Actinic ray-sensitive or radiation-sensitive resin composition, actinic ray-sensitive or radiation-sensitive film, pattern forming method, and method for manufacturing electronic device

Abstract

The present invention provides: an active-light-sensitive or radiation-sensitive resin composition containing (A) a resin in which the polarity increases due to the action of an acid, (B) a photoacid generator, and anions (P), which are one or more types of anions selected from the group consisting of NO3 -, SO4 2-, Cl-, and Br-, wherein the anion (P) content is 0.01 ppb to 100 ppm with respect to the total mass of the active-light-sensitive or radiation-sensitive resin composition; an active-light-sensitive or radiation-sensitive film formed of the active-light-sensitive or radiation-sensitive resin composition; a pattern forming method; and an electronic device manufacturing method.

Description

[Technical field]

[0001] The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition, an actinic ray-sensitive or radiation-sensitive film, a pattern forming method, and a method for producing an electronic device. [Background technology]

[0002] Since resists for KrF excimer lasers (248 nm), a pattern formation method using chemical amplification has been used to compensate for the loss of sensitivity due to light absorption. For example, in a positive-type chemical amplification method, a photoacid generator contained in an exposed area is first decomposed by light irradiation to generate an acid. Then, in a post-exposure bake (PEB) process or the like, the generated acid acts as a catalyst to convert an alkali-insoluble group contained in the photosensitive composition into an alkali-soluble group. Then, development is performed using, for example, an alkaline solution. This removes the exposed area to obtain a desired pattern. In the above-mentioned method, various types of alkaline developers have been proposed, for example, an aqueous alkaline developer containing 2.38% by mass of TMAH (tetramethylammonium hydroxide) is widely used.

[0003] In order to miniaturize semiconductor elements, the wavelength of the exposure light source has become shorter and the numerical aperture (NA) of the projection lens has become higher, and currently, an exposure machine using an ArF excimer laser with a wavelength of 193 nm as a light source has been developed. As a technology to further increase the resolution, there is a method in which a liquid with a high refractive index (hereinafter also referred to as "immersion liquid") is filled between the projection lens and the sample (i.e., the liquid immersion method).

[0004] Many types of conventional resist compositions are known, for example, the one described in Patent Document 1. Patent Document 1 describes a photoresist composition that contains a polymer having a structural unit that contains an acid-dissociable group that dissociates when acted on by an acid, a radiation-sensitive acid generator, and a solvent. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 2015-57638 Summary of the Invention [Problem to be solved by the invention]

[0006] The development of 3D structure devices is progressing to increase memory capacity by stacking cells. As the number of layers increases, it becomes necessary to deposit a thicker resist film than before, form a resist pattern, and perform processing such as etching. For resists used in cutting-edge, thick-film processes, stricter quality control is required than ever before as the number of processing operations increases. This has created an issue in which deterioration of the materials in the resist composition during storage has a more pronounced impact on performance. Furthermore, as the resist becomes thicker, it becomes more difficult to maintain sensitivity during exposure, and a larger amount of exposure is required, which leads to a problem that the sensitivity is likely to decrease.

[0007] Here, a resist composition is usually stored for a certain period of time, but the performance of the resist composition tends to deteriorate due to such storage over time. Therefore, in recent years, there has been a demand for a resist composition that can achieve better stability over time. (Good stability over time means that when a composition before forming a resist film is stored over time, there is little effect on a pattern obtained by using the composition after storage over time.) A common countermeasure would be to change the composition of the resist composition to one that improves its stability over time, but it is not easy to improve stability over time without impairing basic performance such as sensitivity.

[0008] An object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive resin composition which is capable of achieving extremely excellent stability over time while suppressing a decrease in sensitivity. A further object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive film, a pattern forming method, and a method for producing an electronic device, which use the actinic ray-sensitive or radiation-sensitive resin composition. [Means for solving the problem]

[0009] Means for solving the above problems include the following aspects.

[0010] <1> (A) a resin whose polarity increases under the action of an acid; (B) a photoacid generator, and No.3 - , SO4 2- , Cl - , and Br - An actinic ray-sensitive or radiation-sensitive resin composition comprising an anion (P) which is one or more anions selected from the group consisting of: the content of the anion (P) is 0.01 ppb or more and 10 ppb or less based on the total mass of the actinic ray-sensitive or radiation-sensitive resin composition, An actinic ray-sensitive or radiation-sensitive resin composition (excluding liquid compositions containing a carbonate), in which the solid content concentration of the composition is 0.5% by mass to 60% by mass. <2> The mass ratio of the anion (P) to the resin (A), represented by the following formula, is 2×10 -11 ~5×10 -4 That is, <1> 2. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 . Mass ratio = (anion (P) content) / (resin (A) content) <3> The solid content of the composition is 10% by mass or more. <1> or <2> 2. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 . <4> the pKa of the acid generated from the photoacid generator upon exposure to actinic rays or radiation is less than 1.1; <3> 2. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 . <5> Further, the composition contains a crosslinking agent. <1> ~ <4> The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 5. 。 Books The invention relates to the above <1> ~< 5 >, but other matters (for example, [1] to [9] below) are also described below. [1] (A) a resin whose polarity increases under the action of an acid; (B) a photoacid generator, and No.3 - , SO4 2- , Cl - , and Br - An actinic ray-sensitive or radiation-sensitive resin composition comprising an anion (P) which is one or more anions selected from the group consisting of: The actinic ray-sensitive or radiation-sensitive resin composition has an anion (P) content of 0.01 ppb or more and 100 ppm or less based on the total mass of the actinic ray-sensitive or radiation-sensitive resin composition.

[0011] [2] The actinic ray-sensitive or radiation-sensitive resin composition according to [1], wherein the content of the anion (P) is 0.01 ppb or more and 1 ppm or less, based on the total mass of the actinic ray-sensitive or radiation-sensitive resin composition. [3] The actinic ray-sensitive or radiation-sensitive resin composition according to [1] or [2], wherein the content of the anion (P) is 0.01 ppb or more and 10 ppb or less, based on the total mass of the actinic ray-sensitive or radiation-sensitive resin composition.

[0012] [4] The mass ratio of the anion (P) to the resin (A), represented by the following formula, is 2×10 -11 ~5×10 -4 The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [3], wherein Mass ratio = (anion (P) content) / (resin (A) content)

[0013] [5] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [4], wherein the solid content concentration of the composition is 10 mass % or more. [6] active light Straight line The actinic ray-sensitive or radiation-sensitive resin composition according to [5], wherein the pKa of an acid generated from the photoacid generator upon irradiation with radiation is less than 1.1.

[0014] [7] An actinic ray-sensitive or radiation-sensitive film formed from the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [6]. [8] A pattern forming method comprising the steps of: exposing the actinic ray-sensitive or radiation-sensitive film according to [7]; and developing the exposed actinic ray-sensitive or radiation-sensitive film with a developer. [9] A method for manufacturing an electronic device, comprising the pattern formation method according to [8]. Effect of the Invention

[0015] According to the present invention, it is possible to provide an actinic ray-sensitive or radiation-sensitive resin composition that can achieve extremely excellent stability over time while suppressing a decrease in sensitivity. The present invention further provides an actinic ray-sensitive or radiation-sensitive film, a pattern forming method, and a method for producing an electronic device, which use the actinic ray-sensitive or radiation-sensitive resin composition. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0016] The present invention will be described in detail below. The following description of the components may be based on representative embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, when a group (atomic group) is described without specifying whether it is substituted or unsubstituted, it includes both those that have no substituent and those that have a substituent. For example, an "alkyl group" includes not only an alkyl group that has no substituent (unsubstituted alkyl group) but also an alkyl group that has a substituent (substituted alkyl group). In addition, in the present specification, an "organic group" refers to a group that contains at least one carbon atom.

[0017] In addition, in the present specification, when it is said that "may have a substituent", the type of the substituent, the position of the substituent, and the number of the substituent are not particularly limited. The number of the substituents may be, for example, one, two, three, or more. Examples of the substituents include monovalent nonmetallic atomic groups other than hydrogen atoms, and can be selected from the following substituents T.

[0018] (substituent T) Examples of the substituent T include halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom; alkoxy groups such as methoxy group, ethoxy group, and tert-butoxy group; aryloxy groups such as phenoxy group and p-tolyloxy group; alkoxycarbonyl groups such as methoxycarbonyl group, butoxycarbonyl group, and phenoxycarbonyl group; acyloxy groups such as acetoxy group, propionyloxy group, and benzoyloxy group; acyl groups such as acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group, and methoxalyl group; Examples of such groups include alkylsulfanyl groups such as phenylsulfanyl group and tert-butylsulfanyl group; arylsulfanyl groups such as phenylsulfanyl group and p-tolylsulfanyl group; alkyl groups; cycloalkyl groups; aryl groups; heteroaryl groups; hydroxyl groups; carboxy groups; formyl groups; sulfo groups; cyano groups; alkylaminocarbonyl groups; arylaminocarbonyl groups; sulfonamide groups; silyl groups; amino groups; monoalkylamino groups; dialkylamino groups; arylamino groups, nitro groups; formyl groups; and combinations thereof.

[0019] In this specification, "actinic rays" or "radiation" refers to, for example, the bright line spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet light (EUV light: extreme ultraviolet), X-rays, and electron beams (EB: electron beams), etc. In this specification, "light" refers to actinic rays or radiation, unless otherwise specified. In this specification, unless otherwise specified, "exposure" includes not only exposure to the emission line spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet light, X-rays, EUV light, and the like, but also exposure to particle beams such as electron beams and ion beams. 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.

[0020] 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 dispersity (also referred to as molecular weight distribution) (Mw / Mn) of the resin component are defined as polystyrene-equivalent values ​​measured using a Gel Permeation Chromatography (GPC) device (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).

[0021] In this specification, the amount of each component in a composition means, when a plurality of substances corresponding to each component are present in the composition, the total amount of the corresponding substances present in the composition, unless otherwise specified. In this specification, the term "process" includes not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the intended purpose of the process is achieved. In this specification, the term "total solid content" refers to the total mass of the components excluding the solvent from the entire composition of the composition. As described above, the term "solid content" refers to the components excluding the solvent, and may be, for example, solid or liquid at 25°C. In this specification, "mass %" and "weight %" are synonymous, and "parts by mass" and "parts by weight" are synonymous. Also herein, a combination of two or more preferred embodiments is a more preferred embodiment.

[0022] (Actinic ray-sensitive or radiation-sensitive resin composition) The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention (hereinafter, also simply referred to as the "composition") comprises: (A) a resin whose polarity increases under the action of an acid; (B) a photoacid generator, and No.3 - , SO4 2- , Cl - , and Br - An actinic ray-sensitive or radiation-sensitive resin composition comprising an anion (P) which is one or more anions selected from the group consisting of: The content of the anion (P) is from 0.01 ppb to 100 ppm based on the total mass of the actinic ray-sensitive or radiation-sensitive resin composition.

[0023] By adopting the above-mentioned configuration, the present invention can achieve extremely excellent stability over time while suppressing a decrease in sensitivity. The reason for this is not clear, but is speculated to be as follows. The photoacid generator that can be contained in the actinic ray-sensitive or radiation-sensitive resin composition decomposes in small amounts during storage over time to generate acid. - , SO4 2- , Cl - , and Br -By incorporating an anion (P) selected from the group consisting of one or more anions at 0.01 ppb or more relative to the total mass of the actinic ray-sensitive or radiation-sensitive resin composition, the acid generated by the decomposition of a small amount of a photoacid generator that may be contained in the actinic ray-sensitive or radiation-sensitive resin composition during storage over time can be captured by the anion (P). It is believed that this suppresses the decomposition of a resin that may be contained in the actinic ray-sensitive or radiation-sensitive resin composition by the acid, resulting in extremely excellent stability over time. Also, NO3 - , SO4 2- , Cl - , and Br - By incorporating one or more anions (P) selected from the group consisting of the following in an amount of 100 ppm or less based on the total mass of the actinic ray-sensitive or radiation-sensitive resin composition, the acid generated in the exposed area of ​​the actinic ray-sensitive or radiation-sensitive film is less likely to be captured by the anion (P). In other words, it is believed that the desired reaction between the acid generated from the photoacid generator by exposure and the resin is not inhibited, and a decrease in sensitivity is inhibited.

[0024] The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention is preferably a so-called resist composition, and may be a positive resist composition or a negative resist composition. In addition, it may be a resist composition for alkali development or a resist composition for organic solvent development. Typically, the composition of the present invention is preferably a chemically amplified resist composition. Hereinafter, each component contained in the actinic ray-sensitive or radiation-sensitive resin composition (also simply referred to as the "composition") according to the present invention will be described in detail.

[0025] <NO3 - , SO4 2- , Cl - , and Br - anion (P) which is one or more anions selected from the group consisting of The composition of the present invention is NO3 - , SO4 2- , Cl- , and Br - The anion (P) (hereinafter, also referred to as "anion (P)") is one or more anions selected from the group consisting of:

[0026] The composition of the present invention includes an anion (P). The anion (P) is NO3 - , SO4 2- , Cl - , and Br - The anion (P) is one or more anions selected from the group consisting of: Thus, when the anion (P) is composed of one anion, the content of the anion is the content of that anion; and when the anion (P) is composed of two or more anions, the content of the anion (P) is the sum of the contents of the respective anions.

[0027] The source of the anion (P) is not particularly limited as long as the content of the anion (P) is 0.01 ppb or more and 100 ppm or less based on the total mass of the actinic ray-sensitive or radiation-sensitive resin composition. The source of the anion (P) is not particularly limited, but may be, for example, an anion additive. The anion additive is not particularly limited, but may be, for example, nitric acid, sulfuric acid, hydrochloric acid, hydrogen bromide, ammonium nitrate, ammonium chloride, etc. Further, the following compounds can also be mentioned as anionic additives. The anion detected in the compound on the left below is SO4 2- It is.

[0028] [ka]

[0029] The content of the anion (P) is from 0.01 ppb to 100 ppm based on the total mass of the actinic ray-sensitive or radiation-sensitive resin composition. If the content of the anion (P) is less than 0.01 ppb, the stability over time cannot be ensured, whereas if the content of the anion (P) is more than 100 ppm, the decrease in sensitivity cannot be suppressed. From the viewpoints of suppressing a decrease in sensitivity and improving stability over time, the content of the anion (P) is preferably from 0.01 ppb to 1 ppm, more preferably from 0.01 ppb to 10 ppb, and even more preferably from 0.01 ppb to 1 ppb, based on the total mass of the actinic ray-sensitive or radiation-sensitive resin composition.

[0030] In the case where the composition of the present invention contains a resin (A) whose polarity increases under the action of an acid described below, the mass ratio of the anion (P) to the resin, represented by the following formula, is 2×10 -11 ~5×10 -4 Preferably, it is 2×10 -11 ~5×10 -5 More preferably, it is 2×10 -11 ~5×10 -6 It is more preferable that: Mass ratio = (anion (P) content) / (resin (A) content)

[0031] The method for adding a small amount of anion (P) using the above anion additive is not particularly limited, but examples thereof include the following methods. By preparing a diluted solution of the anion additive in advance using the solvent used to prepare the resist composition, it is possible to accurately measure a small amount of the anion additive and also to measure the content of the anion (P). In particular, when the amount of the anion (P) added is at a minute level, a solution diluted in several stages is prepared according to the content of the anion (P), and the desired amount of the anion (P) can be adjusted to be present in the resist composition.

[0032] The content of the anion (P) in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention can be measured, for example, by the following method.

[0033] (Method for quantifying anion (P)) After preparing a resist composition (resist solution) containing an anion (P), 10 g of the resist solution was weighed, and 100 g of toluene and 100 g of ion-exchanged water were added to a separatory funnel, mixed, and allowed to stand. The aqueous layer was separated, and water was distilled off under reduced pressure. 1 g of ion-exchanged water was added to the residue, and after shaking well, it was filtered with a 0.2 μm filter (DISMIC-13HP, ADVANTEC), and subjected to an ion chromatograph (ion chromatography: PIA-1000, Shimadzu Corporation), and analyzed using a Shim-pack IC-SA4 (Shimadzu GLC Corporation) as a column. Various anions were quantified by the absolute calibration curve method using an anion mixed standard solution manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd., and the content of anion (P) in the resist solution was calculated.

[0034] <(A) Resin whose polarity increases under the action of acid> The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention contains a resin whose polarity increases under the action of an acid (hereinafter, also referred to as "resin (A)"). Typically, the resin (A) is preferably a resin whose polarity increases under the action of an acid and whose solubility in a developer changes.

[0035] The resin (resin (A)) whose polarity increases under the action of an acid is preferably a resin obtained by polymerizing at least an ethylenically unsaturated compound. The above ethylenically unsaturated compound preferably has 1 to 4 ethylenically unsaturated bonds, and more preferably has 1. Furthermore, the above ethylenically unsaturated compound is preferably a monomer of a monomer. The molecular weight of the ethylenically unsaturated compound is preferably 28-1,000, more preferably 50-800, and particularly preferably 100-600.

[0036] Moreover, the resin whose polarity increases under the action of an acid preferably has an acid-decomposable group, and more preferably has a structural unit having an acid-decomposable group. In this case, in the pattern formation method according to the present invention described below, 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.

[0037] [Structural Unit Having an Acid-Decomposable Group] The resin (A) preferably has a structural unit (also referred to as a "repeating unit") having an acid-decomposable group.

[0038] As the resin (A), a known resin can be appropriately used. For example, the known resins disclosed in paragraphs 0055 to 0191 of US Patent Application Publication No. 2016 / 0274458, paragraphs 0035 to 0085 of US Patent Application Publication No. 2015 / 0004544, and paragraphs 0045 to 0090 of US Patent Application Publication No. 2016 / 0147150 can be suitably used as the resin (A).

[0039] The acid-decomposable group preferably has a structure in which a polar group is protected with a group (leaving group) that is decomposed and eliminated by the action of an acid. Examples of the polar group include acidic groups (groups that dissociate in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide) such as a carboxy group, a phenolic hydroxyl 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, as well as an alcoholic hydroxyl group.

[0040] The alcoholic hydroxyl group refers to a hydroxyl group bonded to a hydrocarbon group other than a hydroxyl group (phenolic hydroxyl group) directly bonded to an aromatic ring, and excludes aliphatic alcohols (e.g., hexafluoroisopropanol group) in which the α-position of the hydroxyl group is substituted with an electron-withdrawing group such as a fluorine atom. The alcoholic hydroxyl group is preferably a hydroxyl group having a pKa (acid dissociation constant) of 12 or more and 20 or less.

[0041] Preferred polar groups include a carboxy group, a phenolic hydroxyl group, and a sulfonic acid group.

[0042] Preferred as the acid-decomposable group are groups in which the hydrogen atom of the above groups is substituted with a group that is eliminated by the action of an acid (a leaving group). Examples of the group that is eliminated by the action of an acid (leaving group) include -C(R 36 )(R 37 )(R 38 ), -C(R 36 )(R 37 )(OR 39 ), and -C(R 01 )(R 02 )(OR 39 ) etc. In the formula, R 36 ~R 39 R each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. 36 and R 37 may be bonded to each other to form a ring. R 01 and R 02 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group.

[0043] R 36 ~R 39 , R 01 and R 02 The alkyl group is preferably an alkyl group having 1 to 8 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a hexyl group, and an octyl group. R36 ~R 39 , R 01 and R 02 The cycloalkyl group may be monocyclic or polycyclic. As the monocyclic group, a cycloalkyl group having 3 to 8 carbon atoms is preferable, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. As the polycyclic group, a cycloalkyl group having 6 to 20 carbon atoms is preferable, and examples thereof include an adamantyl group, a norbornyl group, an isobornyl group, a camphanyl group, a dicyclopentyl group, an α-pinel group, a tricyclodecanyl group, a tetracyclododecyl group, and an androstanyl group. At least one carbon atom in the cycloalkyl group may be substituted with a heteroatom such as an oxygen atom. R 36 ~R 39 , R 01 and R 02 The aryl group 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. R 36 ~R 39 , R 01 and R 02 The aralkyl group is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, and a naphthylmethyl group. R 36 ~R 39 , R 01 and R 02 The alkenyl group is preferably an alkenyl group having 2 to 8 carbon atoms, and examples thereof include a vinyl group, an allyl group, a butenyl group, and a cyclohexenyl group. R 36 and R 37 The ring formed by bonding with each other is preferably a cycloalkyl group (monocyclic or polycyclic). As the cycloalkyl group, monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, or polycyclic cycloalkyl groups such as norbornyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups are preferred.

