Pattern forming method and electronic device manufacturing method

Abstract

Provided are a pattern formation method and a method for producing an electronic device, with which long-period undulation of a formed pattern is suppressed. The pattern formation method includes: a step 1 for producing a laminate having a substrate, a resist layer, an intermediate layer and a conductive layer in that order; a step 2 for irradiating the laminate with an electron beam in the shape of a pattern; and a step 3 for forming a pattern by performing a development process on the laminate irradiated with the electron beam, wherein the thickness of the resist layer is 150 nm or less.

Description

[Technical Field]

[0001] The present invention relates to a pattern forming method and a method for manufacturing an electronic device. [Background technology]

[0002] In recent years, electron beam lithography has been attracting attention as an exposure technique with higher resolution. Patent Document 1 discloses a method for forming a pattern using a laminate having a resist layer, an intermediate layer, and a conductive layer in this order, in order to suppress reaction between the resist layer and the conductive layer. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2010-153641 Summary of the Invention [Problem to be solved by the invention]

[0004] On the other hand, with the further miniaturization of patterns, there has been a demand in recent years for suppression of long-period undulations in the longitudinal direction of the formed patterns. The long-period undulations are a phenomenon in which the position of the line center fluctuates in the longitudinal direction of the pattern while the pattern width remains approximately constant.

[0005] The present inventors have found that when a pattern is formed using the laminate specifically described in Patent Document 1, the above-mentioned long-period waviness occurs and that an improvement is necessary.

[0006] In view of the above circumstances, an object of the present invention is to provide a pattern forming method in which long-period waviness in the formed pattern is suppressed. Another object of the present invention is to provide a method for manufacturing an electronic device. [Means for solving the problem]

[0007] The present inventors have found that the above problems can be solved by the following configuration.

[0008] (1) Step 1 of preparing a laminate having a substrate, a resist layer, an intermediate layer, and a conductive layer in this order; Step 2 of irradiating the laminate with an electron beam in a pattern; and step 3 of developing the laminate irradiated with the electron beam to form a pattern. A pattern forming method, wherein the resist layer has a film thickness of 150 nm or less. (2) The pattern forming method according to (1), wherein step 1 comprises step 1A of applying a composition for forming a resist layer onto a substrate to form a resist layer, step 1B of applying a composition for forming an intermediate layer onto the resist layer to form an intermediate layer, and step 1C of applying a composition for forming a conductive layer onto the intermediate layer to form a conductive layer. (3) The resist layer contains a resin whose solubility in a developer changes under the action of an acid, The pattern forming method according to (1) or (2), which satisfies at least one of requirements 1 and 2 described below. (4) When requirement 1 is satisfied, the content of the compound is 10% by mass or more based on the total mass of the resist layer; The pattern forming method according to (3), wherein when requirement 2 is satisfied, the content of the repeating unit is 10% by mass or more based on the total mass of the resist layer. (5) The pattern forming method according to (3) or (4), wherein the compound capable of generating an acid upon irradiation with an electron beam generates an acid having a pKa of −1.00 or less. (6) The size of the acid generated from the compound that generates an acid upon irradiation with an electron beam is 240 Å. 3 The pattern forming method according to any one of (3) to (5) above. (7) The pattern forming method according to any one of (3) to (6), wherein the compound that generates an acid upon irradiation with an electron beam is one or more compounds selected from the compounds (I) and (II) described below. (8) The pattern forming method according to any one of (3) to (7), wherein the resin contains a repeating unit having an acid group. (9) The pattern forming method according to (8), wherein the acid group is selected from the group consisting of a phenolic hydroxyl group and a fluorinated alcohol group. (10) The pattern forming method according to any one of (3) to (9), wherein the resin contains a repeating unit having a group that decomposes under the action of an acid to generate a carboxyl group. (11) The pattern forming method according to any one of (3) to (9), wherein the resin contains a repeating unit having a group that decomposes under the action of an acid to generate a phenolic hydroxyl group. (12) The pattern forming method according to any one of (3) to (11), wherein the resin contains a repeating unit having at least one group selected from the group consisting of a lactone group, a sultone group, and a carbonate group. (13) The pattern forming method according to any one of (1) to (12), wherein the resist layer contains a basic compound whose basicity is reduced or eliminated by irradiation with an electron beam. (14) The basic compound includes an onium salt compound that generates an acid upon irradiation with an electron beam, The pattern forming method according to (13), wherein the acid generated from the onium salt is weaker than the acid generated from the compound that generates an acid upon irradiation with an electron beam. (15) The pattern forming method according to any one of (1) to (14), wherein the intermediate layer is soluble in a developer used in the development treatment. (16) The intermediate layer is a layer formed using a composition for forming an intermediate layer, The pattern forming method according to any one of (1) to (15), wherein the composition for forming an intermediate layer contains a resin that is soluble in a developer used in the development treatment and a solvent that does not substantially dissolve the resist layer. (17) The solvent that does not substantially dissolve the resist layer is a monohydric alcohol having 4 to 10 carbon atoms, The pattern forming method according to (16), wherein the alkyl group is selected from the group consisting of ethers having 6 to 14 carbon atoms and hydrocarbons having 8 to 14 carbon atoms. (18) The pattern forming method according to (16) or (17), wherein the resin soluble in the developer used in the development treatment contains a repeating unit having at least one group selected from the group consisting of a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfonic acid group, and a sulfonamide group. (19) A method for manufacturing an electronic device, comprising the pattern forming method according to any one of (1) to (18). [Effects of the Invention]

[0009] According to the present invention, it is possible to provide a pattern forming method in which long-period waviness in the formed pattern is suppressed. The present invention also provides a method for manufacturing an electronic device. DETAILED DESCRIPTION OF THE INVENTION

[0010] The present invention will be described in detail below. The following description of the components may be based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment. In the present specification, when a group (atomic group) is represented without specifying whether it is substituted or unsubstituted, it encompasses both unsubstituted and substituted groups, unless it is contrary to the spirit of the present invention. For example, the term "alkyl group" encompasses not only unsubstituted alkyl groups (unsubstituted alkyl groups) but also substituted alkyl groups (substituted alkyl groups). In addition, the term "organic group" used herein refers to a group containing at least one carbon atom. Unless otherwise specified, the substituent is preferably a monovalent substituent. In this specification, the symbol "to" is used to mean that the numerical values ​​before and after it are included as the lower limit and upper limit. The bonding direction of divalent groups represented in this specification is not limited unless otherwise specified. For example, when Y is -COO- in a compound represented by the formula "XYZ", Y may be -CO-O- or -O-CO-. In addition, the above compound may be "X-CO-OZ" or "XO-CO-Z".

[0011] 1Å is 1×10 -10 m.

[0012] In this specification, (meth)acrylate refers to acrylate and methacrylate, and (meth)acrylic refers to acrylic and methacrylic. In this specification, the weight-average molecular weight (Mw), number-average molecular weight (Mn), and polydispersity (also referred to as molecular weight distribution) (Mw / Mn) of a resin are defined as polystyrene-equivalent values ​​measured using a Gel Permeation Chromatography (GPC) apparatus (HLC-8120GPC manufactured by Tosoh Corporation) (solvent: tetrahydrofuran, flow rate (sample injection amount): 10 μL, column: TSK gel Multipore HXL-M manufactured by Tosoh Corporation, column temperature: 40°C, flow rate: 1.0 mL / min, detector: refractive index detector).

[0013] As used herein, the acid dissociation constant (pKa) refers to the pKa in an aqueous solution, and specifically, is a value determined by calculation using the following software package 1 based on a database of Hammett's substituent constants and known literature values. Software package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs).

[0014] On the other hand, pKa can also be calculated by molecular orbital calculations. This method is based on the thermodynamic cycle and calculates the pKa of H in aqueous solution. +One method is to calculate the dissociation free energy. + The dissociation free energy can be calculated by, for example, DFT (density functional theory), but various other methods have been reported in the literature, and the method is not limited to these. There are several software programs that can perform DFT, such as Gaussian 16.

[0015] As described above, the pKa in this specification refers to a value calculated using the software package 1 based on a database of Hammett's substituent constants and known literature values. However, if the pKa cannot be calculated by this method, a value obtained by Gaussian 16 based on DFT (density functional theory) will be used. Furthermore, as mentioned above, the pKa in this specification refers to the "pKa in aqueous solution," but when the pKa in aqueous solution cannot be calculated, the "pKa in dimethyl sulfoxide (DMSO) solution" will be used.

[0016] In this specification, examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. In this specification, the solid content refers to all components other than the solvent. Even if the solid content is in a liquid state, it is counted as the solid content.

[0017] A characteristic feature of the pattern forming method of the present invention is that the thickness of the resist layer in a laminate having a substrate, a resist layer, an intermediate layer, and a conductive layer in this order is 150 nm or less. The inventors have found that by making the thickness of the resist layer thinner than conventional methods, long-period waviness in the formed pattern can be suppressed.

[0018] The pattern forming method of the present invention includes the following steps 1 to 3. Step 1: A step of preparing a laminate having a substrate, a resist layer, an intermediate layer, and a conductive layer in this order. Step 2: Irradiating the laminate with an electron beam in a pattern Step 3: A step of developing the laminate irradiated with electron beams to form a pattern. First, the procedure of each step will be described below.

[0019] <Process 1> Step 1 is a step of producing a laminate having a substrate, a resist layer, an intermediate layer, and a conductive layer in this order. The substrate, resist layer, intermediate layer, and conductive layer are described in detail below.

[0020] The method for producing the laminate is not particularly limited, and examples thereof include a method in which compositions for forming each layer are sequentially applied onto a substrate to sequentially form each layer, and a method in which a resist layer, an intermediate layer, and a conductive layer, which are separately prepared, are sequentially transferred onto a substrate. In particular, from the viewpoint of excellent productivity, it is preferable that step 1 comprises step 1A of applying a resist layer-forming composition onto a substrate to form a resist layer, step 1B of applying an intermediate layer-forming composition onto the resist layer to form an intermediate layer, and step 1C of applying a conductive layer-forming composition onto the intermediate layer to form a conductive layer. The above steps 1A to 1C will be described in detail below.

[0021] Step 1A is a step of forming a resist layer by applying a composition for forming a resist layer onto a substrate. The resist layer forming composition will be described in detail later. The method for applying the resist layer-forming composition onto the substrate is not particularly limited, and examples thereof include application methods using a spinner or a coater, etc. Among these, spin application using a spinner is preferred. The rotation speed when spin coating using a spinner is preferably 1000 to 3000 rpm.

[0022] If necessary, after the application of the resist layer forming composition, a drying treatment may be carried out. The drying method may be, for example, a method of drying by heating. Heating can be carried out by means provided in a normal exposure machine and / or developing machine, or may be carried out using a hot plate or the like. The heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C. The heating time is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds.

[0023] The resist layer is preferably insoluble in the solvent contained in the composition for forming an intermediate layer used in step 1B. The term "insoluble" means that when a 100 nm thick resist layer is immersed in 30 ml of the solvent contained in the composition for forming an intermediate layer for 30 seconds, the amount of film loss of the resist layer is 3.0 nm or less. The amount of film loss of the resist layer is preferably 1.5 nm or less.

[0024] The thickness of the resist layer is 150 nm or less. In particular, it is preferably 120 nm or less, and more preferably 90 nm or less, in that long-period waviness of the formed pattern is further suppressed (hereinafter simply referred to as "the point where the effect of the present invention is better"). There is no particular lower limit, but it is preferably 20 nm or more, and more preferably 30 nm or more. The thickness of the resist layer can be measured by measuring the thickness at any 10 points on the resist layer, calculating the arithmetic average of the thicknesses at the 10 points, and using the average value as the thickness of the resist layer. In other words, the thickness of the resist layer is the average thickness.

[0025] Step 1B is a step of forming an intermediate layer by applying a composition for forming an intermediate layer onto the resist layer. The composition for forming the intermediate layer will be described in detail later. The method for applying the composition for forming an intermediate layer onto the resist layer is not particularly limited, and examples thereof include the method of applying the composition for forming a resist layer described above onto a substrate. If necessary, after the application of the composition for forming an intermediate layer, a drying treatment may be carried out. The drying treatment method may be any drying treatment method that may be carried out after application of the composition for forming a resist layer.

[0026] The intermediate layer is preferably insoluble in the solvent contained in the conductive layer-forming composition used in step 1C. The term "insoluble" means that when a 100 nm thick intermediate layer is immersed in 30 ml of the solvent contained in the conductive layer-forming composition for 30 seconds, the thickness loss of the intermediate layer is 3.0 nm or less, and preferably 1.5 nm or less.

[0027] The intermediate layer is preferably soluble in the developer used in the development treatment carried out in step 3 described below. The term "soluble" means that when a 100 nm thick intermediate layer is immersed for 30 seconds in a developer (30 ml) used in development, the thickness loss of the intermediate layer is 98 nm or more. Preferably, the thickness loss of the intermediate layer is 100 nm.

[0028] The thickness of the intermediate layer is not particularly limited, but is preferably 20 to 100 nm, more preferably 40 to 80 nm, in terms of achieving better effects of the present invention. The thickness of the intermediate layer can be measured by measuring the thickness of the intermediate layer at any 10 points, calculating the arithmetic average of the thicknesses at the 10 points, and using the average value as the thickness of the intermediate layer. In other words, the thickness of the intermediate layer is the average thickness.

[0029] Step 1C is a step of forming a conductive layer by applying a conductive layer-forming composition onto the intermediate layer. The conductive layer-forming composition will be described in detail later. The method for applying the conductive layer-forming composition onto the intermediate layer is not particularly limited, and examples thereof include a method for applying the above-mentioned resist layer-forming composition onto a substrate. If necessary, after the application of the conductive layer-forming composition, a drying treatment may be carried out. The drying treatment method may be any drying treatment method that may be carried out after application of the composition for forming a resist layer.

[0030] The conductive layer is preferably soluble in the developer used in the development treatment carried out in step 3 described below. The term "soluble" means that when a 100 nm thick conductive layer is immersed for 30 seconds in a developer (30 ml) used in development, the conductive layer loses at least 98 nm in thickness. Preferably, the conductive layer loses at least 100 nm in thickness.

[0031] The thickness of the conductive layer is not particularly limited, but is preferably 10 to 60 nm, more preferably 20 to 40 nm, in terms of achieving better effects of the present invention. The thickness of the conductive layer can be measured by measuring the thickness at any 10 points on the conductive layer, calculating the arithmetic mean of the thicknesses at the 10 points, and using the average value as the thickness of the conductive layer. In other words, the thickness of the conductive layer is the average thickness.

[0032] <Process 2> Step 2 is a step of irradiating the laminate with an electron beam in a pattern. The region of the laminate to be irradiated with the electron beam is patterned, for example, the electron beam is irradiated in a line shape. The electron beam is usually irradiated onto the laminate from the conductive layer side.

[0033] After the electron beam irradiation, it is preferable to perform baking (heating) before carrying out step 3. Baking promotes the reaction in the area irradiated with the electron beam, resulting in better sensitivity and pattern shape. The heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C. The heating time is preferably from 10 to 1000 seconds, more preferably from 10 to 500 seconds. Heating can be carried out by means provided in a normal exposure machine and / or developing machine, and may also be carried out using a hot plate or the like.

[0034] <Process 3> Step 3 is a step of developing the laminate irradiated with the electron beam to form a pattern. The developer used in the development process may be an alkaline developer or a developer containing an organic solvent (hereinafter also referred to as an organic developer).

[0035] Examples of development methods include a method in which a substrate is immersed in a tank filled with developer for a certain period of time (dip method), a method in which developer is piled up on the surface of the substrate by surface tension and left to stand for a certain period of time for development (puddle method), a method in which developer is sprayed onto the surface of the substrate (spray method), and a method in which developer is continuously dispensed by scanning a developer dispensing nozzle at a constant speed onto a substrate that is rotating at a constant speed (dynamic dispense method). After the development step, a step of stopping the development while replacing the solvent with another solvent may be carried out. The development time is preferably from 10 to 300 seconds, more preferably from 20 to 120 seconds. The temperature of the developer is preferably from 0 to 50°C, more preferably from 15 to 35°C.

[0036] The alkaline developer is preferably an aqueous alkaline solution containing an alkali. The type of alkaline aqueous solution is not particularly limited, and examples thereof include alkaline aqueous solutions containing quaternary ammonium salts such as tetramethylammonium hydroxide, inorganic alkalis, primary amines, secondary amines, tertiary amines, alcohol amines, cyclic amines, etc. Among these, an aqueous solution of a quaternary ammonium salt such as tetramethylammonium hydroxide (TMAH) is preferred as the alkaline developer. The alkaline developer may contain an appropriate amount of alcohols, surfactants, etc. The alkali concentration of the alkaline developer is usually 0.1 to 20% by mass, and the pH of the alkaline developer is usually 10.0 to 15.0.

[0037] The organic developer is preferably a developer containing at least one organic solvent selected from the group consisting of ketone-based solvents, ester-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, and hydrocarbon-based solvents.

[0038] The developer may contain a mixture of two or more of the above solvents, or may contain water or a solvent other than the above solvents. The water content of the developer as a whole is preferably less than 50% by mass, more preferably less than 20% by mass, and even more preferably less than 10% by mass, and particularly preferably substantially no water. The content of the organic solvent in the organic developer is preferably from 50 to 100% by mass, more preferably from 80 to 100% by mass, and even more preferably from 90 to 100% by mass, based on the total amount of the developer.

[0039] <Other processes> The pattern formation method preferably includes, after step 3, a step of washing with a rinse liquid.

[0040] The rinse liquid used in the rinse step after the step of developing using an alkaline developer may be, for example, pure water. A suitable amount of a surfactant may be added to the rinse solution.

[0041] The rinse liquid used in the rinse step after the development step using an organic developer is not particularly limited as long as it does not dissolve the pattern, and a solution containing a general organic solvent can be used. As the rinse liquid, a rinse liquid containing at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents is preferred.

[0042] The method for the rinsing step is not particularly limited, and examples thereof include a method in which a rinsing liquid is continuously discharged onto a substrate rotating at a constant speed (spin coating method), a method in which a substrate is immersed in a tank filled with a rinsing liquid for a certain period of time (dip method), and a method in which a rinsing liquid is sprayed onto the surface of the substrate (spray method). The pattern formation method of the present invention may also include a heating step (post-bake) after the rinsing step. This step removes the developer and rinsing solution remaining between and within the pattern due to baking. This step also has the effect of annealing the resist pattern and improving the surface roughness of the pattern. The heating temperature in the heating step after the rinsing step is preferably 40 to 250°C (preferably 90 to 200°C), and the heating time is preferably 10 seconds to 3 minutes (preferably 30 to 120 seconds).

[0043] Furthermore, the formed pattern may be used as a mask to perform an etching process on the substrate. That is, the pattern formed in step 3 may be used as a mask to process the substrate and form a pattern on the substrate. Although the method for processing the substrate is not particularly limited, a preferred method is to form a pattern on the substrate by dry etching the substrate using the pattern formed in step 3 as a mask. The dry etching is preferably oxygen plasma etching.

[0044] The various materials used in the pattern formation method of the present invention (e.g., the resist layer-forming composition, intermediate layer-forming composition, conductive layer-forming composition, developer, and rinse) preferably do not contain impurities such as metals. The content of impurities contained in these materials is preferably 1 ppm by mass or less, more preferably 10 ppb by mass or less, even more preferably 100 ppt by mass or less, particularly preferably 10 ppt by mass or less, and most preferably 1 ppt by mass or less. Here, examples of metal impurities include Na, K, Ca, Fe, Cu, Mg, Al, Li, Cr, Ni, Sn, Ag, As, Au, Ba, Cd, Co, Pb, Ti, V, W, and Zn.

[0045] Examples of methods for removing impurities such as metals from various materials include filtration using a filter. Details of filtration using a filter are described in paragraph

[0321] of WO 2020 / 004306.

[0046] Methods for reducing impurities such as metals contained in various materials include, for example, selecting raw materials with a low metal content as the raw materials for the various materials, filtering the raw materials for the various materials, and performing distillation under conditions that minimize contamination as much as possible, for example by lining the inside of the apparatus with Teflon (registered trademark).

[0047] In addition to filtration, impurities may be removed using an adsorbent, or a combination of filtration and an adsorbent may be used. Known adsorbents can be used as the adsorbent, including inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon. In order to reduce impurities such as metals contained in the various materials, it is necessary to prevent the incorporation of metal impurities during the manufacturing process. Whether metal impurities have been sufficiently removed from the manufacturing equipment can be confirmed by measuring the content of metal components contained in the cleaning solution used to clean the manufacturing equipment. The content of metal components contained in the used cleaning solution is preferably 100 parts per trillion (ppt) by mass or less, more preferably 10 ppt by mass or less, and even more preferably 1 ppt by mass or less.

