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

Abstract

The present invention provides a pattern forming method, a method for manufacturing an electronic device, and an actinic ray-sensitive or radiation-sensitive resin composition. The pattern forming method comprises: (i) forming an actinic ray-sensitive or radiation-sensitive film having a film thickness of 700 nm or more from a specific actinic ray-sensitive or radiation-sensitive resin composition; (ii) irradiating the actinic ray-sensitive or radiation-sensitive film with actinic rays or radiation having a wavelength of 200 nm or less; and (iii) developing the actinic ray-sensitive or radiation-sensitive film irradiated with actinic rays or radiation having a wavelength of 200 nm or less using a developer.

Description

Technical Field

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

[0002] To compensate for the reduced sensitivity of resists due to light absorption after exposure to KrF excimer lasers (248 nm), patterning methods using chemical amplification are used. For example, in positive chemical amplification, a photoacid generator contained in the exposed area is first decomposed by light irradiation to generate acid. Then, during a post-exposure bake (PEB) process, the generated acid catalyzes the conversion of alkali-insoluble groups in the photosensitive composition into alkali-soluble groups. Development is then performed, for example, using an alkaline solution. This removes the exposed area, resulting in the desired pattern.

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

[0004] To further miniaturize semiconductor devices, the wavelength of exposure light sources has been shortened, and the numerical aperture (NA) of projection lenses has been increased. Currently, exposure systems 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 has been proposed in which the space between the projection lens and the sample is filled with a high-refractive-index liquid (hereinafter referred to as "immersion liquid") (i.e., the liquid immersion method).

[0005] Patent Document 1 describes a negative pattern forming method comprising: (a) forming a film having a thickness of 200 nm or greater using a chemically amplified resist composition; (b) exposing the film to light; and (c) developing the exposed film using a developer containing an organic solvent. The chemically amplified resist composition comprises: (A) a resin whose polarity increases due to the action of an acid and whose solubility in a developer containing an organic solvent decreases; (B) a compound that generates an acid upon irradiation with actinic rays or radiation; and (C) a solvent.

[0006] Patent Document 2 describes a positive resist composition for an ion implantation process, comprising: (A) a resin whose dissolution rate in an alkaline developer is increased by the action of an acid, and (B) a compound that generates an acid by irradiation with actinic rays. The positive resist composition for an ion implantation process is characterized in that a resist film formed from the positive resist composition has a transmittance of 30 to 60% at 193 nm.

[0007] Previous technical literature

[0008] Patent Literature

[0009] Patent Document 1: Japanese Patent Application Laid-Open No. 2012-133329

[0010] Patent Document 2: Japanese Patent Application Laid-Open No. 2006-189713 Summary of the Invention

[0011] Technical issues to be solved by the invention

[0012] On the other hand, in recent years, various electronic devices have been required to have higher functionality, and accordingly, there has been a demand for further improvement in the properties of resist patterns used for microfabrication.

[0013] Therefore, the present inventors studied improving the resist performance in thick film (having a thickness of 700 nm or more) resist patterns and found that it is difficult to achieve both excellent resolution and suppression of cracks (breaks) and peeling of the resist pattern.

[0014] The present invention aims to provide a pattern forming method, an electronic device manufacturing method, and an actinic ray-sensitive or radiation-sensitive resin composition using an actinic ray-sensitive or radiation-sensitive resin composition, which have excellent resolution when forming a pattern from a thick actinic ray-sensitive or radiation-sensitive film (having a thickness of 700 nm or more) and can suppress cracking and peeling of the resist pattern.

[0015] Means for solving technical problems

[0016] That is, the present inventors have found that the above-mentioned problems can be solved by the following configuration.

[0017] [1] A pattern forming method comprising:

[0018] (i) forming an actinic ray-sensitive or radiation-sensitive film having a film thickness of 700 nm or more from the actinic ray-sensitive or radiation-sensitive resin composition;

[0019] (ii) irradiating the actinic ray or radiation-sensitive film with actinic rays or radiation having a wavelength of 200 nm or less; and

[0020] (iii) a step of developing the actinic ray- or radiation-sensitive film irradiated with the actinic ray or radiation having a wavelength of 200 nm or less using a developer, wherein:

[0021] The actinic ray-sensitive or radiation-sensitive resin composition contains (A) a polymer having an acid-decomposable group and (B) a photoacid generator.

[0022] The polymer (A) includes a repeating unit having a hydrophilic group, and the weight average molecular weight of the polymer (A) is 8,000 or less.

[0023] [2] The pattern forming method according to [1], wherein

[0024] The photoacid generator (B) includes a compound represented by the following general formula (ZI-3) or a compound represented by the following general formula (ZI-4).

[0025] [Chemical Formula 1]

[0026]

[0027] In the above general formula (ZI-3),

[0028] R1 represents an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group or an alkenyl group.

[0029] R2 and R3 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, or an aryl group. R2 and R3 may be linked to form a ring.

[0030] R1 and R2 may be linked to each other to form a ring.

[0031] R X and R y R each independently represents an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group or an alkoxycarbonylcycloalkyl group. X With R y They may be connected to each other to form a ring, and the ring structure may contain an oxygen atom, a nitrogen atom, a sulfur atom, a keto group, an ether bond, an ester bond, or an amide bond.

[0032] Z - Indicates anion.

[0033] [Chemical Formula 2]

[0034]

[0035] In the general formula (ZI-4),

[0036] l represents an integer from 0 to 2.

[0037] r represents an integer from 0 to 8.

[0038] R 13 represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group or an alkoxycarbonyl group.

[0039] R 14represents a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group or a cycloalkylsulfonyl group. 14 When multiple R 14 They may be the same as or different from each other.

[0040] R 15 Each independently represents an alkyl group, a cycloalkyl group or a naphthyl group. 15 Can bond to each other to form a ring. 15 When they are bonded to each other to form a ring, the ring structure may contain an oxygen atom, a nitrogen atom, a sulfur atom, a keto group, an ether bond, an ester bond, or an amide bond.

[0041] X - Indicates anion.

[0042] [3] The pattern forming method according to [2], wherein

[0043] The above Z - or the above X - It is an anion represented by any of the following general formulae (A1) to (A3).

[0044] [Chemical Formula 3]

[0045]

[0046] In the above general formula (A1),

[0047] R 21 、R 22 Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a fluorine atom, an alkyl group substituted by a fluorine atom, or a cycloalkyl group substituted by a fluorine atom. 21 、R 22 At least one of them is a fluorine atom, an alkyl group substituted with a fluorine atom, or a cycloalkyl group substituted with a fluorine atom.

[0048] L represents a single bond or a divalent linking group.

[0049] X represents an organic group.

[0050] In the above general formula (A2),

[0051] R 23 represents a hydrogen atom, an alkyl group, a cycloalkyl group, a fluorine atom, -C(=O)-Rx or -S(=O)2-Rx. Rx represents an organic group.

[0052] R 24 represents a hydrogen atom, an alkyl group, a cycloalkyl group or a fluorine atom,

[0053] A1 represents -C(=O)- or -S(=O)2-.

[0054] R 23 With R 24 They may be bonded to each other to form a ring.

[0055] In the above general formula (A3),

[0056] R 25 、R 26 、R 27 Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group or a fluorine atom.

[0057] A2 to A4 each independently represent -C(=O)- or -S(=O)2-.

[0058] R 25 、R 26 、R 27 At least two of them may be bonded to each other to form a ring.

[0059] [4] The pattern forming method according to any one of [1] to [3], wherein

[0060] The (A) polymer has an Onishi parameter of 4.2 or less.

[0061] [5] The pattern forming method according to any one of [1] to [4], wherein

[0062] The polymer (A) includes two or more repeating units having a hydrophilic group, and the repeating units are different from each other.

[0063] [6] The pattern forming method according to [5], wherein

[0064] The polymer (A) includes three or more repeating units having a hydrophilic group, and the repeating units are different from each other.

[0065] [7] The pattern forming method according to any one of [1] to [6], wherein

[0066] The repeating unit having a hydrophilic group includes a repeating unit having a carboxyl group or a hydroxyl group.

[0067] [8] The pattern forming method according to any one of [1] to [7], wherein

[0068] The repeating unit having a hydrophilic group includes a repeating unit having a carboxyl group.

[0069] [9] The pattern forming method according to any one of [1] to [8], wherein

[0070] The polymer (A) includes one or more repeating units having a carboxyl group and one or more repeating units having a hydroxyl group.

[0071]

[10] The pattern forming method according to [9], wherein

[0072] The repeating unit having a carboxyl group is a repeating unit represented by the following general formula (1).

[0073] [Chemical Formula 4]

[0074]

[0075] In the above general formula (1),

[0076] R 31 represents a hydrogen atom or an alkyl group.

[0077] A 31 represents a single bond or a (r+1)-valent linking group.

[0078] Y represents a carboxyl group.

[0079] r represents an integer greater than or equal to 1.

[0080]

[11] The pattern forming method according to [9] or

[10] , wherein

[0081] The repeating unit having a hydroxyl group is a repeating unit represented by the following general formula (2).

[0082] [Chemical Formula 5]

[0083]

[0084] In the above general formula (2),

[0085] R 41 represents a hydrogen atom or an alkyl group.

[0086] A 41 represents a single bond or a (s+1) valence linking group. 41 It does not have an aromatic ring.

[0087] Z represents a hydroxyl group.

[0088] s represents an integer greater than or equal to 1.

[0089]

[12] The pattern forming method according to any one of [1] to

[11] , wherein

[0090] The weight average molecular weight of the polymer (A) is 7,000 or less.

[0091]

[13] The pattern forming method according to any one of [1] to

[12] , wherein

[0092] The weight average molecular weight of the polymer (A) is 6,000 or less.

[0093]

[14] The pattern forming method according to any one of [1] to

[13] , wherein

[0094] The photoacid generator (B) is a mixture of two compounds represented by the following general formula (ZI-3).

[0095] [Chemical Formula 6]

[0096]

[0097] In the above general formula (ZI-3),

[0098] R1 represents an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group or an alkenyl group.

[0099] R2 and R3 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, or an aryl group. R2 and R3 may be linked to form a ring.

[0100] R1 and R2 may be linked to each other to form a ring.

[0101] R X and R y R each independently represents an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group or an alkoxycarbonylcycloalkyl group. X With R y They may be connected to each other to form a ring, and the ring structure may contain an oxygen atom, a nitrogen atom, a sulfur atom, a keto group, an ether bond, an ester bond, or an amide bond.

[0102] Z - It represents an anion represented by any of the following general formulae (A1) to (A3).

[0103] [Chemical Formula 7]

[0104]

[0105] In the above general formula (A1),

[0106] R 21 、R 22 Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a fluorine atom, an alkyl group substituted by a fluorine atom, or a cycloalkyl group substituted by a fluorine atom. 21 、R 22 At least one of them is a fluorine atom, an alkyl group substituted with a fluorine atom, or a cycloalkyl group substituted with a fluorine atom.

[0107] L represents a single bond or a divalent linking group.

[0108] X represents an organic group.

[0109] In the above general formula (A2),

[0110] R 23 represents a hydrogen atom, an alkyl group, a cycloalkyl group, a fluorine atom, -C(=O)-Rx or -S(=O)2-Rx. Rx represents an organic group.

[0111] R 24 represents a hydrogen atom, an alkyl group, a cycloalkyl group or a fluorine atom,

[0112] A1 represents -C(=O)- or -S(=O)2-.

[0113] R 23 With R 24 They may be bonded to each other to form a ring.

[0114] In the above general formula (A3),

[0115] R 25 、R 26 、R 27 Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group or a fluorine atom.

[0116] A2 to A4 each independently represent -C(=O)- or -S(=O)2-.

[0117] R 25 、R 26 、R 27 At least two of them may be bonded to each other to form a ring.

[0118]

[15] The pattern forming method according to

[14] , wherein

[0119] The photoacid generator (B) is a mixture of two compounds represented by the general formula (ZI-3) and generates two acids upon irradiation with actinic rays or radiation, wherein the acid dissociation constants pKa values ​​of the two acids at 25°C differ by 0.5 or more.

[0120]

[16] The pattern forming method according to any one of [1] to

[15] , wherein

[0121] The content of the photoacid generator (B) is 6% by mass or less based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition.

[0122]

[17] The pattern forming method according to any one of [1] to

[16] , wherein

[0123] The actinic ray-sensitive or radiation-sensitive resin composition contains (D) an acid diffusion controller, and the content of the (D) acid diffusion controller is 0.40 or less in a molar ratio relative to the content of the (B) photoacid generator.

[0124]

[18] The pattern forming method according to any one of [1] to

[17] , wherein

[0125] The developer is an alkaline developer.

[0126]

[19] A method for manufacturing an electronic device, comprising the pattern forming method according to any one of [1] to

[18] .

[0127]

[20] An actinic ray-sensitive or radiation-sensitive resin composition for use in a pattern forming method,

[0128] The pattern forming method comprises:

[0129] (i) forming an actinic ray-sensitive or radiation-sensitive film having a film thickness of 700 nm or more from the actinic ray-sensitive or radiation-sensitive resin composition;

[0130] (ii) irradiating the actinic ray or radiation-sensitive film with actinic rays or radiation having a wavelength of 200 nm or less; and

[0131] (iii) a step of developing the actinic ray- or radiation-sensitive film irradiated with the actinic ray or radiation having a wavelength of 200 nm or less using a developer,

[0132] The actinic ray-sensitive or radiation-sensitive resin composition contains (A) a polymer having an acid-decomposable group and (B) a photoacid generator.

[0133] The polymer (A) includes a repeating unit having a hydrophilic group, and the weight average molecular weight of the polymer (A) is 8,000 or less.

[0134] Effects of the Invention

[0135] According to the present invention, a pattern forming method using an actinic ray-sensitive or radiation-sensitive resin composition, a method for manufacturing an electronic device, and an actinic ray-sensitive or radiation-sensitive resin composition can be provided. When a pattern is formed from a thick actinic ray-sensitive or radiation-sensitive film (having a thickness of 700 nm or more), the resolution is excellent and cracking and peeling of the resist pattern can be suppressed. DETAILED DESCRIPTION

[0136] Hereinafter, the present invention will be described in detail.

[0137] The constituent elements described below will be described based on representative embodiments of the present invention, but the present invention is not limited to these embodiments.

[0138] In the marking of groups (atomic groups) in this specification, the markings that do not record substitution and unsubstituted include groups with substituents in addition to groups without substituents. For example, "alkyl" includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups). In addition, "organic group" in this specification refers to a group containing at least one carbon atom.

[0139] Furthermore, in this specification, when a compound "may have a substituent", the type, position, and number of substituents are not particularly limited. The number of substituents may be, for example, 1, 2, 3, or more. Examples of substituents include monovalent non-metallic atomic groups other than hydrogen atoms, and can be selected from the following substituents T.

[0140] (Substituent T)

[0141] 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 methoxyacetyl; 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; formyl groups; and combinations thereof.

[0142] "Actinic rays" or "radiation" as used herein include, for example, the bright-line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams (EB). "Light" as used herein refers to actinic rays or radiation.

[0143] Unless otherwise specified, "exposure" in this specification includes not only exposure using the bright line spectrum of a mercury lamp, far ultraviolet light represented by excimer laser, extreme ultraviolet light, X-rays and EUV light, but also drawing using particle beams such as electron beams and ion beams.

[0144] 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.

[0145] In the present specification, (meth)acrylate means acrylate and methacrylate, and (meth)acrylic acid means acrylic acid and methacrylic acid.

[0146] 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 are defined as polystyrene-equivalent 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).

[0147] In this 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.

[0148] In this specification, the term "process" refers not only to an independent process but also to a process that cannot be clearly distinguished from other processes as long as the intended purpose of the process can be achieved.

[0149] In this specification, "total solids" refers to the total mass of the components of the entire composition excluding the solvent. Furthermore, "solids" refers to the components excluding the solvent as described above and may be solid or liquid at 25°C, for example.

[0150] In this specification, "mass %" and "weight %" have the same meaning, and "parts by mass" and "parts by weight" have the same meaning.

[0151] Furthermore, in this specification, a combination of two or more preferred aspects is a more preferred aspect.

[0152] [Pattern Formation Method]

[0153] The pattern forming method of the present invention will be described.

[0154] The pattern forming method of the present invention comprises:

[0155] (i) a step of forming an actinic ray-sensitive or radiation-sensitive film having a film thickness of 700 nm or more from the actinic ray-sensitive or radiation-sensitive resin composition (film forming step);

[0156] (ii) a step of irradiating the actinic ray or radiation-sensitive film with an actinic ray or radiation having a wavelength of 200 nm or less (exposure step); and

[0157] (iii) a step of developing the actinic ray- or radiation-sensitive film irradiated with the actinic ray or radiation having a wavelength of 200 nm or less using a developer (developing step), wherein:

[0158] The actinic ray-sensitive or radiation-sensitive resin composition contains (A) a polymer having an acid-decomposable group and (B) a photoacid generator.

[0159] The polymer (A) includes a repeating unit having a hydrophilic group, and the weight average molecular weight of the polymer (A) is 8,000 or less.

[0160] According to this structure, when forming a pattern with a thick film (having a thickness of 700 nm or more) of an actinic ray-sensitive or radiation-sensitive film, the resolution is excellent and cracking and peeling of the resist pattern can be suppressed.

[0161] Although the mechanism by which the present invention can exhibit the above-mentioned effects is not necessarily clear, the present inventors believe the following.

[0162] First, in step (ii) of the pattern forming method of the present invention, the actinic ray or radiation-sensitive film is irradiated with actinic rays or radiation having a wavelength of 200 nm or less. This can improve the resolution of the obtained pattern.

[0163] The actinic ray-sensitive or radiation-sensitive resin composition used in step (i) of the pattern forming method of the present invention comprises (A) a polymer having an acid-degradable group and (B) a photoacid generator, wherein the polymer (A) includes a repeating unit having a hydrophilic group, and the weight average molecular weight of the polymer (A) is 8,000 or less.

[0164] Conventionally, resist films irradiated with actinic rays or radiation (e.g., ArF light) having a wavelength of 200 nm or less are generally thin films (typically less than 700 nm). To ensure the strength of the film itself and to increase the glass transition temperature (Tg) of the resin contained in the resist composition used to form the film, the weight-average molecular weight of the resin has typically tended to be around 10,000 (e.g., exceeding 8,000 and falling below 12,000). Using such a resin can suppress acid diffusion even in thin films, thereby improving resolution.

[0165] Research into using thick films (700 nm or more) as resist films revealed cracking and peeling in the resist films (and, consequently, the resist patterns). The present inventors discovered that when the weight-average molecular weight of the resin is 9,000 or greater, as the film thickness increases to 700 nm or more, the film cannot withstand stress during pattern formation, resulting in cracking and pattern peeling. Therefore, to account for this stress, the weight-average molecular weight of the resin needs to be further reduced.

[0166] However, even if the weight average molecular weight of the resin is further reduced, it is difficult to improve cracks and pattern peeling. Furthermore, even if the weight average molecular weight is further reduced, excellent resolution cannot be obtained.

[0167] Furthermore, as a result of in-depth research conducted by the present inventors and others, it was discovered that by having the above-mentioned (A) polymer contain repeating units having a hydrophilic group and having a weight-average molecular weight of 8,000 or less, cracks or peeling can be reduced in thick films, especially in resist films (and thus resist patterns), and resolution can be improved.

