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

Abstract

The present invention provides an actinic ray-sensitive or radiation-sensitive resin composition, an actinic ray-sensitive or radiation-sensitive film formed by the actinic ray-sensitive or radiation-sensitive resin composition, a pattern forming method, and a method for manufacturing an electronic device. The actinic ray-sensitive or radiation-sensitive resin composition contains: (A) a resin whose polarity is increased by the action of an acid; (B) a photoacid generator; and an anion (P) selected from NO3 ‑ 、SO4 2‑ , Cl ‑ and Br ‑ One or more anions in the group consisting of the above-mentioned anions (P) are contained in an amount of 0.01 ppb to 100 ppm based on the total mass of the actinic ray-sensitive or radiation-sensitive resin composition.

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 Art

[0002] In order to compensate for the decrease in sensitivity caused by light absorption after the KrF excimer laser (248nm) resist is used, a pattern forming method using chemical amplification is used. For example, in the positive chemical amplification method, first, the photoacid generator contained in the exposure part is decomposed by light irradiation to generate acid. Then, in the post-exposure baking (PEB: Post Exposure Bake) process, the alkali-insoluble groups contained in the photosensitive composition are converted into alkali-soluble groups by the catalytic action of the generated acid. Thereafter, development is performed using, for example, an alkaline solution. Thus, the exposure part is removed to obtain the desired pattern.

[0003] In the above method, various alkaline developers have been proposed. For example, as the alkaline developer, an aqueous alkaline developer containing 2.38% by mass of TMAH (tetramethylammonium hydroxide aqueous solution) is generally used.

[0004] In order to miniaturize semiconductor elements, the wavelength of exposure light sources has been shortened and the numerical aperture (NA) of projection lenses has been increased. Currently, exposure machines using ArF excimer lasers with a wavelength of 193 nm as light sources are being developed. As a technique for further improving resolution, a method of filling the space between the projection lens and the sample with a high refractive index liquid (hereinafter also referred to as "immersion liquid") (i.e., liquid immersion method) can be cited.

[0005] Various resist compositions are known in the related art. For example, a resist composition described in Patent Document 1 is known.

[0006] Patent Document 1 describes a photoresist composition containing a polymer having a structural unit including an acid-dissociable group that dissociates by the action of an acid, a radiation-sensitive acid generator, and a solvent.

[0007] Previous technical literature

[0008] Patent Literature

[0009] Patent Document 1: Japanese Patent Application Publication No. 2015-57638 Summary of the invention

[0010] Technical issues to be solved by the invention

[0011] Development of three-dimensional structure devices that achieve large-capacity memory by stacking cells is underway. As the number of stacked layers increases, it is necessary to form a thicker resist film than before, form a resist pattern, and perform etching and other processes.

[0012] In the case of resists used in the most advanced high-thickness processes, stricter quality management than ever before is required as the number of processes increases, and there has arisen a problem that deterioration of raw materials during storage of resist compositions more significantly affects performance.

[0013] Furthermore, as the resist film thickness increases, it becomes more difficult to maintain sensitivity during exposure, and a large amount of exposure is required, which tends to reduce sensitivity.

[0014] Here, the 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, a resist composition that can achieve better stability over time is sought. (Excellent stability over time means that when the composition before the formation of the resist film is stored over time, the effect on the pattern obtained using the composition after the storage over time is small.)

[0015] As a general countermeasure, it is conceivable to change the composition of the resist composition to a composition that can improve the original temporal stability. However, it is not easy to improve the temporal stability without impairing basic performance such as sensitivity.

[0016] An object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive resin composition capable of achieving extremely excellent stability over time while suppressing a decrease in sensitivity.

[0017] Another 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 using the actinic ray-sensitive or radiation-sensitive resin composition.

[0018] Means for solving technical problems

[0019] Methods for solving the above-mentioned problems include the following. [1]

[0021] An actinic ray-sensitive or radiation-sensitive resin composition comprising:

[0022] (A) A resin whose polarity is increased by the action of an acid;

[0023] (B) a photoacid generator; and

[0024] Anion (P) selected from NO3 - 、SO4 2- , Cl - and Br- One or more anions in the group consisting of

[0025] The content of the anion (P) is 0.01 ppb or more and 100 ppm or less relative to the total mass of the actinic ray-sensitive or radiation-sensitive resin composition. [2]

[0027] The actinic ray-sensitive or radiation-sensitive resin composition according to [1], wherein

[0028] The content of the anion (P) is 0.01 ppb or more and 1 ppm or less relative to the total mass of the actinic ray-sensitive or radiation-sensitive resin composition. [3]

[0030] The actinic ray-sensitive or radiation-sensitive resin composition according to [1] or [2], wherein

[0031] The content of the anion (P) is 0.01 ppb or more and 10 ppb or less relative to the total mass of the actinic ray-sensitive or radiation-sensitive resin composition. [4]

[0033] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [3], wherein

[0034] The mass ratio of the anion (P) to the resin (A) represented by the following formula is 2×10 -11 ~5×10 -4 .

[0035] Mass ratio = (content of anion (P)) / (content of resin (A)) [5]

[0037] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [4], wherein the composition has a solid content concentration of 10% by mass or more. [6]

[0039] The actinic ray-sensitive or radiation-sensitive resin composition according to [5], wherein

[0040] The pKa of the acid generated by the photoacid generator upon irradiation with actinic rays or radiation is less than 1.1. [7]

[0042] 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]

[0044] 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 using a developer. [9]

[0046] A method for manufacturing an electronic device, comprising the pattern forming method described in [8].

[0047] Effects of the Invention

[0048] According to the present invention, there can be provided an actinic ray-sensitive or radiation-sensitive resin composition capable of achieving extremely excellent stability over time while suppressing a decrease in sensitivity.

[0049] According to the present invention, there can also be provided an actinic ray-sensitive or radiation-sensitive film, a pattern forming method, and a method for producing an electronic device using the actinic ray-sensitive or radiation-sensitive resin composition. DETAILED DESCRIPTION

[0050] Hereinafter, the contents of the present invention will be described in detail.

[0051] The constituent elements described below will be described based on typical embodiments of the present invention, but the present invention is not limited to these embodiments.

[0052] In the marking of the group (atomic group) in this specification, the marking that does not record substitution and unsubstituted includes not only the group without substitution but also the group with substitution. For example, "alkyl" includes not only the alkyl without substitution (unsubstituted alkyl) but also the alkyl with substitution (substituted alkyl). In addition, "organic group" in this specification refers to a group containing at least one carbon atom.

[0053] In addition, in the present specification, when it is stated that "may have a substituent", the type of substituent, the position of the substituent and the number of the substituent are not particularly limited. The number of substituents may be, for example, 1, 2, 3 or more. As an example of a substituent, a monovalent non-metallic atomic group other than a hydrogen atom may be cited, for example, the substituent T below may be selected.

[0054] (Substituent T)

[0055] Examples of the substituent T include halogen atoms such as fluorine, chlorine, bromine and iodine atoms; alkoxy groups such as methoxy, ethoxy and tert-butoxy; aryloxy groups such as phenoxy and p-tolyloxy; alkoxycarbonyl groups such as methoxycarbonyl, butoxycarbonyl and phenoxycarbonyl; acyloxy groups such as acetoxy, propionyloxy and benzoyloxy; acyl groups such as acetyl, benzoyl, isobutyryl, acryloyl, methacryloyl and methoxyvaleryl; alkylsulfanyl groups such as methylsulfanyl and tert-butylsulfanyl; arylsulfanyl groups such as phenylsulfanyl and p-tolylsulfanyl; alkyl groups; cycloalkyl groups; aryl groups; heteroaryl groups; hydroxyl groups; carboxyl groups; formyl groups; sulfo groups; cyano groups; alkylaminocarbonyl groups; arylaminocarbonyl groups; sulfonamido groups; silyl groups; amino groups; monoalkylamino groups; dialkylamino groups; arylamino groups, nitro groups; and combinations thereof.

[0056] The "actinic rays" or "radiation" in this specification refers to, for example, the bright line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light: Extreme Ultraviolet), X-rays, and electron beams (EB: Electron Beam), etc. Unless otherwise specified, the "light" in this specification refers to actinic rays or radiation.

[0057] Unless otherwise specified, the term "exposure" in this specification includes not only exposure using the bright line spectrum of a mercury lamp, far ultraviolet light represented by excimer lasers, extreme ultraviolet light (EUV light), and X-rays, but also exposure using particle beams such as electron beams and ion beams.

[0058] In this specification, "to" is used to mean that the numerical values ​​described before and after it are included as the lower limit and the upper limit.

[0059] In the present specification, (meth)acrylate means acrylate and methacrylate, and (meth)acrylic acid means acrylic acid and methacrylic acid.

[0060] In this specification, the weight average molecular weight (Mw), number average molecular weight (Mn) and dispersion degree (also referred to as molecular weight distribution) (Mw / Mn) of the resin component are defined as polystyrene conversion values ​​obtained by GPC measurement using a GPC (Gel Permeation Chromatography) apparatus (HLC-8120GPC manufactured by TOSOH CORPORATION) (solvent: tetrahydrofuran, flow rate (sample injection amount): 10 μL, column: TSK gel Multipore HXL-M manufactured by TOSOH CORPORATION, column temperature: 40°C, flow rate: 1.0 mL / min, detector: differential refractive index detector).

[0061] In the present specification, when a plurality of substances corresponding to each component are present in a composition, the amount of each component in the composition refers to the total amount of the corresponding plurality of substances present in the composition, unless otherwise specified.

[0062] In the present 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 can be achieved.

[0063] In this specification, "total solid content" refers to the total mass of the components obtained by removing the solvent from all the components of the composition. In addition, as described above, "solid content" refers to the components obtained by removing the solvent, and may be solid or liquid at 25°C, for example.

[0064] In the present specification, "mass %" has the same meaning as "weight %", and "parts by mass" has the same meaning as "parts by weight".

[0065] Furthermore, in this specification, a more preferred embodiment is a combination of two or more preferred embodiments.

[0066] [Acticular ray-sensitive or radiation-sensitive resin composition]

[0067] The actinic ray-sensitive or radiation-sensitive resin composition (hereinafter also referred to simply as "composition") according to the present invention contains:

[0068] An actinic ray-sensitive or radiation-sensitive resin composition comprising:

[0069] (A) A resin whose polarity is increased by the action of an acid;

[0070] (B) a photoacid generator; and

[0071] Anion (P) selected from NO3- 、SO4 2- , Cl - and Br - One or more anions in the group consisting of

[0072] The content of the anion (P) is 0.01 ppb or more and 100 ppm or less relative to the total mass of the actinic ray-sensitive or radiation-sensitive resin composition.

[0073] The present invention, by adopting the above-mentioned structure, can achieve extremely excellent stability over time while suppressing a decrease in sensitivity.

[0074] The reason for this is not clear, but is speculated as follows.

[0075] The photoacid generator that may be contained in the actinic ray or radiation-sensitive resin composition decomposes in trace amounts during storage over time to generate acid. In the present invention, the actinic ray or radiation-sensitive resin composition contains 0.01 ppb or more of a selected from NO3 based on the total mass of the actinic ray or radiation-sensitive resin composition. - 、SO4 2- , Cl - and Br - The anion (P) is one or more anions in the group consisting of the above-mentioned anions. The above-mentioned acid generated by the photoacid generator that may be contained in the actinic ray or radiation-sensitive resin composition when it is slightly decomposed during storage over time can be captured by the above-mentioned anion (P). Therefore, it is considered that the resin that may be contained in the actinic ray or radiation-sensitive resin composition is suppressed from being decomposed by acid, and the stability over time becomes extremely excellent.

[0076] Furthermore, by containing 100 ppm or less of a selected from NO3 based on the total mass of the actinic ray-sensitive or radiation-sensitive resin composition - 、SO4 2- , Cl - and Br - One or more anions in the group of anions (P) make it difficult for the acid generated in the exposed part of the photosensitive or radiation-sensitive film to be captured by the anion (P). That is, it is considered that the desired reaction between the acid generated from the photoacid generator and the resin by exposure is not suppressed, and the decrease in sensitivity is suppressed.

[0077] The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is preferably a so-called resist composition, and may be a positive resist composition or a negative resist composition, and may be a resist composition for alkaline development or a resist composition for organic solvent development.

[0078] The composition of the present invention is typically preferably a chemically amplified resist composition.

[0079] Hereinafter, each component contained in the actinic ray-sensitive or radiation-sensitive resin composition (also simply referred to as “composition”) according to the present invention will be described in detail.

[0080] <Select from NO3 - 、SO4 2- , Cl - and Br - One or more anions in the group consisting of anions (P)>

[0081] The composition of the present invention contains NO3 - 、SO4 2- , Cl - and Br - One or more anions in the group consisting of anions are anions (P) (hereinafter, also referred to as "anions (P)").

[0082] The composition of the present invention contains anions (P). Anions (P) are selected from NO3 - 、SO4 2- , Cl - and Br - Therefore, when the anion (P) is composed of one anion, the content of the anion (P) is the content of its anion. And, when the anion (P) is composed of two or more anions, the content of the anion (P) is the total content of each anion.

[0083] The supply 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.

[0084] The supply source of the anion (P) is not particularly limited, and examples thereof include an anion additive. The anion additive is not particularly limited, and examples thereof include nitric acid, sulfuric acid, hydrochloric acid, hydrogen bromide, ammonium nitrate, and ammonium chloride.

[0085] Furthermore, the following compounds can also be exemplified as anionic additives.

[0086] In addition, the anion detected in the compound on the left below is SO4 2- .

[0087] [Chemical formula 1]

[0088]

[0089] The content of the anion (P) is 0.01 ppb or more and 100 ppm or less relative to the total mass of the actinic ray-sensitive or radiation-sensitive resin composition.

[0090] If the content of the anion (P) is less than 0.01 ppb, the stability over time cannot be ensured, and if the content of the anion (P) exceeds 100 ppm, the decrease in sensitivity cannot be suppressed.

[0091] From the viewpoint of suppressing sensitivity reduction and temporal stability, the content of the anion (P) is preferably 0.01 ppb to 1 ppm, more preferably 0.01 ppb to 10 ppb, and even more preferably 0.01 ppb to 1 ppb, relative to the total mass of the actinic ray-sensitive or radiation-sensitive resin composition.

[0092] When the composition of the present invention contains (A) a resin whose polarity is increased by the action of an acid, the mass ratio of the anion (P) represented by the following formula to the resin is preferably 2×10 -11 ~5×10 -4 , more preferably 2×10 -11 ~5×10 -5 , more preferably 2×10 -11 ~5×10 -6 .

[0093] Mass ratio = (content of anion (P)) / (content of resin (A))

[0094] The method of adding a trace amount of anion (P) using the anion additive is not particularly limited, and examples thereof include the following methods.

[0095] By using the solvent used in the preparation liquid of the resist composition, a dilution liquid of the anion additive is prepared in advance, and a trace amount of the anion additive can be accurately measured, and the content of the anion (P) can also be measured. In particular, when the amount of the anion (P) added is at a very small level, a solution diluted multiple times can be prepared according to the content of the anion (P) to adjust the anion (P) present in the resist composition to a desired amount.

[0096] The content of the anion (P) in the actinic ray-sensitive or radiation-sensitive composition of the present invention can be measured, for example, by the following method.

[0097] (Quantitative method for anions (P))

[0098] After preparing a resist composition (resist solution) containing anions (P), 10 g of the resist solution was weighed, 100 g of toluene and 100 g of ion exchange water were added to a separatory funnel, mixed, and allowed to stand. The water layer was separated and the water was removed by vacuum distillation. 1 g of ion exchange water was added to the residue, and after sufficient shaking, it was filtered with a 0.2 μm filter (DISMIC-13HP, manufactured by ADVANTEC) and placed in an ion chromatograph (ion chromatograph: PIA-1000, manufactured by SHIMADZU CORPORATION), and analyzed with Shim-pack IC-SA4 (manufactured by SHIMADZU GLC Ltd.) 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 Corporation, and the content of anions (P) in the resist solution was calculated.

[0099] <(A) Resin whose polarity is increased by the action of an acid>

[0100] The actinic ray-sensitive or radiation-sensitive resin composition of the present invention contains a resin whose polarity increases due to the action of an acid (hereinafter also referred to as "resin (A)"). Typically, the resin (A) is preferably a resin whose polarity increases due to the action of an acid and whose solubility in a developer changes.

[0101] The resin (resin (A)) whose polarity is increased by the action of an acid is preferably a resin obtained by polymerizing at least an ethylenically unsaturated compound.

[0102] The ethylenically unsaturated compound preferably has 1 to 4 ethylenically unsaturated bonds, and more preferably 1. Furthermore, the ethylenically unsaturated compound is preferably a monomer of a monomer.

[0103] The molecular weight of the ethylenically unsaturated compound is preferably 28 to 1,000, more preferably 50 to 800, and particularly preferably 100 to 600.

[0104] Furthermore, the resin whose polarity is increased by the action of an acid preferably has an acid-decomposable group, and more preferably is a resin containing a structural unit having an acid-decomposable group.

[0105] At this time, in the pattern forming method according to the present invention described later, when an alkaline developer is used as a developer, a positive pattern is preferably formed, and when an organic developer is used as a developer, a negative pattern is preferably formed.

[0106] [Structural unit having an acid-decomposable group]

[0107] The resin (A) preferably contains a structural unit (also referred to as a "repeating unit") having an acid-decomposable group.

[0108] As resin (A), known resins can be used appropriately. For example, known resins disclosed in paragraphs 0055 to 0191 in U.S. Patent Application Publication No. 2016 / 0274458, paragraphs 0035 to 0085 in U.S. Patent Application Publication No. 2015 / 0004544, and paragraphs 0045 to 0090 in U.S. Patent Application Publication No. 2016 / 0147150 can be preferably used as resin (A).

[0109] The acid-decomposable group preferably has a structure in which a polar group is protected by a group (leaving group) that is decomposed and released by the action of an acid.

[0110] Examples of the polar group include acidic groups (groups that dissociate in a 2.38 mass % tetramethylammonium hydroxide aqueous solution) such as a carboxyl 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 tri(alkylcarbonyl)methylene group, and a tri(alkylsulfonyl)methylene group, as well as an alcoholic hydroxyl group.

[0111] In addition, the alcoholic hydroxyl group is a hydroxyl group bonded to a hydrocarbon group, and refers to a hydroxyl group other than a hydroxyl group (phenolic hydroxyl group) directly bonded to an aromatic ring, and as a hydroxyl group, an aliphatic alcohol (for example, a hexafluoroisopropanol group, etc.) whose α position is substituted by an electron-withdrawing group such as a fluorine atom is excluded. As the alcoholic hydroxyl group, a hydroxyl group having a pKa (acid dissociation constant) of 12 or more and 20 or less is preferred.

[0112] Preferred polar groups include a carboxyl group, a phenolic hydroxyl group, and a sulfonic acid group.

[0113] Preferred acid-decomposable groups are groups in which a hydrogen atom in these groups is substituted with a group that is detached by the action of an acid (leaving group).

[0114] Examples of the group that is released by the action of an acid (releasing group) include -C(R 36 )(R 37 )(R 38 )、-C(R 36 )(R 37 )(OR 39 ) and -C(R 01 )(R 02 )(OR 39 )wait.

[0115] In the formula, R36 ~R 39 R each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. 36 With R 37 They may be bonded to each other to form a ring.

[0116] 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.

[0117] 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 methyl, ethyl, propyl, n-butyl, sec-butyl, hexyl and octyl groups.

[0118] R 36 ~R 39 , R 01 and R 02 The cycloalkyl group may be a monocyclic group or a polycyclic group. As a monocyclic group, a cycloalkyl group having 3 to 8 carbon atoms is preferred, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cyclooctyl. As a polycyclic group, a cycloalkyl group having 6 to 20 carbon atoms is preferred, for example, adamantyl, norbornyl, isobornyl, bornyl, dicyclopentyl, α-pinenyl, tricyclodecyl, tetracyclododecyl and androstanyl. In addition, at least one carbon atom in the cycloalkyl group may be substituted by a heteroatom such as an oxygen atom.