[0048] A conductive compound may be added to an organic processing liquid such as a rinse liquid to prevent breakdown of chemical liquid piping and various parts (filters, O-rings, tubes, etc.) due to static charging and subsequent static discharge. The conductive compound is not particularly limited, but examples include methanol. The amount added is not particularly limited, but in order to maintain favorable development or rinsing properties, it is preferably 10% by mass or less, and more preferably 5% by mass or less. For example, SUS (stainless steel), or various pipes coated with antistatic polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) can be used for the chemical liquid piping. Similarly, antistatic polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) can be used for the filter and O-ring.

[0049] <Electronic device manufacturing method> The present invention also relates to a method for manufacturing an electronic device, which includes the above-described pattern formation method, and an electronic device manufactured by this manufacturing method. The electronic device of the present invention is suitably mounted in electrical and electronic equipment (such as home appliances, OA (Office Automation), media-related equipment, optical equipment, and communication equipment).

[0050] <Resist layer> The resist layer is a layer used to form a pattern by irradiation with an electron beam and development processing. The resist layer may contain a resin (hereinafter also referred to as resin (A)) whose solubility in a developer changes under the action of an acid. The resin (A) will be described in detail later. The resin (A) preferably contains a repeating unit having a residue formed by removing one hydrogen atom from a compound that generates an acid upon irradiation with an electron beam. In other words, the resist layer preferably satisfies the following requirement 2. Requirement 2: The resin (A) contains a repeating unit (hereinafter also referred to as a specific unit) having a residue formed by removing one hydrogen atom from a compound that generates an acid upon irradiation with an electron beam.

[0051] When the above requirement 2 is satisfied, the content of the specific unit is preferably 10% by mass or more, more preferably 20% by mass or more, relative to the total mass of the resist layer. There is no particular upper limit, but it is preferably 50% by mass or less.

[0052] As will be described later, the resist layer preferably contains a compound that generates an acid upon irradiation with an electron beam. In other words, the resist layer preferably satisfies the following requirement 1. Requirement 1: The resist layer contains a compound that generates an acid when irradiated with an electron beam. When the above requirement 1 is satisfied, the content of the compound that generates an acid upon irradiation with an electron beam is preferably 10% by mass or more, more preferably 20% by mass or more, based on the total mass of the resist layer. There is no particular upper limit, but it is preferably 50% by mass or less.

[0053] <Resin (A)> The resist layer may contain a resin (A). The resin (A) may be a resin whose solubility in a developer increases under the action of an acid, or a resin whose solubility in a developer decreases under the action of an acid. As the resin (A), a resin having a group that decomposes under the action of an acid and increases its polarity (hereinafter also referred to as an "acid-decomposable group") is usually preferred, and a resin containing a repeating unit having an acid-decomposable group is more preferred. Therefore, in the pattern formation method of the present invention, typically, when an alkaline developer is used as the developer, a positive pattern is preferably formed, and when an organic developer is used as the developer, a negative pattern is preferably formed. As the repeating unit having an acid-decomposable group, in addition to the repeating unit having an acid-decomposable group described below, a repeating unit having an acid-decomposable group containing an unsaturated bond is preferred.

[0054] (Repeating unit having an acid-decomposable group) The acid-decomposable group refers to a group that decomposes under the action of an acid to generate a polar group. The acid-decomposable group preferably has a structure in which a polar group is protected by a leaving group that is released under the action of an acid. That is, the resin (A) contains a repeating unit having a group that decomposes under the action of an acid to generate a polar group. The polarity of a resin containing this repeating unit increases under the action of an acid, increasing its solubility in alkaline developers and decreasing its solubility in organic solvents. The polar group is preferably an alkali-soluble group, and examples thereof include acidic groups such as a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfonic acid group, a phosphate group, a sulfonamide group, a sulfonylimide group, an (alkylsulfonyl)(alkylcarbonyl)methylene group, an (alkylsulfonyl)(alkylcarbonyl)imide group, a bis(alkylcarbonyl)methylene group, a bis(alkylcarbonyl)imide group, a bis(alkylsulfonyl)methylene group, a bis(alkylsulfonyl)imide group, a tris(alkylcarbonyl)methylene group, and a tris(alkylsulfonyl)methylene group, as well as alcoholic hydroxyl groups. Of these, the polar group is preferably a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), or a sulfonic acid group. Therefore, the resin (A) preferably contains a repeating unit having a group that decomposes under the action of an acid to generate a carboxyl group, or a repeating unit having a group that decomposes under the action of an acid to generate a phenolic hydroxyl group. The repeating unit having a group that decomposes under the action of an acid to generate a phenolic hydroxyl group preferably has a group represented by the formula (Y1) described below as a leaving group that is eliminated under the action of an acid.

[0055] Examples of the leaving group that is eliminated by the action of an acid include groups represented by formulae (Y1) to (Y4). Formula (Y1):-C(Rx1)(Rx2)(Rx3) Formula (Y2):-C(=O)OC(Rx1)(Rx2)(Rx3) Formula (Y3):-C(R 36 )(R 37 )(OR 38 ) Formula (Y4):-C(Rn)(H)(Ar)

[0056] In formula (Y1) and formula (Y2), Rx1 to Rx3 each independently represent an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), an alkenyl group (linear or branched), or an aryl group (monocyclic or polycyclic). When all of Rx1 to Rx3 are alkyl groups (linear or branched), it is preferable that at least two of Rx1 to Rx3 are methyl groups. In particular, it is preferable that Rx1 to Rx3 each independently represent a linear or branched alkyl group, and it is more preferable that Rx1 to Rx3 each independently represent a linear alkyl group. Two of Rx1 to Rx3 may be bonded to form a monocycle or polycycle. The alkyl groups of Rx1 to Rx3 are preferably alkyl groups having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group. The cycloalkyl groups of Rx1 to Rx3 are preferably monocyclic cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group, and polycyclic cycloalkyl groups such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. The aryl group of Rx1 to Rx3 is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group. The alkenyl group of Rx1 to Rx3 is preferably a vinyl group. The ring formed by combining two of Rx1 to Rx3 is preferably a cycloalkyl group. The cycloalkyl group formed by combining two of Rx1 to Rx3 is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group, and more preferably a monocyclic cycloalkyl group having 5 to 6 carbon atoms. In the cycloalkyl group formed by combining two of Rx1 to Rx3, one of the methylene groups constituting the ring may be replaced with a heteroatom such as an oxygen atom, a group containing a heteroatom such as a carbonyl group, or a vinylidene group. Furthermore, in these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group. In the group represented by formula (Y1) or formula (Y2), for example, Rx1 is preferably a methyl group or an ethyl group, and Rx2 and Rx3 are bonded to form the above-mentioned cycloalkyl group.

[0057] In formula (Y3), R 36 ~R 38 R each independently represents a hydrogen atom or a monovalent organic group. 37 and R 38 may be bonded to each other to form a ring. Examples of the monovalent organic group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group. R 36 is also preferably a hydrogen atom. The alkyl group, cycloalkyl group, aryl group, and aralkyl group may contain a group containing a heteroatom such as an oxygen atom and / or a heteroatom such as a carbonyl group. For example, in the alkyl group, cycloalkyl group, aryl group, and aralkyl group, one or more methylene groups may be replaced with a group containing a heteroatom such as an oxygen atom and / or a heteroatom such as a carbonyl group. Also, R 38 may bond with another substituent on the main chain of the repeating unit to form a ring. 38 The group formed by bonding together the repeating unit and another substituent carried by the main chain of the repeating unit is preferably an alkylene group such as a methylene group.

[0058] Formula (Y3) is preferably a group represented by the following formula (Y3-1).

[0059] [ka]

[0060] Here, L1 and L2 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group combining these (for example, a group combining an alkyl group and an aryl group). M represents a single bond or a divalent linking group. Q represents an alkyl group which may contain a heteroatom, a cycloalkyl group which may contain a heteroatom, an aryl group which may contain a heteroatom, an amino group, an ammonium group, a mercapto group, a cyano group, an aldehyde group, or a group combining these (for example, a group combining an alkyl group and a cycloalkyl group). The alkyl and cycloalkyl groups may, for example, have one methylene group replaced with a heteroatom such as an oxygen atom or a group containing a heteroatom such as a carbonyl group. Preferably, 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 formed by combining an alkylene group and an aryl group. At least two of Q, M, and L1 may be bonded to form a ring (preferably a 5- or 6-membered ring). From the viewpoint of pattern miniaturization, L2 is preferably a secondary or tertiary alkyl group, more preferably a tertiary alkyl group. Examples of secondary alkyl groups include an isopropyl group, a cyclohexyl group, and a norbornyl group, and examples of tertiary alkyl groups include a tert-butyl group and an adamantane group. In these embodiments, Tg (glass transition temperature) and activation energy are increased, thereby ensuring film strength and suppressing fogging.

[0061] In formula (Y4), Ar represents an aromatic ring group. Rn represents an alkyl group, a cycloalkyl group, or an aryl group. Rn and Ar may be bonded to each other to form a non-aromatic ring. Ar is preferably an aryl group.

[0062] In terms of excellent acid decomposition properties of the repeating unit, when a non-aromatic ring is directly bonded to the polar group (or a residue thereof) in the leaving group protecting the polar group, it is also preferable that the ring atom in the non-aromatic ring adjacent to the ring atom directly bonded to the polar group (or a residue thereof) does not have a halogen atom such as a fluorine atom as a substituent.

[0063] Other leaving groups that are eliminated by the action of an acid include a 2-cyclopentenyl group having a substituent (such as an alkyl group), such as a 3-methyl-2-cyclopentenyl group, and a cyclohexyl group having a substituent (such as an alkyl group), such as a 1,1,4,4-tetramethylcyclohexyl group.

[0064] The repeating unit having an acid-decomposable group is also preferably a repeating unit represented by formula (A).

[0065] [ka]

[0066] L1 represents a divalent linking group which may have a fluorine atom or an iodine atom, R1 represents a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group which may have a fluorine atom or an iodine atom, or an aryl group which may have a fluorine atom or an iodine atom, and R2 represents a leaving group which is eliminated by the action of an acid and which may have a fluorine atom or an iodine atom, provided that at least one of L1, R1, and R2 has a fluorine atom or an iodine atom. L1 represents a divalent linking group which may have a fluorine atom or an iodine atom. Examples of the divalent linking group which may have a fluorine atom or an iodine atom include -CO-, -O-, -S-, -SO-, -SO2-, hydrocarbon groups which may have a fluorine atom or an iodine atom (for example, an alkylene group, a cycloalkylene group, an alkenylene group, an arylene group, etc.), and linking groups in which a plurality of these groups are linked together. Among these, L1 is preferably -CO-, an arylene group, or -arylene group-alkylene group having a fluorine atom or an iodine atom-, and more preferably -CO- or -arylene group-alkylene group having a fluorine atom or an iodine atom-. The arylene group is preferably a phenylene group. The alkylene group may be linear or branched. The number of carbon atoms in the alkylene group is not particularly limited, but is preferably 1 to 10, and more preferably 1 to 3. The total number of fluorine atoms and iodine atoms contained in the alkylene group having a fluorine atom or an iodine atom is not particularly limited, but is preferably 2 or more, more preferably 2 to 10, and even more preferably 3 to 6.

[0067] R1 represents a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group which may have a fluorine atom or an iodine atom, or an aryl group which may have a fluorine atom or an iodine atom. The alkyl group may be linear or branched. 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. The total number of fluorine atoms and iodine atoms contained in the alkyl group having a fluorine atom or an iodine atom is not particularly limited, but is preferably 1 or more, more preferably 1 to 5, and even more preferably 1 to 3. The alkyl group may contain a heteroatom other than a halogen atom, such as an oxygen atom.

[0068] R2 represents a leaving group which is eliminated by the action of an acid and which may have a fluorine atom or an iodine atom. Examples of the leaving group which may have a fluorine atom or an iodine atom include the leaving groups represented by the above formulae (Y1) to (Y4) and which have a fluorine atom or an iodine atom.

[0069] The repeating unit having an acid-decomposable group is also preferably a repeating unit represented by formula (AI).

[0070] [ka]

[0071] In formula (AI), Xa1 represents a hydrogen atom or an alkyl group which may have a substituent. T represents a single bond or a divalent linking group. Rx1 to Rx3 each independently represent an alkyl group (straight-chain or branched), a cycloalkyl group (monocyclic or polycyclic), an alkenyl group (straight-chain or branched), or an aryl group (monocyclic or polycyclic). However, when all of Rx1 to Rx3 are alkyl groups (straight-chain or branched), it is preferable that at least two of Rx1 to Rx3 are methyl groups. Two of Rx1 to Rx3 may be bonded to form a monocyclic or polycyclic ring (such as a monocyclic or polycyclic cycloalkyl group).

[0072] The alkyl group represented by Xa1, which may have a substituent, is, for example, a methyl group or -CH2-R 11 Examples of such groups include groups represented by R 11 represents a halogen atom (such as a fluorine atom), a hydroxyl group, or a monovalent organic group, and examples thereof include an alkyl group having 5 or less carbon atoms which may be substituted with a halogen atom, an acyl group having 5 or less carbon atoms which may be substituted with a halogen atom, and an alkoxy group having 5 or less carbon atoms which may be substituted with a halogen atom, with an alkyl group having 3 or less carbon atoms being preferred, and a methyl group being more preferred. Xa1 is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

[0073] Examples of the divalent linking group for T include an alkylene group, an aromatic ring group, a -COO-Rt- group, and an -O-Rt- group, where Rt represents an alkylene group or a cycloalkylene group. 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, more preferably a -CH2- group, a -(CH2)2- group, or a -(CH2)3- group.

[0074] The alkyl group of Rx1 to Rx3 is preferably an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group. The cycloalkyl groups of Rx1 to Rx3 are preferably monocyclic cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group, or polycyclic cycloalkyl groups such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. The aryl group of Rx1 to Rx3 is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group. The alkenyl group of Rx1 to Rx3 is preferably a vinyl group. The cycloalkyl group formed by combining two of Rx1 to Rx3 is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group. Also, a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group is preferred. Of these, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is preferred. In the cycloalkyl group formed by combining two of Rx1 to Rx3, for example, one of the methylene groups constituting the ring may be replaced with a heteroatom such as an oxygen atom, a group containing a heteroatom such as a carbonyl group, or a vinylidene group. Furthermore, in these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group. In the repeating unit represented by formula (AI), for example, Rx1 is a methyl group or an ethyl group, and Rx2 and Rx3 are bonded to form the above-mentioned cycloalkyl group.

[0075] When each of the above groups has a substituent, examples of the substituent include an alkyl group (having 1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (having 1 to 4 carbon atoms), a carboxyl group, and an alkoxycarbonyl group (having 2 to 6 carbon atoms).The number of carbon atoms in the substituent is preferably 8 or less.

[0076] The repeating unit represented by formula (AI) is preferably an acid-decomposable (meth)acrylic acid tertiary alkyl ester repeating unit (a repeating unit in which Xa1 represents a hydrogen atom or a methyl group and T represents a single bond).

[0077] Specific examples of repeating units having an acid-decomposable group are shown below, but the present invention is not limited thereto. In the formula, Xa1 represents H, CH3, CF3, or CH2OH, and Rxa and Rxb each independently represent a linear or branched alkyl group having 1 to 5 carbon atoms.

[0078] [ka]

[0079] [ka]

[0080] [ka]

[0081] [ka]

[0082] [ka]

[0083] The resin (A) may contain, as the repeating unit having an acid-decomposable group, a repeating unit having an acid-decomposable group containing an unsaturated bond. The repeating unit having an acid-decomposable group containing an unsaturated bond is preferably a repeating unit represented by formula (B).

[0084] [ka]

[0085] In formula (B), Xb represents a hydrogen atom, a halogen atom, or an alkyl group which may have a substituent. L represents a single bond or a divalent linking group which may have a substituent. Ry1 to Ry3 each independently represent a linear or branched alkyl group, a monocyclic or polycyclic cycloalkyl group, an alkenyl group, an alkynyl group, or a monocyclic or polycyclic aryl group, with the proviso that at least one of Ry1 to Ry3 represents an alkenyl group, an alkynyl group, a monocyclic or polycyclic cycloalkenyl group, or a monocyclic or polycyclic aryl group. Two of Ry1 to Ry3 may be bonded to form a monocyclic or polycyclic ring (such as a monocyclic or polycyclic cycloalkyl group or cycloalkenyl group).

[0086] The alkyl group represented by Xb, which may have a substituent, is, for example, a methyl group or -CH2-R 11 Examples of such groups include groups represented by R 11 represents a halogen atom (such as a fluorine atom), a hydroxyl group, or a monovalent organic group, and examples thereof include an alkyl group having 5 or less carbon atoms which may be substituted with a halogen atom, an acyl group having 5 or less carbon atoms which may be substituted with a halogen atom, and an alkoxy group having 5 or less carbon atoms which may be substituted with a halogen atom, with an alkyl group having 3 or less carbon atoms being preferred, and a methyl group being more preferred. Xb is preferably a hydrogen atom, a fluorine atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

[0087] Examples of the divalent linking group represented by L include a -Rt- group, a -CO- group, a -COO-Rt- group, a -COO-Rt-CO- group, a -Rt-CO- group, and a -O-Rt- group, where Rt represents an alkylene group, a cycloalkylene group, or an aromatic ring group, and an aromatic ring group is preferred. L is preferably a -Rt- group, a -CO- group, a -COO-Rt-CO- group, or a -Rt-CO- group. Rt may have a substituent such as a halogen atom, a hydroxyl group, or an alkoxy group. An aromatic group is preferred.

[0088] The alkyl groups Ry1 to Ry3 are preferably alkyl groups having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group. The cycloalkyl groups of Ry1 to Ry3 are preferably monocyclic cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group, or polycyclic cycloalkyl groups such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. The aryl group of Ry1 to Ry3 is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group. The alkenyl group of Ry1 to Ry3 is preferably a vinyl group. The alkynyl group of Ry1 to Ry3 is preferably an ethynyl group. The cycloalkenyl groups of Ry1 to Ry3 are preferably monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, which have a structure containing a double bond in part thereof. The cycloalkyl group formed by combining two of Ry1 to Ry3 is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, an adamantyl group, etc. Among these, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferred. In the cycloalkyl group or cycloalkenyl group formed by combining two of Ry1 to Ry3, for example, one of the methylene groups constituting the ring may be replaced with a heteroatom such as an oxygen atom, a carbonyl group, a group containing a heteroatom such as a -SO2- group or a -SO3- group, a vinylidene group, or a combination thereof. Furthermore, in these cycloalkyl groups or cycloalkenyl groups, one or more of the ethylene groups constituting the cycloalkane ring or cycloalkene ring may be replaced with a vinylene group. In the repeating unit represented by formula (B), for example, Ry1 is a methyl group, ethyl group, vinyl group, allyl group, or aryl group, and Ry2 and Rx3 are bonded to form the above-mentioned cycloalkyl group or cycloalkenyl group.

[0089] When each of the above groups has a substituent, examples of the substituent include an alkyl group (having 1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (having 1 to 4 carbon atoms), a carboxyl group, and an alkoxycarbonyl group (having 2 to 6 carbon atoms).The number of carbon atoms in the substituent is preferably 8 or less.

[0090] The repeating unit represented by formula (B) is preferably an acid-decomposable (meth)acrylic acid tertiary ester repeating unit (a repeating unit in which Xb represents a hydrogen atom or a methyl group and L represents a -CO- group), an acid-decomposable hydroxystyrene tertiary alkyl ether repeating unit (a repeating unit in which Xb represents a hydrogen atom or a methyl group and L represents a phenyl group), or an acid-decomposable styrene carboxylic acid tertiary ester repeating unit (a repeating unit in which Xb represents a hydrogen atom or a methyl group and L represents a -Rt-CO- group (Rt is an aromatic group)).

[0091] Specific examples of repeating units having an acid-decomposable group containing an unsaturated bond are shown below, but the present invention is not limited to these. In the formula, Xb and L1 represent any of the substituents and linking groups described above, Ar represents an aromatic group, R represents a substituent such as a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR''' or -COOR''': R''' represents an alkyl group or a fluorinated alkyl group having 1 to 20 carbon atoms), or a carboxyl group, R' represents a linear or branched alkyl group, a monocyclic or polycyclic cycloalkyl group, an alkenyl group, an alkynyl group, or a monocyclic or polycyclic aryl group, Q represents a heteroatom such as an oxygen atom, a carbonyl group, a group containing a heteroatom such as an -SO2- group or an -SO3- group, a vinylidene group, or a combination thereof, and n and m represent integers of 0 or more.

[0092] [ka]

[0093] [ka]

[0094] [ka]

[0095] [ka]

[0096] The content of the repeating units having an acid-decomposable group is preferably 10 mol% or more, more preferably 20 mol% or more, and even more preferably 30 mol% or more, based on the total repeating units in the resin (A), and the upper limit thereof is preferably 90 mol% or less, more preferably 80 mol% or less, even more preferably 70 mol% or less, and particularly preferably 60 mol% or less, based on the total repeating units in the resin (A).

[0097] The content of the repeating units having an acid-decomposable group containing an unsaturated bond is preferably 10 mol% or more, more preferably 20 mol% or more, and even more preferably 30 mol% or more, based on all repeating units in the resin (A).The upper limit is preferably 80 mol% or less, more preferably 70 mol% or less, and particularly preferably 60 mol% or less, based on all repeating units in the resin (A).