[0168] It is considered that the polymer (A) having a hydrophilic group interacts with the acid generated in the exposed area to suppress the diffusion of the acid to the unexposed area, thereby achieving excellent resolution despite a thick film.

[0169] In addition, it is believed that the hydrophilic groups of the above-mentioned (A) polymer interact with each other to strengthen the strength of the film itself, so that it can be used in thick films while reducing the weight-average molecular weight. Furthermore, by setting the weight-average molecular weight to below 8000, it is less susceptible to stress even in thick films, thereby suppressing cracks in the resist film (and thus the resist pattern) and peeling of the resist pattern.

[0170] Furthermore, since the polymer (A) has a hydrophilic group, the interaction with the substrate becomes stronger, and thus the adhesion with the resist film tends to be improved.

[0171] As described above, in step (ii) of the pattern forming method of the present invention, the actinic ray-sensitive or radiation-sensitive film is irradiated with actinic rays or radiation having a wavelength of 200 nm or less. The polymer (A) contained in the actinic ray-sensitive or radiation-sensitive composition used in the pattern forming method of the present invention includes a repeating unit having a hydrophilic group, and the weight-average molecular weight of the polymer (A) is 8,000 or less. It is believed that, as a result, surprisingly, when a pattern is formed from a thick film (having a thickness of 700 nm or more) of the actinic ray-sensitive or radiation-sensitive film, excellent resolution is achieved, and cracking and peeling of the resist pattern can be suppressed.

[0172] [Acticular ray-sensitive or radiation-sensitive resin composition]

[0173] The actinic ray-sensitive or radiation-sensitive resin composition used in step (i) of the above-mentioned pattern forming method will be described.

[0174] The actinic ray-sensitive or radiation-sensitive resin composition contains (A) a polymer having an acid-decomposable group and (B) a photoacid generator.

[0175] The polymer (A) includes a repeating unit having a hydrophilic group, and the weight average molecular weight of the polymer (A) is 8,000 or less.

[0176] The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is preferably a resist composition, and may be a positive resist composition or a negative resist composition, and may be a resist composition for alkaline development or for organic solvent development.

[0177] The resist composition of the present invention is typically a chemically amplified resist composition.

[0178] Hereinafter, the components contained in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention (hereinafter also referred to as “the composition of the present invention”) will be described in detail.

[0179] <(A) Polymer>

[0180] The actinic ray-sensitive or radiation-sensitive resin composition of the present invention contains a polymer (also referred to as "(A) polymer" or "polymer (A)") having an acid-decomposable group, the polymer including repeating units having a hydrophilic group, and the weight-average molecular weight of the polymer being 8,000 or greater.

[0181] In this case, in the pattern forming method of the present invention, typically, when an alkaline developer is used as the developer, a positive pattern is preferably formed, and when an organic developer is used as the developer, a negative pattern is preferably formed.

[0182] (Repeating unit having a hydrophilic group)

[0183] The polymer (A) contains a repeating unit having a hydrophilic group.

[0184] The hydrophilic group is not particularly limited as long as it has affinity for water. Examples thereof include carboxyl groups, hydroxyl groups, lactone groups, sultone groups, cyano groups, sulfonamide groups, and groups having ester groups (wherein the ester group does not form a ring).

[0185] The repeating unit having the above-mentioned hydrophilic group preferably includes a repeating unit having a carboxyl group or a hydroxyl group.

[0186] The repeating units having the above-mentioned hydrophilic groups preferably include repeating units having carboxyl groups. The carboxyl groups have strong hydrophilicity and interact more strongly with other hydrophilic groups, thereby achieving more excellent effects of the present invention.

[0187] The polymer (A) particularly preferably contains a repeating unit having a carboxyl group.

[0188] The repeating unit having a carboxyl group is not particularly limited, but is preferably a repeating unit represented by the following general formula (1).

[0189] [Chemical Formula 8]

[0190]

[0191] In the above general formula (1),

[0192] R 31 represents a hydrogen atom or an alkyl group.

[0193] A 31 represents a single bond or a (r+1)-valent linking group.

[0194] Y represents a carboxyl group.

[0195] r represents an integer greater than or equal to 1.

[0196] R 31 The alkyl group of R is not particularly limited, but is preferably an alkyl group having 1 to 4 carbon atoms. 31 The alkyl group may have a substituent, and examples of the substituent include the substituent T described above.

[0197] In A 31 Among the (r+1)-valent linking groups, the divalent linking group when r is 1 is not particularly limited, and examples thereof include an alkylene group, a cycloalkylene group, an aromatic group, -CO-, -COO-, and a group formed by combining two or more of these.

[0198] The alkylene group may be linear or branched, and preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms.

[0199] The cycloalkylene group may be monocyclic or polycyclic, and preferably has 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms.

[0200] The aromatic group is a divalent aromatic group, preferably an aromatic group having 6 to 20 carbon atoms, more preferably an aromatic group having 6 to 15 carbon atoms.

[0201] The aromatic ring constituting the aromatic group is not particularly limited, and examples thereof include aromatic rings having 6 to 20 carbon atoms, specifically benzene rings, naphthalene rings, anthracene rings, thiophene rings, etc. A benzene ring or a naphthalene ring is preferred, and a benzene ring is more preferred.

[0202] The alkylene group, cycloalkylene group, and aromatic group may further have a substituent. The further substituent is not particularly limited, but is preferably the substituent T described above.

[0203] Specific examples of the (r+1)-valent linking group when r is an integer of 2 or greater include preferably groups obtained by removing (r-1) arbitrary hydrogen atoms from the above-mentioned specific examples of the divalent linking group.

[0204] The (r+1)-valent linking group may further have a substituent.

[0205] r represents an integer greater than or equal to 1. In addition, r represents the number of Y.

[0206] The upper limit of r is not particularly limited, but is preferably an integer of 9 or less.

[0207] r is preferably an integer of 1-5, more preferably an integer of 1-2.

[0208] Specific examples of monomers corresponding to the repeating unit represented by general formula (1) are given below, but the present invention is not limited to these specific examples.

[0209] [Chemical Formula 9]

[0210]

[0211] The repeating unit having the hydroxyl group is not particularly limited, but is preferably a repeating unit represented by the following general formula (2).

[0212] [Chemical Formula 10]

[0213]

[0214] In the above general formula (2),

[0215] R 41 represents a hydrogen atom or an alkyl group.

[0216] A 41 represents a single bond or a (s+1) valence linking group. 41 It does not have an aromatic ring.

[0217] Z represents a hydroxyl group.

[0218] s represents an integer greater than or equal to 1.

[0219] R 41 The alkyl group of R is not particularly limited, but is preferably an alkyl group having 1 to 4 carbon atoms. 41 The alkyl group may have a substituent, and examples of the substituent include the substituent T described above.

[0220] In A41 Among the (s+1)-valent linking groups, the divalent linking group when s is 1 is not particularly limited, and examples thereof include alkylene, cycloalkylene, -CO-, -COO-, and a group formed by combining two or more of these.

[0221] The alkylene group may be linear or branched, and preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms.

[0222] The cycloalkylene group may be monocyclic or polycyclic, and preferably has 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms.

[0223] The alkylene group and the cycloalkylene group may further have a substituent. The further substituent is not particularly limited, but is preferably the substituent T described above.

[0224] Specific examples of the (s+1)-valent linking group when s is an integer of 2 or greater include preferably groups obtained by removing (s-1) arbitrary hydrogen atoms from the above-mentioned specific examples of the divalent linking group.

[0225] The (s+1)-valent linking group may further have a substituent.

[0226] In addition, A 41 It does not have an aromatic ring.

[0227] s represents an integer greater than or equal to 1. In addition, s represents the number of Z.

[0228] The upper limit of s is not particularly limited, but is preferably an integer of 6 or less.

[0229] s is preferably an integer of 1-5, more preferably an integer of 1-2.

[0230] Specific examples of monomers corresponding to the repeating unit represented by general formula (2) are given below, but the present invention is not limited to these specific examples.

[0231] [Chemical Formula 11]

[0232]

[0233] The lactone group and the sultone group are described below.

[0234] Any lactone or sultone group can be used as long as it has a lactone or sultone structure. A 5- to 7-membered ring lactone structure or a 5- to 7-membered ring sultone structure is preferred. More preferred are structures in which another ring structure is fused to the 5- to 7-membered ring lactone structure to form a bicyclic or spiro structure, or structures in which another ring structure is fused to the 5- to 7-membered ring sultone structure to form a bicyclic or spiro structure. It is further preferred to include repeating units having a lactone structure represented by any of the following general formulas (LC1-1) to (LC1-21) or a sultone structure represented by any of the following general formulas (SL1-1) to (SL1-3). Furthermore, the lactone or sultone structure may be directly bonded to the main chain. Preferred structures include (LC1-1), (LC1-4), (LC1-5), (LC1-8), (LC1-16), (LC1-21), and (SL1-1).

[0235] [Chemical Formula 12]

[0236]

[0237] The lactone structure part or the sultone structure part may have a substituent (Rb2) or may not have a substituent (Rb2). Preferred substituents (Rb2) 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, hydroxyl groups, cyano groups, and acid-decomposable groups. More preferred are alkyl groups having 1 to 4 carbon atoms, cyano groups, and acid-decomposable groups. n2 represents an integer from 0 to 4. When n2 is 2 or more, the multiple substituents (Rb2) present may be the same or different. Furthermore, the multiple substituents (Rb2) present may be bonded to each other to form a ring.

[0238] The repeating unit having a lactone group or a sultone group is preferably a repeating unit represented by the following general formula (III).

[0239] [Chemical Formula 13]

[0240]

[0241] In the above general formula (III),

[0242] A represents an ester bond (a group represented by -COO-) or an amide bond (a group represented by -CONH-).

[0243] n is the number of repetitions of the structure represented by -R0-Z-, and represents an integer from 0 to 5, preferably 0 or 1, and more preferably 0. However, when n is 0, -R0-Z- does not exist, and a single bond is formed.

[0244] R0 represents an alkylene group, a cycloalkylene group, or a combination thereof. When there are multiple R0 groups, each group independently represents an alkylene group, a cycloalkylene group, or a combination thereof.

[0245] Z represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond, or a urea bond. When there are multiple Zs, each independently represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond, or a urea bond.

[0246] R8 represents a monovalent organic group having a lactone structure or a sultone structure.

[0247] R7 represents a hydrogen atom, a halogen atom or a monovalent organic group (preferably a methyl group).

[0248] The alkylene group or cycloalkylene group of R0 may have a substituent.

[0249] Z is preferably an ether bond or an ester bond, more preferably an ester bond.

[0250] The following are specific examples of monomers corresponding to the repeating unit represented by general formula (III), but the present invention is not limited to these specific examples. The following specific examples correspond to the case where R7 in general formula (III) is a methyl group, and R7 can be arbitrarily substituted with a hydrogen atom, a halogen atom, or a monovalent organic group.

[0251] [Chemical Formula 14]

[0252]

[0253] In addition to the above-mentioned monomers, the monomers shown below can also be preferably used as the raw materials of the polymer (A).

[0254] [Chemical Formula 15]

[0255]

[0256] Sulfonamide group is -SO2NR 51 R 52 The group represented by R 51 、R 52 Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group.

[0257] As R 51 、R 52 The alkyl group is not particularly limited and may be linear or branched. It is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably an alkyl group having 1 to 4 carbon atoms.

[0258] As R 51 、R 52The cycloalkyl group is not particularly limited and may be monocyclic or polycyclic. It is preferably a cycloalkyl group having 3 to 15 carbon atoms, more preferably a cycloalkyl group having 3 to 10 carbon atoms, and even more preferably a cycloalkyl group having 3 to 6 carbon atoms.

[0259] As R 51 、R 52 The aryl group is not particularly limited, but is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, and still more preferably an aryl group having 6 to 10 carbon atoms.

[0260] The alkyl group, cycloalkyl group, and aryl group may have a substituent. The substituent is not particularly limited, and examples thereof include the substituent T described above.

[0261] Specific examples of monomers corresponding to the repeating unit having a sulfonamide group are given below, but the present invention is not limited to these specific examples.

[0262] [Chemical Formula 16]

[0263]

[0264] The group having an ester group (wherein the ester group does not form a ring) (hereinafter, also simply referred to as "a group having an ester group") is a group having an ester group (-COO-). Wherein the ester group does not form a ring.

[0265] The ester group in the group having an ester group is not directly bonded to the main chain of the polymer (A).

[0266] The group having an ester group is not particularly limited, but is preferably -COO-R 61 or-OCO-R 62 . R 61 、R 62 Each independently represents an alkyl group, a cycloalkyl group or an aryl group.

[0267] As R 61 、R 62 The alkyl group is not particularly limited and may be linear or branched. It is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably an alkyl group having 1 to 4 carbon atoms.

[0268] As R 61 、R 62 The cycloalkyl group is not particularly limited and may be monocyclic or polycyclic. It is preferably a cycloalkyl group having 3 to 15 carbon atoms, more preferably a cycloalkyl group having 3 to 10 carbon atoms, and even more preferably a cycloalkyl group having 3 to 6 carbon atoms.

[0269] The carbon constituting the cycloalkyl group (the carbon contributing to the ring formation) may be a carbonyl carbon, and may also be substituted with a heteroatom (eg, an oxygen atom or a sulfur atom).

[0270] In a preferred embodiment, one carbon atom constituting the cycloalkyl group (the carbon atom contributing to the ring formation) is preferably a carbonyl carbon, and the other carbon atom constituting the cycloalkyl group (the carbon atom contributing to the ring formation) is preferably substituted with a heteroatom.

[0271] As R 61 、R 62 The aryl group is not particularly limited, but is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, and still more preferably an aryl group having 6 to 10 carbon atoms.

[0272] The alkyl group, cycloalkyl group, and aryl group may have a substituent. The substituent is not particularly limited, and examples thereof include the substituent T described above.

[0273] Specific examples of monomers corresponding to the repeating unit containing a group having an ester group are given below, but the present invention is not limited to these specific examples.

[0274] [Chemical Formula 17]

[0275]

[0276] The repeating unit having a hydrophilic group may have one hydrophilic group or multiple hydrophilic groups. The repeating unit having a hydrophilic group preferably has 1 to 8 hydrophilic groups, more preferably 1 to 4, even more preferably 1 to 2, and most preferably 1. When the repeating unit having a hydrophilic group has multiple hydrophilic groups, the multiple hydrophilic groups may be the same or different.

[0277] The repeating unit having a hydrophilic group may also have an acid-decomposable group. The acid-decomposable group is described below. When the repeating unit having a hydrophilic group has an acid-decomposable group, the repeating unit having the hydrophilic group is also equivalent to the repeating unit having the acid-decomposable group described below.

[0278] The repeating unit having a hydrophilic group preferably does not have an acid-decomposable group.

[0279] The content of the repeating unit having a hydrophilic group contained in the polymer (A) (the total of the repeating units having a hydrophilic group when there are multiple repeating units having a hydrophilic group) is preferably 10 to 80 mol%, more preferably 20 to 70 mol%, and even more preferably 30 to 70 mol% relative to all the repeating units of the polymer (A).

[0280] The content of the repeating unit having a carboxyl group contained in the polymer (A) (the total of the repeating units having a carboxyl group when there are multiple repeating units having a carboxyl group) is preferably 1 to 30 mol%, more preferably 5 to 25 mol%, and even more preferably 5 to 20 mol% based on all the repeating units of the polymer (A).

[0281] Furthermore, the content of the repeating unit having a carboxyl group contained in the repeating unit having a hydrophilic group of the polymer (A) (the total of the repeating units having a carboxyl group when there are multiple repeating units having a carboxyl group) is preferably 1 to 40 mol%, more preferably 1 to 30 mol%, and even more preferably 1 to 20 mol% relative to all the repeating units having a hydrophilic group.

[0282] (Repeating unit having an acid-decomposable group)

[0283] The polymer (A) preferably contains a repeating unit having an acid-decomposable group.

[0284] 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.

[0285] Examples of the polar group include acidic groups (typically, groups that dissociate in a 2.38% by mass tetramethylammonium hydroxide aqueous solution) such as a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonylimide group, an (alkylsulfonyl)(alkylcarbonyl)methylene group, an (alkylsulfonyl)(alkylcarbonyl)imide group, a bis(alkylcarbonyl)methylene group, a bis(alkylcarbonyl)imide group, a bis(alkylsulfonyl)methylene group, a bis(alkylsulfonyl)imide group, a tri(alkylcarbonyl)methylene group, and a tri(alkylsulfonyl)methylene group, and an alcoholic hydroxyl group.

[0286] 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 directly bonded to an aromatic ring (phenolic hydroxyl group), and excludes aliphatic alcohol groups (e.g., hexafluoroisopropanol group) whose α position is substituted with an electron-withdrawing group such as a fluorine atom. As the alcoholic hydroxyl group, a hydroxyl group having a pKa (acid dissociation constant) of 12 or more and 20 or less is preferably used.

[0287] Preferred polar groups include a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), and a sulfonic acid group.

[0288] Preferred acid-decomposable groups are groups in which the hydrogen atoms of these groups are substituted with groups that are detached by the action of an acid (leaving group).

[0289] 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.

[0290] Where R 36 ~R 39 R each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. 36 With R 37 They may be bonded to each other to form a ring.

[0291] 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.

[0292] R 36 ~R 39 、R 01 and R 02 The alkyl group is not particularly limited, but 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.

[0293] R 36 ~R 39 、R 01 and R 02 The cycloalkyl group may be monocyclic or polycyclic. The monocyclic group is not particularly limited, but preferably has a cycloalkyl group having 3 to 8 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl. The polycyclic group is preferably a cycloalkyl group having 6 to 20 carbon atoms, such as adamantyl, norbornyl, isobornyl, bornyl, dicyclopentyl, α-pinenyl, tricyclodecyl, tetracyclododecyl, and androstyl. In addition, at least one carbon atom in the cycloalkyl group may be substituted with a heteroatom such as an oxygen atom.

[0294] R 36 ~R 39 、R 01 and R 02 The aryl group is not particularly limited, but is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include phenyl, naphthyl, and anthracenyl.

[0295] R 36 ~R 39 、R 01 and R 02 The aralkyl group is not particularly limited, but is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof include benzyl, phenethyl, and naphthylmethyl.

[0296] R 36 ~R 39 、R 01 and R 02 The alkenyl group is not particularly limited, but is preferably an alkenyl group having 2 to 8 carbon atoms, and examples thereof include vinyl, allyl, butenyl, and cyclohexenyl.

[0297] As R 36 With R 37 The ring formed by bonding together 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.

[0298] The acid-decomposable group is preferably a cumyl ester group, an enol ester group, an acetal ester group, or a tertiary alkyl ester group, and more preferably an acetal group or a tertiary alkyl ester group.

[0299] The polymer (A) preferably contains a repeating unit represented by the following general formula (AI) as a repeating unit having an acid-decomposable group.

[0300] [Chemical Formula 18]

[0301]

[0302] In the general formula (AI),

[0303] Xa1 represents a hydrogen atom, a halogen atom or a monovalent organic group.

[0304] T represents a single bond or a divalent linking group.

[0305] Rx1 to Rx3 each independently represent an alkyl group or a cycloalkyl group.

[0306] Any two of Rx1 to Rx3 may be bonded to form a ring structure, or may not form a ring structure.

