same time. In fact, it has been confirmed that by using an acrylic resin incorporating a hexafluoroisopropanol structure, the above performance is improved to a practically close level, and the etching resistance is improved by introducing an aliphatic cyclic structure. However, since the polymer compound has a low glass transition temperature (Tg), the pattern of the resist formed from the polymer compound has a high diffusion rate of the acid generated from the photoacid generator. It has been found that there are drawbacks such as the pattern size being smaller than the mask pattern. At the same time, since the resist material has a low glass transition temperature (Tg), it takes time and effort to change the patterning process conditions, such as the baking temperature, and to make adjustments by readjustment.

  On the other hand, since the fluorinated acrylate represented by the general formulas (1) to (4) has a bulky hexafluoroisopropanol structure in the vicinity of the polymerizable group, the polymer compound containing it has a polymer main chain. The movement can be suppressed, and the glass transition temperature (Tg) has been dramatically increased compared to before. As a result, it has been clarified that normal patterning process conditions can be applied, and that the acid diffusion rate can be suppressed and the rectangular patterning can be obtained without changing the normal conditions. In addition, since it also has an annular structure, the etching resistance was satisfactory.

  Therefore, the present invention provides a fluorine-containing acrylate compound represented by the general formulas (1) to (4) and a polymer compound thereof, and a resist material using the acrylate compound has high transparency, substrate adhesion and The present inventors have found that rectangular patterning can be obtained by dramatically improving the glass transition temperature (Tg) while having film formability, developer permeability and high etching resistance.

In the compounds represented by the general formulas (1) to (4) of the present invention, R ¹ is a hydrogen atom, a methyl group or a trifluoromethyl group, but has a lower refractive index and higher transparency, particularly transparency in the ultraviolet wavelength region. In the case where the material is required to have a property, a trifluoromethyl group is preferably used.

In the compounds represented by the general formulas (1) to (3) of the present invention, R ² is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 25 carbon atoms, a part of which is fluorine. A functional group that may contain an atom, oxygen atom, nitrogen atom, sulfur atom, or carbonyl bond, but the linear, branched or cyclic alkyl group having 1 to 25 carbon atoms that can be used for R ² includes a methyl group , Ethyl group, propyl group, isopropyl group, cyclopropyl group, n-propyl group, sec-butyl group, tert-butyl group, cyclobutyl group, n-pentyl group, cyclopentyl group, sec-pentyl group, neopentyl group, hexyl group Cyclohexyl group, ethylhexyl group, pentenyl group, octyl group, nonanyl group, decanyl group, norbornel group, adamantyl group, vinyl group, allyl group, Thenyl group, pentenyl group, ethynyl group. Examples of an oxygen atom, a nitrogen atom, a sulfur atom, as containing carbonyl bonds, ^-OH in the alkyl group, -OR 15, -O -, - C (= O ) -, - S -, - S (= O) -, - S (= O) 2 -, - NH 2 -, - NHR 15 -, - N (R 15) 2 - containing or intervening in the form of such It is a functional group. R ¹⁵ represents a linear, branched or cyclic alkyl group having 1 to 25 carbon atoms. A functional group in which a part or all of the alkyl group and the alkyl group containing a hetero atom is substituted with a fluorine atom can also be used.

In the compound represented by the general formula (1) of the present invention, R ^{3 to} R ¹⁴ are a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 25 carbon atoms, and part of which is an oxygen atom , A functional group that may contain a nitrogen atom, a sulfur atom, or a hydroxyl group. Examples of the linear, branched, or cyclic alkyl group having 1 to 25 carbon atoms that can be used for R ^{3 to} R ¹⁴ include a methyl group, Ethyl, propyl, isopropyl, cyclopropyl, n-propyl, sec-butyl, tert-butyl, cyclobutyl, n-pentyl, cyclopentyl, sec-pentyl, neopentyl, hexyl, Cyclohexyl, ethylhexyl, pentenyl, octyl, nonanyl, decanyl, norbornel, adamantyl, vinyl, allyl, butyl Examples thereof include a tenenyl group, a pentenyl group, and an ethynyl group, and those containing a fluorine atom, an oxygen atom, a nitrogen atom, a sulfur atom, or a hydroxyl group include —OH, —OR ¹⁵ , —O—, and —S. _{-, - S (= O)} -, - S (= O) 2 -, - NH 2 -, - NHR 15 -, - N (R 15) 2 - is a functional group containing or intervening in the form of such. R ¹⁵ represents a linear, branched or cyclic alkyl group having 1 to 25 carbon atoms. A functional group in which a part or all of the alkyl group and the alkyl group containing a hetero atom is substituted with a fluorine atom can also be used. Also, an alkylene group having 1 to 25 carbon atoms in which two of R ³ and R ⁵ , R ⁷ and R ⁹ , or R ^{11 to} R ¹⁴ are combined to form a ring can be used. Can be exemplified by a form in which one hydrogen atom in the alkyl group is eliminated, and those containing an oxygen atom, a sulfur atom, or a nitrogen atom include an alkylene group, -O-, -S-, -S. _{(= O) -, - S} (= O) 2 -, - NH 2 -, - NHR 15 -, - N (R 15) 2 - is a functional group containing or intervening in the form of such. A functional group in which part or all of the alkylene group or alkylene group containing a hetero atom is substituted with a fluorine atom can also be used.

  In the compound represented by the general formula (1) of the present invention, l is 0 or 1, m and n are any integers from 0 to 4, and in the compound represented by the general formula (2), n is 0 to 8 Indicates an arbitrary integer.

Next, the acid labile group that can be used for R ² of the present invention will be described. The acid labile group of R ² is a so-called acid leaving group, and a part thereof may contain an oxygen atom, a carbonyl bond, or a fluorine atom.

  The purpose of using the acid labile group is that the positive photosensitivity due to the acid unstable group and far-infrared rays having a wavelength of 300 nm or less, excimer laser, X-ray or the like, or exposure to an alkaline aqueous solution after exposure to an electron beam In order to express solubility, those having a fluorine atom in the functional group provide transparency, and those containing a cyclic structure further impart characteristics such as etching resistance and high glass transition temperature (Tg). It can be properly used for each application field of the invention.

The acid labile group that can be used in the present invention can be used without particular limitation as long as it is a group that can be eliminated by the effects of photoacid generators and hydrolysis. A cicarbonyl group, an acetal group, a silyl group, an acyl group, etc. can be mentioned. Examples of the alkoxycarbonyl group include a tert-butoxycarbonyl group, a tert-amyloxycarbonyl group, a methoxycarbonyl group, an ethoxycarbonyl group, and an i-propoxycarbonyl group. As an acetal group, methoxymethyl group, ethoxyethyl group, butoxyethyl group, cyclohexyloxyethyl group, benzyloxyethyl group, phenethyloxyethyl group, ethoxypropyl group, benzyloxypropyl group, phenethyloxypropyl group, ethoxybutyl group, An ethoxyisobutyl group etc. are mentioned. Moreover, when R < ² >, R < ³ > is a hydrogen atom, the acetal group which added vinyl ether to the hydroxyl group can also be used. Examples of the silyl group include trimethylsilyl group, ethyldimethylsilyl group, methyldiethylsilyl group, triethylsilyl group, i-propyldimethylsilyl group, methyldi-i-propylsilyl group, tri-i-propylsilyl group, and t-butyl. Examples thereof include a dimethylsilyl group, a methyldi-t-butylsilyl group, a tri-t-butylsilyl group, a phenyldimethylsilyl group, a methyldiphenylsilyl group, and a triphenylsilyl group. As the acyl group, acetyl group, propionyl group, butyryl group, heptanoyl group, hexanoyl group, valeryl group, pivaloyl group, isovaleryl group, lauryl group, myristoyl group, palmitoyl group, stearoyl group, oxalyl group, malonyl group, succinyl group, Glutaryl group, adipoyl group, piperoyl group, suberoyl group, azelaoil group, sebacoyl group, acryloyl group, propioroyl group, methacryloyl group, crotonoyl group, oleoyl group, maleoyl group, fumaroyl group, mesaconoyl group, canholoyl group, benzoyl group, phthaloyl group Group, isophthaloyl group, terephthaloyl group, naphthoyl group, toluoyl group, hydroatropoyl group, atropoyl group, cinnamoyl group, furoyl group, thenoyl group, nicotinoyl group, isonicotinoyl group And the like can be given. Further, those in which some or all of the hydrogen atoms of these acid labile groups are substituted with fluorine atoms can also be used.

Moreover, according to the present invention, the compound represented by the general formula (4) is suitably employed as the base compound of the fluorine-containing acrylate compound of the present invention. According to the present invention, the compound represented by the general formula (4) (wherein R ¹ represents any one functional group of a hydrogen atom, a methyl group, and a trifluoromethyl group) is represented by the general formula (1 ) To (3) are the most basic fluorine-containing acrylate compounds for deriving various fluorine-containing acrylate compounds.

  Next, a method for synthesizing the compounds represented by the general formulas (1) to (4) will be described.

  The compounds represented by the general formulas (1) to (4) are derived from the corresponding alcohol. If exemplified by the general formula (4), the fluorinated alcohol derivative represented by the structural formula (5) is converted to an acid or a base. In this method, a fluorine-containing acrylate compound represented by the general formula (4) is synthesized by reacting with an acrylic acid derivative in the presence.

  Examples of acrylic acid derivatives include acrylic acid, methacrylic acid, trifluoromethacrylic acid, acrylic anhydride, methacrylic anhydride, trifluoromethacrylic anhydride, acrylic chloride, methacrylic chloride, and trifluoromethacrylic chloride. Carboxylic acid can be used in the presence of an acid, and anhydride and acid chloride can be used in the presence of an acid and a base. When an anhydride is used, an appropriate reaction rate can be obtained, which is preferably employed. The amount of the acrylic acid derivative used may be at least 1 mol per mol of the fluorine-containing alcohol derivative (structural formula (5)) used as a raw material, and the reaction rate and the desired fluorine-containing acrylate (general formula ( From the viewpoint of the yield of 4)), an amount of 1.1 to 2 moles is preferred.