[0044] As the acid-decomposable group, a cumyl ester group, an enol ester group, an acetal ester group, a tertiary alkyl ester group, or the like is preferred, and an acetal group or a tertiary alkyl ester group is more preferred.

[0045] The resin (A) preferably has a structural unit represented by the following formula AI as a structural unit having an acid-decomposable group.

[0046] [ka]

[0047] In formula AI, Xa 1 represents a hydrogen atom, a halogen atom other than a fluorine atom, or a monovalent organic group; T represents a single bond or a divalent linking group; Rx 1 ~Rx 3 Rx each independently represents an alkyl group or a cycloalkyl group; 1 ~Rx 3 Any two of these may or may not be bonded to form a ring structure.

[0048] Examples of the divalent linking group of T include an alkylene group, an arylene group, -COO-Rt-, and -O-Rt-, in which Rt represents an alkylene group, a cycloalkylene group, or an arylene group; T is preferably a single bond or -COO-Rt-. Rt is preferably a chain alkylene group having 1 to 5 carbon atoms, more preferably -CH2-, -(CH2)2-, or -(CH2)3-. T is more preferably a single bond.

[0049] Xa 1 is preferably a hydrogen atom or an alkyl group. Xa 1 The alkyl group may have a substituent, and examples of the substituent include a hydroxyl group and a halogen atom other than a fluorine atom. Xa 1The alkyl group of Xa preferably has 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, and a hydroxymethyl group. 1 The alkyl group is preferably a methyl group.

[0050] Rx 1 , Rx 2 and Rx 3 The alkyl group of Rx may be linear or branched, and preferable examples thereof include 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 number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 5, and further preferably 1 to 3. 1 , Rx 2 and Rx 3 In the alkyl group, some of the carbon-carbon bonds may be double bonds. Rx 1 , Rx 2 and Rx 3 The cycloalkyl group 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.

[0051] Rx 1 , Rx 2 and Rx 3 The ring structure formed by combining the two is preferably a monocyclic cycloalkane ring such as a cyclopentyl ring, a cyclohexyl ring, a cycloheptyl ring, or a cyclooctane ring, or a polycyclic cycloalkyl ring such as a norbornane ring, a tetracyclodecane ring, a tetracyclododecane ring, or an adamantane ring. A cyclopentyl ring, a cyclohexyl ring, or an adamantane ring is more preferred. 1 , Rx 2 and Rx 3 As the ring structure formed by combining the above two, the structure shown below is also preferred.

[0052] [ka]

[0053] Specific examples of monomers corresponding to the structural unit represented by formula AI are given below, but the present invention is not limited to these specific examples. 1 corresponds to the case where Xa is a methyl group, 1 can be optionally substituted with a hydrogen atom, a halogen atom other than a fluorine atom, or a monovalent organic group.

[0054] [ka]

[0055] It is also preferable that the resin (A) has a structural unit having an acid-decomposable group, which is a structural unit described in paragraphs 0336 to 0369 of US Patent Application Publication No. 2016 / 0070167.

[0056] Furthermore, the resin (A) may have, as a structural unit having an acid-decomposable group, a structural unit containing a group that decomposes under the action of an acid to generate an alcoholic hydroxyl group, as described in paragraphs 0363 to 0364 of U.S. Patent Application Publication No. 2016 / 0070167.

[0057] In addition, the resin (A) preferably has a repeating unit having a structure (acid-decomposable group) in which a phenolic hydroxyl group is protected by a leaving group that is decomposed and removed by the action of an acid, as a repeating unit having an acid-decomposable group. In this specification, the phenolic hydroxyl group is a group obtained by substituting a hydrogen atom of an aromatic hydrocarbon group with a hydroxyl group. The aromatic ring of the aromatic hydrocarbon group is a monocyclic or polycyclic aromatic ring, and examples thereof include a benzene ring and a naphthalene ring.

[0058] Examples of the leaving group that is decomposed and 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(R36 )(R 37 )(OR 38 ) Formula (Y4):-C(Rn)(H)(Ar)

[0059] In formulae (Y1) and (Y2), Rx1 to Rx3 each independently represent an alkyl group (linear or branched) or a cycloalkyl group (monocyclic or polycyclic). However, 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. Among them, it is more preferable that Rx1 to Rx3 are each independently a repeating unit representing a linear or branched alkyl group, and it is further preferable that Rx1 to Rx3 are each independently a repeating unit representing a linear alkyl group. Two of Rx1 to Rx3 may be bonded to form a monocycle or polycycle. 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 group 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. 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. Among them, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable. 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, or a group having a heteroatom such as a carbonyl group. In the groups represented by formulae (Y1) and (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.

[0060] 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 preferably a hydrogen atom.

[0061] In formula (Y4), Ar represents an aromatic hydrocarbon 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 more preferably an aryl group.

[0062] As a repeating unit having a structure in which a phenolic hydroxyl group is protected with a leaving group that is decomposed and eliminated by the action of an acid (acid-decomposable group), a repeating unit having a structure in which a hydrogen atom in the phenolic hydroxyl group is protected with a group represented by any of the formulae (Y1) to (Y4) is preferable.

[0063] As a repeating unit having a structure in which a phenolic hydroxyl group is protected with a leaving group that is decomposed and eliminated by the action of an acid (acid-decomposable group), a repeating unit represented by the following general formula (AII) is preferable.

[0064] [ka]

[0065] In the general formula (AII), R 61 , R 62 and R 63 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group.62 may be bonded to Ar6 to form a ring, in which case R 62 represents a single bond or an alkylene group. X6 is a single bond, -COO-, or -CONR 64 - stands for R 64 represents a hydrogen atom or an alkyl group. L6 represents a single bond or an alkylene group. Ar6 represents an aromatic hydrocarbon group having a valence of (n+1); R 62 When it bonds with the to form a ring, it represents an (n+2)-valent aromatic hydrocarbon group. When n≧2, each Y2 independently represents a hydrogen atom or a group which is eliminated by the action of an acid. However, at least one Y2 represents a group which is eliminated by the action of an acid. The group which is eliminated by the action of an acid as Y2 is preferably any one of formulae (Y1) to (Y4). n represents an integer of 1 to 4.

[0066] The above groups may each have a substituent. Examples of the substituent include an alkyl group (having 1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (having 1 to 4 carbon atoms), a carboxyl group, and an alkoxycarbonyl group (having 2 to 6 carbon atoms), and those having 8 or less carbon atoms are preferred.

[0067] [ka]

[0068] [ka]

[0069] The resin (A) may contain one type of structural unit having an acid-decomposable group alone, or may contain two or more types.

[0070] The content of the structural units having an acid-decomposable group contained in the resin (the total content when a plurality of structural units having an acid-decomposable group are present) is preferably 5 mol % to 90 mol %, more preferably 10 mol % to 80 mol %, and even more preferably 15 mol % to 70 mol %, based on all the structural units of the resin (A). In the present invention, when the content of the "structural unit" is specified by a molar ratio, the "structural unit" is synonymous with the "monomer unit". In the present invention, the "monomer unit" may be modified after polymerization by a polymer reaction or the like. The same applies hereinafter.

[0071] [Structural Unit Having at Least One Structure Selected from the Group Consisting of Lactone Structure, Sultone Structure, and Carbonate Structure] The resin (A) preferably has a structural unit having at least one structure selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure.

[0072] As the lactone structure or sultone structure, any structure having a lactone structure or sultone structure can be used, but a 5- to 7-membered lactone structure or a 5- to 7-membered sultone structure is preferred, and a 5- to 7-membered lactone structure is more preferred in which another ring structure is condensed to form a bicyclo structure or a spiro structure, or a 5- to 7-membered sultone structure is more preferred in which another ring structure is condensed to form a bicyclo structure or a spiro structure. It is more preferred to have a structural unit having 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. The lactone structure or sultone structure may be directly bonded to the main chain. Preferred structures are LC1-1, LC1-4, LC1-5, LC1-8, LC1-16, LC1-21, and SL1-1.

[0073] [ka]

[0074] The lactone structure portion or the sultone structure portion is a substituent (Rb2 ) may or may not be present. 2 Examples of the substituent (Rb) 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 2 to 8 carbon atoms, a carboxyl group, a halogen atom other than a fluorine atom, a hydroxyl group, a cyano group, and an acid-decomposable group. More preferred are an alkyl group having 1 to 4 carbon atoms, a cyano group, and an acid-decomposable group. n2 represents an integer of 0 to 4. When n2 is 2 or more, a plurality of substituents (Rb 2 ) may be the same or different. In addition, when multiple substituents (Rb 2 ) may be bonded to each other to form a ring.

[0075] The constitutional unit having a lactone structure or a sultone structure is preferably a constitutional unit represented by the following formula III. In addition, the resin having a structural unit having an acid-decomposable group preferably contains a structural unit represented by the following formula III.

[0076] [ka]

[0077] In the above formula III, A represents an ester bond (a group represented by -COO-) or an amide bond (a group represented by -CONH-). n is -R 0 It is the number of repetitions of the structure represented by -Z-, and represents an integer of 0 to 5, preferably 0 or 1, and more preferably 0. When n is 0, -R 0 -Z- does not exist, A and R 8 are bonded by a single bond. R 0 R represents an alkylene group, a cycloalkylene group, or a combination thereof. 0 When there are a plurality of them, each independently represents an alkylene group, a cycloalkylene group, or a combination thereof. Z represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond. When there are multiple Z's, each independently represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond. R 8 represents a monovalent organic group having a lactone structure or a sultone structure. R 7 represents a hydrogen atom, a halogen atom other than a fluorine atom, or a monovalent organic group (preferably a methyl group).

[0078] R 0 The alkylene group or cycloalkylene group may have a substituent. Z is preferably an ether bond or an ester bond, more preferably an ester bond.

[0079] Specific examples of monomers corresponding to the structural unit represented by formula III and the structural unit represented by formula A-1 described below are given below, but the present invention is not limited to these specific examples. 7 and R in Formula A-1 described below. A 1 corresponds to the case where R is a methyl group, 7 and R A 1 can be optionally substituted with a hydrogen atom, a halogen atom other than a fluorine atom, or a monovalent organic group.

[0080] [ka]

[0081] In addition to the above monomers, the following monomers are also suitably used as raw materials for the resin (A).

[0082] [ka]

[0083] The resin (A) may have a structural unit having a carbonate structure. The carbonate structure is preferably a cyclic carbonate ester structure. The structural unit having a cyclic carbonate structure is preferably a structural unit represented by the following formula A-1.

[0084] [ka]

[0085] In formula A-1, R A 1 represents a hydrogen atom, a halogen atom other than a fluorine atom, or a monovalent organic group (preferably a methyl group), n represents an integer of 0 or more, R A 2 R represents a substituent. A 2 When n is 2 or more, each independently represents a substituent, A represents a single bond or a divalent linking group, and Z represents an atomic group forming a monocyclic structure or a polycyclic structure together with the group represented by -O-C(=O)-O- in the formula.

[0086] Resin (A) also preferably has a structural unit described in paragraphs 0370 to 0414 of U.S. Patent Application Publication No. 2016 / 0070167 as a structural unit having at least one type selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure.

[0087] The resin (A) preferably has a structural unit (a) having at least two lactone structures (hereinafter also referred to as "structural unit (a)"). The at least two lactone structures may be, for example, a structure in which at least two lactone structures are condensed, or a structure in which at least two lactone structures are linked by a single bond or a linking group. The lactone structure of the structural unit (a) is not particularly limited, but is preferably a 5- to 7-membered ring lactone structure, and is preferably a 5- to 7-membered ring lactone structure to which another ring structure is condensed in the form of a bicyclo structure or spiro structure. Preferred examples of the lactone structure include the lactone structures represented by any of the above-mentioned LC1-1 to LC1-21.

[0088] The structural unit having at least two lactone structures (hereinafter also referred to as "structural unit (a)") is preferably a structural unit represented by the following formula L-1.

[0089] [ka]

[0090] In formula L-1, Ra represents a hydrogen atom or an alkyl group, and Rb represents a partial structure having two or more lactone structures.

[0091] The alkyl group of Ra is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group. The alkyl group of Ra may be substituted. Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, and bromine atom, mercapto group, hydroxy group, alkoxy group such as methoxy group, ethoxy group, isopropoxy group, t-butoxy group, and benzyloxy group, and acetoxy group such as acetyl group and propionyl group. Ra is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, and a hydroxymethyl group.

[0092] Examples of the lactone structure contained in the Rb partial structure include the lactone structures described above. The partial structure of Rb having two or more lactone structures is preferably, for example, a structure in which at least two lactone structures are linked by a single bond or a linking group, and a structure in which at least two lactone structures are condensed. The structural unit (a1) having a structure in which at least two lactone structures are condensed, and the structural unit (a2) having a structure in which at least two lactone structures are linked by a single bond or a linking group are each described below.

[0093] -Structural unit (a1) having a structure in which at least two lactone structures are condensed-ring The structure in which at least two lactone structures are fused is preferably a structure in which two or three lactone structures are fused, and more preferably a structure in which two lactone structures are fused. An example of a structural unit having a structure in which at least two lactone structures are fused together (hereinafter, also referred to as "structural unit (a1)") is a structural unit represented by the following formula L-2.

[0094] [ka]

[0095] In formula L-2, Ra has the same meaning as Ra in formula L-1, Re1 to Re8 each independently represent a hydrogen atom or an alkyl group, Me1 represents a single bond or a divalent linking group, and Me2 and Me3 each independently represent a divalent linking group.

[0096] The alkyl group of Re1 to Re8 preferably has, for example, 5 or less carbon atoms, and more preferably has 1 carbon atom. Examples of the alkyl group having 5 or less carbon atoms for Re1 to Re8 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, an isopentyl group, an s-pentyl group, and a t-pentyl group. Among these, Re1 to Re8 are preferably hydrogen atoms.

[0097] Examples of the divalent linking group for Me1 include an alkylene group, a cycloalkylene group, -O-, -CO-, -COO-, -OCO-, and a combination of two or more of these groups. The alkylene group of Me1 preferably has, for example, 1 to 10 carbon atoms, and more preferably has 1 or 2 carbon atoms, and the alkylene group having 1 or 2 carbon atoms is preferably, for example, a methylene group or an ethylene group. The alkylene group of Me1 may be linear or branched, and examples thereof include a methylene group, an ethane-1,1-diyl group, an ethane-1,2-diyl group, a propane-1,1-diyl group, a propane-1,3-diyl group, a propane-2,2-diyl group, a pentane-1,5-diyl group, and a hexane-1,6-diyl group. The cycloalkylene group of Me1 preferably has 5 to 10 carbon atoms, and more preferably has 5 or 6 carbon atoms, for example. Examples of the cycloalkylene group of Me1 include a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclooctylene group, and a cyclodecylene group. As the divalent linking group of Me1, the group combining the above two or more groups is preferably, for example, a group combining an alkylene group with -COO-, and a group combining -OCO- with an alkylene group.Moreover, the group combining the above two or more groups is more preferably a group combining a methylene group with -COO-, and a group combining a -COO- with a methylene group.

[0098] Examples of the divalent linking group of Me2 and Me3 include an alkylene group, -O-, etc. The divalent linking group of Me2 and Me3 is preferably a methylene group, an ethylene group, or -O-, and more preferably -O-.

[0099] A monomer corresponding to the structural unit (a1) can be synthesized, for example, by the method described in JP-A-2015-160836.

[0100] Specific examples of the structural unit (a1) are shown below, but the present invention is not limited thereto. In each of the following formulae, R9 represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group, and * represents the bonding position to other structural units.

[0101] [ka]

[0102] [ka]

[0103] [ka]

[0104] -Structural unit (a2) having a structure in which at least two lactone structures are linked by a single bond or a linking group- The structure in which at least two lactone structures are linked by a single bond or a linking group is preferably a structure in which two to four lactone structures are linked by a single bond or a linking group, and more preferably a structure in which two lactone structures are linked by a single bond or a linking group. Examples of the linking group include the same groups as those exemplified as the linking group of M2 in formula L-3 described below. An example of a structural unit having a structure in which two or more lactone structures are linked via a single bond or a linking group (hereinafter also referred to as "structural unit (a2)") includes a structural unit represented by the following formula L-3.

[0105] [ka]

[0106] In formula L-3, Ra has the same meaning as Ra in formula L-1 above, M1 and M2 each independently represent a single bond or a linking group, and Lc1 and Lc2 each independently represent a group having a lactone structure.

[0107] Examples of the linking group for M1 include an alkylene group, a cycloalkylene group, -O-, -CO-, -COO-, -OCO-, and a combination of two or more of these groups. The alkylene group of M1 preferably has 1 to 10 carbon atoms, for example. The alkylene group of M1 may be linear or branched, and examples thereof include a methylene group, an ethane-1,1-diyl group, an ethane-1,2-diyl group, a propane-1,1-diyl group, a propane-1,3-diyl group, a propane-2,2-diyl group, a pentane-1,5-diyl group, and a hexane-1,6-diyl group. The cycloalkylene group of M1 preferably has 5 to 10 carbon atoms, for example. Examples of the cycloalkylene group of M1 include a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclooctylene group, and a cyclodecylene group. As the linking group of M1, the group combining the above two or more groups is preferably, for example, a group combining an alkylene group with -COO-, and a group combining -OCO- with an alkylene group.Moreover, the group combining the above two or more groups is more preferably a group combining a methylene group with -COO-, and a group combining a -COO- with a methylene group. Examples of the linking group for M2 include the same groups as those exemplified as the linking group for M1.

[0108] The lactone structure of Lc1 is preferably, for example, a 5- to 7-membered ring lactone structure, and preferably a 5- to 7-membered ring lactone structure to which another ring structure is condensed to form a bicyclo structure or a spiro structure. The lactone structure is more preferably a lactone structure represented by any one of the above LC1-1 to LC1-21. More preferred lactone structures include LC1-1, LC1-4, LC1-5, LC1-6, LC1-13, LC1-14 and LC1-17. The lactone structure of Lc1 may contain a substituent. Examples of the substituent that may be contained in the lactone structure of Lc1 include the same substituents as the substituent (Rb2) of the lactone structure described above. Examples of the lactone structure contained in Lc2 include the same lactone structures as those contained in Lc1.

[0109] The structural unit (a2) is preferably a structural unit represented by the following formula L-4 as the structural unit represented by the above formula L-3.

[0110] [ka]

[0111] In formula L-4, Ra has the same meaning as Ra in formula L-1 above, Mf1 and Mf2 each independently represent a single bond or a linking group, Rf1, Rf2, and Rf3 each independently represent a hydrogen atom or an alkyl group, Mf1 and Rf1 may be bonded to each other to form a ring, and Mf2 and Rf2 or Rf3 may each be bonded to each other to form a ring.

[0112] The linking group of Mf1 has the same meaning as the linking group of M1 in the above formula L-3. The linking group of Mf2 has the same meaning as the linking group of M2 in the above formula L-3. Examples of the alkyl group of Rf1 include alkyl groups having 1 to 4 carbon atoms. The alkyl group of Rf1 having 1 to 4 carbon atoms is preferably a methyl group or an ethyl group, more preferably a methyl group. The alkyl group of Rf1 may have a substituent. Examples of the substituent that the alkyl group of Rf1 may have include alkoxy groups such as a hydroxy group, a methoxy group, and an ethoxy group, a cyano group, and a halogen atom such as a fluorine atom. The alkyl groups of Rf2 and Rf3 have the same meaning as the alkyl group of Rf1.

[0113] Mf1 and Rf1 may be bonded to each other to form a ring. Examples of the structure in which Mf1 and Rf1 are bonded to each other to form a ring include the lactone structures represented by LC1-13, LC1-14, or LC1-17 among the lactone structures described above. Mf2 and Rf2 or Rf3 may be bonded to each other to form a ring. Examples of the structure in which Mf2 and Rf2 are bonded to each other to form a ring include the lactone structures represented by LC1-7, LC1-8, or LC1-15 among the above-mentioned lactone structures. Examples of the structure in which Mf2 and Rf3 are bonded to each other to form a ring include the lactone structures represented by any of the above-mentioned LC1-3 to LC1-6 among the above-mentioned lactone structures. Specific examples of the structural unit (a2) are shown below, but the present invention is not limited to these. * indicates the bonding position to other structural units.