[0307] Examples of the divalent linking group for T include an alkylene group, an arylene group, -COO-Rt-, and -O-Rt-. In the formula, Rt represents an alkylene group, a cycloalkylene group, or an arylene group.

[0308] T is preferably a single bond or -COO-Rt-. Rt is preferably a chain alkylene group having 1 to 5 carbon atoms, more preferably -CH2-, -(CH2)2-, or -(CH2)3-. T is more preferably a single bond.

[0309] Xa1 is preferably a hydrogen atom or an alkyl group.

[0310] The alkyl group of Xa1 may have a substituent, and examples of the substituent include a hydroxyl group and a halogen atom (preferably a fluorine atom).

[0311] The alkyl group of Xa1 preferably has 1 to 4 carbon atoms, and examples thereof include methyl, ethyl, propyl, hydroxymethyl, and trifluoromethyl. The alkyl group of Xa1 is preferably methyl.

[0312] The alkyl group represented by Rx1, Rx2, and Rx3 may be linear or branched, and preferably includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl. The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3. In the alkyl group represented by Rx1, Rx2, and Rx3, a portion of the carbon-carbon bond may be a double bond.

[0313] The cycloalkyl group represented by Rx1, Rx2 and Rx3 is preferably a monocyclic cycloalkyl group such as cyclopentyl and cyclohexyl, or a polycyclic cycloalkyl group such as norbornyl, tetracyclodecyl, tetracyclododecyl and adamantyl.

[0314] As the ring structure formed by two bonds among Rx1, Rx2 and Rx3, 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. As the ring structure formed by two bonds among Rx1, Rx2 and Rx3, the structure shown below is also preferred.

[0315] [Chemical Formula 19]

[0316]

[0317] Specific examples of monomers corresponding to the repeating unit represented by general formula (AI) are given below, but the present invention is not limited to these specific examples. The following specific examples correspond to the case where Xa1 in general formula (AI) is a methyl group, and Xa1 can be arbitrarily substituted with a hydrogen atom, a halogen atom, or a monovalent organic group.

[0318] [Chemical Formula 20]

[0319]

[0320] The polymer (A) also preferably contains, as a repeating unit having an acid-decomposable group, the repeating units described in paragraphs

[0336] to

[0369] of U.S. Patent Application Publication No. 2016 / 0070167A1.

[0321] Furthermore, polymer (A) may further include, as a repeating unit having an acid-decomposable group, a repeating unit having a group that decomposes by acid to generate an alcoholic hydroxyl group as described in paragraphs

[0363] to

[0364] of U.S. Patent Application Publication No. 2016 / 0070167A1.

[0322] The repeating unit having an acid-decomposable group may have the above-mentioned hydrophilic group. When the repeating unit having an acid-decomposable group has the above-mentioned hydrophilic group, the repeating unit having the acid-decomposable group also corresponds to the repeating unit having the hydrophilic group.

[0323] The polymer (A) may contain the repeating unit having an acid-decomposable group alone or in combination of two or more.

[0324] The content of the repeating unit having an acid-decomposable group contained in the polymer (A) (the total of repeating units having an acid-decomposable group when there are multiple repeating units having an acid-decomposable group) is preferably 10 to 90 mol%, more preferably 20 to 80 mol%, and even more preferably 30 to 70 mol% based on all the repeating units of the polymer (A).

[0325] (Other repeating units)

[0326] The polymer (A) may further have a repeating unit that does not have either an acid-decomposable group or a hydrophilic group. The repeating unit that does not have either an acid-decomposable group or a hydrophilic group preferably has an alicyclic hydrocarbon structure. Examples of repeating units that do not have either an acid-decomposable group or a hydrophilic group include the repeating units described in paragraphs

[0236] to

[0237] of U.S. Patent Application Publication No. 2016 / 0026083A1. Preferred examples of monomers corresponding to repeating units that do not have either an acid-decomposable group or a hydrophilic group are shown below.

[0327] [Chemical Formula 21]

[0328]

[0329] In addition, specific examples of repeating units that do not have either an acid-decomposable group or a hydrophilic group include repeating units disclosed in paragraph

[0433] of U.S. Patent Application Publication No. 2016 / 0070167A1.

[0330] The polymer (A) may contain one type of repeating unit having neither an acid-decomposable group nor a hydrophilic group alone, or may contain two or more types in combination.

[0331] The content of the repeating units having neither an acid-decomposable group nor a hydrophilic group is preferably more than 0 to 50 mol%, more preferably more than 0 to 30 mol%, and even more preferably more than 0 to 20 mol% based on all the repeating units in the polymer (A).

[0332] In addition to the above-mentioned repeating structural units, the polymer (A) may have various repeating structural units for the purpose of adjusting dry etching resistance, compatibility with standard developer solutions, substrate adhesion, resist profile, and resolution, heat resistance, sensitivity, and other properties generally required of resists. Examples of such repeating structural units include, but are not limited to, repeating structural units corresponding to monomers.

[0333] Examples of the monomer include compounds having one addition-polymerizable unsaturated bond selected from acrylates, methacrylates, acrylamides, methacrylamides, allyl compounds, vinyl ethers, and vinyl esters.

[0334] In addition, any addition-polymerizable unsaturated compound that can copolymerize with the monomer corresponding to the various repeating structural units described above may also be copolymerized.

[0335] In the polymer (A), the molar ratio of each repeating unit is appropriately set in order to adjust various properties.

[0336] The Daxi parameter of the polymer (A) is not particularly limited, but is preferably 4.2 or less, more preferably 3.9 or less, and even more preferably 3.7 or less.

[0337] If the value of the Daxi parameter of the above-mentioned polymer (A) is reduced, it will have a high carbon density. By setting the value of the above-mentioned Daxi parameter to 4.2 or less, the hydrophobicity of the resist film based on the high carbon density is improved while having hydrophilic groups. In the case of a hydrophobic environment such as when the resist film is exposed, the diffusion of acid caused by exposure to the unexposed part can be further suppressed by the above-mentioned hydrophilic groups, thereby achieving excellent developability.

[0338] Furthermore, the presence of the hydrophilic group in such a hydrophobic environment relatively increases the hydrophilic effect, and cracking of the resist pattern and peeling of the resist pattern can be further suppressed.

[0339] The lower limit of the Onishi parameter of the polymer (A) is not particularly limited, but is preferably 2.0 or more.

[0340] The Oasis parameter of the polymer (A) can be measured as follows.

[0341] When the polymer (A) contains only one type of repeating unit, the Maximal parameter of the monomer corresponding to the repeating unit becomes the Maximal parameter of the polymer (A).

[0342] The Ohnishi parameter is a parameter generally used to express carbon density, and can be obtained by the following formula (H. Goken, S. Esho, Y. Ohnishi, J. Electrochem. Soc., 130, 423 (1983)).

[0343] Daxi parameter = (total number of atoms in the monomer) / [(number of carbon atoms in the monomer) - (number of oxygen atoms in the monomer)]

[0344] Furthermore, when the above-mentioned polymer (A) contains two or more repeating units, the Daxi parameter of the monomer corresponding to each repeating unit is calculated by the above-mentioned method, and the sum of the values ​​obtained by multiplying the Daxi parameter of each monomer by the content (mass %) of each repeating unit in the above-mentioned polymer (A) and dividing by 100 is set as the Daxi parameter of the above-mentioned polymer (A).

[0345] When the polymer (A) comprises repeating unit 1, repeating unit 2, ..., repeating unit X, the Daxi parameter of the polymer (A) is calculated by the following formula (1).

[0346] The Onishi parameter of polymer (A) = N1 (Onishi parameter of the monomer corresponding to repeating unit 1) × W1 (content of repeating unit 1 (mass %)) / 100 + N2 (Onishi parameter of the monomer corresponding to repeating unit 2) × W2 (content of repeating unit 2 (mass %)) / 100 + ... N X (equivalent to the Onishi parameter of the monomer of repeating unit X) × W X (Content ratio of repeating unit X (mass %)) / 100……(1)

[0347] The method for setting the Daxi parameter of polymer (A) to 4.2 or less is not particularly limited. As a preferred embodiment, the polymer (A) may include a repeating unit having a high carbon density such as adamantane.

[0348] The polymer (A) preferably includes two or more repeating units having a hydrophilic group, and the repeating units are preferably different.

[0349] Thereby, when forming a pattern using a thick actinic ray-sensitive or radiation-sensitive film, the resolution is further improved, and cracking of the resist pattern and peeling of the resist pattern can be further suppressed.

[0350] Furthermore, the polymer (A) preferably includes three or more types of repeating units having a hydrophilic group, and the repeating units are preferably different.

[0351] The repeating unit having the above-mentioned hydrophilic group preferably includes a repeating unit having a carboxyl group or a hydroxyl group.

[0352] Furthermore, it is particularly preferred that the repeating unit having the hydrophilic group include a repeating unit having a carboxyl group.

[0353] The polymer (A) preferably contains one or more types of each of a repeating unit having a carboxylic acid group and a repeating unit having a hydroxyl group.

[0354] The repeating structural unit having the carboxylic acid group is preferably a repeating unit represented by the above-mentioned general formula (1).

[0355] Furthermore, the repeating unit having the hydroxyl group is preferably a repeating unit represented by the general formula (2).

[0356] When the composition of the present invention is for ArF exposure, polymer (A) preferably contains substantially no aromatic groups from the perspective of ArF light transmittance. More specifically, among all repeating units in polymer (A), repeating units containing aromatic groups preferably account for no more than 5 mol%, more preferably no more than 3 mol%, and ideally 0 mol%, i.e., even more preferably, no repeating units containing aromatic groups. Furthermore, polymer (A) preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure.

[0357] The polymer (A) preferably has repeating units composed entirely of (meth)acrylate repeating units. In this case, any of the following repeating units can be used: a repeating unit in which all repeating units are methacrylate repeating units, a repeating unit in which all repeating units are acrylate repeating units, or a repeating unit in which all repeating units are composed of methacrylate repeating units and acrylate repeating units. The proportion of acrylate repeating units relative to the total repeating units of the polymer (A) is preferably 50 mol% or less.

[0358] The weight average molecular weight of the polymer (A) is 8,000 or less.

[0359] When the polymer (A) contains a repeating unit having a hydrophilic group and the weight-average molecular weight of the polymer (A) is 8,000 or less, the resolution is further improved when a pattern is formed from a thick actinic ray-sensitive or radiation-sensitive film, and cracking and peeling of the resist pattern can be further suppressed.

[0360] On the other hand, when the weight average molecular weight of the polymer (A) exceeds 8,000, the above-mentioned effects cannot be achieved, and when forming a pattern from a thick actinic ray-sensitive or radiation-sensitive film, it is difficult to suppress cracking and peeling of the resist pattern.

[0361] The weight average molecular weight of the polymer (A) is preferably 7,000 or less, more preferably 6,000 or less.

[0362] The lower limit of the weight average molecular weight of the polymer (A) is not particularly limited, but is preferably 1,000 or more.

[0363] The dispersion degree (Mw / Mn) of the polymer (A) is usually 1.0 to 3.0, preferably 1.0 to 2.6, more preferably 1.0 to 2.0, and even more preferably 1.1 to 2.0.

[0364] The polymer (A) may be used alone or in combination of two or more.

[0365] The content of polymer (A) in the total solids content of the composition of the present invention is generally 50.0% by mass or more. It is preferably 60.0% by mass or more, more preferably 70.0% by mass or more, and even more preferably 80.0% by mass or more. The upper limit is not particularly limited, but is preferably 99.8% by mass or less, more preferably 99.5% by mass or less, and even more preferably 99.2% by mass or less.

[0366] (B) Photoacid generator

[0367] The composition of the present invention contains a photoacid generator (hereinafter also referred to as "photoacid generator (B)").

[0368] The photoacid generator is a compound that generates an acid upon irradiation with actinic rays or radiation.

[0369] The photoacid generator is preferably a compound that generates an organic acid upon irradiation with actinic rays or radiation. Examples thereof include 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.

[0370] As the photoacid generator, a known compound that generates an acid upon irradiation with actinic rays or radiation can be used alone or as a mixture thereof. For example, known compounds disclosed in paragraphs

[0125] to

[0319] of U.S. Patent Application Publication No. 2016 / 0070167A1, paragraphs

[0086] to

[0094] of U.S. Patent Application Publication No. 2015 / 0004544A1, and paragraphs

[0323] to

[0402] of U.S. Patent Application Publication No. 2016 / 0237190A1 can be preferably used as the photoacid generator (B).

[0371] Preferred embodiments of the photoacid generator (B) include compounds represented by the following general formulae (ZI), (ZII), and (ZIII).

[0372] [Chemical Formula 22]

[0373]

[0374] In the above general formula (ZI),

[0375] R 201 、R 202 and R 203 Each independently represents an organic group.

[0376] As R 201 、R 202 and R 203The number of carbon atoms in the organic group is generally 1 to 30, preferably 1 to 20.

[0377] 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 bonding two of the above groups includes an alkylene group (for example, a butylene group, a pentylene group, etc.) and -CH2-CH2-O-CH2-CH2-.

[0378] Z - Indicates anion.

[0379] Preferred embodiments of the cation in the general formula (ZI) include corresponding groups in the compounds (ZI-1), (ZI-2), (ZI-3), and (ZI-4) described later.

[0380] In addition, the photoacid generator (B) may be a compound having a plurality of structures represented by the general formula (ZI). For example, the photoacid generator (B) may be a compound having R represented by the general formula (ZI). 201 ~R 203 At least one of the compounds is R of another compound represented by the general formula (ZI) 201 ~R 203 A compound having a structure in which at least one of the compounds is bonded via a single bond or a linking group.

[0381] First, compound (ZI-1) will be described.

[0382] Compound (ZI-1) is the above general formula (ZI) R 201 ~R 203 An arylsulfonium compound in which at least one of the groups is an aryl group, that is, a compound having an arylsulfonium cation.

[0383] In the arylsulfonium compound, R 201 ~R 203 All are aryl groups, and R 201 ~R 203 Part of the alkyl group is an aryl group, and the rest are an alkyl group or a cycloalkyl group.

[0384] Examples of the arylsulfonium compound include triarylsulfonium compounds, diarylalkylsulfonium compounds, aryldialkylsulfonium compounds, diarylcycloalkylsulfonium compounds, and aryldicycloalkylsulfonium compounds.

[0385] 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. Examples of the heterocyclic structure include a pyrrole residue, a furan residue, a thiophene residue, an indole residue, a benzofuran residue, and a benzothiophene residue. When the arylsulfonium compound has two or more aryl groups, the two or more aryl groups may be the same or different.

[0386] The alkyl group or cycloalkyl group that the arylsulfonium compound may have as needed is preferably a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cycloalkyl group having 3 to 15 carbon atoms, and examples thereof include methyl, ethyl, propyl, n-butyl, sec-butyl, tert-butyl, cyclopropyl, cyclobutyl, and cyclohexyl.

[0387] R 201 ~R 203 The aryl group, alkyl group and cycloalkyl group may each independently have an alkyl group (e.g., having 1 to 15 carbon atoms), a cycloalkyl group (e.g., having 3 to 15 carbon atoms), an aryl group (e.g., having 6 to 14 carbon atoms), an alkoxy group (e.g., having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group or a phenylthio group as a substituent.

[0388] Next, compound (ZI-2) will be described.

[0389] Compound (ZI-2) is R in formula (ZI) 201 ~R 203 Each independently represents a compound of an organic group that does not have an aromatic ring. Here, the aromatic ring also includes an aromatic ring containing a heteroatom.

[0390] As R 201 ~R 203 The organic group having no aromatic ring usually has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.

[0391] 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.

[0392] As R 201 ~R 203 The alkyl and cycloalkyl groups can preferably include straight-chain alkyl groups having 1 to 10 carbon atoms or branched-chain alkyl groups having 3 to 10 carbon atoms (for example, methyl, ethyl, propyl, butyl and pentyl), and cycloalkyl groups having 3 to 10 carbon atoms (for example, cyclopentyl, cyclohexyl and norbornyl).

[0393] R 201~R 203 It may be further substituted with a halogen atom, an alkoxy group (for example, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group.

[0394] Next, compound (ZI-3) will be described.

[0395] Compound (ZI-3) is a compound represented by the following general formula (ZI-3), and is a compound having a phenacylsulfonium salt structure.

[0396] [Chemical Formula 23]

[0397]

[0398] In the above general formula (ZI-3),

[0399] R1 represents an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group or an alkenyl group.

[0400] R2 and R3 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, or an aryl group. R2 and R3 may be linked to form a ring.

[0401] R1 and R2 may be bonded to each other to form a ring.

[0402] R X and R y R each independently represents an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group or an alkoxycarbonylcycloalkyl group. X With R y They may be connected to each other to form a ring, and the ring structure may contain an oxygen atom, a nitrogen atom, a sulfur atom, a keto group, an ether bond, an ester bond, or an amide bond.

[0403] Z - Indicates anion.

[0404] The alkyl group for R1 is not particularly limited and may be linear or branched. It is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 15 carbon atoms, and even more preferably an alkyl group having 1 to 10 carbon atoms.

[0405] The alkyl group may have a substituent. The substituent is not particularly limited, and examples thereof include the substituent T described above.

[0406] The cycloalkyl group for R1 is not particularly limited and may be monocyclic or polycyclic. It is preferably a cycloalkyl group having 3 to 20 carbon atoms, more preferably a cycloalkyl group having 3 to 15 carbon atoms, and even more preferably a cycloalkyl group having 3 to 10 carbon atoms.

[0407] Specific examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, and a decahydronaphthyl group.

[0408] The cycloalkyl group may have a substituent. The substituent is not particularly limited, and examples thereof include the substituent T described above.

[0409] The alkoxy group of R1 is not particularly limited, but is preferably an alkoxy group having 1 to 20 carbon atoms, more preferably an alkoxy group having 1 to 15 carbon atoms, and still more preferably an alkoxy group having 1 to 10 carbon atoms.

[0410] The alkoxy group may have a substituent. The substituent is not particularly limited, and examples thereof include the substituent T described above.

[0411] The cycloalkoxy group for R1 is not particularly limited, but is preferably a cycloalkoxy group having 3 to 20 carbon atoms, more preferably a cycloalkoxy group having 3 to 15 carbon atoms, and still more preferably a cycloalkoxy group having 3 to 10 carbon atoms.

[0412] The cycloalkoxy group may have a substituent. The substituent is not particularly limited, and examples thereof include the substituent T described above.

[0413] The aryl group for R1 is not particularly limited and may be monocyclic or polycyclic. It is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, and even more preferably an aryl group having 6 to 10 carbon atoms.

[0414] The aryl group may have a substituent. The substituent is not particularly limited, and examples thereof include the substituent T described above, and an alkoxy group is preferred.

[0415] The alkenyl group of R1 is not particularly limited, but is preferably an alkenyl group having 1 to 20 carbon atoms, more preferably an alkenyl group having 1 to 15 carbon atoms, and still more preferably an alkenyl group having 1 to 10 carbon atoms.

[0416] The alkenyl group may have a substituent. The substituent is not particularly limited, and examples thereof include the substituent T described above.

[0417] R1 is preferably an aryl group.

[0418] The alkyl groups for R2 and R3 are not particularly limited and may be linear or branched. They are preferably alkyl groups having 1 to 20 carbon atoms, more preferably alkyl groups having 1 to 15 carbon atoms, and even more preferably alkyl groups having 1 to 10 carbon atoms.