[0119] 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 phenyl, naphthyl and anthracenyl.

[0120] 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 benzyl, phenethyl, and naphthylmethyl.

[0121] 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 vinyl, allyl, butenyl and cyclohexenyl.

[0122] As R 36 With R 37The ring formed by mutually bonding is preferably a cycloalkyl group (monocyclic or polycyclic). The cycloalkyl group is preferably a monocyclic cycloalkyl group such as cyclopentyl and cyclohexyl or a polycyclic cycloalkyl group such as norbornyl, tetracyclodecyl, tetracyclododecyl and adamantyl.

[0123] The acid-decomposable group is preferably a cumyl ester group, an enol ester group, an acetal ester group, a tertiary alkyl ester group, or the like, and more preferably an acetal group or a tertiary alkyl ester group.

[0124] The resin (A) preferably has a structural unit represented by the following formula AI as a structural unit having an acid-decomposable group.

[0125] [Chemical formula 2]

[0126]

[0127] In 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 Each independently represents an alkyl group or a cycloalkyl group, Rx 1 ~Rx 3 Any two of them may be bonded to form a ring structure, or may not form a ring structure.

[0128] Examples of the divalent linking group of T include alkylene, arylene, -COO-Rt- and -O-Rt-. In the formula, Rt represents an alkylene, cycloalkylene or arylene,

[0129] T is preferably a single bond or -COO-Rt-. Rt is preferably a chain alkylene group having 1 to 5 carbon atoms, and more preferably -CH2-, -(CH2)2- or -(CH2)3-. T is more preferably a single bond.

[0130] XA 1 A hydrogen atom or an alkyl group is preferred.

[0131] 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.

[0132] XA 1 The alkyl group in Xa preferably has 1 to 4 carbon atoms, and examples thereof include methyl, ethyl, propyl, and hydroxymethyl. 1 The alkyl group is preferably a methyl group.

[0133] As Rx 1 , Rx 2 and Rx 3The alkyl group may be linear or branched, and preferably includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc. The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 5, and further preferably 1 to 3. 1 , Rx 2 Rx 3 A portion of the carbon-carbon bonds in the alkyl group may be double bonds.

[0134] As Rx 1 , Rx 2 Rx 3 The cycloalkyl group is preferably a monocyclic cycloalkyl group such as cyclopentyl and cyclohexyl, or a polycyclic cycloalkyl group such as norbornyl, tetracyclodecyl, tetracyclododecyl, and adamantyl.

[0135] As Rx 1 , Rx 2 Rx 3 The ring structure formed by bonding two of the rings in is preferably a monocyclic cycloalkane ring such as a cyclopentyl ring, a cyclohexyl ring, a cycloheptyl ring, and a cyclooctane ring, or a polycyclic cycloalkyl ring such as a norbornane ring, a tetracyclodecane ring, a tetracyclododecane ring, and an adamantane ring. More preferably, it is a cyclopentyl ring, a cyclohexyl ring, or an adamantane ring. 1 , Rx 2 Rx 3 The ring structure formed by two of them being bonded together is also preferably the structure shown below.

[0136] [Chemical formula 3]

[0137]

[0138] 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. The following specific examples correspond to Xa in formula AI: 1 In the case of methyl, but Xa 1 It may be arbitrarily substituted with a hydrogen atom, a halogen atom other than a fluorine atom, or a monovalent organic group.

[0139] [Chemical formula 4]

[0140]

[0141] The resin (A) also preferably has a structural unit described in paragraphs 0336 to 0369 in US Patent Application Publication No. 2016 / 0070167 as a structural unit having an acid-decomposable group.

[0142] Furthermore, the resin (A) may have, as a structural unit having an acid-decomposable group, a structural unit including a group that generates an alcoholic hydroxyl group when decomposed by an acid as described in paragraphs 0363 to 0364 of US Patent Application Publication No. 2016 / 0070167.

[0143] Furthermore, 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 released by the action of an acid. In addition, in this specification, a phenolic hydroxyl group is a group formed by replacing 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.

[0144] Examples of the leaving group that is decomposed and released by the action of an acid include groups represented by formulae (Y1) to (Y4).

[0145] Formula (Y1): -C(Rx1)(Rx2)(Rx3)

[0146] Formula (Y2): -C(=O)OC(Rx1)(Rx2)(Rx3)

[0147] Formula (Y3): -C(R 36 )(R 37 )(OR 38 )

[0148] Formula (Y4): -C(Rn)(H)(Ar)

[0149] In formula (Y1) and formula (Y2), Rx1 to Rx3 each independently represent an alkyl group (linear or branched) or a cycloalkyl group (monocyclic or polycyclic). When all of Rx1 to Rx3 are alkyl groups (linear or branched), it is preferred that at least two of Rx1 to Rx3 are methyl groups.

[0150] Among them, a repeating unit in which Rx1 to Rx3 each independently represent a linear or branched alkyl group is more preferred, and a repeating unit in which Rx1 to Rx3 each independently represent a linear alkyl group is further preferred.

[0151] Two of Rx1 to Rx3 may be bonded to form a monocyclic or polycyclic ring.

[0152] The alkyl group for Rx1 to Rx3 is preferably an alkyl group having 1 to 4 carbon atoms, such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and tert-butyl group.

[0153] The cycloalkyl group for Rx1 to Rx3 is preferably a monocyclic cycloalkyl group such as cyclopentyl and cyclohexyl, or a polycyclic cycloalkyl group such as norbornyl, tetracyclodecyl, tetracyclododecyl and adamantyl.

[0154] The cycloalkyl group formed by bonding two of Rx1 to Rx3 is preferably a monocyclic cycloalkyl group such as cyclopentyl and cyclohexyl, or a polycyclic cycloalkyl group such as norbornyl, tetracyclodecyl, tetracyclododecyl and adamantyl. Among them, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferred.

[0155] In the cycloalkyl group formed by bonding two of Rx1 to Rx3, for example, one of the methylene groups constituting the ring may be substituted with a group having a hetero atom such as an oxygen atom or a hetero atom such as a carbonyl group.

[0156] The group represented by the formula (Y1) or (Y2) is preferably a mode in which, for example, Rx1 is a methyl group or an ethyl group, and Rx2 and Rx3 are bonded to form the above-mentioned cycloalkyl group.

[0157] In formula (Y3), R 36 ~R 38 R each independently represents a hydrogen atom or a monovalent organic group. 37 With R 38 They 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. 36 Preferred is a hydrogen atom.

[0158] 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.

[0159] The repeating unit having a structure in which the phenolic hydroxyl group is protected by a leaving group that is decomposed and released by the action of an acid (acid-decomposable group) is preferably a repeating unit having a structure in which the hydrogen atom in the phenolic hydroxyl group is protected by a group represented by formulae (Y1) to (Y4).

[0160] The repeating unit having a structure in which a phenolic hydroxyl group is protected by a leaving group that is decomposed and released by the action of an acid (acid-decomposable group) is preferably a repeating unit represented by the following general formula (AII).

[0161] [Chemical formula 5]

[0162]

[0163] In the general formula (AII),

[0164] 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 It can bond with Ar6 to form a ring. In this case, R 62 represents a single bond or an alkylene group.

[0165] X6 represents a single bond, -COO- or -CONR 64 -. R 64 represents a hydrogen atom or an alkyl group.

[0166] L6 represents a single bond or an alkylene group.

[0167] Ar6 represents an (n+1)-valent aromatic hydrocarbon group. 62 When they are bonded to form a ring, they represent an aromatic hydrocarbon group having a valence of (n+2).

[0168] When n≥2, Y2 each independently represents a hydrogen atom or a group that can be separated by the action of an acid. At least one of Y2 represents a group that can be separated by the action of an acid. The group that can be separated by the action of an acid as Y2 is preferably a group of formula (Y1) to (Y4).

[0169] n represents an integer of 1 to 4.

[0170] Each of the above groups may 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). Preferably, the substituent has 8 or less carbon atoms.

[0171] [Chemical formula 6]

[0172]

[0173] [Chemical formula 7]

[0174]

[0175] The resin (A) may contain one kind of structural unit having an acid-decomposable group alone, or may contain two or more kinds of such structural units.

[0176] The content of the structural unit having an acid-decomposable group contained in the resin (A) (when there are a plurality of structural units having an acid-decomposable group, the total) is preferably 5 mol% to 90 mol%, more preferably 10 mol% to 80 mol%, and further preferably 15 mol% to 70 mol%, relative to all the structural units in the resin (A).

[0177] In addition, in the present invention, when the content of a "structural unit" is specified by a molar ratio, the "structural unit" is assumed to have the same meaning as a "monomer unit". In addition, in the present invention, the "monomer unit" may be modified by a polymer reaction or the like after polymerization. The same applies to the following.

[0178] [A structural unit having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure]

[0179] The resin (A) preferably has at least one structural unit selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure.

[0180] As the lactone structure or sultone structure, any one can be used as long as it has a lactone structure or a sultone structure, preferably a 5- to 7-membered ring lactone structure or a 5- to 7-membered ring sultone structure, more preferably a structure in which another ring structure is fused to the 5- to 7-membered ring lactone structure in the form of a bicyclic structure or a spirocyclic structure, or a structure in which another ring structure is fused to the 5- to 7-membered ring sultone structure in the form of a bicyclic structure or a spirocyclic structure. It is further preferred to include a structural unit having a lactone structure represented by any one of the following formulas LC1-1 to LC1-21 or a sultone structure represented by any one of the following formulas SL1-1 to SL1-3. In addition, the lactone structure or the 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.

[0181] [Chemical formula 8]

[0182]

[0183] The lactone structure part or the sultone structure part may have a substituent (Rb 2 ), or may not have the substituent. As a preferred substituent (Rb 2 ), and examples thereof include alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 4 to 7 carbon atoms, alkoxy groups having 1 to 8 carbon atoms, alkoxycarbonyl groups having 2 to 8 carbon atoms, carboxyl groups, halogen atoms other than fluorine atoms, hydroxyl groups, cyano groups, and acid-decomposable groups. Alkyl groups having 1 to 4 carbon atoms, cyano groups, and acid-decomposable groups are more preferred. n2 represents an integer of 0 to 4. When n2 is 2 or more, there are multiple substituents (Rb 2 ) may be the same or different. Also, there are multiple substituents (Rb 2 ) may be bonded to each other to form a ring.

[0184] The structural unit having a lactone structure or a sultone structure is preferably a structural unit represented by the following formula III.

[0185] Furthermore, the resin including a structural unit having an acid-decomposable group preferably includes a structural unit represented by the following formula III.

[0186] [Chemical formula 9]

[0187]

[0188] In the above formula III,

[0189] A represents an ester bond (a group represented by -COO-) or an amide bond (a group represented by -CONH-).

[0190] n is by-R 0 The number of repetitions of the structure represented by -Z- represents an integer from 0 to 5, preferably 0 or 1, more preferably 0. When n is 0, -R 0 -Z- does not exist, and A and R 8 Bonded by a single bond.

[0191] R 0 represents an alkylene group, a cycloalkylene group or a combination thereof. 0 When there are plural groups, they each independently represent an alkylene group, a cycloalkylene group, or a combination thereof.

[0192] Z represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond. When there are plural Zs, they each independently represent a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond.

[0193] R 8 It represents a monovalent organic group having a lactone structure or a sultone structure.

[0194] R 7 represents a hydrogen atom, a halogen atom other than a fluorine atom, or a monovalent organic group (preferably a methyl group).

[0195] R 0 The alkylene group or cycloalkylene group may have a substituent.

[0196] Z is preferably an ether bond or an ester bond, more preferably an ester bond.

[0197] Specific examples of monomers corresponding to the structural unit represented by formula III and specific examples of monomers corresponding to the structural unit represented by formula A-1 described later are given below, but the present invention is not limited to these specific examples. 7 and R in the formula A-1 described below A 1 In the case of methyl, but R 7 and R A 1 It may be arbitrarily substituted with a hydrogen atom, a halogen atom other than a fluorine atom, or a monovalent organic group.

[0198] [Chemical formula 10]

[0199]

[0200] In addition to the above-mentioned monomers, the monomers shown below can also be suitably used as a raw material of the resin (A).

[0201] [Chemical formula 11]

[0202]

[0203] The resin (A) may contain a repeating unit having a carbonate structure. The carbonate structure is preferably a cyclic carbonate structure.

[0204] The structural unit having a cyclic carbonate structure is preferably a structural unit represented by the following formula A-1.

[0205] [Chemical formula 12]

[0206]

[0207] 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 greater than 0, and R A 2 represents a substituent. When n is 2 or more, R A 2 Each independently represents a substituent, A represents a single bond or a divalent linking group, and Z represents an atomic group that forms a monocyclic structure or a polycyclic structure together with the group represented by -OC(=O)-O- in the formula.

[0208] The resin (A) also preferably has the structural units described in paragraphs 0370 to 0414 of US Patent Application Publication No. 2016 / 0070167 as the structural units having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure.

[0209] The resin (A) preferably contains a structural unit (a) having at least two lactone structures (hereinafter, also referred to as “structural unit (a)”).

[0210] The at least two lactone structures may be, for example, a structure in which at least two lactone structures are fused together, or a structure in which at least two lactone structures are connected via a single bond or a connecting group.

[0211] The lactone structure of the structural unit (a) is not particularly limited, but is preferably a 5- to 7-membered ring lactone structure, and preferably a structure in which another ring structure is fused to the 5- to 7-membered ring lactone structure to form a bicyclic structure or a spirocyclic structure.

[0212] Preferred examples of the lactone structure include lactone structures represented by any one of LC1-1 to LC1-21.

[0213] 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.

[0214] [Chemical formula 13]

[0215]

[0216] 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.

[0217] 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. As the substituent, for example, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an alkoxy group such as a mercapto group, a hydroxyl group, a methoxy group, an ethoxy group, an isopropoxy group, a tert-butoxy group, a benzyloxy group, or an acetoxy group such as an acetyl group or a propionyl group. Ra is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, and a hydroxymethyl group.

[0218] Examples of the lactone structure of the Rb partial structure include the above-mentioned lactone structures.

[0219] 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 connected via a single bond or a linking group, or a structure in which at least two lactone structures are condensed.

[0220] The structural unit (a1) having a structure in which at least two lactone structures are fused and the structural unit (a2) having a structure in which at least two lactone structures are connected via a single bond or a connecting group are described below.

[0221] -Structural unit (a1) having a structure in which at least two lactone structures are fused-

[0222] The structure in which at least two lactone structures are condensed is preferably a structure in which two or three lactone structures are condensed, and more preferably a structure in which two lactone structures are condensed.

[0223] Examples of the structural unit having a structure in which at least two lactone structures are fused (hereinafter, also referred to as "structural unit (a1)") include a structural unit represented by the following formula L-2.

[0224] [Chemical formula 14]

[0225]

[0226] 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.

[0227] The alkyl group of Re1 to Re8 preferably has 5 or less carbon atoms, and more preferably has 1 carbon atom, for example.

[0228] Examples of the alkyl group having 5 or less carbon atoms in Re1 to Re8 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl and tert-pentyl.

[0229] Among them, Re1 to Re8 are preferably hydrogen atoms.

[0230] Examples of the divalent linking group of Me1 include an alkylene group, a cycloalkylene group, -O-, -CO-, -COO-, -OCO-, and a group formed by combining two or more of these groups.

[0231] The alkylene group of Me1 preferably has, for example, 1 to 10 carbon atoms, and more preferably has 1 or 2 carbon atoms. Examples of the alkylene group having 1 or 2 carbon atoms preferably include a methylene group and an ethylene group.

[0232] The alkylene group of Me1 may be linear or branched, and examples thereof include methylene, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,1-diyl, propane-1,3-diyl, propane-2,2-diyl, pentane-1,5-diyl, and hexane-1,6-diyl.

[0233] The cycloalkylene group of Me1 preferably has 5 to 10 carbon atoms, and more preferably has 5 or 6 carbon atoms.

[0234] Examples of the cycloalkylene group of Me1 include cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene, and cyclodecylene.

[0235] As a divalent linking group of Me1, a group formed by combining the above two or more groups is preferably a group formed by combining an alkylene group with -COO- and a group formed by combining -OCO- and an alkylene group. Furthermore, a group formed by combining the above two or more groups is more preferably a group formed by combining a methylene group with a -COO- group and a group formed by combining a -COO- group with a methylene group.

[0236] Examples of the divalent linking group of Me2 and Me3 include alkylene, -O-, etc. The divalent linking group of Me2 and Me3 is preferably methylene, ethylene, -O-, and more preferably -O-.

[0237] The monomer corresponding to the structural unit (a1) can be synthesized by the method described in, for example, JP-A-2015-160836.

[0238] Specific examples of the structural unit (a1) are shown below, but the present invention is not limited thereto. In the following formulae, R9 represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group, and * represents a bonding position with other structural units.

[0239] [Chemical formula 15]

[0240]

[0241] [Chemical formula 16]

[0242]

[0243] [Chemical formula 17]

[0244]

[0245] -Structural unit (a2) having a structure in which at least two lactone structures are connected by a single bond or a linking group-

[0246] 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 2 to 4 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.

[0247] Examples of the linking group include the same groups as those exemplified as the linking group of M2 in the formula L-3 described later.

[0248] Examples of the structural unit having a structure in which two or more lactone structures are linked by a single bond or a linking group (hereinafter also referred to as "structural unit (a2)") include a structural unit represented by the following formula L-3.

[0249] [Chemical formula 18]

[0250]

[0251] In formula L-3, Ra has the same meaning as Ra in the above formula L-1, 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.

[0252] Examples of the linking group of M1 include an alkylene group, a cycloalkylene group, -O-, -CO-, -COO-, -OCO-, and a group formed by combining two or more of these groups.

[0253] The alkylene group of M1 preferably has 1 to 10 carbon atoms, for example.

[0254] The alkylene group of M1 may be linear or branched, and examples thereof include methylene, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,1-diyl, propane-1,3-diyl, propane-2,2-diyl, pentane-1,5-diyl, and hexane-1,6-diyl.

[0255] The cycloalkylene group of M1 preferably has 5 to 10 carbon atoms, for example.

[0256] Examples of the cycloalkylene group of M1 include cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene, and cyclodecylene.

[0257] As the linking group of M1, a group formed by combining the above two or more groups is preferably a group formed by combining an alkylene group and -COO-, and a group formed by combining -OCO- and an alkylene group. Furthermore, a group formed by combining the above two or more groups is more preferably a group formed by combining a methylene group and a -COO- group, and a group formed by combining a -COO- group and a methylene group.

[0258] Examples of the linking group of M2 include the same groups as exemplified for the linking group of M1.

[0259] The lactone structure possessed by Lc1 is preferably, for example, a 5- to 7-membered ring lactone structure, and preferably a structure in which other ring structures are fused to the 5- to 7-membered ring lactone structure in the form of a bicyclic structure or a spirocyclic structure. The above lactone structure is more preferably a lactone structure represented by any one of the above LC1-1 to LC1-21. As further preferred lactone structures, LC1-1, LC1-4, LC1-5, LC1-6, LC1-13, LC1-14 and LC1-17 can be cited.

[0260] The lactone structure of Lc1 may contain a substituent. The substituent that the lactone structure of Lc1 may contain includes, for example, the substituent that is the same as the substituent of the lactone structure (Rb 2 ) the same substituents.

[0261] Examples of the lactone structure included in Lc2 include the same structures as those exemplified for the lactone structure included in Lc1.

[0262] 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.

[0263] [Chemical formula 19]

[0264]

[0265] In formula L-4, Ra has the same meaning as Ra in the above formula L-1, Mf1 and Mf2 each independently represent a single bond or a connecting group, Rf1, Rf2 and Rf3 each independently represent a hydrogen atom or an alkyl group, Mf1 and Rf1 can be bonded to each other to form a ring, and Mf2 and Rf2 or Rf3 can be bonded to each other to form a ring.