Examples of acids that can be used include proton acids and Lewis acids. For example, proton acids such as hydrogen fluoride, sulfuric acid, phosphoric acid, hydrogen chloride, methanesulfonic acid, trifluoromethanesulfonic acid, trifluoroacetic acid, aluminum chloride, Aluminum bromide, gallium chloride, gallium bromide, ferric chloride (FeCl ₃ ), zinc chloride, antimony chloride, titanium tetrachloride, tin tetrachloride, boron trifluoride, Ti (OCH ₃ ) ₄ , Ti (OC ₂ Lewis acids such as H ₅ ) ₄ , Ti (OC ₄ H ₉ ) ₄ , Ti (OCH (CH ₃ ) ₂ ) ₄ , Zn (CH ₃ COO) ₂ .2H ₂ O can be mentioned. Among these, when a protonic acid is used, the desired product can be obtained with good yield, and therefore, it is preferably employed. More preferably, methanesulfonic acid is used which proceeds rapidly and is easily available.

  As the amount of the acid, an amount of 0.01 to 10 times mol can be used with respect to 1 mol of the fluorine-containing alcohol derivative (structural formula (5)) as a raw material. Is too slow and the yield of the target fluorine-containing acrylate (general formula (4)) is very small, and it is not realistic. And by-products are increased. More preferably, 0.1 to 1.5 moles of acid are used with respect to the substrate to achieve an appropriate reaction rate and good yield.

  The reason for using a base in this reaction is to capture an acid (carboxylic acid or hydrogen chloride) generated in the reaction when anhydride or acid chloride is used as an acrylic acid derivative. Sodium hydroxide, sodium carbonate, carbonate In addition to inorganic bases such as sodium hydride, potassium hydroxide, potassium carbonate, potassium bicarbonate, sodium hydride, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium tert-butoxide, pyridine, lutidine, triethylamine, diethylamine, Organic bases such as piperidine, pyrrolidine, and 1,8-diazabicyclo [5,4,0] -7-undecene can be used. Preferably, an organic base is used, especially lutidine. The base is used in an amount of 1 to 10 mol, preferably 1 to 3 mol, per 1 mol of the compound of the structural formula (5).

  The solvent is not particularly limited as long as it does not participate in the reaction and dissolves the fluorinated alcohol derivative (structural formula (5)) as a raw material. For example, hydrocarbons such as hexane, heptane, benzene, toluene and xylene Examples include ethers such as diethyl ether, tetrahydrofuran and dioxane, halogenated hydrocarbons such as dichloromethane and chloroform, aprotic polar solvents such as acetonitrile, N, N-dimethylformamide, dimethyl sulfoxide and hexamethylphosphoric triamide These may be used alone or in admixture of two or more.

  Although reaction temperature is not specifically limited, Usually, reaction is possible in the range of room temperature to 200 degreeC. Since the reaction time varies depending on the kind and amount of the above-mentioned acrylic acid derivative, acid and base, reaction temperature, etc., the reaction time is appropriately changed according to this. In practice, it is possible to carry out the reaction while sequentially analyzing the reaction solution during the reaction, and to react until the raw materials are consumed. The treatment after the reaction is not particularly limited, but it is possible to add the reaction solution to water or ice water and then extract the target product by extraction with an organic solvent or to extract the target product by flash distillation.

  Next, the polymer compound according to the present invention will be described. The polymer compound of the present invention is a polymer material obtained by homopolymerizing or copolymerizing the fluorine-containing acrylate compound of any one of the general formulas (1) to (4).

  Specific examples of the monomer copolymerizable with the polymerizable fluorine-containing acrylate compound of the present invention include at least acrylic ester, methacrylic ester, fluorine-containing acrylic ester, fluorine-containing methacrylate ester, and styrene. Copolymerization with one or more monomers selected from compounds, fluorine-containing styrene compounds, vinyl ethers, fluorine-containing vinyl ethers, allyl ethers, fluorine-containing allyl ethers, olefins, fluorine-containing olefins, norbornene compounds, and fluorine-containing norbornene compounds Is preferred.

  The acrylic ester or methacrylic ester that can be used in the present invention can be used without any particular limitation on the ester side chain, but examples of known compounds include methyl acrylate or methacrylate, ethyl acrylate or methacrylate, n-propyl acrylate or methacrylate. , Isopropyl acrylate or methacrylate, n-butyl acrylate or methacrylate, isobutyl acrylate or methacrylate, n-hexyl acrylate or methacrylate, n-octyl acrylate or methacrylate, 2-ethylhexyl acrylate or methacrylate, lauryl acrylate or methacrylate, 2-hydroxyethyl acrylate or Methacrylate, 2-hydroxypropyl acrylate or methacrylate Alkyl esters of acrylic acid or methacrylic acid such as rate, ethylene glycol, propylene glycol, acrylate or methacrylate containing tetramethylene glycol group, acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, diacetone acrylamide, etc. Unsaturated amides, acrylonitrile, methacrylonitrile, alkoxysilane-containing vinyl silanes, acrylic acid or methacrylic acid esters, tert-butyl acrylate or methacrylate, 3-oxocyclohexyl acrylate or methacrylate, adamantyl acrylate or methacrylate, alkyladamantyl acrylate or methacrylate, Cyclohexyl acrylate or methacrylate DOO, tricyclodecanyl acrylate or methacrylate, acrylate or methacrylate having a ring structure such as lactone ring or norbornene ring, acrylic acid, methacrylic acid, and the like. Furthermore, it is possible to copolymerize the above acrylate compounds containing a cyano group at the α-position, and maleic acid, fumaric acid, maleic anhydride and the like as similar compounds.

  Further, as the fluorine-containing acrylic ester and fluorine-containing methacrylate used in the present invention, a fluorine atom or a monomer having a fluorine atom contained in the α-position of the acrylic, or a fluorine atom contained in the ester site A fluorine-containing compound which is an acrylic ester or methacrylic ester comprising a substituent and contains fluorine at both the α-position and the ester portion is also suitable. Furthermore, a cyano group may be introduced at the α-position. For example, as a monomer having a fluorine-containing alkyl group introduced at the α-position, a trifluoromethyl group, a trifluoroethyl group, or a nonafluoro-n- A monomer having a butyl group or the like is preferably employed, and the ester moiety in that case does not necessarily contain fluorine. When α-trifluoromethylacrylic acid alkyl ester is used as a copolymerization component, the yield of the polymer is relatively high, and the solubility of the resulting polymer in an organic solvent is good, which is preferably employed.

  On the other hand, the monomer containing fluorine at the ester site includes a perfluoroalkyl group as the ester site, a fluoroalkyl group as a fluoroalkyl group, and a unit having a cyclic structure and a fluorine atom at the ester site. , Units having a fluorinated benzene ring, a fluorinated cyclopentane ring, a fluorinated cyclohexane ring, a fluorinated cycloheptane ring, etc., whose cyclic structure is substituted with, for example, a fluorine atom, a trifluoromethyl group, a hexafluorocarbinol group, etc. Acrylic acid ester or methacrylic acid ester having An ester of acrylic acid or methacrylic acid in which the ester moiety is a fluorine-containing t-butyl ester group can also be used. As these fluorine-containing functional groups, a monomer used in combination with the α-position fluorine-containing alkyl group can be used. Among such units, particularly representative ones are exemplified in the form of monomers, 2,2,2-trifluoroethyl acrylate, 2,2,3,3-tetrafluoropropyl acrylate, 1,1 , 1,3,3,3-hexafluoroisopropyl acrylate, heptafluoroisopropyl acrylate, 1,1-dihydroheptafluoro-n-butyl acrylate, 1,1,5-trihydrooctafluoro-n-pentyl acrylate, 1, 1,2,2-tetrahydrotridecafluoro-n-octyl acrylate, 1,1,2,2-tetrahydroheptadecafluoro-n-decyl acrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,3 , 3-Tetrafluoropropyl methacrylate, 1,1,1,3,3,3-hexafluo Isopropyl methacrylate, heptafluoroisopropyl methacrylate, 1,1-dihydroheptafluoro-n-butyl methacrylate, 1,1,5-trihydrooctafluoro-n-pentyl methacrylate, 1,1,2,2-tetrahydrotridecafluoro- n-octyl methacrylate, 1,1,2,2-tetrahydroheptadecafluoro-n-decyl methacrylate, perfluorocyclohexylmethyl acrylate, perfluorocyclohexylmethyl methacrylate, 6- [3,3,3-trifluoro-2-hydroxy -2- (trifluoromethyl) propyl] bicyclo [2.2.1] heptyl-2-yl acrylate, 6- [3,3,3-trifluoro-2-hydroxy-2- (trifluoromethyl) propyl] Bisik [2.2.1] Heptyl-2-yl 2- (trifluoromethyl) acrylate, 6- [3,3,3-trifluoro-2-hydroxy-2- (trifluoromethyl) propyl] bicyclo [2. 2.1] Heptyl-2-yl methacrylate, 1,4-bis (1,1,1,3,3,3-hexafluoro-2-hydroxyisopropyl) cyclohexyl acrylate, 1,4-bis (1,1,1, 1,3,3,3-hexafluoro-2-hydroxyisopropyl) cyclohexyl methacrylate, 1,4-bis (1,1,1,3,3,3-hexafluoro-2-hydroxyisopropyl) cyclohexyl 2-trifluoro And methyl acrylate.

  Furthermore, styrene compounds and fluorine-containing styrene compounds that can be used in the present invention include styrene, fluorinated styrene, hydroxystyrene, etc., and one or more functional groups modified with a hexafluorocarbinol group or its hydroxyl group. Can be used. That is, styrene or hydroxystyrene substituted with hydrogen by a fluorine atom or a trifluoromethyl group, the above styrene having a halogen, an alkyl group or a fluorine-containing alkyl group bonded to the α-position, a styrene containing a perfluorovinyl group, or the like can be preferably used. is there.