[0419] The alkyl group may have a substituent. The substituent is not particularly limited, and examples thereof include the substituent T described above.

[0420] The cycloalkyl group for R2 and R3 is not particularly limited and may be monocyclic or polycyclic. It is preferably a cycloalkyl group having 3 to 20 carbon atoms, more preferably a cycloalkyl group having 3 to 15 carbon atoms, and even more preferably a cycloalkyl group having 3 to 10 carbon atoms.

[0421] Specific examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, and a decahydronaphthyl group.

[0422] The cycloalkyl group may have a substituent. The substituent is not particularly limited, and examples thereof include the substituent T described above.

[0423] The aryl group for R2 and R3 is not particularly limited and may be monocyclic or polycyclic. It is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, and even more preferably an aryl group having 6 to 10 carbon atoms.

[0424] The aryl group may have a substituent. The substituent is not particularly limited, and examples thereof include the substituent T described above.

[0425] The alkoxy groups for R2 and R3 are not particularly limited, but are preferably alkoxy groups having 1 to 20 carbon atoms, more preferably alkoxy groups having 1 to 15 carbon atoms, and still more preferably alkoxy groups having 1 to 10 carbon atoms.

[0426] The alkoxy group may have a substituent. The substituent is not particularly limited, and examples thereof include the substituent T described above.

[0427] The cycloalkoxy groups for R2 and R3 are not particularly limited, but are preferably cycloalkoxy groups having 3 to 20 carbon atoms, more preferably cycloalkoxy groups having 3 to 15 carbon atoms, and still more preferably cycloalkoxy groups having 3 to 10 carbon atoms.

[0428] The cycloalkoxy group may have a substituent. The substituent is not particularly limited, and examples thereof include the substituent T described above.

[0429] R2 and R3 are each independently preferably a hydrogen atom, an alkyl group, a cycloalkyl group or an alkoxy group, more preferably a hydrogen atom or an alkyl group.

[0430] R2 and R3 may be linked to each other to form a ring. Examples of the ring structure include 3- to 10-membered rings, preferably 4- to 8-membered rings, and more preferably 5- or 6-membered rings.

[0431] Furthermore, R1 and R2 may be linked to each other to form a ring. Examples of the ring structure include 3- to 10-membered rings, preferably 4- to 8-membered rings, and more preferably 5- or 6-membered rings.

[0432] As R X and R y The alkyl group is not particularly limited and may be linear or branched. It is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 15 carbon atoms, and even more preferably an alkyl group having 1 to 10 carbon atoms.

[0433] The alkyl group may have a substituent. The substituent is not particularly limited, and examples thereof include the substituent T described above.

[0434] As R X and R y The cycloalkyl group is not particularly limited and may be monocyclic or polycyclic. It is preferably a cycloalkyl group having 3 to 20 carbon atoms, more preferably a cycloalkyl group having 3 to 15 carbon atoms, and even more preferably a cycloalkyl group having 3 to 10 carbon atoms.

[0435] Specific examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, and a decahydronaphthyl group.

[0436] The cycloalkyl group may have a substituent. The substituent is not particularly limited, and examples thereof include the substituent T described above.

[0437] As R X and R y The alkenyl group is not particularly limited, but is preferably an alkenyl group having 1 to 20 carbon atoms, more preferably an alkenyl group having 1 to 15 carbon atoms, and still more preferably an alkenyl group having 1 to 10 carbon atoms.

[0438] The alkenyl group may have a substituent. The substituent is not particularly limited, and examples thereof include the substituent T described above.

[0439] As R X and R y The aryl group is not particularly limited and may be monocyclic or polycyclic. It is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, and even more preferably an aryl group having 6 to 10 carbon atoms.

[0440] The aryl group may have a substituent. The substituent is not particularly limited, and examples thereof include the substituent T described above.

[0441] As R X and R y The 2-oxoalkyl group is not particularly limited, but is preferably a 2-oxoalkyl group having 1 to 20 carbon atoms, more preferably a 2-oxoalkyl group having 1 to 15 carbon atoms, and still more preferably a 2-oxoalkyl group having 1 to 10 carbon atoms.

[0442] The 2-oxoalkyl group may have a substituent. The substituent is not particularly limited, and examples thereof include the substituent T described above.

[0443] As R X and R y The 2-oxocycloalkyl group is not particularly limited, but is preferably a 2-oxocycloalkyl group having 3 to 20 carbon atoms, more preferably a 2-oxocycloalkyl group having 3 to 15 carbon atoms, and still more preferably a 2-oxocycloalkyl group having 3 to 10 carbon atoms.

[0444] The 2-oxocycloalkyl group may have a substituent. The substituent is not particularly limited, and examples thereof include the substituent T described above.

[0445] As R X and R y The alkoxycarbonylalkyl group is not particularly limited, but is preferably an alkoxycarbonylalkyl group having 3 to 22 carbon atoms, more preferably an alkoxycarbonylalkyl group having 3 to 17 carbon atoms, and still more preferably an alkoxycarbonylalkyl group having 3 to 12 carbon atoms.

[0446] The alkoxycarbonylalkyl group may have a substituent. The substituent is not particularly limited, and examples thereof include the substituent T described above.

[0447] As R X and R y The alkoxycarbonylcycloalkyl group is not particularly limited, but is preferably an alkoxycarbonylcycloalkyl group having 5 to 24 carbon atoms, more preferably an alkoxycarbonylcycloalkyl group having 5 to 19 carbon atoms, and still more preferably an alkoxycarbonylcycloalkyl group having 5 to 14 carbon atoms.

[0448] The alkoxycarbonylcycloalkyl group may have a substituent. The substituent is not particularly limited, and examples thereof include the substituent T described above.

[0449] R X With R y They may be connected to each other to form a ring, and the ring structure may contain an oxygen atom, a nitrogen atom, a sulfur atom, a keto group, an ether bond, an ester bond, or an amide bond.

[0450] The above-mentioned ring structure preferably contains an oxygen atom.

[0451] Examples of the ring structure include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic heterocyclic rings, and polycyclic condensed rings formed by combining two or more of these rings. Examples of the ring structure include 3- to 10-membered rings, preferably 4- to 8-membered rings, and more preferably 5- or 6-membered rings.

[0452] Next, compound (ZI-4) will be described.

[0453] Compound (ZI-4) is a compound represented by the following general formula (ZI-4).

[0454] [Chemical Formula 24]

[0455]

[0456] In the general formula (ZI-4),

[0457] l represents an integer from 0 to 2.

[0458] r represents an integer from 0 to 8.

[0459] R 13 represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group or an alkoxycarbonyl group.

[0460] R 14 represents a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group or a cycloalkylsulfonyl group. 14 When multiple R 14 They may be the same as or different from each other.

[0461] R 15 Each independently represents an alkyl group, a cycloalkyl group or a naphthyl group. 15 Can bond to each other to form a ring. 15 When they are bonded to each other to form a ring, the ring structure may contain an oxygen atom, a nitrogen atom, a sulfur atom, a keto group, an ether bond, an ester bond, or an amide bond.

[0462] X - Indicates anion.

[0463] As R 13 The alkyl group is not particularly limited and may be linear or branched. It is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 15 carbon atoms, and even more preferably an alkyl group having 1 to 10 carbon atoms.

[0464] The alkyl group may have a substituent. The substituent is not particularly limited, and examples thereof include the substituent T described above.

[0465] As R 13 The cycloalkyl group is not particularly limited and may be monocyclic or polycyclic. It is preferably a cycloalkyl group having 3 to 20 carbon atoms, more preferably a cycloalkyl group having 3 to 15 carbon atoms, and even more preferably a cycloalkyl group having 3 to 10 carbon atoms.

[0466] Specific examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, and a decahydronaphthyl group.

[0467] The cycloalkyl group may have a substituent. The substituent is not particularly limited, and examples thereof include the substituent T described above.

[0468] As R 13 The alkoxy group is not particularly limited, but is preferably an alkoxy group having 1 to 20 carbon atoms, more preferably an alkoxy group having 1 to 15 carbon atoms, and still more preferably an alkoxy group having 1 to 10 carbon atoms.

[0469] The alkoxy group may have a substituent. The substituent is not particularly limited, and examples thereof include the substituent T described above.

[0470] As R 13The alkoxycarbonyl group is not particularly limited, but is preferably an alkoxycarbonyl group having 2 to 21 carbon atoms, more preferably an alkoxycarbonyl group having 2 to 16 carbon atoms, and still more preferably an alkoxycarbonyl group having 2 to 11 carbon atoms.

[0471] The alkoxycarbonyl group may have a substituent. The substituent is not particularly limited, and examples thereof include the substituent T described above.

[0472] As R 14 The alkyl group is not particularly limited and may be linear or branched. It is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 15 carbon atoms, and even more preferably an alkyl group having 1 to 10 carbon atoms.

[0473] The alkyl group may have a substituent. The substituent is not particularly limited, and examples thereof include the substituent T described above.

[0474] As R 14 The cycloalkyl group is not particularly limited and may be monocyclic or polycyclic. It is preferably a cycloalkyl group having 3 to 20 carbon atoms, more preferably a cycloalkyl group having 3 to 15 carbon atoms, and even more preferably a cycloalkyl group having 3 to 10 carbon atoms.

[0475] Specific examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, and a decahydronaphthyl group.

[0476] The cycloalkyl group may have a substituent. The substituent is not particularly limited, and examples thereof include the substituent T described above.

[0477] As R 14 The alkoxy group is not particularly limited, but is preferably an alkoxy group having 1 to 20 carbon atoms, more preferably an alkoxy group having 1 to 15 carbon atoms, and still more preferably an alkoxy group having 1 to 10 carbon atoms.

[0478] The alkoxy group may have a substituent. The substituent is not particularly limited, and examples thereof include the substituent T described above.

[0479] As R 14 The alkoxycarbonyl group is not particularly limited, but is preferably an alkoxycarbonyl group having 2 to 21 carbon atoms, more preferably an alkoxycarbonyl group having 2 to 16 carbon atoms, and still more preferably an alkoxycarbonyl group having 2 to 11 carbon atoms.

[0480] The alkoxycarbonyl group may have a substituent. The substituent is not particularly limited, and examples thereof include the substituent T described above.

[0481] As R 14 The alkylcarbonyl group is not particularly limited, but is preferably an alkylcarbonyl group having 2 to 21 carbon atoms, more preferably an alkylcarbonyl group having 2 to 16 carbon atoms, and still more preferably an alkylcarbonyl group having 2 to 11 carbon atoms.

[0482] The alkoxycarbonyl group may have a substituent. The substituent is not particularly limited, and examples thereof include the substituent T described above.

[0483] As R 14 The alkylsulfonyl group is not particularly limited, but is preferably an alkylsulfonyl group having 1 to 20 carbon atoms, more preferably an alkylsulfonyl group having 1 to 15 carbon atoms, and still more preferably an alkylsulfonyl group having 1 to 10 carbon atoms.

[0484] The alkylsulfonyl group may have a substituent. The substituent is not particularly limited, and examples thereof include the substituent T described above.

[0485] As R 14 The cycloalkylsulfonyl group is not particularly limited, but is preferably a cycloalkylsulfonyl group having 3 to 20 carbon atoms, more preferably a cycloalkylsulfonyl group having 3 to 15 carbon atoms, and still more preferably a cycloalkylsulfonyl group having 3 to 10 carbon atoms.

[0486] The cycloalkylsulfonyl group may have a substituent. The substituent is not particularly limited, and examples thereof include the substituent T described above.

[0487] When there are multiple R 14 When multiple R 14 They may be the same as or different from each other.

[0488] As R 15 The alkyl group is not particularly limited and may be linear or branched. It is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 15 carbon atoms, and even more preferably an alkyl group having 1 to 10 carbon atoms.

[0489] The alkyl group may have a substituent. The substituent is not particularly limited, and examples thereof include the substituent T described above.

[0490] As R 15 The cycloalkyl group is not particularly limited and may be monocyclic or polycyclic. It is preferably a cycloalkyl group having 3 to 20 carbon atoms, more preferably a cycloalkyl group having 3 to 15 carbon atoms, and even more preferably a cycloalkyl group having 3 to 10 carbon atoms.

[0491] Specific examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, and a decahydronaphthyl group.

[0492] The cycloalkyl group may have a substituent. The substituent is not particularly limited, and examples thereof include the substituent T described above.

[0493] As R 15 The naphthyl group may have a substituent. The substituent is not particularly limited, and examples thereof include the substituent T described above.

[0494] 2 Rs 15 Can bond to each other to form a ring. 15 When they are bonded to each other to form a ring, the ring structure may contain an oxygen atom, a nitrogen atom, a sulfur atom, a keto group, an ether bond, an ester bond, or an amide bond.

[0495] The above-mentioned ring structure preferably contains an oxygen atom.

[0496] Examples of the ring structure include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic heterocyclic rings, and polycyclic condensed rings formed by combining two or more of these rings. Examples of the ring structure include 3- to 10-membered rings, preferably 4- to 8-membered rings, and more preferably 5- or 6-membered rings.

[0497] In a preferred embodiment, preferably 2 R 15 are alkylene groups, and are bonded to each other to form a ring structure.

[0498] Next, general formulae (ZII) and (ZIII) are described.

[0499] In the general formulas (ZII) and (ZIII), R 204 ~R 207 Each independently represents an aryl group, an alkyl group or a cycloalkyl group.

[0500] 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 207 It 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.

[0501] As R 204 ~R 207 Examples of the alkyl and cycloalkyl groups include linear alkyl groups having 1 to 10 carbon atoms, branched 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).

[0502] 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, alkyl and cycloalkyl groups may have include, for example, alkyl groups (e.g., having 1 to 15 carbon atoms), cycloalkyl groups (e.g., having 3 to 15 carbon atoms), aryl groups (e.g., having 6 to 15 carbon atoms), alkoxy groups (e.g., having 1 to 15 carbon atoms), halogen atoms, hydroxyl groups and phenylthio groups.

[0503] Z - Indicates anion.

[0504] The photoacid generator (B) preferably contains a compound represented by the general formula (ZI-3) or a compound represented by the general formula (ZI-4).

[0505] By using such a compound, the transparency of the resist film is improved, and therefore, more excellent resolution can be obtained particularly when exposure is performed under ArF light.

[0506] Z in the general formula (ZI) - , Z in the general formula (ZII) - Although not particularly limited, anions represented by any of the following general formulae (A1) to (A3) are preferred.

[0507] Furthermore, Z in the above general formula (ZI-3) - Or X in the above general formula (ZI-4) -、 Although not particularly limited, anions represented by any of the following general formulae (A1) to (A3) are preferred.

[0508] Z in the above general formula (ZI-3) - and X in the above general formula (ZI-4) - Anions represented by any of the following general formulae (A1) to (A3) are preferred.

[0509] [Chemical Formula 25]

[0510]

[0511] In the above general formula (A1),

[0512] R 21 、R 22 Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a fluorine atom, an alkyl group substituted by a fluorine atom, or a cycloalkyl group substituted by a fluorine atom. 21 、R 22 At least one of them is a fluorine atom, an alkyl group substituted with a fluorine atom, or a cycloalkyl group substituted with a fluorine atom.

[0513] L represents a single bond or a divalent linking group.

[0514] X represents an organic group.

[0515] In the above general formula (A2),

[0516] R 23 represents a hydrogen atom, an alkyl group, a cycloalkyl group, a fluorine atom, -C(=O)-Rx or -S(=O)2-Rx. Rx represents an organic group.

[0517] R 24 represents a hydrogen atom, an alkyl group, a cycloalkyl group or a fluorine atom.

[0518] A1 represents -C(=O)- or -S(=O)2-.

[0519] R 23 With R 24 They may be bonded to each other to form a ring.

[0520] In the above general formula (A3),

[0521] R 25 、R 26 、R 27 Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group or a fluorine atom.

[0522] A2 to A4 each independently represent -C(=O)- or -S(=O)2-.

[0523] R 25 、R 26 、R 27 At least two of them may be bonded to each other to form a ring.

[0524] As R 21 、R 22 The alkyl group is not particularly limited and may be linear or branched. It is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably an alkyl group having 1 to 4 carbon atoms.

[0525] As R 21 、R 22 The cycloalkyl group is not particularly limited and may be monocyclic or polycyclic. It is preferably a cycloalkyl group having 3 to 15 carbon atoms, more preferably a cycloalkyl group having 3 to 10 carbon atoms, and even more preferably a cycloalkyl group having 3 to 6 carbon atoms.

[0526] As R 21 、R 22 Specifically, the alkyl group substituted with a fluorine atom is 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.

[0527] As R 21 、R 22 Specifically, the cycloalkyl group substituted with a fluorine atom is a cycloalkyl 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.

[0528] The alkyl group, cycloalkyl group, alkyl group substituted by a fluorine atom, and cycloalkyl group substituted by a fluorine atom may have a substituent. The substituent is not particularly limited, and examples thereof include the substituent T described above.

[0529] R 21 、R 22 At least one of them is a fluorine atom, an alkyl group substituted with a fluorine atom, or a cycloalkyl group substituted with a fluorine atom.

[0530] Examples of the divalent linking group of L 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 formed by combining a plurality thereof.

[0531] Among them, preferred are alkylene, -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -O-, -SO2-, -SO2-alkylene-, -COO-alkylene-, -alkylene-COO-, -OCO-alkylene-, -alkylene-OCO-, -CONH-alkylene- or -NHCO-alkylene-, and more preferred are alkylene, -COO-, -OCO-, -CONH-, -SO2-, -COO-alkylene-, -alkylene-COO-, -OCO-alkylene- or -alkylene-OCO-.

[0532] The alkylene group, cycloalkylene group, and alkenylene group may have a substituent.

[0533] The substituent may have a substituent. The substituent is not particularly limited, and examples thereof include the substituent T described above, and a fluorine atom is preferred.

[0534] X represents an organic group.

[0535] The number of carbon atoms in the organic group is not particularly limited, but is generally 1 to 30, preferably 1 to 20.

[0536] The organic group is not particularly limited, and examples thereof include an alkyl group and an alkoxy group.

[0537] The alkyl group is not particularly limited and may be linear or branched. It is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably an alkyl group having 1 to 4 carbon atoms.

[0538] The alkoxy group is not particularly limited, but is preferably an alkoxy group having 1 to 10 carbon atoms, more preferably an alkoxy group having 1 to 6 carbon atoms, and still more preferably an alkoxy group having 1 to 4 carbon atoms.

[0539] The alkyl group and the alkoxy group may have a substituent. The substituent is not particularly limited, and examples thereof include the substituent T described above, and a fluorine atom is preferred.

[0540] Furthermore, X may represent an organic group containing a cyclic structure, among which a cyclic organic group is preferred.

[0541] Examples of the cyclic organic group include an alicyclic group, an aryl group, and a heterocyclic group.

[0542] The alicyclic group may be monocyclic or polycyclic. Examples of monocyclic alicyclic groups include monocyclic cycloalkyl groups such as cyclopentyl, cyclohexyl, and cyclooctyl. Examples of polycyclic alicyclic groups include polycyclic cycloalkyl groups such as norbornyl, tricyclodecyl, tetracyclodecyl, tetracyclododecyl, and adamantyl. Preferred are alicyclic groups having a bulky structure with 7 or more carbon atoms such as norbornyl, tricyclodecyl, tetracyclodecyl, tetracyclododecyl, and adamantyl.