[0266] The meaning of the connecting group of Mf1 is the same as the connecting group of M1 in the above formula L-3.

[0267] The meaning of the connecting group of Mf2 is the same as the connecting group of M2 in the above formula L-3.

[0268] The alkyl group of Rf1 may be, for example, an alkyl group having 1 to 4 carbon atoms. The alkyl group having 1 to 4 carbon atoms of Rf1 is preferably a methyl group or an ethyl group, more preferably a methyl group. The alkyl group of Rf1 may have a substituent. The substituent that the alkyl group of Rf1 may have may be, for example, a hydroxyl group, an alkoxy group such as a methoxy group and an ethoxy group, a cyano group, a halogen atom such as a fluorine atom.

[0269] The alkyl groups of Rf2 and Rf3 have the same meaning as the alkyl group of Rf1.

[0270] 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 structure represented by LC1-13, LC1-14 or LC1-17 among the above lactone structures.

[0271] Mf2 and Rf2 or Rf3 may be bonded to each other to form a ring.

[0272] Examples of the structure in which Mf2 and Rf2 are bonded to each other to form a ring include the lactone structure represented by LC1-7, LC1-8 or LC1-15 among the above lactone structures.

[0273] Examples of the structure in which Mf2 and Rf3 are bonded to each other to form a ring include the lactone structure represented by any one of LC1-3 to LC1-6 among the above lactone structures.

[0274] Specific examples of the structural unit (a2) are shown below, but the present invention is not limited thereto. * indicates a bonding position to other structural units.

[0275] [Chemical formula 20]

[0276]

[0277] The structural unit having at least two lactone structures usually has optical isomers, but any optical isomers can be used. In addition, one optical isomer can be used alone, or a plurality of optical isomers can be used in combination. When one optical isomer is mainly used, its optical purity (ee) is preferably 90% or more, more preferably 95% or more.

[0278] The content of the structural unit having at least two lactone structures is preferably 10 to 60 mol %, more preferably 20 to 50 mol %, and further preferably 30 to 50 mol % relative to all structural units in the resin (A).

[0279] In order to improve the effect of the present invention, two or more structural units having at least two lactone structures may be used in combination. When two or more repeating units having at least two lactone structures are contained, the total content of the structural units having at least two lactone structures is preferably within the above range.

[0280] The resin (A) may contain one kind of structural unit having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure alone, or may contain two or more kinds of such structural units in combination.

[0281] The content of the structural unit having at least one selected from the group consisting of a lactone structure, a sultone structure and a carbonate structure contained in the resin (A) is preferably 5 mol% to 70 mol%, more preferably 10 mol% to 65 mol%, and further preferably 20 mol% to 60 mol%, relative to all the structural units in the resin (A) (when there are a plurality of structural units having at least one selected from the group consisting of a lactone structure, a sultone structure and a carbonate structure, the total amount thereof).

[0282] [Structural unit with polar group]

[0283] The resin (A) preferably contains a structural unit having a polar group.

[0284] Examples of the polar group include a hydroxyl group, a cyano group, and a carboxyl group.

[0285] The structural unit having a polar group is preferably a structural unit having an alicyclic hydrocarbon structure substituted with a polar group. Furthermore, the structural unit having a polar group preferably does not have an acid-decomposable group. The alicyclic hydrocarbon structure in the alicyclic hydrocarbon structure substituted with a polar group is preferably adamantyl or norbornyl.

[0286] 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, although the following specific examples are described as methacrylate compounds, they may also be acrylate compounds.

[0287] [Chemical formula 21]

[0288]

[0289] Specific examples of the structural unit having a polar group include the structural units disclosed in paragraphs 0415 to 0433 of US Patent Application Publication No. 2016 / 0070167.

[0290] The resin (A) may contain one kind of the structural unit having a polar group alone, or may contain two or more kinds of the structural units in combination.

[0291] The content of the structural unit having a polar group is preferably 5 to 40 mol %, more preferably 5 to 30 mol %, and further preferably 10 to 25 mol %, based on all repeating units in the resin (A).

[0292] [Structural unit having neither an acid-decomposable group nor a polar group]

[0293] The resin (A) may also 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. As a structural unit having neither an acid-decomposable group nor a polar group, for example, the structural units described in paragraphs 0236 to 0237 in the specification of U.S. Patent Application Publication No. 2016 / 0026083 can be cited. Preferred examples of monomers corresponding to structural units having neither an acid-decomposable group nor a polar group are shown below.

[0294] [Chemical formula 22]

[0295]

[0296] Specific examples of the structural unit having neither an acid-decomposable group nor a polar group include the structural unit disclosed in paragraph 0433 of US Patent Application Publication No. 2016 / 0070167.

[0297] The resin (A) may contain one kind of the structural unit having neither an acid-decomposable group nor a polar group alone, or may contain two or more kinds of such structural units in combination.

[0298] The content of the structural unit having neither an acid-decomposable group nor a polar group is preferably 5 to 40 mol %, more preferably 5 to 30 mol %, and further preferably 5 to 25 mol % based on all structural units in the resin (A).

[0299] [Repeating unit (a1)]

[0300] The resin (A) may further have the following repeating unit (a1).

[0301] The repeating unit (a1) is a repeating unit derived from a monomer having a glass transition temperature of 50° C. or lower when forming a homopolymer (also referred to as “monomer a1”).

[0302] Furthermore, the repeating unit (a1) is a non-acid-decomposable repeating unit. Therefore, the repeating unit (a1) does not have an acid-decomposable group.

[0303] (Method for measuring glass transition temperature of homopolymer)

[0304] For the glass transition temperature of the homopolymer, the catalog value or literature value was used when there was one, and when there was none, it was measured by differential scanning calorimetry (DSC). The weight average molecular weight (Mw) of the homopolymer used for Tg measurement was set to 18,000, and the dispersion (Mw / Mn) was set to 1.7. As a DSC device, a thermal analysis DSC differential scanning calorimeter Q1000 manufactured by TA Instruments was used, and the measurement was performed at a heating rate of 10°C / min.

[0305] The homopolymer used for Tg measurement may be synthesized by a known method using a corresponding monomer, and may be synthesized by, for example, a common dropping polymerization method, etc. An example is shown below.

[0306] 54 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) were heated to 80°C under a nitrogen stream. While stirring the solution, 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 a period of 6 hours. After the addition was completed, it was further stirred at 80°C for 2 hours. After the reaction solution was naturally cooled, it was reprecipitated and filtered with a large amount of methanol / water (mass ratio 9:1), and the obtained solid was dried to obtain a homopolymer (Mw: 18000, Mw / Mn: 1.7). The obtained homopolymer was used for DSC measurement. The DSC device and the heating rate are set as described above.

[0307] For monomer a1, there is no particular limitation as long as the glass transition temperature (Tg) when it is made into a homopolymer is 50°C or less. From the viewpoint of improving the resolution of the dot pattern and suppressing the roughness of the side wall of the resist pattern that may be generated during etching, the Tg when it is made into a homopolymer is preferably 30°C or less. The lower limit of Tg when monomer a1 is made into a homopolymer is not particularly limited, but is preferably -80°C or more, more preferably -70°C or more, further preferably -60°C or more, and particularly preferably -50°C or more. By setting the lower limit of Tg when monomer a1 is made into a homopolymer within the above range, the fluidity of the pattern during heating can be suppressed, and the verticality of the dot pattern can be further improved, so it is preferred.

[0308] From the viewpoint of easier volatilization of the residual solvent, the repeating unit (a1) is preferably a repeating unit which may contain a heteroatom in the chain and has a non-acid-decomposable alkyl group having 2 or more carbon atoms. In the present specification, "non-acid-decomposable" means having a property of not undergoing a release / decomposition reaction by an acid generated by a photoacid generator.

[0309] More specifically, the “non-acid-decomposable alkyl group” includes 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.

[0310] The non-acid-decomposable alkyl group may be either linear or branched.

[0311] Hereinafter, the repeating unit which may contain a heteroatom in the chain and has a non-acid-decomposable alkyl group having 2 or more carbon atoms will be described.

[0312] The non-acid-decomposable alkyl group having 2 or more carbon atoms and which may contain a heteroatom in the chain is not particularly limited, and examples thereof include alkyl groups having 2 to 20 carbon atoms and alkyl groups having 2 to 20 carbon atoms and containing a heteroatom in the chain.

[0313] Examples of alkyl groups having 2 to 20 carbon atoms and containing heteroatoms in the chain include alkyl groups in which one or more -CH2- groups are substituted with -O-, -S-, -CO-, -NR6-, or a divalent organic group obtained by combining two or more of these groups. The above R6 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0314] Specifically, as the non-acid-decomposable alkyl group which may contain a heteroatom in the chain and has 2 or more carbon atoms, there can be mentioned methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, lauryl, stearyl, isobutyl, sec-butyl, 1-ethylpentyl, 2-ethylhexyl and monovalent alkyl groups in which one or more -CH2- of these groups are substituted by -O- or -O-CO-.

[0315] The number of carbon atoms of the non-acid-decomposable alkyl group having 2 or more carbon atoms and which may contain a heteroatom in the chain is preferably 2 or more and 16 or less, more preferably 2 or more and 10 or less, and even more preferably 2 or more and 8 or less. The lower limit of the number of carbon atoms of the non-acid-decomposable alkyl group having 2 or more carbon atoms is preferably 4 or more.

[0316] Furthermore, the non-acid-decomposable alkyl group having 2 or more carbon atoms may have a substituent (eg, substituent T).

[0317] The repeating unit (a1) is preferably a repeating unit represented by the following general formula (1-2).

[0318] [Chemical formula 23]

[0319]

[0320] 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 and which may contain a heteroatom in the chain.

[0321] The halogen atom represented by R1 is not particularly limited, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0322] The alkyl group represented by R1 is not particularly limited, and examples thereof include alkyl groups having 1 to 10 carbon atoms, and specific examples thereof include methyl, ethyl, and tert-butyl groups, among which alkyl groups having 1 to 3 carbon atoms are preferred, and methyl groups are more preferred.

[0323] The cycloalkyl group represented by R1 is not particularly limited, and examples thereof include cycloalkyl groups having 5 to 10 carbon atoms, and more specifically, cyclohexyl groups and the like.

[0324] Among them, R1 is preferably a hydrogen atom or a methyl group.

[0325] The definition and preferred embodiment of the non-acid-decomposable alkyl group having 2 or more carbon atoms and optionally containing a heteroatom in the chain represented by R2 are as described above.

[0326] Furthermore, from the viewpoint of more easily volatilizing the residual solvent, the repeating unit (a1) may be a repeating unit containing a non-acid-decomposable alkyl group which may contain a heteroatom in the chain and has a carboxyl group or a hydroxyl group, or a non-acid-decomposable cycloalkyl group which may contain a heteroatom in the ring and has a carboxyl group or a hydroxyl group.

[0327] Hereinafter, a repeating unit including a non-acid-decomposable alkyl group which may contain a heteroatom in the chain and has a carboxyl group or a hydroxyl group, or a non-acid-decomposable cycloalkyl group which may contain a heteroatom in the ring and has a carboxyl group or a hydroxyl group will be described.

[0328] The non-acid-decomposable alkyl group may be either linear or branched.

[0329] The number of carbon atoms of the non-acid-decomposable alkyl group is preferably 2 or more, and the upper limit of the number of carbon atoms of the non-acid-decomposable alkyl group is preferably, for example, 20 or less from the viewpoint of making the Tg of the homopolymer 50° C. or less.

[0330] 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 containing a heteroatom in the chain. In addition, at least one of the hydrogen atoms in the alkyl group is substituted with a carboxyl group or a hydroxyl group.

[0331] Examples of alkyl groups having 2 to 20 carbon atoms and containing heteroatoms in the chain include alkyl groups in which one or more -CH2- groups are substituted with -O-, -S-, -CO-, -NR6-, or a divalent organic group obtained by combining two or more of these groups. The above R6 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0332] The number of carbon atoms of 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 from the viewpoint of better crack resistance (less prone to cracking).

[0333] Furthermore, the non-acid-decomposable alkyl group may have a substituent (eg, substituent T).

[0334] Specific examples of the repeating unit containing a non-acid-decomposable alkyl group having a carboxyl group and a heteroatom in the chain include repeating units having the following structures.

[0335] [Chemical formula 24]

[0336]

[0337] The number of carbon atoms of the non-acid-decomposable cycloalkyl group is preferably 5 or more. From the viewpoint of setting the Tg of the homopolymer to 50° C. or less, the upper limit of the number of carbon atoms of 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.

[0338] The non-acid-decomposable cycloalkyl group which may contain a hetero atom on 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 hetero atom on the ring. In addition, at least one of the hydrogen atoms in the cycloalkyl group is substituted with a carboxyl group or a hydroxyl group.

[0339] Examples of cycloalkyl groups having 5 to 20 carbon atoms and containing heteroatoms on the ring include alkyl groups in which one or more -CH2- groups are substituted with -O-, -S-, -CO-, -NR6-, or a divalent organic group obtained by combining two or more of these groups. The above R6 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0340] Furthermore, the non-acid-decomposable cycloalkyl group may have a substituent (eg, substituent T).

[0341] As a repeating unit containing a non-acid-decomposable alkyl group which may contain a heteroatom in the chain and has a carboxyl group or a hydroxyl group, or a non-acid-decomposable cycloalkyl group which may contain a heteroatom in the ring and has a carboxyl group or a hydroxyl group, a repeating unit represented by the following general formula (1-3) is preferred from the viewpoint of further improving the effect of the present invention.

[0342] [Chemical formula 25]

[0343]

[0344] 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 which may contain a heteroatom in the chain and has a carboxyl group or a hydroxyl group, or a non-acid decomposable cycloalkyl group which may contain a heteroatom in the ring and has a carboxyl group or a hydroxyl group.

[0345] In the general formula (1-3), R3 has the same meaning as R1 above, and preferred aspects are also the same.

[0346] The definition and preferred embodiment of the non-acid-decomposable alkyl group which may contain a heteroatom in the chain and has a carboxyl group or a hydroxyl group, or the non-acid-decomposable cycloalkyl group which may contain a heteroatom in the ring and has a carboxyl group or a hydroxyl group represented by R4 are as described above.

[0347] Among them, R4 is preferably a non-acid decomposable cycloalkyl group which may contain a heteroatom on the ring and has a carboxyl group or a hydroxyl group. As this embodiment, for example, a repeating unit of the following structure can be mentioned.

[0348] [Chemical formula 26]

[0349]

[0350] Examples of the 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), and hexadecyl acrylate (35°C). The term in parentheses indicates Tg (°C) when the homopolymer is prepared.

[0351] Methoxypolyethylene glycol monomethacrylate (n=2) is a compound having the following structure.

[0352] [Chemical formula 27]

[0353]

[0354] 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, and a compound represented by the following MA-5.

[0355] [Chemical formula 28]

[0356]

[0357] The resin (A) may contain only one type of repeating unit (a1), or may contain two or more types of the repeating unit (a1).

[0358] In resin (A), the content of repeating unit (a1) relative to all repeating units in resin (A) (when there are multiple repeating units (a1), the total amount 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 further preferably 30 mol% or less. Among them, the content of repeating unit (a1) in resin (A) relative to all repeating units in resin (A) (when there are multiple repeating units (a1), the total amount thereof) is preferably 5 to 50 mol%, more preferably 5 to 40 mol%, and further preferably 5 to 30 mol%.

[0359] [Repeating unit (a4) having a phenolic hydroxyl group]

[0360] The resin (A) may contain a repeating unit (a4) having a phenolic hydroxyl group.

[0361] The resin (A) contains the repeating unit (a4), so that the dissolution rate during alkaline development is further improved and the etching resistance is excellent.

[0362] The repeating unit having a phenolic hydroxyl group is not particularly limited, and examples thereof include a hydroxystyrene repeating unit and a hydroxystyrene (meth)acrylate repeating unit. The repeating unit having a phenolic hydroxyl group is preferably a repeating unit represented by the following general formula (I).

[0363] [Chemical formula 29]

[0364]

[0365] In the formula,

[0366] 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 It can bond with Ar4 to form a ring. In this case, R 42 represents a single bond or an alkylene group.

[0367] X4 represents a single bond, -COO- or -CONR 64 -, R 64 represents a hydrogen atom or an alkyl group.

[0368] L4 represents a single bond or a divalent linking group.

[0369] Ar4 represents an (n+1)-valent aromatic hydrocarbon group. 42 When they are bonded to form a ring, they represent an aromatic hydrocarbon group having a valence of (n+2).

[0370] n represents an integer of 1-5.

[0371] In order to make the repeating unit represented by the general formula (I) highly polar, it is also preferred that n is an integer of 2 or more or X4 is -COO- or -CONR 64 -.

[0372] In the general formula (I), R 41 , R 42 and R 43 The alkyl group represented by is preferably an alkyl group having 20 or less carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, hexyl, 2-ethylhexyl, octyl and dodecyl, which may have a substituent, more preferably an alkyl group having 8 or less carbon atoms, and further preferably an alkyl group having 3 or less carbon atoms.

[0373] In the general formula (I), R 41 , R 42 and R 43 The cycloalkyl group represented by may be a monocyclic or polycyclic group, and among them, preferably a monocyclic cycloalkyl group having 3 to 8 carbon atoms, such as an optionally substituted group, a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group, is preferred.

[0374] In the general formula (I), R 41 , R 42 , and R 43 Examples of the halogen atom represented by include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferred.

[0375] In the general formula (I), R 41 , R 42 and R 43 The alkyl group contained in the alkoxycarbonyl group represented by is preferably the same as the above R 41 , R 42 and R 43 The alkyl group in is the same as the alkyl group.

[0376] Preferred substituents in the above-mentioned groups include, for example, alkyl groups, cycloalkyl groups, aryl groups, amino groups, amide groups, urea groups, carbamate groups, hydroxyl groups, carboxyl groups, halogen atoms, alkoxy groups, thioether groups, acyl groups, acyloxy groups, alkoxycarbonyl groups, cyano groups and nitro groups, and preferably the substituents have 8 or less carbon atoms.

[0377] Ar4 represents an (n+1)-valent aromatic hydrocarbon group. The divalent aromatic hydrocarbon group in the case where n is 1 may have a substituent, and is preferably an arylene group having 6 to 18 carbon atoms such as phenylene, tolylene, naphthylene and anthracene, or an aromatic hydrocarbon group containing a heterocycle such as thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole and thiazole.

[0378] Specific examples of the (n+1)-valent aromatic hydrocarbon group when n is an integer of 2 or more include preferably groups obtained by removing (n-1) arbitrary hydrogen atoms from the above-mentioned specific examples of the divalent aromatic hydrocarbon group.

[0379] The (n+1)-valent aromatic hydrocarbon group may further have a substituent.

[0380] Examples of the substituents that the alkyl group, cycloalkyl group, alkoxycarbonyl group and (n+1)-valent aromatic hydrocarbon group may have include R 41 , R 42 and R 43alkyl groups such as methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy and butoxy; aryl groups such as phenyl; and the like.

[0381] As -CONR represented by X4 64 -(R 64 represents a hydrogen atom or an alkyl group) 64 The alkyl group is preferably an alkyl group having 20 or less carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, hexyl, 2-ethylhexyl, octyl and dodecyl which may have a substituent, and more preferably an alkyl group having 8 or less carbon atoms.

[0382] X4 is preferably a single bond, -COO- or -CONH-, and more preferably a single bond or -COO-.

[0383] The divalent linking group of L4 is preferably an alkylene group, and the alkylene group is preferably an alkylene group having 1 to 8 carbon atoms such as methylene, ethylene, propylene, butylene, hexylene and octylene which may have a substituent.

[0384] 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. Among them, the repeating unit represented by the general formula (I) is preferably a repeating unit derived from hydroxystyrene. That is, Ar4 is preferably a benzene ring group.

[0385] Specific examples of the repeating unit having a phenolic hydroxyl group are shown below, but the present invention is not limited thereto.

