Chemical agent, rinsing liquid, and method for forming resist pattern

Abstract

The present invention provides a chemical solution, a rinse solution, and a method for forming a resist pattern that have excellent residue removal performance. The chemical solution of the present invention is a chemical solution containing a specific compound selected from the group consisting of an alcohol-based solvent having a ClogP value greater than -1.00 and less than or equal to 3.00, a compound represented by Formula (1), and a compound represented by Formula (2), wherein the content of the specific compound is 0.0010 to 10 mass ppb with respect to the total mass of the chemical solution.

Description

Technology Field

[0001] The present invention relates to a chemical solution, a rinse solution, and a method for forming a resist pattern. Background Technology

[0002] When manufacturing a semiconductor device by a wiring formation process including photolithography, a chemical solution containing water and / or an organic solvent is used as a processing solution such as a developer and a rinse solution.

[0003] As a chemical solution used for conventional resist pattern formation, Patent Document 1 discloses "a method for manufacturing an organic treatment solution for patterning a chemically amplified resist film capable of reducing particle generation in a pattern formation technology (paragraph

[0010] )". In Patent Document 1, an embodiment is disclosed in which the organic treatment solution is used as a developer or a rinse solution. Prior art literature

[0004] Patent Document 1: Japanese Published Patent Application No. 2015-84122 The problem to be solved

[0005] Recently, alcohol-based solvents are sometimes used in the manufacture of semiconductor devices.

[0006] The inventors examined the residue removal performance of conventional alcohol-based solvents and found that there is room for further improvement.

[0007] The present invention aims to provide a chemical solution with excellent residue removal performance.

[0008] In addition, the present invention also has the objective of providing a rinse solution and a method for forming a resist pattern. means of solving the problem

[0009] The inventors, as a result of careful consideration to solve the above problem, found that the above problem can be solved by the following configuration.

[0010] (1) an alcohol-based solvent with a ClogP value greater than -1.00 and less than or equal to 3.00, and

[0011] A medicinal solution containing a specific compound selected from the group consisting of a compound represented by Formula (1) described below and a compound represented by Formula (2) described below,

[0012] A drug solution containing 0.0010 to 10 mass ppb with respect to the total mass of the drug solution.

[0013] (2) A drug solution described in (1) in which the content of a specific compound is 0.010 to 5.0 mass ppb relative to the total mass of the drug solution.

[0014] (3) A chemical solution described in (1) or (2) containing 3 to 12 carbon atoms in an alcohol-based solvent.

[0015] (4) A chemical solution described in any one of (1) to (3), wherein the ratio of the number of carbon atoms to the number of oxygen atoms contained in the alcohol-based solvent is 3.0 or higher.

[0016] (5) A chemical solution described in any one of (1) to (4), wherein the vapor pressure of the alcohol-based solvent at 25°C is 0.01 to 10.0 kPa.

[0017] (6) An alcohol-based solvent selected from the group consisting of methyl isobutylcarbinol, 2,6-dimethyl-4-heptanol, 2,4-diethyl-1,5-pentanediol, 2-ethyl-1-hexanol, 3-methyl-1,5-pentanediol, 2-octanol, 3-methyl-1-butanol, 2,4-dimethyl-3-pentanol, 2-methylpentan-2,4-diol, 3,5,5-trimethyl-1-hexanol, 2-methylcyclohexanol, 1,3-butanediol, 2-ethyl-1,3-hexanediol, 2-butyl-2-ethyl-1,3-propanediol, 3-methyl-1,3-butanediol, and trimethylolpropane, as described in any one of (1) to (5). Medicine solution.

[0018] (7) A drug solution described in any one of (1) to (6), wherein the content of the alcohol-based solvent is 85.000 to 99.999 mass% with respect to the total mass of the drug solution.

[0019] (8) A drug solution described in any one of (1) to (7), wherein the alcohol-based solvent is methyl isobutylcarbinol, 3-methyl-1-butanol, or 2,4-dimethyl-3-pentanol.

[0020] (9) Contains more metal components,

[0021] A drug solution described in any one of (1) to (8), wherein the content of the metal component is 0.10 to 100 mass ppt relative to the total mass of the drug solution.

[0022] (10) A rinse solution containing a medicine solution described in any one of (1) to (9).

[0023] (11) A method for forming a resist pattern having a process A of forming a film on a substrate using a light-sensitive or radiation-sensitive resin composition, a process B of exposing the film, a process C of developing the exposed film using an alkaline developer, and a process D of cleaning the developed film using a rinse solution described in (10).

[0024] (12) A method for forming a resist pattern as described in (11), having a process E of cleaning the developed film using water between process C and process D.

[0025] (13) A method for forming a resist pattern as described in (11) or (12), wherein the alkaline developer contains a quaternary ammonium salt.

[0026] (14) A method for forming a resist pattern as described in (13), wherein the content of the quaternary ammonium salt is 0.75 to 7.5 mass% relative to the total mass of the alkaline developer. Effects of the invention

[0027] According to the present invention, a chemical solution with excellent residue removal performance can be provided.

[0028] In addition, according to the present invention, a rinse solution and a method for forming a resist pattern may also be provided. Specific details for implementing the invention

[0029] The present invention will be described in detail below.

[0030] The description of the constituent requirements described below may be based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

[0031] Additionally, in this specification, a numerical range indicated by "~" means a range that includes the values ​​listed before and after "~" as lower and upper limits.

[0032] Also, in the present invention, "ppm" refers to "parts-per-million(10 -6 )" means, and "ppb" means "parts-per-billion(10 -9 It means )", and "ppt" is "parts-per-trillion(10 -12 It means )".

[0033] In addition, regarding the notation of groups (atomic groups) in the present invention, notations that do not indicate substitution or non-substitution include groups containing substituents along with groups without substituents, to the extent that the effects of the present invention are not impaired. For example, the term "hydrocarbon group" includes not only hydrocarbon groups without substituents (non-substituted hydrocarbon groups) but also hydrocarbon groups containing substituents (substituted hydrocarbon groups). This point has the same meaning for each compound.

[0034] Furthermore, in the present invention, "radiation" refers to, for example, far ultraviolet rays, extreme ultraviolet rays (EUV), X-rays, or electron beams. Also, in the present invention, "light" refers to active light or radiation. Unless otherwise specifically stated, in the present invention, "exposure" includes not only exposure by far ultraviolet rays, X-rays, or EUV, but also drawing by particle beams such as electron beams or ion beams.

[0035] The inventors, after examining the characteristics of alcohol-based solvents, discovered that by mixing a predetermined amount of a specific compound with an alcohol-based solvent, a chemical solution with excellent residue removal performance can be obtained.

[0036] The drug solution of the present invention (hereinafter also simply referred to as "drug solution") is a drug solution containing a specific compound selected from the group consisting of an alcohol-based solvent having a ClogP value greater than -1.00 and less than or equal to 3.00, a compound represented by Formula (1) described below, and a compound represented by Formula (2) described below.

[0037] Hereinafter, the components contained in the drug solution of the present invention will be described in detail.

[0038] Alcohol-based solvents

[0039] The drug solution contains an alcohol-based solvent with a ClogP value greater than -1.00 and less than or equal to 3.00.

[0040] The ClogP value of the alcohol-based solvent is greater than -1.00 and less than or equal to 3.00, and in terms of superior residue removal performance (hereinafter simply referred to as "superior effect of the present invention"), -0.50 to 3.00 is more preferable, -0.50 to 2.50 is more preferable, and 0.00 to 2.00 is particularly preferable.

[0041] The ClogP value is a value obtained by calculating the common logarithm logP of the partition coefficient P for 1-octanol and water. While known methods and software may be used for calculating the ClogP value, unless specifically described otherwise, the present invention uses the ClogP program introduced in Cambridge Soft's ChemBioDraw Ultra 12.0.

[0042] Alcohol-based solvents contain hydroxyl groups, but the number of hydroxyl groups included is not particularly limited; however, 1 to 3 is preferred, and 1 is more preferred, in terms of superior effects of the present invention.

[0043] Alcohol-based solvents may be in a straight chain or a branched chain. Additionally, alcohol-based solvents may have a ring structure.

[0044] The number of carbon atoms included in the alcohol-based solvent is not particularly limited, but 3 to 12 is preferred, 4 to 10 is more preferred, and 5 to 9 is more preferred in terms of superior effects of the present invention.

[0045] The ratio of the number of carbon atoms to the number of oxygen atoms contained in the alcohol-based solvent (C / O ratio) is not particularly limited and is often 2.0 or higher; however, for the superior effect of the present invention, it is preferable to have a ratio of 3.0 or higher, more preferable to have a ratio of 4.0 or higher, and more preferable to have a ratio of 5.0 or higher. The upper limit is not particularly limited, but for the superior effect of the present invention, it is preferable to have a ratio of 10.0 or lower, more preferable to have a ratio of 9.0 or lower, and more preferable to have a ratio of 8.0 or lower.

[0046] The vapor pressure of the alcohol-based solvent at 25°C is not particularly limited and is often 0.01 to 15 kPa, but 0.01 to 10.0 kPa is more preferable for superior effects of the present invention, 0.10 to 1.0 kPa is more preferable, and 0.30 to 0.60 kPa is particularly preferable.

[0047] Although the type of alcohol-based solvent is not particularly limited, methyl isobutylcarbinol, 2,6-dimethyl-4-heptanol, 2,4-diethyl-1,5-pentanediol, 2-ethyl-1-hexanol, 3-methyl-1,5-pentanediol, 2-octanol, 3-methyl-1-butanol, 2,4-dimethyl-3-pentanol, 2-methylpentan-2,4-diol, 3,5,5-trimethyl-1-hexanol, 2-methylcyclohexanol, 1,3-butanediol, 2-ethyl-1,3-hexanediol, 2-butyl-2-ethyl-1,3-propanediol, 3-methyl-1,3-butanediol, or trimethylolpropane is preferred in that it provides a more superior effect of the present invention. Methyl isobutylcarbinol, 3-methyl-1-butanol, or 2,4-dimethyl-3-pentanol are more preferred.

[0048] The content of the alcohol-based solvent in the liquid medicine is not particularly limited, but for superior effects of the present invention, 85.000 to 99.999 mass% is preferred with respect to the total mass of the liquid medicine, 95.000 to 99.999 mass% is more preferred, 99.500 to 99.995 mass% is more preferred, 99.700 to 99.990 mass% is particularly preferred, and 99.900 to 99.990 mass% is most preferred.

[0049] Specific Compounds

[0050] The medicine solution contains a specific compound selected from the group consisting of the compound represented by formula (1) and the compound represented by formula (2).

[0051] [Chemical Formula 1]

[0052]

[0053] R 1 and R 2 Each independently represents an alkyl group.

[0054] R 1 and R 2 The alkyl group represented by may be a straight chain or a branched chain.

[0055] R1 and R 2 The number of carbon atoms included in the alkyl group represented by is not particularly limited, but 2 to 10 is preferred and 3 to 8 is more preferred in terms of superior effects of the present invention.

[0056] R 3 and R 5 Each represents, independently, a hydrogen atom or an alkyl group.

[0057] R 3 and R 5 The alkyl group represented by may be a straight chain or a branched chain.

[0058] R 3 and R 5 The number of carbon atoms included in the alkyl group represented by is not particularly limited, but 1 to 10 is preferred and 2 to 5 is more preferred in terms of superior effects of the present invention.

[0059] R 4 represents a hydrogen atom or a hydroxyl group.

[0060] R 6 It represents a silver, hydrogen atom, or alkoxy group.

[0061] R 6 The number of carbon atoms included in the alkoxy group is not particularly limited, but 3 to 10 is preferred and 4 to 8 is more preferred in terms of superior effects of the present invention.

[0062] In Equation (2), R 3 ~R 5 is a hydrogen atom, and also R 6 This alkoxy group, modality 1, or, R 3 and R 5 ga is an alkyl group, and R 4 α is a hydroxyl group, and R 6 This hydrogen atom, Modification 2, is preferred.

[0063] Specific examples of the compound represented by Formula (1) and the compound represented by Formula (2) include specific compounds A to D as follows.

[0064] [Chemical Formula 2]

[0065]

[0066] The content of a specific compound (total content) in the drug solution is 0.0010 to 10 mass ppb with respect to the total mass of the drug solution, and 0.010 to 5.0 mass ppb is preferred and 0.10 to 2.0 mass ppb is more preferred in that the effect of the present invention is superior.

[0067] When multiple compounds are contained in the drug solution as specific compounds, the total amount is within the above range.

[0068] The drug solution may contain components other than alcohol-based solvents and specific compounds.

[0069] The other components are described in detail below.

[0070] Metal Components

[0071] The medicine solution may contain metal components.

[0072] In the present invention, metal components may include metal particles and metal ions, and, for example, when referring to the content of metal components, the total content of metal particles and metal ions is indicated.

[0073] The medicinal solution may contain either metal particles or metal ions, or both.

[0074] Examples of metal elements in the metal component include Na (sodium), K (potassium), Ca (calcium), Fe (iron), Cu (copper), Mg (magnesium), Mn (manganese), Li (lithium), Al (aluminum), Cr (chromium), Ni (nickel), Ti (titanium), and Zr (zirconium). The metal component may contain one type of metal element or two or more types of metal elements.

[0075] The metal particles may be in the form of a single element or an alloy.

[0076] The metal component may be a metal component that is inevitably included in each component (raw material) included in the liquid medicine, a metal component that is inevitably included during the manufacture, storage, and / or transport of the liquid medicine, or may be intentionally added.

[0077] When the chemical solution contains a metal component, the content is not particularly limited, and may be 0.01 to 500 mass ppt with respect to the total mass of the chemical solution. Among these, 0.10 to 100 mass ppt is preferred in that it provides a more superior effect of the present invention.

[0078] In addition, the types and content of metal ions and metal particles in the chemical solution can be measured using the SP-ICP-MS method (Single Nano Particle Inductively Coupled Plasma Mass Spectrometry).

[0079] Here, the SP-ICP-MS method uses the same equipment as the conventional ICP-MS method (Inductively Coupled Plasma Mass Spectrometry), differing only in data analysis. Data analysis for the SP-ICP-MS method can be performed using commercially available software.

[0080] In the ICP-MS method, the content of the metal component being measured is determined regardless of its form of existence. Therefore, the total mass of the metal particles and metal ions being measured is quantified as the content of the metal component.

[0081] Meanwhile, the SP-ICP-MS method can measure the content of metal particles. Therefore, by subtracting the content of metal particles from the content of metal components in the sample, the content of metal ions in the sample can be calculated.

[0082] As an apparatus for the SP-ICP-MS method, for example, the Agilent 8800 triple quadrupole ICP-MS (inductively coupled plasma mass spectrometry, for semiconductor analysis, Option #200) manufactured by Agilent Technologies can be used, and measurements can be taken by the method described in the example. As other apparatus besides the above, in addition to the PerkinElmer NexION350S, the Agilent 8900 manufactured by Agilent Technologies can also be used.

[0083] In addition to the above, the medicine solution may also contain water.

[0084] Method for preparing the medicine solution

[0085] The method of preparing the above-mentioned drug solution is not particularly limited, and known preparation methods may be cited.

[0086] For example, a drug solution may be prepared by adding a specific compound to an alcohol-based solvent, or by purchasing a commercially available product and performing a purification process. Among these, a method for preparing the drug solution may include a process of distilling the product to be purified (distillation process) and a process of filtering the product to be purified (filtration process). In addition, commercially available alcohol-based solvents may be used as the product to be purified. Commercially available products often contain impurities, and for example, there may be cases where a specific compound is contained in excess as an impurity in an alcohol-based solvent (particularly methyl isobutylcarbinol).

[0087] The following describes in detail the sequence of the above distillation and filtration processes.

[0088] (Distillation process)

[0089] The distillation process is a process of distilling a product to be purified (e.g., a solution containing an alcoholic solvent and a specific compound) and obtaining the purified product after distillation is completed.

[0090] The method of distilling the material to be purified is not particularly limited, and known methods may be used. Typically, a distillation column is placed on the primary side of the purification device provided for the filtration process described below, and the distilled material to be purified is introduced into a manufacturing tank.

[0091] At this time, the liquid contact portion of the distillation column is not particularly limited, but it is preferable to form it with the corrosion-resistant material described below.

[0092] In the distillation process, the material to be purified may be passed through the same distillation column multiple times, or it may be passed through different distillation columns. When passing the material to be purified through different distillation columns, for example, a method may be used in which a crude distillation treatment is performed by passing the material to be purified through a distillation column to remove low-boiling point components, and then a rectification treatment is performed by passing it through a distillation column different from the one used for the crude distillation treatment to remove other components.

[0093] Examples of distillation towers include lathe-type distillation towers and vacuum lathe-type distillation towers.

[0094] In addition, vacuum distillation may be performed to achieve both thermal stability during distillation and precision of purification.

[0095] (Filtering process)

[0096] The filtration process is a process of filtering the above-mentioned material to be purified using a filter.

[0097] The method of filtering the substance to be purified using a filter is not particularly limited, but it is preferable to pass the substance to be purified through a filter unit having a housing and a filter cartridge housed in the housing under pressure or without pressure.

[0098] The diameter of the micropores of the filter is not particularly limited, and a filter with a micropore diameter commonly used for filtering the material to be purified may be used. Among these, the micropore diameter of the filter is preferably 200 nm or less, more preferably 20 nm or less, and even more preferably 10 nm or less. The lower limit is not particularly limited, but generally, 1 nm or more is preferred from the perspective of productivity.