[0543] The aryl group may be monocyclic or polycyclic. Examples of the aryl group include phenyl, naphthyl, phenanthrenyl, and anthracenyl.

[0544] The heterocyclic group may be monocyclic or polycyclic. Polycyclic heterocyclic groups can further inhibit acid diffusion. Furthermore, the heterocyclic group may or may not be aromatic. Examples of aromatic heterocyclic rings include furan rings, thiophene rings, benzofuran rings, benzothiophene rings, dibenzofuran rings, dibenzothiophene rings, and pyridine rings. Examples of non-aromatic heterocyclic rings include tetrahydropyran rings, lactone rings, sultone rings, and decahydroisoquinoline rings. Examples of lactone and sultone rings include the lactone and sultone structures exemplified in the aforementioned resins. Particularly preferred heterocyclic rings in the heterocyclic group are furan rings, thiophene rings, pyridine rings, and decahydroisoquinoline rings.

[0545] The cyclic organic group may have a substituent. Examples of such substituents include alkyl groups (which may be linear or branched, preferably having 1 to 12 carbon atoms), cycloalkyl groups (which may be monocyclic, polycyclic, or spirocyclic, preferably having 3 to 20 carbon atoms), aryl groups (preferably having 6 to 14 carbon atoms), hydroxyl groups, alkoxy groups, ester groups, amide groups, carbamate groups, urea groups, thioether groups, sulfonamide groups, and sulfonate groups. Furthermore, the carbon atoms that constitute the cyclic organic group (the carbon atoms that contribute to ring formation) may be carbonyl carbon atoms.

[0546] As R 23 The alkyl group is not particularly limited and may be linear or branched. It is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably an alkyl group having 1 to 4 carbon atoms.

[0547] As R 23 The cycloalkyl group is not particularly limited and may be monocyclic or polycyclic. It is preferably a cycloalkyl group having 3 to 15 carbon atoms, more preferably a cycloalkyl group having 3 to 10 carbon atoms, and even more preferably a cycloalkyl group having 3 to 6 carbon atoms.

[0548] The alkyl group and the cycloalkyl group may have a substituent. The substituent is not particularly limited, and examples thereof include the substituent T described above, and a fluorine atom is preferred.

[0549] R x Represents an organic group.

[0550] As R x The organic group is the same as the organic group described as X above.

[0551] As R 24 The alkyl group as R 23 The alkyl groups described are the same.

[0552] As R 24 The cycloalkyl group as R 23 The cycloalkyl groups described are the same.

[0553] A1 represents -C(=O)- or -S(=O)2-. A1 is preferably -S(=O)2-.

[0554] R 23 With R 24 Can bond to each other to form a ring. 15 When they are bonded to each other to form a ring, the ring structure may contain an oxygen atom, a nitrogen atom, a sulfur atom, a keto group, an ether bond, an ester bond, an amide bond, or a sulfonyl bond.

[0555] Examples of the ring structure include non-aromatic heterocyclic rings and polycyclic condensed rings formed by combining two or more of these rings. Examples of the ring structure include 3- to 10-membered rings, preferably 4- to 8-membered rings, and more preferably 5- or 6-membered rings.

[0556] As R 25 、R 26 、R 27 The alkyl group as R 23 The alkyl groups described are the same.

[0557] As R 25 、R 26 、R 27 The cycloalkyl group as R 23 The cycloalkyl groups described are the same.

[0558] A2 to A4 each independently represent -C(=O)- or -S(=O)2-. A2 to A4 each independently represent -S(=O)2-.

[0559] R 25 、R 26 、R 27 At least two of them can be bonded to each other to form a ring. 25 、R 26 、R 27 When at least two of the groups are bonded to each other to form a ring, the ring structure may contain an oxygen atom, a nitrogen atom, a sulfur atom, a keto group, an ether bond, an ester bond, an amide bond, or a sulfonyl bond.

[0560] Examples of the ring structure include non-aromatic hydrocarbon rings, non-aromatic heterocycles, and polycyclic condensed rings formed by combining two or more of these rings. Examples of the ring structure include 3- to 10-membered rings, preferably 4- to 8-membered rings, and more preferably 5- or 6-membered rings.

[0561] Preferred examples of the sulfonium cation in the general formula (ZI) and the iodonium cation in the general formula (ZII) are shown below.

[0562] [Chemical Formula 26]

[0563]

[0564] [Chemical Formula 27]

[0565]

[0566] [Chemical Formula 28]

[0567]

[0568] The anion Z in the general formula (ZI) and the general formula (ZII) is shown below: - 、Z in the general formula (ZI-3) - , and X in the general formula (ZI-4) - The preferred example.

[0569] [Chemical Formula 29]

[0570]

[0571] [Chemical formula 30]

[0572]

[0573] The above-mentioned cations and anions can be used in any combination as a photoacid generator. In addition, the following photoacid generators can also be preferably used: Bu represents a butyl group.

[0574] [Chemical Formula 31]

[0575]

[0576] [Chemical Formula 32]

[0577]

[0578] The photoacid generators (PAG-A to PAG-Z, PAG-AA to PAG-AK) used in the examples can also be preferably used.

[0579] 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 low molecular weight compound form and the form of being embedded in a part of a polymer may be used in combination.

[0580] The photoacid generator is preferably in the form of a low molecular weight compound.

[0581] When the photoacid generator is in the form of a low molecular weight compound, the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, and even more preferably 1,000 or less.

[0582] When the photoacid generator is in a form of being embedded in a part of the polymer, it may be embedded in a part of the resin (A) or in a resin different from the resin (A).

[0583] The photoacid generator may be used alone or in combination of two or more.

[0584] The content of the photoacid generator in the composition (the total when multiple types are present) is preferably 0.1 to 35 mass %, more preferably 0.5 to 25 mass %, further preferably 0.8 to 15 mass %, and particularly preferably 1 to 10 mass % based on the total solid content of the composition.

[0585] As a preferred embodiment, the content of the photoacid generator in the composition (the total when multiple types are present) is preferably 6% by mass or less, more preferably 5% by mass or less, based on the total solid content of the composition.

[0586] As a preferred embodiment, it is preferred to use two or more photoacid generators in combination.

[0587] The photoacid generator (B) is preferably a mixture of two compounds represented by the following general formula (ZI-3).

[0588] [Chemical Formula 33]

[0589]

[0590] In the above general formula (ZI-3),

[0591] R1 represents an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group or an alkenyl group.

[0592] R2 and R3 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, or an aryl group. R2 and R3 may be linked to form a ring.

[0593] R1 and R2 may be bonded to each other to form a ring.

[0594] R X and R y R each independently represents an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group or an alkoxycarbonylcycloalkyl group. X With R y They may be connected to each other to form a ring, and the ring structure may contain an oxygen atom, a nitrogen atom, a sulfur atom, a keto group, an ether bond, an ester bond, or an amide bond.

[0595] Z - It represents an anion represented by any of the following general formulae (A1) to (A3).

[0596] [Chemical Formula 34]

[0597]

[0598] In the above general formula (A1),

[0599] R 21 、R 22 Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a fluorine atom, an alkyl group substituted by a fluorine atom, or a cycloalkyl group substituted by a fluorine atom. 21 、R 22 At least one of them is a fluorine atom, an alkyl group substituted with a fluorine atom, or a cycloalkyl group substituted with a fluorine atom.

[0600] L represents a single bond or a divalent linking group.

[0601] X represents an organic group.

[0602] In the above general formula (A2),

[0603] R 23 represents a hydrogen atom, an alkyl group, a cycloalkyl group, a fluorine atom, -C(=O)-Rx or -S(=O)2-Rx. Rx represents an organic group.

[0604] R 24 represents a hydrogen atom, an alkyl group, a cycloalkyl group or a fluorine atom,

[0605] A1 represents -C(=O)- or -S(=O)2-.

[0606] R 23With R 24 They may be bonded to each other to form a ring.

[0607] In the above general formula (A3),

[0608] R 25 、R 26 、R 27 Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group or a fluorine atom.

[0609] A2 to A4 each independently represent -C(=O)- or -S(=O)2-.

[0610] R 25 、R 26 、R 27 At least two of them may be bonded to each other to form a ring.

[0611] The respective groups in the cation portion of the general formula (ZI-3) are as described above.

[0612] As Z - The anions represented by any of the general formulae (A1) to (A3) are as described above.

[0613] In a preferred embodiment, when two photoacid generators are used in combination and two acids are generated by irradiation with actinic rays or radiation, the acid dissociation constants pKa values ​​of the two acids preferably differ by 0.5 or more, more preferably by 1.0 or more, and even more preferably by 1.5 or more.

[0614] The acid dissociation constant pKa represents the acid dissociation constant pKa in an aqueous solution, as defined in, for example, Chemistry Handbook (II) (Revision 4, 1993, compiled by the Chemical Society of Japan, MARUZEN Co., Ltd.). The lower the value representing the acid dissociation constant pKa, the greater the acid strength. Specifically, the acid dissociation constant pKa in an aqueous solution can be actually measured by measuring the acid dissociation constant at 25° C. using an infinite dilution aqueous solution. Alternatively, the following software package 1 can be used and the Hammett's substituent constant and the value based on the known literature value database can be obtained by calculation. The pKa values ​​recorded in this specification all represent the values ​​obtained by calculation using the following software package 1.

[0615] Software package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs).

[0616] In a preferred embodiment, the photoacid generator (B) is a mixture of two compounds represented by the general formula (ZI-3), which generates two acids upon irradiation with actinic rays or radiation, and the acid dissociation constants pKa values ​​of the two acids at 25°C preferably differ by 0.5 or more, more preferably by 1.0 or more, and even more preferably by 1.5 or more.

[0617] Furthermore, the acid dissociation constant pKa value at 25° C. of the acid generated by the photoacid generator upon irradiation with actinic rays or radiation preferably satisfies pKa<−1, and more preferably satisfies pKa<−3.

[0618] <Acid diffusion controller (D)>

[0619] The composition of the present invention preferably contains an acid diffusion controller (D). The acid diffusion controller (D) captures the acid generated from the acid generator etc. during exposure and plays the role of a quencher that suppresses the reaction of the acid-decomposable resin in the unexposed portion caused by excessive acid generation. For example, a basic compound (DA), a basic compound (DB) whose alkalinity is reduced or disappears by irradiation with actinic rays or radiation, an onium salt (DC) that becomes 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 cationic portion can be used as an acid diffusion controller. In the composition of the present invention, a well-known acid diffusion controller can be appropriately used. For example, known compounds disclosed in paragraphs

[0627] to

[0664] in U.S. Patent Application Publication No. 2016 / 0070167A1, paragraphs

[0095] to

[0187] in U.S. Patent Application Publication No. 2015 / 0004544A1, paragraphs

[0403] to

[0423] in U.S. Patent Application Publication No. 2016 / 0237190A1, and paragraphs

[0259] to

[0328] in U.S. Patent Application Publication No. 2016 / 0274458A1 can be preferably used as the acid diffusion controller (D).

[0620] Preferred examples of the basic compound (DA) include compounds having structures represented by the following formulae (A) to (E).

[0621] [Chemical Formula 35]

[0622]

[0623] In general formula (A) and general formula (E),

[0624] R 200 、R 201 and R 202They may be the same or different and each independently represents a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group (preferably having 6 to 20 carbon atoms). 201 With R 202 They may be bonded to each other to form a ring.

[0625] R 203 、R 204 、R 205 and R 206 They may be the same or different and each independently represents an alkyl group having 1 to 20 carbon atoms.

[0626] The alkyl group in the general formula (A) and the general formula (E) may have a substituent or may be unsubstituted.

[0627] As 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 preferable.

[0628] The alkyl group in the general formula (A) and the general formula (E) is more preferably unsubstituted.

[0629] As the basic compound (DA), guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine or piperidine are preferred, and compounds having an imidazole structure, a diazabicyclic structure, an onium hydroxide structure, an onium carboxylate structure, a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, or an aniline derivative having a hydroxyl group and / or an ether bond are more preferred.

[0630] 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, upon decomposition by irradiation with actinic rays or radiation, thereby reducing or eliminating the proton-accepting property or changing from proton-accepting property to acidic property.

[0631] A proton-accepting functional group is a functional group having a group or electron capable of electrostatically interacting with a proton, and includes, for example, a functional group having a macrocyclic compound structure such as a cyclic polyether, or a functional group having a nitrogen atom with an unshared electron pair that does not contribute to π conjugation. An example of a nitrogen atom having an unshared electron pair that does not contribute to π conjugation is a nitrogen atom having a partial structure represented by the following formula.

[0632] [Chemical Formula 36]

[0633] Unshared electron pairs

[0634] Preferred partial structures of the proton-accepting functional group include, for example, crown ether, azacrown ether, primary amine, secondary amine, tertiary amine, pyridine, imidazole, and pyrazine structures.

[0635] Compound (DB) decomposes upon irradiation with actinic rays or radiation, resulting in a decrease or loss of proton-accepting properties, or a change from proton-accepting properties to acidic properties. Here, the decrease or loss of proton-accepting properties, or the change from proton-accepting properties to acidic properties, refers to a change in proton-accepting properties caused by the addition of a proton to a proton-accepting functional group. Specifically, this refers to a decrease in the equilibrium constant in the chemical equilibrium when a proton adduct is formed between a compound (DB) having a proton-accepting functional group and a proton.

[0636] The proton acceptor property can be confirmed by measuring pH.

[0637] The acid dissociation constant pKa of the compound generated by decomposition of the compound (DB) by irradiation with actinic rays or radiation preferably satisfies pKa<-1, more preferably -13<pKa<-1, and further preferably -13<pKa<-3.

[0638] The acid dissociation constant pKa represents the acid dissociation constant pKa in an aqueous solution, as defined in, for example, Chemistry Handbook (II) (Revision 4, 1993, compiled by the Chemical Society of Japan, MARUZEN Co., Ltd.). The lower the value representing the acid dissociation constant pKa, the greater the acid strength. Specifically, the acid dissociation constant pKa in an aqueous solution can be actually measured by measuring the acid dissociation constant at 25° C. using an infinite dilution aqueous solution. Alternatively, the following software package 1 can be used and the value of Hammett's substituent constant and the value based on a known literature value database can be obtained by calculation. The pKa values ​​recorded in this specification all represent the values ​​obtained by using the software package and by calculation.

[0639] Software package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs).

[0640] In the composition of the present invention, an onium salt (DC) that is a relatively weak acid relative to the acid generator can be used as an acid diffusion controller.

[0641] When an acid generator is mixed with an onium salt that generates an acid relatively weak compared to the acid generated by the acid generator, if the acid generated by the acid generator collides with the onium salt containing unreacted weak acid anions due to irradiation with actinic rays or radiation, the weak acid is released through salt exchange, and an onium salt containing a strong acid anion is generated. In this process, the strong acid is exchanged for a weaker acid with lower catalytic activity, thus apparently deactivating the acid and enabling control of acid diffusion.

[0642] As the onium salt that forms a relatively weak acid with respect to the acid generator, compounds represented by the following general formulae (d1-1) to (d1-3) are preferred.

[0643] [Chemical Formula 37]

[0644]

[0645] Where R 51 is a hydrocarbon group which may have a substituent, Z 2c is a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent (wherein the fluorine atom in the carbon adjacent to S is assumed to be unsubstituted), R 52 is an organic group, Y 3 is a linear, branched or cyclic alkylene or arylene group, Rf is a hydrocarbon group containing a fluorine atom, M + are each independently an ammonium cation, a sulfonium cation or an iodonium cation.

[0646] As M + Preferred examples of the sulfonium cation or iodonium cation represented by the formula include the sulfonium cation represented by the general formula (ZI) and the iodonium cation represented by the general formula (ZII).

[0647] The onium salt (DC) that forms a relatively weak acid relative to the acid generator may be a compound having a cationic site and an anionic site in the same molecule, wherein the cationic site and the anionic site are linked by a covalent bond (hereinafter also referred to as "compound (DCA)").

[0648] As the compound (DCA), a compound represented by any of the following general formulae (C-1) to (C-3) is preferred.

[0649] [Chemical Formula 38]

[0650]

[0651] In the general formulas (C-1) to (C-3),

[0652] R1, R2, and R3 each independently represent a substituent having 1 or more carbon atoms.

[0653] L1 represents a divalent linking group or a single bond that links the cationic portion and the anionic portion.

[0654] -X - Indicates a group selected from -COO - 、-SO3 - 、-SO2 - and -N --Anionic site in R4. R4 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 site of connection with the adjacent N atom.

[0655] R1, R2, R3, R4, and L1 may be bonded to each other to form a ring structure. In general formula (C-3), two of R1 to R3 together represent a divalent substituent, which may be bonded to the nitrogen atom via a double bond.

[0656] Examples of the substituent having 1 or more carbon atoms in R1 to R3 include alkyl, cycloalkyl, aryl, alkoxycarbonyl, cycloalkyloxycarbonyl, aryloxycarbonyl, alkylaminocarbonyl, cycloalkylaminocarbonyl, and arylaminocarbonyl groups, preferably alkyl, cycloalkyl, or aryl.

[0657] Examples of the divalent linking group L1 include linear or branched chain alkylene groups, cycloalkylene groups, arylene groups, carbonyl groups, ether bonds, ester bonds, amide bonds, urethane bonds, urea bonds, and groups combining two or more of these. L1 is preferably an alkylene group, an arylene group, an ether bond, an ester bond, or a group combining two or more of these.

[0658] The low molecular weight compound (DD) having a nitrogen atom and a group detachable by the action of an acid (hereinafter also referred to as "compound (DD)") is preferably an amine derivative having a group detachable by the action of an acid on the nitrogen atom.

[0659] 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 hemiaminal ether group, and more preferably a carbamate group or a hemiaminal ether group.

[0660] 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.

[0661] Compound (DD) may have a carbamate group having a protecting group on the nitrogen atom. The protecting group constituting the carbamate group can be represented by the following general formula (d-1).

[0662] [Chemical Formula 39]

[0663]

[0664] In the general formula (d-1),

[0665] Rb's each independently represent 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). Rb's may be linked to each other to form a ring.

[0666] The alkyl, cycloalkyl, aryl and aralkyl groups represented by Rb may be independently substituted with a functional group such as cyano, amino, pyrrolidino, piperidino, morpholino, oxo, alkoxy or halogen. The same applies to the alkoxyalkyl group represented by Rb.

[0667] Rb is preferably a linear or branched alkyl group, a cycloalkyl group or an aryl group, and more preferably a linear or branched alkyl group or a cycloalkyl group.

[0668] Examples of the ring formed by mutually linking two Rb groups include alicyclic hydrocarbons, aromatic hydrocarbons, heterocyclic hydrocarbons, and derivatives thereof.

[0669] As a specific structure of the group represented by general formula (d-1), the structure disclosed in paragraph

[0466] of the specification of US Patent Publication No. US2012 / 0135348A1 can be cited, but the present invention is not limited thereto.

[0670] The compound (DD) is preferably a compound having a structure represented by the following general formula (6).

[0671] [Chemical Formula 40]

[0672]

[0673] In general formula (6),

[0674] l represents an integer from 0 to 2, m represents an integer from 1 to 3, and l+m=3 is satisfied.