[0386] [Chemical formula 30]

[0387]

[0388] The resin (A) may have one type of repeating unit (a4) alone, or may have two or more types of the repeating units (a4) in combination.

[0389] In the resin (A), the content of the repeating unit (a4) is preferably 40 mol% or more, more preferably 50 mol% or more, and further preferably 60 mol% or more relative to all the repeating units in the resin (A). Furthermore, the content of the repeating unit (a4) is preferably 85 mol% or less, and more preferably 80 mol% or less relative to all the repeating units in the resin (A).

[0390] In addition to the above-mentioned structural units, the resin (A) may have various structural units for the purpose of adjusting dry etching resistance, standard developer adaptability, substrate adhesion, resist profile, and further adjusting resolution, heat resistance, sensitivity, etc., which are generally necessary characteristics of resists. As such structural units, structural units corresponding to other monomers may be cited, but are not limited to these.

[0391] Examples of other monomers include compounds having one addition-polymerizable unsaturated bond selected from acrylates, methacrylates, acrylamides, methacrylamides, allyl compounds, vinyl ethers, and vinyl esters.

[0392] Furthermore, any addition-polymerizable unsaturated compound that is copolymerizable with the monomers corresponding to the above-mentioned various structural units may be copolymerized.

[0393] In the resin (A), the molar ratio of each structural unit is appropriately set in order to adjust various properties.

[0394] When the photosensitive ray or radiation-sensitive resin composition of the present invention is for argon fluoride (ArF) laser exposure, it is preferred that the resin (A) substantially does not have an aromatic group from the viewpoint of the transmittance of ArF light. More specifically, among all the structural units in the resin (A), the structural units having an aromatic group preferably account for less than 5 mol% of the total, more preferably less than 3 mol%, and ideally 0 mol%, that is, it is further preferred that the structural units having an aromatic group are not included. In addition, the resin (A) preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure.

[0395] It is preferred that all structural units of the resin (A) are composed of (meth)acrylate structural units. In this case, any one of the following structural units can be used, i.e., a structural unit in which all structural units are methacrylate structural units, a structural unit in which all structural units are acrylate structural units, and a structural unit in which all structural units are composed of methacrylate structural units and acrylate structural units, but the acrylate structural units are preferably 50 mol% or less relative to all structural units in the resin (A).

[0396] When the actinic ray-sensitive or radiation-sensitive resin composition of 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. The resin (A) more preferably contains a structural unit having a phenolic hydroxyl group.

[0397] As a structural unit which has a phenolic hydroxyl group, the said repeating unit (a4) is mentioned, for example.

[0398] When the actinic ray-sensitive or radiation-sensitive resin composition of 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 the phenolic hydroxyl group is protected by a group (leaving group) that is decomposed and released by the action of an acid.

[0399] The content of the structural unit having an aromatic hydrocarbon group in the resin (A) is preferably 30 mol% to 100 mol%, more preferably 40 mol% to 100 mol%, and further preferably 50 mol% to 100 mol%, relative to all repeating units in the resin (A).

[0400] The weight average molecular weight of the resin (A) is preferably 1,000 to 200,000, more preferably 2,000 to 20,000, further preferably 3,000 to 15,000, particularly preferably 3,000 to 11,000.

[0401] The dispersion degree (Mw / Mn) is preferably 1.0 to 3.0, more preferably 1.0 to 2.6, further preferably 1.0 to 2.0, and particularly preferably 1.1 to 2.0.

[0402] Specific examples of the resin (A) include resins A-1 to A-17 used in Examples, but are not limited thereto.

[0403] The resin (A) may be used alone or in combination of two or more.

[0404] The content of the resin (A) is preferably 20% by mass or more, more preferably 40% by mass or more, further preferably 60% by mass or more, and particularly preferably 80% by mass or more, relative to the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition of 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 further preferably 97% by mass or less.

[0405] [Alkali-soluble resin having phenolic hydroxyl groups]

[0406] When the actinic ray-sensitive or radiation-sensitive resin composition of the present invention contains the crosslinking agent (G) described below, the actinic ray-sensitive or radiation-sensitive resin composition of 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 contains a structural unit having a phenolic hydroxyl group.

[0407] At this time, typically, it is preferred to form a negative pattern.

[0408] The crosslinking agent (G) may be in a form supported on the resin (C).

[0409] In addition, among the resins (C), the resins whose polarity increases by the action of an acid are treated as the resins whose polarity increases by the action of an acid. In this case, the actinic ray-sensitive or radiation-sensitive resin composition of the present invention may contain the resin whose polarity increases by the action of an acid as the resin (C), and may also 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.

[0410] The resin (C) may contain the above-mentioned acid-decomposable group.

[0411] The structural unit having a phenolic hydroxyl group of the resin (C) is not particularly limited, but is preferably the above-mentioned repeating unit (a4).

[0412] The resin (C) may be used alone or in combination of two or more.

[0413] The content of the resin (C) in the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is preferably 30% by mass or more, more preferably 40% by mass or more, and further preferably 50% by mass or more. The upper limit is not particularly limited, but is preferably 99% by mass or less, more preferably 90% by mass or less, and further preferably 85% by mass or less.

[0414] As the resin (C), the resins disclosed in paragraphs 0142 to 0347 of US Patent Application Publication No. 2016 / 0282720 can be preferably used.

[0415] 〔Hydrophobic resin〕

[0416] The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention preferably further contains a hydrophobic resin (also referred to as a hydrophobic resin (E)).

[0417] 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 is increased by the action of an acid and a resin whose polarity is increased by the action of an acid.

[0418] The actinic ray-sensitive or radiation-sensitive resin composition of the present invention contains a hydrophobic resin (E), so that the static / dynamic contact angle of the actinic ray-sensitive or radiation-sensitive film surface can be controlled, thereby improving the developing characteristics, suppressing degassing, improving the immersion liquid followability in immersion exposure, and reducing immersion defects.

[0419] The hydrophobic resin is preferably designed to be localized on the surface of the resist film, but unlike the surfactant, it is not necessarily required to have a hydrophilic group in the molecule and may not contribute to uniform mixing of polar substances and non-polar substances.

[0420] In the present invention, the resin having fluorine atoms is treated as a hydrophobic resin and a fluorine-containing resin described below. In addition, the resin containing a structural unit having an acid-decomposable group preferably does not have fluorine atoms.

[0421] From the viewpoint of being preferentially applied to the film 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 of the resin.

[0422] When the hydrophobic resin (E) contains fluorine atoms or silicon atoms, the fluorine atoms or silicon atoms in the hydrophobic resin (E) may be contained in the main chain of the resin or in the side chain.

[0423] The hydrophobic resin (E) preferably has at least one group selected from the following group (x) to (z).

[0424] (x) Acid group

[0425] (y) A group that is decomposed by the action of an alkaline developer and has increased solubility in the alkaline developer (hereinafter also referred to as a polarity conversion group).

[0426] (z) Groups that decompose by the action of an acid

[0427] 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 sulfonimide 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.

[0428] The acid group is preferably a fluorinated alcohol group (preferably a hexafluoroisopropanol group), a sulfonimide group or a bis(alkylcarbonyl)methylene group.

[0429] Examples of the group (y) that is decomposed by the action of an alkaline developer and has increased solubility in the alkaline developer include a lactone group, a carboxylate group (-COO-), an anhydride group (-C(O)OC(O)-), an acid imide group (-NHCONH-), a carboxylic acid thioester group (-COS-), a carbonate group (-OC(O)O-), a sulfate group (-OSO2O-) and a sulfonate group (-SO2O-), preferably a lactone group or a carboxylate group (-COO-).

[0430] 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 formed from acrylate and methacrylate. The structural unit can be bonded to the main chain of the resin via a connecting group from these groups. Alternatively, the structural unit can also be used when polymerizing a polymerization initiator or chain transfer agent having these groups, and introduced to the end of the resin.

[0431] Examples of the structural unit having a lactone group include the same structural units as those described above in the section of the resin (A) and having a lactone structure.

[0432] Based on all the structural units in the hydrophobic resin (E), the content of the structural unit having a group (y) that is decomposed by the action of an alkaline developer and has increased solubility in an alkaline developer is preferably 1 to 100 mol %, more preferably 3 to 98 mol %, and further preferably 5 to 95 mol %.

[0433] The structural unit having a group (z) decomposed by the action of an acid in the hydrophobic resin (E) may include the same structural units as the structural units 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 relative to all structural units in the resin (E) is preferably 1 mol% to 80 mol%, more preferably 10 mol% to 80 mol%, and further preferably 20 mol% to 60 mol%.

[0434] The hydrophobic resin (E) may have a structural unit different from the above-mentioned structural units.

[0435] The content of the structural unit containing a fluorine atom is preferably 10 mol% to 100 mol%, more preferably 30 mol% to 100 mol%, relative to all the structural units contained in the hydrophobic resin (E). Furthermore, the content of the structural unit containing a silicon atom is preferably 10 mol% to 100 mol%, more preferably 20 mol% to 100 mol%, relative to all the structural units contained in the hydrophobic resin (E).

[0436] On the other hand, particularly when the hydrophobic resin (E) contains a CH3 partial structure in the side chain portion, it is also preferred that the hydrophobic resin (E) substantially does not contain fluorine atoms and silicon atoms. In addition, the hydrophobic resin (E) is preferably substantially composed of the following structural units, which are composed of atoms selected from carbon atoms, oxygen atoms, hydrogen atoms, nitrogen atoms and sulfur atoms.

[0437] The weight average molecular weight of the hydrophobic resin (E) in terms of standard polystyrene is preferably from 1,000 to 100,000, more preferably from 1,000 to 50,000.

[0438] The total content of residual monomers and oligomer components contained in the hydrophobic resin (E) is preferably 0.01 to 5% by mass, more preferably 0.01 to 3% by mass. The dispersion degree (Mw / Mn) is preferably in the range of 1 to 5, more preferably 1 to 3.

[0439] As hydrophobic resin (E), known resins can be appropriately selected as single or mixtures thereof. For example, known resins disclosed in paragraphs 0451 to 0704 in U.S. Patent Application Publication No. 2015 / 0168830 and paragraphs 0340 to 0356 in U.S. Patent Application Publication No. 2016 / 0274458 can be preferably used as hydrophobic resin (E). In addition, the structural units disclosed in paragraphs 0177 to 0258 in U.S. Patent Application Publication No. 2016 / 0237190 are also preferably used as structural units constituting hydrophobic resin (E).

[0440] -Fluorine-containing resin-

[0441] The hydrophobic resin (E) is preferably a resin containing fluorine atoms (also referred to as a fluorine-containing resin).

[0442] When the hydrophobic resin (E) contains a fluorine atom, the partial structure having a fluorine atom is preferably a resin containing an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom.

[0443] 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.

[0444] 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.

[0445] Examples of the aryl group having a fluorine atom include groups in which at least one hydrogen atom in an aryl group such as a phenyl group and a naphthyl group is substituted with a fluorine atom.

[0446] 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 formulae F2 to F4 are preferred.

[0447] [Chemical formula 31]

[0448]

[0449] In formulas F2 to F4,

[0450] R 57 ~R 68 Each independently represents a hydrogen atom, a fluorine atom or an alkyl group (straight chain or branched chain). 57 ~R 61 At least one of R 62 ~R 64 At least one of R 65 ~R 68 At least one of them independently represents a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted by a fluorine atom.

[0451] Preferred R 57 ~R 61 and R 65 ~R 67 are all fluorine atoms. 62 , R 63 and R 68 It is preferably an alkyl group (preferably having 1 to 4 carbon atoms) in which at least one hydrogen atom is substituted by a fluorine atom, and more preferably a perfluoroalkyl group having 1 to 4 carbon atoms. 62 With R 63 Can be connected to each other to form a ring.

[0452] Among them, from the viewpoint of achieving more excellent effects of the present invention, the fluorine-containing resin preferably has alkali decomposability.

[0453] The fact that the fluorine-containing resin is alkaline decomposable means that, when 100 mg of the fluorine-containing resin is added to a mixed solution of 2 mL of a pH 10 buffer solution and 8 mL of THF and allowed to stand at 40°C for 10 minutes, 30 mol% or more of the total amount of decomposable groups in the fluorine-containing resin is hydrolyzed. In addition, the decomposition rate can be calculated from the ratio of the raw material to the decomposition product based on NMR analysis.

[0454] The fluorine-containing resin preferably has a structural unit represented by Formula X from the viewpoints of focus depth tolerance, pattern linearity, improvement of development characteristics, suppression of degassing, improvement of immersion liquid followability in immersion exposure, and reduction of immersion defects.

[0455] Furthermore, from the viewpoints of focal depth tolerance, pattern linearity, improvement of development characteristics, suppression of degassing, improvement of immersion liquid followability in immersion exposure, and reduction of immersion defects, the actinic ray-sensitive or radiation-sensitive resin composition of the present invention preferably further contains a fluorine-containing resin having a structural unit represented by formula X.

[0456] [Chemical formula 32]

[0457]

[0458] In formula X, Z represents a halogen atom, R 11 The group represented by OCH2- or R12 OC(=O)CH2- represented group, R 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 and thus increases the solubility of the fluorine-containing resin in the alkaline aqueous solution, wherein n represents a positive integer, and when n is 2 or more, a plurality of R 10 They can be the same as each other or different.

[0459] 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 preferred.

[0460] As R 11 and R 12 Examples of the substituents of include alkyl groups (preferably having 1 to 4 carbon atoms), cycloalkyl groups (preferably having 6 to 10 carbon atoms), and aryl groups (preferably having 6 to 10 carbon atoms). 11 and R 12 The substituent may further have a substituent, and examples of such a further substituent include 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 carboxyl group.

[0461] The linking group of 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 of L is preferably a linking group selected from the group consisting of an aliphatic group, an aromatic group, and a combination thereof.

[0462] For example, when n is 1 and the linking group of L is a divalent linking group, examples of the divalent aliphatic group include an alkylene group, an alkenylene group, an alkynylene group, or a polyalkyleneoxy group. Among them, an alkylene group or an alkenylene group is preferred, and an alkylene group is more preferred.

[0463] The divalent aliphatic group may be a chain structure or a cyclic structure, but a chain structure is preferred to a cyclic structure, and a straight-chain structure is preferred to 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.

[0464] Examples of the divalent aromatic group include an arylene group, among which a phenylene group and a naphthylene group are preferred.

[0465] The divalent aromatic group may have a substituent, and examples of the substituent in the above-mentioned divalent aliphatic group include an alkyl group.

[0466] Furthermore, L may be a divalent group obtained by removing two hydrogen atoms at arbitrary positions from the structure represented by the above-mentioned Formula LC1-1 to Formula LC1-21 or Formula SL1-1 to Formula SL-3.

[0467] When n is 2 or more, specific examples of the (n+1)-valent linking group include groups obtained by removing arbitrary (n-1) hydrogen atoms from the specific examples of the above-mentioned divalent linking groups.

[0468] Specific examples of L include the following linking groups.

[0469] [Chemical formula 33]

[0470] -CH2- -CH2CH2- -CH2CH2CH2- -CH2CH2CH2CH2-

[0471] -CH2CH2CH2CH2CH2- -CH2CH2CH2CH2CH2CH2-

[0472]

[0473] In addition, as described above, these linking groups may further have a substituent.

[0474] As R 10 , preferably a group represented by the following formula W.

[0475] -YR 20 Formula W

[0476] In the above formula W, Y represents a group which is decomposed by the action of an aqueous alkali solution and has increased solubility in an aqueous alkali solution. 20 Represents an electron withdrawing group.

[0477] As Y, there can be mentioned a carboxylate group (-COO- or OCO-), an 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 (-SO2O-), preferably a carboxylate group.

[0478] The electron withdrawing group is preferably a partial structure represented by the following formula EW: * in the formula EW represents a bond directly connected to the group Y in the formula W.

[0479] [Chemical formula 34]

[0480]

[0481] In the formula EW,

[0482] n ew For -C(R ew1 )(R ew2 )- represents the number of repetitions of the linking group, which is an integer of 0 or 1. ew When it is 0, it means a single bond, indicating direct bonding with Y ew1 .

[0483] Y ew1 Examples include a halogen atom, a cyano group, a nitro group, and -C(R f1 )(R f2 )-R f3 alkyl, halogenated aryl, oxy, carbonyl, sulfonyl, sulfinyl and combinations thereof. ew1 When it is a halogen atom, cyano group or nitro group, n ew is 1. )

[0484] 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).

[0485] R ew1 , R ew 2 and Y ew1 At least two of them may be connected to each other to form a ring.

[0486] Furthermore, the term "halo(cyclo)alkyl" refers to an alkyl group or cycloalkyl group that is at least partially halogenated, and the term "halogenated aryl group" refers to an aryl group that is at least partially halogenated.

[0487] As Y ew1 , preferably a halogen atom, -C(R f1 )(R f2 )-R f3 Represents a halogen(cyclo)alkyl or halogenated aryl group.

[0488] R f1 represents a halogen atom, a perhalogenated alkyl group, a perhalogenated cycloalkyl group or a perhalogenated aryl group, preferably a fluorine atom, a perfluoroalkyl group or a perfluorocycloalkyl group, more preferably a fluorine atom or a trifluoromethyl group.

[0489] R f2 and R f3 Each independently represents a hydrogen atom, a halogen atom or an organic group, R f2 With R f3Examples 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). f2 and R f3 It is preferably (halo)alkyl or (halo)cycloalkyl. f2 Represents R f1 The same group or f3 Connect to form a ring.

[0490] As R f2 With R f3 Examples of the ring formed by connecting the two groups include a (halo)cycloalkyl ring.

[0491] As R f1 ~R f3 The (halo)alkyl group in the above may be either linear or branched. The linear (halo)alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms.

[0492] As R f1 ~R f3 In, or R f2 With R f3 The (halogen)cycloalkyl group in the ring formed by connecting may be a monocyclic type or a polycyclic type. When it is a polycyclic type, the (halogen)cycloalkyl group may be a bridged type. That is, in this case, the (halogen)cycloalkyl group may have a bridged structure.

[0493] Examples of these (halogen)cycloalkyl groups include groups represented by the following formulae and groups obtained by halogenation thereof: In addition, a part of carbon atoms in the cycloalkyl group may be substituted with heteroatoms such as oxygen atoms.

[0494] [Chemical formula 35]

[0495]

[0496] As R f2 and R f3 In, or R f2 With R f3 The (halogen) cycloalkyl group in the ring formed by connecting is preferably -C (n) F (2n-2) The fluorocycloalkyl group represented by H. The number of carbon atoms n is not particularly limited, but is preferably 5 to 13, and more preferably 6.

[0497] As Y ew1 In, or R f1 The (per)halogenated aryl group in the (n) F (n-1) Here, the number of carbon atoms n is not particularly limited, but is preferably 5 to 13, and more preferably 6.

[0498] As R ew1 , R ew 2 and Y ew1 At least two of them may be linked to each other to form a ring, which is preferably a cycloalkyl group or a heterocyclic group.

[0499] Each group and each ring constituting the partial structure represented by the above formula EW may further have a substituent.

[0500] In the above formula W, R 20 It 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 still 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, more preferably 1 to 5 carbon atoms.

[0501] More specifically, R 20 Preferably, -C(R' 1 )(R' f1 )(R' f2 ) or -C(R' 1 )(R' 2 )(R' f1 ) represents an atomic group. R' 1 and R' 2 Each independently represents a hydrogen atom or an alkyl group which is not substituted by 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.

[0502] As R' 1 and R' 2 The alkyl group may be linear or branched, and preferably has 1 to 6 carbon atoms.

[0503] As R' f1 and R' f2 The perfluoroalkyl group may be linear or branched, and preferably has 1 to 6 carbon atoms.

[0504] As R 20 Preferred specific examples include -CF3, -C2F5, -C3F7, -C4F9, -CF(CF3)2, -CF(CF3)C2F5, -CF2CF(CF3)2, -C(CF3)3, -C5F 11 、-C6F 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 are preferred, -CH2CF3, -CH2C2F5, -CH2C3F7, -CH(CF3)2 or -CH2CN are more preferred, -CH2C2F5, -CH(CF3)2 or -CH2CN are further preferred, and -CH2C2F5, -CH(CF3)2 or -CH2CN are particularly preferred, and -CH2C2F5 or -CH(CF3)2 are particularly preferred.