[0099] In addition, in this specification, the micropore diameter of the filter refers to the micropore diameter determined by the bubble point of isopropanol.

[0100] There are no particular limitations on the form of sequentially using two or more types of filters with different micropore diameters, but a method may be used in which multiple filter units containing filters are arranged along a conduit through which the material to be purified is transported. In this case, if the flow rate of the material to be purified per unit time is to be kept constant throughout the entire conduit, a greater pressure may be applied to the filter with a smaller micropore diameter compared to the filter with a larger micropore diameter. In this case, it is desirable to increase the filtration area by placing a pressure regulating valve and a damper between the filters to keep the pressure applied to the filter with the smaller micropore diameter constant, or by arranging filter units containing the same filter in parallel along the conduit.

[0101] The material of the filter is not particularly limited, and known materials may be used as the material of the filter. Specifically, in the case of a resin, polyamides such as nylon (e.g., 6-nylon and 6,6-nylon); polyolefins such as polyethylene and polypropylene; polystyrene; polyimide; polyamideimide; poly(meth)acrylate; fluorinated resins such as polytetrafluoroethylene, perfluoroalkoxyalkane, perfluoroethylenepropene copolymer, ethylene-tetrafluoroethylene copolymer, ethylene-chlorotrifluoroethylene copolymer, polychlorotrifluoroethylene, polyvinylidene fluoride, and polyvinyl fluoride; polyvinyl alcohol; polyester; cellulose; cellulose acetate, etc.

[0102] Among these, at least one type selected from the group consisting of nylon (among which 6,6-nylon is preferred), polyolefin (among which polyethylene is preferred), poly(meth)acrylate, and fluorinated resin (among which polytetrafluoroethylene (PTFE) or perfluoroalkoxyalkane (PFA) is preferred) is preferred in that it has superior solvent resistance and the resulting liquid has superior defect suppression performance. These polymers can be used alone or in combination of two or more types.

[0103] In addition to resin, diatomaceous earth and glass may also be used.

[0104] In addition, a polymer obtained by graft copolymerizing a polyamide (e.g., nylon-6 or nylon-6,6, etc.) onto a polyolefin (e.g., UPE (ultra-high molecular weight polyethylene) described later) may be used as a filter material (e.g., nylon graft UPE).

[0105] Additionally, the filter may be a surface-treated filter. The method of surface treatment is not particularly limited, and known methods may be used. Examples of surface treatment methods include chemical modification, plasma treatment, hydrophobic treatment, coating, gas treatment, and sintering.

[0106] As a chemical modification treatment, it is preferable to introduce an ion exchanger into the filter.

[0107] In other words, as a filter, a filter equipped with an ion exchanger may be used.

[0108] Examples of ion exchangers include cation exchangers and anion exchangers. Examples of cation exchangers include sulfonic acid groups, carboxyl groups, and phosphate groups. Examples of anion exchangers include quaternary ammonium groups. The method of introducing the ion exchangers into the filter is not particularly limited, but a method of reacting a compound containing the ion exchangers and polymerizable groups with the filter (typically a grafting method) may be used.

[0109] The method of introducing ion exchangers is not particularly limited, but ionizing radiation (α-rays, β-rays, γ-rays, X-rays, and electron beams, etc.) is irradiated onto a filter to generate active parts (radicals). After this irradiation, the filter is immersed in a monomer-containing solution to graft polymerize the monomer onto the filter. As a result, the polymer obtained by polymerizing the monomer is grafted onto the filter. The ion exchangers can be introduced into the polymer by reacting the generated polymer with a compound containing an anion exchanger or a cation exchanger.

[0110] By using a filter equipped with an ion exchanger, it is easier to control the content of metal particles and metal ions in the chemical solution to a desired range. The material constituting the filter equipped with an ion exchanger is not particularly limited, but examples include fluorinated resins and materials in which ion exchangers are introduced into polyolefins, and materials in which ion exchangers are introduced into fluorinated resins are more preferred.

[0111] The diameter of the micropores of the filter having an ion exchanger is not particularly limited, but 1 to 30 nm is preferred, and 5 to 20 nm is more preferred.

[0112] As for the filter used in the filtration process, two or more types of filters made of different materials may be used, for example, two or more types selected from the group consisting of polyolefins, fluoropolymers, polyamides, and filters made of materials to which ion exchangers have been introduced.

[0113] The micropore structure of the filter is not particularly limited and can be appropriately selected depending on the components of the material to be purified. In this specification, the micropore structure of the filter refers to the micropore diameter distribution, the positional distribution of micropores within the filter, and the shape of the micropores, and is typically controllable by the manufacturing method of the filter.

[0114] For example, a porous membrane is obtained by sintering a powder such as resin, and a fibrous membrane is obtained by methods such as electro-spinning, electro-blowing, and melt-blowing. Each of these has a different micropore structure.

[0115] "Porous membrane" refers to a membrane that retains components of the material to be purified, such as gels, particles, colloids, cells, and oligomers, but allows components substantially smaller than the micropores to pass through the micropores. The retention of components of the material to be purified by the porous membrane may depend on operating conditions, such as face velocity, the use of surfactants, pH, and combinations thereof, and may also depend on the pore diameter and structure of the porous membrane, as well as the size and structure of the particles to be removed (whether they are hard particles, gels, etc.).

[0116] The micropore structure of the porous membrane (e.g., a porous membrane containing UPE and PTFE, etc.) is not particularly limited, but the shapes of the micropores may include, for example, lace-like, string-like, and node-like shapes.

[0117] The distribution of pore sizes and locations within a porous membrane is not particularly limited. The size distribution may be smaller and the distribution locations within the membrane may be symmetric. Alternatively, the size distribution may be larger and the distribution locations within the membrane may be asymmetric (such a membrane is also referred to as an "asymmetric porous membrane"). In an asymmetric porous membrane, the pore size varies within the membrane, and typically, the pore diameter increases from one surface of the membrane toward the other. In this case, the surface with many pores of large diameters is referred to as the "open side," and the surface with many pores of small diameters is referred to as the "tight side."

[0118] In addition, as an asymmetric porous membrane, for example, a membrane in which the size of the micropores is minimized at a predetermined position within the thickness of the membrane (this is also called an "hourglass shape") can be cited.

[0119] In addition, it is advisable to thoroughly clean the filter before use.

[0120] If a fine filter (or a filter that has not been sufficiently cleaned) is used, impurities contained in the filter are likely to be introduced into the chemical solution.

[0121] As described above, the filtration process may be a multi-stage filtration process in which the material to be purified is passed through two or more different types of filters. In addition, the other filters refer to those in which at least one of the micropore diameter, micropore structure, and material is different.

[0122] In addition, the material to be purified may be passed through the same filter multiple times, or the material to be purified may be passed through multiple filters of the same type.

[0123] In addition, it is preferable to use a filter containing a fluorine resin to facilitate the preparation of the chemical solution of the present invention. Among these, multi-stage filtration using multiple filters containing the fluorine resin is preferred. As for the filter containing the fluorine resin, a filter having a fine pore diameter of 20 nm or less is preferred.

[0124] In particular, for ease of preparing the liquid of the present invention, it is preferable to carry out a first filtration process in which a substance to be purified is filtered using a filter with a hole diameter of 100 nm or more, and a second filtration process in which a substance to be purified is filtered using a filter containing a fluorine-based resin with a hole diameter of 10 nm or less (preferably, a filter made of PTFE) in this order. In the first filtration process, coarse particles are removed.

[0125] The material of the liquid contact part of the purification device used in the filtration process (meaning the inner wall surface, etc., where the substance to be purified and the liquid may come into contact) is not particularly limited, but it is preferred to be formed of at least one type selected from the group consisting of non-metallic materials (fluoropolymer resin, etc.) and electrolytically polished metal materials (stainless steel, etc.) (hereinafter, these are collectively referred to as "corrosion-resistant materials").

[0126] The above non-metallic materials are not particularly limited and include known materials.

[0127] As non-metallic materials, at least one type selected from the group consisting of, for example, polyethylene resin, polypropylene resin, polyethylene-polypropylene resin, and fluorinated resin (for example, tetrafluorinated ethylene resin, tetrafluorinated ethylene-perfluoroalkyl vinyl ether copolymer resin, tetrafluorinated ethylene-hexafluorinated propylene copolymer resin, tetrafluorinated ethylene-ethylene copolymer resin, trifluorinated ethylene chloride-ethylene copolymer resin, fluorinated vinylidene resin, trifluorinated ethylene chloride copolymer resin, and fluorinated vinyl resin, etc.) may be cited.

[0128] The above metal material is not particularly limited and may include known materials.

[0129] As for the metal material, for example, a metal material in which the sum of the chromium and nickel contents exceeds 25 mass% with respect to the total mass of the metal material may be cited, and among these, 30 mass% or more is more preferable. The upper limit of the sum of the chromium and nickel contents in the metal material is not particularly limited, but generally 90 mass% or less is preferred.

[0130] Examples of metallic materials include stainless steel and nickel-chromium alloys.

[0131] The stainless steel is not particularly limited and known stainless steels may be used. Among these, an alloy containing 8 mass% or more of nickel is preferred, and an austenitic stainless steel containing 8 mass% or more of nickel is more preferred. Examples of austenitic stainless steels include SUS (Steel Use Stainless) 304 (Ni content 8 mass%, Cr content 18 mass%), SUS 304L (Ni content 9 mass%, Cr content 18 mass%), SUS 316 (Ni content 10 mass%, Cr content 16 mass%), and SUS 316L (Ni content 12 mass%, Cr content 16 mass%).

[0132] The nickel-chromium alloy is not particularly limited, and known nickel-chromium alloys may be used. Among these, a nickel-chromium alloy having a nickel content of 40 to 75 mass% and a chromium content of 1 to 30 mass% is preferred.

[0133] Examples of nickel-chromium alloys include Hastelloy (trade name, hereinafter the same), Monel (trade name, hereinafter the same), and Inconel (trade name, hereinafter the same). More specifically, Hastelloy C-276 (Ni content 63 mass%, Cr content 16 mass%), Hastelloy-C (Ni content 60 mass%, Cr content 17 mass%), and Hastelloy C-22 (Ni content 61 mass%, Cr content 22 mass%) may be cited.

[0134] In addition, the nickel-chromium alloy may, if necessary, further contain boron, silicon, tungsten, molybdenum, copper, and cobalt, etc., in addition to the alloy mentioned above.

[0135] The method of electrolytically polishing metal materials is not particularly limited, and known methods may be used. For example, methods described in paragraphs

[0011] to

[0014] of Japanese Patent Publication No. 2015-227501 and paragraphs

[0036] to

[0042] of Japanese Patent Publication No. 2008-264929 may be used.

[0136] It is presumed that in metal materials, the chromium content in the surface passivation layer becomes higher than the chromium content in the matrix phase due to electrolytic polishing. Therefore, it is presumed that if a purification device is used in which the liquid contact part is formed from an electrolytically polished metal material, it is difficult for metal particles to leak out into the material to be purified.

[0137] Additionally, the metal material may be buff-polished. The method of buff-polishing is not particularly limited, and known methods may be used. The size of the abrasive particles used to complete the buff-polishing is not particularly limited, but #400 or smaller is preferred as it tends to result in smaller surface irregularities on the metal material. Furthermore, it is preferable that buff-polishing be performed before electrolytic polishing.

[0138] It is preferable that the purification of the material to be purified, along with the accompanying opening of the container, cleaning of the container and equipment, reception of the solution, and analysis, be carried out in a clean room. The clean room is preferably a clean room with a cleanliness level of Class 4 or higher as defined in the international standard ISO 14644-1:2015 established by the International Organization for Standardization. Specifically, it is preferable to satisfy any one of ISO Class 1, ISO Class 2, ISO Class 3, and ISO Class 4, it is more preferable to satisfy ISO Class 1 or ISO Class 2, and it is even more preferable to satisfy ISO Class 1.

[0139] Drug Receptor

[0140] The above-mentioned liquid medicine may be stored in a container until use. Such a container and the liquid medicine contained in the container are collectively referred to as a liquid medicine reservoir. The liquid medicine is dispensed from the stored liquid medicine reservoir and used.

[0141] As a container for storing the above-mentioned liquid, for use in manufacturing semiconductor devices, a container with a high degree of cleanliness inside the container and low leaching of impurities is preferred.

[0142] The containers that can be used are not particularly limited, but examples include the "Clean Bottle" series from Icelor Kagaku Co., Ltd. and the "Pure Bottle" from Kodama Jushi High School.

[0143] As for the container, it is also desirable to use a multilayer bottle in which the inner wall of the container has a 6-layer structure made of 6 types of resin, or a multilayer bottle in which the inner wall has a 7-layer structure made of 6 types of resin, for the purpose of preventing contamination of impurities into the liquid medicine. Examples of such containers include the container described in Japanese Patent Publication No. 2015-123351.

[0144] The liquid contact portion of the container may be made of the corrosion-resistant material described above (preferably electrolytically polished stainless steel or fluoropolymer resin) or glass. For superior effects of the present invention, it is preferable that 90% or more of the surface area of ​​the liquid contact portion be made of the above material, and it is even more preferable that the entire liquid contact portion be made of the above material.

[0145] The porosity within the container of the drug solution receiver is preferably 2 to 35 volume%, and more preferably 5 to 30 volume%. That is, in the method for manufacturing the drug solution receiver, it is preferable to carry out a receiving process to receive the obtained drug solution into the container so that the porosity within the container becomes 2 to 35 volume%.

[0146] In addition, the above porosity is calculated according to Equation (1).

[0147] Equation (1): Porosity = {1 - (Volume of liquid in container / Volume of container)} × 100

[0148] The above container volume has the same meaning as the internal volume (capacity) of the container.

[0149] By setting the porosity within this range, storage stability can be ensured by limiting contamination such as impurities.

[0150] Uses of the medicine solution

[0151] The chemical solution of the present invention is preferably used in the manufacture of a semiconductor device (preferably, a semiconductor chip).

[0152] In addition, the above chemical solution can be used for other purposes other than manufacturing semiconductor devices, and can also be used as a developer solution for polyimide, sensor resist, and lens resist, and as a rinsing solution.

[0153] In addition, the above-mentioned chemical solution can also be used as a solvent for medical or cleaning purposes. For example, it can be suitably used for cleaning pipes, containers, and substrates (e.g., wafers, glass, etc.).

[0154] For the above cleaning purposes, it is also desirable to use it as a cleaning solution (pipe cleaning solution and container cleaning solution, etc.) for cleaning pipes and containers that come into contact with the liquid, such as the pre-wet liquid described above.

[0155] <Resist Pattern Formation Method>

[0156] The chemical solution of the present invention is preferably used as a rinse solution, and more preferably as a rinse solution when forming a resist pattern.

[0157] Specifically, in the resist pattern forming method having the following processes A to E, it is preferable to use the above chemical solution as the rinsing solution. Additionally, process E is an optional process and may not be performed. Furthermore, if process E is not performed, process D corresponds to a process of cleaning the developed film (film obtained in process C) using the chemical solution of the present invention described above.

[0158] Process A: A process of forming a film on a substrate using a photosensitive or radiation-sensitive resin composition.

[0159] Process B: Process of exposing the film

[0160] Process C: A process of developing the exposed film using an alkaline developer.

[0161] Process E: Process of cleaning the developed film using water

[0162] Process D: A process for cleaning the film cleaned in Process D using the chemical solution of the present invention described above.

[0163] In addition, as described below, a heating process (PB; Prebake) may be performed between process A and process B, and a heating process (PEB; Post Exposure Bake) may be performed between process (B) and process (C), respectively.

[0164] The following describes these processes.

[0165] (Process A)

[0166] Process A is a process of forming a film on a substrate using a photosensitive or radiation-sensitive resin composition.

[0167] The photosensitive or radiation-sensitive resin composition will be described in detail in the following paragraph.

[0168] The method of forming a film on a substrate using a photosensitive or radiation-sensitive resin composition is not particularly limited, and known methods may be employed. Among these, from the perspective of making it easier to adjust the thickness of the film, a method of forming a film by applying a photosensitive or radiation-sensitive resin composition onto a substrate may be cited.

[0169] In addition, the coating method is not particularly limited, and known methods may be adopted. Among these, spin coating is preferably used in the semiconductor manufacturing field.

[0170] In addition, after applying the photosensitive or radiation-sensitive resin composition, a drying treatment to remove the solvent may be performed as needed. The method of the drying treatment is not particularly limited and may include heat treatment or air drying.

[0171] The substrate forming the film is not particularly limited, and may use inorganic substrates such as silicon, SiN, SiO2, and SiN, coating-type inorganic substrates such as SOG (Spin On Glass), and substrates generally used in semiconductor manufacturing processes such as IC (Integrated Circuit), manufacturing processes for circuit boards such as liquid crystals and thermal heads, and furthermore, substrates generally used in other photofabrication lithography processes.

[0172] In addition, an organic anti-reflective film may be placed between the film and the substrate if necessary.

[0173] The receding contact angle of a film (resist film) formed using a photosensitive or radiation-sensitive resin composition is preferably 70° or greater at a temperature of 23±3℃ and a humidity of 45±5%, more preferably 75° or greater, and even more preferably 75 to 85°. When the receding contact angle of the resist film is within the above range, it is suitable for exposure through an immersion medium.