  Further, as vinyl ether, fluorine-containing vinyl ether, allyl ether, fluorine-containing allyl ether, alkyl vinyl ether which may contain hydroxy group such as methyl group, ethyl group, propyl group, butyl group, hydroxyethyl group, hydroxybutyl group or the like Alkyl allyl ether, cyclohexyl group, cyclic vinyl having hydrogen or carbonyl bond in its cyclic structure, allyl ether, fluorine-containing vinyl ether in which part or all of hydrogen of the above functional group is substituted with fluorine atom, fluorine-containing Allyl ether can also be used. In addition, if it is a compound containing vinyl ester, vinyl silane, an olefin, a fluorine-containing olefin, a norbornene compound, a fluorine-containing norbornene compound, and another polymerizable unsaturated bond, it can be used without a restriction | limiting in particular.

  Examples of olefins include ethylene, propylene, isobutene, cyclopentene, and cyclohexene. Examples of fluorine-containing olefins include vinyl fluoride, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, hexafluoropropylene, and hexafluoroisobutene. It can be illustrated.

  The norbornene compound and the fluorine-containing norbornene compound are norbornene monomers having a mononuclear structure or a plurality of nuclear structures. In this case, fluorine-containing olefin, allyl alcohol, fluorine-containing allyl alcohol, homoallyl alcohol, and fluorine-containing homoallyl alcohol are acrylic acid, α-fluoroacrylic acid, α-trifluoromethylacrylic acid, methacrylic acid, described in the present specification. All acrylates, methacrylates, fluorine-containing acrylic esters or fluorine-containing methacrylates, 2- (benzoyloxy) pentafluoropropane, 2- (methoxyethoxymethyloxy) pentafluoropropene, 2- (tetrahydroxy Dies of unsaturated compounds such as pyranyloxy) pentafluoropropene, 2- (benzoyloxy) trifluoroethylene, 2- (methoxymethyloxy) trifluoroethylene with cyclopentadiene and cyclohexadiene Norbornene compound produced by ls-Alder addition reaction, which is 3- (5-bicyclo [2.2.1] hepten-2-yl) -1,1,1-trifluoro-2- (trifluoromethyl) -2 -Propanol and the like can be exemplified. The above copolymerizable compounds may be used alone or in combination of two or more.

  The copolymer composition ratio of the fluorine-containing acrylate compound of the present invention is not particularly limited, and is preferably selected from 10 to 100%. More preferably, it is 30 to 100%. If it is less than 30%, sufficient transparency and film formability are not exhibited depending on the wavelength range of the application field.

  The polymerization method of the polymer compound according to the present invention is not particularly limited as long as it is a generally used method, but radical polymerization, ionic polymerization and the like are preferable, and in some cases, coordination anion polymerization, living anion polymerization and the like are performed. It is also possible to use it. Here, a more general radical polymerization method will be described. That is, in the presence of a radical polymerization initiator or a radical initiator, by a known polymerization method such as bulk polymerization, solution polymerization, suspension polymerization or emulsion polymerization, either batchwise, semi-continuous or continuous operation can be performed. Just do it.

  The radical polymerization initiator is not particularly limited, and examples thereof include azo compounds, peroxide compounds, and redox compounds. Particularly, azobisisobutyronitrile, t-butylperoxypivalate, Di-t-butyl peroxide, i-butyryl peroxide, lauroyl peroxide, succinic acid peroxide, dicinnamyl peroxide, di-n-propyl peroxydicarbonate, t-butyl peroxyallyl monocarbonate, benzoyl peroxide, Hydrogen peroxide, ammonium persulfate and the like are preferable.

  The reaction vessel used for the polymerization reaction is not particularly limited. In the polymerization reaction, a polymerization solvent may be used. As the polymerization solvent, those which do not inhibit radical polymerization are preferable, and typical ones are ester-based solvents such as ethyl acetate and n-butyl acetate, ketone-based solvents such as acetone and methyl isobutyl ketone, and hydrocarbons such as toluene and cyclohexane. And alcohol solvents such as methanol, isopropyl alcohol, and ethylene glycol monomethyl ether. It is also possible to use various solvents such as water, ethers, cyclic ethers, chlorofluorocarbons, and aromatics. These solvents can be used alone or in admixture of two or more. Moreover, you may use together molecular weight regulators, such as a mercaptan. The reaction temperature of the copolymerization reaction is appropriately changed depending on the radical polymerization initiator or the radical polymerization initiation source, and is usually preferably 20 to 200 ° C, particularly preferably 30 to 140 ° C.

  As a method for removing the organic solvent or water as a medium from the solution or dispersion of the polymer compound according to the present invention thus obtained, any known method can be used. There are methods such as filtration or heating distillation under reduced pressure. The number average molecular weight of the obtained polymer compound of the present invention is usually in the range of 1,000 to 100,000, preferably 3,000 to 50,000.

  Next, a copolymer with a compound having an acid labile group will be described. The purpose of the acid-anxious group is to develop positive photosensitivity and solubility in an alkaline aqueous solution after exposure to high energy rays such as far-infrared rays, excimer lasers, X-rays or electron beams of 300 nm or less, and electron beams. Those having a fluorine atom in the functional group provide transparency, and those having a cyclic structure further impart characteristics such as etching resistance and high glass transition temperature (Tg) point, and can be used for each application field of the present invention. Is possible.

The compound having an acid labile group is a compound having both an acid labile group and a polymerizable group shown below, and the acid labile group is a group that undergoes elimination due to effects such as a photoacid generator or hydrolysis. Examples thereof include an alkoxycarbonyl group, an acetal group, a silyl group, and an acyl group. Examples of the alkoxycarbonyl group include a tert-butoxycarbonyl group, a tert-amyloxycarbonyl group, a methoxycarbonyl group, an ethoxycarbonyl group, and an i-propoxycarbonyl group. As an acetal group, methoxymethyl group, ethoxyethyl group, butoxyethyl group, cyclohexyloxyethyl group, benzyloxyethyl group, phenethyloxyethyl group, ethoxypropyl group, benzyloxypropyl group, phenethyloxypropyl group, ethoxybutyl group, An ethoxyisobutyl group etc. are mentioned. Moreover, when R < ² >, R < ³ > is a hydrogen atom, the acetal group which added vinyl ether to the hydroxyl group can also be used. Examples of the silyl group include trimethylsilyl group, ethyldimethylsilyl group, methyldiethylsilyl group, triethylsilyl group, i-propyldimethylsilyl group, methyldi-i-propylsilyl group, tri-i-propylsilyl group, and t-butyl. Examples thereof include a dimethylsilyl group, a methyldi-t-butylsilyl group, a tri-t-butylsilyl group, a phenyldimethylsilyl group, a methyldiphenylsilyl group, and a triphenylsilyl group. As the acyl group, acetyl group, propionyl group, butyryl group, heptanoyl group, hexanoyl group, valeryl group, pivaloyl group, isovaleryl group, lauryl group, myristoyl group, palmitoyl group, stearoyl group, oxalyl group, malonyl group, succinyl group, Glutaryl group, adipoyl group, piperoyl group, suberoyl group, azelaoil group, sebacoyl group, acryloyl group, propioroyl group, methacryloyl group, crotonoyl group, oleoyl group, maleoyl group, fumaroyl group, mesaconoyl group, canholoyl group, benzoyl group, phthaloyl group Group, isophthaloyl group, terephthaloyl group, naphthoyl group, toluoyl group, hydroatropoyl group, atropoyl group, cinnamoyl group, furoyl group, thenoyl group, nicotinoyl group, isonicotinoyl group And the like can be given. Furthermore, those in which some or all of the hydrogen atoms of these acid labile groups are substituted with fluorine atoms can also be used.

  As the polymerizable group, acrylic ester, methacrylic ester, fluorine-containing acrylic ester, fluorine-containing methacrylate ester, styrene compound, fluorine-containing styrene compound, vinyl ether, fluorine-containing vinyl ether, allyl ether, fluorine-containing allyl ether, olefin And fluorine-containing olefins, norbornene compounds, fluorine-containing norbornene compounds, and the like. A copolymer with a compound having an acid labile group is a copolymer of the compound having both the acid labile group and the polymerizable group and the fluorine-containing acrylate compound represented by the general formulas (1) to (4). Polymerized polymer material.

  Next, a copolymer with a compound having a lactone structure will be described. The purpose of containing the lactone structure is to improve the adhesion of the resin to the substrate and the film-forming property, and to suppress the repelling of the developer, but those having a fluorine atom in the functional group are transparent and contain a cyclic structure. Is for further imparting characteristics such as etching resistance and high glass transition temperature (Tg), and can be used for each application field of the present invention.

A compound having a lactone structure is a compound having both a lactone structure and a polymerizable group. The following can be illustrated as a lactone structure. R ¹⁶ represents —CH 2 —, —NH—, —S—, —O—, and R ¹⁷ represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 25 carbon atoms. As the polymerizable group, acrylic ester, methacrylic ester, fluorine-containing acrylic ester, fluorine-containing methacrylate ester, styrene compound, fluorine-containing styrene compound, vinyl ether, fluorine-containing vinyl ether, allyl ether, fluorine-containing allyl ether, olefin And fluorine-containing olefins, norbornene compounds, fluorine-containing norbornene compounds, and the like.

  A copolymer with a compound having a lactone structure is a copolymer obtained by copolymerizing a compound having both the following lactone structure and a polymerizable group and a fluorine-containing acrylate compound represented by the general formulas (1) to (4). It is a molecular material.

  The polymer compound of the present invention can be used as a base resin for resist materials, particularly chemically amplified, particularly chemically amplified positive resist materials. However, the polymer physical properties, thermal properties, alkali solubility, and other physical properties of the film can be used. Other polymer compounds can be mixed for the purpose of changing. In this case, the range of the polymer compound to be mixed is not particularly limited, but it can be mixed with a known polymer compound for resist in an arbitrary range.

  The resist material of the present invention can be prepared using known components except that the polymer compound of the present invention is used as a base resin. In particular, the chemically amplified positive resist material includes the above polymer compound (base resin), organic Contains solvent and acid generator. In this case, you may mix | blend a basic compound and a dissolution inhibitor with these resist materials.