[0114] [ka]

[0115] A structural unit having at least two lactone structures usually has optical isomers, and any of the optical isomers may be used. In addition, one type of optical isomer may be used alone, or a mixture of multiple optical isomers may be used. When one type of optical isomer is mainly used, the optical purity (ee) is preferably 90% or more, more preferably 95% or more.

[0116] The content of the structural unit having at least two lactone structures is preferably 10 mol % to 60 mol %, more preferably 20 mol % to 50 mol %, and even more preferably 30 mol % to 50 mol %, based on all structural units in the resin (A). In order to enhance the effects of the present invention, it is possible to use two or more types of constitutional units having at least two lactone structures in combination. When two or more types of repeating units having at least two lactone structures are contained, it is preferable that the total content of the constitutional units having at least two lactone structures is within the above-mentioned range.

[0117] The resin (A) may contain one type of structural unit having at least one type selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure, or may contain two or more types of structural units in combination.

[0118] The content of structural units having at least one selected from the group consisting of lactone structures, sultone structures, and carbonate structures contained in resin (the total content in cases where there are a plurality of structural units having at least one selected from the group consisting of lactone structures, sultone structures, and carbonate structures) is preferably 5 mol % to 70 mol %, more preferably 10 mol % to 65 mol %, and even more preferably 20 mol % to 60 mol %, relative to all structural units of resin (A).

[0119] [Structural Unit Having a Polar Group] The resin (A) preferably has a structural unit having a polar group. Examples of the polar group include a hydroxyl group, a cyano group, and a carboxy group. The structural unit having a polar group is preferably a structural unit having an alicyclic hydrocarbon structure substituted with a polar group. The structural unit having a polar group is preferably free of an acid-decomposable group. The alicyclic hydrocarbon structure in the alicyclic hydrocarbon structure substituted with a polar group is preferably an adamantyl group or a norbornyl group.

[0120] Specific examples of monomers corresponding to the structural unit having a polar group are given below, but the present invention is not limited to these specific examples. In addition, the following specific examples are described as methacrylic acid ester compounds, but may be acrylic acid ester compounds.

[0121] [ka]

[0122] Other specific examples of structural units having a polar group include the structural units disclosed in paragraphs 0415 to 0433 of US Patent Application Publication No. 2016 / 0070167. The resin (A) may contain one type of structural unit having a polar group on its own, or may contain two or more types in combination. The content of the structural unit having a polar group is preferably from 5 mol % to 40 mol %, more preferably from 5 mol % to 30 mol %, and even more preferably from 10 mol % to 25 mol %, based on all structural units in the resin (A).

[0123] [Structural Unit Having Neither an Acid-Decomposable Group nor a Polar Group] The resin (A) may further have a structural unit having neither an acid decomposable group nor a polar group. The structural unit having neither an acid decomposable group nor a polar group preferably has an alicyclic hydrocarbon structure. Examples of the structural unit having neither an acid decomposable group nor a polar group include the structural units described in paragraphs 0236 to 0237 of US Patent Application Publication No. 2016 / 0026083. Preferred examples of monomers corresponding to the structural unit having neither an acid decomposable group nor a polar group are shown below.

[0124] [ka]

[0125] In addition, specific examples of structural units having neither an acid-decomposable group nor a polar group include the structural units disclosed in paragraph 0433 of the specification of US Patent Application Publication No. 2016 / 0070167. The resin (A) may contain one type of structural unit having neither an acid-decomposable group nor a polar group, or may contain two or more types of structural units in combination. The content of the structural units having neither an acid-decomposable group nor a polar group is preferably from 5 to 40 mol %, more preferably from 5 to 30 mol %, and even more preferably from 5 to 25 mol %, based on all structural units in the resin (A).

[0126] [Repeating unit (a1)] The resin (A) may further have the following repeating unit (a1): The repeating unit (a1) is a repeating unit derived from a monomer (also referred to as "monomer a1") that has a glass transition temperature of 50°C or lower when made into a homopolymer. The repeating unit (a1) is a non-acid-decomposable repeating unit, and therefore does not have an acid-decomposable group.

[0127] (Method for measuring the glass transition temperature of homopolymer) The glass transition temperature of the homopolymer is measured by differential scanning calorimetry (DSC) if a catalog value or literature value is available, or if not, by differential scanning calorimetry (DSC). The weight average molecular weight (Mw) of the homopolymer used for Tg measurement is 18,000, and the dispersity (Mw / Mn) is 1.7. The DSC device used is a thermal analysis DSC differential scanning calorimeter Q1000 manufactured by TA Instruments Japan, Inc., and the measurement is performed at a heating rate of 10°C / min. The homopolymer to be subjected to the Tg measurement may be synthesized by a known method using the corresponding monomer, for example, a general drop polymerization method, etc. An example is shown below. 54 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) was heated to 80°C under a nitrogen stream. While stirring this liquid, 125 parts by mass of a PGMEA solution containing 21% by mass of the corresponding monomer and 0.35% by mass of dimethyl 2,2'-azobisisobutyrate was added dropwise over 6 hours. After the dropwise addition was completed, the mixture was stirred at 80°C for another 2 hours. The reaction liquid was allowed to cool, then reprecipitated with a large amount of methanol / water (mass ratio 9:1), filtered, and the obtained solid was dried to obtain a homopolymer (Mw: 18000, Mw / Mn: 1.7). The obtained homopolymer was subjected to DSC measurement. The DSC device and heating rate were as described above.

[0128] Monomer a1 is not particularly limited as long as the glass transition temperature (Tg) of the homopolymer is 50° C. or less, and from the viewpoint of improving the resolution of the dot pattern and suppressing roughness on the sidewall of the resist pattern that may occur during etching, the Tg of the homopolymer is preferably 30° C. or less. The lower limit of Tg of the monomer a1 as a homopolymer is not particularly limited, but is preferably −80° C. or more, more preferably −70° C. or more, even more preferably −60° C. or more, and particularly preferably −50° C. or more. By setting the lower limit of Tg of the monomer a1 as a homopolymer to the above range, the fluidity of the pattern during heating is suppressed, and the verticality of the dot pattern is further improved, which is preferable.

[0129] The repeating unit (a1) is preferably a repeating unit having a non-acid decomposable alkyl group having 2 or more carbon atoms, which may contain a heteroatom in the chain, in order to facilitate the volatilization of residual solvents. In this specification, "non-acid decomposable" means that the photoacid generator generates an acid and the photoacid generator generates an acid-based compound that does not cause an elimination / decomposition reaction. In other words, the "non-acid-decomposable alkyl group" is, more specifically, an alkyl group that is not detached from the resin (A) by the action of an acid generated by a photoacid generator, or an alkyl group that is not decomposed by the action of an acid generated by a photoacid generator. The non-acid-decomposable alkyl group may be either linear or branched. Hereinafter, a repeating unit having a non-acid-decomposable alkyl group having 2 or more carbon atoms which may contain a heteroatom in the chain will be described.

[0130] The non-acid-decomposable alkyl group having 2 or more carbon atoms which may contain a heteroatom in the chain is not particularly limited, but examples thereof include an alkyl group having 2 to 20 carbon atoms and an alkyl group having 2 to 20 carbon atoms and which contains a heteroatom in the chain. Examples of the alkyl group having 2 to 20 carbon atoms and containing a heteroatom in the chain include an alkyl group in which one or more -CH2- groups are substituted with -O-, -S-, -CO-, -NR6-, or a divalent organic group formed by combining two or more of these. The R6 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Specific examples of the non-acid-decomposable alkyl group having 2 or more carbon atoms which may contain a heteroatom in the chain include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, lauryl, stearyl, isobutyl, sec-butyl, 1-ethylpentyl, and 2-ethylhexyl groups, as well as monovalent alkyl groups in which one or more -CH2- are substituted with -O- or -O-CO-.

[0131] The number of carbon atoms in a non-acid-decomposable alkyl group having 2 or more carbon atoms, which may contain a heteroatom in the chain, is preferably 2 to 16, more preferably 2 to 10, and even more preferably 2 to 8. The lower limit of the number of carbon atoms in a non-acid-decomposable alkyl group having 2 or more carbon atoms is preferably 4 or more. The non-acid-decomposable alkyl group having 2 or more carbon atoms may have a substituent (for example, the substituent T).

[0132] The repeating unit (a1) is preferably a repeating unit represented by the following general formula (1-2).

[0133] [ka]

[0134] In the general formula (1-2), R1 represents a hydrogen atom, a halogen atom, an alkyl group, or a cycloalkyl group, and R2 represents a non-acid-decomposable alkyl group having 2 or more carbon atoms which may contain a heteroatom in the chain.

[0135] The halogen atom represented by R1 is not particularly limited, but examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The alkyl group represented by R1 is not particularly limited, but examples thereof include alkyl groups having 1 to 10 carbon atoms, specifically, methyl groups, ethyl groups, tert-butyl groups, etc. Among them, alkyl groups having 1 to 3 carbon atoms are preferred, and methyl groups are more preferred. The cycloalkyl group represented by R1 is not particularly limited, but examples thereof include cycloalkyl groups having 5 to 10 carbon atoms, and more specifically, examples thereof include a cyclohexyl group. Of these, R1 is preferably a hydrogen atom or a methyl group.

[0136] The definition and preferred embodiments of the non-acid-decomposable alkyl group having 2 or more carbon atoms which may contain a heteroatom in the chain represented by R2 are as described above.

[0137] In addition, the repeating unit (a1) may be a repeating unit having a non-acid-decomposable alkyl group having a carboxy group or a hydroxy group, which may contain a heteroatom in the chain, or a non-acid-decomposable cycloalkyl group having a carboxy group or a hydroxy group, which may contain a heteroatom in the ring, in order to make the residual solvent more easily volatilizable. Hereinafter, a repeating unit having a non-acid-decomposable alkyl group having a carboxy group or a hydroxy group, which may contain a heteroatom in the chain, or a non-acid-decomposable cycloalkyl group having a carboxy group or a hydroxy group, which may contain a heteroatom in the ring member, will be described.

[0138] The non-acid-decomposable alkyl group may be either linear or branched. The non-acid-decomposable alkyl group preferably has 2 or more carbon atoms, and from the viewpoint of making the Tg of the homopolymer 50° C. or less, the upper limit of the carbon number of the non-acid-decomposable alkyl group is preferably, for example, 20 or less.

[0139] The non-acid-decomposable alkyl group which may contain a heteroatom in the chain is not particularly limited, and examples thereof include an alkyl group having 2 to 20 carbon atoms and an alkyl group having 2 to 20 carbon atoms and containing a heteroatom in the chain. At least one of the hydrogen atoms in the alkyl group is substituted with a carboxy group or a hydroxyl group. Examples of the alkyl group having 2 to 20 carbon atoms and containing a heteroatom in the chain include an alkyl group in which one or more -CH2- groups are substituted with -O-, -S-, -CO-, -NR6-, or a divalent organic group formed by combining two or more of these. The R6 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0140] The number of carbon atoms in the non-acid-decomposable alkyl group, which may contain a heteroatom in the chain, is preferably 2 to 16, more preferably 2 to 10, and even more preferably 2 to 8, in terms of superior crack resistance (less likely occurrence of cracks). The non-acid-decomposable alkyl group may have a substituent (for example, the substituent T). Specific examples of repeating units having a non-acid-decomposable alkyl group having a carboxy group and containing a heteroatom in the chain include repeating units having the following structures.

[0141] [ka]

[0142] The number of carbon atoms in the non-acid-decomposable cycloalkyl group is preferably 5 or more, and from the viewpoint of making the Tg of the homopolymer 50°C or less, the upper limit of the number of carbon atoms in the non-acid-decomposable cycloalkyl group is, for example, preferably 20 or less, more preferably 16 or less, and even more preferably 10 or less.

[0143] The non-acid-decomposable cycloalkyl group, which may contain a heteroatom in the ring, is not particularly limited, and examples thereof include a cycloalkyl group having 5 to 20 carbon atoms (more specifically, a cyclohexyl group) and a cycloalkyl group having 5 to 20 carbon atoms and containing a heteroatom in the ring. At least one of the hydrogen atoms in the cycloalkyl group is substituted with a carboxy group or a hydroxyl group. Examples of cycloalkyl groups having 5 to 20 carbon atoms and containing a heteroatom in the ring include cycloalkyl groups in which one or more -CH2- are substituted with -O-, -S-, -CO-, -NR6-, or a divalent organic group formed by combining two or more of these. The R6 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. The non-acid-decomposable cycloalkyl group may have a substituent (for example, the substituent T).

[0144] As a repeating unit having a non-acid-decomposable alkyl group having a carboxy group or a hydroxy group and which may contain a heteroatom in the chain, or a non-acid-decomposable cycloalkyl group having a carboxy group or a hydroxy group and which may contain a heteroatom in the ring member, a repeating unit represented by the following general formula (1-3) is particularly preferred in terms of superior effects of the present invention.

[0145] [ka]

[0146] In the general formula (1-3), R3 represents a hydrogen atom, a halogen atom, an alkyl group, or a cycloalkyl group. R4 represents a non-acid-decomposable alkyl group having a carboxy group or a hydroxy group, which may contain a heteroatom in the chain, or a non-acid-decomposable cycloalkyl group having a carboxy group or a hydroxy group, which may contain a heteroatom in the ring.

[0147] In the general formula (1-3), R3 has the same meaning as R1 described above, and the preferred embodiments are also the same.

[0148] The definition and preferred embodiments of the non-acid-decomposable alkyl group having a carboxy group or a hydroxy group and optionally containing a heteroatom in the chain, represented by R4, or the non-acid-decomposable cycloalkyl group having a carboxy group or a hydroxy group and optionally containing a heteroatom in the ring member, are as described above. Among them, R4 is preferably a non-acid-decomposable cycloalkyl group having a carboxy group or a hydroxyl group, which may contain a heteroatom in the ring. Examples of this embodiment include repeating units of the following structure.

[0149] [ka]

[0150] Examples of monomer a1 include ethyl acrylate (-22°C), n-propyl acrylate (-37°C), isopropyl acrylate (-5°C), n-butyl acrylate (-55°C), n-butyl methacrylate (20°C), n-hexyl acrylate (-57°C), n-hexyl methacrylate (-5°C), n-octyl methacrylate (-20°C), 2-ethylhexyl acrylate (-70°C), isononyl acrylate (-82°C), ), lauryl methacrylate (-65°C), 2-hydroxyethyl acrylate (-15°C), 2-hydroxypropyl methacrylate (26°C), 1-[2-(methacryloyloxy)ethyl] succinate (9°C), 2-ethylhexyl methacrylate (-10°C), sec-butyl acrylate (-26°C), methoxypolyethylene glycol monomethacrylate (n=2) (-20°C), hexadecyl acrylate (35°C), etc. The values ​​in parentheses indicate the Tg (°C) when made into a homopolymer.

[0151] Methoxypolyethylene glycol monomethacrylate (n=2) is a compound having the following structure.

[0152] [ka]

[0153] Monomer a1 is preferably n-butyl acrylate, n-hexyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, 2-ethylhexyl acrylate, lauryl methacrylate, hexadecyl acrylate, 2-hydroxyethyl acrylate, or a compound represented by the following MA-5.

[0154] [ka]

[0155] The resin (A) may contain only one type of repeating unit (a1), or may contain two or more types of repeating units (a1). In the resin (A), the content of the repeating unit (a1) (when there are a plurality of repeating units (a1), the total content thereof) is preferably 5 mol % or more, more preferably 10 mol % or more, and preferably 50 mol % or less, more preferably 40 mol % or less, and even more preferably 30 mol % or less, based on all repeating units of the resin (A). In particular, the content of the repeating unit (a1) in the resin (when there are a plurality of repeating units (a1), the total content thereof) is preferably 5 to 50 mol %, more preferably 5 to 40 mol %, and even more preferably 5 to 30 mol %, based on all repeating units of the resin (A).

[0156] [Repeating unit (a4) having a phenolic hydroxyl group] The resin (A) may contain a repeating unit (a4) having a phenolic hydroxyl group. By containing the repeating unit (a4), the resin (A) has an excellent dissolution rate during alkaline development and excellent etching resistance.

[0157] The repeating unit having a phenolic hydroxyl group is not particularly limited, but may be a hydroxystyrene repeating unit or a hydroxystyrene (meth)acrylate repeating unit. As the repeating unit having a phenolic hydroxyl group, a repeating unit represented by the following general formula (I) is preferable.

[0158] [ka]

[0159] During the ceremony, R 41 , R 42 and R 43 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. 42 may be bonded to Ar4 to form a ring, in which case R 42 represents a single bond or an alkylene group. X4 is a single bond, -COO-, or -CONR 64 - represents R 64 represents a hydrogen atom or an alkyl group. L4 represents a single bond or a divalent linking group. Ar4 represents an aromatic hydrocarbon group having a valence of (n+1); R 42 When it bonds with the to form a ring, it represents an (n+2)-valent aromatic hydrocarbon group. n represents an integer of 1 to 5. For the purpose of increasing the polarity of the repeating unit represented by the general formula (I), n is an integer of 2 or more, or X4 is -COO- or -CONR 64 It is also preferable that

[0160] R in general formula (I) 41 , R 42 , and R 43 The alkyl group represented by the formula (I) is preferably an alkyl group having 20 or less carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, or a dodecyl group, which may have a substituent, more preferably an alkyl group having 8 or less carbon atoms, and even more preferably an alkyl group having 3 or less carbon atoms.

[0161] R in general formula (I) 41 , R 42 , and R 43The cycloalkyl group represented by the following formula may be a monocyclic or polycyclic cycloalkyl group having 3 to 8 carbon atoms, such as a cyclopropyl group, a cyclopentyl group, or a cyclohexyl group, which may have a substituent. R in general formula (I) 41 , R 42 , and R 43 Examples of the halogen atom represented by the formula (I) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, with a fluorine atom being preferred. R in general formula (I) 41 , R 42 , and R 43 The alkyl group contained in the alkoxycarbonyl group represented by the above R 41 , R 42 , and R 43 The same alkyl groups as those in the above are preferred.

[0162] Preferred examples of the substituent in each of the above groups include an alkyl group, a cycloalkyl group, an aryl group, an amino group, an amido group, a ureido group, a urethane group, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group, a thioether group, an acyl group, an acyloxy group, an alkoxycarbonyl group, a cyano group, and a nitro group, and the number of carbon atoms of the substituent is preferably 8 or less.

[0163] Ar4 represents an aromatic hydrocarbon group having a valence of (n+1). When n is 1, the divalent aromatic hydrocarbon group may have a substituent, and is preferably an arylene group having 6 to 18 carbon atoms, such as a phenylene group, a tolylene group, a naphthylene group, or an anthracenylene group, or an aromatic hydrocarbon group containing a heterocycle, such as thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, or thiazole.

[0164] Specific examples of the (n+1)-valent aromatic hydrocarbon group when n is an integer of 2 or greater are preferably groups obtained by removing any (n-1) hydrogen atoms from the above-mentioned specific examples of the divalent aromatic hydrocarbon group. The (n+1)-valent aromatic hydrocarbon group may further have a substituent.

[0165] Examples of the substituent that the above-mentioned alkyl group, cycloalkyl group, alkoxycarbonyl group, and (n+1)-valent aromatic hydrocarbon group may have include R 41 , R 42 , and R 43 alkoxy groups such as a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, a hydroxypropoxy group, and a butoxy group; and aryl groups such as a phenyl group. -CONR represented by X4 64 -(R 64 represents a hydrogen atom or an alkyl group) 64 The alkyl group may have a substituent, and is preferably an alkyl group having 20 or less carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, or a dodecyl group, and more preferably an alkyl group having 8 or less carbon atoms. X4 is preferably a single bond, -COO- or -CONH-, more preferably a single bond or -COO-.

[0166] The divalent linking group as L4 is preferably an alkylene group, and the alkylene group is preferably an alkylene group having 1 to 8 carbon atoms, such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, or an octylene group, which may have a substituent. Ar4 is preferably an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent, and more preferably a benzene ring group, a naphthalene ring group, or a biphenylene ring group. Of these, the repeating unit represented by general formula (I) is preferably a repeating unit derived from hydroxystyrene. That is, Ar4 is preferably a benzene ring group.