[0505] As the structural unit represented by the formula X, a structural unit represented by the following formula X-1 or formula X-2 is preferred, and a structural unit represented by the formula X-1 is more preferred.

[0506] [Chemical formula 36]

[0507]

[0508] In formula X-1, R 20 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.

[0509] 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.

[0510] As L 2 and L 3 Specific examples and preferred examples of the divalent linking group are the same as those described in the above-mentioned L as the divalent linking group in the formula X.

[0511] As R 2 and R 3 The electron withdrawing group is preferably a partial structure represented by the above formula EW, and specific examples and preferred examples are as described above, and a halogen (cyclo)alkyl group is more preferred.

[0512] In the above formula X-1, L 2 With R 2 will not bond to each other to form a ring. In the above formula X-2, L 3 With R 3 They do not bond to each other to form a ring.

[0513] As X2 and X 3 , preferably an oxygen atom.

[0514] As Z 2 and Z 3 , preferably a fluorine atom or a chlorine atom, more preferably a fluorine atom.

[0515] Furthermore, as the structural unit represented by the formula X, a structural unit represented by the formula X-3 is also preferred.

[0516] [Chemical formula 37]

[0517]

[0518] 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.

[0519] As L 4 Specific examples and preferred examples of the divalent linking group are the same as those described with respect to L in formula X as the divalent linking group.

[0520] As R 4 The electron withdrawing group is preferably a partial structure represented by the above formula EW, and specific examples and preferred examples are as described above, and a halogen (cyclo)alkyl group is more preferred.

[0521] In the above formula X-3, L 4 With R 4 They do not bond to each other to form a ring.

[0522] As X 4 , preferably an oxygen atom.

[0523] Furthermore, as the structural unit represented by the formula X, a structural unit represented by the formula Y-1 or a structural unit represented by the formula Y-2 is also preferred.

[0524] [Chemical formula 38]

[0525]

[0526] In formula Y-1 and formula Y-2, Z represents a halogen atom, R 11 The group represented by OCH2- or R 12 OC(=O)CH2- represented group, R 11 and R 12 Each independently represents a substituent, R 20 Represents an electron withdrawing group.

[0527] As R 20 The electron withdrawing group is preferably a partial structure represented by the above formula EW, and specific examples and preferred examples are as described above, and a halogen (cyclo)alkyl group is more preferred.

[0528] As the halogen atom of Z, R 11 The group represented by OCH2- and the group represented by R 12 Specific examples and preferred examples of the group represented by OC(=O)CH2- are the same as those described in the above formula 1.

[0529] The content of the structural unit represented by the formula X is preferably 10 to 100 mol %, more preferably 20 to 100 mol %, further preferably 30 to 100 mol %, based on all structural units in the fluorine-containing resin.

[0530] Preferred examples of the structural unit constituting the hydrophobic resin (E) are shown below.

[0531] Preferred examples of the hydrophobic resin (E) include resins obtained by arbitrarily combining these structural units or resins F-1 and F-2 used in Examples, but the present invention is not limited thereto.

[0532] [Chemical formula 39]

[0533]

[0534] [Chemical formula 40]

[0535]

[0536] The hydrophobic resin (E) may be used alone or in combination of two or more.

[0537] From the viewpoint of achieving both immersion liquid followability and development characteristics in liquid immersion exposure, it is preferred to use a mixture of two or more hydrophobic resins (E) having different surface energies.

[0538] The content of the hydrophobic resin (E) in the composition is preferably 0.01 to 10% by mass, more preferably 0.05 to 8% by mass, based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition of the present invention.

[0539] <(B) Photoacid generator>

[0540] The composition according to the present invention contains a photoacid generator (hereinafter, also referred to as “photoacid generator (B)”).

[0541] The photoacid generator is a compound that generates an acid when irradiated with actinic rays or radiation.

[0542] The photoacid generator is preferably a compound that generates an organic acid by irradiation with actinic rays or radiation, for example, sulfonium salt compounds, iodonium salt compounds, diazonium salt compounds, phosphonium salt compounds, imide sulfonate compounds, oxime sulfonate compounds, diazodisulfone compounds, disulfone compounds and o-nitrobenzylsulfonate compounds.

[0543] 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, known compounds disclosed in paragraphs 0125 to 0319 in the specification of U.S. Patent Application Publication No. 2016 / 0070167, paragraphs 0086 to 0094 in the specification of U.S. Patent Application Publication No. 2015 / 0004544, and paragraphs 0323 to 0402 in the specification of U.S. Patent Application Publication No. 2016 / 0237190 can be preferably used as the photoacid generator (B).

[0544] [Compounds represented by formula ZI, ZII and ZIII]

[0545] As a preferable embodiment of the photoacid generator (B), compounds represented by the following formulae ZI, ZII and ZIII are mentioned, for example.

[0546] [Chemical formula 41]

[0547]

[0548] In the above formula ZI,

[0549] R 201 , R 202 and R 203 Each independently represents an organic group.

[0550] As R 201 , R 202 and R 203 The number of carbon atoms of the organic group is preferably 1-30, more preferably 1-20.

[0551] And, R 201 ~R 203 Two of them may be bonded to form a ring structure, and may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group in the ring. 201 ~R 203 The group formed by two bonds in the group may be an alkylene group (e.g., a butylene group and a pentylene group) and -CH2-CH2-O-CH2-CH2-.

[0552] Z - Represents an anion.

[0553] [Cation in the compound represented by the formula ZI]

[0554] Preferred embodiments of the cation in the formula ZI include corresponding groups in the compounds (ZI-1), (ZI-2), (ZI-3) and (ZI-4) described later.

[0555] In addition, the photoacid generator (C) may be a compound having a plurality of structures represented by the formula ZI. For example, R 201 ~R 203 At least one of the compounds is R of another compound represented by formula ZI 201 ~R 203 A compound having a structure in which at least one of the compounds is bonded by a single bond or a connecting group.

[0556] -Compound ZI-1-

[0557] First, compound (ZI-1) will be described.

[0558] Compound (ZI-1) is the above formula ZI wherein R 201 ~R 203 An arylsulfonium compound in which at least one of the groups is an aryl group, that is, a compound in which the arylsulfonium is used as a cation.

[0559] In the arylsulfonium compound, R 201 ~R 203 All are aromatic, and R 201 ~R 203 Part of them is aryl, and the rest is alkyl or cycloalkyl.

[0560] Examples of the arylsulfonium compound include triarylsulfonium compounds, diarylalkylsulfonium compounds, aryldialkylsulfonium compounds, diarylcycloalkylsulfonium compounds, and aryldicycloalkylsulfonium compounds.

[0561] 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 containing a heterocyclic structure having an oxygen atom, a nitrogen atom or a sulfur atom. As the heterocyclic structure, pyrrole residues, furan residues, thiophene residues, indole residues, benzofuran residues and benzothiophene residues may be cited. When the arylsulfonium compound has two or more aryl groups, the two or more aryl groups may be the same or different.

[0562] The alkyl group or cycloalkyl group which the arylsulfonium compound has as required 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 methyl, ethyl, propyl, n-butyl, sec-butyl, tert-butyl, cyclopropyl, cyclobutyl and cyclohexyl.

[0563] R 201 ~R 203 The aryl group, alkyl group and cycloalkyl group in the above-mentioned 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.

[0564] -Compound ZI-2-

[0565] Next, compound (ZI-2) is described.

[0566] Compound (ZI-2) is a compound of formula ZI wherein R 201 ~R 203 Each of the above is independently a compound of an organic group having no aromatic ring. Here, the aromatic ring also includes an aromatic ring containing a heteroatom.

[0567] As R 201 ~R 203 The organic group having no aromatic ring preferably has 1 to 30 carbon atoms, and more preferably has 1 to 20 carbon atoms.

[0568] R 201 ~R 203 Each independently is 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.

[0569] As R 201 ~R 203 The alkyl and cycloalkyl groups in the above-mentioned are preferably straight-chain alkyl groups having 1 to 10 carbon atoms or branched-chain alkyl groups having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl and pentyl), and cycloalkyl groups having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl and norbornyl).

[0570] R 201 ~R 203 It may be further substituted by a halogen atom, an alkoxy group (for example, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group or a nitro group.

[0571] -Compound ZI-3-

[0572] Next, compound (ZI-3) is described.

[0573] The compound (ZI-3) is a compound represented by the following formula ZI-3 and has a phenacylsulfonium salt structure.

[0574] [Chemical formula 42]

[0575]

[0576] In formula ZI-3, R 1c ~R 5c each 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, and 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, and 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.

[0577] R 1c ~R 5c Any two or more of R 5c With R 6c , R 6c With R 7c , R 5c With R x and R x With R y They may be bonded to form a ring structure, and the ring structure may independently contain an oxygen atom, a sulfur atom, a keto group, an ester bond, or an amide bond.

[0578] As the ring structure, there can be mentioned 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. As the ring structure, there can be mentioned 3-10-membered rings, preferably 4-8-membered rings, and more preferably 5-membered rings or 6-membered rings.

[0579] As R 1c ~R 5c Any two or more of R 6c With R 7c and R x With R y Examples of the group formed by bonding include butylene and pentylene.

[0580] As R 5c With R 6c and R 5c With R x The group formed by bonding is preferably a single bond or an alkylene group. Examples of the alkylene group include a methylene group and an ethylene group.

[0581] Zc - Represents an anion.

[0582] -Compound ZI-4-

[0583] Next, compound (ZI-4) is described.

[0584] The compound (ZI-4) is represented by the following formula ZI-4.

[0585] [Chemical formula 43]

[0586]

[0587] In formula ZI-4, l represents an integer of 0 to 2, r represents an integer of 0 to 8, and 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, and R 14 Each independently represents 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 group having a cycloalkyl group, and these groups may have a substituent, and R 15 Each independently represents an alkyl group, a cycloalkyl group or a naphthyl group, which may have a substituent, and the two R 15 They may be bonded to each other to form a ring.

[0588] When 2 R 15 When they are bonded to each other to form a ring, heteroatoms such as oxygen atoms and nitrogen atoms may be contained in the ring skeleton. 15 The alkylene groups are preferably bonded to each other to form a ring structure.

[0589] Z - Represents an anion.

[0590] In formula ZI-4, R 13 , R 14 and R 15 The alkyl group is linear or branched, preferably an alkyl group having 1 to 10 carbon atoms, more preferably a methyl group, an ethyl group, an n-butyl group, a tert-butyl group or the like.

[0591] [Cation in the compound represented by formula ZII or formula ZIII]

[0592] Next, formulae ZII and ZIII are described.

[0593] In Formula ZII and Formula ZIII, R 204 ~R 207 Each independently represents an aryl group, an alkyl group or a cycloalkyl group.

[0594] As R 204 ~R 207 R is an aryl group, preferably a phenyl group or a naphthyl group, more preferably a phenyl group. 204 ~R 207The aryl group may be an aryl group containing a heterocyclic structure having 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.

[0595] As R 204 ~R 207 The alkyl group and the cycloalkyl group may preferably be a straight-chain alkyl group having 1 to 10 carbon atoms, a branched-chain alkyl group having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl and pentyl) or a cycloalkyl group having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl and norbornyl).

[0596] R 204 ~R 207 The aryl group, alkyl group and cycloalkyl group of R may each independently have a substituent. 204 ~R 207 The substituents that the aryl group, alkyl group and cycloalkyl group may have include, for example, 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.

[0597] Z - Represents an anion.

[0598] [Anions in compounds represented by formula ZI to formula ZIII]

[0599] As Z in formula ZI - , Z in formula ZII - , Zc in formula ZI-3 - And Z in formula ZI-4 - , preferably an anion represented by the following formula An-1.

[0600] [Chemical formula 44]

[0601]

[0602] In the 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, Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom, when rf is an integer greater than 2, a plurality of -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. When pf is an integer greater than 2, a plurality of -CR 4f R 5f - can be the same or different, L frepresents a divalent linking group, and when qf is an integer greater than 2, a plurality of L f They may be the same or different, and W represents an organic group including a cyclic structure.

[0603] Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 4. The alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group.

[0604] 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 preferred that both Xf are fluorine atoms.

[0605] R 4f and R 5f Each 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 They may be the same or different.

[0606] As R 4f and R 5f The alkyl group may have a substituent, and preferably has 1 to 4 carbon atoms. 4f and R 5f Preferred is a hydrogen atom.

[0607] 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.

[0608] L f represents a divalent linking group, and when there are multiple L f They may be the same or different.

[0609] Examples of the divalent linking group include -COO-(-C(=O)-O-), -OCO-, -CONH-, -NHCO-, -CO-, -O-, -S-, -SO-, -SO2-, alkylene (preferably having 1 to 6 carbon atoms), cycloalkylene (preferably having 3 to 15 carbon atoms), alkenylene (preferably having 2 to 6 carbon atoms), and divalent linking groups obtained by combining a plurality of these. Among these, -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -O-, -SO2-, -COO-alkylene-, -OCO-alkylene-, -CONH-alkylene-, or -NHCO-alkylene- are preferred, and -COO-, -OCO-, -CONH-alkylene-, -SO2-, -COO-alkylene-, or -OCO-alkylene- are more preferred.

[0610] W represents an organic group including a cyclic structure, among which a cyclic organic group is preferred.

[0611] Examples of the cyclic organic group include an alicyclic group, an aromatic group, and a heterocyclic group.

[0612] The alicyclic group may be monocyclic or polycyclic. As the monocyclic alicyclic group, for example, monocyclic cycloalkyl groups such as cyclopentyl, cyclohexyl and cyclooctyl can be cited. As the polycyclic alicyclic group, for example, polycyclic cycloalkyl groups such as norbornyl, tricyclodecyl, tetracyclodecyl, tetracyclododecyl and adamantyl can be cited. Among them, the alicyclic group having a bulky structure with a carbon number of 7 or more, such as norbornyl, tricyclodecyl, tetracyclodecyl, tetracyclododecyl and adamantyl, is preferred.

[0613] The aryl group may be monocyclic or polycyclic. Examples of the aryl group include phenyl, naphthyl, phenanthryl and anthracenyl.

[0614] The heterocyclic group may be monocyclic or polycyclic. Polycyclic heterocyclic groups can further inhibit the diffusion of acids. In addition, the heterocyclic group may or may not be aromatic. As heterocyclic rings with aromaticity, for example, furan rings, thiophene rings, benzofuran rings, benzothiophene rings, dibenzofuran rings, dibenzothiophene rings and pyridine rings may be cited. As heterocyclic rings without aromaticity, for example, tetrahydropyran rings, lactone rings, sultone rings and decahydroisoquinoline rings may be cited. As an example of lactone rings and sultone rings, lactone structures and sultone structures exemplified in the above-mentioned resins may be cited. As heterocyclic rings in heterocyclic groups, furan rings, thiophene rings, pyridine rings or decahydroisoquinoline rings are particularly preferred.

[0615] The above-mentioned cyclic organic group may have a substituent. Examples of the substituent include an alkyl group (which may be any of a straight chain or a branched chain, preferably having 1 to 12 carbon atoms), a cycloalkyl group (which may be any of a monocyclic, polycyclic, and spirocyclic ring, preferably having 3 to 20 carbon atoms), an aryl group (preferably having 6 to 14 carbon atoms), a hydroxyl group, an alkoxy group, an ester group, an amide group, a carbamate group, a urea group, a thioether group, a sulfonamide group, and a sulfonate group. In addition, the carbon constituting the cyclic organic group (the carbon that contributes to the formation of the ring) may be a carbonyl carbon.

[0616] As the anion represented by the formula An-1, SO3 can be preferably mentioned. - -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. Here, L f , qf and W are the same as those in formula An-1. q' represents an integer of 0 to 10.

[0617] In one embodiment, Z in formula ZI - , Z in formula ZII - , Zc in formula ZI-3 - And Z in formula ZI-4 - , and an anion represented by the following formula 4 is also preferred.

[0618] [Chemical formula 45]

[0619]

[0620] In formula 4, X B1 and X B2 Each independently represents a hydrogen atom or a monovalent organic group having no fluorine atom. B1 and X B2 Preferred is a hydrogen atom.

[0621] X B3 and X B4 Each independently represents a hydrogen atom or a monovalent organic group. B3 and X B4 At least one of X is a fluorine atom or a monovalent organic group having a fluorine atom, and more preferably X B3 and X B4 Both of them are fluorine atoms or monovalent organic groups having fluorine atoms. B3 and X B4 Both of these are alkyl groups substituted with fluorine.

[0622] L f , qf and W are the same as those in Formula 3.

[0623] As Z in formula ZI - , Z in formula ZII - , Zc in formula ZI-3 - And Z in formula ZI-4 - , preferably an anion represented by the following formula 5.

[0624] [Chemical formula 46]

[0625]

[0626] In Formula 5, Xa each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom, and Xb each independently represents a hydrogen atom or an organic group without a fluorine atom. 4f , R 5f , L f The definitions and preferred methods of W are the same as those of Formula 3.

[0627] The Z in the formula ZI - , Z in formula ZII - , Zc in formula ZI-3 - And Z in formula ZI-4 - It may be a benzenesulfonate anion, and preferably a benzenesulfonate anion substituted with a branched alkyl group or a cycloalkyl group.

[0628] As Z in formula ZI - , Z in formula ZII - , Zc in formula ZI-3 - And Z in formula ZI-4 - , and an aromatic sulfonic acid anion represented by the following formula SA1 is also preferred.

[0629] [Chemical formula 47]

[0630]

[0631] In Formula SA1, Ar represents an aromatic group and may further have a sulfonic acid anion and -(DR B ) other than a substituent. As a substituent which may be possessed, a fluorine atom, a hydroxyl group, etc. can be mentioned.

[0632] n represents an integer greater than 0. n is preferably 1 to 4, more preferably 2 to 3, and particularly preferably 3.

[0633] 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 composed of two or more of these.

[0634] R B It represents a hydrocarbon group.

[0635] Preferably D is a single bond, R B It is an aliphatic hydrocarbon structure. B More preferred is isopropyl or cyclohexyl.

[0636] Preferred examples of the sulfonium cation in Formula ZI and the sulfonium cation or iodonium cation in Formula ZII are shown below.

[0637] [Chemical formula 48]

[0638]

[0639] The anion Z in formula ZI and formula ZII is shown below: - , Zc in formula ZI-3 - And Z in formula ZI-4 - A preferred example of .

[0640] [Chemical formula 49]

[0641]

[0642] Any combination of the above-mentioned cations and anions can be used as the photoacid generator.

[0643] The photoacid generator is an ionic compound containing a cation and an anion, and the anion preferably contains an ion represented by any one of the above formula An-1, the following formula An-2, and the following formula An-3.

[0644] [Chemical formula 50]

[0645]

[0646] In the formula An-2 and the formula An-3, Rfa each independently represents a monovalent organic group having a fluorine atom, and a plurality of Rfa may be bonded to each other to form a ring.

[0647] Rfa is preferably an alkyl group substituted with at least one fluorine atom. The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 4. Furthermore, the alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group.

[0648] Furthermore, it is preferred that a plurality of Rfa's are bonded to each other to form a ring.

[0649] Furthermore, as the photoacid generator, preferably, compounds C-1 to C-15 used in Examples are mentioned, but the present invention is not limited thereto.

[0650] The acid dissociation constant pKa of the acid generated by 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.

[0651] The lower limit of the acid dissociation constant pKa of the acid generated by the photoacid generator by irradiation with actinic rays or radiation is not particularly limited, but is usually -10.