[0174] To achieve a desirable receding contact angle, it is preferable to include a hydrophobic resin in the above-mentioned photosensitive or radioactive composition. Alternatively, the receding contact angle may be improved by forming a coating layer (so-called "top coat") made of a hydrophobic resin composition on the resist film. As the top coat, a material known in the art may be appropriately used.

[0175] In addition, as a top coat, it is also desirable to apply a top coat containing not only a resin but also a basic compound (quencher), such as that described in Japanese Patent Publication No. 2013-061647, particularly in OC-5 to OC-11 of Example Table 3 thereof.

[0176] The thickness of the resist film is not particularly limited, but it is preferable to be 1 to 500 nm, and more preferable to be 1 to 100 nm, for the reason that it can form a fine pattern of higher precision.

[0177] (Prebake process (PB))

[0178] In the resist pattern formation method, it is also preferable to have a pre-heating process (PB; Prebake) after film formation and before process B described later.

[0179] The heating temperature is preferably 70 to 130°C, and more preferably 80 to 120°C. The heating time is preferably 30 to 300 seconds, and more preferably 30 to 180 seconds.

[0180] Heating can be performed using means provided in a conventional exposure machine and / or developer, or by using a hot plate, etc. By baking, the reaction of the exposure area is promoted, and the sensitivity and / or pattern profile is improved.

[0181] (Process B)

[0182] Process B is a process of exposing the film formed in Process A. More specifically, it is a process of selectively exposing the film to form a desired pattern. As a result, the film is exposed in a patterned manner, and the solubility of the resist film changes only in the exposed areas.

[0183] In addition, "exposure" means intending to irradiate with active light or radiation.

[0184] The wavelength of the light source used for exposure is not particularly limited and may include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, and electron beams, preferably 250 nm or less, more preferably 220 nm or less, and even more preferably 1 to 200 nm of wavelength. Specifically, may include a KrF excimer laser (248 nm), an ArF excimer laser (193 nm), an F2 excimer laser (157 nm), X-rays, EUV (13 nm), and electron beams, and KrF excimer laser, ArF excimer laser, EUV, or electron beams are preferred, and an ArF excimer laser is more preferred.

[0185] The method for selectively exposing the film is not particularly limited, and known methods may be used. For example, a binary mask with a light-blocking portion with a transmittance of 0% or a halftone phase-shift mask with a light-blocking portion with a transmittance of 6% may be used.

[0186] A binary mask is generally used in which a chromium film and / or a chromium oxide film, etc., are formed as a light-blocking layer on a quartz glass substrate.

[0187] A halftone phase shift mask is generally used in which a MoSi (molybdenum silicide) film, a chromium film, a chromium oxide film, and / or a silicon oxynitride film are formed as a light-blocking layer on a quartz glass substrate.

[0188] In addition, the present invention is not limited to exposure performed through a photomask, and selective exposure (pattern exposure) may be performed by exposure without a photomask, for example, by drawing with an electron beam.

[0189] This process may include multiple exposures.

[0190] (Suitable mode: immersion exposure)

[0191] As a suitable mode of exposure, for example, immersion exposure can be cited. By using immersion exposure, finer patterns can be formed. In addition, immersion exposure can be combined with super-resolution techniques such as phase shifting and modified illumination methods.

[0192] As for the immersion liquid used for immersion exposure, it is preferable to use a liquid that is transparent to the exposure wavelength and has a temperature coefficient of refractive index as small as possible to minimize optical distortion projected onto the resist film. In particular, when the exposure light source is an ArF excimer laser (wavelength: 193 nm), in addition to the above considerations, it is preferable to use water from the perspectives of ease of availability and ease of handling.

[0193] When water is used as the immersion solution, an additive (liquid) that reduces the surface tension of water and increases surfactant may be added in a small proportion. It is desirable that this additive does not dissolve the resist film and that its effect on the optical coating on the underside of the lens element can be ignored.

[0194] As such an additive, for example, an aliphatic alcohol having a refractive index approximately equal to that of water is preferred, specifically, methyl alcohol, ethyl alcohol, and isopropyl alcohol. By adding an alcohol having a refractive index approximately equal to that of water to the liquid immersion solution, the advantage is obtained that the change in the refractive index of the entire liquid can be kept very small even if the alcohol component in the water evaporates and the concentration changes.

[0195] Distilled water is preferred as the water to be used. Alternatively, pure water filtered through an ion exchange filter or the like may be used.

[0196] It is preferable that the water used as the immersion solution has an electrical resistance of 18.3 MΩcm or higher. Alternatively, it is preferable that the TOC (organic matter concentration) in the water is 20 mass ppb or lower. In addition, it is preferable that the water be degassed.

[0197] In addition, it is possible to improve lithography performance by increasing the refractive index of the immersion solution. In this regard, additives that increase the refractive index may be added to the water, or heavy water (D2O) may be used instead of water.

[0198] In immersion exposure, the surface of the resist film may be cleaned with an aqueous chemical solution before and / or after exposure (before heat treatment).

[0199] (Heating Process (PEB; Post Exposure Bake))

[0200] The resist pattern formation method preferably includes a post-exposure bake (PEB) process after process B and before process C.

[0201] It is preferable to perform heating at a temperature of 70 to 130°C, and more preferable to perform heating at 80 to 120°C. It is preferable to heat for 30 to 300 seconds, more preferable to heat for 30 to 180 seconds, and more preferable to heat for 30 to 90 seconds.

[0202] Heating can be performed using means provided in a conventional exposure and developing machine, or by using a hot plate, etc. By baking, the reaction of the exposure area is promoted, and sensitivity or pattern profile is improved.

[0203] (Process C)

[0204] Process C is a process of developing the exposed film using an alkaline developer. By performing this process, a desired pattern is formed. By this method, parts with high exposure intensity are removed.

[0205] As alkalis contained in the alkaline developer, for example, inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia water; primary amines such as ethylamine and n-propylamine; secondary amines such as diethylamine and di-n-butylamine; tertiary amines such as triethylamine and methyldiethylamine; alcoholamines such as dimethylethanolamine and triethanolamine; Examples include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltriamylammonium hydroxide, and dibutyldipentylammonium hydroxide, as well as tetraalkylammonium hydroxides, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, and triethylbenzylammonium hydroxide; cyclic amines such as pyrrole and piperidine, and quaternary ammonium salts are preferred.

[0206] The alkali concentration of the alkali developer is preferably 0.1 to 20 mass%, and is more preferably 0.75 to 15 mass%, and more preferably 0.75 to 7.5 mass%, in order to provide a more superior effect of the present invention.

[0207] The pH of the alkaline developer is preferably 10.0 to 15.0.

[0208] The alkaline developer may contain a chelating agent.

[0209] A chelating agent is a compound that has the function of chelating with metal ions. Among them, a compound having two or more functional groups (coordination groups) that form coordinate bonds with metal ions in one molecule is preferred.

[0210] Examples of coordination groups include carboxyl groups.

[0211] Examples of coordination groups possessed by the chelating agent include acid groups and cationic groups. Examples of acid groups include carboxyl groups, phosphonic acid groups, sulfo groups, and phenolic hydroxyl groups.

[0212] Examples of chelating agents include organic chelating agents and inorganic chelating agents.

[0213] Organic chelating agents are chelating agents composed of organic compounds, and examples include carboxylic acid chelating agents having a carboxyl group as a coordinating group and phosphonic acid chelating agents having a phosphonic acid group as a coordinating group, and carboxylic acid chelating agents are preferred.

[0214] Examples of inorganic chelating agents include condensed phosphates.

[0215] Carboxylic acid-based chelating agents are chelating agents having a carboxyl group as a coordination group within the molecule, and examples include aminopolycarboxylic acid-based chelating agents (e.g., butylenediamine tetraacetic acid and diethylenetriamine oxacetic acid, etc.), amino acid-based chelating agents (e.g., glycine, etc.), hydroxycarboxylic acid-based chelating agents (e.g., malic acid and citric acid, etc.), and aliphatic carboxylic acid-based chelating agents (e.g., oxalic acid and malonic acid, etc.).

[0216] The content of the chelating agent is preferably 10 to 10,000 mass ppm with respect to the total mass of the alkaline developer, and more preferably 100 to 1,000 mass ppm.

[0217] The alkaline developer may contain a surfactant.

[0218] The surfactant contained in the alkaline developer is not particularly limited, but cationic surfactants, anionic surfactants, and nonionic surfactants may be used, and anionic surfactants or nonionic surfactants are preferred.

[0219] The content of the surfactant is preferably 0.001 to 5 mass% with respect to the total mass of the alkaline developer, more preferably 0.005 to 2 mass%, and even more preferably 0.01 to 0.5 mass%.

[0220] Examples of development methods include a method of immersing a substrate in a tank filled with a developer solution for a certain period of time (dip method), a method of developing by raising the developer solution on the surface of the substrate by surface tension and stopping it for a certain period of time (puddle method), a method of spraying the developer solution onto the surface of the substrate (spray method), and a method of continuously dispensing the developer solution while scanning a developer solution dispensing nozzle at a certain speed onto a substrate rotating at a certain speed (dynamic dispensing method).

[0221] When the above-mentioned various developing methods include a process of discharging a developer solution from a developing nozzle of a developing device toward a resist film, the discharge pressure of the discharged developer solution (flow rate per unit area of ​​the discharged developer solution) is 2 mL / sec / mm 2 The following is preferable, and 1.5 mL / sec / mm 2 The following is more preferable, 1 mL / sec / mm 2 The following is more preferable. The lower limit of the flow rate is not specifically restricted, but in terms of throughput, 0.2 mL / sec / mm 2 Ideally, this is desirable.

[0222] By setting the discharge pressure of the discharged developer to the above range, pattern defects originating from resist residue after development can be significantly reduced.

[0223] Although the details of this mechanism are not certain, it is likely because by setting the discharge pressure to the above range, the pressure exerted by the developer on the resist film is reduced, thereby suppressing the inadvertent erosion or collapse of the resist film and resist pattern.

[0224] In addition, the discharge pressure of the developer (mL / sec / mm²) 2 ) is the value at the development nozzle outlet in the development device.

[0225] Methods for adjusting the discharge pressure of the developer include, for example, adjusting the discharge pressure with a pump, and changing the pressure by adjusting it through supply from a pressurized tank.

[0226] (Process E)

[0227] Process E is a process of cleaning the developed film using water. As described above, Process E is an optional process, and by performing Process E, the effects of the present invention are superior.

[0228] The type of water used is not particularly limited, but ultrapure water commonly used in semiconductor processes is preferred.

[0229] The cleaning method is not particularly limited and may include, for example, a method of continuously discharging water onto a substrate rotating at a constant speed (rotary coating method), a method of immersing the substrate in a tank filled with water for a certain period of time (dip method), and a method of spraying water onto the surface of the substrate (spray method).

[0230] Among these, a cleaning treatment is performed using a rotary coating method, and after cleaning, the substrate is rotated at a rotational speed of 2000 to 4000 rpm to remove water from the substrate.

[0231] (Process D)

[0232] Process D is a process of cleaning the film cleaned in Process E using the chemical solution of the present invention.

[0233] The medicine used is as described above.

[0234] The method of cleaning treatment is not particularly limited and may include, for example, a method of continuously discharging the chemical solution of the present invention onto a substrate rotating at a constant speed (rotary coating method), a method of immersing the substrate in a tank filled with the chemical solution of the present invention for a certain period of time (dip method), and a method of spraying the chemical solution of the present invention onto the surface of the substrate (spray method).

[0235] In addition, after the above process D, a process for drying the resist pattern may be performed.

[0236] As a method of drying treatment, heat treatment (Post Bake) can be cited.

[0237] By carrying out this process, the developer and rinse solution remaining between and inside the patterns are removed.

[0238] When heat treatment is performed as a drying treatment, the heating temperature during heat treatment is preferably 40 to 250°C, and more preferably 150 to 220°C. The heating time is preferably 10 seconds to 10 minutes, and more preferably 100 to 360 seconds.

[0239] <Resin composition that is sensitive to light or radiation>

[0240] The photosensitive or radiation-sensitive resin composition (hereinafter simply referred to as "composition") used in the above pattern forming method contains at least a resin (A) whose polarity increases by the action of an acid and a photogenerator (P).

[0241] The following describes in detail the components that may be contained in the light-sensitive or radiation-sensitive resin composition.

[0242] (Suzy (A))

[0243] A desensitizing photoreactive or radiation-reducing resin composition contains a resin (A) whose polarity increases by the action of an acid.

[0244] (Repeating unit having an acid-degrading group (Aa))

[0245] The resin (A) has a repeating unit (Aa) having an acid-degradable group (hereinafter also simply referred to as "repeating unit (Aa)").

[0246] An acid-degradable group refers to a group that decomposes by the action of an acid and generates a polar group. It is desirable for the acid-degradable group to have a structure in which the polar group is protected by a detaching group that is detached by the action of an acid. That is, the resin (A) has a repeating unit (Aa) having a group that decomposes by the action of an acid and generates a polar group. The resin having this repeating unit (Aa) has increased polarity by the action of an acid and increased solubility in an alkaline developer, and decreased solubility in an organic solvent.

[0247] As for the polar group, an alkali-soluble group is preferred, and examples include an acidic group such as a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonylimide group, a (alkylsulfonyl)(alkylcarbonyl)methylene group, a (alkylsulfonyl)(alkylcarbonyl)imide group, a bis(alkylcarbonyl)methylene group, a bis(alkylsulfonyl)imide group, a bis(alkylsulfonyl)methylene group, a bis(alkylsulfonyl)imide group, a tris(alkylcarbonyl)methylene group, and a tris(alkylsulfonyl)methylene group, and an alcoholic hydroxyl group.

[0248] Among these, as polar groups, a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), or a sulfonic acid group is preferred.

[0249] Examples of groups that are removed by the action of acid include the groups represented by equations (Y1) to (Y4).

[0250] Equation (Y1): -C(Rx1)(Rx2)(Rx3)

[0251] Equation (Y2): -C(=O)OC(Rx1)(Rx2)(Rx3)

[0252] Equation (Y3): -C(R 36 )(R 37 )(OR 38 )

[0253] Equation (Y4): -C(Rn)(H)(Ar)

[0254] In formulas (Y1) and (Y2), Rx1 to Rx3 each independently represent an alkyl group (straight or branched) or a cycloalkyl group (single or polycyclic). Additionally, when all of Rx1 to Rx3 are alkyl groups (straight or branched), it is preferable that at least two of Rx1 to Rx3 are methyl groups.

[0255] Among these, it is preferable that Rx1 to Rx3 each independently represent a straight-chain or branched-chain alkyl group, and it is more preferable that Rx1 to Rx3 each independently represent a straight-chain alkyl group.

[0256] Two of Rx1 to Rx3 may combine to form a monocyclic or polycyclic ring.

[0257] As for the alkyl groups of Rx1 to Rx3, alkyl groups having 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and t-butyl groups, are preferred.

[0258] As for the cycloalkyl groups of Rx1 to Rx3, monocyclic cycloalkyl groups such as cyclopentyl groups and cyclohexyl groups, and polycyclic cycloalkyl groups such as norbornyl groups, tetracyclodecaneyl groups, tetracyclododecaneyl groups, and adamantyl groups are preferred.

[0259] As for the cycloalkyl group formed by combining two of Rx1 to Rx3, a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, and a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecaneyl group, a tetracyclododecaneyl group, and an adamantyl group are preferred, and a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferred.

[0260] The cycloalkyl group formed by the combination of two of Rx1 to Rx3 may, for example, have one of the methylene groups constituting the ring substituted with a heteroatom such as an oxygen atom or a group having a heteroatom such as a carbonyl group.

[0261] The group represented by equation (Y1) or equation (Y2), for example, Rx1 It is a methyl group or an ethyl group, and an embodiment in which Rx2 and Rx3 are combined to form the aforementioned cycloalkyl group is preferred.

[0262] In equation (Y3), R 36 ~R 38 Each independently represents a hydrogen atom or a monovalent organic group. R 37 and R 38 Silver may combine with one another to form a ring. Examples of monovalent organic groups include alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, and alkenyl groups. R 36 It is also desirable that it be a hydrogen atom.

[0263] As for Equation (Y3), it is preferable to have a group represented by the following Equation (Y3-1).

[0264] [Chemical Formula 3]

[0265]

[0266] Here, L1 and L2 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a combination thereof (e.g., a combination of an alkyl group and an aryl group).

[0267] M represents a single bond or a divalent linker.

[0268] Q represents an alkyl group that may have heteroatoms, a cycloalkyl group that may have heteroatoms, an aryl group that may have heteroatoms, an amino group, an ammonium group, a mercapto group, a cyano group, an aldehyde group, or a combination thereof (e.g., a combination of an alkyl group and a cycloalkyl group).

[0269] The alkyl group and the cycloalkyl group may be substituted, for example, with one of the methylene group having a heteroatom such as an oxygen atom or a heteroatom such as a carbonyl group.

[0270] In addition, it is preferable that one of L1 and L2 is a hydrogen atom, and the other is an alkyl group, a cycloalkyl group, an aryl group, or a group combining an alkylene group and an aryl group.

[0271] At least two of Q, M, and L1 may be combined to form a ring (preferably, a 5-membered or 6-membered ring).

[0272] In terms of pattern miniaturization, it is preferable that L2 be a secondary or tertiary alkyl group, and more preferable that it be a tertiary alkyl group. Examples of secondary alkyl groups include isopropyl groups, cyclohexyl groups, or norbornyl groups, and examples of tertiary alkyl groups include tert-butyl groups or adamantane groups. In these embodiments, since the Tg (glass transition temperature) and activation energy are increased, in addition to ensuring film strength, fogging can be suppressed.