  The organic solvent that can be used in the present invention may be any as long as it can dissolve the base resin, the acid generator, other additives, and the like. Examples of such an organic solvent include ketones such as cyclohexanone and methyl-2-n-amyl ketone, 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2. -Alcohols such as propanol, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, and other ethers, propylene glycol monomethyl ether acetate, propylene glycol monoethyl Ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, 3-ethoxy Propionate ethyl acetate tert- butyl, tert- butyl propionate, and propylene glycol monobutyl tert- butyl ether acetate.

  A fluorinated organic solvent can also be used. Specifically, 2-fluoroanisole, 3-fluoroanisole, 4-fluoroanisole, 2,3-difluoroanisole, 2,4-difluoroanisole, 2,5-difluoro Anisole, 5,8-difluoro-1,4-benzodioxane, 2,3-difluorobenzyl alcohol, 1,3-difluoro-2-propanol, 2 ', 4'-difluoropropiophenone, 2,4- Difluorotoluene, trifluoroacetaldehyde ethyl hemiacetal, trifluoroacetamide, trifluoroethanol, 2,2,2-trifluoroethyl butyrate, ethyl heptafluorobutyrate, ethyl heptafluorobutyl acetate, ethyl hexafluoroglutaryl Methyl, ethyl-3-hydroxy-4,4,4-trifluoro Lobutylate, ethyl-2-methyl-4,4,4-trifluoroacetoacetate, ethylpentafluorobenzoate, ethylpentafluoropropionate, ethylpentafluoropropynylacetate, ethylperfluorooctanoate, ethyl-4,4,4 4-trifluoroacetoacetate, ethyl-4,4,4-trifluorobutyrate, ethyl-4,4,4-trifluorocrotonate, ethyltrifluorosulfonate, ethyl-3- (trifluoromethyl) butyrate, ethyl Trifluoropyruvate, sec-ethyl trifluoroacetate, fluorocyclohexane, 2,2,3,3,4,4,4-heptafluoro-1-butanol, 1,1,1,2,2,3,3- Heptafluoro-7,7-dimethyl-4,6-o Tandione, 1,1,1,3,5,5,5-heptafluoropentane-2,4-dione, 3,3,4,4,5,5,5-heptafluoro-2-pentanol, 3, 3,4,4,5,5,5-heptafluoro-2-pentanone, isopropyl-4,4,4-trifluoroacetoacetate, methyl perfluorodenanoate, methyl perfluoro (2-methyl-3-oxa Hexanoate), methyl perfluorononanoate, methyl perfluorooctanoate, methyl-2,3,3,3-tetrafluoropropionate, methyl trifluoroacetoacetate, methyl trifluoroacetoacetate, 1,1, 1,2,2,6,6,6-octafluoro-2,4-hexanedione, 2,2,3,3,4,4,5,5-octafluoro-1- Pentanol, 1H, 1H, 2H, 2H-perfluoro-1-decanol, perfluoro (2,5-dimethyl-3,6-dioxane anionic) acid methyl ester, 2H-perfluoro-5-methyl-3, 6-dioxanonane, 1H, 1H, 2H, 3H, 3H-perfluorononane-1,2-diol, 1H, 1H, 9H-perfluoro-1-nonanol, 1H, 1H-perfluorooctanol, 1H, 1H , 2H, 2H-perfluorooctanol, 2H-perfluoro-5,8,11,14-tetramethyl-3,6,9,12,15-pentaoxaoctadecane, perfluorotributylamine, perfluorotrihexylamine, Perfluoro-2,5,8-trimethyl-3,6,9-trioxadodecanoic acid methyl ester, Fluorotripentylamine, perfluorotripropylamine, 1H, 1H, 2H, 3H, 3H-perfluoroundecane-1,2-diol, trifluorobutanol, 1,1,1-trifluoro-5-methyl- 2,4-hexanedione, 1,1,1-trifluoro-2-propanol, 3,3,3-trifluoro-1-propanol, 1,1,1-trifluoro-2-propyl acetate, perfluoro ( Butyltetrahydrofuran), perfluorodecalin, perfluoro (1,2-dimethylcyclohexane), perfluoro (1,3-dimethylcyclohexane), propylene glycol trifluoromethyl ether acetate, propylene glycol methyl ether trifluoromethyl acetate, trifluoromethyl Butyl acetate Examples include methyl 3-trifluoromethoxypropionate, perfluorocyclohexanone, propylene glycol trifluoromethyl ether, butyl trifluoroacetate, 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione, and the like. . These solvents may be used alone or in combination of two or more, but are not limited thereto.

  In the present invention, among these organic solvents, propylene glycol monomethyl acetate, which is a safety solvent, and mixed solvents thereof, in addition to diethylene glycol dimethyl ether and 1-ethoxy-2-propanol, which have the highest solubility of the acid generator in the resist component Are preferably used. In addition, the usage-amount of the said solvent is 300-10,000 parts with respect to 100 parts of base resins (a weight part, hereafter the same), Especially 500-5,000 parts are preferable.

  Examples of the acid generator include onium salts, diazomethane derivatives, glyoxime derivatives, β-ketosulfonic acid derivatives, disulfone derivatives, nitrobenzyl sulfonate derivatives, sulfonic acid ester derivatives, imidoyl sulfonate derivatives, and the like. Specifically, for example, trifluoromethanesulfonic acid diphenyliodonium, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) phenyliodonium, p-toluenesulfonic acid diphenyliodonium, p-toluenesulfonic acid (p-tert-butoxyphenyl) phenyl Iodonium, triphenylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonate (p-tert-butoxyphenyl) diphenylsulfonium, bis (p-tert-butoxyphenyl) phenylsulfonium trifluoromethanesulfonate, tris (p-tert) trifluoromethanesulfonate -Butoxyphenyl) sulfonium, p-toluenesulfonic acid triphenylsulfonium, p-toluenesulfonic acid (pt rt-butoxyphenyl) diphenylsulfonium, bis (p-tert-butoxyphenyl) phenylsulfonium p-toluenesulfonate, tris (p-tert-butoxyphenyl) sulfonium p-toluenesulfonate, triphenylsulfonium nonafluorobutanesulfonate, Triphenylsulfonium butanesulfonate, trimethylsulfonium trifluoromethanesulfonate, trimethylsulfonium p-toluenesulfonate, cyclohexylmethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, cyclohexylmethyl (2-oxocyclohexyl) sulfonium p-toluenesulfonate , Dimethylphenylsulfonium trifluoromethanesulfonate, dimethylphenol p-toluenesulfonate Nylsulfonium, dicyclohexylphenylsulfonium trifluoromethanesulfonate, dicyclohexylphenylsulfonium p-toluenesulfonate, trinaphthylsulfonium trifluoromethanesulfonate, cyclohexylmethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, trifluoromethanesulfonic acid (2-norbornyl) ) Onium salts such as methyl (2-oxocyclohexyl) sulfonium, ethylene bis [methyl (2-oxocyclopentyl) sulfonium trifluoromethanesulfonate], 1,2'-naphthylcarbonylmethyltetrahydrothiophenium triflate, bis ( Benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (xylenesulfur Phonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (cyclopentylsulfonyl) diazomethane, bis (n-butylsulfonyl) diazomethane, bis (isobutylsulfonyl) diazomethane, bis (sec-butylsulfonyl) diazomethane, bis (n-propylsulfonyl) Diazomethane, bis (isopropylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, bis (n-amylsulfonyl) diazomethane, bis (isoamylsulfonyl) diazomethane, bis (sec-amylsulfonyl) diazomethane, bis (tert-amylsulfonyl) Diazomethane, 1-cyclohexylsulfonyl-1- (tert-butylsulfonyl) diazomethane, 1-cyclohexylsulfonyl- Diazomethane derivatives such as-(tert-amylsulfonyl) diazomethane, 1-tert-amylsulfonyl-1- (tert-butylsulfonyl) diazomethane, bis-O- (p-toluenesulfonyl) -α-dimethylglyoxime, bis-O -(P-toluenesulfonyl) -α-diphenylglyoxime, bis-O- (p-toluenesulfonyl) -α-dicyclohexylglyoxime, bis-O- (p-toluenesulfonyl) -2,3-pentanedione glyoxime Bis-O- (p-toluenesulfonyl) -2-methyl-3,4-pentanedione glyoxime, bis-O- (n-butanesulfonyl) -α-dimethylglyoxime, bis-O- (n-butane Sulfonyl) -α-diphenylglyoxime, bis-O- (n-butanesulfonyl) -Α-dicyclohexylglyoxime, bis-O- (n-butanesulfonyl) -2,3-pentanedione glyoxime, bis-O- (n-butanesulfonyl) -2-methyl-3,4-pentanedione glyoxime Bis-O- (methanesulfonyl) -α-dimethylglyoxime, bis-O- (trifluoromethanesulfonyl) -α-dimethylglyoxime, bis-O- (1,1,1-trifluoroethanesulfonyl) -α -Dimethylglyoxime, bis-O- (tert-butanesulfonyl) -α-dimethylglyoxime, bis-O- (perfluorooctanesulfonyl) -α-dimethylglyoxime, bis-O- (cyclohexanesulfonyl) -α- Dimethylglyoxime, bis-O- (benzenesulfonyl) -α-dimethylglyoxime, bi -O- (p-fluorobenzenesulfonyl) -α-dimethylglyoxime, bis-O- (p-tert-butylbenzenesulfonyl) -α-dimethylglyoxime, bis-O- (xylenesulfonyl) -α-dimethylglyoxime Glyoxime derivatives such as oxime, bis-O- (camphorsulfonyl) -α-dimethylglyoxime, 2-cyclohexylcarbonyl-2- (p-toluenesulfonyl) propane, 2-isopropylcarbonyl-2- (p-toluenesulfonyl) propane Β-ketosulfone derivatives such as diphenyldisulfone, dicyclohexyldisulfone and the like, nitrobenzylsulfonate derivatives such as p-toluenesulfonic acid 2,6-dinitrobenzyl, p-toluenesulfonic acid 2,4-dinitrobenzyl, 1,2 , 3 Sulfonic acid ester derivatives such as tris (methanesulfonyloxy) benzene, 1,2,3-tris (trifluoromethanesulfonyloxy) benzene, 1,2,3-tris (p-toluenesulfonyloxy) benzene, phthalimido-yl-trif Rate, phthalimido-yl-tosylate, 5-norbornene-2,3-dicarboximido-yl-triflate, 5-norbornene-2,3-dicarboximido-yl-tosylate, 5-norbornene-2,3-di Examples thereof include imidoylsulfonate derivatives such as carboxyimido-yl-n-butyl trifuresulfonate, trifluoromethanesulfonic acid triphenylsulfonium, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, Trifluoromethanesulfonic acid tris (p-tert-butoxyphenyl) sulfonium, p-toluenesulfonic acid triphenylsulfonium, p-toluenesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, p-toluenesulfonic acid tris (p- tert-butoxyphenyl) sulfonium, trinaphthylsulfonium trifluoromethanesulfonate, cyclohexylmethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, (2-norbornyl) methyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, 1,2 Onium salts such as' -naphthylcarbonylmethyltetrahydrothiophenium triflate, bis (benzenesulfonyl) diazomethane, bis (p-tolue) Enesulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (n-butylsulfonyl) diazomethane, bis (isobutylsulfonyl) diazomethane, bis (sec-butylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl) ) Diazomethane derivatives such as diazomethane, bis (tert-butylsulfonyl) diazomethane, bis-O- (p-toluenesulfonyl) -α-dimethylglyoxime, bis-O- (n-butanesulfonyl) -α-dimethylglyoxime, etc. The glyoxime derivative is preferably used. In addition, the said acid generator can be used individually by 1 type or in combination of 2 or more types. Since onium salts are excellent in rectangularity improving effect and diazomethane derivatives and glyoxime derivatives are excellent in standing wave reducing effect, it is possible to finely adjust the profile by combining both.