[0098] The resin (A) may contain at least one repeating unit selected from the group consisting of Group A below and / or at least one repeating unit selected from the group consisting of Group B below. Group A: A group consisting of the following repeating units (20) to (29). (20) A repeating unit having an acid group, as described below (21) A repeating unit having neither an acid-decomposable group nor an acid group, but having a fluorine atom, a bromine atom, or an iodine atom, as described below. (22) A repeating unit having a lactone group, a sultone group, or a carbonate group, as described later. (23) A repeating unit having an acid-generating group, as described later. (24) A repeating unit represented by formula (V-1) or formula (V-2) described below: (25) A repeating unit represented by formula (A) described below (26) A repeating unit represented by formula (B) described below (27) A repeating unit represented by formula (C) described below (28) A repeating unit represented by formula (D) described below (29) A repeating unit represented by formula (E) described below Group B: A group consisting of the following repeating units (30) to (32). (30) A repeating unit having at least one group selected from a lactone group, a sultone group, a carbonate group, a hydroxyl group, a cyano group, and an alkali-soluble group, as described below. (31) A repeating unit having an alicyclic hydrocarbon structure and not exhibiting acid decomposition, as described below. (32) A repeating unit represented by formula (III) described below, which does not have either a hydroxyl group or a cyano group.

[0099] The resin (A) preferably has an acid group, and as described below, preferably contains a repeating unit having an acid group. The definition of the acid group will be explained later together with preferred embodiments of the repeating unit having an acid group. When the resin (A) has an acid group, the interaction between the resin (A) and the acid generated from the acid generator is more excellent. As a result, the diffusion of the acid is further suppressed, and the cross-sectional shape of the formed pattern can become more rectangular.

[0100] (Repeating unit having an acid group) The resin (A) may contain a repeating unit having an acid group. The acid group preferably has a pKa of 13 or less. The acid dissociation constant of the acid group is preferably 13 or less, more preferably 3 to 13, and even more preferably 5 to 10. When the resin (A) has an acid group with a pKa of 13 or less, the content of the acid group in the resin (A) is not particularly limited, but is often 0.2 to 6.0 mmol / g. Among these, 0.8 to 6.0 mmol / g is preferred, 1.2 to 5.0 mmol / g is more preferred, and 1.6 to 4.0 mmol / g is even more preferred. When the acid group content is within the above range, development proceeds well, and the formed pattern shape is excellent, and the resolution is also excellent. The acid group is preferably, for example, a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), a sulfonic acid group, a sulfonamide group, or an isopropanol group, more preferably a phenolic hydroxyl group or a fluorinated alcohol group, and even more preferably a fluorinated alcohol group. In addition, one or more (preferably one to two) fluorine atoms of the hexafluoroisopropanol group may be substituted with a group other than a fluorine atom (such as an alkoxycarbonyl group). The acid group thus formed, -C(CF3)(OH)-CF2-, is also preferred. In addition, one or more fluorine atoms may be substituted with a group other than a fluorine atom to form a ring containing -C(CF3)(OH)-CF2-. The repeating unit having an acid group is preferably a repeating unit different from the repeating units described above. The repeating unit having an acid group may have a fluorine atom or an iodine atom.

[0101] Examples of the repeating unit having an acid group include the following repeating units.

[0102] [ka]

[0103] The repeating unit having an acid group is preferably a repeating unit represented by the following formula (1).

[0104] [ka]

[0105] In formula (1), A represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, or a cyano group. 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, and when there are multiple Rs, they may be the same or different. When there are multiple Rs, they may join together to form a ring. R is preferably a hydrogen atom. a represents an integer of 1 to 3. b represents an integer of 0 to (5-a).

[0106] Examples of repeating units having an acid group are shown below: wherein a represents 1 or 2.

[0107] [ka]

[0108] [ka]

[0109] [ka]

[0110] [ka]

[0111] Among the above repeating units, the repeating units specifically described below are preferred: In the formula, R represents a hydrogen atom or a methyl group, and a represents 2 or 3.

[0112] [ka]

[0113] [ka]

[0114] The content of the repeating units having an acid group is preferably 10 mol% or more, more preferably 15 mol% or more, based on all repeating units in the resin (A), and the upper limit thereof is preferably 70 mol% or less, more preferably 65 mol% or less, and even more preferably 60 mol% or less, based on all repeating units in the resin (A).

[0115] (Repeating units having neither an acid-decomposable group nor an acid group, and having a fluorine atom, a bromine atom, or an iodine atom) In addition to the above-mentioned <repeating unit having an acid-decomposable group> and <repeating unit having an acid group>, the resin (A) may also have a repeating unit that has neither an acid-decomposable group nor an acid group, but has a fluorine atom, a bromine atom, or an iodine atom (hereinafter also referred to as unit X). Furthermore, the <repeating unit that has neither an acid-decomposable group nor an acid group, but has a fluorine atom, a bromine atom, or an iodine atom> is preferably different from other types of repeating units belonging to Group A, such as the <repeating unit having a lactone group, a sultone group, or a carbonate group> and the <repeating unit having an acid-generating group> described below.

[0116] The unit X is preferably a repeating unit represented by formula (C).

[0117] [ka]

[0118] L5 represents a single bond or an ester group. R9 represents a hydrogen atom or an alkyl group which may have a fluorine atom or an iodine atom. R 10 represents a hydrogen atom, an alkyl group which may have a fluorine atom or an iodine atom, a cycloalkyl group which may have a fluorine atom or an iodine atom, an aryl group which may have a fluorine atom or an iodine atom, or a group which is a combination of these.

[0119] Examples of repeating units having a fluorine atom or an iodine atom are shown below.

[0120] [ka]

[0121] The content of units X is preferably 0 mol% or more, more preferably 5 mol% or more, and even more preferably 10 mol% or more, based on all repeating units in resin (A), and the upper limit is preferably 50 mol% or less, more preferably 45 mol% or less, and even more preferably 40 mol% or less, based on all repeating units in resin (A).

[0122] The total content of repeating units containing at least one of a fluorine atom, a bromine atom, and an iodine atom in the repeating units of the resin (A) is preferably 10 mol% or more, more preferably 20 mol% or more, even more preferably 30 mol% or more, and particularly preferably 40 mol% or more, based on all repeating units of the resin (A). There is no particular upper limit, but it is, for example, 100 mol% or less based on all repeating units of the resin (A). Examples of the repeating unit containing at least one of a fluorine atom, a bromine atom, and an iodine atom include a repeating unit having a fluorine atom, a bromine atom, or an iodine atom and an acid-decomposable group, a repeating unit having a fluorine atom, a bromine atom, or an iodine atom and an acid group, and a repeating unit having a fluorine atom, a bromine atom, or an iodine atom.

[0123] (Repeating units having a lactone group, a sultone group, or a carbonate group) The resin (A) may have a repeating unit (hereinafter also referred to as "unit Y") having at least one group selected from the group consisting of a lactone group, a sultone group, and a carbonate group. It is also preferred that the unit Y does not have a hydroxyl group or an acid group such as a hexafluoropropanol group.

[0124] The lactone group or sultone group may have a lactone structure or a sultone structure. The lactone structure or the sultone structure is preferably a 5- to 7-membered cyclic lactone structure or a 5- to 7-membered cyclic sultone structure. Among these, a 5- to 7-membered cyclic lactone structure to which another ring structure is fused in the form of a bicyclo structure or a spiro structure, or a 5- to 7-membered cyclic sultone structure to which another ring structure is fused in the form of a bicyclo structure or a spiro structure, is more preferred. Resin (A) preferably contains a repeating unit having a lactone group or a sultone group, which is formed by abstracting one or more hydrogen atoms from a ring atom of a lactone structure represented by any one of the following formulae (LC1-1) to (LC1-21) or a sultone structure represented by any one of the following formulae (SL1-1) to (SL1-3). Furthermore, the lactone group or sultone group may be directly bonded to the main chain, for example, the ring atoms of the lactone group or sultone group may constitute the main chain of the resin (A).

[0125] [ka]

[0126] The lactone structure or sultone structure may have a substituent (Rb2). Preferred examples of the substituent (Rb2) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, a carboxyl group, a halogen atom, a cyano group, and an acid-decomposable group. n2 represents an integer of 0 to 4. When n2 is 2 or greater, multiple Rb2s may be different from each other, or multiple Rb2s may be bonded to form a ring.

[0127] Examples of repeating units having a group containing a lactone structure represented by any one of formulas (LC1-1) to (LC1-21) or a sultone structure represented by any one of formulas (SL1-1) to (SL1-3) include repeating units represented by the following formula (AI):

[0128] [ka]

[0129] In formula (AI), Rb0 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. Preferred examples of the substituent that the alkyl group of Rb0 may have include a hydroxyl group and a halogen atom. Examples of the halogen atom of Rb0 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Rb0 is preferably a hydrogen atom or a methyl group. Ab represents a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a divalent group combining these. Among these, Ab is preferably a single bond or a linking group represented by -Ab1-CO2-. Ab1 is a linear or branched alkylene group, or a monocyclic or polycyclic cycloalkylene group, and is preferably a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group, or a norbornylene group. V represents a group obtained by removing one hydrogen atom from a ring member atom of a lactone structure represented by any one of formulas (LC1-1) to (LC1-21), or a group obtained by removing one hydrogen atom from a ring member atom of a sultone structure represented by any one of formulas (SL1-1) to (SL1-3).

[0130] When optical isomers exist in the repeating unit having a lactone group or a sultone group, any optical isomer may be used. One optical isomer may be used alone, or multiple optical isomers may be used in combination. When one optical isomer is primarily used, its optical purity (ee) is preferably 90 or more, more preferably 95 or more.

[0131] The carbonate group is preferably a cyclic carbonate group. The repeating unit having a cyclic carbonate group is preferably a repeating unit represented by the following formula (A-1).

[0132] [ka]

[0133] In formula (A-1), R A 1 represents a hydrogen atom, a halogen atom, or a monovalent organic group (preferably a methyl group). n represents an integer of 0 or more. R A 2represents a substituent. When n is 2 or more, multiple R A 2 may be the same or different. A represents a single bond or a divalent linking group. The divalent linking group is preferably an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a divalent group formed by combining these. Z represents an atomic group that forms a monocyclic or polycyclic ring together with the group represented by -O-CO-O- in the formula.

[0134] Examples of the unit Y are shown below.

[0135] [ka]

[0136] [ka]

[0137] [ka]

[0138] The content of the unit Y is preferably 1 mol% or more, more preferably 10 mol% or more, based on all repeating units in the resin (A), and the upper limit thereof is preferably 85 mol% or less, more preferably 80 mol% or less, even more preferably 70 mol% or less, and particularly preferably 60 mol% or less, based on all repeating units in the resin (A).

[0139] (Repeating unit having an acid generating group) The resin (A) may contain, as a repeating unit other than those described above, a repeating unit having a residue formed by removing one hydrogen atom from a compound that generates an acid upon irradiation with an electron beam (hereinafter also referred to as an "acid generating group"). Examples of the repeating unit having an acid generating group include a repeating unit represented by formula (4).

[0140] [ka]

[0141] R 41 represents a hydrogen atom or a methyl group. 41 represents a single bond or a divalent linking group. 42 represents a divalent linking group. 40 represents a residue formed by removing one hydrogen atom from a compound that generates an acid when irradiated with an electron beam. Examples of repeating units having an acid generating group are shown below.

[0142] [ka] JPEG0007828308000032.jpg5049

[0143] Other examples of the repeating unit represented by formula (4) include the repeating units described in paragraphs

[0094] to

[0105] of JP 2014-041327 A and the repeating unit described in paragraph

[0094] of WO 2018 / 193954 A.

[0144] The content of the repeating unit having an acid generating group is preferably 1 mol% or more, more preferably 5 mol% or more, based on all repeating units in the resin (A), and the upper limit thereof is preferably 40 mol% or less, more preferably 35 mol% or less, and even more preferably 30 mol% or less, based on all repeating units in the resin (A).

[0145] (Repeating unit represented by formula (V-1) or the following formula (V-2)) The resin (A) may contain a repeating unit represented by the following formula (V-1) or the following formula (V-2). The repeating units represented by the following formula (V-1) and the following formula (V-2) are preferably repeating units different from the repeating units described above.

[0146] [ka]

[0147] In the formula, R6 and R7 each independently represent a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR or -COOR: R is an alkyl group or a fluorinated alkyl group having 1 to 6 carbon atoms), or a carboxyl group. The alkyl group is preferably a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms. n3 represents an integer of 0 to 6. n4 represents an integer of 0 to 4. X 4 is a methylene group, an oxygen atom, or a sulfur atom. Examples of the repeating unit represented by formula (V-1) or (V-2) are shown below. Examples of the repeating unit represented by formula (V-1) or (V-2) include the repeating units described in paragraph

[0100] of WO 2018 / 193954.

[0148] (Repeating unit to reduce the mobility of the main chain) Resin (A) preferably has a high glass transition temperature (Tg) in order to prevent excessive diffusion of generated acid or pattern collapse during development. Tg is preferably higher than 90°C, more preferably higher than 100°C, even more preferably higher than 110°C, and particularly preferably higher than 125°C. In order to achieve a superior dissolution rate in a developer, Tg is preferably 400°C or lower, more preferably 350°C or lower. In this specification, the glass transition temperature (Tg) of a polymer such as resin (A) (hereinafter referred to as "Tg of a repeating unit") is calculated by the following method. First, the Tg of a homopolymer consisting of each repeating unit contained in the polymer is calculated using the Bicerano method. Next, the mass proportion (%) of each repeating unit relative to all repeating units in the polymer is calculated. Next, the Tg for each mass proportion is calculated using the Fox formula (described in Materials Letters 62 (2008) 3152, etc.), and these values ​​are summed to obtain the Tg (°C) of the polymer. The Bicerano method is described in Prediction of Polymer Properties, Marcel Dekker Inc., New York (1993). Calculation of Tg by the Bicerano method can be performed using polymer property estimation software MDL Polymer (MDL Information Systems, Inc.).

[0149] In order to increase the Tg of the resin (A) (preferably to make the Tg exceed 90°C), it is preferable to reduce the mobility of the main chain of the resin (A). Methods for reducing the mobility of the main chain of the resin (A) include the following methods (a) to (e). (a) Introduction of bulky substituents into the main chain (b) Introduction of multiple substituents into the main chain (c) Introduction of a substituent group that induces interactions between resins (A) near the main chain (d) Main chain formation in a cyclic structure (e) Linking of cyclic structures to the main chain The resin (A) preferably contains a repeating unit whose homopolymer exhibits a Tg of 130° C. or higher. The repeating units exhibiting a homopolymer Tg of 130° C. or higher are not particularly limited as long as they are repeating units exhibiting a homopolymer Tg of 130° C. or higher as calculated by the Bicerano method. Depending on the type of functional group in the repeating units represented by formulas (A) to (E) described below, they may be considered as repeating units exhibiting a homopolymer Tg of 130° C. or higher.

[0150] One example of a specific means for achieving the above (a) is to introduce a repeating unit represented by formula (A) into resin (A).

[0151] [ka]

[0152] Formula (A), R A represents a group containing a polycyclic structure. x represents a hydrogen atom, a methyl group, or an ethyl group. The group containing a polycyclic structure is a group containing a plurality of ring structures, and the plurality of ring structures may or may not be condensed. Specific examples of the repeating unit represented by formula (A) include those described in paragraphs

[0107] to

[0119] of WO 2018 / 193954.

[0153] One example of a specific means for achieving the above (b) is a method of introducing a repeating unit represented by formula (B) into resin (A).

[0154] [ka]

[0155] In formula (B), R b1 ~R b4 each independently represents a hydrogen atom or an organic group, R b1 ~R b4 At least two of these represent organic groups. In addition, when at least one of the organic groups is a group in which a ring structure is directly linked to the main chain in the repeating unit, the types of the other organic groups are not particularly limited. Furthermore, if none of the organic groups has a ring structure directly linked to the main chain in the repeating unit, at least two of the organic groups are substituents having three or more constituent atoms excluding hydrogen atoms. Specific examples of the repeating unit represented by formula (B) include those described in paragraphs

[0113] to

[0115] of WO 2018 / 193954.

[0156] One example of a specific means for achieving the above (c) is a method of introducing a repeating unit represented by formula (C) into resin (A).

[0157] [ka]

[0158] In formula (C), R c1 ~R c4 each independently represents a hydrogen atom or an organic group, R c1 ~R c4 At least one of the groups is a group containing a hydrogen-bonding hydrogen atom within three atoms from the main chain carbon. In particular, in order to induce interaction between the main chains of the resin (A), it is preferable to have a hydrogen-bonding hydrogen atom within two atoms (closer to the main chain). Specific examples of the repeating unit represented by formula (C) include those described in paragraphs

[0119] to

[0121] of WO 2018 / 193954.

[0159] One example of a specific means for achieving the above (d) is to introduce a repeating unit represented by formula (D) into resin (A).

[0160] [ka]

[0161] In formula (D), "cyclic" refers to a group that forms a main chain with a cyclic structure. The number of atoms constituting the ring is not particularly limited. Specific examples of the repeating unit represented by formula (D) include those described in paragraphs

[0126] to

[0127] of WO 2018 / 193954.

[0162] One example of a specific means for achieving the above (e) is to introduce a repeating unit represented by formula (E) into resin (A).

[0163] [ka]

[0164] In formula (E), each Re independently represents a hydrogen atom or an organic group, such as an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group, each of which may have a substituent. "Cyclic" refers to a cyclic group containing carbon atoms in the main chain. There are no particular restrictions on the number of atoms contained in the cyclic group. Specific examples of the repeating unit represented by formula (E) include those described in paragraphs

[0131] to

[0133] of WO 2018 / 193954.

[0165] (Repeating units having at least one group selected from a lactone group, a sultone group, a carbonate group, a hydroxyl group, a cyano group, and an alkali-soluble group) The resin (A) may contain a repeating unit having at least one type of group selected from a lactone group, a sultone group, a carbonate group, a hydroxyl group, a cyano group, and an alkali-soluble group. Examples of the repeating unit having a lactone group, a sultone group, or a carbonate group contained in the resin (A) include the repeating units described above in <Repeating units having a lactone group, a sultone group, or a carbonate group>. The preferred content is also as described above in <Repeating units having a lactone group, a sultone group, or a carbonate group>.

[0166] The resin (A) may contain a repeating unit having a hydroxyl group or a cyano group, which improves the adhesion to the substrate and the affinity for the developer. The repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group. It is preferred that the repeating unit having a hydroxyl group or a cyano group does not have an acid-decomposable group. Examples of repeating units having a hydroxyl group or a cyano group include those described in paragraphs

[0081] to

[0084] of JP-A No. 2014-098921.

[0167] The resin (A) may contain a repeating unit having an alkali-soluble group. Examples of alkali-soluble groups include carboxyl groups, sulfonamide groups, sulfonylimide groups, bissulfonylimide groups, and aliphatic alcohol groups (e.g., hexafluoroisopropanol groups) substituted at the α-position with an electron-withdrawing group, with carboxyl groups being preferred. Resin (A) containing a repeating unit having an alkali-soluble group enhances resolution in contact hole applications. Examples of repeating units having an alkali-soluble group include those described in paragraphs

[0085] and

[0086] of JP 2014-098921 A.

[0168] (Repeating units that have an alicyclic hydrocarbon structure and are not acid decomposable) Resin (A) may contain a repeating unit that has an alicyclic hydrocarbon structure and is not acid-decomposable, such as a repeating unit derived from 1-adamantyl (meth)acrylate, diamantyl (meth)acrylate, tricyclodecanyl (meth)acrylate, or cyclohexyl (meth)acrylate.

[0169] (Repeating unit represented by formula (III) having neither a hydroxyl group nor a cyano group) The resin (A) may contain a repeating unit represented by formula (III) that does not have either a hydroxyl group or a cyano group.

[0170] [ka]

[0171] In formula (III), R5 represents a hydrocarbon group having at least one cyclic structure and having neither a hydroxyl group nor a cyano group. Ra represents a hydrogen atom, an alkyl group, or a -CH2-O-Ra2 group, where Ra2 represents a hydrogen atom, an alkyl group, or an acyl group. Examples of the repeating unit represented by formula (III) that does not have either a hydroxyl group or a cyano group include those described in paragraphs

[0087] to

[0094] of JP-A No. 2014-098921.

[0172] (Other repeating units) Furthermore, the resin (A) may contain repeating units other than the repeating units mentioned above. For example, the resin (A) may contain a repeating unit selected from the group consisting of a repeating unit having an oxathiane ring group, a repeating unit having an oxazolone ring group, a repeating unit having a dioxane ring group, and a repeating unit having a hydantoin ring group. Examples of such repeating units are shown below.

[0173] [ka]

[0174] In addition to the above repeating structural units, the resin (A) may contain various repeating structural units for the purpose of adjusting dry etching resistance, suitability for a standard developer, substrate adhesion, resist profile, resolution, heat resistance, sensitivity, and the like.