[0273] In formula (Y4), Ar represents an aromatic group. Rn represents an alkyl group, a cycloalkyl group, or an aryl group. Rn and Ar may bond to each other to form a non-aromatic ring. More preferably, Ar is an aryl group.

[0274] As for the repeating unit (Aa), the repeating unit represented by Equation (A) is also desirable.

[0275] [Chemical Formula 4]

[0276]

[0277] L1 represents a divalent linker that may have a fluorine atom or an iodine atom, R1 represents a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group that may have a fluorine atom or an iodine atom, or an aryl group that may have a fluorine atom or an iodine atom, and R2 represents a detaching group that is detached by the action of an acid and may have a fluorine atom or an iodine atom. Provided, at least one of L1, R1, and R2 has a fluorine atom or an iodine atom.

[0278] L1 represents a divalent linker that may have a fluorine atom or an iodine atom. Examples of divalent linkers that may have a fluorine atom or an iodine atom include -CO-, -O-, -S-, -SO-, -SO2-, hydrocarbon groups that may have a fluorine atom or an iodine atom (e.g., alkylene groups, cycloalkylene groups, alkenylene groups, arylene groups, etc.), and linkers formed by connecting multiple of these. Among these, as L1, -CO-, -arylene group-alkylene group having a fluorine atom or an iodine atom- are preferred.

[0279] As for the arylene group, a phenylene group is preferred.

[0280] The alkylene group may be in a straight chain or a branched chain. The number of carbon atoms in the alkylene group is not particularly limited, but 1 to 10 is preferred, and 1 to 3 is more preferred.

[0281] The total number of fluorine atoms and iodine atoms included in the alkylene group having fluorine atoms or iodine atoms is not particularly limited, but 2 or more is preferred, 2 to 10 is more preferred, and 3 to 6 is more preferred.

[0282] R1 represents a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group that may have a fluorine atom or an iodine atom, or an aryl group that may have a fluorine atom or an iodine atom.

[0283] The alkyl group may be in a straight chain or a branched chain. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 10, and more preferably 1 to 3.

[0284] The total number of fluorine atoms and iodine atoms included in an alkyl group having a fluorine atom or an iodine atom is not particularly limited, but 1 or more is preferred, 1 to 5 is more preferred, and 1 to 3 is more preferred.

[0285] The above alkyl group may have heteroatoms, such as oxygen atoms other than halogen atoms.

[0286] R2 represents a detachable molecule that is desorbed by the action of an acid and may contain a fluorine or iodine atom.

[0287] Among them, as for the extraction, the energy represented by equations (Z1) to (Z4) can be cited.

[0288] Equation (Z1): -C(Rx 11 )(Rx 12 )(Rx 13 )

[0289] Equation (Z2): -C(=O)OC(Rx 11 )(Rx 12 )(Rx 13 )

[0290] Equation (Z3): -C(R 136 )(R 137 )(OR 138 )

[0291] Equation (Z4): -C(Rn1)(H)(Ar1)

[0292] Among equations (Z1) and (Z2), Rx 11 ~Rx 13 Each represents, independently, an alkyl group (straight or branched) that may have a fluorine or iodine atom, or a cycloalkyl group (monocyclic or polycyclic) that may have a fluorine or iodine atom. Additionally, Rx 11 ~Rx 13 When all are alkyl groups (straight or branched), Rx 11 ~Rx 13 It is preferable that at least two of them are methyl groups.

[0293] Rx 11 ~Rx 13 Except for the fact that it may have silver, fluorine atoms or iodine atoms, it is identical to Rx1~Rx3 among (Y1) and (Y2) described above, and is identical to the definition and suitable range of alkyl groups and cycloalkyl groups.

[0294] In equation (Z3), R 136 ~R 138 R represents a monovalent organic group that may, independently, have a hydrogen atom, or a fluorine atom, or an iodine atom. 137 and R 138 Examples of monovalent organic groups that may have a fluorine atom or an iodine atom include an alkyl group that may have a fluorine atom or an iodine atom, a cycloalkyl group that may have a fluorine atom or an iodine atom, an aryl group that may have a fluorine atom or an iodine atom, an aryl group that may have a fluorine atom or an iodine atom, and a group that combines these (for example, a group that combines an alkyl group and a cycloalkyl group).

[0295] In addition, the above alkyl group, cycloalkyl group, aryl group, and aralkyl group may include heteroatoms such as oxygen atoms in addition to fluorine atoms and iodine atoms. That is, the above alkyl group, cycloalkyl group, aryl group, and aralkyl group may, for example, have one of the methylene group substituted with a heteroatom such as an oxygen atom or a group having a heteroatom such as a carbonyl group.

[0296] As for Equation (Z3), it is preferable to have the form represented by the following Equation (Z3-1).

[0297] [Chemical Formula 5]

[0298]

[0299] Here, L 11 and L 12Each represents, independently, a hydrogen atom; an alkyl group that may have a heteroatom selected from the group consisting of a fluorine atom, an iodine atom, and an oxygen atom; a cycloalkyl group that may have a heteroatom selected from the group consisting of a fluorine atom, an iodine atom, and an oxygen atom; an aryl group that may have a heteroatom selected from the group consisting of a fluorine atom, an iodine atom, and an oxygen atom; or a group that combines these (e.g., a group that combines an alkyl group and a cycloalkyl group that may have a heteroatom selected from the group consisting of a fluorine atom, an iodine atom, and an oxygen atom).

[0300] M1 represents a single coupling or a divalent coupling.

[0301] Q1 represents an alkyl group that may have a heteroatom selected from the group consisting of a fluorine atom, an iodine atom, and an oxygen atom; a cycloalkyl group that may have a heteroatom selected from the group consisting of a fluorine atom, an iodine atom, and an oxygen atom; an aryl group selected from the group consisting of a fluorine atom, an iodine atom, and an oxygen atom; an amino group; an ammonium group; a mercapto group; a cyano group; an aldehyde group; or a combination thereof (e.g., a combination of an alkyl group and a cycloalkyl group that may have a heteroatom selected from the group consisting of a fluorine atom, an iodine atom, and an oxygen atom).

[0302] In formula (Y4), Ar1 represents an aromatic group that may have a fluorine atom or an iodine atom. Rn1 represents an alkyl group that may have a fluorine atom or an iodine atom, a cycloalkyl group that may have a fluorine atom or an iodine atom, or an aryl group that may have a fluorine atom or an iodine atom. Rn1 and Ar1 may combine with each other to form a non-aromatic ring.

[0303] As for the repeating unit (Aa), the repeating unit represented by the general formula (AI) is also desirable.

[0304] [Chemical Formula 6]

[0305]

[0306] In the general formula (AI),

[0307] Xa1 represents an alkyl group that may have a hydrogen atom or a substituent.

[0308] T represents a single bond or a divalent linker.

[0309] Rx1 to Rx3 each independently represent an alkyl group (straight-chain or branched-chain) or a cycloalkyl group (single-ring or polycyclic). However, if all of Rx1 to Rx3 are alkyl groups (straight-chain or branched-chain), it is preferable that at least two of Rx1 to Rx3 are methyl groups.

[0310] Two of Rx1 to Rx3 may be combined to form a cycloalkyl group (monocyclic or polycyclic).

[0311] As for the alkyl group that may have a substituent represented by Xa1, for example, a methyl group or -CH2-R 11 One example is the energy manifested as. R 11 It represents a halogen atom (such as a fluorine atom), a hydroxyl group, or a monovalent organic group, and examples include an alkyl group having 5 or fewer carbon atoms that may be substituted with a halogen atom, an acyl group having 5 or fewer carbon atoms that may be substituted with a halogen atom, and an alkoxy group having 5 or fewer carbon atoms that may be substituted with a halogen atom, wherein an alkyl group having 3 or fewer carbon atoms is preferred, and a methyl group is more preferred. As Xa1, a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group is preferred.

[0312] Examples of the divalent linking groups of T include alkylene groups, aromatic groups, -COO-Rt- groups, and -O-Rt- groups. In the formula, Rt represents an alkylene group or a cycloalkylene group.

[0313] T is preferably a single bond or a -COO-Rt- group. When T represents a -COO-Rt- group, Rt is preferably an alkylene group having 1 to 5 carbon atoms, and more preferably a -CH2- group, a -(CH2)2- group, or a -(CH2)3- group.

[0314] As for the alkyl groups of Rx1 to Rx3, alkyl groups having 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and t-butyl groups, are preferred.

[0315] As for the cycloalkyl groups of Rx1 to Rx3, a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecaneyl group, a tetracyclododecaneyl group, and an adamantyl group is preferred.

[0316] As for the cycloalkyl group formed by the combination of two of Rx1 to Rx3, a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group is preferred, and additionally, a polycyclic cycloalkyl group such as a norvonyl group, a tetracyclodecaneyl group, a tetracyclododecaneyl group, and an adamantyl group is preferred. Among these, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is preferred.

[0317] The cycloalkyl group formed by the combination of two of Rx1 to Rx3 may, for example, have one of the methylene groups constituting the ring substituted with a heteroatom such as an oxygen atom or a group having a heteroatom such as a carbonyl group.

[0318] The iteration unit represented by the general formula (AI) is, for example, Rx1 It is a methyl group or an ethyl group, and an embodiment in which Rx2 and Rx3 are combined to form the aforementioned cycloalkyl group is preferred.

[0319] When each of the above groups has a substituent, examples of the substituents include alkyl groups (1 to 4 carbon atoms), halogen atoms, hydroxyl groups, alkoxy groups (1 to 4 carbon atoms), carboxyl groups, and alkoxycarbonyl groups (2 to 6 carbon atoms). The number of carbon atoms in the substituents is preferably 8 or less.

[0320] As a repeating unit represented by the general formula (AI), preferably, an acid-degradable (meth)acrylic acid tertiary alkyl ester repeating unit (Xa1) It is a repeating unit in which T represents a hydrogen atom or a methyl group and also represents a single bond.

[0321] The resin (A) may have only one type of repeating unit (Aa) or two or more types.

[0322] The content of repeating units (Aa) (total content in cases where two or more types of repeating units (Aa) exist) is preferably 15 to 80 mol% with respect to the total repeating units in the resin (A), and more preferably 20 to 70 mol%.

[0323] In addition, the content of repeating units in the resin (A) that decompose by the action of acid to generate carboxyl groups is preferably 25 to 70 mol% with respect to the total repeating units in the resin (A).

[0324] Preferably, resin (A) has at least one repeating unit selected from the group consisting of repeating units represented by the following general formulas (A-VIII) to (A-XII), as a repeating unit (Aa).

[0325] [Chemical Formula 7]

[0326]

[0327] In general formula (A-VIII), R5 represents a tert-butyl group, -CO-O-(tert-butyl) group.

[0328] In general formula (A-IX), R6 and R7 each independently represent a monovalent organic group. Examples of monovalent organic groups include alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, and alkenyl groups.

[0329] In the general formula (AX), p represents 1 or 2.

[0330] In general formulas (AX) to (A-XII), R8 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R9 represents an alkyl group having 1 to 3 carbon atoms.

[0331] Among the general formula (A-XII), R 10 It represents a carbon alkyl group having 1 to 3 carbon atoms or an adamantyl group.

[0332] Specific examples of repeating units (Aa) are shown below, but the present invention is not limited thereto. In addition, in the formula, Xa1 represents any one of H, CH3, CF3, and CH2OH, and Rxa and Rxb each represent a straight-chain or branched-chain alkyl group having 1 to 4 carbon atoms.

[0333] [Chemical Formula 8]

[0334]

[0335] [Chemical Formula 9]

[0336]

[0337] [Chemical Formula 10]

[0338]

[0339] [Chemical Formula 11]

[0340]

[0341] [Chemical Formula 12]

[0342]

[0343] (Repetitive unit with a variability)

[0344] The resin (A) may have repeating units having a dispersal.

[0345] As a repeating unit having a repeating unit, a repeating unit represented by the following general formula (B) is preferred.

[0346] [Chemical Formula 13]

[0347]

[0348] R3 represents a monovalent organic group that may have a hydrogen atom, or a fluorine atom, or an iodine atom. As a monovalent organic group that may have a fluorine atom or an iodine atom, a group represented as -L4-R8 is preferred. L4 represents a single bond or an ester group. R8 may be an alkyl group that may have a fluorine atom or an iodine atom, a cycloalkyl group that may have a fluorine atom or an iodine atom, an aryl group that may have a fluorine atom or an iodine atom, or a group that combines these.

[0349] R4 and R5 each independently represent a hydrogen atom, a fluorine atom, an iodine atom, or an alkyl group that may have a fluorine atom or an iodine atom.

[0350] L2 represents a single bond or an ester group.

[0351] L3 represents an aromatic hydrocarbon group of (n+m+1) valence or an alicyclic hydrocarbon group of (n+m+1) valence. Examples of aromatic hydrocarbon groups include benzene groups and naphthalene groups. Examples of alicyclic hydrocarbon groups include monocyclic and polycyclic groups, such as cycloalkyl groups.

[0352] R6 represents a hydroxyl group or a fluorinated alcohol group (preferably a hexafluoroisopropanol group). Additionally, when R6 is a hydroxyl group, L3 is preferably an aromatic hydrocarbon group of (n+m+1) value.

[0353] R7 represents a halogen atom. Examples of halogen atoms include fluorine, chlorine, bromine, or iodine.

[0354] m represents an integer greater than or equal to 1. m is preferably an integer between 1 and 3, and preferably an integer between 1 and 2.

[0355] n represents an integer greater than or equal to 0 or 1. n is preferably an integer between 1 and 4.

[0356] In addition, (n+m+1) is preferably an integer from 1 to 5.

[0357] As a repeating unit having a repeating unit, a repeating unit represented by the following general formula (I) is also desirable.

[0358] [Chemical Formula 14]

[0359]

[0360] Among general formula (I),

[0361] R 41 , R 42 and R 43 Each represents, independently, a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. provided that R 42 It may combine with Ar4 to form a ring, and in that case, R 42 represents a single bond or an alkylene group.

[0362] X4 is a single bond, -COO-, or -CONR 64 - indicates, R 64 represents a hydrogen atom or an alkyl group.

[0363] L4 represents a single bond or an alkylene group.

[0364] Ar4 represents (n+1) directional ventilation, and R 42 When combined with to form a ring, it exhibits (n+2) directional ventilation.

[0365] n represents an integer from 1 to 5.

[0366] R in general formula (I) 41 , R 42 , and, R 43 As for the alkyl group, alkyl groups having 20 or fewer carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, hexyl, 2-ethylhexyl, octyl, and dodecyl groups, are preferred, alkyl groups having 8 or fewer carbon atoms are more preferred, and alkyl groups having 3 or fewer carbon atoms are even more preferred.

[0367] R in general formula (I) 41 , R 42 , and, R 43 The cycloalkyl group may be monocyclic or polycyclic. Among these, a monocyclic cycloalkyl group having 3 to 8 carbon atoms, such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group, is preferred.

[0368] R in general formula (I) 41 , R 42 , and, R 43 Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, and fluorine atoms are preferred.

[0369] R in general formula (I) 41 , R 42 , and, R 43 As an alkyl group included in the alkoxycarbonyl group of, the above R 41 , R 42 , R 43 It is preferable that it be the same as the alkyl group in.

[0370] Ar4 represents an (n+1) valence aroma. In the case where n is 1, the divalent aroma may have substituents, and for example, an arylene group having 6 to 18 carbon atoms, such as a phenylene group, tolylene group, naphthylene group, and anthracenylene group, or an aroma comprising a heterocyclic ring such as a thiophene ring, furan ring, pyrrole ring, benzothiophene ring, benzofuran ring, benzopyrrole ring, triazine ring, imidazole ring, benzimidazole ring, triazole ring, thiadiazole ring, and thiazole ring is preferred.

[0371] A specific example of an (n+1) valence directional group in the case where n is an integer greater than or equal to 2 is a group formed by removing any (n-1) hydrogen atoms from the above-described specific example of a divalence directional group. The (n+1) valence directional group may have additional substituents.

[0372] As substituents that the above-described alkyl group, cycloalkyl group, alkoxycarbonyl group, alkylene group, and (n+1) valence aromatic group may have, for example, R in general formula (I). 41 , R 42 , and, R 43 Examples include alkoxy groups such as alkyl groups, methoxy groups, ethoxy groups, hydroxyethoxy groups, propoxy groups, hydroxypropoxy groups, and butoxy groups; and aryl groups such as phenyl groups.

[0373] -CONR appearing by X4 64 -(R 64 R in (represents a hydrogen atom or an alkyl group) 64 Examples of alkyl groups include alkyl groups with 20 or fewer carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, hexyl, 2-ethylhexyl, octyl, and dodecyl groups, and alkyl groups with 8 or fewer carbon atoms are preferred.

[0374] As for X4, a single bond, -COO-, or -CONH- is preferred, and a single bond, or -COO- is more preferred.

[0375] As for the alkylene group in L4, alkylene groups having 1 to 8 carbon atoms, such as methylene, ethylene, propylene, butylene, hexylene, and octylene, are preferred.

[0376] As for Ar4, a carbon atom having 6 to 18 carbon atoms is preferred, and a benzene atom, a naphthalene atom, and a biphenylene atom are more preferred.

[0377] Specific examples of repeating units represented by general formula (I) are shown below, but the present invention is not limited thereto. In the formula, a represents 1 or 2.