[0167] Specific examples of repeating units having a phenolic hydroxyl group are shown below, but the present invention is not limited thereto.

[0168] [ka]

[0169] The resin (A) may have one type of repeating unit (a4) alone, or may have two or more types in combination. In the resin (A), the content of the repeating unit (a4) is preferably 40 mol% or more, more preferably 50 mol% or more, and even more preferably 60 mol% or more, based on the total repeating units in the resin (A). The content of the repeating unit (a4) is preferably 85 mol% or less, more preferably 80 mol% or less, based on the total repeating units in the resin (A).

[0170] In addition to the above structural units, the resin (A) may have various structural units for the purpose of adjusting dry etching resistance, suitability for a standard developer, substrate adhesion, resist profile, and furthermore, general required properties of a resist, such as resolution, heat resistance, sensitivity, etc. Examples of such structural units include, but are not limited to, structural units corresponding to other monomers.

[0171] Examples of the other monomers include compounds having one addition-polymerizable unsaturated bond selected from acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, and vinyl esters. In addition, any addition-polymerizable unsaturated compound that is copolymerizable with the monomers corresponding to the various structural units described above may be copolymerized. In the resin (A), the molar ratio of each constituent unit is appropriately set in order to adjust various properties.

[0172] When the actinic ray- or radiation-sensitive resin composition according to the present invention is for exposure to an argon fluoride (ArF) laser, from the viewpoint of the transmittance of ArF light, it is preferable that the resin (A) does not substantially have an aromatic group. More specifically, among all the structural units of the resin (A), structural units having an aromatic group are preferably 5 mol% or less of the total, more preferably 3 mol% or less, and ideally 0 mol%, that is, it is even more preferable that the resin (A) has no structural units having an aromatic group. In addition, it is preferable that the resin (A) has a monocyclic or polycyclic alicyclic hydrocarbon structure.

[0173] It is preferable that all of the structural units of the resin (A) are (meth)acrylate-based structural units. In this case, any of those in which all of the structural units are methacrylate-based structural units, all of the structural units are acrylate-based structural units, and all of the structural units are a combination of methacrylate-based structural units and acrylate-based structural units can be used, but it is preferable that the acrylate-based structural units account for 50 mol% or less of the total structural units of the resin (A).

[0174] When the actinic ray- or radiation-sensitive resin composition according to the present invention is for krypton fluoride (KrF) exposure, electron beam (EB) exposure, or extreme ultraviolet (EUV) exposure, the resin (A) preferably contains a structural unit having an aromatic hydrocarbon group, and more preferably contains a structural unit having a phenolic hydroxyl group. An example of a structural unit having a phenolic hydroxyl group is the repeating unit (a4) described above. When the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention is for KrF exposure, EB exposure, or EUV exposure, the resin (A) preferably has a structure in which the hydrogen atom of a phenolic hydroxyl group is protected with a group (leaving group) that is decomposed and eliminated by the action of an acid. The content of the structural units having an aromatic hydrocarbon group contained in the resin (A) is preferably 30 mol% to 100 mol%, more preferably 40 mol% to 100 mol%, and even more preferably 50 mol% to 100 mol%, based on all structural units in the resin (A).

[0175] The weight average molecular weight of the resin (A) is preferably from 1,000 to 200,000, more preferably from 2,000 to 20,000, further preferably from 3,000 to 15,000, and particularly preferably from 3,000 to 11,000. The dispersity (Mw / Mn) is preferably from 1.0 to 3.0, more preferably from 1.0 to 2.6, further preferably from 1.0 to 2.0, and particularly preferably from 1.1 to 2.0.

[0176] Specific examples of the resin (A) include resins A-1 to A-17 used in the examples, but are not limited thereto.

[0177] The resin (A) may be used alone or in combination of two or more kinds. The content of the resin (A) is preferably 20% by mass or more, more preferably 40% by mass or more, even more preferably 60% by mass or more, and particularly preferably 80% by mass or more, based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention. The upper limit is not particularly limited, but is preferably 99.5% by mass or less, more preferably 99% by mass or less, and even more preferably 97% by mass or less.

[0178] [Alkali-soluble resin having a phenolic hydroxyl group] When the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention contains a crosslinking agent (G) described later, the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention preferably contains an alkali-soluble resin having a phenolic hydroxyl group (hereinafter, also referred to as "resin (C)"). The resin (C) preferably has a structural unit having a phenolic hydroxyl group. In this case, typically, a negative pattern is preferably formed. The crosslinking agent (G) may be in a form supported on the resin (C). Among the resins (C), those that correspond to resins whose polarity increases by the action of an acid are treated as resins whose polarity increases by the action of an acid. In that case, the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention may contain a resin whose polarity increases by the action of an acid as the resin (C), or may contain at least a resin (C) other than the resin whose polarity increases by the action of an acid and a resin whose polarity increases by the action of an acid. The resin (C) may contain the above-mentioned acid-decomposable group. The structural unit having a phenolic hydroxyl group contained in the resin (C) is not particularly limited, but is preferably the above repeating unit (a4).

[0179] The resin (C) may be used alone or in combination of two or more kinds. The content of the resin (C) in the total solid content of the actinic ray- or radiation-sensitive resin composition according to the present invention is preferably 30% by mass or more, more preferably 40% by mass or more, and even more preferably 50% by mass or more. There is no particular upper limit, but it is preferably 99% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less. As the resin (C), the resins disclosed in paragraphs 0142 to 0347 of US Patent Application Publication No. 2016 / 0282720 can be suitably used.

[0180] [Hydrophobic resin] The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention preferably contains a hydrophobic resin (also referred to as "hydrophobic resin (E)"). The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention preferably contains at least a hydrophobic resin (E) other than a resin whose polarity increases by the action of an acid, and a resin whose polarity increases by the action of an acid. The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention contains a hydrophobic resin (E), and thus the static / dynamic contact angle on the surface of the actinic ray-sensitive or radiation-sensitive film can be controlled, which makes it possible to improve development characteristics, suppress outgassing, improve immersion liquid tracking in immersion exposure, and reduce immersion defects. The hydrophobic resin (E) is preferably designed so as to be unevenly distributed on the surface of the resist film. However, unlike a surfactant, it does not necessarily have to have a hydrophilic group in the molecule, and does not necessarily have to contribute to uniformly mixing polar / non-polar substances. In the present invention, the resin having a fluorine atom is treated as a hydrophobic resin and a fluorine-containing resin described later. The resin having a structural unit having an acid-decomposable group preferably does not have a fluorine atom.

[0181] From the viewpoint of uneven distribution on the membrane surface layer, the hydrophobic resin (E) is preferably a resin containing a structural unit having at least one selected from the group consisting of a "fluorine atom", a "silicon atom", and a "CH3 partial structure contained in a side chain portion of the resin". When the hydrophobic resin (E) contains a fluorine atom or a silicon atom, the fluorine atom or silicon atom in the hydrophobic resin (E) may be contained in the main chain or in a side chain of the resin.

[0182] The hydrophobic resin (E) preferably has at least one group selected from the group consisting of (x) to (z) below. (x) Acid group (y) A group that is decomposed by the action of an alkaline developer to increase the solubility in the alkaline developer (hereinafter also referred to as a polarity conversion group). (z) Groups that decompose when subjected to the action of acid

[0183] Examples of the acid group (x) include a phenolic hydroxyl group, a carboxylic acid 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. The acid group is preferably a fluorinated alcohol group (preferably hexafluoroisopropanol), a sulfonimide group, or a bis(alkylcarbonyl)methylene group.

[0184] Examples of the group (y) that is decomposed by the action of an alkaline developer to increase its solubility in an alkaline developer include a lactone group, a carboxylate group (-COO-), an acid anhydride group (-C(O)OC(O)-), an acid imide group (-NHCONH-), a carboxylate thioester group (-COS-), a carbonate group (-OC(O)O-), a sulfate group (-OSO-), and a sulfonate group (-SOO-), and the like are mentioned, with a lactone group or a carboxylate group (-COO-) being preferred. The structural unit containing these groups is a structural unit in which these groups are directly bonded to the main chain of the resin, and examples thereof include structural units of acrylic acid ester and methacrylic acid ester. In this structural unit, these groups may be bonded to the main chain of the resin via a linking group. Alternatively, this structural unit may be introduced to the end of the resin by using a polymerization initiator or chain transfer agent having these groups during polymerization. Examples of structural units having a lactone group include the same structural units having a lactone structure as those explained above in the section on resin (A).

[0185] The content of the structural unit having a group (y) that is decomposed by the action of an alkaline developer to increase the solubility in the alkaline developer is preferably from 1 to 100 mol %, more preferably from 3 to 98 mol %, and even more preferably from 5 to 95 mol %, based on all structural units in the hydrophobic resin (E).

[0186] In the hydrophobic resin (E), the structural unit having a group (z) decomposed by the action of an acid may be the same as the structural unit having an acid decomposable group exemplified in the resin (A). The structural unit having a group (z) decomposed by the action of an acid may have at least one of a fluorine atom and a silicon atom. The content of the structural unit having a group (z) decomposed by the action of an acid is preferably 1 mol% to 80 mol%, more preferably 10 mol% to 80 mol%, and even more preferably 20 mol% to 60 mol%, based on the total structural units in the resin (E).

[0187] The hydrophobic resin (E) may further have a structural unit other than the structural units described above.

[0188] The fluorine atom-containing structural unit preferably accounts for 10 mol% to 100 mol%, more preferably 30 mol% to 100 mol%, of all structural units contained in the hydrophobic resin (E), and the silicon atom-containing structural unit preferably accounts for 10 mol% to 100 mol%, more preferably 20 mol% to 100 mol%, of all structural units contained in the hydrophobic resin (E).

[0189] On the other hand, particularly when the hydrophobic resin (E) contains a CH3 partial structure in the side chain portion, the hydrophobic resin (E) is preferably substantially free of fluorine atoms and silicon atoms. Also, the hydrophobic resin (E) is preferably substantially composed of structural units composed only of atoms selected from carbon atoms, oxygen atoms, hydrogen atoms, nitrogen atoms, and sulfur atoms.

[0190] The weight average molecular weight of the hydrophobic resin (E) in terms of standard polystyrene is preferably from 1,000 to 100,000, and more preferably from 1,000 to 50,000.

[0191] The total content of residual monomer and oligomer components contained in the hydrophobic resin (E) is preferably 0.01% by mass to 5% by mass, more preferably 0.01% by mass to 3% by mass, and the dispersity (Mw / Mn) is preferably in the range of 1 to 5, more preferably 1 to 3.

[0192] As the hydrophobic resin (E), known resins can be appropriately selected and used alone or as a mixture thereof. For example, known resins disclosed in paragraphs 0451-0704 of US Patent Application Publication No. 2015 / 0168830 and paragraphs 0340-0356 of US Patent Application Publication No. 2016 / 0274458 can be suitably used as the hydrophobic resin (E). In addition, the structural units disclosed in paragraphs 0177-0258 of US Patent Application Publication No. 2016 / 0237190 are also preferred as structural units constituting the hydrophobic resin (E).

[0193] -Fluorine-containing resin- The hydrophobic resin (E) is preferably a resin containing fluorine atoms (also referred to as a "fluorine-containing resin"). When the hydrophobic resin (E) contains a fluorine atom, it is preferable that the hydrophobic resin (E) is a resin having, as a partial structure having a fluorine atom, an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom.

[0194] The alkyl group having a fluorine atom is a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and preferably has 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms. The cycloalkyl group having a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted with a fluorine atom. Examples of aryl groups having a fluorine atom include aryl groups such as a phenyl group and a naphthyl group in which at least one hydrogen atom is substituted with a fluorine atom.

[0195] As the alkyl group having a fluorine atom, the cycloalkyl group having a fluorine atom, and the aryl group having a fluorine atom, groups represented by the formulae F2 to F4 are preferred.

[0196] [ka]

[0197] In formulas F2 to F4, R 57 ~R 68 each independently represents a hydrogen atom, a fluorine atom, or an alkyl group (linear or branched), provided that R 57 ~R 61 At least one of R 62 ~R 64 At least one of, and R 65 ~R 68 At least one of each independently represents a fluorine atom or an alkyl group having at least one hydrogen atom substituted with a fluorine atom. R 57 ~R 61 and R 65 ~R 67 It is preferable that all of R are fluorine atoms. 62 , R 63 and R 68 R is preferably an alkyl group (preferably having 1 to 4 carbon atoms) in which at least one hydrogen atom is substituted with a fluorine atom, and more preferably a perfluoroalkyl group having 1 to 4 carbon atoms. 62 and R 63 may be linked to each other to form a ring.

[0198] Among these, it is preferable that the fluorine-containing resin has alkali decomposability, in that the effect of the present invention is more excellent. The term "fluorine-containing resin is alkali decomposable" means that 30 mol % or more of the total amount of decomposable groups in the fluorine-containing resin is hydrolyzed after 10 minutes when 100 mg of the fluorine-containing resin is added to a mixture of 2 mL of a pH 10 buffer solution and 8 mL of THF and allowed to stand at 40° C. The decomposition rate can be calculated from the ratio of the raw material and the decomposed product by NMR analysis.

[0199] From the viewpoints of improving the latitude of focal depth, pattern linearity, development characteristics, suppressing outgassing, improving the immersion liquid followability in immersion exposure, and reducing immersion defects, the fluorine-containing resin preferably has a constitutional unit represented by formula X. From the viewpoints of improving the latitude of focal depth, pattern linearity, development characteristics, suppressing outgassing, improving immersion liquid tracking in immersion exposure, and reducing immersion defects, it is preferable that the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention further contains a fluorine-containing resin having a structural unit represented by formula X.

[0200] [ka]

[0201] In the formula X, Z is a halogen atom, R 11 A group represented by OCH2- or R 12 R represents a group represented by OC(=O)CH2-. 11 and R 12 each independently represents a substituent, X represents an oxygen atom or a sulfur atom, L represents a (n+1)-valent linking group, R 10 represents a group having a group which is decomposed by the action of an alkaline aqueous solution to increase the solubility of the fluororesin in the alkaline aqueous solution, n represents a positive integer, and when n is 2 or more, a plurality of R 10 may be the same or different from each other.

[0202] Examples of the halogen atom represented by Z include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable. R 11 and R 12 Examples of the substituent as R include an alkyl group (preferably having 1 to 4 carbon atoms), a cycloalkyl group (preferably having 6 to 10 carbon atoms), and an aryl group (preferably having 6 to 10 carbon atoms). 11 and R 12The substituent as may further have a substituent, and such further substituent includes an alkyl group (preferably having 1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (preferably having 1 to 4 carbon atoms), and a carboxy group. The linking group represented by L is preferably a divalent or trivalent linking group (in other words, n is preferably 1 or 2), and more preferably a divalent linking group (in other words, n is preferably 1). The linking group represented by L is preferably a linking group selected from the group consisting of an aliphatic group, an aromatic group, and a combination thereof. For example, when n is 1 and the linking group as L is a divalent linking group, examples of the divalent aliphatic group include an alkylene group, an alkenylene group, an alkynylene group, and a polyalkyleneoxy group. Among these, an alkylene group or an alkenylene group is preferable, and an alkylene group is more preferable. The divalent aliphatic group may have a chain structure or a cyclic structure, but a chain structure is more preferable than a cyclic structure, and a straight chain structure is more preferable than a branched chain structure. The divalent aliphatic group may have a substituent, and examples of the substituent include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), a hydroxyl group, a carboxyl group, an amino group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a monoalkylamino group, a dialkylamino group, an arylamino group, and a diarylamino group. The divalent aromatic group may be an arylene group, of which a phenylene group and a naphthylene group are preferred. The divalent aromatic group may have a substituent, and examples of the substituent in the divalent aliphatic group include an alkyl group. Furthermore, L may be a divalent group obtained by removing two hydrogen atoms at any position from the structure represented by the above formulae LC1-1 to LC1-21 or SL1-1 to SL-3. When n is 2 or more, specific examples of the (n+1)-valent linking group include groups obtained by removing any (n-1) hydrogen atoms from the specific examples of the divalent linking groups mentioned above. Specific examples of L include the following linking groups.

[0203] [ka]

[0204] As described above, these linking groups may further have a substituent.

[0205] R 10 is preferably a group represented by the following formula W. -YR 20 formula W

[0206] In the above formula W, Y represents a group that is decomposed by the action of an alkaline aqueous solution and has an increased solubility in the alkaline aqueous solution. 20 represents an electron-withdrawing group.

[0207] Examples of Y include a carboxylate group (-COO- or OCO-), an acid anhydride group (-C(O)OC(O)-), an acid imide group (-NHCONH-), a carboxylate thioester group (-COS-), a carbonate group (-OC(O)O-), a sulfate group (-OSO2O-), and a sulfonate group (-S02O-), and a carboxylate group is preferred.

[0208] The electron-withdrawing group is preferably a partial structure represented by the following formula EW: In formula EW, * represents a bond directly bonded to group Y in formula W.

[0209] [ka]

[0210] In the formula EW, n ew -C(R ew1 )(R ew2 n is the number of repetitions of the linking group represented by -, and represents an integer of 0 or 1. ew If is 0, it represents a single bond, and Y ew1indicates that the bond is Y ew1 is a halogen atom, a cyano group, a nitro group, or -C(R f1 )(R f2 )-R f3 Examples of the halo(cyclo)alkyl group include a haloaryl group, an oxy group, a carbonyl group, a sulfonyl group, a sulfinyl group, and combinations thereof. (Note that Y ew1 is a halogen atom, a cyano group, or a nitro group, n ew is 1.) R ew1 and R ew2 each independently represents an arbitrary group, for example, a hydrogen atom, an alkyl group (preferably having 1 to 8 carbon atoms), a cycloalkyl group (preferably having 3 to 10 carbon atoms) or an aryl group (preferably having 6 to 10 carbon atoms). R ew1 , R ew2 and Y ew1 At least two of these may be linked to each other to form a ring. The term "halo(cyclo)alkyl group" refers to an alkyl group or cycloalkyl group which is at least partially halogenated, and the term "haloaryl group" refers to an aryl group which is at least partially halogenated.

[0211] Y ew1 Examples of the halogen atom include -C(R f1 )(R f2 )-R f3 A halo(cyclo)alkyl group represented by the following formula: or a haloaryl group is preferred.

[0212] R f1 represents a halogen atom, a perhaloalkyl group, a perhalocycloalkyl group, or a perhaloaryl group, preferably a fluorine atom, a perfluoroalkyl group, or a perfluorocycloalkyl group, more preferably a fluorine atom or a trifluoromethyl group. R f2 and R f3 each independently represents a hydrogen atom, a halogen atom, or an organic group; R f2 and R f3and may be linked to form a ring. Examples of the organic group include an alkyl group, a cycloalkyl group, and an alkoxy group, which may be substituted with a halogen atom (preferably a fluorine atom). R f2 and R f3 R is preferably a (halo)alkyl group or a (halo)cycloalkyl group. f2 is R f1 or R f3 It is more preferable that they are linked to form a ring. R f2 and R f3 Examples of the ring formed by linking these include a (halo)cycloalkyl ring.

[0213] R f1 ~R f3 The (halo)alkyl group in the formula (I) may be either linear or branched, and the linear (halo)alkyl group preferably has 1 to 30 carbon atoms, and more preferably has 1 to 20 carbon atoms.

[0214] R f1 ~R f3 In or R f2 and R f3 The (halo)cycloalkyl group in the ring formed by linking and may be a monocyclic or polycyclic group. In the case of a polycyclic group, the (halo)cycloalkyl group may be a bridged group. That is, in this case, the (halo)cycloalkyl group may have a bridged structure. Examples of these (halo)cycloalkyl groups include those represented by the following formulae and halogenated versions of these: In addition, some of the carbon atoms in the cycloalkyl group may be substituted with heteroatoms such as oxygen atoms.

[0215] [ka]

[0216] R f2 and R f3 In or R f2 and R f3As the (halo)cycloalkyl group in the ring formed by linking with (n) F (2n-2) Preferred is a fluorocycloalkyl group represented by H. Here, the carbon number n is not particularly limited, but is preferably 5 to 13, and more preferably 6.

[0217] Y ew1 In or R f1 The (per)haloaryl group in the formula (I) is -C (n) F (n-1) Here, the carbon number n is not particularly limited, but is preferably 5 to 13, and more preferably 6.