[0652] The acid dissociation constant pKa represents the acid dissociation constant pKa in aqueous solution, for example, it is defined in Chemistry Handbook (II) (revised 4th edition, 1993, compiled by the Chemical Society of Japan, Maruzen Company, Limited). The lower the value of the acid dissociation constant pKa, the greater the acid strength. The acid dissociation constant pKa in aqueous solution can be specifically measured by using an infinite dilution aqueous solution to measure the acid dissociation constant at 25°C. Alternatively, it can be calculated by using the following software package 1 and the value of the database based on the Hammett substituent constant and the known literature value. The values ​​of all pKa recorded in this specification represent the values ​​obtained by using the software package and calculating.

[0653] Software package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007ACD / Labs).

[0654] The photoacid generator may be in the form of a low molecular weight compound or in the form of being embedded in a part of a polymer. Furthermore, the form of a low molecular weight compound and the form of being embedded in a part of a polymer may be used in combination.

[0655] The photoacid generator is preferably in the form of a low molecular weight compound.

[0656] 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 further preferably 1,000 or less.

[0657] When the photoacid generator is in a form embedded in a part of the polymer, it may be embedded in a part of the above-mentioned resin (A) or in a resin different from the resin (A).

[0658] The photoacid generator may be used alone or in combination of two or more.

[0659] The content of the photoacid generator in the composition (when there are two or more types, the total) is preferably 0.1% to 35% by mass, more preferably 0.5% to 25% by mass, further preferably 2% to 20% by mass, and particularly preferably 2.5% to 20% by mass, based on the total solid content of the composition.

[0660] When the photoacid generator is contained in the composition and the compound represented by the above-mentioned formula ZI-3 or formula ZI-4 is contained, the content of the photoacid generator contained in the composition (when there are multiple types, the total) is preferably 5% by mass to 35% by mass, and more preferably 7% by mass to 30% by mass, based on the total solid content of the composition.

[0661] <Acid diffusion control agent>

[0662] 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)").

[0663] The acid diffusion controller (D) captures the acid generated from the acid generator or the like during exposure and functions as a quencher that suppresses the reaction of the acid-decomposable resin in the unexposed portion due to the excessively generated acid. 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) that is a relatively weak acid relative to the acid generator, a low molecular weight compound (DD) having a nitrogen atom and a group that is separated by the action of an acid, or an onium salt compound (DE) having a nitrogen atom in the cation portion can be used as the acid diffusion controller.

[0664] Among them, from the viewpoint of linearity of a pattern obtained after time, the actinic ray-sensitive or radiation-sensitive resin composition of the present invention preferably contains a nitrogen-containing compound as an acid diffusion controller, and more preferably contains a nitrogen-containing basic compound.

[0665] In the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, a known acid diffusion controller can be used appropriately. For example, known compounds disclosed in paragraphs 0627 to 0664 in U.S. Patent Application Publication No. 2016 / 0070167, paragraphs 0095 to 0187 in U.S. Patent Application Publication No. 2015 / 0004544, paragraphs 0403 to 0423 in U.S. Patent Application Publication No. 2016 / 0237190, and paragraphs 0259 to 0328 in U.S. Patent Application Publication No. 2016 / 0274458 can be preferably used as the acid diffusion controller (D).

[0666] 〔Basic compounds (DA)〕

[0667] Preferred examples of the basic compound (DA) include compounds having structures represented by the following formulas A to E.

[0668] [Chemical formula 51]

[0669]

[0670] In formula A and E,

[0671] R 200 , R 201 and R 202R 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 (having 6 to 20 carbon atoms). 201 With R 202 They may be bonded to each other to form a ring.

[0672] R 203 , R 204 , R 205 and R 206 The groups may be the same or different and each independently represents an alkyl group having 1 to 20 carbon atoms.

[0673] The alkyl group in Formula A and Formula E may have a substituent or may be unsubstituted.

[0674] As for the alkyl group having a substituent, 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 is preferred.

[0675] The alkyl groups in Formula A and Formula E are more preferably unsubstituted.

[0676] The basic compound (DA) is preferably guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine or piperidine, and more preferably an imidazole structure, a diazabicyclic structure, an onium hydroxide structure, an onium carboxylate structure, a trialkylamine structure, a compound having 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.

[0677] [Basic compounds whose basicity is reduced or eliminated by irradiation with actinic rays or radiation (DB)]

[0678] A basic compound (DB) whose basicity is reduced or eliminated by irradiation with actinic rays or radiation (hereinafter also referred to as "compound (DB)") is a compound having a proton accepting functional group and which is decomposed by irradiation with actinic rays or radiation so that the proton accepting property is reduced or eliminated, or changes from proton accepting property to acidic property.

[0679] The proton accepting functional group is a functional group having a group or electron capable of electrostatically interacting with a proton, and for example, represents a functional group having a macrocyclic compound 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 represented by the following formula:

[0680] [Chemical formula 52]

[0681]

[0682] Preferred partial structures of the proton accepting functional group include crown ether, azacrown ether, primary amine, secondary amine, tertiary amine, pyridine, imidazole and pyrazine structures.

[0683] Compound (DB) generates a compound that is decomposed by irradiation with actinic rays or radiation, thereby reducing or eliminating proton accepting properties, or changing from proton accepting properties to acidic properties. Here, the reduction or disappearance of proton accepting properties or the change from proton accepting properties to acidic properties is a change in proton accepting properties caused by the addition of protons to the proton accepting functional group, and specifically, it means that when a proton adduct is generated from a compound (DB) having a proton accepting functional group and a proton, the equilibrium constant in the chemical equilibrium decreases.

[0684] The proton acceptor property can be confirmed by performing pH measurement.

[0685] [Onium salt (DC) that is a relatively weak acid relative to the photoacid generator]

[0686] 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 with respect to the photoacid generator may be used as an acid diffusion controller.

[0687] When a photoacid generator and an onium salt that generates an acid that is relatively weak relative to the acid generated by the photoacid generator are used in combination, if the acid generated by the photoacid generator collides with the onium salt having unreacted weak acid anions by irradiation with actinic rays or radiation, the weak acid is released by salt exchange to generate an onium salt having strong acid anions. In this process, the strong acid is exchanged for a weak acid with lower catalytic ability, so that the acid can be inactivated on the surface and the acid diffusion can be controlled.

[0688] From the viewpoint of depth of focus tolerance and pattern linearity, the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention preferably further contains at least one compound selected from the group consisting of compounds represented by Formula d1-1 to Formula d1-3.

[0689] [Chemical formula 53]

[0690]

[0691] In formula d1-1 to formula d1-3, R 51 represents 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, wherein no fluorine atom is bonded to the carbon atom adjacent to the S atom, and R 52 represents an organic group, Y 3 represents a linear, branched or cyclic alkylene 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.

[0692] As M + Preferred examples of the sulfonium cation or iodonium cation represented by include the sulfonium cation exemplified by the formula ZI and the iodonium cation exemplified by the formula ZII.

[0693] The onium salt (DC) that is a relatively weak acid to the photoacid generator may be a compound having a cation site and an anion site in the same molecule, and the cation site and anion site are linked by a covalent bond (hereinafter also referred to as "compound (DCA)").

[0694] As the compound (DCA), a compound represented by any one of the following formulae C-1 to C-3 is preferred.

[0695] [Chemical formula 54]

[0696]

[0697] 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.

[0698] L 1 It represents a divalent linking group or a single bond that links a cationic part and an anionic part.

[0699] -X - Indicates selected from -COO - 、-SO3 - 、-SO2 - and -N - -R 4 The anionic site in R 4 It 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 to the adjacent N atom.

[0700] R 1 , R 2 , R 3 , R 4 and L 1 can be bonded to each other to form a ring structure. Also, in formula C-3, R 1 ~R 3 The two of them together represent a divalent substituent, and may be bonded to the N atom via a double bond.

[0701] As R 1 ~R3 The substituent having 1 or more carbon atoms in , includes alkyl, cycloalkyl, aryl, alkoxycarbonyl, cycloalkyloxycarbonyl, aryloxycarbonyl, alkylaminocarbonyl, cycloalkylaminocarbonyl and arylaminocarbonyl, etc. Preferably, it is alkyl, cycloalkyl or aryl.

[0702] L as a divalent linking group 1 Examples of the group include 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 An alkylene group, an arylene group, an ether bond, an ester bond, or a group formed by combining two or more of them is preferred.

[0703] [Low molecular weight compound having a nitrogen atom and a group that can be separated by the action of an acid (DD)]

[0704] The low molecular compound (DD) having a nitrogen atom and a group that is dissociated by the action of an acid (hereinafter, also referred to as "compound (DD)") is preferably an amine derivative having a group that is dissociated by the action of an acid on the nitrogen atom.

[0705] The group that is released 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 hemiamalin ether group, and more preferably a carbamate group or a hemiamalin ether group.

[0706] The molecular weight of the compound (DD) is preferably 100 to 1,000, more preferably 100 to 700, and even more preferably 100 to 500.

[0707] Compound (DD) may have a carbamate group having a protecting group on the nitrogen atom. The protecting group constituting the carbamate group may be represented by the following formula d-1.

[0708] [Chemical formula 55]

[0709]

[0710] In formula d-1,

[0711] R b 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 Can be connected to each other to form a ring.

[0712] R bThe alkyl, cycloalkyl, aryl and aralkyl groups represented by the above-mentioned groups may be independently substituted by a hydroxyl group, a cyano group, an amino group, a pyrrolidino group, a piperidino group, a morpholino group, an oxo group or the like, an alkoxy group or a halogen atom. b The same applies to the alkoxyalkyl groups represented.

[0713] As R b , preferably a linear or branched alkyl group, a cycloalkyl group or an aryl group, more preferably a linear or branched alkyl group or a cycloalkyl group.

[0714] As 2 R b Examples of the ring formed by mutually connecting hydrocarbons include alicyclic hydrocarbons, aromatic hydrocarbons, heterocyclic hydrocarbons, and derivatives thereof.

[0715] As a specific structure of the group represented by formula d-1, the structure disclosed in paragraph 0466 of the specification of US Patent Application Publication No. 2012 / 0135348 can be cited, but the present invention is not limited thereto.

[0716] The compound (DD) preferably has a structure represented by Formula 6 below.

[0717] [Chemical formula 56]

[0718]

[0719] In formula 6,

[0720] l represents an integer of 0 to 2, m represents an integer of 1 to 3, and l+m=3 is satisfied.

[0721] R a represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. a Can be the same or different, 2 R a They may be linked to each other to form a heterocyclic ring together with the nitrogen atom in the formula. The heterocyclic ring may contain a hetero atom other than the nitrogen atom in the formula.

[0722] R b The meaning is the same as R in the above formula d-1 b The same, preferred examples are also the same.

[0723] In formula 6, as R a The alkyl, cycloalkyl, aryl and aralkyl groups may be substituted independently by the same groups as those mentioned above as the following groups, which may be substituted as R b The alkyl, cycloalkyl, aryl and aralkyl groups are substituted.

[0724] As the above R aSpecific examples of the alkyl, cycloalkyl, aryl and aralkyl groups (these groups may be substituted by the above groups) include the same as for R b The same groups as the above specific examples.

[0725] As a specific structure of the compound (DD) which is particularly preferred in the present invention, the compound disclosed in paragraph 0475 of the specification of US Patent Application Publication No. 2012 / 0135348 can be cited, but the present invention is not limited thereto.

[0726] The onium salt compound (DE) having a nitrogen atom in the cation portion (hereinafter also referred to as "compound (DE)") is preferably a compound having a basic site containing a nitrogen atom in the cation portion. The basic site is preferably an amino group, more preferably an aliphatic amino group. It is further preferred that all atoms adjacent to the nitrogen atom in the basic site are hydrogen atoms or carbon atoms. Furthermore, from the viewpoint of improving basicity, it is preferred that the electron-withdrawing functional group (carbonyl, sulfonyl, cyano, halogen atom, etc.) is not directly connected to the nitrogen atom.

[0727] Preferred specific structures of compound (DE) include compounds disclosed in paragraph 0203 of US Patent Application Publication No. 2015 / 0309408, but are not limited thereto.

[0728] Preferred examples of other acid diffusion control agents are shown below:

[0729] [Chemical formula 57]

[0730]

[0731] [Chemical formula 58]

[0732]

[0733] [Chemical formula 59]

[0734]

[0735] [Chemical formula 60]

[0736]

[0737] 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.

[0738] The content of the acid diffusion controller in the composition (when there are two or more types, the total) is preferably 0.1% by mass to 10% by mass, more preferably 0.1% by mass to 5% by mass, based on the total solid content of the composition.

[0739] <Solvent>

[0740] 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.

[0741] In the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, a known resist solvent can be used appropriately. For example, known solvents disclosed in paragraphs 0665 to 0670 in U.S. Patent Application Publication No. 2016 / 0070167, paragraphs 0210 to 0235 in U.S. Patent Application Publication No. 2015 / 0004544, paragraphs 0424 to 0426 in U.S. Patent Application Publication No. 2016 / 0237190, and paragraphs 0357 to 0366 in U.S. Patent Application Publication No. 2016 / 0274458 can be preferably used.

[0742] Examples of the solvent 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 that may have a ring (preferably having 4 to 10 carbon atoms), alkylene carbonates, alkyl alkoxyacetates, and alkyl pyruvates.

[0743] As the organic solvent, a mixed solvent of a solvent containing a hydroxyl group in its structure and a solvent not containing a hydroxyl group can be used.

[0744] As the solvent containing hydroxyl group and the solvent not containing hydroxyl group, the above-mentioned exemplary compounds can be appropriately selected, and as the solvent containing hydroxyl group, alkylene glycol monoalkyl ether or lactic acid alkyl ester is preferred, and propylene glycol monomethyl ether (PGME: 1-methoxy-2-isopropanol), propylene glycol monoethyl ether (PGEE), methyl 2-hydroxyisobutyrate or ethyl lactate is more preferred. In addition, as the solvent not containing hydroxyl group, alkylene glycol monoalkyl ether acetate, alkyl alkoxy propionate, monoketone compound which may contain a ring, cyclic lactone or alkyl acetate is preferred, 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 preferred, and propylene glycol monomethyl ether acetate, γ-butyrolactone, ethyl ethoxypropionate, cyclohexanone, cyclopentanone or 2-heptanone is further preferred. As the solvent not containing hydroxyl group, propylene carbonate is also preferred. Among them, it is particularly preferred that the solvent contains γ-butyrolactone from the viewpoint of uniformity of the formed layer.

[0745] The mixing ratio (mass ratio) of the hydroxyl-containing solvent to the hydroxyl-free solvent is 1 / 99 to 99 / 1, preferably 10 / 90 to 90 / 10, and more preferably 20 / 80 to 60 / 40. From the viewpoint of coating uniformity, a mixed solvent containing 50% by mass or more of the hydroxyl-free solvent is preferred.

[0746] The solvent preferably contains propylene glycol monomethyl ether acetate, and may be a single solvent of propylene glycol monomethyl ether acetate or a mixed solvent of two or more solvents containing propylene glycol monomethyl ether acetate.

[0747] The solid content 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 to 60% by mass, more preferably 1.0 to 45% by mass, and even more preferably 1.0 to 40% by mass.

[0748] When a film formed from the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is exposed to KrF excimer laser, the solid content concentration of the actinic ray-sensitive or radiation-sensitive resin composition is preferably 10% by mass or more, preferably 15% by mass or more, and preferably 20% by mass or more.

[0749] The solid content concentration refers to the mass percentage of the mass of other resist components excluding the solvent relative to the total mass of the composition.

[0750] <Exposure process>

[0751] The exposure step is a step of exposing the resist film to light.

[0752] The exposure method may be immersion exposure.

[0753] The pattern forming method according to the present invention may include multiple exposure steps.

[0754] The type of light (actinic rays or radiation) used in exposure can be selected in consideration of the properties of the photoacid generator and the desired pattern shape, and examples thereof 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.

[0755] For example, the wavelength of the actinic ray is preferably 250 nm or less, more preferably 220 nm or less, and still more preferably 1 to 200 nm.

[0756] The light used is specifically KrF excimer laser (248 nm), ArF excimer laser (193 nm), F2 excimer laser (157 nm), X-ray, EUV (13 nm), or electron beam, and preferably ArF excimer laser, EUV, or electron beam.

[0757] The solid content concentration refers to the mass percentage of the mass of other resist components excluding the solvent and the anion additive relative to the total mass of the composition.

[0758] <Cross-linking agent>

[0759] The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention may contain a compound that crosslinks the resin by the action of an acid (hereinafter, also referred to as a "crosslinking agent (G)").

[0760] As the crosslinking agent (G), a known compound can be used appropriately. For example, known compounds disclosed in paragraphs 0379 to 0431 of U.S. Patent Application Publication No. 2016 / 0147154 and paragraphs 0064 to 0141 of U.S. Patent Application Publication No. 2016 / 0282720 can be preferably used as the crosslinking agent (G).

[0761] The crosslinking agent (G) is a compound having a crosslinking group capable of crosslinking a resin, and examples of the crosslinking group include a hydroxymethyl group, an alkoxymethyl group, an acyloxymethyl group, an alkoxymethyl ether group, a xylan ring, and an oxetane ring.

[0762] The crosslinkable group is preferably a hydroxymethyl group, an alkoxymethyl group, a xylan ring, or an oxetane ring.

[0763] The crosslinking agent (G) is preferably a compound (including a resin) having two or more crosslinking groups.

[0764] 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 methylol group or an alkoxymethyl group.

[0765] The cross-linking agent may be used alone or in combination of two or more.

[0766] The content of the crosslinking agent (G) is preferably 1 to 50% by mass, more preferably 3 to 40% by mass, and even more preferably 5 to 30% by mass, based on the total solid content of the composition.

[0767] <Surfactant>

[0768] The actinic ray-sensitive or radiation-sensitive resin composition of the present invention may or may not contain a surfactant (also referred to as "surfactant (H)"). When containing a surfactant, it preferably contains at least one of a fluorine-based surfactant 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).

[0769] By making the actinic ray-sensitive or radiation-sensitive resin composition of the present invention contain a surfactant, when using an exposure light source with a wavelength of 250 nm or less, particularly a wavelength of 220 nm or less, a resist pattern having good sensitivity and resolution, adhesion and few development defects can be obtained.

[0770] Examples of the fluorine-based or silicone-based surfactant include the surfactants described in paragraph 0276 of US Patent Application Publication No. 2008 / 0248425.

[0771] Furthermore, other surfactants than the fluorine-based or silicone-based surfactants described in paragraph 0280 of US Patent Application Publication No. 2008 / 0248425 may also be used.

[0772] These surfactants may be used alone or in combination of two or more.

[0773] When the actinic ray-sensitive or radiation-sensitive resin composition of the present invention contains a surfactant, the content of the surfactant is preferably 0.0001 to 2% by mass, more preferably 0.0005 to 1% by mass, based on the total solid content of the composition.

[0774] On the other hand, by setting the surfactant content to 0.0001% by mass or more relative to the total solid content of the composition, the uneven distribution of the surface of the hydrophobic resin increases, thereby making the surface of the actinic ray-sensitive or radiation-sensitive film more hydrophobic and improving water followability during immersion exposure.

[0775] <Other additives>

[0776] The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention may further contain other known additives.

[0777] Examples of other additives include acid growth agents, dyes, plasticizers, photosensitizers, light absorbers, alkali-soluble resins, dissolution inhibitors, and dissolution accelerators.

[0778] The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is preferably prepared by dissolving the above components in a predetermined organic solvent, preferably the above mixed solvent, filtering the resultant organic solvent, and then applying the resultant organic solvent on a predetermined support (substrate) for use.

[0779] The pore size (pore diameter) of the filter used for filter filtration is preferably 0.2 μm or less, more preferably 0.05 μm or less, and further preferably 0.03 μm or less.

[0780] When the solid content concentration of the actinic ray or radiation sensitive resin composition is high (for example, 25 mass % or more), the pore size of the filter used for filter filtration is preferably 3 μm or less, more preferably 0.5 μm or less, and further preferably 0.3 μm or less.

[0781] The filter is preferably a filter made of polytetrafluoroethylene, polyethylene or nylon. In the filter filtration, for example, as disclosed in Japanese Patent Publication No. 2002-62667, a circulating filtration can be performed, and a plurality of filters can be connected in series or in parallel for filtration. In addition, the composition can also be filtered multiple times. In addition, the composition can also be degassed before and after the filter filtration.