[0378] [Chemical Formula 15]

[0379]

[0380] [Chemical Formula 16]

[0381]

[0382] [Chemical Formula 17]

[0383]

[0384] <<Repeating unit derived from hydroxystyrene (A-1)>>

[0385] It is preferable that the resin (A) has a repeating unit (A-1) derived from hydroxystyrene as a repeating unit having an acid group.

[0386] As a repeating unit (A-1) derived from hydroxystyrene, the repeating unit represented by the following general formula (1) can be cited.

[0387] [Chemical Formula 18]

[0388]

[0389] Among general formulas (1),

[0390] A represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, or a cyano group.

[0391] R represents a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an aralkyl group, an alkoxy group, an alkylcarbonyloxy group, an alkylsulfonyloxy group, an alkyloxycarbonyl group, or an aryloxycarbonyl group. If multiple Rs are present, they may be identical or different. If multiple Rs are present, they may form a ring together. A hydrogen atom is preferred as R.

[0392] a represents an integer from 1 to 3, and b represents an integer from 0 to (5-a).

[0393] As for the repeating unit (A-1), the repeating unit represented by the following general formula (AI) is preferred.

[0394] [Chemical Formula 19]

[0395]

[0396] A composition containing a resin (A) having repeating units (A-1) is preferred for KrF exposure, EB exposure, or EUV exposure. In this case, the content of the repeating units (A-1) is preferably 30 to 100 mol% with respect to the total repeating units in the resin (A), more preferably 40 to 100 mol%, and even more preferably 50 to 100 mol%.

[0397] (Repeating unit (A-2) containing at least one selected from the group consisting of a lactone structure, a sulfone structure, a carbonate structure, and a hydroxyadamanthene structure)

[0398] The resin (A) may have a repeating unit (A-2) having at least one selected from the group consisting of a lactone structure, a carbonate structure, a sulfone structure, and a hydroxyadamantane structure.

[0399] <<Repeating unit having a lactone or sulfonate structure>>

[0400] In a repeating unit having a lactone structure or a selton structure, the lactone structure or selton structure is not particularly limited, but a 5- to 7-membered ring lactone structure or a 5- to 7-membered ring selton structure is preferred, and it is more preferable that another ring structure is condensed in a manner forming a bicyclo structure or a spiro structure in the 5- to 7-membered ring lactone structure, or that another ring structure is condensed in a manner forming a bicyclo structure or a spiro structure in the 5- to 7-membered ring selton structure. It is more preferable to have a repeating unit having a lactone structure represented by any one of the following general formulas (LC1-1) to (LC1-21), or a selton structure represented by any one of the following general formulas (SL1-1) to (SL1-3). In addition, the lactone structure or selton structure may be directly bonded to the main chain. The preferred structure is general formula (LC1-1), general formula (LC1-4), general formula (LC1-5), general formula (LC1-8), general formula (LC1-16), general formula (LC1-21), or general formula (SL1-1).

[0401] [Chemical Formula 20]

[0402]

[0403] The lactone structural part or the sulfonate structural part is a substituent (Rb 2 It may or may not have ). Substituent (Rb 2 As ), an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, a carboxyl group, a halogen atom other than a fluorine atom, a hydroxyl group, a cyano group, or an acid-degradable group is preferred, and an alkyl group having 1 to 4 carbon atoms, a cyano group, or an acid-degradable group is more preferred. n2 represents an integer from 0 to 4. When n2 is 2 or more, multiple substituents (Rb 2 ) may be the same or different. Also, multiple existing substituents (Rb 2 ) may combine to form a ring.

[0404] As a repeating unit having a lactone structure or a sulfonate structure, a repeating unit represented by the following Equation III is preferred in terms of the allowability of depth of focus and pattern linearity.

[0405] In addition, regarding the tolerance of depth of focus and pattern linearity, it is preferable for the resin having repeating units having repeating units represented by the following Equation III to have repeating units.

[0406] [Chemical Formula 21]

[0407]

[0408] Among the above Equation III,

[0409] A represents an ester bond (a group represented as -COO-) or an amide bond (a group represented as -CONH-).

[0410] n is, -R 0 It is the number of repetitions of the structure represented by -Z-, representing an integer from 0 to 5, preferably 0 or 1, and more preferably 0. When n is 0, -R 0 -Z- does not exist, and A and R 8 It is joined by this single bond.

[0411] R 0 It represents silver, an alkylene group, a cycloalkylene group, or a combination thereof. R 0 If multiple are present, each independently represents an alkylene group, a cycloalkylene group, or a combination thereof.

[0412] Z represents a single bond, ether bond, ester bond, amide bond, uretane bond, or urea bond. If multiple Zs exist, each independently represents a single bond, ether bond, ester bond, amide bond, uretane bond, or urea bond.

[0413] R 8 It represents a monovalent organic group having a lactone structure or a sulfone structure.

[0414] R 7 It represents a halogen atom other than silver, hydrogen atoms, or fluorine atoms, or a monovalent organic group (preferably a methyl group).

[0415] R 0 The alkylene group or cycloalkylene group of may have a substituent.

[0416] Z is preferably an ether bond or an ester bond, and more preferably an ester bond.

[0417] As a repeating unit having a lactone structure or a sulfone structure, at least one repeating unit selected from the group consisting of repeating units represented by the following general formulas (A-II) to (AV) is also preferred.

[0418] [Chemical Formula 22]

[0419]

[0420] In general formulas (A-II) to (AV), R1 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

[0421] R2 is an alkyl group having 1 to 4 carbon atoms, a cyano group, or -CO-OR 21 It represents. R 21 It represents an alkyl group having 1 to 4 carbon atoms.

[0422] X1 represents a single bond, an alkylene group having 1 to 3 carbon atoms, or -R3-CO-O-, and R3 represents an alkylene group having 1 to 3 carbon atoms.

[0423] m represents 0 or 1.

[0424] Specific examples of monomers corresponding to the repeating unit represented by Formula III or the repeating unit represented by general formulas (A-II) to (AV) are given below. The following specific examples are R in Formula III 7 and R1 in general formulas (A-II) to (AV) Although it is equivalent to a methyl group, the above methyl group can be optionally substituted with a hydrogen atom or an alkyl group having 2 to 3 carbon atoms.

[0425] [Chemical Formula 23]

[0426]

[0427] In addition to the monomers mentioned above, the monomers shown below are also suitably used as repeating units having a lactone structure or a sulfone structure.

[0428] [Chemical Formula 24]

[0429]

[0430] <<Repeating unit having a carbonate structure>>

[0431] The resin (A) may have repeating units having a carbonate structure. The carbonate structure is preferably a cyclic carbonate ester structure.

[0432] The repeating unit having a cyclic carbonate ester structure is preferably a repeating unit represented by the following formula A-1.

[0433] [Chemical Formula 25]

[0434]

[0435] In Equation A-1, R A 1 Represents a halogen atom other than silver, hydrogen, or fluorine atoms, or a monovalent organic group (preferably a methyl group), where n represents an integer greater than or equal to 0, and R A 2 represents a substituent. R A 2 In cases where n is 2 or greater, each represents a substituent independently, A represents a single bond or a divalent linker, and Z represents an atomic group that forms a monocyclic or polycyclic structure together with the group represented by -OC(=O)-O- in the formula.

[0436] As a repeating unit having a carbonate structure, a repeating unit represented by the following general formula (A-VI) is more preferable.

[0437] [Chemical Formula 26]

[0438]

[0439] In general formula (A-VI), R1 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

[0440] X1 represents a single bond, an alkylene group having 1 to 3 carbon atoms, or -R3-CO-O-, and R3 represents an alkylene group having 1 to 3 carbon atoms.

[0441] The resin (A) is a repeating unit having at least one selected from the group consisting of a lactone structure, a sulfone structure, and a carbonate structure, and it is also preferable to have a repeating unit described in paragraphs 0370 to 0414 of U.S. Patent Application Publication No. 2016 / 0070167.

[0442] <<Repeating unit having a hydroxyadamanthene structure>>

[0443] Resin (A) may have repeating units having a hydroxyadamantane structure. Examples of repeating units having a hydroxyadamantane structure include repeating units represented by the following general formula (AIIa).

[0444] [Chemical Formula 27]

[0445]

[0446] Among the general formula (AIIa), R 1c represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group. R 2c ~R 4c represents, respectively, a hydrogen atom or a hydroxyl group. However, R 2c ~R 4c At least one of them represents a hydroxyl group. R 2c ~R 4cIt is preferable that one or two of them are hydroxyl groups and the rest are hydrogen atoms.

[0447] As a repeating unit having a hydroxyadamantane structure, a repeating unit represented by the following general formula (A-VII) is more preferred.

[0448] [Chemical Formula 28]

[0449]

[0450] In general formulas (A-VII), R1 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. n represents 0 or 1.

[0451] Specific examples of repeating units having a hydroxyadamanthene structure are given below, but the present invention is not limited to these.

[0452] [Chemical Formula 29]

[0453]

[0454] When the resin (A) has repeating units having a hydroxyadamantane structure, the content of repeating units having a hydroxyadamantane structure is preferably 5 to 40 mol% with respect to the total repeating units in the resin (A), more preferably 5 to 30 mol%, and even more preferably 10 to 25 mol%.

[0455] The resin (A) may have a repeating unit (A-2) having at least one selected from the group consisting of a lactone structure, a carbonate structure, a sulfone structure, and a hydroxyadamantane structure, either alone or in combination with two or more types.

[0456] As the repeating unit (A-2), it is preferable to have a repeating unit derived from a (meth)acrylic acid ester containing at least one selected from the group consisting of a lactone structure, a carbonate structure, a sulfone structure, and a hydroxyadamantane structure.

[0457] The content of repeating units (A-2) included in the resin (A) (the total content if there are multiple repeating units (A-2)) is preferably 5 to 70 mol% with respect to the total repeating units of the resin (A), more preferably 10 to 65 mol%, and more preferably 20 to 60 mol%.

[0458] It is preferable that the resin (A) has at least one of a repeating unit (A-1) derived from the above-described hydroxystyrene, and a repeating unit (A-2) containing at least one selected from the group consisting of a lactone structure, a carbonate structure, a sulfone structure, and a hydroxyadamantane structure.

[0459] Among these, it is preferable that the repeating unit (A-1) is a repeating unit represented by the general formula (AI) described above, and that the repeating unit (A-2) contains at least one type selected from the group consisting of repeating units represented by the general formulas (A-II) to (A-VII) described above.

[0460] With respect to the repeating unit (A-1), repeating unit (A-2) and the repeating unit represented by general formulas (AI) to (A-VII), the preferred modes thereof are included as described above.

[0461] (Other repeating units)

[0462] The resin (A) may have repeating units other than the repeating unit (Aa) having the acid-degrading group described above, the repeating unit having an acid group, and the repeating unit (A-2).

[0463] <<Repeating unit having a fluorine atom or an iodine atom>>

[0464] The resin (A) may have repeating units having fluorine atoms or iodine atoms. However, the repeating units having fluorine atoms or iodine atoms do not include the repeating units (Aa) having acid-degradable groups, repeating units having acid groups, and repeating units (A-2) described above.

[0465] As a repeating unit having a fluorine atom or an iodine atom, the repeating unit represented by formula (C) is preferred.

[0466] [Chemical Formula 30]

[0467]

[0468] L5 represents a single bond or an ester group.

[0469] R9 represents an alkyl group that may have a hydrogen atom, or a fluorine atom, or an iodine atom.

[0470] R 10 It represents an alkyl group that may have a hydrogen atom, a fluorine atom, or an iodine atom, a cycloalkyl group that may have a fluorine atom or an iodine atom, an aryl group that may have a fluorine atom or an iodine atom, or a combination thereof.

[0471] The content of repeating units having fluorine atoms or iodine atoms is preferably 0 to 50 mol% with respect to the total repeating units in resin (A), more preferably 5 to 45 mol%, and even more preferably 10 to 40 mol%.

[0472] <<Repetitive unit with a mine generator>>

[0473] Resin (A) may have a repeating unit other than the above that has a device that generates acid upon irradiation with radiation (hereinafter also referred to as a "mine generator").

[0474] In this case, the repeating unit having this photogenerator can be considered to correspond to the photogenerator (P).

[0475] As such a repeating unit, for example, the repeating unit represented by the following general formula (4) can be cited.

[0476] [Chemical Formula 31]

[0477]

[0478] R 41It represents silver, a hydrogen atom, or a methyl group. L 41 It represents a single bond, or a divalent linker. L 42 represents a divalent connector. R 40 It represents a structural region that decomposes upon radiation irradiation and generates acid in the side chain.

[0479] Below, specific examples of repeating units represented by general formula (4) are shown, but the present invention is not limited thereto.

[0480] [Chemical Formula 32]

[0481]

[0482] In addition, as a repeating unit represented by general formula (4), for example, the repeating unit described in paragraphs

[0094] to

[0105] of Japanese Patent Publication No. 2014-041327 can be cited.

[0483] The content of repeating units having a photogenerative group is preferably 1 to 40 mol% with respect to the total repeating units in the resin (A), more preferably 5 to 35 mol%, and even more preferably 5 to 30 mol%.

[0484] <<Repeating unit having alkali-soluble groups>>

[0485] The resin (A) may have repeating units having alkali-soluble groups.

[0486] Examples of alkali-soluble groups include carboxyl groups, sulfonamide groups, sulfonylimide groups, bissulfonylimide groups, and aliphatic alcohols in which the α-position is substituted with an electron-withdrawing group (e.g., hexafluoroisopropanol groups), and carboxyl groups are preferred. As the resin (A) has repeating units having alkali-soluble groups, the resolution for contact hole applications is increased.

[0487] Examples of repeating units having alkali-soluble groups include repeating units in which the alkali-soluble group is directly bonded to the main chain of the resin, such as repeating units made of acrylic acid and methacrylic acid, or repeating units in which the alkali-soluble group is bonded to the main chain of the resin through a linker. Additionally, the linker may have a monocyclic or polycyclic cyclic hydrocarbon structure.

[0488] As a repeating unit having an alkali-soluble group, a repeating unit made of acrylic acid or methacrylic acid is preferred.

[0489] The content of repeating units having alkali-soluble groups is preferably 0 to 20 mol% with respect to the total repeating units in resin (A), more preferably 3 to 15 mol%, and more preferably 5 to 10 mol%.

[0490] Specific examples of repeating units having alkali-soluble groups are shown below, but the present invention is not limited thereto. In the specific examples, Rx represents H, CH3, CH2OH, or CF3.

[0491] [Chemical Formula 33]

[0492]

[0493] <<Repeating unit that does not have both acid-degrading and polar groups>>

[0494] The resin (A) may further have repeating units that do not have both acid-degradable and polar groups. The repeating units that do not have both acid-degradable and polar groups preferably have a cycloaliphatic hydrocarbon structure.

[0495] Examples of repeating units that do not have both acid-degrading and polar groups include, for instance, the repeating unit described in paragraphs 0236–0237 of U.S. Patent Application Publication No. 2016 / 0026083, and the repeating unit described in paragraph 0433 of U.S. Patent Application Publication No. 2016 / 0070167.

[0496] Preferred examples of monomers corresponding to repeating units that do not possess both acid-degradable and polar groups are shown below.

[0497] [Chemical Formula 34]

[0498]

[0499] Resin (A) may have a repeating unit that does not have both an acid-degradable group and a polar group, either as a single type or as a combination of two or more types.

[0500] The content of repeating units that do not have both acid-degradable and polar groups is preferably 5 to 40 mol% with respect to the total repeating units in resin (A), more preferably 5 to 30 mol%, and more preferably 5 to 25 mol%.

[0501] In addition to the repeating structure unit described above, the resin (A) may have various repeating structure units for the purpose of controlling dry etching resistance, standard developer suitability, substrate adhesion, resist profile, resolution, heat resistance, and sensitivity.

[0502] (Characteristics of Resin (A))

[0503] As for the resin (A), it is preferable that all repeating units consist of repeating units derived from (meth)acrylate-based monomers. In this case, any resin may be used in which all repeating units are derived from methacrylate-based monomers, all repeating units are derived from acrylate-based monomers, or all repeating units are derived from methacrylate-based monomers and acrylate-based monomers. It is preferable that the repeating units derived from acrylate-based monomers are 50 mol% or less of the total repeating units in the resin (A).

[0504] When the composition is for fluorinated argon (ArF) exposure, it is preferable that the resin (A) substantially does not have aromatic groups for the sake of the transmittance of ArF light. More specifically, it is preferable that the repeating units having aromatic groups be 5 mol% or less with respect to the total repeating units of the resin (A), more preferable that they be 3 mol% or less, and ideally 0 mol%, that is, it is more preferable that there are no repeating units having aromatic groups.

[0505] Also, when the composition is for ArF exposure, it is preferable that the resin (A) has a monocyclic or polycyclic alicyclic hydrocarbon structure, and it is also preferable that it does not contain both fluorine atoms and silicon atoms.

[0506] When the composition is for krypton fluoride (KrF) exposure, EB exposure, or EUV exposure, it is preferable that the resin (A) has repeating units having aromatic hydrocarbon groups, and more preferable that it has repeating units having phenolic hydroxyl groups.

[0507] Examples of repeating units having a phenolic hydroxyl group include the repeating unit derived from hydroxystyrene (A-1) and the repeating unit derived from hydroxystyrene (meth)acrylate.