[0175] It is preferable that all of the repeating units of the resin (A) be composed of repeating units derived from a compound having an ethylenically unsaturated bond (particularly when the composition is used as an actinic ray- or radiation-sensitive resin composition for ArF). It is also particularly preferable that all of the repeating units be composed of (meth)acrylate repeating units. In this case, any of the repeating units may be used, all of which are methacrylate repeating units, all of which are acrylate repeating units, or all of which are a mixture of methacrylate repeating units and acrylate repeating units, and it is preferable that the acrylate repeating units account for 50 mol % or less of all the repeating units.

[0176] The resin (A) can be synthesized by a conventional method (for example, radical polymerization). The weight average molecular weight of the resin (A), as measured by GPC in terms of polystyrene, is preferably 30,000 or less, more preferably from 1,000 to 30,000, still more preferably from 3,000 to 30,000, and particularly preferably from 5,000 to 15,000. The polydispersity (molecular weight distribution) of the resin (A) is preferably from 1 to 5, more preferably from 1 to 3, even more preferably from 1.2 to 3.0, and particularly preferably from 1.2 to 2.0. The smaller the polydispersity, the better the resolution and resist shape, and further the smoother the sidewalls of the resist pattern and the better the roughness.

[0177] When the resist layer contains the resin (A), the content of the resin (A) is preferably 40.0 to 99.9 mass %, more preferably 60.0 to 90.0 mass %, based on the total mass of the resist layer. The resin (A) may be used alone or in combination of two or more.

[0178] (Compounds that generate acids when irradiated with electron beams) The resist layer may contain a compound that generates an acid when irradiated with an electron beam (hereinafter, also referred to as an acid generator (B)). The acid generator (B) may be in the form of a low molecular weight compound, or may be in the form of being incorporated into a part of a polymer (for example, the resin (A) described below). In addition, the form of a low molecular weight compound and the form of being incorporated into a part of a polymer (for example, the resin (A) described below) may be used in combination. When the acid generator (B) is in the form of a low molecular weight compound, the molecular weight of the acid generator is preferably 3000 or less, more preferably 2000 or less, and even more preferably 1000 or less. There is no particular lower limit, but a molecular weight of 100 or more is preferred. When the acid generator (B) is in a form in which it is incorporated into a part of a polymer, it may be incorporated into a part of the resin (A) or into a resin different from the resin (A). In the present invention, the acid generator (B) is preferably in the form of a low molecular weight compound.

[0179] The pKa of the acid generated from the acid generator (B) is not particularly limited, but is often 0 or less, and is preferably -1.00 or less in terms of providing better effects of the present invention. The lower limit is not particularly limited, but is often -4.00 or more. The size of the acid generated from the acid generator (B) is not particularly limited, and may be 150 Å or less. 3 In most cases, the effect of the present invention is more excellent, and therefore, 240 Å 3 The upper limit is not particularly limited, but is preferably 700 Å or more. 3 The following cases are common:

[0180] Examples of the acid generator (B) include "M + X - The compound is preferably an onium salt that generates an organic acid when exposed to an electron beam. Examples of the organic acid include sulfonic acids (aliphatic sulfonic acids, aromatic sulfonic acids, camphorsulfonic acids, etc.), carboxylic acids (aliphatic carboxylic acids, aromatic carboxylic acids, aralkyl carboxylic acids, etc.), carbonylsulfonylimide acids, bis(alkylsulfonyl)imide acids, and tris(alkylsulfonyl)methide acids.

[0181] "M + X -In the compound represented by ", M + represents an organic cation. The organic cation is not particularly limited, and the valence of the organic cation may be monovalent or divalent or higher. Among these, the organic cation is preferably a cation represented by formula (ZaI) (hereinafter also referred to as "cation (ZaI)") or a cation represented by formula (ZaII) (hereinafter also referred to as "cation (ZaII)").

[0182] [ka]

[0183] In the above formula (ZaI), R 201 , R 202 , and R 203 each independently represents an organic group. R 201 , R 202 , and R 203 The number of carbon atoms in the organic group represented by R is preferably 1 to 30, and more preferably 1 to 20. 201 ~R 203 Two of these may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group. 201 ~R 203 Examples of groups formed by combining two of these include alkylene groups (such as butylene and pentylene groups) and -CH2-CH2-O-CH2-CH2-.

[0184] Suitable embodiments of the organic cation in formula (ZaI) include the cation (ZaI-1), cation (ZaI-2), an organic cation represented by formula (ZaI-3b) (cation (ZaI-3b)), and an organic cation represented by formula (ZaI-4b) (cation (ZaI-4b)), which will be described later.

[0185] First, the cation (ZaI-1) will be explained. The cation (ZaI-1) is R in the above formula (ZaI). 201 ~R 203 is an arylsulfonium cation, in which at least one of the groups is an aryl group. The arylsulfonium cation is R 201 ~R 203 All of R may be aryl groups, or 201 ~R 203 A part of the group may be an aryl group, and the remainder may be an alkyl group or a cycloalkyl group. Also, R 201 ~R 203 one of which is an aryl group, and R 201 ~R 203 The remaining two of R may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group. 201 ~R 203 Examples of groups formed by combining two of these include alkylene groups in which one or more methylene groups may be substituted with an oxygen atom, a sulfur atom, an ester group, an amide group, and / or a carbonyl group (e.g., butylene group, pentylene group, and -CH2-CH2-O-CH2-CH2-). Examples of arylsulfonium cations include triarylsulfonium cations, diarylalkylsulfonium cations, aryldialkylsulfonium cations, diarylcycloalkylsulfonium cations, and aryldicycloalkylsulfonium cations.

[0186] The aryl group contained in the arylsulfonium cation is preferably a phenyl group or a naphthyl group, more preferably a phenyl group. The aryl group may be an aryl group having a heterocyclic structure containing an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Examples of heterocyclic structures include pyrrole residues, furan residues, thiophene residues, indole residues, benzofuran residues, and benzothiophene residues. When the arylsulfonium cation has two or more aryl groups, the two or more aryl groups may be the same or different. The alkyl group or cycloalkyl group that the arylsulfonium cation optionally has is preferably a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cycloalkyl group having 3 to 15 carbon atoms, and more preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a cyclopropyl group, a cyclobutyl group, or a cyclohexyl group.

[0187] R 201 ~R 203 Preferred examples of the substituent that the aryl group, alkyl group, and cycloalkyl group may have include an alkyl group (e.g., having 1 to 15 carbon atoms), a cycloalkyl group (e.g., having 3 to 15 carbon atoms), an aryl group (e.g., having 6 to 14 carbon atoms), an alkoxy group (e.g., having 1 to 15 carbon atoms), a cycloalkylalkoxy group (e.g., having 1 to 15 carbon atoms), a halogen atom (e.g., fluorine and iodine), a hydroxyl group, a carboxyl group, an ester group, a sulfinyl group, a sulfonyl group, an alkylthio group, or a phenylthio group. The above substituents may further have a substituent, if possible, and it is also preferred that the above alkyl group has a halogen atom as a substituent to form a halogenated alkyl group such as a trifluoromethyl group. It is also preferred that the above substituents are combined in any desired manner to form an acid-decomposable group. The acid-decomposable group is intended to be a group that decomposes under the action of an acid to generate a polar group, and preferably has a structure in which the polar group is protected with a leaving group that is released under the action of an acid. The polar group and leaving group are as described above.

[0188] Next, the cation (ZaI-2) will be explained. The cation (ZaI-2) is R in formula (ZaI). 201 ~R 203 are each independently a cation representing an organic group that does not have an aromatic ring. The aromatic ring also includes an aromatic ring containing a heteroatom. R 201 ~R 203 The organic group not having an aromatic ring as the aromatic ring preferably has 1 to 30 carbon atoms, and more preferably 1 to 20 carbon atoms. R 201 ~R 203 are each independently preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, more preferably a linear or branched 2-oxoalkyl group, a 2-oxocycloalkyl group, or an alkoxycarbonylmethyl group, and still more preferably a linear or branched 2-oxoalkyl group.

[0189] R 201 ~R 203 Examples of the alkyl group and cycloalkyl group include a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl, and pentyl), and a cycloalkyl group having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl, and norbornyl). R 201 ~R 203 may be further substituted with a halogen atom, an alkoxy group (for example, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group. Also, R 201 ~R 203 It is also preferred that the substituents independently form an acid-decomposable group by any combination of the substituents.

[0190] Next, the cation (ZaI-3b) will be explained. The cation (ZaI-3b) is a cation represented by the following formula (ZaI-3b).

[0191] [ka]

[0192] In the formula (ZaI-3b), R 1c ~R 5ceach independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, a halogen atom, a hydroxyl group, a nitro group, an alkylthio group, or an arylthio group. R 6c and R 7c each independently represents a hydrogen atom, an alkyl group (for example, a t-butyl group), a cycloalkyl group, a halogen atom, a cyano group, or an aryl group. R x and R y each independently represents an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group. Also, R 1c ~R 7c , and R x and R y It is also preferred that the substituents independently form an acid-decomposable group by any combination of the substituents.

[0193] R 1c ~R 5c Two or more of the following, R 5c and R 6c , R 6c and R 7c , R 5c and R x , and R x and R y may be bonded to each other to form a ring, and each of these rings may independently contain an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond. Examples of the ring include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic heterocycles, and polycyclic fused rings formed by combining two or more of these rings. Examples of the ring include 3- to 10-membered rings, preferably 4- to 8-membered rings, and more preferably 5- or 6-membered rings.

[0194] R 1c ~R 5c Two or more of the following, R 6c and R7c , and R x and R y Examples of the group formed by bonding include alkylene groups such as butylene and pentylene, in which the methylene group may be substituted with a heteroatom such as an oxygen atom. R 5c and R 6c , and R 5c and R x The group formed by bonding is preferably a single bond or an alkylene group. Examples of the alkylene group include a methylene group and an ethylene group.

[0195] R 1c ~R 5c , R 6c , R 7c , R x , R y , and R 1c ~R 5c Two or more of the following, R 5c and R 6c , R 6c and R 7c , R 5c and R x , and R x and R y The ring formed by bonding together may have a substituent.

[0196] Next, the cation (ZaI-4b) will be explained. The cation (ZaI-4b) is a cation represented by the following formula (ZaI-4b).

[0197] [ka]

[0198] In the formula (ZaI-4b), l represents an integer of 0 to 2. r represents an integer of 0 to 8. R 13represents a hydrogen atom, a halogen atom (for example, a fluorine atom or an iodine atom), a hydroxyl group, an alkyl group, a halogenated alkyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, or a group containing a cycloalkyl group (which may be a cycloalkyl group itself or a group containing a cycloalkyl group as a part). These groups may have a substituent. R 14 represents a hydroxyl group, a halogen atom (e.g., a fluorine atom, an iodine atom, etc.), an alkyl group, a halogenated alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a group containing a cycloalkyl group (which may be a cycloalkyl group itself or a group containing a cycloalkyl group as a part). These groups may have a substituent. R 14 When a plurality of groups are present, each independently represents the above group such as a hydroxyl group. R 15 Each of R independently represents an alkyl group, a cycloalkyl group, or a naphthyl group. 15 may be bonded to each other to form a ring. 15 When they are bonded to each other to form a ring, the ring skeleton may contain a heteroatom such as an oxygen atom or a nitrogen atom. In one embodiment, two R 15 are preferably alkylene groups and bonded to each other to form a ring structure. 15 The ring formed by bonding together may have a substituent.

[0199] In formula (ZaI-4b), R 13 , R 14 , and R 15 The alkyl group may be linear or branched. The number of carbon atoms in the alkyl group is preferably 1 to 10. The alkyl group is preferably a methyl group, an ethyl group, an n-butyl group, a t-butyl group, or the like. Also, R 13 ~R 15 , and R x and R yIt is also preferred that each of the substituents independently form an acid-decomposable group by any combination of the substituents.

[0200] Next, formula (ZaII) will be explained. In formula (ZaII), R 204 and R 205 each independently represents an aryl group, an alkyl group, or a cycloalkyl group. R 204 and R 205 The aryl group in R is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. 204 and R 205 The aryl group may be an aryl group having a heterocycle containing an oxygen atom, a nitrogen atom, a sulfur atom, etc. Examples of the skeleton of the aryl group having a heterocycle include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene. R 204 and R 205 The alkyl group and cycloalkyl group are preferably a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, or a pentyl group), or a cycloalkyl group having 3 to 10 carbon atoms (for example, a cyclopentyl group, a cyclohexyl group, or a norbornyl group).

[0201] R 204 and R 205 The aryl group, alkyl group, and cycloalkyl group in R may each independently have a substituent. 204 and R 205 Examples of the substituents that the aryl group, alkyl group, and cycloalkyl group may have include alkyl groups (e.g., having 1 to 15 carbon atoms), cycloalkyl groups (e.g., having 3 to 15 carbon atoms), aryl groups (e.g., having 6 to 15 carbon atoms), alkoxy groups (e.g., having 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, and phenylthio groups. 204 and R 205It is also preferred that the substituents independently form an acid-decomposable group by any combination of the substituents.

[0202] Specific examples of organic cations are shown below, but the present invention is not limited to these.

[0203] [ka]

[0204] [ka]

[0205] [ka]

[0206] "M + X - In the compound represented by ", X - represents an organic anion. The organic anion is not particularly limited, and examples thereof include monovalent or divalent or higher organic anions. As the organic anion, an anion having a significantly low ability to cause a nucleophilic reaction is preferred, and a non-nucleophilic anion is more preferred.

[0207] Examples of non-nucleophilic anions include sulfonate anions (aliphatic sulfonate anions, aromatic sulfonate anions, camphorsulfonate anions, etc.), carboxylate anions (aliphatic carboxylate anions, aromatic carboxylate anions, aralkyl carboxylate anions, etc.), sulfonylimide anions, bis(alkylsulfonyl)imide anions, and tris(alkylsulfonyl)methide anions.

[0208] The aliphatic moiety in the aliphatic sulfonate anion and the aliphatic carboxylate anion may be a linear or branched alkyl group or a cycloalkyl group, and is preferably a linear or branched alkyl group having 1 to 30 carbon atoms or a cycloalkyl group having 3 to 30 carbon atoms. The alkyl group may be, for example, a fluoroalkyl group (which may have a substituent other than a fluorine atom, or may be a perfluoroalkyl group).

[0209] The aryl group in the aromatic sulfonate anion and aromatic carboxylate anion is preferably an aryl group having 6 to 14 carbon atoms, and examples thereof include a phenyl group, a tolyl group, and a naphthyl group.

[0210] The alkyl group, cycloalkyl group, and aryl group mentioned above may have a substituent. The substituent is not particularly limited, but examples thereof include a nitro group, a halogen atom such as a fluorine atom or a chlorine atom, a carboxyl group, a hydroxyl group, an amino group, a cyano group, an alkoxy group (preferably having 1 to 15 carbon atoms), an alkyl group (preferably having 1 to 10 carbon atoms), a cycloalkyl group (preferably having 3 to 15 carbon atoms), an aryl group (preferably having 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably having 2 to 7 carbon atoms), an acyl group (preferably having 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably having 2 to 7 carbon atoms), an alkylthio group (preferably having 1 to 15 carbon atoms), an alkylsulfonyl group (preferably having 1 to 15 carbon atoms), an alkyliminosulfonyl group (preferably having 1 to 15 carbon atoms), and an aryloxysulfonyl group (preferably having 6 to 20 carbon atoms).

[0211] The aralkyl group in the aralkyl carboxylate anion is preferably an aralkyl group having 7 to 14 carbon atoms. Examples of the aralkyl group having 7 to 14 carbon atoms include a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, and a naphthylbutyl group.

[0212] An example of the sulfonylimide anion is a saccharin anion.

[0213] The alkyl group in the bis(alkylsulfonyl)imide anion and the tris(alkylsulfonyl)methide anion is preferably an alkyl group having 1 to 5 carbon atoms. Examples of the substituent on these alkyl groups 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. Furthermore, the alkyl groups in the bis(alkylsulfonyl)imide anion may be bonded to each other to form a ring structure, which increases the acid strength.

[0214] Other non-nucleophilic anions include, for example, fluorinated phosphorus (e.g., PF6 - ), boron fluorides (e.g., BF4 - ), and antimony fluorides (e.g., SbF6 - ) are listed.

[0215] The non-nucleophilic anion is preferably an aliphatic sulfonate anion in which at least the α-position of the sulfonic acid is substituted with a fluorine atom, an aromatic sulfonate anion substituted with a fluorine atom or a group having a fluorine atom, 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. 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 perfluorooctane sulfonate anion, a pentafluorobenzenesulfonate anion, or a 3,5-bis(trifluoromethyl)benzenesulfonate anion is even more preferred.

[0216] The non-nucleophilic anion is also preferably an anion represented by the following formula (AN1).

[0217] [ka]

[0218] In formula (AN1), R 1 and R 2 each independently represents a hydrogen atom or a substituent. The substituent is not particularly limited, but is preferably a group that is not an electron-withdrawing group, such as a hydrocarbon group, a hydroxyl group, an oxyhydrocarbon group, an oxycarbonylhydrocarbon group, an amino group, a hydrocarbon-substituted amino group, and a hydrocarbon-substituted amide group. Furthermore, the groups that are not electron-withdrawing groups are preferably each independently -R', -OH, -OR', -OCOR', -NH2, -NR'2, -NHR', or -NHCOR', where R' is a monovalent hydrocarbon group.

[0219] Examples of the monovalent hydrocarbon group represented by R' include monovalent linear or branched hydrocarbon groups such as alkyl groups such as methyl, ethyl, propyl, and butyl; alkenyl groups such as ethenyl, propenyl, and butenyl; alkynyl groups such as ethynyl, propynyl, and butynyl; cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, and adamantyl; monovalent alicyclic hydrocarbon groups such as cycloalkenyl groups such as cyclopropenyl, cyclobutenyl, cyclopentenyl, and norbornenyl; aryl groups such as phenyl, tolyl, xylyl, mesityl, naphthyl, methylnaphthyl, anthryl, and methylanthryl; and monovalent aromatic hydrocarbon groups such as aralkyl groups such as benzyl, phenethyl, phenylpropyl, naphthylmethyl, and anthrylmethyl. Among them, R 1 and R 2 are each independently preferably a hydrocarbon group (preferably a cycloalkyl group) or a hydrogen atom.

[0220] L represents a divalent linking group. When a plurality of L's are present, each L may be the same or different. Examples of the divalent linking group include -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -S-, -SO-, -SO2-, alkylene groups (preferably having 1 to 6 carbon atoms), cycloalkylene groups (preferably having 3 to 15 carbon atoms), alkenylene groups (preferably having 2 to 6 carbon atoms), and divalent linking groups combining a plurality of these. Among these, the divalent linking group is preferably -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -SO2-, -O-CO-O-alkylene group-, -COO-alkylene group-, or -CONH-alkylene group-, and more preferably -O-CO-O-, -O-CO-O-alkylene group-, -COO-, -CONH-, -SO2-, or -COO-alkylene group-.

[0221] L is preferably, for example, a group represented by the following formula (AN1-1). * a -(CR 2a 2) X -Q-(CR 2b 2) Y -* b (AN1-1)

[0222] In formula (AN1-1), * a is R in formula (AN1) 3 represents the bonding position with * b is -C(R 1 )(R 2 )- represents the bonding position. X and Y each independently represent an integer of 0 to 10, and preferably an integer of 0 to 3. R 2a and R 2b each independently represents a hydrogen atom or a substituent. R 2a and R 2b If there are multiple instances of each, there are multiple instances of R 2a and R 2bmay be the same or different. However, when Y is 1 or more, -C(R 1 )(R 2 )- and CR 2b R in 2 2b is other than a fluorine atom. Q is * A -O-CO-O-* B , * A -CO-* B , * A -CO-O-* B , * A -O-CO-* B , * A -O-* B , * A -S-* B , or * A -SO2-* B Represents. However, X+Y in formula (AN1-1) is 1 or more, and R in formula (AN1-1) 2a and R 2b are all hydrogen atoms, Q is * A -O-CO-O-* B , * A -CO-* B , * A -O-CO-* B , * A -O-* B , * A -S-* B , or * A -SO2-* B Represents. * A is R in formula (AN1) 3 represents the bond position on the side, and * B is -SO3 in formula (AN1) - represents the bonding position on the side.

[0223] In formula (AN1), R 3 represents an organic group. The organic group is not particularly limited as long as it has one or more carbon atoms, and may be a linear group (e.g., a linear alkyl group), a branched group (e.g., a branched alkyl group such as a t-butyl group), or a cyclic group. The organic group may or may not have a substituent. The organic group may or may not have a heteroatom (e.g., an oxygen atom, a sulfur atom, and / or a nitrogen atom).