[0782] The film thickness of the resist film made of the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is not particularly limited, but is preferably 90 nm or less, more preferably 85 nm or less from the viewpoint of improving resolution. Such a film thickness can be achieved by setting the solid content concentration in the composition within an appropriate range to give it an appropriate viscosity and improving coating properties or film-forming properties.

[0783] <Application>

[0784] The photosensitive or radiation-sensitive resin composition of the present invention is a photosensitive or radiation-sensitive resin composition that reacts by irradiation with light and changes its properties. In more detail, the photosensitive or radiation-sensitive resin composition of the present invention relates to a photosensitive or radiation-sensitive resin composition used in semiconductor manufacturing processes such as IC (Integrated Circuit), the manufacture of circuit substrates such as liquid crystals or thermal heads, the preparation of mold structures for imprinting, other photosensitive etching processes, or the manufacture of lithographic printing plates or acid-curable compositions. The resist pattern formed by the photosensitive or radiation-sensitive resin composition of the present invention can be used in etching processes, ion implantation processes, bump electrode formation processes, rewiring formation processes, and MEMS (Micro Electro Mechanical Systems).

[0785] (Photosensitive or radiation-sensitive film)

[0786] The actinic ray or radiation-sensitive film (preferably a resist film) of the present invention is a film formed from the actinic ray or radiation-sensitive resin composition of the present invention. The actinic ray or radiation-sensitive film of the present invention is a cured product of the actinic ray or radiation-sensitive resin composition of the present invention.

[0787] The cured product in the present invention may be a cured 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.

[0788] Specifically, the actinic ray-sensitive or radiation-sensitive film according to the present invention can be obtained by, for example, applying the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention on a support such as a substrate and then drying the coating.

[0789] The drying means removing at least a part of the solvent contained in the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention.

[0790] The drying method is not particularly limited, and a known method may be used, and examples thereof include drying by heating (for example, 70° C. to 130° C., 30 seconds to 300 seconds).

[0791] The heating method is not particularly limited, and a known heating method can be used, and examples thereof include a heater, an oven, a hot plate, an infrared lamp, and an infrared laser.

[0792] The components contained in the actinic ray-sensitive or radiation-sensitive film according to the present invention are the same as the components obtained by removing the solvent from the components contained in the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention, and the preferred aspects are also the same.

[0793] The content of each component contained in the actinic ray or radiation-sensitive film involved in the present invention is equivalent to replacing the description of "total solid content" in the description of the content of each component other than the solvent of the actinic ray or radiation-sensitive resin composition involved in the present invention with "total mass of the actinic ray or radiation-sensitive film".

[0794] The thickness of the actinic ray-sensitive or radiation-sensitive film according to the present invention is not particularly limited, but is preferably 50 nm to 150 nm, and more preferably 80 nm to 130 nm.

[0795] Furthermore, as memory devices become three-dimensional, when it is desired to form a thick photosensitive or radiation-sensitive film, the thickness is preferably 2 μm or more, more preferably 2 μm or more and 50 μm or less, and further preferably 2 μm or more and 20 μm or less.

[0796] [Pattern Formation Method]

[0797] The pattern forming method involved in the present invention comprises the following steps:

[0798] a step of exposing the actinic ray-sensitive or radiation-sensitive film (preferably a resist film) according to the present invention to actinic rays or radiation (exposure step); and

[0799] A step of developing the actinic ray-sensitive or radiation-sensitive film after the exposure step using a developer (development step).

[0800] Furthermore, the pattern forming method of the present invention may include the following steps: 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 of the present invention (film forming step);

[0801] a step of exposing the above-mentioned actinic ray-sensitive or radiation-sensitive film to actinic rays or radiation (exposure step); and

[0802] A step of developing the actinic ray-sensitive or radiation-sensitive film after the exposure step using a developer (development step).

[0803] <Film forming process>

[0804] The pattern forming method of the present invention may include a film forming step. As a method of forming an actinic ray or radiation sensitive film in the film forming step, for example, there can be mentioned a method of forming an actinic ray or radiation sensitive film by drying as described in the item of the actinic ray or radiation sensitive film.

[0805] 〔Carrier〕

[0806] The carrier is not particularly limited, and in addition to the manufacturing process of semiconductors such as ICs, the manufacturing process of circuit substrates such as liquid crystals or thermal heads, it can also be used as a substrate commonly used in the photolithography process of other photosensitive etching processes. As specific examples of the carrier, inorganic substrates such as silicon, SiO2 and SiN can be cited.

[0807] <Exposure process>

[0808] The exposure step is a step of exposing the actinic ray-sensitive or radiation-sensitive film to light.

[0809] The exposure method may be immersion exposure.

[0810] The pattern forming method according to the present invention may include multiple exposure steps.

[0811] The type of light (actinic rays or radiation) used in exposure can be selected in consideration of the properties of the photoacid generator and the desired pattern shape, and examples thereof 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.

[0812] For example, the wavelength of the actinic ray is preferably 250 nm or less, more preferably 220 nm or less, and still more preferably 1 to 200 nm.

[0813] The light used is specifically KrF excimer laser (248 nm), ArF excimer laser (193 nm), F2 excimer laser (157 nm), X-ray, EUV (13 nm), or electron beam, and preferably ArF excimer laser, EUV, or electron beam.

[0814] Among them, the exposure in the exposure step is preferably performed by liquid immersion exposure using an argon fluoride laser.

[0815] The exposure dose is preferably 5 mJ / cm 2 ~200mJ / cm 2 , more preferably 10 mJ / cm 2 ~100mJ / cm 2 .

[0816] <Development process>

[0817] 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.

[0818] 〔Alkaline developer〕

[0819] As the alkaline developer, a quaternary ammonium salt represented by tetramethylammonium hydroxide is preferably used, but in addition, an aqueous alkaline solution of an inorganic base, a primary amine, a secondary amine, a tertiary amine, an alkanolamine, a cyclic amine or the like may also be used.

[0820] The alkaline developer may contain an appropriate amount of at least one of alcohols and surfactants. The alkaline developer preferably has an alkali concentration of 0.1% to 20% by mass. The alkaline developer preferably has a pH of 10 to 15.

[0821] The development time using the alkaline developer is preferably 10 seconds to 300 seconds.

[0822] The alkali concentration, pH and development time of the alkaline developer can be appropriately adjusted according to the pattern to be formed.

[0823] 〔Organic developer〕

[0824] The organic developer is preferably a developer containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents.

[0825] -Ketone solvents-

[0826] Examples of the ketone solvent 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, diacetone alcohol, acetyl carbinol, acetophenone, methyl naphthyl ketone, isophorone, and propylene carbonate.

[0827] -Ester solvents-

[0828] Examples of the ester solvent include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl 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 butyrate, methyl 2-hydroxyisobutyrate, isobutyl isobutyrate, and butyl propionate.

[0829] -Other solvents-

[0830] As the alcohol solvent, amide solvent, ether solvent, and hydrocarbon solvent, solvents disclosed in paragraphs 0715 to 0718 of U.S. Patent Application Publication No. 2016 / 0070167 can be used.

[0831] The above solvents may be mixed with multiple types or with other solvents or water. The water content of the developer as a whole is preferably less than 50% by mass, more preferably less than 20% by mass, further preferably less than 10% by mass, and particularly preferably substantially free of water.

[0832] 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, further 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, relative to the total amount of the developer.

[0833] -Surfactant-

[0834] The organic developer may contain an appropriate amount of a known surfactant as required.

[0835] The content of the surfactant is preferably 0.001% by mass to 5% by mass, more preferably 0.005% by mass to 2% by mass, and even more preferably 0.01% by mass to 0.5% by mass, relative to the total mass of the developer.

[0836] -Acid Diffusion Controller-

[0837] The organic developer may contain the above-mentioned acid diffusion controller.

[0838] 〔Development method〕

[0839] As a developing method, for example, a method of immersing a substrate in a tank filled with a developer for a certain period of time (dip method), a method of causing the developer to bulge on the surface of the substrate by surface tension and let it stand for a certain period of time (puddle method), a method of spraying the developer onto the surface of the substrate (spray method), or a method of continuously spraying the developer on a substrate rotating at a certain speed while scanning a developer spray nozzle at a certain speed (dynamic dispense method) can be applied.

[0840] The process of developing with an alkaline aqueous solution (alkaline developing process) and the process of developing with a developer containing an organic solvent (organic solvent developing process) may be combined. This allows patterning to be performed while only the region with the intermediate exposure intensity is not dissolved, thereby forming a finer pattern.

[0841] <Preheating process, post-exposure heating process>

[0842] The pattern forming method according to the present invention preferably includes a pre-heating (PB: PreBake) step before the exposure step.

[0843] The pattern forming method according to the present invention may include a plurality of preheating steps.

[0844] The pattern forming method according to the present invention preferably includes a post-exposure baking (PEB: Post Exposure Bake) step after the exposure step and before the development step.

[0845] The pattern forming method according to the present invention may include multiple post-exposure heating steps.

[0846] The heating temperature is preferably 70°C to 130°C, more preferably 80°C to 120°C, in both the preheating step and the post-exposure heating step.

[0847] The heating time is preferably 30 seconds to 300 seconds, more preferably 30 seconds to 180 seconds, and even more preferably 30 seconds to 90 seconds in both the preheating step and the post-exposure heating step.

[0848] Heating may be performed by a mechanism provided in the exposure device and the developing device, or by using a heating plate or the like.

[0849] <Resist underlayer film forming step>

[0850] 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) before the film forming step.

[0851] 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 carrier. As the resist underlayer film, a known organic or inorganic material can be used appropriately.

[0852] <Protective film forming process>

[0853] The pattern forming method according to the present invention may further include a step of forming a protective film (protective film forming step) before the developing step.

[0854] The protective film forming process is a process for forming a protective film (top coat) in the upper layer of the resist film. As a protective film, known materials can be used appropriately. For example, it is preferred to use a protective film forming composition disclosed in U.S. Patent Application Publication No. 2007 / 0178407, U.S. Patent Application Publication No. 2008 / 0085466, U.S. Patent Application Publication No. 2007 / 0275326, U.S. Patent Application Publication No. 2016 / 0299432, U.S. Patent Application Publication No. 2013 / 0244438, and International Publication No. 2016 / 157988. As a protective film forming composition, it is preferred to contain the above-mentioned acid diffusion control agent.

[0855] A protective film may be formed on the upper layer of the resist film containing the hydrophobic resin.

[0856] <Rinsing process>

[0857] The pattern forming method according to the present invention preferably includes a step of performing cleaning using a rinsing liquid (rinsing step) after the developing step.

[0858] [In the case of a development step using an alkaline developer]

[0859] The rinse liquid used in the rinse process after the development process using the alkaline developer can be, for example, pure water. The pure water can contain an appropriate amount of surfactant. In this case, after the development process or the rinse process, a treatment using a supercritical fluid to remove the developer or rinse liquid attached to the pattern can be added. In addition, after the rinse process or the treatment using the supercritical fluid, a heat treatment can also be performed to remove the residual moisture in the pattern.

[0860] [In the case of a development process using an organic developer]

[0861] The rinse solution used in the rinse step after the development step using the developer containing an organic solvent is not particularly limited as long as it does not dissolve the resist pattern, and a common solution containing an organic solvent can be used. As the rinse solution, a rinse solution containing at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents is preferably used.

[0862] Specific examples of the hydrocarbon solvent, ketone solvent, ester solvent, alcohol solvent, amide solvent, and ether solvent include the same solvents as described for the developer containing an organic solvent.

[0863] As the rinsing liquid used in the rinsing step in this case, a rinsing liquid containing a monohydric alcohol is more preferably used.

[0864] As the monohydric alcohol used in the rinsing step, linear, branched or cyclic monohydric alcohols can be mentioned. Specifically, 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-hexanol, 3-octanol, 4-octanol and methyl isobutyl carbinol can be mentioned. As the monohydric alcohol having 5 or more carbon atoms, 1-hexanol, 2-hexanol, 4-methyl-2-pentanol, 1-pentanol, 3-methyl-1-butanol and methyl isobutyl carbinol can be mentioned.

[0865] The components may be mixed in plural types or may be used in a mixture with organic solvents other than those mentioned above.

[0866] The water content in the rinse liquid is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 3% by mass or less. By setting the water content to 10% by mass or less, good development characteristics can be obtained.

[0867] The rinsing solution may contain an appropriate amount of a surfactant.

[0868] In the rinsing process, a rinsing liquid containing an organic solvent is used to clean the substrate that has been developed using an organic developer. The method of the cleaning process is not particularly limited, and for example, a method of continuously spraying a rinsing liquid on a substrate rotating at a certain speed (spin coating method), a method of immersing a substrate in a tank filled with a rinsing liquid for a certain period of time (immersion method), or a method of spraying a rinsing liquid onto the surface of a substrate (spray coating method) can be applied. Among them, it is preferred to use a spin coating method for cleaning, and after cleaning, the substrate is rotated at a speed of 2,000 rpm to 4,000 rpm (revolutions / minute), and the rinsing liquid is removed from the substrate. In addition, it is also preferred to include a heating process (Post Bake) after the rinsing process. The developer and rinsing liquid remaining between and inside the pattern are removed by this heating process. In the heating process after the rinsing process, the heating temperature is preferably 40 to 160°C, and more preferably 70 to 95°C. The heating time is preferably 10 seconds to 3 minutes, and more preferably 30 seconds to 90 seconds.

[0869] <Improvement of surface roughness>

[0870] The method for improving the surface roughness of the pattern can also be applied to the pattern formed by the pattern forming method involved in the present invention. As a method for improving the surface roughness of the pattern, for example, the method disclosed in the specification of U.S. Patent Application Publication No. 2015 / 0104957, which is a method for treating the resist pattern by a plasma containing a hydrogen gas, can be cited. In addition, the known methods such as those described in Japanese Patent Publication No. 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" can also be applied.

[0871] Furthermore, the resist pattern formed by the above method can be used as a core of a spacer process disclosed in, for example, Japanese Patent Application Laid-Open No. 3-270227 and US Patent Application Publication No. 2013 / 0209941.

[0872] (Method for manufacturing electronic device)

[0873] The method for manufacturing an electronic device according to the present invention includes the method for forming a pattern according to the present invention. The electronic device manufactured by the method for manufacturing an electronic device according to the present invention is preferably mounted on electrical and electronic equipment (e.g., home appliances, OA (Office Automation) related equipment, media related equipment, optical equipment, and communication equipment, etc.).

[0874] Example

[0875] Below, examples are given to further specifically describe the embodiments of the present invention. As long as it does not depart from the purpose of the embodiments of the present invention, the materials, usage, ratio, processing content and processing steps shown in the following examples can be appropriately changed. Therefore, the scope of the embodiments of the present invention is not limited to the specific examples shown below. In addition, unless otherwise specified, "parts", "%" are mass references.

[0876] <Resin (A)>

[0877] The structures of the resins (A-1 to A-17) used are shown below.

[0878] In addition, as described above, the weight average molecular weight (Mw), number average molecular weight (Mn), and dispersion (Mw / Mn) (in terms of polystyrene) of the resin were measured by GPC (carrier: tetrahydrofuran (THF)). 13 The composition ratio (mol %) of the resin was measured by C-NMR (Nuclear Magnetic Resonance).

[0879] [Chemical formula 61]

[0880]

[0881] [Chemical formula 62]

[0882]

[0883] [Chemical formula 63]

[0884]

[0885] In addition, the unit of the content ratio of each repeating unit of the above-mentioned resin is mol %.

[0886] Regarding the value of the glass transition temperature (Tg) when the monomer a1 corresponding to the repeating unit (a1) derived from a monomer (monomer a1) having a glass transition temperature (Tg) of 50°C or less when formed into a homopolymer in this specification and examples is formed into a homopolymer, reference can be made to the description of PCT / JP2018 / 018239.

[0887] <Photoacid generator>

[0888] The structures of the photoacid generators (C-1 to C-15) used are shown below: nBu represents an n-butyl group, and tBu represents a tert-butyl group.

[0889] [Chemical formula 64]

[0890]

[0891] [Chemical formula 65]

[0892]

[0893] [Chemical formula 66]

[0894]

[0895] Table 1 shows the pKa values ​​of the acids generated from C-1 to C-15.

[0896] [Table 1]

[0897] Photoacid generator pKa of the acid produced C-1 -3.57 C-2 -3.57 C-3 -8.68 C-4 -3.91 C-5 -3.57 C-6 -3.29 C-7 -3.57 C-8 -1.97 C-9 -3.57 C-10 -3.29 C-11 -3.39 C-12 -2.7 C-13 -2.81 C-14 -3.36 C-15 -3.36

[0898] <Acid diffusion control agent>

[0899] The structure of the acid diffusion controller used is shown below.

[0900] [Chemical formula 67]

[0901]

[0902] Tri-n-pentylamine (D-9)

[0903] The structures of the cross-linking agents used are shown below.

[0904] [Chemical formula 68]

[0905]

[0906] The structure of the hydrophobic resin used is shown below. In addition, as described above, the weight average molecular weight (Mw), number average molecular weight (Mn) and dispersion (Mw / Mn) (in terms of polystyrene) of the hydrophobic resin were measured by GPC (carrier: tetrahydrofuran (THF)). 13 The composition ratio (mol %) of the resin was measured by C-NMR (Nuclear Magnetic Resonance).

[0907] [Chemical formula 69]

[0908]

[0909] The structures of the anion additives used to add the anions (P) are shown in Table 2 below.

[0910] [Table 2]

[0911]

[0912] The surfactant (E) used is shown below.

[0913] [Chemical formula 70]

[0914]

[0915] E-2: Megafac R-41 (manufactured by DIC Corporation)

[0916] E-3: KF-53 (manufactured by Shin-Etsu Chemical Co., Ltd.)

[0917] E-4: Megafac F176 (manufactured by DIC Corporation)

[0918] E-5: Megafac R08 (manufactured by DIC Corporation)

[0919] The solvents used are shown below.

[0920] S-1: Propylene glycol monomethyl ether acetate (PGMEA)

[0921] S-2: Propylene glycol monomethyl ether (PGME)

[0922] S-3: Ethyl lactate

[0923] S-4: Ethyl 3-ethoxypropionate

[0924] S-5: 2-Heptanone

[0925] S-6: 3-methoxypropionic acid methyl ester

[0926] S-7: 3-Methoxybutyl acetate

[0927] S-8: Butyl acetate

[0928] (Examples 1 to 46 and Comparative Examples 1 to 3)

[0929] <Preparation of Actinic Ray-Sensitive or Radiation-Sensitive Resin Composition> (KrF Exposure)

[0930] (Examples 1 to 7, 15 to 18, 23 to 29, 36 to 46, Comparative Examples 1 to 3)

[0931] The components shown in Table 3 were mixed to obtain a solution having the solid content concentration (mass %) described in Table 3. Next, the obtained solution was filtered with a polyethylene filter having a pore size of 3 μm to prepare an actinic ray-sensitive or radiation-sensitive resin composition (resist composition).

[0932] In the examples and comparative examples, the solid content in the resist composition refers to all components except the solvent and the anion additive. The obtained resist composition was used in the examples and comparative examples.

[0933] In addition, in the table, the content (mass %) of each component other than the solvent refers to the content ratio relative to the total solid content. In addition, the table describes the content ratio (mass %) of the solvent used relative to the total solvent.

[0934] <Determination of Anion (P) Content of Actinic Ray-Sensitive or Radiation-Sensitive Resin Composition>

[0935] The anion (P) in the photosensitive or radiation-sensitive resin composition shown in Table 3 was added in the amount described in Table 3. The structure of the anion (P) is distinct from the structure of the anion additive used. In addition, the anion (P) based on the anion additive AE-6 is SO4 2- .

[0936] In addition, the content of anions (P) was measured as follows.