[0508] In addition, when the composition is for KrF exposure, EB exposure, or EUV exposure, it is also preferable that the resin (A) has repeating units having a structure in which the hydrogen atoms of the phenolic hydroxyl groups are decomposed and detached by the action of an acid (detachers).

[0509] When the composition is for KrF exposure, EB exposure, or EUV exposure, the content of repeating units having aromatic hydrocarbon groups included in the resin (A) is preferably 30 to 100 mol% with respect to the total repeating units in the resin (A), more preferably 40 to 100 mol%, and more preferably 50 to 100 mol%.

[0510] Resin (A) can be synthesized by a conventional method (e.g., radical polymerization).

[0511] The weight average molecular weight (Mw) of the resin (A) is preferably 1,000 to 200,000, more preferably 3,000 to 20,000, and more preferably 5,000 to 15,000. By setting the weight average molecular weight (Mw) of the resin (A) to 1,000 to 200,000, deterioration of heat resistance and dry etching resistance can be prevented, and deterioration of developability and deterioration of film-forming ability due to increased viscosity can also be prevented. In addition, the weight average molecular weight (Mw) of the resin (A) is a polystyrene equivalent value measured by the GPC method described above.

[0512] The degree of dispersion (molecular weight distribution) of the resin (A) is typically 1 to 5, preferably 1 to 3, and more preferably 1.1 to 2.0. The smaller the degree of dispersion, the better the resolution and resist shape, and the smoother the sidewalls of the pattern, the better the roughness.

[0513] In the composition, the content of resin (A) is preferably 50 to 99.9 mass% with respect to the total solid content of the composition, and more preferably 60 to 99.0 mass%.

[0514] Also, resin (A) may be used as a single type or in combination with two or more types.

[0515] (Ore-generating agent (P))

[0516] The photosensitive or radiation-sensitive resin composition contains a photogenerator (P). The photogenerator (P) is not particularly limited as long as it is a compound that generates acid upon irradiation with radiation.

[0517] The photogenerator (P) may be in the form of a low-molecular-weight compound or introduced into a part of the polymer. In addition, the form of a low-molecular-weight compound and the form introduced into a part of the polymer may be used in combination.

[0518] When the photogenerator (P) is in the form of a low molecular weight compound, it is preferable that the weight average molecular weight (Mw) is 3000 or less, more preferable that it is 2000 or less, and more preferable that it is 1000 or less.

[0519] When the photocatalytic agent (P) is introduced into a part of the polymer, it may be introduced into a part of the resin (A) or into a resin different from the resin (A).

[0520] In the present invention, the photogenerator (P) is preferably in the form of a low molecular weight compound.

[0521] As for the photogenerator (P), it is not particularly limited as long as it is a known one, but a compound that generates an organic acid upon irradiation with radiation is preferred, and a photogenerator having a fluorine atom or an iodine atom in its molecule is more preferred.

[0522] Examples of the above organic acids include sulfonic acid (aliphatic sulfonic acid, aromatic sulfonic acid, and camphorsulfonic acid, etc.), carboxylic acid (aliphatic carboxylic acid, aromatic carboxylic acid, and aralkylcarboxylic acid, etc.), carbonylsulfonylimide, bis(alkylsulfonyl)imide, and tris(alkylsulfonyl)methide.

[0523] The volume of acid generated from the photogenerative agent (P) is not particularly limited, but in order to suppress the diffusion of acid generated by exposure to the unexposed area and to improve resolution, 240 Å 3 The above is desirable, and 305Å 3 The above is more preferable, and 350Å 3 The above is more desirable, and 400Å 3 The above is particularly desirable. In addition, in terms of sensitivity or solubility in a coating solvent, the volume of acid generated from the photogenerator (P) is 1500 Å. 3 The following is preferable, and 1000 Å 3 The following is more preferable, and 700Å 3 The following is more desirable.

[0524] The above volume values ​​are obtained using "WinMOPAC" manufactured by Fujitsu Corporation. In calculating the above volume values, first, the chemical structure of the acid for each example is input, and next, using this structure as the initial structure, the most stable stereochemical position of each acid is determined by calculating the molecular force field using the MM (Molecular Mechanics) 3 method, and then, the "accessible volume" of each acid can be calculated by performing molecular orbital calculations using the PM (Parameterized Model Number) 3 method for these most stable stereochemical positions.

[0525] The structure of the acid generated from the photogenerator (P) is not particularly limited, but it is desirable that the interaction between the acid generated from the photogenerator (P) and the resin (A) be strong in order to suppress the diffusion of the acid and improve the resolution. In this regard, when the acid generated from the photogenerator (P) is an organic acid, for example, it is desirable to have additional polar groups in addition to organic acid groups such as sulfonic acid groups, carboxylic acid groups, carbonylsulfonilimide groups, bissulfonilimide groups, and trissulfonilmedide groups.

[0526] Examples of polar groups include, for instance, ether groups, ester groups, amide groups, acyl groups, sulfo groups, sulfonyloxy groups, sulfonamide groups, thioether groups, thioester groups, urea groups, carbonate groups, carbamate groups, hydroxyl groups, and mercapto groups.

[0527] The number of polar groups of the acid generated is not particularly limited, but it is preferable to have one or more, and more preferable to have two or more. However, from the perspective of suppressing excessive phenomena, it is preferable that the number of polar groups be less than 6, and more preferable to have less than 4.

[0528] As the photogenerator (P), the compounds exemplified below are preferred. In addition, for each compound, the calculated value of the volume of acid generated from each compound by exposure to light is noted (unit Å). 3 ).

[0529] [Chemical Formula 35]

[0530]

[0531] [Chemical Formula 36]

[0532]

[0533] [Chemical Formula 37]

[0534]

[0535] Among them, it is preferable that the photogenerator (P) be a photogenerator composed of an anionic part and a cation part.

[0536] As a photogenerator (P), a compound represented by the following general formula (ZI) or a compound represented by the general formula (ZII) is preferred.

[0537] [Chemical Formula 38]

[0538]

[0539] In the above general formula (ZI),

[0540] R 201 , R 202 and R 203 Each independently represents an organic group.

[0541] R 201 , R 202 and R 203 The number of carbon atoms in the organic group is preferably 1 to 30, and more preferably 1 to 20.

[0542] Also, R 201 ~R 203 Two of them may combine to form a ring structure, and the ring may contain oxygen atoms, sulfur atoms, ester bonds, amide bonds, or carbonyl groups. R 201 ~R 203Examples of groups formed by the combination of two of them include alkylene groups (e.g., butylene groups, or pentylene groups).

[0543] Z - represents a non-nucleated anion (anion with a significantly low ability to cause a nucleation reaction).

[0544] Examples of non-nucleated anions include sulfonate anions (aliphatic sulfonate anions, aromatic sulfonate anions, and camphorsulfonate anions, etc.), carboxylate anions (aliphatic carboxylate anions, aromatic carboxylate anions, and aralkylcarboxylate anions, etc.), sulfonylimide anions, bis(alkylsulfonyl)imide anions, and tris(alkylsulfonyl)methide anions, etc.

[0545] The aliphatic portion of the aliphatic sulfonic acid anion and the aliphatic carboxylic acid anion may be an alkyl group or a cycloalkyl group, and is preferably a straight-chain or branched-chain alkyl group having 1 to 30 carbon atoms and a cycloalkyl group having 3 to 30 carbon atoms.

[0546] As for the aromatic group in the aromatic sulfonic acid anion and the aromatic carboxylic acid anion, an aryl group having 6 to 14 carbon atoms is preferred, and examples include a phenyl group, a tolyl group, and a naphthyl group.

[0547] Specific examples of substituents that the alkyl group, cycloalkyl group, and aryl group described above may have include a nitro group, a halogen atom such as a fluorine atom, a carboxyl group, a hydroxyl group, an amino group, a cyano group, an alkoxy group (preferably 1 to 15 carbon atoms), a cycloalkyl group (preferably 3 to 15 carbon atoms), an aryl group (preferably 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably 2 to 7 carbon atoms), an acyl group (preferably 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably 2 to 7 carbon atoms), an alkylthio group (preferably 1 to 15 carbon atoms), an alkylsulfonyl group (preferably 1 to 15 carbon atoms), an alkyliminosulfonyl group (preferably 1 to 15 carbon atoms), and an aryloxysulfonyl group (preferably 6 to 20 carbon atoms). Examples include an alkylaryl oxysulfonyl group (preferably 7 to 20 carbon atoms), a cycloalkylaryl oxysulfonyl group (preferably 10 to 20 carbon atoms), an alkyloxyalkyloxy group (preferably 5 to 20 carbon atoms), and a cycloalkylalkyloxyalkyloxy group (preferably 8 to 20 carbon atoms).

[0548] As for the aralkyl group in the aralkylcarboxylic acid anion, an aralkyl group having 7 to 12 carbon atoms is preferred, and examples include a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, and a naphthylbutyl group.

[0549] Examples of sulfonylimide anions include saccharin anions.

[0550] As the alkyl group in the bis(alkylsulfonyl)imide anion and the tris(alkylsulfonyl)methide anion, an alkyl group having 1 to 5 carbon atoms is preferred. As substituents of these alkyl groups, examples include a halogen atom, an alkyl group substituted with a halogen atom, an alkoxy group, an alkylthio group, an alkyloxysulfonyl group, an aryloxysulfonyl group, and a cycloalkylaryloxysulfonyl group, and a fluorine atom or an alkyl group substituted with a fluorine atom is preferred.

[0551] In addition, the alkyl groups in the bis(alkylsulfonyl)imide anion may bond with each other to form a ring structure. This increases the acid strength.

[0552] Other non-nucleated anions include, for example, phosphorus fluoride (e.g., PF6) - ), boron fluoride (e.g., BF4 - ), and, antimony fluoride (e.g., SbF6 - ...can be cited.

[0553] As non-nucleated anions, an aliphatic sulfonate anion in which at least the α-site of the sulfonic acid is substituted with a fluorine atom, an aromatic sulfonate anion substituted with a fluorine atom or a group having a fluorine atom, a bis(alkylsulfonyl)imide anion in which an alkyl group is substituted with a fluorine atom, or a tris(alkylsulfonyl)methide anion in which an alkyl group is substituted with a fluorine atom are preferred. Among these, a perfluoroaliphatic sulfonate anion (preferably having 4 to 8 carbon atoms) or a benzenesulfonate anion having a fluorine atom is more preferred, and a nonafluorobutanesulfonate anion, a perfluorooctanesulfonate anion, a pentafluorobenzenesulfonate anion, or a 3,5-bis(trifluoromethyl)benzenesulfonate anion is more preferred.

[0554] From the perspective of acid strength, it is desirable for the pKa of the generated acid to be -1 or lower to improve sensitivity.

[0555] In addition, as a non-nucleated anion, an anion represented by the following general formula (AN1) is also preferred.

[0556] [Chemical Formula 39]

[0557]

[0558] During the meal,

[0559] Xf represents, respectively, a fluorine atom or an alkyl group substituted with at least one fluorine atom.

[0560] R 1 and R 2represents, respectively, a hydrogen atom, a fluorine atom, or an alkyl group, and R in the case where multiple are present. 1 and R 2 Each can be the same or different.

[0561] L represents a 2-valent linker, and in the case of multiple links, L may be the same or different.

[0562] A represents an illusory organic device.

[0563] x represents an integer from 1 to 20, y represents an integer from 0 to 10, and z represents an integer from 0 to 10.

[0564] The general formula (AN1) is explained in more detail.

[0565] The number of carbon atoms in the alkyl group substituted with a fluorine atom of Xf is preferably 1 to 10, and more preferably 1 to 4. In addition, as the alkyl group substituted with a fluorine atom of Xf, a perfluoroalkyl group is preferred.

[0566] As Xf, a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms is preferred. Specifically, examples of Xf include a fluorine atom, CF3, C2F5, C3F7, C4F9, CH2CF3, CH2CH2CF3, CH2C2F5, CH2CH2C2F5, CH2C3F7, CH2CH2C3F7, CH2C4F9, and CH2CH2C4F9, among others; among these, a fluorine atom or CF3 is preferred. In particular, it is preferred that both Xf are fluorine atoms.

[0567] R 1 and R 2 The alkyl group may have a substituent (preferably a fluorine atom), and the number of carbon atoms in the substituent is preferably 1 to 4. As a substituent, a perfluoroalkyl group having 1 to 4 carbon atoms is preferred. R 1 and R 2 Specific examples of alkyl groups having substituents include CF3, C2F5, C3F7, C4F9, and C5F 11, C6F 13 , C7F 15 , C8F 17 Examples include CH2CF3, CH2CH2CF3, CH2C2F5, CH2CH2C2F5, CH2C3F7, CH2CH2C3F7, CH2C4F9, and CH2CH2C4F9, among which CF3 is preferred.

[0568] R 1 and R 2 As for, fluorine atoms or CF3 are preferred.

[0569] x is preferably an integer from 1 to 10, and more preferably from 1 to 5.

[0570] y is preferably an integer between 0 and 4, and 0 is more preferable.

[0571] z is preferably an integer from 0 to 5, and more preferably an integer from 0 to 3.

[0572] The divalent linker of L is not particularly limited and may include -COO-, -CO-, -O-, -S-, -SO-, -SO2-, alkylene groups, cycloalkylene groups, alkenylene groups, and linkers formed by connecting multiple groups thereof, and linkers with a total carbon number of 12 or fewer are preferred. Among these, -COO-, -OCO-, -CO-, or -O- are preferred, and -COO- or -OCO- are more preferred.

[0573] As for the cyclic induced energizer of A, it is not particularly limited as long as it has a cyclic structure, and examples include radiating energizers, directional energizers, and complex energizers (including not only those that have aromaticity but also those that do not have aromaticity).

[0574] As for the alicyclic group, it may be monocyclic or polycyclic, and monocyclic cycloalkyl groups such as cyclopentyl groups, cyclohexyl groups, and cyclooctyl groups are preferred, and additionally, polycyclic cycloalkyl groups such as norbornyl groups, tricyclodecaneyl groups, tetracyclodecaneyl groups, tetracyclododecaneyl groups, and adamantyl groups are preferred. Among these, alicyclic groups having a bulky structure with 7 or more carbon atoms, such as norbornyl groups, tricyclodecaneyl groups, tetracyclodecaneyl groups, tetracyclododecaneyl groups, and adamantyl groups, are preferred from the perspective of improving MEEF (Mask Error Enhancement Factor) because they can suppress diffusivity within the film during the heating process after exposure.

[0575] Examples of directional radiators include the benzene ring, naphthalene ring, phenanthrene ring, and anthracene ring.

[0576] Examples of complex ring-forming elements include elements derived from furan rings, thiophene rings, benzofuran rings, benzothiophene rings, dibenzofuran rings, dibenzothiophene rings, and pyridine rings. Among these, elements derived from furan rings, thiophene rings, and pyridine rings are preferred.

[0577] In addition, as a cyclic organic group, a group having a lactone structure may be cited, and as a specific example, a group having a lactone structure represented by the general formulas (LC1-1) to (LC1-17) described above may be cited.

[0578] The above-mentioned cyclic organic group may have a substituent. Examples of the substituents include an alkyl group (which may be straight-chain, branched-chain, and cyclic, and preferably has 1 to 12 carbon atoms), a cycloalkyl group (which may be monocyclic and polycyclic, and in the case of polycyclic, may be a spirocyclic, and preferably has 3 to 20 carbon atoms), an aryl group (preferably has 6 to 14 carbon atoms), a hydroxyl group, an alkoxy group, an ester group, an amide group, a uretane group, a ureido group, a thioether group, a sulfonamide group, and a sulfonic acid ester group. Additionally, the carbon constituting the cyclic organic group (the carbon contributing to ring formation) may be a carbonyl carbon.

[0579] R 201 , R 202 and R 203 Examples of organic groups include aryl groups, alkyl groups, and cycloalkyl groups.

[0580] R 201 , R 202 and R 203 It is preferable that at least one of them is an aryl group, and it is more preferable that all three are aryl groups. As for the aryl groups, heteroaryl groups such as indole residues and pyrrole residues are also possible, in addition to phenyl groups and naphthyl groups.

[0581] R 201 ~R 203 As for the alkyl group, a straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms is preferred, and a methyl group, ethyl group, n-propyl group, i-propyl group, or n-butyl group is more preferred.

[0582] R 201 ~R 203 As for the cycloalkyl group, a cycloalkyl group having 3 to 10 carbon atoms is preferred, and a cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, or cycloheptyl group is more preferred.

[0583] Examples of substituents that these groups may have include nitro groups, halogen atoms such as fluorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably 1 to 15 carbon atoms), cycloalkyl groups (preferably 3 to 15 carbon atoms), aryl groups (preferably 6 to 14 carbon atoms), alkoxycarbonyl groups (preferably 2 to 7 carbon atoms), acyl groups (preferably 2 to 12 carbon atoms), and alkoxycarbonyloxy groups (preferably 2 to 7 carbon atoms).

[0584] Among the general formula (ZII),

[0585] R 204 ~R 205 Each represents, independently, an aryl group, an alkyl group, or a cycloalkyl group.

[0586] R 204 ~R 205 As the aryl group, alkyl group, and cycloalkyl group, R in the general formula (ZI) described above. 201 ~R 203 It is the same as the group described as the aryl group, alkyl group, and cycloalkyl group.

[0587] R 204 ~R 205 As substituents that may have aryl groups, alkyl groups, and cycloalkyl groups, R in the compound (ZI) described above 201 ~R 203 Examples include aryl groups, alkyl groups, and cycloalkyl groups.