  The amount of the acid generator added is preferably 0.2 to 15 parts with respect to 100 parts of the base resin. If the amount is less than 0.2 parts, the amount of acid generated during exposure is small, and the sensitivity and resolution may be poor. If it is more than 15 parts, the transparency may be lowered and the resolution may be lowered.

  As the basic compound, a compound capable of suppressing the diffusion rate when the acid generated from the acid generator diffuses into the resist film is suitable. By blending such a basic compound, the acid diffusion rate in the resist film is suppressed, the resolution is improved, the sensitivity change after exposure is suppressed, the substrate and environment dependency is reduced, and the exposure margin is reduced. And the pattern profile can be improved.

  Examples of such basic compounds include ammonia, primary, secondary, and tertiary aliphatic amines, hybrid amines, aromatic amines, heterocyclic amines, nitrogen-containing compounds having a carboxyl group, Examples thereof include nitrogen-containing compounds having a sulfonyl group, nitrogen-containing compounds having a hydroxyl group, nitrogen-containing compounds having a hydroxyphenyl group, alcoholic nitrogen-containing compounds, amide derivatives, imide derivatives, and the like.

  Specific examples of primary aliphatic amines include methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, pentylamine, tert-amylamine, cyclopentyl. Examples include amine, hexylamine, cyclohexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, cetylamine, methylenediamine, ethylenediamine, tetraethylenepentamine and the like.

  Specific examples of secondary aliphatic amines include dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, dipentylamine, dicyclopentylamine. , Dihexylamine, dicyclohexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, didodecylamine, dicetylamine, N, N-dimethylmethylenediamine, N, N-dimethylethylenediamine, N, N-dimethyltetraethylenepentamine, etc. Illustrated.

  Specific examples of tertiary aliphatic amines include trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tripentylamine, tripentylamine, Cyclopentylamine, trihexylamine, tricyclohexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, tridodecylamine, tricetylamine, N, N, N ′, N′-tetramethylmethylenediamine, Examples thereof include N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethyltetraethylenepentamine and the like.

  Specific examples of the hybrid amines include dimethylethylamine, methylethylpropylamine, benzylamine, phenethylamine, benzyldimethylamine and the like.

  Specific examples of aromatic amines include aniline, N-methylaniline, N-ethylaniline, N-propylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline and ethyl. Aniline, propylaniline, trimethylaniline, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2,4-dinitroaniline, 2,6-dinitroaniline, 3,5-dinitroaniline, N, N-dimethyltoluidine And aniline derivatives such as diphenyl (p-tolyl) amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, and diaminonaphthalene.

  Specific examples of the heterocyclic amines include pyrrole derivatives such as pyrrole, 2H-pyrrole, 1-methylpyrrole, 2,4-dimethylpyrrole, 2,5-dimethylpyrrole, N-methylpyrrole, oxazole, isoxazole and the like. Oxazole derivatives, thiazole derivatives such as thiazole, isothiazole, imidazole derivatives such as imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, pyrazole derivatives, furazane derivatives, pyrroline, pyrroline such as 2-methyl-1-pyrroline Derivatives, pyrrolidine derivatives such as pyrrolidine, N-methylpyrrolidine, pyrrolidinone, N-methylpyrrolidone, imidazoline derivatives, imidazolidine derivatives, pyridine, methylpyridine, ethylpyridine, propylpyridine, butylpyridine, 4 (1-butylpentyl) pyridine, dimethylpyridine, trimethylpyridine, triethylpyridine, phenylpyridine, 3-methyl-2-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine Pyridine derivatives such as 1-methyl-2-pyridine, 4-pyrrolidinopyridine, 1-methyl-4-phenylpyridine, 2- (1-ethylpropyl) pyridine, aminopyridine, dimethylaminopyridine, pyridazine derivatives, pyrimidine derivatives , Pyrazine derivatives, pyrazoline derivatives, pyrazolidine derivatives, piperidine derivatives, piperazine derivatives, morpholine derivatives, indole derivatives, isoindole derivatives, 1H-indazole derivatives, indoline Conductors, quinoline, quinoline derivatives such as 3-quinolinecarbonitrile, isoquinoline derivatives, cinnoline derivatives, quinazoline derivatives, quinoxaline derivatives, phthalazine derivatives, purine derivatives, pteridine derivatives, carbazole derivatives, phenanthridine derivatives, acridine derivatives, phenazine derivatives, 1 , 10-phenanthroline derivative, adenine derivative, adenosine derivative, guanine derivative, guanosine derivative, uracil derivative, uridine derivative and the like.

  Specific examples of nitrogen-containing compounds having a carboxyl group include aminobenzoic acid, indolecarboxylic acid, nicotinic acid, alanine, arginine, aspartic acid, glutamic acid, glycine, histidine, isoleucine, glycylleucine, leucine, methionine, phenylalanine. And amino acid derivatives such as threonine, lysine, 3-aminopyrazine-2-carboxylic acid and methoxyalanine. Specific examples of the nitrogen-containing compound having a sulfonyl group include 3-pyridinesulfonic acid and pyridinium p-toluenesulfonate.

  Specific examples of the nitrogen-containing compound and alcoholic nitrogen-containing compound containing a hydroxyl group and a hydroxyphenyl group include 2-hydroxypyridine, aminocresol, 2,4-quinolinediol, 3-indolemethanol hydrate, monoethanolamine, diethanolamine , Triethanolamine, N-ethyldiethanolamine, N, N-diethylethanolamine, triisopropanolamine, 2,2′-iminodiethanol, 2-aminoethanol, 3-amino-1-propanol, 4-amino-1-butanol 4- (2-hydroxyethyl) morpholine, 2- (2-hydroxyethyl) pyridine, 1- (2-hydroxyethyl) piperazine, 1- [2- (2-hydroxyethoxy) ethyl] piperazine, piperidine ethanol, 1 − 2-hydroxyethyl) pyrrolidine, 1- (2-hydroxyethyl) -2-pyrrolidinone, 3-piperidino-1,2-propanediol, 3-pyrrolidino-1,2-propanediol, 8-hydroxyeurolidine, 3- Examples include quinuclidinol, 3-tropanol, 1-methyl-2-pyrrolidine ethanol, 1-aziridine ethanol, N- (2-hydroxyethyl) phthalimide, N- (2-hydroxyethyl) isonicotinamide.

  Specific examples of the amide derivative include formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide and the like.

  Specific examples of the imide derivative include phthalimide, succinimide, maleimide and the like.