[0675] Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group. When l is 2, the two Ra may be the same or different, and the two Ra may be linked together to form a heterocyclic ring together with the nitrogen atom in the formula. The heterocyclic ring may also contain heteroatoms other than the nitrogen atom in the formula.

[0676] Rb has the same meaning as Rb in the above-mentioned general formula (d-1), and preferred examples are also the same.

[0677] In the general formula (6), the alkyl group, cycloalkyl group, aryl group and aralkyl group as Ra may be substituted with the same groups as the above-mentioned alkyl group, cycloalkyl group, aryl group and aralkyl group which may be substituted independently of Rb.

[0678] Specific examples of the alkyl group, cycloalkyl group, aryl group, and aralkyl group (these groups may be substituted with the above groups) for Ra include the same groups as the above-mentioned specific examples for Rb.

[0679] As specific structures of particularly preferred compounds (DD) in the present invention, the compounds disclosed in paragraph

[0475] of US Patent Application Publication No. 2012 / 0135348A1 can be cited, but the present invention is not limited thereto.

[0680] 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.

[0681] Preferred specific structures of compound (DE) include the compounds disclosed in paragraph

[0203] of US Patent Application Publication No. 2015 / 0309408A1, but are not limited thereto.

[0682] Preferred examples of the acid diffusion controller (D) are shown below.

[0683] [Chemical Formula 41]

[0684]

[0685] [Chemical Formula 42]

[0686]

[0687] Quencher-A to Quencher-K used in Examples can also be preferably used.

[0688] In the composition of the present invention, the acid diffusion controller (D) may be used alone or in combination of two or more.

[0689] The content of the acid diffusion controller (D) in the composition (the total amount when multiple types are present) is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, based on the total solids content of the composition. Furthermore, the molar ratio of the content of the acid diffusion controller (D) in the composition (the total amount when multiple types are present) to the content of the photoacid generator (B) in the composition (the total amount when multiple types are present) is preferably 0.40 or less, more preferably 0.30 or less, and even more preferably 0.25 or less.

[0690] <Hydrophobic resin (E)>

[0691] The composition of the present invention may contain a hydrophobic resin (E) different from the above-mentioned polymer (A).

[0692] The composition of the present invention contains a hydrophobic resin (E), which can control the static and dynamic contact angles on the surface of an actinic ray-sensitive or radiation-sensitive film. This can improve developing characteristics, suppress outgassing, enhance immersion liquid conformability during immersion exposure, and reduce immersion defects.

[0693] The hydrophobic resin (E) is preferably designed to be localized on the surface of the resist film, but unlike a surfactant, it does not necessarily need to have a hydrophilic group in the molecule and does not need to contribute to uniform mixing of polar and non-polar substances.

[0694] From the perspective of concentrating it on the surface of the film, the hydrophobic resin (E) is preferably a resin containing the following repeating units, wherein the repeating units have at least one selected from the group consisting of "fluorine atom", "silicon atom" and "CH3 partial structure contained in the side chain part of the resin".

[0695] When the hydrophobic resin (E) contains fluorine atoms and / or silicon atoms, the fluorine atoms and / or silicon atoms in the hydrophobic resin (E) may be contained in the main chain or in the side chain of the resin.

[0696] When the hydrophobic resin (E) has a fluorine atom, it 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 as a partial structure having a fluorine atom.

[0697] The hydrophobic resin (E) preferably has at least one group selected from the following group (x) to (z).

[0698] (x) acid group

[0699] (y) A group that decomposes by the action of an alkaline developer and increases its solubility in an alkaline developer (hereinafter also referred to as a polarity conversion group)

[0700] (z) Groups that decompose by the action of an acid

[0701] Examples of the acid group (x) include a phenolic hydroxyl group, a carboxyl 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.

[0702] As the acid group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), a sulfonimide group or a bis(alkylcarbonyl)methylene group is preferred.

[0703] Examples of the group (y) that decomposes under the action of an alkaline developer and increases its solubility in an alkaline developer include a lactone group, a carboxylate group (-COO-), 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 sulfonic acid ester group (-SO2O-), preferably a lactone group or a carboxylate group (-COO-).

[0704] Repeating units containing these groups are repeating units in which these groups are directly bonded to the main chain of the resin, and examples thereof include repeating units based on acrylates and methacrylates. These repeating units may be bonded to the main chain of the resin via a linker. Alternatively, these repeating units may be used during the polymerization of polymerization initiators or chain transfer agents containing these groups, thereby introducing these groups into the terminals of the resin.

[0705] Examples of the repeating unit having a lactone group include the same repeating units as those described above in the section regarding the resin (A) and having a lactone structure.

[0706] The content of the repeating unit having a group (y) that decomposes by the action of an alkaline developer and increases its solubility in an alkaline developer is preferably 1 to 100 mol %, more preferably 3 to 98 mol %, and even more preferably 5 to 95 mol %, based on all the repeating units in the hydrophobic resin (E).

[0707] The repeating units having a group (z) decomposable by the action of an acid in the hydrophobic resin (E) may be the same repeating units as those having an acid-decomposable group mentioned for the resin (A). The repeating units having a group (z) decomposable by the action of an acid may have at least one of a fluorine atom and a silicon atom. The content of the repeating units having a group (z) decomposable by the action of an acid is preferably 1 to 80 mol %, more preferably 10 to 80 mol %, and even more preferably 20 to 60 mol % relative to all the repeating units in the resin (E).

[0708] The hydrophobic resin (E) may have a repeating unit different from the above-mentioned repeating units.

[0709] The content of the repeating unit containing a fluorine atom is preferably 10 to 100 mol%, more preferably 30 to 100 mol%, based on the total repeating units contained in the hydrophobic resin (E). Furthermore, the content of the repeating unit containing a silicon atom is preferably 10 to 100 mol%, more preferably 20 to 100 mol%, based on the total repeating units contained in the hydrophobic resin (E).

[0710] On the other hand, particularly when the hydrophobic resin (E) contains a CH3 partial structure in the side chain, it is also preferred that the hydrophobic resin (E) contains substantially no fluorine atoms and silicon atoms. Furthermore, the hydrophobic resin (E) is preferably composed essentially only of repeating units consisting only of atoms selected from carbon atoms, oxygen atoms, hydrogen atoms, nitrogen atoms, and sulfur atoms.

[0711] The weight average molecular weight of the hydrophobic resin (E) in terms of standard polystyrene is preferably more than 8,000 to 100,000, more preferably more than 8,000 to 50,000.

[0712] The total content of residual monomers and / or oligomers in the hydrophobic resin (E) is preferably 0.01 to 5% by mass, more preferably 0.01 to 3% by mass. Furthermore, the dispersion degree (Mw / Mn) is preferably in the range of 1 to 5, more preferably 1 to 3.

[0713] As the hydrophobic resin (E), known resins can be appropriately selected and used alone or as mixtures thereof. For example, known resins disclosed in sections

[0451] to

[0704] of U.S. Patent Application Publication No. 2015 / 0168830A1 and sections

[0340] to

[0356] of U.S. Patent Application Publication No. 2016 / 0274458A1 can be preferably used as the hydrophobic resin (E). In addition, the repeating units disclosed in sections

[0177] to

[0258] of U.S. Patent Application Publication No. 2016 / 0237190A1 are also preferably used as the repeating units constituting the hydrophobic resin (E).

[0714] Preferred examples of monomers corresponding to the repeating unit (E) constituting the hydrophobic resin are shown below.

[0715] [Chemical Formula 43]

[0716]

[0717] [Chemical Formula 44]

[0718]

[0719] The hydrophobic resin (E) may be used alone or in combination of two or more.

[0720] 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.

[0721] 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 in the composition of the present invention.

[0722] Solvent (F)

[0723] The composition of the present invention generally contains a solvent.

[0724] In the composition of the present invention, known resist solvents can be used as appropriate. For example, known solvents disclosed in paragraphs

[0665] to

[0670] in U.S. Patent Application Publication No. 2016 / 0070167A1, paragraphs

[0210] to

[0235] in U.S. Patent Application Publication No. 2015 / 0004544A1, paragraphs

[0424] to

[0426] in U.S. Patent Application Publication No. 2016 / 0237190A1, and paragraphs

[0357] to

[0366] in U.S. Patent Application Publication No. 2016 / 0274458A1 can be preferably used.

[0725] 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.

[0726] As the organic solvent, a mixed solvent of a solvent having a hydroxyl group in its structure and a solvent not containing a hydroxyl group can be used.

[0727] As the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group, the compounds exemplified above can be appropriately selected. However, as the solvent containing a hydroxyl group, alkylene glycol monoalkyl ethers or alkyl lactates are preferred, and propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether (PGEE), 2-hydroxyisobutyric acid methyl, or ethyl lactate are more preferred. Furthermore, as the solvent not containing a hydroxyl group, alkylene glycol monoalkyl ether acetates, alkyl alkoxypropionates, monoketone compounds that may contain a ring, cyclic lactones, or alkyl acetates are preferred. Among them, propylene glycol monomethyl ether acetate (PGMEA), ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, cyclopentanone, or butyl acetate are more preferred, and propylene glycol monomethyl ether acetate, γ-butyrolactone, ethyl ethoxypropionate, cyclohexanone, cyclopentanone, or 2-heptanone are further preferred. As the solvent not containing a hydroxyl group, propionic carbonate is also preferred.

[0728] 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.

[0729] 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.

[0730] <Surfactant (H)>

[0731] The composition of the present invention may or may not contain a surfactant. When containing a surfactant, it is preferably a fluorine-based and / or silicon-based surfactant (specifically, a fluorine-based surfactant, a silicon-based surfactant, or a surfactant having both fluorine atoms and silicon atoms).

[0732] Since the composition of the present invention contains a surfactant, when an exposure light source of 250 nm or less, particularly 220 nm or less, is used, a resist pattern with good adhesion and few development defects can be obtained with good sensitivity and resolution.

[0733] Examples of the fluorine-based and / or silicon-based surfactants include the surfactants described in paragraph

[0276] of US Patent Application Publication No. 2008 / 0248425.

[0734] Furthermore, surfactants other than fluorine-based and / or silicon-based surfactants described in paragraph

[0280] of U.S. Patent Application Publication No. 2008 / 0248425 can also be used.

[0735] These surfactants may be used alone or in combination of two or more.

[0736] When the 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.

[0737] On the other hand, by setting the surfactant content to 10 ppm or more relative to the total solids content of the composition, the surface unevenness of the hydrophobic resin is increased, thereby making the surface of the actinic ray-sensitive or radiation-sensitive film more hydrophobic and improving water-conformability during liquid immersion exposure.

[0738] (Other additives)

[0739] The composition of the present invention may further contain an acid growth agent, a dye, a plasticizer, a photosensitizer, a light absorber, an alkali-soluble resin, a dissolution inhibitor or a dissolution accelerator, and the like.

[0740] The film thickness of the actinic ray-sensitive film or radiation-sensitive film (typically a resist film) formed from the composition of the present invention is 700 nm or more.

[0741] The upper limit of the film thickness is not particularly limited, but is usually 10 μm.

[0742] The film thickness is preferably 700 to 5000 nm, more preferably 700 to 3000 nm, and even more preferably 700 to 2000 nm.

[0743] Such a film thickness can be formed by adjusting the solid content concentration in the composition to an appropriate range so as to have an appropriate viscosity and thereby improving coating properties and film forming properties.

[0744] The solid content concentration of the composition of the present invention is usually 8 to 40% by mass, preferably 10 to 30% by mass, and more preferably 12 to 25% by mass. The solid content concentration is the mass percentage of the resist components other than the solvent relative to the total mass of the composition.

[0745] The composition of the present invention is dissolved in a prescribed organic solvent, preferably in the above-mentioned mixed solvent, and after filtering it through a filter, it is applied to a prescribed support (substrate) for use. The pore size of the filter used for filtering is preferably 0.1 μm or less, more preferably 0.05 μm or less, and further preferably 0.03 μm or less. In addition, when the solid content concentration of the composition is high (for example, 25% by mass or more), the pore size of the filter used for filtering is preferably 3 μm or less, more preferably 0.5 μm or less, and further preferably 0.3 μm or less. The filter is preferably a polytetrafluoroethylene, polyethylene or nylon filter. In the filter filtration, as disclosed in Japanese Patent Application Publication No. 2002-62667 (Japanese Patent Application Publication No. 2002-62667), circulation filtration can be performed, or multiple 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.

[0746] <Application>

[0747] The composition of the present invention relates to an actinic or radiation-sensitive resin composition that reacts and changes its properties upon exposure to actinic rays or radiation. More specifically, the composition of the present invention relates to an actinic or radiation-sensitive resin composition used in semiconductor manufacturing processes such as integrated circuits (ICs), the manufacture of circuit boards for liquid crystal displays (LCDs) or thermal heads, the fabrication of imprint mold structures, other photosensitive processing processes, and the manufacture of lithographic printing plates or acid-curable compositions. The resist pattern formed in the present invention can be used in etching processes, ion implantation processes, bump electrode formation processes, redistribution processes, and MEMS (micro electro mechanical systems).

[0748] The pattern forming method of the present invention has the following characteristics as described above:

[0749] (i) a step of forming an actinic ray-sensitive or radiation-sensitive film having a film thickness of 700 nm or more from the actinic ray-sensitive or radiation-sensitive resin composition (film forming step);

[0750] (ii) a step of irradiating the actinic ray or radiation-sensitive film with an actinic ray or radiation having a wavelength of 200 nm or less (exposure step); and

[0751] (iii) A step of developing the actinic ray- or radiation-sensitive film irradiated with the actinic ray or radiation having a wavelength of 200 nm or less using a developer (development step).

[0752] The pattern forming method of the present invention is not particularly limited as long as it includes the steps (i) to (iii) above, and may further include the following steps.

[0753] In the pattern forming method of the present invention, the exposure method in the (ii) exposure step may be liquid immersion exposure.

[0754] The pattern forming method of the present invention preferably includes a (iv) preheating (PB: PreBake) step before the (ii) exposure step.

[0755] The pattern forming method of the present invention preferably includes a (v) post-exposure bake (PEB) step after the (ii) exposure step and before the (iii) development step.

[0756] The pattern forming method of the present invention may include a plurality of (ii) exposure steps.

[0757] The pattern forming method of the present invention may include the (iv) preheating step a plurality of times.

[0758] The pattern forming method of the present invention may include a plurality of (v) post-exposure heating steps.

[0759] (i) The film forming step is specifically a step of forming an actinic ray-sensitive or radiation-sensitive film having a film thickness of 700 nm or more on a support using an actinic ray-sensitive or radiation-sensitive resin composition.

[0760] In the pattern forming method of the present invention, the (i) film forming step, (ii) exposure step, and (iii) development step can be performed by generally known methods.

[0761] Furthermore, as needed, a resist underlayer film (e.g., SOG (Spin On Glass), SOC (Spin On Carbon), or an antireflective film) may be formed between the photosensitive or radiation-sensitive film and the support. As the resist underlayer film, a known organic or inorganic material can be used as appropriate.

[0762] A protective film (top coat) can be formed on the upper layer of the photosensitive ray or radiation-sensitive film. As a protective film, known materials can be appropriately used. For example, the 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 Patent Application Publication No. 2016 / 157988A can be preferably used. As a protective film-forming composition, it is preferred to include the above-mentioned acid diffusion control agent.

[0763] A protective film may be formed on the upper layer of the actinic ray-sensitive or radiation-sensitive film containing the above-mentioned hydrophobic resin.

[0764] The support is not particularly limited, and in addition to the manufacturing process of semiconductors such as ICs, or the manufacturing process of circuit substrates for liquid crystals or thermal heads, substrates generally used in photolithography processes such as other photosensitive etching processes can be used. Specific examples of the support include inorganic substrates such as silicon, SiO2, and SiN.

[0765] The heating temperature is preferably 70 to 130°C, more preferably 80 to 120°C, in both the (iv) preheating step and the (v) post-exposure heating step.

[0766] The heating time in either the (iv) preheating step or the (v) post-exposure heating step is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and even more preferably 30 to 90 seconds.

[0767] Heating can be performed by a mechanism included in the exposure apparatus and the developing apparatus, or can be performed using a hot plate or the like.

[0768] The wavelength of the light source used in the exposure process is 200 nm or less. This allows the obtained pattern to have excellent resolution. On the other hand, if the wavelength of the light source exceeds 200 nm, it is impossible to obtain a pattern with the desired resolution in a thick film.

[0769] The light source is not particularly limited as long as the wavelength is 200 nm or less. Specifically, ArF excimer laser (193 nm), F2 excimer laser (157 nm), X-rays, EUV (13 nm) or electron beams are preferred, and ArF excimer laser, EUV or electron beams are more preferred.

[0770] In the development step (iii), the developer may be an alkaline developer or a developer containing an organic solvent (hereinafter also referred to as an organic developer), but is preferably an alkaline developer.

[0771] As the alkaline developer, a quaternary ammonium salt represented by tetramethylammonium hydroxide is generally used, but an alkaline aqueous solution of an inorganic base, a primary or tertiary amine, an alcoholamine, a cyclic amine, or the like can also be used.

[0772] The alkaline developer may contain an appropriate amount of alcohol and / or surfactant. The alkaline developer generally has an alkali concentration of 0.1 to 20% by mass and a pH of 10 to 15.

[0773] The development time using an alkaline developer is usually 10 to 300 seconds.

[0774] The alkali concentration, pH, and development time of the alkaline developer can be appropriately adjusted depending on the pattern to be formed.

[0775] 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.

[0776] Examples of ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonylacetone, ionone, diacetone alcohol, acetyl carbinol, acetophenone, methyl naphthyl ketone, isophorone, and propylene carbonate.

[0777] Examples of the ester solvent include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, butyl butanoate, methyl 2-hydroxyisobutyrate, isoamyl acetate, isobutyl isobutyrate, and butyl propionate.

[0778] As the alcohol solvent, amide solvent, ether solvent, and hydrocarbon solvent, the solvents disclosed in paragraphs

[0715] to

[0718] of U.S. Patent Application Publication No. 2016 / 0070167A1 can be used.

[0779] The developer may contain a plurality of solvents or other solvents or water. The developer may contain water in an amount of less than 50% by mass, more preferably less than 20% by mass, further preferably less than 10% by mass, and particularly preferably substantially no water.

[0780] 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.

[0781] The organic developer may contain an appropriate amount of a known surfactant as needed.

[0782] The content of the surfactant is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass, based on the total amount of the developer.

[0783] The organic developer may contain the above-mentioned acid diffusion controller.

[0784] As developing methods, for example, the following can be applied: a method of immersing a substrate in a tank filled with a developer for a certain period of time (dip method); a method of allowing the developer to accumulate on the surface of the substrate by surface tension and allowing it to 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 while scanning a developer nozzle at a certain speed on a substrate rotating at a certain speed (dynamic dispense method), etc.

[0785] A development step using an alkaline aqueous solution (alkaline development step) and a development step using a developer containing an organic solvent (organic solvent development step) can also be combined. This allows patterning to be performed without dissolving only the region with intermediate exposure intensity, thereby enabling the formation of a finer pattern.

[0786] It is preferable to include a step of washing with a rinsing liquid (rinsing step) after the (iii) development step.