[0937] (Quantitative method for anions (P))

[0938] After preparing a resist composition (resist solution) containing anions (P), 10 g of the resist solution was weighed, 100 g of toluene and 100 g of ion exchange water were added to a separatory funnel, mixed, and allowed to stand. The water layer was separated and the water was removed by vacuum distillation. 1 g of ion exchange water was added to the residue, and after sufficient shaking, it was filtered with a 0.2 μm filter (DISMIC-13HP, manufactured by ADVANTEC) and placed in an ion chromatograph (ion chromatograph: PIA-1000, manufactured by SHIMADZU CORPORATION), and analyzed with Shim-pack IC-SA4 (manufactured by SHIMADZU GLC Ltd.) 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 Corporation, and the content of anions (P) in the resist solution was calculated.

[0939] <Pattern formation method (1): KrF exposure, alkaline aqueous solution development>

[0940] Using a spin coater "ACT-8" manufactured by Tokyo Electron Limited, an 8-inch Si substrate (manufactured by Advanced Materials Technology (hereinafter also referred to as "substrate") treated with hexamethyldisilazane was dripped with the resist composition described in Table 3 prepared above without an anti-reflection layer, while the substrate was stationary. After the dripping, the substrate was rotated, and its rotation speed was maintained at a speed of 500 rpm for 3 seconds, then at a speed of 100 rpm for 2 seconds, further at a speed of 500 rpm for 3 seconds, and again at a speed of 100 rpm for 2 seconds, and then increased to the film thickness setting speed (1200 rpm) for 60 seconds. After that, it was dried by heating at 130° C. on a hot plate for 60 seconds, thereby forming a positive resist film with a film thickness of 12 μm.

[0941] For this resist film, a mask having a line and space pattern with a space width of 4.5 μm and a pitch width of 25 μm, which is formed after reduced projection exposure and development, was used to expose the pattern under exposure conditions of NA=0.60 and σ=0.75 using a KrF excimer laser scanner (manufactured by ASML, PAS5500 / 850C wavelength 248 nm). After irradiation, it was baked at 120°C for 60 seconds, immersed in a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, rinsed with pure water for 30 seconds and dried, and then baked at 110°C for 60 seconds, thereby forming an isolated space pattern with a space width of 4.5 μm and a pitch width of 25 μm.

[0942] The pattern exposure was performed by using a mask having a line and space pattern with a space width of 4.5 μm and a pitch width of 25 μm after reduced projection exposure, and the exposure amount was set to the optimum exposure amount (sensitivity) (mJ / cm 2 In the determination of the sensitivity described above, the spatial width of the pattern was measured using a scanning electron microscope (SEM: Scanning Electron Microscope) (9380II manufactured by Hitachi High-Technologies Corporation).

[0943] Through the above steps, a pattern wafer for evaluation having a substrate and a pattern formed on the surface of the substrate was obtained.

[0944] <Performance Evaluation>

[0945] [Stability over time]

[0946] After the resist composition was stored at 40°C for 4 weeks, an isolated space pattern was formed in the same manner as described above. In the obtained isolated space pattern, the sensitivity was determined in the same manner as described above, and the difference in sensitivity between the isolated space pattern formed using the resist composition before storage over time and the isolated space pattern formed using the resist composition after storage over time (4 weeks at 40°C), that is, the degree of sensitivity change, was evaluated based on the following criteria.

[0947] (Judgment Criteria)

[0948] A: The observed sensitivity variation is less than 1mJ / cm 2

[0949] B: Observed sensitivity change is 1mJ / cm 2 Above and less than 2mJ / cm 2

[0950] C: Observed sensitivity change is 2mJ / cm 2 Above and less than 3mJ / cm 2

[0951] D: Observed sensitivity change is 3mJ / cm 2 above

[0952] [Sensitivity]

[0953] For each resist composition, except that the resist composition does not contain anions (P), the same resist composition was prepared and an isolated space pattern was formed in the same manner as above. In the obtained isolated space pattern, the sensitivity was calculated as above. Based on the sensitivity of the isolated space pattern formed using the resist composition not containing anions (P), the sensitivity of the isolated space pattern formed using the resist composition containing anions (P) was evaluated according to the following judgment criteria to evaluate how much the sensitivity of the isolated space pattern was reduced.

[0954] (Judgment Criteria)

[0955] A: The observed sensitivity reduction is less than 1mJ / cm 2

[0956] B: Observed sensitivity reduction is 1 mJ / cm 2 Above and less than 2mJ / cm 2

[0957] C: Observed sensitivity reduction is 2 mJ / cm 2 Above and less than 3mJ / cm 2

[0958] D: Observed sensitivity reduction is 3 mJ / cm 2 above

[0959] Among them, the resist composition of Comparative Example 1 did not contain amine oxide (P), and the sensitivity was evaluated as A.

[0960] <Preparation of Actinic Ray-Sensitive or Radiation-Sensitive Resin Composition> (ArF Exposure)

[0961] (Examples 8-10, 19-20, 30-31)

[0962] The various components shown in Table 3 were mixed so as to have the solid content concentration (mass %) described in Table 3 to obtain a solution. The obtained liquid was first filtered through a polyethylene filter having a pore size of 50 nm, then filtered through a nylon filter having a pore size of 10 nm, and finally filtered through a polyethylene filter having a pore size of 5 nm. The obtained actinic ray-sensitive or radiation-sensitive resin composition (resist composition) was used in Examples and Comparative Examples.

[0963] In the examples, the solid content in the resist composition refers to all components except the solvent and the anion (P).

[0964] In addition, in the table, the content (mass %) of each component other than the solvent refers to the content ratio relative to the total solid content. In addition, the table describes the content ratio (mass %) of the solvent used relative to the total solvent.

[0965] The content of anions (P) was measured in the same manner as above.

[0966] <Pattern formation method (2): ArF immersion exposure, alkaline aqueous solution development (positive)>

[0967] The organic anti-reflection film-forming composition SOC9110D and the Si-containing anti-reflection film-forming composition HM9825 were applied on a silicon wafer to form an anti-reflection film. The anti-reflection film was coated with a resist composition and baked at 100°C for 60 seconds (PB: Prebake) to form a resist film with a film thickness of 100 nm.

[0968] The resulting wafer was exposed using an ArF excimer laser immersion scanner (manufactured by ASML; XT1700i, NA0.85, Annular, outer sigma 0.9, inner sigma 0.6) through a 6% halftone mask of a 1:1 line and space pattern with a line width of 100nm. Ultrapure water was used as the immersion liquid. Then, it was baked at 90°C (PEB: PostExposure Bake) for 60 seconds. Next, a tetramethylammonium hydroxide aqueous solution (2.38% by mass) was used as a developer to immerse for 30 seconds for development, and rinsed with pure water to form a 1:1 line and space (LS) pattern with a line width of 100nm.

[0969] In addition, the optimal exposure dose (sensitivity) (mJ / cm 2 In the determination of the sensitivity described above, the spatial width of the pattern was measured using a scanning electron microscope (SEM: Scanning Electron Microscope) (9380II manufactured by Hitachi High-Technologies Corporation).

[0970] Through the above steps, a pattern wafer for evaluation having a substrate and a pattern formed on the surface of the substrate was obtained.

[0971] <Pattern formation method (3): ArF immersion exposure, organic solvent development (negative)>

[0972] The organic anti-reflection film-forming composition SOC9110D and the Si-containing anti-reflection film-forming composition HM9825 were applied on a silicon wafer to form an anti-reflection film. The anti-reflection film was coated with a resist composition and baked at 100°C for 60 seconds (PB: Prebake) to form a resist film with a film thickness of 100 nm.

[0973] The resulting wafer was exposed using an ArF excimer laser immersion scanner (manufactured by ASML; XT1700i, NA0.85, Annular, outer sigma 0.9, inner sigma 0.6) through a 6% halftone mask of a 1:1 line and space pattern with a line width of 100nm. Ultrapure water was used as the immersion liquid. Then, it was baked at 90°C (PEB: PostExposure Bake) for 60 seconds. Next, it was developed by immersion in butyl acetate for 30 seconds as a developer and rinsed with methyl isobutyl carbinol (MIBC), thereby forming a 1:1 line and space (LS) pattern with a line width of 100nm.

[0974] In addition, the optimal exposure dose (sensitivity) (mJ / cm 2 In the determination of the sensitivity described above, the spatial width of the pattern was measured using a scanning electron microscope (SEM: Scanning Electron Microscope) (9380II manufactured by Hitachi High-Technologies Corporation).

[0975] Through the above steps, a pattern wafer for evaluation having a substrate and a pattern formed on the surface of the substrate was obtained.

[0976] <Performance Evaluation>

[0977] [Stability over time]

[0978] After the resist composition was stored at 40°C for 4 weeks, a line-and-space pattern was formed in the same manner as described above. In the obtained line-and-space pattern, the sensitivity was determined in the same manner as described 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 (4 weeks at 40°C), i.e., the degree of sensitivity change, was evaluated according to the following judgment criteria.

[0979] (Judgment Criteria)

[0980] A: The observed sensitivity variation is less than 1mJ / cm 2

[0981] B: Observed sensitivity change is 1mJ / cm 2 Above and less than 2mJ / cm 2

[0982] C: Observed sensitivity change is 2mJ / cm 2 Above and less than 3mJ / cm 2

[0983] D: Observed sensitivity change is 3mJ / cm 2 above

[0984] [Sensitivity]

[0985] For each resist composition, except that it does not contain anions (P), the same resist composition was prepared and a line and space pattern was formed in the same manner as above. In the resulting line and space pattern, the sensitivity was obtained as above. Based on the sensitivity of the line and space pattern formed using the resist composition not containing anions (P), the sensitivity of the line and space pattern formed using the resist composition containing anions (P) was evaluated according to the following judgment criteria to evaluate how much the sensitivity of the line and space pattern was reduced.

[0986] (Judgment Criteria)

[0987] A: The observed sensitivity reduction is less than 1mJ / cm 2

[0988] B: Observed sensitivity reduction is 1 mJ / cm 2 Above and less than 2mJ / cm 2

[0989] C: Observed sensitivity reduction is 2 mJ / cm 2 Above and less than 3mJ / cm 2

[0990] D: Observed sensitivity reduction is 3 mJ / cm 2 above

[0991] <Preparation of actinic ray-sensitive or radiation-sensitive resin composition> (EUV exposure)

[0992] (Examples 11-12, 21, 32-33)

[0993] The various components shown in Table 3 were mixed so as to have the solid content concentration (mass %) described in Table 3 to obtain a solution. The obtained liquid was first filtered through a polyethylene filter having a pore size of 50 nm, then filtered through a nylon filter having a pore size of 10 nm, and finally filtered through a polyethylene filter having a pore size of 5 nm. The obtained actinic ray-sensitive or radiation-sensitive resin composition (resist composition) was used in Examples and Comparative Examples.

[0994] In the examples, the solid content in the resist composition refers to all components except the solvent and the anion (P).

[0995] In addition, in the table, the content (mass %) of each component other than the solvent refers to the content ratio relative to the total solid content. In addition, the table describes the content ratio (mass %) of the solvent used relative to the total solvent.

[0996] The content of anions (P) was measured in the same manner as above.

[0997] <Pattern formation method (4): EUV exposure, alkaline development (positive)>

[0998] AL412 (manufactured by Brewer Science) was coated on 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 coated thereon and baked (PB) at 120°C for 60 seconds to form a resist film with a thickness of 30 nm.

[0999] The resist film was pattern irradiated using an EUV exposure device (manufactured by Exitech Corporation, Micro Exposure Tool, NA0.3, Quadrupol, outer sigma 0.68, inner sigma 0.36). In addition, as a reticle, a mask with a line size of 40 nm and a line:pitch of 1:1 was used.

[1000] The exposed resist film was baked (PEB) at 120°C for 60 seconds, developed with a tetramethylammonium hydroxide aqueous solution (TMAH, 2.38 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).

[1001] In addition, the optimal exposure dose (sensitivity) (mJ / cm 2 In the determination of the sensitivity described above, the spatial width of the pattern was measured using a scanning electron microscope (SEM: Scanning Electron Microscope) (9380II manufactured by Hitachi High-Technologies Corporation).

[1002] Through the above steps, a pattern wafer for evaluation having a substrate and a pattern formed on the surface of the substrate was obtained.

[1003] <Pattern formation method (5): EUV exposure, organic solvent development (negative)>

[1004] AL412 (manufactured by Brewer Science) was applied on a silicon wafer and baked at 205°C for 60 seconds to form an underlayer film with a thickness of 30 nm. The 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.

[1005] The resist film was pattern irradiated using an EUV exposure device (manufactured by Exitech Corporation, Micro Exposure Tool, NA0.3, Quadrupol, outer sigma 0.68, inner sigma 0.36). In addition, as a reticle, a mask with a line size of 40 nm and a line:pitch of 1:1 was used.

[1006] 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).

[1007] In addition, the optimal exposure dose (sensitivity) (mJ / cm 2 In the determination of the sensitivity described above, the spatial width of the pattern was measured using a scanning electron microscope (SEM: Scanning Electron Microscope) (9380II manufactured by Hitachi High-Technologies Corporation).

[1008] Through the above steps, a pattern wafer for evaluation having a substrate and a pattern formed on the surface of the substrate was obtained.

[1009] <Performance Evaluation>

[1010] [Stability over time]

[1011] After the resist composition was stored at 40°C for 4 weeks, a line-and-space pattern was formed in the same manner as described above. In the obtained line-and-space pattern, the sensitivity was determined in the same manner as described 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 (4 weeks at 40°C), i.e., the degree of sensitivity change, was evaluated according to the following judgment criteria.

[1012] (Judgment Criteria)

[1013] A: The observed sensitivity variation is less than 1mJ / cm 2

[1014] B: Observed sensitivity change is 1mJ / cm 2 Above and less than 2mJ / cm 2

[1015] C: Observed sensitivity change is 2mJ / cm2 Above and less than 3mJ / cm 2

[1016] D: Observed sensitivity change is 3mJ / cm 2 above

[1017] [Sensitivity]

[1018] For each resist composition, except that it does not contain anions (P), the same resist composition was prepared and a line and space pattern was formed in the same manner as above. In the resulting line and space pattern, the sensitivity was obtained as above. Based on the sensitivity of the line and space pattern formed using the resist composition not containing anions (P), the sensitivity of the line and space pattern formed using the resist composition containing anions (P) was evaluated according to the following judgment criteria to evaluate how much the sensitivity of the line and space pattern was reduced.

[1019] (Judgment Criteria)

[1020] A: The observed sensitivity reduction is less than 1mJ / cm 2

[1021] B: Observed sensitivity reduction is 1 mJ / cm 2 Above and less than 2mJ / cm 2

[1022] C: Observed sensitivity reduction is 2 mJ / cm 2 Above and less than 3mJ / cm 2

[1023] D: Observed sensitivity reduction is 3 mJ / cm 2 above

[1024] <Preparation of Actinic Ray-Sensitive or Radiation-Sensitive Resin Composition> (EB Exposure)

[1025] (Examples 13, 14, 22, 34, 35)

[1026] The various components shown in Table 3 were mixed so as to have the solid content concentration (mass %) described in Table 3 to obtain a solution. The obtained liquid 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 obtained actinic ray-sensitive or radiation-sensitive resin composition (resist composition) was used in the examples.

[1027] In the present example, the solid content in the resist composition refers to all components except the solvent and the anion (P).

[1028] In addition, in the table, the content (mass %) of each component other than the solvent refers to the content ratio relative to the total solid content. In addition, the table describes the content ratio (mass %) of the solvent used relative to the total solvent.

[1029] The content of anions (P) was measured in the same manner as above.

[1030] <Pattern formation method (6): EB exposure, alkaline development (positive)>

[1031] The resist composition shown in Table 3 was applied on a 6-inch wafer using a spin coater Mark 8 manufactured by Tokyo Electron Limited and baked (PB) on a hot plate at 110° C. for 90 seconds to obtain a resist film with a film thickness of 80 nm.

[1032] The resist film was pattern irradiated using an electron beam drawing device (manufactured by ELIONIX INC.; ELS-7500, accelerating voltage 50 KeV). In addition, as a reticle, a mask with a line size of 100 nm and a line: space ratio of 1:1 was used. After irradiation, it was baked (PEB) on a hot plate at 110°C for 90 seconds, immersed in a 2.38% by 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 spacing of 200 nm and a line width of 100 nm (space width of 100 nm).

[1033] In addition, the optimal exposure dose (sensitivity) (μC / cm 2 In the determination of the sensitivity described above, the spatial width of the pattern was measured using a scanning electron microscope (SEM: Scanning Electron Microscope) (9380II manufactured by Hitachi High-Technologies Corporation).

[1034] Through the above steps, a pattern wafer for evaluation having a substrate and a pattern formed on the surface of the substrate was obtained.

[1035] <Performance Evaluation>

[1036] [Stability over time]

[1037] After the resist composition was stored at 40°C for 4 weeks, a line-and-space pattern was formed in the same manner as described above. In the obtained line-and-space pattern, the sensitivity was determined in the same manner as described 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 (4 weeks at 40°C), i.e., the degree of sensitivity change, was evaluated according to the following judgment criteria.

[1038] (Judgment Criteria)

[1039] A: The observed sensitivity variation is less than 1μC / cm 2

[1040] B: Observed sensitivity change is 1μC / cm 2 Above and less than 2μC / cm 2

[1041] C: Observed sensitivity variation is 2μC / cm 2 Above and less than 3μC / cm 2

[1042] D: Observed sensitivity change is 3μC / cm 2 above

[1043] [Sensitivity]

[1044] For each resist composition, except that it does not contain anions (P), the same resist composition was prepared and a line and space pattern was formed in the same manner as above. In the resulting line and space pattern, the sensitivity was obtained as above. Based on the sensitivity of the line and space pattern formed using the resist composition not containing anions (P), the sensitivity of the line and space pattern formed using the resist composition containing anions (P) was evaluated according to the following judgment criteria to evaluate how much the sensitivity of the line and space pattern was reduced.

[1045] (Judgment Criteria)

[1046] A: The observed sensitivity reduction is less than 1μC / cm 2

[1047] B: Observed sensitivity reduction is 1μC / cm 2 Above and less than 2μC / cm 2

[1048] C: Observed sensitivity reduction is 2μC / cm 2 Above and less than 3μC / cm 2

[1049] D: Observed sensitivity reduction is 3μC / cm 2 above

[1050] The obtained evaluation results are shown in Table 4.

[1051]

[1052]

[1053] [Table 5]

[1054]

[1055] [Table 6]

[1056]

[1057] 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.

[1058] Industrial Applicability

[1059] According to the present invention, there can be provided an actinic ray-sensitive or radiation-sensitive resin composition capable of achieving extremely excellent stability over time while suppressing a decrease in sensitivity.

[1060] According to the present invention, there can also be provided an actinic ray-sensitive or radiation-sensitive film, a pattern forming method, and a method for producing an electronic device using the actinic ray-sensitive or radiation-sensitive resin composition.

[1061] While the present invention has been described in detail and with reference to specific embodiments, it will be apparent to one skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention.

[1062] This application claims priority based on Japanese patent application (Japanese patent application 2019-157428) filed on August 29, 2019, the contents of which are incorporated into this specification by reference.

Claims

1. An actinic ray-sensitive or radiation-sensitive resin composition comprising: (A) Resins whose polarity is increased by the action of acids; (B) photoacid generators; and Anion (P) selected from NO3 - 、SO4 2- , Cl - and Br - One or more anions in the group consisting of The content of the anion (P) is 0.01 ppb or more and 10 ppb or less relative to the total mass of the actinic ray-sensitive or radiation-sensitive resin composition.

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

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

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

1. 5 . An actinic ray-sensitive or radiation-sensitive film, which is formed from the actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 .

6. A pattern forming method comprising the following steps: A step of exposing the actinic ray-sensitive or radiation-sensitive film according to claim 5; and A step of developing the exposed actinic ray-sensitive or radiation-sensitive film using a developer.

7. A method for manufacturing an electronic device, comprising the pattern forming method according to claim 6.

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