[0218] R ew1 , R ew2 and Y ew1 The ring which may be formed by combining at least two of these is preferably a cycloalkyl group or a heterocyclic group.

[0219] Each group and each ring constituting the partial structure represented by the above formula EW may further have a substituent.

[0220] In the above formula W, R 20 is preferably an alkyl group substituted with one or more selected from the group consisting of a halogen atom, a cyano group, and a nitro group, more preferably an alkyl group substituted with a halogen atom (haloalkyl group), and even more preferably a fluoroalkyl group. The alkyl group substituted with one or more selected from the group consisting of a halogen atom, a cyano group, and a nitro group preferably has 1 to 10 carbon atoms, and more preferably has 1 to 5 carbon atoms. More specifically, R 20 is -C(R' 1 )(R' f1 )(R' f2 ) or -C(R' 1 )(R' 2 )(R' f1 R' is preferably an atomic group represented by the formula: 1 and R' 2R' each independently represents a hydrogen atom or an alkyl group that is not substituted with an electron-withdrawing group (preferably unsubstituted). f1 and R' f2 each independently represents a halogen atom, a cyano group, a nitro group, or a perfluoroalkyl group. R' 1 and R' 2 The alkyl group as the radical may be linear or branched, and preferably has 1 to 6 carbon atoms. R' f1 and R' f2 The perfluoroalkyl group may be linear or branched, and preferably has 1 to 6 carbon atoms. R 20 Preferred specific examples of the above include -CF3, -C2F5, -C3F7, -C4F9, -CF(CF3)2, -CF(CF3)C2F5, -CF2CF(CF3)2, -C(CF3)3, -C5F 11 , -CF 13 , -C7F 15 , -C8F 17 , -CH2CF3, -CH2C2F5, -CH2C3F7, -CH(CF3)2, -CH(CF3)C2F5, -CH2CF(CF3)2, and -CH2CN. Among them, -CF3, -C2F5, -C3F7, -C4F9, -CH2CF3, -CH2C2F5, -CH2C3F7, -CH(CF3)2, or -CH2CN is preferred, -CH2CF3, -CH2C2F5, -CH2C3F7, -CH(CF3)2, or -CH2CN is more preferred, -CH2C2F5, -CH(CF3)2, or -CH2CN is even more preferred, and -CH2C2F5 or -CH(CF3)2 is particularly preferred.

[0221] As the constitutional unit represented by formula X, a constitutional unit represented by the following formula X-1 or formula X-2 is preferable, and a constitutional unit represented by formula X-1 is more preferable.

[0222] [ka]

[0223] In formula X-1, R20 represents an electron-withdrawing group, L 2 represents a divalent linking group; X 2 represents an oxygen atom or a sulfur atom, Z 2 represents a halogen atom. In formula X-2, R 20 represents an electron-withdrawing group, L 3 represents a divalent linking group; X 3 represents an oxygen atom or a sulfur atom, Z 3 represents a halogen atom.

[0224] L 2 and L 3 Specific examples and preferred examples of the divalent linking group as are the same as those explained for L as the divalent linking group in formula X above. R 2 and R 3 The electron-withdrawing group as is preferably a partial structure represented by the above formula EW, and specific and preferred examples are as described above, with a halo(cyclo)alkyl group being more preferred.

[0225] In the above formula X-1, L 2 and R 2 and do not bond to each other to form a ring, and in the above formula X-2, L 3 and R 3 do not bond to each other to form a ring.

[0226] X 2 and X 3 As the group, an oxygen atom is preferable. Z 2 and Z 3 is preferably a fluorine atom or a chlorine atom, and more preferably a fluorine atom.

[0227] As the constitutional unit represented by the formula X, a constitutional unit represented by the formula X-3 is also preferred.

[0228] [ka]

[0229] In formula X-3, R 20 represents an electron-withdrawing group, R 21 represents a hydrogen atom, an alkyl group, or an aryl group; L 4 represents a divalent linking group; X 4 represents an oxygen atom or a sulfur atom, and m represents 0 or 1.

[0230] L 4 Specific examples and preferred examples of the divalent linking group as are the same as those explained for L as the divalent linking group of formula X. R 4 The electron-withdrawing group as is preferably a partial structure represented by the above formula EW, and specific and preferred examples are as described above, but is more preferably a halo(cyclo)alkyl group.

[0231] In the above formula X-3, L 4 and R 4 do not bond to each other to form a ring. X 4 As the group, an oxygen atom is preferable.

[0232] As the constitutional unit represented by formula X, a constitutional unit represented by formula Y-1 or a constitutional unit represented by formula Y-2 is also preferred.

[0233] [ka]

[0234] In formula Y-1 and formula Y-2, Z is a halogen atom, R 11 A group represented by OCH2- or R 12 R represents a group represented by OC(=O)CH2-. 11 and R 12 each independently represents a substituent; R 20 represents an electron-withdrawing group.

[0235] R 20The electron-withdrawing group as is preferably a partial structure represented by the above formula EW, and specific and preferred examples are as described above, but is more preferably a halo(cyclo)alkyl group.

[0236] Z as halogen atom, R 11 A group represented by OCH2- and R 12 Specific and preferred examples of the group represented by OC(=O)CH2- are the same as those explained in formula 1 above.

[0237] The content of the constitutional unit represented by formula X is preferably from 10 mol % to 100 mol %, more preferably from 20 mol % to 100 mol %, and further preferably from 30 mol % to 100 mol %, based on all constitutional units of the fluorine-containing resin.

[0238] Preferred examples of the structural units constituting the hydrophobic resin (E) are shown below. Preferred examples of the hydrophobic resin (E) include resins containing any combination of these structural units, and resins F-1 and F-2 used in the examples, but are not limited to these.

[0239] [ka]

[0240] [ka]

[0241] The hydrophobic resin (E) may be used alone or in combination of two or more kinds. It is preferable to use a mixture of two or more hydrophobic resins (E) having different surface energies from the viewpoint of achieving both immersion liquid followability in immersion exposure and development characteristics. The content of the hydrophobic resin (E) in the composition is preferably 0.01 to 10 mass %, more preferably 0.05 to 8 mass %, based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention.

[0242] <(B) Photoacid generator> The composition according to the present invention contains a photoacid generator (hereinafter also referred to as "photoacid generator (B)"). A photoacid generator is a compound that generates an acid when exposed to actinic rays or radiation. The photoacid generator is preferably a compound that generates an organic acid upon irradiation with actinic rays or radiation, such as a sulfonium salt compound, an iodonium salt compound, a diazonium salt compound, a phosphonium salt compound, an imide sulfonate compound, an oxime sulfonate compound, a diazodisulfone compound, a disulfone compound, and an o-nitrobenzylsulfonate compound.

[0243] As the photoacid generator, a known compound that generates an acid by irradiation with actinic rays or radiation can be appropriately selected and used alone or as a mixture thereof. For example, the known compounds disclosed in paragraphs 0125 to 0319 of US Patent Application Publication No. 2016 / 0070167, paragraphs 0086 to 0094 of US Patent Application Publication No. 2015 / 0004544, and paragraphs 0323 to 0402 of US Patent Application Publication No. 2016 / 0237190 can be suitably used as the photoacid generator (B).

[0244] [Compounds represented by formulae ZI, ZII and ZIII] Suitable embodiments of the photoacid generator (B) include, for example, compounds represented by the following formulae ZI, ZII, and ZIII.

[0245] [ka]

[0246] In the above formula ZI, R 201 , R 202 and R 203 each independently represents an organic group. R 201 , R 202 and R 203The organic group as the substituent preferably has 1 to 30 carbon atoms, and more preferably has 1 to 20 carbon atoms. Also, R 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 bond, an amide bond, or a carbonyl group. 201 ~R 203 Examples of the group formed by combining two of these groups include an alkylene group (for example, a butylene group, a pentylene group) and -CH2-CH2-O-CH2-CH2-. Z - represents an anion.

[0247] [Cation in the compound represented by formula ZI] Suitable embodiments of the cation in formula ZI include the corresponding groups in the compounds (ZI-1), (ZI-2), (ZI-3) and (ZI-4) described below. The photoacid generator (C) may be a compound having a plurality of structures represented by formula ZI. For example, R 201 ~R 203 and R of another compound represented by formula ZI. 201 ~R 203 and at least one of the above may be bonded via a single bond or a linking group.

[0248] -Compound ZI-1- First, the compound (ZI-1) will be described. Compound (ZI-1) is a compound represented by the formula ZI 201 ~R 203 At least one of the above is an aryl group, that is, an arylsulfonium compound having an arylsulfonium cation. Arylsulfonium compounds are R 201 ~R 203 may all be aryl groups, or R 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. Examples of the arylsulfonium compound include triarylsulfonium compounds, diarylalkylsulfonium compounds, aryldialkylsulfonium compounds, diarylcycloalkylsulfonium compounds, and aryldicycloalkylsulfonium compounds.

[0249] The aryl group of the arylsulfonium compound 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 with an oxygen atom, a nitrogen atom, or a sulfur atom. Examples of the heterocyclic structure include a pyrrole residue, a furan residue, a thiophene residue, an indole residue, a benzofuran residue, and a benzothiophene residue. When the arylsulfonium compound 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 compound may have as needed 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 examples thereof include 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, and a cyclohexyl group.

[0250] R 201 ~R 203 The aryl group, alkyl group, and cycloalkyl group may each independently have 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 halogen atom, a hydroxyl group, or a phenylthio group as a substituent.

[0251] -Compound ZI-2- Next, the compound (ZI-2) will be described. Compound (ZI-2) is a compound represented by the formula ZI 201 ~R 203are each independently an organic group having no aromatic ring. Here, the aromatic ring also includes an aromatic ring containing a hetero atom. R 201 ~R 203 The organic group having no aromatic ring as the aromatic ring preferably has 1 to 30 carbon atoms, and more preferably has 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 further preferably a linear or branched 2-oxoalkyl group.

[0252] R 201 ~R 203 The alkyl group and cycloalkyl group preferably include a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (e.g., a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group), and a cycloalkyl group having 3 to 10 carbon atoms (e.g., a cyclopentyl group, a cyclohexyl group, and a norbornyl group). R 201 ~R 203 may be further substituted with a halogen atom, an alkoxy group (eg, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group.

[0253] -Compound ZI-3- Next, the compound (ZI-3) will be described. Compound (ZI-3) is represented by the following formula ZI-3, and is a compound having a phenacylsulfonium salt structure.

[0254] [ka]

[0255] In formula ZI-3, 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, 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.

[0256] R 1c ~R 5c Any 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 structure, and each of these ring structures may independently contain an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond. Examples of the ring structure include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic heterocyclic rings, and polycyclic condensed rings formed by combining two or more of these rings. Examples of the ring structure include 3- to 10-membered rings, preferably 4- to 8-membered rings, and more preferably 5- or 6-membered rings.

[0257] R 1c ~R 5c Any two or more of the following, R 6c and R 7c , and R x and R y Examples of the group formed by bonding include a butylene group and a pentylene group. R 5c and R 6c , and R 5c and R xThe 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. Zc - represents an anion.

[0258] -Compound ZI-4- Next, the compound (ZI-4) will be described. The compound (ZI-4) is represented by the following formula ZI-4.

[0259] [ka]

[0260] In formula ZI-4, l represents an integer of 0 to 2, r represents an integer of 0 to 8, R 13 represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, or a group having a cycloalkyl group, and these groups may have a substituent; R 14 each independently represents a group having a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a cycloalkyl group, and these groups may have a substituent; R 15 each independently represents an alkyl group, a cycloalkyl group, or a naphthyl group, and these groups may have a substituent; 15 may be bonded to each other to form a ring. The Two R's 15 When R are bonded to each other to form a ring, the ring structure may contain heteroatoms such as oxygen or nitrogen atoms. 15 are preferably alkylene groups and are bonded to each other to form a ring structure. Z - represents an anion.

[0261] In formula ZI-4, R 13 , R 14 and R 15The alkyl group is linear or branched and preferably has 1 to 10 carbon atoms, more preferably a methyl group, an ethyl group, an n-butyl group, a t-butyl group, or the like.

[0262] [Cation in the compound represented by formula ZII or formula ZIII] Next, formulae ZII and ZIII will be explained. In formulas ZII and ZIII, R 204 ~R 207 each independently represents an aryl group, an alkyl group, or a cycloalkyl group. R 204 ~R 207 The aryl group of R is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. 204 ~R 207 The aryl group may be an aryl group having a heterocyclic structure containing an oxygen atom, a nitrogen atom, a sulfur atom, etc. Examples of the skeleton of the aryl group having a heterocyclic structure include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene. R 204 ~R 207 The alkyl group and cycloalkyl group preferably include a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (e.g., a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group), and a cycloalkyl group having 3 to 10 carbon atoms (e.g., a cyclopentyl group, a cyclohexyl group, and a norbornyl group).

[0263] R 204 ~R 207 The aryl group, alkyl group, and cycloalkyl group in R may each independently have a substituent. 204 ~R 207 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 15 carbon atoms), an alkoxy group (e.g., having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, and a phenylthio group. Z - represents an anion.

[0264] [Anions in the compounds represented by formulae ZI to ZIII] Z in the formula ZI - , Z in formula ZII - , Zc in formula ZI-3 - and Z in formula ZI-4 - is preferably an anion represented by the following formula An-1.

[0265] [ka]

[0266] In formula An-1, pf represents an integer of 0 to 10, qf represents an integer of 0 to 10, rf represents an integer of 1 to 3, each Xf independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom, and when rf is an integer of 2 or more, multiple -C(Xf)2- may be the same or different, and R 4 and R 5 each independently represents a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom, and when pf is an integer of 2 or more, a plurality of -CR 4f R 5f - may be the same or different, L f represents a divalent linking group, and when qf is an integer of 2 or more, a plurality of L f may be the same or different, and W represents an organic group containing a cyclic structure.

[0267] Xf 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. In addition, 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. Xf is more preferably a fluorine atom or CF3. It is particularly preferable that both Xf are fluorine atoms.

[0268] R 4f and R 5f Each of R independently represents a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. 4f and R 5f may be the same or different. R 4f and R 5f The alkyl group represented by R may have a substituent and preferably has 1 to 4 carbon atoms. 4f and R 5f is preferably a hydrogen atom. Specific examples and preferred embodiments of the alkyl group substituted with at least one fluorine atom are the same as the specific examples and preferred embodiments of Xf in formula An-1.

[0269] L f represents a divalent linking group, and when a plurality of L f may be the same or different. Examples of the divalent linking group include -COO-(-C(=O)-O-), -OCO-, -CONH-, -NHCO-, -CO-, -O-, -S-, -SO-, -SO2-, an alkylene group (preferably having 1 to 6 carbon atoms), a cycloalkylene group (preferably having 3 to 15 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), and a divalent linking group formed by combining a plurality of these. Among these, -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -O-, -SO2-, -COO-alkylene group-, -OCO-alkylene group-, -CONH-alkylene group-, or -NHCO-alkylene group- are preferred, and -COO-, -OCO-, -CONH-, -SO2-, -COO-alkylene group-, or -OCO-alkylene group- are more preferred.

[0270] W represents an organic group containing a cyclic structure. Among these, a cyclic organic group is preferable. 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 the monocyclic alicyclic group include monocyclic cycloalkyl groups such as cyclopentyl, cyclohexyl, and cyclooctyl. Examples of the polycyclic alicyclic group include polycyclic cycloalkyl groups such as norbornyl, tricyclodecanyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl. Among them, alicyclic groups having a bulky structure with 7 or more carbon atoms, such as norbornyl, tricyclodecanyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl, are preferred.

[0271] The aryl group may be monocyclic or polycyclic and includes, for example, phenyl, naphthyl, phenanthryl and anthryl groups. The heterocyclic group may be monocyclic or polycyclic. The polycyclic group can suppress the diffusion of the acid more effectively. The heterocyclic group may have aromaticity or may not have aromaticity. Examples of heterocyclic rings having aromaticity include furan ring, thiophene ring, benzofuran ring, benzothiophene ring, dibenzofuran ring, dibenzothiophene ring, and pyridine ring. Examples of heterocyclic rings not having aromaticity include tetrahydropyran ring, lactone ring, sultone ring, and decahydroisoquinoline ring. Examples of lactone ring and sultone ring include the lactone structure and sultone structure exemplified in the above-mentioned resin. As the heterocyclic ring in the heterocyclic group, a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring is particularly preferable.

[0272] 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 that constitutes the cyclic organic group (the carbon that contributes to the ring formation) may be a carbonyl carbon.

[0273] The anion represented by the formula An-1 is SO3 - -CF2-CH2-OCO-(L f )q'-W, SO3 - -CF2-CHF-CH2-OCO-(L f )q'-W, SO3 - -CF2-COO-(L f )q'-W, SO3 - -CF2-CF2-CH2-CH2-(L f ) qf -W, SO3 - -CF2-CH(CF3)-OCO-(L f )q'-W is preferred. f , qf and W are the same as in formula An-1. q' represents an integer of 0 to 10.

[0274] In one embodiment, Z in formula ZI - , Z in formula ZII - , Zc in formula ZI-3 - and Z in formula ZI-4 - The anion represented by the following formula 4 is also preferred.

[0275] [ka]

[0276] In formula 4, X B1 and X B2Each of X independently represents a hydrogen atom or a monovalent organic group that does not contain a fluorine atom. B1 and X B2 is preferably a hydrogen atom. X B3 and X B4 Each of X independently represents a hydrogen atom or a monovalent organic group. B3 and X B4 At least one of X is preferably a fluorine atom or a monovalent organic group having a fluorine atom, B3 and X B4 It is more preferable that both of X are fluorine atoms or monovalent organic groups having fluorine atoms. B3 and X B4 It is more preferable that both of the above are fluorine-substituted alkyl groups. L f , qf and W are the same as in Equation 3.

[0277] Z in the formula ZI - , Z in formula ZII - , Zc in formula ZI-3 - and Z in formula ZI-4 - is preferably an anion represented by the following formula 5.

[0278] [ka]

[0279] In formula 5, each Xa independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom, and each Xb independently represents a hydrogen atom or an organic group having no fluorine atom. 4f , R 5f , L f The definitions and preferred embodiments of and W are the same as those of formula 3.

[0280] Z in the formula ZI - , Z in formula ZII - , Zc in formula ZI-3 - and Z in formula ZI-4 -may be a benzenesulfonate anion, preferably a benzenesulfonate anion substituted with a branched alkyl or cycloalkyl group.

[0281] Z in the formula ZI - , Z in formula ZII - , Zc in formula ZI-3 - and Z in formula ZI-4 - Also preferred as the anion is an aromatic sulfonate anion represented by the following formula SA1.

[0282] [ka]

[0283] In formula SA1, Ar represents an aryl group, and the sulfonate anion and -(DR B ) may further have a substituent other than the above. Examples of the substituent that may further be had include a fluorine atom and a hydroxyl group.

[0284] n represents an integer of 0 or more. n is preferably 1 to 4, more preferably 2 to 3, and particularly preferably 3.

[0285] 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 group, an ester group, and a group consisting of a combination of two or more of these groups.

[0286] R B represents a hydrocarbon group.

[0287] Preferably, D is a single bond and R B is an aliphatic hydrocarbon structure. B is more preferably an isopropyl group or a cyclohexyl group.

[0288] Preferred examples of the sulfonium cation in formula ZI and the sulfonium or iodonium cation in formula ZII are shown below.

[0289] [ka]

[0290] Anion Z in formula ZI and formula ZII - , Zc in formula ZI-3 - and Z in formula ZI-4 - Preferred examples are shown below.

[0291] [ka]

[0292] Any combination of the above cations and anions can be used as a photoacid generator. In particular, it is preferable that the photoacid generator is an ionic compound containing a cation and an anion, and the anion contains an ion represented by any one of the above formula An-1, the following formula An-2, and the following formula An-3.

[0293] [ka]

[0294] In formulae An-2 and An-3, Rfa each independently represents a monovalent organic group having a fluorine atom, and multiple Rfa may be bonded to each other to form a ring.

[0295] Rfa is preferably 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. In addition, the alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group. In addition, a plurality of Rfa are preferably bonded to each other to form a ring.

[0296] In addition, preferred examples of the photoacid generator include compounds C-1 to C-15 used in the examples, but are not limited thereto.