[0787] The rinse solution used in the rinse step following the development step using an alkaline developer can be, for example, pure water. The pure water may contain an appropriate amount of a surfactant. In this case, after the development step or the rinse step, a treatment using a supercritical fluid may be performed to remove the developer or rinse solution adhering to the pattern. Furthermore, after the rinse step or the treatment using a supercritical fluid, a heat treatment may be performed to remove any moisture remaining in the pattern.

[0788] The rinsing liquid used in the rinsing step following the development step using a developer containing an organic solvent is not particularly limited as long as it does not dissolve the resist pattern, and a solution containing a common organic solvent can be used. The rinsing liquid preferably contains at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents.

[0789] 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.

[0790] As the rinsing liquid used in the rinsing step at this time, a rinsing liquid containing a monohydric alcohol is more preferably used.

[0791] Examples of the monohydric alcohol used in the rinsing step include linear, branched, or cyclic monohydric alcohols. Specifically, examples include 1-butanol, 2-butanol, 3-methyl-1-butanol, tert-butanol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methyl-2-pentanol, 1-heptanol, 1-octanol, 2-hexanol, cyclopentanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol, and methyl isobutyl carbinol. Examples of the monohydric alcohol having 5 or more carbon atoms include 1-hexanol, 2-hexanol, 4-methyl-2-pentanol, 1-pentanol, 3-methyl-1-butanol, and methyl isobutyl carbinol.

[0792] The components may be mixed in multiple forms or may be mixed with organic solvents other than those listed above.

[0793] The water content of the rinse liquid is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less. By setting the water content to 10% by mass or less, good development characteristics can be obtained.

[0794] The rinsing solution may contain an appropriate amount of a surfactant.

[0795] 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 cleaning is not particularly limited, and can be applied to, 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 the substrate (spray coating method). 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 to 4,000 rpm to remove the rinsing liquid 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 can be removed by this heating process. In the heating process after the rinsing process, the heating temperature is generally 40 to 160°C, preferably 70 to 95°C, and the heating time is generally 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.

[0796] The various materials used in the actinic ray- or radiation-sensitive resin composition of the present invention and the pattern forming method of the present invention (e.g., resist solvents, developers, rinse solutions, antireflective film-forming compositions, or topcoat layer-forming compositions) preferably do not contain impurities such as metal components, isomers, and residual monomers. The content of these impurities in the various materials is preferably 1 ppm or less, more preferably 100 ppt or less, even more preferably 10 ppt or less, and particularly preferably substantially free (below the detection limit of the measuring device).

[0797] As a method for removing impurities such as metals from the above-mentioned various materials, for example, filtration using a filter can be cited. As the filter pore size, the preferred pore size is 10nm or less, more preferably 5nm or less, and further preferably 3nm or less. As the material of the filter, a filter made of polytetrafluoroethylene, polyethylene or nylon is preferred. The filter can use a filter that has been pre-cleaned with an organic solvent. In the filter filtration process, multiple filters can be connected in series or in parallel and used. When using multiple filters, filters with different pore sizes and / or materials can be used in combination. In addition, various materials can be filtered multiple times, and the process of filtering multiple times can be a circulating filtration process. As the filter, a filter with reduced dissolution as disclosed in Japanese Patent Application Publication No. 2016-201426 (Japanese Patent Application Publication No. 2016-201426) is preferred.

[0798] In addition to filtration, impurities can be removed by adsorption materials, or a combination of filtration and adsorption materials can be used. As the adsorption material, known adsorption materials can be used, for example, inorganic adsorption materials such as silica gel and zeolite, or organic adsorption materials such as activated carbon. Examples of metal adsorbents include those disclosed in Japanese Patent Application Publication No. 2016-206500 (JP-A-2016-206500).

[0799] Furthermore, methods for reducing impurities such as metals contained in the various materials mentioned above include selecting raw materials with low metal content, filtering the raw materials, and performing distillation under conditions that minimize contamination by lining the interior of the equipment with Teflon (registered trademark). To reduce metals to the ppt level, it is also preferable to implement glass lining in all processes of the manufacturing equipment for the various materials (binder, PAG, etc.) that synthesize the resist components. The preferred conditions for filtering the raw materials are the same as those described above.

[0800] In order to prevent the mixing of impurities, the above-mentioned various materials are preferably stored in containers described in U.S. Patent Application Publication No. 2015 / 0227049, Japanese Patent Application Publication No. 2015-123351 (JP-A-2015-123351), Japanese Patent Application Publication No. 2017-13804 (JP-A-2017-13804), etc.

[0801] The pattern formed by the pattern forming method of the present invention can also be applied to improve the surface roughness of the pattern. As a method for improving the surface roughness of the pattern, for example, the method disclosed in U.S. Patent Application Publication No. 2015 / 0104957, which is disclosed in the specification, by treating the resist pattern with a plasma containing a hydrogen gas, can be cited. In addition, the known methods described in Japanese Patent Application Publication No. 2004-235468 (Japanese Patent Application Publication No. 2004-235468), U.S. Patent Application Publication No. 2010 / 0020297, Proc. of SPIE Vol. 8328 83280N-1 "EUV Resist Curing Technique for LWR Reduction and Etch Selectivity Enhancement" can also be applied.

[0802] Furthermore, the resist pattern formed by the above method can be used as a core material (Core) of the spacer process disclosed in Japanese Patent Application Publication No. 1991-270227 (Japanese Patent Application Laid-Open No. 3-270227) and US Patent Application Publication No. 2013 / 0209941, for example.

[0803] In the present invention, it is preferred that a pattern having a very high cross-sectional aspect ratio (ratio of the line width of the space pattern to the film thickness of the resist pattern, i.e., (film thickness of the resist pattern) / (line width of the space pattern)) be formed by a thick film of actinic ray-sensitive or radiation-sensitive film.

[0804] The aspect ratio is not particularly limited, but is preferably 2 or greater, more preferably 3 or greater, and even more preferably 4 or greater.

[0805] The upper limit is not particularly limited, and is, for example, 30 or less.

[0806] The formed resist pattern can be used for implantation.

[0807] Furthermore, the formed resist pattern can be used for etching.

[0808] [Method for manufacturing electronic device]

[0809] The present invention also relates to a method for manufacturing an electronic device including the above-described pattern forming method. The electronic device manufactured by the method of the present invention can be preferably incorporated into electrical and electronic equipment (e.g., home appliances, OA (Office Automation)-related equipment, media-related equipment, optical equipment, and communication equipment).

[0810] [Acticular ray-sensitive or radiation-sensitive resin composition]

[0811] Furthermore, the present invention is an actinic ray-sensitive or radiation-sensitive resin composition for use in a pattern forming method, the pattern forming method comprising:

[0812] A pattern forming method comprising:

[0813] (i) forming an actinic ray-sensitive or radiation-sensitive film having a film thickness of 700 nm or more from the actinic ray-sensitive or radiation-sensitive resin composition;

[0814] (ii) irradiating the actinic ray or radiation-sensitive film with actinic rays or radiation having a wavelength of 200 nm or less; and

[0815] (iii) a step of developing the actinic ray- or radiation-sensitive film irradiated with the actinic ray or radiation having a wavelength of 200 nm or less using a developer,

[0816] The actinic ray-sensitive or radiation-sensitive resin composition contains (A) a polymer having an acid-decomposable group and (B) a photoacid generator.

[0817] The polymer (A) includes a repeating unit having a hydrophilic group, and the weight average molecular weight of the polymer (A) is 8,000 or less.

[0818] The (A) polymer and (B) photoacid generator are as described above.

[0819] Example

[0820] Hereinafter, the present invention will be further described in detail with reference to the examples. As long as it does not depart from the purpose of the present invention, the materials, usage amounts, ratios, processing contents, processing steps, etc. shown in the following examples can be appropriately changed. The scope of the present invention should not be construed as being limited by the following examples. In addition, unless otherwise specified, "parts" and "%" are weight references.

[0821] <Polymer (A)>

[0822] The structures of the polymers (A) (polymers-A to -V, polymer-AA, polymer-AB, and polymer-AC) used are shown below.

[0823] The weight average molecular weight (Mw), number average molecular weight (Mn), and dispersion (Mw / Mn) of the polymer (A) were measured by GPC (carrier: tetrahydrofuran (THF)) as described above (in terms of polystyrene conversion). 13 The measurement was performed by C-NMR (Nuclear Magnetic Resonance).

[0824] In addition, the polymers (polymer-W to polymer-Z) are not polymer (A) and are described below for convenience.

[0825] [Chemical Formula 45]

[0826]

[0827] [Chemical Formula 46]

[0828]

[0829] [Chemical Formula 47]

[0830]

[0831] [Chemical Formula 48]

[0832]

[0833] [Chemical Formula 49]

[0834]

[0835] [Chemical Formula 50]

[0836]

[0837] <Photoacid generator (B)>

[0838] The structures of the photoacid generators used (PAG-A to PAG-Z, PAG-AA to PAG-AK) are shown below. Table 1 below also shows the structure of the acid generated by each photoacid generator upon irradiation with actinic rays or radiation. Table 1 also lists the acid dissociation constant (pKa) of each compound at 25°C. pKa values ​​were calculated using Software Package 1.

[0839] Software package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs).

[0840] [Chemical Formula 51]

[0841]

[0842] [Chemical Formula 52]

[0843]

[0844] [Chemical Formula 53]

[0845]

[0846] [Table 1]

[0847] Table 1

[0848]

[0849] The acid generated by PAG-A upon irradiation with actinic rays or radiation is the same as the acid generated by PAG-I to PAG-S and PAG-AA to PAG-AC upon irradiation with actinic rays or radiation.

[0850] The acid generated by PAG-B upon irradiation with actinic rays or radiation is the same as the acid generated by PAG-T upon irradiation with actinic rays or radiation.

[0851] The acid generated by PAG-C upon irradiation with actinic rays or radiation is the same as the acid generated by PAG-U and PAG-AD to PAG-AE upon irradiation with actinic rays or radiation.

[0852] The acid generated by PAG-D upon irradiation with actinic rays or radiation is the same as the acid generated by PAG-V upon irradiation with actinic rays or radiation.

[0853] The acid generated by PAG-E upon irradiation with actinic rays or radiation is the same as the acid generated by PAG-W and PAG-AF to PAG-AG upon irradiation with actinic rays or radiation.

[0854] The acid generated by PAG-F upon irradiation with actinic rays or radiation is the same as the acid generated by PAG-X upon irradiation with actinic rays or radiation.

[0855] The acid generated by PAG-G upon irradiation with actinic rays or radiation is the same as the acid generated by PAG-Y and PAG-AH to PAG-AI upon irradiation with actinic rays or radiation.

[0856] The acid generated by PAG-H upon irradiation with actinic rays or radiation is the same as the acid generated by PAG-Z and PAG-AJ to PAG-AK upon irradiation with actinic rays or radiation.

[0857] <Acid diffusion controller (D)>

[0858] The structures of the acid diffusion controller (D) (Quencher-A to Quencher-K) used are shown below.

[0859] [Chemical Formula 54]

[0860]

[0861] The structures of the surfactants (surfactant-A to surfactant-D) used are shown below.

[0862] Surfactant-A: Megaface R-41 (manufactured by DIC Corporation)

[0863] [Chemical Formula 55]

[0864]

[0865] The solvents used are shown below.

[0866] PGMEA: Propylene glycol monomethyl ether acetate (PGMEA)

[0867] PGME: Propylene glycol monomethyl ether (PGME)

[0868] CyHx: Cyclohexanone

[0869] EEP: Ethyl ethoxypropionate

[0870] EL: Ethyl lactate

[0871] GBL: gamma-butyrolactone

[0872] <Preparation of Actinic Ray-Sensitive or Radiation-Sensitive Resin Composition> (ArF Exposure)

[0873] (Examples 1 to 42, 44 to 99, Reference Example 1, Comparative Examples 2 to 4, 6 to 11, 13 to 14)

[0874] The various components listed in Table 2 were mixed to obtain solutions having the solid content concentrations (mass %) listed in Table 2. The resulting solution was filtered through a UPE (ultra high molecular weight polyethylene) filter having a pore size of 0.1 μm. The resulting actinic ray-sensitive or radiation-sensitive resin compositions (resist compositions) were used in the Examples and Comparative Examples.

[0875] In addition, in the present Examples and Comparative Examples, the solid content in the resist composition refers to all components except the solvent.

[0876] In the tables, the contents (mass %) of the components other than the solvent are expressed as a percentage of the total solid content. Furthermore, the contents (mass %) of the solvents used relative to the total solvent content are also expressed.

[0877] The Ohnishi parameters of the polymer (A) are also shown in Table 2. The Ohnishi parameters can be determined by the above-mentioned method.

[0878] <Pattern formation method (1): ArF exposure, alkaline aqueous solution development (positive)>

[0879] The resist composition prepared above was applied to a Si substrate (manufactured by Advanced Materials Technology) treated with hexamethyldisilazane without providing an antireflection layer, at a rotation speed to achieve the target film thickness (film thickness described in Table 2), and then baked (PreBake; PB) at 120°C for 60 seconds to form an actinic ray-sensitive or radiation-sensitive film (resist film) having various film thicknesses.

[0880] A wafer with a resist film formed thereon was exposed using an ArF excimer laser scanner (ASML, PAS5500 / 1500, wavelength 193 nm, NA 0.50) through a mask containing a line-and-space pattern with a spatial pattern width (hereinafter referred to as "space width") of 500 nm and a pitch width of 1500 nm. The pattern formed after reduced projection exposure and development was then baked (Post Exposure Bake; PEB (Post Exposure Bake)) at 115°C for 60 seconds, developed with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAHaq) for 30 seconds, rinsed with pure water, and spin-dried. This resulted in an isolated spatial pattern with a spatial width of 500 nm and a pitch width of 1500 nm.

[0881] Through the above steps, a pattern wafer for evaluation having a substrate and a pattern formed on the surface of the substrate was obtained.

[0882] (film thickness)

[0883] The formed actinic ray-sensitive or radiation-sensitive film (resist film) was measured at 16 locations in a circle at a distance of 10 cm from the center using VM-3210 (manufactured by SCREEN Corporation), and the average value was defined as the film thickness.

[0884] Performance Evaluation

[0885] [Resolution]

[0886] The resolution was evaluated by reducing the mask size of the space width (transparent portion) from 500 nm to 500 nm for a space width of 1500 nm and a pitch width of 1500 nm after reduced projection exposure, and taking the minimum value of the space width for resolving the space pattern as the resolving power.

[0887] The spatial pattern width was measured using a scanning electron microscope (SEM) (9380II manufactured by Hitachi, Ltd.) The smaller the resolution value, the better it was judged to be.

[0888] [Cracks in the Resist Pattern and Peeling of the Resist Pattern]

[0889] The evaluation pattern wafer was observed using a defect evaluation device KLA2360 (manufactured by KLA Corporation), and the number of cracks and pattern peelings in the pattern formed within one shot (i.e., a rectangle of 12 mm in length and 6 mm in width) was confirmed using the defect evaluation device KLA2360.

[0890] The number of cracks in the pattern formed and the number of pattern peelings mentioned above refers to the total number of cracks in the pattern formed and the number of pattern peelings.

[0891] <Pattern Formation Method (2): ArF Exposure, Organic Solvent Development (Negative)>

[0892] The resist composition prepared above was applied to a Si substrate (manufactured by Advanced Materials Technology) treated with hexamethyldisilazane without providing an antireflection layer, at a rotation speed to achieve the target film thickness (film thickness described in Table 2), and then baked (PreBake; PB) at 120°C for 60 seconds to form an actinic ray-sensitive or radiation-sensitive film (resist film) having various film thicknesses.

[0893] A wafer with a resist film formed on it was exposed using an ArF excimer laser scanner (ASML, PAS5500 / 1500, wavelength 193nm, NA 0.50) through a mask containing a line-and-space pattern with a spatial pattern width (hereinafter referred to as "space width") of 500nm and a pitch width of 1500nm. The pattern formed after reduced projection exposure and development was then baked (Post Exposure Bake; PEB (Post Exposure Bake)) at 115°C for 60 seconds, developed with nBAs or MAK for 30 seconds, rinsed with pure water, and spin-dried. This resulted in an isolated spatial pattern with a space width of 500nm and a pitch width of 1500nm.

[0894] In addition, nBA represents n-butyl acetate, and MAK represents 2-heptanone (methyl amyl ketone).

[0895] Through the above steps, a pattern wafer for evaluation having a substrate and a pattern formed on the surface of the substrate was obtained.

[0896] The film thickness was measured in the same manner as above.

[0897] Performance Evaluation

[0898] [Resolution]

[0899] The resolution was evaluated by reducing the mask size of the space width (light shielding portion) from 500 nm to 500 nm for a space width of 1500 nm and a pitch width of 1500 nm after reduced projection exposure, and taking the minimum value of the space width for resolving the space pattern as the resolving power.

[0900] The spatial pattern width was measured using a scanning electron microscope (SEM) (9380II manufactured by Hitachi, Ltd.) The smaller the resolution value, the better it was judged to be.

[0901] [Cracks in the Resist Pattern and Peeling of the Resist Pattern]

[0902] The evaluation pattern wafer was observed using a defect evaluation device KLA2360 (manufactured by KLA Corporation), and the number of cracks and pattern peelings in the pattern formed within one shot (i.e., a rectangle of 12 mm in length and 6 mm in width) was confirmed using the defect evaluation device KLA2360.

[0903] The number of cracks in the pattern formed and the number of pattern peelings mentioned above refers to the total number of cracks in the pattern formed and the number of pattern peelings.

[0904] <Preparation of Actinic Ray-Sensitive or Radiation-Sensitive Resin Composition> (EUV Exposure)

[0905] (Example 43)

[0906] The various components shown in Table 2 were mixed to obtain solutions having the solid content concentrations (mass %) described in Table 2. The obtained solutions were filtered first through a polyethylene filter with a pore size of 50 nm, then through a nylon filter with a pore size of 10 nm, and finally through a polyethylene filter with a pore size of 3 nm, thereby preparing actinic ray-sensitive or radiation-sensitive resin compositions (resist compositions).

[0907] In addition, in the present example, the solid content in the resist composition means all components except the solvent.

[0908] In the tables, the contents (mass %) of the components other than the solvent are expressed as a percentage of the total solid content. Furthermore, the contents (mass %) of the solvents used relative to the total solvent content are also expressed.

[0909] The Ohnishi parameters of the polymer (A) are also shown in Table 2. The Ohnishi parameters can be determined by the above-mentioned method.

[0910] <Pattern Formation Method (3): EUV Exposure, Alkali Development (Positive)>

[0911] AL412 (manufactured by Brewer Science) was applied to a silicon wafer and baked at 205°C for 60 seconds to form a 30 nm thick underlayer film. The resist composition shown in the table was applied thereto and baked (PB) at 120°C for 60 seconds to form a 700 nm thick positive resist film.

[0912] The resist film was pattern-irradiated using an EUV exposure apparatus (manufactured by Exitech Corporation, Micro Exposure Tool, NA 0.3, Quadrupol, outer sigma 0.68, inner sigma 0.36). A reticle with a line size of 40 nm and a line:space ratio of 1:1 was used.

[0913] The exposed resist film was baked (PEB) at 120°C for 60 seconds, then developed with an aqueous tetramethylammonium hydroxide solution (TMAH, 2.38 mass %) (TMAHaq) for 30 seconds, followed by rinsing with pure water for 30 seconds. The silicon wafer was rotated at 1500 rpm for 30 seconds and then baked at 90°C for 60 seconds, resulting in a line-and-space pattern with an 80nm pitch and a 40nm line width (40nm space width).