[0224] Among them, R 3 is preferably an organic group having a cyclic structure. The cyclic structure may be monocyclic or polycyclic, and may have a substituent. The ring in the organic group containing a cyclic structure is preferably directly bonded to L in formula (AN1). The organic group having a cyclic structure may or may not have a heteroatom (such as an oxygen atom, a sulfur atom, and / or a nitrogen atom), and the heteroatom may substitute for one or more of the carbon atoms forming the cyclic structure. The organic group having a cyclic structure is preferably, for example, a hydrocarbon group having a cyclic structure, a lactone ring group, or a sultone ring group, and among these, the organic group having a cyclic structure is preferably a hydrocarbon group having a cyclic structure. The hydrocarbon group having a cyclic structure is preferably a monocyclic or polycyclic cycloalkyl group, which may have a substituent. The cycloalkyl group may be monocyclic (such as a cyclohexyl group) or polycyclic (such as an adamantyl group), and preferably has 5 to 12 carbon atoms. As the lactone group and sultone group, for example, a group obtained by removing one hydrogen atom from a ring member atom constituting the lactone structure or sultone structure in any of the structures represented by the above formulae (LC1-1) to (LC1-21) and (SL1-1) to (SL1-3) is preferred.

[0225] The non-nucleophilic anion may be a benzenesulfonate anion, and is preferably a benzenesulfonate anion substituted with a branched alkyl group or a cycloalkyl group.

[0226] The non-nucleophilic anion is also preferably an anion represented by the following formula (AN2).

[0227] [ka]

[0228] In formula (AN2), o represents an integer of 1 to 3. p represents an integer of 0 to 10. q represents an integer of 0 to 10.

[0229] Xf represents a hydrogen atom, a fluorine atom, an alkyl group substituted with at least one fluorine atom, or an organic group having no fluorine atoms. The number of carbon atoms in this alkyl group is preferably 1 to 10, more preferably 1 to 4. Furthermore, the alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group. Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, more preferably a fluorine atom or CF3, and further preferably both Xf's are fluorine atoms.

[0230] R 4 and R 5 R each independently represents a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. 4 and R 5 If there are multiple 4 and R 5 may be the same or different. R 4 and R 5 The alkyl group represented by the following formula preferably has 1 to 4 carbon atoms. The alkyl group may have a substituent. R4 and R5 are preferably hydrogen atoms.

[0231] L represents a divalent linking group, and is defined as L in formula (AN1).

[0232] W represents an organic group containing a cyclic structure, and is preferably a cyclic organic group. Examples of the cyclic organic group include an alicyclic group, an aryl group, and a heterocyclic group. The alicyclic group may be monocyclic or polycyclic. Examples of monocyclic alicyclic groups include monocyclic cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. Examples of polycyclic alicyclic groups include polycyclic cycloalkyl groups such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. Among these, alicyclic groups having a bulky structure with 7 or more carbon atoms, such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group, are preferred.

[0233] The aryl group may be monocyclic or polycyclic, and examples of the aryl group include a phenyl group, a naphthyl group, a phenanthryl group, and an anthryl group. The heterocyclic group may be monocyclic or polycyclic. In particular, polycyclic heterocyclic groups can better suppress acid diffusion. The heterocyclic group may or may not have aromaticity. Examples of heterocyclic rings having aromaticity include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Examples of heterocyclic rings having no aromaticity include a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring. The heterocyclic ring in the heterocyclic group is preferably a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring.

[0234] The cyclic organic group may have a substituent. Examples of the substituent include an alkyl group (which may be linear or branched, and preferably has 1 to 12 carbon atoms), a cycloalkyl group (which may be monocyclic, polycyclic, or spirocyclic, and preferably has 3 to 20 carbon atoms), an aryl group (which preferably has 6 to 14 carbon atoms), a hydroxyl group, an alkoxy group, an ester group, an amide group, a urethane group, a ureido group, a thioether group, a sulfonamide group, and a sulfonate ester group. The carbon constituting the cyclic organic group (the carbon contributing to ring formation) may be a carbonyl carbon.

[0235] The anion represented by formula (AN1) is SO3 - -CF2-CH2-OCO-(L) q’ -W, SO3 - -CF2-CHF-CH2-OCO-(L) q’ -W, SO3 - -CF2-COO-(L) q’ -W, SO3 - -CF2-CF2-CH2-CH2-(L) q -W or SO3 - -CF2-CH(CF3)-OCO-(L) q’ -W is preferred. Here, L, q and W are the same as those in formula (AN2). q' represents an integer of 0 to 10.

[0236] The non-nucleophilic anion is also preferably an aromatic sulfonate anion represented by the following formula (AN3).

[0237] [ka]

[0238] In formula (AN3), Ar represents an aryl group (e.g., a phenyl group) and may further have a substituent other than the sulfonate anion and the -(DB) group, such as a fluorine atom or a hydroxyl group. n represents an integer of 0 or greater. n is preferably 1 to 4, more preferably 2 or 3, and even more preferably 3.

[0239] D represents a single bond or a divalent linking group. Examples of the divalent linking group include an ether group, a thioether group, a carbonyl group, a sulfoxide group, a sulfone group, a sulfonate ester group, an ester group, and a group formed by combining two or more of these groups.

[0240] B represents a hydrocarbon group. B is preferably an aliphatic hydrocarbon group, more preferably an isopropyl group, a cyclohexyl group, or an aryl group which may further have a substituent (such as a tricyclohexylphenyl group).

[0241] The non-nucleophilic anion is also preferably a disulfonamide anion. Disulfonamide anions are, for example, N - (SO2-R q )2 is an anion. where R q represents an alkyl group which may have a substituent, preferably a fluoroalkyl group, more preferably a perfluoroalkyl group. q may be bonded to each other to form a ring. q The group formed by bonding together is preferably an alkylene group which may have a substituent, more preferably a fluoroalkylene group, and even more preferably a perfluoroalkylene group. The alkylene group preferably has 2 to 4 carbon atoms.

[0242] Further, examples of the non-nucleophilic anion include anions represented by the following formulas (d1-1) to (d1-4).

[0243] [ka]

[0244] [ka]

[0245] In formula (d1-1), R 51 represents a hydrocarbon group (for example, an aryl group such as a phenyl group) which may have a substituent (for example, a hydroxyl group).

[0246] In formula (d1-2), Z 2c represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent (provided that the carbon atom adjacent to S is not substituted with a fluorine atom). Z 2c The hydrocarbon group in the formula (I) may be linear or branched, or may have a cyclic structure. Furthermore, a carbon atom in the hydrocarbon group (preferably, a carbon atom that is a ring atom when the hydrocarbon group has a cyclic structure) may be a carbonyl carbon (-CO-). Examples of the hydrocarbon group include a group having a norbornyl group that may have a substituent. The carbon atom forming the norbornyl group may be a carbonyl carbon. Also, "Z" in formula (d1-2) 2c -SO3 - " is preferably different from the anions represented by the above formulae (AN1) to (AN3). For example, Z 2c is preferably other than an aryl group. 2c In -SO3 - The atoms at the α-position and β-position to Z are preferably atoms other than carbon atoms having a fluorine atom as a substituent. 2c is -SO3 - The atom at the α-position and / or the atom at the β-position to the is preferably a ring atom in a cyclic group.

[0247] In formula (d1-3), R 52 represents an organic group (preferably a hydrocarbon group having a fluorine atom), Y 3 represents a linear, branched, or cyclic alkylene group, an arylene group, or a carbonyl group, and Rf represents a hydrocarbon group.

[0248] In formula (d1-4), R 53 and R 54 R each independently represents an organic group (preferably a hydrocarbon group having a fluorine atom).53 and R 54 may be bonded to each other to form a ring.

[0249] The organic anions may be used alone or in combination of two or more.

[0250] The acid generator is also preferably at least one selected from the group consisting of compounds (I) to (II).

[0251] (Compound (I)) Compound (I) is a compound having one or more structural moieties X and one or more structural moieties Y, which generates an acid containing a first acidic moiety derived from the structural moiety X and a second acidic moiety derived from the structural moiety Y when irradiated with an electron beam. Structural site X: Anion site A1 - and cationic moiety M1 + and a structural portion that forms a first acidic site represented by HA1 upon irradiation with an electron beam. Structural site Y: Anionic site A2 - and cationic moiety M2 + and a structural portion that forms a second acidic site represented by HA2 upon irradiation with an electron beam. However, one or more cationic moieties M1 in the structural moiety X + and one or more cationic moieties M2 in the structural moiety Y + At least one of the groups represents a cation represented by formula (X). Furthermore, the compound (I) satisfies the following condition I.

[0252] Condition I: In the compound (I), the cation moiety M1 in the structural moiety X + and the cationic moiety M2 in the structural moiety Y. + H + The compound PI in which the cationic moiety M1 in the structural moiety X is replaced by + H + and the cationic moiety M2 in the structural moiety Y.+ H + and an acid dissociation constant a2 derived from the acidic site represented by HA2 in which the acid dissociation constant a1 is replaced by the acid dissociation constant a2, which is greater than the acid dissociation constant a1.

[0253] Condition I will be explained in more detail below. For example, when compound (I) is an acid-generating compound having one of the first acidic moieties derived from the structural moiety X and one of the second acidic moieties derived from the structural moiety Y, compound PI corresponds to a "compound having HA1 and HA2." More specifically, the acid dissociation constant a1 and the acid dissociation constant a2 of the compound PI are determined by determining whether the compound PI is "A1 - The pKa at which the compound is formed is the acid dissociation constant a1, and the above "A1 - and HA2" is "A1 - and A2 - The pKa at which the compound becomes "a compound having the above formula" is the acid dissociation constant a2.

[0254] Furthermore, when compound (I) is, for example, an acid-generating compound having two of the first acidic sites derived from the structural moiety X and one of the second acidic sites derived from the structural moiety Y, compound PI corresponds to a "compound having two HA1s and one HA2." When the acid dissociation constant of such a compound PI is calculated, it is found that the compound PI is "one A1 - and one HA1 and one HA2,” and the acid dissociation constant when “one A1 - and one HA1 and one HA2" is "a compound with two A1 - The acid dissociation constant when "a compound having two A1 - and one HA2" is "a compound with two A1 - and A2 -The acid dissociation constant when it becomes a "compound having" corresponds to the acid dissociation constant a2. That is, in such a compound PI, the cationic site M1 in the structural site X + is replaced with H + If it has a plurality of acid dissociation constants derived from the acidic site represented by HA1 formed by replacement, the value of the acid dissociation constant a2 is larger than the largest value among the plurality of acid dissociation constants a1. Note that when the compound PI is a "compound having one A1 - and one HA1 and one HA2", the acid dissociation constant is aa, and when the "compound having one A1 - and one HA1 and one HA2" becomes a "compound having two A1 - and one HA2", and the acid dissociation constant at this time is ab, the relationship between aa and ab satisfies aa < ab.

[0255] The acid dissociation constant a1 and the acid dissociation constant a2 are determined by the measurement method of the acid dissociation constant described above. The above compound PI corresponds to the acid generated when the compound (I) is irradiated with an electron beam. When the compound (I) has two or more structural sites X, the structural sites X may be the same or different from each other. Also, two or more of the above A1 - , and two or more of the above M1 + may be the same or different from each other. Also, in the compound (I), the above A1 - and the above A2 - , and the above M1 + and the above M2 + may be the same or different from each other, but the above A1 - and the above A2 - are preferably different from each other.

[0256] In the compound PI, the difference (absolute value) between the acid dissociation constant a1 (the maximum value when there are multiple acid dissociation constants a1) and the acid dissociation constant a2 is preferably 0.1 or more, more preferably 0.5 or more, and even more preferably 1.0 or more. The upper limit of the difference (absolute value) between the acid dissociation constant a1 (the maximum value when there are multiple acid dissociation constants a1) and the acid dissociation constant a2 is not particularly limited, but is, for example, 16 or less.

[0257] In the compound PI, the acid dissociation constant a2 is preferably not more than 20, more preferably not more than 15. The lower limit of the acid dissociation constant a2 is preferably not less than −4.0.

[0258] In the compound PI, the acid dissociation constant a1 is preferably not more than 2.0, more preferably not more than 0. The lower limit of the acid dissociation constant a1 is preferably not less than −20.0.

[0259] Anionic site A1 - and anionic site A2 - is a structural moiety containing a negatively charged atom or atomic group, and examples thereof include structural moieties selected from the group consisting of formulae (AA-1) to (AA-3) and formulae (BB-1) to (BB-6) shown below. Anionic site A1 - As the acid group, those capable of forming an acidic site with a small acid dissociation constant are preferred, and among these, any of formulas (AA-1) to (AA-3) is more preferred, and any of formulas (AA-1) and (AA-3) is even more preferred. In addition, the anionic site A2 - As the anion moiety A1 - Preferably, it is one that can form an acidic site with a larger acid dissociation constant than the above, more preferably any one of formulas (BB-1) to (BB-6), and even more preferably any one of formulas (BB-1) and (BB-4). In the following formulae (AA-1) to (AA-3) and (BB-1) to (BB-6), * represents a bonding position. In formula (AA-2), R A represents a monovalent organic group. AThe monovalent organic group represented by the formula (I) is not particularly limited, but examples thereof include a cyano group, a trifluoromethyl group, and a methanesulfonyl group.

[0260] [ka] JPEG0007828308000053.jpg24160

[0261] In addition, the cationic moiety M1 + and cationic moiety M2 + is a structural moiety containing a positively charged atom or atomic group, and examples thereof include monovalent organic cations. + Examples of the organic cation include those represented by the following formula:

[0262] The specific structure of compound (I) is not particularly limited, and examples thereof include compounds represented by formulae (Ia-1) to (Ia-5) described below.

[0263] -Compound represented by formula (Ia-1)- First, the compound represented by formula (Ia-1) will be described below.

[0264] M 11 + A 11 - -L1-A 12 - M 12 + (Ia-1)

[0265] The compound represented by formula (Ia-1) can be converted into HA by irradiation with an electron beam. 11 -L1-A 12 It generates an acid represented by H.

[0266] In formula (Ia-1), M 11 + and M 12 + each independently represents an organic cation. A 11- and A 12 - each independently represents a monovalent anionic functional group. L1 represents a divalent linking group. M 11 + and M 12 + may be the same or different. A 11 - and A 12 - may be the same or different, but are preferably different from each other. However, in the above formula (Ia-1), M 11 + and M 12 + The cation represented by H + Compound PIa (HA 11 -L1-A 12 In H), A 12 The acid dissociation constant a2 derived from the acidic site represented by H is HA 11 The acid dissociation constant a1 is larger than the acid dissociation constant a1 derived from the acidic moiety represented by formula (Ia-1). The preferred values ​​of the acid dissociation constant a1 and the acid dissociation constant a2 are as described above. The acid generated from the compound PIa and the compound represented by formula (Ia-1) upon irradiation with an electron beam is the same. Also, M 11 + , M 12 + , A 11 - , A 12 - At least one of L1 and L2 may have an acid-decomposable group as a substituent.

[0267] In formula (Ia-1), M1 + and M2 + The organic cation represented by the formula (I) is as described above.

[0268] A 11 - The monovalent anionic functional group represented by the formula (I) is the anionic moiety A1- Also, A is intended to be a monovalent group containing 12 - The monovalent anionic functional group represented by the formula (I) is the anionic moiety A2 - is intended to mean a monovalent radical comprising: A 11 - and A 12 - The monovalent anionic functional group represented by the formula (AA-1) to (AA-3) and the formula (BB-1) to (BB-6) is preferably a monovalent anionic functional group containing an anionic moiety, and more preferably a monovalent anionic functional group selected from the group consisting of the formula (AX-1) to (AX-3) and the formula (BX-1) to (BX-7). 11 - Among them, the monovalent anionic functional group represented by formula (AX-1) to (AX-3) is preferable. 12 - Of the monovalent anionic functional groups represented by formula (BX-1), a monovalent anionic functional group represented by any one of formulas (BX-1) to (BX-7) is preferred, and a monovalent anionic functional group represented by any one of formulas (BX-1) to (BX-6) is more preferred.

[0269] [ka]

[0270] In formulas (AX-1) to (AX-3), R A1 and R A2 each independently represents a monovalent organic group. * represents a bonding position. R A1 The monovalent organic group represented by the formula (I) is not particularly limited, but examples thereof include a cyano group, a trifluoromethyl group, and a methanesulfonyl group.

[0271] R A2 The monovalent organic group represented by the formula (I) is preferably a linear, branched, or cyclic alkyl group or an aryl group. The alkyl group preferably has 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 6 carbon atoms. The alkyl group may have a substituent. The substituent is preferably a fluorine atom or a cyano group, more preferably a fluorine atom. When the alkyl group has a fluorine atom as a substituent, it may be a perfluoroalkyl group.

[0272] The aryl group is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group may have a substituent. The substituent is preferably a fluorine atom, an iodine atom, a perfluoroalkyl group (for example, preferably having 1 to 10 carbon atoms, more preferably having 1 to 6 carbon atoms), or a cyano group, and more preferably a fluorine atom, an iodine atom, or a perfluoroalkyl group.

[0273] In formulas (BX-1) to (BX-4) and (BX-6), R B represents a monovalent organic group. * represents a bonding position. R B The monovalent organic group represented by the formula (I) is preferably a linear, branched, or cyclic alkyl group or an aryl group. The alkyl group preferably has 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 6 carbon atoms. The alkyl group may have a substituent. The substituent is not particularly limited, but is preferably a fluorine atom or a cyano group, more preferably a fluorine atom. When the alkyl group has a fluorine atom as a substituent, it may be a perfluoroalkyl group. In addition, the carbon atom that is the bonding position in the alkyl group (for example, in the case of formulas (BX-1) and (BX-4), the carbon atom that is directly bonded to -CO- specified in the formula in the alkyl group corresponds to this, in the case of formulas (BX-2) and (BX-3), the carbon atom that is directly bonded to -SO2- specified in the formula in the alkyl group corresponds to this, and in the case of formula (BX-6), the carbon atom that is directly bonded to -SO2- specified in the formula in the alkyl group corresponds to this -When ) has a substituent, the substituent is preferably a fluorine atom or a cyano group. In addition, the alkyl group may have a carbon atom substituted with a carbonyl carbon.

[0274] The aryl group is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group may have a substituent. The substituent is preferably a fluorine atom, an iodine atom, a perfluoroalkyl group (for example, preferably having 1 to 10 carbon atoms, more preferably having 1 to 6 carbon atoms), a cyano group, an alkyl group (for example, preferably having 1 to 10 carbon atoms, more preferably having 1 to 6 carbon atoms), an alkoxy group (for example, preferably having 1 to 10 carbon atoms, more preferably having 1 to 6 carbon atoms), or an alkoxycarbonyl group (for example, preferably having 2 to 10 carbon atoms, more preferably having 2 to 6 carbon atoms), and more preferably a fluorine atom, an iodine atom, a perfluoroalkyl group, an alkyl group, an alkoxy group, or an alkoxycarbonyl group.

[0275] In formula (Ia-1), the divalent linking group represented by L1 is not particularly limited, and may be -CO-, -NR-, -CO-, -O-, -S-, -SO-, -SO2-, an alkylene group (preferably having 1 to 6 carbon atoms, which may be linear or branched), a cycloalkylene group (preferably having 3 to 15 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), a divalent aliphatic heterocyclic group (having at least one N atom, O atom, S atom, or Se atom in the ring structure), or Examples of the R include a 5- to 10-membered ring having at least one N atom, O atom, S atom, or Se atom in the ring structure, preferably a 5- to 7-membered ring, more preferably a 5- to 6-membered ring, divalent aromatic heterocyclic group (a 5- to 10-membered ring having at least one N atom, O atom, S atom, or Se atom in the ring structure, preferably a 5- to 7-membered ring, more preferably a 5- to 6-membered ring), divalent aromatic hydrocarbon ring group (a 6- to 10-membered ring, more preferably a 6-membered ring), and a divalent linking group combining two or more of these. The R is, for example, a hydrogen atom or a monovalent organic group. The monovalent organic group is not particularly limited, but an alkyl group (preferably having 1 to 6 carbon atoms) is preferable. The alkylene group, the cycloalkylene group, the alkenylene group, the divalent aliphatic heterocyclic group, the divalent aromatic heterocyclic group, and the divalent aromatic hydrocarbon ring group may have a substituent, such as a halogen atom (preferably a fluorine atom).

[0276] Among these, the divalent linking group represented by L1 is preferably a divalent linking group represented by formula (L1).