[0297] The acid dissociation constant pKa of the acid generated from the photoacid generator upon irradiation with actinic rays or radiation is not particularly limited, but is preferably less than 1.1, and more preferably less than −1.0. The lower limit of the acid dissociation constant pKa of the acid generated from the photoacid generator upon irradiation with actinic rays or radiation is not particularly limited, but is usually −10.

[0298] The acid dissociation constant pKa refers to the acid dissociation constant pKa in an aqueous solution, and is defined, for example, in Chemistry Handbook (II) (revised 4th edition, 1993, edited by the Chemical Society of Japan, Maruzen Co., Ltd.). The lower the value of the acid dissociation constant pKa, the greater the acid strength. Specifically, the acid dissociation constant pKa in an aqueous solution can be measured by measuring the acid dissociation constant at 25°C using an infinitely diluted aqueous solution. Alternatively, the value can be calculated based on a database of Hammett's substituent constants and known literature values ​​using the following software package 1. All pKa values ​​described in this specification are values ​​calculated using this software package.

[0299] Software package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs).

[0300] The photoacid generator may be in the form of a low molecular weight compound, or may be incorporated into a part of a polymer. Also, the photoacid generator may be in the form of a low molecular weight compound and in the form of a polymer in combination. The photoacid generator is preferably in the form of a low molecular weight compound. When the photoacid generator is in the form of a low molecular weight compound, the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, and even more preferably 1,000 or less. When the photoacid generator is in a form in which it is incorporated into a part of a polymer, it may be incorporated into a part of the above-mentioned resin (A), or may be incorporated into a resin different from the resin (A). The photoacid generator may be used alone or in combination of two or more kinds. The content of the photoacid generator in the composition (the total content if multiple types are present) is preferably 0.1 mass % to 35 mass %, more preferably 0.5 mass % to 25 mass %, even more preferably 2 mass % to 20 mass %, and particularly preferably 2.5 mass % to 20 mass %, based on the total solid content of the composition. When the photoacid generator contains a compound represented by the above formula ZI-3 or ZI-4, the content of the photoacid generator contained in the composition (the total content when multiple types are present) is preferably 5% by mass to 35% by mass, more preferably 7% by mass to 30% by mass, based on the total solid content of the composition.

[0301] <Acid diffusion control agent> The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention preferably contains an acid diffusion controller (also referred to as "acid diffusion controller (D)"). The acid diffusion controller (D) traps the acid generated from the acid generator etc. upon exposure and acts as a quencher to suppress the reaction of the acid-decomposable resin in the unexposed area due to excess acid generated. For example, a basic compound (DA), a basic compound (DB) whose basicity is reduced or eliminated by irradiation with actinic rays or radiation, an onium salt (DC) whose acidity is relatively weaker than that of the acid generator, a low molecular weight compound (DD) having a nitrogen atom and a group that is eliminated by the action of an acid, or an onium salt compound (DE) having a nitrogen atom in the cation moiety can be used as the acid diffusion controller. In particular, from the viewpoint of linearity of a pattern obtained after aging, the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention preferably contains a nitrogen-containing compound, and more preferably contains a nitrogen-containing basic compound, as an acid diffusion controller. In the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention, a known acid diffusion controller can be appropriately used. For example, the known compounds disclosed in paragraphs 0627-0664 of US Patent Application Publication No. 2016 / 0070167, paragraphs 0095-0187 of US Patent Application Publication No. 2015 / 0004544, paragraphs 0403-0423 of US Patent Application Publication No. 2016 / 0237190, and paragraphs 0259-0328 of US Patent Application Publication No. 2016 / 0274458 can be suitably used as the acid diffusion controller (D).

[0302] [Basic compounds (DA)] Preferred examples of the basic compound (DA) include compounds having structures represented by the following formulae A to E.

[0303] [ka]

[0304] In formula A and formula E, R 200 , R 201 and R 202 may be the same or different, and each independently represents a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably having 3 to 20 carbon atoms), or an aryl group (preferably having 6 to 20 carbon atoms). R 201 and R 202 may be bonded to each other to form a ring. R 203 , R 204 , R 205 and R 206 may be the same or different, and each independently represents an alkyl group having 1 to 20 carbon atoms.

[0305] The alkyl groups in formulae A and E may be substituted or unsubstituted. Regarding the above alkyl group, the alkyl group having a substituent is preferably an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms. More preferably, the alkyl groups in formulae A and E are unsubstituted.

[0306] The basic compound (DA) is preferably guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine, or the like, and more preferably a compound having an imidazole structure, a diazabicyclo structure, an onium hydroxide structure, an onium carboxylate structure, a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, or an aniline derivative having a hydroxyl group and / or an ether bond.

[0307] [Basic compounds (DB) whose basicity decreases or disappears when exposed to actinic rays or radiation] A basic compound (DB) (hereinafter, also referred to as "compound (DB)") whose basicity is reduced or eliminated by irradiation with actinic rays or radiation is a compound that has a proton acceptor functional group and is decomposed by irradiation with actinic rays or radiation, and the proton acceptor property is reduced or eliminated, or the proton acceptor property is changed from a proton acceptor property to an acidic property.

[0308] The proton acceptor functional group is a functional group having a group or electrons capable of electrostatically interacting with a proton, and means, for example, a functional group having a macrocyclic structure such as a cyclic polyether, or a functional group having a nitrogen atom having an unshared electron pair that does not contribute to π conjugation. The nitrogen atom having 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.

[0309] [ka]

[0310] Preferred partial structures of the proton acceptor functional group include, for example, crown ether, azacrown ether, primary to tertiary amine, pyridine, imidazole, and pyrazine structures.

[0311] Compound (DB) decomposes upon irradiation with actinic rays or radiation to generate a compound in which the proton acceptor property is reduced or eliminated, or which has changed from proton acceptor property to acidic. Here, the reduction or elimination of proton acceptor property, or the change from proton acceptor property to acidic, refers to the change in proton acceptor property caused by the addition of a proton to a proton acceptor functional group, and specifically, when a proton adduct is generated from compound (DB) having a proton acceptor functional group and a proton, the equilibrium constant in the chemical equilibrium decreases. The proton acceptor property can be confirmed by performing a pH measurement.

[0312] [Onium salts (DC) that are weak acids relative to photoacid generators] In the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention, an onium salt (DC) that is a relatively weak acid to the photoacid generator can be used as an acid diffusion controller. When a photoacid generator is used in combination with an onium salt that generates an acid that is weaker than the acid generated by the photoacid generator, when the acid generated by the photoacid generator upon irradiation with actinic rays or radiation collides with an onium salt having an unreacted weak acid anion, the weak acid is released by salt exchange to generate an onium salt having a strong acid anion. In this process, the strong acid is exchanged for a weak acid with a lower catalytic activity, and the acid appears to be deactivated, thereby enabling control of acid diffusion.

[0313] From the viewpoints of the latitude of the focal depth and the pattern linearity, it is preferable that the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention further contains at least one compound selected from the group consisting of the compounds represented by formulae d1-1 to d1-3.

[0314] [ka]

[0315] In formulas d1-1 to d1-3, R 51represents a hydrocarbon group which may have a substituent; Z 2c represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and a fluorine atom is not bonded to the carbon atom adjacent to the S atom; R 52 represents an organic group, and Y 3 represents a linear, branched or cyclic alkylene group or arylene group, Rf represents a hydrocarbon group containing a fluorine atom, M + each independently represents an ammonium cation, a sulfonium cation, or an iodonium cation.

[0316] M + Preferred examples of the sulfonium cation or iodonium cation represented by the formula ZI and the iodonium cation represented by the formula ZII can be mentioned.

[0317] The onium salt (DC) which is a weak acid relative to the photoacid generator may be a compound having a cationic moiety and an anionic moiety in the same molecule, and in which the cationic moiety and the anionic moiety are linked by a covalent bond (hereinafter, also referred to as "compound (DCA)"). The compound (DCA) is preferably a compound represented by any one of the following formulas C-1 to C-3.

[0318] [ka]

[0319] In formulas C-1 to C-3, R 1 , R 2 , and R 3 each independently represents a substituent having 1 or more carbon atoms. L 1 represents a divalent linking group or a single bond that links a cationic moiety and an anionic moiety. -X - -COO - , -SO3 - , -SO2 - , and -N - -R 4R represents an anionic moiety selected from 4 represents a monovalent substituent having at least one of a carbonyl group (-C(=O)-), a sulfonyl group (-S(=O)2-), and a sulfinyl group (-S(=O)-) at the bonding site with the adjacent N atom. R 1 , R 2 , R 3 , R 4 , and L 1 may be bonded to each other to form a ring structure. 1 ~R 3 Two of these may be combined to represent one divalent substituent, which may be bonded to the N atom via a double bond.

[0320] R 1 ~R 3 Examples of the substituent having one or more carbon atoms in the formula (I) include an alkyl group, a cycloalkyl group, an aryl group, an alkyloxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, a cycloalkylaminocarbonyl group, and an arylaminocarbonyl group. An alkyl group, a cycloalkyl group, or an aryl group is preferable.

[0321] L as a divalent linking group 1 L includes a linear or branched alkylene group, a cycloalkylene group, an arylene group, a carbonyl group, an ether bond, an ester bond, an amide bond, a urethane bond, a urea bond, and a group formed by combining two or more of these. 1 is preferably an alkylene group, an arylene group, an ether bond, an ester bond, or a group formed by combining two or more of these.

[0322] [Low molecular weight compound (DD) having a nitrogen atom and a group that is cleaved by the action of an acid] The low molecular weight compound (DD) having a nitrogen atom and a group that can be eliminated by the action of an acid (hereinafter also referred to as "compound (DD)") is preferably an amine derivative having, on the nitrogen atom, a group that can be eliminated by the action of an acid. The group which is eliminated by the action of an acid is preferably an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group, or a hemiaminal ether group, more preferably a carbamate group or a hemiaminal ether group. The molecular weight of the compound (DD) is preferably from 100 to 1,000, more preferably from 100 to 700, and even more preferably from 100 to 500. Compound (DD) may have a carbamate group having a protecting group on the nitrogen atom. The protecting group constituting the carbamate group can be represented by the following formula d-1.

[0323] [ka]

[0324] In formula d-1, R b R each independently represents a hydrogen atom, an alkyl group (preferably having 1 to 10 carbon atoms), a cycloalkyl group (preferably having 3 to 30 carbon atoms), an aryl group (preferably having 3 to 30 carbon atoms), an aralkyl group (preferably having 1 to 10 carbon atoms), or an alkoxyalkyl group (preferably having 1 to 10 carbon atoms). b may be linked to each other to form a ring. R b The alkyl group, cycloalkyl group, aryl group, and aralkyl group represented by R may each independently be substituted with a functional group such as a hydroxy group, a cyano group, an amino group, a pyrrolidino group, a piperidino group, a morpholino group, or an oxo group, an alkoxy group, or a halogen atom. b The same applies to the alkoxyalkyl group represented by the formula:

[0325] R b As the alkyl group, a linear or branched alkyl group, a cycloalkyl group, or an aryl group is preferable, and a linear or branched alkyl group, or a cycloalkyl group is more preferable. The Two R's b Examples of the ring formed by linking together include alicyclic hydrocarbons, aromatic hydrocarbons, heterocyclic hydrocarbons, and derivatives thereof. Specific examples of the group represented by formula d-1 include, but are not limited to, the structures disclosed in paragraph 0466 of US Patent Application Publication No. 2012 / 0135348.

[0326] The compound (DD) preferably has a structure represented by the following formula 6.

[0327] [ka]

[0328] In Equation 6, l represents an integer of 0 to 2, m represents an integer of 1 to 3, and l+m=3 is satisfied. R a represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group. When l is 2, two R a can be the same or different, and the two R a may be linked together to form a heterocycle together with the nitrogen atom in the formula. This heterocycle may contain heteroatoms other than the nitrogen atom in the formula. R b is R in the above formula d-1 b The same applies to preferred examples. In formula 6, R a The alkyl group, cycloalkyl group, aryl group, and aralkyl group represented by R b The alkyl group, cycloalkyl group, aryl group, and aralkyl group as the optionally substituted group may be substituted with the same groups as those mentioned above as the optionally substituted group.

[0329] Above R a Specific examples of the alkyl group, cycloalkyl group, aryl group, and aralkyl group (which may be substituted with the above groups) include R b The same groups as those specifically mentioned above can be mentioned. Specific examples of the particularly preferred compound (DD) in the present invention include, but are not limited to, the compounds disclosed in paragraph 0475 of U.S. Patent Application Publication No. 2012 / 0135348.

[0330] The onium salt compound (DE) having a nitrogen atom in the cationic moiety (hereinafter also referred to as "compound (DE)") is preferably a compound having a basic moiety containing a nitrogen atom in the cationic moiety. The basic moiety is preferably an amino group, more preferably an aliphatic amino group. It is further preferable that all atoms adjacent to the nitrogen atom in the basic moiety are hydrogen atoms or carbon atoms. Furthermore, from the viewpoint of improving basicity, it is preferable that an electron-withdrawing functional group (such as a carbonyl group, a sulfonyl group, a cyano group, or a halogen atom) is not directly bonded to the nitrogen atom. A preferred specific structure of compound (DE) may include, but is not limited to, the compound disclosed in paragraph 0203 of US Patent Application Publication No. 2015 / 0309408.

[0331] Other preferred examples of the acid diffusion controller are given below.

[0332] [ka]

[0333] [ka]

[0334] [ka]

[0335] [ka]

[0336] In the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention, the acid diffusion controller may be used alone or in combination of two or more kinds. The content of the acid diffusion controller in the composition (the total content when multiple types are present) is preferably 0.1 to 10 mass %, more preferably 0.1 to 5 mass %, based on the total solid content of the composition.

[0337] <Solvent> The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention preferably contains a solvent (also referred to as "solvent (F)"), and more preferably contains an organic solvent. In the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention, known resist solvents can be appropriately used. For example, known solvents disclosed in paragraphs 0665-0670 of US Patent Application Publication No. 2016 / 0070167, paragraphs 0210-0235 of US Patent Application Publication No. 2015 / 0004544, paragraphs 0424-0426 of US Patent Application Publication No. 2016 / 0237190, and paragraphs 0357-0366 of US Patent Application Publication No. 2016 / 0274458 can be suitably used. Examples of solvents that can be used when preparing the composition include organic solvents such as alkylene glycol monoalkyl ether carboxylates, alkylene glycol monoalkyl ethers, alkyl lactates, alkyl alkoxypropionates, cyclic lactones (preferably having 4 to 10 carbon atoms), monoketone compounds which may have a ring (preferably having 4 to 10 carbon atoms), alkylene carbonates, alkyl alkoxyacetates, and alkyl pyruvates.

[0338] As the organic solvent, a mixed solvent obtained by mixing a solvent containing a hydroxyl group in the structure with a solvent not containing a hydroxyl group may be used. The solvent containing a hydroxyl group and the solvent not containing a hydroxyl group can be appropriately selected from the above-mentioned exemplary compounds. As the solvent containing a hydroxyl group, an alkylene glycol monoalkyl ether, an alkyl lactate, or the like is preferable, and propylene glycol monomethyl ether (PGME: 1-methoxy-2-propanol), propylene glycol monoethyl ether (PGEE), methyl 2-hydroxyisobutyrate, or ethyl lactate is more preferable. In addition, as the solvent not containing a hydroxyl group, alkylene glycol monoalkyl ether acetate, alkyl alkoxypropionate, monoketone compound which may contain a ring, cyclic lactone, alkyl acetate, etc. are preferable, among which, propylene glycol monomethyl ether acetate (PGMEA: 1-methoxy-2-acetoxypropane), ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, cyclopentanone or butyl acetate is more preferable, and propylene glycol monomethyl ether acetate, γ-butyrolactone, ethyl ethoxypropionate, cyclohexanone, cyclopentanone or 2-heptanone is even more preferable. As the solvent not containing a hydroxyl group, propylene carbonate is also preferable. Among these, from the viewpoint of uniformity of the layer to be formed, it is particularly preferable that the solvent contains γ-butyrolactone. The mixing ratio (mass ratio) of the solvent containing a hydroxyl group to the solvent not containing a hydroxyl group is 1 / 99 to 99 / 1, preferably 10 / 90 to 90 / 10, and more preferably 20 / 80 to 60 / 40. A mixed solvent containing 50 mass % or more of a solvent not containing a hydroxyl group is preferred from the viewpoint of coating uniformity. The solvent preferably contains propylene glycol monomethyl ether acetate, and may be a solvent containing propylene glycol monomethyl ether acetate alone or a mixed solvent containing propylene glycol monomethyl ether acetate.

[0339] The solids concentration of the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention is not particularly limited, but is preferably 0.5% by mass to 60% by mass, more preferably 1.0% by mass to 45% by mass, and even more preferably 1.0% by mass to 40% by mass. When a film formed from the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention is exposed with a KrF excimer laser, the solids concentration of the actinic ray-sensitive or radiation-sensitive resin composition is preferably 10 mass % or more, preferably 15 mass % or more, and more preferably 20 mass % or more. The solid content concentration is the mass percentage of the mass of resist components other than the solvent with respect to the total mass of the composition.

[0340] <Exposure process> The exposure step is a step of exposing the resist film to light. The exposure method may be immersion exposure. The pattern formation method according to the present invention may include the exposure step multiple times. The type of light (actinic rays or radiation) used for exposure may be selected in consideration of the properties of the photoacid generator and the desired pattern shape, and examples of the light include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light (EUV), X-rays, and electron beams, with far ultraviolet light being preferred. For example, actinic rays having a wavelength of 250 nm or less are preferred, 220 nm or less is more preferred, and 1 to 200 nm is even more preferred. Specific examples of light used include KrF excimer laser (248 nm), ArF excimer laser (193 nm), F2 excimer laser (157 nm), X-rays, EUV (13 nm), and electron beams, with ArF excimer laser, EUV, and electron beams being preferred. The solid content concentration is the mass percentage of the mass of the resist components other than the solvent and the anionic additive, relative to the total mass of the composition.

[0341] <Crosslinking agent> The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention may contain a compound that crosslinks a resin by the action of an acid (hereinafter, also referred to as a crosslinking agent (G)). As the crosslinking agent (G), a known compound can be appropriately used. For example, the known compounds disclosed in paragraphs 0379 to 0431 of US Patent Application Publication No. 2016 / 0147154 and paragraphs 0064 to 0141 of US Patent Application Publication No. 2016 / 0282720 can be suitably used as the crosslinking agent (G). The crosslinking agent (G) is a compound having a crosslinkable group capable of crosslinking a resin. Examples of the crosslinkable group include a hydroxymethyl group, an alkoxymethyl group, an acyloxymethyl group, an alkoxymethyl ether group, an oxirane ring, and an oxetane ring. The crosslinkable group is preferably a hydroxymethyl group, an alkoxymethyl group, an oxirane ring, or an oxetane ring. The crosslinking agent (G) is preferably a compound (including a resin) having two or more crosslinkable groups. The crosslinking agent (G) is more preferably a phenol derivative, a urea compound (a compound having a urea structure), or a melamine compound (a compound having a melamine structure) having a hydroxymethyl group or an alkoxymethyl group. The crosslinking agent may be used alone or in combination of two or more kinds. The content of the crosslinking agent (G) is preferably from 1 to 50% by mass, more preferably from 3 to 40% by mass, and even more preferably from 5 to 30% by mass, based on the total solid content of the composition.

[0342] <Surfactant> The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention may or may not contain a surfactant (also referred to as "surfactant (H)"). When a surfactant is contained, it is preferable that the composition contains at least one of a fluorine-based and a silicone-based surfactant (specifically, a fluorine-based surfactant, a silicone-based surfactant, or a surfactant having both a fluorine atom and a silicon atom).

[0343] By containing a surfactant in the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention, a resist pattern with good sensitivity and resolution, excellent adhesion and few development defects can be obtained when an exposure light source having a wavelength of 250 nm or less, particularly 220 nm or less, is used. Examples of fluorine-based or silicone-based surfactants include those described in paragraph 0276 of US Patent Application Publication No. 2008 / 0248425. Also, surfactants other than fluorine-based or silicone-based surfactants described in paragraph 0280 of US Patent Application Publication No. 2008 / 0248425 can be used.