  Furthermore, the basic compounds other than the above are specifically exemplified below. 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, 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo [8.8.8] hexacosane, 4,7,13,18-tetraoxa-1,10-diazabicyclo [8.5.5] Eicosane, 1,4,10,13-tetraoxa-7,16-diazabicyclooctadecane, 1-aza-12-crown-4 1-aza-15-crown-5, 1-aza-18-crown-6, tris (2-formyloxyethyl) amine, tris (2-formyloxyethyl) amine, tris (2-acetoxyethyl) amine, Tris (2-propionyloxyethyl) amine, tris (2-butyryloxyethyl) amine, tris (2-isobutyryloxyethyl) amine, tris (2-valeryloxyethyl) amine, tris (2-pivalloy) Ruoxyxyethyl) amine, N, N-bis (2-acetoxyethyl) 2- (acetoxyacetoxy) ethylamine, tris (2-methoxycarbonyloxyethyl) amine, tris (2-tert-butoxycarbonyloxyethyl) amine, tris [2- (2-oxopropoxy) ethyl] amine, tris [2- Methoxycarbonylmethyl) oxyethyl] amine, tris [2- (tert-butoxycarbonylmethyloxy) ethyl] amine, tris [2- (cyclohexyloxycarbonylmethyloxy) ethyl] amine, tris (2-methoxycarbonylethyl) amine, tris (2-ethoxycarbonylethyl) amine, N, N-bis (2-hydroxyethyl) 2- (methoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (methoxycarbonyl) ethylamine, N, N -Bis (2-hydroxyethyl) 2- (ethoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (ethoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2- (2 -Methoxyethoxycarbonyl) Tylamine, N, N-bis (2-acetoxyethyl) 2- (2-methoxyethoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2- (2-hydroxyethoxycarbonyl) ethylamine, N, N- Bis (2-acetoxyethyl) 2- (2-acetoxyethoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2-[(methoxycarbonyl) methoxycarbonyl] ethylamine, N, N-bis (2-acetoxy) Ethyl) 2-[(methoxycarbonyl) methoxycarbonyl] ethylamine, N, N-bis (2-hydroxyethyl) 2- (2-oxopropoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- ( 2-oxopropoxycarbonyl) ethylamine, N, N-bis ( -Hydroxyethyl) 2- (tetrahydrofurfuryloxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (tetrahydrofurfuryloxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2- [(2-oxotetrahydrofuran-3-yl) oxycarbonyl] ethylamine, N, N-bis (2-acetoxyethyl) 2-[(2-oxotetrahydrofuran-3-yl) oxycarbonyl] ethylamine, N, N-bis (2-hydroxyethyl) 2- (4-hydroxybutoxycarbonyl) ethylamine, N, N-bis (2-formyloxyethyl) 2- (4-formyloxybutoxycarbonyl) ethylamine, N, N-bis (2-formyl) Oxyethyl) 2- (2-formyloxyate) Sicarbonyl) ethylamine, N, N-bis (2-methoxyethyl) 2- (methoxycarbonyl) ethylamine, N- (2-hydroxyethyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (2-acetoxy) Ethyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (2-hydroxyethyl) bis [2- (ethoxycarbonyl) ethyl] amine, N- (2-acetoxyethyl) bis [2- (ethoxycarbonyl) Ethyl] amine, N- (3-hydroxy-1-propyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (3-acetoxy-1-propyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (2-methoxyethyl) bis [2- (methoxycarbonyl) ethyl] amine, N-butylbis [2 -(Methoxycarbonyl) ethyl] amine, N-butylbis [2- (2-methoxyethoxycarbonyl) ethyl] amine, N-methylbis (2-acetoxyethyl) amine, N-ethylbis (2-acetoxyethyl) amine, N- Methylbis (2-pivaloyloxyoxyethyl) amine, N-ethylbis [2- (methoxycarbonyloxy) ethyl] amine, N-ethylbis [2- (tert-butoxycarbonyloxy) ethyl] amine, tris (methoxycarbonylmethyl) Amine, tris (ethoxycarbonylmethyl) amine, N-butylbis (methoxycarbonylmethyl) amine, N-hexylbis (methoxycarbonylmethyl) amine, β- (diethylamino) -δ-valerolactone, 1- [2- (methoxymethoxy) Ethyl] pyro Lysine, 1- [2- (methoxymethoxy) ethyl] piperidine, 4- [2- (methoxymethoxy) ethyl] morpholine, 1- [2-[(2-methoxyethoxy) methoxy] ethyl] pyrrolidine, 1- [2 -[(2-methoxyethoxy) methoxy] ethyl] piperidine, 4- [2-[(2-methoxyethoxy) methoxy] ethyl] morpholine, 2- (1-pyrrolidinyl) ethyl acetate, 2-piperidinoethyl acetate, 2-acetate Morpholinoethyl, 2- (1-pyrrolidinyl) ethyl formate, 2-piperidinoethyl propionate, 2-morpholinoethyl acetoxyacetate, 2- (1-pyrrolidinyl) ethyl methoxyacetate, 4- [2- (methoxycarbonyloxy) ethyl] morpholine 1- [2- (t-butoxycarbonyloxy) ethyl] piperidine, 4 [2- (2-methoxyethoxycarbonyloxy) ethyl] morpholine, methyl 3- (1-pyrrolidinyl) propionate, methyl 3-piperidinopropionate, methyl 3-morpholinopropionate, 3- (thiomorpholino) propionic acid Methyl, methyl 2-methyl-3- (1-pyrrolidinyl) propionate, ethyl 3-morpholinopropionate, methoxycarbonylmethyl 3-piperidinopropionate, 2-hydroxyethyl 3- (1-pyrrolidinyl) propionate, 3 -2-Acetoxyethyl morpholinopropionate, 2-oxotetrahydrofuran-3-yl 3- (1-pyrrolidinyl) propionate, tetrahydrofurfuryl 3-morpholinopropionate, glycidyl 3-piperidinopropionate, 3-morpholinopropionic acid 2-me Xylethyl, 2- (2-methoxyethoxy) ethyl 3- (1-pyrrolidinyl) propionate, butyl 3-morphonopropionate, cyclohexyl 3-piperidinopropionate, α- (1-pyrrolidinyl) methyl-γ-butyrolactone Β-piperidino-γ-butyrolactone, β-morpholino-δ-valerolactone, methyl 1-pyrrolidinyl acetate, methyl piperidinoacetate, methyl morpholinoacetate, methyl thiomorpholinoacetate, ethyl 1-pyrrolidinylacetate, 2-methoxyethyl morpholinoacetate Can be mentioned.

  Furthermore, a basic compound containing a cyano group can be added. Specifically, 3- (diethylamino) propiononitrile, N, N-bis (2-hydroxyethyl) -3-aminopropiononitrile, N, N-bis (2-acetoxyethyl) -3-aminopropiononitrile, N, N-bis (2-formyloxyethyl) -3-aminopropiononitrile, N, N-bis (2-methoxyethyl) -3 -Aminopropiononitrile, N, N-bis [2- (methoxymethoxy) ethyl] -3-aminopropiononitrile, N- (2-cyanoethyl) -N- (2-methoxyethyl) -3-aminopropionic acid Methyl, N- (2-cyanoethyl) -N- (2-hydroxyethyl) -3-aminopropionate, N- (2-acetoxyethyl) -N- ( -Cyanoethyl) -3-aminopropionic acid methyl, N- (2-cyanoethyl) -N-ethyl-3-aminopropiononitrile, N- (2-cyanoethyl) -N- (2-hydroxyethyl) -3-amino Propiononitrile, N- (2-acetoxyethyl) -N- (2-cyanoethyl) -3-aminopropiononitrile, N- (2-cyanoethyl) -N- (2-formyloxyethyl) -3-aminopropi Ononitrile, N- (2-cyanoethyl) -N- (2-methoxyethyl) -3-aminopropiononitrile, N- (2-cyanoethyl) -N- [2- (methoxymethoxy) ethyl] -3-amino Propiononitrile, N- (2-cyanoethyl) -N- (3-hydroxy-1-propyl) -3-aminopropiononitrile, N- (3-a Toxi-1-propyl) -N- (2-cyanoethyl) -3-aminopropiononitrile, N- (2-cyanoethyl) -N- (3-formyloxy-1-propyl) -3-aminopropiononitrile, N- (2-cyanoethyl) -N-tetrahydrofurfuryl-3-aminopropiononitrile, N, N-bis (2-cyanoethyl) -3-aminopropiononitrile, diethylaminoacetonitrile, N, N-bis (2- Hydroxyethyl) aminoacetonitrile, N, N-bis (2-acetoxyethyl) aminoacetonitrile, N, N-bis (2-formyloxyethyl) aminoacetonitrile, N, N-bis (2-methoxyethyl) aminoacetonitrile, N , N-bis [2- (methoxymethoxy) ethyl] aminoacetonitrile, N-sia Nomethyl-N- (2-methoxyethyl) -3-aminopropionate methyl, N-cyanomethyl-N- (2-hydroxyethyl) -3-aminopropionate methyl, N- (2-acetoxyethyl) -N-cyanomethyl Methyl 3-aminopropionate, N-cyanomethyl-N- (2-hydroxyethyl) aminoacetonitrile, N- (2-acetoxyethyl) -N- (cyanomethyl) aminoacetonitrile, N-cyanomethyl-N- (2-formyl Oxyethyl) aminoacetonitrile, N-cyanomethyl-N- (2-methoxyethyl) aminoacetonitrile, N-cyanomethyl-N- [2- (methoxymethoxy) ethyl] aminoacetonitrile, N- (cyanomethyl) -N- (3- Hydroxy-1-propyl) aminoacetonitrile, N- ( -Acetoxy-1-propyl) -N- (cyanomethyl) aminoacetonitrile, N-cyanomethyl-N- (3-formyloxy-1-propyl) aminoacetonitrile, N, N-bis (cyanomethyl) aminoacetonitrile, 1-pyrrolidine propi Ononitrile, 1-piperidinepropiononitrile, 4-morpholinepropiononitrile, 1-pyrrolidineacetonitrile, 1-piperidineacetonitrile, 4-morpholineacetonitrile, cyanomethyl 3-diethylaminopropionate, N, N-bis (2-hydroxyethyl) Cyanomethyl-3-aminopropionate, cyanomethyl N, N-bis (2-acetoxyethyl) -3-aminopropionate, cyanomethyl N, N-bis (2-formyloxyethyl) -3-aminopropionate, , N-bis (2-methoxyethyl) -3-aminopropionic acid cyanomethyl, N, N-bis [2- (methoxymethoxy) ethyl] -3-aminopropionic acid cyanomethyl, 3-diethylaminopropionic acid (2-cyanoethyl) N, N-bis (2-hydroxyethyl) -3-aminopropionic acid (2-cyanoethyl), N, N-bis (2-acetoxyethyl) -3-aminopropionic acid (2-cyanoethyl), N, N -Bis (2-formyloxyethyl) -3-aminopropionic acid (2-cyanoethyl), N, N-bis (2-methoxyethyl) -3-aminopropionic acid (2-cyanoethyl), N, N-bis [ 2- (methoxymethoxy) ethyl] -3-aminopropionic acid (2-cyanoethyl), cyanomethyl 1-pyrrolidinepropionate , Cyanomethyl 1-piperidinepropionate, cyanomethyl 4-morpholinepropionate, 1-pyrrolidinepropionic acid (2-cyanoethyl), 1-piperidinepropionic acid (2-cyanoethyl), 4-morpholinepropionic acid (2-cyanoethyl) The

  The basic compound can be used alone or in combination of two or more, and the compounding amount is preferably 0.01 to 2 parts, particularly 0.01 to 1 part with respect to 100 parts of the total base resin. is there. If the blending amount is less than 0.01 part, the effect as an additive may not be sufficiently obtained, and if it exceeds 2 parts, resolution and sensitivity may be lowered.