[0277] [ka]

[0278] In formula (L1), L 111 represents a single bond or a divalent linking group. L 111 The divalent linking group represented by the formula (I) is not particularly limited, and examples thereof include -CO-, -NH-, -O-, -SO-, -SO2-, an alkylene group (preferably having 1 to 6 carbon atoms, and more preferably having a straight chain or branched chain), an optionally substituted cycloalkylene group (preferably having 3 to 15 carbon atoms), an optionally substituted aryl group (preferably having 6 to 10 carbon atoms), and a divalent linking group formed by combining two or more of these. The substituent is not particularly limited, and examples thereof include a halogen atom. p represents an integer of 0 to 3, and preferably an integer of 1 to 3. v represents an integer of 0 or 1. Each Xf1 independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The number of carbon atoms in this alkyl group is preferably 1 to 10, more preferably 1 to 4. Furthermore, the alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group. Each Xf2 independently represents a hydrogen atom, an alkyl group which may have a fluorine atom as a substituent, or a fluorine atom. The number of carbon atoms in this alkyl group is preferably 1 to 10, and more preferably 1 to 4. Among these, Xf2 preferably represents a fluorine atom or an alkyl group substituted with at least one fluorine atom, and more preferably a fluorine atom or a perfluoroalkyl group. Among these, Xf1 and Xf2 are preferably each independently a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, and more preferably a fluorine atom or CF3. In particular, it is even more preferable that both Xf1 and Xf2 are fluorine atoms. * indicates the bond position. L in formula (Ia-1) 11 represents a divalent linking group represented by formula (L1), L in formula (L1) 111 The bond (*) on the side of the A 12 - It is preferred to combine with

[0279] -Compounds represented by formulae (Ia-2) to (Ia-4)- Next, the compounds represented by formulae (Ia-2) to (Ia-4) will be described.

[0280] [ka]

[0281] In formula (Ia-2), A 21a - and A 21b - Each independently represents a monovalent anionic functional group. 21a - and A 21b - The monovalent anionic functional group represented by the formula (I) is the anionic moiety A1 - A is intended to be a monovalent radical containing 21a - and A 21b -The monovalent anionic functional group represented by the formula (AX-1) is not particularly limited, and examples thereof include monovalent anionic functional groups selected from the group consisting of the above formulas (AX-1) to (AX-3). A 22 - represents a divalent anionic functional group. 22 - The divalent anionic functional group represented by the formula (I) is the anionic moiety A2 - A divalent group containing 22 - Examples of the divalent anionic functional group represented by the formula (BX-8) to (BX-11) shown below can be given.

[0282] [ka]

[0283] M 21a + , M 21b + , and M 22 + each independently represents an organic cation. M 21a + , M 21b + , and M 22 + As the organic cation represented by the formula, the above-mentioned M1 + The same definition and preferred embodiments are also the same. L 21 and L 22 each independently represents a divalent organic group.

[0284] In addition, in the above formula (Ia-2), M 21a + , M 21b + , and M 22 + The organic cation represented by H + In compound PIa-2, A is replaced by 22 The acid dissociation constant a2 derived from the acidic site represented by H is A21a Acid dissociation constants a1-1 and A1 derived from H 21b It is larger than the acid dissociation constant a1-2 derived from the acidic site represented by H. The acid dissociation constant a1-1 and the acid dissociation constant a1-2 correspond to the acid dissociation constant a1 described above. In addition, A 21a - and A 21b - may be the same or different. 21a + , M 21b + , and M 22 + may be the same or different from each other. Also, M 21a + , M 21b + , M 22 + , A 21a - , A 21b - , L 21 , and L 22 At least one of them may have an acid-decomposable group as a substituent.

[0285] In formula (Ia-3), A 31a - and A 32 - Each independently represents a monovalent anionic functional group. 31a - The definition of the monovalent anionic functional group represented by A in the above formula (Ia-2) is 21a - and A 21b - The same definition and preferred embodiments are also the same. A 32 - The monovalent anionic functional group represented by the above-mentioned anionic moiety A2 - A is intended to be a monovalent radical containing 32 -The monovalent anionic functional group represented by the formula (BX-1) is not particularly limited, and examples thereof include monovalent anionic functional groups selected from the group consisting of the above formulas (BX-1) to (BX-7). A 31b - represents a divalent anionic functional group. 31b - The divalent anionic functional group represented by the formula (I) is the anionic moiety A1 - A divalent group containing 31b - Examples of the divalent anionic functional group represented by formula (AX-4) include divalent anionic functional groups represented by formula (AX-4) shown below.

[0286] [ka]

[0287] M 31a + , M 31b + , and M 32 + Each independently represents a monovalent organic cation. 31a + , M 31b + , and M 32 + As the organic cation represented by the formula, the above-mentioned M1 + The same definition and preferred embodiments are also the same. L 31 and L 32 each independently represents a divalent organic group.

[0288] In addition, in the above formula (Ia-3), M 31a + , M 31b + , and M 32 + The organic cation represented by H + In compound PIa-3, A is replaced by 32 The acid dissociation constant a2 derived from the acidic site represented by H is A 31aAcid dissociation constants a1-3 and A2 derived from the acidic site represented by H 31b It is larger than the acid dissociation constant a1-4 derived from the acidic site represented by H. The acid dissociation constant a1-3 and the acid dissociation constant a1-4 correspond to the acid dissociation constant a1 described above. In addition, A 31a - and A 32 - may be the same or different. 31a + , M 31b + , and M 32 + may be the same or different from each other. Also, M 31a + , M 31b + , M 32 + , A 31a - , A 32 - , L 31 , and L 32 At least one of them may have an acid-decomposable group as a substituent.

[0289] In formula (Ia-4), A 41a - , A 41b - , and A 42 - Each independently represents a monovalent anionic functional group. 41a - and A 41b - The definition of the monovalent anionic functional group represented by A in the above formula (Ia-2) is 21a - and A 21b - Also, A 42 - The definition of the monovalent anionic functional group represented by A in the above formula (Ia-3) is 32 - The same definition and preferred embodiments are also the same. M 41a +, M 41b + , and M 42 + each independently represents an organic cation. L 41 represents a trivalent organic group.

[0290] In addition, in the above formula (Ia-4), M 41a + , M 41b + , and M 42 + The organic cation represented by H + In compound PIa-4, A is replaced by 42 The acid dissociation constant a2 derived from the acidic site represented by H is A 41a Acid dissociation constants a1-5 and A2 derived from the acidic site represented by H 41b It is larger than the acid dissociation constant a1-6 derived from the acidic site represented by H. The acid dissociation constant a1-5 and the acid dissociation constant a1-6 correspond to the acid dissociation constant a1 described above. In addition, A 41a - , A 41b - , and A 42 - may be the same or different. 41a + , M 41b + , and M 42 + may be the same or different from each other. Also, M 41a + , M 41b + , M 42 + , A 41a - , A 41b - , A 42 - , and L 41 At least one of them may have an acid-decomposable group as a substituent.

[0291] L in formula (Ia-2) 21and L 22 and L in formula (Ia-3). 31 and L 32 The divalent organic group represented by the formula (I) is not particularly limited, and examples thereof include -CO-, -NR-, -O-, -S-, -SO-, -SO2-, an alkylene group (preferably having 1 to 6 carbon atoms, which may be linear or branched), a cycloalkylene group (preferably having 3 to 15 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), a divalent aliphatic heterocyclic group (preferably a 5- to 10-membered ring having at least one N atom, O atom, S atom, or Se atom in the ring structure, more preferably a 5- to 7-membered ring, and even more preferably a 5- to 6-membered ring), a divalent aromatic heterocyclic group (preferably a 5- to 10-membered ring having at least one N atom, O atom, S atom, or Se atom in the ring structure, more preferably a 5- to 7-membered ring, and even more preferably a 5- to 6-membered ring), a divalent aromatic hydrocarbon ring group (preferably a 6- to 10-membered ring, and even more preferably a 6-membered ring), and a divalent organic group formed by combining two or more of these. The above R may be a hydrogen atom or a monovalent organic group. The monovalent organic group is not particularly limited, but is preferably, for example, an alkyl group (preferably having 1 to 6 carbon atoms). The alkylene group, the cycloalkylene group, the alkenylene group, the divalent aliphatic heterocyclic group, the divalent aromatic heterocyclic group, and the divalent aromatic hydrocarbon ring group may have a substituent, such as a halogen atom (preferably a fluorine atom).

[0292] L in formula (Ia-2) 21 and L 22 and L in formula (Ia-3). 31 and L 32 The divalent organic group represented by the formula (L1) is preferably, for example, a divalent organic group represented by the following formula (L2).

[0293] [ka]

[0294] In formula (L2), q represents an integer of 1 to 3. * represents a bonding position. Each Xf independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The number of carbon atoms in this alkyl group is preferably 1 to 10, more preferably 1 to 4. Furthermore, the alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group. Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, more preferably a fluorine atom or CF3, and particularly preferably both Xf are fluorine atoms.

[0295] L A represents a single bond or a divalent linking group. L A The divalent linking group represented by the formula (I) is not particularly limited, and examples thereof include -CO-, -O-, -SO-, -SO2-, an alkylene group (preferably having 1 to 6 carbon atoms, which may be linear or branched), a cycloalkylene group (preferably having 3 to 15 carbon atoms), a divalent aromatic hydrocarbon ring group (preferably a 6- to 10-membered ring, more preferably a 6-membered ring), and a divalent linking group formed by combining two or more of these. The alkylene group, the cycloalkylene group, and the divalent aromatic hydrocarbon ring group may have a substituent, such as a halogen atom (preferably a fluorine atom).

[0296] Examples of the divalent organic group represented by formula (L2) include *-CF2-*, *-CF2-CF2-*, *-CF2-CF2-CF2-*, *-Ph-O-SO2-CF2-*, *-Ph-O-SO2-CF2-CF2-*, *-Ph-O-SO2-CF2-CF2-CF2-*, and *-Ph-OCO-CF2-*. Ph represents a phenylene group which may have a substituent, and is preferably a 1,4-phenylene group. The substituent is not particularly limited, but is preferably an alkyl group (e.g., preferably having 1 to 10 carbon atoms, more preferably having 1 to 6 carbon atoms), an alkoxy group (e.g., preferably having 1 to 10 carbon atoms, more preferably having 1 to 6 carbon atoms), or an alkoxycarbonyl group (e.g., preferably having 2 to 10 carbon atoms, more preferably having 2 to 6 carbon atoms). L in formula (Ia-2) 21 and L 22 represents a divalent organic group represented by formula (L2), L in formula (L2) A The bond (*) on the side of the A 21a - and A 21b - It is preferred to combine with Furthermore, L in formula (Ia-3) 31 and L 32 represents a divalent organic group represented by formula (L2), L in formula (L2) A The bond (*) on the side of the A 31a - and A 32 - It is preferred to combine with

[0297] -Compound represented by formula (Ia-5)- Next, formula (Ia-5) will be described.

[0298] [ka]

[0299] In formula (Ia-5), A 51a - , A 51b - , and A 51c - Each independently represents a monovalent anionic functional group. 51a - , A 51b - , and A 51c - The monovalent anionic functional group represented by the formula (I) is the anionic moiety A1 - A is intended to be a monovalent radical containing 51a - , A 51b - , and A 51c -The monovalent anionic functional group represented by the formula (AX-1) is not particularly limited, and examples thereof include monovalent anionic functional groups selected from the group consisting of the above formulas (AX-1) to (AX-3). A 52a - and A 52b - represents a divalent anionic functional group. 52a - and A 52b - The divalent anionic functional group represented by the formula (I) is the anionic moiety A2 - A divalent group containing 22 - Examples of the divalent anionic functional group represented by the formula (BX-8) to (BX-11) include divalent anionic functional groups selected from the group consisting of the above formulas (BX-8) to (BX-11).

[0300] M 51a + , M 51b + , M 51c + , M 52a + , and M 52b + Each independently represents an organic cation. 51a + , M 51b + , M 51c + , M 52a + , and M 52b + As the organic cation represented by the formula, the above-mentioned M1 + The same definition and preferred embodiments are also the same. L 51 and L 53 L each independently represents a divalent organic group. 51 and L 53 Examples of the divalent organic group represented by the formula (Ia-2) include L 21 and L 22 The same definition and preferred embodiments are also the same. L 52 represents a trivalent organic group. 52The trivalent organic group represented by the formula (Ia-4) is L 41 The same definition and preferred embodiments are also the same.

[0301] In addition, in the above formula (Ia-5), M 51a + , M 51b + , M 51c + , M 52a + , and M 52b + The organic cation represented by H + In compound PIa-5, A is replaced by 52a The acid dissociation constants a2-1 and A2-1 derived from the acidic site represented by H 52b The acid dissociation constant a2-2 derived from the acidic site represented by H is A 51a Acid dissociation constant a1-1, A 51b The acid dissociation constants a1-2 and A2 are derived from the acidic sites represented by H. 51c It is larger than the acid dissociation constant a1-3 derived from the acidic site represented by H. The acid dissociation constants a1-1 to a1-3 correspond to the above-mentioned acid dissociation constant a1, and the acid dissociation constants a2-1 and a2-2 correspond to the above-mentioned acid dissociation constant a2. In addition, A 51a - , A 51b - , and A 51c - may be the same or different. 52a - and A 52b - may be the same or different. 51a + , M 51b + , M 51c + , M 52a + , and M 52b + may be the same or different from each other. Also, M 51b + , M 51c+ , M 52a + , M 52b + , A 51a - , A 51b - , A 51c - , L 51 , L 52 , and L 53 At least one of them may have an acid-decomposable group as a substituent.

[0302] (Compound (II)) Compound (II) is a compound having two or more of the structural moieties X described above and one or more of the structural moieties Z described below, and is a compound that generates an acid containing two or more of the first acidic moieties derived from the structural moiety X and the structural moiety Z when irradiated with an electron beam. Structural site Z: a ​​non-ionic site capable of neutralizing acids

[0303] In compound (II), the definition of the structural moiety X and A1 - and M1 + The definition of the structural moiety X in the compound (I) and A1 - and M1 + The definition and preferred embodiments are also the same.

[0304] In the compound (II), the cation moiety M1 in the structural moiety X + H + In the compound PII, the cationic moiety M1 in the structural moiety X is replaced by + H + The preferred range of the acid dissociation constant a1 derived from the acidic moiety represented by HA1 in which the acid dissociation constant a1 is substituted with HA1 is the same as the acid dissociation constant a1 in the compound PI. In addition, when compound (II) is, for example, a compound that generates an acid having two of the first acidic sites derived from the structural site X and the structural site Z, compound PII corresponds to a "compound having two HA1s." When the acid dissociation constant of this compound PII is calculated, it is considered that compound PII has "one A1 -and one HA1" and the acid dissociation constant when "a compound having one A1" - and one HA1" is "a compound with two A1 - The acid dissociation constant when the compound becomes "a compound having the formula (I)" corresponds to the acid dissociation constant a1.

[0305] The acid dissociation constant a1 can be determined by the above-mentioned method for measuring an acid dissociation constant. The compound PII corresponds to the acid generated when compound (II) is irradiated with an electron beam. The two or more structural moieties X may be the same or different. - , and two or more of the above M1 + may be the same or different.

[0306] The nonionic moiety capable of neutralizing an acid in the structural moiety Z is not particularly limited, and is preferably, for example, a moiety containing a group capable of electrostatically interacting with a proton or a functional group having an electron. Examples of the group capable of electrostatically interacting with a proton or the functional group having an electron include a functional group having a macrocyclic structure such as a cyclic polyether, or a functional group having a nitrogen atom with an unshared electron pair that does not contribute to π-conjugation. The nitrogen atom with an unshared electron pair that does not contribute to π-conjugation is, for example, a nitrogen atom having a partial structure shown in the following formula:

[0307] [ka]

[0308] Examples of the partial structure of a functional group having a group or electron capable of electrostatically interacting with a proton include a crown ether structure, an azacrown ether structure, a primary to tertiary amine structure, a pyridine structure, an imidazole structure, and a pyrazine structure, and among these, a primary to tertiary amine structure is preferred.

[0309] Compound (II) is not particularly limited, but examples thereof include compounds represented by the following formula (IIa-1) and formula (IIa-2).

[0310] [ka]

[0311] In the above formula (IIa-1), A 61a - and A 61b - are A in the above formula (Ia-1), respectively. 11 - The same definition and preferred embodiments are also the same. 61a + and M 61b + are the M in the above formula (Ia-1), 11 + The same definition and preferred embodiments are also the same. In the above formula (IIa-1), L 61 and L 62 have the same meanings as L1 in the above formula (Ia-1), and the preferred embodiments are also the same.

[0312] In formula (IIa-1), R 2X represents a monovalent organic group. 2X The monovalent organic group represented by the formula (I) is not particularly limited, and examples thereof include an alkyl group (preferably having 1 to 10 carbon atoms, which may be linear or branched), a cycloalkyl group (preferably having 3 to 15 carbon atoms), or an alkenyl group (preferably having 2 to 6 carbon atoms), in which -CH2- may be substituted with one or a combination of two or more selected from the group consisting of -CO-, -NH-, -O-, -S-, -SO-, and -SO2-. The alkylene group, cycloalkylene group, and alkenylene group may have a substituent. The substituent is not particularly limited, but examples thereof include a halogen atom (preferably a fluorine atom).

[0313] In addition, in the above formula (IIa-1), M 61a+ and M 61b + The organic cation represented by H + In the compound PIIa-1, A is replaced by 61a Acid dissociation constants a1-7 and A2 derived from the acidic site represented by H 61b The acid dissociation constant a1-8 derived from the acidic site represented by H corresponds to the above-mentioned acid dissociation constant a1. In the compound (IIa-1), the cationic moiety M in the structural moiety X 61a + and M 61b + H + Compound PIIa-1, which is substituted with HA 61a -L 61 -N(R 2X )-L 62 -A 61b The compound PIIa-1 corresponds to H. The acid generated from the compound represented by formula (IIa-1) upon irradiation with an electron beam is the same as that generated from the compound PIIa-1. Also, M 61a + , M 61b + , A 61a - , A 61b - , L 61 , L 62 , and R 2X At least one of them may have an acid-decomposable group as a substituent.

[0314] In the above formula (IIa-2), A 71a - , A 71b - , and A 71c - are A in the above formula (Ia-1), respectively. 11 - The same definition and preferred embodiments are also the same. 71a + , M 71b + , and M 71c + are the M in the above formula (Ia-1), 11+ The same definition and preferred embodiments are also the same. In the above formula (IIa-2), L 71 , L 72 , and L 73 have the same meanings as L1 in the above formula (Ia-1), and the preferred embodiments are also the same.

[0315] In addition, in the above formula (IIa-2), M 71a + , M 71b + , and M 71c + The organic cation represented by H + In the compound PIIa-2, A is replaced by 71a Acid dissociation constant a1-9, A, derived from the acidic site represented by H 71b The acid dissociation constant a1-10 derived from the acidic site represented by H, and A 71c The acid dissociation constant a1-11 derived from the acidic site represented by H corresponds to the acid dissociation constant a1 described above. In the compound (IIa-1), the cationic moiety M in the structural moiety X 71a + , M 71b + , and M 71c + H + Compound PIIa-2, which is substituted with HA 71a -L 71 -N(L 73 -A 71c H)-L 72 -A 71b The compound PIIa-2 corresponds to H. The acid generated from the compound represented by formula (IIa-2) upon irradiation with an electron beam is the same as that generated from the compound PIIa-2. Also, M 71a + , M 71b + , M 71c + , A 71a - , A 71b - , A 71c - , L 71 , L72 , and L 73 At least one of them may have an acid-decomposable group as a substituent.

[0316] Examples of moieties other than cations that can be possessed by compounds (I) and (II) are shown below.

[0317] [ka]

[0318] [ka]

[0319] Specific examples of the acid generator are shown below, but the invention is not limited to these.

[0320] [ka]

[0321] [ka]

[0322] When the resist layer contains an acid generator (B), the content of the acid generator (B) is not particularly limited, but in order to form a more rectangular cross-sectional pattern, the content is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, and even more preferably 10% by mass or more, relative to the total mass of the resist layer. Furthermore, the content is preferably 50.0% by mass or less, more preferably 30.0% by mass or less, and even more preferably 25.0% by mass or less, relative to the total mass of the resist layer. The acid generator (B) may be used alone or in combination of two or more.

[0323] (Acid diffusion controller (C)) The resist layer may contain an acid diffusion controller. The acid diffusion controller traps the acid generated from the acid generator or the like upon electron beam irradiation, and acts as a quencher to suppress the reaction of the acid-decomposable resin in the unirradiated area caused by excess acid generated. The type of acid diffusion controller is not particularly limited, and examples thereof include basic compounds (CA), low molecular weight compounds (CB) having a nitrogen atom and a group that is cleaved by the action of an acid, and compounds (CC) whose acid diffusion control ability is reduced or lost by irradiation with an electron beam. Examples of the compound (CC) include an onium salt compound (CD) that is a weaker acid than the acid generator, and a basic compound (CE) whose basicity is reduced or eliminated by irradiation with an electron beam. The onium salt compound (CC) is an onium salt compound that generates an acid by irradiation with an electron beam, and corresponds to an onium salt compound in which the acid generated from the onium salt is weaker than the acid generated from the acid generator. Furthermore, for example, specific examples of basic compounds (CA) include those described in paragraphs

[0132] to

[0136] of WO 2020 / 066824, specific examples of basic compounds (CE) whose basicity is reduced or eliminated by electron beam irradiation include those described in paragraphs

[0137] to

[0155] of WO 2020 / 066824, specific examples of low molecular weight compounds (CB) having a nitrogen atom and a group that is cleaved by the action of an acid include those described in paragraphs

[0156] to

[0163] of WO 2020 / 066824, and specific examples of onium salt compounds (CE) having a nitrogen atom in the cation moiety include those described in paragraph

[0164] of WO 2020 / 066824. Specific examples of onium salt compounds (CD) that are weakly acidic relative to the acid generator include those described in paragraphs

[0305] to

[0314] of WO 2020 / 158337.