[0588] Z - represents a non-nucleated anion, and Z in the general formula (ZI) - Examples include those identical to the non-nucleated anion.

[0589] Preferred examples of the sulfonium cation in general formula (ZI) and the iodine cation in general formula (ZII) are shown below.

[0590] [Chemical Formula 40]

[0591]

[0592] Suitable photogenerators (P) include compounds represented by the following general formulas (BI) to (BV).

[0593] [Chemical Formula 41]

[0594]

[0595] Among the general formulas (BI)~(BV), M + It represents silver, a sulfonium cation, or an iodine cation. M in general formulas (BI) to (BV). + As such, it is preferable to include a suitable form of the sulfonium cation in the above general formula (ZI) or the iodine cation in the above general formula (ZII).

[0596] Among the general formula (BI), R 11 It represents a carbon-1 to carbon-8 alkyl group that may be substituted with silver or fluorine atoms. R 11 As for the group, an alkyl group having 1 to 8 carbon atoms substituted with at least one fluorine atom is preferred, a perfluoroalkyl group having 1 to 8 carbon atoms is more preferred, and a perfluoroalkyl group having 2 to 4 carbon atoms is more preferred.

[0597] Among general formulas (B-II), R 12 represents a hydrogen atom, a C1- to C6 alkyl group, or -CF3. R 12 A C3 to C6 alkyl group is preferred, and a straight-chain or branched-chain C3 to C6 alkyl group or a cyclohexyl group is preferred. Also, R 12 is, (-SO3 - Regarding the ) it is desirable to position it on the ortho or para position.

[0598] In general formula (B-II), q represents an integer from 1 to 5. q is preferably an integer from 2 to 4, and preferably 2 or 3.

[0599] In general formula (B-III), R 13It represents silver, a hydrogen atom, a fluorine atom, or CF3. R 13 It is preferable that at least one of them represents a fluorine atom or CF3.

[0600] In general formula (B-III), X2 represents -CO-O-, -CH2-CO-O-, or -CH2-O-CO-.

[0601] In general formula (B-III), r represents an integer from 0 to 2. r is preferably 0 or 1.

[0602] In general formula (B-III), s represents an integer from 1 to 3. s is preferably 1 or 2.

[0603] Among general formulas (B-IV), R 13 It represents silver, a hydrogen atom, a fluorine atom, or CF3. In general formula (B-IV), R 13 Preferably, at least one of them represents a fluorine atom or CF3, and 2 or more R 13 It is more preferable to represent this, a fluorine atom, or CF3.

[0604] Among general formulas (B-IV), R 14 ... indicates a monovalent polycyclic group that may have a substituent. As a monovalent polycyclic group, it is not particularly limited as long as it is a group composed of multiple ring structures; for example, a polycyclic group among the cyclic organic groups represented by A in the general formula (AN1) described above may be cited. More specifically, polycyclic cycloalkyl groups such as norbornene groups, tetracyclodecane groups, tetracyclodecane groups, and adamantane groups may be cited, and norbornene groups or adamantane groups are preferred.

[0605] Among the general formula (BV), R 13 It represents silver, a hydrogen atom, a fluorine atom, or CF3. In the general formula (BV), R 13Preferably, at least one of them represents a fluorine atom or CF3, and 2 or more R 13 It is more preferable to represent this, a fluorine atom, or CF3.

[0606] Among the general formula (BV), R 15 represents a monovalent organic group. R 15 Examples of monovalent organic groups that appear include alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, and alkenyl groups, and alkyl groups having 1 to 6 carbon atoms are preferred.

[0607] Among the general formula (BV), X 3 Silver, -O-CO-O-, -SO2-, or -SO2-NR 16 - indicates. R 16 Representing silver, a hydrogen atom, or an alkyl group, or R 15 It represents an alkylene group that forms a ring structure by combining with.

[0608] For compounds represented by the general formula (BV), X3 is -SO2-NR 16 - indicates, R 15 and R 16 The alkylene group having 4 to 6 carbon atoms formed by this bond, and -NR 16 It is desirable to form a heterocyclic ring that may have a substituent with the nitrogen atom in the air.

[0609] The composition preferably contains at least one selected from the group consisting of compounds represented by the general formulas (BI) to (BV) as a photogenerator (P).

[0610] As for the photogenerative agent (P), reference may be made to paragraphs

[0368] –

[0377] of Japanese Patent Publication No. 2014-41328 and paragraphs

[0240] –

[0262] of Japanese Patent Publication No. 2013-228681 (corresponding U.S. Patent Application Publication No. 2015 / 004533

[0339] ), and the contents thereof are incorporated herein. In addition, the following compounds may be cited as preferred embodiments, but are not limited thereto.

[0611] [Chemical Formula 42]

[0612]

[0613] [Chemical Formula 43]

[0614]

[0615] [Chemical Formula 44]

[0616]

[0617] In the composition, the content of the photogenerator (P) is not particularly limited, but with respect to the total solid content of the composition, 5 to 50 mass% is preferred, 10 to 40 mass% is more preferred, and 10 to 35 mass% is more preferred.

[0618] The photocatalytic agent (P) may be used as a single type or in combination of two or more types. When two or more photocatalytic agents (P) are used in combination, it is preferable that the total amount be within the above range.

[0619] ( Acid diffusion control agent (Q))

[0620] The composition may contain an acid diffusion control agent (Q).

[0621] The acid diffusion control agent (Q) acts as a quencher that traps the acid generated from the photogenerative agent (P) during exposure and suppresses the reaction of the acid-degradable resin in the unexposed area caused by the excess generated acid. As for the acid diffusion control agent (Q), examples may be used, such as a basic compound (DA), a basic compound whose basicity is reduced or lost upon irradiation with radiation (DB), an onium salt (DC) that becomes a relatively weak acid with respect to the photogenerative agent (P), a low-molecular-weight compound (DD) having a nitrogen atom and a group that is detached by the action of the acid, and an onium salt compound (DE) having a nitrogen atom in the cation portion.

[0622] In the composition, known acid diffusion control agents may be appropriately used. For example, known compounds disclosed in paragraphs

[0627] –

[0664] of U.S. Patent Application Publication No. 2016 / 0070167, paragraphs

[0095] –

[0187] of U.S. Patent Application Publication No. 2015 / 0004544, paragraphs

[0403] –

[0423] of U.S. Patent Application Publication No. 2016 / 0237190, and paragraphs

[0259] –

[0328] of U.S. Patent Application Publication No. 2016 / 0274458 may be suitably used as acid diffusion control agents (Q).

[0623] When an acid diffusion control agent (Q) is included in the composition, the content of the acid diffusion control agent (Q) (the total if multiple types exist) is preferably 0.1 to 10.0 mass% with respect to the total solid content of the composition, and more preferably 0.1 to 5.0 mass%.

[0624] In the composition, the acid diffusion control agent (Q) may be used alone or in combination with two or more types.

[0625] (Hypohydrophobic resin (E))

[0626] The composition may contain a hydrophobic resin (E) that is different from the resin (A).

[0627] The hydrophobic resin (E) is preferably designed to be localized on the surface of the resist film, but unlike surfactants, it does not necessarily need to have hydrophilic groups within its molecule and does not need to contribute to the uniform mixing of polar and non-polar substances.

[0628] Effects of adding a hydrophobic resin (E) include control of the static and dynamic contact angles of the resist film surface with respect to water, and suppression of out-gas.

[0629] The hydrophobic resin (E) preferably has one or more of “fluorine atoms,” “silicon atoms,” and “CH3 part structures included in the side chain portion of the resin” in terms of localization on the film surface layer, and it is more preferable to have two or more. In addition, the hydrophobic resin (E) preferably has hydrocarbon groups having 5 or more carbon atoms. These groups may be present in the main chain of the resin or may be substituted in the side chain.

[0630] When the hydrophobic resin (E) contains fluorine atoms and / or silicon atoms, the fluorine atoms and / or silicon atoms in the hydrophobic resin may be included in the main chain of the resin or in the side chain.

[0631] When the hydrophobic resin (E) has fluorine atoms, the partial structure having fluorine atoms is preferably an alkyl group having fluorine atoms, a cycloalkyl group having fluorine atoms, or an aryl group having fluorine atoms.

[0632] The alkyl group having a fluorine atom (preferably 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms) is a straight-chain or branched-chain alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may additionally have substituents other than fluorine atoms.

[0633] The cycloalkyl group having a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may additionally have substituents other than the fluorine atom.

[0634] Examples of aryl groups having a fluorine atom include phenyl groups and naphthyl groups in which at least one hydrogen atom is substituted with a fluorine atom, and may also have substituents other than fluorine atoms.

[0635] Examples of repeating units having fluorine atoms or silicon atoms include those exemplified in paragraph

[0519] of US2012 / 0251948.

[0636] In addition, as described above, it is also desirable that the hydrophobic resin (E) has a CH3 part structure in the side chain portion.

[0637] Here, the CH3 part structure having a side chain portion in the hydrophobic resin includes a CH3 part structure having an ethyl group and a propyl group, etc.

[0638] Meanwhile, methyl groups directly bonded to the main chain of the hydrophobic resin (E) (e.g., α-methyl groups of repeating units having a methacrylic acid structure) are not included in the CH3 substructure of the present invention because they contribute little to the surface localization of the hydrophobic resin (E) due to the influence of the main chain.

[0639] When the composition contains a hydrophobic resin (E), the content of the hydrophobic resin (E) is preferably 0.01 to 20 mass% with respect to the total solid content of the composition, and more preferably 0.1 to 15 mass%.

[0640] (Solvent (F))

[0641] The composition may contain a solvent (F).

[0642] When the composition is a radiation-reducing resin composition for EUV, the solvent (F) preferably contains at least one selected from the group consisting of (M1) propylene glycol monoalkyl ether carboxylate and (M2) propylene glycol monoalkyl ether, lactic acid ester, acetic acid ester, alkoxypropionic acid ester, chain ketone, cyclic ketone, lactone, and alkylene carbonate. In this case, the solvent may further contain components other than components (M1) and (M2).

[0643] A solvent containing component (M1) or (M2) is preferred because, when used in combination with the resin (A) described above, the coating properties of the composition are improved and a pattern with a small number of development defects can be formed.

[0644] As for the component (M1), at least one selected from the group consisting of propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether propionate, and propylene glycol monoethyl ether acetate is preferred, and propylene glycol monomethyl ether acetate (PGMEA) is more preferred.

[0645] As for the component (M2), the following is preferred.

[0646] As for the propylene glycol monoalkyl ether, propylene glycol monomethyl ether (PGME) or propylene glycol monoethyl ether is preferred.

[0647] As for the lactic acid ester, ethyl lactate, butyl lactate, or propyl lactate is preferred.

[0648] As for the acetic acid ester, methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, isoamyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, or 3-methoxybutyl acetate is preferred.

[0649] In addition, butyl butyl butyric acid is also desirable.

[0650] As an alkoxypropionic acid ester, methyl 3-methoxypropionate (MMP) or ethyl 3-ethoxypropionate (EEP) is preferred.

[0651] As chain ketones, 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutylketone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetoneylacetone, ionone, diacetoneyl alcohol, acetylcarbinol, acetophenone, methylnaphthyl ketone, or methylamyl ketone is preferred.

[0652] As for cyclic ketones, methylcyclohexanone, isophorone, or cyclohexanone is preferred.

[0653] As for the lactone, γ-butylolactone is preferred.

[0654] As for the alkylene carbonate, propylene carbonate is preferred.

[0655] As for component (M2), propylene glycol monomethyl ether (PGME), ethyl lactate, ethyl 3-ethoxypropionate, methylamyl ketone, cyclohexanone, butyl acetate, pentyl acetate, γ-butyrolactone, or propylene carbonate is more preferred.

[0656] As for the solvent (F), a mixture of two or more types of solvents containing propylene glycol monomethyl ether acetate is preferred.

[0657] The content of the solvent (F) in the composition is preferably set so that the solid content concentration is 0.5 to 30 mass%, and more preferably set so that it is 1 to 20 mass%. By doing so, the coating properties of the composition are better.

[0658] (Other additives)

[0659] The composition may further contain a surfactant, an alkali-soluble resin having a phenolic hydroxyl group, a dissolution inhibitor, a dye, a plasticizer, a photosensitizer, a light absorber, and / or a compound that promotes solubility in a developer (e.g., a phenolic compound having a weight average molecular weight (Mw) of 1000 or less, or a cycloaliphatic or aliphatic compound having a carboxyl group).

[0660] Phenolic compounds having a weight average molecular weight (Mw) of 1000 or less can be easily synthesized by a person skilled in the art by referring to methods described in, for example, Japanese Patent Publication No. Hei 4-122938, Japanese Patent Publication No. Hei 2-28531, U.S. Patent Publication No. 4,916,210, European Patent Publication No. 219294, etc.

[0661] Specific examples of cycloaliphatic or aliphatic compounds having a carboxyl group include carboxylic acid derivatives having a steroid structure such as cholic acid, deoxycholic acid, and litocholic acid, adamantane carboxylic acid derivatives, adamantane dicarboxylic acid, cyclohexane carboxylic acid, and cyclohexane dicarboxylic acid.

[0662] Examples

[0663] The present invention will be described in more detail below based on the examples. The materials, usage amounts, ratios, processing details, and processing procedures shown in the following examples may be appropriately modified without departing from the spirit of the present invention. Accordingly, the scope of the present invention should not be interpreted as being limited by the examples shown below.

[0664] In addition, in the preparation of the drug solution of the examples and comparative examples, the handling of the container, preparation, filling, storage, and analytical measurement of the drug solution were all carried out in a clean room meeting ISO Class 2 or 1 standards.

[0665] (filter)

[0666] As for the filter, the following filter was used.

[0667] · "PP 200nm": Polypropylene filter, made of polypropylene, pore diameter 200nm

[0668] · "IEX 50nm": Ion exchange resin filter, manufactured by Entegris, pore diameter 50nm

[0669] · "PTFE 30nm": Polytetrafluoroethylene filter, manufactured by Entegris, pore diameter 30nm

[0670] · "PTFE 50nm": Polytetrafluoroethylene filter, manufactured by Entegris, pore diameter 50nm

[0671] · "UPE 1nm": Ultra-high molecular weight polyethylene filter, manufactured by Pall, pore diameter 1nm

[0672] · "UPE 3nm": Ultra-high molecular weight polyethylene filter, manufactured by Pall, pore diameter 3nm

[0673] <Retreat Offering>

[0674] For the preparation of the drug solutions of the examples and comparative examples, the solvents listed in the "Type of Solvent" column of the "Raw Material" column of Table 1 were used as the substances to be purified. In addition, each solvent was a commercially available product.

[0675] <Refining Procedure>

[0676] For the above-mentioned purified material, the distillation purification treatment described in Table 1 was performed.

[0677] In addition, "Condition 1" in the "Distillation" column of Table 1 indicates that atmospheric distillation was performed once using a distillation column (theoretical number of stages: 15 stages), "Condition 2" indicates that atmospheric distillation was performed once using a distillation column (theoretical number of stages: 10 stages), "Condition 3" indicates that atmospheric distillation was performed once using a distillation column (theoretical number of stages: 25 stages), "Condition 4" indicates that atmospheric distillation was performed once using a distillation column (theoretical number of stages: 30 stages), and "Condition 5" indicates that atmospheric distillation was performed once using a distillation column (theoretical number of stages: 5 stages).

[0678] Next, the distilled purified product was stored in a storage tank, and the purified product stored in the storage tank was filtered by passing it through filters 1 to 3 listed in Table 1 in this order, and then stored in a storage tank.

[0679] Next, as shown in Table 1 below, in an embodiment where the "first circulation" column is "present," the material to be purified stored in a storage tank was filtered through filters 4 to 5 (filter 4 in the case of filter 4 only) as described in Table 1, and the material to be purified after being filtered through filter 5 (after being filtered through filter 4 in the case of filter 4 only) was circulated to the upstream side of filter 4 and filtered again through filters 4 to 5 to perform a circulation filtration treatment. After the circulation filtration treatment, the chemical solution was placed in a container.

[0680] In addition, as shown in Table 1 below, in the embodiment where the "first circulation" column is "none," the above circulation treatment was not performed, and the product to be purified stored in the storage tank was filtered with the filter 4 described in Table 1.

[0681] In addition, during the aforementioned series of purification processes, the liquid-contacting parts of various devices (e.g., distillation towers, piping, storage tanks, etc.) that come into contact with the material to be purified were made of electrolytically polished stainless steel.

[0682] The above-mentioned drug solution contained the following four specific compounds. Additionally, specific compounds A and B correspond to the compounds represented by formula (1), and specific compounds C and D correspond to the compounds represented by formula (2).

[0683] [Chemical Formula 45]

[0684]

[0685] The content of organic and metal components of the drug solution was measured using the method shown below.

[0686] Content of specific compounds

[0687] The content of a specific compound in the drug solution was measured using a gas chromatography-mass spectrometry (GC / MS) device (Agilent, GC: 7890B, MS: 5977B EI / CI MSD).

[0688] In addition, as described below, the column "Specific Compound A" in Table 1 indicates the content of Specific Compound A in the drug solution, the column "Specific Compound B" indicates the content of Specific Compound B in the drug solution, the column "Specific Compound C" indicates the content of Specific Compound C in the drug solution, and the column "Specific Compound D" indicates the content of Specific Compound D in the drug solution.