  The dissolution inhibitor is a compound whose solubility in an alkaline aqueous solution is changed by the action of an acid, that is, a compound having an acid labile group, but its structure can be used without any particular limitation. The general acid labile group is the acid labile group described above, and is a functional group that is cleaved by an acid. A polymer compound using such a dissolution inhibitor is insoluble or hardly soluble in an alkaline aqueous solution before being irradiated with active energy rays, and is generated by the acid generated from the acid generator by irradiation with active energy rays. It is hydrolyzed and becomes soluble in alkaline aqueous solution.

  The dissolution inhibitor is a compound having a molecular weight of 3,000 or less whose solubility in an alkaline developer is changed by the action of an acid, particularly a hydroxyl group of a compound containing a phenol, a carboxylic acid derivative or hexafluoroisopropanol having a molecular weight of 2,500 or less. Compounds in which part or all are substituted with an acid labile group are suitable, and 3,3 ′, 5,5′-tetrafluoro [(1,1′-biphenyl) -4,4′-di-tert-butoxycarbonyl ], 4,4 '-[2,2,2-trifluoro-1- (trifluoromethyl) ethylidene] bisphenol-4,4'-di-tert-butoxycarbonyl, bis (4- (2'-tetrahydropyrani) Ruoxy) phenyl) methane, bis (4- (2′-tetrahydrofuranyloxy) phenyl) methane, bis (4-tert-butoxypheny ) Methane, bis (4-tert-butoxycarbonyloxyphenyl) methane, bis (4-tert-butoxycarbonylmethyloxyphenyl) methane, bis (4- (1′-ethoxyethoxy) phenyl) methane, bis (4- ( 1′-ethoxypropyloxy) phenyl) methane, 2,2-bis (4 ′-(2 ″ -tetrahydropyranyloxy)) propane, 2,2-bis (4 ′-(2 ″ -tetrahydrofuranyloxy) ) Phenyl) propane, 2,2-bis (4′-tert-butoxyphenyl) propane, 2,2-bis (4′-tert-butoxycarbonyloxyphenyl) propane, 2,2-bis (4-tert-butoxy) Carbonylmethyloxyphenyl) propane, 2,2-bis (4 ′-(1 ″ -ethoxyethoxy) phen L) propane, 2,2-bis (4 ′-(1 ″ -ethoxypropyloxy) phenyl) propane, 4,4-bis (4 ′-(2 ″ -tetrahydropyranyloxy) phenyl) valeric acid tert -Butyl, 4-tert-butyl 4,4-bis (4 '-(2 "-tetrahydrofuranyloxy) phenyl) valerate, tert-butyl 4,4-bis (4'-tert-butoxyphenyl) valerate, 4, , 4-Bis (4-tert-butoxycarbonyloxyphenyl) valerate, tert-butyl 4,4-bis (4′-tert-butoxycarbonylmethyloxyphenyl) valerate, 4,4-bis (4 '-(1 ″ -Ethoxyethoxy) phenyl) tert-butyl valerate, 4,4-bis (4 ′-(1 ″ -ethoxypropyloxy) pheny L) tert-butyl valerate, tris (4- (2′-tetrahydropyranyloxy) phenyl) methane, tris (4- (2′-tetrahydrofuranyloxy) phenyl) methane, tris (4-tert-butoxyphenyl) Methane, tris (4-tert-butoxycarbonyloxyphenyl) methane, tris (4-tert-butoxycarbonyloxymethylphenyl) methane, tris (4- (1′-ethoxyethoxy) phenyl) methane, tris (4- (1 '-Ethoxypropyloxy) phenyl) methane, 1,1,2-tris (4'-(2 ''-tetrahydropyranyloxy) phenyl) ethane, 1,1,2-tris (4 '-(2' ' -Tetrahydrofuranyloxy) phenyl) ethane, 1,1,2-tris (4'-tert-butoxy) Phenyl) ethane, 1,1,2-tris (4′-tert-butoxycarbonyloxyphenyl) ethane, 1,1,2-tris (4′-tert-butoxycarbonylmethyloxyphenyl) ethane, 1,1,2 -Tris (4 '-(1'-ethoxyethoxy) phenyl) ethane, 1,1,2-tris (4'-(1'-ethoxypropyloxy) phenyl) ethane, 2-trifluoromethylbenzenecarboxylic acid 1, 1-tert-butyl, tert-butyl 2-trifluoromethylcyclohexanecarboxylate, tert-butyl decahydronaphthalene-2,6-dicarboxylate, tert-butyl cholate, tert-butyl deoxycholate, tert-adamantanecarboxylate Butyl, adamantane acetate tert-butyl, 1,1'-bishi Rohekishiru 3,3 ', 4,4'-tetracarboxylic acid tetramethyl tert- butyl and the like.

  The addition amount of the dissolution inhibitor in the resist material of the present invention is 20 parts or less, preferably 15 parts or less with respect to 100 parts of the base resin in the resist material. If it exceeds 20 parts, the heat resistance of the resist material is lowered.

  In addition to the above components, a surfactant conventionally used for improving the coating property can be added to the resist material of the present invention. In addition, the addition amount of an arbitrary component can be made into a normal amount in the range which does not inhibit the effect of this invention. Here, the surfactant is preferably nonionic, such as perfluoroalkyl polyoxyethylene ethanol, fluorinated alkyl ester, perfluoroalkylamine oxide, perfluoroalkyl EO adduct, fluorine-containing organosiloxane compound, etc. Is mentioned. For example, Florard “FC-430”, “FC-431” (all manufactured by Sumitomo 3M Limited), Surflon “S-141”, “S-145” (all manufactured by Asahi Glass Co., Ltd.), Unidyne “DS-401” , “DS-403”, “DS-451” (manufactured by Daikin Industries, Ltd.), MegaFuck “F-8151” (manufactured by Dainippon Ink Industries, Ltd.), “X-70-092”, “X- 70-093 "(all manufactured by Shin-Etsu Chemical Co., Ltd.). Preferably, Florard “FC-430” (manufactured by Sumitomo 3M Co., Ltd.) and “X-70-093” (manufactured by Shin-Etsu Chemical Co., Ltd.) are used.

In order to form a pattern using the resist material of the present invention, a known lithography technique can be employed. For example, it is applied onto a substrate such as a silicon wafer by spin coating or the like so that the film thickness becomes 0.1 to 1.0 μm, and this is applied on a hot plate at 60 to 200 ° C. for 10 seconds to 10 minutes, preferably Pre-bake at 80 to 150 ° C. for 30 seconds to 5 minutes. Next, a mask for forming a target pattern is placed on the resist film, and high energy rays such as deep ultraviolet rays, excimer laser, and X-rays or electron beams are applied in an exposure amount of about 1 to 200 mJ / cm ² , preferably 10 Irradiating to about 100 mJ / cm ² , followed by heat treatment, that is, post exposure baking on a hot plate at 60 to 150 ° C. for 10 seconds to 5 minutes, preferably 80 to 130 ° C. for 30 seconds to 3 minutes (PEB). Further, using an aqueous developer solution of 0.1 to 5%, preferably 2-3% tetramethylammonium hydroxide (TMAH) or the like, it is immersed for 10 seconds to 3 minutes, preferably 30 seconds to 2 minutes. The target pattern is formed on the substrate by developing by a conventional method such as a dip method, a paddle method, or a spray method. The material of the present invention is an ultraviolet ray or excimer laser of 300 to 120 nm, particularly 248 nm of KrF, 193 nm of ArF, 157 nm of F ₂ , 146 nm of Kr ₂ , 134 nm of KrAr, 126 nm of Ar ₂ , among high energy rays. It is most suitable for fine patterning by laser such as EUV and X-ray.

  Hereinafter, the present invention will be specifically described with reference to examples.

[Comparative example]
Polymerization of the compound represented by the structural formula (6)

  Into a three-necked flask equipped with a reflux condenser and a stirrer, a compound (1.0 g) represented by the structural formula (6) is added, perbutyl PV (4 mol%) is added as a polymerization initiator, and methyl ethyl ketone (50 wt%) is used as a polymerization solvent. ) The flask was heated in an oil bath at 75 ° C. and reacted for 15 hours. After the reaction, the reaction solution was added to n-hexane and stirred. The resulting precipitate was filtered off and dried in vacuo at 50 ° C. for 10 hours. Comparing the glass transition temperature (Tg) of the homopolymer of the compound represented by Structural Formula (6) with that of the homopolymer of the compound represented by Structural Formula (7), the compound represented by Structural Formula (6) It was found that the glass transition temperature (Tg) of this homopolymer was considerably low, and the normal baking temperature was not applicable.