[0324] In addition to the above, known compounds disclosed in, for example, U.S. Patent Application Publication No. 2016 / 0070167A1, paragraphs

[0627] to

[0664] , U.S. Patent Application Publication No. 2015 / 0004544A1, paragraphs

[0095] to

[0187] , U.S. Patent Application Publication No. 2016 / 0237190A1, paragraphs

[0403] to

[0423] , and U.S. Patent Application Publication No. 2016 / 0274458A1, paragraphs

[0259] to

[0328] can be suitably used as the acid diffusion controller.

[0325] When the resist layer contains an acid diffusion controller, the content of the acid diffusion controller (the total content if there are multiple types) is preferably 0.1 to 15.0 mass %, more preferably 1.0 to 15.0 mass %, based on the total mass of the resist layer. The acid diffusion controller may be used alone or in combination of two or more kinds.

[0326] (Hydrophobic resin (D)) The composition for forming a resist layer may further contain a hydrophobic resin different from the resin (A). The hydrophobic resin is preferably designed to be unevenly distributed on the surface of the resist film, but unlike surfactants, it does not necessarily have to have a hydrophilic group in its molecule, and it does not necessarily have to contribute to uniform mixing of polar and non-polar substances. The effects of adding a hydrophobic resin include control of the static and dynamic contact angle of water on the surface of the resist film and suppression of outgassing.

[0327] From the viewpoint of uneven distribution in the film surface layer, the hydrophobic resin preferably has one or more of a fluorine atom, a silicon atom, and a CH3 partial structure contained in a side chain portion of the resin, and more preferably has two or more of these. Furthermore, the hydrophobic resin preferably has a hydrocarbon group having 5 or more carbon atoms. These groups may be contained in the main chain of the resin or may be substituted on the side chain. Examples of hydrophobic resins include the compounds described in paragraphs

[0275] to

[0279] of WO 2020 / 004306.

[0328] When the resist layer contains a hydrophobic resin, the content of the hydrophobic resin is preferably 0.01 to 20.0 mass %, more preferably 0.1 to 15.0 mass %, relative to the total mass of the resist layer.

[0329] (Surfactant (E)) The resist layer may contain a surfactant, which provides better adhesion and allows the formation of a pattern with fewer development defects. The surfactant is preferably a fluorine-based and / or silicon-based surfactant. Examples of fluorine-based and / or silicone-based surfactants include surfactants disclosed in paragraphs

[0218] and

[0219] of WO 2018 / 19395. These surfactants may be used alone or in combination of two or more.

[0330] When the resist layer contains a surfactant, the content of the surfactant is preferably 0.0001 to 2.0 mass %, more preferably 0.0005 to 1.0 mass %, and even more preferably 0.1 to 1.0 mass %, relative to the total mass of the resist layer.

[0331] (Other additives) The resist layer may further contain a dissolution-inhibiting compound, 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 molecular weight of 1000 or less, or an alicyclic or aliphatic compound containing a carboxyl group).

[0332] The method for forming the resist layer is not particularly limited, and examples thereof include a method using a composition for forming a resist layer, as described above. The composition for forming a resist layer preferably contains the above-mentioned resin (A), an acid generator, and a solvent, and further preferably contains the above-mentioned acid diffusion controller. The composition for forming a resist layer may contain materials other than the resin (A), acid generator, and acid diffusion controller described above.

[0333] As described above, the composition for forming a resist layer preferably contains a solvent. The solvent preferably contains (M1) propylene glycol monoalkyl ether carboxylate and (M2) at least one selected from the group consisting of propylene glycol monoalkyl ether, lactate ester, acetate ester, alkoxypropionate ester, linear ketone, cyclic ketone, lactone, and alkylene carbonate. The solvent may further contain components other than components (M1) and (M2).

[0334] The present inventors have found that using such a solvent in combination with the above-mentioned resin improves the coatability of the composition for forming a resist layer and enables the formation of a pattern with fewer development defects. Although the reason for this is not entirely clear, the present inventors believe that this is due to the fact that these solvents have a good balance of the solubility, boiling point, and viscosity of the above-mentioned resin, making it possible to suppress unevenness in the thickness of the resist film and the occurrence of precipitates during spin coating. Details of the components (M1) and (M2) are described in paragraphs

[0218] to

[0226] of WO 2020 / 004306, the contents of which are incorporated herein by reference.

[0335] When the solvent further contains components other than the components (M1) and (M2), the content of the components other than the components (M1) and (M2) is preferably 5 to 30 mass % based on the total amount of the solvent.

[0336] The content of the solvent in the composition for forming a resist layer is preferably determined so that the solid content concentration is 0.5 to 30 mass %, more preferably 1 to 20 mass %.

[0337] <Middle class> The intermediate layer is a layer disposed between the resist layer and the conductive layer. The intermediate layer is a layer different from both the resist layer and the conductive layer. The intermediate layer preferably does not contain a resin (A). Furthermore, the intermediate layer preferably does not contain a conductive polymer. The intermediate layer preferably contains a resin (hereinafter also referred to as resin (X)). That is, the intermediate layer is preferably a resin layer containing resin (X). Note that the resin (X) contained in the intermediate layer and the resin (A) contained in the resist layer are usually different resins. The resin (X) is preferably a resin soluble in the developer used in the development process. When the developer is an alkaline developer, the resin is preferably soluble in the alkaline developer, and when the developer is an organic developer, the resin is preferably soluble in the organic developer. The term "resin soluble in a developer" refers to a resin that, when a 100 nm thick resin layer is formed by applying a composition X containing only resin (X) as a solid content and baking the resulting coating at 100°C for 300 seconds, and then immersing the resulting resin layer in a developer (30 ml) for 30 seconds, reduces the thickness of the resin layer by 98 nm or more. The thickness reduction of the resin layer is preferably 100 nm. Note that the composition X contains, in addition to the resin (X), a solvent capable of dissolving the resin (X). The solvent capable of dissolving the resin (X) refers to a solvent in which 10 g or more of the resin (X) can be dissolved per liter of the solvent. Generally, both resins soluble in alkaline developers and resins soluble in organic developers are poorly soluble in water. Therefore, as described below, when the conductive layer-forming composition is an aqueous composition containing water, the intermediate layer is less likely to dissolve even when the conductive layer-forming composition is applied onto the intermediate layer, and the desired laminate can be produced with good productivity.

[0338] (Resin (X)) The resin (X) may contain a repeating unit having an alkali-soluble group. When the resin (X) contains a repeating unit having an alkali-soluble group, the solubility of the resin (X) in an alkaline developer is improved. Examples of the alkali-soluble group include a phenolic hydroxyl group, a carboxyl group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonylimide group, an (alkylsulfonyl)(alkylcarbonyl)methylene group, an (alkylsulfonyl)(alkylcarbonyl)imide group, a bis(alkylcarbonyl)methylene group, a bis(alkylcarbonyl)imide group, a bis(alkylsulfonyl)methylene group, a bis(alkylsulfonyl)imide group, a tris(alkylcarbonyl)methylene group, and a tris(alkylsulfonyl)methylene group, of which a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfonic acid group, or a sulfonamide group is preferred. Examples of fluorinated alcohol groups include -CF2OH, -CH2CF2OH, -CH2CF2CF2OH, -C(CF3)2OH, -CF2CF(CF3)OH, and -CH2C(CF3)2OH. A preferred fluorinated alcohol group is a hexafluoroisopropanol group.

[0339] The repeating unit having an alkali-soluble group is preferably a repeating unit represented by formula (A).

[0340] [ka]

[0341] R a1 represents a hydrogen atom or an alkyl group. L a represents a single bond or an (n+1)-valent linking group. Examples of the (n+1)-valent linking group include divalent linking groups and trivalent linking groups. More specific examples include -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -S-, -SO-, -SO2-, alkylene groups (preferably having 1 to 6 carbon atoms), divalent or trivalent aliphatic cyclic groups (preferably having 3 to 15 carbon atoms), alkenylene groups (preferably having 2 to 6 carbon atoms), divalent or trivalent aromatic cyclic groups, and divalent or trivalent linking groups formed by combining a plurality of these groups. R a2 represents an alkali-soluble group. n represents an integer of 1 or more, preferably 1 to 5, and more preferably 1 to 2.

[0342] Examples of repeating units having an alkali-soluble group include those described in paragraphs

[0278] to

[0287] of JP-A No. 2008-309878.

[0343] When the resin (X) contains a repeating unit having an alkali-soluble group, the content of the repeating unit having an alkali-soluble group is preferably 30 to 100 mol %, more preferably 50 to 90 mol %, based on the total repeating units of the resin (X). The resin (X) may contain only one type of repeating unit having an alkali-soluble group, or may contain two or more types.

[0344] The resin (X) may contain a repeating unit having a monocyclic or polycyclic cycloalkyl group. The monocyclic or polycyclic cycloalkyl group may be contained in either the main chain or the side chain of the repeating unit. Examples of the monocyclic cycloalkyl group include a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. Examples of polycyclic cycloalkyl groups include norbornyl, tricyclodecanyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups. The monocyclic or polycyclic cycloalkyl group may further be substituted with a substituent, such as a hydroxyl group.

[0345] When the resin (X) contains a repeating unit having a monocyclic or polycyclic cycloalkyl group, the content of the repeating unit having a monocyclic or polycyclic cycloalkyl group is preferably 5 to 30 mol %, more preferably 10 to 20 mol %, based on the total repeating units of the resin (X). The resin (X) may contain only one type of repeating unit having a monocyclic or polycyclic cycloalkyl group, or may contain two or more types.

[0346] The resin (X) may contain a repeating unit having a CH3 partial structure in the side chain portion. Furthermore, the resin (X) may contain a repeating unit having at least two CH3 partial structures in the side chain portion, or may contain a repeating unit having at least three CH3 partial structures in the side chain portion. Here, the CH3 partial structure possessed by the side chain portion in the resin (X) includes the CH3 partial structures possessed by an ethyl group, a propyl group, and the like. On the other hand, methyl groups directly bonded to the main chain of resin (X) (for example, α-methyl groups of repeating units having a methacrylic acid structure) are not included in the CH3 partial structure of the present invention because they have little contribution to the uneven distribution of resin (X) on the surface due to the influence of the main chain.

[0347] The repeating unit having a CH3 partial structure in the side chain is preferably a repeating unit represented by formula (B).

[0348] [ka]

[0349] R b1 represents a hydrogen atom, an alkyl group, a cyano group, or a halogen atom. b1 is preferably a hydrogen atom or a methyl group.

[0350] R b2 represents an organic group having one or more CH3 moieties. R b2 Examples of the alkyl group include alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, and aralkyl groups having one or more CH3 moieties. R b2 As the alkyl group, an alkyl group or an alkyl-substituted cycloalkyl group having one or more CH3 moieties is preferred. The alkyl group having one or more CH3 partial structures is preferably a branched alkyl group having 3 to 20 carbon atoms. The cycloalkyl group having one or more CH3 partial structures may be monocyclic or polycyclic, and specific examples include groups having monocyclo, bicyclo, tricyclo, and tetracyclo structures having 5 or more carbon atoms.

[0351] When the resin (X) contains a repeating unit having a CH3 partial structure in the side chain portion, the content of the repeating unit having a CH3 partial structure in the side chain portion is preferably 30 to 100 mol %, more preferably 50 to 90 mol %, based on the total repeating units of the resin (X). The resin (X) may contain only one type of repeating unit having a CH3 partial structure in the side chain portion, or may contain two or more types.

[0352] The resin (X) may contain other repeating units (for example, repeating units having at least one selected from the group consisting of a fluorine atom and a silicon atom) in addition to the repeating units described above.

[0353] The weight average molecular weight of the resin (X) in terms of standard polystyrene is not particularly limited, but is preferably from 1,000 to 100,000, more preferably from 1,000 to 50,000, still more preferably from 2,000 to 15,000, and particularly preferably from 3,000 to 15,000. The molecular weight distribution of the resin (X) is preferably 1-5, and more preferably 1-3.

[0354] Resin (X) may be any of various commercially available products or may be synthesized by a conventional method (for example, radical polymerization).

[0355] When the intermediate layer contains resin (X), the content of resin (X) is not particularly limited, but is preferably 80 to 100% by mass, more preferably 90 to 100% by mass, based on the total mass of the intermediate layer.

[0356] The intermediate layer may contain materials other than the resin (X). Examples of other materials include an acid generator and an acid diffusion controller, such as the compounds exemplified above as materials that may be contained in the resist film.

[0357] The method for forming the intermediate layer is not particularly limited, and examples thereof include a method using a composition for forming an intermediate layer, as described above. The composition for forming an intermediate layer preferably contains the above-mentioned resin (X) and a solvent. The type of solvent is not particularly limited, but is preferably a solvent that does not substantially dissolve the resist layer. When the solvent is used, dissolution of the resist layer is suppressed when the intermediate layer-forming composition is applied onto the resist layer, and the desired laminate can be obtained efficiently. A solvent that does not substantially dissolve a resist layer refers to a solvent that, when a 100 nm thick resist layer is immersed in the solvent (30 ml) for 30 seconds, reduces the thickness of the resist layer by 3.0 nm or less, and preferably reduces the thickness of the resist layer by 1.5 nm or less.

[0358] The solvent is not particularly limited, and examples thereof include water and organic solvents. Examples of the organic solvent include alcohol-based solvents, ether-based solvents, hydrocarbon-based solvents, ester-based solvents, and fluorine-based solvents, and alcohol-based solvents, ether-based solvents, and hydrocarbon-based solvents are preferred. As the alcohol-based solvent, from the viewpoint of solubility of the resist layer, a monohydric alcohol is preferred, and a monohydric alcohol having 4 to 8 carbon atoms is more preferred. Examples of the monohydric alcohol include linear, branched, and cyclic monohydric alcohols, and linear or branched monohydric alcohols are preferred. Examples of alcohol-based solvents include alcohols such as 1-butanol, 2-butanol, 3-methyl-1-butanol, 4-methyl-1-pentanol, 4-methyl-2-pentanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 2-hexanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, and 4-octanol; glycols such as ethylene glycol, propylene glycol, diethylene glycol, and triethylene glycol; and glycol ethers such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and methoxymethylbutanol.

[0359] From the viewpoint of solubility of the resist layer, the ether solvent is preferably an ether having a carbon number of 6 to 14. Examples of the ether solvent include dioxane, tetrahydrofuran, isoamyl ether, and diisoamyl ether.

[0360] From the viewpoint of solubility of the resist layer, the hydrocarbon solvent is preferably a hydrocarbon having a carbon number of 8 to 14. Examples of the hydrocarbon solvent include aromatic hydrocarbon solvents such as toluene, xylene, and anisole, and aliphatic hydrocarbon solvents such as n-heptane, n-nonane, n-octane, n-decane, 2-methylheptane, 3-methylheptane, 3,3-dimethylhexane, and 2,3,4-trimethylpentane.

[0361] These solvents may be used alone or in combination, for example, as a mixed solvent containing an alcohol solvent and a hydrocarbon solvent, or as a mixed solvent containing an alcohol solvent and an ester solvent.

[0362] The content of the solvent in the composition for forming an intermediate layer is not particularly limited, but the solids concentration in the composition for forming an intermediate layer is preferably 1.0 to 4.0 mass %, more preferably 1.5 to 3.0 mass %, relative to the total mass of the composition for forming an intermediate layer.

[0363] <Conductive layer> The conductive layer is a layer disposed on the opposite side of the intermediate layer from the resist layer side, and by providing the conductive layer, it is possible to suppress misalignment of the electron beam due to charging. The conductive layer preferably comprises a conductive polymer, such as polypyrrole, polythiophene, polythiophene vinylene, polytellurophene, polyphenylene, polyphenylene vinylene, polyaniline, polyacene, polyacetylene, or derivatives thereof.

[0364] The conductive polymer is preferably water-soluble or water-dispersible. When the conductive polymer is water-soluble or water-dispersible, the coating property of the conductive layer-forming composition is improved, and a conductor with a uniform film thickness is easily obtained. Furthermore, when the conductive polymer is water-soluble or water-dispersible, if the intermediate layer contains a resin soluble in an alkaline developer or a resin soluble in an organic developer, the conductive layer can be formed without dissolving the intermediate layer by using a conductive layer-forming composition containing water as a solvent.

[0365] The conductive polymer preferably has an acid group or a salt thereof. The acid groups include sulfonic acid groups and carboxyl groups. Furthermore, salts of acid groups include alkali metal salts, alkaline earth metal salts, ammonium salts, and substituted ammonium salts of sulfonic acid groups or carboxylic acid groups.

[0366] The conductive polymer is preferably a π-conjugated conductive polymer containing, as a repeating unit, at least one selected from the group consisting of phenylenevinylene, vinylene, thienylene, pyrrolylene, phenylene, iminophenylene, isothianaphthene, furylene, and carbazolylene, substituted at the α-position or β-position with at least one group selected from the group consisting of a sulfonic acid group and a carboxyl group.

[0367] The conductive polymer is preferably a conductive polymer having a sulfonic acid group or polyaniline.

[0368] The conductive polymer may be any of various commercially available products or may be synthesized according to a conventional method.

[0369] When the conductive layer contains a conductive polymer, the content of the conductive polymer is not particularly limited, but is preferably 80 to 100 mass %, more preferably 90 to 100 mass %, based on the total mass of the conductive layer.

[0370] The conductive layer may include materials other than conductive polymers. Other materials include, for example, surfactants and antioxidants.

[0371] The method for forming the conductive layer is not particularly limited, and examples thereof include a method using a conductive layer-forming composition, as described above. The conductive layer-forming composition preferably contains the above-mentioned conductive polymer and solvent. The type of solvent is not particularly limited, but is preferably a solvent that does not substantially dissolve the intermediate layer. If the solvent is one of these, dissolution of the intermediate layer is suppressed when the conductive layer-forming composition is applied onto the intermediate layer, and the desired laminate can be obtained efficiently. A solvent that does not substantially dissolve the intermediate layer refers to a solvent that, when a 100 nm thick intermediate layer is immersed in 30 ml of the solvent for 30 seconds, reduces the thickness of the intermediate layer by 3.0 nm or less, and preferably reduces the thickness of the intermediate layer by 1.5 nm or less.

[0372] The solvent is not particularly limited, and examples thereof include water and organic solvents. Examples of the organic solvent include alcohol-based solvents, ether-based solvents, hydrocarbon-based solvents, ester-based solvents, and fluorine-based solvents, and alcohol-based solvents, ether-based solvents, and hydrocarbon-based solvents are preferred.

[0373] The content of the solvent in the conductive layer-forming composition is not particularly limited, but the solids concentration in the conductive layer-forming composition is preferably 0.5 to 4.0 mass %, more preferably 1.0 to 3.0 mass %, relative to the total mass of the conductive layer-forming composition.

[0374] A preferred combination of the intermediate layer-forming composition and the conductive layer-forming composition is one in which either the solvent in the intermediate layer-forming composition or the solvent in the conductive layer-forming composition is water, and the other is an organic solvent. In this embodiment, the conductive layer can be formed on the intermediate layer while suppressing dissolution of the intermediate layer. [Example]

[0375] The features of the present invention will be explained in more detail below with reference to examples and comparative examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.

[0376] <Various components of the composition for forming a resist layer> (acid decomposable resin) Resins P-1 to P-13 shown in Table 1 are as follows. Resins P-1 to P-13 were synthesized according to the synthesis method for Resin P-1 (Synthesis Example 1) described below. Table 1 shows the composition ratio (mol % ratio; corresponding from left to right) of each repeating unit of Resins P-1 to P-13, the weight average molecular weight (Mw), and the dispersity (Mw / Mn). The weight average molecular weight (Mw) and dispersity (Mw / Mn) of resins P-1 to P-13 were measured by GPC (carrier: tetrahydrofuran (THF)) (values ​​converted into polystyrene). The composition ratios (mol %) of the resins were: 13Measurement was performed by C-NMR (Nuclear Magnetic Resonance).

[0377] [Table 1]

[0378] (Synthesis Example 1: Synthesis of Resin P-1) Under a nitrogen stream, cyclohexanone (194.3 g) was placed in a three-neck flask and heated to 80 °C. To this was added dropwise over 6 hours 15.3 g and 45.8 g of monomers corresponding to the repeating units of Resin P-1 (described below), respectively, and a solution of polymerization initiator V-601 (Fujifilm Wako Pure Chemical Industries, Ltd., 3.17 g) dissolved in 105 g of cyclohexanone. After the addition was completed, the reaction solution was further reacted at 80 °C for 2 hours. After allowing the reaction solution to cool, it was added dropwise over 20 minutes to a mixture of methanol and water. The powder precipitated by the addition was then filtered and dried to obtain Resin P-1 (31.6 g), an acid-decomposable resin. The molar ratio of the repeating units determined by NMR was 40 / 60. The weight average molecular weight of the resulting resin P-1 was 8,000 in terms of standard polystyrene, and the dispersity (Mw / Mn) was 1.6.