[0914] Through the above steps, a pattern wafer for evaluation having a substrate and a pattern formed on the surface of the substrate was obtained.

[0915] The film thickness was measured in the same manner as above.

[0916] Performance Evaluation

[0917] [Resolution]

[0918] The resolution was evaluated by reducing the mask size of the space width (transparent portion) from 50 nm to 50 nm in the space width and pitch width of 500 nm after reduced projection exposure, and taking the minimum value of the space width that resolved the spatial pattern as the resolving power.

[0919] The spatial pattern width was measured using a scanning electron microscope (SEM) (9380II manufactured by Hitachi, Ltd.) The smaller the resolution value, the better it was judged to be.

[0920] [Cracks in the Resist Pattern and Peeling of the Resist Pattern]

[0921] The evaluation pattern wafer was observed using a defect evaluation device KLA2360 (manufactured by KLA Corporation), and the number of cracks and pattern peelings in the pattern formed within one shot (i.e., a rectangle of 12 mm in length and 6 mm in width) was confirmed using the defect evaluation device KLA2360.

[0922] The number of cracks in the pattern formed and the number of pattern peelings mentioned above refers to the total number of cracks in the pattern formed and the number of pattern peelings.

[0923] <Preparation of Actinic Ray-Sensitive or Radiation-Sensitive Resin Composition> (KrF Exposure)

[0924] (Comparative Examples 1 and 5)

[0925] The various components listed in Table 2 were mixed to obtain solutions having the solid content concentrations (mass %) listed in Table 2. The resulting solution was filtered using a UPE (ultra high molecular weight polyethylene) filter having a pore size of 0.1 μm. The resulting actinic ray-sensitive or radiation-sensitive resin composition (resist composition) was used in the comparative examples.

[0926] In this comparative example, the solid content in the resist composition refers to all components except the solvent.

[0927] In the tables, the contents (mass %) of the components other than the solvent are expressed as a percentage of the total solid content. Furthermore, the contents (mass %) of the solvents used relative to the total solvent content are also expressed.

[0928] The Ohnishi parameters of the polymer (A) are also shown in Table 2. The Ohnishi parameters can be determined by the above-mentioned method.

[0929] <Pattern Formation Method (4): KrF Exposure, Alkaline Aqueous Solution Development (Positive)>

[0930] In the pattern forming method (1), a KrF excimer laser scanner (manufactured by ASML, PAS5500 / 850C, NA=0.68, σ=0.60, wavelength 248nm) was used as the exposure device instead of an ArF excimer laser scanner (manufactured by ASML, PAS5500 / 1500, wavelength 193nm, NA0.50). Otherwise, a pattern was formed in the same manner as in the pattern forming method (1), and an evaluation graphic chip having a substrate and a pattern formed on the surface of the substrate was obtained.

[0931] The film thickness was measured in the same manner as above.

[0932] Performance Evaluation

[0933] The resolution, cracks in the resist pattern, and peeling of the resist pattern were evaluated in the same manner as in the above-mentioned pattern forming method (1).

[0934] <Preparation of Actinic Ray-Sensitive or Radiation-Sensitive Resin Composition> (i-Ray Exposure)

[0935] (Comparative Example 12)

[0936] The various components listed in Table 2 were mixed to obtain solutions having the solid content concentrations (mass %) listed in Table 2. The resulting solution was filtered using a UPE (ultra high molecular weight polyethylene) filter having a pore size of 0.1 μm. The resulting actinic ray-sensitive or radiation-sensitive resin composition (resist composition) was used in the comparative examples.

[0937] In this comparative example, the solid content in the resist composition refers to all components except the solvent.

[0938] In the tables, the contents (mass %) of the components other than the solvent are expressed as a percentage of the total solid content. Furthermore, the contents (mass %) of the solvents used relative to the total solvent content are also expressed.

[0939] The Ohnishi parameters of the polymer (A) are also shown in Table 2. The Ohnishi parameters can be determined by the above-mentioned method.

[0940] <Pattern Formation Method (5): i-Ray Exposure, Alkaline Aqueous Solution Development (Positive)>

[0941] In the pattern forming method (1), an i-ray excimer laser scanner (CANON FPA-3000i5+, wavelength 365 nm) was used as the exposure device instead of an ArF excimer laser scanner (manufactured by ASML, PAS5500 / 1500, wavelength 193 nm, NA 0.50). Otherwise, a pattern was formed in the same manner as in the pattern forming method (1), and an evaluation graphic wafer having a substrate and a pattern formed on the surface of the substrate was obtained.

[0942] The film thickness was measured in the same manner as above.

[0943] Performance Evaluation

[0944] The resolution, cracks in the resist pattern, and peeling of the resist pattern were evaluated in the same manner as in the above-mentioned pattern forming method (1).

[0945] The obtained evaluation results are shown in the following Table 2. In addition, "cracks in the resist pattern and peeling of the resist pattern" are described as "cracks".

[0946]

[0947]

[0948]

[0949]

[0950]

[0951]

[0952] As shown in Table 2, the pattern forming method of the present invention has excellent resolution and can suppress cracks in the resist pattern and peeling of the resist pattern when forming a pattern from a thick film (having a thickness of 700 nm or more) of an actinic ray-sensitive or radiation-sensitive film.

[0953] Reference Example 1 is a thin film (500 nm), so when a pattern is formed by a photosensitive ray or radiation-sensitive film, the resolution is excellent and cracks in the resist pattern and peeling of the resist pattern can be suppressed. However, if the film thickness becomes 700 nm, as shown in Comparative Example 2, the effect of the present invention cannot be obtained.

[0954] Industrial applicability

[0955] According to the present invention, a pattern forming method using an actinic ray-sensitive or radiation-sensitive resin composition, a method for manufacturing an electronic device, and an actinic ray-sensitive or radiation-sensitive resin composition can be provided. When a pattern is formed from a thick actinic ray-sensitive or radiation-sensitive film (having a thickness of 700 nm or more), the resolution is excellent and cracking and peeling of the resist pattern can be suppressed.

[0956] While the present invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be added without departing from the spirit and scope of the present invention.

[0957] In addition, this application is based on the Japanese patent application (patent application 2020-32445) filed on February 27, 2020 and the Japanese patent application (patent application 2020-136960) filed on August 14, 2020, the contents of which are incorporated herein by reference.

Claims

1. A pattern forming method, comprising: (i) forming an actinic ray-sensitive or radiation-sensitive film having a film thickness of 700 nm or more from the actinic ray-sensitive or radiation-sensitive resin composition; (ii) irradiating the actinic ray or radiation sensitive film with actinic rays or radiation having a wavelength of 200 nm or less; and (iii) a step of developing the actinic ray- or radiation-sensitive film irradiated with the actinic ray or radiation having a wavelength of 200 nm or less using a developer, wherein: The actinic ray-sensitive or radiation-sensitive resin composition contains (A) a polymer having an acid-decomposable group and (B) a photoacid generator. The polymer (A) includes a repeating unit having an acid-decomposable group, and the repeating unit having an acid-decomposable group includes a repeating unit represented by the following general formula (AI): The polymer (A) further comprises a repeating unit having a hydrophilic group, wherein the repeating unit having a hydrophilic group comprises a repeating unit having a carboxyl group or a hydroxyl group, and comprises a repeating unit represented by the following general formula (III): The weight average molecular weight of the polymer (A) is 8000 or less, The photoacid generator (B) includes a triarylsulfonium compound, a compound represented by the following general formula (ZI-3), or a compound represented by the following general formula (ZI-4). The aryl groups of the triarylsulfonium compound may each independently have an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a halogen atom, a hydroxyl group or a phenylthio group as a substituent, In the general formula (AI), Xa1 represents a hydrogen atom, a halogen atom or a monovalent organic group, T represents a single bond or a divalent linking group, Rx1 to Rx3 each independently represent an alkyl group or a cycloalkyl group, Any two of Rx1 to Rx3 may be bonded to form a ring structure or may not form a ring structure. In the above general formula (III), A represents an ester bond or an amide bond, wherein the ester bond is a group represented by -COO-, and the amide bond is a group represented by -CONH-, n is the number of repetitions of the structure represented by -R0-Z- and represents an integer from 0 to 5, R0 represents an alkylene group, a cycloalkylene group, or a combination thereof. When there are multiple R0 groups, each group independently represents an alkylene group, a cycloalkylene group, or a combination thereof. Z represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond, or a urea bond. When there are multiple Zs, they each independently represent a single bond, an ether bond, an ester bond, an amide bond, a urethane bond, or a urea bond. R8 represents a monovalent organic group having a lactone structure or a sultone structure, R7 represents a hydrogen atom, a halogen atom or a monovalent organic group, In the above general formula (ZI-3), R1 represents an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group or an alkenyl group, R2 and R3 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group or an aryl group, and R2 and R3 are optionally linked to each other to form a ring, R1 and R2 are optionally linked to each other to form a ring, R X and R y Each independently represents an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group or an alkoxycarbonylcycloalkyl group, and R X With R y are optionally linked to each other to form a ring, the ring structure optionally comprising an oxygen atom, a nitrogen atom, a sulfur atom, a keto group, an ether bond, an ester bond, an amide bond, Z - represents anions, In the general formula (ZI-4), l represents an integer from 0 to 2, r represents an integer from 0 to 8, R 13 represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group or an alkoxycarbonyl group, R 14 represents a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group or a cycloalkylsulfonyl group. When there are multiple R 14 When multiple R 14 are optionally the same as or different from each other, R 15 Each independently represents an alkyl group, a cycloalkyl group or a naphthyl group, and the two R 15 Optionally bonded to each other to form a ring, when two R 15 When they are bonded to each other to form a ring, the ring structure may optionally contain an oxygen atom, a nitrogen atom, a sulfur atom, a keto group, an ether bond, an ester bond, or an amide bond. X - Indicates anion.

2. The pattern forming method according to claim 1, wherein The (B) photoacid generator includes a compound represented by the general formula (ZI-3) or a compound represented by the general formula (ZI-4).

3. The pattern forming method according to claim 2, wherein: The Z - or the X - is an anion represented by any of the following general formulas (A1) to (A3), In the above general formula (A1), R 21 、R 22 Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a fluorine atom, an alkyl group substituted by a fluorine atom, or a cycloalkyl group substituted by a fluorine atom, wherein R 21 、R 22 At least one of them is a fluorine atom, an alkyl group substituted by a fluorine atom, or a cycloalkyl group substituted by a fluorine atom, L represents a single bond or a divalent linking group, X represents an organic group, In the above general formula (A2), R 23 represents a hydrogen atom, an alkyl group, a cycloalkyl group, a fluorine atom, -C(=O)-Rx or -S(=O)2-Rx, Rx represents an organic group, R 24 represents a hydrogen atom, an alkyl group, a cycloalkyl group or a fluorine atom, A1 represents -C(=O)- or -S(=O)2-, R 23 With R 24 are optionally bonded to each other to form a ring, In the above general formula (A3), R 25 、R 26 、R 27 Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group or a fluorine atom, A2 to A4 each independently represent -C(=O)- or -S(=O)2-, R 25 、R 26 、R 27 At least two of them are optionally bonded to each other to form a ring.

4. The pattern forming method according to any one of claims 1 to 3, wherein The Daxi parameter of the polymer (A) is 4.2 or less, The Daxi parameter is a parameter used to express carbon density and is obtained by the following formula: Daxi parameter = (total number of atoms in the monomer) / [(number of carbon atoms in the monomer) - (number of oxygen atoms in the monomer)].

5. The pattern forming method according to any one of claims 1 to 3, wherein The polymer (A) includes two or more repeating units having a hydrophilic group, and the repeating units are different from each other.

6. The pattern forming method according to claim 5, wherein The polymer (A) includes three or more repeating units having a hydrophilic group, and the repeating units are different from each other.

7. The pattern forming method according to any one of claims 1 to 3, wherein The repeating unit having a hydrophilic group includes a repeating unit having a carboxyl group.

8. The pattern forming method according to any one of claims 1 to 3, wherein The polymer (A) contains one or more repeating units having a carboxyl group and one or more repeating units having a hydroxyl group.

9. The pattern forming method according to claim 8, wherein: The repeating unit having a carboxyl group is a repeating unit represented by the following general formula (1), In the above general formula (1), R 31 represents a hydrogen atom or an alkyl group, A 31 represents a single bond or a (r+1)-valent linking group, Y represents a carboxyl group, r represents an integer greater than or equal to 1.

10. The pattern forming method according to claim 8, wherein The repeating unit having a hydroxyl group is a repeating unit represented by the following general formula (2), In the above general formula (2), R 41 represents a hydrogen atom or an alkyl group, A 41 Represents a single bond or a (s+1)-valent linking group, where A 41 Does not have an aromatic ring, Z represents a hydroxyl group, s represents an integer greater than or equal to 1.

11. The pattern forming method according to any one of claims 1 to 3, wherein The weight average molecular weight of the polymer (A) is 7,000 or less.

12. The pattern forming method according to any one of claims 1 to 3, wherein The weight average molecular weight of the polymer (A) is 6,000 or less.

13. The pattern forming method according to any one of claims 1 to 3, wherein The photoacid generator (B) is a mixture of two compounds represented by the following general formula (ZI-3), In the above general formula (ZI-3), R1 represents an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group or an alkenyl group, R2 and R3 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group or an aryl group, and R2 and R3 are optionally linked to each other to form a ring, R1 and R2 are optionally linked to each other to form a ring, R X and R y Each independently represents an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group or an alkoxycarbonylcycloalkyl group, and R X With R y are optionally linked to each other to form a ring, the ring structure optionally comprising an oxygen atom, a nitrogen atom, a sulfur atom, a keto group, an ether bond, an ester bond, an amide bond, Z - represents an anion represented by any of the following general formulae (A1) to (A3), In the above general formula (A1), R 21 、R 22 Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a fluorine atom, an alkyl group substituted by a fluorine atom, or a cycloalkyl group substituted by a fluorine atom, wherein R 21 、R 22 At least one of them is a fluorine atom, an alkyl group substituted by a fluorine atom, or a cycloalkyl group substituted by a fluorine atom, L represents a single bond or a divalent linking group, X represents an organic group, In the above general formula (A2), R 23 represents a hydrogen atom, an alkyl group, a cycloalkyl group, a fluorine atom, -C(=O)-Rx or -S(=O)2-Rx, Rx represents an organic group, R 24 represents a hydrogen atom, an alkyl group, a cycloalkyl group or a fluorine atom, A1 represents -C(=O)- or -S(=O)2-, R 23 With R 24 are optionally bonded to each other to form a ring, In the above general formula (A3), R 25 、R 26 、R 27 Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group or a fluorine atom, A2 to A4 each independently represent -C(=O)- or -S(=O)2-, R 25 、R 26 、R 27 At least two of them are optionally bonded to each other to form a ring.

14. The pattern forming method according to claim 13, wherein The photoacid generator (B) is a mixture of two compounds represented by the general formula (ZI-3) and generates two acids upon irradiation with actinic rays or radiation, wherein the acid dissociation constants pKa values ​​of the two acids at 25° C. differ by 0.5 or more.

15. The pattern forming method according to any one of claims 1 to 3, wherein The content of the (B) photoacid generator is 6% by mass or less based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition.

16. The pattern forming method according to any one of claims 1 to 3, wherein The actinic ray-sensitive or radiation-sensitive resin composition includes (D) an acid diffusion controller, and the content of the (D) acid diffusion controller is 0.40 or less in a molar ratio relative to the content of the (B) photoacid generator.

17. The pattern forming method according to any one of claims 1 to 3, wherein The developer is an alkaline developer. 18 . A method for manufacturing an electronic device, comprising the pattern forming method according to claim 1 .

19. An actinic ray-sensitive or radiation-sensitive resin composition for use in a pattern forming method. The pattern forming method comprises: (i) forming an actinic ray-sensitive or radiation-sensitive film having a film thickness of 700 nm or more from the actinic ray-sensitive or radiation-sensitive resin composition; (ii) irradiating the actinic ray or radiation sensitive film with actinic rays or radiation having a wavelength of 200 nm or less; and (iii) a step of developing the actinic ray- or radiation-sensitive film irradiated with the actinic ray or radiation having a wavelength of 200 nm or less using a developer, The actinic ray-sensitive or radiation-sensitive resin composition contains (A) a polymer having an acid-decomposable group and (B) a photoacid generator. The polymer (A) includes a repeating unit having an acid-decomposable group, and the repeating unit having an acid-decomposable group includes a repeating unit represented by the following general formula (AI): The polymer (A) further comprises a repeating unit having a hydrophilic group, wherein the repeating unit having a hydrophilic group comprises a repeating unit having a carboxyl group or a hydroxyl group, and comprises a repeating unit represented by the following general formula (III): The weight average molecular weight of the polymer (A) is 8000 or less, The photoacid generator (B) includes a triarylsulfonium compound, a compound represented by the following general formula (ZI-3), or a compound represented by the following general formula (ZI-4). The aryl groups of the triarylsulfonium compound may each independently have an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a halogen atom, a hydroxyl group or a phenylthio group as a substituent, In the general formula (AI), Xa1 represents a hydrogen atom, a halogen atom or a monovalent organic group, T represents a single bond or a divalent linking group, Rx1 to Rx3 each independently represent an alkyl group or a cycloalkyl group, Any two of Rx1 to Rx3 may be bonded to form a ring structure or may not form a ring structure. In the above general formula (III), A represents an ester bond or an amide bond, wherein the ester bond is a group represented by -COO-, and the amide bond is a group represented by -CONH-, n is the number of repetitions of the structure represented by -R0-Z- and represents an integer from 0 to 5, R0 represents an alkylene group, a cycloalkylene group, or a combination thereof. When there are multiple R0 groups, each group independently represents an alkylene group, a cycloalkylene group, or a combination thereof. Z represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond, or a urea bond. When there are multiple Zs, they each independently represent a single bond, an ether bond, an ester bond, an amide bond, a urethane bond, or a urea bond. R8 represents a monovalent organic group having a lactone structure or a sultone structure, R7 represents a hydrogen atom, a halogen atom or a monovalent organic group, In the above general formula (ZI-3), R1 represents an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group or an alkenyl group, R2 and R3 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group or an aryl group, and R2 and R3 are optionally linked to each other to form a ring, R1 and R2 are optionally linked to each other to form a ring, R X and R y Each independently represents an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group or an alkoxycarbonylcycloalkyl group, and R X With R y are optionally linked to each other to form a ring, the ring structure optionally comprising an oxygen atom, a nitrogen atom, a sulfur atom, a keto group, an ether bond, an ester bond, an amide bond, Z - represents anions, In the general formula (ZI-4), l represents an integer from 0 to 2, r represents an integer from 0 to 8, R 13 represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group or an alkoxycarbonyl group, R 14 represents a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group or a cycloalkylsulfonyl group. When there are multiple R 14 When multiple R 14 are optionally the same as or different from each other, R 15 Each independently represents an alkyl group, a cycloalkyl group or a naphthyl group, and the two R 15 Optionally bonded to each other to form a ring, when two R 15 When they are bonded to each other to form a ring, the ring structure may optionally contain an oxygen atom, a nitrogen atom, a sulfur atom, a keto group, an ether bond, an ester bond, or an amide bond. X - Indicates anion.

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