[0689] <Metal Content>

[0690] The content of metal components (metal ions, metal-containing particles) in the chemical solution was measured by methods using ICP-MS and SP-ICP-MS.

[0691] The device used the following device.

[0692] · Manufacturer: PerkinElmer

[0693] · Model: NexION350S

[0694] The following analysis software was used for the analysis.

[0695] · Syngistix Nano Application Module Dedicated to "SP-ICP-MS"

[0696] ·Syngistix for ICP-MS software

[0697] Evaluation Method

[0698] First, an organic anti-reflective film forming composition ARC29SR (manufactured by Nissan Chemical Co., Ltd.) was applied to a silicon substrate with a diameter of 300 mm, and baked at 205°C for 60 seconds to form an anti-reflective film with a thickness of 78 nm.

[0699] To improve coating properties, a pre-wet liquid (FFEM agent, cyclohexanone) was applied to the surface of the anti-reflection film side of a silicon substrate having an anti-reflection film formed thereon, and spin coating was performed.

[0700] Next, any one of compositions 1 to 4 described below was applied onto the anti-reflective film, and pre-baking was performed according to the conditions listed in the "Pre-bak" column of Table 1 to form a film with a thickness of 50 nm.

[0701] Next, using an ArF excimer laser scanner (NA0.75), 25 [mJ / cm²] of the coating film 2 Pattern exposure was performed in ]. Afterwards, it was heated at 120°C for 60 seconds. Subsequently, it was developed by puddle for 30 seconds using the alkaline developer listed in Table 1. Then, a positive resist pattern was formed by rotating the silicon substrate at a rotational speed of 4000 rpm for 30 seconds. Next, the positive resist pattern was washed with water. Next, the positive resist pattern was cleaned using the chemical solution described in each example and comparative example. Afterward, the obtained positive resist pattern was post-baked at 200°C for 300 seconds. Through the above process, an L / S pattern with a line / space ratio of 1:1 was obtained. In addition, the line width was 65 nm.

[0702] By observing the space portion of the L / S pattern obtained above, residue defects (residue degree) were evaluated according to the following criteria.

[0703] "A": The number of residue defects was 5 or less per wafer.

[0704] "B": The number of residue defects was greater than 5 / wafer and less than or equal to 10 / wafer.

[0705] "C": The number of residue defects was greater than 10 / wafer and less than or equal to 20 / wafer.

[0706] "D": The number of residue defects was greater than 20 / wafer and less than or equal to 30 / wafer.

[0707] "E": The number of residue defects exceeded 30 per wafer.

[0708] (Composition 1)

[0709] Acid-degradable resin (resin represented by the following formula (weight average molecular weight (Mw): 7500): the values ​​listed in each repeating unit represent mole%): 100 parts by mass

[0710] [Chemical Formula 46]

[0711]

[0712] Photogenerator shown below: 8 parts by mass

[0713] [Chemical Formula 47]

[0714]

[0715] The quenchers shown below: 5 parts by mass (the mass ratios are set from left to right as 0.1:0.3:0.3:0.2). In addition, among the quenchers below, the polymer type quencher has a weight-average molecular weight (Mw) of 5000. Also, the numerical value indicated for each repeating unit represents the molar ratio.

[0716] [Chemical Formula 48]

[0717]

[0718] The hydrophobic resins shown below: 4 parts by mass (the mass ratio is set to 0.5:0.5 from left to right). In addition, among the hydrophobic resins below, the weight-average molecular weight (Mw) of the hydrophobic resin on the left is 7000, and the weight-average molecular weight (Mw) of the hydrophobic resin on the right is 8000. In addition, for each hydrophobic resin, the numerical value indicated in each repeating unit represents the molar ratio.

[0719] [Chemical Formula 49]

[0720]

[0721] solvent:

[0722] PGMEA (propylene glycol monomethyl ether acetate): 3 parts by mass

[0723] Cyclohexanone: 600 parts by mass

[0724] γ-BL (γ-butylolactone): 100 parts by mass

[0725] (Composition 2)

[0726] Acid-degradable resin (resin represented by the following formula (weight average molecular weight (Mw): 8000): the value indicated in each repeating unit represents mole%): 100 parts by mass

[0727] [Chemical Formula 50]

[0728]

[0729] Photogeneratives shown below: 12 parts by mass (mass ratios were set to 0.5:0.5, in order from left to right).

[0730] [Chemical Formula 51]

[0731]

[0732] Quencher shown below: 5 mass parts (mass ratios were set to 0.3:0.7 from left to right.)

[0733] [Chemical Formula 52]

[0734]

[0735] The hydrophobic resins shown below: 5 parts by mass (the mass ratios are set to 0.8:0.2 in order from top to bottom). In addition, among the hydrophobic resins below, the weight-average molecular weight (Mw) of the top hydrophobic resin is 8000, and the weight-average molecular weight (Mw) of the bottom hydrophobic resin is 6000. In addition, for each hydrophobic resin, the numerical value indicated in each repeating unit represents the molar ratio.

[0736] [Chemical Formula 53]

[0737]

[0738] [Chemical Formula 54]

[0739]

[0740] solvent:

[0741] PGMEA (propylene glycol monomethyl ether acetate): 3 parts by mass

[0742] Cyclohexanone: 600 parts by mass

[0743] γ-BL (γ-butylolactone): 100 parts by mass

[0744] (Composition 3)

[0745] Acid-degradable resin (resin represented by the following formula (weight average molecular weight (Mw): 8000): the value indicated in each repeating unit represents mole%): 100 parts by mass

[0746] [Chemical Formula 55]

[0747]

[0748] Photogenerator shown below: 15 parts by mass

[0749] [Chemical Formula 56]

[0750]

[0751] Quencher shown below: 7 parts by mass (mass ratios are set to 1:1, in order from left to right.)

[0752] [Chemical Formula 57]

[0753]

[0754] Hydrophobic resins shown below: 20 parts by mass (the mass ratio is 3:7, in order from top). Also, among the hydrophobic resins below, the weight-average molecular weight (Mw) of the top hydrophobic resin is 10,000, and the weight-average molecular weight (Mw) of the bottom hydrophobic resin is 7,000. Also, in the hydrophobic resins shown at the bottom, the molar ratios of each repeating unit are 0.67 and 0.33, in order from left.

[0755] [Chemical Formula 58]

[0756]

[0757] [Chemical Formula 59]

[0758]

[0759] solvent:

[0760] PGMEA (propylene glycol monomethyl ether acetate): 50 parts by mass

[0761] PGME (propylene glycol monomethyl ether): 100 parts by mass

[0762] 2-Heptanone: 100 parts by mass

[0763] γ-BL (γ-butylolactone): 500 parts by mass

[0764] (Composition 4)

[0765] Acid-degradable resin (resin represented by the following formula (weight average molecular weight (Mw): 6500): the values ​​listed in each repeating unit represent mole%): 80 parts by mass

[0766] [Chemical Formula 60]

[0767]

[0768] Photogenerator shown below: 15 parts by mass

[0769] [Chemical Formula 61]

[0770]

[0771] Quencher indicated below: 5 parts by mass

[0772] [Chemical Formula 62]

[0773]

[0774] Hydrophobic resin shown below (weight average molecular weight (Mw) 5000): 60 parts by mass

[0775] [Chemical Formula 63]

[0776]

[0777] solvent:

[0778] PGMEA (propylene glycol monomethyl ether acetate): 70 parts by mass

[0779] HBM (methyl-2-hydroxybutyrate): 100 parts by mass

[0780] Cyclohexanone: 700 parts by mass

[0781] In Table 1, the column "Alkaline Developer" indicates the components included in the alkaline developer, and each symbol represents the following.

[0782] "TMAH": Tetramethylammonium hydroxide

[0783] "EDTA": Ethylenediamine tetraacetic acid

[0784] "DTPA": Diethylenetriamine pentacetic acid

[0785] "DBSA": p-dodecylbenzenesulfonic acid

[0786] "Surfynol 440": Surfynol 440

[0787] "Surfynol 480": Surfynol 480

[0788] The concentration in the "Alkaline Developer" column indicates the concentration of each compound relative to the total amount of the alkaline developer.

[0789] In addition, each alkaline developer contains water in addition to the components listed in Table 1.

[0790] The "ClogP" column in Table 1 indicates the ClogP value of the solvent used (e.g., methyl isobutylcarbinol in Example 1). However, for Example 25, the ClogP value of "isopropyl alcohol" is indicated.

[0791] Also, the "vapor pressure (kPa)" listed in Table 1 represents the vapor pressure of the solvent used at 25°C. However, for Example 25, it represents the vapor pressure of "isopropyl alcohol" at 25°C.

[0792] Also, the "number of carbons" listed in Table 1 indicates the number of carbons contained in the solvent used. However, for Example 25, it indicates the number of carbons of "isopropyl alcohol".

[0793] Also, the "C / O ratio" listed in Table 1 indicates the ratio of the number of carbon atoms to the number of oxygen atoms contained in the solvent used. However, for Example 25, the above ratio of "isopropyl alcohol" is indicated.

[0794] In addition, the "Solvent Concentration (Mass%)" column in Table 1 indicates the content (mass%) of the solvent (alcohol-based solvent) relative to the total mass of the liquid in each example and comparative example. However, for Example 25, the content of "isopropyl alcohol" is indicated.

[0795] Also, the column "Metal component (mass ppt)" in Table 1 indicates the content of the metal component (mass ppt) relative to the total mass of the liquid in each example and comparative example.

[0796] Also, the column "Concentration of specific compound A (mass ppb)" in Table 1 indicates the content of specific compound A (mass ppb) relative to the total mass of the drug solution in each example and comparative example.

[0797] Also, the column "Concentration of specific compound B (mass ppb)" in Table 1 indicates the content of specific compound B (mass ppb) relative to the total mass of the drug solution in each example and comparative example.

[0798] Also, the column "Concentration of specific compound C (mass ppb)" in Table 1 indicates the content of specific compound C (mass ppb) relative to the total mass of the drug solution in each example and comparative example.

[0799] Also, the column "Concentration of specific compound D (mass ppb)" in Table 1 indicates the content of specific compound D (mass ppb) relative to the total mass of the drug solution in each example and comparative example.

[0800] Also, the "Total Amount (Mass ppb)" column in Table 1 indicates the total content (mass ppb) of specific compounds A to D.

[0801] [Table 1]

[0802]

[0803] [Table 2]

[0804]

[0805] [Table 3]

[0806]

[0807] [Table 4]

[0808]

[0809] [Table 5]

[0810]

[0811] Among Tables 1 (the 1) to 1 (the 5), the data regarding each example and comparative example are shown across each row.

[0812] For example, in Example 1, methyl isobutylcarbinol is used as shown in Table 1 (Part 1), the distillation condition is "Condition 1" as shown in Table 1 (Part 2), the solvent concentration (mass%) of the liquid is 99.95 mass% as shown in Table 1 (Part 3), the type of composition is "Composition 1" as shown in Table 1 (Part 4), and the residue evaluation is "A" as shown in Table 1 (Part 5). The same applies to other examples and comparative examples.

[0813] As shown in Table 1 above, the desired effect is obtained according to the drug solution of the present invention.

[0814] Among them, from a comparison of Examples 1 to 4, it was confirmed that the effect is superior when the content of the metal component is 0.10 to 100 mass ppt relative to the total mass of the liquid.

[0815] In addition, from a comparison of Examples 5 and 6 with other examples, it was confirmed that the effect is superior when the content of a specific compound (total content) is 0.010 to 5.0 mass ppb relative to the total mass of the drug solution.

[0816] In addition, from a comparison of Examples 7 to 10, it was confirmed that the effect is superior when the content of the quaternary ammonium salt is 0.75 to 7.5 mass% relative to the total mass of the alkaline developer.

[0817] In addition, from a comparison of Examples 19 to 23, it was confirmed that the effect is superior when the heating temperature of process G (pre-bake) is 80 to 120°C and the heating time is 30 to 180 seconds.

[0818] In addition, from a comparison of Examples 24 and 25, it was confirmed that the effect is superior when the content of the alcohol-based solvent is 85.000 to 99.999 mass% relative to the total mass of the liquid.

[0819] In addition, from a comparison of Examples 36 and 40 with other examples, it was confirmed that when the ratio of the number of carbon atoms to the number of oxygen atoms contained in the alcohol-based solvent is 3.0 or higher (when the ClogP value of the alcohol-based solvent is -0.50 to 3.00), the effect is superior.

[0820] From Table 1 above, it was confirmed that the effect is superior when the alcohol-based solvent is methyl isobutylcarbinol, 3-methyl-1-butanol, or 2,4-dimethyl-3-pentanol.

Claims

Claim 1 A chemical solution containing a specific compound selected from the group consisting of an alcohol-based solvent having a ClogP value greater than -1.00 and less than or equal to 3.00, a compound represented by Formula (1), and a compound represented by Formula (2), wherein the content of the alcohol-based solvent is 99.95 mass% or more and 99.999999903995 mass% or less with respect to the total mass of the chemical solution, the content of the specific compound is 0.96 to 1.9 mass ppb with respect to the total mass of the chemical solution, and further contains a metal component, wherein the content of the metal component is 0.05 to 112 mass ppt with respect to the total mass of the chemical solution. [Chemical Formula 1] R 1 and R 2 Each independently represents an alkyl group. 3 and R 5 represents, respectively, a hydrogen atom or an alkyl group. 4 represents a hydrogen atom or a hydroxyl group. R 6 It represents a silver, hydrogen atom, or alkoxy group. Claim 2 A chemical solution according to claim 1, wherein the alcohol-based solvent contains 3 to 12 carbon atoms. Claim 3 A chemical solution according to claim 1 or claim 2, wherein the ratio of the number of carbon atoms to the number of oxygen atoms contained in the alcohol-based solvent is 3.0 or higher. Claim 4 A chemical solution according to claim 1 or claim 2, wherein the vapor pressure of the alcohol-based solvent at 25°C is 0.01 to 10.0 kPa. Claim 5 A chemical solution according to claim 1 or claim 2, wherein the alcohol-based solvent is selected from the group consisting of methyl isobutylcarbinol, 2,6-dimethyl-4-heptanol, 2,4-diethyl-1,5-pentanediol, 2-ethyl-1-hexanol, 3-methyl-1,5-pentanediol, 2-octanol, 3-methyl-1-butanol, 2,4-dimethyl-3-pentanol, 2-methylpentan-2,4-diol, 3,5,5-trimethyl-1-hexanol, 2-methylcyclohexanol, 1,3-butanediol, 2-ethyl-1,3-hexanediol, 2-butyl-2-ethyl-1,3-propanediol, 3-methyl-1,3-butanediol, and trimethylolpropane. Claim 6 delete Claim 7 A pharmaceutical solution according to claim 1 or claim 2, wherein the alcohol-based solvent is methyl isobutylcarbinol, 3-methyl-1-butanol, or 2,4-dimethyl-3-pentanol. Claim 8 A rinse solution containing the drug solution described in claim 1 or claim 2. Claim 9 A method for forming a resist pattern comprising: a process A for forming a film on a substrate using a photosensitive or radiation-sensitive resin composition; a process B for exposing the film to light; a process C for developing the exposed film using an alkaline developer; and a process D for cleaning the developed film using a rinse solution described in claim 8. Claim 10 A resist pattern forming method according to claim 9, further comprising a process E of cleaning the developed film using water between process C and process D. Claim 11 A method for forming a resist pattern according to claim 9, wherein the alkaline developer contains a quaternary ammonium salt. Claim 12 A method for forming a resist pattern according to claim 11, wherein the content of the quaternary ammonium salt is 0.75 to 7.5 mass% with respect to the total mass of the alkaline developer. Claim 13 A chemical solution according to claim 1, containing a compound represented by formula (1) and a compound represented by formula (2) as the specific compound. Claim 14 In claim 1, the compound represented by formula (2) is contained as the specific compound, and in formula (2), the R 3 and R 5 ga is an alkyl group, and R 4 α is a hydroxyl group, and the above R 6 A chemical solution in which hydrogen atoms are present. Claim 15 A chemical solution containing an alcohol-based solvent having a ClogP value greater than -1.00 and less than or equal to 3.00, and a specific compound comprising a compound represented by Formula (1) and a compound represented by Formula (2), wherein the content of the alcohol-based solvent is 99.95 mass% or more and 99.999999903995 mass% or less with respect to the total mass of the chemical solution, the content of the specific compound is 0.96 to 1.9 mass ppb with respect to the total mass of the chemical solution, and further contains a metal component, wherein the content of the metal component is 0.05 to 112 mass ppt with respect to the total mass of the chemical solution. [Chemical Formula 1] R 1 and R 2 Each independently represents an alkyl group. 3 and R 5 represents, respectively, a hydrogen atom or an alkyl group. 4 represents a hydrogen atom or a hydroxyl group. R 6 It represents a silver, hydrogen atom, or alkoxy group. Claim 16 A chemical solution containing an alcohol-based solvent having a ClogP value greater than -1.00 and less than or equal to 3.00, and a specific compound comprising the following specific compounds A to D, wherein the content of the alcohol-based solvent is 99.95 mass% or more and 99.999999903995 mass% or less with respect to the total mass of the chemical solution, the content of the specific compound is 0.96 to 1.9 mass ppb with respect to the total mass of the chemical solution, and further contains a metal component, wherein the content of the metal component is 0.05 to 112 mass ppt with respect to the total mass of the chemical solution.

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