[0379] The structural formulas of the resins P-1 to P-13 used are shown below.

[0380] [ka]

[0381] (acid generator) The structures of the acid generators (PAG-1 to PAG-10) used are shown below.

[0382] [ka]

[0383] Table 2 shows the acid dissociation constants (pKa) and sizes (volumes of generated acids) of the acids generated from the acid generators (PAG-1 to PAG-10). In addition, when measuring the acid dissociation constant (pKa) of the acid generated from the acid generators (PAG-1 to PAG-10), specifically, each cationic site in PAG-1 to PAG-10 is converted to H + For example, in the case of X-1, the triphenylsulfonium cation is replaced with H + For the compounds formed by replacing , as described above, values ​​were calculated using the software package 1 from ACD / Labs based on a database of Hammett's substituent constants and known literature values. When the pKa could not be calculated using the above method, values ​​obtained using Gaussian 16 based on DFT (density functional theory) were used. The smaller the pKa value, the higher the acidity.

[0384] [Table 2]

[0385] (acid diffusion control agent) The structures of the acid diffusion controllers (Q-1 to Q-4) used are shown below.

[0386] [ka]

[0387] (Crosslinking agent) The structure of the crosslinker (CL-1) used is shown below.

[0388] [ka]

[0389] (Intermediate layer resin) The structures of the resins (MLP-1 to MLP-3) used to form the intermediate layer are shown below. The numerical values ​​shown for each repeating unit in the structural formula (e.g., 85, 10, and 5 in the case of MLP-1) represent the content (mol %) of each repeating unit relative to all repeating units. In the structural formula, Mw represents the weight-average molecular weight, and Pd represents the molecular weight distribution.

[0390] [ka]

[0391] (Resin for conductive layer) The procedure for producing the resin (ULP-1) used to form the conductive layer is shown below. ULP-1: A polymer of 2-aminoanisole-4-sulfonic acid obtained by the following production method. Pyridine (100 mmol) and water (100 mL) were added to 2-aminoanisole-4-sulfonic acid (100 mmol) to obtain a monomer solution. An aqueous solution of ammonium peroxodisulfate (100 mmol) (oxidant solution) was added dropwise to the obtained monomer solution at 10°C. After the addition was completed, the reaction solution was stirred for an additional 15 hours at 25°C, then heated to 35°C and stirred for an additional 2 hours to obtain a reaction solution in which the reaction product had precipitated (polymerization step). The obtained reaction solution was filtered using a centrifugal filter, and the precipitate (reaction product) was collected. The reaction product was washed with 1 L of methanol and then dried to obtain a powdered conductive polymer (ULP-1) (purification step).

[0392] (surfactant) The surfactants used are listed below. W-1: Megafac F176 (DIC Corporation; fluorine-based) W-2: Megafac R08 (DIC Corporation; fluorine and silicone type)

[0393] (solvent) The solvents used are listed below. SL-1: Propylene glycol monomethyl ether acetate (PGMEA) SL-2: Propylene glycol monomethyl ether (PGME) SL-3: Diacetone alcohol SL-4: γ-butyrolactone SL-5: 4-methyl-2-pentanol SL-6: Diisoamyl ether SL-7: n-undecane SL-8: Pure water SL-9: Isopropanol

[0394] <Preparation of Resist Layer-Forming Composition> Resist layer-forming compositions were prepared by mixing the materials according to the formulations shown in Table 3 below and filtering the resulting mixture through a polyethylene filter with a pore size of 0.03 μm. The solids concentration of each resist layer-forming composition was adjusted appropriately so that it could be applied to the film thicknesses shown in Tables 6, 8, and 10 below. The solids concentration in each resist layer-forming composition was 2.0 to 6.0 mass % relative to the total mass of the resist layer-forming composition.

[0395] [Table 3]

[0396] <Preparation of composition for forming intermediate layer> Compositions for forming an intermediate layer were prepared by mixing the materials according to the formulation shown in Table 4 below and filtering the resulting mixture through a polyethylene filter having a pore size of 0.03 μm. The solids concentration of each composition for forming an intermediate layer was appropriately adjusted so that it could be applied to the film thicknesses shown in Tables 6, 8, and 10 below. The solids concentration in each composition for forming an intermediate layer was 2.0 to 4.0 mass % relative to the total mass of the composition for forming an intermediate layer. In each example, the following solvents contained in the composition for forming an intermediate layer were all solvents that did not substantially dissolve the resist layer. In addition, the resin contained in the composition for forming an intermediate layer in each example was a resin soluble in a developer.

[0397] [Table 4]

[0398] <Preparation of Conductive Layer-Forming Composition> Conductive layer-forming compositions were prepared by mixing the materials according to the formulations shown in Table 5 below and filtering the resulting mixtures through a polyethylene filter with a pore size of 0.03 μm. The solids concentration of each conductive layer-forming composition was appropriately adjusted so that it could be applied to the film thicknesses shown in Tables 6, 8, and 10 below. The solids concentration in the conductive layer-forming composition was 1.0 to 3.0 mass % relative to the total mass of the conductive layer-forming composition. In each example, the following solvents contained in the conductive layer-forming composition were solvents that did not substantially dissolve the intermediate layer.

[0399] [Table 5]

[0400] <Developer and rinse> The developer and rinse used are shown below. D-1: 2.38% by mass tetramethylammonium hydroxide aqueous solution D-2: Pure water D-3: FIRM Extreme 10 (AZEM) D-4: Butyl acetate D-5: n-Undecane

[0401] <Examples 1 to 24 and Comparative Examples 1 to 5> Using ACTM (Tokyo Electron Limited), a laminate was formed by spin-coating a resist layer-forming composition, an intermediate layer-forming composition, and a conductive layer-forming composition in this order onto a 152 mm square mask blank having a Cr outermost surface under the conditions shown in Table 6. After coating each composition, a heat treatment was carried out under the conditions shown in the "Pre Bake" column in Table 6. Next, the film was exposed using an electron beam exposure device (EBM-9000 manufactured by NuFlare Technology Inc., accelerating voltage 50 kV), followed by PEB (post-exposure bake) under the conditions shown in Table 6. Thereafter, a development process was carried out using a developer shown in Table 6, and a rinse process was further carried out using a rinse solution shown in Table 6 to obtain a positive pattern.

[0402] <Evaluation> The fabricated patterned mask blank was observed with a top-down SEM (scanning electron microscope) to determine the optimal exposure dose (μC / cm) for resolving a 50 nm 1:1 line and space (LS) at 1:1. 2 ) and the PSD(0)LER (nm) of 50 nmLS at that exposure dose 3 ) was calculated. The results are summarized in Table 6. The PSD(0)LER was calculated by analyzing measurement data obtained using an overhead SEM (scanning electron microscope) using Fractilia's MetroLER software, and calculating the PSD(0)LER under conditions that remove measurement noise. The PSD(0)LER represents the low-frequency component of the PSD. The smaller the PSD(0)LER value, the smaller the long-period waviness in the longitudinal direction of the pattern, indicating better performance.

[0403] <Method for evaluating the amount of film loss for each layer> The amount of film loss of the resist layer was evaluated by the following method. First, the resist layer-forming composition used in each Example and Comparative Example was applied to a silicon wafer with a diameter of 200 mm, and the wafer was heated under the conditions listed in the "Pre-Bake" column of the "Resist Coating Conditions" column in Table 6 to prepare a resist layer (100 nm thick). Next, the resist layer prepared in each Example and Comparative Example was immersed for 30 seconds in the solvent (30 ml) contained in the intermediate layer-forming composition applied to the resist layer, and the thickness loss (nm) of the resist layer was measured. The thickness loss refers to the thickness lost after the immersion treatment from an initial thickness of 100 nm. For example, in Example 1, a resist layer (100 nm thick) was prepared using the resist layer-forming composition R-1 under specified heating conditions, and the prepared resist layer was immersed for 30 seconds in the solvent (SL-6 / SL-7 = 80 / 20) contained in the intermediate layer-forming composition, and the thickness loss of the resist layer was measured. The results are summarized in Table 7. The amount of film loss of the intermediate layer was evaluated by the following method. First, the composition for forming an intermediate layer used in each Example and Comparative Example was applied to a silicon wafer with a diameter of 200 mm, and the wafer was heated under the conditions listed in the "Pre-Bake" column of the "Intermediate Layer Application Conditions" column in Table 6 to prepare an intermediate layer (100 nm thick). Next, the intermediate layer prepared in each Example and Comparative Example was immersed for 30 seconds in the solvent (30 ml) contained in the conductive layer-forming composition to be applied to the intermediate layer, and the amount of film loss (nm) of the intermediate layer was measured. The amount of film loss refers to the film thickness lost after the immersion treatment from an initial film thickness of 100 nm. The results are summarized in Table 7. The thickness loss of the intermediate layer due to the developer was evaluated by the following method. First, the composition for forming an intermediate layer used in each Example and Comparative Example was applied to a silicon wafer with a diameter of 200 mm, and the wafer was heated under the conditions listed in the "Pre-Bake" column of the "Intermediate Layer Application Conditions" column in Table 6 to form an intermediate layer (100 nm thick). Next, the intermediate layer thus prepared was immersed in the developer (30 ml) used in each Example and Comparative Example for 30 seconds, and the amount of film loss (nm) of the intermediate layer was measured. The amount of film loss refers to the film thickness lost after the immersion treatment from an initial film thickness of 100 nm. The results are summarized in Table 7. The amount of film loss of the conductive layer due to the developer was evaluated by the following method. First, the conductive layer-forming composition used in each Example and Comparative Example was applied to a silicon wafer with a diameter of 200 mm, and the wafer was heated under the conditions listed in the "Pre-Bake" column of the "Conductive Layer Application Conditions" column in Table 6 to prepare a conductive layer (100 nm thick). Next, the prepared conductive layer was immersed in the developer (30 ml) used in each Example and Comparative Example for 30 seconds, and the amount of film loss (nm) of the conductive layer was measured. The amount of film loss refers to the film thickness lost after the immersion treatment from an initial film thickness of 100 nm. The results are summarized in Table 7.

[0404] In Table 6, the "Film thickness (nm)" column in the "Resist coating conditions" column means the film thickness of the resist layer, the "Film thickness (nm)" column in the "Intermediate layer coating conditions" column means the film thickness of the intermediate layer, and the "Film thickness (nm)" column in the "Conductive layer coating conditions" column means the film thickness of the conductive layer.

[0405] [Table 6]

[0406] [Table 7]

[0407] As shown in Table 6, the pattern formation method of the present invention achieved the desired effects. Furthermore, a comparison between Example 1 and Examples 3 and 4 confirmed that better effects were obtained when the content of the compound that generates an acid upon irradiation with an electron beam relative to the total mass of the resist layer was 10 mass % or more. Furthermore, a comparison between Example 1 and Example 5 confirmed that better effects were obtained when the pKa of the acid generated from the compound that generates an acid upon irradiation with an electron beam was −1.00 or less. Furthermore, a comparison between Example 1 and Example 6 shows that the size of the acid generated from the compound that generates an acid upon irradiation with an electron beam is 240 Å. 3 It has been confirmed that better effects can be obtained when the above conditions are met. Furthermore, a comparison between Example 1 and Examples 7 and 8 confirmed that better effects were obtained when the resist layer contained a basic compound whose basicity was reduced or eliminated by irradiation with an electron beam. Furthermore, a comparison between Example 1 and Example 9 confirmed that a more excellent effect can be obtained when the resist layer contains the above-mentioned compound (I). Furthermore, a more excellent effect can be obtained when the resist layer contains the above-mentioned compound (II). Furthermore, a comparison between Example 1 and Example 10 confirmed that when the resin contained in the resist layer contains a repeating unit having a fluorinated alcohol group, better effects can be obtained. Furthermore, a comparison between Example 1 and Example 11 confirmed that better effects could be obtained when the resin contained in the resist layer contained a repeating unit having a group that decomposes under the action of acid to generate a carboxyl group. Furthermore, a comparison between Example 1 and Example 12 confirmed that better effects could be obtained when the resin contained in the resist layer contained a group that decomposed by the action of an acid to generate a phenolic hydroxyl group and contained a repeating unit having a group represented by the above-mentioned formula (Y1) as a leaving group that is eliminated by the action of an acid. Furthermore, a comparison between Example 1 and Example 13 confirmed that a more excellent effect can be obtained when the resin contained in the resist layer contains a repeating unit having a lactone group. Furthermore, a more excellent effect can be obtained when the resin contained in the resist layer contains a repeating unit having a sultone group or a carbonate group.

[0408] <Examples 25 to 26, Comparative Examples 6 to 9> Using ACTM (Tokyo Electron Limited), a laminate was formed by spin-coating a resist layer-forming composition, an intermediate layer-forming composition, and a conductive layer-forming composition in this order onto a 152 mm square mask blank having a Cr outermost surface under the conditions shown in Table 8. After coating each composition, a heat treatment was carried out under the conditions shown in the "Pre Bake" column in Table 8. Next, the film was exposed using an electron beam exposure device (EBM-9000 manufactured by NuFlare Technology Inc., accelerating voltage 50 kV), followed by PEB (post-exposure bake) under the conditions shown in Table 8. Thereafter, a development process was carried out using a developer shown in Table 8, and a rinse process was further carried out using a rinse solution shown in Table 8 to obtain a negative pattern. The obtained patterns were subjected to the above-mentioned evaluation. The results are summarized in Table 8. In addition, the <Method for Evaluating the Amount of Film Loss of Each Layer> was carried out. The results are summarized in Table 9.

[0409] [Table 8]

[0410] [Table 9]

[0411] As shown in Table 8, the pattern formation method of the present invention achieved the desired effects.

[0412] <Examples 27 to 28, Comparative Examples 10 to 13> Using ACTM (Tokyo Electron Limited), a laminate was formed by spin-coating a resist layer-forming composition, an intermediate layer-forming composition, and a conductive layer-forming composition in this order onto a 152 mm square mask blank having a Cr outermost surface under the conditions shown in Table 10. After coating each composition, a heat treatment was carried out under the conditions shown in the "Pre Bake" column in Table 10. Next, the film was exposed using an electron beam exposure device (EBM-9000 manufactured by NuFlare Technology Inc., accelerating voltage 50 kV), followed by PEB (post-exposure bake) under the conditions shown in Table 10. Thereafter, a development process was carried out using a developer shown in Table 10, and a rinse process was further carried out using a rinse solution shown in Table 10 to obtain a negative pattern. The obtained patterns were subjected to the above-mentioned evaluation. The results are summarized in Table 10. In addition, the <Method for Evaluating the Amount of Film Loss of Each Layer> was carried out. The results are summarized in Table 11.

[0413] [Table 10]

[0414] [Table 11]

[0415] As shown in Table 10, the pattern formation method of the present invention achieved the desired effects.

Claims

1. Step 1 of preparing a laminate having a substrate, a resist layer, an intermediate layer, and a conductive layer in this order; a step 2 of irradiating the laminate with an electron beam in a pattern; and step 3 of developing the laminate irradiated with the electron beam to form a pattern. A pattern forming method, wherein the resist layer has a film thickness of 150 nm or less, the resist layer contains a resin whose solubility in a developer changes due to the action of an acid, At least one of the following requirements 1 and 2 is met: the intermediate layer has a thickness of 20 to 100 nm; the intermediate layer contains a resin containing a repeating unit having an alkali-soluble group, the content of the resin containing a repeating unit having an alkali-soluble group is 80 to 100% by mass relative to the total mass of the intermediate layer; the conductive layer has a thickness of 10 to 60 nm; the conductive layer comprises a conductive polymer; The pattern forming method, wherein the content of the conductive polymer is 80 to 100% by mass based on the total mass of the conductive layer. Requirement 1: The resist layer contains a compound that generates an acid when irradiated with an electron beam. Requirement 2: The resin contains a repeating unit having a residue formed by removing one hydrogen atom from a compound that generates an acid upon irradiation with an electron beam.

2. 2. The pattern forming method according to claim 1, wherein the step 1 comprises: step 1A of applying a composition for forming a resist layer onto a substrate to form the resist layer; step 1B of applying a composition for forming an intermediate layer onto the resist layer to form the intermediate layer; and step 1C of applying a composition for forming a conductive layer onto the intermediate layer to form the conductive layer.

3. When the requirement 1 is satisfied, the content of the compound is 10% by mass or more relative to the total mass of the resist layer, 3. The pattern forming method according to claim 1, wherein when the requirement 2 is satisfied, the content of the repeating unit is 10% by mass or more with respect to the total mass of the resist layer.

4. 4. The pattern forming method according to claim 1, wherein the compound capable of generating an acid upon irradiation with an electron beam generates an acid having a pKa of −1.00 or less.

5. The size of the acid generated from the compound that generates an acid upon irradiation with an electron beam is 240 Å. ３ The pattern forming method according to any one of claims 1 to 4, wherein

6. The pattern formation method according to any one of claims 1 to 5, wherein the compound that generates an acid upon irradiation with an electron beam is one or more compounds selected from the following compounds (I) and (II): Compound (I): A compound having one or more structural moieties X and one or more structural moieties Y, which generates an acid containing a first acidic moiety derived from the structural moiety X and a second acidic moiety derived from the structural moiety Y when irradiated with an electron beam. Structural moiety X: Anionic moiety A １ － and the cationic moiety M １ ＋ and HA by irradiation with electron beams. １ A structural portion forming a first acidic site represented by Structural portion Y: Anionic portion A ２ － and the cationic moiety M ２ ＋ and HA by irradiation with electron beams. ２ A structural portion forming a second acidic site represented by However, compound (I) satisfies the following condition I. Condition I: In the compound (I), the cationic moiety M in the structural moiety X １ ＋ and the cationic moiety M in the structural moiety Y ２ ＋ H ＋ The compound PI in which the cationic moiety M in the structural moiety X is replaced by １ ＋ H ＋ and the cationic moiety M in the structural moiety Y. ２ ＋ H ＋ HA is replaced by ２ and the acid dissociation constant a2 is greater than the acid dissociation constant a1. Compound (II): A compound having two or more of the structural moieties X and one or more of the following structural moieties Z, wherein the compound generates an acid containing two or more of the first acidic moieties derived from the structural moiety X and the structural moiety Z when irradiated with an electron beam. Structural moiety Z: a ​​nonionic moiety capable of neutralizing an acid

7. 7. The pattern formation method according to claim 1, wherein the resin whose solubility in a developer changes due to the action of an acid contains a repeating unit having an acid group.

8. 8. The pattern formation method according to claim 7, wherein the acid group whose solubility in a developer changes due to the action of an acid is selected from the group consisting of a phenolic hydroxyl group and a fluorinated alcohol group.

9. 9. The pattern formation method according to claim 1, wherein the resin whose solubility in a developer changes due to the action of an acid contains a repeating unit having a group that decomposes due to the action of an acid to generate a carboxyl group.

10. 9. The pattern formation method according to claim 1, wherein the resin whose solubility in a developer changes due to the action of an acid contains a repeating unit having a group that is decomposed by the action of an acid to generate a phenolic hydroxyl group.

11. 11. The pattern formation method according to claim 1, wherein the resin whose solubility in a developer changes due to the action of an acid contains a repeating unit having at least one group selected from the group consisting of a lactone group, a sultone group, and a carbonate group.

12. 12. The pattern forming method according to claim 1, wherein the resist layer contains a basic compound whose basicity is reduced or eliminated by irradiation with an electron beam.

13. the basic compound includes an onium salt compound that generates an acid when irradiated with an electron beam, 13. The pattern formation method according to claim 12, wherein the acid generated from the onium salt is weaker than the acid generated from the compound that generates an acid when irradiated with an electron beam.

14. The pattern forming method according to any one of claims 1 to 13, wherein the intermediate layer is soluble in a developer used in the development treatment.

15. the intermediate layer is a layer formed using a composition for forming an intermediate layer, The pattern forming method according to any one of claims 1 to 14, wherein the composition for forming an intermediate layer comprises a resin including a repeating unit having the alkali-soluble group, and a solvent that does not substantially dissolve the resist layer.

16. 16. The pattern formation method according to claim 15, wherein the solvent that does not substantially dissolve the resist layer is selected from the group consisting of monohydric alcohols having 4 to 10 carbon atoms, ethers having 6 to 14 carbon atoms, and hydrocarbons having 8 to 14 carbon atoms.

17. 17. The pattern formation method according to claim 15, wherein the resin containing a repeating unit having an alkali-soluble group contains a repeating unit having at least one group selected from the group consisting of a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfonic acid group, and a sulfonamide group.

18. A pattern forming method according to any one of claims 1 to 17, wherein the conductive polymer is a conductive polymer having a sulfonic acid group or polyaniline.

19. A pattern formation method described in any one of claims 1 to 18, wherein the content of the resin whose solubility in the developer changes due to the action of the acid is 40.0 to 99.9 mass% relative to the total mass of the resist layer.

20. A method for manufacturing an electronic device, comprising the pattern formation method according to any one of claims 1 to 19.

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