[0344] These surfactants may be used alone or in combination of two or more. When the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention contains a surfactant, the content of the surfactant is preferably 0.0001 mass % to 2 mass %, and more preferably 0.0005 mass % to 1 mass %, based on the total solid content of the composition. On the other hand, by making the content of the surfactant 0.0001% by mass or more based on the total solid content of the composition, the hydrophobic resin is more unevenly distributed on the surface, which makes the surface of the actinic ray-sensitive or radiation-sensitive film more hydrophobic and improves water tracking during immersion exposure.

[0345] <Other additives> The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention may further contain other known additives. Other additives include acid amplifiers, dyes, plasticizers, photosensitizers, light absorbers, alkali-soluble resins, dissolution inhibitors, and dissolution promoters.

[0346] The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention is preferably used by dissolving the above-mentioned components in a predetermined organic solvent, preferably the above-mentioned mixed solvent, filtering the resultant solution through a filter, and then coating the resultant solution on, for example, a predetermined support (substrate). The pore size (hole diameter) of the filter used for filtration is preferably 0.2 μm or less, more preferably 0.05 μm or less, and even more preferably 0.03 μm or less. Furthermore, when the solid content concentration of the actinic ray-sensitive or radiation-sensitive resin composition is high (for example, 25 mass % or more), the pore size of the filter used for filtration is preferably 3 μm or less, more preferably 0.5 μm or less, and even more preferably 0.3 μm or less. The filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon. In the filter filtration, for example, as disclosed in JP-A-2002-62667, circulatory filtration may be performed, or multiple types of filters may be connected in series or parallel to perform filtration. The composition may also be filtered multiple times. Furthermore, the composition may be subjected to degassing treatment before or after filter filtration.

[0347] The thickness of the resist film made of the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention is not particularly limited, but from the viewpoint of improving resolution, it is preferably 90 nm or less, more preferably 85 nm or less. Such a thickness can be achieved by setting the solid content concentration in the composition within an appropriate range to provide a suitable viscosity and improve coatability or film-forming property.

[0348] <Application> The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention is an actinic ray-sensitive or radiation-sensitive resin composition whose properties change when exposed to light. More specifically, the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition used in a semiconductor manufacturing process such as an IC (Integrated Circuit), manufacturing a circuit board such as a liquid crystal or thermal head, preparing a mold structure for imprinting, or other photofabrication processes, or manufacturing a lithographic printing plate or an acid-curable composition. The resist pattern formed by the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention can be used in an etching process, an ion implantation process, a bump electrode forming process, a rewiring forming process, and MEMS (Micro Electro Mechanical Systems), etc.

[0349] (actinic ray-sensitive or radiation-sensitive film) The actinic ray-sensitive or radiation-sensitive film (preferably a resist film) according to the present invention is a film formed from the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention. The actinic ray-sensitive or radiation-sensitive film according to the present invention is a solidified product of the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention. The solidified product in the present invention may be any product obtained by removing at least a part of the solvent from the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention. Specifically, the actinic ray-sensitive or radiation-sensitive film according to the present invention can be obtained, for example, by applying the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention onto a support such as a substrate, and then drying the applied composition. The above-mentioned drying refers to removing at least a part of the solvent contained in the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention. The drying method is not particularly limited, and a known method can be used, including drying by heating (for example, 70° C. to 130° C., for 30 to 300 seconds). The heating method is not particularly limited, and any known heating means can be used, including, for example, a heater, an oven, a hot plate, an infrared lamp, and an infrared laser.

[0350] The components contained in the actinic ray-sensitive or radiation-sensitive film of the present invention are the same as the components contained in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention excluding the solvent, and preferred embodiments are also the same. The content of each component contained in the actinic ray-sensitive or radiation-sensitive film according to the present invention corresponds to the content of each component other than the solvent in the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention being replaced with "total solids content" being read as "total mass of the actinic ray-sensitive or radiation-sensitive film."

[0351] The thickness of the actinic ray-sensitive or radiation-sensitive film according to the present invention is not particularly limited, but is preferably from 50 nm to 150 nm, and more preferably from 80 nm to 130 nm. Furthermore, in order to accommodate the three-dimensionalization of memory devices, when it is desired to form a thick actinic ray-sensitive or radiation-sensitive film, the thickness is preferably, for example, 2 μm or more, more preferably 2 μm to 50 μm, and even more preferably 2 μm to 20 μm.

[0352] (Pattern formation method) The pattern forming method according to the present invention comprises the steps of: A step of exposing the actinic ray-sensitive or radiation-sensitive film (preferably a resist film) of the present invention to actinic rays or radiation (exposure step), and The method includes a step of developing the actinic ray-sensitive or radiation-sensitive film after the exposure step using a developer (development step). The pattern forming method according to the present invention includes a step of forming an actinic ray-sensitive or radiation-sensitive film on a support using the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention (film formation step); a step of exposing the actinic ray-sensitive or radiation-sensitive film to actinic rays or radiation (exposure step); and The method may also include a step of developing the actinic ray-sensitive or radiation-sensitive film after the exposure step using a developer (development step).

[0353] <Film forming process> The pattern forming method according to the present invention may include a film forming step. Examples of the method for forming an actinic ray-sensitive or radiation-sensitive film in the film forming step include the method for forming an actinic ray-sensitive or radiation-sensitive film by drying described above in the section on actinic ray-sensitive or radiation-sensitive film.

[0354] [Support] The support is not particularly limited, and may be a substrate generally used in the manufacturing process of semiconductors such as ICs, or in the manufacturing process of circuit boards such as liquid crystal or thermal heads, as well as in other lithography processes for photofabrication, etc. Specific examples of the support include inorganic substrates such as silicon, SiO2, and SiN.

[0355] <Exposure process> The exposure step is a step of exposing the actinic ray-sensitive or radiation-sensitive film to light. The exposure method may be immersion exposure. The pattern formation method according to the present invention may include the exposure step multiple times. The type of light (actinic rays or radiation) used for exposure may be selected in consideration of the properties of the photoacid generator and the desired pattern shape, and examples of the light include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light (EUV), X-rays, and electron beams, with far ultraviolet light being preferred. For example, actinic rays having a wavelength of 250 nm or less are preferred, 220 nm or less is more preferred, and 1 to 200 nm is even more preferred. Specific examples of light used include KrF excimer laser (248 nm), ArF excimer laser (193 nm), F2 excimer laser (157 nm), X-rays, EUV (13 nm), and electron beams, with ArF excimer laser, EUV, and electron beams being preferred. Among these, the exposure in the exposure step is preferably performed by immersion exposure using an argon fluoride laser. The exposure dose was 5 mJ / cm 2 ~200mJ / cm 2 and preferably 10 mJ / cm 2 ~100mJ / cm2 It is more preferable that:

[0356] <Developing process> The developer used in the development step may be an alkaline developer or a developer containing an organic solvent (hereinafter also referred to as an organic developer), and is preferably an alkaline aqueous solution.

[0357] [Alkaline developer] As the alkaline developer, a quaternary ammonium salt such as tetramethylammonium hydroxide is preferably used, but other alkaline aqueous solutions of inorganic alkali, primary to tertiary amines, alkanolamines, cyclic amines, and the like can also be used. Furthermore, the alkaline developer may contain at least one of alcohols and surfactants in an appropriate amount. The alkaline developer preferably has an alkali concentration of 0.1% by mass to 20% by mass. The alkaline developer preferably has a pH of 10 to 15. The time for developing using an alkaline developer is preferably 10 seconds to 300 seconds. The alkali concentration and pH of the alkaline developer and the developing time can be appropriately adjusted depending on the pattern to be formed.

[0358] [Organic Developer] 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.

[0359] -Ketone-based solvents- Examples of ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetyl carbinol, acetophenone, methyl naphthyl ketone, isophorone, and propylene carbonate.

[0360] -Ester-based solvent- Examples of ester-based solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, butyl butanoate, methyl 2-hydroxyisobutyrate, isoamyl acetate, isobutyl isobutyrate, and butyl propionate.

[0361] -Other solvents- As the alcohol-based solvent, the amide-based solvent, the ether-based solvent, and the hydrocarbon-based solvent, the solvents disclosed in paragraphs 0715 to 0718 of US Patent Application Publication No. 2016 / 0070167 can be used.

[0362] The above solvents may be mixed in combination, or may be mixed with a solvent other than the above solvents or with water. 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 free of water. The content of the organic solvent in the organic developer is preferably 50% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, still more preferably 90% by mass or more and 100% by mass or less, and particularly preferably 95% by mass or more and 100% by mass or less, based on the total amount of the developer.

[0363] -Surfactants- The organic developer may contain a suitable amount of a known surfactant, if necessary. The content of the surfactant is preferably from 0.001% by mass to 5% by mass, more preferably from 0.005% by mass to 2% by mass, and further preferably from 0.01% by mass to 0.5% by mass, based on the total mass of the developer.

[0364] -Acid diffusion control agent- The organic developer may contain the above-mentioned acid diffusion controller.

[0365] [Developing method] Examples of the developing method that can be applied include a method of immersing a substrate in a tank filled with a developing solution for a certain period of time (dip method), a method of piling up a developing solution on the substrate surface by surface tension and leaving it to stand for a certain period of time (paddle method), a method of spraying the developing solution on the substrate surface (spray method), and a method of continuously discharging the developing solution while scanning a developing solution discharge nozzle at a constant speed onto a substrate rotating at a constant speed (dynamic dispense method).

[0366] A step of developing using an alkaline aqueous solution (alkaline developing step) and a step of developing using a developer containing an organic solvent (organic solvent developing step) may be combined. This allows pattern formation without dissolving only the areas with intermediate exposure intensity, making it possible to form finer patterns.

[0367] <Pre-baking process, post-exposure baking process> The pattern formation method according to the present invention preferably includes a pre-bake (PB) step prior to the exposure step. The pattern formation method according to the present invention may include the pre-heating step multiple times. The pattern formation method according to the present invention preferably includes a post-exposure bake (PEB) step after the exposure step and before the development step. The pattern formation method according to the present invention may include the post-exposure baking step multiple times. The heating temperature is preferably from 70°C to 130°C, more preferably from 80°C to 120°C, in both the pre-bake step and the post-exposure bake step. The heating time in both the pre-heating step and the post-exposure heating step is preferably from 30 seconds to 300 seconds, more preferably from 30 seconds to 180 seconds, and even more preferably from 30 seconds to 90 seconds. Heating can be performed by means provided in the exposure device and the development device, and may be performed using a hot plate or the like.

[0368] <Resist underlayer film formation process> The pattern forming method according to the present invention may further include a step of forming a resist underlayer film (resist underlayer film forming step) prior to the film forming step. The resist underlayer film forming step is a step of forming a resist underlayer film (e.g., SOG (Spin On Glass), SOC (Spin On Carbon), anti-reflective film, etc.) between the resist film and the support. As the resist underlayer film, a known organic or inorganic material can be appropriately used.

[0369] <Protective film formation process> The pattern forming method according to the present invention may further include a step of forming a protective film (protective film forming step) prior to the development step. The protective film forming step is a step of forming a protective film (topcoat) on the upper layer of the resist film. As the protective film, a known material can be appropriately used. For example, the protective film forming composition disclosed in US Patent Application Publication No. 2007 / 0178407, US Patent Application Publication No. 2008 / 0085466, US Patent Application Publication No. 2007 / 0275326, US Patent Application Publication No. 2016 / 0299432, US Patent Application Publication No. 2013 / 0244438, and International Publication No. 2016 / 157988 can be suitably used. As the protective film forming composition, one containing the above-mentioned acid diffusion controller is preferable. A protective film may be formed on the resist film containing the hydrophobic resin described above.

[0370] <Rinse process> The pattern forming method according to the present invention preferably includes a step of washing with a rinsing liquid (rinsing step) after the development step.

[0371] [In the case of a development process using an alkaline developer] The rinse liquid used in the rinse step after the development step using an alkaline developer can be, for example, pure water. The pure water may contain an appropriate amount of a surfactant. In this case, after the development step or the rinse step, a treatment may be added to remove the developer or rinse liquid adhering to the pattern using a supercritical fluid. Furthermore, after the rinse treatment or the treatment using a supercritical fluid, a heat treatment may be performed to remove moisture remaining in the pattern.

[0372] [In the case of a development process using an organic developer] The rinse liquid used in the rinse step after the development step using a developer containing an organic solvent is not particularly limited as long as it does not dissolve the resist pattern, and a solution containing a general organic solvent can be used. As the rinse liquid, it is preferable to use 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. Specific examples of the hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents include those similar to those described in the developer containing an organic solvent. In this case, the rinse liquid used in the rinsing step is preferably a rinse liquid containing a monohydric alcohol.

[0373] The monohydric alcohol used in the rinsing step may be a linear, branched, or cyclic monohydric alcohol.Specific examples include 1-butanol, 2-butanol, 3-methyl-1-butanol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methyl-2-pentanol, 1-heptanol, 1-octanol, 2-hexanol, cyclopentanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol, and methylisobutylcarbinol.Examples of the monohydric alcohol having 5 or more carbon atoms include 1-hexanol, 2-hexanol, 4-methyl-2-pentanol, 1-pentanol, 3-methyl-1-butanol, and methylisobutylcarbinol.

[0374] Each component may be used in combination with a plurality of other components, or may be used in combination with an organic solvent other than those mentioned above. The water content in the rinse liquid is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less. By keeping the water content at 10% by mass or less, good development characteristics can be obtained.

[0375] The rinse solution may contain a suitable amount of a surfactant. In the rinsing step, the substrate developed using an organic developer is washed with a rinse solution containing an organic solvent. The method of the washing step is not particularly limited, but for example, a method of continuously discharging a rinse solution onto a substrate rotating at a constant speed (spin coating method), a method of immersing a substrate in a tank filled with a rinse solution for a certain period of time (dip method), or a method of spraying a rinse solution onto the substrate surface (spray method) can be applied. Among them, it is preferable to perform the washing step by the spin coating method, rotate the substrate after washing at a rotation speed of 2,000 rpm to 4,000 rpm (revolutions / min) and remove the rinse solution from the substrate. It is also preferable to include a heating step (Post Bake) after the rinsing step. The developing solution and the rinse solution remaining between and inside the patterns are removed by this heating step. In the heating step after the rinsing step, the heating temperature is preferably 40 to 160°C, more preferably 70 to 95°C. The heating time is preferably 10 seconds to 3 minutes, more preferably 30 seconds to 90 seconds.

[0376] <Improvement of surface roughness> A method for improving the surface roughness of a pattern may be applied to the pattern formed by the pattern forming method according to the present invention. For example, a method for improving the surface roughness of a pattern may be disclosed in U.S. Patent Application Publication No. 2015 / 0104957, which treats a resist pattern with plasma of a gas containing hydrogen. In addition, known methods such as those described in JP-A-2004-235468, U.S. Patent Application Publication No. 2010 / 0020297, and Proc. of SPIE Vol.8328 83280N-1 "EUV Resist Curing Technique for LWR Reduction and Etch Selectivity Enhancement" may be applied. Furthermore, the resist pattern formed by the above method can be used as a core in the spacer process disclosed in, for example, JP-A-03-270227 and US Patent Application Publication No. 2013 / 0209941.

[0377] (Electronic device manufacturing method) The method for manufacturing an electronic device according to the present invention includes the pattern formation method according to the present invention. The electronic device manufactured by the method for manufacturing an electronic device according to the present invention is suitable for use in electric and electronic equipment (e.g., home appliances, OA (Office Automation) related equipment, media related equipment, optical equipment, communication equipment, etc.). EXAMPLES

[0378] The following examples further illustrate the embodiments of the present invention. The materials, amounts, ratios, processing contents, and processing procedures shown in the following examples can be changed as appropriate without departing from the spirit of the embodiments of the present invention. Therefore, the scope of the embodiments of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are based on mass.

[0379] <Resin (A)> The structures of the resins (A-1 to A-17) used are shown below. The weight average molecular weight (Mw), number average molecular weight (Mn), and dispersity (Mw / Mn) of the resin were measured by GPC (carrier: tetrahydrofuran (THF)) as described above (polystyrene equivalent). The composition ratio (mol %) of the resin was: 13 Measurements were performed using C-NMR (Nuclear Magnetic Resonance).

[0380] [ka]

[0381] [ka]

[0382] [ka]

[0383] The content ratio of each repeating unit in the above resin is expressed in mol %.

[0384] In the present specification and examples, the glass transition temperature (Tg) of a homopolymer of a monomer a1 corresponding to a repeating unit (a1) derived from a monomer (monomer a1) having a glass transition temperature (Tg) of 50° C. or lower when made into a homopolymer can be found by reference to the description in PCT / JP2018 / 018239.

[0385] <Photoacid generator> The structures of the photoacid generators (C-1 to C-15) used are shown below, where nBu represents an n-butyl group, and tBu represents a t-butyl group.

[0386] [ka]

[0387] [ka]

[0388] [ka]

[0389] The pKa values ​​of the acids generated from C-1 to C-15 are shown in Table 1.

[0390] [Table 1]

[0391] <Acid diffusion control agent> The structure of the acid diffusion controller used is shown below.

[0392] [ka]

[0393] Tri-n-pentylamine (D-9)

[0394] The structure of the crosslinking agent used is shown below.

[0395] [ka]

[0396] The structure of the hydrophobic resin used is shown below. The weight average molecular weight (Mw), number average molecular weight (Mn), and dispersity (Mw / Mn) of the hydrophobic resin were measured by GPC (carrier: tetrahydrofuran (THF)) as described above (polystyrene equivalent). The composition ratio (mol %) of the resin was: 13 Measurements were performed using C-NMR (Nuclear Magnetic Resonance).

[0397] [ka]

[0398] The structures of the anion additives used to add the anion (P) are shown in Table 2 below.

[0399] [Table 2]

[0400] The surfactant (E) used is shown below.

[0401] [ka]

[0402] E-2: Megafac R-41 (DIC Corporation) E-3: KF-53 (Shin-Etsu Chemical Co., Ltd.) E-4: Megafac F176 (DIC Corporation) E-5: Megafac R08 (DIC Corporation)

[0403] The solvents used are shown below. S-1: Propylene glycol monomethyl ether acetate (PGMEA) S-2: Propylene glycol monomethyl ether (PGME) S-3: Ethyl lactate S-4: Ethyl 3-ethoxypropionate S-5: 2-Heptanone S-6: 3-Methoxypropionic acid methyl ester S-7: 3-Methoxybutyl acetate S-8: Butyl acetate

[0404] (Examples 1 to 46 and Comparative Examples 1 to 3) <Preparation of actinic ray-sensitive or radiation-sensitive resin composition> (KrF exposure) (Examples 1 to 7, 15 to 18, 23 to 29, 36 to 46, Comparative Examples 1 to 3) A solution was obtained by mixing the components shown in Table 3 to obtain the solid content concentration (mass %) shown in Table 3. The resulting solution was then filtered through a polyethylene filter having a pore size of 3 μm to prepare an actinic ray-sensitive or radiation-sensitive resin composition (resist composition). In the resist composition in the examples and comparative examples, the solid content means all components other than the solvent and the anionic additive. The resist composition thus obtained was used in the examples and comparative examples. In the table, the content (% by mass) of each component other than the solvent means the content ratio to the total solid content. The table also shows the content (% by mass) of the solvent used to the total solvent.

[0405] <Measurement of the Anion (P) Content of Actinic Ray- or Radiation-Sensitive Resin Composition> The anion (P) in the actinic ray-sensitive or radiation-sensitive resin composition shown in Table 3 was added in the amount shown in Table 3. The structure of the anion (P) is clear from the structure of the anion additive used. The anion (P) based on the anion additive AE-6 is SO4 2- It is. The content of anion (P) was measured as follows.

[0406] (Method for quantifying anion (P)) After preparing a resist composition (resist solution) containing an anion (P), 10 g of the resist solution was weighed, and 100 g of toluene and 100 g of ion-exchanged water were added to a separatory funnel, mixed, and allowed to stand. The aqueous layer was separated, and water was distilled off under reduced pressure. 1 g of ion-exchanged water was added to the residue, and after shaking well, it was filtered with a 0.2 μm filter (DISMIC-13HP, ADVANTEC), and subjected to an ion chromatograph (ion chromatography: PIA-1000, Shimadzu Corporation), and analyzed using a Shim-pack IC-SA4 (Shimadzu GLC Corporation) as a column. Various anions were quantified by the absolute calibration curve method using an anion mixed standard solution manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd., and the content of anion (P) in the resist solution was calculated.