[Example 1]
Synthesis of the compound represented by the structural formula (7)

A compound (230.36 g) represented by the structural formula (5), toluene (1.2 L), methacrylic anhydride (146.77 g), methanesulfonic acid (
20.97 g) was added in order, and the mixture was stirred at an internal temperature of 85 ° C. for 2 hours. The reaction mixture was poured into saturated aqueous sodium hydrogen carbonate, diluted with toluene and separated into two layers. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate and filtered, and the filtrate was concentrated with an evaporator. The residue was distilled under reduced pressure, and the obtained fraction was recrystallized from toluene to obtain a compound (241.79 g, 83%) represented by the structural formula (7).
¹ H-NMR (TMS, CDCl ₃ ): 1.39 (m, 1H), 1.58 (m, 3H), 1.81 (q, 1H), 1.96 (t, 3H), 1.96 (M, 4H), 2.28 (d, 1H), 4.87 (s, 1H), 5.47 (d, 1H), 5.64 (m, 1H), 6.16 (t, 1H)
¹⁹ F-NMR (CClF, CDCl ₃ ): −76.4 (q, 3H), −72.0 (q, 3H) IR (cm ⁻¹ ): 3370, 2995, 2958, 2932, 2854, 1699, 1636 , 1214, 1187, 898 GC-MS (EI method): m / e 334 (M ⁺ ), 316 (—H ₂ O), 265 (—CF ₃ )
[Example 2]

  Polymerization of the compound represented by the structural formula (7)

Into a three-necked flask equipped with a reflux condenser and a stirrer, a compound (1.0 g) represented by the structural formula (7) was added, perbutyl PV (4 mol%) was added as a polymerization initiator, and methyl ethyl ketone (50 wt%) as a polymerization solvent. ) The flask was heated in an oil bath at 75 ° C. and reacted for 15 hours. After the reaction, the reaction solution was added to n-hexane and stirred. The resulting precipitate was filtered off and dried in vacuo at 50 ° C. for 10 hours. The composition of the obtained polymer was determined from ¹ H-NMR and ¹⁹ F-NMR, the molecular weight (Mn, Mw / Mn) was determined from GPC analysis (standard polystyrene), and the glass transition temperature (Tg) was determined from DSC. The results are shown in Table 1.
[Example 3]

  Copolymerization of the compound represented by Structural Formula (7) and the compound represented by Structural Formula (8)

Using a compound represented by structural formula (7) (0.84 g) and a compound represented by structural formula (8) (0.16 g), perbutyl PV (4 mol%) was added as a polymerization initiator, and methyl ethyl ketone ( 100 wt%). The flask was heated in an oil bath at 75 ° C. and reacted for 15 hours. After the reaction, the reaction solution was added to n-hexane and stirred. The resulting precipitate was filtered off and dried in vacuo at 50 ° C. for 10 hours. The results are shown in Table 1.
[Example 4]

  Compound represented by structural formula (7), copolymer of compound represented by structural formula (8) and compound represented by structural formula (9)

A polymerization initiator using a compound represented by Structural Formula (7) (0.46 g), a compound represented by Structural Formula (8) (0.26 g), and a compound represented by Structural Formula (9) (0.17 g) Perbutyl PV (4 mol%) was added as a polymerization solvent, and methyl ethyl ketone (100 wt%) was added as a polymerization solvent. The flask was heated in an oil bath at 75 ° C. and reacted for 15 hours. After the reaction, the reaction solution was added to n-hexane and stirred. The resulting precipitate was filtered off and dried in vacuo at 50 ° C. for 10 hours. The results are shown in Table 1.
[Example 5]

  Compound represented by Structural Formula (7), Copolymer of Compound represented by Structural Formula (8) and Compound represented by Structural Formula (10)

Using a compound represented by Structural Formula (7) (0.54 g), a compound represented by Structural Formula (8) (0.24 g), and a compound represented by Structural Formula (10) (0.22 g), a polymerization initiator Perbutyl PV (4 mol%) was added as a polymerization solvent, and methyl ethyl ketone (100 wt%) was added as a polymerization solvent. The flask was heated in an oil bath at 75 ° C. and reacted for 15 hours. After the reaction, the reaction solution was added to n-hexane and stirred. The resulting precipitate was filtered off and dried in vacuo at 50 ° C. for 10 hours. The results are shown in Table 1.
[Example 6]

  Copolymer of the compound represented by the structural formula (11), the compound represented by the structural formula (8) and the compound represented by the structural formula (9)

Using a compound represented by Structural Formula (11) (0.38 g), a compound represented by Structural Formula (8) (0.41 g), and a compound represented by Structural Formula (9) (0.21 g), a polymerization initiator Perbutyl PV (4 mol%) was added as a polymerization solvent, and methyl ethyl ketone (100 wt%) was added as a polymerization solvent. The flask was heated in a 75 oil bath and allowed to react for 15 hours. After the reaction, the reaction solution was added to n-hexane and stirred. The resulting precipitate was filtered off and dried in vacuo at 50 ° C. for 10 hours. The results are shown in Table 1.
[Example 7]

  Compound represented by Structural Formula (12), Copolymer of Compound represented by Structural Formula (8) and Compound represented by Structural Formula (9)

Using a compound represented by Structural Formula (12) (0.30 g), a compound represented by Structural Formula (8) (0.48 g), and a compound represented by Structural Formula (9) (0.22 g), a polymerization initiator Perbutyl PV (4 mol%) was added as a polymerization solvent, and methyl ethyl ketone (100 wt%) was added as a polymerization solvent. The flask was heated in a 75 oil bath and allowed to react for 15 hours. After the reaction, the reaction solution was added to n-hexane and stirred. The resulting precipitate was filtered off and dried in vacuo at 50 ° C. for 10 hours. The results are shown in Table 1.
[Example 8]

  A compound represented by the structural formula (13), a copolymer of the compound represented by the structural formula (14) and the compound represented by the structural formula (15).

  Using a compound represented by Structural Formula (13) (0.48 g), a compound represented by Structural Formula (14) (0.18 g), and a compound represented by Structural Formula (15) (0.36 g), a polymerization initiator Perbutyl PV (4 mol%) was added as a polymerization solvent, and methyl ethyl ketone (100 wt%) was added as a polymerization solvent. The flask was heated in an oil bath at 75 ° C. and reacted for 15 hours. After the reaction, the reaction solution was added to n-hexane and stirred. The resulting precipitate was filtered off and dried in vacuo at 50 ° C. for 10 hours. The results are shown in Table 1.

In Examples 3 to 7, the elimination of the ethyladamantyl group of the structural formula (8) occurs near 150 ° C. before reaching the glass transition temperature (Tg), and the glass transition temperature (Tg) is higher than 150 ° C. It was in the range and could not be measured.
[Example 9]

  Preparation and evaluation of resist materials and patterns

  The polymer compounds of Examples 3 to 8 were dissolved in propylene glycol methyl acetate and adjusted to a solid content of 14%. Furthermore, Midori Chemical's triphenylsulfonium triflate (TPS105) was dissolved in 2 parts by weight as an acid generator with respect to 100 parts by weight of the polymer compound to prepare two types of resist solutions. When these were spin-coated and the light transmittance at a film thickness of 100 nm was measured at a wavelength of 193 nm, they were 92%, 86%, 90%, 84%, 88%, and 94%, respectively, with respect to Examples 3 to 8. High transparency was developed at wavelengths in the vacuum ultraviolet region.

  Next, the entire resist solution was filtered through a high membrane filter having a pore size of 0.2 and each composition solution was spin-coated on a silicon wafer to obtain a resist film having a thickness of 250 nm. After pre-baking at 110 ° C., exposure with 248 nm ultraviolet light was performed through a photomask, and then post-exposure baking was performed at 120 ° C. Thereafter, development was performed at 23 ° C. for 1 minute using a 2.38 wt% tetramethylammonium hydroxide aqueous solution. As a result, a pattern shape free from resist film peeling and development defects was obtained.

Claims (11)

Fluorine-containing acrylate compound represented by the general formula (1) (wherein R ¹ is any one functional group of a hydrogen atom, a methyl group and a trifluoromethyl group, and R ² is a hydrogen atom having 1 carbon atom) A linear, branched or cyclic alkyl group having a molecular weight of 25 to 25, a part of which may include a fluorine atom, an oxygen atom, a nitrogen atom, a sulfur atom, or a carbonyl bond, and R ^{3 to} R ¹⁴ are each a hydrogen atom. , A linear, branched or cyclic alkyl group having 1 to 25 carbon atoms, which may include a fluorine atom, an oxygen atom, a nitrogen atom, a sulfur atom, or a hydroxyl group as part of R ³ and R ^5. , R ⁷ and R ⁹ , or two groups out of R ^{11 to} R ¹⁴ may be combined to form a ring as an alkylene group having 1 to 25 carbon atoms, part of which is an oxygen atom or a sulfur atom And may contain a nitrogen atom, l is 0 or 1 , M, n represents any integer of 0 to 4.).
Fluorine-containing acrylate compound represented by general formula (2) (wherein R ¹ represents any one functional group of a hydrogen atom, a methyl group, and a trifluoromethyl group. R ² represents a hydrogen atom, a carbon number of 1 to 25 linear, branched or cyclic alkyl groups, part of which may contain a fluorine atom, an oxygen atom, a nitrogen atom, a sulfur atom, or a carbonyl bond, where n is any integer from 0 to 8. Represents.)
Fluorine-containing acrylate compound represented by general formula (3) (wherein R ¹ represents any one functional group of a hydrogen atom, a methyl group, and a trifluoromethyl group. R ² represents a hydrogen atom, a carbon number of 1 to 25, a functional group containing a linear, branched or cyclic hydrocarbon group, part of which may contain a fluorine atom, an oxygen atom, a nitrogen atom, a sulfur atom or a carbonyl bond.
4. The acid labile group in R ² (the acid labile group is an acid leaving group, part of which may contain a fluorine atom, an oxygen atom, or a carbonyl bond). 2. The fluorine-containing acrylate compound according to item 1. A fluorine-containing acrylate compound represented by the general formula (4) (wherein R ¹ represents any one functional group of a hydrogen atom, a methyl group, and a trifluoromethyl group).
A fluorine-containing polymer compound polymerized or copolymerized using the fluorine-containing acrylate compound according to any one of claims 1 to 5. The fluorine-containing high molecular compound which is a copolymer of the compound which has an acid labile group, and the fluorine-containing acrylate compound of any one of Claims 1-5. A fluorine-containing polymer compound which is a copolymer of a compound having a lactone structure and the fluorine-containing acrylate compound according to any one of claims 1 to 5. A resist material containing the polymer compound according to claim 6. A step of applying the resist material according to claim 9 on a substrate, a step of exposing with a high energy beam having a wavelength of 1 to 300 nm through a photomask, and a step of developing with a developer after the heat treatment A pattern forming method comprising: The pattern forming method according to claim 10, wherein the high energy beam is a KrF laser, an ArF laser, an F2 laser, an EUV laser, or an X-ray.