[0407] <Pattern formation method (1): KrF exposure, alkaline aqueous solution development> Using a spin coater "ACT-8" manufactured by Tokyo Electron, the resist composition prepared above and described in Table 3 was dropped onto an 8-inch Si substrate (manufactured by Advanced Materials Technology Co., Ltd. (hereinafter also referred to as "substrate")) that had been treated with hexamethyldisilazane, without providing an anti-reflective layer, while the substrate was stationary. After dropping, the substrate was rotated, and the rotation speed was maintained at 500 rpm for 3 seconds, then at 100 rpm for 2 seconds, then at 500 rpm for another 3 seconds, then at 100 rpm for 2 seconds again, and then increased to the film thickness setting rotation speed (1200 rpm) and maintained for 60 seconds. Thereafter, the substrate was heated and dried at 130°C for 60 seconds on a hot plate to form a positive resist film with a film thickness of 12 μm. This resist film was exposed to light using a KrF excimer laser scanner (ASML, PAS5500 / 850C, wavelength 248 nm) under the exposure conditions of NA=0.60 and σ=0.75 through a mask having a line and space pattern such that the space width of the pattern formed after reduction projection exposure and development would be 4.5 μm and the pitch width would be 25 μm. After irradiation, the resist film was baked at 120° C. for 60 seconds, immersed in a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, rinsed with pure water for 30 seconds, dried, and then baked at 110° C. for 60 seconds to form an isolated space pattern with a space width of 4.5 μm and a pitch width of 25 μm. The above pattern exposure is performed through a mask having a line and space pattern such that the space width after reduced projection exposure is 4.5 μm and the pitch width is 25 μm. The exposure dose is set to the optimum exposure dose (sensitivity) (mJ / cm) for forming an isolated space pattern having a space width of 4.5 μm and a pitch width of 25 μm. 2 In determining the above sensitivity, a scanning electron microscope (SEM: Scanning Electron Microscope) (9380II manufactured by Hitachi High-Technologies Corporation) was used to measure the space width of the pattern. By the above procedure, a patterned wafer for evaluation having a substrate and a pattern formed on the surface of the substrate was obtained.

[0408] <Performance evaluation>

[0409] [Stability over time] The resist composition was stored at 40° C. for 4 weeks, and then an isolated space pattern was formed in the same manner as above. The sensitivity of the resulting isolated space pattern was determined in the same manner as above, and the difference between the sensitivity of the isolated space pattern formed using the resist composition before storage over time and the sensitivity of the isolated space pattern formed using the resist composition after storage over time (40° C. for 4 weeks), i.e., the degree of sensitivity variation, was evaluated according to the following criteria. (Judgment criteria) A: The observed sensitivity fluctuation is 1 mJ / cm 2 less than B: Observed sensitivity fluctuation is 1 mJ / cm 2 More than 2mJ / cm 2 less than C: Observed sensitivity fluctuation is 2 mJ / cm 2 More than 3mJ / cm 2 less than D: Observed sensitivity fluctuation is 3 mJ / cm 2 End

[0410] [sensitivity] For each resist composition, a similar resist composition was separately prepared except that it did not contain anion (P), and an isolated space pattern was formed in the same manner as above. The sensitivity of the isolated space pattern thus obtained was determined in the same manner as above. The sensitivity of the isolated space pattern formed using a resist composition containing anion (P) was used as a standard, and the degree to which the sensitivity of the isolated space pattern formed using a resist composition containing anion (P) had decreased was evaluated according to the following criteria. (Judgment criteria) A: The observed sensitivity loss is 1 mJ / cm 2 less than B: Observed sensitivity loss of 1 mJ / cm 2 More than 2mJ / cm 2 less than C: Observed sensitivity loss of 2 mJ / cm 2 More than 3mJ / cm 2 less than D: Observed sensitivity loss of 3 mJ / cm 2 End However, the resist composition of Comparative Example 1 did not contain the amine oxide (P) and was rated A for sensitivity.

[0411] <Preparation of actinic ray-sensitive or radiation-sensitive resin composition> (ArF exposure) (Examples 8 to 10, 19 to 20, 30 to 31) The various components shown in Table 3 were mixed to obtain a solution having the solid content concentration (mass%) shown in Table 3. The obtained liquid was first filtered through a polyethylene filter having a pore size of 50 nm, then a nylon filter having a pore size of 10 nm, and finally a polyethylene filter having a pore size of 5 nm, in that order. The obtained actinic ray-sensitive or radiation-sensitive resin composition (resist composition) was used in the examples and comparative examples. In the resist composition, the solid content in the examples means all components other than the solvent and the anion (P). In the table, the content (% by mass) of each component other than the solvent means the content ratio to the total solid content. The table also shows the content (% by mass) of the solvent used to the total solvent. The content of anion (P) was measured in the same manner as above.

[0412] <Pattern formation method (2): ArF immersion exposure, alkaline aqueous solution development (positive)> An organic anti-reflective coating composition SOC9110D and a Si-containing anti-reflective coating composition HM9825 were applied onto a silicon wafer to form an anti-reflective coating. A resist composition was applied onto the resulting anti-reflective coating, and baked at 100° C. for 60 seconds (PB: Prebake) to form a resist film with a thickness of 100 nm. The obtained wafer was exposed to light through a 6% halftone mask with a 1:1 line and space pattern with a line width of 100 nm using an ArF excimer laser immersion scanner (manufactured by ASML; XT1700i, NA 0.85, Annular, outer sigma 0.9, inner sigma 0.6). Ultrapure water was used as the immersion liquid. After that, the wafer was baked at 90°C for 60 seconds (PEB: Post Exposure Bake). Next, the wafer was puddled with a tetramethylammonium hydroxide aqueous solution (2.38% by mass) as a developer for 30 seconds, and then rinsed with pure water to form a 1:1 line and space (LS) pattern with a line width of 100 nm. The optimum exposure dose (sensitivity) for forming a 1:1 line and space (LS) pattern with a line width of 100 nm (mJ / cm 2In determining the above sensitivity, a scanning electron microscope (SEM: Scanning Electron Microscope) (9380II manufactured by Hitachi High-Technologies Corporation) was used to measure the space width of the pattern. By the above procedure, a patterned wafer for evaluation having a substrate and a pattern formed on the surface of the substrate was obtained.

[0413] <Pattern formation method (3): ArF immersion exposure, organic solvent development (negative)> An organic anti-reflective coating composition SOC9110D and a Si-containing anti-reflective coating composition HM9825 were applied onto a silicon wafer to form an anti-reflective coating. A resist composition was applied onto the resulting anti-reflective coating, and baked at 100° C. for 60 seconds (PB: Prebake) to form a resist film with a thickness of 100 nm. The obtained wafer was exposed to light through a 6% halftone mask with a 1:1 line and space pattern with a line width of 100 nm using an ArF excimer laser immersion scanner (ASML; XT1700i, NA 0.85, Annular, outer sigma 0.9, inner sigma 0.6). Ultrapure water was used as the immersion liquid. After that, the wafer was baked at 90°C for 60 seconds (PEB: Post Exposure Bake). The wafer was then developed by puddling with butyl acetate as the developer for 30 seconds, and rinsed with methyl isobutyl carbinol (MIBC) to form a 1:1 line and space (LS) pattern with a line width of 100 nm. The optimum exposure dose (sensitivity) for forming a 1:1 line and space (LS) pattern with a line width of 100 nm (mJ / cm 2 In determining the above sensitivity, a scanning electron microscope (SEM: Scanning Electron Microscope) (9380II manufactured by Hitachi High-Technologies Corporation) was used to measure the space width of the pattern. By the above procedure, a patterned wafer for evaluation having a substrate and a pattern formed on the surface of the substrate was obtained.

[0414] <Performance evaluation> [Stability over time] The resist composition was stored at 40° C. for 4 weeks, and then a line and space pattern was formed in the same manner as above. The sensitivity of the resulting line and space pattern was determined in the same manner as above, and the difference between the sensitivity of the line and space pattern formed using the resist composition before storage over time and the sensitivity of the line and space pattern formed using the resist composition after storage over time (40° C. for 4 weeks), i.e., the degree of sensitivity fluctuation, was evaluated according to the following criteria. (Judgment criteria) A: The observed sensitivity fluctuation is 1 mJ / cm 2 less than B: Observed sensitivity fluctuation is 1 mJ / cm 2 More than 2mJ / cm 2 less than C: Observed sensitivity fluctuation is 2 mJ / cm 2 More than 3mJ / cm 2 less than D: Observed sensitivity fluctuation is 3 mJ / cm 2 End

[0415] [sensitivity] For each resist composition, a similar resist composition was prepared separately except that it did not contain anion (P), and a line and space pattern was formed in the same manner as above. The sensitivity of the obtained line and space pattern was determined in the same manner as above. The sensitivity of the line and space pattern formed using the resist composition containing anion (P) was used as a standard to evaluate how much the sensitivity of the line and space pattern formed using the resist composition containing anion (P) was reduced according to the following criteria. (Judgment criteria) A: The observed sensitivity loss is 1 mJ / cm 2 less than B: Observed sensitivity loss of 1 mJ / cm 2 More than 2mJ / cm 2 less than C: Observed sensitivity loss of 2 mJ / cm 2 More than 3mJ / cm 2 less than D: Observed sensitivity loss of 3 mJ / cm 2 End

[0416] <Preparation of actinic ray-sensitive or radiation-sensitive resin composition> (EUV exposure) (Examples 11 to 12, 21, 32 to 33) The various components shown in Table 3 were mixed to obtain a solution having the solid content concentration (mass%) shown in Table 3. The obtained liquid was first filtered through a polyethylene filter having a pore size of 50 nm, then a nylon filter having a pore size of 10 nm, and finally a polyethylene filter having a pore size of 5 nm, in that order. The obtained actinic ray-sensitive or radiation-sensitive resin composition (resist composition) was used in the examples and comparative examples. In the resist composition, the solid content in the examples means all components other than the solvent and the anion (P). In the table, the content (% by mass) of each component other than the solvent means the content ratio to the total solid content. The table also shows the content (% by mass) of the solvent used to the total solvent. The content of anion (P) was measured in the same manner as above.

[0417] <Pattern formation method (4): EUV exposure, alkaline development (positive)> AL412 (manufactured by Brewer Science) was applied onto a silicon wafer and baked at 205° C. for 60 seconds to form an underlayer film with a thickness of 30 nm. A resist composition was applied thereon and baked (PB) at 120° C. for 60 seconds to form a resist film with a thickness of 30 nm. This resist film was pattern-irradiated using an EUV exposure device (Exitech, Micro Exposure Tool, NA 0.3, Quadrupol, outer sigma 0.68, inner sigma 0.36). As a reticle, a mask with a line size of 40 nm and a line:space ratio of 1:1 was used. The exposed resist film was baked at 120°C for 60 seconds (PEB), developed with a tetramethylammonium hydroxide aqueous solution (TMAH, 2.38% by mass) for 30 seconds, and then rinsed with pure water for 30 seconds. The silicon wafer was rotated at 4000 rpm for 30 seconds and further baked at 90°C for 60 seconds to obtain a line and space pattern with a pitch of 80 nm and a line width of 40 nm (space width of 40 nm). The optimum exposure dose (sensitivity) for forming a line and space (LS) pattern with a line width of 40 nm (mJ / cm 2 In determining the above sensitivity, a scanning electron microscope (SEM: Scanning Electron Microscope) (9380II manufactured by Hitachi High-Technologies Corporation) was used to measure the space width of the pattern. By the above procedure, a patterned wafer for evaluation having a substrate and a pattern formed on the surface of the substrate was obtained.

[0418] <Pattern formation method (5): EUV exposure, organic solvent development (negative)> AL412 (manufactured by Brewer Science) was applied onto a silicon wafer and baked at 205° C. for 60 seconds to form an underlayer film with a thickness of 30 nm. A resist composition shown in Table 3 was applied thereon and baked (PB) at 120° C. for 60 seconds to form a resist film with a thickness of 30 nm. This resist film was pattern-irradiated using an EUV exposure device (Exitech, Micro Exposure Tool, NA 0.3, Quadrupol, outer sigma 0.68, inner sigma 0.36). As a reticle, a mask with a line size of 40 nm and a line:space ratio of 1:1 was used. The exposed resist film was baked (PEB) at 120°C for 60 seconds, and then developed with butyl acetate for 30 seconds. The silicon wafer was rotated at 4000 rpm for 30 seconds and further baked at 90°C for 60 seconds to obtain a line and space pattern with a pitch of 80 nm and a line width of 40 nm (space width of 40 nm). The optimum exposure dose (sensitivity) for forming a line and space (LS) pattern with a line width of 40 nm (mJ / cm 2 In determining the above sensitivity, a scanning electron microscope (SEM: Scanning Electron Microscope) (9380II manufactured by Hitachi High-Technologies Corporation) was used to measure the space width of the pattern. By the above procedure, a patterned wafer for evaluation having a substrate and a pattern formed on the surface of the substrate was obtained.

[0419] <Performance evaluation> [Stability over time] The resist composition was stored at 40° C. for 4 weeks, and then a line and space pattern was formed in the same manner as above. The sensitivity of the resulting line and space pattern was determined in the same manner as above, and the difference between the sensitivity of the line and space pattern formed using the resist composition before storage over time and the sensitivity of the line and space pattern formed using the resist composition after storage over time (40° C. for 4 weeks), i.e., the degree of sensitivity fluctuation, was evaluated according to the following criteria. (Judgment criteria) A: The observed sensitivity fluctuation is 1 mJ / cm 2 less than B: Observed sensitivity fluctuation is 1 mJ / cm 2 More than 2mJ / cm 2 less than C: Observed sensitivity fluctuation is 2 mJ / cm 2 More than 3mJ / cm 2 less than D: Observed sensitivity fluctuation is 3 mJ / cm 2 End

[0420] [sensitivity] For each resist composition, a similar resist composition was prepared separately except that it did not contain anion (P), and a line and space pattern was formed in the same manner as above. The sensitivity of the obtained line and space pattern was determined in the same manner as above. The sensitivity of the line and space pattern formed using the resist composition containing anion (P) was used as a standard to evaluate how much the sensitivity of the line and space pattern formed using the resist composition containing anion (P) was reduced according to the following criteria. (Judgment criteria) A: The observed sensitivity loss is 1 mJ / cm 2 less than B: Observed sensitivity loss of 1 mJ / cm 2 More than 2mJ / cm 2 less than C: Observed sensitivity loss of 2 mJ / cm 2 More than 3mJ / cm 2 less than D: Observed sensitivity loss of 3 mJ / cm 2 End

[0421] <Preparation of actinic ray-sensitive or radiation-sensitive resin composition> (EB exposure) (Examples 13, 14, 22, 34, and 35) The various components shown in Table 3 were mixed together to obtain a solution having a solid content concentration (mass%) shown in Table 3. The resulting solution was filtered through a polytetrafluoroethylene filter having a pore size of 0.03 μm to obtain an actinic ray-sensitive or radiation-sensitive resin composition (resist composition). The resulting actinic ray-sensitive or radiation-sensitive resin composition (resist composition) was used in the examples. In the resist composition, the solid content in this embodiment means all components other than the solvent and the anion (P). In the table, the content (% by mass) of each component other than the solvent means the content ratio to the total solid content. The table also shows the content (% by mass) of the solvent used to the total solvent. The content of anion (P) was measured in the same manner as above.

[0422] <Pattern formation method (6): EB exposure, alkaline development (positive)> A resist composition shown in Table 3 was applied onto a 6-inch wafer using a spin coater Mark 8 manufactured by Tokyo Electron Ltd., and baked on a hot plate (PB) at 110° C. for 90 seconds to obtain a resist film with a thickness of 80 nm. This resist film was pattern-irradiated using an electron beam lithography device (ELS-7500, manufactured by Elionix Co., Ltd., acceleration voltage 50 KeV). As a reticle, a mask with a line size of 100 nm and a line:space ratio of 1:1 was used. After irradiation, the film was baked (PEB) on a hot plate at 110° C. for 90 seconds, immersed in a 2.38 mass % tetramethylammonium hydroxide aqueous solution as a developer for 60 seconds, rinsed with pure water for 30 seconds, and dried to obtain a line and space pattern with a pitch of 200 nm and a line width of 100 nm (space width 100 nm). The optimum exposure dose (sensitivity) for forming a line and space (LS) pattern with a line width of 100 nm (μC / cm 2 In determining the above sensitivity, a scanning electron microscope (SEM: Scanning Electron Microscope) (9380II manufactured by Hitachi High-Technologies Corporation) was used to measure the space width of the pattern. By the above procedure, a patterned wafer for evaluation having a substrate and a pattern formed on the surface of the substrate was obtained.

[0423] <Performance evaluation> [Stability over time] The resist composition was stored at 40° C. for 4 weeks, and then a line and space pattern was formed in the same manner as above. The sensitivity of the resulting line and space pattern was determined in the same manner as above, and the difference between the sensitivity of the line and space pattern formed using the resist composition before storage over time and the sensitivity of the line and space pattern formed using the resist composition after storage over time (40° C. for 4 weeks), i.e., the degree of sensitivity fluctuation, was evaluated according to the following criteria. (Judgment criteria) A: Observed sensitivity fluctuation is 1μC / cm 2 less than B: Observed sensitivity fluctuation is 1μC / cm 2 More than 2μC / cm 2 less than C: Observed sensitivity fluctuation is 2μC / cm 2 More than 3μC / cm 2 less than D: Observed sensitivity fluctuation is 3μC / cm 2 End

[0424] [sensitivity] For each resist composition, a similar resist composition was prepared separately except that it did not contain anion (P), and a line and space pattern was formed in the same manner as above. The sensitivity of the obtained line and space pattern was determined in the same manner as above. The sensitivity of the line and space pattern formed using the resist composition containing anion (P) was used as a standard to evaluate how much the sensitivity of the line and space pattern formed using the resist composition containing anion (P) was reduced according to the following criteria. (Judgment criteria) A: The observed sensitivity loss is 1μC / cm 2 less than B: Observed sensitivity loss of 1μC / cm 2 More than 2μC / cm 2 less than C: Observed sensitivity loss of 2μC / cm 2 More than 3μC / cm 2 less than D: The observed sensitivity loss is 3μC / cm 2 End

[0425] The evaluation results obtained are shown in Table 4.

[0426] [Table 3]

[0427] [Table 4]

[0428] [Table 5]

[0429] [Table 6]

[0430] The results in Table 4 show that the composition of the present invention can achieve extremely excellent stability over time while suppressing a decrease in sensitivity. In addition, in Examples 1 to 2, 4-6, 8-11, 13, 15-22, 24-25, 28, 30, 32-36, 39, 41-42, and 44 are respectively Reference example 1~ 2、4~6、8~11、13、15~22、24~25、28、30、32~36、39、41~42、44 shall be read as follows. [Industrial Applicability]

[0431] According to the present invention, it is possible to provide an actinic ray-sensitive or radiation-sensitive resin composition that can achieve extremely excellent stability over time while suppressing a decrease in sensitivity. The present invention further provides an actinic ray-sensitive or radiation-sensitive film, a pattern forming method, and a method for producing an electronic device, which use the actinic ray-sensitive or radiation-sensitive resin composition.

[0432] Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope of the invention. This application is based on a Japanese patent application (Patent Application No. 2019-157428) filed on August 29, 2019, the contents of which are incorporated herein by reference.

Claims

1. (A) a resin whose polarity increases under the action of an acid; (B) a photoacid generator, and NO ３ － , S.O. ４ ２－ , Cl － , and Br － An actinic ray-sensitive or radiation-sensitive resin composition comprising an anion (P) which is one or more anions selected from the group consisting of: the content of the anion (P) is 0.01 ppb or more and 10 ppb or less based on the total mass of the actinic ray-sensitive or radiation-sensitive resin composition, An actinic ray-sensitive or radiation-sensitive resin composition (excluding liquid compositions containing a carbonate), in which the solids concentration of the composition is 0.5% by mass to 60% by mass.

2. The mass ratio of the anion (P) to the resin (A), represented by the following formula, is 2 × 10 －１１ ~5×10 －４ The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 , Mass ratio=(content of anion (P)) / (content of resin (A))

3. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein the solid content concentration of the composition is 10% by mass or more.

4. 4. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 3, wherein the pKa of an acid generated from the photoacid generator upon irradiation with actinic rays or radiation is less than 1.

1.

5. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 4, further comprising a crosslinking agent.

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